WO2021212314A1 - 热固性树脂组成物 - Google Patents

热固性树脂组成物 Download PDF

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Publication number
WO2021212314A1
WO2021212314A1 PCT/CN2020/085893 CN2020085893W WO2021212314A1 WO 2021212314 A1 WO2021212314 A1 WO 2021212314A1 CN 2020085893 W CN2020085893 W CN 2020085893W WO 2021212314 A1 WO2021212314 A1 WO 2021212314A1
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resin
epoxy resin
resin composition
content
thermosetting resin
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PCT/CN2020/085893
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English (en)
French (fr)
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黄昱霖
陈怡伶
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穗晔实业股份有限公司
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Priority to PCT/CN2020/085893 priority Critical patent/WO2021212314A1/zh
Publication of WO2021212314A1 publication Critical patent/WO2021212314A1/zh

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/092—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising epoxy resins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/04—Layered products comprising a layer of synthetic resin as impregnant, bonding, or embedding substance
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/62—Alcohols or phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L35/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L35/06—Copolymers with vinyl aromatic monomers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors

Definitions

  • the invention relates to a resin composition, in particular to a thermosetting resin composition.
  • thermosetting resin composition with low dielectric constant and low dielectric loss, while still having high glass transition temperature (Tg) and high heat resistance, and can be applied to copper foil substrates and printed circuit boards.
  • the thermosetting resin composition of the present invention includes epoxy resin, styrene maleic anhydride copolymer, cyanate ester resin, maleimide resin, flame retardant and filler.
  • Epoxy resins include bromine-containing epoxy resins, dicyclopentadiene epoxy resins, or trifunctional epoxy resins.
  • the flame retardant includes a halogen-containing flame retardant or a halogen-free flame retardant, and the halogen-containing flame retardant includes tetrabromobisphenol A.
  • the content of the bromine-containing epoxy resin is 3wt% to 10wt%
  • the content of the dicyclopentadiene epoxy resin is 3wt% to 10wt%
  • the content of functional epoxy resin is 1wt% to 5wt%
  • the content of styrene maleic anhydride copolymer is 5wt% to 31wt%
  • the content of cyanate ester resin is 7wt% to 36wt%
  • the content of maleimide resin The content is 4wt% to 18wt%
  • the content of tetrabromobisphenol A is 2wt% to 16wt%
  • the content of the filler is 9wt% to 69wt%.
  • the molecular weight of the styrene maleic anhydride copolymer is 3000 to 10000, and the molar ratio of styrene:maleic anhydride is 1 to 8:1.
  • the cyanate ester resin includes bisphenol A type cyanate ester resin, dicyclopentadiene type cyanate ester resin, bisphenol F type cyanate ester resin, novolac type cyanate ester resin or the like combination.
  • the maleimide resin includes 4,4'-diphenylmethane bismaleimide, phenylmethane maleimide oligomer, m-phenylene bismaleimide Imide, bisphenol A diphenyl ether bismaleimide, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide Amine, 4-methyl-1,3-phenylene bismaleimide, 1,6-bismaleimide-(2,2,4-trimethyl)hexane, or a combination thereof.
  • the trifunctional epoxy resin includes a trifunctional novolac epoxy resin.
  • the epoxy resin further includes novolac epoxy resin, tetrafunctional epoxy resin, bisphenol type epoxy resin, phosphorus-containing epoxy resin, o-cresol novolac epoxy resin, and bisphenol A novolac epoxy resin.
  • the halogen-free flame retardant includes a phosphorus-containing flame retardant.
  • the phosphorus-containing flame retardant includes a phosphazene compound, a phosphate ester compound, a phosphorus-containing epoxy resin, a phosphorus-containing phenol resin, a phosphorus-containing cyanate resin or a combination thereof.
  • the present invention also provides a prepreg made of the above-mentioned thermosetting resin composition, wherein the substrate is impregnated or coated with the thermosetting resin composition, and the impregnated or coated substrate is dried.
  • thermosetting resin composition including a trifunctional epoxy resin, styrene maleic anhydride copolymer, maleimide resin, cyanate ester resin and other hardeners, so it has a low dielectric Constant, low dielectric loss, while still having high glass transition temperature (Tg) and high heat resistance, and can be applied to copper foil substrates and printed circuit boards.
