WO2016138760A1 - 一种树脂组合物以及使用它的预浸料和层压板 - Google Patents

一种树脂组合物以及使用它的预浸料和层压板 Download PDF

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Publication number
WO2016138760A1
WO2016138760A1 PCT/CN2015/089907 CN2015089907W WO2016138760A1 WO 2016138760 A1 WO2016138760 A1 WO 2016138760A1 CN 2015089907 W CN2015089907 W CN 2015089907W WO 2016138760 A1 WO2016138760 A1 WO 2016138760A1
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Prior art keywords
weight
maleimide
parts
tert
polyphenylene ether
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PCT/CN2015/089907
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English (en)
French (fr)
Inventor
曾宪平
陈广兵
关迟记
杨文华
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广东生益科技股份有限公司
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Priority to US15/555,212 priority Critical patent/US10858514B2/en
Publication of WO2016138760A1 publication Critical patent/WO2016138760A1/zh

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    • C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08L71/12—Polyphenylene oxides
    • C08L71/126—Polyphenylene oxides modified by chemical after-treatment
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Definitions

  • the invention belongs to the technical field of copper clad laminates, and relates to a resin composition and a prepreg and a laminate thereof using the same.
  • the relationship between the signal transmission rate and the dielectric constant Dk of the insulating material is such that the lower the dielectric constant Dk of the insulating material, the faster the signal transmission rate. Therefore, in order to increase the speed of the signal transmission rate, it is necessary to develop a substrate having a low dielectric constant. As the signal rate increases, the loss of signal in the substrate can no longer be ignored.
  • the relationship between the signal loss and the rate, the dielectric constant Dk, and the dielectric loss factor Df is such that the smaller the dielectric constant Dk of the substrate is, the smaller the dielectric loss factor Df is, and the smaller the signal loss is.
  • the polyphenylene ether resin has a large amount of benzene ring structure and no strong polar groups, which gives the polyphenylene ether resin excellent properties, such as high glass transition temperature, good dimensional stability, small linear expansion coefficient, and water absorption.
  • the low rate, especially excellent low dielectric constant and low dielectric loss, is an ideal resin material for preparing high-speed circuit substrates.
  • butadiene-styrene copolymer does not contain a polar group, has good dielectric properties, low water absorption, and good flexibility.
  • Butadiene-styrene copolymers contain reactive vinyl groups, usually applied as crosslinkers Fast electronic circuit substrate resin system.
  • Maleimide has excellent heat resistance, flame retardancy, mechanical properties and dimensional stability, and is generally used as a crosslinking agent in a high-speed electronic circuit substrate resin system.
  • CN103965606A discloses a low dielectric material comprising 40 to 80 parts by weight of polyphenylene ether; 5 to 30 parts by weight of bismaleimide; and 5 to 30 parts by weight of a polymeric additive.
  • the structural formula of the polyphenylene ether is as follows;
  • Polymer additives white polybutadiene, styrene-butadiene copolymer, styrene-butadiene-divinylbenzene copolymer, styrene-maleic anhydride copolymer, maleic anhydride polybutadiene And their compositions. Since the styrene-butadiene copolymer, the polybutadiene, the styrene-butadiene copolymer-divinylbenzene copolymer, and the polyphenylene ether are incompatible with the maleimide, the compounding process is performed. There is a stratification of the glue layer, and the prepreg has an appearance of a skin-like crack, and a phase separation problem occurs in the resin region of the substrate.
  • CN101643650A discloses a phosphorus-containing flame retardant which is added to a resin system of an unsaturated double bond, an engineering plastic or a polymer of a polyolefin to function as a crosslinking and a flame retardant.
  • the unsaturated double bond resin includes butadiene, styrene, isoprene, divinylbenzene, toluene vinyl, acrylate, acrylonitrile, N-phenylmaleimide, N-vinyl A homopolymer or copolymer of phenylmaleimide, a vinyl substituted polyphenylene ether.
  • a copolymer of butadiene, styrene, and N-phenylmaleimide with a vinyl-substituted polyphenylene ether resin composition or butadiene, styrene, and N-vinylphenylmaleyl
  • a resin composition comprising:
  • the weight of the bifunctional maleimide or polyfunctional maleimide is 5 to 20 parts by weight, for example, 5 parts by weight, 10 parts by weight, 15 parts by weight based on 100 parts by weight of the vinyl thermosetting polyphenylene ether. Parts, or 20 parts by weight.
  • the difunctional maleimide or polyfunctional maleimide is used in an amount ranging from 5 to 20 parts by weight, based on 100 parts by weight of the vinyl thermosetting polyphenylene ether, and not only 100 parts by weight of polyphenylene.
  • the ether undergoes a good prepolymerization reaction and the prepared sheet has good dielectric properties.
  • the weight of the polyolefin resin is from 5 to 100 parts by weight, such as 10 parts by weight, based on 100 parts by weight of the weight of the vinyl thermosetting polyphenylene ether and the bifunctional maleimide or polyfunctional maleimide prepolymer. Parts, 15 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, 50 parts by weight, 55 parts by weight, 60 parts by weight, 65 parts by weight, 70 parts by weight, 75 parts by weight, 80 parts by weight, 85 parts by weight, 90 parts by weight or 95 parts by weight.
  • the polyolefin resin may be used in an amount of from 5 to 100 parts by weight based on 100 parts by weight of the weight of the vinyl thermosetting polyphenylene ether and the bifunctional maleimide or polyfunctional maleimide prepolymer. Realize The prepared sheets have good crosslink density and dielectric properties.
  • the structure of the vinyl thermosetting polyphenylene ether is as shown in the formula (1):
  • a and b are independently an integer of 1 to 30, for example, 2, 5, 8, 11, 14, 17, 20, 23, 26 or 29, and Z is a formula (2) or (3)
  • Z is a formula (2) or (3)
  • -(-OY-)- is a structure represented by the formula (4)
  • -(-OXO-)- is a structure represented by the structural formula (5):
  • A is an arylene group, a carbonyl group or an alkylene group having 1 to 10 (for example, 2, 3, 4, 5, 6, 7, 8, or 9) carbon atoms, and m is 0 to 10 ( An integer of, for example, 1 , 2 , 3 , 4, 5, 6, 7, 8, or 9), wherein R 1 , R 2 and R 3 are the same or different and are independently hydrogen or an alkyl group having 10 or less carbon atoms;
  • R 4 and R 6 are the same or different and each independently represents a hydrogen atom, a halogen atom, an alkyl group having 8 or less carbon atoms or a phenyl group having 8 or less carbon atoms, and R 5 and R 7 are the same or different. And independently a hydrogen atom, a halogen atom, an alkyl group having 8 or less carbon atoms or a phenyl group having 8 or less carbon atoms;
  • R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 and R 15 are the same or different and independently represent a hydrogen atom, a halogen atom or an alkyl group having 8 or less carbon atoms. Or a phenyl group having 8 or less carbon atoms, and B is an alkylene group, -O-, -CO-, -SO-, -SC-, -SO 2 - or -C(CH 3 ) 2 -.
  • Exemplary vinyl thermosetting polyphenylene ethers such as Sabic's methacrylate-modified polyphenylene ether MX9000, Mitsubishi Chemical's styryl-modified polyphenylene ether St-PPE-1.
