CN110885428B - Halogen-free thermosetting resin composition, prepreg using same, laminated board and printed circuit board - Google Patents

Abstract

Translated fromChinese

本发明提供一种无卤热固性树脂组合物、使用它的预浸料、层压板及印制电路板，所述无卤热固性树脂组合物包括无卤环氧树脂以及固化剂，所述固化剂包括氰酸酯树脂和含磷酸酐树脂，各组分含量如下：5～50份氰酸酯树脂、30～60份无卤环氧树脂和15～40份含磷酸酐树脂。本发明以氰酸酯和含磷酸酐共同作为无卤环氧树脂的固化剂，二者协同作用，增强组合物的高耐热性，并具有低介质损耗值，并且三种树脂混合固化，共同作用还带来体系具有优异的抗剥离强度和层间粘合力以及优异的阻燃性。

The present invention provides a halogen-free thermosetting resin composition, a prepreg, a laminate and a printed circuit board using the same. The halogen-free thermosetting resin composition includes a halogen-free epoxy resin and a curing agent, and the curing agent includes The cyanate ester resin and the phosphoric acid anhydride-containing resin have the following components: 5-50 parts of cyanate ester resin, 30-60 parts of halogen-free epoxy resin and 15-40 parts of phosphoric acid anhydride-containing resin. The invention uses cyanate ester and phosphoric anhydride as curing agent for halogen-free epoxy resin together, the two act synergistically to enhance the high heat resistance of the composition, and have low dielectric loss value, and the three resins are mixed and cured together, The effect also results in systems having excellent peel strength and interlayer adhesion as well as excellent flame retardancy.

Description

Translated fromChinese

一种无卤热固性树脂组合物、使用它的预浸料、层压板及印制 电路板A halogen-free thermosetting resin composition, prepregs, laminates and printed circuit boards using the same

技术领域technical field

本发明属于层压板技术领域，涉及一种无卤热固性树脂组合物、使用它的预浸料、层压板及印制电路板。The invention belongs to the technical field of laminates, and relates to a halogen-free thermosetting resin composition, a prepreg using the same, a laminate and a printed circuit board.

背景技术Background technique

传统的印制电路用层压板通常采用溴系阻燃剂来实现阻燃，特别是采用四溴双酚A型环氧树脂，这种溴化环氧树脂具有良好的阻燃性，但它在燃烧时会产生溴化氢气体。此外，近年来在含溴、氯等卤素的电子电气设备废弃物的燃烧产物中已检测出二噁英、二苯并呋喃等致癌物质，因此溴化环氧树脂的应用受到限制。2006年7月1日，欧盟的两份环保指令《关于报废电气电子设备指令》和《关于在电气电子设备中限制使用某些有害物质指令》正式实施，无卤阻燃覆铜箔层压板的开发成为业界的热点，各覆铜箔层压板厂家都纷纷推出自己的无卤阻燃覆铜箔层压板。Traditional printed circuit laminates usually use brominated flame retardants to achieve flame retardancy, especially tetrabromobisphenol A epoxy resin. This brominated epoxy resin has good flame retardancy, but it is When burned, hydrogen bromide gas is produced. In addition, in recent years, carcinogens such as dioxins and dibenzofurans have been detected in the combustion products of electrical and electronic equipment wastes containing halogens such as bromine and chlorine, so the application of brominated epoxy resins has been limited. On July 1, 2006, the EU's two environmental protection directives "Directive on Scrap Electrical and Electronic Equipment" and "Directive on Restriction of the Use of Certain Hazardous Substances in Electrical and Electronic Equipment" were officially implemented. Development has become a hot spot in the industry, and all copper clad laminate manufacturers have launched their own halogen-free flame retardant copper clad laminates.

在覆铜板的树脂基体中引入含磷化合物，成为覆铜板无卤阻燃的主要技术路线。目前覆铜板领域上广泛采用的含磷阻燃剂主要分为反应型与添加型两种。反应型主要为DOPO类化合物，以含磷环氧树脂、含磷酚醛树脂为主，磷含量在2％～10％之间。然而，实际应用中发现，此类反应型含磷阻燃剂，在固化后形成极性大的二次羟基，具有较大的吸水率和较差的介电性能及板材耐湿热性差。添加型主要为磷腈和膦酸酯类化合物，添加型阻燃剂的阻燃效率较低，需要添加更多的量才能达到阻燃要求。同时因其较低的熔点(一般低于150℃)，在层压板加工过程中，易迁移至板材表面，影响板材性能。The introduction of phosphorus-containing compounds into the resin matrix of CCL has become the main technical route of halogen-free flame retardant for CCL. At present, phosphorus-containing flame retardants widely used in the field of copper clad laminates are mainly divided into two types: reactive and additive. The reactive type is mainly DOPO compound, mainly phosphorus-containing epoxy resin and phosphorus-containing phenolic resin, and the phosphorus content is between 2% and 10%. However, it has been found in practical applications that such reactive phosphorus-containing flame retardants form secondary hydroxyl groups with high polarity after curing, and have high water absorption, poor dielectric properties and poor resistance to heat and humidity. The additive type is mainly phosphazene and phosphonate compounds. The flame retardant efficiency of the additive type flame retardant is low, and more amount needs to be added to meet the flame retardant requirements. At the same time, due to its low melting point (generally lower than 150°C), it is easy to migrate to the surface of the sheet during the processing of the laminate, which affects the performance of the sheet.

另外，对于覆铜箔基板材料而言，为了满足PCB加工性能以及终端电子产品的性能要求，必须具备良好的介电性能、耐热性以及机械性能，同时还应具有良好的工艺加工特性，高的剥离强度，优异的耐湿热性以及UL94V-0无卤阻燃级别。In addition, for the copper clad substrate material, in order to meet the performance requirements of PCB processing performance and terminal electronic products, it must have good dielectric properties, heat resistance and mechanical properties, as well as good processing characteristics, high high peel strength, excellent heat and humidity resistance and UL94V-0 halogen-free flame retardant grade.

端羟苯氧基烃基氧化膦为具有反应活性的含磷固化剂，能与环氧树脂发生固化反应，但是由于其活性基团为酚羟基，其与环氧树脂反应后会生成极性较大的二次羟基，导致固化物的介电性能较差。CN103384674A中选用具有羟基的聚膦酸酯和/或膦酸酯-碳酸酯共聚物与环氧组成组合物，其活性基团为酚羟基，同样存在介电性能较差的问题；CN103694642A中公开了采用环氧树脂、氰酸酯化合物和/或氰酸酯预聚物、聚膦酸酯和/或膦酸酯-碳酸酯共聚物制备了介电性能、耐湿热性好的无卤UL94V-0阻燃的预浸料及覆铜箔层压板，但其抗剥离强度、层间粘合力及弯曲强度较低。CN108117633A中公开了酸酐化的膦酸酯同氰酸酯树脂、环氧树脂制作无卤覆铜板，但是其酸酐化的膦酸酯中过多的P-O键，使得耐湿热性稍显不足。Hydroxyphenoxy-terminated hydrocarbyl phosphine oxide is a reactive phosphorus-containing curing agent, which can undergo curing reaction with epoxy resin, but because its active group is phenolic hydroxyl group, it will generate a higher polarity after reacting with epoxy resin. secondary hydroxyl groups, resulting in poor dielectric properties of the cured product. In CN103384674A, polyphosphonate and/or phosphonate-carbonate copolymer with hydroxyl group and epoxy composition are selected, and the active group is phenolic hydroxyl group, which also has the problem of poor dielectric performance; CN103694642A discloses Halogen-free UL94V-0 with good dielectric properties and good heat and humidity resistance was prepared by using epoxy resin, cyanate ester compound and/or cyanate ester prepolymer, polyphosphonate and/or phosphonate-carbonate copolymer Flame retardant prepreg and copper clad laminate, but with low peel strength, interlayer adhesion and flexural strength. CN108117633A discloses acid anhydrided phosphonates with cyanate resins and epoxy resins to make halogen-free copper clad laminates, but the anhydrided phosphonates have too many P-O bonds, making the heat and humidity resistance slightly insufficient.

众所周知，目前有多种材料具备低的介电常数、介质损耗正切值特性，如：聚烯烃、氟树脂、聚苯乙烯、聚苯醚、改性聚苯醚、双马来酰亚胺-三嗪树脂、聚乙烯基苯树脂。以上树脂虽然具有良好的介电性能，但是都存在工艺加工难、耐热性差等缺陷，剥离强度、层间粘合力差，无法满足高频高速无卤阻燃的覆铜箔基板的要求。As we all know, there are many materials with low dielectric constant and dielectric loss tangent, such as: polyolefin, fluororesin, polystyrene, polyphenylene ether, modified polyphenylene ether, bismaleimide-tri oxazine resin, polyvinyl benzene resin. Although the above resins have good dielectric properties, they all have defects such as difficult processing, poor heat resistance, and poor peel strength and interlayer adhesion, which cannot meet the requirements of high-frequency, high-speed, halogen-free, flame-retardant copper-clad substrates.

发明内容SUMMARY OF THE INVENTION

针对现有技术的不足，本发明的目的在于提供一种无卤热固性树脂组合物、使用它的预浸料、层压板及印制电路板。In view of the deficiencies of the prior art, the purpose of the present invention is to provide a halogen-free thermosetting resin composition, a prepreg, a laminate and a printed circuit board using the same.

为达此目的，本发明采用以下技术方案：For this purpose, the present invention adopts the following technical solutions:

一方面，本发明提供一种无卤热固性树脂组合物，所述无卤热固性树脂组合物包括无卤环氧树脂以及固化剂，所述固化剂包括氰酸酯树脂和含磷酸酐树脂，各组分含量如下：In one aspect, the present invention provides a halogen-free thermosetting resin composition, the halogen-free thermosetting resin composition includes a halogen-free epoxy resin and a curing agent, the curing agent includes a cyanate ester resin and a phosphoric anhydride-containing resin, each group The content is as follows:

氰酸酯树脂 5～50份Cyanate resin 5～50 parts

无卤环氧树脂 30～60份Halogen-free epoxy resin 30～60 parts

含磷酸酐树脂 15～40份；15-40 parts of phosphoric anhydride resin;

所述含磷酸酐树脂为DOPO型含磷酸酐树脂。The phosphoric acid anhydride-containing resin is DOPO type phosphoric acid anhydride-containing resin.

