TW202102604A - Polyphenylene ether-containing resin composition demanding that the resin composition have good miscibility with PPE, good coatability on a base material and the like, and excellent substrate characteristics when applied to an electronic circuit board - Google Patents

Abstract

For the resin composition containing polyphenylene ether (PPE), the industry requires the resin composition to have good miscibility with PPE, good coatability on a base material and the like, and excellent substrate characteristics when applied to an electronic circuit board. Therefore, the purpose of the present invention is to meet these requirements. The present invention provides a resin composition, which comprises: (a) a PPE component, which has the structure represented by the following formula (1), where x, a, R5, K, y, N, a, and L are defined in the specification, and the number average molecular weight is 500-8000; (b) a crosslinking agent; (c) an organic peroxide; and (d) a thermoplastic resin, which is selected from at least one of the group consisting of a block copolymer of a vinyl aromatic compound and an olefin-based olefin compound and a hydride thereof, and a homopolymer of the vinyl aromatic compound, and the weight average molecular weight is 150000-800000. Based on the total mass of polyphenylene ether component A and crosslinking agent as 100 parts by mass, the content of the thermoplastic resin is 2 parts by mass to 20 parts by mass.

Description

Resin composition containing polyphenylene ether

The present invention relates to a resin composition containing polyphenylene ether and the like.

In recent years, with the obvious advancement of information network technology, or the expansion of services using information networks, electronic devices are required to increase the amount of information and increase the processing speed. In order to meet these requirements, for substrate materials such as printed wiring boards, in addition to the previously required characteristics such as flame retardancy, heat resistance, and peel strength from copper foil, low dielectric constant and low dielectric loss tangent are also required化. Therefore, research is underway to further improve the resin composition used for substrate materials such as printed wiring boards.

Among substrate materials, polyphenylene ether (PPE) has a relatively low dielectric constant and relatively low dielectric loss tangent, so it is more suitable as a material for printed wiring boards that can meet the above requirements. For example, the polyphenylene ether-containing resin composition described in Patent Document 1 is achieved by controlling the average number of phenolic hydroxyl groups per molecule of the polyphenylene ether within a specific range, or a plurality of polyphenylene ethers having different molecular weights. Those who seek to improve formability, heat resistance, adhesiveness and electrical properties. [Prior technical literature] [Patent literature]

[Patent Document 1] International Publication No. 2012/081705

[The problem to be solved by the invention]

For resin compositions containing polyphenylene ether (PPE), good compatibility with PPE, good coating properties to substrates, etc., and excellent substrate characteristics when assembled into electronic circuit substrates are required. Regarding the polyphenylene ether-containing resin composition described in Patent Document 1, there is still room for research from the viewpoint of meeting all of these requirements.

Therefore, the object of the present invention is to provide a polyphenylene ether-containing resin composition having excellent compatibility, coating properties, and substrate properties, and electronic circuit board materials, resin films, prepregs, and laminates formed using the polyphenylene ether-containing resin composition. [Technical means to solve the problem]

{式中，  X為a價之任意連結基，a為2.5以上之數，  R⁵ 分別獨立為任意取代基，k分別獨立為1～4之整數，k個R⁵ 中之至少1個包含下述式(2)：  [化2]

(式中，R¹¹ 分別獨立為C_1-8 之烷基，R¹² 分別獨立為C_1-8 之伸烷基，b分別獨立為0或1，R¹³ 表示氫原子、C_1-8 之烷基或苯基之任一者，且上述烷基、伸烷基及苯基於滿足C_1-8 之條件之限度下可具有取代基)  所表示之部分結構，  Y分別獨立為具有下述式(3)：  [化3]

