CN111373019A - Liquid crystal composition and liquid crystal display element - Google Patents

Abstract

The invention provides a liquid crystal composition with excellent vertical alignment and burn-in characteristics, and provides a liquid crystal display element using the liquid crystal composition. The present invention provides a liquid crystal composition containing 1 or more kinds of self-aligning monomers having a 1 st mesogenic skeleton, at least one polymerizable group represented by general formula (PG1), and at least one adsorption group, and containing 2 or more kinds of polymerizable monomers selected from the group consisting of polymerizable monomers represented by general formula (I) having a different chemical structure from the self-aligning monomers.

Description

Translated fromChinese

液晶组合物及液晶显示元件Liquid crystal composition and liquid crystal display element

技术领域technical field

本发明涉及含有3种以上的单体的液晶组合物及使用该液晶组合物的液晶显示元件。The present invention relates to a liquid crystal composition containing three or more monomers, and a liquid crystal display element using the liquid crystal composition.

背景技术Background technique

一般而言，液晶面板、液晶显示器等液晶显示元件通过电场等外部刺激来改变液晶分子的排列状态，并将伴随其的光学特性的变化利用于显示。这种液晶显示元件具有在两片透明基板的间隙填充有液晶分子的状态的构成，通常在与该液晶分子抵接的基板的表面形成有用于预先使液晶分子沿特定方向排列的取向膜。In general, a liquid crystal display element such as a liquid crystal panel and a liquid crystal display changes the arrangement state of liquid crystal molecules by external stimulation such as an electric field, and utilizes the change in optical properties accompanying the change in the display. Such a liquid crystal display element has a structure in which a gap between two transparent substrates is filled with liquid crystal molecules, and an alignment film for aligning the liquid crystal molecules in a specific direction in advance is usually formed on the surface of the substrate in contact with the liquid crystal molecules.

但是，在液晶显示元件的制造工序中，具有下述问题：因取向膜表面所产生的损伤、尘埃而产生取向缺陷；伴随基板尺寸大型化，难以设计及管理用于得到基板整面的均匀取向性及长时间的均匀取向的取向膜。However, in the production process of the liquid crystal display element, there are problems in that alignment defects are generated due to damage and dust on the surface of the alignment film, and it is difficult to design and manage the uniform alignment for the entire substrate surface as the size of the substrate increases. The orientation film of uniform orientation for long-term stability and long-term performance.

因此，近年来，要求开发出通过将含有控制液晶分子取向的自取向剂的液晶组合物用于液晶层，而无需以聚酰亚胺层为代表的取向膜的液晶显示元件。Therefore, in recent years, development of a liquid crystal display element which does not require an alignment film represented by a polyimide layer by using a liquid crystal composition containing a self-alignment agent for controlling the alignment of liquid crystal molecules for a liquid crystal layer is required.

例如专利文献1中，记载了一种含有自取向材料的液晶组合物，该液晶组合物含有具备辛基且显示出高直线性的单官能的联苯单体和具备硬脂基且显示出低直线的双官能的联苯单体，来代替与液晶分子的相互作用相对较弱的丙烯酸月桂酯，通过该液晶组合物来抑制电压保持率下降。For example, Patent Document 1 describes a liquid crystal composition containing a self-alignment material containing a monofunctional biphenyl monomer having an octyl group and showing high linearity, and a stearyl group and showing a low A linear bifunctional biphenyl monomer is used instead of lauryl acrylate, which has a relatively weak interaction with liquid crystal molecules, and this liquid crystal composition suppresses a decrease in voltage retention.

另外，专利文献2中，公开了各种在不使用取向膜的情况下控制液晶分子取向的含有聚合性自取向添加剂的液晶组合物。具体而言，记载了：若将含有低分子量非聚合性液晶成分及聚合性自取向添加剂的液晶组合物填充于无聚酰亚胺取向层的测试单元(没有预取向层的测试用单元)中，则相对于基板表面会有自发的垂直(homeotropic)取向，该取向可稳定地保持至透明点，所形成的VA单元通过施加电压能够可逆地开关。In addition, Patent Document 2 discloses various liquid crystal compositions containing a polymerizable self-alignment additive that control the alignment of liquid crystal molecules without using an alignment film. Specifically, it is described that when a liquid crystal composition containing a low molecular weight non-polymerizable liquid crystal component and a polymerizable self-alignment additive is filled in a test cell without a polyimide alignment layer (a test cell without a pre-alignment layer) , there will be a spontaneous homeotropic orientation relative to the substrate surface, which can be stably maintained to the point of transparency, and the formed VA unit can be reversibly switched on and off by applying a voltage.

现有技术文献prior art literature

专利文献Patent Literature

专利文献1：美国专利公开2017-0123275号公报Patent Document 1: US Patent Publication No. 2017-0123275

专利文献2：日本特表2017-523289号公报Patent Document 2: Japanese Patent Publication No. 2017-523289

发明内容SUMMARY OF THE INVENTION

发明要解决的课题The problem to be solved by the invention

然而，上述专利文献1所示那样的含有2种烷基链长且具备联苯骨架的疏水性单体的组合物，虽然被认为与填充于一对基板间的液晶层的液晶分子的相互作用比丙烯酸月桂酯强，但会发生因对基板的吸附力低而无法控制液晶分子的取向方向的问题。However, a composition containing two types of hydrophobic monomers having a biphenyl skeleton with an alkyl chain length as shown in the above-mentioned Patent Document 1 is considered to interact with liquid crystal molecules in a liquid crystal layer filled between a pair of substrates. It is stronger than lauryl acrylate, but has a problem that the orientation direction of the liquid crystal molecules cannot be controlled due to the low adsorption force to the substrate.

另外，专利文献2中，由于记载了对具有设为羟基、氨基的吸附基团的聚合性自取向添加剂混合非聚合性自取向添加剂、1种聚合性单体的形态，因此被认为是考虑了对基板的吸附力的分子设计。然而，若聚合性自取向添加剂对基板的吸附力过高，则由于聚合性自取向添加剂无法均匀地展开于基板上，因此会产生发生取向不均这样的问题。另外，未考虑过在聚合性自取向添加剂吸附于基板的状态下进行聚合的层的状态。即，就专利文献2所记载的组合物而言，由于为将非聚合性自取向添加剂与聚合性自取向添加剂混合而成的组合物、聚合成分仅为聚合性自取向添加剂或为1种聚合性单体中的任一者，因此难以形成致密的层。若无法形成致密的层，则由于自取向添加剂所具备的垂直取向成分无法固定化，因此会发生预倾角的变化量变大、烧屏特性下降的问题。In addition, Patent Document 2 describes a form in which a non-polymerizable self-alignment additive and one type of polymerizable monomer are mixed with a polymerizable self-alignment additive having an adsorption group set to a hydroxyl group or an amino group, so it is considered to be considered. Molecular design of adsorption to substrates. However, when the adsorption force of the polymerizable self-alignment additive to the substrate is too high, the polymerizable self-alignment additive cannot be spread on the substrate uniformly, and thus there is a problem that alignment unevenness occurs. In addition, the state of the layer polymerized in the state where the polymerizable self-alignment additive is adsorbed on the substrate is not considered. That is, in the composition described in Patent Document 2, since it is a composition obtained by mixing a non-polymerizable self-alignment additive and a polymerizable self-alignment additive, the polymerization component is only the polymerizable self-alignment additive or one type of polymerization It is difficult to form a dense layer because of any of the monomers. If a dense layer cannot be formed, since the vertical alignment component included in the self-alignment additive cannot be immobilized, the amount of change in the pretilt angle becomes large and the burn-in characteristic decreases.

因此，本发明所要解决的课题在于提供一种垂直取向性与烧屏特性优异的液晶组合物，及提供使用了该液晶组合物的液晶显示元件。Therefore, the subject to be solved by the present invention is to provide a liquid crystal composition having excellent vertical alignment and burn-in properties, and to provide a liquid crystal display element using the liquid crystal composition.

本发明所要解决的另一课题在于提供一种垂直取向性、低温溶解性及烧屏特性这3种特性优异的液晶组合物，及提供使用了该液晶组合物的液晶显示元件。Another problem to be solved by the present invention is to provide a liquid crystal composition excellent in three properties of vertical alignment, low temperature solubility, and burn-in properties, and to provide a liquid crystal display element using the liquid crystal composition.

用于解决课题的方法methods for solving problems

本发明人等进行了潜心研究，结果发现，通过含有1种以上的自取向聚合性单体和2种以上具有特定化学结构的聚合性单体的液晶组合物及使用了该液晶组合物的液晶显示元件，可解决上述课题，从而完成本申请发明。As a result of intensive research by the present inventors, it was found that a liquid crystal composition containing one or more types of self-aligning polymerizable monomers and two or more types of polymerizable monomers having a specific chemical structure, and a liquid crystal composition using the same The display element can solve the above-mentioned problems, thereby completing the invention of the present application.

发明效果Invention effect

本发明涉及的液晶组合物显示出对液晶分子的优异的垂直取向性和优异的烧屏特性。The liquid crystal composition according to the present invention exhibits excellent vertical alignment to liquid crystal molecules and excellent burn-in characteristics.

本发明涉及的液晶组合物对基板显示出优异的展开性(润湿扩展)。The liquid crystal composition according to the present invention exhibits excellent spreadability (wetting spread) with respect to a substrate.

本发明涉及的液晶组合物没有取向不均或能够减少取向不均。The liquid crystal composition according to the present invention has no uneven orientation or can reduce the uneven orientation.

本发明涉及的液晶显示元件没有取向不均或显示出减少了的取向不均。The liquid crystal display element according to the present invention exhibits no or reduced alignment unevenness.

具体实施方式Detailed ways

本发明的第一方式为一种液晶组合物，其含有：具有介晶基、通式(PG1)表示的至少一个聚合性基团、及至少一个吸附基团的1种以上的自取向性单体，以及具备与前述自取向性单体不同化学结构式的选自由下述通式(I)所表示的化合物组成的组中的2种以上的聚合性单体。A first aspect of the present invention is a liquid crystal composition containing at least one self-aligning monolith having a mesogenic group, at least one polymerizable group represented by the general formula (PG1), and at least one adsorption group. body, and two or more polymerizable monomers selected from the group consisting of compounds represented by the following general formula (I) having a different chemical structural formula from the aforementioned self-aligning monomers.

[化1][hua 1]

*——S¹¹-P¹¹ (PG1)*——S¹¹ -P¹¹ (PG1)

上述式中，前述P¹¹为以下的式(P-I)～式(P-IX)表示的任一个基团，In the above formula, the aforementioned P¹¹ is any one of the groups represented by the following formulae (PI) to (P-IX),

[化2][hua 2]

(式中，R^p11及R^p12各自独立地表示氢原子、碳原子数1～5的烷基或碳原子数1～5的卤代烷基，W^p11表示单键、-O-、-COO-或亚甲基，t^p11表示0、1或2，前述聚合性基团P¹¹的1个以上的氢原子可以被取代成前述吸附基团。)(wherein, R^p11 and R^p12 each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms, and W^p11 represents a single bond, -O-, -COO- or Methylene group, t^p11 represents 0, 1, or 2, and one or more hydrogen atoms of the aforementioned polymerizable group P¹¹ may be substituted with the aforementioned adsorption group.)

S¹¹表示单键或碳原子数1～15的亚烷基，该亚烷基中的1个-CH₂-或未邻接的2个以上的-CH₂-可以以氧原子不直接邻接的方式被-O-、-OCO-或-COO-取代，前述S¹¹的1个以上的氢原子可以被取代成前述吸附基团。上述化学式中的＊表示连接键。)S¹¹ represents a single bond or an alkylene group having 1 to 15 carbon atoms, and one -CH₂ - or two or more non-adjacent -CH₂ - in the alkylene group may not be directly adjacent to an oxygen atom. Substituted by -O-, -OCO- or -COO-, one or more hydrogen atoms of the aforementioned S¹¹ may be substituted into the aforementioned adsorption group. * in the above chemical formula represents a bond. )

[化3][hua 3]

(上述通式(I)中，R¹⁰¹、R¹⁰²、R¹⁰³、R¹⁰⁴、R¹⁰⁵、R¹⁰⁶、R¹⁰⁷、R¹⁰⁸、R¹⁰⁹及R¹¹⁰各自独立地表示P²¹-S²¹-、碳原子数1至18的烷基、碳原子数1至18的烷氧基、卤素原子或氢原子中的任一者，上述P²¹为上述式(R-I)～式(R-IX)表示的任一个基团，(In the above general formula (I), R¹⁰¹ , R¹⁰² , R¹⁰³ , R¹⁰⁴ , R¹⁰⁵ , R¹⁰⁶ , R¹⁰⁷ , R¹⁰⁸ , R¹⁰⁹ and R¹¹⁰ each independently represent P²¹ -S²¹ -, carbon Any of an alkyl group having 1 to 18 atoms, an alkoxy group having 1 to 18 carbon atoms, a halogen atom, or a hydrogen atom, and the above P²¹ is any one represented by the above formula (RI) to formula (R-IX) a group,

上述S²¹表示单键或碳原子数1～15的亚烷基，该亚烷基中的1个或2个以上的-CH₂-可以以氧原子不直接邻接的方式被-O-、-OCO-或-COO-取代，The above-mentioned S²¹ represents a single bond or an alkylene group having 1 to 15 carbon atoms, and one or more -CH₂ - in the alkylene group may be -O-, - so that the oxygen atoms are not directly adjacent to each other. OCO- or -COO- substituted,

n¹¹表示0、1或2，n¹¹ means 0, 1 or 2,

n¹²及n¹³各自独立地表示0或1，n¹² and n¹³ each independently represent 0 or 1,

n¹¹+n¹²+n¹³＝1、2或3，n¹¹ +n¹² +n¹³ =1, 2 or 3,

A¹¹表示选自由下述的基团(a)、基团(b)及基团(c)组成的组中的基团：A¹¹ represents a group selected from the group consisting of the following group (a), group (b) and group (c):

(a)1,4-亚环己基(存在于该基团中的1个-CH₂-或未邻接的2个以上的-CH₂-可以被取代成-O-。)(a) 1,4-cyclohexylene group (One -CH₂ - or two or more non-adjacent -CH₂ - present in this group may be substituted with -O-.)

(b)1,4-亚苯基(存在于该基团中的1个-CH＝或未邻接的2个以上的-CH＝可以被取代成-N＝。)及(b) 1,4-phenylene (one -CH= present in this group or two or more non-adjacent -CH= may be substituted with -N=.) and

(c)萘-2,6-二基、2,7-菲二基、1,2,3,4-四氢萘-2,6-二基或十氢萘-2,6-二基(存在于萘-2,6-二基或1,2,3,4-四氢萘-2,6-二基中的1个-CH＝或未邻接的2个以上的-CH＝可以被取代成-N＝。)(c) Naphthalene-2,6-diyl, 2,7-phenanthrenediyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl or decahydronaphthalene-2,6-diyl ( One -CH= or two or more non-adjacent -CH= present in naphthalene-2,6-diyl or 1,2,3,4-tetrahydronaphthalene-2,6-diyl may be substituted into -N=.)

上述基团(a)、基团(b)及基团(c)可以各自独立地被碳原子数1～12的烷基、碳原子数1～12的烷氧基、卤素、氰基、硝基或P¹¹-S¹¹-取代，The above-mentioned group (a), group (b) and group (c) may be independently replaced by an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, halogen, cyano, nitro base or P¹¹ -S¹¹ - substituted,

L¹⁰及L¹¹各自独立地表示单键、-OCH₂-、-CH₂O-、-C₂H₄-、-OC₂H₄O-、-COO-、-OCO-、-CH＝CR^a-COO-、-CH＝CR^a-OCO-、-COO-CR^a＝CH-、-OCO-CR^a＝CH-、-(CH₂)_z-COO-、-(CH₂)_z-OCO-、-OCO-(CH₂)_z-、-COO-(CH₂)_z-、-CH＝CH-、-CF₂O-、-OCF₂-或-C≡C-(式中，R^a各自独立地表示氢原子或碳原子数1～3的烷基，前述式中，z各自独立地表示1～4的整数。)，L¹⁰ and L¹¹ each independently represent a single bond, -OCH₂ -, -CH₂ O-, -C₂ H₄ -, -OC₂ H₄ O-, -COO-, -OCO-, -CH=CR^a -COO-, -CH=CR^a -OCO-, -COO-CR^a =CH-, -OCO-CR^a =CH-, -(CH₂ )_z -COO-, -(CH₂ )_z -OCO -, -OCO-(CH₂ )_z -, -COO-(CH₂ )_z -, -CH=CH-, -CF₂ O-, -OCF₂ - or -C≡C- (wherein R^a each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and in the above formula, z each independently represents an integer of 1 to 4.),

当P²¹、S²¹、L¹¹及A¹¹存在多个的情形时，各自可相同也可不同。)When there are a plurality of P²¹ , S²¹ , L¹¹ and A¹¹ , each of them may be the same or different. )

本发明涉及的液晶组合物由于含有化学结构不同的至少3种单体，因此容易应对各种聚合条件，容易进行聚合反应，从而能够形成致密的聚合物的网络层。另外，认为通过使用2种以上的聚合性单体，可含有参与聚合反应的聚合性单体组与有助于垂直取向性的聚合性单体组的功能分离的2种以上的单体，因此能够实现高垂直取向性与小预倾变化量。Since the liquid crystal composition according to the present invention contains at least three kinds of monomers having different chemical structures, it is easy to cope with various polymerization conditions, and the polymerization reaction is easy to proceed, so that a dense polymer network layer can be formed. In addition, it is considered that by using two or more kinds of polymerizable monomers, two or more kinds of monomers that contribute to the functional separation of the polymerizable monomer group participating in the polymerization reaction and the polymerizable monomer group contributing to the vertical alignment can be contained. High vertical orientation and small pretilt variation can be achieved.

以下，本发明涉及的液晶组合物含有为必须构成成分的自取向性单体及聚合性单体作为聚合性成分，并含有非聚合性液晶化合物作为液晶成分。以下，在说明作为必须构成成分的自取向性单体及聚合性单体后，再详述液晶组合物所含的液晶成分。Hereinafter, the liquid crystal composition according to the present invention contains a self-aligning monomer and a polymerizable monomer, which are essential constituent components, as a polymerizable component, and contains a non-polymerizable liquid crystal compound as a liquid crystal component. Hereinafter, the liquid crystal component contained in the liquid crystal composition will be described in detail after the self-aligning monomer and the polymerizable monomer, which are essential constituent components, are described.

＜自取向性单体＞<Self-aligning monomer>

本发明涉及的自取向性单体主要添加于液晶组合物来使用，相对于与含有该液晶组合物的液晶层直接抵接的构件(电极(例如，ITO)、基板(例如，玻璃基板、丙烯酸基板、透明基板、柔性基板等)、树脂层(例如，滤色器、取向膜、保护层等)、绝缘膜(例如，无机材料膜、SiNx等))发生相互作用，具备诱发液晶层的液晶分子的垂直排列或水平取向的功能。The self-aligning monomer according to the present invention is mainly used by being added to a liquid crystal composition, and is used for members (electrodes (for example, ITO), substrates (for example, glass substrates, acrylics) that are in direct contact with the liquid crystal layer containing the liquid crystal composition. substrates, transparent substrates, flexible substrates, etc.), resin layers (eg, color filters, alignment films, protective layers, etc.), insulating films (eg, inorganic material films, SiNx, etc.) interact with each other, and a liquid crystal having an induced liquid crystal layer A function of the vertical alignment or horizontal orientation of molecules.

上述自取向性单体优选具有用于聚合的聚合性基团、与液晶分子类似的介晶基团、以及能够和与液晶层直接抵接的构件相互作用的吸附基团，并根据需要进一步具有诱发液晶分子取向的柔性基团。The self-aligning monomer preferably has a polymerizable group for polymerization, a mesogenic group similar to liquid crystal molecules, and an adsorption group capable of interacting with a member directly in contact with the liquid crystal layer, and further as necessary Flexible groups that induce the orientation of liquid crystal molecules.

“聚合性基团”"polymeric group"

本发明涉及的聚合性基团为通式(PG1)表示的基团，P¹¹为选自下述通式(P-I)～通式(P-IX)表示的组中的基团。The polymerizable group according to the present invention is a group represented by the general formula (PG1), and P¹¹ is a group selected from the group represented by the following general formula (PI) to (P-IX).

[化4][hua 4]

(式中，R^p11及R^p12各自独立地表示氢原子、碳原子数1～5的烷基或碳原子数1～5的卤代烷基，W^p11表示单键、-O-、-COO-或亚甲基，t^p11表示0、1或2。)(wherein, R^p11 and R^p12 each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms, and W^p11 represents a single bond, -O-, -COO- or methylene, t^p11 represents 0, 1 or 2.)

上述P¹¹优选为选自下述通式(P-I)～通式(P-IX)表示的组中的基团，优选为通式(P-I)。The above-mentioned P¹¹ is preferably a group selected from the group represented by the following general formula (PI) to general formula (P-IX), and preferably general formula (PI).

本发明涉及的自取向性单体中，P¹¹-S¹¹-可以键结于介晶基团、吸附基团和/或柔性基团。In the self-aligning monomer involved in the present invention, P¹¹ -S¹¹ - may be bonded to a mesogenic group, an adsorption group and/or a flexible group.

另外，在本发明的自取向性单体中，聚合性基团优选直接或通过间隔基团键结于介晶基团、吸附基团或柔性基团，更优选直接或通过间隔基团键结于介晶基团或吸附基团。In addition, in the self-aligning monomer of the present invention, the polymerizable group is preferably bonded directly or through a spacer group to a mesogenic group, an adsorption group or a flexible group, more preferably directly or through a spacer group. in mesogenic groups or adsorption groups.

上述间隔基团(Sp¹¹)优选表示单键或直链状或者分支状的碳原子数1～20个的亚烷基，更优选表示单键或直链状的碳原子数1～20个的亚烷基，更优选表示单键或直链状的碳原子数2～10个的亚烷基。另外，在上述间隔基团(Sp¹¹)中，亚烷基中的1个或未邻接的2个以上的-CH₂-可以各自独立地被-CH＝CH-、-C≡C-、-O-、-CO-、-COO-或-OCO-取代。The spacer group (Sp¹¹ ) preferably represents a single bond or a linear or branched alkylene group having 1 to 20 carbon atoms, more preferably a single bond or a linear or linear alkylene group having 1 to 20 carbon atoms The alkylene group more preferably represents a single bond or a linear alkylene group having 2 to 10 carbon atoms. In addition, in the above spacer group (Sp¹¹ ), one or two or more -CH₂ - not adjacent to the alkylene group may be independently replaced by -CH=CH-, -C≡C-, - O-, -CO-, -COO- or -OCO- substituted.

在本发明涉及的自取向性单体中，聚合性基团(P¹¹-S¹¹-)的数目优选为1以上5以下，更优选为1以上4以下，进一步优选为2以上4以下，进一步优选为2或3，更进一步优选为2。In the self-aligning monomer according to the present invention, the number of polymerizable groups (P¹¹ -S¹¹ -) is preferably 1 or more and 5 or less, more preferably 1 or more and 4 or less, still more preferably 2 or more and 4 or less, and furthermore 2 or 3 are preferable, and 2 is more preferable.

P¹¹-S¹¹-中的氢原子可以被聚合性基团、吸附基团和/或柔性基团取代。The hydrogen atom in P¹¹ -S¹¹ - may be substituted with a polymerizable group, an adsorption group and/or a flexible group.

“介晶基团”"Mesogenic group"

本发明涉及的介晶基团是指具备刚性部分的基团，例如具备1个以上的环式基的基团，优选具有2～4个环式基，更优选具有3～4个环式基，根据需要，环式基可以用连结基进行连结。介晶基团优选为与液晶层所使用的液晶化合物类似的骨架。The mesogenic group in the present invention refers to a group having a rigid moiety, for example, a group having one or more cyclic groups, preferably 2 to 4 cyclic groups, more preferably 3 to 4 cyclic groups , if necessary, the cyclic group can be linked with a linking group. The mesogenic group is preferably a skeleton similar to the liquid crystal compound used in the liquid crystal layer.

需要说明的是，本说明书中，“环式基”是指构成的原子键结成环状的原子团，包含碳环、杂环、饱和或不饱和环式结构、单环、2环式结构、多环式结构、芳香族、非芳香族等。另外，环式基可以含有至少1个杂原子，进一步，可以被至少1个取代基(卤素原子、反应性官能团、有机基(烷基、芳基等)取代。当环式基为单环的情形时，介晶基团优选含有2个以上的单环。It should be noted that, in this specification, "cyclic group" refers to an atomic group in which the constituent atoms are bonded to form a ring, including carbocyclic, heterocyclic, saturated or unsaturated cyclic structures, monocyclic, bicyclic structures, Polycyclic structure, aromatic, non-aromatic, etc. In addition, the cyclic group may contain at least one heteroatom, and further, may be substituted with at least one substituent (halogen atom, reactive functional group, organic group (alkyl, aryl, etc.). When the cyclic group is monocyclic In this case, the mesogenic group preferably contains two or more monocyclic rings.

上述介晶基团例如优选由通式(AL)表示。The above-mentioned mesogenic group is preferably represented by the general formula (AL), for example.

[化5][hua 5]

(式中，Z^AL表示单键、-CH＝CH-、-CF＝CF-、-C≡C-、-COO-、-OCO-、-OCOO-、-CF₂O-、-OCF₂-、-CH＝CHCOO-、-OCOCH＝CH-、-CH₂-CH₂COO-、-OCOCH₂-CH₂-、-CH＝C(CH₃)COO-、-OCOC(CH₃)＝CH-、-CH₂-CH(CH₃)COO-、-OCOCH(CH₃)-CH₂-、-OCH₂CH₂O-或碳原子数1～20的亚烷基，该亚烷基中的1个或不邻接的2个以上的-CH₂-可以被-O-、-COO-或-OCO-取代，(wherein, Z^AL represents a single bond, -CH=CH-, -CF=CF-, -C≡C-, -COO-, -OCO-, -OCOO-, -CF₂ O-, -OCF₂ - , -CH=CHCOO-, -OCOCH=CH-, -CH₂ -CH₂ COO-, -OCOCH₂ -CH₂ -, -CH=C(CH₃ )COO-, -OCOC(CH₃ )=CH- , -CH₂ -CH(CH₃ )COO-, -OCOCH(CH₃ )-CH₂ -, -OCH₂ CH₂ O- or an alkylene group having 1 to 20 carbon atoms, wherein 1 of the alkylene groups Two or more -CH₂ - which are not adjacent to each other may be substituted by -O-, -COO- or -OCO-,

A^AL表示2价的环式基，A^AL represents a divalent cyclic group,

Z^AL及A^AL中的1个或2个以上的氢原子可以各自独立地被卤素原子、吸附基团、P¹¹-S¹¹-或1价有机基取代，当Z^AL及A^AL各自存在多个的情形时，各自彼此可相同也可不同，m^AL表示1～5的整数，上述式中的左端的＊及右端的＊表示连接键。)One or more hydrogen atoms in Z^AL and A^AL may be independently substituted by halogen atoms, adsorbing groups, P¹¹ -S¹¹ - or monovalent organic groups, and when Z^AL and A^AL exist more than one In the case of two, each of them may be the same or different from each other, m^AL represents an integer of 1 to 5, and * in the left end and * in the right end in the above formula represent a connecting bond. )

通式(AL)中，Z^AL优选为单键或碳原子数2～20的亚烷基，更优选为单键或碳原子数2～10的亚烷基。上述亚烷基中的1个或不邻接的2个以上的-CH₂-可以被-O-、-COO-或-OCO-取代。进一步，当以棒状分子的直线性为目的的情形时，优选环与环直接连结的形态即单键或直接连结环与环的原子的数目为偶数个的形态。例如，当-CH₂-CH₂COO-的情形时，直接连结环与环的原子的数目为4个。In the general formula (AL), Z^AL is preferably a single bond or an alkylene group having 2 to 20 carbon atoms, more preferably a single bond or an alkylene group having 2 to 10 carbon atoms. One or two or more non-adjacent -CH₂ - in the above alkylene group may be substituted with -O-, -COO- or -OCO-. Furthermore, when the linearity of the rod-shaped molecule is aimed at, a form in which a ring is directly connected to a ring, that is, a form in which the number of atoms directly connecting a single bond or a ring and a ring is an even number is preferable. For example, in the case of -CH₂ -CH₂ COO-, the number of atoms directly connecting the ring and the ring is four.

通式(AL)中，环式基优选表示选自由1,4-亚苯基、1,4-亚环己基、1,4-环己烯基、四氢吡喃-2,5-二基、1,3-二

烷-2,5-二基、四氢噻喃-2,5-二基、噻吩-2,5-二基、1,4-双环(2,2,2)亚辛基、十氢萘-2,6-二基、吡啶-2,5-二基、嘧啶-2,5-二基、吡嗪-2,5-二基、噻吩-2,5-二基、1,2,3,4-四氢萘-2,6-二基、2,6-亚萘基、菲-2,7-二基、9,10-二氢菲-2,7-二基、1,2,3,4,4a,9,10a-八氢菲-2,7-二基、1,4-亚萘基、苯并[1,2-b：4,5-b‘]二噻吩-2,6-二基、苯并[1,2-b：4,5-b‘]二硒吩-2,6-二基、[1]苯并噻吩并[3,2-b]噻吩-2,7-二基、[1]苯并硒吩并[3,2-b]硒吩-2,7-二基及芴-2,7-二基组成的组中的1种结构，这些结构可未经取代或经取代，更优选为1,4-亚苯基、1,4-亚环己基、2,6-亚萘基或菲-2,7-二基，优选为1,4-亚苯基或1,4-亚环己基。另外，环式基中的1个或2个以上的氢原子可以被卤素原子、吸附基团、P¹¹-S¹¹-或1价有机基取代。In the general formula (AL), the cyclic group preferably represents a group selected from 1,4-phenylene, 1,4-cyclohexylene, 1,4-cyclohexenyl, and tetrahydropyran-2,5-diyl , 1,3-two

Alkane-2,5-diyl, tetrahydrothiopyran-2,5-diyl, thiophene-2,5-diyl, 1,4-bicyclo(2,2,2)octylene, decahydronaphthalene- 2,6-diyl, pyridine-2,5-diyl, pyrimidine-2,5-diyl, pyrazine-2,5-diyl, thiophene-2,5-diyl, 1,2,3, 4-Tetrahydronaphthalene-2,6-diyl, 2,6-naphthylene, phenanthrene-2,7-diyl, 9,10-dihydrophenanthrene-2,7-diyl, 1,2,3 ,4,4a,9,10a-octahydrophenanthrene-2,7-diyl, 1,4-naphthylene, benzo[1,2-b:4,5-b']dithiophene-2,6 -diyl, benzo[1,2-b:4,5-b']diselenophene-2,6-diyl, [1]benzothieno[3,2-b]thiophene-2,7 -diyl, [1]benzoselenopheno[3,2-b]selenophene-2,7-diyl and fluorene-2,7-diyl group consisting of 1 structure, these structures may not be Substituted or substituted, more preferably 1,4-phenylene, 1,4-cyclohexylene, 2,6-naphthylene or phenanthrene-2,7-diyl, preferably 1,4-phenylene or 1,4-cyclohexylene. In addition, one or more hydrogen atoms in the cyclic group may be substituted with a halogen atom, an adsorption group, P¹¹ -S¹¹ - or a monovalent organic group.

