WO2022266951A1 - 热固性树脂组成物以及预浸渍片 - Google Patents

热固性树脂组成物以及预浸渍片 Download PDF

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WO2022266951A1
WO2022266951A1 PCT/CN2021/102151 CN2021102151W WO2022266951A1 WO 2022266951 A1 WO2022266951 A1 WO 2022266951A1 CN 2021102151 W CN2021102151 W CN 2021102151W WO 2022266951 A1 WO2022266951 A1 WO 2022266951A1
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resin composition
thermosetting resin
resin
composition according
maleimide
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PCT/CN2021/102151
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English (en)
French (fr)
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黄昱霖
陈怡伶
蔡政欣
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穗晔实业股份有限公司
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Priority to PCT/CN2021/102151 priority Critical patent/WO2022266951A1/zh
Publication of WO2022266951A1 publication Critical patent/WO2022266951A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • 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
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • 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 and a prepreg, in particular to a thermosetting resin composition and a prepreg.
  • thermosetting resin composition has been developed to achieve excellent dimensional stability, high Tg (glass transition temperature) and high heat resistance, and can be applied to copper foil substrates and printed circuit boards.
  • Tg glass transition temperature
  • heat resistance high heat resistance
  • the present invention provides a thermosetting resin composition in which the crosslinking agent can achieve excellent dimensional stability and has high Tg (glass transition temperature) and high heat resistance, and can be applied to copper foil substrates and printed circuit boards .
  • thermosetting resin composition of the present invention includes maleimide resin, cyanate resin and crosslinking agent.
  • the crosslinking agent is a silane-modified diallyl bisphenol compound, and its structure is represented by formula (1):
  • X is straight chain or branched C1 to C6 alkyl, cycloalkyl or sulfonyl
  • R1 is straight chain or branched C1 to C6 alkyl or aryl
  • R2 is C1 to C6
  • R3 is a functional group with a crosslinkable double bond
  • n+m is a positive integer from 1 to 8.
  • the functional group with a crosslinkable double bond includes allyl, vinyl, acrylate or methacrylate.
  • n+m is 2 or 3.
  • the content of the cyanate resin is 30 phr to 210 phr, and the content of the crosslinking agent is 15 phr to 150 phr.
  • the equivalent ratio of reactive groups of the maleimide resin to the cyanate resin is 1:1 to 3:1.
  • the cyanate resin includes bisphenol A type cyanate resin, dicyclopentadiene type (DCPD) cyanate resin, bisphenol F type cyanate resin, novolak type cyanate resin resins or combinations thereof.
  • the maleimide resin includes 4,4'-diphenylmethane bismaleimide, benzyl 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 combinations thereof.
  • the prepreg of the present invention is made of the above thermosetting resin composition by impregnating or coating a base material with the thermosetting resin composition and drying the impregnated or coated base material.
  • thermosetting resin composition of the present invention contains a silane-modified diallyl bisphenol compound as a crosslinking agent. Therefore, it can achieve excellent dimensional stability and have a high Tg (glass transition) by increasing the crosslinking density of the resin. temperature) and high heat resistance, and can be used in copper foil substrates and printed circuit boards.
  • a range indicated by "one value to another value” is a general expression to avoid enumerating all values in the range in the specification. Therefore, the description of a specific numerical range covers any numerical value within the numerical range and the smaller numerical range bounded by any numerical value within the numerical range, as if the arbitrary numerical value and the smaller numerical value are written in the specification. same range.
  • thermosetting resin composition including maleimide resin, cyanate resin, crosslinking agent, filler, catalyst and solvent.
  • the maleimide resin of the present invention may include 4,4'-diphenylmethane bismaleimide, benzyl 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 cyanate resin of the present invention may include bisphenol A type cyanate resin, dicyclopentadiene type (DCPD) cyanate resin, bisphenol F type cyanate resin, novolak type cyanate resin or combinations thereof.
  • the equivalent ratio of reactive groups of the maleimide resin to the cyanate resin is about 1:1 to 3:1. Based on 100 phr of the maleimide resin, the content of the cyanate resin is, for example, 30 phr to 210 phr.
  • Crosslinking agent of the present invention is silane modified diallyl bisphenol compound, and its structure is represented by formula (1):
  • X is straight chain or branched C1 to C6 alkyl, cycloalkyl or sulfonyl
  • R1 is straight chain or branched C1 to C6 alkyl or aryl
  • R2 is C1 to C6
  • R3 is a functional group with a crosslinkable double bond
  • n+m is a positive integer from 1 to 8
  • n+m is preferably 2 or 3.
  • the content of the crosslinking agent is, for example, 15 phr to 150 phr.
