技术领域technical field
本发明涉及反射膜，所述反射膜反射光而具有金属光泽，且具有优异的表面平滑性和镜面反射特性。The present invention relates to a reflective film which reflects light to have metallic luster, and which has excellent surface smoothness and specular reflection characteristics.
背景技术Background technique
以往，作为对反射面赋予金属光泽的方法，可以使用将金属高度抛光而形成反射面的方法。该方法的生产率低，且所使用的金属在加工上存在问题，因此，近年来使用了在塑料上包覆薄金属而成的金属包覆塑料来作为显示装置、照明等的反射膜。通常，金属层的包覆可以使用电镀、真空蒸镀、蒸镀、化学吸附等方法。然而，对于这样的金属包覆而言，随着时间经过金属会被腐蚀，因此必须在金属包覆层上再设置保护层，在生产率、费用方面更加不利。Conventionally, as a method of imparting a metallic luster to a reflective surface, a method of highly polishing a metal to form a reflective surface has been used. The productivity of this method is low, and the metal used is problematic in terms of processing. Therefore, in recent years, metal-clad plastics in which thin metal is coated on plastics have been used as reflective films for display devices, lighting, and the like. Generally, methods such as electroplating, vacuum evaporation, evaporation, and chemical adsorption can be used for coating the metal layer. However, in such a metal cladding, since the metal corrodes with time, it is necessary to provide a protective layer on the metal cladding layer, which is further disadvantageous in terms of productivity and cost.
另外，作为其它方法，还有使用具有多个层的多层光学膜的方法。这些金属光泽的反射膜利用叠层界面的反射特性而对其赋予反射特性，通过精密地控制各层的厚度来表现出高反射特性。In addition, as another method, there is also a method of using a multilayer optical film having a plurality of layers. These metallic luster reflective films are given reflective properties by utilizing the reflective properties of the lamination interface, and exhibit high reflective properties by precisely controlling the thickness of each layer.
作为使用具有多个层的多层光学膜的方法，报道了至少包含第1异种聚合物及第2异种聚合物的反射聚合物体(专利文献1～3)。在这些专利文献中报道了一种反射聚合物体，所述反射聚合物体包含足够的由相互的折射率相差0.03以上的第1聚合物材料及第2聚合物材料形成的交替的层，且各层的半数以上具有0.09μm以下或0.45μm以上的光学厚度。As a method of using a multilayer optical film having a plurality of layers, a reflective polymer body including at least a first different polymer and a second different polymer has been reported (Patent Documents 1 to 3). In these patent documents, a reflective polymer body is reported, which comprises sufficient alternating layers of a first polymer material and a second polymer material having a mutual refractive index difference of more than 0.03, and each layer More than half of them have an optical thickness of 0.09 μm or less or 0.45 μm or more.
现有技术文献prior art literature
专利文献patent documents
专利文献1：日本特开平03-041401号公报Patent Document 1: Japanese Patent Application Laid-Open No. 03-041401
专利文献2：日本特开平04-295804号公报Patent Document 2: Japanese Patent Application Laid-Open No. 04-295804
专利文献3：日本特开平05-193040号公报Patent Document 3: Japanese Patent Application Laid-Open No. 05-193040
发明内容Contents of the invention
发明要解决的课题The problem to be solved by the invention
上述专利文献1～3中公开的多层光学膜需要均匀的多层叠层化、对各层厚度进行精密控制，因此存在制造工序变得复杂、生产率显著降低的隐患。The multilayer optical films disclosed in the aforementioned Patent Documents 1 to 3 require uniform multilayer lamination and precise control of the thickness of each layer, which may complicate the manufacturing process and significantly reduce productivity.
本发明的目的在于提供一种反射膜，所述反射膜具有高反射率和镜面反射特性，带有金属光泽且具有高生产率。An object of the present invention is to provide a reflective film having high reflectance and specular reflection characteristics, metallic luster, and high productivity.
解决课题的方法Solution to the problem
本发明人等经过研究查明，作为充分提高反射率和镜面反射特性的因素，控制分散相的形态是很重要的，从而完成了本发明。The inventors of the present invention found out through studies that it is important to control the morphology of the dispersed phase as a factor to sufficiently improve the reflectance and specular reflection characteristics, and completed the present invention.
本发明提出了一种反射膜，其至少具有一层含有至少2种热塑性树脂、且具有由连续相(I)与分散相(II)形成的海岛结构的层，所述分散相(II)在传送方向(挤出方向)上的平均尺寸(L1)、以及在宽度方向上的平均尺寸(L2)为0.45μm以上且100μm以下，所述分散相(II)在厚度方向上的平均尺寸(L3)为0.01μm以上且0.45μm以下，并且形成该连续相(I)的热塑性树脂(A)与形成该分散相(II)的热塑性树脂(B)的平均折射率差为0.05以上，在该膜的测定波长400nm～700nm的平均反射率为80％以上。The present invention provides a reflective film, which has at least one layer containing at least two kinds of thermoplastic resins and has a sea-island structure formed by a continuous phase (I) and a dispersed phase (II), and the dispersed phase (II) is in The average size (L1) in the conveying direction (extrusion direction) and the average size (L2) in the width direction are 0.45 μm or more and 100 μm or less, and the average size (L3) in the thickness direction of the dispersed phase (II) is ) is 0.01 μm or more and 0.45 μm or less, and the average refractive index difference between the thermoplastic resin (A) forming the continuous phase (I) and the thermoplastic resin (B) forming the dispersed phase (II) is 0.05 or more, in the film The average reflectance of the measured wavelength of 400nm to 700nm is 80% or more.
本发明还提出了一种反射膜，其至少具有一层含有至少2种热塑性树脂、且具有由连续相(I)与分散相(II)形成的海岛结构的层，其中，形成所述连续相(I)的热塑性树脂(A)与形成所述分散相(II)的热塑性树脂(B)中的任一者以聚酯类树脂为主成分，另一者以含氟树脂为主成分，且该含氟树脂的熔融吸热峰温度为130℃以上且250℃以下。The present invention also provides a reflective film having at least one layer containing at least two thermoplastic resins and having a sea-island structure formed by a continuous phase (I) and a dispersed phase (II), wherein the continuous phase is formed Either one of the thermoplastic resin (A) of (I) and the thermoplastic resin (B) forming the dispersed phase (II) contains a polyester-based resin as a main component, and the other contains a fluorine-containing resin as a main component, and The melting endothermic peak temperature of the fluorine-containing resin is not less than 130°C and not more than 250°C.
发明的效果The effect of the invention
本发明提出的上述反射膜均不需要以往的具有多个层的多层光学膜所要求的均匀多层叠层化、对各层厚度的精密控制，因此，在具有高生产率的同时实现了本发明给定的形态控制或熔融吸热峰温度的控制，从而能够提供可以表现出准多层效果、具有高反射特性和镜面反射特性、且具有金属光泽的反射膜。None of the reflective films proposed by the present invention require uniform multilayer lamination and precise control of the thickness of each layer required by conventional multilayer optical films. Given the shape control or the control of the melting endothermic peak temperature, it is possible to provide a reflective film that can exhibit a quasi-multilayer effect, have high reflection characteristics and specular reflection characteristics, and have metallic luster.
具体实施方式Detailed ways
以下，对于作为本发明的实施方式的一个例子的反射膜(称为“本反射膜”)进行说明。Hereinafter, a reflective film (referred to as "this reflective film") as an example of an embodiment of the present invention will be described.
需要说明的是，在本发明中记载为“主成分”时，在没有特别限定的情况下，包含在不损害该主成分功能的范围内允许含有其它成分的含义，特别是包含如下含义：虽然对该主成分的含有比例没有特别指定，但主成分占作为对象的组合物的50质量％以上，优选为70质量％以上，特别优选为90质量％以上(含100％)。另外，在2种以上树脂构成主成分的情况下，作为对象的组合物中各树脂的比例为10质量％以上，优选为20质量％以上，特别优选为30质量％以上。It should be noted that when it is described as "main component" in the present invention, it includes the meaning of allowing other components to be included within the scope of not impairing the function of the main component, especially the following meanings: although The content ratio of the main component is not particularly specified, but the main component accounts for 50% by mass or more, preferably 70% by mass or more, particularly preferably 90% by mass or more (including 100%) of the target composition. In addition, when two or more resins constitute the main component, the proportion of each resin in the target composition is 10% by mass or more, preferably 20% by mass or more, particularly preferably 30% by mass or more.
另外，在本说明书中记载为“X～Y”(X、Y为任意数字)时，在没有特别限定的情况下，代表“X以上且Y以下”的含义，还包含“优选大于X”或“优选小于Y”的含义。In addition, when described as "X to Y" (X, Y are arbitrary numbers) in this specification, unless otherwise specified, it represents the meaning of "more than X and less than Y", and also includes "preferably greater than X" or The meaning of "preferably less than Y".
另外，记载为“X以上”(X为任意数字)或“Y以下”(Y为任意数字)时，包含“优选大于X”或“优选小于Y”的含义。In addition, when described as "X or more" (X is an arbitrary number) or "Y or less" (Y is an arbitrary number), the meaning of "preferably greater than X" or "preferably less than Y" is included.
＜本反射膜＞＜This reflective film＞
本反射膜至少具有一层含有至少2种热塑性树脂、且具有由连续相(I)与分散相(II)形成的海岛结构的层。The reflective film has at least one layer containing at least two kinds of thermoplastic resins and having a sea-island structure formed of the continuous phase (I) and the dispersed phase (II).
一般来说，在混合不同的树脂时，将其相状态大致分为以下4种：(1)完全相容(单相)、(2)海岛结构(多相)、(3)共连续结构(多相)、(4)层状结构(多相)。这里，(2)海岛结构是指在多种成分中的一种的连续相中以粒子状(岛状)分布有另一种的结构。另外，(3)共连续结构是指形成了多种成分分别连续的相且相互混合的结构。另外，(4)层状结构是指虽然各个成分形成连续相，但相互成分独立而不混合的结构。Generally speaking, when mixing different resins, their phase states are roughly divided into the following four types: (1) fully compatible (single phase), (2) sea-island structure (multi-phase), (3) co-continuous structure ( multiphase), (4) layered structure (multiphase). Here, the (2) sea-island structure refers to a structure in which one of the various components is distributed in the form of particles (islands) in the continuous phase. In addition, (3) a co-continuous structure means a structure in which a plurality of components are respectively continuous phases and are mixed with each other. In addition, (4) lamellar structure means that although each component forms a continuous phase, mutual components are independent and do not mix.
本反射膜的海岛结构是指上述(2)的情况，连续相为海部、分散相为岛部。通常，作为分散相的岛部是不连续的，且表现出微小的基本呈球状的结构。本反射膜的岛部虽然是不连续的，但由于上述膜沿传送方向(挤出方向)和宽度方向被拉伸，因此岛部表现出扁平的椭圆状结构或圆盘状结构。是否具有上述结构可以通过扫描电子显微镜(SEM)对本反射膜的MD截面或TD截面进行观察来确认。The sea-island structure of the reflective film refers to the case of (2) above, where the continuous phase is the sea portion and the dispersed phase is the island portion. In general, the islands as the dispersed phase are discontinuous and exhibit a minute, substantially spherical structure. Although the islands of the reflective film are discontinuous, since the film is stretched in the conveying direction (extrusion direction) and the width direction, the islands exhibit a flat oval or disk-like structure. Whether or not it has the above structure can be confirmed by observing the MD cross-section or TD cross-section of the reflective film with a scanning electron microscope (SEM).