通式(AL)中，所谓一价有机基，为通过有机化合物形成1价基团的形态而构成化学结构的基团，是指从有机化合物去除1个氢原子而成的原子团，例如可列举：碳原子数1～15的烷基、碳原子数2～15的烯基、碳原子数1～14的烷氧基、碳原子数2～15的烯氧基等，优选为碳原子数1～15的烷基或碳原子数1～14的烷氧基。另外，上述烷基、烯基、烷氧基、烯氧基中的1个或不邻接的2个以上的-CH₂-可以被-O-、-COO-或-OCO-取代。进一步，上述一价有机基可以具有作为后述的柔性基团的作用。In the general formula (AL), the monovalent organic group is a group that forms a monovalent group by an organic compound to form a chemical structure, and refers to an atomic group obtained by removing one hydrogen atom from an organic compound, and examples thereof include : an alkyl group having 1 to 15 carbon atoms, an alkenyl group having 2 to 15 carbon atoms, an alkoxy group having 1 to 14 carbon atoms, an alkenyloxy group having 2 to 15 carbon atoms, etc., preferably 1 carbon atom ~15 alkyl group or C1-14 alkoxy group. In addition, one of the above-mentioned alkyl groups, alkenyl groups, alkoxy groups, and alkenyloxy groups, or two or more non-adjacent -CH₂ - may be substituted with -O-, -COO-, or -OCO-. Furthermore, the above-mentioned monovalent organic group may function as a flexible group to be described later.

上述通式(AL)中，m^AL优选为2～4的整数。In the above general formula (AL), m^AL is preferably an integer of 2 to 4.

作为上述介晶基团的优选形态，可列举以下的式(me-1)～(me-42)。通式(AL)为这些结构中的2个氢原子脱离后的结构。As a preferable aspect of the said mesogenic group, the following formulae (me-1)-(me-42) are mentioned. The general formula (AL) is a structure in which two hydrogen atoms in these structures are removed.

这些式(me-1)～(me-44)中的环己烷环、苯环或萘环中的1个或2个以上氢原子可以被取代成卤素原子、P¹¹-S¹¹-、1价有机基(例如，碳原子数1～15的烷基、碳原子数1～14的烷氧基)、吸附基团或柔性基团。One or more hydrogen atoms in the cyclohexane ring, benzene ring, or naphthalene ring in these formulae (me-1) to (me-44) may be substituted with halogen atoms, P¹¹ -S¹¹ -, 1 A valent organic group (eg, an alkyl group having 1 to 15 carbon atoms, an alkoxy group having 1 to 14 carbon atoms), an adsorption group, or a flexible group.

[化6][hua 6]

[化7][hua 7]

[化8][hua 8]

[化9][Chemical 9]

[化10][Chemical 10]

上述介晶基团中，优选的形态为式(me-8)～(me-44)，更优选为式(me-8)～(me-10)、式(me-12)～(me-18)、式(me-22)～(me-24)、式(me-26)～(me-27)及式(me-29)～(me-44)，进一步优选为式(me-12)、(me-15)～(me-16)、(me-22)～(me-24)、(me-29)、(me-34)、(me-36)～(me-37)、(me-42)～(me-44)。Among the above mesogenic groups, the preferred forms are the formulae (me-8) to (me-44), and the more preferred forms are the formulae (me-8) to (me-10) and the formulae (me-12) to (me- 18), formula (me-22)～(me-24), formula (me-26)～(me-27) and formula (me-29)～(me-44), more preferably formula (me-12) ), (me-15)～(me-16), (me-22)～(me-24), (me-29), (me-34), (me-36)～(me-37), (me-42)～(me-44).

上述介晶基团中，特别优选的形态由以下的通式(AL-1)或(AL-2)表示，更优选为式(AL-2)。Among the above-mentioned mesogenic groups, a particularly preferable form is represented by the following general formula (AL-1) or (AL-2), and a formula (AL-2) is more preferable.

[化11][Chemical 11]

(上述式中，X^al1～X^al18各自独立地表示氢原子、卤素原子、P¹¹-S¹¹-、吸附基团或柔性基团，环A及环B各自独立地表示环己烷环或苯环，(In the above formula, X^a11 to X^a18 each independently represent a hydrogen atom, a halogen atom, P¹¹ -S¹¹ -, an adsorption group or a flexible group, and Ring A and Ring B each independently represent a cyclohexane ring or a benzene ring ring,

X^al1～X^al18的任1种或2种以上被取代成前述吸附基团，Any one or two or more of X^a11 to X^a18 are substituted into the aforementioned adsorption groups,

X^al1～X^al18的任1种或2种以上被取代成前述柔性基团，Any one or two or more of X^a11 to X^a18 are substituted into the aforementioned flexible groups,

前述吸附基团及前述柔性基团可以被取代成前述P¹¹-S¹¹-，The aforementioned adsorption group and the aforementioned flexible group may be substituted into the aforementioned P¹¹ -S¹¹ -,

通式(AL-1)或通式(AL-2)中各自具有1种或2种以上的前述P¹¹-S¹¹-。)Each of the general formula (AL-1) or the general formula (AL-2) has one or two or more of the aforementioned P¹¹ -S¹¹ -. )

上述式(AL-1)中，优选X^a11或X^a18～X^a112的至少1种或2种以上被取代成吸附基团，更优选X^a11或X^a110的至少1种或2种以上被取代成吸附基团。需要说明的是，在该情形时，前述吸附基团可以被取代成P¹¹-S¹¹-。尤其是当环A为环己烷环的情形时，优选X^a110被取代成吸附基团。In the above formula (AL-1), preferably at least one or two or more of X^a11 or X^a18 to X^a112 are substituted into adsorption groups, more preferably at least one or two or more of X^a11 or X^a110 are substituted into adsorption groups. It should be noted that, in this case, the aforementioned adsorption group may be substituted with P¹¹ -S¹¹ -. Especially when the ring A is a cyclohexane ring, it is preferable that X^a110 is substituted into an adsorption group.

上述式(AL-1)中，优选X^a16～X^a114的至少1种或2种以上被取代成聚合性基团，更优选X^al9或X^a111的任一者被取代成P¹¹-S¹¹-。In the above formula (AL-1), preferably at least one or two or more of X^a16 to X^a114 are substituted with a polymerizable group, and more preferably any one of X^{a19 or X a111is} substituted with P¹¹ -S¹¹ -.

上述式(AL-1)中，优选X^a11～X^a13、X^a6～X^a114、X^a117～X^a118的至少1种或2种以上被取代成柔性基团，优选X^a11～X^a13、X^a6～X^a19、X^a111～X^a114或X^a117～X^a118的至少1种或2种以上被取代成柔性基团。更优选X^a11被取代成柔性基团，且X^a6～X^a19或X^a111～X^a114的任1种被取代成柔性基团。在该情形时，进一步优选前者的X^a11中的柔性基团的碳原子数比后者的柔性基团多。柔性基团也可以被取代成P¹¹-S¹¹-。In the above formula (AL-1), preferably at least one or two or more of X^a11 to X^a13 , X^a6 to X^a114 , and X^a117 to X^a118 are substituted into flexible groups, preferably X^a11 to X^a13 , X At least one or two or more of^a6 to X^a19 , X^a111 to X^a114 or X^a117 to X^a118 are substituted with a flexible group. More preferably, X^a11 is substituted with a flexible group, and any one of X^a6 to X^a19 or X^a111 to X^a114 is substituted with a flexible group. In this case, it is more preferable that the number of carbon atoms of the flexible group in X^a11 of the former is larger than that of the latter. The flexible group can also be substituted as P¹¹ -S¹¹ -.

上述式(AL-2)中，优选X^a11或X^a16～X^a110的至少1种或2种以上被取代成吸附基团，更优选X^a11或X^a18被取代成吸附基团。需要说明的是，在该情形时，吸附基团可以被取代成P¹¹-S¹¹-。尤其是当环A为环己烷环的情形时，优选X^a18被取代成吸附基团。In the above formula (AL-2), at least one or two or more of X^a11 or X^a16 to X^a110 are preferably substituted as adsorption groups, more preferably X^a11 or X^a18 are substituted into adsorption groups. It should be noted that, in this case, the adsorption group may be substituted with P¹¹ -S¹¹ -. Especially when the ring A is a cyclohexane ring, it is preferable that X^a18 is substituted into an adsorption group.

上述式(AL-2)中，优选X^al6～X^a110的任1种或2种以上被取代成P¹¹-S¹¹-，更优选X^al7或X^a19的任一者被取代成P¹¹-S¹¹-。In the above formula (AL-2), preferably any one or two or more of X^{a16 to X a110are} substituted with P¹¹ -S¹¹ -, more preferably any one of X^a17 or X^a19 is substituted with P¹¹ - S^11- .

上述式(AL-2)中，优选X^a16～X^a110的至少1种或2种以上被取代成P¹¹-S¹¹-，更优选X^a17或X^a14的任一者被取代成P¹¹-S¹¹-。In the above formula (AL-2), preferably at least one or two or more of X^a16 to X^a110 are substituted with P¹¹ -S¹¹ -, and more preferably any one of X^a17 or X^a14 is substituted with P¹¹ - S^11- .

上述式(AL-2)中，优选X^a11～X^a17或X^a9～X^a114的至少1种或2种以上被取代成柔性基团，优选X^a11、X^a4～X^a17或X^a19～X^a112的至少1种或2种以上被取代成柔性基团。更优选X^a11被取代成柔性基团，且X^al4～X^a17或X^a19～X^a112的任1种被取代成柔性基团。在该情形时，进一步优选前者的X^a11中的柔性基团的碳原子数比后者的柔性基团多。柔性基团也可以被取代成P¹¹-S¹¹-。In the above formula (AL-2), preferably at least one or two or more of X^a11 to X^a17 or X^a9 to X^a114 are substituted into flexible groups, preferably X^a11 , X^a4 to X^a17 or X^a19 to X At least one or two or more of^a112 are substituted with flexible groups. More preferably, X^a11 is substituted with a flexible group, and any one of X^{a14 to X a17 or X a19 to X a112issubstitutedwith} a flexible group. In this case, it is more preferable that the number of carbon atoms of the flexible group in X^a11 of the former is larger than that of the latter. The flexible group can also be substituted as P¹¹ -S¹¹ -.

“吸附基团”"Adsorbent group"

本发明涉及的吸附基团为具备与基板、膜、电极等吸附介质吸附的作用的基团。吸附一般分为形成化学键(共价键、离子键或金属键)而在吸附介质与被吸附物质之间吸附的化学吸附、或该化学吸附以外的物理吸附，本说明书的吸附可为化学吸附或物理吸附的任一者，优选通过物理吸附而与吸附介质吸附。因此，本发明涉及的吸附基团优选为能够与吸附介质作物理吸附的基团，该吸附基团更优选通过分子间作用力而与吸附介质结合。作为通过该分子间作用力而与吸附介质结合的形态，可列举通过永久偶极、永久四极、分散力、电荷移动力或氢键等相互作用而与吸附介质结合。作为本发明涉及的吸附基团的优选形态，可列举能够通过氢键而与吸附介质结合的形态。在该情形时，本发明涉及的吸附基团可为通过氢键的质子的施体或者受体，另外也可以为两者。The adsorption group according to the present invention is a group having the function of adsorbing to adsorption media such as substrates, membranes, and electrodes. Adsorption is generally divided into chemical adsorption that forms chemical bonds (covalent bonds, ionic bonds or metal bonds) between the adsorption medium and the adsorbed substance, or physical adsorption other than chemical adsorption. The adsorption in this specification can be chemical adsorption or chemical adsorption. Any of physical adsorption is preferably adsorbed to the adsorption medium by physical adsorption. Therefore, the adsorption group involved in the present invention is preferably a group capable of physical adsorption with the adsorption medium, and the adsorption group is more preferably bound to the adsorption medium by intermolecular force. Examples of the form of binding to the adsorption medium by this intermolecular force include binding to the adsorption medium by interaction such as permanent dipole, permanent quadrupole, dispersion force, charge transfer force, or hydrogen bonding. As a preferable form of the adsorption group which concerns on this invention, the form which can be combined with an adsorption medium by a hydrogen bond is mentioned. In this case, the adsorption group according to the present invention may be a donor or an acceptor of protons passing through hydrogen bonds, and may be both.

本发明涉及的吸附基团优选为含有极性要素的基团，该极性要素具有碳原子与杂原子连结而成的原子团。本说明书中所说的极性要素是指碳原子与杂原子直接连结而成的原子团。作为上述杂原子，优选为选自由N、O、S、P、B及Si组成的组中的至少1种，优选为选自由N、O及S组成的组中的至少1种，优选为选自由N及O组成的组中的至少1种，优选为O。The adsorption group according to the present invention is preferably a group containing a polar element having an atomic group in which a carbon atom and a hetero atom are linked. The polar element referred to in this specification refers to an atomic group in which a carbon atom and a hetero atom are directly linked. The above-mentioned heteroatom is preferably at least one selected from the group consisting of N, O, S, P, B, and Si, preferably at least one selected from the group consisting of N, O, and S, and preferably selected from the group consisting of N, O, and S. At least one kind selected from the group consisting of free N and O, preferably O.

另外，在本发明涉及的自取向性单体中，本发明涉及的极性要素的价数为一价、二价、三价等，并无特别限定，另外，吸附基团中的极性要素的个数也无特别限制。In addition, in the self-aligning monomer according to the present invention, the valence of the polar element according to the present invention is monovalent, bivalent, trivalent, etc., and is not particularly limited. In addition, the polar element in the adsorption group The number is not particularly limited.

本发明涉及的自取向性单体中，上述吸附基团优选在一分子中具有1～8个，更优选具有1～4个，进一步优选具有1～3个。In the self-aligning monomer which concerns on this invention, it is preferable that the said adsorption group has 1-8 pieces in one molecule, It is more preferable that it has 1-4 pieces, and it is still more preferable that it has 1-3 pieces.

需要说明的是，本发明涉及的吸附基团不包含P¹¹-S¹¹-及柔性基团。It should be noted that the adsorption groups involved in the present invention do not include P¹¹ -S¹¹ - and flexible groups.

本发明涉及的吸附基团含有1个或2个以上的极性要素，吸附基团大致可分为环式基型与链式基型。环式基型为在其结构中含有环式基的形态，该环式基具备含有极性要素的环状结构，链式基型为在其结构中不含环式基(该环式基具备含有极性要素的环状结构)的形态。链式基为在直链或分支的链状基中具有极性要素的形态，也可以在其一部分具有不含极性要素的环状结构。The adsorption group involved in the present invention contains one or more than two polar elements, and the adsorption group can be roughly divided into a cyclic group type and a chain group type. The cyclic group type is a form that contains a cyclic group in its structure, and the cyclic group has a cyclic structure containing a polar element, and the chain group type does not contain a cyclic group in its structure (the cyclic group has a cyclic group). cyclic structure containing polar elements). The chain group is a linear or branched chain group having a polar element, and may have a cyclic structure that does not contain a polar element in a part thereof.

所谓本发明涉及的吸附基团为含有环式基的形态，是指在环状的原子排列内含有至少1个极性要素的形态。需要说明的是，本说明书中的环式基如上所述。因此，当本发明涉及的吸附基团为含有环式基的形态的情形时，只要含有包含极性要素的环式基即可，吸附基团整体上可以分支，也可以为直链状。The term that the adsorption group according to the present invention is in a form containing a cyclic group means a form in which at least one polar element is contained in a cyclic atomic arrangement. In addition, the cyclic group in this specification is as mentioned above. Therefore, when the adsorption group according to the present invention is in a form containing a cyclic group, the adsorption group may be branched or linear as a whole as long as it contains a cyclic group containing a polar element.

所谓本发明涉及的吸附基团为链式基的形态，是指下述形态：分子内没有含有极性要素的环状原子排列，且在线状的原子排列(可以分支)内含有至少1个极性要素。需要说明的是，所谓本说明书中的链式基，是指结构式中没有环状的原子排列且构成的原子键结成线状(可以分支)的原子团，是指非环式基。换言之，为下述概念：是指直链状或分支状的脂肪族基，可含有饱和键或不饱和键的任一者，例如包含烷基、烯基、烷氧基、酯、醚或酮等，可以被至少1个取代基(反应性官能团(乙烯基、丙烯酰基、甲基丙烯酰基等)、链状有机基(烷基、氰基等))取代。另外，本发明的链式基可为直链状或分支状的任一者。The form in which the adsorption group according to the present invention is a chain group refers to a form in which there is no cyclic atomic arrangement containing polar elements in the molecule, and at least one polar element is contained in the linear atomic arrangement (branching possible). sexual element. In addition, the chain group in this specification means the atomic group which does not have a cyclic atomic arrangement in a structural formula, and the constituting atoms are bonded linearly (branchable), and means an acyclic group. In other words, it is the following concept: a linear or branched aliphatic group, which may contain either a saturated bond or an unsaturated bond, for example, an alkyl group, an alkenyl group, an alkoxy group, an ester, an ether, or a ketone. etc., may be substituted by at least one substituent (reactive functional group (vinyl, acryloyl, methacryloyl, etc.), chain organic group (alkyl, cyano, etc.)). In addition, the chain group of the present invention may be linear or branched.

本发明涉及的吸附基团优选具有链式基或环式基，当重视吸附能力的情形时，优选为链式基，从对液晶组合物的稳定性的观点考虑，优选为环式基。The adsorption group according to the present invention preferably has a chain group or a cyclic group, and when the adsorption capacity is important, a chain group is preferable, and a cyclic group is preferable from the viewpoint of stability to the liquid crystal composition.

本发明涉及的吸附基团为环式基的情形时，更优选为碳原子数3～20个的杂芳香族基(包含缩合环)或碳原子数3～20个的杂脂肪族基(包含缩合环)，进一步优选为碳原子数3～12个的杂芳香族基(包含缩合环)或碳原子数3～12个的杂脂肪族基(包含缩合环)，更进一步优选表示5元环杂芳香族基、5元环杂脂肪族基、6元环杂芳香族基或6元环杂脂肪族基，这些环结构中的氢原子可以被取代成卤素原子、碳原子数1～5的直链状或者分支状的烷基或烷基氧基。When the adsorption group according to the present invention is a cyclic group, it is more preferably a heteroaromatic group (including a condensed ring) having 3 to 20 carbon atoms or a heteroaliphatic group (including a condensed ring) having 3 to 20 carbon atoms. condensed ring), more preferably a heteroaromatic group (including a condensed ring) having 3 to 12 carbon atoms or a heteroaliphatic group (including a condensed ring) having 3 to 12 carbon atoms, and still more preferably a 5-membered ring Heteroaromatic group, 5-membered cyclic heteroaliphatic group, 6-membered cyclic heteroaromatic group or 6-membered cyclic heteroaliphatic group, the hydrogen atoms in these ring structures can be substituted with halogen atoms, 1-5 carbon atoms Linear or branched alkyl or alkyloxy.

当本发明涉及的吸附基团为链式基的情形时，优选直链状或者分支状的碳原子数1～20个的烷基中的氢原子、-CH₂-被取代成极性要素，该烷基中的1个或未邻接的2个以上的-CH₂-可以被-CH＝CH-、-C≡C-、-O-、-CO-、-COO-、-OCO-或-OCO-COO-取代。另外，当本发明涉及的吸附基团为链式基的情形时，优选在端部含有极性要素或含有2个以上的极性要素。When the adsorption group in the present invention is a chain group, it is preferable that the hydrogen atom and -CH₂ - in the linear or branched alkyl group having 1 to 20 carbon atoms are substituted with a polar element, One or two or more non-adjacent -CH₂ - in the alkyl group may be -CH=CH-, -C≡C-, -O-, -CO-, -COO-, -OCO- or - OCO-COO-substituted. In addition, when the adsorption group according to the present invention is a chain group, it is preferable to contain a polar element or two or more polar elements at the end.

本发明涉及的吸附基团的氢原子可以被取代成聚合性基团。The hydrogen atom of the adsorption group according to the present invention may be substituted into a polymerizable group.

本发明涉及的极性要素的种类，具体而言，优选为由含有氧原子的极性要素(以下，称为含氧极性要素)、含有氮原子的极性要素(以下，称为含氮极性要素)、含有磷原子的极性要素(以下，称为含磷极性要素)、含有硼原子的极性要素(以下，称为含硼极性要素)、含有硅原子的极性要素(以下，称为含硅极性要素)或含有硫原子的极性要素(以下，称为含硫极性要素)表示的部分结构，从吸附能力的观点考虑，更优选为含氮极性要素、含氮极性要素或含氧极性要素，进一步优选为含氧极性要素。Specifically, the types of polar elements according to the present invention are preferably composed of polar elements containing oxygen atoms (hereinafter referred to as oxygen-containing polar elements) and polar elements containing nitrogen atoms (hereinafter referred to as nitrogen-containing polar elements) polar elements), polar elements containing phosphorus atoms (hereinafter referred to as phosphorus-containing polar elements), polar elements containing boron atoms (hereinafter referred to as boron-containing polar elements), polar elements containing silicon atoms A partial structure represented by a polar element (hereinafter referred to as a silicon-containing polar element) or a polar element containing a sulfur atom (hereinafter referred to as a sulfur-containing polar element) is more preferably a nitrogen-containing polar element from the viewpoint of adsorption capacity , a nitrogen-containing polar element or an oxygen-containing polar element, more preferably an oxygen-containing polar element.

作为上述含氧极性要素，优选为选自由羟基(-OH)、烷醇基(-R^t-OH；R^t为亚烷基)、烷氧基(-OR；其中，R为烷基)、甲酰基(-CHO)、羧基(-COOH)、醚基(-R^tOR^t’-；其中，R^t、R^t’为亚烷基或亚烯基)、羰基(-R^t-C(＝O)-R^t’-；其中，R^t、R^t’为亚烷基或亚烯基)、碳酸酯基(-O-C(＝O)-O-)及酯基(-COOR^t’-；其中，R^t’为亚烷基或亚烯基)组成的组中的至少1种基团或在碳原子上连结该基团而成的基团。The oxygen-containing polar element is preferably selected from a hydroxyl group (—OH), an alkanol group (—R^t —OH; R^t is an alkylene group), and an alkoxy group (—OR; where R is an alkyl group) , formyl (-CHO), carboxyl (-COOH), ether group (-R^t OR^t '-; wherein R^t and R^t' are alkylene or alkenylene), carbonyl (-R^t -C (=O)-R^t' -; wherein, R^t and R^t' are alkylene or alkenylene), carbonate group (-OC(=O)-O-) and ester group (-COOR^t' -; wherein, R^t' is at least one group in the group consisting of an alkylene group or an alkenylene group) or a group formed by linking the group to a carbon atom.

作为上述含氮极性要素，优选为选自由氰基(-CN)、伯氨基(-NH₂)、仲氨基(-NH-)、叔氨基(-NRR’；其中，R、R’为烷基)、吡啶基、氨基甲酰基(-CONH₂)及脲基(-NHCONH₂)组成的组中的至少1种基团或在碳原子上连结该基团而成的基团。The nitrogen-containing polar element is preferably selected from cyano group (-CN), primary amino group (-NH₂ ), secondary amino group (-NH-), and tertiary amino group (-NRR'; wherein R and R' are alkanes group), a pyridyl group, a carbamoyl group (-CONH₂ ), and a ureido group (-NHCONH₂ ) group consisting of at least one group or a group formed by linking this group to a carbon atom.

作为上述含磷极性要素，优选为选自由膦基(-CX₂-P(＝O)H₂)及磷酸基(-CX₂-OP(＝O)(OH)₂)组成的组中的至少1种基团或在碳原子上连结该基团而成的基团。The phosphorus-containing polar element is preferably selected from the group consisting of a phosphine group (-CX₂ -P(=O)H₂ ) and a phosphoric acid group (-CX₂ -OP(=O)(OH)₂ ). At least one type of group or a group formed by linking the group to a carbon atom.

作为上述含硼极性要素，优选为在碳原子上连结硼酸基(-B(OH)₂)而成的基团。The boron-containing polar element is preferably a group formed by linking a boronic acid group (-B(OH)₂ ) to a carbon atom.

作为上述含硅极性要素，优选为-Si(OH)₃基或-Si(OR)(OR’)(OR”)(其中，R、R’、R”为烷基)基连结于碳原子而成的基团。As the above-mentioned silicon-containing polar element, a -Si(OH)₃ group or a -Si(OR)(OR')(OR") group (wherein R, R', and R" are alkyl groups) is preferably bonded to a carbon atom formed group.

作为上述含硫极性要素，优选为选自由巯基(-SH)、硫醚基(-S-)、亚磺酰基(-S(＝O)-)、磺酰基(-SO₂-)、磺酰胺基(-SO₂NH₂)、磺酸基(-SO₃H)及亚磺酸基(-S(＝O)OH)组成的组中的至少1种基团或在碳原子上连结该基团而成的基团。The above-mentioned sulfur-containing polar element is preferably selected from the group consisting of a mercapto group (-SH), a thioether group (-S-), a sulfinyl group (-S(=O)-), a sulfonyl group (-SO₂ -), a sulfonyl group At least one group selected from the group consisting of an amide group (-SO₂ NH₂ ), a sulfonic acid group (-SO₃ H), and a sulfinic acid group (-S(=O)OH) or a carbon atom bonded to the group group of groups.

因此，本发明涉及的吸附基团优选为选自由环式基具备含氧极性要素的基团(以下，称为含氧环式基)、环式基具备氮原子极性要素的基团(以下，称为含氮环式基)、环式基具备含磷极性要素的基团(以下，称为含磷环式基)、环式基具备含硼极性要素的基团(以下，称为含硼环式基)、环式基具备含硅极性要素的基团(以下，称为含硅环式基)、环式基具备含硫极性要素的基团(以下，称为含硫环式基)、链式基具备含氧极性要素的基团(以下，称为含氧链式基)、链式基具备氮原子极性要素的基团(以下，称为含氮链式基)、链式基具备含磷极性要素的基团(以下，称为含磷链式基)、链式基具备含硼极性要素的基团(以下，称为含硼链式基)、链式基具备含硅极性要素的基团(以下，称为含硅链式基)及链式基具备含硫极性要素的基团(以下，称为含硫链式基)组成的组中的1种或2种以上的基团本身或含有该基团，从吸附能力的观点考虑，更优选含有选自由含氧环式基、含硫环式基、含氧链式基及含氮链式基组成的组中的1种或2种以上的基团。Therefore, the adsorption group according to the present invention is preferably selected from a group having an oxygen-containing polar element in a cyclic group (hereinafter, referred to as an oxygen-containing cyclic group), and a group having a nitrogen atom polar element in a cyclic group ( Hereinafter, referred to as a nitrogen-containing cyclic group), a cyclic group with a phosphorus-containing polar element (hereinafter referred to as a phosphorus-containing cyclic group), and a cyclic group with a boron-containing polar element (hereinafter, referred to as a group). referred to as a boron-containing cyclic group), a cyclic group having a silicon-containing polar element (hereinafter referred to as a silicon-containing cyclic group), and a cyclic group having a sulfur-containing polar element (hereinafter referred to as a group Sulfur-containing cyclic group), chain group with oxygen-containing polar element (hereinafter referred to as oxygen-containing chain group), chain group with nitrogen atom polar element (hereinafter referred to as nitrogen-containing chain group) chain group), a chain group having a phosphorus-containing polar element (hereinafter referred to as a phosphorus-containing chain group), a chain group having a boron-containing polar element (hereinafter referred to as a boron-containing chain group) group), a chain group having a silicon-containing polar element (hereinafter, referred to as a silicon-containing chain group), and a chain group having a sulfur-containing polar element (hereinafter, referred to as a sulfur-containing chain group) One or two or more groups in the group consisting of the group itself or contains the group, and from the viewpoint of adsorption capacity, it is more preferable to contain an oxygen-containing cyclic group, a sulfur-containing cyclic group, and an oxygen-containing chain group. and one or more groups of the group consisting of nitrogen-containing chain groups.

作为上述含氧环式基，优选在环内具有醚基或羰基，作为该醚基，优选包含以下基团。The oxygen-containing cyclic group preferably has an ether group or a carbonyl group in the ring, and the ether group preferably contains the following groups.

[化12][Chemical 12]

另外，作为前述羰基，优选包含以下基团的任一者。Moreover, as said carbonyl group, it is preferable to contain any one of the following groups.

[化13][Chemical 13]

作为上述含氮环式基，优选包含以下基团的任一者。As said nitrogen-containing cyclic group, it is preferable to contain any one of the following groups.

[化14][Chemical 14]

作为上述含硫环式基，优选含有以下基团的任一者。As the above-mentioned sulfur-containing cyclic group, any one of the following groups is preferably contained.

[化15][Chemical 15]

作为上述含硼环式基，优选包含以下基团的任一者。As the above-mentioned boron-containing cyclic group, any one of the following groups is preferably included.

[化16][Chemical 16]

作为上述含硅环式基，优选包含倍半硅氧烷基[-(R)_n(SiO_1.5)_n-1]。As the above-mentioned silicon-containing cyclic group, a silsesquioxane group [-(R)_n (SiO_1.5 )_n-1 ] is preferably contained.

作为上述含氧链式基，优选包含以下基团的任一者。As the above-mentioned oxygen-containing chain group, any one of the following groups is preferably contained.

[化17][Chemical 17]

(上述通式中，R^at各自独立地表示氢原子或碳原子数1～5的烷基。上述通式中，Z^at表示单键、碳原子数1～15个的直链状或者分支状的亚烷基或碳原子数2～18个的直链状或者分支状的亚烯基，该亚烷基或该亚烯基的-CH₂-可以以氧原子不直接邻接的方式被取代成-O-、-COO-、-C(＝O)-、-OCO-，X^at表示碳原子数1～5的烷基，该烷基的-CH₂-可以以氧原子不直接邻接的方式被取代成-O-、-COO-、-C(＝O)-、-OCO-。)(In the above general formula, R^at each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. In the above general formula, Z^at represents a single bond, a linear or branched form with 1 to 15 carbon atoms The alkylene group or the straight-chain or branched alkenylene group having 2 to 18 carbon atoms, the -CH₂ - of the alkylene group or the alkenylene group may be substituted in such a way that the oxygen atoms are not directly adjacent to each other. -O-, -COO-, -C(=O)-, -OCO-, X^at represents an alkyl group having 1 to 5 carbon atoms, and -CH₂ - of the alkyl group may be such that oxygen atoms are not directly adjacent to each other Replaced by -O-, -COO-, -C(=O)-, -OCO-.)

作为上述含氮链式基，优选包含以下的基团。As the above-mentioned nitrogen-containing chain group, the following groups are preferably included.

[化18][Chemical 18]

(上述通式中，R^at、R^bt、R^ct及R^dt各自独立地表示氢原子或碳原子数1～5的烷基。)(In the above general formula, R^at , R^bt , R^ct and R^dt each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.)

作为上述含硫链式基，优选包含以下的基团。As the above-mentioned sulfur-containing chain group, the following groups are preferably included.

[化19][Chemical 19]

作为上述含硅链式基，优选包含-Si(OH)₃或-Si(OR)(OR’)(OR”)；其中，R、R’、R”为烷基)。作为上述含硼链式基，优选包含-B(OH)₂。作为上述含磷链式基，优选包含-OP(＝O)(OH)₂。The above-mentioned silicon-containing chain group preferably contains -Si(OH)₃ or -Si(OR)(OR')(OR"); wherein R, R', and R" are alkyl groups). As the above-mentioned boron-containing chain group, -B(OH)₂ is preferably contained. As the phosphorus-containing chain group, -OP(=O)(OH)₂ is preferably contained.

作为本发明涉及的吸附基团，优选为由下述通式(T)表示的基团。The adsorption group according to the present invention is preferably a group represented by the following general formula (T).