在本发明中，以氰酸酯和含磷酸酐共同作为无卤环氧树脂的固化剂，二者协同作用，增强组合物的高耐热性，并具有低介质损耗值，含磷酸酐与环氧树脂反应不会生成极性大、介电性差的二次羟基，带来优异的介电性能。并且三种树脂混合固化，共同作用还带来体系具有优异的抗剥离强度和层间粘合力。此外，含磷酸酐自身含有无卤阻燃的DOPO结构，作为反应性的阻燃组分，其阻燃效率高，能使体系具有无卤阻燃特性，在本发明所述添加量下，能够使得所述组合物的固化物阻燃性达到UL94V-0无卤阻燃的效果。并且该含磷酸酐与氰酸酯树脂和无卤环氧树脂的联合使用可以保证组合物具有较高的耐热性。In the present invention, cyanate ester and phosphoric acid anhydride are used together as curing agent for halogen-free epoxy resin, and the two synergistic effects enhance the high heat resistance of the composition and have low dielectric loss value. The oxygen resin reaction does not generate secondary hydroxyl groups with high polarity and poor dielectric properties, resulting in excellent dielectric properties. And the three resins are mixed and cured, and the joint action also brings the system to have excellent peel strength and interlayer adhesion. In addition, phosphoric anhydride itself contains a halogen-free flame retardant DOPO structure, as a reactive flame retardant component, its flame retardant efficiency is high, and the system can have halogen-free flame retardant properties. The flame retardancy of the cured product of the composition achieves the effect of UL94V-0 halogen-free flame retardancy. And the combined use of the phosphoric anhydride-containing cyanate resin and the halogen-free epoxy resin can ensure that the composition has high heat resistance.

本发明利用氰酸酯、含磷酸酐、环氧树脂三者之间的协同效应，可以显著提高使用该树脂组合物制作的预浸料以及印制电路用层压板的玻璃化温度和耐热性，并使其具有优异的介电性能、低吸水率、高抗剥离强度、高层间粘合力、好的耐湿热性以及良好的工艺加工性，并实现无卤阻燃，达到UL94V-0。The present invention utilizes the synergistic effect among cyanate ester, phosphoric anhydride-containing and epoxy resin, and can significantly improve the glass transition temperature and heat resistance of prepregs and printed circuit laminates made by using the resin composition , and make it have excellent dielectric properties, low water absorption, high peel strength, adhesion between layers, good heat and humidity resistance and good processability, and achieve halogen-free flame retardant, reaching UL94V-0.

优选地，所述含磷酸酐树脂为具有如下结构的树脂：Preferably, the phosphoric anhydride-containing resin is a resin having the following structure:

在本发明中，所述无卤热固性树脂组合物中含磷酸酐树脂的添加量可以为15份、18份、20份、22份、24份、26份、28份、30份、33份、35份、38份或40份，以及上述数值之间的具体点值，限于篇幅及出于简明的考虑，本发明不再穷尽列举所述范围包括的具体点值。In the present invention, the addition amount of phosphoric anhydride-containing resin in the halogen-free thermosetting resin composition may be 15 parts, 18 parts, 20 parts, 22 parts, 24 parts, 26 parts, 28 parts, 30 parts, 33 parts, 35 copies, 38 copies or 40 copies, as well as the specific point values between the above-mentioned values, due to space limitations and for the sake of simplicity, the present invention will not exhaustively list the specific point values included in the range.

在本发明中，所述无卤热固性树脂组合物中氰酸酯树脂的添加量可以为5份、8份、10份、13份、15份、18份、20份、25份、28份、30份、35份、38份、40份、43份、45份、48份或50份。以及上述数值之间的具体点值，限于篇幅及出于简明的考虑，本发明不再穷尽列举所述范围包括的具体点值。In the present invention, the addition amount of the cyanate resin in the halogen-free thermosetting resin composition may be 5 parts, 8 parts, 10 parts, 13 parts, 15 parts, 18 parts, 20 parts, 25 parts, 28 parts, 30, 35, 38, 40, 43, 45, 48 or 50 servings. As for the specific point values between the above numerical values, due to space limitations and for the sake of simplicity, the present invention will not exhaustively list the specific point values included in the range.

优选地，所述氰酸酯树脂具有如下结构：Preferably, the cyanate ester resin has the following structure:

其中，R₅为-CH₂-、

中的任意一种或至少两种的混合物；R₁、R₂、R₃、R₄、R₆、R₇、R₈、R₉各自独立地选自氢原子、取代或未取代的含碳数1～4(例如1、2、3或4)的直链烷基或支链烷基中的任意一种(例如可以是甲基、乙基、丙基、丁基、异丙基、异丁基或叔丁基中的任意一种)。Wherein, R₅ is -CH₂ -,

Any one or a mixture of at least two of them; R₁ , R₂ , R₃ , R₄ , R₆ , R₇ , R₈ , R₉ are each independently selected from hydrogen atoms, substituted or unsubstituted carbon-containing Any one of linear or branched alkyl groups of 1 to 4 (such as 1, 2, 3 or 4) (such as methyl, ethyl, propyl, butyl, isopropyl, isopropyl either butyl or tert-butyl).

优选地，所述氰酸酯树脂选自2,2-双(4-氰氧基苯基)丙烷、双(4-氰氧基苯基)乙烷、双(3,5-二甲基-4-氰氧基苯基)甲烷、2,2-双(4-氰氧基苯基)-1,1,1,3,3,3-六氟丙烷、α,α′-双(4-氰氧基苯基)-间二异丙基苯、环戊二烯型氰酸酯、苯酚酚醛型氰酸酯、甲酚酚醛型氰酸酯、2,2-双(4-氰氧基苯基)丙烷预聚物、双(4-氰氧基苯基)乙烷预聚物、双(3,5-二甲基-4-氰氧基苯基)甲烷预聚物、2,2-双(4-氰氧基苯基)-1,1,1,3,3,3-六氟丙烷预聚物、α,α′-双(4-氰氧基苯基)-间二异丙基苯预聚物、双环戊二烯型氰酸酯预聚物、苯酚酚醛型氰酸酯预聚物或甲酚酚醛型氰酸酯预聚物中的任意一种或至少两种的混合物，优选为2,2-双(4-氰氧基苯基)丙烷、α,α′-双(4-氰氧基苯基)-间二异丙基苯、双(3,5-二甲基-4-氰氧基苯基)甲烷、2,2-双(4-氰氧基苯基)丙烷预聚物、α,α′-双(4-氰氧基苯基)-间二异丙基苯预聚物或双(3,5-二甲基-4-氰氧基苯基)甲烷预聚物中的任意一种或至少两种的混合物。Preferably, the cyanate ester resin is selected from 2,2-bis(4-cyanoxyphenyl)propane, bis(4-cyanoxyphenyl)ethane, bis(3,5-dimethyl- 4-Cyanooxyphenyl)methane, 2,2-bis(4-cyanooxyphenyl)-1,1,1,3,3,3-hexafluoropropane, α,α′-bis(4- Cyanooxyphenyl)-m-diisopropylbenzene, cyclopentadiene cyanate, phenol novolac cyanate, cresol novolac cyanate, 2,2-bis(4-cyanoxybenzene base) propane prepolymer, bis(4-cyanooxyphenyl)ethane prepolymer, bis(3,5-dimethyl-4-cyanooxyphenyl)methane prepolymer, 2,2- Bis(4-cyanooxyphenyl)-1,1,1,3,3,3-hexafluoropropane prepolymer, α,α′-bis(4-cyanooxyphenyl)-m-diisopropyl any one or a mixture of at least two of the base benzene prepolymer, dicyclopentadiene cyanate prepolymer, phenol novolac cyanate prepolymer or cresol novolac cyanate prepolymer, Preferred are 2,2-bis(4-cyanoxyphenyl)propane, α,α′-bis(4-cyanoxyphenyl)-m-diisopropylbenzene, bis(3,5-dimethyl -4-Cyanooxyphenyl)methane, 2,2-bis(4-cyanoxyphenyl)propane prepolymer, α,α′-bis(4-cyanooxyphenyl)-m-diisopropyl Any one or a mixture of at least two of the bis(3,5-dimethyl-4-cyanoxyphenyl)methane prepolymer.

在本发明中，所述无卤热固性树脂组合物中无卤环氧树脂的添加量可以为30份、33份、35份、38份、40份、43份、45份、48份、50份、53份、55份、58份或60份，以及上述数值之间的具体点值，限于篇幅及出于简明的考虑，本发明不再穷尽列举所述范围包括的具体点值。In the present invention, the addition amount of the halogen-free epoxy resin in the halogen-free thermosetting resin composition may be 30 parts, 33 parts, 35 parts, 38 parts, 40 parts, 43 parts, 45 parts, 48 parts, 50 parts , 53 copies, 55 copies, 58 copies or 60 copies, as well as the specific point values between the above-mentioned values, due to space limitations and for the sake of simplicity, the present invention will not exhaustively list the specific point values included in the range.

本发明优选采用无卤环氧树脂，所述无卤环氧树脂是指在1个分子中具有两个或两个以上环氧基团的环氧树脂。The present invention preferably adopts a halogen-free epoxy resin, and the halogen-free epoxy resin refers to an epoxy resin having two or more epoxy groups in one molecule.

优选地，所述无卤环氧树脂为缩水甘油醚类环氧树脂、缩水甘油酯类环氧树脂、缩水甘油胺类环氧树脂、脂环族环氧树脂、环氧化烯烃类环氧树脂、海因环氧树脂或酰亚胺环氧树脂中的任意一种或至少两种的混合物，其中典型但非限制性的混合物为：缩水甘油醚类环氧树脂和缩水甘油酯类环氧树脂的混合物，脂环族环氧树脂和环氧化烯烃类环氧树脂的混合物，缩水甘油胺类环氧树脂和海因环氧树脂的混合物。Preferably, the halogen-free epoxy resin is glycidyl ether epoxy resin, glycidyl ester epoxy resin, glycidyl amine epoxy resin, alicyclic epoxy resin, and epoxidized olefin epoxy resin , any one of hydantoin epoxy resin or imide epoxy resin or a mixture of at least two, wherein typical but non-limiting mixtures are: glycidyl ether epoxy resin and glycidyl ester epoxy resin A mixture of cycloaliphatic epoxy resins and epoxidized olefin epoxy resins, a mixture of glycidylamine epoxy resins and hydantoin epoxy resins.

优选地，所述缩水甘油醚类环氧树脂包括双酚A型环氧树脂、双酚F型环氧树脂、邻甲酚酚醛环氧树脂、双酚A型酚醛环氧树脂、三酚型酚醛环氧树脂、双环戊二烯酚醛环氧树脂、联苯型酚醛环氧树脂、烷基苯型酚醛环氧树脂或萘酚型酚醛环氧树脂中的任意一种或至少两种的混合物。Preferably, the glycidyl ether epoxy resin includes bisphenol A epoxy resin, bisphenol F epoxy resin, o-cresol novolac epoxy resin, bisphenol A novolac epoxy resin, trisphenol novolac epoxy resin Any one or a mixture of at least two of epoxy resin, dicyclopentadiene novolac epoxy resin, biphenyl novolac epoxy resin, alkylbenzene novolac epoxy resin or naphthol novolac epoxy resin.