  • Figure 1 shows the IR spectrum of the cured sheet and trifunctional epoxy resin
  • Figure 2 is a gel permeation chromatography (Gel Permeation Chromatography, GPC) diagram of a trifunctional epoxy resin.
  • thermosetting resin composition including epoxy resin, styrene maleic anhydride copolymer, cyanate ester resin, maleimide resin, flame retardant and filler.
  • the epoxy resin of the present invention may mainly include bromine-containing epoxy resin, dicyclopentadiene epoxy resin (DCPD) or trifunctional epoxy resin.
  • the trifunctional epoxy resin is preferably, for example, trifunctional novolac epoxy.
  • Resin Tris(4-hydroxyphenyl)methane triglycidyl ether).
  • Figure 1 shows the IR spectra of the cured sheet and trifunctional epoxy resin.
  • Figure 2 is a gel permeation chromatography (Gel Permeation Chromatography, GPC) diagram of a trifunctional epoxy resin.
  • the epoxy resin of the present invention may further include novolac epoxy resin, tetrafunctional epoxy resin, bisphenol epoxy resin, phosphorus-containing epoxy resin, o-cresol novolac epoxy resin, and bisphenol A novolac epoxy resin.
  • the content of the bromine-containing epoxy resin is, for example, 3 wt% to 10 wt%
  • the content of the dicyclopentadiene epoxy resin is, for example, 3 wt% to 10 wt%
  • the content of the trifunctional epoxy resin For example, it is 1 wt% to 5 wt%.
  • the molecular weight of the styrene maleic anhydride copolymer of the present invention is, for example, 3000 to 10,000, and the molar ratio of styrene:maleic anhydride is, for example, 1 to 8:1. Based on the total weight of the thermosetting resin composition, the content of the styrene maleic anhydride copolymer is, for example, 5 wt% to 31 wt%.
  • the cyanate ester resin of the present invention may include bisphenol A type cyanate ester resin, dicyclopentadiene type cyanate ester resin, bisphenol F type cyanate ester resin, novolac type cyanate ester resin, or a combination thereof. Based on the total weight of the thermosetting resin composition, the content of the cyanate ester resin is, for example, 7 wt% to 36 wt%.
  • the maleimide resin of the present invention may include 4,4'-diphenylmethane bismaleimide, phenylmethane maleimide oligomer, m-phenylene bismaleimide, bis Phenol A diphenyl ether bismaleimide, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, 4-methyl 1,3-phenylene bismaleimide, 1,6-bismaleimide-(2,2,4-trimethyl)hexane, or a combination thereof.
  • the content of the maleimide resin is, for example, 4 wt% to 18 wt%.
  • the flame retardant of the present invention includes a halogen-containing flame retardant or a halogen-free flame retardant, and the halogen-containing flame retardant may include decabromodiphenylethane, ethyl-bis(tetrabromophthalamide), tetrabromobis Phenol A, dibromobiphenyl, tris(tribromophenoxy)triazine or a combination thereof, preferably tetrabromobisphenol A, for example. Based on the total weight of the thermosetting resin composition, the content of tetrabromobisphenol A is, for example, 2 wt% to 16 wt%.
  • the halogen-free flame retardant may include, but is not limited to, nitrogen-containing compounds, phosphorus-containing compounds or metal hypophosphorous acid salts, preferably, for example, phosphorus-containing compounds.
  • Phosphorus-containing flame retardants include phosphazene compounds, phosphate ester compounds, phosphorus-containing epoxy resins, phosphorus-containing phenolic resins, phosphorus-containing cyanate ester resins, or combinations thereof.
  • the filler of the present invention may include silicon dioxide, aluminum oxide, magnesium oxide, magnesium hydroxide, calcium carbonate, talc, clay, aluminum nitride, boron nitride, aluminum hydroxide, aluminum silicon carbide, silicon carbide, sodium carbonate, titanium dioxide , Zinc oxide, zirconia, quartz, diamond, diamond-like, graphite, calcined kaolin, kaolin, mica, hydrotalcite, hollow silica, polytetrafluoroethylene (PTFE) powder, glass beads, nano-carbon Tube, nano-scale inorganic powder or a combination thereof. Based on the total weight of the thermosetting resin composition, the content of the filler is 9 wt% to 69 wt%.