[化20][hua 20]

(上述通式(T)中，X^t1表示碳原子数1～18个的直链状或分支状的烷基或-NH₂，前述烷基中的氢原子可以被取代成氰基、P¹¹-S¹¹-，或前述烷基的-CH₂-可以以氧原子不直接邻接的方式被取代成-O-、-COO-、-C(＝O)-、-OCO-、-CH＝CH-，(In the above general formula (T), X^t1 represents a linear or branched alkyl group having 1 to 18 carbon atoms or -NH₂ , and the hydrogen atom in the aforementioned alkyl group may be substituted with a cyano group, P¹¹ -S¹¹ -, or -CH₂ - of the aforementioned alkyl group may be substituted into -O-, -COO-, -C(=O)-, -OCO-, -CH=CH in such a manner that the oxygen atoms are not directly adjacent to each other -,

上述R^t1表示氢原子、碳原子数1～5个的烷基或可以与Z^t1键结的碳原子数1～8个的直链状或者分支状的亚烷基或可以与Z^t1键结的碳原子数2～8个的直链状或者分支状的亚烯基，上述Z^t2表示单键、碳原子数1～18个的直链状或者分支状的亚烷基或碳原子数2～18个的直链状或者分支状的亚烯基，该亚烷基或该亚烯基的-CH₂-可以以氧原子不直接邻接的方式被取代成-O-、-COO-、-C(＝O)-、-OCO-，The above-mentioned R^t1 represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a straight-chain or branched alkylene group having 1 to 8 carbon atoms that can be bonded to Z^t1 , or an alkylene group that can be bonded to Z^t1 A straight-chain or branched alkenylene group having 2 to 8 carbon atoms, the above Z^t2 represents a single bond, a straight-chain or branched alkylene group having 1 to 18 carbon atoms, or a carbon number of 2 ~18 straight-chain or branched alkenylene groups, the -CH₂ - of the alkylene group or the alkenylene group may be substituted into -O-, -COO-, - in a manner that the oxygen atoms are not directly adjacent to each other C(=O)-, -OCO-,

Z^t1表示单键、碳原子数1～18个的直链状或者分支状的亚烷基或碳原子数2～18个的直链状或者分支状的亚烯基，该亚烷基的-CH₂-可以以氧原子不直接邻接的方式被取代成-O-、-COO-、-C(＝O)-、-OCO-，另外，当X^t1为-Z^t2-O-R^at基，且R^at为亚烷基或亚烯基的情形时，可以将Z^t1的氢原子取代而与R^t1键结，Z^t1 represents a single bond, a straight-chain or branched alkylene group having 1 to 18 carbon atoms, or a straight-chain or branched alkenylene group having 2 to 18 carbon atoms, and the - CH₂ - may be substituted into -O-, -COO-, -C(=O)-, -OCO- in such a way that oxygen atoms are not directly adjacent to each other, in addition, when X^t1 is -Z^t2 -OR^at group, and When R^at is an alkylene group or an alkenylene group, the hydrogen atom of Z^t1 may be substituted to bond with R^t1 ,

W^t0表示碳原子数1～18个的直链状或者分支状的亚烷基，该亚烷基的-CH₂-可以以氧原子不直接邻接的方式被取代成-O-、-CH＝CH-、-COO-、-C(＝O)-、-OCO-，另外，前述亚烷基的氢原子可以被取代成通式(T)，W^t0 represents a straight-chain or branched alkylene group having 1 to 18 carbon atoms, and -CH₂ - of the alkylene group may be substituted with -O-, -CH= so that oxygen atoms are not directly adjacent to each other. CH-, -COO-, -C(=O)-, -OCO-, in addition, the hydrogen atom of the aforementioned alkylene group may be substituted into the general formula (T),

W^t1表示单键或直链状或者分支状的亚烷基，该亚烷基的-CH₂-可以以氧原子不直接邻接的方式被取代成-O-、-COO-、-C(＝O)-、-OCO-，W^t1 represents a single bond or a straight-chain or branched alkylene group, and -CH₂ - of the alkylene group may be substituted into -O-, -COO-, -C(= O)-, -OCO-,

n^t1表示0以上4以下的整数，n^t1 represents an integer of 0 or more and 4 or less,

分子内的氢原子可以被取代成上述聚合性基团P¹¹-S¹¹-，＊表示连接键，与介晶基团、聚合性基团、柔性基团或间隔基团键结。)The hydrogen atom in the molecule may be substituted with the above-mentioned polymerizable group P¹¹ -S¹¹ -, and * represents a bond, and is bonded to a mesogenic group, a polymerizable group, a flexible group or a spacer group. )

上述通式(T)中，优选的X^t1表示碳原子数1～17个的直链状或分支状的烷基、-NH₂或-Z^t2-O-R^t1基，该烷基中的氢原子可以被取代成氰基、P¹¹-S¹¹-，上述R^t1表示氢原子、碳原子数1～5个的烷基或可以与Z^t1键结的碳原子数1～8个的直链状或者分支状的亚烷基或可以与Z^t1键结的碳原子数2～8个的直链状或者分支状的亚烯基，上述Z^t2表示单键、碳原子数1～18个的直链状或者分支状的亚烷基或碳原子数2～18个的直链状或者分支状的亚烯基，该亚烷基或该亚烯基的-CH₂-可以以氧原子不直接邻接的方式被取代成-O-、-COO-、-C(＝O)-、-OCO-。In the above general formula (T), preferably X^t1 represents a linear or branched alkyl group having 1 to 17 carbon atoms, -NH₂ or -Z^t2 -OR^t1 group, and the hydrogen atom in the alkyl group is Can be substituted with cyano group, P¹¹ -S¹¹ -, the above R^t1 represents a hydrogen atom, an alkyl group with 1 to 5 carbon atoms, or a straight chain with 1 to 8 carbon atoms that can be bonded to Z^t1 Or a branched alkylene group or a straight-chain or branched alkenylene group having 2 to 8 carbon atoms which can be bonded to Z^t1 , and the above-mentioned Z^t2 represents a single bond and a straight chain having 1 to 18 carbon atoms. A chain-like or branched alkylene group or a straight-chain or branched alkenylene group having 2 to 18 carbon atoms, the -CH₂ - of the alkylene group or the alkenylene group may not be directly adjacent to an oxygen atom is substituted into -O-, -COO-, -C(=O)-, -OCO-.

上述通式(T)中，作为吸附基团(通式(T))可以被吸附基团(通式(T))取代的形态，可列举上述通式(T)由下述通式(t)表示的基团。In the above-mentioned general formula (T), as the form in which the adsorption group (general formula (T)) may be substituted by the adsorption group (general formula (T)), the above general formula (T) can be exemplified by the following general formula (t) ) represents the group.

[化21][Chemical 21]

(上述通式(t)中，X^t1、Z^t1、W^t1及n^t1与上述通式(T)中的记号相同，(In the above general formula (t), X^t1 , Z^t1 , W^t1 and n^t1 are the same as the symbols in the above general formula (T),

W^t2表示单键或2价～4价的有机基，W^t2 represents a single bond or a divalent to tetravalent organic group,

m^t1表示1以上3以下的整数，分子内的氢原子可以被取代成上述聚合性基团Pd-S¹¹-，＊表示连接键，与介晶基团、聚合性基团、柔性基团或间隔基团键结。)m^t1 represents an integer of 1 or more and 3 or less, the hydrogen atom in the molecule can be substituted with the above-mentioned polymerizable group Pd-S¹¹ -, * represents a bond, and a mesogenic group, a polymerizable group, a flexible group or a spacer group bonding. )

上述通式(t)中的“-W^t2-Any”表示：W^t2表示单键～多价基团，连接键为1价～多价(Any)。"-W^t2 -Any" in the above general formula (t) means that W^t2 represents a single bond to a polyvalent group, and the connecting bond is a monovalent to a polyvalent (Any).

上述通式(t)中，所谓2～4价的有机基，是通过有机化合物成为2～4价基团的形态而构成了化学结构的基团，是指从有机化合物去除2～4个氢原子而成的原子团。In the above general formula (t), the 2- to 4-valent organic group refers to a group that constitutes a chemical structure when an organic compound becomes a 2- to 4-valent group, and refers to the removal of 2 to 4 hydrogens from the organic compound. A group of atoms.

上述通式(t)中，为2价～4价有机基的-W^t2-Any优选为链状有机基，例如，可列举：直链状或者分支状的碳原子数1个～10个的亚烷基(该亚烷基的-CH₂-可以以氧原子不直接邻接的方式被取代成-O-、-COO-、-C(＝O)-、-OCO-)、直链状或者分支状的碳原子数1个～10个的亚烷基多价基团(该亚烷基的-CH₂-可以以氧原子不直接邻接的方式被取代成-O-、-COO-、-C(＝O)-、-OCO-)、-PH-、-POH-、-NH-、氮原子或磷原子等。该亚烷基多价基团是指从亚烷基进一步去除1～2个氢原子而形成的3价或4价的基团，是指在所谓的烃链上具有游离原子价的3～4价基团。In the above-mentioned general formula (t), -W^t2 -Any which is a divalent to tetravalent organic group is preferably a chain organic group, for example, a linear or branched one having 1 to 10 carbon atoms. Alkylene (the -CH₂ - of the alkylene may be substituted into -O-, -COO-, -C(=O)-, -OCO- in such a way that the oxygen atoms are not directly adjacent to each other), linear or A branched polyvalent alkylene group having 1 to 10 carbon atoms (the -CH₂ - of the alkylene group may be substituted with -O-, -COO-, - so that the oxygen atoms are not directly adjacent to each other. C(=O)-, -OCO-), -PH-, -POH-, -NH-, nitrogen atom or phosphorus atom, etc. The alkylene polyvalent group refers to a trivalent or tetravalent group formed by further removing 1 to 2 hydrogen atoms from an alkylene group, and refers to a 3 to 4 valent group having a free atomic valence in a so-called hydrocarbon chain. valence group.

由上述通式(t)表示的基团为通式(T)中的W^t0的优选方式，即吸附基团(通式(T))可以被吸附基团(通式(T))取代的形态的一个方式，作为由上述通式(t)表示的基团的优选形态，例如当W^t2为3价有机基的情形时，即m^t1’为2、W^t2为氮原子或亚烷基多价基团的情形时，例如可列举以下的通式(t-a)或(t-b)。The group represented by the above general formula (t) is a preferred mode of W^t0 in the general formula (T), that is, the adsorption group (the general formula (T)) may be substituted by the adsorption group (the general formula (T)) One form of the form, as a preferable form of the group represented by the general formula (t), for example, when W^t2 is a trivalent organic group, that is, m^t1' is 2, and W^t2 is a nitrogen atom or an alkylene group. In the case of a polyvalent group, the following general formula (ta) or (tb) is mentioned, for example.

[化22][Chemical 22]

(上述式(t-a)及(t-b)中，R^tc由氢原子、直链状或者分支状的碳原子数1个～10个的烷基或聚合性基团P¹¹-S¹¹-表示，(In the above formulae (ta) and (tb), R^tc is represented by a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, or a polymerizable group P¹¹ -S¹¹ -,

Z^t1及Z^t1’各自独立地表示与通式(T)中的Z^t1相同的意义，Z^t1 and Z^t1' each independently represent the same meaning as Z^t1 in the general formula (T),

X^t1及X^t1’各自独立地表示与通式(T)中的Z^t1相同的意义，X^t1 and X^t1' each independently represent the same meaning as Z^t1 in the general formula (T),

W^t1表示与通式(T)中的W^t1相同的意义，W^t1 has the same meaning as W^t1 in the general formula (T),

n^t1及n^t1’各自独立地表示与通式(T)中的n^t1相同的意义，n^t1 and n^t1' each independently represent the same meaning as n^t1 in the general formula (T),

分子内的氢原子可以被取代成上述聚合性基团P¹¹-S¹¹-，＊表示连接键，与介晶基团、聚合性基团、柔性基团或间隔基团键结。)The hydrogen atom in the molecule may be substituted with the above-mentioned polymerizable group P¹¹ -S¹¹ -, and * represents a bond, and is bonded to a mesogenic group, a polymerizable group, a flexible group or a spacer group. )

通式(t)中，例如当-W^t2-Any为4价有机基的情形时，即m^t1’为3、-W^t2-Any为亚烷基多价基团的情形时，例如可列举以下的通式(t-c)。In the general formula (t), for example, when -W^t2 -Any is a tetravalent organic group, that is, when m^t1' is 3 and -W^t2 -Any is an alkylene polyvalent group, for example The following general formula (tc).

[化23][Chemical 23]

(上述式(t-c)中，Z^t1、Z^t1’及Z^t1”各自独立地表示与通式(T)中的Z^t1相同的意义，(In the above formula (tc), Z^t1 , Z^{t1 ′} and Z^t1 " each independently represent the same meaning as Z^t1 in the general formula (T),

X^t1、X^t1’及X^t1”各自独立地表示与通式(T)中的X^t1相同的意义，X^t1 , X^{t1 ′} and X^t1 ″ each independently represent the same meaning as X^t1 in the general formula (T),

W^t1表示与通式(T)中的W^t1相同的意义，W^t1 has the same meaning as W^t1 in the general formula (T),

n^t1、n^t1’及n^t1”各自独立地表示与通式(T)中的n^t1相同的意义，分子内的氢原子可以被取代成上述聚合性基团P¹¹-S¹¹-，＊表示连接键，与介晶基团、聚合性基团、柔性基团或间隔基团键结。)n^t1 , n^t1' and n^t1 " each independently have the same meaning as n^t1 in the general formula (T), and the hydrogen atom in the molecule may be substituted with the above-mentioned polymerizable group P¹¹ -S¹¹ -, * Indicates a linking bond, which is bonded to a mesogenic group, a polymerizable group, a flexible group or a spacer group.)

上述通式(t)中，mt1’优选为1或2，mt1’更优选为1。另外，在由上述通式(t-a)、通式(t-b)、通式(t-c)表示的形态中，优选为由上述通式(t-a)表示的形态。In the above general formula (t), mt1' is preferably 1 or 2, and mt1' is more preferably 1. In addition, among the forms represented by the general formula (t-a), the general formula (t-b), and the general formula (t-c), the form represented by the general formula (t-a) is preferable.

上述通式(t)中，-W^t2-Any优选为单键或2价～3价有机基，更优选为单键、直链状或者分支状的碳原子数1～8个的亚烷基(该亚烷基的-CH₂-可以以氧原子不直接邻接的方式被取代成-O-。)、直链状或者分支状的碳原子数1～8个的烷三基(alkanetriyl)(该烷三基的-CH₂-可以以氧原子不直接邻接的方式被取代成-O-。)或直链状或者分支状的烷基-亚基(该烷基-亚基的-CH₂-可以以氧原子不直接邻接的方式被取代成-O-。)。例如，可列举以下的基团。In the general formula (t), -W^t2 -Any is preferably a single bond or a divalent to trivalent organic group, more preferably a single bond, a linear or branched alkylene group having 1 to 8 carbon atoms (The -CH₂ - of the alkylene group may be substituted with -O- so that the oxygen atoms are not directly adjacent to each other.), a linear or branched alkanetriyl group having 1 to 8 carbon atoms ( The -CH₂ - of the alkanetriyl group may be substituted into -O- in such a way that the oxygen atoms are not directly adjacent.) or a linear or branched alkyl-subunit (-CH₂ of the alkyl-subunit - can be substituted to -O- in such a way that the oxygen atoms are not directly adjacent.). For example, the following groups can be mentioned.

[化24][Chemical 24]

(上述式中，R^tc表示碳原子数1～8个的烷基或聚合性基团(P¹¹-S¹¹-)，nt0表示1～7的整数，＊表示连接键。)另外，可以将W^t2的氢原子取代成聚合性基团(P¹¹-S¹¹-)。(In the above formula, R^tc represents an alkyl group or a polymerizable group (P¹¹ -S¹¹ -) having 1 to 8 carbon atoms, nt0 represents an integer of 1 to 7, and * represents a bond.) In addition, it is possible to use The hydrogen atom of W^t2 is substituted into a polymerizable group (P¹¹ -S¹¹ -).

上述通式(t)中，mt1优选表示1或2。In the above general formula (t), mt1 preferably represents 1 or 2.

上述通式(T)或通式(t)中，W^t1优选表示单键或直链状或者分支状的碳原子数1～8个的亚烷基(表示单键或直链状或者分支状的亚烷基，该亚烷基的-CH₂-可以以氧原子不直接邻接的方式被取代成-O-、-COO-、-C(＝O)-、-OCO-。)，更优选表示单键或直链状或者分支状的碳原子数1～7个的亚烷基(表示单键或直链状或者分支状的亚烷基，该亚烷基的-CH₂-可以以氧原子不直接邻接的方式被取代成-O-。)。另外，W^t1可以取代于介晶基团、聚合性基团或柔性基团的氢原子而键结。In the above general formula (T) or general formula (t), W^t1 preferably represents a single bond or a linear or branched alkylene group having 1 to 8 carbon atoms (represents a single bond, a linear or branched The alkylene group, the -CH₂ - of the alkylene group can be substituted into -O-, -COO-, -C(=O)-, -OCO- in such a way that the oxygen atom is not directly adjacent.), more preferably Represents a single bond or a linear or branched alkylene group having 1 to 7 carbon atoms (represents a single bond or a linear or branched alkylene group, -CH₂ - of the alkylene group may be oxygen Atoms that are not directly adjacent are substituted with -O-.). In addition, W^t1 may be substituted for a hydrogen atom of a mesogenic group, a polymerizable group, or a flexible group and bonded.

上述通式(T)或通式(t)中，包含X^t1不与Z^t1键结的形态(链式基)及X^t1与Z^t1键结而形成环的形态(环式基)。In the above general formula (T) or general formula (t), the form (chain group) in which X^t1 is not bonded to Z^t1 and the form (cyclic group) in which X^t1 and Z^t1 are bonded to form a ring are included.

在前者的形态的情形时，优选为碳原子数1～8个的直链状或者分支状的烷基、被-NH₂、-Z^t2-O-R^t1基或氰基取代的碳原子数1～7个的直链状或者分支状的烷基，更优选为碳原子数1～7个的直链状或分支状的烷基、被-Z^t2-O-R^t1基、氰基取代的碳原子数1～7个的直链状或分支状的烷基。另外，在前者的形态的情形时，前述R^t1各自独立地表示氢原子、碳原子数1～5个的烷基，上述Z^t2优选为单键、碳原子数1～10个的直链状或者分支状的亚烷基或碳原子数2～10个的直链状或者分支状的亚烯基(该亚烷基或该亚烯基的-CH₂-可以以氧原子不直接邻接的方式被取代成-O-、-COO-、-C(＝O)-、-OCO-)。In the case of the former form, it is preferably a linear or branched alkyl group having 1 to 8 carbon atoms, a carbon number 1 to 1 substituted with -NH₂ , -Z^t2 -OR^t1 group or a cyano group 7 straight-chain or branched alkyl groups, more preferably straight-chain or branched alkyl groups having 1 to 7 carbon atoms, carbon atoms substituted with -Z^t2 -OR^t1 groups, and cyano groups 1 to 7 straight-chain or branched alkyl groups. Moreover, in the case of the former form, the aforementioned R^t1 each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and the aforementioned Z^t2 is preferably a single bond and a straight chain having 1 to 10 carbon atoms. Alternatively, a branched alkylene group or a straight-chain or branched alkenylene group having 2 to 10 carbon atoms (-CH₂ - of the alkylene group or the alkenylene group may not be directly adjacent to oxygen atoms) Substituted as -O-, -COO-, -C(=O)-, -OCO-).

在后者的形态的情形时，优选为n^t1为1以上，X^t1为-Z^t2-O-R^t1，R^t1为碳原子数1～7个的直链状或者分支状的亚烷基或碳原子数2～7个的直链状或者分支状的亚烯基，并将Z^t1的氢原子取代而与R^t1键结，例如，优选由下述通式(T’)表示。In the case of the latter form, it is preferable that n^t1 is 1 or more, X^t1 is -Z^t2 -OR^t1 , and R^t1 is a linear or branched alkylene group having 1 to 7 carbon atoms or a carbon A linear or branched alkenylene group having 2 to 7 atoms in which the hydrogen atom of Z^t1 is substituted and bonded to R^t1 is preferably represented, for example, by the following general formula (T′).

[化25][Chemical 25]

(上述通式(T’)中，R^t1’各自独立地表示碳原子数1～8的直链状或者分支状的亚烷基或碳原子数2～8的直链状或者分支状的亚烯基，(In the above general formula (T'), R^t1' each independently represents a linear or branched alkylene group having 1 to 8 carbon atoms or a linear or branched alkylene group having 2 to 8 carbon atoms. alkenyl,

Z^t2’各自独立地表示单键、碳原子数1～10的直链状或者分支状的亚烷基或碳原子数2～10的直链状或者分支状的亚烯基，该亚烷基或该亚烯基的-CH₂-可以以氧原子不直接邻接的方式被取代成-O-、-COO-、-C(＝O)-、-OCO-，Z^t2' each independently represents a single bond, a linear or branched alkylene group having 1 to 10 carbon atoms, or a linear or branched alkenylene group having 2 to 10 carbon atoms, and the alkylene group Or -CH₂ - of the alkenylene group may be substituted into -O-, -COO-, -C(=O)-, -OCO- in a manner that the oxygen atom is not directly adjacent,

Z^t1’表示碳原子数1～18个的直链状或者分支状的亚烷基3价基团或碳原子数1～18个的直链状或者分支状的亚烯基3价基团，该亚烷基3价基团或亚烯基3价基团的-CH₂-可以以氧原子不直接邻接的方式被取代成-O-、-COO-、-C(＝O)-或OCO-，Z^t1' represents a straight-chain or branched alkylene trivalent group having 1 to 18 carbon atoms or a straight-chain or branched alkenylene trivalent group having 1 to 18 carbon atoms, The -CH₂ - of the alkylene trivalent group or the alkenylene trivalent group may be substituted into -O-, -COO-, -C(=O)- or OCO in such a way that the oxygen atoms are not directly adjacent to each other -,

W^t2表示单键或2价～4价的有机基，W^t2 represents a single bond or a divalent to tetravalent organic group,

-W^t1-表示单键或直链状或者分支状的亚烷基，该亚烷基的-CH₂-可以以氧原子不直接邻接的方式被取代成-O-、-COO-、-C(＝O)-、-OCO-，-W^t1 - represents a single bond or a linear or branched alkylene group, and -CH₂ - of the alkylene group may be substituted with -O-, -COO-, -C in a manner that the oxygen atom is not directly adjacent to each other (=O)-, -OCO-,

n^t1’表示1以上4以下的整数，n^t1' represents an integer of 1 or more and 4 or less,

m^t1’表示1以上3以下的整数，分子内的氢原子可以被取代成上述聚合性基团P¹¹-S¹¹-，＊表示连接键，与介晶基团、聚合性基团、柔性基团或间隔基团键结。)m^t1' represents an integer of 1 or more and 3 or less, the hydrogen atom in the molecule may be substituted with the above-mentioned polymerizable group P¹¹ -S¹¹ -, and * represents a bond, and a mesogenic group, a polymerizable group, a flexible group groups or spacer groups. )

该亚烷基3价基团是指从亚烷基进一步去除1个氢原子而形成的3价基团。该亚烯基3价基团是指从亚烯基进一步去除1个氢原子而形成的3价基团，包含所谓在烃链上具有游离原子价的3价基团，例如烷三基、烷基-亚基等。The alkylene trivalent group refers to a trivalent group formed by further removing one hydrogen atom from an alkylene group. The alkenylene trivalent group refers to a trivalent group formed by further removing one hydrogen atom from an alkenylene group, and includes so-called trivalent groups having free atomic valences in the hydrocarbon chain, such as alkanetriyl, alkane base-subunit, etc.

上述通式(T)中，当X^t1为不与Z^t1键结的形态(链式基)的情形时，Z^t1表示单键、碳原子数1～12个的直链状或者分支状的亚烷基或碳原子数2～12个的直链状或者分支状的亚烯基，该亚烷基的-CH₂-可以被取代成-O-、-COO-、-C(＝O)-、-OCO-。In the above-mentioned general formula (T), when X^t1 is in a form (chain group) not bonded to Z^t1 , Z^t1 represents a single bond, a linear or branched one having 1 to 12 carbon atoms. An alkylene group or a straight-chain or branched alkenylene group having 2 to 12 carbon atoms, the -CH₂ - of the alkylene group may be substituted with -O-, -COO-, -C(=O) -, -OCO-.

上述通式(T)中，当X^t1为与Z^t1键结的形态(环式基)的情形时，如上述通式(T’)所示。In the above-mentioned general formula (T), when X^t1 is a form (cyclic group) bonded to Z^t1 , it is represented by the above-mentioned general formula (T').

上述通式(T)中，n^t1优选表示0以上3以下的整数，n^t1更优选表示0以上2以下的整数。In the above general formula (T), n^t1 preferably represents an integer of 0 or more and 3 or less, and n^t1 more preferably represents an integer of 0 or more and 2 or less.

上述通式(T)优选为选自由通式(T-1-1)～(T-4-1)表示的环式基及通式(T-5-1)～(T-7-1)表示的链式基组成的组中的至少1种。当本发明涉及的通式(T)表示的吸附基团选择环式基的情形时，从吸附能力及对液晶组合物的相容性的观点考虑，优选为通式(T-1-1)或通式(T-2-1)。当本发明涉及的通式(T)表示的吸附基团选择链式基的情形时，从吸附能力及对液晶组合物的稳定性的观点考虑，优选为通式(T-5-1)或通式(T-6-1)。The above general formula (T) is preferably selected from cyclic groups represented by general formulae (T-1-1) to (T-4-1) and general formulae (T-5-1) to (T-7-1) At least one of the group consisting of the chain group represented. When a cyclic group is selected as the adsorption group represented by the general formula (T) according to the present invention, the general formula (T-1-1) is preferable from the viewpoints of adsorption capacity and compatibility with the liquid crystal composition. or general formula (T-2-1). When a chain group is selected as the adsorption group represented by the general formula (T) according to the present invention, from the viewpoints of adsorption capacity and stability to the liquid crystal composition, the general formula (T-5-1) or General formula (T-6-1).

[化26][Chemical 26]

(上述通式(T-1-1)～(T-7-1)中，X^ta及X^tb各自独立地表示-O-、-S-或-CH₂-，(In the above general formulae (T-1-1) to (T-7-1), X^ta and X^tb each independently represent -O-, -S- or -CH₂ -,

R^t5表示碳原子数1～8个的直链状或分支状的烷基、氰基化烷基或碳原子数1～8个的直链状或分支状的烷氧基，这些烷基中的至少2个以上的-CH₂-可以以氧原子不直接邻接的方式被取代成-CH＝CH-、-C≡C-、-O-或-NH-，R^t5 represents a straight-chain or branched alkyl group having 1 to 8 carbon atoms, a cyanated alkyl group, or a straight-chain or branched alkoxy group having 1 to 8 carbon atoms. At least 2 or more of -CH₂ - can be substituted into -CH=CH-, -C≡C-, -O- or -NH- in such a way that the oxygen atoms are not directly adjacent to each other,

Z^t3表示单键、碳原子数1～18个的直链状或者分支状的亚烷基或碳原子数2～18个的直链状或者分支状的亚烯基，该亚烷基或该亚烯基的-CH₂-可以以氧原子不直接邻接的方式被取代成-O-、-COO-、-C(＝O)-、-OCO-，Z^t3 represents a single bond, a linear or branched alkylene group having 1 to 18 carbon atoms, or a linear or branched alkenylene group having 2 to 18 carbon atoms, the alkylene group or the The -CH₂ - of the alkenylene group can be substituted into -O-, -COO-, -C(=O)-, -OCO- in such a way that the oxygen atoms are not directly adjacent,

W^t2表示单键或1价～4价的有机基，W^t2 represents a single bond or a monovalent to tetravalent organic group,

W^t1表示单键或直链状或者分支状的亚烷基，W^t1 represents a single bond or a straight-chain or branched alkylene group,

n^t1表示0以上4以下的整数，n^t1 represents an integer of 0 or more and 4 or less,

mt1表示1以上3以下的整数，分子内的氢原子可以被取代成上述聚合性基团P¹¹-S¹¹-，＊表示连接键，与介晶基团、聚合性基团、柔性基团或间隔基团键结。)mt1 represents an integer of 1 or more and 3 or less, the hydrogen atom in the molecule can be substituted into the above-mentioned polymerizable group P¹¹ -S¹¹ -, and * represents a bond, which is connected with a mesogenic group, a polymerizable group, a flexible group or a spacer group bonding. )

上述通式(T-1-1)～(T-4-1)中，优选X^ta或X^tb的任一者为-O-，更优选X^ta及X^tb为-O-。In the above general formulae (T-1-1) to (T-4-1), it is preferable that either X^ta or X^tb is -O-, and it is more preferable that X^ta and X^tb are -O-.

作为上述通式(T-1-1)～(T-4-1)的具体例，可列举以下的基团。Specific examples of the above-mentioned general formulae (T-1-1) to (T-4-1) include the following groups.

[化27][Chemical 27]

(上述式中，R^tc由氢原子、碳原子数1～7个的烷基或聚合性基团P¹¹-S¹¹-表示，分子内的氢原子可以被取代成上述聚合性基团P¹¹-S¹¹-，＊表示连接键，与介晶基团、聚合性基团、柔性基团或间隔基团键结。)(In the above formula, R^tc is represented by a hydrogen atom, an alkyl group having 1 to 7 carbon atoms, or a polymerizable group P¹¹ -S¹¹ -, and the hydrogen atom in the molecule may be substituted into the above polymerizable group P¹¹ -S¹¹ -, * represents a bond, which is bonded to a mesogenic group, a polymerizable group, a flexible group or a spacer group.)

上述通式(T-5-1)优选表示通式(T-5-2)。The above general formula (T-5-1) preferably represents the general formula (T-5-2).

[化28][Chemical 28]

(上述通式(T-5-2)中，W^t1表示与上述通式(T-5)中的W^t1相同的意义，R^t51及R^t52各自独立地表示碳原子数1～8个的直链状或分支状的烷基或氰基化烷基，这些烷基中的至少2个以上的-CH₂-可以以氧原子不直接邻接的方式被-CH＝CH-、-C≡C-、-O-或-NH-取代，R^tc由氢原子、碳原子数1～7个的烷基或聚合性基团P¹¹-S¹¹-表示，n^t1、n^t2及n^t3各自独立地表示0或1，分子内的氢原子可以被取代成P¹¹-S¹¹-。)(In the above general formula (T-5-2), W^t1 represents the same meaning as W^t1 in the above general formula (T-5), and R^t51 and R^t52 each independently represent a carbon atom having 1 to 8 carbon atoms. Linear or branched alkyl groups or cyanoalkyl groups, at least two or more of -CH₂ - in these alkyl groups may be replaced by -CH=CH-, -C≡C in such a manner that oxygen atoms are not directly adjacent to each other -, -O- or -NH- substituted, R^tc is represented by a hydrogen atom, an alkyl group having 1 to 7 carbon atoms or a polymerizable group P¹¹ -S¹¹ -, n^t1 , n^t2 and n^t3 are each independently The ground represents 0 or 1, and the hydrogen atom in the molecule can be substituted into P¹¹ -S¹¹ -.)

作为上述通式(T-5-1)的具体例，可列举以下的基团。As a specific example of the said general formula (T-5-1), the following groups are mentioned.

[化29][Chemical 29]

[化30][Chemical 30]

(上述式中，R^tc由氢原子、碳原子数1～7个的烷基或聚合性基团P¹¹-S¹¹-表示，分子内的氢原子可以被取代成上述聚合性基团P¹¹-S¹¹-，＊表示连接键，与介晶基团、聚合性基团、柔性基团或间隔基团键结。)(In the above formula, R^tc is represented by a hydrogen atom, an alkyl group having 1 to 7 carbon atoms, or a polymerizable group P¹¹ -S¹¹ -, and the hydrogen atom in the molecule may be substituted into the above polymerizable group P¹¹ -S¹¹ -, * represents a bond, which is bonded to a mesogenic group, a polymerizable group, a flexible group or a spacer group.)

[化31][Chemical 31]

[化32][Chemical 32]

(上述式中，R^tc由氢原子、碳原子数1～7个的烷基或聚合性基团P¹¹-S¹¹-表示，分子内的氢原子可以被取代成上述聚合性基团P¹¹-S¹¹-。)(＊表示连接键，与介晶基团、聚合性基团、柔性基团或间隔基团键结。)(In the above formula, R^tc is represented by a hydrogen atom, an alkyl group having 1 to 7 carbon atoms, or a polymerizable group P¹¹ -S¹¹ -, and the hydrogen atom in the molecule may be substituted into the above polymerizable group P¹¹ -S¹¹ -.) (* represents a linking bond, which is bonded to a mesogenic group, a polymerizable group, a flexible group or a spacer group.)

