CN101643571B - Thermosetting resin composition, prepreg prepared from thermosetting resin composition and laminated board for printed circuit - Google Patents

Abstract

The invention relates to a thermosetting resin composition and a prepreg and a laminated board for a printed circuit prepared by using the same, wherein the thermosetting resin composition comprises an epoxy resin with at least one component of a structural formula ; and a curing agent. The epoxy resin composition of the present invention has a molecular structure containing a styrene structure with low polarity, so that the dielectric properties of the resin are optimized, and the dielectric constant and the dielectric loss tangent are reduced compared with those of common epoxy resins. The resin composition of the present invention can also be used for producing resin sheets, resin composite metal copper foils, laminates and printed wiring boards.

Wherein R is:

Description

Translated fromChinese

热固性树脂组合物及用其制成的半固化片与印制电路用层压板Thermosetting resin composition, prepreg and laminate for printed circuit made of it

技术领域technical field

本发明涉及一种树脂组合物，尤其涉及含一种热固性树脂组合物及用其制成的半固化片与印制电路用层压板。The invention relates to a resin composition, in particular to a thermosetting resin composition and a prepreg and a laminated board for printed circuits made of the thermosetting resin composition.

背景技术Background technique

现有的用于印制电路基板的材料中，广泛使用粘接特性优异的环氧树脂。环氧树脂是泛指分子中含有两个或两个以上环氧基团，以脂肪族、脂环族或芳香族等有机化合物为骨架，并能够通过环氧基团在适当的化学试剂(固化剂)存在下反应生成三维网状固化物的化合物的总称。它是热固性高分子材料中重要的品种之一。环氧树脂由于具有良好的化学稳定性、电绝缘性、耐腐蚀性、粘结性和机械强度因而被广泛使用在粘合剂、涂料、层压板、模塑材料、浇铸材料、印制电路基板等领域。Among conventional printed circuit board materials, epoxy resins excellent in adhesive properties are widely used. Epoxy resin generally refers to molecules containing two or more epoxy groups, with organic compounds such as aliphatic, alicyclic or aromatic as the skeleton, and can be cured by appropriate chemical reagents (curing) through epoxy groups. A general term for compounds that react to form a three-dimensional network cured product in the presence of an agent). It is one of the most important varieties of thermosetting polymer materials. Epoxy resins are widely used in adhesives, coatings, laminates, molding materials, casting materials, printed circuit boards due to their good chemical stability, electrical insulation, corrosion resistance, adhesion and mechanical strength. and other fields.

近年来，随着计算机和信息通讯设备高性能化、高功能化以及网络化的发展，为了高速传输及处理大容量信息，操作信号趋向于高频化，因而对电路基板的材料提出了要求。这些要求包含：1、良好的介电性能(即低的介电常数和低的介质损耗因素)，并能在较宽范围的温度和频率条件下保持稳定；2、能够耐PCB加工过程酸碱、高温和高湿环境冲击而不发生吸潮膨胀以致分层爆裂；3、适应高温下的加工和安装工艺要求。以上要求需要环氧树脂在高湿环境中保证较低的吸水率，较低的极性。In recent years, with the development of high-performance, high-functionality and networking of computers and information communication equipment, in order to transmit and process large-capacity information at a high speed, the operating signal tends to be high-frequency, so the material of the circuit board is required. These requirements include: 1. Good dielectric properties (that is, low dielectric constant and low dielectric loss factor), and can remain stable under a wide range of temperature and frequency conditions; 2. Can withstand acid and alkali in PCB processing , high temperature and high humidity environment impact without moisture absorption expansion resulting in layered burst; 3, to meet the processing and installation process requirements under high temperature. The above requirements require epoxy resin to ensure low water absorption and low polarity in a high-humidity environment.

然而，普通的环氧树脂电路基板(FR-4覆铜板)一般介电常数和介质损耗角正切较高(介电常数4.4，介质损耗角正切0.02左右)，高频特性不充分，不能适应信号高频化的要求。However, ordinary epoxy resin circuit substrates (FR-4 copper clad laminates) generally have high dielectric constant and dielectric loss tangent (dielectric constant 4.4, dielectric loss tangent about 0.02), and the high-frequency characteristics are not sufficient, so they cannot adapt to signal high frequency requirements.

比利时专利第627887号揭示了一个使用苯乙烯-马来酸酐共聚物(SMA，见下图的结构式)作为环氧树脂交联剂的环氧树脂组合物。此环氧树脂组合物的缺点是它们的玻璃化转变温度低和热稳定性差，使其不适合于应用在印制电路板(PCB)的基材覆铜板中使用。Belgian Patent No. 627887 discloses an epoxy resin composition using styrene-maleic anhydride copolymer (SMA, see the structural formula in the figure below) as an epoxy resin crosslinking agent. The disadvantages of this epoxy resin composition are their low glass transition temperature and poor thermal stability, making them unsuitable for use in copper clad laminates as base materials for printed circuit boards (PCBs).

美国专利第6509414号使用苯乙烯-马来酸酐共聚物、环氧树脂以及四溴双酚A制作覆铜板。此专利虽然通过采用双酚A或四溴双酚A与苯乙烯-马来酸酐共聚物配合，组成混合固化剂来克服单用苯乙烯-马来酸酐共聚物做环氧树脂固化剂存在的玻璃化转变温度低和热稳定性差缺点。但是因为四溴双酚A分子结构中存在两个极性很大的羟基，四溴双酚A的引入却在一定程度上劣化了体系的介电性能；同时四溴双酚A单体容易在体系中结晶析出使得层压板在制造和应用过程中存在隐患。US Patent No. 6509414 uses styrene-maleic anhydride copolymer, epoxy resin and tetrabromobisphenol A to make copper clad laminates. Although this patent is combined with bisphenol A or tetrabromobisphenol A and styrene-maleic anhydride copolymer to form a mixed curing agent to overcome the glass that exists in the single use of styrene-maleic anhydride copolymer as an epoxy resin curing agent. The disadvantages of low transition temperature and poor thermal stability. However, because there are two very polar hydroxyl groups in the molecular structure of tetrabromobisphenol A, the introduction of tetrabromobisphenol A deteriorates the dielectric properties of the system to a certain extent; Crystallization in the system makes laminates a hidden danger in the process of manufacture and application.

另一方面，在电子材料中，通过环氧树脂的高分子量化降低交联密度改善介电特性，日本专利第2001-240654号揭露使用酚和双环戊二烯的加聚体酚树脂进行缩水甘油醚化的技术。然而这种环氧树脂虽然获得了优良的耐湿性和介电常数，尤其是获得了低的介电常数。但是在高频下的介电损耗因子却偏大，高频特性不充分。On the other hand, in electronic materials, the dielectric properties are improved by reducing the crosslink density by increasing the molecular weight of epoxy resins. Japanese Patent No. 2001-240654 discloses the use of polyaddition polymer phenol resins of phenol and dicyclopentadiene to carry out glycidol Etherification technology. However, this epoxy resin achieves excellent moisture resistance and dielectric constant, especially low dielectric constant. However, the dielectric loss factor at high frequencies is relatively large, and the high-frequency characteristics are not sufficient.

另外，在以上技术方案中，采用苯乙烯一马来酸酐及其衍生物作为固化剂来对环氧树脂组合物进行改进，使得作为体系中主要组分的环氧树脂对固化剂的选择余地变小，也使得在提升介电性能和耐湿热性方面的改性受到了局限。In addition, in the above technical scheme, styrene-maleic anhydride and its derivatives are used as the curing agent to improve the epoxy resin composition, so that the epoxy resin, which is the main component in the system, has more options for the curing agent. The small size also limits the modification in improving the dielectric properties and heat and humidity resistance.

发明内容Contents of the invention

本发明的目的在于提供一种热固性树脂组合物，其含低极性苯乙烯结构，从而与传统采用的马来酸酐一苯乙烯共聚物相比，具有更好的热稳定性及耐湿热性。The object of the present invention is to provide a thermosetting resin composition, which contains a low-polarity styrene structure, so that it has better thermal stability and heat and humidity resistance compared with the traditionally used maleic anhydride-styrene copolymer.

本发明的另一目的在于提供一种用热固性树脂组合物制成的半固化片，其具有低介电常数、低介电损耗因子，耐热性、耐浸焊性、耐湿性、及耐湿热性好的特点。Another object of the present invention is to provide a prepreg made of a thermosetting resin composition, which has low dielectric constant, low dielectric loss factor, good heat resistance, dip soldering resistance, moisture resistance, and heat and humidity resistance. features.

本发明的又一目的在于提供一种用热固性树脂组合物制成的印制电路用层压板，其具有低介电常数、低介电损耗因子，耐热性、耐浸焊性、耐湿性、及耐湿热性好的特点。为了实现上述目的，本发明提供一种热固性树脂组合物，其包含至少一种具有下述结构式(I)的环氧树脂，及固化剂；Another object of the present invention is to provide a laminate for printed circuit made of a thermosetting resin composition, which has low dielectric constant, low dielectric dissipation factor, heat resistance, dip soldering resistance, moisture resistance, and Good heat and humidity resistance characteristics. In order to achieve the above object, the present invention provides a thermosetting resin composition, which comprises at least one epoxy resin with the following structural formula (I), and a curing agent;

其中R为：where R is:

n和m为自然数。n and m are natural numbers.