  • the vinyl thermosetting polyphenylene ether has a number average molecular weight of from 500 to 10,000 g/mol, preferably from 800 to 8000 g/mol, further preferably from 1,000 to 7,000 g/mol.
  • the bifunctional maleimide or polyfunctional maleimide structural formula is as follows:
  • R 16 is a z-valent aliphatic or aromatic organic group
  • R 17 and R 18 are independently a hydrogen atom, a halogen atom, a substituted or unsubstituted C1-C8 linear alkyl group, a substituted or unsubstituted C1-C8 Any one of branched alkyl groups
  • z represents an integer of 2 or more.
  • An exemplary bifunctional maleimide such as K-I chemical difunctional maleimide has the structural formula shown below:
  • An exemplary polyfunctional maleimide such as the polyfunctional maleimide of Jinyi Chemical has the following structural formula:
  • the prepolymerization reaction of the vinyl thermosetting polyphenylene ether with the difunctional maleimide or polyfunctional maleimide prepolymer comprises the following steps:
  • Vinyl thermosetting polyphenylene ether is dissolved in a weakly polar solvent such as toluene or methyl ethyl ketone, and difunctional maleimide or polyfunctional maleimide is N, N-dimethylformamide or N-methyl.
  • a strong polar solvent such as pyrrolidone
  • the free radical initiator is selected from the group consisting of an organic peroxide initiator, and further preferably dilauroyl peroxide, dibenzoyl peroxide, cumene peroxide, and t-butyl peroxylate.
  • the polyolefin resin is selected from any one of a styrene-butadiene copolymer, a polybutadiene or a styrene-butadiene-divinylbenzene copolymer or a mixture of at least two,
  • the polyolefin resin is white-modified, maleic anhydride-modified, epoxy-modified, acrylate-modified, hydroxyl-modified or carboxyl-modified styrene-butadiene copolymer Any one or a mixture of at least two of polybutadiene, styrene-butadiene-divinylbenzene copolymer.
  • Exemplary polyolefin resins such as styrene-butadiene copolymer R100 of Sammeter, polybutadiene B-1000 of Japan's Soda, or styrene-butadiene-divinylbenzene copolymer R250 of Samtomer.
  • the resin composition further comprises a component (C) initiator.
  • the initiator is a free radical initiator, the free radical initiator is selected as an organic peroxide initiator, and further preferably dilauroyl peroxide, dibenzoyl peroxide, and cumene peroxide.
  • the weight of the initiator is from 1 to 3 parts by weight based on 100 parts by weight of the weight of the vinyl thermosetting polyphenylene ether and the bifunctional maleimide or polyfunctional maleimide prepolymer and the polyolefin resin. For example, 1.2 parts by weight, 1.4 parts by weight, 1.6 parts by weight, 1.8 parts by weight, 2.0 parts by weight, 2.2 parts by weight, 2.4 parts by weight, 2.6 parts by weight or 2.8 parts by weight.
  • the resin composition further comprises a component (D) flame retardant, which is a bromine-containing flame retardant or/and a phosphorus-containing flame retardant.
  • D flame retardant
  • the flame retardant is a phosphorus-containing flame retardant containing a DOPO structure, and its molecular structural formula is as follows:
  • n is an integer from 0 to 10, such as 1, 2, 3, 4, 5, 6, 7, 8, or 9.
  • the phosphorus-containing flame retardant containing the DOPO structure of the exemplary example is the phosphorus-containing flame retardant XP-7866 of Yabao, USA.
  • the weight of the flame retardant is 0-40 based on 100 parts by weight of the prepolymer of the bifunctional thermosetting polyphenylene ether and the bifunctional maleimide or polyfunctional maleimide, the polyolefin resin and the initiator. Parts by weight, for example, 2 parts by weight, 5 parts by weight, 9 parts by weight, 13 parts by weight, 17 parts by weight, 21 parts by weight, 25 parts by weight, 29 parts by weight, 33 parts by weight or 37 parts by weight.
  • the resin composition further comprises a component (E) filler selected from white crystalline silica, amorphous silica, spherical silica, titania, silicon carbide, glass fiber, alumina, Any one or a mixture of at least two of aluminum nitride, boron nitride, barium titanate or barium titanate.
  • a component (E) filler selected from white crystalline silica, amorphous silica, spherical silica, titania, silicon carbide, glass fiber, alumina, Any one or a mixture of at least two of aluminum nitride, boron nitride, barium titanate or barium titanate.
  • the weight of the filler is 100 parts by weight based on 100 parts by weight of the copolymer of the vinyl thermosetting polyphenylene ether and the bifunctional maleimide or polyfunctional maleimide, the polyolefin resin, the initiator and the flame retardant. 0 to 150 parts by weight, for example, 10 parts by weight, 20 parts by weight, 30 parts by weight, 40 parts by weight, 50 parts by weight, 60 parts by weight, 70 parts by weight, 80 parts by weight, 90 parts by weight, 100 parts by weight, 110 parts by weight 120 parts by weight, 130 parts by weight or 140 parts by weight.
  • the resin composition may further contain various additives, and specific examples thereof include an antioxidant, a heat stabilizer, an antistatic agent, an ultraviolet absorber, a pigment, a colorant, a lubricant, and the like. These various additives may be used singly or in combination of two or more kinds.
  • the present invention provides a prepreg produced using the above resin composition, comprising a substrate and a resin composition as described above which is adhered to the substrate by impregnation and drying.
  • the present invention provides a laminate produced using the above resin composition, comprising a plurality of laminated prepregs.
  • the present invention provides a copper-clad laminate produced using the above resin composition, comprising a plurality of laminated prepregs and a copper foil which is laminated on one side or both sides of the laminated prepreg.
  • the present invention provides a printed circuit board produced using the above resin composition, comprising a plurality of laminated prepregs.
  • the preparation of a high speed electronic circuit substrate using the above formulation comprises the following steps:
  • the weight of the bifunctional maleimide or polyfunctional maleimide is from 5 to 100 parts by weight based on 100 parts by weight of the vinyl thermosetting polyphenylene ether;
  • the weight of the polyolefin resin is 100 parts by weight based on 100 parts by weight of the prepolymer of the vinyl thermosetting polyphenylene ether and the bifunctional maleimide or the polyfunctional maleimide 5-100 parts by weight; based on 100 parts by weight of the weight of the vinyl thermosetting polyphenylene ether and the bifunctional maleimide or polyfunctional maleimide prepolymer, the polyolefin resin, the weight of the initiator is 1-3 parts by weight; based on 100 parts by weight of the weight of the vinyl thermosetting polyphenylene ether and the bifunctional maleimide or polyfunctional maleimide prepolymer, polyolefin resin and initiator, flame retardant
  • the weight of the agent is 0-40 parts by weight; the weight of the prepolymer of the vinyl thermosetting polyphenylene ether and the bifunctional maleimide or polyfunctional maleimide, the polyolefin resin, the initiator and the flame retardant is 100 parts by weight, the weight of the filler is
  • the present invention has the following beneficial effects:
  • the present invention solves the problem of difunctional maleimide or polyfunctional maleimide and ethylene by prepolymerizing a vinyl thermosetting polyphenylene ether with a bifunctional maleimide or a polyfunctional maleimide.