(式中，R²¹ 分別獨立為C_1-6 之飽和或不飽和烴基，R²² 分別獨立為氫原子或C_1-6 之飽和或不飽和烴基，且上述飽和或不飽和烴基於滿足C_1-6 之條件之限度下可具有取代基)  所表示之結構之二價連結基，n表示Y之重複數，分別獨立為1～200之整數，  L為任意二價連結基、或單鍵，且  A分別獨立表示含有碳-碳雙鍵及/或環氧鍵之取代基}  所表示之結構，且數量平均分子量為500～8,000；  (b)交聯劑；  (c)有機過氧化物；及  (d)熱塑性樹脂，其為選自由乙烯基芳香族化合物與烯烴系烯烴化合物之嵌段共聚物及其氫化物、以及上述乙烯基芳香族化合物之均聚物所組成之群中之至少1種，且重量平均分子量為150,000～800,000；  且上述熱塑性樹脂之含量以上述聚苯醚成分A及上述交聯劑之合計質量100質量份為基準，為2質量份～20質量份。  [2]  如項目1中記載之樹脂組合物，其中上述嵌段共聚物或其氫化物中之源自上述乙烯基芳香族化合物之單元之含有率為20質量%以上且70質量%以下。  [3]  如項目1或2中記載之樹脂組合物，其中上述交聯劑於1分子中具有平均2個以上碳-碳不飽和雙鍵，上述交聯劑之數量平均分子量為4,000以下，且上述聚苯醚成分A：上述交聯劑之重量比為25：75～95：5。  [4]  如項目1至3中任一項所記載之樹脂組合物，其中上述交聯劑包含選自由氰尿酸三烯丙酯、異氰尿酸三烯丙酯、及聚丁二烯所組成之群中之至少一種化合物。  [5]  如項目1至4中任一項所記載之樹脂組合物，其中上述有機過氧化物之1分鐘半衰期溫度為155℃～185℃。  [6]  如項目1至5中任一項所記載之樹脂組合物，其中上述有機過氧化物之含量以上述聚苯醚成分A與上述交聯劑之合計質量100質量份為基準，為0.05質量份～5質量份。  [7]  如項目1至6中任一項所記載之樹脂組合物，其中上述樹脂組合物進而包含阻燃劑，且上述阻燃劑於上述樹脂組合物硬化後在上述樹脂組合物中不會與其他含有成分相溶。  [8]  一種電子電路基板材料，其包含如項目1至7中任一項所記載之樹脂組合物。  [9]  一種樹脂膜，其包含如項目1至7中任一項所記載之樹脂組合物。  [10]  一種預浸體，其為基材與如項目1至7中任一項所記載之樹脂組合物之複合體。  [11]  如項目10中記載之預浸體，其中上述基材為玻璃布。  [12]  一種積層體，其為如項目9中記載之樹脂膜、或如項目10或11中記載之預浸體之硬化物與金屬箔之積層體。  [發明之效果]In order to solve the above-mentioned problems, the inventors have conducted intensive research and found that the structure and molecular weight of a specific polyphenylene ether in a resin composition containing polyphenylene ether, crosslinking agent, organic peroxide, and thermoplastic resin The structure, molecular weight, and content of the thermoplastic resin are excellent in compatibility, coating properties, and substrate characteristics, thus completing the present invention. Examples of embodiments of the present invention are listed below. [1] A resin composition comprising: (a) polyphenylene ether component A, which has the following formula (1): [化1]

{Where X is an arbitrary linking group with a valence, a is a number greater than 2.5, R ^{5 is} each independently an arbitrary substituent, k is each independently an integer from 1 to 4, and at least one of ^{k R 5 includes the following} Formula (2): [化2]

(In the formula, R ^{11 is} each independently a C _1-8 alkylene group, R ^{12 is} each independently a C _1-8 alkylene group, b is each independently 0 or 1, R ¹³ represents a hydrogen atom, C _1-8 Either an alkyl group or a phenyl group, and the above-mentioned alkyl group, alkylene group, and phenyl group _{may have a substituent within the limit of satisfying the condition of C 1-8} ), and Y each independently has the following formula (3): [化3]

(In the formula, R ^{21 is} independently a saturated or unsaturated hydrocarbon group _{of C 1-6} ^{, and R 22 is} independently a hydrogen atom or a _{saturated or unsaturated hydrocarbon group of C 1-6} , and the above saturated or unsaturated hydrocarbon is based on satisfying C _{1 The} divalent linking group of the structure represented by the condition of -6 may have a substituent), n represents the repeating number of Y, each independently an integer of 1 to 200, and L is any divalent linking group or a single bond, And A each independently represents a structure represented by a substituent containing a carbon-carbon double bond and/or an epoxy bond}, and the number average molecular weight is 500 to 8,000; (b) crosslinking agent; (c) organic peroxide; And (d) a thermoplastic resin, which is at least 1 selected from the group consisting of block copolymers of vinyl aromatic compounds and olefin-based olefin compounds and their hydrogenated products, and homopolymers of the aforementioned vinyl aromatic compounds And the weight average molecular weight is 150,000 to 800,000; and the content of the thermoplastic resin is 2 parts by mass to 20 parts by mass based on 100 parts by mass of the total mass of the polyphenylene ether component A and the crosslinking agent. [2] The resin composition according to item 1, wherein the content of the unit derived from the vinyl aromatic compound in the block copolymer or its hydrogenated product is 20% by mass or more and 70% by mass or less. [3] The resin composition as described in item 1 or 2, wherein the crosslinking agent has an average of 2 or more carbon-carbon unsaturated double bonds in one molecule, and the number average molecular weight of the crosslinking agent is 4,000 or less, and The weight ratio of the polyphenylene ether component A: the crosslinking agent is 25:75 to 95:5. [4] The resin composition as described in any one of items 1 to 3, wherein the crosslinking agent comprises one selected from triallyl cyanurate, triallyl isocyanurate, and polybutadiene At least one compound in the group. [5] The resin composition according to any one of items 1 to 4, wherein the one-minute half-life temperature of the organic peroxide is 155°C to 185°C. [6] The resin composition according to any one of items 1 to 5, wherein the content of the organic peroxide is 0.05 based on 100 parts by mass of the total mass of the polyphenylene ether component A and the crosslinking agent Parts by mass ~ 5 parts by mass. [7] The resin composition according to any one of items 1 to 6, wherein the resin composition further contains a flame retardant, and the flame retardant does not appear in the resin composition after the resin composition is cured. Compatible with other ingredients. [8] An electronic circuit board material comprising the resin composition as described in any one of items 1 to 7. [9] A resin film comprising the resin composition as described in any one of items 1 to 7. [10] A prepreg, which is a composite of a substrate and the resin composition as described in any one of items 1 to 7. [11] The prepreg as described in item 10, wherein the substrate is glass cloth. [12] A laminate which is a laminate of the resin film described in item 9 or the hardened product of the prepreg as described in item 10 or 11 and a laminate of metal foil. [Effects of Invention]