本发明还提供一种用所述的热固性树脂组合物制备的半固化片，包括基料及通过含浸干燥之后附着在基料上的热固性树脂组合物。The present invention also provides a prepreg prepared with the thermosetting resin composition, comprising a base material and a thermosetting resin composition attached to the base material after being impregnated and dried.

本发明还包括一种用所述的热固性树脂组合物制成的印制电路用层压板，包括数个叠合的半固化片，及设于叠合后的半固化片的单面或双面的金属箔，每一半固化片包括基料及通过含浸干燥之后附着在基料上的热固性树脂组合物。本发明的有益效果是：本发明的环氧树脂组合物因为分子结构中含有极性低的苯乙烯结构，因此该树脂的介电性能得到了优化，介电常数和介质损耗角正切和一般的环氧树脂相比，得到了的降低，随着结构中苯乙烯单元含量的增大，介电常数和介质损耗角正切更小。另外，该树脂组合物和传统采用的马来酸酐苯乙烯共聚物相比，具有更好的热稳定性及耐湿热性。本发明的环氧树脂组合物的环氧树脂可单独使用，或者和其它环氧树脂混合使用，其具有低介电常数、低介电损耗因子，耐热性、耐浸焊性、耐湿性、耐湿热性以及和铜箔的粘结性较好的特点；将此树脂组合物涂覆在基材上得到的半固化片材以及通过层压该半固化片材制造的层压板，其同时具有低介电常数、低介电损耗因子，耐热性、耐浸焊性、耐湿性、耐湿热性以及和铜箔的粘结性较好的特点，可以作为电子仪器用印制线路板。The present invention also includes a laminated board for printed circuits made of the thermosetting resin composition, comprising several laminated prepregs, and metal foils arranged on one or both sides of the laminated prepregs, Each prepreg includes a base material and a thermosetting resin composition attached to the base material after being impregnated and dried. The beneficial effect of the present invention is: the epoxy resin composition of the present invention is because contain the styrene structure with low polarity in molecular structure, so the dielectric property of this resin has been optimized, dielectric constant and dielectric loss tangent and general Compared with the epoxy resin, the reduction is obtained. With the increase of the content of styrene units in the structure, the dielectric constant and dielectric loss tangent are smaller. In addition, compared with the traditionally used maleic anhydride styrene copolymer, the resin composition has better thermal stability and heat and humidity resistance. The epoxy resin of the epoxy resin composition of the present invention can be used alone, or mixed with other epoxy resins, which has low dielectric constant, low dielectric loss factor, heat resistance, dip soldering resistance, moisture resistance, resistance The characteristics of good moisture heat and adhesion to copper foil; the prepreg obtained by coating the resin composition on the base material and the laminate made by laminating the prepreg have low dielectric constant, Low dielectric loss factor, heat resistance, dip soldering resistance, moisture resistance, heat and humidity resistance, and good adhesion with copper foil can be used as printed circuit boards for electronic instruments.

具体实施方式Detailed ways

本发明提供一种热固性树脂组合物，其包含有至少有一种结构式(I)的环氧树脂，及固化剂；The invention provides a thermosetting resin composition, which comprises at least one epoxy resin of structural formula (I), and a curing agent;

其中R为：where R is:

n和m为自然数。n and m are natural numbers.

本发明中含低极性苯乙烯结构的多官能团环氧化合物是使用一种多酚化合物和表卤代醇，在惰性气氛下反应获得。The polyfunctional epoxy compound containing low polarity styrene structure in the present invention is obtained by using a polyphenol compound and epihalohydrin to react under an inert atmosphere.

本发明中用来制作含低极性苯乙烯结构的环氧树脂的多酚化合物在结构中含有低极性的苯乙烯结构，本发明中的多酚化合物是一种不饱和酚和苯乙烯的共聚物，该不饱和酚为对羟基苯乙烯。对羟基苯乙烯/苯乙烯共聚物可由已知的方法合成，如JP61-275307、DongJin Woo，Polymer47(2006)：3287-3291、JungKi Kim，Polymer47(2006)：5799-5809中所描述的方法。本发明中使用的对羟基苯乙烯/苯乙烯共聚物具有以下结构。其中m/n＝0.8～19。In the present invention, the polyphenol compound used to make the epoxy resin containing low polar styrene structure contains low polar styrene structure in the structure, and the polyphenol compound among the present invention is a kind of unsaturated phenol and styrene Copolymer, the unsaturated phenol is p-hydroxystyrene. The p-hydroxystyrene/styrene copolymer can be synthesized by known methods such as those described in JP61-275307, DongJin Woo, Polymer47(2006):3287-3291, JungKi Kim, Polymer47(2006):5799-5809. The p-hydroxystyrene/styrene copolymer used in the present invention has the following structure. Wherein m/n=0.8～19.

本发明中使用的表卤代醇优选表氯醇和表溴代醇，再优选为表氯醇。使用的惰性气氛为氮气。The epihalohydrin used in the present invention is preferably epichlorohydrin and epibromohydrin, more preferably epichlorohydrin. The inert atmosphere used was nitrogen.

一种制备本发明含低极性苯乙烯结构的环氧树脂的方法是采用一步法，即对羟基苯乙烯/苯乙烯共聚物和表氯醇的混合物物直接在碱的作用下缩合得到环氧树脂。其具体步骤为：将有机溶剂、对羟基苯乙烯/苯乙烯共聚物和表氯醇混合，对羟基苯乙烯/苯乙烯共聚物和表氯醇按1∶1～20的摩尔比投料，在惰性气体保护下在50-150℃加热反应1～5小时，同时滴加碱液，碱液和对羟基苯乙烯/苯乙烯共聚物的摩尔比为1～2∶1，反应完毕后经过过滤，水洗除去盐分，减压蒸馏除去过量表氯醇，最后得到含低极性苯乙烯结构的多官能团环氧树脂。A method for preparing the epoxy resin containing low polar styrene structure of the present invention is to adopt a one-step method, that is, the mixture of p-hydroxystyrene/styrene copolymer and epichlorohydrin is directly condensed under the action of alkali to obtain epoxy resin. resin. The specific steps are: mixing organic solvent, p-hydroxystyrene/styrene copolymer and epichlorohydrin, feeding p-hydroxystyrene/styrene copolymer and epichlorohydrin at a molar ratio of 1:1 to 20, inert Heating and reacting at 50-150°C for 1 to 5 hours under gas protection, while adding lye dropwise, the molar ratio of lye and p-hydroxystyrene/styrene copolymer is 1 to 2:1, after the reaction is completed, filter and wash with water Salt content is removed, excess epichlorohydrin is removed by vacuum distillation, and finally a multifunctional epoxy resin containing a low-polarity styrene structure is obtained.

其中使用的碱液可以采用氢氧化钠，氢氧化钾等，所用的碱液最好选用较浓的溶液，优选的浓度在20-50wt％之间。The lye used therein can be sodium hydroxide, potassium hydroxide, etc. The lye used is preferably a thicker solution, with a preferred concentration of 20-50 wt%.

对羟基苯乙烯/苯乙烯共聚物和表氯醇的摩尔比优选为1∶2-15。The molar ratio of p-hydroxystyrene/styrene copolymer to epichlorohydrin is preferably 1:2-15.

有机溶剂的例子包含酮类如甲基乙基酮和甲基异丁基酮，烃类如甲苯和二甲苯，醇类如甲醇、乙醇、伯醇，溶纤剂如甲基溶纤剂和乙基溶纤剂，醚类如二噁烷和二乙氧基乙烷，二甲基亚砜和二甲基甲酰胺。Examples of organic solvents include ketones such as methyl ethyl ketone and methyl isobutyl ketone, hydrocarbons such as toluene and xylene, alcohols such as methanol, ethanol, primary alcohols, cellosolves such as methyl cellosolve and ethyl cellosolve. based cellosolves, ethers such as dioxane and diethoxyethane, dimethylsulfoxide and dimethylformamide.

另一种制备本发明中含低极性苯乙烯结构的多官能团环氧树脂的方法是采用二步法，即先将对羟基苯乙烯/苯乙烯共聚物和表氯醇在催化剂的作用下醚化，然后在碱液的作用下闭环得到环氧树脂，具体包含如下步骤：Another kind of method that contains the multifunctional epoxy resin of low polarity styrene structure among the present invention is to adopt two-step method, namely earlier p-hydroxystyrene/styrene copolymer and epichlorohydrin ether under the effect of catalyzer Then, under the effect of lye, the ring closure obtains epoxy resin, which specifically includes the following steps:

在惰性气体氮气保护下，在对羟基苯乙烯/苯乙烯共聚物和表氯醇中加入催化剂，在50-120℃加热进行醚化反应1～5小时，其中对羟基苯乙烯/苯乙烯共聚物和表氯醇摩尔比为：1∶1～20。Under the protection of inert gas nitrogen, add catalyst to p-hydroxystyrene/styrene copolymer and epichlorohydrin, and heat at 50-120°C for etherification reaction for 1-5 hours, wherein p-hydroxystyrene/styrene copolymer The molar ratio with epichlorohydrin is: 1:1～20.