  • the incompatibility problem of the base thermosetting polyphenylene ether and the polyolefin resin, the mixed glue solution is uniform and uniform, and the prepreg is uniform and uniform. There is no phase separation problem in the resin region of the substrate;
  • the maleimide used in the present invention is a bifunctional maleimide or a polyfunctional maleimide, and the prepared substrate has higher heat resistance than the monofunctional maleimide. Performance, smaller coefficient of thermal expansion, longer thermal delamination time and higher thermal decomposition temperature.
  • the 2116 glass fiber cloth was used to impregnate the glue, and the clamp shaft was controlled to be a single weight, and the sheet was baked in an oven to remove the toluene solvent to obtain a 2116 bonded sheet.
  • Four sheets of 2116 bonding sheets were overlapped, and the upper and lower sides were coated with a copper foil of 1 OZ thickness, vacuum laminated and cured for 90 minutes in a press, a curing pressure of 50 kg/cm 2 , and a curing temperature of 200 ° C to obtain a high-speed electronic circuit substrate. Physical properties are shown in Table 2.
  • the 2116 glass fiber cloth was used to impregnate the glue, and the clamp shaft was controlled to be a single weight, and the sheet was baked in an oven to remove the toluene solvent to obtain a 2116 bonded sheet.
  • Four sheets of 2116 bonding sheets were overlapped, and the upper and lower sides were coated with a copper foil of 1 OZ thickness, vacuum laminated and cured for 90 minutes in a press, a curing pressure of 50 kg/cm 2 , and a curing temperature of 200 ° C to obtain a high-speed electronic circuit substrate. Physical properties are shown in Table 2.
  • the 2116 glass fiber cloth was used to impregnate the glue, and the clamp shaft was controlled to be a single weight, and the sheet was baked in an oven to remove the toluene solvent to obtain a 2116 bonded sheet.
  • Four sheets of 2116 bonding sheets were overlapped, and the upper and lower sides were coated with a copper foil of 1 OZ thickness, vacuum laminated and cured for 90 minutes in a press, a curing pressure of 50 kg/cm 2 , and a curing temperature of 200 ° C to obtain a high-speed electronic circuit substrate. Physical properties are shown in Table 2.
  • the 2116 glass fiber cloth was used to infiltrate the glue, and the clamp shaft was controlled to be a single weight, and the sheet was baked in an oven to remove the toluene solvent to obtain a 2116 bonded sheet.
  • Four sheets of 2116 bonding sheets were overlapped, and the upper and lower sides were coated with a copper foil of 1 OZ thickness, vacuum laminated and cured for 90 minutes in a press, a curing pressure of 50 kg/cm 2 , and a curing temperature of 200 ° C to obtain a high-speed electronic circuit substrate. Physical properties are shown in Table 2.
  • the 2116 glass fiber cloth was used to impregnate the glue, and the clamp shaft was controlled to be a single weight, and the sheet was baked in an oven to remove the toluene solvent to obtain a 2116 bonded sheet.
  • Four sheets of 2116 bonding sheets were overlapped, and the upper and lower sides were coated with a copper foil of 1 OZ thickness, vacuum laminated and cured for 90 minutes in a press, a curing pressure of 50 kg/cm 2 , and a curing temperature of 200 ° C to obtain a high-speed electronic circuit substrate.
  • the physical properties are shown in Table 3.
  • the 2116 glass fiber cloth was used to impregnate the glue, and the clamp shaft was controlled to be a single weight, and the sheet was baked in an oven to remove the toluene solvent to obtain a 2116 bonded sheet.
  • Four sheets of 2116 bonding sheets were overlapped, and the upper and lower sides were coated with a copper foil of 1 OZ thickness, vacuum laminated and cured for 90 minutes in a press, a curing pressure of 50 kg/cm 2 , and a curing temperature of 200 ° C to obtain a high-speed electronic circuit substrate.
  • the physical properties are shown in Table 3.
  • the 2116 glass fiber cloth was used to impregnate the glue, and the clamp shaft was controlled to be a single weight, and the sheet was baked in an oven to remove the toluene solvent to obtain a 2116 bonded sheet.
  • Four sheets of 2116 bonding sheets were overlapped, and the upper and lower sides were coated with a copper foil of 1 OZ thickness, vacuum laminated and cured for 90 minutes in a press, a curing pressure of 50 kg/cm 2 , and a curing temperature of 200 ° C to obtain a high-speed electronic circuit substrate.
  • the physical properties are shown in Table 3.
  • the 2116 glass fiber cloth was used to impregnate the glue, and the clamp shaft was controlled to be a single weight, and the sheet was baked in an oven to remove the toluene solvent to obtain a 2116 bonded sheet.
  • Four sheets of 2116 bonding sheets were overlapped, and the upper and lower sides were coated with a copper foil of 1 OZ thickness, vacuum laminated and cured for 90 minutes in a press, a curing pressure of 50 kg/cm 2 , and a curing temperature of 200 ° C to obtain a high-speed electronic circuit substrate.
  • the physical properties are shown in Table 3.
  • the 2116 glass fiber cloth was used to impregnate the glue, and the clamp shaft was controlled to be a single weight, and the sheet was baked in an oven to remove the toluene solvent to obtain a 2116 bonded sheet.
  • Four sheets of 2116 bonding sheets were overlapped, and the upper and lower sides were coated with a copper foil having a thickness of 1 OZ, vacuum-laminated and cured for 90 minutes in a press, a curing pressure of 50 kg/cm 2 , and a curing temperature of 200 ° C to obtain a high-speed electronic circuit substrate. Physical properties are shown in Table 2.
  • the 2116 glass fiber cloth was used to impregnate the glue, and the clamp shaft was controlled to be a single weight, and the sheet was baked in an oven to remove the toluene solvent to obtain a 2116 bonded sheet.
  • Four sheets of 2116 bonding sheets were overlapped, and the upper and lower sides were coated with a copper foil of 1 OZ thickness, vacuum laminated and cured for 90 minutes in a press, a curing pressure of 50 kg/cm 2 , and a curing temperature of 200 ° C to obtain a high-speed electronic circuit substrate. Physical properties are shown in Table 2.