(用于本反射膜的热塑性树脂)(Thermoplastic resin used for this reflective film)
作为形成上述连续相(I)的热塑性树脂(A)和形成上述分散相(II)的热塑性树脂(B)，只要不脱离本发明给定的范围就没有特别限定。其中，形成该连续相(I)的热塑性树脂(A)与形成该分散相(II)的热塑性树脂(B)的平均折射率差优选为0.05以上。The thermoplastic resin (A) forming the continuous phase (I) and the thermoplastic resin (B) forming the dispersed phase (II) are not particularly limited as long as they do not depart from the scope of the present invention. Among them, the average refractive index difference between the thermoplastic resin (A) forming the continuous phase (I) and the thermoplastic resin (B) forming the dispersed phase (II) is preferably 0.05 or more.
通过使平均折射率差为0.05以上，能够容易在连续相和分散相的界面处发生光的反射，从而可以赋予高反射特性。When the average refractive index difference is 0.05 or more, reflection of light can easily occur at the interface between the continuous phase and the dispersed phase, and high reflection characteristics can be imparted.
由于以上原因，形成该连续相(I)的热塑性树脂(A)和形成该分散相(II)的热塑性树脂(B)的平均折射率差更优选为0.10以上，进一步优选为0.15以上。For the above reasons, the average refractive index difference between the thermoplastic resin (A) forming the continuous phase (I) and the thermoplastic resin (B) forming the dispersed phase (II) is more preferably 0.10 or more, still more preferably 0.15 or more.
从这样的观点考虑，优选形成上述连续相(I)的热塑性树脂(A)和形成上述分散相(II)的热塑性树脂(B)中的任一者以聚酯类树脂为主成分，另一者以含氟树脂为主成分。From such a viewpoint, it is preferable that either one of the thermoplastic resin (A) forming the continuous phase (I) and the thermoplastic resin (B) forming the dispersed phase (II) contains a polyester resin as the main component, and the other The main component is fluorine-containing resin.
另外，本反射膜优选至少在一个方向上发生了取向，更优选在膜的传送方向(挤出方向)(以下也记为MD)和宽度方向(以下也记为TD)这2个方向上发生了取向。In addition, the reflective film is preferably oriented in at least one direction, and more preferably in two directions, the conveying direction (extrusion direction) (hereinafter also referred to as MD) and the width direction (hereinafter also referred to as TD) of the film. Oriented.
通过拉伸操作等对膜赋予取向，从而使形成上述连续相(I)的热塑性树脂(A)和形成上述分散相(II)的热塑性树脂(B)的折射率发生变化，因此能够更进一步增大上述(A)与上述(B)的折射率差。另外，可以在本发明的给定范围内调节上述分散相(II)在传送方向、宽度方向及厚度方向的平均尺寸，从而能够对本发明的膜赋予更高的反射特性。Orientation is given to the film by a stretching operation or the like to change the refractive index of the thermoplastic resin (A) forming the above-mentioned continuous phase (I) and the thermoplastic resin (B) forming the above-mentioned dispersed phase (II), so that the film can be further enhanced. The refractive index difference between the above-mentioned (A) and the above-mentioned (B) is large. In addition, the average size of the dispersed phase (II) in the transport direction, width direction, and thickness direction can be adjusted within a given range of the present invention, so that higher reflective properties can be imparted to the film of the present invention.
作为使本反射膜至少在一个方向上取向、进一步增大折射率差的方法，可以列举例如按照使形成上述连续相(I)的热塑性树脂(A)与形成上述分散相(II)的热塑性树脂(B)的平均折射率之差的绝对值大于0.05的方式选择上述热塑性树脂(A)与上述热塑性树脂(B)，并且进行拉伸，由此使形成上述连续相(I)的热塑性树脂(A)和/或形成上述分散相(II)的热塑性树脂(B)取向，并利用热塑性树脂(A)与热塑性树脂(B)的双折射率之差调整至优选范围。作为此时的拉伸方法，可以列举例如：自由宽度单轴拉伸、给定宽度单轴拉伸、牵引拉伸法、辊间拉伸法、辊轧法等拉伸方法。As a method of orienting the reflective film in at least one direction to further increase the refractive index difference, for example, the thermoplastic resin (A) forming the above-mentioned continuous phase (I) and the thermoplastic resin (A) forming the above-mentioned dispersed phase (II) can be listed. (B) The above-mentioned thermoplastic resin (A) and the above-mentioned thermoplastic resin (B) are selected so that the absolute value of the difference in average refractive index is greater than 0.05, and stretched, thereby forming the thermoplastic resin of the above-mentioned continuous phase (I) ( A) and/or the thermoplastic resin (B) forming the dispersed phase (II) are oriented and adjusted to a preferred range by using the difference in birefringence between the thermoplastic resin (A) and the thermoplastic resin (B). Examples of stretching methods in this case include stretching methods such as free width uniaxial stretching, predetermined width uniaxial stretching, traction stretching, roll stretching, and roll rolling.
另外，作为其它方法，还可以列举向形成上述连续相(I)的热塑性树脂(A)和/或形成上述分散相(II)的热塑性树脂(B)中添加相容的其它热塑性树脂、折射率调整剂等，从而调整至优选范围的方法等。In addition, as another method, adding compatible other thermoplastic resins, refractive index and/or other thermoplastic resins to the thermoplastic resin (A) forming the above-mentioned continuous phase (I) and/or thermoplastic resin (B) forming the above-mentioned dispersed phase (II) can also be mentioned. Adjusting agents, etc., thereby adjusting the method to the preferred range, etc.
形成连续相(I)的热塑性树脂(A)的内禀双折射率与形成上述分散相(II)的热塑性树脂(B)的内禀双折射率可以均为正值，也可以均为负值。或者还可以任一者为正值、另外一者为负值。The intrinsic birefringence of the thermoplastic resin (A) forming the continuous phase (I) and the intrinsic birefringence of the thermoplastic resin (B) forming the dispersed phase (II) can both be positive or negative . Alternatively, either one may be a positive value and the other may be a negative value.
内禀双折射率是指高分子链处于完全单轴取向的状态、即高分子链在单轴方向上完全伸展的状态下的双折射率，双折射率是指与拉伸方向平行的方向的折射率减去与拉伸方向垂直的方向的折射率而得到的值。因此，内禀双折射率为正值，表示单轴拉伸时与拉伸方向平行的方向的折射率大于与拉伸方向垂直的方向的折射率的状态。Intrinsic birefringence refers to the state where the polymer chain is in a completely uniaxial orientation, that is, the birefringence when the polymer chain is fully stretched in the uniaxial direction, and the birefringence refers to the direction parallel to the stretching direction. The value obtained by subtracting the refractive index in the direction perpendicular to the stretching direction from the refractive index. Therefore, the intrinsic birefringence is a positive value, which means that the refractive index in the direction parallel to the stretching direction is larger than the refractive index in the direction perpendicular to the stretching direction during uniaxial stretching.
一般来说，在内禀双折射率为正值时，与拉伸方向平行的方向的折射率比平均折射率更大。另一方面，在内禀双折射率为负值时，与拉伸方向平行的方向的折射率比平均折射率更小。In general, when the intrinsic birefringence is positive, the refractive index in the direction parallel to the stretching direction is larger than the average refractive index. On the other hand, when the intrinsic birefringence is negative, the refractive index in the direction parallel to the stretching direction is smaller than the average refractive index.
实际上，由于难以使高分子链完全地单轴取向，因此，内禀双折射率的计算是困难的。但是，内禀双折射率是正值还是负值，可以通过确认以适当倍率进行单轴拉伸时的双折射率的值是正值还是负值来进行判断。即，如果双折射率为正值，则可以判断内禀双折射率也为正值。Actually, since it is difficult to completely uniaxially align the polymer chains, the calculation of the intrinsic birefringence is difficult. However, whether the intrinsic birefringence is positive or negative can be judged by checking whether the birefringence is positive or negative when uniaxially stretched at an appropriate magnification. That is, if the birefringence is positive, it can be judged that the intrinsic birefringence is also positive.
另外，上述(A)和上述(B)的平均折射率的大小关系优选与上述(A)和上述(B)的双折射率的大小关系相等。即，上述(A)和上述(B)的平均折射率的大小关系为(A)＞(B)的情况下，上述(A)和上述(B)的双折射率的大小关系优选为(A)＞(B)。在该大小关系相同的情况下，如果上述(A)和上述(B)的平均折射率之差为0.05以上，则在通过拉伸等对本反射膜赋予取向时，连续相(I)与分散相(II)在取向方向上的平均折射率差有增大的倾向，因此应该能使平均折射率之差在拉伸后为0.05以上。在满足该大小关系的情况下，可认为在通过拉伸等对本反射膜赋予取向时，在连续相(I)与分散相(II)的取向方向上难以产生平均折射率差。In addition, it is preferable that the magnitude relation of the average refractive index of the said (A) and the said (B) is equal to the magnitude|size relation of the birefringence index of the said (A) and the said (B). That is, when the magnitude relation of the average refractive index of the above-mentioned (A) and the above-mentioned (B) is (A)>(B), the magnitude relation of the birefringence index of the above-mentioned (A) and the above-mentioned (B) is preferably (A )>(B). When the size relationship is the same, if the difference between the average refractive index of the above (A) and the above (B) is 0.05 or more, when the reflective film is oriented by stretching or the like, the continuous phase (I) and the dispersed phase (II) The average refractive index difference in the orientation direction tends to increase, so the average refractive index difference after stretching should be 0.05 or more. When this size relationship is satisfied, it is considered that an average refractive index difference hardly occurs in the orientation direction of the continuous phase (I) and the dispersed phase (II) when the reflective film is oriented by stretching or the like.
然而，只要至少在单轴方向上发生了取向的本反射膜在本发明给定的范围内，则不限于满足上述(A)和上述(B)的平均折射率与双折射率的大小关系。However, as long as the reflective film oriented at least in the uniaxial direction is within the scope of the present invention, it is not limited to satisfy the relationship between the average refractive index and the birefringence of the above (A) and (B).
上述形成连续相(I)的热塑性树脂(A)与上述形成分散相(II)的热塑性树脂(B)可以是一种热塑性树脂，也可以是两种以上热塑性树脂的混合树脂。The above-mentioned thermoplastic resin (A) forming the continuous phase (I) and the above-mentioned thermoplastic resin (B) forming the dispersed phase (II) may be one type of thermoplastic resin, or may be a mixed resin of two or more types of thermoplastic resins.
其中，优选形成上述连续相(I)的热塑性树脂(A)与形成上述分散相(II)的热塑性树脂(B)中至少一者为结晶性热塑性树脂。如果是结晶性热塑性树脂，则高分子链容易取向，容易增大取向方向上连续相(I)与分散相(II)的折射率差，从而容易使反射特性提高，因此优选。另外，在热处理时，结晶性热塑性树脂容易取向结晶化，从尺寸稳定性的观点考虑也是优选的。Among them, at least one of the thermoplastic resin (A) forming the continuous phase (I) and the thermoplastic resin (B) forming the dispersed phase (II) is preferably a crystalline thermoplastic resin. If it is a crystalline thermoplastic resin, the polymer chains are easily oriented, and the refractive index difference between the continuous phase (I) and the dispersed phase (II) is easily increased in the direction of orientation, thereby improving the reflective properties, which is preferable. In addition, crystalline thermoplastic resins tend to be oriented and crystallized during heat treatment, which is also preferable from the viewpoint of dimensional stability.
需要说明的是，结晶性热塑性树脂是指通常存在结晶熔化峰温度(熔点)的热塑性树脂，更具体而言，是指在按照JIS K7121标准进行的差示扫描量热测定(DSC)中能够观测到熔点的热塑性树脂，包含所谓的半结晶性状态。反之，在DSC中未观测到熔点的热塑性树脂称为“非晶性”。It should be noted that a crystalline thermoplastic resin refers to a thermoplastic resin that generally has a crystalline melting peak temperature (melting point), and more specifically, refers to a thermoplastic resin that can be observed in differential scanning calorimetry (DSC) in accordance with JIS K7121. A thermoplastic resin up to the melting point includes a so-called semi-crystalline state. Conversely, a thermoplastic resin whose melting point is not observed in DSC is called "amorphous".