醚化反应结束后滴加碱溶液进行闭环反应，在80-120℃下反应1～5小时，碱液的加入量为对羟基苯乙烯/苯乙烯共聚物按摩尔比为1～2∶1，反应完毕后经过过滤，水洗除去盐分，减压蒸馏除去过量的表氯醇，最后得到含低极性苯乙烯结构的多官能团环氧树脂。After the etherification reaction is finished, add alkali solution dropwise to carry out ring closure reaction, and react at 80-120°C for 1 to 5 hours. After the reaction is completed, filter, wash with water to remove salt, and distill under reduced pressure to remove excess epichlorohydrin, and finally obtain a multifunctional epoxy resin containing a low-polarity styrene structure.

其中步骤1中对羟基苯乙烯/苯乙烯共聚物和表氯醇的摩尔比在1∶1～20之间，优选1∶2-15。Wherein the molar ratio of p-hydroxystyrene/styrene copolymer to epichlorohydrin in step 1 is between 1:1-20, preferably 1:2-15.

催化剂可使用胆碱及盐、三苯基磷酸盐、铵盐等。铵盐可选自四甲基溴化铵、苄基三甲基氯化铵、苄基三乙基氯化铵、十六烷基三甲基溴化铵、四乙基溴化铵等。As a catalyst, choline and its salt, triphenylphosphate, ammonium salt, etc. can be used. The ammonium salt may be selected from tetramethylammonium bromide, benzyltrimethylammonium chloride, benzyltriethylammonium chloride, cetyltrimethylammonium bromide, tetraethylammonium bromide and the like.

其中使用的碱液可以采用氢氧化钠，氢氧化钾等所用的碱液最好选用较浓的溶液，优选的浓度在20-50wt％之间。Wherein the lye used can be sodium hydroxide, potassium hydroxide, etc. The lye used is preferably a thicker solution, and the preferred concentration is between 20-50wt%.

以上反应的的化学反应式表示如下：The chemical reaction formula of the above reaction is expressed as follows:

其中in

X：Br或Cl或I或FX: Br or Cl or I or F

R：

R:

最终合成本发明热固性树脂组合物中的含低极性苯乙烯结构的环氧树脂的结构式(I)。Finally synthesize the structural formula (I) of the epoxy resin containing the low polarity styrene structure in the thermosetting resin composition of the present invention.

本发明中结构式(I)的环氧树脂的数均分子量(Wn)在1000-50000之间。数均分子量是通过使用四氢呋喃作为流动相，用标准聚苯乙烯为固定相的凝胶渗透色谱法测定。The number average molecular weight (Wn) of the epoxy resin of structural formula (I) in the present invention is between 1000-50000. The number average molecular weight was determined by gel permeation chromatography using tetrahydrofuran as mobile phase and standard polystyrene as stationary phase.

本发明的结构式(I)所示的环氧树脂因为分子结构中含有极性低的苯乙烯结构，因此该树脂的介电性能得到了优化，介电常数和介质损耗角正切和一般的环氧树脂相比，得到了的降低，随着结构中苯乙烯单元含量的增大，介电常数和介质损耗角正切更小。另外，该树脂和对比专利中采用的马来酸酐苯乙烯共聚物相比，具有更好的热稳定性及耐湿热性。The epoxy resin shown in structural formula (I) of the present invention is because contain the low styrene structure of polarity in the molecular structure, so the dielectric property of this resin has been optimized, dielectric constant and dielectric loss tangent and general epoxy Compared with the resin, the decrease is obtained. With the increase of the content of styrene units in the structure, the dielectric constant and dielectric loss tangent are smaller. In addition, compared with the maleic anhydride styrene copolymer used in the comparative patent, the resin has better thermal stability and heat and humidity resistance.

本发明中结构式(I)所示的环氧树脂可以单独使用，也可以和其它类型的环氧树脂混合使用。The epoxy resin represented by structural formula (I) in the present invention can be used alone, and can also be used in combination with other types of epoxy resins.

上述结构式(I)所示的环氧树脂当和其它类型的环氧树脂配合使用时，可以获得良好的工艺性能和耐热性。另外，因为结构式(I)所示的环氧树脂具有低极性的苯乙烯结构，优化了混合树脂体系的介电性能。When the epoxy resin represented by the above structural formula (I) is used in conjunction with other types of epoxy resins, good process performance and heat resistance can be obtained. In addition, because the epoxy resin represented by the structural formula (I) has a low-polarity styrene structure, the dielectric properties of the mixed resin system are optimized.

作为其它类型的环氧树脂，可以提及的是在1个分子树脂中具有多于两个或两个以上环氧基团的环氧树脂，例如双酚A型环氧树脂、双酚F型环氧树脂、联苯型环氧树脂、萘类环氧树脂、脂环族类环氧树脂、间苯二酚型环氧树脂、聚乙二醇型环氧树脂、三官能团环氧树脂、四官能团环氧树脂和酚醛型环氧树脂以及其它类型的环氧树脂，其它类型的环氧树脂不仅限上述几种，上述其它类型的环氧树脂可以1种或2种以上混合使用。As other types of epoxy resins, mention may be made of epoxy resins having more than two or more epoxy groups in 1 molecule of resin, such as bisphenol A type epoxy resin, bisphenol F type Epoxy resin, biphenyl epoxy resin, naphthalene epoxy resin, cycloaliphatic epoxy resin, resorcinol epoxy resin, polyethylene glycol epoxy resin, trifunctional epoxy resin, tetrafunctional epoxy resin Functional group epoxy resins, novolac epoxy resins and other types of epoxy resins, other types of epoxy resins are not limited to the above-mentioned types, and the above-mentioned other types of epoxy resins can be used in combination of one or more than two types.

作为本发明的优选实施例，可以列举的有以下通式所示的环氧树脂：As a preferred embodiment of the present invention, can enumerate have the epoxy resin shown in following general formula:

其中R1代表氢原子、卤素原子或苯基，n是包括0的整数，Wherein R represents a hydrogen atom, a halogen atom or a phenyl group, and n is an integer including 0,

其中X是-CH2-、-O-、-CO-、-SO2-、-S-、-CH(C6H5)-、C(C6H5)2-、CH(CH3)、C(CH3)2或化学式Where X is -CH2-, -O-, -CO-, -SO2-, -S-, -CH(C6H5)-, C(C6H5)2-, CH(CH3), C(CH3)2 or chemical formula

(II)(II)

其中R2代表氢原子、卤素原子、有1-8个线性、支链的烷基或环状脂环族烷基、1-10个碳原子的烷氧基、苯基，n代表0到20的整数。Wherein R2 represents a hydrogen atom, a halogen atom, an alkyl group with 1-8 linear or branched chains or a cycloaliphatic alkyl group, an alkoxy group with 1-10 carbon atoms, or a phenyl group, and n represents 0 to 20 integer.

其中R3代表氢原子、卤素原子、有1-8个线性、支链的烷基或环状脂环族烷基、1-10个碳原子的烷氧基、苯基，n代表0到20的整数。Where R3 represents hydrogen atom, halogen atom, 1-8 linear, branched alkyl or cycloaliphatic alkyl, 1-10 carbon atom alkoxy, phenyl, n represents 0 to 20 integer.

其中R4代表氢原子、卤素原子或苯基，m是包括0的整数Wherein R4 represents a hydrogen atom, a halogen atom or a phenyl group, and m is an integer including 0

其中R5代表氢原子、卤素原子、有1-8个线性、支链的烷基或环状脂环族烷基、1-10个碳原子的烷氧基、苯基，n代表0到20的整数。Wherein R5 represents a hydrogen atom, a halogen atom, an alkyl group with 1-8 linear or branched chains or a cycloaliphatic alkyl group, an alkoxy group with 1-10 carbon atoms, or a phenyl group, and n represents 0 to 20 integer.

作为其他类型的环氧树脂，能够改善树脂组合物的耐湿性、耐热性、特别是改善吸湿后的耐热性。按重量记，结构式(I)所示的环氧树脂∶其它类型的环氧树脂＝1∶0.1～10。As another type of epoxy resin, it is possible to improve the moisture resistance and heat resistance of the resin composition, especially the heat resistance after moisture absorption. Record by weight, the epoxy resin shown in structural formula (I): the epoxy resin of other types=1: 0.1～10.

本发明热固性树脂组合物中的固化剂，可以使用环氧树脂常用的固化剂，例如酸酐、胺类、酚类、多羟基酚及酚醛树脂、苯并噁嗪树脂、双酚、溴化双酚A、酚、苯二酚(如邻苯二酚、间苯二酚、对苯二酚)、羧酸、硅氧烷、聚硅氧烷、及具有-Ph-X-Ph-基团(其中X为CH2、C(CH3)2、CH(CH3)、O、S、C＝O、SO2等)或其它含可与环氧基团反应的化合物，这些固化剂可以单独或相互配合使用。The curing agent in the thermosetting resin composition of the present invention can use commonly used curing agents for epoxy resins, such as acid anhydrides, amines, phenols, polyhydric phenols and phenolic resins, benzoxazine resins, bisphenols, brominated bisphenols A. Phenol, hydroquinone (such as catechol, resorcinol, hydroquinone), carboxylic acid, siloxane, polysiloxane, and -Ph-X-Ph-group (wherein X is CH2, C(CH3)2, CH(CH3), O, S, C=O, SO2, etc.) or other compounds that can react with epoxy groups. These curing agents can be used alone or in conjunction with each other.