  • the type of the catalyst is not particularly limited, as long as it can promote the ring opening of the epoxy functional group and reduce the curing reaction temperature of the resin composition.
  • the catalyst may include 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, dimethylbenzylamine, 2-(dimethylaminomethyl)phenol, 2,4, 6-Tris(dimethylaminomethyl)phenol, 2,3-diaminopyridine, 2,5-diaminopyridine, 2,6-diaminopyridine, 4-dimethylaminopyridine, 2-amine 3-methylpyridine, 2-amino-4-methylpyridine, 2-amino-3-nitropyridine, zinc oxide, or a combination thereof.
  • the present invention also provides a prepreg made of the above-mentioned thermosetting resin composition, which is produced by impregnating or coating a substrate with the thermosetting resin composition, and drying the impregnated or coated substrate.
  • the substrate may include glass fiber reinforcement materials (glass fiber fabric or non-woven fabric, cellophane, glass felt, etc.), kraft paper, short-staple cotton paper, natural fiber cloth, organic fiber cloth, liquid crystal polymer fiber mat, etc. .
  • 2116 glass fiber cloth can be used as a reinforcing material (base material) and heated and dried at a temperature of 130° C. to 200° C. for 2 minutes to 10 minutes, thereby preparing a semi-cured prepreg sheet. Take several semi-cured prepreg sheets and stack them in a hot press for high-temperature curing.
  • the curing conditions are, for example, curing at a temperature of 170° C. to 280° C. for 1 hour to 4 hours.
  • thermosetting resin composition proposed by the present invention will be explained in detail through experimental examples. However, the following experimental examples are not intended to limit the present invention.
  • thermosetting resin composition proposed by the present invention has a low dielectric constant, low dielectric loss, while still having a high glass transition temperature (Tg) and high heat resistance
  • this experimental example is specifically made as follows.