作为上述结晶性热塑性树脂，对其种类没有特别限定。可以列举例如：聚对苯二甲酸乙二醇酯、聚萘二甲酸乙二醇酯、聚对苯二甲酸丁二醇酯、聚对苯二甲酸丙二醇酯、聚对苯二甲酸1,4-环己烷二甲醇酯、聚琥珀酸乙二醇酯、聚琥珀酸丁二醇酯、聚乳酸、聚ε-己内酰胺等聚酯类树脂、高密度聚乙烯、低密度聚乙烯、直链聚乙烯等聚乙烯类树脂、乙烯-乙酸乙烯酯共聚物、乙烯-(甲基)丙烯酸共聚物、乙烯-(甲基)丙烯酸酯共聚物、乙烯-乙烯醇共聚物、乙烯-氯乙烯共聚物、乙烯-乙酸乙烯酯-一氧化碳共聚物、乙烯-乙酸乙烯酯-氯乙烯共聚物、乙烯-α-烯烃共聚物等烯烃类共聚物、聚丙烯类树脂、聚丁烯类树脂、聚酰胺类树脂、聚甲醛类树脂、聚甲基戊烯类树脂、聚乙烯醇类树脂、聚四氟乙烯、聚偏氟乙烯、乙烯-四氟乙烯类树脂等含氟树脂、纤维素类树脂、聚醚醚酮、聚醚酮、聚苯硫醚、聚对苯二甲酰对苯二胺等工程塑料、超级工程塑料等，可以单独使用这些化合物，也可以组合使用2种以上。其中，优选以聚酯类树脂为主成分，其中更优选结晶性芳香族聚酯类树脂。The kind of the above-mentioned crystalline thermoplastic resin is not particularly limited. Examples include: polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polypropylene terephthalate, polyethylene terephthalate 1,4- Cyclohexanedimethanol, polyethylene glycol succinate, polybutylene succinate, polylactic acid, polyε-caprolactam and other polyester resins, high-density polyethylene, low-density polyethylene, linear polyethylene Polyethylene resin, ethylene-vinyl acetate copolymer, ethylene-(meth)acrylic acid copolymer, ethylene-(meth)acrylate copolymer, ethylene-vinyl alcohol copolymer, ethylene-vinyl chloride copolymer, ethylene - Olefin copolymers such as vinyl acetate-carbon monoxide copolymers, ethylene-vinyl acetate-vinyl chloride copolymers, ethylene-α-olefin copolymers, polypropylene resins, polybutene resins, polyamide resins, polyamide resins, Fluorine-containing resins such as formaldehyde-based resins, polymethylpentene-based resins, polyvinyl alcohol-based resins, polytetrafluoroethylene, polyvinylidene fluoride, and ethylene-tetrafluoroethylene-based resins, cellulose-based resins, polyetheretherketone, Engineering plastics such as polyether ketone, polyphenylene sulfide, and poly-p-phenylene terephthalamide, super engineering plastics, and the like may be used alone or in combination of two or more. Among them, polyester resins are preferred as the main component, and crystalline aromatic polyester resins are more preferred.
优选形成上述连续相(I)的热塑性树脂(A)和形成上述分散相(II)的热塑性树脂(B)中的至少一者以聚酯类树脂为主成分。Preferably, at least one of the thermoplastic resin (A) forming the continuous phase (I) and the thermoplastic resin (B) forming the dispersed phase (II) contains a polyester-based resin as a main component.
(聚酯类树脂)(polyester resin)
优选上述聚酯类树脂为结晶性热塑性树脂。如果对结晶性聚酯类树脂进行拉伸，则高分子链容易取向，容易使连续相(I)与分散相(II)在取向方向上的折射率差增大，容易提高反射特性，因此优选。另外，在热处理时，容易发生取向结晶化，从尺寸稳定性的观点考虑也优选结晶性聚酯类树脂。It is preferable that the above-mentioned polyester-based resin is a crystalline thermoplastic resin. If the crystalline polyester resin is stretched, the polymer chain is easily oriented, and the refractive index difference between the continuous phase (I) and the dispersed phase (II) is easily increased in the orientation direction, and the reflection characteristics are easily improved, so it is preferred . In addition, oriented crystallization is likely to occur during heat treatment, and a crystalline polyester-based resin is also preferable from the viewpoint of dimensional stability.
一般来说，聚酯类树脂的内禀双折射率大多为正值，其中，芳香族聚酯类树脂具有高双折射率，因此容易使连续相(I)与分散相(II)在取向方向上的折射率差增大，容易提高反射特性，因此优选。In general, the intrinsic birefringence of polyester resins is mostly positive. Among them, aromatic polyester resins have high birefringence, so it is easy to align the continuous phase (I) and the dispersed phase (II) in the direction of orientation. The difference in refractive index increases, and it is easy to improve the reflection characteristics, so it is preferable.
另外，优选形成上述连续相(I)的热塑性树脂(A)和形成上述分散相(II)的热塑性树脂(B)中的任一者含有聚酯类树脂作为主成分，另一者含有含氟树脂作为主成分。In addition, it is preferable that either one of the thermoplastic resin (A) forming the continuous phase (I) and the thermoplastic resin (B) forming the dispersed phase (II) contains a polyester-based resin as a main component, and the other contains fluorine-containing resin as the main component.
一般来说，聚酯类树脂、特别是芳香族聚酯类树脂的平均折射率较高，含氟树脂的平均折射率较低，因此容易使连续相(I)与分散相(II)的折射率差增大，容易提高反射特性，因此优选。Generally speaking, the average refractive index of polyester resins, especially aromatic polyester resins, is relatively high, and the average refractive index of fluorine-containing resins is low, so it is easy to make the refractive index of the continuous phase (I) and the dispersed phase (II) The increase in the rate difference makes it easier to improve the reflection characteristics, which is preferable.
作为聚酯类树脂，对其种类没有特别限定。可以列举例如：聚对苯二甲酸乙二醇酯、聚萘二甲酸乙二醇酯、聚对苯二甲酸丁二醇酯、聚对苯二甲酸丙二醇酯、聚对苯二甲酸1,4-环己烷二甲醇酯、聚琥珀酸乙二醇酯、聚琥珀酸丁二醇酯、聚乳酸、聚ε-己内酰胺等聚酯类树脂等。The type of polyester-based resin is not particularly limited. Examples include: polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polypropylene terephthalate, polyethylene terephthalate 1,4- Polyester resins such as cyclohexanedimethanol ester, polyethylene glycol succinate, polybutylene succinate, polylactic acid, and polyε-caprolactam.
上述当中，从具有高平均折射率和高双折射率的观点考虑，优选结晶性芳香族聚酯类树脂，特别优选聚萘二甲酸乙二醇酯类树脂。另外，从调整玻璃化转变温度(Tg)、折射率的观点考虑，还可以将上述树脂组合使用。Among the above, from the viewpoint of having a high average refractive index and high birefringence, crystalline aromatic polyester-based resins are preferable, and polyethylene naphthalate-based resins are particularly preferable. In addition, from the viewpoint of adjusting the glass transition temperature (Tg) and the refractive index, the above resins may be used in combination.
另外，聚对苯二甲酸乙二醇酯(PET)和聚萘二甲酸乙二醇酯(PEN)的混合树脂也是一个优选的例子。由于PEN与PET相容，因此通过向PEN中混合PET，可以调整Tg、折射率。In addition, a mixed resin of polyethylene terephthalate (PET) and polyethylene naphthalate (PEN) is also a preferable example. Since PEN is compatible with PET, Tg and refractive index can be adjusted by mixing PET into PEN.
在使用聚萘二甲酸乙二醇酯类树脂时，从耐冲击性、成膜性的观点考虑，该树脂的重均分子量优选为3万以上，更优选为4万以上。When polyethylene naphthalate-based resin is used, the resin has a weight average molecular weight of preferably 30,000 or more, more preferably 40,000 or more, from the viewpoint of impact resistance and film-forming properties.
从成膜性的观点考虑，上述聚酯类树脂的特性粘度更优选为0.5dl/g以上。From the viewpoint of film-forming properties, the intrinsic viscosity of the polyester-based resin is more preferably 0.5 dl/g or more.
上述聚酯类树脂的玻璃化转变温度(Tg)优选为70℃～120℃的范围，更优选为80℃～120℃的范围。在玻璃化转变温度为70℃以上时，能够保持膜的刚性，在120℃以下时，容易进行拉伸，因此优选该范围。The glass transition temperature (Tg) of the polyester-based resin is preferably in the range of 70°C to 120°C, more preferably in the range of 80°C to 120°C. When the glass transition temperature is 70° C. or higher, the rigidity of the film can be maintained, and when it is 120° C. or lower, stretching is easy, so this range is preferable.
另外，上述聚酯类树脂的熔点(Tm)优选为240℃～270℃的范围，更优选为250℃～270℃的范围。在熔点为240℃以上时，能够赋予其充分的耐热性，在270℃以下时，进行熔融挤出时可以抑制聚萘二甲酸乙二醇酯类树脂以外的共存热塑性树脂的热分解，因此优选该范围。In addition, the melting point (Tm) of the polyester-based resin is preferably in the range of 240°C to 270°C, more preferably in the range of 250°C to 270°C. When the melting point is 240°C or higher, sufficient heat resistance can be imparted, and when the melting point is 270°C or lower, thermal decomposition of coexisting thermoplastic resins other than polyethylene naphthalate-based resins can be suppressed. This range is preferred.
在使用聚萘二甲酸乙二醇酯类树脂作为上述聚酯类树脂的情况下，优选使用YI值在-10～10范围内的树脂，特别优选使用YI值在-3～3范围内的树脂。In the case of using a polyethylene naphthalate resin as the polyester resin, it is preferable to use a resin having a YI value in the range of -10 to 10, and it is particularly preferable to use a resin in the range of -3 to 3. .
在聚萘二甲酸乙二醇酯类树脂由各种混合物构成的情况下，优选各树脂的YI值均在-10～10的范围内。YI值在-10～10的范围内时，可以通过例如组装入液晶显示器等使图像的色彩鲜艳度更好，能够更进一步提高亮度提高率。When the polyethylene naphthalate-based resin is composed of various mixtures, it is preferable that the YI value of each resin is within the range of -10-10. When the YI value is in the range of -10 to 10, for example, by incorporating in a liquid crystal display or the like, the color vividness of the image can be improved, and the luminance improvement rate can be further improved.
作为聚萘二甲酸乙二醇酯类树脂，可以使用市售品。As polyethylene naphthalate resin, a commercially available item can be used.
作为优选的例子，可以列举例如：TEONEX TN8065S(聚萘二甲酸乙二醇酯的均聚物、帝人化成株式会社制造、特性粘度0.71dl/g)、TEONEX TN8065SC(聚萘二甲酸乙二醇酯的均聚物、帝人化成株式会社制造、特性粘度0.55dl/g)、TEONEX TN8756C(聚萘二甲酸乙二醇酯与聚对苯二甲酸乙二醇酯的共聚物、帝人化成株式会社制造、特性粘度0.65dl/g)等。As a preferable example, for example: TEONEX TN8065S (homopolymer of polyethylene naphthalate, manufactured by Teijin Chemicals Co., Ltd., intrinsic viscosity 0.71dl/g), TEONEX TN8065SC (polyethylene naphthalate Homopolymer of Teijin Chemicals Co., Ltd., intrinsic viscosity 0.55dl/g), TEONEX TN8756C (copolymer of polyethylene naphthalate and polyethylene terephthalate, manufactured by Teijin Chemicals Co., Ltd., Intrinsic viscosity 0.65dl/g), etc.