According to the present invention, it is possible to provide an electronic circuit board material, a resin film, a prepreg, and a laminate that has excellent compatibility and coatability of a polyphenylene ether-containing resin composition, and excellent substrate characteristics by using the polyphenylene ether.

Hereinafter, an embodiment of the present invention (hereinafter, simply referred to as "this embodiment") will be described in detail. In addition, the present invention is not limited to the following embodiments, and can be implemented with various changes within the scope of the gist.

Resin composition The PPE-containing resin composition of this embodiment (hereinafter, also simply referred to as the "resin composition") includes polyphenylene ether (PPE), crosslinking agent, organic peroxide, and thermoplastic resin, and depends on the requirements. If necessary, it may further contain flame retardants, other additives, silica fillers, solvents, etc. Hereinafter, the constituent elements of the resin composition of the present embodiment will be described.

Polyphenylene ether (PPE) Generally, polyphenylene ether (PPE) has a repeating structure containing substituted or unsubstituted phenyl ether units. In this specification, the term "polyphenylene ether" includes dimers, trimers, oligomers, and polymers. PPE may contain copolymerization component units other than phenyl ether units, but the amount of such copolymerization component units relative to the number of all unit structures is typically 0% or more or more than 0%, and 30% or less, 25% or less , 20% or less, 15% or less, 10% or less or 5% or less.

As a typical PPE, for example, poly(2,6-dimethyl-1,4-phenylene ether), poly(2-methyl-6-ethyl-1,4-phenylene ether), poly(2,6-dimethyl-1,4-phenylene ether), poly(2,6-dimethyl-1,4-phenylene ether), and poly(2,6-dimethyl-1,4-phenylene ether) can be cited as typical PPE. -Methyl-6-phenyl-1,4-phenylene ether), poly(2,6-dichloro-1,4-phenylene ether), etc., and further examples include: 2,6-dimethylphenol and other phenols (For example, 2,3,6-trimethylphenol, 2-methyl-6-butylphenol, etc.) copolymers, and the coupling of 2,6-dimethylphenol with biphenols or bisphenols The resulting PPE copolymer, etc.

所表示之結構，且數量平均分子量為500～8,000。Polyphenylene ether component A (PPE-A) The resin composition of this embodiment contains polyphenylene ether component A as a polyphenylene ether component, and this polyphenylene ether component A has the following formula (1): [Chemical Formula 4]

The structure represented, and the number average molecular weight is 500 to 8,000.

In formula (1), X is an arbitrary linking group with a valence, and a is a number of 2.5 or more, preferably an integer of 3 or more, and more preferably an integer of 3-6. Specific examples of X include, for example, a hydrocarbon group; a hydrocarbon group containing one or more elements selected from nitrogen, phosphorus, silicon, or oxygen; or elements such as nitrogen, phosphorus, and silicon, or groups containing them.

所表示之部分結構。In addition, R ⁵ is an optional substituent, k is an integer of 1 to 4, and when k is 2 or more, two R ⁵ may be connected to form a ring, and at least one of the ^{k R 5 includes the following formula (} 2): [化5]

Part of the structure shown.

In formula (2), R ^{11 is} each independently a C _1-8 alkyl group, R ^{12 is} each independently a C _1-8 alkylene group, b is independently 0 or 1, R ¹³ represents a hydrogen atom, a C _1-8 alkyl group Or any of the phenyl group, the alkyl group, the alkylene group, and the phenyl group may have a substituent within the limit of _{satisfying the condition of C 1-8.}

The partial structure represented by formula (2) may preferably have secondary and/or tertiary carbons, for example, isopropyl, isobutyl, second butyl, tertiary butyl, tertiary pentyl, 2, 2-Dimethylpropyl group, or a structure having a phenyl group at the end thereof, etc. The partial structure represented by the formula (2) is preferably directly bonded to the benzene ring bonded to ^{R 5 in the formula (1).} Furthermore, the partial structure represented by the formula (2) is preferably bonded to the 2-position and/or the 6-position (ortho position relative to -O-) of the benzene ring bonded to ^{R 5 in the formula (1).}

之部分較佳為以下任一結構：  [化7]