  • the resin compositions of Examples 1 to 5 and Comparative Examples 1 to 3 were prepared.
  • the curing conditions are, for example, curing at a temperature of 170° C. to 280° C. for 1 hour to 4 hours. After that, the electrothermal properties of the test piece were tested, and the test results are listed in Table 1 and Table 2 below.
  • the epoxy resins are bisphenol A type epoxy resins and dicyclopentadiene epoxy resins.
  • the trifunctional epoxy resin is a trifunctional novolac type epoxy resin (Tris(4-hydroxyphenyl)methane triglycidyl ether).
  • Styrene maleic anhydride is SMA EF40.
  • the cyanate ester resin is a bisphenol A type cyanate ester resin.
  • the maleimide resin is 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide.
  • the bromine-containing flame retardant is tetrabromobisphenol A.
  • the filler is silica RCS525.
  • Example 1 As shown in Table 1, from Example 1, Comparative Example 2 and Example 3, and Comparative Example 1, it can be known that the excessive addition of tetrabromobisphenol A leads to a decrease in the overall cross-linking degree, resulting in deterioration of thermal properties. It can be known from Example 1 and Example 2 that increasing the amount of trifunctional epoxy resin can increase the Tg and Td of the resin composition. From Example 3 to Example 5, it can be known that increasing the amount of cyanate ester can reduce Dk and Df. It can be seen from Comparative Example 1 and Comparative Example 2 that although the styrene maleic anhydride copolymer in Comparative Example 2 is added in a large amount, the overall reaction is incomplete due to the excessive amount of tetrabromobisphenol A added. Unreacted styrene maleic anhydride copolymer causes Dk to rise
  • the present invention provides a thermosetting resin composition, including epoxy resin, styrene maleic anhydride copolymer, cyanate ester resin, maleimide resin, tetrabromobisphenol A and filler, epoxy resin
  • the resin includes a trifunctional epoxy resin, and the above composition is added in a specific ratio range, so it has a low dielectric constant, low dielectric loss, while still having a high glass transition temperature (Tg) and high heat resistance, vitrification