作为上述通式(T-6-1)的具体例，可列举以下的例子。As a specific example of the said general formula (T-6-1), the following examples are mentioned.

[化33][Chemical 33]

(上述式中，R^c由氢原子、碳原子数1～7个的烷基或聚合性基团P¹¹-S¹¹-表示，分子内的氢原子可以被取代成上述聚合性基团P¹¹-S¹¹-，＊表示连接键，与介晶基团、聚合性基团、柔性基团或间隔基团键结。)(In the above formula, R^c is represented by a hydrogen atom, an alkyl group having 1 to 7 carbon atoms, or a polymerizable group P¹¹ -S¹¹ -, and the hydrogen atom in the molecule may be substituted with the above-mentioned polymerizable group P¹¹ -S¹¹ -, * represents a bond, which is bonded to a mesogenic group, a polymerizable group, a flexible group or a spacer group.)

作为上述通式(T-7-1)的具体例，可列举以下的例子。As a specific example of the said general formula (T-7-1), the following examples are mentioned.

[化34][Chemical 34]

(上述式中，R^tc由氢原子、碳原子数1～7个的烷基或聚合性基团P¹¹-S¹¹-表示，分子内的氢原子可以被取代成上述聚合性基团P¹¹-S¹¹-，＊表示连接键，与介晶基团、聚合性基团、柔性基团或间隔基团键结。)(In the above formula, R^tc is represented by a hydrogen atom, an alkyl group having 1 to 7 carbon atoms, or a polymerizable group P¹¹ -S¹¹ -, and the hydrogen atom in the molecule may be substituted into the above polymerizable group P¹¹ -S¹¹ -, * represents a bond, which is bonded to a mesogenic group, a polymerizable group, a flexible group or a spacer group.)

本发明涉及的自取向性单体中，优选为使吸附基团所含的极性要素、聚合性基团所含的极性要素局部存在的形态。吸附基团为用于使液晶组合物垂直取向的重要结构，通过吸附基团与聚合性基团邻接，可得到更良好的取向性，另外，显示出对液晶组合物的良好的溶解性。具体而言，优选为在介晶基团的同一环上具有聚合性基团及吸附基团的形态。在该情形时，包含：1个以上的聚合性基团及1个以上的吸附基团各自键结于同一环上的形态；以及1个以上的聚合性基团的至少一个或1个以上的吸附基团的至少一个中，其中一者键结于另一者，在同一环上具有聚合性基团及吸附基团的形态。另外，在该情形时，聚合性基团的间隔基团(S¹¹)的氢原子可以被吸附基团取代，进一步也包含吸附基团的分子的氢原子与聚合性基团的间隔基团(S¹¹)结合的形态。In the self-aligning monomer according to the present invention, the polar element contained in the adsorption group and the polar element contained in the polymerizable group are preferably localized. The adsorption group is an important structure for vertically aligning the liquid crystal composition, and when the adsorption group is adjacent to the polymerizable group, more favorable orientation can be obtained, and good solubility in the liquid crystal composition is exhibited. Specifically, it is preferably a form having a polymerizable group and an adsorption group on the same ring as the mesogenic group. In this case, it includes: a form in which one or more polymerizable groups and one or more adsorption groups are each bonded to the same ring; and at least one or one or more of the one or more polymerizable groups are included. Among at least one of the adsorption groups, one of them is bonded to the other, and has the form of a polymerizable group and an adsorption group on the same ring. In addition, in this case, the hydrogen atom of the spacer group (S¹¹ ) of the polymerizable group may be substituted by the adsorption group, and the hydrogen atom of the molecule of the adsorption group and the spacer group (S 11 ) of the polymerizable group are also included. S¹¹ ) The form of binding.

另外，在本发明涉及的自取向性单体中，聚合性基团的1个以上的氢原子可以被取代成吸附基团。作为该情形的优选形态，可列举聚合基P¹¹或根据需要的连结于该聚合基的间隔基团(S¹¹)的1个以上的氢原子被取代成吸附基团的形态，作为更优选的形态，可列举聚合性基团(P¹¹-S¹¹-)中的1个以上的氢原子被取代成上述通式(T)表示的吸附基团的形态。In addition, in the self-aligning monomer according to the present invention, one or more hydrogen atoms of the polymerizable group may be substituted with an adsorption group. A preferred form in this case is a form in which one or more hydrogen atoms of the polymer group P¹¹ or, if necessary, a spacer group (S¹¹ ) linked to the polymer group is substituted with an adsorption group, and more preferred The form includes a form in which one or more hydrogen atoms in the polymerizable group (P¹¹ -S¹¹ -) are substituted with the adsorption group represented by the general formula (T).

例如，作为吸附基团与聚合性基团连结的适合的形态，可列举以下的式(T-1-1.1)、(T-6-1.1)或(T-5-1.1)。For example, the following formula (T-1-1.1), (T-6-1.1) or (T-5-1.1) can be mentioned as a suitable form in which an adsorption group and a polymerizable group are connected.

[化35][Chemical 35]

(上述式中，R^t11a、R^t16a及R^t151a各自独立地表示氢原子或碳原子数1～3的烷基，R^t151b及R^t151c各自独立地表示碳原子数1～3的烷基、碳原子数1～3的氰基化烷基，(In the above formula, R^t11a , R^t16a and R^t151a each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R^t151b and R^t151c each independently represent an alkyl group having 1 to 3 carbon atoms, a carbon Cyanolated alkyl groups of 1 to 3 atoms,

X^a及X^b表示-O-、-S-或-CH₂-，X^a and X^b represent -O-, -S- or -CH₂ -,

L^t151a及L^t151b各自独立地表示单键、亚甲基、亚乙基、亚丙基、乙烯叉基、亚乙烯基、亚异丙烯基或乙叉基，L^t151a and L^t151b each independently represent a single bond, methylene group, ethylene group, propylene group, vinylidene group, vinylidene group, isopropenylene group or ethylidene group,

n^t11c，n^t151c、n^t16c、n^t151d、n^t151e、n^t151f及n^t151g各自独立地表示0或1，n^t11a、n^t11b、n^t16a、n^t16b、n^t151a及n^t151b各自独立地表示1～11的整数，＊表示对介晶基团的连接键。)n^t11c , n^t151c , n^t16c , n^t151d , n^t151e , n^t151f and n^t151g each independently represent 0 or 1, and n^t11a , n^t11b , n^t16a , n^t16b , n^t151a and n^t151b each independently represent 1 An integer of ~11, and * represents a bond to a mesogenic group. )

上述式(T-1-1.1)中，优选X^a或X^b的任一者为-O-，更优选X^ta及X^tb为-O-。In the above formula (T-1-1.1), it is preferable that either X^a or X^b is -O-, and it is more preferable that X^ta and X^tb are -O-.

上述式(T-5-1.1)中，优选L^t151a及L^t151b各自独立地为亚甲基、亚乙基、乙烯叉基、亚乙烯基、亚异丙烯基或乙叉基。In the above formula (T-5-1.1), it is preferable that L^t151a and L^t151b are each independently a methylene group, an ethylene group, a vinylidene group, a vinylidene group, an isopropenylene group or an ethylidene group.

上述式(T-1-1.1)、(T-6-1.1)及(T-5-1.1)中，In the above formulas (T-1-1.1), (T-6-1.1) and (T-5-1.1),

n^t11a、n^t11b、n^t16a、n^t16b、n^t151a及n^t151b优选各自独立地为1～8的整数，更优选为1～5的整数。n^t11a , n^t11b , n^t16a , n^t16b , n^t151a and n^t151b are each independently preferably an integer of 1-8, more preferably an integer of 1-5.

“柔性基团”"Flexible group"

本发明涉及的柔性基团具有诱导液晶分子的取向的功能，优选表示直链状或者分支状的碳原子数1～20的亚烷基，更优选表示直链状的碳原子数1～20的亚烷基，更优选表示直链状的碳原子数2～15的亚烷基。另外，该亚烷基中的1个或未邻接的2个以上的-CH₂-可以各自独立地被-CH＝CH-、-C≡C-、-O-、-CO-、-COO-或-OCO-取代。The flexible group according to the present invention has a function of inducing alignment of liquid crystal molecules, and preferably represents a linear or branched alkylene group having 1 to 20 carbon atoms, and more preferably represents a linear or branched alkylene group having 1 to 20 carbon atoms. The alkylene group more preferably represents a linear alkylene group having 2 to 15 carbon atoms. In addition, one or two or more non-adjacent -CH₂ - in the alkylene group may be independently -CH=CH-, -C≡C-, -O-, -CO-, -COO- or -OCO- substitution.

从自取向性单体对于液晶层具备所谓的两亲性的观点考虑，上述柔性基团优选键结于介晶基团。From the viewpoint that the self-aligning monomer has so-called amphiphilicity with respect to the liquid crystal layer, the above-mentioned flexible group is preferably bonded to a mesogenic group.

本发明涉及的自取向性单体中，上述柔性基团优选具有1～6个，更优选具有1～4个，进一步优选具有1～3个。In the self-aligning monomer which concerns on this invention, it is preferable to have 1-6 pieces of the said flexible group, it is more preferable to have 1-4 pieces, and it is still more preferable to have 1-3 pieces.

本发明涉及的自取向性化合物优选为以下的通式(SAL)所表示的化合物。The self-aligning compound according to the present invention is preferably a compound represented by the following general formula (SAL).

[化36][Chemical 36]

(上述通式(SAL)中，-Sp^al-P^al表示上述聚合性基团，T表示上述通式(T)所表示的吸附基团，MG表示上述通式(AL)所表示的介晶基团，Cg表示氢原子、前述通式(T)所表示的吸附基团、前述作为聚合性基团的-Sp^al-P^al或作为柔性基团的直链状或者分支状的碳原子数1～20的亚烷基，该亚烷基中的1个或未邻接的2个以上的-CH₂-可以各自独立地被-CH＝CH-、-C≡C-、-O-、-CO-、-COO-或-OCO-取代，Cg、MG及T的任一者均可以被取代成上述作为聚合性基团的-Sp^al-P^al，(In the above-mentioned general formula (SAL), -Sp^al -P^al represents the above-mentioned polymerizable group, T represents the adsorption group represented by the above-mentioned general formula (T), and MG represents the above-mentioned mesogen represented by the general formula (AL) group, Cg represents a hydrogen atom, an adsorption group represented by the aforementioned general formula (T), the aforementioned -Sp^al -P^al as a polymerizable group, or a linear or branched carbon atom number as a flexible group 1-20 alkylene groups, one or two or more non-adjacent -CH₂ - in the alkylene group may be independently replaced by -CH=CH-, -C≡C-, -O-, - CO-, -COO- or -OCO- is substituted, and any one of Cg, MG and T may be substituted with the above-mentioned -Sp^al -P^al which is a polymerizable group,

n^sal1、n^sal2及n^sal3各自独立地表示1～5的自然数。)n^sal1 , n^sal2 , and n^sal3 each independently represent a natural number of 1 to 5. )

(上述式中，P^al表示通式(P-I)～通式(P-IX)所表示的基团，(In the above formula, P^a1 represents a group represented by general formula (PI) to general formula (P-IX),

[化37][Chemical 37]

(式中，R^p11及R^p12各自独立地表示氢原子、碳原子数1～5的烷基或碳原子数1～5的卤代烷基，W^p11表示单键、-O-、-COO-或亚甲基，t^p11表示0、1或2。)(wherein, R^p11 and R^p12 each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms, and W^p11 represents a single bond, -O-, -COO- or methylene, t^p11 represents 0, 1 or 2.)

Sp^al表示单键或直链状或者分支状的碳原子数1～20个的亚烷基，亚烷基中的1个或未邻接的2个以上的-CH₂-可以各自独立地被-CH＝CH-、-C≡C-、-O-、-CO-、-COO-或-OCO-取代，Sp^al represents a single bond or a linear or branched alkylene group having 1 to 20 carbon atoms, and one or two or more non-adjacent -CH₂ - in the alkylene group may each independently be - CH=CH-, -C≡C-, -O-, -CO-, -COO- or -OCO- substituted,

T表示吸附基团，T represents the adsorption group,

MG表示介晶基团，MG represents a mesogenic group,

Cg表示氢原子、前述吸附基团、前述-Sp^al-P^al或直链状或者分支状的碳原子数1～20的亚烷基，该亚烷基中的1个或未邻接的2个以上的-CH₂-可以各自独立地被-CH＝CH-、-C≡C-、-O-、-CO-、-COO-或-OCO-取代，Cg、MG及T的任一者均可以被取代成上述作为聚合性基团的-Sp^al-P^al-，Cg represents a hydrogen atom, the aforementioned adsorption group, the aforementioned -Sp^al -P^al , or a linear or branched alkylene group having 1 to 20 carbon atoms, and one or two non-adjacent alkylene groups in the alkylene group The above -CH₂ - may be independently substituted by -CH=CH-, -C≡C-, -O-, -CO-, -COO- or -OCO-, and any of Cg, MG and T may be may be substituted with the above-mentioned -Sp^al -P^al - as a polymerizable group,

n^sal1、n^sal2及n^sal3各自独立地表示1～5的自然数。)n^sal1 , n^sal2 , and n^sal3 each independently represent a natural number of 1 to 5. )

作为本发明涉及的优选的自取向性单体，优选为选自由以下的通式(al-1)～通式(al-3)组成的组中的至少1种。As a preferable self-aligning monomer concerning this invention, it is preferable that it is at least 1 sort(s) chosen from the group which consists of the following general formula (al-1) - general formula (al-3).

[化38][Chemical 38]

(式中，R^al1、R^al2、Z^al1、Z^al2、L^al1、L^al2、L^al3、L^al4、Sp¹¹¹、Sp¹¹²、Sp¹¹³、Sp¹¹⁴、P¹¹¹、P¹¹²、P¹¹³、P¹¹⁴、m^al1、m^al2、m^al3、m^al4、n^al1、n^al2、n^al3、n^al4、P¹¹¹及P¹¹²各自彼此独立，(wherein, R^al1 , R^al2 , Z^al1 , Z^al2 , L^al1 , L^al2 , L^al3 , L^al4 , Sp¹¹¹ , Sp¹¹² , Sp¹¹³ , Sp¹¹⁴ , P¹¹¹ , P¹¹² , P¹¹³ , P¹¹⁴ , m^al1 , m^al2 , m^al3 , m^al4 , n^al1 , n^al2 , n^al3 , n^al4 , P¹¹¹ and P¹¹² are independent of each other,

R^al1表示氢原子、卤素原子、碳原子数1～20个的直链状或分支状的烷基，该烷基中的1个-CH₂-或未邻接的2个以上的-CH₂-可以以氧原子不直接邻接的方式被-O-、-OCO-或-COO-取代，R^a11 represents a hydrogen atom, a halogen atom, a straight-chain or branched alkyl group having 1 to 20 carbon atoms, and one -CH₂ - or two or more non-adjacent -CH₂ - in the alkyl group may be substituted by -O-, -OCO- or -COO- in such a way that the oxygen atoms are not directly adjacent,

R^al2表示可以被取代成上述聚合基P¹¹-S¹¹-的吸附基团，优选表示可以被取代成上述聚合基P¹¹-S¹¹-的上述通式(T)所表示的吸附基团，更优选R^al2为选自由通式(T-1-1)～(T-7-1)组成的组中的至少1者，进一步优选为选自由通式(T-1-1)、(T-2-1)、(T-5-1)、(T-6-1)组成的组中的至少1者，R^al2 represents an adsorption group that can be substituted into the above-mentioned polymer group P¹¹ -S¹¹ -, preferably represents an adsorption group represented by the above-mentioned general formula (T) that can be substituted into the above-mentioned polymer group P¹¹ -S¹¹ -, More preferably, R^al2 is at least one selected from the group consisting of general formulae (T-1-1) to (T-7-1), and further preferably, it is selected from general formulae (T-1-1) and (T -2-1), (T-5-1), at least one of the group consisting of (T-6-1),

更进一步优选为选自由式(T-1-1.1)、(T-6-1.1)及(T-5-1.1)组成的组中的至少1者，More preferably, at least one selected from the group consisting of formula (T-1-1.1), (T-6-1.1) and (T-5-1.1),

环A^al1、A^al2各自独立地表示1,4-亚苯基、1,4-亚环己基、2,6-亚萘基或菲-2,7-二基，Rings A^a11 and A^a12 each independently represent 1,4-phenylene, 1,4-cyclohexylene, 2,6-naphthylene or phenanthrene-2,7-diyl,

Sp¹¹¹、Sp¹¹²及Sp¹¹³各自彼此独立地表示碳原子数1～12个的亚烷基或单键，该亚烷基中的1个-CH₂-或未邻接的2个以上的-CH₂-可以以氧原子不直接邻接的方式被-O-、-OCO-或-COO-取代，Sp¹¹¹ , Sp¹¹² and Sp¹¹³ each independently represent an alkylene group having 1 to 12 carbon atoms or a single bond, one -CH₂ - or two or more non-adjacent -CH in the alkylene group₂ - may be substituted by -O-, -OCO- or -COO- in such a way that the oxygen atoms are not directly adjacent,

P¹¹¹、P¹¹²、P¹¹³及P¹¹⁴各自彼此独立地表示丙烯酰基、甲基丙烯酰基，P¹¹¹ , P¹¹² , P¹¹³ and P¹¹⁴ each independently represent an acryloyl group and a methacryloyl group,

Z^al1及Z^al2各自彼此独立地表示单键、-O-、-CO-、-CO-O-、-OCO-、-O-CO-O-、-OCH₂-、-CH₂O-、-CF₂O-、-OCF₂-、-(CH₂)n^al-、-CF₂CH₂-、-CH₂CF₂-、-(CF₂)n^al-、-CH＝CH-、-CF＝CF-、-C≡C-、-CH＝CH-COO-或-OCO-CH＝CH-，上述n^al表示1～4的整数，Z^a11 and Z^a12 each independently represent a single bond, -O-, -CO-, -CO-O-, -OCO-, -O-CO-O-, -OCH₂ -, -CH₂ O-, -CF₂ O-, -OCF₂ -, -(CH₂ )n^al -, -CF₂ CH₂ -, -CH₂ CF₂ -, -(CF₂ )n^al -, -CH=CH-, - CF=CF-, -C≡C-, -CH=CH-COO- or -OCO-CH=CH-, the above n^al represents an integer from 1 to 4,

L^al1、L^al2、L^al3及L^al4各自彼此独立地表示氢原子、卤素原子、碳原子数1～15个的烷基、碳原子数1～14个的烷氧基或R^al2，此处，该烷基的1个以上的氢原子可以被卤素原子取代，L^al1 , L^al2 , L^al3 and L^al4 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 15 carbon atoms, an alkoxy group having 1 to 14 carbon atoms, or R^al2 , where , one or more hydrogen atoms of the alkyl group may be replaced by halogen atoms,

P¹¹¹及P¹¹²各自彼此独立地表示0或1，m^al1、m^al2、m^al3及m^al4各自彼此独立地表示0～3的整数，n^al1、n^al2、n^al3及n^al4各自彼此独立地表示0～3的整数。)P¹¹¹ and P¹¹² each independently represent 0 or 1, m^al1 , m^al2 , m^al3 and m^al4 each independently represent an integer of 0 to 3, and n^al1 , n^al2 , n^al3 and n^al4 each independently of each other ground represents an integer from 0 to 3. )

通式(al-2)：General formula (al-2):

[化39][Chemical 39]

(式中，Z^ad1及Z^ad2各自独立地表示单键、-CH＝CH-、-CF＝CF-、-C≡C-、-COO-、-OCO-、-OCOO-、-OOCO-、-CF₂O-、-OCF₂-、-CH＝CHCOO-、-OCOCH＝CH-、-CH₂-CH₂COO-、-OCOCH₂-CH₂-、-CH＝C(CH₃)COO-、-OCOC(CH₃)＝CH-、-CH₂-CH(CH₃)COO-、-OCOCH(CH₃)-CH₂-、-OCH₂CH₂O-或碳原子数2～20的亚烷基，该亚烷基中的1个或未邻接的2个以上的-CH₂-可以被-O-、-COO-或-OCO-取代，(wherein, Z^ad1 and Z^ad2 each independently represent a single bond, -CH=CH-, -CF=CF-, -C≡C-, -COO-, -OCO-, -OCOO-, -OOCO-, -CF₂ O-, -OCF₂ -, -CH=CHCOO-, -OCOCH=CH-, -CH₂ -CH₂ COO-, -OCOCH₂ -CH₂ -, -CH=C(CH₃ )COO- , -OCOC(CH₃ )=CH-, -CH₂ -CH(CH₃ )COO-, -OCOCH(CH₃ )-CH₂ -, -OCH₂ CH₂ O-, or a sub-group with 2 to 20 carbon atoms Alkyl group, one or two or more non-adjacent -CH₂ - in the alkylene group may be substituted by -O-, -COO- or -OCO-,

A^ad1及A^ad2各自独立地表示2价的6元环芳香族基或2价的6元环脂肪族基，2价的未经取代的6元环芳香族基、2价的未经取代的6元环脂肪族基或这些环结构中的氢原子优选未经取代或被碳原子数1～15的烷基、碳原子数1～6的烷氧基、卤素原子取代，优选为2价的未经取代的6元环芳香族基或者该环结构中的氢原子被氟原子取代后的基团、或2价的未经取代的6元环脂肪族基，优选为取代基上的氢原子可以被卤素原子、烷基或烷氧基取代的1,4-亚苯基、2,6-萘基或1,4-环己基，但至少一个取代基被P¹¹-S¹¹-取代，A^ad1 and A^ad2 each independently represent a divalent 6-membered cyclic aromatic group or a divalent 6-membered cyclic aliphatic group, a divalent unsubstituted 6-membered cyclic aromatic group, a divalent unsubstituted The 6-membered cycloaliphatic group or the hydrogen atom in these ring structures is preferably unsubstituted or substituted with an alkyl group having 1 to 15 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and a halogen atom, preferably a divalent An unsubstituted 6-membered cyclic aromatic group or a group in which the hydrogen atom in the ring structure is substituted by a fluorine atom, or a bivalent unsubstituted 6-membered cyclic aliphatic group, preferably a hydrogen atom on the substituent 1,4-phenylene, 2,6-naphthyl or 1,4-cyclohexyl which may be substituted by halogen atom, alkyl or alkoxy, but at least one substituent is substituted by P¹¹ -S¹¹ -,

当Z^ad1、A^ad1及Aa^ad2各自存在多个的情形时，各自彼此可相同也可不同，When there are multiple Z^ad1 , A^ad1 and Aa^ad2 , they may be the same or different from each other,

R^ad1表示氢原子、碳原子数1～20的直链或分支的烷基、卤代烷基或P¹¹-S¹¹-，该烷基中的-CH₂-优选为-O-、-OCO-或-COO-(其中，-O-不连续)，更优选表示氢原子、碳原子数1～18的直链或分支的烷基或P¹¹-S¹¹-，该烷基中的-CH₂-以氧原子不直接邻接的方式表示-O-、-OCO-。R^ad1 represents a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, a haloalkyl group or P¹¹ -S¹¹ -, and -CH₂ - in the alkyl group is preferably -O-, -OCO- or -COO- (wherein, -O- is discontinuous), more preferably a hydrogen atom, a linear or branched alkyl group having 1 to 18 carbon atoms, or P¹¹ -S¹¹ -, and -CH₂ - in the alkyl group -O- and -OCO- are represented so that oxygen atoms are not directly adjacent to each other.

Ab^ad1表示可以被取代成上述聚合基P¹¹-S¹¹-的吸附基团，优选表示可以被取代成上述聚合基P¹¹-S¹¹-的上述通式(T)所表示的吸附基团，更优选R^al2为选自由通式(T-1-1)～(T-7-1)组成的组中的至少1者，进一步优选为选自由通式(T-1-1)、(T-2-1)、(T-5-1)、(T-6-1)组成的组中的至少1者，Ab^ad1 represents an adsorption group which can be substituted into the above-mentioned polymer group P¹¹ -S¹¹ -, preferably represents an adsorption group represented by the above general formula (T) which can be substituted into the above-mentioned polymer group P¹¹ -S¹¹ -, More preferably, R^al2 is at least one selected from the group consisting of general formulae (T-1-1) to (T-7-1), and further preferably, it is selected from general formulae (T-1-1) and (T -2-1), (T-5-1), at least one of the group consisting of (T-6-1),

更进一步优选为选自由式(T-1-1.1)、(T-6-1.1)及(T-5-1.1)组成的组中的至少1者，More preferably, at least one selected from the group consisting of formula (T-1-1.1), (T-6-1.1) and (T-5-1.1),

P¹¹-S¹¹-表示上述聚合性基团，P¹¹ -S¹¹ - represents the above-mentioned polymerizable group,

当Z^ad1、Z^ad2、A^ad1、m^ad1和/或A^ad2各自存在多个的情形时，各自彼此可相同也可不同，其中，A^ad1及A^ad2的任一者被至少一个P¹¹-S¹¹-取代，When there are a plurality of Z^ad1 , Z^ad2 , A^ad1 ,^mad1 and/or A^ad2 , each of them may be the same or different from each other, wherein any one of A^ad1 and A^ad2 is replaced by at least one P¹¹ − S¹¹ - substituted,

m^ad1表示1～5的整数，m^ad1 represents an integer from 1 to 5,

m^ad2表示1～5的整数，m^ad2 represents an integer from 1 to 5,

G^ad1表示2价、3价、4价的任一分支结构，或2价、3价、4价的任一脂肪族或芳香族的环结构，G^ad1 represents any branched structure of divalent, trivalent and tetravalent, or any aliphatic or aromatic ring structure of divalent, trivalent or tetravalent,

m^ad3表示比G^ad1的价数小1的整数。)m^ad3 represents an integer smaller than the valence of G^ad1 by 1. )

通式(al-3)；General formula (al-3);

[化40][Chemical 40]

(上述通式(al-3)中，R^al31表示碳原子数1～15的烷基，在该烷基中，1个或未邻接的2个以上的-CH₂-可以被-O-、-S-、-CH＝CH-或-C≡C-取代，在这些基团中，至少1个氢原子可以被卤素原子取代，(In the above general formula (al-3), R^a131 represents an alkyl group having 1 to 15 carbon atoms, and in this alkyl group, one or two or more non-adjacent -CH₂ - may be replaced by -O-, -S-, -CH=CH- or -C≡C- substituted, in these groups, at least one hydrogen atom may be replaced by a halogen atom,

A^al31及A^al34各自独立地表示1,4-亚环己基、1,4-亚苯基、萘-2,6-二基或菲-2,7-二基，在这些环中，至少1个氢原子可以被卤素原子、碳原子数1至12的烷基、碳原子数2至12的烯基、碳原子数1至11的烷氧基或碳原子数2至11的烯氧基取代，在这些基团中，至少1个氢原子可以被氟原子或氯原子取代，A^a131 and A^a134 each independently represent 1,4-cyclohexylene, 1,4-phenylene, naphthalene-2,6-diyl or phenanthrene-2,7-diyl, and among these rings, at least 1 hydrogen atoms may be substituted by a halogen atom, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkoxy group having 1 to 11 carbon atoms, or an alkenyloxy group having 2 to 11 carbon atoms , in these groups, at least one hydrogen atom can be replaced by a fluorine atom or a chlorine atom,

Z^al31表示单键或碳原子数1～10的亚烷基，在该亚烷基中，1个或未邻接的2个以上的-CH₂-可以被-O-、-S-、-CH＝CH-或-C≡C-取代，在这些基团中，至少1个氢原子可以被卤素原子取代，Z^al31 represents a single bond or an alkylene group having 1 to 10 carbon atoms, and in the alkylene group, one or two or more non-adjacent -CH₂ - may be replaced by -O-, -S-, -CH =CH- or -C≡C-substituted, in these groups, at least one hydrogen atom may be replaced by a halogen atom,

S^al31表示单键或碳原子数1～10的亚烷基，在该亚烷基中，1个或未邻接的2个以上的-CH₂-可以被-O-、-S-、-CH＝CH-或-C≡C-取代，在这些基团中，至少1个氢原子可以被卤素原子取代，S^al31 represents a single bond or an alkylene group having 1 to 10 carbon atoms, and in the alkylene group, one or two or more -CH₂ - which are not adjacent to each other may be replaced by -O-, -S-, -CH =CH- or -C≡C-substituted, in these groups, at least one hydrogen atom may be replaced by a halogen atom,

K^al31及K^al32各自独立地表示氢原子、卤素原子、碳原子数1～5的烷基或至少1个氢原子被卤素原子(例如氟原子)取代后的碳原子数1至5的烷基，K^al31 and K^al32 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms in which at least one hydrogen atom is substituted with a halogen atom (for example, a fluorine atom). ,

n^al31为由0～4表示的整数，n^al31 is an integer represented by 0 to 4,

R^al32为由式(al3-1)或式(al3-2)表示的基团，R al32 is a group represented by formula (^al3-1 ) or formula (al3-2),

[化41][Chemical 41]

·——S^a131-X^a131(a13-1)·——S^a131 -X^a131 (a13-1)

式(al3-1)及式(al3-2)中，In formula (al3-1) and formula (al3-2),

S^al32及S^al33各自独立地为单键或碳原子数1至10的亚烷基，在该亚烷基中，1个或未邻接的2个以上的-CH₂-可以被-O-、-S-、-CH＝CH-或-C≡C-取代，在这些基团中，至少1个氢原子可以被卤素原子取代，S^al32 and S^al33 are each independently a single bond or an alkylene group having 1 to 10 carbon atoms, and in the alkylene group, one or two or more non-adjacent -CH₂ - may be replaced by -O-, -S-, -CH=CH- or -C≡C- substituted, in these groups, at least one hydrogen atom may be replaced by a halogen atom,

S^al31为＝CH-或＝N-，S^al31 is =CH- or =N-,

X^al31为-OH、-NH₂、-OR³、-N(R³)₂、式(X^al31)、-COOH、-SH、-B(OH)₂或-Si(R³)₃所表示的基团，此处，R³为氢原子或碳原子数1～10的烷基，在该烷基中，1个或未邻接的2个以上的-CH₂-可以被-O-、-S-、-CH＝CH-或-C≡C-取代，在这些基团中，至少1个氢原子可以被卤素原子取代，X^al31 is represented by -OH, -NH₂ , -OR³ , -N(R³ )₂ , formula (X^al31 ), -COOH, -SH, -B(OH)₂ or -Si(R³ )₃ group, where R³ is a hydrogen atom or an alkyl group with 1 to 10 carbon atoms, and in the alkyl group, one or two or more non-adjacent -CH₂ - may be replaced by -O-, - S-, -CH=CH- or -C≡C- substituted, in these groups, at least one hydrogen atom may be replaced by a halogen atom,

式(X^al31)：Formula (X^al31 ):

[化42][Chemical 42]

(n^al32为1～5的整数。)(n^al32 is an integer of 1 to 5.)

上述自取向性单体中，不易与液晶层融合的吸附基团、聚合性基团等极性部分及容易与液晶层融合的介晶基团、柔性基团等非极性部分优选在分子内不均匀地存在，优选对所谓的液晶层显示出两亲性。因此，本发明涉及的自取向性单体优选为下述结构：在介晶基团的一端部具有使液晶分子取向的柔性基团，而在介晶基团的另一端部具有聚合性基团及吸附基团。认为：由于在液晶层与基板的界面附近，界面自由能变高，因此在一分子内具有对液晶层有亲和性的非极性部分和对液晶层的亲和性低的极性部分的物质会排列于界面上，因而使界面自由能降低。Among the above self-aligning monomers, polar moieties such as adsorption groups and polymerizable groups that are not easily fused with the liquid crystal layer, and non-polar moieties such as mesogenic groups and flexible groups that are easily fused with the liquid crystal layer are preferably within the molecule. It exists unevenly, and preferably exhibits amphiphilicity to the so-called liquid crystal layer. Therefore, the self-aligning monomer according to the present invention preferably has a structure in which one end of the mesogenic group has a flexible group for aligning liquid crystal molecules, and the other end of the mesogenic group has a polymerizable group and adsorption groups. It is considered that since the interface free energy becomes high in the vicinity of the interface between the liquid crystal layer and the substrate, a non-polar portion having affinity for the liquid crystal layer and a polar portion having low affinity for the liquid crystal layer are included in one molecule. Substances will be aligned at the interface, thereby reducing the free energy of the interface.