  • R3 is a functional group with a crosslinkable double bond
  • the functional group with a crosslinkable double bond may include allyl (allyl), vinyl (vinyl), acrylic acid (acrylate) or methacrylate (methacrylate), but the present invention is not limited thereto.
  • R3 may or may not contain an oxygen atom. If R3 contains an oxygen atom, for example, an oxygen atom may be connected first, and then a functional group with a crosslinkable double bond may be connected.
  • Fillers of the present invention may include silica, alumina, magnesia, 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 Tubes, nanoscale inorganic powders or combinations thereof, preferably vinyl-modified silica. Based on 100 phr of the maleimide resin, the content of the filler is, for example, 150 phr to 400 phr.
  • the type of the catalyst is not particularly limited, as long as it can promote the reaction of the functional group and reduce the curing reaction temperature of the resin composition.
  • the catalyst may include dibenzoyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, 2,5-di Methyl-2,5-bis(tert-butylperoxy)-3-hexyne, di-tert-butyl peroxide, bis(tert-butylperoxyisopropyl)benzene, bis(tert-butylperoxy) ) phthalate, bis(tert-butylperoxy) isophthalate, tert-butyl peroxybenzoate, 2,2-bis(tert-butylperoxy)butane, 2, 2-bis(tert-butylperoxy)octane, 2,5-dimethyl-2,5-bis(benzoylperoxy)hexane,
  • the type of solvent is not particularly limited, as long as it can make the viscosity of the resin composition moderate, easy to operate and cure. More specifically, the solvent may be dimethylacetamide, but the present invention is not limited thereto.
  • the present invention also provides a prepreg made of the above thermosetting resin composition, which is prepared by impregnating or coating a base material with the thermosetting resin composition, and drying the impregnated or coated base material.
  • the substrate may include glass fiber reinforced materials (glass fiber fabric or non-woven fabric, glass paper, glass mat, 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 (substrate), and heated and dried at a temperature of 130° C. to 200° C. for 2 minutes to 10 minutes, so as to prepare a semi-cured pre-impregnated sheet. Take several semi-cured pre-impregnated sheets and stack them in a hot press for high-temperature curing.
  • the curing conditions are, for example, curing at a temperature of 210° C. to 280° C. for 1 hour to 4 hours.
  • thermosetting resin composition proposed by the present invention will be described in detail through experimental examples.
  • the following experimental examples are not intended to limit the present invention.
  • thermosetting resin composition proposed by the present invention has excellent thermal properties and dimensional stability
  • the following experiment example is specially made.
  • the resin compositions of Examples 1 to 5 and Comparative Examples 1 to 5 were prepared according to the composition ratios listed in Table 1 below.
  • the curing conditions are, for example, curing at a temperature of 210° C. to 280° C. for 1 hour to 4 hours. Afterwards, various properties of the test piece were tested, and the test results were listed in Table 1 below.
  • the cyanate resin is bisphenol A type cyanate resin
  • the maleimide resin is 3,3'-dimethyl-5,5'-diethyl-4,4'- Diphenylmethane bismaleimide
  • the filler is silicon dioxide
  • the catalyst is dicumyl peroxide
  • the solvent is dimethylacetamide
  • the crosslinking agent is a silane-modified diene represented by formula (1) Propyl bisphenol compound.
  • example 1 to example 5 show, when maleimide resin, cyanate resin and crosslinking agent meet the content range proposed by the present invention in the thermosetting resin composition (with maleimide
  • the content of the resin is 100phr
  • the content of the cyanate resin is 30phr to 210phr
  • the content of the crosslinking agent is 15phr to 150phr.
  • the cured resin composition has excellent thermal properties and dimensional stability.
  • Comparative Example 1 shows that when the resin composition does not add the crosslinking agent of the present invention (silane-modified diallyl bisphenol compound represented by formula (1)), its dimensional stability is poor and thermal properties are poor .
  • Comparative Example 2 shows that when no cyanate resin is added, the CTE value is relatively high and the copper foil peeling force is abnormally reduced.
  • Comparative Example 3 shows that when the addition amount of cyanate resin is insufficient, Tg is lower than 200° C. and CTE is a negative value.
  • Comparative Example 4 shows that when the cyanate resin is added in excess, it cannot pass the tin oven explosion test.
  • Comparative Example 5 shows that when the cyanate ester resin and the crosslinking agent of the present invention (silane-modified diallyl bisphenol compound represented by formula (1)) are added in excess, the Tg is lower than 200° C. and the CTE is negative.
  • thermosetting resin composition of the present invention comprises maleimide resin, cyanate resin and crosslinking agent, and crosslinking agent is the silane modified diallyl bisphenol compound represented by formula (1) .
  • crosslinking agent is the silane modified diallyl bisphenol compound represented by formula (1) .