进一步优选地，所述缩水甘油醚类环氧树脂选自具有如下结构的环氧树脂：Further preferably, the glycidyl ether epoxy resin is selected from epoxy resins with the following structure:

其中，Z₁、Z₂和Z₃各自独立地选自

R选自氢原子、取代或未取代的含碳数1～5(例如1、2、3、4或5)的直链烷基或支链烷基中的任意一种，例如可以是甲基、乙基、丙基、丁基、戊基、异丙基、异丁基、叔丁基或异戊基中的任意一种；wherein Z₁ , Z₂ and Z₃ are each independently selected from

R is selected from any one of a hydrogen atom, a substituted or unsubstituted straight-chain or branched-chain alkyl group containing 1 to 5 carbon atoms (for example, 1, 2, 3, 4 or 5), for example, it can be a methyl group , any one of ethyl, propyl, butyl, pentyl, isopropyl, isobutyl, tert-butyl or isopentyl;

Y₁和Y₂各自独立地选自-CH₂-、

中的任意一种；R₁₀选自氢原子、取代或未取代的含碳数1～5(例如1、2、3、4或5)的直链烷基或支链烷基中的任意一种；例如可以是甲基、乙基、丙基、丁基、戊基、异丙基、异丁基、叔丁基或异戊基中的任意一种；Y₁ and Y₂ are each independently selected from -CH₂ -,

Any one; R₁₀ is selected from any one of hydrogen atom, substituted or unsubstituted straight-chain or branched-chain alkyl group containing 1 to 5 (eg 1, 2, 3, 4 or 5) carbon atoms species; for example, it can be any one of methyl, ethyl, propyl, butyl, pentyl, isopropyl, isobutyl, tert-butyl or isopentyl;

n₂为1～10的任意整数，例如1、2、3、4、5、6、7、8、9或10。n₂ is any integer from 1 to 10, for example, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10.

优选地，所述缩水甘油胺类环氧树脂选自三缩水甘油基对氨基苯酚、三缩水甘油基三聚异氰酸酯、四缩水甘油基二氨基二亚甲基苯、四缩水甘油基-4,4′-二氨基二苯甲烷、四缩水甘油基-3,4′-二胺基二苯醚、四缩水甘油基-4,4′-二胺基二苯醚或四缩水甘油基-1,3-二氨基甲基环己烷中的任意一种或至少两种的混合物。Preferably, the glycidyl amine epoxy resin is selected from triglycidyl-p-aminophenol, triglycidyl tripolyisocyanate, tetraglycidyl diaminodimethylene benzene, tetraglycidyl-4,4 '-diaminodiphenylmethane, tetraglycidyl-3,4'-diaminodiphenyl ether, tetraglycidyl-4,4'-diaminodiphenyl ether or tetraglycidyl-1,3 - any one or a mixture of at least two of diaminomethylcyclohexane.

优选地，所述固化剂还包含SMA树脂，在本发明中，所述SMA树脂意指苯乙烯-马来酸酐树脂，例如可以采用由苯乙烯和马来酸酐按1:1～8:1(例如1:1、1.5:1、1.8:1、2:1、2.5:1、3:1、3.5:1、4:1、4.5:1、5:1、5.5:1、6:1、6.5:1、7:1、7.5:1或8:1)的比例共聚得到。Preferably, the curing agent further comprises SMA resin. In the present invention, the SMA resin means styrene-maleic anhydride resin. For example 1:1, 1.5:1, 1.8:1, 2:1, 2.5:1, 3:1, 3.5:1, 4:1, 4.5:1, 5:1, 5.5:1, 6:1, 6.5 :1, 7:1, 7.5:1 or 8:1) by copolymerization.

在本发明中，以无卤环氧树脂和固化剂的总量为100重量份计，所述SMA树脂的添加量为0～40重量份，例如1重量份、3重量份、5重量份、8重量份、10重量份、12重量份、15重量份、18重量份、20重量份、23重量份、25重量份、28重量份、30重量份、33重量份、35重量份、38重量份或40重量份，以及上述数值之间的具体点值，限于篇幅及出于简明的考虑，本发明不再穷尽列举所述范围包括的具体点值。In the present invention, based on the total amount of the halogen-free epoxy resin and the curing agent as 100 parts by weight, the addition amount of the SMA resin is 0 to 40 parts by weight, such as 1 part by weight, 3 parts by weight, 5 parts by weight, 8 parts by weight, 10 parts by weight, 12 parts by weight, 15 parts by weight, 18 parts by weight, 20 parts by weight, 23 parts by weight, 25 parts by weight, 28 parts by weight, 30 parts by weight, 33 parts by weight, 35 parts by weight, 38 parts by weight parts or 40 parts by weight, as well as the specific point values between the above-mentioned values, due to space limitations and for the sake of simplicity, the present invention will not exhaustively list the specific point values included in the range.

在本发明中，所述固化剂还包括酚醛树脂，所述酚醛树脂为含磷或不含磷的酚醛树脂，其为本领域公知的酚醛树脂，本发明不做特殊限定。In the present invention, the curing agent further includes a phenolic resin, and the phenolic resin is a phosphorus-containing or phosphorus-free phenolic resin, which is a well-known phenolic resin in the art, and is not particularly limited in the present invention.

根据本发明，以无卤环氧树脂和固化剂的总量为100重量份计，所述酚醛树脂的添加量为0～20重量份，例如0重量份、2重量份、4重量份、5重量份、8重量份、10重量份、12重量份、14重量份、15重量份、17重量份或20重量份，以及上述数值之间的具体点值，限于篇幅及出于简明的考虑，本发明不再穷尽列举所述范围包括的具体点值。According to the present invention, based on the total amount of the halogen-free epoxy resin and the curing agent being 100 parts by weight, the addition amount of the phenolic resin is 0-20 parts by weight, for example, 0 parts by weight, 2 parts by weight, 4 parts by weight, 5 parts by weight Parts by weight, 8 parts by weight, 10 parts by weight, 12 parts by weight, 14 parts by weight, 15 parts by weight, 17 parts by weight or 20 parts by weight, as well as the specific point values between the above-mentioned values, are limited to space and for the sake of simplicity, The present invention does not exhaustively enumerate the specific point values included in the stated ranges.

根据本发明，所述固化剂还可以包含小分子化的聚苯醚树脂；所述小分子化的聚苯醚树脂为本领域公知的小分子化的聚苯醚树脂，本发明不做特殊限定。According to the present invention, the curing agent may also include a small-molecule polyphenylene ether resin; the small-molecule polyphenylene ether resin is a small-molecule polyphenylene ether resin known in the art, which is not particularly limited in the present invention .

根据本发明，以无卤环氧树脂和固化剂的总量为100重量份计，所述小分子化的聚苯醚树脂的添加量为0～20重量份，例如0重量份、2重量份、4重量份、5重量份、8重量份、10重量份、12重量份、14重量份、15重量份、17重量份或20重量份，以及上述数值之间的具体点值，限于篇幅及出于简明的考虑，本发明不再穷尽列举所述范围包括的具体点值。According to the present invention, based on the total amount of the halogen-free epoxy resin and the curing agent being 100 parts by weight, the addition amount of the small-molecule polyphenylene ether resin is 0 to 20 parts by weight, for example, 0 parts by weight, 2 parts by weight , 4 parts by weight, 5 parts by weight, 8 parts by weight, 10 parts by weight, 12 parts by weight, 14 parts by weight, 15 parts by weight, 17 parts by weight or 20 parts by weight, and the specific point value between the above-mentioned values, limited by space and For the sake of brevity, the present invention does not exhaustively enumerate the specific point values included in the range.

优选地，所述固化剂还包含活性酯固化剂。Preferably, the curing agent further comprises an active ester curing agent.

在本发明中，以无卤环氧树脂和固化剂的总量为100重量份计，所述活性酯固化剂的添加量为0～20重量份，例如0重量份、2重量份、4重量份、5重量份、8重量份、10重量份、12重量份、14重量份、15重量份、17重量份或20重量份，以及上述数值之间的具体点值，限于篇幅及出于简明的考虑，本发明不再穷尽列举所述范围包括的具体点值。In the present invention, based on the total amount of the halogen-free epoxy resin and the curing agent as 100 parts by weight, the active ester curing agent is added in an amount of 0 to 20 parts by weight, such as 0 parts by weight, 2 parts by weight, 4 parts by weight parts by weight, 5 parts by weight, 8 parts by weight, 10 parts by weight, 12 parts by weight, 14 parts by weight, 15 parts by weight, 17 parts by weight or 20 parts by weight, and the specific point values between the above-mentioned values are limited to space and for brevity Considering that the present invention does not exhaustively list the specific point values included in the range.

优选地，所述固化剂还包含双马来酰亚胺-三嗪树脂。Preferably, the curing agent further comprises a bismaleimide-triazine resin.

在本发明中，以无卤环氧树脂和固化剂的总量为100重量份计，所述双马来酰亚胺-三嗪树脂的添加量为0～50重量份，例如0重量份、5重量份、8重量份、10重量份、15重量份、18重量份、20重量份、25重量份、30重量份、35重量份、40重量份、45重量份或50重量份。In the present invention, based on the total amount of the halogen-free epoxy resin and the curing agent as 100 parts by weight, the addition amount of the bismaleimide-triazine resin is 0 to 50 parts by weight, for example, 0 parts by weight, 5 parts by weight, 8 parts by weight, 10 parts by weight, 15 parts by weight, 18 parts by weight, 20 parts by weight, 25 parts by weight, 30 parts by weight, 35 parts by weight, 40 parts by weight, 45 parts by weight, or 50 parts by weight.

优选地，在本发明中，所述无卤热固性树脂组合物，有机固形物按100重量份计，其具体包含：20～60份含磷酸酐树脂、30～60份无卤环氧树脂、5～50份氰酸酯树脂、0～50份双马来酰亚胺-三嗪树脂、0～40份SMA树脂、0～20份酚醛树脂、0～20份聚苯醚树脂和0～20份活性酯树脂。Preferably, in the present invention, the halogen-free thermosetting resin composition, based on 100 parts by weight of organic solids, specifically comprises: 20-60 parts of phosphoric anhydride-containing resin, 30-60 parts of halogen-free epoxy resin, 5 parts by weight ~50 parts of cyanate resin, 0 to 50 parts of bismaleimide-triazine resin, 0 to 40 parts of SMA resin, 0 to 20 parts of phenolic resin, 0 to 20 parts of polyphenylene ether resin, and 0 to 20 parts of Active ester resin.