，  作為其等之具體例，可列舉自以下之化合物去除所有末端之酚性羥基之氫而成者：  4,6-二-第三丁基苯1,2,3-三醇、2,6-雙(3-第三丁基-2-羥基-5-甲基苄基)-4-甲基苯酚、1,1,3-三(2-甲基-4-羥基-5-第三丁基苯基)丁烷、2,4,6-三(3',5'-二-第三丁基-4'-羥基苄基)均三甲苯、季戊四醇四[3-(3,5-二第三丁基-4-羥基苯基)丙酸酯]、1,3,5-三[[3,5-雙(1,1-二甲基乙基)-4-羥基苯基]甲基]-1,3,5-三𠯤-2,4,6(1H,3H,5H)-三酮、1,3,5-三[[4-(1,1-二甲基乙基)-3-羥基-2,6-二甲基苯基]甲基]-1,3,5-三𠯤-2,4,6(1H,3H,5H)-三酮。The structure represented by formula (1) is as follows: [化6]

The part is preferably any of the following structures: [化7]

, As specific examples thereof, can be exemplified by removing the hydrogen of all terminal phenolic hydroxyl groups from the following compounds: 4,6-di-tert-butylbenzene 1,2,3-triol, 2,6 -Bis(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenol, 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butyl) Phenyl)butane, 2,4,6-tris (3',5'-di-tert-butyl-4'-hydroxybenzyl) mesitylene, pentaerythritol tetrakis[3-(3,5-di Tert-butyl-4-hydroxyphenyl)propionate], 1,3,5-tris[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl ]-1,3,5-Tris -2,4,6(1H,3H,5H)-triketone, 1,3,5-tris[[4-(1,1-dimethylethyl)- 3-Hydroxy-2,6-dimethylphenyl]methyl]-1,3,5-tris-2,4,6(1H,3H,5H)-trione.

所表示之結構之二價連結基(具有取代基之苯酚單元)，而且，式(1)中之n表示Y之重複數，分別獨立為0～200之整數。Y in the formula (1) is independently of the following formula (3): [化 8]

The divalent linking group (phenol unit having a substituent) of the structure shown, and n in the formula (1) represents the number of repetitions of Y, and each independently is an integer of 0 to 200.

In formula (3), R ^{21 is} independently a C _1-6 saturated or unsaturated hydrocarbon group, preferably methyl, ethyl, n-propyl, vinyl, allyl, ethynyl, propargyl, etc., Methyl and ethyl are more preferred, and methyl is still more preferred. R ^{22 is} independently a hydrogen atom or a C _1-6 saturated or unsaturated hydrocarbon group, preferably a hydrogen atom, a methyl group, an ethyl group, a n-propyl group, etc., more preferably a hydrogen atom, a methyl group, and still more preferably a hydrogen atom . Here, the saturated or unsaturated hydrocarbon may have a substituent as long as it _{satisfies the condition of C 1-6.}

。A in the formula (1) is a substituent containing a carbon-carbon double bond and/or an epoxy bond, and specific examples of A are represented by the following formulas (4) to (8): [化9]

.

In formulas (4) to (8), R ^{31 is} each independently hydrogen, hydroxyl, or C _1-30 hydrocarbon group, aryl group, alkoxy group, allyloxy group, amino group or hydroxyalkyl group. R ^{32 is} each independently a C _1-30 hydrocarbon group. R ^{33 is} independently hydrogen, hydroxyl, or C _1-30 hydrocarbon group, aryl, alkoxy, allyloxy, amino, hydroxyalkyl, vinyl or isopropenyl, at least one of ^{R 33} It is vinyl or isopropenyl. s and t are integers of 0-5.