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Abstract

本发明属于覆铜板技术领域，涉及一种树脂组合物及其使用它的预浸料和层压板。所述树脂组合物包含：(A)乙烯基热固性聚苯醚与双官能马来酰亚胺或多官能马来酰亚胺的预聚物；(B)聚烯烃树脂。本发明采用乙烯基热固性聚苯醚与双官能马来酰亚胺或多官能马来酰亚胺预聚，解决了双官能马来酰亚胺或多官能马来酰亚胺与乙烯基热固性聚苯醚、聚烯烃树脂的不相容问题，所混制的胶水溶液均匀一致，预浸料表观均匀、基材树脂区域无分相问题。另外，采用的马来酰亚胺为双官能马来酰亚胺或多官能马来酰亚胺，相对于单官能马来酰亚胺，所制备的基材具有更高的耐热性能，热膨胀系数更小、热分层时间更长和热分解温度更高。

Description

一种树脂组合物以及使用它的预浸料和层压板 技术领域
本发明属于覆铜板技术领域，涉及一种树脂组合物及其使用它的预浸料和层压板。
背景技术
近年来，随着电子信息技术的发展，电子设备安装的小型化、高密度化，信息的大容量化、高速化，对电路基板的耐热性、吸水性、耐化学性、机械性能、尺寸稳定性和介电性能等综合性能提出了更高的要求。
就介电性能而言，在高速电路中，信号的传输速率与绝缘材料介质常数Dk的关系为绝缘材料介质常数Dk越低，信号传输速率越快。因此要实现信号传输速率的高速化，必须开发低介电常数的基板。随着信号速率的高速化，基板中信号的损耗不能再忽略不计。信号损耗与速率、介电常数Dk、介质损耗因子Df的关系为基板介电常数Dk越小、介质损耗因子Df越小，信号损失就越小。
因此开发具有低的介质常数Dk及低的介质损耗因子Df，且耐热性能良好的高速电路基板，成为CCL厂家共同关注的研发方向。
聚苯醚树脂分子结构中含有大量的苯环结构，且无强极性基团，赋予了聚苯醚树脂优异的性能，如玻璃化转变温度高、尺寸稳定性好、线性膨胀系数小、吸水率低，尤其是出色的低介电常数、低介电损耗，成为制备高速电路基板的理想树脂材料。
丁二烯-苯乙烯共聚物不含极性基团，介电性能好、吸水率低、柔韧性好。丁二烯-苯乙烯共聚物含可反应的乙烯基基团，通常作为交联剂应用于高 速电子电路基材树脂体系。
马来酰亚胺具有优异的耐热性、阻燃性、力学性能和尺寸稳定性，通常作为交联剂应用于高速电子电路基材树脂体系。
CN103965606A公开了一种低介电材料，其包含40～80重量份的聚苯醚；5～30重量份的双马来酰亚胺；5～30重量份的高分子添加剂。在该发明中，聚苯醚的结构式如下所示；
Figure PCTCN2015089907-appb-000001
高分子添加剂选白聚丁二烯、苯乙烯-丁二烯共聚物、苯乙烯-丁二烯-二乙烯基苯共聚物、苯乙烯-马来酸酐共聚物、马来酸酐化聚丁二烯，以及它们的组合物。由于苯乙烯-丁二烯共聚物、聚丁二烯、苯乙烯-丁二烯共聚物-二乙烯基苯共聚物以及聚苯醚，与马来酰亚胺不相容，则在混胶工艺中出现胶液分层，预浸料表观有龟皮状裂纹，基材树脂区域出现分相的问题。
CN101643650A公开了一种含磷阻燃剂，该含磷阻燃剂添加在不饱和双键的树脂体系、工程塑料或聚烯烃的聚合物中，起到交联和阻燃的作用。其中，不饱和双键的树脂包括丁二烯、苯乙烯、异戊二烯、二乙烯基苯、甲苯乙烯基、丙烯酸酯、丙烯腈、N-苯基马来酰亚胺、N-乙烯基苯基马来酰亚胺的均聚物或共聚物、乙烯基取代的聚苯醚。如将丁二烯、苯乙烯以及N-苯基马来酰亚胺的共聚物与乙烯基取代的聚苯醚树脂组合物，或者丁二烯、苯乙烯以及N-乙烯基苯基马来酰亚胺的共聚物与乙烯基取代的聚苯醚树脂组合物，用于电子电路基材的制作。由于所采用的马来酰亚胺为单马来酰亚胺结构，相对于双官能马来酰亚胺结构或多官能马来酰亚胺结构，降低了基材的耐热性，热膨胀系数 大、热分层时间短、热分解温度低。
发明内容
针对已有技术的问题，本发明的目的之一在于提供一种树脂组合物，采用该树脂组合物能够满足高速电子电路基板对介电性能和耐热性能等综合性能的要求。
为了实现上述目的，本发明采用了如下技术方案：
一种树脂组合物，其包含：
(A)乙烯基热固性聚苯醚与双官能马来酰亚胺或多官能马来酰亚胺的预聚物；
(B)聚烯烃树脂。
以乙烯基热固性聚苯醚的重量为100重量份计，双官能马来酰亚胺或多官能马来酰亚胺的重量为5～20重量份，例如5重量份、10重量份、15重量份、或20重量份。
以乙烯基热固性聚苯醚的重量为100重量份计，双官能马来酰亚胺或多官能马来酰亚胺采用的重量范围为5～20重量份，不仅可与100重量份的聚苯醚进行很好的预聚反应，而且所制备的板材具有良好的介电性能。
以乙烯基热固性聚苯醚与双官能马来酰亚胺或多官能马来酰亚胺的预聚物的重量为100重量份计，聚烯烃树脂的重量为5～100重量份，例如10重量份、15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、50重量份、55重量份、60重量份、65重量份、70重量份、75重量份、80重量份、85重量份、90重量份或95重量份。
以乙烯基热固性聚苯醚与双官能马来酰亚胺或多官能马来酰亚胺的预聚物的重量为100重量份计，聚烯烃树脂采用的重量范围为5～100重量份，可实现 制备的板材具有良好的交联密度和介电性能。
在树脂组合物中，所述乙烯基热固性聚苯醚的结构如式(1)所示：
Figure PCTCN2015089907-appb-000002
式(1)中，a和b独立地为1～30的整数，例如2、5、8、11、14、17、20、23、26或29，Z为式(2)或(3)所示的结构，-(-O-Y-)-为式(4)所示的结构，-(-O-X-O-)-为结构式(5)所示的结构：
Figure PCTCN2015089907-appb-000003
Figure PCTCN2015089907-appb-000004
式(3)中，A为亚芳香基、羰基或碳原子数为1～10(例如2、3、4、5、6、7、8或9)的亚烷基，m为0～10(例如1、2、3、4、5、6、7、8或9)的整数，R1、R2和R3相同或不同，独立地为氢或碳原子数10以下的烷基；
Figure PCTCN2015089907-appb-000005
式(4)中，R4与R6相同或不同，独立地为氢原子、卤素原子、碳原子数8以下的烷基或碳原子数8以下的苯基，R5与R7相同或不同，独立地为氢原子、卤素原子、碳原子数8以下的烷基或碳原子数8以下的苯基；
Figure PCTCN2015089907-appb-000006