本发明中所提及的“所述热固性树脂组合物中无卤环氧树脂和固化剂总重量”是指参与交联聚合反应的组分的总重量，其中，固化剂是指起到固化环氧树脂作用的含磷酸酐以及氰酸酯树脂和任选地双马来酰亚胺-三嗪树脂、SMA树脂、酚醛树脂或聚苯醚树脂、活性酯树脂，其不包含填料、促进剂以及阻燃剂等组分。The "total weight of halogen-free epoxy resin and curing agent in the thermosetting resin composition" mentioned in the present invention refers to the total weight of the components participating in the cross-linking polymerization reaction, wherein the curing agent refers to the function of curing ring Oxygenated resins containing phosphoric anhydride and cyanate ester resins and optionally bismaleimide-triazine resins, SMA resins, phenolic resins or polyphenylene ether resins, active ester resins, which do not contain fillers, accelerators and components such as flame retardants.

在本发明中，所述无卤热固性树脂组合物还包括无卤阻燃剂，所述无卤阻燃剂为有机无卤阻燃剂和/或无机无卤阻燃剂。In the present invention, the halogen-free thermosetting resin composition further includes a halogen-free flame retardant, and the halogen-free flame retardant is an organic halogen-free flame retardant and/or an inorganic halogen-free flame retardant.

优选地，所述阻燃剂为含磷阻燃剂和/或含氮阻燃剂。Preferably, the flame retardant is a phosphorus-containing flame retardant and/or a nitrogen-containing flame retardant.

根据本发明，所述阻燃剂选自三(2,6-二甲基苯基)膦、10-(2,5-二羟基苯基)-9,10-二氢-9-氧杂-10-膦菲-10-氧化物、2,6-二(2,6-二甲基苯基)膦基苯、10-苯基-9,10-二氢-9-氧杂-10-膦菲-10-氧化物、苯氧基磷腈化合物、磷酸酯、聚磷酸酯、聚膦酸酯或膦酸酯-碳酸酯共聚物、三聚氰胺聚磷酸盐、三聚氰胺聚磷酸酯、三聚氰胺氰尿酸盐或聚磷酸铵中的任意一种或至少两种的混合物。According to the present invention, the flame retardant is selected from tris(2,6-dimethylphenyl)phosphine, 10-(2,5-dihydroxyphenyl)-9,10-dihydro-9-oxa- 10-Phosphinophenanthrene-10-oxide, 2,6-bis(2,6-dimethylphenyl)phosphinobenzene, 10-phenyl-9,10-dihydro-9-oxa-10-phosphine phenanthrene-10-oxide, phenoxyphosphazene compounds, phosphates, polyphosphates, polyphosphonates or phosphonate-carbonate copolymers, melamine polyphosphates, melamine polyphosphates, melamine cyanurates Or any one of ammonium polyphosphate or a mixture of at least two.

在本发明中，以无卤环氧树脂和固化剂总量为100重量份计，所述无卤阻燃剂的添加量为0～15重量份，例如1重量份、3重量份、5重量份、6重量份、8重量份、9重量份、10重量份、11重量份、12重量份、13重量份或15重量份，以及上述数值之间的具体点值，限于篇幅及出于简明的考虑，本发明不再穷尽列举所述范围包括的具体点值。In the present invention, the halogen-free flame retardant is added in an amount of 0 to 15 parts by weight, for example, 1 part by weight, 3 parts by weight, 5 parts by weight, based on 100 parts by weight of the total amount of halogen-free epoxy resin and curing agent. parts by weight, 6 parts by weight, 8 parts by weight, 9 parts by weight, 10 parts by weight, 11 parts by weight, 12 parts by weight, 13 parts by weight or 15 parts by weight, and the specific point values between the above-mentioned values are limited to space and for brevity Considering that the present invention does not exhaustively list the specific point values included in the range.

优选地，所述无卤热固性树脂组合物还包含固化促进剂。Preferably, the halogen-free thermosetting resin composition further comprises a curing accelerator.

优选地，所述固化促进剂包括有机金属盐和选自咪唑类化合物、咪唑类化合物的衍生物、哌啶类化合物、吡啶类化合物、路易斯酸或三苯基膦中的任意一种或至少两种的混合物。Preferably, the curing accelerator comprises an organic metal salt and any one or at least two selected from imidazoles, derivatives of imidazoles, piperidines, pyridines, Lewis acids or triphenylphosphine species mixture.

优选地，所述有机金属盐包括辛酸金属盐、异辛酸金属盐、乙酰丙酮金属盐、环烷酸金属盐、水杨酸金属盐或硬脂酸金属盐中的任意一种或至少两种的混合物；Preferably, the organic metal salt includes any one or at least two of metal octanoate, metal isooctanoate, metal acetylacetonate, metal naphthenate, metal salicylate or metal stearate. mixture;

优选地，所述有机金属盐中所含金属选自锌、铜、铁、锡、钴或铝中的任意一种或至少两种的混合物。Preferably, the metal contained in the organometallic salt is selected from any one or a mixture of at least two of zinc, copper, iron, tin, cobalt or aluminum.

优选地，所述咪唑类化合物为2-甲基咪唑、2-乙基-4-甲基咪唑、2-苯基咪唑或2-十一烷基咪唑中的任意一种或至少两种的混合物。Preferably, the imidazole compound is any one or a mixture of at least two of 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole or 2-undecylimidazole .

优选地，所述哌啶类化合物为2,3-二氨基哌啶、2,5-二氨基哌啶、2,6-二氨基哌啶、2-氨基-3-甲基哌啶、2-氨基-4-甲基哌啶、2-氨基-3-硝基哌啶、2-氨基-5-硝基哌啶或2-氨基-4,4-二甲基哌啶中的任意一种或至少两种的混合物。Preferably, the piperidine compounds are 2,3-diaminopiperidine, 2,5-diaminopiperidine, 2,6-diaminopiperidine, 2-amino-3-methylpiperidine, 2- Any one of amino-4-methylpiperidine, 2-amino-3-nitropiperidine, 2-amino-5-nitropiperidine or 2-amino-4,4-dimethylpiperidine or A mixture of at least two.

优选地，所述吡啶类化合物为4-二甲氨基吡啶、2-氨基吡啶、3-氨基吡啶或4-氨基吡啶中的任意一种或至少两种混合物。Preferably, the pyridine compound is any one or a mixture of at least two of 4-dimethylaminopyridine, 2-aminopyridine, 3-aminopyridine or 4-aminopyridine.

优选地，以无卤环氧树脂和固化剂总量为100重量份计，所述固化促进剂的添加量为0.01～1重量份，例如0.01重量份、0.025重量份、0.05重量份、0.07重量份、0.085重量份、0.1重量份、0.3重量份、0.5重量份、0.8重量份、0.9重量份或1重量份，优选为0.025～0.85重量份。Preferably, based on the total amount of the halogen-free epoxy resin and the curing agent being 100 parts by weight, the addition amount of the curing accelerator is 0.01 to 1 part by weight, for example, 0.01 part by weight, 0.025 part by weight, 0.05 part by weight, 0.07 part by weight part, 0.085 part by weight, 0.1 part by weight, 0.3 part by weight, 0.5 part by weight, 0.8 part by weight, 0.9 part by weight, or 1 part by weight, preferably 0.025 to 0.85 part by weight.

本发明的无卤热固性树脂组合物还可以包括填料。The halogen-free thermosetting resin composition of the present invention may further include fillers.

优选地，所述填料选自有机填料或无机填料，优选无机填料，进一步优选经过表面处理的无机填料，最优选经过表面处理的二氧化硅。Preferably, the filler is selected from organic fillers or inorganic fillers, preferably inorganic fillers, further preferably surface-treated inorganic fillers, most preferably surface-treated silica.

优选地，所述表面处理的表面处理剂选自硅烷偶联剂、有机硅低聚物或钛酸酯偶联剂中的任意一种或至少两种的混合物。Preferably, the surface treatment agent for the surface treatment is selected from any one or a mixture of at least two of a silane coupling agent, an organosilicon oligomer or a titanate coupling agent.

优选地，以无机填料为100重量份计，所述表面处理剂的添加量为0.1～5重量份，优选0.5～3重量份，更优选0.75～2重量份。Preferably, based on 100 parts by weight of the inorganic filler, the surface treatment agent is added in an amount of 0.1-5 parts by weight, preferably 0.5-3 parts by weight, more preferably 0.75-2 parts by weight.

优选地，所述无机填料选自非金属氧化物、金属氮化物、非金属氮化物、无机水合物、无机盐、金属水合物或无机磷中的任意一种或至少两种的混合物，优选熔融二氧化硅、结晶型二氧化硅、球型二氧化硅、空心二氧化硅、氢氧化铝、氧化铝、滑石粉、氮化铝、氮化硼、碳化硅、硫酸钡、钛酸钡、钛酸锶、碳酸钙、硅酸钙或云母中的任意一种或至少两种的混合物。Preferably, the inorganic filler is selected from any one or a mixture of at least two of non-metal oxides, metal nitrides, non-metal nitrides, inorganic hydrates, inorganic salts, metal hydrates or inorganic phosphorus, preferably molten Silica, crystalline silica, spherical silica, hollow silica, aluminum hydroxide, alumina, talc, aluminum nitride, boron nitride, silicon carbide, barium sulfate, barium titanate, titanium Any one or a mixture of at least two of strontium acid, calcium carbonate, calcium silicate or mica.

优选地，所述有机填料选自聚四氟乙烯粉末、聚苯硫醚或聚醚砜粉末中的任意一种或至少两种的混合物。Preferably, the organic filler is selected from any one or a mixture of at least two of polytetrafluoroethylene powder, polyphenylene sulfide or polyethersulfone powder.

优选地，所述填料的中位粒径为0.01～50μm，优选0.01～20μm，进一步优选0.1～10μm。Preferably, the median particle size of the filler is 0.01-50 μm, preferably 0.01-20 μm, more preferably 0.1-10 μm.

优选地，以无卤环氧树脂和固化剂总量为100重量份计，所述填料的添加量为5～300重量份，例如5重量份、10重量份、20重量份、50重量份、80重量份、100重量份、130重量份、150重量份、180重量份、200重量份、230重量份、250重量份、280重量份或300重量份，优选5～200重量份，进一步优选5～150重量份。Preferably, based on the total amount of the halogen-free epoxy resin and the curing agent being 100 parts by weight, the filler is added in an amount of 5 to 300 parts by weight, such as 5 parts by weight, 10 parts by weight, 20 parts by weight, 50 parts by weight, 80 parts by weight, 100 parts by weight, 130 parts by weight, 150 parts by weight, 180 parts by weight, 200 parts by weight, 230 parts by weight, 250 parts by weight, 280 parts by weight or 300 parts by weight, preferably 5 to 200 parts by weight, more preferably 5 parts by weight ~150 parts by weight.