Specific examples of the hydrocarbon group of R ³¹ include: methyl, ethyl, n-propyl, 2-propyl, n-butyl, isobutyl, tert-butyl, n-pentyl, 1-ethylpropyl , 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, pentyl, cyclopentyl, 2,2-dimethylpropyl, 1,1-dimethylpropyl, n-hexyl Group, cyclohexyl, 1-ethylbutyl, 2-ethylbutyl, 3-ethylbutyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4- Methylpentylene, 1,1-dimethylbutylene, 2,2-dimethylbutylene, 3,3-dimethylbutyl, 1,2-dimethylbutyl, 1, 3-dimethylbutyl, 2,3-dimethylbutyl, n-heptyl, 1-methylhexyl, 2-methylhexyl, 3-methylhexyl, 4-methylhexyl, 5-methyl Hexyl, 1-ethylpentyl, 2-ethylpentyl, 3-ethylpentyl, 1,1-dimethylpentyl, 2,2-dimethylpentyl, 3,3-dimethyl Pentyl, 4,4-dimethylpentyl, 1,2-dimethylpentyl, 1,3-dimethylpentyl, 1,4-dimethylpentyl, 2,3-dimethyl Pentyl, 2,4-dimethylpentyl, 3,4-dimethylpentyl, 2-methyl-3,3-dimethylbutyl, 1-methyl-3,3-dimethyl Butyl, 1,2,3-trimethylbutyl, 1,3-dimethyl-2-pentyl, 2-isopropylbutyl, 2-methylcyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 1-cyclohexylmethyl, 2-ethylcyclopentyl, 3-ethylcyclopentyl, 2,3-dimethylcyclopentyl, 2,4-dimethylcyclopentyl Base, 2-methylcyclopentylmethyl, 2-cyclopentylethyl, 1-cyclopentylethyl, n-octyl, 2-octyl, 3-octyl, 4-octyl, 2-methyl Heptyl, 3-methylheptyl, 4-methylheptyl, 5-methylheptyl, 6-methylheptyl, 2-ethylhexyl, 3-ethylhexyl, 4-ethylhexyl, 5-ethylhexyl, 1,1-dimethylhexyl, 2,2-dimethylhexyl, 3,3-dimethylhexyl, 4,4-dimethylhexyl, 5,5-dimethylhexyl , 1,2-dimethylhexyl, 1,3-dimethylhexyl, 1,4-dimethylhexyl, 1,5-dimethylhexyl, 2,3-dimethylhexyl, 2,4- Dimethylhexyl, 2,5-dimethylhexyl, 1,1-ethylmethylpentyl, 2,2-ethylmethylpentyl, 3,3-ethylmethylpentyl, 4,4 -Ethylmethylpentyl, 1-ethyl-2-methylpentyl, 1-ethyl-3-methylpentyl, 1-ethyl-4-methylpentyl, 2-ethyl-1 -Methylpentyl, 3-ethyl-1-methylpentyl, 4-ethyl-1-methylpentyl, 2-ethyl-3-methylpentyl, 2-ethyl-4-methyl Pentyl, 3-ethyl-2-methylpentyl, 4-ethyl-3-methylpentyl, 3-ethyl-4-methylpentyl, 4-ethyl-3-methylpentyl Group, 1-(2-methylpropyl)butyl, 1-(2-methylpropyl)-2-methylbutyl, 1,1-(2-methylpropyl)ethyl, 1, 1-(2-methylpropyl)ethylpropyl, 1, 1-Diethylpropyl, 2,2-Diethylpropyl, 1,1-ethylmethyl-2,2-dimethylpropyl, 2,2-ethylmethyl-1,1- Dimethylpropyl, 2-ethyl-1,1-dimethylbutyl, 2,3-dimethylcyclohexyl, 2,3-dimethylcyclohexyl, 2,5-dimethylcyclohexyl , 2,6-Dimethylcyclohexyl, 3,5-dimethylcyclohexyl, 2-methylcyclohexylmethyl, 3-methylcyclohexylmethyl, 4-methylcyclohexylmethyl, 2- Ethylcyclohexyl, 3-ethylcyclohexyl, 4-ethylcyclohexyl, 2-cyclohexylethyl, 1-cyclohexylethyl, 1-cyclohexyl-2-ethylene, nonyl, isononyl , Decyl, isodecyl, undecyl, dodecyl, benzyl, 2-phenylethyl, etc.

The hydrocarbon group of R ³¹ is preferably methyl, ethyl, n-propyl, 2-propyl, n-butyl, isobutyl, tertiary butyl, n-pentyl, 1-ethylpropyl, 1-methyl Butyl, 2-methylbutyl, 3-methylbutyl, pentyl, cyclopentyl, n-hexyl, cyclohexyl, 1-ethylbutyl, 2-ethylbutyl, 3-ethylbutyl , 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, n-heptyl, 1-methylhexyl, 2-methylhexyl, 3-methylhexyl , 4-methylhexyl, 5-methylhexyl, 1-ethylpentyl, 2-ethylpentyl, 3-ethylpentyl, 2-methylcyclohexyl, 3-methylcyclohexyl, 4- Methylcyclohexyl, n-octyl, 2-octyl, 3-octyl, 4-octyl, 2-methylheptyl, 3-methylheptyl, 4-methylheptyl, 5-methylheptyl Base, 6-methylheptyl, 2-ethylhexyl, 3-ethylhexyl, 4-ethylhexyl, 5-ethylhexyl, nonyl, isononyl, decyl, isodecyl, undecane Group, dodecyl, benzyl, etc., more preferably methyl, ethyl, n-propyl, 2-propyl, n-butyl, isobutyl, tert-butyl, n-pentyl, 1-ethyl Propyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, pentyl, cyclopentyl, n-hexyl, cyclohexyl, n-heptyl, n-octyl, 2-octyl, 3-octyl, 4-octyl, 2-methylheptyl, 3-methylheptyl, 4-methylheptyl, 5-methylheptyl, 6-methylheptyl, 2-ethylhexyl , 3-ethylhexyl, 4-ethylhexyl, 5-ethylhexyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, benzyl, etc., more preferably For methyl, ethyl, n-propyl, 2-propyl, n-butyl, isobutyl, tertiary butyl, n-pentyl, pentyl, cyclopentyl, n-hexyl, cyclohexyl, n-heptyl, N-octyl, 2-octyl, 3-octyl, 4-octyl, 2-methylheptyl, 3-methylheptyl, 4-methylheptyl, 5-methylheptyl, 6-methyl Heptyl, 2-ethylhexyl, 3-ethylhexyl, 4-ethylhexyl, 5-ethylhexyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl Benzyl, benzyl, etc.