胺类的具体实例包括：二氰二胺、二氨基二苯甲烷(DDM)、二氨基二苯砜(DDS)、间苯二胺、二氨基二苯醚(DDE)、间二甲苯二胺、联苯胺、乙二胺、二亚乙基三胺、异佛尔酮二胺、2，4，6-三(二甲胺基甲基)苯酚(商品名为DMP-30)、1，8-二氮杂-双环[5.4.0]十一烯-7(简称DBU)等。Specific examples of amines include: dicyandiamine, diaminodiphenylmethane (DDM), diaminodiphenylsulfone (DDS), m-phenylenediamine, diaminodiphenyl ether (DDE), m-xylylenediamine, Benzidine, ethylenediamine, diethylenetriamine, isophoronediamine, 2,4,6-tris(dimethylaminomethyl)phenol (trade name DMP-30), 1,8- Diaza-bicyclo[5.4.0]undecene-7 (abbreviated as DBU), etc.

酸酐的具体实例包括：邻苯二甲酸酐、四氢邻苯二甲酸酐、六氢邻苯二甲酸酐、甲基四氢邻苯二甲酸酐、甲基纳迪克酸酐、甲基六氢邻苯二甲酸酐、十二烯基琥珀酸酐、氯茵酸酐、顺丁烯二酸酐、聚壬二酸酐、均苯四甲酸二酐、偏苯三酸酐等。Specific examples of acid anhydrides include: phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, methylhexahydrophthalic anhydride Diformic anhydride, dodecenyl succinic anhydride, chlorendic anhydride, maleic anhydride, polyazelaic anhydride, pyromellitic dianhydride, trimellitic anhydride, etc.

羧酸包括：邻苯二甲酸、间苯二甲酸、对苯二甲酸、四氢化邻苯二甲酸、六氢化邻苯二甲酸4-羟基苯甲酸、水杨酸、1，3-二羧基环己烷等。Carboxylic acids include: phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, 4-hydroxybenzoic acid, salicylic acid, 1,3-dicarboxycyclohexyl alkanes etc.

多羟基酚包括：三(4-羟基苯基)甲烷、三(4羟基苯基)乙烷、三(4-羟基苯基)丙烷、三(4-羟基苯基)丁烷、三(3-甲基-4-羟基苯基)甲烷、三(3，5-二甲基-羟基苯基)甲烷、四(4羟基苯基)乙烷、四(3-甲基-4-羟基苯基)乙烷等。Polyhydric phenols include: tris(4-hydroxyphenyl)methane, tris(4-hydroxyphenyl)ethane, tris(4-hydroxyphenyl)propane, tris(4-hydroxyphenyl)butane, tris(3- Methyl-4-hydroxyphenyl)methane, tris(3,5-dimethyl-hydroxyphenyl)methane, tetrakis(4-hydroxyphenyl)ethane, tetrakis(3-methyl-4-hydroxyphenyl) Ethane, etc.

双酚的具体实例包括：2，6-二羟基萘、2，2-双(4-羟基苯基)丙烷(双酚A)、2-(3-羟基苯基)2-(4’-羟基苯基)丙烷、双(4-羟基苯基)甲烷(双酚F)、双(4-羟基苯基)砜(双酚S)、双(4-羟基苯基)甲基环己烷等。Specific examples of bisphenols include: 2,6-dihydroxynaphthalene, 2,2-bis(4-hydroxyphenyl)propane (bisphenol A), 2-(3-hydroxyphenyl)2-(4'-hydroxy Phenyl)propane, bis(4-hydroxyphenyl)methane (bisphenol F), bis(4-hydroxyphenyl)sulfone (bisphenol S), bis(4-hydroxyphenyl)methylcyclohexane, and the like.

酚醛树脂的具体实例包括：苯酚甲醛缩合物、甲酚酚醛缩合物、苯并噁嗪树脂、双酚A酚醛缩合物等。Specific examples of the phenol resin include: phenol formaldehyde condensate, cresol novolac condensate, benzoxazine resin, bisphenol A novolac condensate, and the like.

固化剂的用量视固化剂中反应活性氢当量与环氧树脂的环氧当量而定。固化剂中反应活性氢当量与环氧树脂的环氧当量比在0.5～1.5之间。反应活性氢当量与环氧树脂的环氧当量比优选为0.7-1.4。对于二氰二胺来说此比例控制在0.3-0.8之间，优选为0.4-0.7。The amount of curing agent depends on the reactive hydrogen equivalent in the curing agent and the epoxy equivalent of the epoxy resin. The ratio of the reactive hydrogen equivalent in the curing agent to the epoxy equivalent of the epoxy resin is between 0.5 and 1.5. The ratio of the reactive hydrogen equivalent to the epoxy equivalent of the epoxy resin is preferably 0.7-1.4. For dicyandiamide, this ratio is controlled between 0.3-0.8, preferably 0.4-0.7.

本发明的热固性树脂组合物中还可以包含有填料，所选用的填料，可以提及的是无机填料例如氢氧化铝、氢氧化镁、高岭土、水滑石、氧化钛、硅酸钙、氧化铍、氮化硼、玻璃粉或硅微粉、硼酸锌、铝氮化合物、氮化硅、碳化硅、氧化镁、氧化锆、莫来石、二氧化钛、钛酸钾、中空玻璃微珠、聚四氟乙烯粉末、聚苯乙烯粉体等粉体以及钛酸钾、碳化硅、氮化硅、氧化铝等单晶纤维、玻璃短纤维等。硅微粉可以使球型二氧化硅、熔融二氧化硅、结晶性二氧化硅。填料的添加可以是以上的一种或几种混合使用，其使用量在热固性树脂组合组合物中占0～60wt％。The thermosetting resin composition of the present invention may also contain fillers, the selected fillers, inorganic fillers such as aluminum hydroxide, magnesium hydroxide, kaolin, hydrotalcite, titanium oxide, calcium silicate, beryllium oxide, Boron nitride, glass powder or silicon powder, zinc borate, aluminum nitride, silicon nitride, silicon carbide, magnesium oxide, zirconia, mullite, titanium dioxide, potassium titanate, hollow glass beads, polytetrafluoroethylene powder , polystyrene powder and other powders, potassium titanate, silicon carbide, silicon nitride, alumina and other single crystal fibers, glass short fibers, etc. Silica powder can be made of spherical silica, fused silica, and crystalline silica. The addition of fillers may be one or more of the above in combination, and the usage amount thereof accounts for 0-60 wt% in the thermosetting resin composition.

本发明的热固性树脂组合物中，视情况需要另外添加催化剂，催化剂包括三级胺、三级膦、季铵盐、季鏻盐或咪唑化合物。三级胺的实例为：三乙基胺、三丁基胺、二甲基胺乙醇、N，N-二甲基-胺基甲基酚、苯甲基二甲基胺等；三级膦的实例包括：三苯基膦等；季铵盐的实例包括：四甲基溴化铵、四甲基氯化铵、四甲基碘化铵、苄基三甲基氯化铵、苄基三乙基氯化铵、十六烷基三甲基溴化铵等；季鏻盐的具体实例包括：四丁基氯化鏻、四丁基溴化鏻、四丁基碘化鏻、四苯基氯化鏻、四苯基溴化鏻、四苯基碘化鏻、乙基三苯基氯化鏻、丙基三苯基氯化鏻、丙基三苯基溴化鏻、丙基三苯基碘化鏻、丁基三苯基氯化鏻、丁基三苯基溴化鏻、丁基三苯基碘化鏻等；咪唑类化合物实例包括：2-甲基咪唑、2-乙基-4甲基咪唑、2-苯基咪唑、2-十一烷基咪唑、1-苄基-2-甲基咪唑、2-十七烷基咪唑、2-异丙基咪唑、2-苯基-4-甲基咪唑、2-十二烷基咪唑、1-氰乙基-2-甲基咪唑等，上述催化剂可以是单一形式或其混合物使用。In the thermosetting resin composition of the present invention, a catalyst is additionally added as needed, and the catalyst includes a tertiary amine, a tertiary phosphine, a quaternary ammonium salt, a quaternary phosphonium salt or an imidazole compound. Examples of tertiary amines are: triethylamine, tributylamine, dimethylamine ethanol, N,N-dimethyl-aminomethylphenol, benzyldimethylamine, etc.; Examples include: triphenylphosphine, etc.; examples of quaternary ammonium salts include: tetramethylammonium bromide, tetramethylammonium chloride, tetramethylammonium iodide, benzyltrimethylammonium chloride, benzyltriethylammonium Ammonium chloride, cetyltrimethylammonium bromide, etc.; specific examples of quaternary phosphonium salts include: tetrabutylphosphonium chloride, tetrabutylphosphonium bromide, tetrabutylphosphonium iodide, tetraphenylphosphonium chloride Phosphonium chloride, tetraphenylphosphonium bromide, tetraphenylphosphonium iodide, ethyltriphenylphosphonium chloride, propyltriphenylphosphonium chloride, propyltriphenylphosphonium bromide, propyltriphenylphosphonium iodide Phosphonium chloride, butyltriphenylphosphonium chloride, butyltriphenylphosphonium bromide, butyltriphenylphosphonium iodide, etc.; examples of imidazole compounds include: 2-methylimidazole, 2-ethyl-4-methyl Imidazole, 2-phenylimidazole, 2-undecylimidazole, 1-benzyl-2-methylimidazole, 2-heptadecylimidazole, 2-isopropylimidazole, 2-phenyl-4- Methylimidazole, 2-dodecylimidazole, 1-cyanoethyl-2-methylimidazole, etc., the above catalysts can be used in a single form or a mixture thereof.