(含氟树脂)(Fluororesin)
另一方面，上述含氟树脂优选熔融吸热峰温度为130℃以上且250℃以下。On the other hand, the fluorine-containing resin preferably has a melting endothermic peak temperature of not less than 130°C and not more than 250°C.
在含氟树脂的熔融吸热峰温度小于130℃的情况下，与聚酯类树脂混炼、挤出时会产生表面粗糙，或者降低反射膜的耐热性，因此不优选。反射膜根据其性质大多被设置在光源附近，因此要求耐热性。因此，优选上述含氟树脂的熔融吸热峰温度为130℃以上，其中更优选为150℃以上，特别优选为180℃以上。When the melting endothermic peak temperature of the fluorine-containing resin is less than 130° C., it is not preferable because the surface becomes rough during kneading and extrusion with the polyester resin, or the heat resistance of the reflective film decreases. Since the reflective film is often installed near the light source due to its properties, heat resistance is required. Therefore, the melting endothermic peak temperature of the fluorine-containing resin is preferably 130°C or higher, more preferably 150°C or higher, and particularly preferably 180°C or higher.
另外，在含氟树脂的熔融吸热峰温度超过300℃的情况下，与聚酯类树脂混炼、挤出时容易促进聚酯类树脂的分解，从而成型变得困难，因此不优选。此外，在含氟树脂的熔融吸热峰温度大于250℃且小于300℃的情况下，容易产生表面粗糙、或者分散相(II)的形态容易变得粗糙，因此不优选。由于以上原因，含氟树脂的熔融吸热峰温度优选为245℃以下，更优选为240℃以下，特别优选为235℃以下。In addition, when the melting endothermic peak temperature of the fluorine-containing resin exceeds 300°C, it is not preferable because the decomposition of the polyester resin tends to be accelerated during kneading and extrusion of the polyester resin, making molding difficult. In addition, when the melting endothermic peak temperature of the fluorine-containing resin exceeds 250° C. and is less than 300° C., it is not preferable because the surface tends to be rough or the form of the dispersed phase (II) tends to become rough. For the above reasons, the melting endothermic peak temperature of the fluorine-containing resin is preferably 245°C or lower, more preferably 240°C or lower, particularly preferably 235°C or lower.
另外，从上述含氟树脂具有低平均折射率的观点、具有聚酯类树脂附近的玻璃化转变温度(50℃～100℃附近)的观点、以及具有优异的拉伸性的观点等考虑，优选为乙烯-四氟乙烯类树脂。In addition, from the viewpoint of the above-mentioned fluorine-containing resin having a low average refractive index, the viewpoint of having a glass transition temperature (around 50°C to 100°C) near the polyester resin, and the viewpoint of having excellent stretchability, it is preferable to use It is ethylene-tetrafluoroethylene resin.
例如，在使用上述乙烯-四氟乙烯类树脂时，从赋予拉伸性的观点考虑，该树脂的玻璃化转变温度(Tg)优选为50℃～100℃的范围，其中更优选为60℃以上或80℃以下的范围。For example, when the above-mentioned ethylene-tetrafluoroethylene resin is used, from the viewpoint of imparting stretchability, the glass transition temperature (Tg) of the resin is preferably in the range of 50°C to 100°C, and more preferably 60°C or higher. Or the range below 80°C.
另外，从赋予耐热性的观点考虑，该含氟树脂的熔点(Tm)优选为130℃～250℃的范围，其中更优选为180℃以上或240℃以下的范围。In addition, from the viewpoint of imparting heat resistance, the melting point (Tm) of the fluorine-containing resin is preferably in the range of 130°C to 250°C, and more preferably in the range of 180°C or higher or 240°C or lower.
作为乙烯-四氟乙烯类树脂，可以使用市售品。Commercially available items can be used as the ethylene-tetrafluoroethylene resin.
作为优选的例子，可以列举例如：Fluon ETFE、Fluon LM-ETFE、Fluon LM-ETFE AH系列(旭硝子株式会社制造)、Neoflon ETFE EP系列(大金工业株式会社制造)等。Preferable examples include Fluon ETFE, Fluon LM-ETFE, Fluon LM-ETFE AH series (manufactured by Asahi Glass Co., Ltd.), Neoflon ETFE EP series (manufactured by Daikin Industries, Ltd.), and the like.
(本反射膜的组成)(Composition of this reflective film)
构成本反射膜的形成上述连续相(I)的热塑性树脂(A)与形成上述分散相(II)的热塑性树脂(B)的混合质量比优选为(A)/(B)＝90质量％/10质量％～50质量％/50质量％，其中更优选为80质量％/20质量％～55质量％/45质量％，其中特别优选为75质量％/25质量％～60质量％/40质量％。通过为上述混合质量比，不会使分散相变得过少，连续相与分散相的界面处的散射减少，不存在降低反射特性等隐患，因此优选。The mixing mass ratio of the thermoplastic resin (A) forming the continuous phase (I) and the thermoplastic resin (B) forming the dispersed phase (II) constituting the reflective film is preferably (A)/(B)=90% by mass/ 10% by mass to 50% by mass/50% by mass, more preferably 80% by mass/20% by mass to 55% by mass/45% by mass, particularly preferably 75% by mass/25% by mass to 60% by mass/40% by mass %. By setting the mixing mass ratio as described above, the dispersed phase is not reduced too much, the scattering at the interface between the continuous phase and the dispersed phase is reduced, and there is no risk of lowering the reflection characteristics, which is preferable.
需要说明的是，本反射膜至少含有上述热塑性树脂(A)和上述热塑性树脂(B)中的各1种即可，还可以含有其它热塑性树脂，例如，可以含有2种以上相当于上述热塑性树脂(B)的热塑性树脂。It should be noted that the reflective film may contain at least one of the above-mentioned thermoplastic resin (A) and the above-mentioned thermoplastic resin (B), and may also contain other thermoplastic resins, for example, may contain two or more types of thermoplastic resins corresponding to the above-mentioned thermoplastic resins. (B) thermoplastic resin.
(其它成分)(other ingredients)
为了提高上述分散相(II)的分散性，可以根据需要向本反射膜中添加相容剂(C)等添加剂。In order to improve the dispersibility of the dispersed phase (II), additives such as a compatibilizer (C) may be added to the reflective film as needed.
作为相容剂(C)，可以根据连续相和分散相的种类从常用的相容剂中选择。可以列举例如由选自聚碳酸酯树脂、酯类树脂、具有环氧基团的树脂、带有唑啉环的树脂、具有吖内酯基的树脂中的至少1种树脂与选自苯乙烯类树脂、聚苯醚、聚酰胺中的至少1种树脂形成的嵌段共聚物或接枝共聚物。其中，从提高分散性的观点考虑，特别优选具有环氧基团、唑啉基的树脂等，特别优选环氧改性的树脂。As the compatibilizer (C), it can be selected from commonly used compatibilizers according to the types of the continuous phase and the dispersed phase. For example, polycarbonate resins, ester resins, resins with epoxy groups, resins with A block copolymer or a graft copolymer formed of at least one resin of oxazoline rings, resins with azlactone groups, and at least one resin selected from styrene resins, polyphenylene ethers, and polyamides . Among them, from the viewpoint of improving dispersibility, it is particularly preferable to have an epoxy group, An oxazoline-based resin or the like, and an epoxy-modified resin is particularly preferable.
相对于上述热塑性树脂(A)和上述热塑性树脂(B)总计100质量份，添加相容剂(C)时的配合比例为0.1～20质量份，优选为0.2～15质量份，更优选为0.2～10质量份，进一步优选为1～10质量份。The blending ratio when adding the compatibilizer (C) is 0.1 to 20 parts by mass, preferably 0.2 to 15 parts by mass, more preferably 0.2 -10 parts by mass, more preferably 1-10 parts by mass.
作为上述相容剂(C)以外的添加剂，在不损害本发明特性的范围内可以添加抗氧剂、热稳定剂、光稳定剂、防水解剂、冲击改良剂等各种添加剂。As additives other than the above-mentioned compatibilizer (C), various additives such as antioxidants, heat stabilizers, light stabilizers, anti-hydrolysis agents, and impact modifiers can be added within the range that does not impair the characteristics of the present invention.
(分散相(II)的分散径)(Dispersion diameter of dispersed phase (II))
本反射膜的上述分散相(II)在传送方向上的平均尺寸(L1)、以及在宽度方向上的平均尺寸(L2)优选为0.45μm以上且100μm以下，上述分散相(II)在厚度方向上的平均尺寸(L3)优选为0.01μm以上且0.45μm以下。分散径可以通过后面叙述的方法来测定。The average size (L1) of the dispersed phase (II) in the reflective film in the conveying direction and the average size (L2) in the width direction are preferably 0.45 μm or more and 100 μm or less, and the dispersed phase (II) is preferably 0.45 μm or more in the thickness direction. The average size (L3) on the surface is preferably not less than 0.01 μm and not more than 0.45 μm. The dispersion diameter can be measured by the method described later.
本反射膜的分散相(II)为扁平的椭圆状或圆盘状。上述分散相(II)在传送方向上的平均尺寸(L1)和在宽度方向上的平均尺寸(L2)为0.45μm以上时，由于充分大于光的波长的数量级，因此入射到膜面内的光能够在连续相(I)与分散相(II)的界面充分地反射，可以赋予膜高反射特性。The dispersed phase (II) of the reflective film has a flat oval or disk shape. When the average size (L1) of the above-mentioned dispersed phase (II) in the transport direction and the average size (L2) in the width direction are 0.45 μm or more, since it is sufficiently larger than the order of the wavelength of light, the light incident on the film surface It can sufficiently reflect at the interface between the continuous phase (I) and the dispersed phase (II), and can impart high reflective properties to the film.
从上述观点考虑，上述L1和L2的下限值更优选为0.80μm以上，进一步优选为1.20μm以上。From the above viewpoint, the lower limit values of L1 and L2 are more preferably 0.80 μm or more, and still more preferably 1.20 μm or more.
另一方面，从提高分散性的观点考虑，上述L1和L2的上限值优选为80μm以下，更优选为50μm以下，进一步优选为20μm以下。On the other hand, from the viewpoint of improving dispersibility, the upper limits of L1 and L2 are preferably 80 μm or less, more preferably 50 μm or less, and still more preferably 20 μm or less.
另外，上述分散相(II)在厚度方向上的平均尺寸(L3)优选为0.01μm以上且0.45μm以下。通过使上述(L3)为0.01μm以上，在本反射膜的厚度方向上的截面中，由上述分散相(II)所形成的非常薄的截面处于多层叠合的状态。即，能够通过具有连续相(I)和分散相(II)形成的海岛结构的至少2种热塑性树脂的含有物来形成准超多层结构。从上述观点考虑，(L3)的下限值更优选为0.02μm以上，进一步优选为0.03μm以上。In addition, the average size (L3) of the dispersed phase (II) in the thickness direction is preferably 0.01 μm or more and 0.45 μm or less. When the above (L3) is 0.01 μm or more, in the cross section in the thickness direction of the reflective film, a very thin cross section formed by the dispersed phase (II) is multilayered. That is, a quasi-super multilayer structure can be formed by containing at least two kinds of thermoplastic resins having a sea-island structure formed by the continuous phase (I) and the dispersed phase (II). From the above viewpoint, the lower limit of (L3) is more preferably 0.02 μm or more, and still more preferably 0.03 μm or more.