Specific examples of the hydrocarbon group of R ³² include: methylene, ethylene, trimethylene, 1,2-propylene, tetramethylene, 2-methyl-1,3-trimethylene, 1,1-Dimethylethylene, pentamethylene, 1-ethyl-1,3-propylene, 1-methyl-1,4-butylene, 2-methyl-1,4 -Butyl, 3-methyl-1,4-butylene, 2,2-dimethyl-1,3-propylidene, 1,2-cyclopentylene, 1,3-cyclopentylene Group, 2,2-dimethyl-1,3-propylene, 1,1-dimethyl-1,3-propylene, 3,3-dimethyl-1,3-propylene, Hexamethylene, 1,2-cyclohexylene, 1,3-cyclohexylene, 1,4-cyclohexylene, 1-ethyl-1,4-butylene, 2-ethyl-1,4 -Butyl, 3-ethyl-1,4-butylene, 1-methyl-1,5-pentylene, 2-methyl-1,5-pentylene, 3-methyl-1 ,5-Pentylene, 4-methylpentylene, 1,1-dimethyl-1,4-butylene, 2,2-dimethyl-1,4-butylene, 3,3 -Dimethyl-1,4-butylene, 1,2-dimethyl-1,4-butylene, 1,3-dimethyl-1,4-butylene, 2,3-bis Methyl-1,4-butylene, heptamethylene, 1-methyl-1,6-hexylene, 2-methyl-1,6-hexylene, 3-methyl-1,6-hexylene Hexyl, 4-methyl-1,6-hexylene, 5-methyl-1,6-hexylene, 1-ethyl-1,5-pentylene, 2-ethyl-1,5-pentylene Group, 3-ethyl-1,5-pentylene, 1,1-dimethyl-1,5-pentylene, 2,2-dimethyl-1,5-pentylene, 3,3 -Dimethyl-1,5-pentylene, 4,4-dimethyl-1,5-pentylene, 1,2-dimethyl-1,5-pentylene, 1,3-bis Methyl-1,5-pentylene, 1,4-dimethyl-1,5-pentylene, 2,3-dimethyl-1,5-pentylene, 2,4-dimethyl -1,5-pentylene, 3,4-dimethyl-1,5-pentylene, 2-methyl-3,3-dimethyl-1,4-butylene, 1-methyl -3,3-Dimethyl-1,4-butylene, 1,2,3-trimethyl-1,4-butylene, etc.

In addition, ^{specific examples of the hydrocarbon group of R 32} include: 1,3-dimethyl-1,4-pentylene, 2-isopropyl-1,4-butylene, 2-methyl-1 ,4-cyclohexylene, 3-methyl-1,4-cyclohexylene, 4-methyl-1,4-cyclohexylene, 1-cyclohexylmethylene, 2-ethyl-1,3- Cyclopentyl, 3-ethyl-1,3-cyclopentyl, 2,3-dimethyl-1,3-cyclopentyl, 2,4-dimethyl-1,3-cyclopentyl Pentyl, 2-methyl-1,3-cyclopentylmethylene, 2-cyclopentylethylene, 1-cyclopentylethylene, octamethylene, 1-methyl-1,7-ethylene Heptyl, 1-ethyl-1,6-hexylene, 1-propyl-1,5-pentyl, 2-methyl-1,7-heptyl, 3-methyl-1,7-hexyl Heptyl, 4-methyl-1,7-heptyl, 5-methyl-1,7-heptyl, 6-methyl-1,7-heptyl, 2-ethyl-1,6 -Hexylene, 3-ethyl-1,6-hexylene, 4-ethyl-1,6-hexylene, 5-ethyl-1,6-hexylene, 1,1-dimethyl-1, 6-hexylene, 2,2-dimethyl-1,6-hexylene, 3,3-dimethyl-1,6-hexylene, 4,4-dimethyl-1,6-hexylene, 5,5-Dimethyl-1,6-hexylene, 1,2-dimethyl-1,6-hexylene, 1,3-dimethyl-1,6-hexylene, 1,4-bis Methyl-1,6-hexylene, 1,5-dimethyl-1,6-hexylene, 2,3-dimethyl-1,6-hexylene, 2,4-dimethyl-1, 6-hexylene, 2,5-dimethyl-1,6-hexylene, 1,1-ethylmethyl-1,5-pentylene, 2,2-ethylmethyl-1,5- Pentylene, 3,3-ethylmethyl-1,5-pentylene, 4,4-ethylmethyl-1,5-pentylene, 1-ethyl-2-methyl-1, 5-pentylene, 1-ethyl-3-methyl-1,5-pentylene, 1-ethyl-4-methyl-1,5-pentylene, 2-ethyl-1-methyl Pentylene-1,5-pentylene, 3-ethyl-1-methyl-1,5-pentylene, 4-ethyl-1-methyl-1,5-pentylene, 2-ethyl -3-methyl-1,5-pentylene, 2-ethyl-4-methyl-1,5-pentylene, 3-ethyl-2-methyl-1,5-pentylene, 4-ethyl-3-methyl-1,5-pentylene, 3-ethyl-4-methyl-1,5-pentylene, 4-ethyl-3-methyl-1,5- Pentyl and so on.