  • Tg glass transition temperature
  • the transition temperature (Tg) can reach above 200°C, and it can be applied to copper foil substrates and printed circuit boards.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Reinforced Plastic Materials (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

一种热固性树脂组成物，包括环氧树脂、苯乙烯马来酸酐共聚物、氰酸酯树脂、马来酰亚胺树脂、四溴双酚A以及填料。环氧树脂包括含溴环氧树脂、双环戊二烯环氧树脂或三官能基环氧树脂。

Description

热固性树脂组成物 技术领域
本发明涉及一种树脂组成物，尤其涉及一种热固性树脂组成物。
背景技术
近年来，随着通讯技术的高速发展，电子产品在轻量化与高密度化方面的需求与日俱增。电子产品在使用的过程中，消耗功率将产生大量热能，导致电子产品温度升高，进而使基板容易损毁。因此，开发一种树脂组成物，具有优良电气性能的同时还具有良好的耐热性，并且可应用于铜箔基板与印刷电路板，为本领域技术人员亟欲发展的目标。
发明内容
本发明提供一种热固性树脂组成物，具有低介电常数、低介电损耗，同时仍具有高玻璃化转变温度(Tg)及高耐热性，且可应用于铜箔基板与印刷电路板。
本发明的热固性树脂组成物包括环氧树脂、苯乙烯马来酸酐共聚物、氰酸酯树脂、马来酰亚胺树脂、阻燃剂以及填料。环氧树脂包括含溴环氧树脂、双环戊二烯环氧树脂或三官能基环氧树脂。阻燃剂包括含卤阻燃剂或无卤阻燃剂，含卤阻燃剂包括四溴双酚A。
在本发明的一实施例中，以热固性树脂组成物的总重量计，含溴环氧树脂的含量为3wt％至10wt％，双环戊二烯环氧树脂的含量为3wt％至10wt％，三官能基环氧树脂的含量为1wt％至5wt％，苯乙烯马来酸酐共聚物的含量为5wt％至31wt％，氰酸酯树脂的含量为7wt％至36wt％，马来酰亚胺树脂的含量为4wt％至18wt％，四溴双酚A的含量为2wt％至16wt％，填料的含量为9wt％至69wt％。
在本发明的一实施例中，苯乙烯马来酸酐共聚物的分子量为3000至10000，且苯乙烯:马来酸酐的摩尔比为1至8:1。
在本发明的一实施例中，氰酸酯树脂包括双酚A型氰酸酯树脂、双环戊 二烯型氰酸酯树脂、双酚F型氰酸酯树脂、酚醛型氰酸酯树脂或其组合。
在本发明的一实施例中，马来酰亚胺树脂包括4,4’-二苯甲烷双马来酰亚胺、苯甲烷马来酰亚胺寡聚物、间-亚苯基双马来酰亚胺、双酚A二苯基醚双马来酰亚胺、3,3’-二甲基-5,5’-二乙基-4,4’-二苯基甲烷双马来酰亚胺、4-甲基-1,3-亚苯基双马来酰亚胺、1,6-双马来酰亚胺-(2,2,4-三甲基)己烷或其组合。
在本发明的一实施例中，三官能基环氧树脂包括三官能酚醛型环氧树脂。
在本发明的一实施例中，环氧树脂更包括酚醛环氧树脂、四官能基环氧树脂、双酚型环氧树脂、含磷环氧树脂、邻甲酚醛环氧树脂、双酚A酚醛环氧树脂、苯酚酚醛环氧树脂、萘环型环氧树脂、异氰酸酯改性环氧树脂、联苯型环氧树脂、含三嗪结构环氧树脂、含茀结构脂环氧树脂或其组合。
在本发明的一实施例中，无卤阻燃剂包括含磷阻燃剂。
在本发明的一实施例中，含磷阻燃剂包括磷腈化合物、磷酸酯化合物、含磷环氧树脂、含磷酚醛树脂、含磷氰酸酯树脂或其组合。
本发明也提供一种预浸渍片，由上述热固性树脂组成物所制成，其中通过将基材含浸或涂布热固性树脂组成物，并干燥经含浸或涂布的基材而制成。
基于上述，本发明提供一种热固性树脂组成物，包括三官能基环氧树脂以及苯乙烯马来酸酐共聚物、马来酰亚胺树脂及氰酸酯树脂等硬化剂，因此，具有低介电常数、低介电损耗，同时仍具有高玻璃化转变温度(Tg)及高耐热性，且可应用于铜箔基板与印刷电路板。
附图说明
包含附图以便进一步理解本发明，且附图并入本说明书中并构成本说明书的一部分。附图说明本发明的实施例，并与描述一起用于解释本发明的原理。
图1为固化后板材及三官能基环氧树脂的IR光谱图；
图2为三官能基环氧树脂的凝胶渗透层析法(Gel Permeation Chromatography，GPC)图。
具体实施方式
以下，将详细描述本发明的实施例。然而，这些实施例为例示性，且本发明揭示不限于此。