本发明涉及的液晶组合物中的自取向性单体的含量下限优选为0.02质量％，优选为0.03质量％，优选为0.04质量％，优选为0.05质量％，优选为0.06质量％，优选为0.07质量％，优选为0.08质量％，优选为0.09质量％，优选为0.1质量％，优选为0.12质量％，优选为0.15质量％，优选为0.17质量％，优选为0.2质量％，优选为0.22质量％，优选为0.25质量％，优选为0.27质量％，优选为0.3质量％，优选为0.32质量％，优选为0.35质量％，优选为0.37质量％，优选为0.4质量％，优选为0.42质量％，优选为0.45质量％，优选为0.5质量％，优选为0.55质量％。本发明涉及的液晶组合物中的通式(I)所表示的聚合性单体的含量上限优选为2.5质量％，优选为2.3质量％，优选为2.1质量％，优选为2质量％，优选为1.8质量％，优选为1.6质量％，优选为1.5质量％，优选为1质量％，优选为0.95质量％，优选为0.9质量％，优选为0.85质量％，优选为0.8质量％，优选为0.75质量％，优选为0.7质量％，优选为0.65质量％，优选为0.6质量％，优选为0.55质量％，优选为0.5质量％，优选为0.45质量％，优选为0.4质量％。The lower limit of the content of the self-aligning monomer in the liquid crystal composition according to the present invention is preferably 0.02 mass %, preferably 0.03 mass %, preferably 0.04 mass %, preferably 0.05 mass %, preferably 0.06 mass %, preferably 0.07 mass % mass %, preferably 0.08 mass %, preferably 0.09 mass %, preferably 0.1 mass %, preferably 0.12 mass %, preferably 0.15 mass %, preferably 0.17 mass %, preferably 0.2 mass %, preferably 0.22 mass % , preferably 0.25 mass%, preferably 0.27 mass%, preferably 0.3 mass%, preferably 0.32 mass%, preferably 0.35 mass%, preferably 0.37 mass%, preferably 0.4 mass%, preferably 0.42 mass%, preferably It is 0.45 mass %, Preferably it is 0.5 mass %, Preferably it is 0.55 mass %. The upper limit of the content of the polymerizable monomer represented by the general formula (I) in the liquid crystal composition according to the present invention is preferably 2.5% by mass, preferably 2.3% by mass, preferably 2.1% by mass, preferably 2% by mass, and preferably 1.8 mass %, preferably 1.6 mass %, preferably 1.5 mass %, preferably 1 mass %, preferably 0.95 mass %, preferably 0.9 mass %, preferably 0.85 mass %, preferably 0.8 mass %, preferably 0.75 mass % %, preferably 0.7% by mass, preferably 0.65% by mass, preferably 0.6% by mass, preferably 0.55% by mass, preferably 0.5% by mass, preferably 0.45% by mass, preferably 0.4% by mass.

本发明涉及的自取向性单体的特别合适的具体例为以下的通式(al-1-1)所表示的化合物。A particularly suitable specific example of the self-aligning monomer according to the present invention is a compound represented by the following general formula (al-1-1).

[化43][Chemical 43]

(上述通式(al-1-1)中，R^al3表示碳原子数1～12的直链状的烷基，在该烷基中，1个或未邻接的2个以上的-CH₂-可以被-O-或-CH＝CH-取代，(In the above-mentioned general formula (al-1-1), R^a13 represents a straight-chain alkyl group having 1 to 12 carbon atoms, and in this alkyl group, one or two or more non-adjacent -CH₂ - can be substituted by -O- or -CH=CH-,

L^al5、L^al6、L^al7及L^al8各自独立地表示氢原子、碳原子数1～12个的烷基、卤素原子或上述P¹¹-S¹¹-，在该烷基中，1个或未邻接的2个以上的-CH₂-可以被-O-或-CH＝CH-取代，L^al5 , L^al6 , L^al7 and L^al8 each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a halogen atom, or the above-mentioned P¹¹ -S¹¹ -, and among the alkyl groups, one or none Two or more adjacent -CH₂ - may be substituted by -O- or -CH=CH-,

环A^al3表示1,4-亚环己基或1,4-亚苯基，Ring A^al3 represents 1,4-cyclohexylene or 1,4-phenylene,

R^ala或R^alb各自独立地表示氢原子或上述P¹¹-S¹¹-，R^ala或R^alb的至少一者表示上述P¹¹-S¹¹-，R^ala or R^alb each independently represents a hydrogen atom or the above-mentioned P¹¹ -S¹¹ -, at least one of R^ala or R^alb represents the above-mentioned P¹¹ -S¹¹ -,

Z^al3表示单键、-CH₂-CH₂-、-CH₂-O-或O-CH₂-，Z^al3 represents a single bond, -CH₂ -CH₂ -, -CH₂ -O- or O-CH₂ -,

R^al4表示由上述通式(T)表示的吸附基团，R^al4 represents an adsorption group represented by the above general formula (T),

P¹¹³及P¹¹⁴各自独立地表示0或1。)P¹¹³ and P¹¹⁴ each independently represent 0 or 1. )

上述通式(al-1-1)中，优选L^al7及L^al8中的一者表示碳原子数1～5个的烷基。In the above general formula (al-1-1), it is preferable that one of L^a17 and L^a18 represents an alkyl group having 1 to 5 carbon atoms.

上述通式(al-1-1)中，R^ala及R^alb优选表示上述P¹¹-S¹¹-。In the aforementioned general formula (al-1-1), R^ala and R^alb preferably represent the aforementioned P¹¹ -S¹¹ -.

上述通式(al-1-1)中，R^al4优选为上述通式(T-1-1)～(T-7-1)或式(T-1-1.1)、(T-6-1.1)或(T-5-1.1)。In the above-mentioned general formula (al-1-1), R^al4 is preferably the above-mentioned general formulae (T-1-1) to (T-7-1) or formulae (T-1-1.1), (T-6-1.1) ) or (T-5-1.1).

作为上述通式(al-1)所表示的优选化合物，可列举以下的式(AL-1.1)～(AL-1.18)所表示的化合物。As a preferable compound represented by the said general formula (al-1), the compound represented by the following formula (AL-1.1) - (AL-1.18) is mentioned.

作为上述通式(al-2)所表示的优选化合物，可列举以下的式(AL-2.1)～(AL-2.48)所表示的化合物。As a preferable compound represented by the said general formula (al-2), the compound represented by the following formula (AL-2.1) - (AL-2.48) is mentioned.

[化44][Chemical 44]

[化45][Chemical 45]

[化46][Chemical 46]

[化47][Chemical 47]

[化48][Chemical 48]

[化49][Chemical 49]

[化50][Chemical 50]

[化51][Chemical 51]

[化52][Chemical 52]

[化53][Chemical 53]

[化54][Chemical 54]

[化55][Chemical 55]

[化56][Chemical 56]

[化57][Chemical 57]

[化58][Chemical 58]

[化59][Chemical 59]

＜聚合性单体＞<Polymerizable monomer>

本发明涉及的聚合性单体具备与上述自取向性单体不同的化学结构式，该聚合性单体在液晶组合物中含有选自由下述通式(I)所表示的化合物组成的组中的2种以上。The polymerizable monomer according to the present invention has a different chemical structural formula from the self-aligning monomer described above, and the polymerizable monomer contains, in the liquid crystal composition, a compound selected from the group consisting of compounds represented by the following general formula (I) 2 or more.

[化60][Chemical 60]

(上述通式(I)中，R¹⁰¹、R¹⁰²、R¹⁰³、R¹⁰⁴、R¹⁰⁵、R¹⁰⁶、R¹⁰⁷、R¹⁰⁸、R¹⁰⁹及R¹¹⁰各自独立地表示P²¹-S²¹-、碳原子数1至18的烷基、碳原子数1至18的烷氧基、卤素原子或氢原子中的任一者，上述P²¹为下述式(P-I)～式(P-IX)所表示的任一基团，(In the above general formula (I), R¹⁰¹ , R¹⁰² , R¹⁰³ , R¹⁰⁴ , R¹⁰⁵ , R¹⁰⁶ , R¹⁰⁷ , R¹⁰⁸ , R¹⁰⁹ and R¹¹⁰ each independently represent P²¹ -S²¹ -, carbon Any of an alkyl group having 1 to 18 atoms, an alkoxy group having 1 to 18 carbon atoms, a halogen atom, or a hydrogen atom, and the above P²¹ is represented by the following formulae (PI) to (P-IX) any group of

[化61][Chemical 61]

(式中，R^p11及R^p12各自独立地表示氢原子、碳原子数1～5的烷基或碳原子数1～5的卤代烷基，W^p11表示单键、-O-、-COO-或亚甲基，t^p11表示0、1或2。)(wherein, R^p11 and R^p12 each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms, and W^p11 represents a single bond, -O-, -COO- or methylene, t^p11 represents 0, 1 or 2.)

上述S²¹表示单键或碳原子数1～15的亚烷基，该亚烷基中的1个或2个以上的-CH₂-可以以氧原子不直接邻接的方式被-O-、-OCO-或-COO-取代，The above-mentioned S²¹ represents a single bond or an alkylene group having 1 to 15 carbon atoms, and one or more -CH₂ - in the alkylene group may be -O-, - so that the oxygen atoms are not directly adjacent to each other. OCO- or -COO- substituted,

n¹¹表示0、1或2，n¹¹ means 0, 1 or 2,

n¹²及n¹³各自独立地表示0或1，n¹² and n¹³ each independently represent 0 or 1,

n¹¹+n¹²+n¹³＝1、2或3，n¹¹ +n¹² +n¹³ =1, 2 or 3,

A¹¹表示选自由下述的基团(a)、基团(b)及基团(c)组成的组中的基团：A¹¹ represents a group selected from the group consisting of the following group (a), group (b) and group (c):

(a)1,4-亚环己基(存在于该基团中的1个-CH₂-或未邻接的2个以上的-CH₂-可以被取代成-O-。)(a) 1,4-cyclohexylene group (One -CH₂ - or two or more non-adjacent -CH₂ - present in this group may be substituted with -O-.)

(b)1,4-亚苯基(存在于该基团中的1个-CH＝或未邻接的2个以上的-CH＝可以被取代成-N＝。)及(b) 1,4-phenylene (one -CH= present in this group or two or more non-adjacent -CH= may be substituted with -N=.) and

(c)萘-2,6-二基、2,7-菲二基、1,2,3,4-四氢萘-2,6-二基或十氢萘-2,6-二基(存在于萘-2,6-二基或1,2,3,4-四氢萘-2,6-二基中的1个-CH＝或未邻接的2个以上的-CH＝可以被取代成-N＝。)(c) Naphthalene-2,6-diyl, 2,7-phenanthrenediyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl or decahydronaphthalene-2,6-diyl ( One -CH= or two or more non-adjacent -CH= present in naphthalene-2,6-diyl or 1,2,3,4-tetrahydronaphthalene-2,6-diyl may be substituted into -N=.)

上述基团(a)、基团(b)及基团(c)可以各自独立地被碳原子数1～12的烷基、碳原子数1～12的烷氧基、卤素、氰基、硝基或P²¹-S²¹-取代，The above-mentioned group (a), group (b) and group (c) may be independently replaced by an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, halogen, cyano, nitro base or P²¹ -S²¹ - substituted,

L¹⁰及L¹¹各自独立地表示单键、-OCH₂-、-CH₂O-、-C₂H₄-、-OC₂H₄O-、-COO-、-OCO-、-CH＝CR^a-COO-、-CH＝CR^a-OCO-、-COO-CR^a＝CH-、-OCO-CR^a＝CH-、-(CH₂)_z-COO-、-(CH₂)_z-OCO-、-OCO-(CH₂)_z-、-COO-(CH₂)_z-、-CH＝CH-、-CF₂O-、-OCF₂-或-C≡C-(式中，R^a各自独立地表示氢原子或碳原子数1～3的烷基，前述式中，z各自独立地表示1～4的整数。)L¹⁰ and L¹¹ each independently represent a single bond, -OCH₂ -, -CH₂ O-, -C₂ H₄ -, -OC₂ H₄ O-, -COO-, -OCO-, -CH=CR^a -COO-, -CH=CR^a -OCO-, -COO-CR^a =CH-, -OCO-CR^a =CH-, -(CH₂ )_z -COO-, -(CH₂ )_z -OCO -, -OCO-(CH₂ )_z -, -COO-(CH₂ )_z -, -CH=CH-, -CF₂ O-, -OCF₂ - or -C≡C- (wherein R^a each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and in the above formula, z each independently represents an integer of 1 to 4.)

当P²¹、S²¹、L¹¹及A¹¹存在多个的情形时，各自可相同也可不同。)When there are a plurality of P²¹ , S²¹ , L¹¹ and A¹¹ , each of them may be the same or different. )

若本发明的液晶组合物中含有2种以上的聚合性单体，则通过存在于组合物中的聚合性单体与自取向性单体的最初聚合过程，会变得容易构成可形成液晶分子的倾斜角的聚合物网络。在液晶组合物中，存在具备各自不同的化学结构的、1种以上的自取向性单体与2种以上的聚合性单体这至少3种单体。认为由于这3种单体的聚合反应性不同，因此能够应对大范围的反应条件，可成为聚合反应的触发物(trigger)的单体能够促进其他单体的反应。更详细而言，认为当通过UV照射进行聚合的情形时，由于化学结构、尤其是对光的吸收影响最大的介晶骨架或键结于该介晶骨架的取代基这3者均不同，因此该3种单体中吸收波长最长的单体能够促进其他两种以上的单体的反应。由此认为，在组合物中所存在的聚合性单体与自取向性单体的最初聚合过程中，容易构成可形成液晶分子的倾斜角的大小的聚合物网络。When two or more kinds of polymerizable monomers are contained in the liquid crystal composition of the present invention, it becomes easy to form liquid crystal molecules through the initial polymerization process of the polymerizable monomer and the self-aligning monomer present in the composition. the tilt angle of the polymer network. In the liquid crystal composition, there are at least three types of monomers, one or more types of self-aligning monomers and two or more types of polymerizable monomers, each having a different chemical structure. Since these three monomers have different polymerization reactivity, it is considered that they can cope with a wide range of reaction conditions, and that the monomer that can be a trigger of the polymerization reaction can promote the reaction of other monomers. In more detail, it is considered that when the polymerization is carried out by UV irradiation, the chemical structure, especially the mesogenic skeleton that has the greatest influence on light absorption, and the substituents bonded to the mesogenic skeleton are different. The monomer with the longest absorption wavelength among the three monomers can promote the reaction of the other two or more monomers. From this, it is considered that in the initial polymerization process of the polymerizable monomer and the self-aligning monomer present in the composition, a polymer network having a size that can form the tilt angle of the liquid crystal molecules is easily formed.

本发明涉及的聚合性单体优选含有具备与上述自取向性单体不同化学结构式的选自由上述通式(I)所表示的化合物组成的组中的2种～4种聚合性单体，更优选为2～3种，特别优选为2种。The polymerizable monomer according to the present invention preferably contains two to four types of polymerizable monomers selected from the group consisting of compounds represented by the above-mentioned general formula (I), which have a different chemical structural formula from the above-mentioned self-aligning monomers, and more 2 to 3 types are preferable, and 2 types are especially preferable.

上述通式(I)中，优选R¹⁰¹及R¹¹⁰各自独立地为P²¹-S²¹-。上述P²¹优选为通式(P-I)。In the above general formula (I), it is preferable that R¹⁰¹ and R¹¹⁰ are each independently P²¹ -S²¹ -. The above-mentioned P²¹ is preferably the general formula (PI).

上述通式(I)中，优选S²¹表示单键或碳原子数1～8的亚烷基，该亚烷基中的1个或2个以上的-CH₂-可以以氧原子不直接邻接的方式被-O-、-OCO-或-COO-取代，更优选表示单键或碳原子数1～5的亚烷基。In the above-mentioned general formula (I), it is preferable that S²¹ represents a single bond or an alkylene group having 1 to 8 carbon atoms, and one or more -CH₂ - in the alkylene group may not be directly adjacent to an oxygen atom. is substituted by -O-, -OCO- or -COO- in the form of, more preferably represents a single bond or an alkylene group having 1 to 5 carbon atoms.

上述通式(I)中，优选A¹¹表示选自由1,4-亚环己基、1,4-亚苯基、萘-2,6-二基及2,7-菲二基组成的组中的基团，上述A¹¹可以被碳原子数1～5的烷基、碳原子数1～5的烷氧基或氟原子取代。In the above general formula (I), preferably A¹¹ represents a group selected from the group consisting of 1,4-cyclohexylene, 1,4-phenylene, naphthalene-2,6-diyl and 2,7-phenanthrenediyl The above-mentioned A¹¹ may be substituted by an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms or a fluorine atom.

上述通式(I)中，优选L¹⁰及L¹¹各自独立地表示单键、-OCH₂-、-CH₂O-、-C₂H₄-、-OC₂H₄O-、-COO-或-OCO-，L¹⁰及L¹¹更优选表示单键。In the above general formula (I), it is preferable that L¹⁰ and L¹¹ each independently represent a single bond, -OCH₂ -, -CH₂ O-, -C₂ H₄ -, -OC₂ H₄ O-, -COO- Or -OCO-, L¹⁰ and L¹¹ more preferably represent a single bond.

当含有2种聚合性单体的情形时，上述通式(I)中，优选由通式(I)表示的聚合性单体的一者中n¹¹为0，且R¹⁰²、R¹⁰³、R¹⁰⁴、R¹⁰⁵、R¹⁰⁶、R¹⁰⁷、R¹⁰⁸或R¹⁰⁹的任一者为碳原子数1至18的烷基，R¹⁰¹及R¹¹⁰各自独立地为P²¹-S²¹-。In the case where two types of polymerizable monomers are contained, in the general formula (I), it is preferable that n¹¹ in one of the polymerizable monomers represented by the general formula (I) is 0, and R¹⁰² , R¹⁰³ , and R Any one of¹⁰⁴ , R¹⁰⁵ , R¹⁰⁶ , R¹⁰⁷ , R¹⁰⁸ or R¹⁰⁹ is an alkyl group having 1 to 18 carbon atoms, and R¹⁰¹ and R¹¹⁰ are each independently P²¹ -S²¹ -.

本发明涉及的由通式(I)表示的聚合性单体，具体而言，优选为选自下述通式(RM-1)、通式(RM-2)及通式(RM-3)所表示的聚合性单体组中的2种以上。Specifically, the polymerizable monomer represented by the general formula (I) according to the present invention is preferably selected from the group consisting of the following general formula (RM-1), general formula (RM-2) and general formula (RM-3) Two or more of the indicated polymerizable monomer groups.

[化62][Chemical 62]

(上述通式(RM-1)及通式(RM-2)中，R¹⁰¹表示P³³-S³³-，R¹¹⁰表示P⁴⁴-S⁴⁴-，P³³及P⁴⁴各自独立地表示上述式(P-I)至式(P-IX)的任一者，S³³及S⁴⁴各自独立地表示单键或碳数1～10的亚烷基，该亚烷基中的1个或2个以上的-CH₂-可以以氧原子不直接邻接的方式被-O-、-OCO-或-COO-取代，(In the above general formula (RM-1) and general formula (RM-2), R¹⁰¹ represents P³³ -S³³ -, R¹¹⁰ represents P⁴⁴ -S⁴⁴ -, and P³³ and P⁴⁴ each independently represent the above formula (PI) to any one of formula (P-IX), S³³ and S⁴⁴ each independently represent a single bond or an alkylene group having 1 to 10 carbon atoms, and one or more of the alkylene groups -CH₂ - may be substituted by -O-, -OCO- or -COO- in such a way that the oxygen atoms are not directly adjacent,

R¹⁰²、R¹⁰⁴、R¹⁰⁷及R¹⁰⁹各自独立地表示碳原子数1至3的烷基、碳原子数1至3的烷氧基、氟原子或氢原子中的任一者，R¹⁰² , R¹⁰⁴ , R¹⁰⁷ and R¹⁰⁹ each independently represent any one of an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine atom or a hydrogen atom,

A¹¹表示1,4-亚苯基、1,4-亚环己基、萘-2,6-二基或2,7-菲二基，该A¹¹为未经取代或可以被碳原子数1至5的烷基、碳原子数1至5的烷氧基或卤素(氟原子、氯原子)取代，A¹¹ represents 1,4-phenylene, 1,4-cyclohexylene, naphthalene-2,6-diyl or 2,7-phenanthrenediyl, and A¹¹ is unsubstituted or may be replaced by 1 carbon atom substituted with an alkyl group of to 5, an alkoxy group of 1 to 5 carbon atoms, or a halogen (fluorine atom, chlorine atom),

L¹¹表示单键、-OCH₂-、-CH₂O-、-C₂H₄-、-COO-、-OCO-、-CH＝CR^a-COO-、-CH＝CR^a-OCO-、-COO-CR^a＝CH-、-OCO-CR^a＝CH-、-(CH₂)_Y-COO-、-(CH₂)_Y-OCO-、-OCO-(CH₂)_Y-、-COO-(CH₂)_Y-、-CH＝CH-、-CF₂O-、-OCF₂-或-C≡C-(式中，R^a各自独立地表示氢原子或碳原子数1至3的烷基，前述式中，Y表示1至4的整数。)，L¹¹ represents a single bond, -OCH₂ -, -CH₂ O-, -C₂ H₄ -, -COO-, -OCO-, -CH=CR^a -COO-, -CH=CR^a -OCO-, -COO-CR^a =CH-, -OCO-CR^a =CH-, -(CH₂ )_Y -COO-, -(CH₂ )_Y -OCO-, -OCO-(CH₂ )_Y -, -COO -(CH₂ )_Y -, -CH=CH-, -CF₂ O-, -OCF₂ - or -C≡C- (in the formula, R^a each independently represents a hydrogen atom or a carbon atom having 1 to 3 carbon atoms. alkyl, in the aforementioned formula, Y represents an integer of 1 to 4.),

R¹⁰³、R¹⁰⁵、R¹⁰⁶及R¹⁰⁸各自独立地表示碳原子数1至3的烷基、碳原子数1至3的烷氧基、氟原子或氢原子中的任一者。)R¹⁰³ , R¹⁰⁵ , R¹⁰⁶ and R¹⁰⁸ each independently represent any one of an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine atom or a hydrogen atom. )

[化63][Chemical 63]

(上述通式(RM-3)中，X^M1～X^M8各自独立地表示氢原子或氟原子，(In the above general formula (RM-3), X^M1 to X^M8 each independently represent a hydrogen atom or a fluorine atom,

S^M2及S^M3各自独立地表示碳原子数1～12的亚烷基或单键，该亚烷基中的-CH₂-可以以氧原子彼此不直接键结的形态被取代成氧原子、-COO-、-OCO-或-OCOO-，S^M2 and S^M3 each independently represent an alkylene group having 1 to 12 carbon atoms or a single bond, and -CH₂ - in the alkylene group may be substituted with an oxygen atom, -COO-, -OCO- or -OCOO-,

R^M2及R^M3表示上述式(P-1)至式(P-15)中的任一者。)R^M2 and R^M3 represent any one of the above formulae (P-1) to (P-15). )

在本发明涉及的液晶组合物中，优选含有至少1种吸收波长较长的聚合性单体。作为该吸收波长较长的聚合性单体，优选为含有联苯骨架且具有2个以上的(甲基)丙烯酸系官能团的结构，该联苯骨架可以被卤素原子、烷基或烷氧基取代。The liquid crystal composition according to the present invention preferably contains at least one polymerizable monomer having a long absorption wavelength. The polymerizable monomer having such a long absorption wavelength is preferably a structure containing a biphenyl skeleton which may be substituted with a halogen atom, an alkyl group or an alkoxy group and having two or more (meth)acrylic functional groups. .

在本发明涉及的液晶组合物中，作为具有2种以上由通式(I)表示的聚合性单体的优选方式，可列举含有2种以上由通式(RM-2)表示的聚合性单体的方式、含有由通式(RM-1)表示的聚合性单体与由通式(RM-2)表示的聚合性单体的方式、或含有由通式(RM-2)表示的聚合性单体与由通式(RM-3)表示的聚合性单体的方式这3种。In the liquid crystal composition according to the present invention, as a preferred embodiment having two or more types of polymerizable monomers represented by general formula (I), those containing two or more types of polymerizable monomers represented by general formula (RM-2) can be mentioned. form, form containing a polymerizable monomer represented by general formula (RM-1) and a polymerizable monomer represented by general formula (RM-2), or contain a polymerizable monomer represented by general formula (RM-2) There are three types of the form of the polymerizable monomer and the polymerizable monomer represented by the general formula (RM-3).

一般而言，PSA工序、使用含有自发性取向剂或聚合性单体的液晶组合物的液晶显示元件，通过光照射1次或2次以上而使液晶组合物中的自发性取向单体或聚合性单体固化而将聚合物网络形成于基板表面，通过该网络来控制液晶分子的倾斜角。认为：此时若在最初的光照射工序中形成可控制液晶分子倾斜角的大小的聚合物网络，则能够减少液晶显示元件随着时间的倾斜角变化量、减少烧屏。因此，认为通过使用含有1种以上的自发性取向单体与2种以上的聚合性单体的液晶组合物，能够在这至少3种单体的光吸收区段进行聚合，因此会变得容易发生聚合反应，并且该至少3种单体中吸收波长最长的单体可作为聚合触发物(所谓的引发剂的作用)促进其他2种以上的单体的反应。因此，优选含有至少1种吸收波长较长的聚合性单体。具体而言，优选为含有2种以上由上述通式(RM-2)表示的聚合性单体的方式、含有由通式(RM-1)表示的聚合性单体与由通式(RM-2)表示的聚合性单体的方式、或含有由通式(RM-2)表示的聚合性单体与由通式(RM-3)表示的聚合性单体的方式。Generally, in a PSA process, a liquid crystal display element using a liquid crystal composition containing a spontaneous alignment agent or a polymerizable monomer, the spontaneous alignment monomer or polymer in the liquid crystal composition is irradiated with light once or twice or more. The polymer network is formed on the surface of the substrate by curing the monomer, and the tilt angle of the liquid crystal molecules is controlled by the network. In this case, if a polymer network capable of controlling the magnitude of the tilt angle of the liquid crystal molecules is formed in the first light irradiation step, the amount of change in the tilt angle of the liquid crystal display element with time can be reduced, and burn-in can be reduced. Therefore, it is considered that by using a liquid crystal composition containing one or more spontaneous alignment monomers and two or more polymerizable monomers, polymerization can be performed in the light-absorbing regions of at least three monomers, and therefore, it is considered to be easy to A polymerization reaction occurs, and the monomer with the longest absorption wavelength among the at least three kinds of monomers can act as a polymerization trigger (the action of a so-called initiator) to promote the reaction of the other two or more kinds of monomers. Therefore, it is preferable to contain at least one polymerizable monomer having a long absorption wavelength. Specifically, it is preferable that two or more types of polymerizable monomers represented by the general formula (RM-2) are contained, and the polymerizable monomers represented by the general formula (RM-1) and the polymerizable monomers represented by the general formula (RM-1) are preferably contained. 2) The form of the polymerizable monomer represented by, or the form containing the polymerizable monomer represented by the general formula (RM-2) and the polymerizable monomer represented by the general formula (RM-3).

另一方面，在含有1种自发性取向单体与1种聚合性单体的液晶组合物、或仅含有自发性取向单体的液晶组合物的情形时，为了在最初的光照射工序中形成可控制液晶分子倾斜角的大小的聚合物网络，而使用吸收波长较长的聚合性单体，但吸收波长较长的聚合性单体会变成含有大量芳香族环的结构，从对于液晶组合物的相容性、低温稳定性的观点等考虑，无法添加所期望的浓度。另外，若使用反应性低的聚合性单体、自取向性单体，则构成聚合物网络的区域会变得稀疏，因而无法控制相对于液晶分子的倾斜角，通过进行多次光照射工序，使在最初的光照射工序后残存的聚合性单体或自取向性单体固化来补强聚合物网络的方法中，一般认为倾斜角的稳定性低。On the other hand, in the case of a liquid crystal composition containing one kind of spontaneous alignment monomer and one kind of polymerizable monomer, or a liquid crystal composition containing only a spontaneous alignment monomer, in order to form in the first light irradiation step A polymer network that can control the tilt angle of liquid crystal molecules, and a polymerizable monomer with a longer absorption wavelength is used, but the polymerizable monomer with a longer absorption wavelength becomes a structure containing a large number of aromatic rings. From the viewpoint of compatibility with substances, low temperature stability, etc., it cannot be added at a desired concentration. In addition, when a polymerizable monomer or a self-aligning monomer with low reactivity is used, the region constituting the polymer network becomes sparse, and thus the tilt angle with respect to the liquid crystal molecules cannot be controlled. In the method of reinforcing the polymer network by curing the polymerizable monomer or self-aligning monomer remaining after the initial light irradiation step, the stability of the tilt angle is generally considered to be low.

本发明涉及的液晶组合物中，作为具有2种以上的聚合性单体的更优选方式，可列举：含有2种以上由下述通式(RM-2-1)表示的聚合性单体的方式、含有由下述通式(RM-1-1)表示的聚合性单体与由下述通式(RM-2-1)表示的聚合性单体的方式、或含有由下述通式(RM-2-1)表示的聚合性单体与由下述通式(RM-3)表示的聚合性单体的方式这3种。In the liquid crystal composition according to the present invention, as a more preferable embodiment having two or more types of polymerizable monomers, those containing two or more types of polymerizable monomers represented by the following general formula (RM-2-1) can be mentioned. Form, Form containing the polymerizable monomer represented by the following general formula (RM-1-1) and the polymerizable monomer represented by the following general formula (RM-2-1) Form, or containing the following general formula There are three forms of the polymerizable monomer represented by (RM-2-1) and the polymerizable monomer represented by the following general formula (RM-3).

[化64][Chemical 64]

(上述通式(RM-1-1)及通式(RM-2-1)中，P^RM1及P^RM2各自独立地表示上述式(P-I)至式(P-IX)的任一者，Sp^RM1及Sp^RM2各自独立地表示单键或碳数1～7的亚烷基，该亚烷基中的1个或2个以上的-CH₂-可以以氧原子不直接邻接的方式被-O-、-OCO-或-COO-取代，(In the above-mentioned general formula (RM-1-1) and general formula (RM-2-1), P^RM1 and P^RM2 each independently represent any one of the above-mentioned formula (PI) to formula (P-IX), Sp^RM1 and Sp^RM2 each independently represent a single bond or an alkylene group having 1 to 7 carbon atoms, and one or more -CH₂ - in the alkylene group may be -O such that an oxygen atom is not directly adjacent to each other. -, -OCO- or -COO- substituted,

R¹⁰²～R¹⁰⁹各自独立地表示碳原子数1至4的烷基、碳原子数1至4的烷氧基、氟原子或氢原子中的任一者，R¹⁰² to R¹⁰⁹ each independently represent any one of an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a fluorine atom or a hydrogen atom,

R¹¹¹、R¹¹²、R¹¹³及R¹¹⁴各自独立地表示碳原子数1至3的烷基、碳原子数1至3的烷氧基、氟原子或氢原子中的任一者。)R¹¹¹ , R¹¹² , R¹¹³ and R¹¹⁴ each independently represent any one of an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine atom or a hydrogen atom. )

上述通式(RM-1-1)中，优选Sp^RM1或Sp^RM2的任一者表示碳数1～7的亚烷基，而另一者表示单键。In the above general formula (RM-1-1), it is preferable that either Sp^RM1 or Sp^RM2 represents an alkylene group having 1 to 7 carbon atoms, and the other represents a single bond.