催化剂的使用量视环氧树脂种类、固化剂的种类和催化剂种类而定。本发明中催化剂的用量相对于热固性树脂组合物的总量为0.001～5.0wt％，优选为0.05～4.0wt％，更优选为0.005～3.0wt％。催化剂的用量过多(超过5.0wt％)将会导致环氧树脂组合物的反应性过快，对副产物的生成及固化反应的转化率的均匀性产生不良影响；若组合物中催化剂的用量低于0.005wt％，反应性过慢，不利于半固化片的制作。使用催化剂的一个原则为，胶水的凝胶化时间不应低于120s。The amount of catalyst used depends on the type of epoxy resin, the type of curing agent and the type of catalyst. The amount of the catalyst used in the present invention is 0.001-5.0 wt%, preferably 0.05-4.0 wt%, more preferably 0.005-3.0 wt%, relative to the total amount of the thermosetting resin composition. Too much (over 5.0wt%) consumption of catalyst will cause the reactivity of epoxy resin composition to be too fast, and the uniformity of the generation of by-product and the conversion rate of curing reaction will be adversely affected; if the consumption of catalyst in composition If it is less than 0.005wt%, the reactivity is too slow, which is not conducive to the production of prepregs. A principle of using a catalyst is that the gelation time of the glue should not be lower than 120s.

根据本发明作为阻燃剂的例子，例如溴化苯酚树脂、乙撑双四溴邻苯二甲酰亚胺、1，2-双(2，3，4，5，6-五溴苯基)乙烷、六溴代苯、溴化聚碳酸酯等卤素类阻燃剂，磷酸三苯酯和双酚A双(二苯基磷酸酯)等磷酸酯类阻燃剂，红磷、氢氧化铝、氢氧化镁和三氧化锑等无机阻燃剂等。Examples of flame retardants according to the invention, such as brominated phenol resins, ethylene bis-tetrabromophthalimide, 1,2-bis(2,3,4,5,6-pentabromophenyl) Halogen flame retardants such as ethane, hexabromobenzene, and brominated polycarbonate, phosphate flame retardants such as triphenyl phosphate and bisphenol A bis(diphenyl phosphate), red phosphorus, aluminum hydroxide , magnesium hydroxide and antimony trioxide and other inorganic flame retardants.

本发明的环氧树脂组合物中可以添加溶剂调制成胶水。可使用的溶剂的例子包含酮类如丙酮、甲基乙基酮和甲基异丁基酮；烃类如甲苯和二甲苯；醇类如甲醇、乙醇、伯醇；醚类如乙二醇单甲醚、丙二醇单甲醚；酯类如丙二醇甲醚醋酸酯、乙酸乙酯；非质子溶剂如N，N-二甲基甲酰胺、N，N-二乙基甲酰胺，上述溶剂中的一种或多种可以与另一种任意混合使用。A solvent can be added to the epoxy resin composition of the present invention to prepare glue. Examples of usable solvents include ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; hydrocarbons such as toluene and xylene; alcohols such as methanol, ethanol, primary alcohols; ethers such as ethylene glycol mono Methyl ether, propylene glycol monomethyl ether; esters such as propylene glycol methyl ether acetate, ethyl acetate; aprotic solvents such as N,N-dimethylformamide, N,N-diethylformamide, one of the above solvents One or more can be used in any combination with another.

本发明还提供一种用所述的热固性树脂组合物制备的半固化片，包括基料及通过含浸干燥之后附着在基料上的热固性树脂组合物。The present invention also provides a prepreg prepared with the thermosetting resin composition, comprising a base material and a thermosetting resin composition attached to the base material after being impregnated and dried.

本发明还包括一种用所述的热固性树脂组合物制成的印制电路用层压板，包括数个叠合的半固化片，及设于叠合后的半固化片的单面或双面的金属箔，每一半固化片包括基料及通过含浸干燥之后附着在基料上的热固性树脂组合物。此外，本发明的树脂组合物还可以用作来制作树脂片、树脂复合物金属铜箔、层压板、印制线路板。The present invention also includes a laminated board for printed circuits made of the thermosetting resin composition, comprising several laminated prepregs, and metal foils arranged on one or both sides of the laminated prepregs, Each prepreg includes a base material and a thermosetting resin composition attached to the base material after being impregnated and dried. In addition, the resin composition of the present invention can also be used to make resin sheets, resin composite metal copper foils, laminated boards, and printed wiring boards.

本发明环氧树脂组合物制作树脂片的方法列举如下，但制备树脂片的方法不限于此。将上述环氧树脂组合物涂覆于载体膜上，该载体膜可为聚酯膜或聚酰亚胺膜，厚度在5-150μm。然后在100-250℃下加热10秒-30分钟，形成片材，所形成的树脂片厚度在5-100μm。The method for preparing the resin sheet from the epoxy resin composition of the present invention is listed below, but the method for preparing the resin sheet is not limited thereto. The above epoxy resin composition is coated on a carrier film, the carrier film can be a polyester film or a polyimide film with a thickness of 5-150 μm. Then heat at 100-250° C. for 10 seconds to 30 minutes to form a sheet, and the thickness of the formed resin sheet is 5-100 μm.

本发明环氧树脂组合物制作树脂复合金属铜箔(RCC)的方法列举如下，然而制作树脂复合金属铜箔的方法不仅限于此。作为金属箔，可以使用铜、黄铜、铝、镍、以及这些金属的合金或复合金属箔，金属箔的厚度在5-150μm。通过手工或机械滚涂装置将所述的环氧树脂组合物胶水涂覆到上述金属箔上，然后将此涂覆有环氧树脂组合物的金属箔进行加热干燥，使得环氧树脂组合物处于半固化状态(B-Stage)，此处的加热温度在100-250℃，加热时间为10秒-30分钟，最后形成的树脂复合金属的树脂层厚度在1-150μm，该树脂复合物金属铜箔可作为印制线路板的内层或外层而对印制线路板进行增层。The methods for producing resin composite metal copper foil (RCC) from the epoxy resin composition of the present invention are listed below, but the method for producing resin composite metal copper foil is not limited thereto. As the metal foil, copper, brass, aluminum, nickel, and alloys or composite metal foils of these metals can be used, and the thickness of the metal foil is 5-150 μm. The epoxy resin composition glue is coated on the above-mentioned metal foil by manual or mechanical roller coating device, and then the metal foil coated with the epoxy resin composition is heated and dried, so that the epoxy resin composition is in In the semi-cured state (B-Stage), the heating temperature here is 100-250°C, the heating time is 10 seconds-30 minutes, and the resin layer thickness of the finally formed resin composite metal is 1-150μm. The resin composite metal copper Foils can be used to build up printed wiring boards as an inner or outer layer of printed wiring boards.

使用本发明的环氧树脂组合物制造半固化片(prepreg)的方法列举如下，然而制作半固化片的方法不仅限于此。将环氧树脂组合物胶水(此处已使用溶剂调节黏度)浸渍在基料上，并对浸渍有环氧树脂组合物的半固化片进行加热干燥，使得半固化片中的环氧树脂组合物处于半固化阶段(B-Stage)，即可获得半固化片。其中使用到的基料可为无机或有机材料。无机材料可列举的有玻璃纤维、碳纤维、硼纤维、金属等的机织织物或无纺布或纸。其中的玻璃纤维布或无纺布可以使E-glass、Q型布、NE布、D型布、S型布、高硅氧布等。有机纤维如聚酯、聚胺、聚丙烯酸、聚酰亚胺、芳纶、聚四氟乙烯、间规聚苯乙烯等制造的织布或无纺布或纸。然而增强材料不限于此。可列举的对半固化片的加热温度为80-250℃，时间为1-30分钟。半固化片中的树脂含量在25-70％之间。The method of manufacturing a prepreg using the epoxy resin composition of the present invention is listed below, but the method of manufacturing a prepreg is not limited thereto. The epoxy resin composition glue (here the viscosity has been adjusted by solvent) is impregnated on the base material, and the prepreg impregnated with the epoxy resin composition is heated and dried, so that the epoxy resin composition in the prepreg is in the semi-cured stage (B-Stage), the prepreg can be obtained. The base materials used therein can be inorganic or organic materials. Examples of inorganic materials include woven or nonwoven fabrics or paper of glass fibers, carbon fibers, boron fibers, metals, and the like. The glass fiber cloth or non-woven fabric can be E-glass, Q-type cloth, NE cloth, D-type cloth, S-type cloth, high silica cloth, etc. Woven or non-woven fabric or paper made of organic fibers such as polyester, polyamine, polyacrylic acid, polyimide, aramid, polytetrafluoroethylene, syndiotactic polystyrene, etc. However, the reinforcing material is not limited thereto. Exemplary heating temperatures for prepregs are 80-250° C. for 1-30 minutes. The resin content in the prepreg is between 25-70%.