上述(L3)为0.45μm以下时，分散相的厚度足够薄，因此能够抑制膜表面的表面粗糙度，从而可以使膜具有金属光泽且赋予高反射率和镜面反射特性。从上述观点考虑，(L3)的上限值更优选为0.35μm以下，进一步优选为0.25μm以下。When the above (L3) is 0.45 μm or less, the thickness of the dispersed phase is sufficiently thin, so the surface roughness of the film surface can be suppressed, and the film can be given metallic luster and high reflectance and specular reflection characteristics. From the above viewpoint, the upper limit of (L3) is more preferably 0.35 μm or less, and still more preferably 0.25 μm or less.
上述分散相(II)在传送方向上的平均尺寸(L1)和在宽度方向上的平均尺寸(L2)为0.45μm以上且100μm以下，上述分散相(II)在厚度方向上的平均尺寸(L3)为0.01μm以上且0.45μm以下，作为使上述尺寸分别在上述范围内的方法，可以列举：使用单螺杆挤出机或双螺杆挤出机等将形成上述连续相(I)的热塑性树脂(A)和形成上述分散相(II)的热塑性树脂(B)充分地混炼至不相容的程度的方法；通过单轴拉伸对形成上述分散相(II)的热塑性树脂(B)充分地进行拉伸的方法；通过同时双轴拉伸对形成上述分散相(II)的热塑性树脂(B)充分地进行拉伸的方法；通过依次双轴拉伸对形成上述分散相(II)的热塑性树脂(B)充分地进行拉伸的方法；通过在T型口模流延法成膜时加快接取速度(流延辊的速度)而对形成上述分散相(II)的热塑性树脂(B)充分地进行拉伸的方法；在流延法中加快接取速度，对形成上述分散相(II)的热塑性树脂(B)进行拉伸，然后再在宽度方向上进行单轴拉伸，从而对形成分散相(II)的热塑性树脂(B)进行拉伸的方法；在用吹胀法成膜时通过加快接取速度而对形成上述分散相(II)的热塑性树脂(B)充分地进行拉伸的方法；通过轧制、压制来对形成上述分散相(II)的热塑性树脂(B)充分地进行拉伸的方法等。The average size (L1) of the above-mentioned dispersed phase (II) in the conveying direction and the average size (L2) in the width direction are 0.45 μm or more and 100 μm or less, and the average size of the above-mentioned dispersed phase (II) in the thickness direction (L3 ) is not less than 0.01 μm and not more than 0.45 μm, and as a method of making the above-mentioned dimensions within the above-mentioned ranges, there may be mentioned: using a single-screw extruder or a twin-screw extruder or the like to form the thermoplastic resin ( A) A method of sufficiently kneading the thermoplastic resin (B) forming the above-mentioned dispersed phase (II) to the extent of incompatibility; fully kneading the thermoplastic resin (B) forming the above-mentioned dispersed phase (II) by uniaxial stretching A method of stretching; a method of sufficiently stretching the thermoplastic resin (B) forming the above-mentioned dispersed phase (II) by simultaneous biaxial stretching; A method in which the resin (B) is fully stretched; by increasing the take-up speed (speed of the casting roll) during film formation by the T-die casting method, the thermoplastic resin (B) that forms the above-mentioned dispersed phase (II) A method of sufficiently stretching; speeding up the take-up speed in the casting method, stretching the thermoplastic resin (B) forming the above-mentioned dispersed phase (II), and then performing uniaxial stretching in the width direction, thereby A method of stretching the thermoplastic resin (B) forming the dispersed phase (II); fully stretching the thermoplastic resin (B) forming the dispersed phase (II) by increasing the take-up speed when forming a film by an inflation method stretching method; a method of sufficiently stretching the thermoplastic resin (B) forming the dispersed phase (II) by rolling or pressing; and the like.
(平均透射率)(average transmittance)
优选本反射膜在测定波长400nm～700nm的平均透射率小于20％。通过使上述平均透射率小于20％，可以确保膜的反射特性。由于上述原因，上述平均透射率更优选小于18％，特别优选小于16％。The reflective film preferably has an average transmittance of less than 20% at a measurement wavelength of 400 nm to 700 nm. By making the above-mentioned average transmittance less than 20%, the reflective properties of the film can be ensured. For the above reasons, the above-mentioned average transmittance is more preferably less than 18%, particularly preferably less than 16%.
为了使上述平均透射率小于20％，可以通过对形成上述连续相(I)的热塑性树脂(A)的平均折射率与形成上述分散相(II)的热塑性树脂(B)的平均折射率之差的绝对值、上述分散相(II)的分散径进行控制来实现。In order to make the above-mentioned average transmittance less than 20%, the difference between the average refractive index of the thermoplastic resin (A) forming the above-mentioned continuous phase (I) and the average refractive index of the thermoplastic resin (B) forming the above-mentioned dispersed phase (II) can be obtained. The absolute value of , the dispersion diameter of the above-mentioned dispersed phase (II) is controlled to realize.
(平均反射率)(average reflectance)
优选本反射膜在测定波长400nm～700nm的平均反射率为80％以上。通过使上述平均反射率为80％以上，可以确保膜的反射特性。由于上述原因，上述平均反射率更优选为82％以上，特别优选为84％以上。The reflective film preferably has an average reflectance of 80% or more at a measurement wavelength of 400 nm to 700 nm. By making the above-mentioned average reflectance 80% or more, the reflection characteristic of a film can be ensured. For the reasons described above, the average reflectance is more preferably 82% or higher, particularly preferably 84% or higher.
为了使上述平均反射率为80％以上，可以通过对形成上述连续相(I)的热塑性树脂(A)的平均折射率与形成上述分散相(II)的热塑性树脂(B)的平均折射率之差的绝对值、上述分散相(II)的分散径进行控制来实现。In order to make the above-mentioned average reflectance 80% or more, the average refractive index of the thermoplastic resin (A) forming the above-mentioned continuous phase (I) and the average refractive index of the thermoplastic resin (B) forming the above-mentioned dispersed phase (II) can be determined. This is achieved by controlling the absolute value of the difference and the dispersion diameter of the above-mentioned dispersed phase (II).
(成膜方法)(film formation method)
作为制造本反射膜的方法，首先，可以将含有至少2种热塑性树脂(A)(B)及其它原料的混合树脂组合物熔融而成膜为片状。此时，对成膜方法没有特别限定，可以例示出T型口模流延法、压延法、吹胀法等。其中，从成膜稳定性、生产效率的观点考虑，优选T型口模流延法。As a method of producing the reflective film, first, a mixed resin composition containing at least two kinds of thermoplastic resins (A) and (B) and other raw materials can be melted to form a film in a sheet shape. At this time, the film forming method is not particularly limited, and examples thereof include a T-die casting method, a calendering method, and an inflation method. Among them, the T-die casting method is preferable from the viewpoint of film formation stability and production efficiency.
采用T型口模流延法的情况下，例如可以使至少2种热塑性树脂干燥并供给于挤出机，加热至树脂的熔点以上的温度使其熔融，然后，从T型口模的狭缝状挤出口挤出熔融的组合物，使其紧密贴合于冷却辊上并冷却而形成流延片。In the case of the T-die casting method, for example, at least two kinds of thermoplastic resins can be dried and supplied to the extruder, heated to a temperature higher than the melting point of the resins to melt them, and then, from the slit of the T-die The melted composition is extruded through the extrusion port, closely attached to the cooling roll and cooled to form a cast sheet.
片的挤出温度根据各种树脂的流动特性而不同，但在使用聚萘二甲酸乙二醇酯类树脂时，优选大致为270℃～340℃，更优选为280℃～320℃的范围。挤出温度在270℃以上时，熔融树脂流动，能够进行充分的片成型，另一方面，挤出温度在340℃以下时，不易发生树脂的热分解等导致的片特性降低，因此优选。The extrusion temperature of the sheet varies depending on the flow characteristics of various resins, but when polyethylene naphthalate-based resin is used, it is preferably about 270°C to 340°C, more preferably in the range of 280°C to 320°C. When the extrusion temperature is 270° C. or higher, the molten resin flows and sufficient sheet molding can be performed. On the other hand, when the extrusion temperature is 340° C. or lower, degradation of sheet properties due to thermal decomposition of the resin is less likely to occur, so it is preferable.
本反射膜优选至少在单轴方向拉伸而成。拉伸方向可以是MD和TD中任一者，也可以是双轴。其中，为了更有效地表现出本反射膜具有的特性，优选在MD、TD两个方向拉伸，从而使膜取向。The reflective film is preferably stretched at least in a uniaxial direction. The stretching direction may be any of MD and TD, and may be biaxial. Among them, in order to express the characteristics of the reflective film more effectively, it is preferable to stretch the film in both directions of MD and TD to orient the film.
作为使膜在MD、TD两个方向上取向的方法，除了上述通过拉伸的方法以外，还可以举出例如：用T型口模流延法成膜时，通过加快接取速度(流延辊的速度)在MD上施加拉伸后在TD上进行拉伸的方法；用吹胀法成膜时，通过加快接取速度在MD上施加拉伸后在TD上进行拉伸的方法等。As a method of orienting the film in the two directions of MD and TD, in addition to the above-mentioned method of stretching, it is also possible to enumerate, for example: when forming a film with a T-die casting method, by accelerating the take-up speed (casting) The speed of the roll) is stretched on the MD and then stretched on the TD; when the film is formed by the inflation method, the stretching is applied on the MD and then stretched on the TD by increasing the pick-up speed.
其中，在考虑成膜稳定性、生产效率的情况下，优选如上所述的将T型口模流延法成膜的片在MD、TD进行双轴拉伸的方法。Among them, in consideration of film formation stability and production efficiency, the method of biaxially stretching in MD and TD the sheet formed by the T-die casting method as described above is preferable.
通过进行上述双轴拉伸，能够使分散相(II)在连续相(I)中基本排列成恒定方向而定形，因此连续相(I)与分散相(II)的折射率差在拉伸方向增大，同时分散相(II)在拉伸方向被拉伸，使分散相的分散径包含在本发明的优选范围内。因此，能够制作分散相(II)具有准超多层结构且具有金属光泽的反射膜。By carrying out the above-mentioned biaxial stretching, the dispersed phase (II) can be substantially arranged in a constant direction in the continuous phase (I) and fixed, so the refractive index difference between the continuous phase (I) and the dispersed phase (II) is greater than that in the stretching direction. increase, while the dispersed phase (II) is stretched in the stretching direction, so that the dispersion diameter of the dispersed phase is included in the preferred range of the present invention. Therefore, it is possible to produce a reflective film in which the dispersed phase (II) has a quasi-super multilayer structure and has metallic luster.
拉伸方法可以采用牵引拉伸法、辊间拉伸法、辊轧法、其它方法中的任一种。As the stretching method, any one of the drawing stretching method, the rolling stretching method, the rolling method, and other methods can be used.
拉伸温度优选为从树脂的玻璃化转变温度(Tg)到(Tg+50℃)范围内的温度。如果拉伸温度在该范围内，则拉伸时不会断裂，能够稳定地进行拉伸。The stretching temperature is preferably a temperature ranging from the glass transition temperature (Tg) of the resin to (Tg+50°C). If the stretching temperature is within this range, the stretching can be performed stably without breaking during stretching.