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Reinforced Plastic Materials (AREA)

Abstract

本发明提供一种热固性树脂组成物以及预浸渍片。热固性树脂组成物包括马来酰亚胺树脂、氰酸酯树脂以及交联剂。交联剂为硅烷改质二烯丙基双酚化合物，其结构由式(1)表示：在式(1)中，X为直链或支链的C1至C6烷基、环烷基或磺酰基，R1为直链或支链的C1至C6烷基或芳基，R2为C1至C6的烷基，R3为带有可交联双键的官能基，n+m为1至8的正整数。

Description

热固性树脂组成物以及预浸渍片 技术领域
本发明涉及一种树脂组成物以及预浸渍片，尤其涉及一种热固性树脂组成物以及预浸渍片。
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的消耗功率将产生大量热能，导致电子产品温度升高，不停地热胀冷缩，使基板容易损毁，因此，对于电子产品的尺寸安定性也愈加严苛。对于尺寸安定性的优化，现有手段为提高填料的含量，但此方法会使胶水黏度大幅提升，导致施工难度提升且成品外观不良。另一方法为提高树脂的交联密度，能够提高尺寸安定性的同时也提高耐热性。
基于上述，开发出一种热固性树脂组合物，以达到优良的尺寸安定性且拥有高Tg(玻璃化转变温度)及高耐热性，并可应用在铜箔基板与印刷电路板当中，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合物，其中的交联剂可达到优良的尺寸安定性且拥有高Tg(玻璃化转变温度)及高耐热性，并可应用在铜箔基板与印刷电路板当中。
本发明的热固性树脂组成物，包括马来酰亚胺树脂、氰酸酯树脂以及交联剂。交联剂为硅烷改质二烯丙基双酚化合物，其结构由式(1)表示：
Figure PCTCN2021102151-appb-000001
式(1)
在式(1)中，X为直链或支链的C1至C6烷基、环烷基或磺酰基，R1为直链或支链的C1至C6烷基或芳基，R2为C1至C6的烷基，R3为带有可交联双键的官能基，n+m为1至8的正整数。
在本发明的一实施例中，带有可交联双键的官能基包括丙烯基(allyl)、乙烯基(vinyl)、丙烯酸基(acrylate)或甲基丙烯酸基(methacrylate)。
在本发明的一实施例中，n+m为2或3。
在本发明的一实施例中，以马来酰亚胺树脂的含量为100phr计，氰酸酯树脂的含量为30phr至210phr，交联剂的含量为15phr至150phr。
在本发明的一实施例中，马来酰亚胺树脂与氰酸酯树脂的反应基当量比例为1：1至3：1。
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(DCPD)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。
本发明的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，本发明的热固性树脂组合物含有硅烷改质二烯丙基双酚化合物作为交联剂，因此，可通过提高树脂交联密度进而达到优良的尺寸安定性且拥有高Tg(玻璃化转变温度)及高耐热性，并可应用在铜箔基板与印刷电路板当中。
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，且本发明公开不限于此。
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，包括马来酰亚胺树脂、氰酸酯树脂、交联剂、填料、催化剂以及溶剂。以下，将对上述各种组分进行详细说明。
<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。
<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(DCPD)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。在本实施例中，马来酰亚胺树脂与氰酸酯树脂的反应基当量比例为约1：1至3：1。以马来酰亚胺树脂的含量为100phr计，氰酸酯树脂的含量例如是30phr至210phr。
<交联剂>
本发明的交联剂为硅烷改质二烯丙基双酚化合物，其结构由式(1)表示：
Figure PCTCN2021102151-appb-000002
式(1)
在式(1)中，X为直链或支链的C1至C6烷基、环烷基或磺酰基，R1为直链或支链的C1至C6烷基或芳基，R2为C1至C6的烷基，R3为带有可交联双键的官能基，n+m为1至8的正整数，n+m较佳为2或3。
以马来酰亚胺树脂的含量为100phr计，交联剂的含量例如是15phr至150phr。
更详细而言，在式(1)中，R3为带有可交联双键的官能基，带有可交 联双键的官能基可包括丙烯基(allyl)、乙烯基(vinyl)、丙烯酸基(acrylate)或甲基丙烯酸基(methacrylate)，但本发明并不以此为限。此外，必须说明的是，在式(1)中，R3可以是含有氧原子或不含有氧原子的。若R3含有氧原子，例如可以是先接上一个氧原子，再接上带有可交联双键的官能基。
<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，优选为乙烯基(vinyl)改质的二氧化硅。以马来酰亚胺树脂的含量为100phr计，填料的含量例如是150phr至400phr。