层压板、覆铜箔层压板、印制线路板可以使用上述的树脂片、树脂复合金属箔、和半固化片制作。以覆铜箔层压板为例来说明此制作方式，但不仅限于此。在使用半固化片制作覆铜箔层压板时，将一个或多个半固化片裁剪成一定尺寸进行叠片后送入层压设备中进行层压，同时将金属箔放置在半固化片的一侧或两侧，通过热压成型将半固化压制形成覆金属箔层压板。作为金属箔可以使用铜、黄铜、铝、镍、以及这些金属的合金或复合金属箔，作为层压板的压制条件，应根据环氧树脂组合物的实际情况选择合适的层压固化条件。如果压制压力过低，会使层压板中存在空隙，其电性能会下降；层压压力过大会使层压板中存在过多的内应力，使得层压板的尺寸稳定性能下降，这些都需要通过合适的满足模塑的压力来压制板材来达到所需的要求。对于常规的压制层压板的通常指导原则为，层压温度在130～250℃，压力：3-50kgf/cm2，热压时间：60-240分钟。可以使用树脂片材、树脂复合金属箔、半固化片、覆金属层压板通过加成或减层法制作印制线路板或复杂的多层电路板。Laminates, copper-clad laminates, and printed wiring boards can be produced using the above-mentioned resin sheets, resin-composite metal foils, and prepregs. Taking copper clad laminate as an example to illustrate this production method, but it is not limited to this. When using prepregs to make copper-clad laminates, one or more prepregs are cut into a certain size and laminated, and then sent to the lamination equipment for lamination. At the same time, the metal foil is placed on one or both sides of the prepreg. Thermoforming presses the prepreg to form a metal clad laminate. Copper, brass, aluminum, nickel, and alloys or composite metal foils of these metals can be used as the metal foil. As the pressing conditions of the laminate, suitable lamination curing conditions should be selected according to the actual situation of the epoxy resin composition. If the pressing pressure is too low, there will be voids in the laminate, and its electrical properties will decrease; if the lamination pressure is too large, there will be too much internal stress in the laminate, which will reduce the dimensional stability of the laminate. To meet the molding pressure to press the plate to meet the required requirements. The general guideline for conventional pressed laminates is that the lamination temperature is 130-250°C, the pressure: 3-50kgf/cm2, and the hot-pressing time: 60-240 minutes. Resin sheets, resin composite metal foils, prepregs, and metal-clad laminates can be used to make printed circuit boards or complex multilayer circuit boards by adding or subtracting layers.

本发明的环氧树脂组合物除了可以用作制作树脂片、树脂复合物金属铜箔、半固化片、层压板、覆铜箔层压板、印制线路板之外，还可用于用来制作胶黏剂、涂料、复合材料，也可用于建筑、航空、船舶、汽车工业。The epoxy resin composition of the present invention can also be used to make adhesives in addition to being used to make resin sheets, resin composite metal copper foils, prepregs, laminates, copper-clad laminates, and printed circuit boards. , coatings, composite materials, and can also be used in construction, aviation, shipbuilding, and automotive industries.

以下实施例说明本发明的各个实施方案。然而这些实施例并不以任何方式限制本发明。具体实施方式如下。The following examples illustrate various embodiments of the invention. However, these examples do not limit the invention in any way. The specific implementation method is as follows.

合成例1：Synthesis example 1:

将对羟基苯乙烯/苯乙烯共聚物、表氯醇和二噁烷混合，对羟基苯乙烯/苯乙烯共聚物和表氯醇按1∶5的摩尔比投料。二噁烷为对羟基苯乙烯/苯乙烯共聚物重量比1.89。对羟基苯乙烯/苯乙烯共聚物按已知方法合成，Wn为4300。上述混合物在氮气保护下加热，加热温度在80度，并不断搅拌，同时滴加氢氧化钠溶液，所用氢氧化钠溶液的浓度为25wt％，氢氧化钠和对羟基苯乙烯/苯乙烯共聚物的摩尔比为2/1，碱液在3小时内滴加完毕，在反应过程中体系中的水分和表氯醇共沸不断从体系中分出，分层后的表氯醇返回体系。减压蒸馏除去过量的表氯醇和二噁烷，向剩余物中加入甲基异丁酮，通过洗涤和过滤除去盐分，接着使用水洗涤至中性，得到环氧树脂(1)。环氧树脂(1)的Wn为4900。Mix p-hydroxystyrene/styrene copolymer, epichlorohydrin and dioxane, and feed the p-hydroxystyrene/styrene copolymer and epichlorohydrin at a molar ratio of 1:5. Dioxane has a p-hydroxystyrene/styrene copolymer weight ratio of 1.89. p-Hydroxystyrene/styrene copolymer synthesized by known method, Wn is 4300. Above-mentioned mixture is heated under nitrogen protection, and heating temperature is at 80 degree, and constantly stirs, and dropwise adds sodium hydroxide solution simultaneously, the concentration of used sodium hydroxide solution is 25wt%, sodium hydroxide and p-hydroxystyrene/styrene copolymer The molar ratio of the lye is 2/1, and the lye is added dropwise within 3 hours. During the reaction process, the moisture and epichlorohydrin in the system are continuously separated from the system by azeotropic, and the stratified epichlorohydrin returns to the system. Excess epichlorohydrin and dioxane were distilled off under reduced pressure, methyl isobutyl ketone was added to the residue, salt was removed by washing and filtration, and then washed to neutrality with water to obtain epoxy resin (1). Wn of the epoxy resin (1) was 4900.

合成例2：Synthesis example 2:

将对羟基苯乙烯/苯乙烯共聚物、表氯醇和甲苯混合，对羟基苯乙烯/苯乙烯共聚物和表氯醇按1∶10的摩尔比投料。二噁烷为对羟基苯乙烯/苯乙烯共聚物重量比为1.89。对羟基苯乙烯/苯乙烯共聚物按已知方法合成，Wn为30000。上述混合物在氮气保护下加热，加热温度在100度，并不断搅拌，同时滴加氢氧化钠溶液，所用氢氧化钠溶液的浓度为25wt％，氢氧化钠和对羟基苯乙烯/苯乙烯共聚物的摩尔比为2/1，碱液在2小时内滴加完毕，在反应过程中体系中的水分和表氯醇共沸不断从体系中分出，分层后的表氯醇返回体系。减压蒸馏除去过量的表氯醇和甲苯，向剩余物中加入甲基异丁酮，通过洗涤和过滤除去盐分，接着使用水洗涤至中性，得到环氧树脂(2)。环氧树脂(2)的Wn为34000。Mix p-hydroxystyrene/styrene copolymer, epichlorohydrin and toluene, and feed the p-hydroxystyrene/styrene copolymer and epichlorohydrin at a molar ratio of 1:10. Dioxane has a p-hydroxystyrene/styrene copolymer weight ratio of 1.89. p-Hydroxystyrene/styrene copolymer synthesized by known method, Wn is 30000. Above-mentioned mixture is heated under the protection of nitrogen, heating temperature is at 100 degree, and constantly stirs, dropwise adds sodium hydroxide solution simultaneously, the concentration of used sodium hydroxide solution is 25wt%, sodium hydroxide and p-hydroxystyrene/styrene copolymer The molar ratio of the lye is 2/1, and the lye is added dropwise within 2 hours. During the reaction, the moisture and epichlorohydrin in the system are continuously separated from the system by azeotropy, and the stratified epichlorohydrin returns to the system. Excess epichlorohydrin and toluene were distilled off under reduced pressure, methyl isobutyl ketone was added to the residue, salt was removed by washing and filtration, and then washed with water to neutrality to obtain epoxy resin (2). Wn of the epoxy resin (2) was 34,000.