式(5)中，R8、R9、R10、R11、R12、R13、R14及R15相同或不同，独立地为氢原子、卤素原子、碳原子数8以下的烷基或碳原子数8以下的苯基，B为亚烃基、-O-、-CO-、-SO-、-SC-、-SO2-或-C(CH3)2-。
示范例的乙烯基热固性聚苯醚如Sabic的甲基丙烯酸酸酯基改性的聚苯醚MX9000、三菱化学的苯乙烯基改性的聚苯醚St-PPE-1。
优选地，所述乙烯基热固性聚苯醚的数均分子量为500-10000g/mol，优选800～8000g/mol，进一步优选1000～7000g/mol。
上述树脂组合物中，所述双官能马来酰亚胺或多官能马来酰亚胺结构式如下所示：
Figure PCTCN2015089907-appb-000007
R16为z价的脂肪族或芳香族的有机基团；R17和R18独立为氢原子、卤原子、取代或未取代的C1-C8直链烷基、取代或未取代的C1-C8支链烷基的任意一种；z表示2及2以上的整数。
示范例的双官能马来酰亚胺如K-I chemical的双官能马来酰亚胺，其结构式如下所示：
Figure PCTCN2015089907-appb-000008
示范例的多官能马来酰亚胺如晋一化工的多官能马来酰亚胺，其结构式如下所示：
Figure PCTCN2015089907-appb-000009
上述树脂组合物中，乙烯基热固性聚苯醚与双官能马来酰亚胺或多官能马来酰亚胺的预聚物的预聚反应包括以下步骤：
(1)乙烯基热固性聚苯醚采用甲苯或丁酮等弱极性溶剂溶解，双官能马来酰亚胺或多官能马来酰亚胺采用N，N-二甲基甲酰胺或N-甲基吡咯烷酮等强极性溶剂溶解；
(2)将乙烯基热固性聚苯醚与双官能马来酰亚胺或多官能马来酰亚胺溶液混合均匀，加热到设定的温度，然后加入自由基引发剂，在设定的温度下预聚一定的时间；采用GPC监控双官能马来酰亚胺或多官能马来酰亚胺的转化率，双官能马来酰亚胺或多官能马来酰亚胺的转化率控制范围为10-80％。
所述自由基引发剂选白有机过氧化物引发剂，进一步优选白过氧化二月桂酰、过氧化二苯甲酰、过氧化新葵酸异丙苯酯、过氧化新葵酸叔丁酯、过氧化特戊酸特戊酯、过氧化特戊酸叔丁酯、叔丁基过氧化异丁酸酯、叔丁基过氧化-3，5，5-三甲基己酸酯、过氧化乙酸叔丁酯、过氧化苯甲酸叔丁酯、1，1-二叔丁基过氧化-3，5，5-三甲基环己烷、1，1-二叔丁基过氧化环己烷、2，2-二(叔丁基过氧 化)丁烷、双(4-叔丁基环己基)过氧化二碳酸酯、过氧化二碳酸酯十六酯、过氧化二碳酸酯十四酯、二特戊己过氧化物、二异丙苯过氧化物、双(叔丁基过氧化异丙基)苯、2，5-二甲基-2，5-二叔丁基过氧化己烷、2，5-二甲基-2，5-二叔丁基过氧化己炔、二异丙苯过氧化氢、异丙苯过氧化氢、特戊基过氧化氢、叔丁基过氧化氢、叔丁基过氧化异丙苯、二异丙苯过氧化氢、过氧化碳酸酯-2-乙基己酸叔丁酯、叔丁基过氧化碳酸-2-乙基己酯、4，4-二(叔丁基过氧化)戊酸正丁酯、过氧化甲乙酮、过氧化换己烷中的任意一种或者至少两种的混合物。
上述树脂组合物中，聚烯烃树脂选白苯乙烯-丁二烯共聚物、聚丁二烯或苯乙烯-丁二烯-二乙烯基苯共聚物中的任意一种或者至少两种的混合物，优选所述聚烯烃树脂选白氨基改性的、马来酸酐改性的、环氧基改性的、丙烯酸酯改性的、羟基改性的或羧基改性的苯乙烯-丁二烯共聚物、聚丁二烯、苯乙烯-丁二烯-二乙烯基苯共聚物中的任意一种或者至少两种的混合物。
示范例的聚烯烃树脂如Samtomer的苯乙烯-丁二烯共聚物R100、日本曹达的聚丁二烯B-1000或Samtomer的苯乙烯-丁二烯-二乙烯基苯共聚物R250。
优选地，所述树脂组合物还包括组分(C)引发剂。所述引发剂为自由基引发剂，所述自由基引发剂选白有机过氧化物引发剂，进一步优选白过氧化二月桂酰、过氧化二苯甲酰、过氧化新葵酸异丙苯酯、过氧化新葵酸叔丁酯、过氧化特戊酸特戊酯、过氧化特戊酸叔丁酯、叔丁基过氧化异丁酸酯、叔丁基过氧化-3，5，5-三甲基己酸酯、过氧化乙酸叔丁酯、过氧化苯甲酸叔丁酯、1，1-二叔丁基过氧化-3，5，5-三甲基环己烷、1，1-二叔丁基过氧化环己烷、2，2-二(叔丁基过氧化)丁烷、双(4-叔丁基环己基)过氧化二碳酸酯、过氧化二碳酸酯十六酯、过氧化二碳酸酯十四酯、二特戊己过氧化物、二异丙苯过氧化物、双(叔丁基过氧化异丙基)苯、2，5-二甲基-2，5-二叔丁基过氧化己烷、2，5-二甲基-2，5-二叔丁 基过氧化己炔、二异丙苯过氧化氢、异丙苯过氧化氢、特戊基过氧化氢、叔丁基过氧化氢、叔丁基过氧化异丙苯、二异丙苯过氧化氢、过氧化碳酸酯-2-乙基己酸叔丁酯、叔丁基过氧化碳酸-2-乙基己酯、4，4-二(叔丁基过氧化)戊酸正丁酯、过氧化甲乙酮、过氧化换己烷中的任意一种或者至少两种的混合物。
以乙烯基热固性聚苯醚与双官能马来酰亚胺或多官能马来酰亚胺的预聚物、聚烯烃树脂的重量为100重量份计，引发剂的重量为1～3重量份，例如1.2重量份、1.4重量份、1.6重量份、1.8重量份、2.0重量份、2.2重量份、2.4重量份、2.6重量份或2.8重量份。
优选地，所述树脂组合物还包括组分(D)阻燃剂，所述阻燃剂为含溴阻燃剂或/和含磷阻燃剂。
上述树脂组合物中，所述阻燃剂为一种含DOPO结构的含磷阻燃剂，其分子结构式如下所示：
Figure PCTCN2015089907-appb-000010
其中，n为0～10的整数，例如1、2、3、4、5、6、7、8或9。
示范例的含DOPO结构的含磷阻燃剂为美国雅宝的含磷阻燃剂XP-7866。
以乙烯基热固性聚苯醚与双官能马来酰亚胺或多官能马来酰亚胺的预聚物、聚烯烃树脂和引发剂的重量为100重量份计，阻燃剂重量为0～40重量份，例如2重量份、5重量份、9重量份、13重量份、17重量份、21重量份、25重量份、29重量份、33重量份或37重量份。
优选地，所述树脂组合物还包括组分(E)填料，所述填料选白结晶性二氧化硅、无定形二氧化硅、球形二氧化硅、二氧化钛、碳化硅、玻璃纤维、氧化铝、氮化铝、氮化硼、钛酸钡或钛酸锶中的任意一种或者至少两种的混合物。
以乙烯基热固性聚苯醚与双官能马来酰亚胺或多官能马来酰亚胺的预聚物、聚烯烃树脂、引发剂和阻燃剂的重量为100重量份计，填料的重量为0～150重量份，例如10重量份、20重量份、30重量份、40重量份、50重量份、60重量份、70重量份、80重量份、90重量份、100重量份、110重量份、120重量份、130重量份或140重量份。
本发明所述的“包括”，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树脂组合物不同的特性。除此之外，本发明所述的“包括”，还可以替换为封闭式的“为”或“由……组成”。