本发明所述的“包含”，意指其除所述组份外，还可以包括其他组份，这些其他组份赋予所述无卤热固性树脂组合物不同的特性。除此之外，本发明所述的“包含”，还可以替换为封闭式的“为”或“由……组成”。In the present invention, "comprising" means that in addition to the above-mentioned components, other components may be included, and these other components impart different properties to the halogen-free thermosetting resin composition. Besides, "comprising" described in the present invention can also be replaced with closed "is" or "consisting of".

例如，所述无卤热固性树脂组合物还可以含有各种添加剂，作为具体例，可以举出抗氧剂、热稳定剂、抗静电剂、紫外线吸收剂、颜料、着色剂或润滑剂等。这些添加剂可以单独使用，也可以两种或者两种以上混合使用。For example, the halogen-free thermosetting resin composition may further contain various additives, and specific examples thereof include antioxidants, thermal stabilizers, antistatic agents, ultraviolet absorbers, pigments, colorants, and lubricants. These additives may be used alone or in combination of two or more.

另一方面，本发明提供一种树脂胶液，所述树脂胶液是将如上所述的无卤树脂组合物溶解或分散在溶剂中得到。On the other hand, the present invention provides a resin glue solution obtained by dissolving or dispersing the above-mentioned halogen-free resin composition in a solvent.

本发明的树脂胶液的制备方法为本领域的常规技术手段，其具体方法为：先将固形物放入，然后加入液态溶剂，搅拌至固形物完全溶解后，再加入液态树脂和促进剂，继续搅拌均匀即可。The preparation method of the resin glue solution of the present invention is a conventional technical means in the field, and the specific method is as follows: firstly put the solid matter, then add a liquid solvent, stir until the solid matter is completely dissolved, and then add the liquid resin and the accelerator, Continue to stir evenly.

作为本发明中的溶剂，没有特别的限定，作为具体例，可以列举出甲醇、乙醇、丁醇等醇类，乙基溶纤剂、丁基溶纤剂、乙二醇甲醚、卡必醇、丁基卡必醇等醚类，丙酮、丁酮、甲基乙基甲酮、环己酮等酮类；甲苯、二甲苯等芳香烃类；醋酸乙酯、乙氧基乙基乙酸酯等酯类；N,N-二甲基甲酰胺、N,N-二甲基乙酰胺等含氮类溶剂。以上溶剂可单独使用，也可两种或两种以上混合使用。优选丙酮、丁酮、甲基乙基甲酮、环己酮等酮类。所述溶剂的添加量由本领域技术人员根据自己经验来选择，使得树脂胶液达到适合使用的粘度即可。The solvent in the present invention is not particularly limited, and specific examples include alcohols such as methanol, ethanol, and butanol, ethyl cellosolve, butyl cellosolve, ethylene glycol methyl ether, carbitol, and butyl alcohol. Ethers such as base carbitol; ketones such as acetone, methyl ethyl ketone, methyl ethyl ketone, cyclohexanone; aromatic hydrocarbons such as toluene and xylene; esters such as ethyl acetate and ethoxyethyl acetate N,N-dimethylformamide, N,N-dimethylacetamide and other nitrogen-containing solvents. The above solvents may be used alone or in combination of two or more. Ketones such as acetone, butanone, methyl ethyl ketone, and cyclohexanone are preferred. The addition amount of the solvent can be selected by those skilled in the art according to their own experience, so that the resin glue can reach a suitable viscosity for use.

另一方面，本发明提供一种预浸料，所述预浸料包括增强材料及通过含浸干燥后附着其上的如上所述的无卤热固性树脂组合物。In another aspect, the present invention provides a prepreg comprising a reinforcing material and the above halogen-free thermosetting resin composition adhered thereon after being impregnated and dried.

在本发明中，所使用的增强材料无特别的限定，可以为有机纤维、无机纤维编织布或无纺布。所述的有机纤维可以选择芳纶无纺布，所述的无机纤维编织布可以为E-玻纤布、D-玻纤布、S-玻纤布、T玻纤布、NE-玻纤布或石英布。所述增强材料的厚度无特别限定，处于层压板有良好的尺寸稳定性的考虑，所述编织布及无纺布厚度优选0.01～0.2mm，且最好是经过开纤处理及硅烷偶联剂表面处理的，为了提供良好的耐水性和耐热性，所述硅烷偶联剂优选为环氧硅烷偶联剂、氨基硅烷偶联剂或乙烯基硅烷偶联剂中的任意一种或至少两种的混合物。In the present invention, the reinforcing material used is not particularly limited, and may be an organic fiber, an inorganic fiber woven cloth, or a non-woven fabric. The organic fibers can be selected from aramid non-woven fabrics, and the inorganic fiber woven fabrics can be E-glass fiber cloth, D-glass fiber cloth, S-glass fiber cloth, T-glass fiber cloth, NE-glass fiber cloth or quartz cloth. The thickness of the reinforcing material is not particularly limited. Considering the good dimensional stability of the laminate, the thickness of the woven fabric and non-woven fabric is preferably 0.01 to 0.2 mm, and it is best to undergo fiber-opening treatment and silane coupling agent. For surface treatment, in order to provide good water resistance and heat resistance, the silane coupling agent is preferably any one or at least two of epoxy silane coupling agent, amino silane coupling agent or vinyl silane coupling agent. species mixture.

在本发明中，将增强材料通过含浸上述的无卤热固性树脂组合物，在100～250℃(例如100℃、130℃、150℃、180℃、200℃、220℃或250℃)条件下，烘烤1～15分钟(例如1分钟、3分钟、5分钟、7分钟、9分钟、10分钟、12分钟或15分钟)得到所述预浸料。In the present invention, the reinforcing material is impregnated with the above-mentioned halogen-free thermosetting resin composition under the condition of 100-250°C (for example, 100°C, 130°C, 150°C, 180°C, 200°C, 220°C or 250°C), The prepreg is obtained by baking for 1-15 minutes (eg, 1 minute, 3 minutes, 5 minutes, 7 minutes, 9 minutes, 10 minutes, 12 minutes or 15 minutes).

另一方面，本发明提供一种层压板，所述层压板包括至少一张如上所述的预浸料。In another aspect, the present invention provides a laminate comprising at least one prepreg as described above.

另一方面，本发明提供一种覆金属箔层压板，所述覆金属箔层压板含有至少一张如上所述的预浸料以及覆于叠合后的预浸料一侧或两侧的金属箔。In another aspect, the present invention provides a metal foil-clad laminate, the metal foil-clad laminate comprising at least one prepreg as described above and a metal foil covering one or both sides of the laminated prepreg foil.

在本发明中，所述覆金属箔层压板在热压机中固化制得，固化温度为150～250℃(例如150℃、160℃、170℃、180℃、190℃、200℃、210℃、220℃、230℃、240℃或250℃)，固化压力为10～60kg/cm²(例如10kg/cm²、13kg/cm²、15kg/cm²、18kg/cm²、20kg/cm²、22kg/cm²、25kg/cm²、28kg/cm²、30kg/cm²、35kg/cm²、40kg/cm²、45kg/cm²、50kg/cm²、55kg/cm²或60kg/cm²)。In the present invention, the metal-clad laminate is prepared by curing in a hot press, and the curing temperature is 150-250°C (for example, 150°C, 160°C, 170°C, 180°C, 190°C, 200°C, 210°C) , 220℃, 230℃, 240℃ or 250℃), the curing pressure is 10～60kg/cm² (such as 10kg/cm² , 13kg/cm² , 15kg/cm² , 18kg/cm² , 20kg/cm² , 22kg/cm² , 25kg/cm² , 28kg/cm² , 30kg/cm² , 35kg/cm² , 40kg/cm² , 45kg/cm² , 50kg/cm² , 55kg/cm² or 60kg/cm² ) .

在本发明中，所述的金属箔为铜箔、镍箔、铝箔及不锈钢箔(SUS箔)等，其材质不限。In the present invention, the metal foil is copper foil, nickel foil, aluminum foil, stainless steel foil (SUS foil), etc., and the material thereof is not limited.

另一方面，本发明提供一种印制电路板，所述印制电路板包括一张或至少两张叠合的如上所述的预浸料。In another aspect, the present invention provides a printed circuit board comprising one or at least two superimposed prepregs as described above.

相对于现有技术，本发明具有以下有益效果：Compared with the prior art, the present invention has the following beneficial effects:

本发明所提供的无卤热固性树脂组合物以氰酸酯和含磷酸酐共同作为无卤环氧树脂的固化剂，二者协同作用，增强组合物的高耐热性，并具有低介质损耗值，并且三种树脂混合固化，共同作用还带来体系具有优异的抗剥离强度和层间粘合力以及优异的阻燃性。由本发明的无卤热固性树脂组合物制成的预浸料和印制电路用层压板，具有高达248℃的玻璃化转变温度，优异的介电性能，吸水率控制在0.05～0.11％范围内，具有高耐热性，优异的耐湿热性和良好的工艺加工性以及优异的阻燃效率，磷含量1.97％阻燃性就可以达到UL94V-0级别。The halogen-free thermosetting resin composition provided by the present invention uses cyanate ester and phosphoric anhydride as curing agent for halogen-free epoxy resin together, and the two synergize, enhance the high heat resistance of the composition, and have low dielectric loss value , and the three resins are mixed and cured, and the joint action also brings the system to have excellent peel strength and interlayer adhesion, as well as excellent flame retardancy. The prepreg and printed circuit laminate made of the halogen-free thermosetting resin composition of the present invention have a glass transition temperature as high as 248° C., excellent dielectric properties, and the water absorption rate is controlled within the range of 0.05-0.11%, With high heat resistance, excellent heat and humidity resistance, good processability and excellent flame retardant efficiency, the flame retardancy of phosphorus content of 1.97% can reach UL94V-0 level.

附图说明Description of drawings

图1为本发明含磷酸酐DOPO-MAH的红外光谱图。Fig. 1 is the infrared spectrogram of phosphoric anhydride-containing DOPO-MAH of the present invention.

具体实施方式Detailed ways

下面通过具体实施方式来进一步说明本发明的技术方案。本领域技术人员应该明了，所述实施例仅仅是帮助理解本发明，不应视为对本发明的具体限制。The technical solutions of the present invention are further described below through specific embodiments. It should be understood by those skilled in the art that the embodiments are only for helping the understanding of the present invention, and should not be regarded as a specific limitation of the present invention.