合成例3：Synthesis example 3:

将对羟基苯乙烯/苯乙烯共聚物、表氯醇和四乙基溴化铵一起加进四口烧瓶中，对羟基苯乙烯/苯乙烯共聚物和表氯醇按1∶8的摩尔比投料，四乙基溴化铵用量为对羟基苯乙烯/苯乙烯共聚物的0.5％(摩尔比)，对羟基苯乙烯/苯乙烯共聚物按已知方法合成，Wn为20000上述混合物在氮气保护下加热，加热温度为90度，反应3小时，醚化反应结束后滴加40wt％的氢氧化钠溶液进行闭环反应反应温度在110度，反应时间3小时。反应完后过滤，水洗除去盐分，减压蒸馏除去过量的表氯醇，最后得到环氧树脂(3)。环氧树脂(3)的Wn在22000。P-hydroxystyrene/styrene copolymer, epichlorohydrin and tetraethylammonium bromide are added in the four-necked flask together, and p-hydroxystyrene/styrene copolymer and epichlorohydrin are fed in a mol ratio of 1:8, Tetraethylammonium bromide consumption is 0.5% (mol ratio) of p-hydroxystyrene/styrene copolymer, and p-hydroxystyrene/styrene copolymer is synthesized by known method, and Wn is 20000 above-mentioned mixture heating under nitrogen protection , the heating temperature is 90 degrees, the reaction is 3 hours, and after the etherification reaction is completed, 40 wt% sodium hydroxide solution is added dropwise to carry out the ring closure reaction. The reaction temperature is 110 degrees, and the reaction time is 3 hours. After the reaction, filter, wash with water to remove salt, and distill under reduced pressure to remove excess epichlorohydrin to finally obtain epoxy resin (3). The Wn of epoxy resin (3) is 22000.

合成例4：Synthesis example 4:

将对羟基苯乙烯/苯乙烯共聚物、表氯醇和苄基三乙基氯化铵一起加进四口烧瓶中，对羟基苯乙烯/苯乙烯共聚物和表氯醇按1∶12的摩尔比投料，苄基三乙基氯化铵用量为对羟基苯乙烯/苯乙烯共聚物的1％(摩尔比)，对羟基苯乙烯/苯乙烯共聚物按已知方法合成，Wn为8500。上述混合物在氮气保护下加热，加热温度为100度，反应2小时，醚化反应结束后滴加40wt％的氢氧化钠溶液进行闭环反应反应温度在110度，反应时间3小时。反应完后过滤，水洗除去盐分，减压蒸馏除去过量的表氯醇，最后得到环氧树脂(3)。环氧树脂(3)的Wn在10000。Add p-hydroxystyrene/styrene copolymer, epichlorohydrin and benzyltriethylammonium chloride into the four-necked flask together, p-hydroxystyrene/styrene copolymer and epichlorohydrin in a molar ratio of 1:12 Feed intake, benzyltriethylammonium chloride consumption is 1% (molar ratio) of p-hydroxystyrene/styrene copolymer, p-hydroxystyrene/styrene copolymer is synthesized by known method, Wn is 8500. The above mixture was heated under the protection of nitrogen at a heating temperature of 100°C and reacted for 2 hours. After the etherification reaction was completed, 40 wt% sodium hydroxide solution was added dropwise to carry out the ring closure reaction. The reaction temperature was 110°C and the reaction time was 3 hours. After the reaction, filter, wash with water to remove salt, and distill under reduced pressure to remove excess epichlorohydrin to finally obtain epoxy resin (3). The Wn of epoxy resin (3) is 10000.

实施例(1～4)：Embodiment (1～4):

将合成例1-4中所得的环氧树脂制备表一中所示的胶水，将此胶水使用2116型电子级玻璃充分浸润，并在155度烘箱中，除去溶剂，获得B-stage的半固化片试样。Prepare the glue shown in Table 1 from the epoxy resin obtained in Synthesis Example 1-4, fully infiltrate the glue with 2116 electronic grade glass, and remove the solvent in an oven at 155 degrees to obtain a B-stage prepreg test Sample.

将八片半固化片和两片一盎司的电解铜箔叠合在一起，通过热压机进行层压得到双面覆铜箔层压板。层压条件如下：1、料温在80-120度时，升温速度控制在1.0-3.0度/分钟；2、压力设置为20kg/cm2；3、固化温度在190度，并保持此温度90分钟。相应性能见表一。Laminate eight prepregs and two one-ounce electrolytic copper foils together, and laminate them with a hot press to obtain a double-sided copper-clad laminate. The lamination conditions are as follows: 1. When the material temperature is 80-120 degrees, the heating rate is controlled at 1.0-3.0 degrees/minute; 2. The pressure is set to 20kg/cm2; 3. The curing temperature is 190 degrees, and keep this temperature for 90 minutes . The corresponding properties are shown in Table 1.

对比例1：Comparative example 1:

使用SMA3000苯乙烯马来酸酐共聚物40份、60份N695并辅以催化剂2-MI，使用MEK120份将上述化合物溶解，并调制成合适粘度的胶水。使用2116型电子级玻璃布浸润此胶水，并在155度烘箱中，除去溶剂，获得B-stage的半固化片试样。Use 40 parts of SMA3000 styrene maleic anhydride copolymer, 60 parts of N695 supplemented with catalyst 2-MI, use 120 parts of MEK to dissolve the above compounds, and prepare a glue with a suitable viscosity. Use 2116-type electronic grade glass cloth to soak the glue, and remove the solvent in a 155-degree oven to obtain a B-stage prepreg sample.

将八片半固化片和两片一盎司的电解铜箔叠合在一起，通过热压机进行层压得到双面覆铜箔层压板。层压条件如下：1、料温在80-120度时，升温速度控制在1.0-3.0度/分钟；2、压力设置为20kg/cm2；3、固化温度在190度，并保持此温度90分钟。相应性能见表一。Laminate eight prepregs and two one-ounce electrolytic copper foils together, and laminate them with a hot press to obtain a double-sided copper-clad laminate. The lamination conditions are as follows: 1. When the material temperature is 80-120 degrees, the heating rate is controlled at 1.0-3.0 degrees/minute; 2. The pressure is set to 20kg/cm2; 3. The curing temperature is 190 degrees, and keep this temperature for 90 minutes . The corresponding properties are shown in Table 1.

对比例2Comparative example 2

使用DER530树脂80份、20份PSM4357并辅以催化剂2-MI，使用MEK100份将上述化合物溶解，并调制成合适粘度的胶水。使用2116型电子级玻璃布浸润此胶水，并在155度烘箱中，除去溶剂，获得B-stage的半固化片试样。Use 80 parts of DER530 resin, 20 parts of PSM4357 supplemented with catalyst 2-MI, use 100 parts of MEK to dissolve the above compounds, and prepare a glue with a suitable viscosity. Use 2116-type electronic grade glass cloth to soak the glue, and remove the solvent in a 155-degree oven to obtain a B-stage prepreg sample.

将八片半固化片和两片一盎司的电解铜箔叠合在一起，通过热压机进行层压得到双面覆铜箔层压板。层压条件和对比例1相同，相应性能见表一。Laminate eight prepregs and two one-ounce electrolytic copper foils together, and laminate them with a hot press to obtain a double-sided copper-clad laminate. The lamination conditions are the same as those of Comparative Example 1, and the corresponding properties are shown in Table 1.

对比例3Comparative example 3

使用HP7200树脂80份、20份PSM4357并辅以催化剂2-MI，使用MEK90份将上述化合物溶解，并调制成合适粘度的胶水。使用2116型电子级玻璃布浸润此胶水，并在155度烘箱中，除去溶剂，获得B-stage的半固化片试样。Use 80 parts of HP7200 resin, 20 parts of PSM4357 supplemented with catalyst 2-MI, use 90 parts of MEK to dissolve the above compounds, and prepare a glue with a suitable viscosity. Use 2116-type electronic grade glass cloth to soak the glue, and remove the solvent in a 155-degree oven to obtain a B-stage prepreg sample.

将八片半固化片和两片一盎司的电解铜箔叠合在一起，通过热压机进行层压得到双面覆铜箔层压板。层压条件和对比例1相同相应性能见表一。Laminate eight prepregs and two one-ounce electrolytic copper foils together, and laminate them with a hot press to obtain a double-sided copper-clad laminate. The lamination conditions are the same as those of Comparative Example 1, and the corresponding properties are shown in Table 1.

表一Table I

注1：Note 1:

表一中各组分皆以固体含量重量份记In Table 1, each component is recorded in parts by weight of solid content

DER530为DOW的双酚A型溴化双官能团环氧树脂DER530 is DOW's bisphenol A type brominated bifunctional epoxy resin

N690为DIC的邻甲基酚醛环氧树脂N690 is DIC's o-methyl novolac epoxy resin

HP7200为DIC的双环戊二烯环氧树脂HP7200 is DIC's Dicyclopentadiene Epoxy Resin

PSM4357为日本群荣化学的酚醛树脂PSM4357 is a phenolic resin produced by Japan Qunyei Chemical

SMA3000为沙多玛的苯乙烯马来酸酐共聚物SMA3000 is Sartomer's styrene maleic anhydride copolymer

DDM为江阴惠峰合成材料有限公司的4，4’-二氨基二苯甲烷DDM is 4,4'-diaminodiphenylmethane from Jiangyin Huifeng Synthetic Materials Co., Ltd.

注2：Note 2:

玻璃化转变温度(Tg)：使用DSC测试，按照IPC-TM-6502.4.25所规定的DSC测试方法进行测定。Glass transition temperature (Tg): use DSC test and measure according to the DSC test method specified in IPC-TM-6502.4.25.