上述通式(RM-1-1)中，优选R¹⁰²～R¹¹⁴中的至少一者具有碳原子数1至4的烷基或氟原子，优选R¹¹¹～R¹¹⁴中的至少一者具有氟原子。In the above general formula (RM-1-1), preferably at least one of R¹⁰² to R¹¹⁴ has an alkyl group having 1 to 4 carbon atoms or a fluorine atom, and preferably at least one of R¹¹¹ to R¹¹⁴ has fluorine atom.

上述通式(RM-2-1)中，优选R¹⁰²～R¹⁰⁹中的至少一者具有碳原子数1至4的烷基。In the above general formula (RM-2-1), at least one of R¹⁰² to R¹⁰⁹ preferably has an alkyl group having 1 to 4 carbon atoms.

＜液晶组合物＞<Liquid crystal composition>

本发明涉及的液晶组合物含有液晶成分，作为该液晶成分，包含非聚合性的液晶化合物。The liquid crystal composition according to the present invention contains a liquid crystal component, and as the liquid crystal component, a non-polymerizable liquid crystal compound is contained.

作为本发明涉及的液晶成分的液晶化合物优选含有选自由通式(L)所表示的化合物、通式(J)所表示的化合物、通式(N-1)所表示的化合物、通式(N-2)所表示的化合物及通式(N-3)所表示的化合物组成的组中的1种或2种以上。当液晶组合物整体上显示出负的介电常数各向异性的情形时，优选含有通式(L)所表示的化合物以及选自由通式(N-1)所表示的化合物、通式(N-2)所表示的化合物及通式(N-3)所表示的化合物组成的组中的1种或2种以上的化合物。另一方面，当液晶组合物整体上显示出负的介电常数各向异性的情形时，优选含有通式(L)所表示的化合物与通式(J)所表示的化合物。The liquid crystal compound as the liquid crystal component according to the present invention preferably contains a compound selected from the group consisting of the compound represented by the general formula (L), the compound represented by the general formula (J), the compound represented by the general formula (N-1), the compound represented by the general formula (N One or more of the group consisting of the compound represented by -2) and the compound represented by the general formula (N-3). When the liquid crystal composition as a whole shows negative dielectric constant anisotropy, it is preferable to contain a compound represented by general formula (L) and a compound represented by general formula (N-1), a compound represented by general formula (N-1) -2) One or more compounds selected from the group consisting of the compound represented by the general formula (N-3) and the compound represented by the general formula (N-3). On the other hand, when the liquid crystal composition as a whole exhibits negative dielectric constant anisotropy, it is preferable to contain the compound represented by the general formula (L) and the compound represented by the general formula (J).

本发明涉及的液晶化合物优选含有1种或2种以上的介电性大致为中性的化合物(Δε值为-2～2)的由通式(L)表示的化合物作为第一成分。The liquid crystal compound according to the present invention preferably contains, as the first component, one or more compounds represented by the general formula (L) having substantially neutral dielectric properties (Δε value -2 to 2).

前述由通式(L)表示的化合物如下所示。The aforementioned compounds represented by the general formula (L) are shown below.

[化65][Chemical 65]

(式中，R^L1及R^L2各自独立地表示碳原子数1～8的烷基，该烷基中的1个或非邻接的2个以上的-CH₂-可以各自独立地被-CH＝CH-、-C≡C-、-O-、-CO-、-COO-或-OCO-取代，(in the formula, R^L1 and R^L2 each independently represent an alkyl group having 1 to 8 carbon atoms, and one or two or more non-adjacent -CH₂ - in the alkyl group may each independently be represented by -CH= CH-, -C≡C-, -O-, -CO-, -COO- or -OCO- substituted,

n^L1表示0、1、2或3，n^L1 represents 0, 1, 2 or 3,

A^L1、A^L2及A^L3各自独立地表示选自由下述(a)、(b)及(c)组成的组中的基团：A^L1 , A^L2 and A^L3 each independently represent a group selected from the group consisting of the following (a), (b) and (c):

(a)1,4-亚环己基(存在于该基团中的1个-CH₂-或未邻接的2个以上的-CH₂-可以被取代成-O-。)(a) 1,4-cyclohexylene group (One -CH₂ - or two or more non-adjacent -CH₂ - present in this group may be substituted with -O-.)

(b)1,4-亚苯基(存在于该基团中的1个-CH＝或未邻接的2个以上的-CH＝可以被取代成-N＝。)及(b) 1,4-phenylene (one -CH= present in this group or two or more non-adjacent -CH= may be substituted with -N=.) and

(c)萘-2,6-二基、1,2,3,4-四氢萘-2,6-二基或十氢萘-2,6-二基(存在于萘-2,6-二基或1,2,3,4-四氢萘-2,6-二基中的1个-CH＝或未邻接的2个以上的-CH＝可以被取代成-N＝。)，(c) Naphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl or decahydronaphthalene-2,6-diyl (existing in naphthalene-2,6-diyl One -CH= in diyl or 1,2,3,4-tetrahydronaphthalene-2,6-diyl group or two or more non-adjacent -CH= may be substituted with -N=.),

上述基团(a)、基团(b)及基团(c)可以各自独立地被氰基、氟原子或氯原子取代，The above-mentioned group (a), group (b) and group (c) may each independently be substituted by a cyano group, a fluorine atom or a chlorine atom,

Z^L1及Z^L2各自独立地表示单键、-CH₂CH₂-、-(CH₂)₄-、-OCH₂-、-CH₂O-、-COO-、-OCO-、-OCF₂-、-CF₂O-、-CH＝N-N＝CH-、-CH＝CH-、-CF＝CF-或-C≡C-，Z^L1 and Z^L2 each independently represent a single bond, -CH₂ CH₂ -, -(CH₂ )₄ -, -OCH₂ -, -CH₂ O-, -COO-, -OCO-, -OCF₂ - , -CF₂ O-, -CH=NN=CH-, -CH=CH-, -CF=CF- or -C≡C-,

当n^L1为2或3而存在多个A^L2的情形时，它们可相同也可不同，当n^L1为2或3而存在多个Z^L2的情形时，它们可相同也可不同。)When n^L1 is 2 or 3 and there are multiple A^L2s , they may be the same or different, and when n^L1 is 2 or 3 and there are multiple Z^L2s , they may be the same or different. )

本发明涉及的液晶组合物含有非聚合性液晶化合物，该非聚合性液晶化合物优选含有1种或2种以上的介电性为正的化合物(Δε大于2。)的由通式(J)表示的化合物和/或介电性为负的化合物(Δε的符号为负，其绝对值大于2。)的由通式(N-1)～(N～3)表示的化合物作为第二成分。The liquid crystal composition according to the present invention contains a non-polymerizable liquid crystal compound, and the non-polymerizable liquid crystal compound preferably contains one or two or more types of compounds having positive dielectric properties (Δε is greater than 2.) represented by the general formula (J) The compound represented by the general formula (N-1) to (N-3) of the compound and/or the compound having negative dielectric properties (the sign of Δε is negative and its absolute value is greater than 2) is used as the second component.

前述介电性为正的化合物(Δε大于2。)的由通式(J)表示的化合物如下所示。The compound represented by the general formula (J) of the compound having positive dielectric properties (Δε is greater than 2.) is shown below.

[化66][Chemical 66]

(式中，R^J1表示碳原子数1～8的烷基，该烷基中的1个或非邻接的2个以上的-CH₂-可以各自独立地被-CH＝CH-、-C≡C-、-O-、-CO-、-COO-或-OCO-取代，(In the formula, R^J1 represents an alkyl group having 1 to 8 carbon atoms, and one or two or more non-adjacent -CH₂ - in the alkyl group may be independently represented by -CH=CH-, -C≡ C-, -O-, -CO-, -COO- or -OCO- substituted,

n^J1表示0、1、2、3或4，n^J1 represents 0, 1, 2, 3 or 4,

A^J1、A^J2及A^J3各自独立地表示选自由下述(a)、(b)及(c)组成的组中的基团：A^J1 , A^J2 and A^J3 each independently represent a group selected from the group consisting of the following (a), (b) and (c):

(a)1,4-亚环己基(存在于该基团中的1个-CH₂-或未邻接的2个以上的-CH₂-可以被取代成-O-。)(a) 1,4-cyclohexylene group (One -CH₂ - or two or more non-adjacent -CH₂ - present in this group may be substituted with -O-.)

(b)1,4-亚苯基(存在于该基团中的1个-CH＝或未邻接的2个以上的-CH＝可以被取代成-N＝。)及(b) 1,4-phenylene (one -CH= present in this group or two or more non-adjacent -CH= may be substituted with -N=.) and

(c)萘-2,6-二基、1,2,3,4-四氢萘-2,6-二基或十氢萘-2,6-二基(存在于萘-2,6-二基或1,2,3,4-四氢萘-2,6-二基中的1个-CH＝或未邻接的2个以上的-CH＝可以被取代成-N＝。)，(c) Naphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl or decahydronaphthalene-2,6-diyl (existing in naphthalene-2,6-diyl One -CH= in diyl or 1,2,3,4-tetrahydronaphthalene-2,6-diyl group or two or more non-adjacent -CH= may be substituted with -N=.),

上述基团(a)、基团(b)及基团(c)可以各自独立地被氰基、氟原子、氯原子、甲基、三氟甲基或三氟甲氧基取代，The above-mentioned group (a), group (b) and group (c) may each independently be substituted with a cyano group, a fluorine atom, a chlorine atom, a methyl group, a trifluoromethyl group or a trifluoromethoxy group,

Z^J1及Z^J2各自独立地表示单键、-CH₂CH₂-、-(CH₂)₄-、-OCH₂-、-CH₂O-、-OCF₂-、-CF₂O-、-COO-、-OCO-或-C≡C-，Z^J1 and Z^J2 each independently represent a single bond, -CH₂ CH₂ -, -(CH₂ )₄ -, -OCH₂ -, -CH₂ O-, -OCF₂ -, -CF₂ O-, - COO-, -OCO- or -C≡C-,

当n^J1为2、3或4而存在多个A^J2的情形时，它们可相同也可不同，当n^J1为2、3或4而存在多个Z^J1的情形时，它们可相同也可不同，When n^J1 is 2, 3 or 4 and there are multiple A^J2s , they may be the same or different, and when n^J1 is 2, 3 or 4 and there are multiple Z^J1s , they may be the same or different different,

X^J1表示氢原子、氟原子、氯原子、氰基、三氟甲基、氟甲氧基、二氟甲氧基、三氟甲氧基或2,2,2-三氟乙基。)X^J1 represents a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group, a trifluoromethyl group, a fluoromethoxy group, a difluoromethoxy group, a trifluoromethoxy group, or a 2,2,2-trifluoroethyl group. )

上述选自由介电性为负的化合物(Δε的符号为负，其绝对值大于2。)的由通式(N-1)～(N-3)表示的化合物组成的组中的1种或2种以上如下所示。One or more selected from the group consisting of compounds represented by general formulae (N-1) to (N-3) which are compounds having negative dielectric properties (the sign of Δε is negative, and the absolute value thereof is greater than 2.) Two or more types are shown below.

[化67][Chemical 67]

(上述式中，R^N11、R^N12、R^N21、R^N22、R^N31及R^N32各自独立地表示碳原子数1～8的烷基，该烷基中的1个或非邻接的2个以上的-CH₂-可以各自独立地被-CH＝CH-、-C≡C-、-O-、-CO-、-COO-或-OCO-取代，(In the above formula, R^N11 , R^N12 , R^N21 , R^N22 , R^N31 and R^N32 each independently represent an alkyl group having 1 to 8 carbon atoms, and one of the alkyl groups or two or more non-adjacent ones The -CH₂ - can be independently replaced by -CH=CH-, -C≡C-, -O-, -CO-, -COO- or -OCO-,

A^N11、A^N12、A^N21、A^N22、A^N31及A^N32各自独立地表示选自由下述(a)、(b)、(c)及(d)组成的组中的基团：A^N11 , A^N12 , A^N21 , A^N22 , A^N31 and A^N32 each independently represent a group selected from the group consisting of the following (a), (b), (c) and (d):

(a)1,4-亚环己基(存在于该基团中的1个-CH₂-或未邻接的2个以上的-CH₂-可以被取代成-O-。)(a) 1,4-cyclohexylene group (One -CH₂ - or two or more non-adjacent -CH₂ - present in this group may be substituted with -O-.)

(b)1,4-亚苯基(存在于该基团中的1个-CH＝或未邻接的2个以上的-CH＝可以被取代成-N＝。)(b) 1,4-phenylene (One -CH= or two or more non-adjacent -CH= present in this group may be substituted with -N=.)

(c)萘-2,6-二基、1,2,3,4-四氢萘-2,6-二基或十氢萘-2,6-二基(存在于萘-2,6-二基或1,2,3,4-四氢萘-2,6-二基中的1个-CH＝或未邻接的2个以上的-CH＝可以被取代成-N＝。)及(c) Naphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl or decahydronaphthalene-2,6-diyl (existing in naphthalene-2,6-diyl One -CH= in the diyl group or 1,2,3,4-tetrahydronaphthalene-2,6-diyl group or two or more non-adjacent -CH= groups may be substituted with -N=.) and

(d)1,4-亚环己烯基，(d) 1,4-cyclohexenylene,

上述基团(a)、基团(b)、基团(c)及基团(d)可以各自独立地被氰基、氟原子或氯原子取代，The above-mentioned group (a), group (b), group (c) and group (d) may each independently be substituted with a cyano group, a fluorine atom or a chlorine atom,

Z^N11、Z^N12、Z^N21、Z^N22、Z^N31及Z^N32各自独立地表示单键、-CH₂CH₂-、-(CH₂)₄-、-OCH₂-、-CH₂O-、-COO-、-OCO-、-OCF₂-、-CF₂O-、-CH＝N-N＝CH-、-CH＝CH-、-CF＝CF-或-C≡C-，Z^N11 , Z^N12 , Z^N21 , Z^N22 , Z^N31 and Z^N32 each independently represent a single bond, -CH₂ CH₂ -, -(CH₂ )₄ -, -OCH₂ -, -CH₂ O-, -COO-, -OCO-, -OCF2-, -CF2O-, -CH=NN=_CH- , -CH=_CH- , -CF=CF- or -C≡C-,

X^N21表示氢原子或氟原子，X^N21 represents a hydrogen atom or a fluorine atom,

T^N31表示-CH₂-或氧原子，T^N31 represents -CH₂ - or oxygen atom,

n^N11、n^N12、n^N21、n^N22、n^N31及n^N32各自独立地表示0～3的整数，n^N11+n^N12、n^N21+n^N22及n^N31+n^N32各自独立地为1、2或3，当A^N11～A^N32、Z^N11～Z^N32存在多个的情形时，它们可相同也可不同。)n^N11 , n^N12 , n^N21 , n^N22 , n^N31 and n^N32 each independently represent an integer of 0 to 3, and n^N11 +n^N12 , n^N21 +n^N22 and n^N31 +n^N32 are each independently 1, 2 or 3, when there are a plurality of A^N11 to A^N32 and Z^N11 to Z^N32 , they may be the same or different. )

由上述通式(L)表示的化合物优选为由下述式(L-1)～(L-13)表示的化合物。The compound represented by the above-mentioned general formula (L) is preferably a compound represented by the following formulae (L-1) to (L-13).

[化68][Chemical 68]

(式中，R^L1及R^L2各自独立地表示与通式(L)相同的意义，A^L1及A^L7各自独立地表示与通式(L)相同的意义，A^L1及A^L2上的氢原子可以各自独立地被氟原子取代，Z^L1表示与通式(L)中的Z^L2相同的意义，X^L1及X^L2各自独立地表示氟原子或氢原子。)(wherein, R^L1 and R^L2 each independently represent the same meaning as in the general formula (L), A^L1 and A^L7 each independently represent the same meaning as in the general formula (L), and the hydrogen on A^L1 and A^L2 Atoms may be independently substituted by fluorine atoms, Z^L1 represents the same meaning as Z^L2 in the general formula (L), and X^L1 and^XL2 each independently represent a fluorine atom or a hydrogen atom.)

作为由通式(J)表示的化合物，优选为由通式(M)表示的化合物及由通式(K)表示的化合物。As the compound represented by the general formula (J), the compound represented by the general formula (M) and the compound represented by the general formula (K) are preferable.

此处，首先对于由通式(M)表示的化合物，可列举下述结构的化合物。Here, first, as the compound represented by the general formula (M), the compound of the following structure can be exemplified.

[化69][Chemical 69]

(式中，R^M1表示碳原子数1～8的烷基，该烷基中的1个或非邻接的2个以上的-CH₂-可以各自独立地被-CH＝CH-、-C≡C-、-O-、-CO-、-COO-或-OCO-取代，(In the formula, R^M1 represents an alkyl group having 1 to 8 carbon atoms, and one or two or more non-adjacent -CH₂ - in the alkyl group may be independently represented by -CH=CH-, -C≡ C-, -O-, -CO-, -COO- or -OCO- substituted,

n^M1表示0、1、2、3或4，n^M1 represents 0, 1, 2, 3 or 4,

A^M1及A^M2各自独立地表示选自由(a)及(b)组成的组中的基团：A^M1 and A^M2 each independently represent a group selected from the group consisting of (a) and (b):

(a)1,4-亚环己基(存在于该基团中的1个-CH₂-或未邻接的2个以上的-CH₂-可以被取代成-O-或-S-。)及(a) 1,4-cyclohexylene (one -CH₂ - or two or more non-adjacent -CH₂ - present in this group may be substituted with -O- or -S-.) and

(b)1,4-亚苯基(存在于该基团中的1个-CH＝或未邻接的2个以上的-CH＝可以被取代成-N＝。)，(b) 1,4-phenylene (one -CH= or two or more non-adjacent -CH= present in the group may be substituted with -N=.),

上述基团(a)及基团(b)上的氢原子可以各自独立地被氰基、氟原子或氯原子取代，The hydrogen atoms on the above-mentioned group (a) and group (b) may be independently substituted by a cyano group, a fluorine atom or a chlorine atom,

Z^M1及Z^M2各自独立地表示单键、-CH₂CH₂-、-(CH₂)₄-、-OCH₂-、-CH₂O-、-OCF₂-、-CF₂O-、-COO-、-OCO-或-C≡C-，Z^M1 and Z^M2 each independently represent a single bond, -CH₂ CH₂ -, -(CH₂ )₄ -, -OCH₂ -, -CH₂ O-, -OCF₂ -, -CF₂ O-, - COO-, -OCO- or -C≡C-,

当n^M1为2、3或4而存在多个A^M2的情形时，它们可相同也可不同，当n^M1为2、3或4而存在多个Z^M1的情形时，它们可相同也可不同，When n^M1 is 2, 3 or 4 and there are multiple A^M2s , they may be the same or different, and when n^M1 is 2, 3 or 4 and there are multiple Z^M1s , they may be the same or different different,

X^M1及X^M3各自独立地表示氢原子、氯原子或氟原子，X^M1 and X^M3 each independently represent a hydrogen atom, a chlorine atom or a fluorine atom,

X^M2表示氢原子、氟原子、氯原子、氰基、三氟甲基、氟甲氧基、二氟甲氧基、三氟甲氧基或2,2,2-三氟乙基。X^M2 represents a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group, a trifluoromethyl group, a fluoromethoxy group, a difluoromethoxy group, a trifluoromethoxy group or a 2,2,2-trifluoroethyl group.

通式(M)中，R^M1优选为碳原子数1～8的烷基、碳原子数1～8的烷氧基、碳原子数2～8的烯基或碳原子数2～8的烯氧基，优选为碳原子数1～5的烷基、碳原子数1～5的烷氧基、碳原子数2～5的烯基或碳原子数2～5的烯氧基，更优选为碳原子数1～5的烷基或碳原子数2～5的烯基，更优选为碳原子数2～5的烷基或碳原子数2～3的烯基，特别优选为碳原子数3的烯基(丙烯基)。In the general formula (M), R^M1 is preferably an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, or an alkene having 2 to 8 carbon atoms. The oxy group is preferably an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkenyloxy group having 2 to 5 carbon atoms, more preferably An alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, more preferably an alkyl group having 2 to 5 carbon atoms or an alkenyl group having 2 to 3 carbon atoms, particularly preferably 3 carbon atoms alkenyl (propenyl).

当重视可靠性的情形时，R^M1优选为烷基，当重视降低粘性的情形时，优选为烯基。When importance is attached to reliability, R^M1 is preferably an alkyl group, and when emphasis is placed on reducing viscosity, it is preferably an alkenyl group.

另外，当其键结的环结构为苯基(芳香族)的情形时，优选为直链状的碳原子数1～5的烷基、直链状的碳原子数1～4的烷氧基及碳原子数4～5的烯基，当其键结的环结构为环己烷、吡喃及二

烷等饱和的环结构的情形时，优选为直链状的碳原子数1～5的烷基、直链状的碳原子数1～4的烷氧基及直链状的碳原子数2～5的烯基。为了使向列相稳定化，碳原子及存在时的氧原子的合计优选为5以下，并且优选为直链状。In addition, when the ring structure to which it is bonded is a phenyl group (aromatic), it is preferably a linear alkyl group having 1 to 5 carbon atoms or a linear alkoxy group having 1 to 4 carbon atoms. and alkenyl with 4 to 5 carbon atoms, when the bonded ring structure is cyclohexane, pyran and

In the case of a saturated ring structure such as an alkane, straight-chain alkyl groups having 1 to 5 carbon atoms, straight-chain alkoxy groups having 1 to 4 carbon atoms, and straight-chain carbon atoms having 2 to 5 are preferred. 5 alkenyl. In order to stabilize the nematic phase, the total of carbon atoms and oxygen atoms when present is preferably 5 or less, and it is preferably linear.

作为烯基，优选选自式(R1)至式(R5)的任一者所表示的基团。(各式中的黑点表示烯基键结的环结构中的碳原子。)The alkenyl group is preferably selected from groups represented by any one of formula (R1) to formula (R5). (The black dots in each formula represent carbon atoms in the alkenyl-bonded ring structure.)

[化70][Chemical 70]

当要求增大Δn的情形时，A^M1及A^M2优选各自独立地为芳香族，为了改善响应速度，优选为脂肪族，优选表示反式-1,4-亚环己基、1,4-亚苯基、2-氟-1,4-亚苯基、3-氟-1,4-亚苯基、3,5-二氟-1,4-亚苯基、2,3-二氟-1,4-亚苯基、1,4-亚环己烯基、1,4-双环[2.2.2]亚辛基、哌啶-1,4-二基、萘-2,6-二基、十氢萘-2,6-二基或1,2,3,4-四氢萘-2,6-二基，更优选表示下述结构，When it is required to increase Δn, A^M1 and A^M2 are preferably each independently aromatic, and in order to improve the response speed, preferably aliphatic, preferably trans-1,4-cyclohexylene, 1,4-cyclohexylene Phenyl, 2-fluoro-1,4-phenylene, 3-fluoro-1,4-phenylene, 3,5-difluoro-1,4-phenylene, 2,3-difluoro-1 ,4-phenylene, 1,4-cyclohexenylene, 1,4-bicyclo[2.2.2]octylene, piperidine-1,4-diyl, naphthalene-2,6-diyl, Decahydronaphthalene-2,6-diyl or 1,2,3,4-tetrahydronaphthalene-2,6-diyl, more preferably represents the following structure,

[化71][Chemical 71]

更优选表示下述结构。More preferably, the following structures are shown.

[化72][Chemical 72]

Z^M1及Z^M2优选各自独立地表示-CH₂O-、-CF₂O-、-CH₂CH₂-、-CF₂CF₂-或单键，更优选为-CF₂O-、-CH₂CH₂-或单键，特别优选为-CF₂O-或单键。Z^M1 and Z^M2 preferably each independently represent -CH₂ O-, -CF₂ O-, -CH₂ CH₂ -, -CF₂ CF₂ - or a single bond, more preferably -CF₂ O-, -CH₂ CH₂ - or a single bond, particularly preferably -CF₂ O- or a single bond.

n^M1优选为0、1、2或3，优选为0、1或2，当重点在于改善Δε的情形时，优选为0或1，当重视T_NI的情形时，则优选为1或2。n^M1 is preferably 0, 1, 2 or 3, preferably 0, 1 or 2, preferably 0 or 1 when the emphasis is on improving Δε, and preferably 1 or 2 when the emphasis is on T_NI .

可组合的化合物的种类并无特别限制，根据低温时的溶解性、转变温度、电可靠性、双折射率等想要的性能进行组合使用。关于使用的化合物的种类，例如作为本发明的一个实施方式，为1种、2种、3种。另外，进一步在本发明的其他实施方式中，为4种、5种、6种、7种以上。The types of compounds that can be combined are not particularly limited, and they are used in combination according to desired properties such as solubility at low temperature, transition temperature, electrical reliability, and birefringence. The types of compounds to be used are, for example, one, two, or three types as one embodiment of the present invention. Moreover, in other embodiment of this invention, it is 4 types, 5 types, 6 types, 7 types or more.

本发明的组合物中，由通式(M)表示的化合物的含量必须根据低温时的溶解性、转变温度、电可靠性、双折射率、工艺适应性、滴痕、烧屏、介电常数各向异性等所要求的性能作适当调整。In the composition of the present invention, the content of the compound represented by the general formula (M) must be based on solubility at low temperature, transition temperature, electrical reliability, birefringence, process suitability, drip marks, burn-in, dielectric constant The required properties such as anisotropy are appropriately adjusted.

相对于本发明的液晶组合物的总量，由式(M)表示的化合物的优选含量的下限值为1质量％、10质量％、20质量％、30质量％、40质量％、50质量％、55质量％、60质量％、65质量％、70质量％、75质量％、80质量％。优选含量的上限值相对于本发明的液晶组合物的总量，例如在本发明的一个方式中，为95质量％、85质量％、75质量％、65质量％、55质量％、45质量％、35质量％、25质量％。The lower limit of the preferable content of the compound represented by the formula (M) is 1 mass %, 10 mass %, 20 mass %, 30 mass %, 40 mass %, 50 mass % with respect to the total amount of the liquid crystal composition of the present invention %, 55 mass %, 60 mass %, 65 mass %, 70 mass %, 75 mass %, 80 mass %. The upper limit of the preferable content is, for example, 95 mass %, 85 mass %, 75 mass %, 65 mass %, 55 mass %, or 45 mass % in one embodiment of the present invention with respect to the total amount of the liquid crystal composition of the present invention. %, 35% by mass, 25% by mass.

当将本发明的组合物的粘度保持较低，需要响应速度快的组合物的情形时，优选使上述下限值低一点，且使上限值低一点。进一步，当将本发明的组合物的T_NI保持较高，需要温度稳定性佳的组合物的情形时，优选使上述下限值低一点，且使上限值低一点。另外，为了将驱动电压保持较低而想要增大介电常数各向异性时，优选使上述下限值高一点，且使上限值高一点。When the viscosity of the composition of the present invention is kept low and a composition with a fast response speed is required, it is preferable to make the lower limit value slightly lower and the upper limit value slightly lower. Furthermore, when the_TNI of the composition of the present invention is kept high and a composition with excellent temperature stability is required, it is preferable to lower the lower limit value and lower the upper limit value. In addition, when it is desired to increase the dielectric constant anisotropy in order to keep the driving voltage low, it is preferable to make the lower limit value higher and the upper limit value higher.

接着，由通式(K)表示的化合物为具有以下化学结构的化合物。Next, the compound represented by the general formula (K) is a compound having the following chemical structure.

[化73][Chemical 73]

(式中，R^K1表示碳原子数1～8的烷基，该烷基中的1个或非邻接的2个以上的-CH₂-可以各自独立地被-CH＝CH-、-C≡C-、-O-、-CO-、-COO-或-OCO-取代，(In the formula, R^K1 represents an alkyl group having 1 to 8 carbon atoms, and one or two or more non-adjacent -CH₂ - in the alkyl group may be independently represented by -CH=CH-, -C≡ C-, -O-, -CO-, -COO- or -OCO- substituted,

n^K1表示0、1、2、3或4，n^K1 represents 0, 1, 2, 3 or 4,

A^K1及A^K2各自独立地表示选自由下述(a)及(b)组成的组中的基团：A^K1 and A^K2 each independently represent a group selected from the group consisting of the following (a) and (b):

(a)1,4-亚环己基(存在于该基团中的1个-CH₂-或未邻接的2个以上的-CH₂-可以被取代成-O-或-S-。)及(a) 1,4-cyclohexylene (one -CH₂ - or two or more non-adjacent -CH₂ - present in this group may be substituted with -O- or -S-.) and

(b)1,4-亚苯基(存在于该基团中的1个-CH＝或未邻接的2个以上的-CH＝可以被取代成-N＝。)，(b) 1,4-phenylene (one -CH= or two or more non-adjacent -CH= present in the group may be substituted with -N=.),

上述基团(a)及基团(b)上的氢原子可以各自独立地被氰基、氟原子或氯原子取代，The hydrogen atoms on the above-mentioned group (a) and group (b) may be independently substituted by a cyano group, a fluorine atom or a chlorine atom,

Z^K1及Z^K2各自独立地表示单键、-CH₂CH₂-、-(CH₂)₄-、-OCH₂-、-CH₂O-、-OCF₂-、-CF₂O-、-COO-、-OCO-或-C≡C-，Z^K1 and Z^K2 each independently represent a single bond, -CH₂ CH₂ -, -(CH₂ )₄ -, -OCH₂ -, -CH₂ O-, -OCF₂ -, -CF₂ O-, - COO-, -OCO- or -C≡C-,

当n^K1为2、3或4而存在多个A^K2的情形时，它们可相同也可不同，当n^K1为2、3或4而存在多个Z^K1的情形时，它们可相同也可不同，When n^K1 is 2, 3 or 4 and there are multiple A^K2s , they can be the same or different; when n^K1 is 2, 3 or 4 and there are multiple Z^K1s , they can be the same or different different,

X^K1及X^K3各自独立地表示氢原子、氯原子或氟原子，X^K1 and X^K3 each independently represent a hydrogen atom, a chlorine atom or a fluorine atom,

X^K2表示氢原子、氟原子、氯原子、氰基、三氟甲基、氟甲氧基、二氟甲氧基、三氟甲氧基或2,2,2-三氟乙基。)X^K2 represents a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group, a trifluoromethyl group, a fluoromethoxy group, a difluoromethoxy group, a trifluoromethoxy group or a 2,2,2-trifluoroethyl group. )

通式(K)中，R^K1优选为碳原子数1～8的烷基、碳原子数1～8的烷氧基、碳原子数2～8的烯基或碳原子数2～8的烯氧基，优选为碳原子数1～5的烷基、碳原子数1～5的烷氧基、碳原子数2～5的烯基或碳原子数2～5的烯氧基，更优选为碳原子数1～5的烷基或碳原子数2～5的烯基，更优选为碳原子数2～5的烷基或碳原子数2～3的烯基，特别优选为碳原子数3的烯基(丙烯基)。In the general formula (K), R^K1 is preferably an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, or an alkene having 2 to 8 carbon atoms. The oxy group is preferably an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkenyloxy group having 2 to 5 carbon atoms, more preferably An alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, more preferably an alkyl group having 2 to 5 carbon atoms or an alkenyl group having 2 to 3 carbon atoms, particularly preferably 3 carbon atoms alkenyl (propenyl).

当重视可靠性的情形时，R^K1优选为烷基，当重视降低粘性的情形时，则优选为烯基。When importance is attached to reliability, R^K1 is preferably an alkyl group, and when emphasis is placed on reducing viscosity, it is preferably an alkenyl group.