在本文中，由“一数值至另一数值”表示的范围，是一种避免在说明书中一一列举该范围中的所有数值的概要性表示方式。因此，某一特定数值范围的记载，涵盖该数值范围内的任意数值以及由该数值范围内的任意数值界定出的较小数值范围，如同在说明书中说明文写出该任意数值和该较小数值范围一样。
本发明提出一种热固型树脂组成物，包括环氧树脂、苯乙烯马来酸酐共聚物、氰酸酯树脂、马来酰亚胺树脂、阻燃剂以及填料。以下，将对上述各种组分进行详细说明。
<环氧树脂>
本发明的环氧树脂主要可包括含溴环氧树脂、双环戊二烯环氧树脂(DCPD)或三官能基环氧树脂，其中三官能基环氧树脂较佳例如是三官能酚醛型环氧树脂(Tris(4-hydroxyphenyl)methane triglycidyl ether)。图1为固化后板材及三官能基环氧树脂的IR光谱图。图2为三官能基环氧树脂的凝胶渗透层析法(Gel Permeation Chromatography，GPC)图。此外，本发明的环氧树脂也可更包括酚醛环氧树脂、四官能基环氧树脂、双酚型环氧树脂、含磷环氧树脂、邻甲酚醛环氧树脂、双酚A酚醛环氧树脂、苯酚酚醛环氧树脂、萘环型环氧树脂、异氰酸酯改性环氧树脂、联苯型环氧树脂、含三嗪结构环氧树脂(triazine)、含茀结构脂环氧树脂(fulorene)或其组合。以热固性树脂组成物的总重量计，含溴环氧树脂的含量例如是3wt％至10wt％，双环戊二烯环氧树脂的含量例如是3wt％至10wt％，三官能基环氧树脂的含量例如是1wt％至5wt％。
<苯乙烯马来酸酐共聚物>
本发明的苯乙烯马来酸酐共聚物的分子量例如是3000至10000，且苯乙烯:马来酸酐的摩尔比例如是1至8:1。以热固性树脂组成物的总重量计，苯乙烯马来酸酐共聚物的含量例如是5wt％至31wt％。
<氰酸酯树脂>
本发明的氰酸酯树脂可包括双酚A型氰酸酯树脂、双环戊二烯型氰酸酯树脂、双酚F型氰酸酯树脂、酚醛型氰酸酯树脂或其组合。以热固性树脂组 成物的总重量计，氰酸酯树脂的含量例如是7wt％至36wt％。
<马来酰亚胺树脂>
本发明的马来酰亚胺树脂可包括4,4’-二苯甲烷双马来酰亚胺、苯甲烷马来酰亚胺寡聚物、间-亚苯基双马来酰亚胺、双酚A二苯基醚双马来酰亚胺、3,3’-二甲基-5,5’-二乙基-4,4’-二苯基甲烷双马来酰亚胺、4-甲基-1,3-亚苯基双马来酰亚胺、1,6-双马来酰亚胺-(2,2,4-三甲基)己烷或其组合。以热固性树脂组成物的总重量计，马来酰亚胺树脂的含量例如是4wt％至18wt％。
<阻燃剂>
本发明的阻燃剂包括含卤阻燃剂或无卤阻燃剂，含卤阻燃剂可包括十溴二苯乙烷、乙基-双(四溴苯邻二甲酰胺)、四溴双酚A、二溴联苯、三(三溴苯氧基)三嗪或其组合，较佳例如是四溴双酚A。以热固性树脂组成物的总重量计，四溴双酚A的含量例如是2wt％至16wt％。无卤阻燃剂可包括但不限于含氮化合物、含磷化合物或次磷酸金属盐，较佳例如是含磷化合物。含磷阻燃剂包括磷腈化合物、磷酸酯化合物、含磷环氧树脂、含磷酚醛树脂、含磷氰酸酯树脂或其组合。
<填料>
本发明的填料可包括二氧化硅、氧化铝、氧化镁、氢氧化镁、碳酸钙、滑石、黏土、氮化铝、氮化硼、氢氧化铝、碳化铝硅、碳化硅、碳酸钠、二氧化钛、氧化锌、氧化锆、石英、钻石、类钻石、石墨、锻烧高岭土、白岭土、云母、水滑石、中空二氧化硅、聚四氟乙烯(polytetrafluoroethylene，PTFE)粉末、玻璃珠、纳米碳管、纳米级无机粉体或其组合。以热固性树脂组成物的总重量计，填料的含量为9wt％至69wt％。
<催化剂>
催化剂的种类并无特殊限制，只要其能促进环氧官能基开环、并降低树脂组成物的固化反应温度即可。具体而言，催化剂可包括2-甲基咪唑、2-乙基-4-甲基咪唑、2-苯基咪唑、二甲芐胺、2-(二甲胺甲基)苯酚、2,4,6-三(二甲胺甲基)苯酚、2,3-二胺基吡啶、2,5-二胺基吡啶、2,6-二胺基吡啶、4-二甲基氨基吡啶、2-胺基-3-甲基吡啶、2-胺基-4-甲基吡啶、2-胺基-3-硝基吡啶、氧化锌或其组合。
本发明也提供一种预浸渍片，由上述热固性树脂组成物所制成，其中通 过将基材含浸或涂布热固性树脂组成物，并干燥经含浸或涂布的基材而制成。更详细而言，基材可包括玻璃纤维补强材料(玻璃纤维织物或不织物、玻璃纸、玻璃毡等)、牛皮纸、短绒棉纸、天然纤维布、有机纤维布、液晶高分子纤维毡等。在本实施例中，例如可使用2116玻璃纤维布作为补强材(基材)，并在温度130℃至200℃下加热干燥2分钟至10分钟，从而制得半固化的预含浸片。取数片半固化的预含浸片堆栈于热压机中进行高温固化，固化条件例如是在温度170℃至280℃下固化1小时至4小时。
以下，通过实验例来详细说明上述本发明所提出的热固性树脂组成物。然而，下述实验例并非用以限制本发明。
实验例
为了证明本发明所提出的的热固性树脂组成物具有低介电常数、低介电损耗，同时仍具有高玻璃化转变温度(Tg)及高耐热性，以下特别作此实验例。