<催化剂>
催化剂的种类并无特殊限制，只要能促进官能基反应、并降低树脂组成物的固化反应温度即可。具体而言，催化剂可包括过氧化二苯甲酰、过氧化二异丙苯、2,5-二甲基-2,5-二(叔丁基过氧基)己烷、2,5-二甲基-2,5-二(叔丁基过氧基)-3-己炔、过氧化二叔丁基、二(叔丁基过氧化异丙基)苯、二(叔丁基过氧基)邻苯二甲酸酯、二(叔丁基过氧基)间苯二甲酸酯、过氧苯甲酸叔丁酯、2,2-双(叔丁基过氧基)丁烷、2,2-双(叔丁基过氧基)辛烷、2,5-二甲基-2,5-二(苯甲酰基过氧基)己烷、过氧化月桂酰、过氧化新戊酸叔己酯、双丁基过氧化异丙基苯、双(4-叔丁基环己基)过氧化二碳酸酯或其至少两种的组合。以马来酰亚胺树脂的含量为100phr计，催化剂的含量例如是2phr至6phr。
<溶剂>
溶剂的种类并无特殊限制，只要其能使树脂组合物的黏度适中，便于操作、固化即可。更具体而言，溶剂可以是二甲基乙酰胺，但本发明并不以此为限。
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210℃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热固性树脂组成物具有优良的热性质与尺寸安定性，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5的树脂组成物。使用2116玻璃纤维布作为基材，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210℃至280℃下固化1小时至4小时。之后，测试试片的各项性质，并将测试结果列于以下表1中。
在以下表1中，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，填料为二氧化硅，催化剂为过氧化二异丙苯，溶剂为二甲基乙酰胺，交联剂为由式(1)表示的硅烷改质二烯丙基双酚化合物。
表1
Figure PCTCN2021102151-appb-000003
(单位：phr)
如表1所示，实例1至实例5显示，当热固性树脂组成物中马来酰亚胺树脂、氰酸酯树脂以及交联剂符合本发明所提出的含量范围时(以马来酰亚胺树脂的含量为100phr计，氰酸酯树脂的含量为30phr至210phr，交联剂的含量为15phr至150phr)，固化后的树脂组合物具有优良的热性质与尺寸安定性。相较之下，比较例1显示，当树脂组合物未添加本发明的交联剂(由式(1)表示的硅烷改质二烯丙基双酚化合物)，其尺寸安定性差、热性质不良。比较例2显示，未添加氰酸酯树脂的情况下，CTE数值偏高且铜箔剥离力异常降低。比较例3显示，氰酸酯树脂添加量不足时，Tg低于200℃且CTE为负值。比较例4显示，氰酸酯树脂添加过量时，无法通过锡炉爆板测试。比较例5显示，氰酸酯树脂与本发明的交联剂(由式(1)表示的硅烷改质二烯丙基双酚化合物)添加过量时，Tg低于200℃且CTE为负值。
综上所述，本发明的热固性树脂组合物包括马来酰亚胺树脂、氰酸酯树脂以及交联剂，交联剂为由式(1)表示的硅烷改质二烯丙基双酚化合物。当本发明的热固性树脂组成物中马来酰亚胺树脂、氰酸酯树脂以及交联剂符合 所提出的含量范围时(以马来酰亚胺树脂的含量为100phr计，氰酸酯树脂的含量为30phr至210phr，交联剂的含量为15phr至150phr)，通过添加交联剂从而提高树脂交联密度的方式，可达到优良的尺寸安定性且拥有高Tg(玻璃化转变温度)及高耐热性，并可应用在铜箔基板与印刷电路板当中。

Claims (8)

  1. 一种热固性树脂组成物，其特征在于，包括：
    马来酰亚胺树脂；
    氰酸酯树脂；以及
    交联剂，所述交联剂为硅烷改质二烯丙基双酚化合物，其结构由式(1)表示：
    Figure PCTCN2021102151-appb-100001
    在式(1)中，X为直链或支链的C1至C6烷基、环烷基或磺酰基，R1为直链或支链的C1至C6烷基或芳基，R2为C1至C6的烷基，R3为带有可交联双键的官能基，n+m为1至8的正整数。
  2. 根据权利要求1所述的热固性树脂组成物，其特征在于，所述带有可交联双键的官能基包括丙烯基、乙烯基、丙烯酸基或甲基丙烯酸基。
  3. 根据权利要求1所述的热固性树脂组成物，其特征在于，n+m为2或3。
  4. 根据权利要求1所述的热固性树脂组成物，其特征在于，以所述马来酰亚胺树脂的含量为100phr计，所述氰酸酯树脂的含量为30phr至210phr，所述交联剂的含量为15phr至150phr。
  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与所述氰酸酯树脂的反应基当量比例为1：1至3：1。
  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。
  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。
  8. 一种预浸渍片，由权利要求1至7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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