另外，当其键结的环结构为苯基(芳香族)的情形时，优选为直链状的碳原子数1～5的烷基、直链状的碳原子数1～4的烷氧基及碳原子数4～5的烯基，当其键结的环结构为环己烷、吡喃及二

烷等饱和的环结构的情形时，优选为直链状的碳原子数1～5的烷基、直链状的碳原子数1～4的烷氧基及直链状的碳原子数2～5的烯基。为了使向列相稳定化，碳原子和存在时的氧原子的合计优选为5以下，并且优选为直链状。In addition, when the ring structure to which it is bonded is a phenyl group (aromatic), it is preferably a linear alkyl group having 1 to 5 carbon atoms or a linear alkoxy group having 1 to 4 carbon atoms. and alkenyl with 4 to 5 carbon atoms, when the bonded ring structure is cyclohexane, pyran and

In the case of a saturated ring structure such as an alkane, straight-chain alkyl groups having 1 to 5 carbon atoms, straight-chain alkoxy groups having 1 to 4 carbon atoms, and straight-chain carbon atoms having 2 to 5 are preferred. 5 alkenyl. In order to stabilize the nematic phase, the total of carbon atoms and oxygen atoms when present is preferably 5 or less, and it is preferably linear.

作为烯基，优选选自式(R1)至式(R5)的任一者所表示的基团。(各式中的黑点表示烯基键结的环结构中的碳原子。)The alkenyl group is preferably selected from groups represented by any one of formula (R1) to formula (R5). (The black dots in each formula represent carbon atoms in the alkenyl-bonded ring structure.)

[化74][Chemical 74]

当要求增大Δn的情形时，A^K1及A^K2优选各自独立地为芳香族，为了改善响应速度，则优选为脂肪族，优选表示反式-1,4-亚环己基、1,4-亚苯基、2-氟-1,4-亚苯基、3-氟-1,4-亚苯基、3,5-二氟-1,4-亚苯基、2,3-二氟-1,4-亚苯基、1,4-亚环己烯基、1,4-双环[2.2.2]亚辛基、哌啶-1,4-二基、萘-2,6-二基、十氢萘-2,6-二基或1,2,3,4-四氢萘-2,6-二基，更优选表示下述结构，When it is required to increase Δn, A^K1 and A^K2 are preferably each independently aromatic, and in order to improve the response speed, preferably aliphatic, preferably trans-1,4-cyclohexylene, 1,4-cyclohexylene Phenylene, 2-fluoro-1,4-phenylene, 3-fluoro-1,4-phenylene, 3,5-difluoro-1,4-phenylene, 2,3-difluoro- 1,4-phenylene, 1,4-cyclohexenylene, 1,4-bicyclo[2.2.2]octylene, piperidine-1,4-diyl, naphthalene-2,6-diyl , decalin-2,6-diyl or 1,2,3,4-tetrahydronaphthalene-2,6-diyl, more preferably representing the following structure,

[化75][Chemical 75]

更优选表示下述结构。More preferably, the following structures are shown.

[化76][Chemical 76]

Z^K1及Z^K2优选各自独立地表示-CH₂O-、-CF₂O-、-CH₂CH₂-、-CF₂CF₂-或单键，更优选为-CF₂O-、-CH₂CH₂-或单键，特别优选为-CF₂O-或单键。Z^K1 and Z^K2 preferably each independently represent -CH₂ O-, -CF₂ O-, -CH₂ CH₂ -, -CF₂ CF₂ - or a single bond, more preferably -CF₂ O-, -CH₂ CH₂ - or a single bond, particularly preferably -CF₂ O- or a single bond.

n^K1优选为0、1、2或3，优选为0、1或2，当重点在于改善Δε的情形时，优选为0或1，当重视T_NI的情形时，则优选为1或2。n^K1 is preferably 0, 1, 2 or 3, preferably 0, 1 or 2, when the emphasis is on improving Δε, it is preferably 0 or 1, and when the emphasis is on T_NI , it is preferably 1 or 2.

可组合的化合物的种类并无特别限制，根据低温时的溶解性、转变温度、电可靠性、双折射率等想要的性能进行组合使用。关于使用的化合物的种类，例如作为本发明的一个实施方式，为1种、2种、3种。另外，进一步在本发明的其他实施方式中，为4种、5种、6种、7种以上。The types of compounds that can be combined are not particularly limited, and they are used in combination according to desired properties such as solubility at low temperature, transition temperature, electrical reliability, and birefringence. The types of compounds to be used are, for example, one, two, or three types as one embodiment of the present invention. Moreover, in other embodiment of this invention, it is 4 types, 5 types, 6 types, 7 types or more.

本发明的组合物中，由通式(K)表示的化合物的含量必须根据低温时的溶解性、转变温度、电可靠性、双折射率、工艺适应性、滴痕、烧屏、介电常数各向异性等所要求的性能作适当调整。In the composition of the present invention, the content of the compound represented by the general formula (K) must be based on solubility at low temperature, transition temperature, electrical reliability, birefringence, process suitability, drip marks, burn-in, dielectric constant The required properties such as anisotropy are appropriately adjusted.

相对于本发明的液晶组合物的总量，由通式(K)表示的化合物的优选含量的下限值为1质量％、10质量％、20质量％、30质量％、40质量％、50质量％、55质量％、60质量％、65质量％、70质量％、75质量％、80质量％。优选含量的上限值相对于本发明的组合物总量，例如在本发明的一个方式中，为95质量％、85质量％、75质量％、65质量％、55质量％、45质量％、35质量％、25质量％。The lower limit of the preferable content of the compound represented by the general formula (K) is 1 mass %, 10 mass %, 20 mass %, 30 mass %, 40 mass %, 50 mass % with respect to the total amount of the liquid crystal composition of the present invention mass %, 55 mass %, 60 mass %, 65 mass %, 70 mass %, 75 mass %, 80 mass %. The upper limit of the preferable content is, for example, 95 mass %, 85 mass %, 75 mass %, 65 mass %, 55 mass %, 45 mass %, 35 mass %, 25 mass %.

当将本发明涉及的液晶组合物的粘度保持较低，需要响应速度快的组合物的情形时，优选使上述的下限值低一点，且使上限值低一点。进一步，当将本发明的液晶组合物的T_NI保持较高，需要温度稳定性佳的组合物的情形时，优选使上述的下限值低一点，且使上限值低一点。另外，为了将驱动电压保持较低而想要增大介电常数各向异性时，优选使上述的下限值高一点，且使上限值高一点。When the viscosity of the liquid crystal composition according to the present invention is kept low and a composition with a fast response speed is required, it is preferable to lower the above-mentioned lower limit value and lower the upper limit value. Furthermore, when the_TNI of the liquid crystal composition of the present invention is kept high and a composition with excellent temperature stability is required, it is preferable to lower the above-mentioned lower limit value and lower the upper limit value. In addition, in order to keep the driving voltage low and to increase the dielectric constant anisotropy, it is preferable to make the above lower limit value higher and the upper limit value higher.

由上述通式(J)表示的化合物优选为由下述式(M-1)～(M-18)表示的化合物。The compound represented by the above-mentioned general formula (J) is preferably a compound represented by the following formulae (M-1) to (M-18).

[化77][Chemical 77]

[化78][Chemical 78]

(上述式中，X^M11～X^M186各自独立地表示氢原子或氟原子，R^J1～R^J181各自独立地表示碳原子数1～5的烷基、碳原子数2～5的烯基或碳原子数1～4的烷氧基，X^J11～X^J181表示氟原子、氯原子或OCF₃，(In the above formula, X^M11 to X^M186 each independently represent a hydrogen atom or a fluorine atom, and R^J1 to R^J181 each independently represent an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or a carbon atom. An alkoxy group having 1 to 4 atoms, X^J11 to X^J181 represent a fluorine atom, a chlorine atom or OCF₃ ,

A^M81及A^M82各自独立地表示1,4-亚环己基、1,4-亚苯基或A^M81 and A^M82 each independently represent 1,4-cyclohexylene, 1,4-phenylene or

[化79][Chemical 79]

1,4-亚苯基上的氢原子可以被氟原子取代，W^M101～W^M172各自独立地表示-CH₂-或-O-。)The hydrogen atom on the 1,4-phenylene group may be substituted with a fluorine atom, and W^M101 to W^M172 each independently represent -CH₂ - or -O-. )

作为本发明涉及的通式(N-1)所表示的化合物，可列举下述的通式(N-1a)～(N-1g)所表示的化合物组。As a compound represented by General formula (N-1) concerning this invention, the compound group represented by following General formula (N-1a) - (N-1g) is mentioned.

[化80][Chemical 80]

(式中，R^N11及R^N12表示与通式(N-1)中的R^N11及R^N12相同的意义，n^Na12表示0或1，n^Nb11表示1或2，n^Nc11表示0或1，n^Nd11表示1或2，n^Ne11表示1或2，n^Nf12表示1或2，n^Ng11表示1或2，A^Ne11表示反式-1,4-亚环己基或1,4-亚苯基，A^Ng11表示反式-1,4-亚环己基、1,4-亚环己烯基或1,4-亚苯基，当n^Ng11为1的情形时，A^Ng11表示1,4-亚环己烯基，当n^Ng11为2的情形时，至少1个A^Ng11表示1,4-亚环己烯基，Z^Ne11表示单键或亚乙基，当n^Ne11为1的情形时，Z^Ne11表示亚乙基。当n^Ne11为2的情形时，至少1个Z^Ne11表示亚乙基。)(wherein, R^N11 and R^N12 have the same meanings as R^N11 and R^N12 in the general formula (N-1), n^{Na12 represents 0 or 1, n Nb11represents} 1 or 2, n^Nc11 represents 0 or 1, n^Nd11 represents 1 or 2, n^Ne11 represents 1 or 2, n^Nf12 represents 1 or 2, n^Ng11 represents 1 or 2, A^Ne11 represents trans-1,4-cyclohexylene or 1,4-phenylene, A^Ng11 represents trans-1,4-cyclohexylene, 1,4-cyclohexenylene or 1,4-phenylene, and when n^Ng11 is 1, A^Ng11 represents 1,4-cyclohexylene Hexenyl, when n^Ng11 is 2, at least one A^Ng11 represents 1,4-cyclohexenylene, Z^Ne11 represents a single bond or ethylene, and when n^Ng11 is 1, Z^Ne11 represents an ethylene group. When n^Ne11 is 2, at least one Z^Ne11 represents an ethylene group.)

本发明涉及的通式(N-2)所表示的化合物优选为选自下述通式(N-2-1)～(N-2-3)所表示的化合物组中的化合物。The compound represented by the general formula (N-2) according to the present invention is preferably a compound selected from the group of compounds represented by the following general formulae (N-2-1) to (N-2-3).

[化81][Chemical 81]

(式中，R^N211及R^N212各自独立地表示与通式(N-2)中的R^N21及R^N22相同的意义。)(In the formula, R^N211 and R^N212 each independently represent the same meanings as R^N21 and R^N22 in the general formula (N-2).)

[化82][Chemical 82]

(式中，R^N221及R^N222各自独立地表示与通式(N-2)中的R^N21及R^N22相同的意义。)(In the formula, R^N221 and R^N222 each independently represent the same meanings as R^N21 and R^N22 in the general formula (N-2).)

[化83][Chemical 83]

(式中，R^N231及R^N232各自独立地表示与通式(N-2)中的R^N21及R^N22相同的意义。)(In the formula, R^N231 and R^N232 each independently represent the same meanings as R^N21 and R^N22 in the general formula (N-2).)

通式(N-3)所表示的化合物优选为选自通式(N-3-2)所表示的化合物组中的化合物。The compound represented by the general formula (N-3) is preferably a compound selected from the group of compounds represented by the general formula (N-3-2).

[化84][Chemical 84]

(式中，R^N321及R^N322各自独立地表示与通式(N-3)中的R^N31及R^N32相同的意义。)(In the formula, R^N321 and R^N322 each independently represent the same meanings as R^N31 and R^N32 in the general formula (N-3).)

当本发明涉及的含有聚合性单体的液晶组合物整体呈现正介电常数各向异性的情形时，优选含有通式(I)所表示的聚合性单体、1种或2种以上选自通式(J)所表示的化合物中的化合物、以及通式(L)所表示的化合物。When the liquid crystal composition containing the polymerizable monomer according to the present invention exhibits positive dielectric constant anisotropy as a whole, it is preferable to contain the polymerizable monomer represented by the general formula (I), one or more selected from the group consisting of A compound among the compounds represented by the general formula (J), and a compound represented by the general formula (L).

本发明涉及的含有聚合性单体的液晶组合物整体中，仅由通式(I)、通式(J)及通式(L)所表示的化合物构成的成分所占的比例上限值优选为100质量％、99质量％、98质量％、97质量％、96质量％、95质量％、94质量％、93质量％、92质量％、91质量％、90质量％、89质量％、88质量％、87质量％、86质量％、85质量％、84质量％。In the entire liquid crystal composition containing the polymerizable monomer according to the present invention, the upper limit of the ratio of the components only composed of the compounds represented by the general formula (I), the general formula (J) and the general formula (L) is preferable 100 mass%, 99 mass%, 98 mass%, 97 mass%, 96 mass%, 95 mass%, 94 mass%, 93 mass%, 92 mass%, 91 mass%, 90 mass%, 89 mass%, 88 mass% mass %, 87 mass %, 86 mass %, 85 mass %, 84 mass %.

另外，本发明涉及的含有聚合性单体的液晶组合物整体中，仅由通式(I)、通式(J)及通式(L)所表示的化合物构成的成分所占的比例下限值优选为78质量％、80质量％、81质量％、83质量％、85质量％、86质量％、87质量％、88质量％、89质量％、90质量％、91质量％、92质量％、93质量％、94质量％、95质量％、96质量％、97质量％、98质量％、99质量％。Moreover, in the whole liquid-crystal composition containing the polymerizable monomer which concerns on this invention, the lower limit of the ratio of the component which consists only of the compound represented by general formula (I), general formula (J), and general formula (L) occupies The value is preferably 78 mass%, 80 mass%, 81 mass%, 83 mass%, 85 mass%, 86 mass%, 87 mass%, 88 mass%, 89 mass%, 90 mass%, 91 mass%, 92 mass% , 93 mass %, 94 mass %, 95 mass %, 96 mass %, 97 mass %, 98 mass %, 99 mass %.

当本发明涉及的含有聚合性单体的液晶组合物整体呈现负介电常数各向异性的情形时，优选含有通式(I)所表示的聚合性单体、1种或2种以上选自通式(N-1)所表示的化合物中的化合物、以及通式(L)所表示的化合物。When the liquid crystal composition containing a polymerizable monomer according to the present invention exhibits a negative dielectric constant anisotropy as a whole, it is preferable to contain the polymerizable monomer represented by the general formula (I), one or more selected from the group consisting of A compound among the compounds represented by the general formula (N-1), and a compound represented by the general formula (L).

本发明涉及的含有聚合性单体的液晶组合物整体中，仅由通式(I)、通式(N-1)及通式(L)所表示的化合物构成的成分所占的比例上限值优选为100质量％、99质量％、98质量％、97质量％、96质量％、95质量％、94质量％、93质量％、92质量％、91质量％、90质量％、89质量％、88质量％、87质量％、86质量％、85质量％、84质量％。In the entire liquid crystal composition containing the polymerizable monomer according to the present invention, the upper limit of the ratio of the components consisting only of the compounds represented by the general formula (I), the general formula (N-1) and the general formula (L) occupies The value is preferably 100 mass%, 99 mass%, 98 mass%, 97 mass%, 96 mass%, 95 mass%, 94 mass%, 93 mass%, 92 mass%, 91 mass%, 90 mass%, 89 mass% , 88 mass %, 87 mass %, 86 mass %, 85 mass %, 84 mass %.

当本发明涉及的液晶组合物为负的液晶组合物的情形时，20℃时的介电常数各向异性(Δε)为-2.0至-8.0，优选为-2.1至-6.2，更优选为-2.2至-5.3，进一步优选为-2.5至-5.0。特别优选为-2.7至-4.8。When the liquid crystal composition according to the present invention is a negative liquid crystal composition, the dielectric constant anisotropy (Δε) at 20°C is -2.0 to -8.0, preferably -2.1 to -6.2, and more preferably - 2.2 to -5.3, more preferably -2.5 to -5.0. Particularly preferred is -2.7 to -4.8.

当本发明涉及的液晶组合物为正的液晶组合物的情形时，20℃时的介电常数各向异性(Δε)为1.5至20，优选为1.5至18.0，更优选为1.5至15.0，进一步优选为1.5至11，特别优选为1.5至8。When the liquid crystal composition according to the present invention is a positive liquid crystal composition, the dielectric constant anisotropy (Δε) at 20° C. is 1.5 to 20, preferably 1.5 to 18.0, more preferably 1.5 to 15.0, and further It is preferably 1.5 to 11, particularly preferably 1.5 to 8.

本发明涉及的液晶组合物在20℃时的折射率各向异性(Δn)为0.08至0.14，更优选为0.09至0.13，特别优选为0.09至0.12。若更进一步详述，则应对薄的单元间隙的情形时，优选为0.10至0.13，而应对厚的单元间隙的情形时，则优选为0.08至0.11。The refractive index anisotropy (Δn) at 20° C. of the liquid crystal composition according to the present invention is 0.08 to 0.14, more preferably 0.09 to 0.13, and particularly preferably 0.09 to 0.12. In more detail, in the case of a thin cell gap, it is preferably 0.10 to 0.13, and in a case of a thick cell gap, it is preferably 0.08 to 0.11.

本发明的液晶组合物在20℃时的粘度(η)为10至50mPa·s，优选为10至45mPa·s，优选为10至40mPa·s，优选为10至35mPa·s，优选为10至30mPa·s，更优选为10至25mPa·s，特别优选为10至22mPa·s。The viscosity (η) of the liquid crystal composition of the present invention at 20°C is 10 to 50 mPa·s, preferably 10 to 45 mPa·s, preferably 10 to 40 mPa·s, preferably 10 to 35 mPa·s, preferably 10 to 40 mPa·s 30 mPa·s, more preferably 10 to 25 mPa·s, particularly preferably 10 to 22 mPa·s.

本发明涉及的液晶组合物在20℃时的旋转粘性(γ₁)为50至160mPa·s，优选为55至160mPa·s，优选为60至160mPa·s，优选为60至150mPa·s，优选为60至140mPa·s，优选为60至130mPa·s，优选为60至125mPa·s。The liquid crystal composition of the present invention has a rotational viscosity (γ₁ ) at 20° C. of 50 to 160 mPa·s, preferably 55 to 160 mPa·s, preferably 60 to 160 mPa·s, preferably 60 to 150 mPa·s, preferably 60 to 150 mPa·s. It is 60 to 140 mPa·s, preferably 60 to 130 mPa·s, preferably 60 to 125 mPa·s.

本发明涉及的液晶组合物的向列相-各向同性液相转变温度(T_ni)为60℃至120℃，更优选为70℃至100℃，特别优选为70℃至85℃。The nematic phase-isotropic liquid phase transition temperature (T_ni ) of the liquid crystal composition of the present invention is 60°C to 120°C, more preferably 70°C to 100°C, and particularly preferably 70°C to 85°C.

使用本发明的含有聚合性单体的液晶组合物的液晶显示元件，具有高速响应这一显著的特征，并且，可充分得到倾斜角，没有未反应的聚合性单体或少到不会成为问题，电压保持率(VHR)高，因此没有取向不良或显示不良等不良情形，或者得到了充分抑制。另外，由于能够容易地控制倾斜角及聚合性单体的残留量，因此容易实现用于制造的能量成本的优化及削减，因此，最适于生产效率的提高与稳定的量产。The liquid crystal display element using the polymerizable monomer-containing liquid crystal composition of the present invention has a remarkable feature of high-speed response, and can obtain a sufficient tilt angle, and there is no unreacted polymerizable monomer or so little that it does not become a problem , and the voltage holding ratio (VHR) was high, so that there were no problems such as poor orientation or poor display, or were sufficiently suppressed. In addition, since the tilt angle and the residual amount of the polymerizable monomer can be easily controlled, optimization and reduction of the energy cost for production can be easily achieved, and therefore, it is most suitable for improvement of production efficiency and stable mass production.

使用本发明的含有聚合性单体的液晶组合物的液晶显示元件，尤其对于主动矩阵驱动用液晶显示元件有用，可用于PSA模式、PSVA模式、VA模式、PS-IPS模式或PS-FFS模式用液晶显示元件。Liquid crystal display elements using the polymerizable monomer-containing liquid crystal composition of the present invention are particularly useful for active matrix driving liquid crystal display elements, and can be used for PSA mode, PSVA mode, VA mode, PS-IPS mode or PS-FFS mode Liquid crystal display element.

实施例Example

以下列举实施例进一步详述本发明，但本发明并不限定于这些实施例。另外，下述实施例及比较例的组合物中的“％”是指“质量％”。实施例中关于化合物的记载，使用以下的代号。The following examples are given to further describe the present invention, but the present invention is not limited to these examples. In addition, "%" in the composition of the following Examples and Comparative Examples means "mass %". For the description of the compounds in the examples, the following symbols are used.

实施例中所测得的特性如下所示。The properties measured in the examples are shown below.

T_ni：向列相-各向同性液相转变温度(℃)T_ni : Nematic phase-isotropic liquid phase transition temperature (°C)

Δn：20℃时的折射率各向异性Δn: Refractive index anisotropy at 20°C

η：20℃时的粘度(mPa·s)η: Viscosity at 20°C (mPa·s)

γ₁：20℃时的旋转粘性(mPa·s)γ₁ : Rotational viscosity at 20°C (mPa·s)

Δε：20℃时的介电常数各向异性Δε: Dielectric constant anisotropy at 20°C

K₃₃：20℃时的弹性常数K₃₃(pN)K₃₃ : Elastic constant K₃₃ (pN) at 20°C

＜环结构＞<Ring structure>

[化85][Chemical 85]

＜侧链结构＞<Side chain structure>

[表1][Table 1]

代号code化学结构chemical structure-n-nC_nH_2n+1C_nH_2n+1n-n-C_nH_2n+1-C_nH_2n+1--On-On-OC_nH_2n+1-OC_nH_2n+1nO-nO-C_nH_2n+1O-C_nH_2n+1O--V-V-CH＝CH₂-CH=CH₂V-V-CH₂＝CH-CH₂=CH--V1-V1-CH＝CH-CH₃-CH=CH-CH₃1V-1V-CH₃-CH＝CH-CH₃-CH=CH--2V-2V-CH₂-CH₂-CH＝CH₂-CH₂-CH₂-CH=CH₂V2-V2-CH₂＝CH-CH₂-CH₂-CH₂=CH-CH₂-CH₂--2V1-2V1-CH₂-CH₂-CH＝CH-CH₃-CH₂-CH₂-CH=CH-CH₃1V2-1V2-CH₃-CH＝CH-CH₂-CH₂-CH₃-CH=CH-CH₂-CH₂-

(其中，表中的n为自然数。)(Wherein, n in the table is a natural number.)

<连结结构><Link structure>

[表2][Table 2]

代号code化学结构chemical structure-n--n-C_nH_2nC_nH_2n-nO--nO--C_nH_2nO--C_nH_2nO--On--On--OC_nH_2n--OC_nH_2n--COO--COO--C(＝O)-O--C(=O)-O--OCO--OCO--O-C(＝O)--O-C(=O)--V--V--CH＝CH--CH=CH--nV--nV--C_nH_2n-CH＝CH--C_nH_2n-CH=CH--Vn--Vn--CH＝CH-C_nH_2n--CH=CH-C_nH_2n--T--T--C≡C--C≡C--CF2O--CF2O--CF₂-O--CF₂-O--OCF2--OCF2--O-CF₂--O-CF₂-

(其中，表中的n为自然数。)(Wherein, n in the table is a natural number.)

本实施例及比较例中的“低温保存性”、“垂直取向性”、“预倾角形成”及“响应特性”的评价通过以下方法进行。The evaluation of "low temperature storage stability", "vertical orientation", "pretilt angle formation", and "response characteristics" in the present Examples and Comparative Examples were performed by the following methods.

(低温保存性的评价试验)(Evaluation test of low temperature storage property)

使用膜滤器(Agilent Technologies公司制，PTFE 13m-0.2μm)对液晶组合物进行过滤，在真空减压条件下静置15分钟，进行溶存空气的去除。用丙酮将其清洗后，称量0.5g至经充分干燥的小玻璃瓶，在-25℃的环境下静置10天。然后，通过目视观察有无析出，以下述2阶段来判定。The liquid crystal composition was filtered using a membrane filter (manufactured by Agilent Technologies, PTFE 13 m-0.2 μm), and was allowed to stand for 15 minutes under vacuum reduced pressure conditions to remove dissolved air. After washing with acetone, 0.5 g was weighed into a well-dried vial, and it was left to stand at -25°C for 10 days. Then, the presence or absence of precipitation was visually observed, and it was determined in the following two steps.

A：无法确认到析出。A: Precipitation cannot be confirmed.

B：1周后析出。B: Precipitation after 1 week.

C：可确认到析出。C: Precipitation was confirmed.

(垂直取向性的评价试验)(Evaluation test for vertical orientation)

制作第一基板(共通电极基板)与第二基板(像素电极基板)，该第一基板在绝缘层上具有由经图案化的透明共通电极构成的透明电极层，不具有具备滤色器层的取向膜；该第二基板没有具有像素电极层的取向膜，该像素电极层具有通过主动元件驱动的透明像素电极。将液晶组合物滴加于第一基板上，在第二基板上夹持，在常压以110℃、2小时的条件使密封材固化，得到单元间隙3.2μm的液晶单元。使用偏光显微镜观察此时的垂直取向性及滴痕等取向不均，以下述5阶段来评价。A first substrate (common electrode substrate) and a second substrate (pixel electrode substrate) are produced. The first substrate has a transparent electrode layer composed of a patterned transparent common electrode on an insulating layer, and does not have a color filter layer. an alignment film; the second substrate does not have an alignment film with a pixel electrode layer, and the pixel electrode layer has a transparent pixel electrode driven by an active element. The liquid crystal composition was dropped on the first substrate, sandwiched between the second substrate, and the sealing material was cured under normal pressure at 110° C. for 2 hours to obtain a liquid crystal cell with a cell gap of 3.2 μm. The vertical alignment at this time and the orientation unevenness such as drip marks were observed with a polarizing microscope, and were evaluated in the following five stages.

S：特别优异，均匀地垂直取向S: particularly excellent, uniformly oriented vertically

A：整面上均匀地垂直取向A: Uniform vertical orientation over the entire surface

B：有极些微的取向缺陷，为可容许的程度B: There is an extremely slight orientation defect, which is an acceptable level

C：具有取向缺陷，为无法容许的程度C: There is an orientation defect, and it is an unacceptable degree

D：取向不良相当严重D: The misorientation is quite serious

(液晶烧屏评价方法(预倾角的经时变化))(Liquid crystal burn-in evaluation method (time-dependent change of pretilt angle))

首先，将会诱发垂直取向的聚酰亚胺取向膜涂布于带ITO的基板后，对前述聚酰亚胺取向膜进行摩擦处理，得到带ITO的基板，然后在含有该带ITO的基板的液晶单元(单元间隙3.5μm)间，使用真空注入法注入液晶组合物。然后，在对注入了液晶组合物的液晶单元以频率100Hz施加10V电压的状态下，使用高压水银灯，通过会将325nm以下的紫外线滤除的过滤器照射紫外线。此时，调整成在中心波长365nm的条件下测得的照度为100mW/cm²，照射累积光量10J/cm²的紫外线。将前述紫外线照射条件设为照射条件1。通过该照射条件1对液晶单元中的液晶分子赋予预倾角。此处，为了无论有无垂直取向性都对预倾形成进行评价而用带聚酰亚胺取向膜的单元来进行评价，但在使用垂直取向性够高的单体的情形时，确认到即使用没有聚酰亚胺取向膜的单元进行相同的评价，也可得到同样的结果。First, after applying a polyimide alignment film that induces vertical alignment to a substrate with ITO, the aforementioned polyimide alignment film is subjected to a rubbing treatment to obtain a substrate with ITO. Between the liquid crystal cells (cell gap 3.5 μm), the liquid crystal composition was injected using a vacuum injection method. Then, in a state where a voltage of 10 V was applied at a frequency of 100 Hz to the liquid crystal cell into which the liquid crystal composition was injected, ultraviolet rays were irradiated through a filter for filtering out ultraviolet rays of 325 nm or less using a high pressure mercury lamp. At this time, it adjusted so that the illuminance measured under the conditions of a center wavelength 365nm might become 100mW/cm<² >, and the ultraviolet-ray of the accumulated light quantity 10J/cm<² > was irradiated. The above-mentioned ultraviolet irradiation conditions were set as irradiation conditions 1. According to this irradiation condition 1, a pretilt angle is given to the liquid crystal molecules in the liquid crystal cell. Here, in order to evaluate pretilt formation regardless of the presence or absence of vertical alignment, the evaluation was performed using a unit with a polyimide alignment film, but when a monomer with sufficiently high vertical alignment was used, it was confirmed that The same evaluation was performed using the cell without a polyimide alignment film, and the same result was obtained.

接着，使用荧光UV灯，调整成在中心波长313nm的条件下测得的照度为3mW/cm²，进一步照射累积光量20J/cm²的紫外线，得到液晶显示元件。将前述紫外线照射条件设为照射条件2。通过照射条件2，使照射条件1下未反应的液晶单元中的聚合性单体的残留量减少。Next, using a fluorescent UV lamp, the illuminance measured under the condition of a center wavelength of 313 nm was adjusted to be 3 mW/cm² , and ultraviolet rays with a cumulative light amount of 20 J/cm² were further irradiated to obtain a liquid crystal display element. The above-mentioned ultraviolet irradiation conditions were set as irradiation conditions 2. By the irradiation condition 2, the residual amount of the polymerizable monomer in the unreacted liquid crystal cell under the irradiation condition 1 is reduced.

照射紫外线后，进行因预倾角的变化所造成的显示不良(烧屏)评价。首先，测量液晶显示元件的预倾角，作为预倾角(初期)。对该液晶显示元件以频率100Hz施加矩形波30V的电压，并且照射背光10小时。然后，测量预倾角，作为预倾角(试验后)。从所测得的预倾角(初期)减掉预倾角(试验后)，将所得到的值作为预倾角变化量(＝预倾角变化的绝对值)[°]。预倾角使用Shintech公司制的OPTIPRO测得。需要说明的是，30V的电压大小为通常的驱动电压的数倍大，成为加速试验。After irradiation with ultraviolet rays, evaluation of display failure (screen burn-in) due to changes in the pretilt angle was performed. First, the pretilt angle of the liquid crystal display element is measured as the pretilt angle (initial stage). A voltage of 30V rectangular wave was applied to the liquid crystal display element at a frequency of 100 Hz, and the backlight was irradiated for 10 hours. Then, the pretilt angle was measured as the pretilt angle (after the test). The pretilt angle (after the test) was subtracted from the measured pretilt angle (initial stage), and the obtained value was used as the pretilt angle change amount (= absolute value of the pretilt angle change) [°]. The pretilt angle was measured using OPTIPRO manufactured by Shintech. In addition, the magnitude of the voltage of 30V is several times as large as the normal driving voltage, which is an accelerated test.

预倾角变化量越接近0[°]，因预倾角的变化而导致显示不良发生的可能性越低。The closer the pretilt angle variation is to 0 [°], the lower the possibility of display failure due to the pretilt angle variation.

将上述测得的预倾角变化量分为以下的4阶段。The pretilt angle change amount measured above is divided into the following four stages.