例如，所述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。这些各种添加剂可以单独使用，也可以两种或者两种以上混合使用。
进一步地，本发明提供一种使用上述树脂组合物制作的预浸料，包括基材及通过含浸干燥后附着于基材上的如上所述的树脂组合物。
另外，本发明还提供一种使用上述树脂组合物制作的层压板，包括数张叠合的预浸料。
另外，本发明还提供一种使用上述树脂组合物制作的覆铜箔层压板，包括数张叠合的预浸料及压覆于叠合后预浸料的一侧或两侧的铜箔。
另外，本发明还提供一种使用上述树脂组合物制作的印制电路板，包括数张叠合的预浸料。
采用上述配方制备高速电子电路基材包括以下步骤：
(1)将乙烯基热固性聚苯醚与双官能马来酰亚胺或多官能马来酰亚胺在自由基引发剂存在的条件下进行预聚，通过GPC检测确定双马来酰亚胺或多马来酰亚胺的转化率，转化率的控制范围为10-80％。以乙烯基热固性聚苯醚的重量为100重量份计，双官能马来酰亚胺或多官能马来酰亚胺的重量为5-100重量份；
(2)称取树脂组合物：以乙烯基热固性聚苯醚与双官能马来酰亚胺或多官能马来酰亚胺的预聚物的重量为100重量份计，聚烯烃树脂的重量为5-100重量份；以乙烯基热固性聚苯醚与双官能马来酰亚胺或多官能马来酰亚胺的预聚物、聚烯烃树脂的重量为100重量份计，引发剂的重量为1-3重量份；以乙烯基热固性聚苯醚与双官能马来酰亚胺或多官能马来酰亚胺的预聚物、聚烯烃树脂和引发剂的重量为100重量份计，阻燃剂重量为0～40重量份；以乙烯基热固性聚苯醚与双官能马来酰亚胺或多官能马来酰亚胺的预聚物、聚烯烃树脂、引发剂和阻燃剂的重量为100重量份计算，填料的重量为0～150重量份；
(3)将乙烯基热固性聚苯醚与双官能马来酰亚胺或多官能马来酰亚胺的预聚物、聚烯烃树脂、任选地引发剂、任选地填料和任选地阻燃剂混合，并加入适量溶剂，搅拌分散均匀，使填料和阻燃剂均匀分散在胶液中；用制备的胶液浸润基材，并在合适温度的烘箱中烘片一定的时间，除去溶剂而形成预浸料；
(4)将几张预浸料整齐重叠，上下配以铜箔，在压机中层压固化，从而得到高速电子电路基材。
与已有技术相比，本发明具有如下有益效果：
(1)本发明采用乙烯基热固性聚苯醚与双官能马来酰亚胺或多官能马来酰亚胺预聚，解决了双官能马来酰亚胺或多官能马来酰亚胺与乙烯基热固性聚苯醚、聚烯烃树脂的不相容问题，所混制的胶水溶液均匀一致，预浸料表观均匀、 基材树脂区域无分相问题；
(2)本发明采用的马来酰亚胺为双官能马来酰亚胺或多官能马来酰亚胺，相对于单官能马来酰亚胺，所制备的基材具有更高的耐热性能，热膨胀系数更小、热分层时间更长和热分解温度更高。
具体实施方式
下面通过具体实施方式来进一步说明本发明的技术方案。
本发明实施例制备高速电子电路基材所选取的原料如下表1所示：
表1
制造厂商 产品名称或牌号 材料描述
Sabic MX9000 甲基丙烯酸甲酯基改性聚苯醚
三菱化学 St-PPE-1 苯乙烯基改性聚苯醚
武汉志晟科技 马来酰亚胺 单官能马来酰亚胺
K-I chemical 马来酰亚胺 双官能马来酰亚胺
晋一化学 马来酰亚胺 三官能马来酰亚胺
Samtomer R100 苯乙烯-丁二烯共聚物
日本曹达 B-1000 聚丁二烯
Samtomer R250 苯乙烯-丁二烯-二乙烯基苯共聚物
上海高桥 DCP 过氧化二异丙苯
东莞芯威化工 BPO 过氧化二苯甲酰
Sibelco 525 熔融硅微粉
美国雅宝 BT-93W 含溴阻燃剂
美国雅宝 XP-7866 含磷阻燃剂
上海宏和 2116 玻璃纤维布
一、乙烯基热固性聚苯醚与双官能马来酰亚胺或多官能马来酰亚胺的预聚
预聚实施例1
称取70g的乙烯基热固性聚苯醚MX9000，采用70g甲苯溶剂溶解。称取5g的K-I chemical的双官能马来酰亚胺，采用20g N，N-二甲基甲酰胺溶剂溶解。将溶解好的乙烯基热固性聚苯醚MX9000溶液和K-I chemical的双官能马来酰亚胺溶液混和搅拌均匀。将混合溶液加热到100℃，加入10g甲苯溶解好的0.1g的DCP，反应4小时。停止加热，冷却备用。
预聚实施例2
称取70g的乙烯基热固性聚苯醚St-PPE-1，采用70g甲苯溶剂溶解。称取5g的K-I chemical的双官能马来酰亚胺，采用20g N，N-二甲基甲酰胺溶剂溶解。将溶解好的乙烯基热固性聚苯醚St-PPE-1溶液和K-I chemical的双官能马来酰亚胺溶液混和搅拌均匀。将混合溶液加热到100℃，加入10g甲苯溶解好的0.1g的DCP，反应4小时。停止加热，冷却备用。
预聚实施例3
称取70g的乙烯基热固性聚苯醚MX9000，采用70g甲苯溶剂溶解。称取5g的晋一化学的三官能马来酰亚胺，采用20g N，N-二甲基甲酰胺溶剂溶解。将溶解好的乙烯基热固性聚苯醚MX9000溶液和晋一化学的三官能马来酰亚胺溶液混和搅拌均匀。将混合溶液加热到100℃，加入10g甲苯溶解好的0.1g的DCP，反应4小时。停止加热，冷却备用。
二、高速电子电路基材的制备
实施例1
将70g重量份的乙烯基热固性聚苯醚MX9000与5g重量份的K-I chemical的双官能马来酰亚胺通过预聚制备的预聚物、25g重量份的丁二烯-苯乙烯共聚物R100、3.0重量份的固化引发剂DCP、30g重量份的含溴阻燃剂BT-93W、50g的熔融硅微粉525，溶解于甲苯溶剂中，并调节至适合粘度。用2116玻纤布浸润胶水，过夹轴控制适合单重，并在烘箱中烘片，除去甲苯溶剂，制得2116粘结片。将4张2116粘结片重叠，上下两面配以1OZ厚度的铜箔，在压机中真空层压固化90min，固化压力50Kg/cm2，固化温度200℃，制得高速电子电路基材。物理性能如表2所示。
实施例2
将70g重量份的乙烯基热固性聚苯醚St-PPE-1与5g重量份的K-I chemical的双官能马来酰亚胺通过预聚制备的预聚物、25g重量份的聚丁二烯B-1000、3.0重量份的固化引发剂DCP、30g重量份的含溴阻燃剂BT-93W、50g的熔融硅微粉525，溶解于甲苯溶剂中，并调节至适合粘度。用2116玻纤布浸润胶水，过夹轴控制适合单重，并在烘箱中烘片，除去甲苯溶剂，制得2116粘结片。将4张2116粘结片重叠，上下两面配以1OZ厚度的铜箔，在压机中真空层压固化90min，固化压力50Kg/cm2，固化温度200℃，制得高速电子电路基材。物理性能如表2所示。
实施例3