Furthermore, ^{specific examples of the hydrocarbon group of R 32} include: 1-(2-methylpropyl)-1,4-butylene, 1-(2-methylpropyl)-2-methyl-1 ,4-butylene, 1,1-(2-methylpropyl)ethylene, 1,1-(2-methylpropyl)ethyl-1,3-propylene, 1,1- Diethyl-1,3-Propylene, 2,2-Diethyl-1,3-Propyl, 1,1-Ethylmethyl-2,2-Dimethyl-1,3-Propyl Propyl, 2,2-ethylmethyl-1,1-dimethyl-1,3-butylene, 2-ethyl-1,1-dimethyl-1,4-butylene, 2 ,3-Dimethyl-1,4-cyclohexylene, 2,3-dimethyl-1,4-cyclohexylene, 2,5-dimethyl-1,4-cyclohexylene, 2,6 -Dimethyl-1,4-cyclohexyl, 3,5-dimethyl-1,4-cyclohexyl, 2-methyl-1,4-cyclohexyl-1-methylene, 3-methyl Base-1,4-cyclohexyl-1-methylene, 4-methyl-1,4-cyclohexyl-1-methylene, 2-ethyl-1,4-cyclohexyl, 3-ethyl -1,4-cyclohexyl, 4-ethyl-1,4-cyclohexyl, 2-cyclohexylethylene, 1-cyclohexylethylene, 1-cyclohexyl-2-ethylene, nonane Methylene, 1-methyl-1,8-octyl, decylmethylene, 1-methyl-1,8-nonyl, undecylmethylene, dodecylmethylene Methyl, 1,4-phenylene, 1,3-phenylene, 1,2-phenylene, methylene-1,4-phenylene-methylene, ethylene-1,4 -Phenylene-ethylene and the like.

The hydrocarbyl group of R ³² is preferably methylene, ethylene, trimethylene, 1,2-propylene, tetramethylene, 2-methyl-1,2-propylene, 1,1-di Methyl ethylene, pentamethylene, 1-ethyl-1,3-butylene, 1-methyl-1,4-butylene, 2-methyl-1,4-butylene, 3-methyl-1,4-butylene, 2,2-dimethyl-1,3-propylidene, 1,3-cyclopentyl, 1,6-hexamethylene, 1,4 -Cyclohexyl, 1-ethyl-1,4-butylene, 2-ethyl-1,4-butylene, 3-ethyl-1,4-butylene, 1-methyl-1 ,5-Pentylene, 2-methyl-1,5-pentylene, 3-methyl-1,5-pentylene, 4-methyl-1,5-pentylene, heptamethylene , 1-methyl-1,6-hexylene, 2-methyl-1,6-hexylene, 3-methyl-1,6-hexylene, 4-methyl-1,6-hexylene, 5 -Methyl-1,6-hexylene, 1-ethyl-1,5-pentylene, 2-ethyl-1,5-pentylene, 3-ethyl-1,5-pentylene, 2-methyl-1,4-cyclohexylene, 3-methyl-1,4-cyclohexylene, 4-methyl-1,4-cyclohexylene, octamethylene, 1-methyl-1 ,7-heptyl, 3-methyl-1,7-heptyl, 4-methyl-1,7-heptyl, 2-methyl-1,7-heptyl, 5-methyl -1,7-heptyl, 6-methyl-1,7-heptyl, 2-ethyl-1,6-hexyl, 3-ethyl-1,6-hexyl, 4-ethyl -1,6-hexylene, 5-ethyl-1,6-hexylene, nonylmethylene, decylmethylene, undecylmethylene, dodecylmethylene, etc., more Preferably, methylene, ethylene, trimethylene, 1,2-propylene, tetramethylene, 2-methyl-1,2-propylene, 1,1-dimethylethylene , Pentamethylene, 1-ethyl-1,3-butylene, 1-methyl-1,4-butylene, 2-methyl-1,4-butylene, 3-methyl- 1,4-butylene, 2,2-dimethyl-1,3-propylidene, 1,3-cyclopentylene, 1,6-hexamethylene, 1,4-cyclohexylene, Heptamethylene, octamethylene, 1-methyl-1,7-heptyl, 3-methyl-1,7-heptyl, 4-methyl-1,7-heptyl, 2 -Methyl-1,7-heptyl, 5-methyl-1,7-heptyl, 6-methyl-1,7-heptyl, 2-ethyl-1,6-hexyl, 3-ethyl-1,6-hexylene, 4-ethyl-1,6-hexylene, 5-ethyl-1,6-hexylene, nonylmethylene, decylmethylene, undecyl Alkylmethylene, dodecylmethylene, etc., more preferably methylene, ethylene, trimethylene, 1,2-propylene, tetramethylene, 2-methyl-1 ,2-Propylene, 1,1-Dimethylethylene, Pentamethylene, 2,2-Dimethyl-1,3-Propylene, 1,3-Cyclopentyl, 1, 6-hexamethylene, 1,4-cyclohexylene, heptamethylene, octamethylene , 1-methyl-1,7-heptyl, 3-methyl-1,7-heptyl, 4-methyl-1,7-heptyl, 2-methyl-1,7-heptyl Heptyl, 5-methyl-1,7-heptyl, 6-methyl-1,7-heptyl, 2-ethyl-1,6-hexyl, 3-ethyl-1,6- Hexylene, 4-ethyl-1,6-hexylene, 5-ethyl-1,6-hexylene, nonylmethylene, decylmethylene, undecylmethylene, dodecane Methylene and so on.