拉伸倍率没有特别限定。例如，MD和/或TD上为2～9倍，优选MD和/或TD上为3～9倍，特别优选MD和/或TD上为4～7倍。如果拉伸倍率在MD和/或TD上为2倍以上，则容易将分散相(II)的拉伸调整到本发明给定的范围内，因此优选。另外，对其赋予取向，使形成连续相(I)的热塑性树脂(A)与形成分散相的热塑性树脂(B)的折射率差增大，能够获得反射率提高的效果，因此优选。另一方面，拉伸倍率为9倍以下时，能够抑制膜的断裂，因此优选。The draw ratio is not particularly limited. For example, 2 to 9 times in MD and/or TD, preferably 3 to 9 times in MD and/or TD, particularly preferably 4 to 7 times in MD and/or TD. When the stretching ratio is 2 times or more in MD and/or TD, it is easy to adjust the stretching of the dispersed phase (II) within the range specified in the present invention, which is preferable. In addition, it is preferable to provide an orientation to increase the refractive index difference between the thermoplastic resin (A) forming the continuous phase (I) and the thermoplastic resin (B) forming the dispersed phase, thereby obtaining an effect of improving the reflectance. On the other hand, when the draw ratio is 9 times or less, it is possible to suppress breakage of the film, which is preferable.
为了对经过拉伸的片赋予耐热性和尺寸稳定性，优选进行热处理。In order to impart heat resistance and dimensional stability to the stretched sheet, heat treatment is preferably performed.
例如，在使用聚萘二甲酸乙二醇酯类树脂时，热处理温度优选为180～230℃，更优选为180～200℃。热处理需要的处理时间优选为1秒钟～5分钟。For example, when polyethylene naphthalate-based resin is used, the heat treatment temperature is preferably 180 to 230°C, more preferably 180 to 200°C. The treatment time required for the heat treatment is preferably 1 second to 5 minutes.
(厚度)(thickness)
本反射膜的厚度没有特别限定。例如，组装到液晶显示器等的情况下，优选为50μm～250μm，特别优选为50μm～200μm。一般来说，反射膜的厚度增加时，散射次数增加，因此可以提高反射特性。The thickness of the reflective film is not particularly limited. For example, when incorporating into a liquid crystal display etc., it is preferable that it is 50 micrometers - 250 micrometers, and it is especially preferable that it is 50 micrometers - 200 micrometers. In general, as the thickness of the reflective film increases, the number of scattering increases, so that reflection characteristics can be improved.
(拉伸强度和伸长率)(tensile strength and elongation)
本反射膜的拉伸强度优选为150MPa以上。在150MPa以上时能够确保膜的刚性。The tensile strength of the reflective film is preferably 150 MPa or more. The rigidity of the membrane can be ensured at 150 MPa or more.
另外，本反射膜的伸长率优选为30％以上。在30％以上时能够抑制膜的断裂。In addition, the elongation of the reflective film is preferably 30% or more. When it is 30% or more, film breakage can be suppressed.
(收缩率)(Shrinkage)
用后面叙述的方法得到的本反射膜的收缩率优选为5％以下。在5％以下时，耐热性和尺寸稳定性优异，不会产生实际使用上的不良情况。用于使收缩率在上述范围内的方法，如上所述，可以列举在拉伸时进行热处理的方法。The shrinkage rate of the reflective film obtained by the method described later is preferably 5% or less. When it is 5% or less, heat resistance and dimensional stability are excellent, and practical problems do not occur. As a method for making the shrinkage ratio within the above-mentioned range, a method of performing heat treatment during stretching is mentioned as described above.
(镜面反射特性)(specular reflection characteristics)
作为本反射膜的反射特性，优选显示出镜面反射性。As the reflective properties of the reflective film, it is preferable to exhibit specular reflectivity.
作为反射特性的评价方法，有变角光度测定，例如，将相对于膜的面的法线方向设为0°，将入射角设为-X°，在光入射到样品时，样品显示出漫反射性的情况下，其反射光沿各个角度分散反射。另一方面，在样品显示出镜面反射性的情况，反射光的分布显示出以反射角X°为峰值的反射光分布。此时，镜面反射性越高，峰越尖锐。此时，将反射光的峰的最大强度标准化为100％，在横轴受光角、纵轴受光相对峰强度中，将受光相对峰强度为1％、10％时的受光角范围作为镜面反射特性的指标。As an evaluation method of reflective properties, there is goniophotometry. For example, if the normal direction relative to the film surface is set to 0°, and the incident angle is set to -X°, when light is incident on the sample, the sample shows diffuse In the case of reflectivity, the reflected light is scattered and reflected at various angles. On the other hand, in the case where the sample exhibits specular reflectivity, the distribution of reflected light shows a distribution of reflected light having a peak at the reflection angle X°. In this case, the higher the specular reflectivity, the sharper the peak. At this time, the maximum intensity of the reflected light peak is normalized to 100%, and among the light receiving angle on the horizontal axis and the relative peak intensity of light receiving on the vertical axis, the range of the light receiving angle when the relative peak intensity of light is 1% and 10% is used as the specular reflection characteristic index of.
该受光相对峰强度10％时的受光角范围优选为5°以下。在5°以下时，能够得到相对于入射角指向性强的反射光，显示出优异的镜面反射特性。另外，受光相对峰强度1％时的受光角范围优选为40°以下。在40°以下时，能够防止入射光的损失，可以得到相对于入射角指向性强的反射光，显示出优异的镜面反射特性。The range of the light receiving angle when the light receiving relative peak intensity is 10% is preferably 5° or less. When it is 5° or less, reflected light with strong directivity with respect to the incident angle can be obtained, and excellent specular reflection characteristics can be exhibited. In addition, it is preferable that the range of the light receiving angle when the light receiving relative peak intensity is 1% is 40° or less. When it is 40° or less, loss of incident light can be prevented, reflected light with strong directivity with respect to the incident angle can be obtained, and excellent specular reflection characteristics can be exhibited.
(表面粗糙度)(Surface roughness)
作为至少一个表面的算术平均粗糙度Ra，本反射膜的表面粗糙度优选为0.1μm以下，更优选为0.09μm以下。As the arithmetic average roughness Ra of at least one surface, the surface roughness of the reflective film is preferably 0.1 μm or less, more preferably 0.09 μm or less.
作为使算术平均粗糙度Ra在上述范围内的方法，例如，在使用作为含氟树脂的乙烯-四氟乙烯类树脂作为分散相(II)时，可以通过选择其熔点在给定范围内的树脂来调整算术平均粗糙度Ra。通过使该树脂的熔点在130℃以上且250℃以下，可以使拉伸变形变得容易，因此能够防止表面粗糙。As a method of making the arithmetic mean roughness Ra within the above-mentioned range, for example, when using ethylene-tetrafluoroethylene-based resin as a fluorine-containing resin as the dispersed phase (II), it is possible to select a resin whose melting point is within a given range. to adjust the arithmetic mean roughness Ra. By setting the melting point of the resin at 130° C. to 250° C., stretching deformation can be facilitated, thereby preventing surface roughness.
另外，在成膜时，将熔融的树脂组合物从T型口模的狭缝状挤出口挤出，使其紧密贴合于冷却辊上并进行冷却时，可以将熔融的树脂组合物的两面夹入到平滑性优异的膜之间、或者通过将熔融的树脂组合物的一面与平滑性优异的膜进行贴合、或者与平滑性优异的金属膜、金属带接触等来防止表面粗糙。In addition, when forming a film, the molten resin composition is extruded from the slit-shaped extrusion port of the T-die, and when it is closely attached to the cooling roll and cooled, both sides of the molten resin composition can be Surface roughness can be prevented by sandwiching between films with excellent smoothness, or by bonding one side of the molten resin composition to a film with excellent smoothness, or by contacting a metal film or belt with excellent smoothness.
(层结构)(layer structure)
在不超出本发明主旨的范围内，可以根据力学特性、其它改良等需要而向本反射膜中适当导入其它层。例如，可以将表现出漫反射性的反射膜等进行叠合。另外，在形成叠层结构时，各层的树脂组成、厚度比可以相同，也可以不同。Within the range not exceeding the gist of the present invention, other layers can be appropriately introduced into the reflective film according to the needs of mechanical properties and other improvements. For example, a reflective film or the like that exhibits diffuse reflectivity may be laminated. In addition, when forming a laminated structure, the resin composition and thickness ratio of each layer may be the same or different.
(用语说明)(Explanation of terms)
本反射膜的形态没有特别限定，包含板状、片状、膜状、其它形态。The form of the reflective film is not particularly limited, and includes plate-like, sheet-like, film-like, and other forms.
一般来说，“膜”是指，与长度及宽度相比，厚度极小，且最大厚度可任意限定的薄且平的制品，其通常以卷的形式供给(日本工业标准JISK6900)；一般来说，“片”是指，在JIS定义上，薄且平(相对于长度和宽度而言，其厚度较小)的制品。但是，片与膜之间并无明显界限，在本发明中，没有必要在文字上将两者区分开，因此在本发明中，称作“膜”时也包括“片”，称作“片”时也包括“膜”。Generally speaking, "film" refers to a thin and flat product whose thickness is extremely small compared with the length and width, and the maximum thickness can be arbitrarily limited, which is usually supplied in the form of a roll (Japanese Industrial Standard JISK6900); generally Said "sheet" refers to a thin and flat product (thickness is small relative to length and width) according to the definition of JIS. However, there is no clear boundary between sheet and film. In the present invention, it is not necessary to distinguish the two in words. Therefore, in the present invention, "film" also includes "sheet", and it is called "sheet". " also includes "membrane".
本发明提出的反射膜具有高反射特性和镜面反射特性，且具有金属光泽，因此能够广泛用于液晶表示装置、照明装置、装饰用物品等用途。The reflective film proposed by the present invention has high reflective properties, specular reflective properties, and metallic luster, so it can be widely used in applications such as liquid crystal display devices, lighting devices, and decorative articles.
实施例Example
以下示出实施例对本发明进行更具体说明。但本发明并不限定于此，可以在不脱离本发明技术思想的范围内进行各种应用。Examples are shown below to describe the present invention more specifically. However, the present invention is not limited thereto, and various applications can be performed without departing from the technical idea of the present invention.
＜测定及评价方法＞＜Measurement and evaluation method＞
首先，对实施例/比较例中得到的样品的各种物性值的测定方法及评价方法进行说明。First, measurement methods and evaluation methods of various physical property values of samples obtained in Examples/Comparative Examples will be described.
(1)热塑性树脂(A)和热塑性树脂(B)的平均折射率差(1) Average refractive index difference between thermoplastic resin (A) and thermoplastic resin (B)
使用株式会社爱宕制造的阿贝折光仪，以钠D线(589nm)为光源，按照JIS K7124标准对实施例和比较例中使用的各原料的平均折射率进行测定，然后计算出平均折射率差。Using an Abbe refractometer manufactured by Atago Co., Ltd., using sodium D line (589 nm) as a light source, the average refractive index of each raw material used in Examples and Comparative Examples was measured in accordance with JIS K7124, and the average refractive index was calculated. Difference.
(2)厚度(2) Thickness
用1/1000mm的千分表对得到的反射膜的面内5处随机部位进行测定，将其平均值作为厚度。Five in-plane random locations of the obtained reflective film were measured with a dial gauge of 1/1000 mm, and the average value thereof was defined as the thickness.
(3)透射率、反射率的评价方法(3) Evaluation method of transmittance and reflectance
在分光光度计(株式会社日立制作所制：U-4000)上安装积分球，使用氧化铝白板(日立计测器服务株式会社制，210-0740)作为标准白色板，对透射率进行了测定。在300nm到800nm的测定波长范围进行测定，计算出测定波长400nm到700nm的透射率的平均值。另外，关于反射率，使用上述装置，进行基线校正使得氧化铝白板(日立计测器服务株式会社制，210-0740)的反射率为100％，然后进行测定，计算出测定波长400nm到700nm的反射率的平均值。An integrating sphere was attached to a spectrophotometer (manufactured by Hitachi, Ltd.: U-4000), and the transmittance was measured using an alumina white plate (manufactured by Hitachi Instrument Service Co., Ltd., 210-0740) as a standard white plate. . The measurement was performed in the measurement wavelength range of 300 nm to 800 nm, and the average value of the transmittance at the measurement wavelength of 400 nm to 700 nm was calculated. In addition, with regard to the reflectance, using the above-mentioned apparatus, baseline correction was performed so that the reflectance of an alumina white plate (manufactured by Hitachi Instrument Service Co., Ltd., 210-0740) was 100%, and then the measurement was performed to calculate the wavelength of 400 to 700 nm. Average reflectivity.