S：0.1°以内(几乎不发生显示不良)S: Within 0.1° (display failure hardly occurs)

A：0.1°以上0.3°以内(不易发生显示不良)A: 0.1° or more and less than 0.3° (display failure is unlikely to occur)

B：0.3°以上0.5°以内(发生相当多的显示不良)B: 0.3° or more and less than 0.5° (a considerable amount of display failure occurs)

C：0.5°以上(发生显示不良，为无法容许的程度)C: 0.5° or more (display failure occurs and cannot be tolerated)

(响应特性的评价试验)(Evaluation test for response characteristics)

对于上述(预倾角形成的评价试验)所使用的单元间隙3.2μm的单元，进一步照射东芝照明技术公司制的UV荧光灯60分钟(313nm时的照度1.7mW/cm²)。对由此所得到的单元测定响应速度。关于响应速度，在25℃的温度条件下，使用AUTRONIC-MELCHERS公司的DMS703测量6V时的Voff。The cell with a cell gap of 3.2 μm used in the above (evaluation test for pretilt angle formation) was further irradiated with a UV fluorescent lamp manufactured by Toshiba Lighting Technology Co., Ltd. for 60 minutes (illuminance at 313 nm: 1.7 mW/cm² ). The response speed of the cell thus obtained was measured. Regarding the response speed, Voff at 6 V was measured using DMS703 from AUTRONIC-MELCHERS under a temperature condition of 25°C.

(液晶组合物的调制与评价结果)(Results of preparation and evaluation of liquid crystal composition)

按照如下述所示的化合物与混合比率调制液晶组合物，将该组合物设为LC-1。以下公开液晶组合物的构成及其物性值的结果。A liquid crystal composition was prepared according to the compound and mixing ratio shown below, and this composition was set to LC-1. The constitution of the liquid crystal composition and the results of its physical properties are disclosed below.

LC-1的向列相-各向同性液相转变温度(T_NI)为75℃，固相-向列相转变温度(T_CN)为-33℃，折射率各向异性(Δn)为0.11，介电常数各向异性(Δε)为-2.8，旋转粘性(γ₁)为98mPa·s。需要说明的是，折射率各向异性(Δn)、介电常数各向异性(Δε)及旋转粘性(γ1)均是25℃时的测定结果(下同)。The nematic phase-isotropic liquid phase transition temperature (T_NI ) of LC-1 is 75°C, the solid phase-nematic phase transition temperature (T_CN ) is -33°C, and the refractive index anisotropy (Δn) is 0.11 , the dielectric constant anisotropy (Δε) is -2.8, and the rotational viscosity (γ₁ ) is 98 mPa·s. In addition, the refractive index anisotropy (Δn), the dielectric constant anisotropy (Δε), and the rotational viscosity (γ1) are the measurement results at 25° C. (the same below).

[表3][table 3]

(比较例1～8)(Comparative Examples 1 to 8)

将LC-1设为100质量份时，将含有下述自取向性单体(P-1)1.0质量份、添加有0.3质量份由式(RM-1)表示的化合物的聚合性单体的液晶组合物作为比较例1。When LC-1 is set to 100 parts by mass, 1.0 parts by mass of the following self-aligning monomer (P-1) and 0.3 parts by mass of the polymerizable monomer to which the compound represented by the formula (RM-1) was added were added. The liquid crystal composition was taken as Comparative Example 1.

将相对于100质量份液晶组合物LC-1含有自取向性单体(P-1)1.0质量份、添加有0.3质量份由式(RM-2)表示的化合物的聚合性单体的液晶组合物作为比较例2。A liquid crystal composition containing 1.0 parts by mass of a self-aligning monomer (P-1) and 0.3 parts by mass of a polymerizable monomer to which the compound represented by the formula (RM-2) was added with respect to 100 parts by mass of the liquid crystal composition LC-1 as Comparative Example 2.

将相对于100质量份液晶组合物LC-1含有自取向性单体(P-1)1.0质量份、添加有0.3质量份由式(RM-3)表示的化合物的聚合性单体的液晶组合物作为比较例3。A liquid crystal composition containing 1.0 parts by mass of the self-aligning monomer (P-1) and 0.3 parts by mass of the polymerizable monomer to which the compound represented by the formula (RM-3) was added with respect to 100 parts by mass of the liquid crystal composition LC-1 as Comparative Example 3.

将相对于100质量份液晶组合物LC-1含有自取向性单体(P-1)1.0质量份、添加有0.3质量份由式(RM-4)表示的化合物的聚合性单体的液晶组合物作为比较例4。A liquid crystal composition containing 1.0 parts by mass of a self-aligning monomer (P-1) and 0.3 parts by mass of a polymerizable monomer to which the compound represented by the formula (RM-4) was added with respect to 100 parts by mass of the liquid crystal composition LC-1 as Comparative Example 4.

将相对于100质量份液晶组合物LC-1含有自取向性单体(P-1)0.5质量份、添加有0.3质量份由式(RM-2)表示的化合物的聚合性单体的液晶组合物作为比较例5。Liquid crystal composition containing 0.5 parts by mass of self-aligning monomer (P-1) and 0.3 parts by mass of a polymerizable monomer to which the compound represented by formula (RM-2) was added with respect to 100 parts by mass of liquid crystal composition LC-1 as Comparative Example 5.

将相对于100质量份液晶组合物LC-1含有自取向性单体(P-1)0.5质量份、添加有0.6质量份由式(RM-1)表示的化合物的聚合性单体的液晶组合物作为比较例6。A liquid crystal composition containing 0.5 parts by mass of a self-aligning monomer (P-1) and 0.6 parts by mass of a polymerizable monomer to which the compound represented by the formula (RM-1) was added with respect to 100 parts by mass of the liquid crystal composition LC-1 as Comparative Example 6.

将相对于100质量份液晶组合物LC-1含有自取向性单体(P-1)1.0质量份、添加有0.6质量份由式(RM-1)表示的化合物的聚合性单体的液晶组合物作为比较例7。A liquid crystal composition containing 1.0 parts by mass of a self-aligning monomer (P-1) and 0.6 parts by mass of a polymerizable monomer to which the compound represented by the formula (RM-1) was added with respect to 100 parts by mass of the liquid crystal composition LC-1 as Comparative Example 7.

将相对于100质量份液晶组合物LC-1含有自取向性单体(P-1)1.0质量份、添加有0.6质量份由式(RM-3)表示的化合物的聚合性单体的液晶组合物作为比较例8。A liquid crystal composition containing 1.0 parts by mass of a self-aligning monomer (P-1) and 0.6 parts by mass of a polymerizable monomer to which the compound represented by the formula (RM-3) was added with respect to 100 parts by mass of the liquid crystal composition LC-1 as Comparative Example 8.

(实施例1～95)(Examples 1 to 95)

除了将下述所示的自取向性单体(P-1)至(P-41)及聚合性单体(RM-1)至(RM-16)分别以下表所示的添加量添加于LC-1以外，与比较例1同样地操作，调制液晶组合物。Except that the self-aligning monomers (P-1) to (P-41) and the polymerizable monomers (RM-1) to (RM-16) shown below were added to the LC in the amounts shown in the following table, respectively. Except -1, it carried out similarly to the comparative example 1, and prepared the liquid crystal composition.

以下，示出本实施例所使用的自取向性单体及聚合性单体的化学结构。以下的结构式中，“Me”表示甲基。The chemical structures of the self-aligning monomers and polymerizable monomers used in this example are shown below. In the following structural formulas, "Me" represents a methyl group.

[化86][Chemical 86]

[化87][Chemical 87]

[化88][Chemical 88]

[化89][Chemical 89]

[化90][Chemical 90]

[化91][Chemical 91]

[化92][Chemical 92]

[化93][Chemical 93]

[化94][Chemical 94]

[化95][Chemical 95]

[化96][Chemical 96]

[化97][Chemical 97]

[化98][Chemical 98]

[化99][Chemical 99]

[化100][Chemical 100]

[化101][Chemical 101]

[化102][Chemical 102]

[化103][Chemical 103]

[表4][Table 4]

[表5][table 5]

[表6][Table 6]

[表7][Table 7]

[表8][Table 8]

[表9][Table 9]

[表10][Table 10]

关于实施例1～95的低温保存性，取代基具有长链烷基的聚合性单体(例如，RM-9～RM-11)若经过1周左右则会开始发生析出。另外，取代基具有短链烷基或者烷氧基的聚合性单体(例如，RM-3～RM-7，RM-12～RM-14)，溶解性佳，低温保存性良好。关于低温保存性，聚合性单体由于溶解性相对较佳，因此主要取决于自取向性单体的溶解性。Regarding the low-temperature storage properties of Examples 1 to 95, the polymerizable monomers having a long-chain alkyl group as a substituent (for example, RM-9 to RM-11) started to precipitate after about 1 week. In addition, polymerizable monomers (for example, RM-3 to RM-7, RM-12 to RM-14) having a short-chain alkyl group or alkoxy group as a substituent have good solubility and good low-temperature storage properties. Regarding low-temperature storage properties, the polymerizable monomer has relatively good solubility, and therefore mainly depends on the solubility of the self-aligning monomer.

另外，将封入了含有2种聚合性单体的液晶组合物的液晶单元放置于偏光元件与检偏镜正交配置的偏光显微镜，观察透射光时，如果液晶分子垂直取向，则光会因偏光板的作用而无法透射，因此单元会呈黑色显示。通过这种试验法来评价上述实施例1～95的液晶组合物的样品，结果确认到，若适当地选择2种聚合性单体并添加于液晶组合物，则可显著地减轻取向不均，显示出一样的垂直取向性。所谓该适当的2种聚合性单体，可列举一个在介晶侧链导入有疏水基的双官能性单体与在300nm以上具有吸收的聚合性单体的组合，通过以适当浓度添加各单体，确认到良好的垂直取向性。In addition, when a liquid crystal cell encapsulated with a liquid crystal composition containing two types of polymerizable monomers is placed in a polarizing microscope with a polarizing element and an analyzer arranged orthogonally, and transmitted light is observed, if the liquid crystal molecules are vertically aligned, the light will be polarized due to the polarization. The action of the plate prevents transmission, so the cell will appear black. As a result of evaluating the samples of the above-mentioned liquid crystal compositions of Examples 1 to 95 by such a test method, it was confirmed that when two types of polymerizable monomers are appropriately selected and added to the liquid crystal composition, the alignment unevenness can be significantly reduced, showed the same vertical orientation. The suitable two types of polymerizable monomers include a combination of a bifunctional monomer having a hydrophobic group introduced into a mesogenic side chain and a polymerizable monomer having absorption at 300 nm or more, and each monomer is added at an appropriate concentration. body, and good vertical orientation was confirmed.

另一方面，比较例1、2、4、5～7中，确认到通过添加聚合性单体，预倾变化量相对较为良好，相对于此，垂直取向性低。比较例3中，虽然垂直取向性高，但预倾变化量大。比较例6～7中，尽管增加了1种聚合性单体的添加量，但垂直取向性并未获得改善。从这些结果可确认，若为1种聚合性单体，则并非可同时兼顾垂直取向性与预倾变化量的单体。On the other hand, in Comparative Examples 1, 2, 4, and 5 to 7, it was confirmed that the amount of change in pretilt was relatively good by adding the polymerizable monomer, and the vertical orientation was low. In Comparative Example 3, although the vertical orientation was high, the amount of pretilt change was large. In Comparative Examples 6 to 7, although the addition amount of one polymerizable monomer was increased, the vertical orientation was not improved. From these results, it was confirmed that if it is a single polymerizable monomer, it is not a monomer that can achieve both the vertical orientation and the amount of pretilt change.

另外，比较例中，对自取向性单体与聚合性单体各自包含1种的组合物评价了取向性、倾斜稳定性，但是当使用在长波长具有吸收的聚合性单体(例如，RM-4)的情形时，结果是虽然倾斜稳定性相对较为良好，但垂直取向性差。另外，若使用导入有疏水性部位的化合物(RM-3)作为聚合性单体，则结果是虽然垂直取向性良好，但无法充分引起通过照射紫外光进行的聚合，无法致密地形成网络，倾斜稳定性变低。进一步，比较例1～8全部为低温保存性比实施例差的结果。In addition, in the comparative example, the orientation and tilt stability were evaluated for the composition containing one type of self-aligning monomer and one type of polymerizable monomer, but when a polymerizable monomer having absorption at long wavelengths (for example, RM In the case of -4), although the tilt stability was relatively good, the vertical alignment was poor. In addition, when a compound (RM-3) into which a hydrophobic moiety was introduced was used as a polymerizable monomer, although the vertical alignment was good, polymerization by irradiation with ultraviolet light was not sufficiently induced, and the network was not formed densely, and the slope was inclined. Stability becomes lower. Furthermore, all of Comparative Examples 1 to 8 showed that the low-temperature storage properties were inferior to those of the Examples.

关于实施例1、12、26、42、50，认为由于使用了2种未导入疏水基的聚合性单体，因此垂直取向性与其他实施例相比为较差的结果。相对于此，实施例5、6、24、27、28、38、39、46由于使用了光的吸收区域未移动至相对较长波长侧的聚合性单体，因此聚合不易进行，在聚合的初期阶段，聚合物网络的形成不充分，作为结果，预倾变化量与其他实施例相比为较差的结果。根据上述实验结果，认为通过适当选择参与聚合的聚合性单体与有助于垂直取向性的聚合性单体的功能分离的2种单体，能够实现高的垂直取向性与小的预倾变化量。在其他实施例中，确认到除了高垂直取向性以外，还显示出足够小的预倾角变化量，且显示不均、烧屏少。尤其是认为导入有疏水基的聚合性单体发挥自取向单体与另1种聚合性单体的媒介功能，保持高垂直取向性，且同时提高聚合层的交联密度，从而使聚合物的强度提高，结果稳定性优异。With regard to Examples 1, 12, 26, 42, and 50, since two types of polymerizable monomers to which a hydrophobic group is not introduced were used, the results of vertical alignment are considered to be inferior to those of the other Examples. In contrast, Examples 5, 6, 24, 27, 28, 38, 39, and 46 used a polymerizable monomer whose light absorption region did not move to the relatively longer wavelength side, so that the polymerization did not proceed easily, and the In the initial stage, the formation of the polymer network was insufficient, and as a result, the pretilt variation was a poor result compared to the other examples. Based on the above experimental results, it is considered that high vertical alignment and small pretilt change can be achieved by appropriately selecting the polymerizable monomer that participates in polymerization and the two monomers that contribute to functional separation of the polymerizable monomer for vertical alignment. quantity. In other examples, in addition to high vertical alignment, it was confirmed that a sufficiently small amount of change in the pretilt angle was exhibited, and display unevenness and screen burn-in were less. In particular, it is considered that the polymerizable monomer into which the hydrophobic group is introduced acts as a mediator between the self-aligning monomer and another polymerizable monomer, maintains high vertical orientation, and at the same time increases the crosslinking density of the polymerized layer, thereby making the polymer The strength is improved, resulting in excellent stability.

另外，评价因通过照射紫外光进行的聚合而形成的预倾角，结果确认到在分别添加有在介晶侧链导入有疏水基的双官能性单体(例如RM-3、RM-5、RM-6、RM-8)与在长波长具有吸收的聚合性单体(例如RM-4、RM-12～RM-14)的样品中，被赋予了适当的倾斜角。使用了它们的液晶显示元件由于被赋予了充分的预倾角，因此暗示了充分高速的响应。In addition, as a result of evaluating the pretilt angle formed by the polymerization by irradiation with ultraviolet light, it was confirmed that bifunctional monomers (for example, RM-3, RM-5, RM, for example, RM-3, RM-5, RM) having hydrophobic groups introduced into the side chains of the mesogens were added, respectively. -6, RM-8) and samples of polymerizable monomers (for example, RM-4, RM-12 to RM-14) that absorb at long wavelengths, were given appropriate tilt angles. Since the liquid crystal display element using them is given a sufficient pretilt angle, a sufficiently high-speed response is suggested.

当利用含有在实施例1～11等中作为聚合性单体使用的RM-1～RM-17的组合物来制作液晶单元时，展开性(润湿扩展)也良好。When liquid crystal cells were produced using the compositions containing RM-1 to RM-17 used as polymerizable monomers in Examples 1 to 11, etc., the spreading properties (wetting spreading) were also favorable.

进一步，当将实施例1～95的自取向性单体的添加量分别置换成1.0质量份至0.5质量份的情形时，也确认到垂直取向性及预倾变化量小，显示不均、烧屏获得抑制。Furthermore, when the addition amounts of the self-aligning monomers in Examples 1 to 95 were replaced by 1.0 to 0.5 parts by mass, respectively, it was confirmed that the vertical orientation and the pretilt change were small, showing unevenness and burning. screen is suppressed.

调制以如下述所示的化合物及混合比率构成的组合物代替组合物LC-1，将该液晶组合物设为LC-2至LC-8。In place of the composition LC-1, compositions composed of the compounds and mixing ratios shown below were prepared, and the liquid crystal compositions were referred to as LC-2 to LC-8.

[表11][Table 11]

(实施例96～103)(Examples 96 to 103)

确认到，即使将实施例3的基础组合物置换成LC1至LC2，垂直取向性及预倾变化量也小，显示不均、烧屏也获得抑制(实施例96)。It was confirmed that even if the base composition of Example 3 was replaced with LC1 to LC2, the amount of change in vertical orientation and pretilt was small, and display unevenness and burn-in were also suppressed (Example 96).

确认到，即使将实施例30的基础组合物置换成LC1至LC3，垂直取向性及预倾变化量也小，显示不均、烧屏也获得抑制(实施例97)。It was confirmed that even if the base composition of Example 30 was replaced with LC1 to LC3, the amount of change in vertical orientation and pretilt was small, and display unevenness and burn-in were also suppressed (Example 97).

确认到，即使将实施例35的基础组合物置换成LC1至LC4，垂直取向性及预倾变化量也小，显示不均、烧屏也获得抑制(实施例98)。It was confirmed that even if the base composition of Example 35 was replaced with LC1 to LC4, the amount of change in vertical orientation and pretilt was small, and display unevenness and burn-in were also suppressed (Example 98).

确认到，即使将实施例36的基础组合物置换成LC1至LC5，并将聚合性化合物置换成P-6至P-11，垂直取向性及预倾变化量也小，显示不均、烧屏也获得抑制(实施例99)。Even if the base composition of Example 36 was replaced by LC1 to LC5, and the polymerizable compound was replaced by P-6 to P-11, the amount of change in vertical orientation and pretilt was small, resulting in uneven display and burn-in. Inhibition was also obtained (Example 99).

确认到，即使将实施例41的基础组合物置换成LC1至LC6，并将聚合性化合物置换成P-6至P-18，垂直取向性及预倾变化量也小，显示不均、烧屏也获得抑制(实施例100)。It was confirmed that even if the base composition of Example 41 was replaced by LC1 to LC6 and the polymerizable compound was replaced by P-6 to P-18, the amount of change in vertical orientation and pretilt was small, and display unevenness and burn-in were confirmed. Inhibition was also obtained (Example 100).

确认到，即使将实施例44的基础组合物置换成LC1至LC7，并将聚合性化合物置换成P-7至P-23，垂直取向性及预倾变化量也小，显示不均、烧屏也获得抑制(实施例101)。It was confirmed that even if the base composition of Example 44 was replaced with LC1 to LC7, and the polymerizable compound was replaced with P-7 to P-23, the amount of change in vertical orientation and pretilt was small, resulting in uneven display and burn-in. Inhibition was also obtained (Example 101).

确认到，即使将实施例47的基础组合物置换成LC1至LC8，并将聚合性化合物置换成P-8至P-30，垂直取向性及预倾变化量也小，显示不均、烧屏也获得抑制(实施102)。Even if the base composition of Example 47 was replaced by LC1 to LC8, and the polymerizable compound was replaced by P-8 to P-30, the amount of change in vertical orientation and pretilt was small, resulting in uneven display and burn-in. Inhibition was also obtained (Example 102).

确认到，即使将实施例56的基础组合物置换成LC1至LC8，并将聚合性化合物置换成P-10至P-34，垂直取向性及预倾变化量也小，显示不均、烧屏也获得抑制(实施例103)。It was confirmed that even if the base composition of Example 56 was replaced with LC1 to LC8, and the polymerizable compound was replaced with P-10 to P-34, the amount of change in vertical orientation and pretilt was small, resulting in uneven display and screen burn-in. Inhibition was also obtained (Example 103).

进一步，当将实施例96～103的自取向性单体的添加量分别置换成1.0质量份至0.5质量份的情形时，也确认到垂直取向性及预倾变化量小，显示不均、烧屏获得抑制。Furthermore, when the addition amounts of the self-aligning monomers in Examples 96 to 103 were replaced by 1.0 to 0.5 parts by mass, respectively, it was confirmed that the vertical orientation and the pretilt change were small, showing unevenness and burning. screen is suppressed.

(实施例104～123)(Examples 104 to 123)

除了将下表所示的自取向性单体(1)0.2质量份及自取向性单体(2)0.4质量份以及下表所示的添加量的聚合性单体(1)及(2)分别添加于组合物LC-1～LC-8的任一者中以外，与比较例1同样地操作，调制液晶组合物。Except for adding 0.2 parts by mass of self-aligning monomer (1) and 0.4 parts by mass of self-aligning monomer (2) shown in the following table, and polymerizable monomers (1) and (2) in addition amounts shown in the following table Except adding each to any one of compositions LC-1-LC-8, it carried out similarly to the comparative example 1, and prepared the liquid crystal composition.

[表12][Table 12]

[表13][Table 13]

评价由2种自取向性单体、2种聚合性单体的组合所得到的低温保存性、垂直取向性、预倾稳定性。可确认：通过以低浓度混合2种溶解性低的自取向性单体，从而在维持低温保存性的状态下提高了垂直取向性。另外，通过将聚合性单体也混合多种来使用，能够提高聚合性单体成分的浓度，能够使预倾稳定性提高。Low-temperature storage properties, vertical alignment properties, and pretilt stability obtained by a combination of two types of self-aligning monomers and two types of polymerizable monomers were evaluated. It was confirmed that by mixing two types of self-aligning monomers with low solubility at a low concentration, the vertical alignment was improved while maintaining low-temperature storage properties. In addition, by mixing and using a plurality of polymerizable monomers, the concentration of the polymerizable monomer component can be increased, and the pretilt stability can be improved.

根据上述各实施例的评价结果，实施例的液晶组合物作为液晶显示元件显示出综合优异的性能。According to the evaluation results of the above-mentioned examples, the liquid crystal compositions of the examples showed comprehensively excellent performance as a liquid crystal display element.

(实施例124～149)(Examples 124 to 149)

除了将实施例1的自取向性单体分别置换成P-1至P-41～P-66以外，与实施例1同样地操作，调制液晶组合物，将它们设为实施例124～149。根据实施例124～149的结果，确认到：使用各种自取向性单体的情形时，垂直取向性及预倾变化量也小，显示不均、烧屏也获得抑制。Except having replaced the self-aligning monomer of Example 1 with P-1-P-41-P-66, respectively, it carried out similarly to Example 1, and prepared the liquid crystal composition, and these were made into Examples 124-149. From the results of Examples 124 to 149, it was confirmed that when various self-aligning monomers were used, the amount of change in vertical alignment and pretilt was also small, and display unevenness and burn-in were also suppressed.

Claims (6)

1. A liquid crystal composition comprising 1 or more kinds of self-aligning monomers having a 1 st mesogenic skeleton, at least one polymerizable group represented by the general formula (PG1), and at least one adsorptive group,

and a liquid crystal composition comprising 2 or more polymerizable monomers selected from the group consisting of polymerizable monomers represented by the following general formula (I) having a chemical structure different from that of the self-aligning monomers,

[ solution 1]

*-S¹¹-P¹¹(PG1)

In the above formula, P¹¹Are groups represented by the following formulae (R-I) to (R-IX),

[ solution 2]

In the formulae (R-I) to (R-IX), R²¹、R³¹、R⁴¹、R⁵¹And R⁶¹Independently of one another, a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a haloalkyl group having 1 to 5 carbon atoms, W¹Is a single bond, -O-or methylene, T¹Is a single bond or COO-, p¹、t¹And q is¹Each independently being 0, 1 or 2, the polymerizable group P¹¹1 or more hydrogen atoms of (a) may be substituted for the adsorption group, or the adsorption group may have a polymerizable group represented by the general formula (PG1) as a substituent,

S¹¹represents a single bond or an alkylene group having 1 to 15 carbon atoms, 1-CH in the alkylene group₂Or 2 or more-CH not adjacent₂May be substituted by the said adsorption group, -O-, -OCO-or-COO-in such a manner that oxygen atoms are not directly adjacent, ＊ in the above formula represents a connecting bond,

[ solution 3]

In the above general formula (I), R¹⁰¹、R¹⁰²、R¹⁰³、R¹⁰⁴、R¹⁰⁵、R¹⁰⁶、R¹⁰⁷、R¹⁰⁸、R¹⁰⁹And R¹¹⁰Each independently represents P¹¹-S¹¹Any one of an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, a halogen atom or a hydrogen atom, P²¹Represented by the following formulae (R-I) to (R-I)Any one of X) or (b) is,

[ solution 4]

In the above formulae (R-I) to (R-IX), R²¹、R³¹、R⁴¹、R⁵¹And R⁶¹Independently of one another, is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, W is a single bond, -O-, or methylene, T is a single bond or-COO-, p, T, and q are each independently 0, 1, or 2,

S²¹represents a single bond or an alkylene group having 1 to 15 carbon atoms, 1 or 2 or more-CH in the alkylene group₂May be substituted by-O-, -OCO-or-COO-in such a way that the oxygen atoms are not directly adjacent,

n¹¹represents a number of 0, 1 or 2,

A¹¹represents a group selected from the group consisting of the following group (a), group (b) and group (c):

(a)1, 4-cyclohexylene radical, 1-CH present in this radical₂Or 2 or more-CH not adjacent₂-may be substituted with-O-;

(b)1, 4-phenylene, 1-CH ═ or nonadjacent 2 or more-CH ═ present in the group may be substituted by-N ═ or; and

(c) naphthalene-2, 6-diyl, 1,2,3, 4-tetrahydronaphthalene-2, 6-diyl or decahydronaphthalene-2, 6-diyl, 1-CH ═ or nonadjacent 2 or more-CH ═ present in naphthalene-2, 6-diyl or 1,2,3, 4-tetrahydronaphthalene-2, 6-diyl may be substituted by — N ═ s,

the group (a), the group (b) and the group (c) may be each independently substituted with an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a halogen, a cyano group, a nitro group or P¹¹-S¹¹-a substitution of a group of formula (I),

L¹⁰and L¹¹Each independently represents a single bond, -OCH₂-、-CH₂O-、-C₂H₄-、-OC₂H₄O-、-COO-、-OCO-、-CH＝CR^a-COO-、-CH＝CR^a-OCO-、-COO-CR^a＝CH-、-OCO-CR^a＝CH-、-(CH₂)_z-COO-、-(CH₂)_z-OCO-、-OCO-(CH₂)_z-、-COO-(CH₂)_z-、-CH＝CH-、-CF₂O-、-OCF₂-or-C ≡ C-, wherein R is^aEach independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, wherein z independently represents an integer of 1 to 4,

when P is present²¹、S²¹、L¹¹And A¹¹When a plurality of the cases exist, they may be the same or different.

2. The liquid crystal composition of claim 1, the adsorption group being a radical having a heteroatom selected from the group consisting of N, O, S, P and Si.

3. The liquid crystal composition according to claim 1 or 2, wherein one of the 2 or more polymerizable monomers represented by the general formula (I) improves the reactivity of the other polymerizable monomer represented by the general formula (I).

4. A liquid crystal composition according to any one of claims 1 to 3, which comprises 1 or 2 or more compounds selected from the group consisting of the compounds represented by the general formulae (N-1), (N-2) and (N-3),

[ solution 5]

In the formula, R^N11、R^N12、R^N21、R^N22、R^N31And R^N32Each independently represents an alkyl group having 1 to 8 carbon atoms, 1 of the alkyl groups being non-adjacent and 2 or more-CH₂-may each be independently substituted by-CH ═ CH-, -C ≡ C-, -O-, -CO-, -COO-or-OCO-,

A^N11、A^N12、A^N21、A^N22、A^N31and A^N32Each independently represents a compound selected from the group consisting of the following (a), (b), (c) and (d)A group of (a):

(a)1, 4-cyclohexylene radical, 1-CH present in this radical₂Or 2 or more-CH not adjacent₂-may be substituted with-O-;

(b)1, 4-phenylene, 1-CH ═ or nonadjacent 2 or more-CH ═ present in the group may be substituted by-N ═ or;

(c) naphthalene-2, 6-diyl, 1,2,3, 4-tetrahydronaphthalene-2, 6-diyl, or decahydronaphthalene-2, 6-diyl, wherein 1-CH ═ or nonadjacent 2 or more-CH ═ present in naphthalene-2, 6-diyl or 1,2,3, 4-tetrahydronaphthalene-2, 6-diyl may be substituted by — N ═ or; and

(d) a 1, 4-cyclohexenylene group,

the above-mentioned group (a), group (b), group (c) and group (d) may each independently be substituted with a cyano group, a fluorine atom or a chlorine atom,

Z^N11、Z^N12、Z^N21、Z^N22、Z^N31and Z^N32Each independently represents a single bond, -CH₂CH₂-、-(CH₂)₄-、-OCH₂-、-CH₂O-、-COO-、-OCO-、-OCF₂-、-CF₂O-, -CH-N-CH-, -CH-, -CF-or-C ≡ C-,

X^N21represents a hydrogen atom or a fluorine atom,

T^N31represents-CH₂-or an oxygen atom,

n^N11、n^N12、n^N21、n^N22、n^N31and n^N32Each independently represents an integer of 0 to 3, n^N11+n^N12、n^N21+n^N22And n^N31+n^N32Each independently is 1,2 or 3, when A^N11～A^N32、Z^N11～Z^N32When a plurality of cases exist, they may be the same or different.

5. The liquid crystal composition according to any one of claims 1 to 4, which comprises 1 or 2 or more compounds selected from the group consisting of compounds represented by the general formula (L):

[ solution 6]

In the formula, R^L1And R^L2Each independently represents an alkyl group having 1 to 8 carbon atoms, 1 of the alkyl groups being non-adjacent and 2 or more-CH₂-may each be independently substituted by-CH ═ CH-, -C ≡ C-, -O-, -CO-, -COO-or-OCO-,

n^L1represents 0, 1,2 or 3,

A^L1、A^L2and A^L3Each independently represents a group selected from the group consisting of (a), (b), and (c):

(a)1, 4-cyclohexylene radical, 1-CH present in this radical₂Or 2 or more-CH not adjacent₂-may be substituted with-O-;

(b)1, 4-phenylene, 1-CH ═ or nonadjacent 2 or more-CH ═ present in the group may be substituted by-N ═ or; and

(c) naphthalene-2, 6-diyl, 1,2,3, 4-tetrahydronaphthalene-2, 6-diyl or decahydronaphthalene-2, 6-diyl, 1-CH ═ or nonadjacent 2 or more-CH ═ present in naphthalene-2, 6-diyl or 1,2,3, 4-tetrahydronaphthalene-2, 6-diyl may be substituted by — N ═ s,

the above-mentioned group (a), group (b) and group (c) may each independently be substituted with a cyano group, a fluorine atom or a chlorine atom,

Z^L1and Z^L2Each independently represents a single bond, -CH₂CH₂-、-(CH₂)₄-、-OCH₂-、-CH₂O-、-COO-、-OCO-、-OCF₂-、-CF₂O-, -CH-N-CH-, -CH-, -CF-or-C ≡ C-,

when n is^L1A plurality of A's being present for 2 or 3^L2In the case of (3), they may be the same or different, when n is^L1A plurality of Z s being 2 or 3^L2In the case of (2), they may be the same or different, but do not include the compounds represented by the general formula (N-1), the general formula (N-2) and the general formula (N-3).

6. The liquid crystal composition according to any one of claims 1 to 5, wherein n is one of the polymerizable monomers represented by the general formula (I)¹¹Is 0, and R¹⁰²、R¹⁰³、R¹⁰⁴、R¹⁰⁵、R¹⁰⁶、R¹⁰⁷、R¹⁰⁸Or R¹⁰⁹Any one of which is an alkyl group having 1 to 18 carbon atoms, R¹⁰¹And R¹¹⁰Each independently is P²¹-S²¹-。