依据以下表1所列出的组成比例，制备实例1至实例5以及比较例1至比较例3的树脂组成物。使用2116玻璃纤维布作为补强材(基材)，将基材含浸或涂布树脂组成物，并在温度130℃至200℃下加热干燥2分钟至10分钟，从而制得半固化的预含浸片。取数片半固化的预含浸片堆栈于热压机中进行高温固化，固化条件例如是在温度170℃至280℃下固化1小时至4小时。之后，测试试片的电热性质，并将测试结果列于以下表1表2中。
在以下表1中，环氧树脂为双酚A型环氧树脂、双环戊二烯环氧树脂。三官能环氧树脂为三官能酚醛型环氧树脂(Tris(4-hydroxyphenyl)methane triglycidyl ether)。苯乙烯马来酸酐为SMA EF40。氰酸酯树脂为双酚A型氰酸酯树脂。马来酰亚胺树脂为3,3’-二甲基-5,5’-二乙基-4,4’-二苯基甲烷双马来酰亚胺。含溴阻燃剂为四溴双酚A。填料为二氧化硅RCS525。
表1
Figure PCTCN2020085893-appb-000001
(单位：重量份)
如表1所示，从实例1、比较例2和实例3、比较例1可以得知，由于四溴双酚A添加过量导致整体交联度下降，造成热性质变差。从实例1及实例2可以得知，提高三官能基环氧树脂用量可以提高树脂组成物的Tg和Td。从实施例3至实施例5可以得知，增加氰酸酯用量可以降低Dk、Df。从比较例1、比较例2可以得知，虽然比较例2的苯乙烯马来酸酐共聚物添加量较多，但是由于四溴双酚A的的添加量过多导致整体反应不完全，过多未反应的苯乙烯马来酸酐共聚物造成Dk上升
综上所述，本发明提供一种热固性树脂组成物，包括环氧树脂、苯乙烯马来酸酐共聚物、氰酸酯树脂、马来酰亚胺树脂、四溴双酚A以及填料，环氧树脂包括三官能基环氧树脂，且上述组成以特定比例范围添加，因此，具有低介电常数、低介电损耗，同时仍具有高玻璃化转变温度(Tg)及高耐热性，玻璃化转变温度(Tg)可达到200℃以上，且可应用于铜箔基板与印刷电路板。

Claims (10)

  1. 一种热固性树脂组成物，其特征在于，包括：
    环氧树脂，包括含溴环氧树脂、双环戊二烯环氧树脂或三官能基环氧树脂；
    苯乙烯马来酸酐共聚物；
    氰酸酯树脂；
    马来酰亚胺树脂；
    阻燃剂，包括含卤阻燃剂或无卤阻燃剂，所述含卤阻燃剂包括四溴双酚A；以及
    填料。
  2. 根据权利要求1所述的热固性树脂组成物，其特征在于，以所述热固性树脂组成物的总重量计，所述含溴环氧树脂的含量为3wt％至10wt％，所述双环戊二烯环氧树脂的含量为3wt％至10wt％，所述三官能基环氧树脂的含量为1wt％至5wt％，所述苯乙烯马来酸酐共聚物的含量为5wt％至31wt％，所述氰酸酯树脂的含量为7wt％至36wt％，所述马来酰亚胺树脂的含量为4wt％至18wt％，所述四溴双酚A的含量为2wt％至16wt％，所述填料的含量为9wt％至69wt％。
  3. 根据权利要求1所述的热固性树脂组成物，其特征在于，所述苯乙烯马来酸酐共聚物的分子量为3000至10000，且苯乙烯:马来酸酐的摩尔比为1至8:1。
  4. 根据权利要求1所述的热固性树脂组成物，其特征在于，所述氰酸酯树脂包括双酚A型氰酸酯树脂、双环戊二烯型氰酸酯树脂、双酚F型氰酸酯树脂、酚醛型氰酸酯树脂或其组合。
  5. 根据权利要求1所述的热固性树脂组成物，其特征在于，所述马来酰亚胺树脂包括4,4’-二苯甲烷双马来酰亚胺、苯甲烷马来酰亚胺寡聚物、间-亚苯基双马来酰亚胺、双酚A二苯基醚双马来酰亚胺、3,3’-二甲基-5,5’-二乙基-4,4’-二苯基甲烷双马来酰亚胺、4-甲基-1,3-亚苯基双马来酰亚胺、1,6-双马来酰亚胺-(2,2,4-三甲基)己烷或其组合。
  6. 根据权利要求1所述的热固性树脂组成物，其特征在于，所述三官能基环氧树脂包括三官能酚醛型环氧树脂。
  7. 根据权利要求1所述的热固性树脂组成物，其特征在于，所述环氧树脂更包括酚醛环氧树脂、四官能基环氧树脂、双酚型环氧树脂、含磷环氧树脂、邻甲酚醛环氧树脂、双酚A酚醛环氧树脂、苯酚酚醛环氧树脂、萘环型环氧树脂、异氰酸酯改性环氧树脂、联苯型环氧树脂、含三嗪结构环氧树脂、含茀结构脂环氧树脂或其组合。
  8. 根据权利要求1所述的热固性树脂组成物，其特征在于，所述无卤阻燃剂包括含磷阻燃剂。
  9. 根据权利要求8所述的热固性树脂组成物，其特征在于，所述含磷阻燃剂包括磷腈化合物、磷酸酯化合物、含磷环氧树脂、含磷酚醛树脂、含磷氰酸酯树脂或其组合。
  10. 一种预浸渍片，由如权利要求1至9中任一项所述的热固性树脂组成物所制成，其中通过将基材含浸或涂布所述热固性树脂组成物，并干燥经含浸或涂布的所述基材而制成。
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