(4)分散相(II)在传送方向的平均尺寸(L1)(4) The average size of the dispersed phase (II) in the conveying direction (L1)
用扫描电子显微镜(SEM)对得到的膜的MD截面进行观察，由得到的照片计算出分散相(II)的分散径的平均值，按照下述标准进行判断。The MD cross-section of the obtained film was observed with a scanning electron microscope (SEM), and the average value of the dispersion diameter of the dispersed phase (II) was calculated from the obtained photograph, and judged according to the following criteria.
○：平均尺寸(L1)为0.45μm以上且100μm以下。◯: The average size (L1) is 0.45 μm or more and 100 μm or less.
×：平均尺寸(L1)小于0.45μm或大于100μm。×: The average size (L1) is smaller than 0.45 μm or larger than 100 μm.
(5)分散相(II)在宽度方向的平均尺寸(L2)(5) The average size of the dispersed phase (II) in the width direction (L2)
用描电子显微镜(SEM)对得到的膜的TD截面进行观察，由得到的照片计算出分散相(II)的分散径的平均值，按照下述标准进行判断。The TD cross-section of the obtained film was observed with a scanning electron microscope (SEM), and the average value of the dispersion diameter of the dispersed phase (II) was calculated from the obtained photograph, and judged according to the following criteria.
○：平均尺寸(L2)为0.45μm以上且100μm以下。◯: The average size (L2) is 0.45 μm or more and 100 μm or less.
×：平均尺寸(L2)小于0.45μm或大于100μm。X: The average size (L2) is smaller than 0.45 μm or larger than 100 μm.
(6)分散相(II)在厚度方向的平均尺寸(L3)(6) The average size of the dispersed phase (II) in the thickness direction (L3)
用扫描电子显微镜(SEM)对得到的膜的MD截面、TD截面进行观察，由得到的照片计算出分散相(II)的分散径的平均值，按照下述标准进行判断。The MD cross-section and TD cross-section of the obtained film were observed with a scanning electron microscope (SEM), and the average value of the dispersion diameter of the dispersed phase (II) was calculated from the obtained photographs, and judged according to the following criteria.
○：平均尺寸(L3)为0.01μm以上且0.45μm以下。◯: The average size (L3) is 0.01 μm or more and 0.45 μm or less.
×：平均尺寸(L3)小于0.01μm或大于0.45μm。×: The average size (L3) is smaller than 0.01 μm or larger than 0.45 μm.
(7)变角光度测定(7) Variable angle photometry
使用Goniophotometer GR200(株式会社村上色彩技术研究所制，自动变角光度计)，将相对于膜的面的法线方向设为0°，以-45°的入射角使光入射到样品，在-60°到90°的范围接受被膜反射的光。此时，将得到的峰的最大强度标准化为100％，制作了横轴为受光角、纵轴为受光相对峰强度的图。从得到的图中计算出受光相对峰强度为1％、10％时的受光角范围。该受光角范围较窄表示镜面反射性更强。根据得到的结果，按照下述标准进行判断。Using Goniophotometer GR200 (manufactured by Murakami Color Technology Laboratory Co., Ltd., automatic variable goniophotometer), set the normal direction relative to the surface of the film to 0°, and make light incident on the sample at an incident angle of -45°. The range of 60° to 90° receives the light reflected by the film. At this time, the maximum intensity of the obtained peak was normalized to 100%, and a graph was prepared in which the horizontal axis represents the light reception angle and the vertical axis represents the relative peak intensity of light reception. From the obtained graphs, the ranges of the light receiving angles when the light receiving relative peak intensity was 1% and 10% were calculated. A narrower range of acceptance angles means more specular reflectivity. Based on the obtained results, judgment was made according to the following criteria.
＝受光相对峰强度10％＝= 10% relative peak intensity of received light =
○；受光相对峰强度10％时的受光角范围为5°以下。○; The light receiving angle range at 10% of the light receiving relative peak intensity is 5° or less.
×；受光相对峰强度10％时的受光角范围大于5°。×; the light receiving angle range is greater than 5° when the light receiving relative peak intensity is 10%.
＝受光相对峰强度1％＝= 1% relative peak intensity of received light =
○；受光相对峰强度1％时的受光角范围为40°以下。○; The light receiving angle range at 1% of the light receiving relative peak intensity is 40° or less.
×；受光相对峰强度1％时的受光角范围大于40°。×; the light receiving angle range is greater than 40° when the light receiving relative peak intensity is 1%.
(8)算术平均粗糙度Ra(8) Arithmetic mean roughness Ra
依据JISB0601-2001标准。According to JISB0601-2001 standard.
首先，按照9mm宽×6mm长切出反射膜。将切出的反射膜用双面碳胶带(日新EM株式会社制造)粘贴于观察用支架上。然后，为了防止观察时试料表面带电(充电)，在试料周围的6个部位设置导电糊，以10mA在表面上蒸镀Pt-Pd 100秒钟。用ESA-2000(ELIONIX公司制造，非接触式三维粗糙度测量仪)在测定倍率250倍(测定范围：480μm×360μm)下观察上述样品，计算出算术平均粗糙度Ra。First, the reflective film was cut out to a width of 9 mm x a length of 6 mm. The cut reflective film was attached to the holder for observation with double-sided carbon tape (manufactured by Nisshin EM Co., Ltd.). Next, in order to prevent electrification (charge) on the surface of the sample during observation, conductive paste was placed on six places around the sample, and Pt-Pd was vapor-deposited on the surface at 10 mA for 100 seconds. The above sample was observed with ESA-2000 (manufactured by ELIONIX, non-contact three-dimensional roughness measuring instrument) at a measurement magnification of 250 times (measurement range: 480 μm×360 μm), and the arithmetic average roughness Ra was calculated.
(9)拉伸断裂强度、拉伸断裂伸长率(9) Tensile breaking strength, tensile elongation at break
对于得到的反射膜，按照JIS K7161(1994年)标准制作样品，在MD、TD两个方向测定拉伸断裂强度(MPa)和拉伸断裂伸长率(％)。For the obtained reflective film, samples were produced in accordance with JIS K7161 (1994), and tensile breaking strength (MPa) and tensile breaking elongation (%) were measured in both MD and TD directions.
＝拉伸断裂强度＝= Tensile breaking strength =
○：拉伸断裂强度为150MPa以上○: Tensile strength at break is 150 MPa or more
×：拉伸断裂强度小于150MPa×: Tensile breaking strength less than 150MPa
＝拉伸断裂伸长率＝= Tensile elongation at break =
○：拉伸断裂伸长率为30％以上○: Tensile elongation at break is 30% or more
×：拉伸断裂伸长率小于30％×: Tensile elongation at break is less than 30%
(10)热收缩率(10) Heat shrinkage rate
在得到的反射膜上沿测定方向画出100mm间隔的标线，并悬吊于事先预热至130℃的烘箱中。30分钟后，取出样品，自然冷却至室温，然后用金属刻度尺测定样品标线之间的长度，将加热前后的变化作为收缩率。在MD、TD两个方向的测定方向上进行了测定。Marked lines at intervals of 100 mm were drawn along the measurement direction on the obtained reflective film, and hung in an oven preheated to 130° C. in advance. After 30 minutes, take out the sample, cool it down to room temperature naturally, then measure the length between the marking lines of the sample with a metal scale, and use the change before and after heating as the shrinkage rate. The measurement was performed in two measurement directions of MD and TD.
○；热收缩率为5％以下○; heat shrinkage rate is less than 5%
×；热收缩率超过5％。×; heat shrinkage rate exceeds 5%.
＜实施例1、2、3＞<Example 1, 2, 3>
将聚萘二甲酸乙二醇酯树脂(平均折射率：1.646、Tg：118℃、Tm：261℃、特性粘度0.71dl/g、重均分子量5万、内禀双折射率：正，以下记为A-1)和乙烯-四氟乙烯类树脂(旭硝子株式会社制造，Fluon LM-720AP；平均折射率：1.3795、Tg：67℃、Tm：227℃、内禀双折射率：正，以下记为B-1)按照表1和表2所示的质量混合比配合，充分进行混合后，用恒定质量进料器进行供给，并且用φ25mm双螺杆挤出机在290℃下进行挤出混炼，用辊温度110℃的浇铸辊进行冷却固化，制作了厚度950μm的流延片。Polyethylene naphthalate resin (average refractive index: 1.646, Tg: 118°C, Tm: 261°C, intrinsic viscosity 0.71dl/g, weight average molecular weight 50,000, intrinsic birefringence: positive, as follows A-1) and ethylene-tetrafluoroethylene resin (manufactured by Asahi Glass Co., Ltd., Fluon LM-720AP; average refractive index: 1.3795, Tg: 67°C, Tm: 227°C, intrinsic birefringence: positive, as follows For B-1) mix according to the mass mixing ratio shown in Table 1 and Table 2, after fully mixing, use a constant mass feeder to supply, and use a φ25mm twin-screw extruder to carry out extrusion mixing at 290°C , cooling and solidification was performed with a casting roll having a roll temperature of 110° C., and a cast sheet having a thickness of 950 μm was produced.
使用由预热辊、拉伸辊、冷却辊构成的纵向拉伸机，在预热温度120℃、拉伸温度130℃、冷却温度70℃的条件下，利用拉伸辊之间的辊速度差将得到的流延片在MD上拉伸了3倍。Using a longitudinal stretching machine consisting of preheating rolls, stretching rolls, and cooling rolls, under the conditions of preheating temperature 120°C, stretching temperature 130°C, and cooling temperature 70°C, use the difference in roll speed between stretching rolls The obtained cast sheet was stretched 3 times in MD.
然后，使用由预热区、拉伸区、热处理区构成的拉幅机，在预热130℃、拉伸130℃、热处理180℃的条件下，将得到的纵向拉伸膜在TD上拉伸了4倍。预热区、拉伸区、热处理区的通过时间分别为32秒钟。将得到的膜的评价结果示于表1和表2。Then, using a tenter frame consisting of a preheating zone, a stretching zone, and a heat treatment zone, the obtained longitudinally stretched film is stretched on TD under the conditions of preheating at 130°C, stretching at 130°C, and heat treatment at 180°C. 4 times. The passing times of the preheating zone, the stretching zone, and the heat treatment zone were 32 seconds, respectively. Table 1 and Table 2 show the evaluation results of the obtained film.
＜实施例4＞<Example 4>
除了将实施例2中使用的B-1更改为乙烯-四氟乙烯类树脂(旭硝子株式会社制造，Fluon LM-730AP；平均折射率：1.3812、Tg：59℃、Tm：228℃、内禀双折射率：正，以下记为B-2)以外，按照与实施例2相同的方法得到了反射膜。将得到的膜的评价结果示于表1和表2。Except that B-1 used in Example 2 was changed to ethylene-tetrafluoroethylene resin (manufactured by Asahi Glass Co., Ltd., Fluon LM-730AP; average refractive index: 1.3812, Tg: 59°C, Tm: 228°C, intrinsic double Refractive index: positive, hereinafter referred to as B-2), a reflective film was obtained in the same manner as in Example 2. Table 1 and Table 2 show the evaluation results of the obtained film.