制备例1Preparation Example 1

含磷酸酐DOPO-MAH的合成Synthesis of DOPO-MAH Containing Phosphoric Anhydride

将49g马来酸酐、108g的DOPO于装有搅拌器、温度计的四颈瓶中搅拌，同时通入氮气，然后升温到125℃，在此温度下反应3h，得到产物，编号为DOPO-MAH。其结构为：49g of maleic anhydride and 108g of DOPO were stirred in a four-necked flask equipped with a stirrer and a thermometer, while nitrogen was introduced, and then the temperature was raised to 125°C, and the reaction was carried out at this temperature for 3h to obtain a product, numbered as DOPO-MAH. Its structure is:

利用红外光谱仪Nicolet TR-460进行表征，如图1所示，为DOPO-MAH的红外光谱图，可以看出，DOPO结构中的P-H在2361cm^-1、2342cm^-1的特征吸收消失，说明其已完全反应；1865cm^-1和1787cm^-1为五元环状酸酐的特征吸收，说明新生成结构中含有五元酸酐的结构，说明合成出以上结构的含磷酸酐。Characterized by infrared spectrometer Nicolet TR-460, as shown in Figure 1, which is the infrared spectrum of DOPO-MAH, it can be seen that the characteristic absorption of PH in DOPO structure at 2361cm^-1 and 2342cm^-1 disappears, indicating that it has been Complete reaction; 1865cm^-1 and 1787cm^-1 are characteristic absorptions of the five-membered cyclic acid anhydride, indicating that the newly generated structure contains the structure of the five-membered acid anhydride, indicating that the phosphoric anhydride containing the above structure was synthesized.

实施例1-9Examples 1-9

如表1和表2(组分用量以重量份计)所示，将含磷酸酐、无卤环氧树脂以及固化促进剂、无卤阻燃剂、填料按一定比例于溶剂中混合均匀，控制胶液固含量为65％，用2116玻纤布浸渍上述胶液，控制合适厚度，然后在115～175℃的烘箱中烘烤2～15min制成预浸料，然后将数张预浸料叠在一起，在其两侧叠上18μRTF铜箔，在固化温度为170～250℃，固化压力为25～60kg/cm²，固化时间为60～300min条件下制成覆铜板，其树脂组合物组成以及覆铜板的性能测试标准如表1和表2所示。As shown in Table 1 and Table 2 (the amount of components is in parts by weight), the phosphoric anhydride, halogen-free epoxy resin, curing accelerator, halogen-free flame retardant and filler are mixed in a solvent in a certain proportion, and the control The solid content of the glue liquid is 65%. Impregnate the above glue liquid with 2116 glass fiber cloth, control the appropriate thickness, and then bake it in an oven at 115 ~ 175 ° C for 2 ~ 15 minutes to make prepregs, and then stack several prepregs. Together, stack 18μRTF copper foil on both sides, and make a copper clad laminate under the conditions that the curing temperature is 170-250°C, the curing pressure is 25-60kg/cm² , and the curing time is 60-300min. And the performance test standards of CCL are shown in Table 1 and Table 2.

比较例1-10Comparative Examples 1-10

树脂组合物的组成如表3和表4(组分用量以重量份计)所示，除此之外，覆铜板的制备方法与实施例1-10相同。The composition of the resin composition is shown in Table 3 and Table 4 (the amount of the components is in parts by weight), except that the preparation method of the copper clad laminate is the same as that of Examples 1-10.

实施例1-9和比较例1-10涉及材料及牌号信息如下：Embodiment 1-9 and comparative example 1-10 relate to material and brand information as follows:

(A)氰酸酯(A) Cyanate ester

CY-40：吴桥树酯厂，DCPD型氰酸酯树脂CY-40: Wuqiao Resin Factory, DCPD type cyanate resin

PT-60S：LONCZ，酚醛型氰酸酯树脂PT-60S: LONCZ, phenolic cyanate resin

CE01PS：江苏天启，双酚A型氰酸酯树脂CE01PS: Jiangsu Tianqi, bisphenol A cyanate resin

CE01MO：江苏天启，双酚A型氰酸酯树脂CE01MO: Jiangsu Tianqi, Bisphenol A Cyanate Resin

(B)环氧树脂(B) Epoxy resin

HP-7200HHH：DIC，DCPD型环氧树脂，环氧当量288HP-7200HHH: DIC, DCPD type epoxy resin, epoxy equivalent 288

HP-7200H-75M：DIC，DCPD型环氧树脂，环氧当量280HP-7200H-75M: DIC, DCPD type epoxy resin, epoxy equivalent weight 280

HP-6000：DIC，环氧树脂，环氧当量250HP-6000: DIC, epoxy resin, epoxy equivalent 250

HP-9900：DIC，萘酚型环氧树脂，环氧当量274HP-9900: DIC, naphthol type epoxy resin, epoxy equivalent weight 274

NC-3000H：日本化药，联苯环氧树脂，环氧当量294NC-3000H: Nippon Kayaku, biphenyl epoxy resin, epoxy equivalent 294

SKE-1：尚科特，特种环氧树脂，环氧当量120SKE-1: Shancote, special epoxy resin, epoxy equivalent 120

SKE-3：尚科特，特种环氧树脂，环氧当量120SKE-3: Shancote, special epoxy resin, epoxy equivalent 120

(C)含磷酸酐(C) containing phosphoric anhydride

DOPO-MAH：

DOPO-MAH:

DOPO-MAH-1：

DOPO-MAH-1:

P-A1：

P-A1:

(D)SMA树脂(D)SMA resin

EF60：克莱维利，苯乙烯-马来酸酐共聚物EF60: Cleverley, styrene-maleic anhydride copolymer

(E)酚醛树脂(E) Phenolic resin

DOW92741：含磷酚醛，陶氏化学DOW92741: Phosphorus-Containing Phenolic, Dow Chemical

(F)小分子聚苯醚树脂(F) Small molecule polyphenylene ether resin

SA90，沙伯基，端羟基小分子化聚苯醚树脂SA90, SABIC, hydroxyl-terminated small molecular polyphenylene ether resin

(G)活性酯树脂(G) Active ester resin

HPC-8000-65T:DIC，DCPD型活性酯树脂HPC-8000-65T: DIC, DCPD type active ester resin

(H)促进剂(H) Accelerator

2E4MZ：2-乙基-4-甲基咪唑，四国化成2E4MZ: 2-ethyl-4-methylimidazole, Shikoku Chemical

DMAP：4-二甲氨基吡啶，广荣化学DMAP: 4-Dimethylaminopyridine, Guangrong Chemical

BICAT Z：异辛酸锌，The Shepherd Chemical CompanyBICAT Z: Zinc isooctanoate, The Shepherd Chemical Company

(I)填料(I) Filler

DQ-1028L：江苏联瑞，球型硅微粉DQ-1028L: Jiangsu Lianrui, spherical silica powder

(J)阻燃剂(J) Flame Retardant

SPB-100：大塚化学，膦腈类阻燃剂，磷含量13.4％SPB-100: Otsuka Chemical, phosphazene flame retardant, phosphorus content 13.4%

MC-15：寿光普尔化工，MCA阻燃剂。MC-15: Shouguang Puer Chemical, MCA flame retardant.

表1-2是实施例1～10，表3-4是比较例1～10的配方组成及其物性数据。Table 1-2 is Examples 1-10, and Table 3-4 is the formulation composition and physical property data of Comparative Examples 1-10.

表1Table 1

实施例1Example 1实施例2Example 2实施例3Example 3实施例4Example 4实施例5Example 5DOPO-MAHDOPO-MAH15152020303035354040CE01MOCE01MO5050CEO1PSCEO1PS4040CY-40CY-401010PT-60SPT-60S5555HP-7200HHHHP-7200HHH6060NC-3000HNC-3000H404060605555SKE-3SKE-33535SPB-100SPB-10044异辛酸锌Zinc isooctanoate0.01250.01250.040.040.020.020.0250.0250.0250.0252-PZ2-PZ110.80.80.60.60.40.40.20.2DQ-1028LDQ-1028L005050150150300300300300P％P%2.02％2.02%1.97％1.97%2.96％2.96%3.45％3.45%3.95％3.95%Tg(DMA)/℃Tg(DMA)/℃248248230230210210182182188188Dk(10GHz)Dk(10GHz)3.723.723.803.804.004.004.204.204.204.20Df(10GHz)Df(10GHz)0.00680.00680.00650.00650.00700.00700.00680.00680.00630.0063PS热应力/N/mmPS thermal stress/N/mm1.21.21.151.150.90.90.80.80.80.8层间结合力/N/mmBonding force between layers/N/mm0.82-1.250.82-1.250.76-1.130.76-1.130.56-0.930.56-0.930.54-0.880.54-0.880.52-0.830.52-0.83吸水性/％Water absorption/%0.110.110.080.080.0650.0650.0520.0520.0550.055PCT/6hPCT/6hOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOT288/minT288/min＞60>60＞60>60＞60>60＞60>60＞60>60难燃烧性IncombustibilityV-0V-0V-0V-0V-0V-0V-0V-0V-0V-0

表2Table 2

表3table 3

表4Table 4

比较例6Comparative Example 6比较例7Comparative Example 7比较例8Comparative Example 8比较例9Comparative Example 9比较例10Comparative Example 10DOPO-MAHDOPO-MAH2020202020202020PA-1PA-11515CE01MOCE01MO20201010101020205050DOW92741DOW927412525EF60EF604545SA90SA902525HPC-8000-65THPC-8000-65T2525HP-6000HP-60004545HP-9900HP-99003535NC-3000HNC-3000H3535SKE-3SKE-325253535SPB100SPB100552244MC-15MC-15101066异辛酸锌Zinc isooctanoate0.040.040.010.010.010.010.020.020.01250.01252E4MZ2E4MZ000.20.20.40.40.80.82-PZ2-PZ11DQ-1028LDQ-1028L505050505050505000P％P%4.47％4.47%2.64％2.64%1.97％1.97%2.24％2.24%1.28％1.28%Tg(DMA)/℃Tg(DMA)/℃125125200200205205145145252252Dk(10GHz)Dk(10GHz)3.93.93.83.83.93.93.83.83.723.72Df(10GHz)Df(10GHz)0.00850.00850.0060.0060.0070.0070.0060.0060.00680.0068PS热应力/N/mmPS thermal stress/N/mm0.650.651.11.10.980.981.231.231.21.2层间结合力/N/mmBonding force between layers/N/mm0.32-0.450.32-0.450.76-1.030.76-1.030.71-1.000.71-1.000.95-1.240.95-1.240.82-1.250.82-1.25吸水性/％Water absorption/%0.150.150.0550.0550.0720.0720.070.070.140.14PCT/6hPCT/6hxxxxxxOOOOOOOOOOOOxxxxxxxxxxxxT288/minT288/min243℃分层243℃ stratification＞60>60＞60>60276℃分层276℃ stratification＞60>60难燃烧性IncombustibilityV-0V-0V-1V-1V-1V-1V-1V-1V-1V-1

PCT/6h性能图标的补充说明：×为分层爆板，O为不分层爆板。Supplementary description of PCT/6h performance icon: × is a layered explosion board, O is a non-layered explosion board.