剥离强度按照IPC-TM-6502.4.8方法中的“热应力后”实验条件测试The peel strength is tested according to the experimental conditions of "after thermal stress" in the IPC-TM-6502.4.8 method

介电常数和介电损耗因子：按照IPC-TM-6502.5.5.9所规定的方法测试Dielectric constant and dielectric loss factor: tested according to the method specified in IPC-TM-6502.5.5.9

耐浸焊性的评价：将覆铜箔层压板浸渍在温度为288℃的锡炉中20秒后取出冷却至室温，然后再浸渍到锡炉中反复5次，通过观察外观评价耐浸焊性，Evaluation of solder dipping resistance: dip the copper-clad laminate in a tin furnace with a temperature of 288°C for 20 seconds, take it out and cool it to room temperature, then dip it into the tin furnace for 5 times, and evaluate the solder dipping resistance by observing the appearance.

吸水测定：将覆铜箔层压板浸渍在铜蚀刻液中，除去表面铜箔评价基板。将基板放置在压力锅中，在121℃，2atm下处理1小时后，测定基板的吸水率。Water absorption measurement: The copper-clad laminate was immersed in a copper etching solution, and the surface copper foil was removed to evaluate the substrate. The substrate was placed in a pressure cooker, and after being treated at 121° C. and 2 atm for 1 hour, the water absorption rate of the substrate was measured.

PCT后耐浸焊性评价：将覆铜箔层压板浸渍在铜蚀刻液中，除去表面铜箔评价基板。将基板放置在压力锅中，在121℃，2atm下处理2小时后，浸渍在温度为288℃的锡炉中，当基材出现起泡或分裂时记录相应的时间。当基材在锡炉中超过5分钟还没有出现起泡或分层可结束评价。Evaluation of post-PCT solder dipping resistance: The copper-clad laminate was immersed in a copper etching solution, and the surface copper foil was removed to evaluate the substrate. Place the substrate in a pressure cooker, treat it at 121°C and 2atm for 2 hours, then immerse it in a tin furnace with a temperature of 288°C, and record the corresponding time when the substrate has blisters or cracks. The evaluation is terminated when the substrate has been in the tin oven for more than 5 minutes without blistering or delamination.

从表一可以看出，本发明的实施例，低介电常数、低介电损耗因子、耐热性、耐浸焊性、耐湿性、耐湿热性以及和铜箔的粘结性均优良。另一方面，比较例的低介电常数、低介电损耗因子、耐热性、耐浸焊性、耐湿性、耐湿热性以及和铜箔的粘结性都不好。It can be seen from Table 1 that the embodiment of the present invention has excellent low dielectric constant, low dielectric dissipation factor, heat resistance, dip soldering resistance, moisture resistance, heat and humidity resistance, and adhesion to copper foil. On the other hand, Comparative Examples were not good in low dielectric constant, low dielectric dissipation factor, heat resistance, solder dip resistance, moisture resistance, heat and humidity resistance, and adhesion to copper foil.

本发明的结构式(I)所示的环氧树脂单独使用，或者和其它环氧树脂混合使用时形成的树脂组合物，低介电常数、低介电损耗因子、耐热性、耐浸焊性、耐湿性、耐湿热性以及和铜箔的粘结性均优良。将此树脂组合物涂覆在基材上得到的半固化片材以及通过层压该半固化片材制造的层压板，低介电常数、低介电损耗因子、耐热性、耐浸焊性、耐湿性、耐湿热性以及和铜箔的粘结性均优良，可以作为电子仪器用印制线路板。The epoxy resin represented by the structural formula (I) of the present invention is used alone, or the resin composition formed when mixed with other epoxy resins, has low dielectric constant, low dielectric dissipation factor, heat resistance, dip soldering resistance, It is excellent in moisture resistance, heat and humidity resistance, and adhesion to copper foil. A prepreg obtained by coating the resin composition on a substrate and a laminate manufactured by laminating the prepreg have low dielectric constant, low dielectric dissipation factor, heat resistance, solder dipping resistance, moisture resistance, resistance It has excellent hygrothermal properties and adhesion to copper foil, and can be used as a printed circuit board for electronic equipment.

综上所述，本发明的环氧树脂组合物因为分子结构中含有极性低的苯乙烯结构，因此该树脂的介电性能得到了优化，介电常数和介质损耗角正切和一般的环氧树脂相比，得到了的降低，随着结构中苯乙烯单元含量的增大，介电常数和介质损耗角正切更小。另外，该树脂组合物和传统采用的马来酸酐苯乙烯共聚物相比，具有更好的热稳定性及耐湿热性。本发明的环氧树脂组合物种的环氧树脂可单独使用，或者和其它环氧树脂混合使用，其具有低介电常数、低介电损耗因子，耐热性、耐浸焊性、耐湿性、耐湿热性以及和铜箔的粘结性较好的特点；将此树脂组合物涂覆在基材上得到的半固化片材以及通过层压该半固化片材制造的层压板，其同时具有低介电常数、低介电损耗因子，耐热性、耐浸焊性、耐湿性、耐湿热性以及和铜箔的粘结性较好的特点，可以作为电子仪器用印制线路板。In summary, because the epoxy resin composition of the present invention contains the styrene structure with low polarity in the molecular structure, the dielectric properties of the resin have been optimized, and the dielectric constant and dielectric loss tangent are the same as those of general epoxy resins. Compared with the resin, the decrease is obtained. With the increase of the content of styrene units in the structure, the dielectric constant and dielectric loss tangent are smaller. In addition, compared with the traditionally used maleic anhydride styrene copolymer, the resin composition has better thermal stability and heat and humidity resistance. The epoxy resin of the epoxy resin composition species of the present invention can be used alone, or mixed with other epoxy resins, it has low dielectric constant, low dielectric loss factor, heat resistance, dip soldering resistance, moisture resistance, resistance The characteristics of good moisture heat and adhesion to copper foil; the prepreg obtained by coating the resin composition on the base material and the laminate made by laminating the prepreg have low dielectric constant, Low dielectric loss factor, heat resistance, dip soldering resistance, moisture resistance, heat and humidity resistance, and good adhesion with copper foil can be used as printed circuit boards for electronic instruments.

以上所述，仅为本发明的较佳实施例，对于本领域的普通技术人员来说，可以根据本方面的技术方案和技术构思作出其他各种相应的改变和变形，而所有这些改变和变形都应属于本发明权利要求的保护范围。The above is only a preferred embodiment of the present invention, and for those skilled in the art, various other corresponding changes and modifications can be made according to the technical scheme and technical concept of this aspect, and all these changes and modifications All should belong to the protection scope of the claims of the present invention.

Claims (8)

1. compositions of thermosetting resin, it is characterized in that: it comprises:

Having a kind of component at least is the epoxy resin of structural formula (I);

Solidifying agent;

Wherein R is:

N and m are natural number;

Structural unit m/n=0.8～19 in the epoxy resin of structural formula (I);

The number-average molecular weight of the epoxy resin of structural formula (I) is between 1000-50000.

2. compositions of thermosetting resin as claimed in claim 1 is characterized in that, the epoxy resin of structural formula (I) is accomplished by the following formula reaction through 1mol para hydroxybenzene ethylene/styrene multipolymer and 2～15mol epihalohydrin:

Wherein

R is:

X is: Br or Cl or I or F.

3. compositions of thermosetting resin as claimed in claim 1 is characterized in that, the epoxy resin of structural formula (I) uses separately or mixes use with the epoxy resin of other type.

4. compositions of thermosetting resin as claimed in claim 3; It is characterized in that; The epoxy resin of said other type is the epoxy resin that has two above epoxide groups in 1 the molecule epoxy resin, and it comprises at least a in bisphenol A type epoxy resin, bisphenol f type epoxy resin, biphenyl type epoxy resin, naphthalene based epoxy resin, alicyclic based epoxy resin, Resorcinol type epoxy resin, polyethylene glycol type epoxy resin, trifunctional epoxy resin, four-functional group epoxy resin or the phenol aldehyde type epoxy resin.

5. compositions of thermosetting resin as claimed in claim 4 is characterized in that, the epoxy resin of structural formula (I): the epoxy resin of other type=1: 0.1～10, remember with weight.

6. compositions of thermosetting resin as claimed in claim 1; It is characterized in that; Said solidifying agent is acid anhydrides, amine, phenols and resol, benzoxazine colophony, carboxylic acid, siloxanes, ZGK 5 and have-the Ph-X-Ph-group contain can with the compound of epoxide group reaction, wherein X is CH₂, C (CH₃)₂, CH (CH₃), O, S, C=O, SO₂

7. a prepreg of processing with the described compositions of thermosetting resin of claim 1 is characterized in that, comprises that base-material reaches through the impregnation drying afterwards attached to the compositions of thermosetting resin on the base-material.

8. laminate for printed circuits of processing with the described compositions of thermosetting resin of claim 1; It is characterized in that; Comprise the prepreg that several are superimposed; And be located at the tinsel of the single or double of the prepreg after superimposed, each sheet prepreg comprise base-material and through the impregnation drying afterwards attached to the compositions of thermosetting resin on the base-material.