＜实施例5＞<Example 5>
除了将实施例2中使用的B-1更改为乙烯-四氟乙烯类树脂(旭硝子株式会社制造，Fluon LM-740AP；平均折射率：1.3819、Tg：62℃、Tm：228℃、内禀双折射率：正，以下记为B-3)以外，按照与实施例2相同的方法得到了反射膜。将得到的膜的评价结果示于表1和表2。Except that B-1 used in Example 2 was changed to ethylene-tetrafluoroethylene resin (manufactured by Asahi Glass Co., Ltd., Fluon LM-740AP; average refractive index: 1.3819, Tg: 62°C, Tm: 228°C, intrinsic double Refractive index: positive, hereinafter referred to as B-3), a reflective film was obtained in the same manner as in Example 2. Table 1 and Table 2 show the evaluation results of the obtained film.
＜比较例1＞＜Comparative example 1＞
除了将实施例2中使用的B-1更改为四氟乙烯-六氟丙烯-偏氟乙烯类树脂(3M公司制造，THV221GZ；平均折射率：1.363、Tm：113℃、内禀双折射率：正，以下记为B-4)以外，按照与实施例2相同的方法得到了反射膜。将得到的膜的评价结果示于表1和表2。Except that B-1 used in Example 2 was changed to tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride resin (manufactured by 3M Company, THV221GZ; average refractive index: 1.363, Tm: 113°C, intrinsic birefringence: A reflective film was obtained in the same manner as in Example 2 except that it was referred to as B-4 below). Table 1 and Table 2 show the evaluation results of the obtained film.
[表1][Table 1]
由上述结果可知，实施例的反射膜具有高反射特性和高镜面反射特性，并且具有优异的表面平滑性和金属光泽。From the above results, it can be seen that the reflective films of Examples have high reflective properties and high specular reflective properties, and have excellent surface smoothness and metallic luster.
与此相对，比较例的片在厚度方向上的平均尺寸(L3)为给定值以上，因此反射特性、镜面反射特性、表面平滑性均不足。On the other hand, the sheet of the comparative example had an average size (L3) in the thickness direction of a given value or more, and thus had insufficient reflection characteristics, specular reflection characteristics, and surface smoothness.
由上述实施例/比较例的结果、以及发明人到目前为止所进行的试验结果等可以认为：对于至少具有一层含有由连续相(I)和分散相(II)形成的海岛结构的层的反射膜而言，只要上述分散相(II)在传送方向的平均尺寸(L1)和在宽度方向的平均尺寸(L2)为0.45μm～100μm，上述分散相(II)在厚度方向的平均尺寸(L3)为0.01μm～0.45μm，形成该连续相(I)的热塑性树脂(A)与形成该分散相(II)的热塑性树脂(B)的平均折射率差为0.05以上，该膜在测定波长400nm～700nm的平均反射率为80％以上，就能够表现出准多层效果，从而具有高反射特性和镜面反射特性，并可以赋予其金属光泽。From the results of the above-mentioned Examples/Comparative Examples, and the test results conducted by the inventors so far, it can be considered that: For the reflective film, as long as the average size (L1) of the above-mentioned dispersed phase (II) in the conveying direction and the average size (L2) in the width direction are 0.45 μm to 100 μm, the average size of the above-mentioned dispersed phase (II) in the thickness direction ( L3) is 0.01 μm to 0.45 μm, the average refractive index difference between the thermoplastic resin (A) forming the continuous phase (I) and the thermoplastic resin (B) forming the dispersed phase (II) is 0.05 or more, and the film is The average reflectance of 400nm-700nm is more than 80%, which can show the quasi-multilayer effect, thereby having high reflection characteristics and specular reflection characteristics, and can give it a metallic luster.
＜比较例2＞＜Comparative example 2＞
除了将实施例2中使用的B-1更改为乙烯-四氟乙烯类树脂(旭硝子株式会社制造，Fluon ETFE C88AXP；平均折射率：1.3894、Tg：81℃、Tm：256℃、内禀双折射率：正，以下记为B-5)以外，按照与实施例2相同的方法得到了反射膜。将得到的膜的评价结果示于表2。Except that B-1 used in Example 2 was changed to ethylene-tetrafluoroethylene resin (manufactured by Asahi Glass Co., Ltd., Fluon ETFE C88AXP; average refractive index: 1.3894, Tg: 81°C, Tm: 256°C, intrinsic birefringence Ratio: Positive, hereinafter referred to as B-5), a reflective film was obtained in the same manner as in Example 2. Table 2 shows the evaluation results of the obtained film.
＜实施例6＞<Example 6>
除了将实施例2的TD拉伸倍率由4倍更改为5倍以外，按照与实施例2相同的方法得到了反射膜。将得到的膜的评价结果示于表3。A reflective film was obtained in the same manner as in Example 2, except that the TD draw ratio in Example 2 was changed from 4 times to 5 times. Table 3 shows the evaluation results of the obtained film.
＜实施例7＞<Example 7>
除了将实施例2的TD拉伸倍率由4倍更改为6倍以外，按照与实施例2相同的方法得到了反射膜。将得到的膜的评价结果示于表3。A reflective film was obtained in the same manner as in Example 2 except that the TD draw ratio in Example 2 was changed from 4 times to 6 times. Table 3 shows the evaluation results of the obtained film.
＜实施例8＞<Example 8>
除了将实施例2的TD拉伸倍率由4倍更改为7倍以外，按照与实施例2相同的方法得到了反射膜。将得到的膜的评价结果示于表3。A reflective film was obtained in the same manner as in Example 2, except that the TD draw ratio in Example 2 was changed from 4 times to 7 times. Table 3 shows the evaluation results of the obtained film.
＜比较例3＞＜Comparative example 3＞
除了将比较例1的TD拉伸倍率由4倍更改为5倍以外，按照与比较例1相同的方法得到了反射膜。将得到的膜的评价结果示于表3。A reflective film was obtained in the same manner as in Comparative Example 1 except that the TD draw ratio of Comparative Example 1 was changed from 4 times to 5 times. Table 3 shows the evaluation results of the obtained film.
＜比较例4＞＜Comparative example 4＞
除了将比较例1的TD拉伸倍率由4倍更改为6倍以外，按照与比较例1相同的方法得到了反射膜。将得到的膜的评价结果示于表3。A reflective film was obtained in the same manner as in Comparative Example 1 except that the TD stretch ratio of Comparative Example 1 was changed from 4 times to 6 times. Table 3 shows the evaluation results of the obtained film.
＜比较例5＞＜Comparative example 5＞
除了将比较例1的TD拉伸倍率由4倍更改为7倍以外，按照与比较例1相同的方法得到了反射膜。将得到的膜的评价结果示于表3。A reflective film was obtained in the same manner as in Comparative Example 1 except that the TD draw ratio of Comparative Example 1 was changed from 4 times to 7 times. Table 3 shows the evaluation results of the obtained film.
＜比较例6＞＜Comparative example 6＞
除了将比较例2的TD拉伸倍率由4倍更改为5倍以外，按照与比较例2相同的方法得到了反射膜。将得到的膜的评价结果示于表3。A reflective film was obtained in the same manner as in Comparative Example 2 except that the TD draw ratio of Comparative Example 2 was changed from 4 times to 5 times. Table 3 shows the evaluation results of the obtained film.
＜比较例7＞＜Comparative example 7＞
除了将比较例2的TD拉伸倍率由4倍更改为6倍以外，按照与比较例2相同的方法得到了反射膜。将得到的膜的评价结果示于表3。A reflective film was obtained in the same manner as in Comparative Example 2 except that the TD draw ratio of Comparative Example 2 was changed from 4 times to 6 times. Table 3 shows the evaluation results of the obtained film.
＜比较例8＞＜Comparative example 8＞
除了将比较例2的TD拉伸倍率由4倍更改为7倍以外，按照与比较例2相同的方法得到了反射膜。将得到的膜的评价结果示于表3。A reflective film was obtained in the same manner as in Comparative Example 2 except that the TD draw ratio of Comparative Example 2 was changed from 4 times to 7 times. Table 3 shows the evaluation results of the obtained film.
[表2][Table 2]
[表3][table 3]
由上述结果可知，本发明的反射膜由于含氟树脂的熔融吸热峰温度在期望范围内、且分散相为非常薄的板状结构多层叠合的状态，因此具有高反射特性和高镜面反射特性，并且具有优异的表面平滑性和金属光泽。From the above results, it can be seen that the reflective film of the present invention has high reflective properties and high specular reflectance because the melting endothermic peak temperature of the fluorine-containing resin is within the desired range, and the dispersed phase is in a state of multilayer stacking of a very thin plate structure. characteristics, and has excellent surface smoothness and metallic luster.
与此相对，比较例1、比较例3～5的片的含氟树脂的熔融吸热峰温度低于期望范围，因此在与聚酯类树脂混炼、挤出时产生表面粗糙，其结果是反射特性、镜面反射特性均不足。On the other hand, in the sheets of Comparative Example 1 and Comparative Examples 3 to 5, the melting endothermic peak temperature of the fluorine-containing resin was lower than the expected range, so the surface roughness occurred during kneading and extrusion with the polyester resin. As a result, Both reflection characteristics and specular reflection characteristics are insufficient.
另外，比较例2、比较例6～8的片的含氟树脂的熔融吸热峰温度高于期望，分散相由大椭圆体形成，入射的光发生散射，因此虽然反射特性显示出良好的值，但镜面反射特性、表面平滑性均不足。In addition, in the sheets of Comparative Example 2 and Comparative Examples 6 to 8, the melting endothermic peak temperature of the fluorine-containing resin was higher than expected, the dispersed phase was formed of a large ellipsoid, and the incident light was scattered, so although the reflection characteristics showed good values , but the specular reflection characteristics and surface smoothness are insufficient.
由上述实施例/比较例的结果、以及发明人到目前为止所进行的试验结果等可以认为：对于至少具有一层含有由连续相(I)和分散相(II)形成的海岛结构的层的反射膜而言，只要形成上述连续相(I)的热塑性树脂(A)与形成上述分散相(II)的热塑性树脂(B)中的任一者以聚酯类树脂为主成分，另一者以含氟树脂为主成分，且该含氟树脂的熔融吸热峰温度为130～250℃，就能够表现出准多层效果，从而具有高反射特性和镜面反射特性，可以赋予其金属光泽。From the results of the above-mentioned Examples/Comparative Examples, and the test results conducted by the inventors so far, it can be considered that: For the reflective film, as long as either one of the thermoplastic resin (A) forming the continuous phase (I) and the thermoplastic resin (B) forming the dispersed phase (II) contains a polyester resin as the main component, the other With fluorine-containing resin as the main component, and the melting endothermic peak temperature of the fluorine-containing resin is 130-250°C, it can exhibit a quasi-multilayer effect, thereby having high reflection characteristics and specular reflection characteristics, and can give it a metallic luster.
| Application Number | Priority Date | Filing Date | Title |
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| JP2013-029709 | 2013-02-19 | ||
| JP2013029707 | 2013-02-19 | ||
| JP2013029709 | 2013-02-19 | ||
| PCT/JP2014/053285WO2014129372A1 (en) | 2013-02-19 | 2014-02-13 | Reflective film, and liquid crystal display device, lighting device and ornamental article, each of which is provided with reflective film |
| Publication Number | Publication Date |
|---|---|
| CN105008968A CN105008968A (en) | 2015-10-28 |
| CN105008968Btrue CN105008968B (en) | 2018-06-19 |
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201480008635.4AActiveCN105008968B (en) | 2013-02-19 | 2014-02-13 | Reflective film, and liquid crystal display device, lighting device, and decorative article provided with the reflective film |
| Country | Link |
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| KR (1) | KR101718276B1 (en) |
| CN (1) | CN105008968B (en) |
| TW (1) | TWI622812B (en) |
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