以上特性的测试方法如下：The test methods for the above characteristics are as follows:

(1)玻璃化转变温度(Tg)：使用DMA测试，按照IPC-TM-650 2.4.24所规定的DMA测试方法进行测定。(1) Glass transition temperature (Tg): measured by DMA test according to the DMA test method specified in IPC-TM-650 2.4.24.

(2)介电常数和介电损耗因子：按照SPDR方法测试。(2) Dielectric constant and dielectric loss factor: tested according to SPDR method.

(3)耐湿热性(PCT)评价：将覆铜板表面的铜箔蚀刻后，评价基板；将基板放置压力锅中，在120℃、105KPa条件下处理6小时后，浸渍在288℃的锡炉中，当基板分层爆板时记录相应时间；当基板在锡炉中超过5min还没出现起泡或分层时即可结束评价。(3) Evaluation of Moisture and Heat Resistance (PCT): After etching the copper foil on the surface of the copper clad laminate, the substrate was evaluated; the substrate was placed in a pressure cooker, treated at 120°C and 105KPa for 6 hours, and then immersed in a tin furnace at 288°C , and record the corresponding time when the substrate is delaminated and exploded; when the substrate has not been blistered or delaminated in the tin furnace for more than 5 minutes, the evaluation can be ended.

(4)T288：用TMA仪，按照IPC-TM-650 2.4.24.1所规定的T300测试方法进行测定。(4) T288: use a TMA instrument to measure according to the T300 test method specified in IPC-TM-650 2.4.24.1.

(5)吸水性：按照IPC-TM-650 2.6.2.1所规定的吸水性测试方法进行测定。(5) Water absorption: measured according to the water absorption test method specified in IPC-TM-650 2.6.2.1.

(6)阻燃性：按照UL 94标准方法进行。(6) Flame retardancy: according to UL 94 standard method.

(7)PS热应力：按IPC-TM-650 2.4.8(12/94C版)标准方法进行。(7) PS thermal stress: according to the standard method of IPC-TM-650 2.4.8 (version 12/94C).

(8)层间结合力：Q/GDSY 6052-2016P01标准方法进行。(8) Interlayer adhesion: Q/GDSY 6052-2016P01 standard method.

从表1-4的数据对比可以看出：From the data comparison in Table 1-4, it can be seen that:

比较例1和实施例1比较，比较例1中使用氰酸酯添加量超上限和含磷酸酐超下限，所制成的覆铜板耐湿热性差，PCT爆板，阻燃性较差，达不到V0级；比较例2和实施例2比较，比较例2中使用环氧树脂不足，导致含磷酸酐添加量太多，板材不能完全固化，导致耐热性、耐湿热性、层间结合力、抗剥离强度都较差；比较例3和实施例3比较，比较例3中环氧树脂较多，固化剂含量相对较少，板材不能很好固化，导致Tg低，电性能差；比较例4和实施例4比较，比较例4中未使用氰酸酯树脂，所制成的覆铜板介电性能较差、Tg低；比较例5和实施例2比较，比较例5中用DOPO-MAH-1此种结构的含磷酸酐，由于DOPO结构相连多一个柔性的次甲基，导致其Tg低和阻燃性差。Comparative Example 1 and Example 1 are compared. In Comparative Example 1, the amount of cyanate ester added exceeds the upper limit and the phosphoric anhydride content exceeds the lower limit. Compared with Example 2, the epoxy resin used in Comparative Example 2 was insufficient, resulting in too much phosphoric anhydride added, and the board could not be fully cured, resulting in heat resistance, damp heat resistance, and interlayer adhesion. Compared with Example 3, Comparative Example 3 has more epoxy resin, and the content of curing agent is relatively small, and the plate cannot be cured well, resulting in low Tg and poor electrical properties; Comparative Example 4 Compared with Example 4, the cyanate ester resin is not used in Comparative Example 4, and the prepared copper clad laminate has poor dielectric properties and low Tg; Comparative Example 5 is compared with Example 2, and DOPO-MAH is used in Comparative Example 5. -1 The phosphoric anhydride containing this structure has a low Tg and poor flame retardancy due to the DOPO structure connecting with one more flexible methine group.

另外，将比较例6与实施例6进行比较可知，比较例6中含磷酚醛较多，导致板材环氧树脂量不足，固化剂含量过量，板材不能很好固化，导致耐热性、耐湿热性、介电性能差。将比较例7与实施例7进行比较可知，比较例7中使用SMA树脂较多，导致所制成的覆铜板Tg低、阻燃性差。将比较例8与实施例8进行比较可知，比较例8中使用PPO树脂较多，导致所制成的覆铜板Tg低、阻燃性差。将比较例9与实施例9进行比较可知，比较例9中含活性酯较多，导致板材环氧树脂量不足，固化剂含量过量，板材不能很好固化，导致Tg低、耐热性、耐湿热性差。比较例10同实施例1比较，PA-1此种结构的含磷酸酐，其吸水率较DOPO结构的含磷酸酐吸水率要高，其PCT容易分层爆板，且由于其磷含量较低，同样添加量，其总磷含量较低，阻燃难以达到V0级。In addition, comparing Comparative Example 6 with Example 6, it can be seen that there are more phosphorus-containing phenolic aldehydes in Comparative Example 6, resulting in insufficient epoxy resin content and excessive curing agent content. Properties and dielectric properties are poor. Comparing Comparative Example 7 with Example 7, it can be seen that in Comparative Example 7, many SMA resins are used, resulting in low Tg and poor flame retardancy of the copper clad laminate produced. Comparing Comparative Example 8 with Example 8, it can be seen that in Comparative Example 8, a large amount of PPO resin is used, resulting in low Tg and poor flame retardancy of the copper clad laminate produced. Comparing Comparative Example 9 with Example 9, it can be seen that Comparative Example 9 contains more active esters, resulting in insufficient epoxy resin content and excessive curing agent content. Poor heat and humidity. Comparative example 10 is compared with embodiment 1, the PA-1 structure containing phosphoric anhydride, its water absorption rate is higher than that of DOPO structure containing phosphoric anhydride, its PCT is easy to be layered and exploded, and because its phosphorus content is low , the same amount of addition, the total phosphorus content is low, the flame retardant is difficult to reach V0 level.

通过上述结果可以看出，通过将本发明所指的含磷酸酐、无卤环氧树脂和氰酸酯树脂，以及其它可能的环氧固化剂复合，所制成的预浸料和印制电路用层压板，具有高达248℃的玻璃化转变温度；优异的介电性能，吸水率控制在0.05～0.11％范围内；高耐热性；优异的耐湿热性和良好的工艺加工性；优异的阻燃效率，磷含量1.97％就可以达到UL94V-0。It can be seen from the above results that by compounding the phosphoric anhydride-containing, halogen-free epoxy resin and cyanate ester resin referred to in the present invention, and other possible epoxy curing agents, the prepreg and printed circuit prepared Laminate with glass transition temperature as high as 248°C; excellent dielectric properties, water absorption controlled within the range of 0.05 to 0.11%; high heat resistance; excellent heat and humidity resistance and good processability; excellent Flame retardant efficiency, phosphorus content of 1.97% can reach UL94V-0.

综上所述，与一般的层压板相比，本发明所提供的无卤热固性树脂组合物制成的预浸料和印制电路用层压板，具有高玻璃化转变温度、优异的介电性能、低吸水率、高耐热性、优异的耐湿热性和良好的工艺加工性，并能实现无卤阻燃，达到UL94V-0无卤阻燃。To sum up, compared with general laminates, the prepregs and printed circuit laminates made from the halogen-free thermosetting resin composition provided by the present invention have high glass transition temperature and excellent dielectric properties. , Low water absorption, high heat resistance, excellent heat and humidity resistance and good processability, and can achieve halogen-free flame retardant, reaching UL94V-0 halogen-free flame retardant.

申请人声明，本发明通过上述实施例来说明本发明的无卤热固性树脂组合物、使用它的预浸料、层压板及印制电路板，但本发明并不局限于上述实施例，即不意味着本发明必须依赖上述实施例才能实施。所属技术领域的技术人员应该明了，对本发明的任何改进，对本发明产品各原料的等效替换及辅助成分的添加、具体方式的选择等，均落在本发明的保护范围和公开范围之内。The applicant declares that the present invention is to illustrate the halogen-free thermosetting resin composition of the present invention, the prepreg using the same, the laminate and the printed circuit board by the above-mentioned examples, but the present invention is not limited to the above-mentioned examples, that is, it is not limited to the above-mentioned examples. It means that the present invention must rely on the above-mentioned embodiments to be implemented. Those skilled in the art should understand that any improvement of the present invention, the equivalent replacement of each raw material of the product of the present invention, the addition of auxiliary components, the selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

Claims (50)

1. The halogen-free thermosetting resin composition is characterized by comprising halogen-free epoxy resin and a curing agent, wherein the curing agent comprises cyanate ester resin and phosphoric anhydride resin and does not comprise SMA resin, and the contents of the components are as follows:

5-50 parts of cyanate ester resin

30-60 parts of halogen-free epoxy resin

15-40 parts of phosphoric anhydride resin;

the phosphoric anhydride resin is DOPO type phosphoric anhydride resin;

the phosphoric anhydride-containing resin is a resin with the following structure:

2. the halogen-free thermosetting resin composition according to claim 1, wherein the cyanate ester resin has the following structure:

wherein R is₅is-CH₂-、

Any one or a mixture of at least two of them; r₁、R₂、R₃、R₄、R₆、R₇、R₈、R₉Each independently selected from any one of hydrogen atom, substituted or unsubstituted straight-chain alkyl or branched-chain alkyl with 1-4 carbon atoms.

3. The halogen-free thermosetting resin composition according to claim 1, wherein the cyanate ester resin is selected from the group consisting of 2, 2-bis (4-cyanatophenyl) propane, bis (4-cyanatophenyl) ethane, bis (3, 5-dimethyl-4-cyanatophenyl) methane, 2-bis (4-cyanatophenyl) -1,1,1,3,3, 3-hexafluoropropane, α' -bis (4-cyanatophenyl) -m-diisopropylbenzene, cyclopentadiene-type cyanate ester, phenol novolac-type cyanate ester, cresol novolac-type cyanate ester, 2-bis (4-cyanatophenyl) propane prepolymer, bis (4-cyanatophenyl) ethane prepolymer, bis (3, 5-dimethyl-4-cyanatophenyl) methane prepolymer, 2, 2-bis (4-cyanatophenyl) -1,1,1,3,3, 3-hexafluoropropane prepolymer, α' -bis (4-cyanatophenyl) -m-diisopropylbenzene prepolymer, dicyclopentadiene type cyanate prepolymer, phenol novolac type cyanate prepolymer or cresol novolac type cyanate prepolymer, or a mixture of at least two thereof.