将70g重量份的乙烯基热固性聚苯醚MX9000与5g重量份的晋一化学的三官能马来酰亚胺通过预聚制备的预聚物、25g重量份的丁二烯-苯乙烯-二乙烯基苯共聚物R250、3.0重量份的固化引发剂BPO、30g重量份的含溴阻燃剂BT-93W、50g的熔融硅微粉525，溶解于甲苯溶剂中，并调节至适合粘度。用2116玻纤布浸润胶水，过夹轴控制适合单重，并在烘箱中烘片，除去甲苯溶剂，制得2116粘结片。将4张2116粘结片重叠，上下两面配以1OZ厚度的铜箔，在压机中真空层压固化90min，固化压力50Kg/cm2，固化温度200℃，制得高速电子电路基材。物理性能如表2所示。
实施例4
将70g重量份的乙烯基热固性聚苯醚MX9000与5g重量份的K-I chemical的双官能马来酰亚胺通过预聚制备的预聚物、25g重量份的丁二烯-苯乙烯共聚物R100、3.0重量份的固化引发剂BPO、30g重量份的含磷阻燃剂XP-7866、50g的熔融硅微粉525，溶解于甲苯溶剂中，并调节至适合粘度。用2116玻纤布浸润胶水，过夹轴控制适合单重，并在烘箱中烘片，除去甲苯溶剂，制得 2116粘结片。将4张2116粘结片重叠，上下两面配以1OZ厚度的铜箔，在压机中真空层压固化90min，固化压力50Kg/cm2，固化温度200℃，制得高速电子电路基材。物理性能如表2所示。
实施例5
将100g重量份的乙烯基热固性聚苯醚MX9000与5g重量份的K-I chemical的双官能马来酰亚胺通过预聚制备的预聚物、5g重量份的丁二烯-苯乙烯共聚物R100、3.0重量份的固化引发剂DCP、30g重量份的含溴阻燃剂BT-93W、50g的熔融硅微粉525，溶解于甲苯溶剂中，并调节至适合粘度。用2116玻纤布浸润胶水，过夹轴控制适合单重，并在烘箱中烘片，除去甲苯溶剂，制得2116粘结片。将4张2116粘结片重叠，上下两面配以1OZ厚度的铜箔，在压机中真空层压固化90min，固化压力50Kg/cm2，固化温度200℃，制得高速电子电路基材。物理性能如表3所示。
实施例6
将100g重量份的乙烯基热固性聚苯醚St-PPE-1与5g重量份的K-I chemical的双官能马来酰亚胺通过预聚制备的预聚物、100g重量份的丁二烯-苯乙烯共聚物R100、3.0重量份的固化引发剂DCP、30g重量份的含溴阻燃剂BT-93W、50g的熔融硅微粉525，溶解于甲苯溶剂中，并调节至适合粘度。用2116玻纤布浸润胶水，过夹轴控制适合单重，并在烘箱中烘片，除去甲苯溶剂，制得2116粘结片。将4张2116粘结片重叠，上下两面配以1OZ厚度的铜箔，在压机中真空层压固化90min，固化压力50Kg/cm2，固化温度200℃，制得高速电子电路基材。物理性能如表3所示。
实施例7
将100g重量份的乙烯基热固性聚苯醚MX9000与20g重量份的K-I  chemical的双官能马来酰亚胺通过预聚制备的预聚物、5g重量份的丁二烯-苯乙烯共聚物R100、3.0重量份的固化引发剂DCP、30g重量份的含溴阻燃剂BT-93W、50g的熔融硅微粉525，溶解于甲苯溶剂中，并调节至适合粘度。用2116玻纤布浸润胶水，过夹轴控制适合单重，并在烘箱中烘片，除去甲苯溶剂，制得2116粘结片。将4张2116粘结片重叠，上下两面配以1OZ厚度的铜箔，在压机中真空层压固化90min，固化压力50Kg/cm2，固化温度200℃，制得高速电子电路基材。物理性能如表3所示。
实施例8
将100g重量份的乙烯基热固性聚苯醚St-PPE-1与20g重量份的K-I chemical的双官能马来酰亚胺通过预聚制备的预聚物、100g重量份的丁二烯-苯乙烯共聚物R100、3.0重量份的固化引发剂DCP、30g重量份的含溴阻燃剂BT-93W、50g的熔融硅微粉525，溶解于甲苯溶剂中，并调节至适合粘度。用2116玻纤布浸润胶水，过夹轴控制适合单重，并在烘箱中烘片，除去甲苯溶剂，制得2116粘结片。将4张2116粘结片重叠，上下两面配以1OZ厚度的铜箔，在压机中真空层压固化90min，固化压力50Kg/cm2，固化温度200℃，制得高速电子电路基材。物理性能如表3所示。
比较例1
将溶于甲苯的70g重量份的乙烯基热固性聚苯醚MX9000、溶于N，N-二甲基甲酰胺的5g重量份的K-I chemical的双官能马来酰亚胺、25g重量份的丁二烯-苯乙烯共聚物R100、3.0重量份的固化引发剂DCP、30g重量份的含溴阻燃剂BT-93W、50g的熔融硅微粉525，溶解于甲苯溶剂中，并调节至适合粘度。用2116玻纤布浸润胶水，过夹轴控制适合单重，并在烘箱中烘片，除去甲苯溶剂，制得2116粘结片。将4张2116粘结片重叠，上下两面配以1OZ厚度的铜 箔，在压机中真空层压固化90min，固化压力50Kg/cm2，固化温度200℃，制得高速电子电路基材。物理性能如表2所示。
比较例2
将溶于甲苯的70g重量份的乙烯基热固性聚苯醚树MX9000、溶于N，N-二甲基甲酰胺的5g重量份的武汉志晟科技的单官能马来酰亚胺、25g重量份的丁二烯-苯乙烯共聚物R100、3.0重量份的固化引发剂DCP、30g重量份的含溴阻燃剂BT-93W、50g的熔融硅微粉525，溶解于甲苯溶剂中，并调节至适合粘度。用2116玻纤布浸润胶水，过夹轴控制适合单重，并在烘箱中烘片，除去甲苯溶剂，制得2116粘结片。将4张2116粘结片重叠，上下两面配以1OZ厚度的铜箔，在压机中真空层压固化90min，固化压力50Kg/cm2，固化温度200℃，制得高速电子电路基材。物理性能如表2所示。
表2
Figure PCTCN2015089907-appb-000011
Figure PCTCN2015089907-appb-000012
表3
Figure PCTCN2015089907-appb-000013
Figure PCTCN2015089907-appb-000014
物性分析：
从表2和表3数据我们可以看出，通过乙烯基热固性聚苯醚与双官能马来酰亚胺或多官能马来酰亚胺的预聚，解决了乙烯基热固性聚苯醚、聚烯烃树脂与马来酰亚胺不相容的问题，所制备的预浸料表观好，所制备的基材树脂区域无树脂分相，且介电性能与耐热性能等综合性能优异。
从比较例1可知，乙烯基热固性聚苯醚与双官能马来酰亚胺没有经过预聚，则导致预浸料表观差，有龟裂缺陷，且基材树脂区域有分相问题。
从比较例2可知，采用单官能马来酰亚胺，且没有与乙烯基热固性聚苯醚预聚，则导致预浸料表观差，有龟裂缺陷，且基材树脂区域有分相问题。与双马来酰亚胺相比，耐热性能更差。
以上所述为本发明的实施例，并非用于限制本发明。凡是根据本发明技术构思对本发明所做等同的变化和修饰，均仍属于本发明保护的范围内。