4. The halogen-free thermosetting resin composition according to claim 3, wherein the cyanate ester resin is selected from any one of 2, 2-bis (4-cyanatophenyl) propane, α '-bis (4-cyanatophenyl) -m-diisopropylbenzene, bis (3, 5-dimethyl-4-cyanatophenyl) methane, 2-bis (4-cyanatophenyl) propane prepolymer, α' -bis (4-cyanatophenyl) -m-diisopropylbenzene prepolymer, or bis (3, 5-dimethyl-4-cyanatophenyl) methane prepolymer, or a mixture of at least two thereof.

5. The halogen-free thermosetting resin composition according to claim 1, wherein the halogen-free epoxy resin is any one or a mixture of at least two of glycidyl ether epoxy resin, glycidyl ester epoxy resin, glycidyl amine epoxy resin, alicyclic epoxy resin, epoxidized olefin epoxy resin, hydantoin epoxy resin or imide epoxy resin.

6. The halogen-free thermosetting resin composition according to claim 5, wherein the glycidyl ether type epoxy resin comprises any one of bisphenol A type epoxy resin, bisphenol F type epoxy resin, o-cresol novolac epoxy resin, bisphenol A type novolac epoxy resin, triphenol type novolac epoxy resin, dicyclopentadiene novolac epoxy resin, biphenyl type novolac epoxy resin, alkylbenzene type novolac epoxy resin or naphthol type novolac epoxy resin or a mixture of at least two thereof.

7. Halogen-free thermosetting resin composition according to claim 5, characterized in that the glycidyl ether based epoxy resin is selected from epoxy resins having the following structure:

wherein Z is₁、Z₂And Z₃Each independently selected from

R is selected from any one of hydrogen atoms, substituted or unsubstituted linear alkyl or branched alkyl containing 1-5 carbon atoms; y is₁And Y₂Each independently selected from-CH₂-、

Any one of the above; r₁₀Selected from any one of hydrogen atom, substituted or unsubstituted linear alkyl or branched alkyl containing 1-5 carbon atoms, n₂Is an arbitrary integer of 1 to 10.

8. Halogen-free thermosetting resin composition according to claim 5, characterized in that the glycidyl amine based epoxy resin is selected from any one or a mixture of at least two of triglycidyl p-aminophenol, triglycidyl isocyanurate, tetraglycidyl diaminodimethylene benzene, tetraglycidyl-4, 4 ' -diaminodiphenylmethane, tetraglycidyl-3, 4 ' -diaminodiphenyl ether, tetraglycidyl-4, 4 ' -diaminodiphenyl ether or tetraglycidyl-1, 3-diaminomethylcyclohexane.

9. The halogen-free thermosetting resin composition according to claim 1, wherein the curing agent further comprises a phenolic resin, and the phenolic resin is a phenolic resin containing phosphorus or not containing phosphorus.

10. The halogen-free thermosetting resin composition according to claim 9, wherein the phenolic resin is added in an amount of 0 to 20 parts by weight, excluding 0, based on 100 parts by weight of the total amount of the halogen-free epoxy resin and the curing agent.

11. The halogen-free thermosetting resin composition as claimed in claim 1, wherein the curing agent further comprises a small molecular polyphenylene ether resin.

12. The halogen-free thermosetting resin composition according to claim 11, wherein the small molecular polyphenylene ether resin is added in an amount of 0 to 20 parts by weight excluding 0, based on 100 parts by weight of the total amount of the halogen-free epoxy resin and the curing agent.

13. The halogen-free thermosetting resin composition according to claim 1, wherein the curing agent further comprises an active ester curing agent.

14. The halogen-free thermosetting resin composition according to claim 13, wherein the active ester curing agent is added in an amount of 0 to 20 parts by weight excluding 0, based on 100 parts by weight of the total amount of the halogen-free epoxy resin and the curing agent.

15. The halogen-free thermosetting resin composition according to claim 1, further comprising a halogen-free flame retardant, wherein the halogen-free flame retardant is an organic halogen-free flame retardant and/or an inorganic halogen-free flame retardant.

16. The halogen-free thermosetting resin composition according to claim 15, wherein the halogen-free flame retardant is a phosphorus-containing flame retardant and/or a nitrogen-containing flame retardant.

17. The halogen-free thermosetting resin composition according to claim 16, the halogen-free flame retardant is selected from any one or a mixture of at least two of tris (2, 6-dimethylphenyl) phosphine, 10- (2, 5-dihydroxyphenyl) -9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2, 6-bis (2, 6-dimethylphenyl) phosphinobenzene, 10-phenyl-9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, a phenoxyphosphazene compound, phosphate ester, polyphosphate ester, polyphosphonate or phosphonate-carbonate copolymer, melamine polyphosphate, melamine cyanurate and ammonium polyphosphate.

18. The halogen-free thermosetting resin composition according to claim 15, wherein the halogen-free flame retardant is added in an amount of 0 to 15 parts by weight excluding 0, based on 100 parts by weight of the total amount of the halogen-free epoxy resin and the curing agent.

19. The halogen-free thermosetting resin composition according to claim 18, further comprising a curing accelerator.

20. The halogen-free thermosetting resin composition according to claim 19, wherein the curing accelerator comprises an organic metal salt and any one or a mixture of at least two selected from imidazole compounds, derivatives of imidazole compounds, piperidine compounds, pyridine compounds, lewis acids or triphenylphosphine.

21. The halogen-free thermosetting resin composition according to claim 20, wherein the organic metal salt comprises any one or a mixture of at least two of a metal salt of caprylic acid, a metal salt of isooctanoic acid, a metal salt of acetylacetone, a metal salt of naphthenic acid, a metal salt of salicylic acid, or a metal salt of stearic acid.

22. The halogen-free thermosetting resin composition according to claim 20, wherein the metal contained in the organic metal salt is selected from any one or a mixture of at least two of zinc, copper, iron, tin, cobalt or aluminum.

23. The halogen-free thermosetting resin composition according to claim 20, wherein the imidazole based compound is any one or a mixture of at least two of 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole and 2-undecylimidazole.

24. The halogen-free thermosetting resin composition according to claim 20, wherein the piperidine compound is any one or a mixture of at least two of 2, 3-diaminopiperidine, 2, 5-diaminopiperidine, 2, 6-diaminopiperidine, 2-amino-3-methylpiperidine, 2-amino-4-methylpiperidine, 2-amino-3-nitropiperidine, 2-amino-5-nitropiperidine, or 2-amino-4, 4-dimethylpiperidine.

25. The halogen-free thermosetting resin composition according to claim 20, wherein the pyridine compound is any one or a mixture of at least two of 4-dimethylaminopyridine, 2-aminopyridine, 3-aminopyridine and 4-aminopyridine.

26. The halogen-free thermosetting resin composition according to claim 20, wherein the curing accelerator is added in an amount of 0.01 to 1 part by weight based on 100 parts by weight of the total amount of the halogen-free epoxy resin and the curing agent.

27. The halogen-free thermosetting resin composition according to claim 26, wherein the curing accelerator is added in an amount of 0.025 to 0.85 parts by weight.

28. The halogen-free thermosetting resin composition according to claim 1, wherein the halogen-free thermosetting resin composition further comprises a filler.

29. Halogen-free thermosetting resin composition according to claim 28, characterised in that the filler is selected from organic or inorganic fillers.

30. The halogen-free thermosetting resin composition according to claim 29, wherein the filler is an inorganic filler.

31. The halogen-free thermosetting resin composition according to claim 30, wherein the filler is an inorganic filler subjected to surface treatment.

32. The halogen-free thermosetting resin composition according to claim 31, wherein the filler is surface-treated silica.

33. The halogen-free thermosetting resin composition according to claim 32, wherein the surface treatment agent is selected from any one or a mixture of at least two of silane coupling agent, silicone oligomer or titanate coupling agent.

34. The halogen-free thermosetting resin composition according to claim 32, wherein the surface treatment agent is added in an amount of 0.1 to 5 parts by weight based on 100 parts by weight of the inorganic filler.

35. The halogen-free thermosetting resin composition according to claim 34, wherein the surface treatment agent is added in an amount of 0.5 to 3 parts by weight based on 100 parts by weight of the inorganic filler.

36. The halogen-free thermosetting resin composition according to claim 35, wherein the surface treatment agent is added in an amount of 0.75 to 2 parts by weight based on 100 parts by weight of the inorganic filler.

37. The halogen-free thermosetting resin composition according to claim 29, wherein the inorganic filler is selected from any one or a mixture of at least two of non-metal oxide, metal nitride, non-metal nitride, inorganic hydrate, inorganic salt, metal hydrate or inorganic phosphorus.

38. The halogen-free thermosetting resin composition according to claim 37, wherein the inorganic filler is selected from any one or a mixture of at least two of fused silica, crystalline silica, spherical silica, hollow silica, aluminum hydroxide, alumina, talc, aluminum nitride, boron nitride, silicon carbide, barium sulfate, barium titanate, strontium titanate, calcium carbonate, calcium silicate or mica.

39. The halogen-free thermosetting resin composition according to claim 29, wherein the organic filler is selected from any one of polytetrafluoroethylene powder, polyphenylene sulfide or polyether sulfone powder or a mixture of at least two of the polytetrafluoroethylene powder, the polyphenylene sulfide and the polyether sulfone powder.

40. The halogen-free thermosetting resin composition according to claim 29, wherein the filler has a median particle diameter of 0.01 to 50 μm.

41. The halogen-free thermosetting resin composition according to claim 40, wherein the filler has a median particle diameter of 0.01 to 20 μm.

42. The halogen-free thermosetting resin composition according to claim 41, wherein the filler has a median particle diameter of 0.1 to 10 μm.

43. The halogen-free thermosetting resin composition according to claim 29, wherein the filler is added in an amount of 5 to 300 parts by weight based on 100 parts by weight of the total amount of the halogen-free epoxy resin and the curing agent.

44. The halogen-free thermosetting resin composition according to claim 43, wherein the filler is added in an amount of 5 to 200 parts by weight.

45. The halogen-free thermosetting resin composition according to claim 44, wherein the filler is added in an amount of 5 to 150 parts by weight.

46. A resin cement, which is obtained by dissolving or dispersing the halogen-free thermosetting resin composition according to any one of claims 1 to 45 in a solvent.

47. A prepreg comprising a reinforcing material and the halogen-free thermosetting resin composition of any one of claims 1-45 attached thereto by drying by impregnation.

48. A laminate comprising at least one prepreg according to claim 47.

49. A metal-clad laminate comprising at least one prepreg according to claim 47 and a metal foil clad on one or both sides of the laminated prepreg.

50. A printed circuit board comprising one or at least two superimposed prepregs according to claim 47.

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