申请人声明，本发明通过上述实施例来说明本发明的详细方法，但本发明并不局限于上述详细方法，即不意味着本发明必须依赖上述详细方法才能实施。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。

Claims (10)

  1. 一种树脂组合物，其特征在于，所述树脂组合物包含：
    (A)乙烯基热固性聚苯醚与双官能马来酰亚胺或多官能马来酰亚胺的预聚物；
    (B)聚烯烃树脂。
  2. 如权利要求1所述的树脂组合物，其特征在于，以乙烯基热固性聚苯醚的重量为100重量份计，双官能马来酰亚胺或多官能马来酰亚胺的重量为5～20重量份；
    优选地，以乙烯基热固性聚苯醚与双官能马来酰亚胺或多官能马来酰亚胺的预聚物的重量为100重量份计，聚烯烃树脂的重量为5～100重量份。
  3. 如权利要求1或2所述的树脂组合物，其特征在于，所述乙烯基热固性聚苯醚的结构如式(1)所示：
    Figure PCTCN2015089907-appb-100001
    式(1)中，a和b独立地为1～30的整数，Z为式(2)或(3)所示的结构，-(-O-Y-)-为式(4)所示的结构，-(-O-X-O-)-为结构式(5)所示的结构：
    Figure PCTCN2015089907-appb-100002
    式(3)中，A为亚芳香基、羰基或碳原子数为1～10的亚烷基，m为0～10的整数，R1、R2和R3相同或不同，独立地为氢或碳原子数10以下的烷基；
    Figure PCTCN2015089907-appb-100003
    式(4)中，R4与R6相同或不同，独立地为氢原子、卤素原子、碳原子数8以下的烷基或碳原子数8以下的苯基，R5与R7相同或不同，独立地为氢原子、卤素原子、碳原子数8以下的烷基或碳原子数8以下的苯基；
    Figure PCTCN2015089907-appb-100004
    式(5)中，R8、R9、R10、R11、R12、R13、R14及R15相同或不同，独立地为氢原子、卤素原子、碳原子数8以下的烷基或碳原子数8以下的苯基，B为亚烃基、-O-、-CO-、-SO-、-SC-、-SO2-或-C(CH3)2-；
    优选地，所述乙烯基热固性聚苯醚的数均分子量为500-10000g/mol，优选800～8000g/mol，进一步优选1000～7000g/mol。
  4. 如权利要求1-3之一所述的树脂组合物，所述双官能马来酰亚胺或多官能马来酰亚胺结构式如下所示：
    Figure PCTCN2015089907-appb-100005
    R16为z价的脂肪族或芳香族的有机基团；R17和R18独立为氢原子、卤原 子、取代或未取代的C1-C8直链烷基、取代或未取代的C1-C8支链烷基的任意一种；z表示2及2以上的整数；
    优选地，双官能马来酰亚胺结构式如下所示：
    Figure PCTCN2015089907-appb-100006
    优选地，多官能马来酰亚胺结构式如下所示：
    Figure PCTCN2015089907-appb-100007
  5. 如权利要求1-4之一所述的树脂组合物，聚烯烃树脂选自苯乙烯-丁二烯共聚物、聚丁二烯或苯乙烯-丁二烯-二乙烯基苯共聚物中的任意一种或者至少两种的混合物，优选所述聚烯烃树脂选自氨基改性的、马来酸酐改性的、环氧基改性的、丙烯酸酯改性的、羟基改性的或羧基改性的苯乙烯-丁二烯共聚物、聚丁二烯、苯乙烯-丁二烯-二乙烯基苯共聚物中的任意一种或者至少两种的混合物；
    优选地，所述树脂组合物还包括组分(C)引发剂；
    优选地，所述引发剂为自由基引发剂，所述自由基引发剂选自有机过氧化物引发剂，进一步优选自过氧化二月桂酰、过氧化二苯甲酰、过氧化新葵酸异丙苯酯、过氧化新葵酸叔丁酯、过氧化特戊酸特戊酯、过氧化特戊酸叔丁酯、叔丁基过氧化异丁酸酯、叔丁基过氧化-3，5，5-三甲基己酸酯、过氧化乙酸叔丁 酯、过氧化苯甲酸叔丁酯、1，1-二叔丁基过氧化-3，5，5-三甲基环己烷、1，1-二叔丁基过氧化环己烷、2，2-二(叔丁基过氧化)丁烷、双(4-叔丁基环己基)过氧化二碳酸酯、过氧化二碳酸酯十六酯、过氧化二碳酸酯十四酯、二特戊己过氧化物、二异丙苯过氧化物、双(叔丁基过氧化异丙基)苯、2，5-二甲基-2，5-二叔丁基过氧化己烷、2，5-二甲基-2，5-二叔丁基过氧化己炔、二异丙苯过氧化氢、异丙苯过氧化氢、特戊基过氧化氢、叔丁基过氧化氢、叔丁基过氧化异丙苯、二异丙苯过氧化氢、过氧化碳酸酯-2-乙基己酸叔丁酯、叔丁基过氧化碳酸-2-乙基己酯、4，4-二(叔丁基过氧化)戊酸正丁酯、过氧化甲乙酮、过氧化换己烷中的任意一种或者至少两种的混合物；
    优选地，以乙烯基热固性聚苯醚与双官能马来酰亚胺或多官能马来酰亚胺的预聚物、聚烯烃树脂的重量为100重量份计，引发剂的重量为1～3重量份。
  6. 如权利要求1-5之一所述的树脂组合物，其特征在于，所述树脂组合物还包括组分(D)阻燃剂；
    优选地，所述阻燃剂为含溴阻燃剂或/和含磷阻燃剂，优选所述阻燃剂为一种含DOPO结构的含磷阻燃剂，其分子结构式如下所示：
    Figure PCTCN2015089907-appb-100008
    其中，n为0～10的整数；
    优选地，以乙烯基热固性聚苯醚与双官能马来酰亚胺或多官能马来酰亚胺的预聚物、聚烯烃树脂和引发剂的重量为100重量份计，阻燃剂重量为0～40重 量份；
    优选地，所述树脂组合物还包括组分(E)填料；
    优选地，所述填料选自结晶性二氧化硅、无定形二氧化硅、球形二氧化硅、二氧化钛、碳化硅、玻璃纤维、氧化铝、氮化铝、氮化硼、钛酸钡或钛酸锶中的任意一种或者至少两种的混合物；
    优选地，以乙烯基热固性聚苯醚与双官能马来酰亚胺或多官能马来酰亚胺的预聚物、聚烯烃树脂、引发剂和阻燃剂的重量为100重量份计，填料的重量为0～150重量份。
  7. 一种预浸料，包括基材及通过含浸干燥后附着于基材上的如权利要求1-6之一所述的树脂组合物。
  8. 一种层压板，包括至少一张叠合的权利要求7所述的预浸料；
  9. 一种覆铜箔层压板，包括至少一张叠合的如权利要求7所述的预浸料及压覆于叠合后预浸料的一侧或两侧的铜箔。
  10. 一种印制电路板，包括至少一张叠合的如权利要求7所述的预浸料。
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