Regarding A in formula (1), specific examples of substituents containing carbon-carbon double bonds include vinyl, allyl, isopropenyl, 1-butenyl, 1-pentenyl, and p- Vinyl phenyl, p-isopropenyl phenyl, m-vinyl phenyl, m-isopropenyl phenyl, o-vinyl phenyl, o-isopropenyl phenyl, p-vinyl benzyl, p-isopropenyl benzyl , M-vinylbenzyl, m-isopropenylbenzyl, o-vinylbenzyl, o-isopropenylbenzyl, p-vinylphenylvinyl, p-vinylphenylpropenyl, p-vinylphenylbutene Group, m-vinylphenylvinyl, m-vinylphenylpropenyl, m-vinylphenylbutenyl, o-vinylphenylvinyl, o-vinylphenylpropenyl, o-vinylphenylbutene Group, methacryloyl group, acryloyl group, 2-ethylacryloyl group, 2-hydroxymethacryloyl group and the like.

表示。又，於L為任意二價連結基之情形時，該L之具體例例如具有下述式：  [化11]

{式中，a、R⁵ 、k、X、Y及n如式(1)之說明中所定義}  所表示之結構。L in formula (1) is any divalent linking group or single bond (direct bonding). When L is a single bond, the structure represented by formula (1) is as follows: [化10]

Said. In addition, when L is an arbitrary divalent linking group, a specific example of the L has the following formula, for example: [化11]

{Where, a, R ⁵ , k, X, Y, and n are as defined in the description of formula (1)} represents the structure.

[化13]

{式中，n表示Y之重複數，為0～200之整數}  所表示之分支結構等。The structure represented by the formula (1) can adopt various branch structures depending on the value of the valence a of X. For example, in the case of a=3 in formula (1), the following formula can be cited: [化12]

[化13]

{Where, n represents the number of repetitions of Y, which is an integer from 0 to 200} the branch structure and so on.

[化15]

As the structure represented by formula (1), specifically, the structure shown below can be mentioned. [化14]

[化15]

In the above formula, Z is an arbitrary linking group corresponding to X in formula (1). R ¹ is a substituent represented by formula (2), and b is an integer of 1-4. Furthermore, ^{the position of R 1} is not limited, and R ¹ can be any position. In addition, when b is 2 or more, ^{each of a plurality of R 1} may have the same structure or different structures. Examples of R ¹ include isopropyl, isobutyl, second butyl, tertiary butyl, tertiary pentyl, 2,2-dimethylpropyl, or having a phenyl group at the terminal. The structure and so on. A is a substituent containing a carbon-carbon double bond and/or an epoxy bond. R ² is hydrogen or a hydrocarbon group having a chain or cyclic structure having 1 to 8 carbon atoms. When there are a plurality of R ² , each substituent may be the same or different. Specific examples of R ² include, for example, methyl, ethyl, n-propyl, n-butyl, n-pentyl, cyclopentyl, n-hexyl, cyclohexyl, n-heptyl, n-octyl, phenyl, Benzyl, 2-ethylhexyl, etc. are preferably hydrogen, methyl, ethyl, n-propyl, n-butyl, n-pentyl, cyclopentyl, and n-hexyl from the viewpoint of reactivity during synthesis. , Cyclohexyl, n-heptyl and n-octyl. However, when the reactivity during synthesis can be controlled by appropriately setting ^{the position of R 2 or the reaction conditions during synthesis, the structure of R 2} is not limited and can be within the range that _{satisfies the conditions of C 1-8.} For any structure. Z is a hydrocarbyl group; a hydrocarbyl group containing one or more elements selected from nitrogen, phosphorus, silicon, and oxygen; or elements such as nitrogen, phosphorus, silicon, or a group containing them.

於上述式中，R⁴ ～R¹⁰ 可相同亦可不同，表示氫或C_1-8 之烴基。又，R³¹ ～R³³ 可相同亦可不同，表示氫或C_1-6 之烴基。j、k、l及m可相同亦可不同，為0～4之整數。作為R⁴ ～R¹⁰ 之具體例，可列舉：氫、甲基、乙基、正丙基、異丙基正丁基、異丁基、第三丁基、正戊基、2-戊基、3-戊基、環戊基、正己基、2-己基、3-己基、環己基、正庚基、2-庚基、3-庚基、正辛基、2-乙基己基等。作為R³¹ ～R³³ 之具體例，可列舉：氫、甲基、乙基、正丙基、異丙基正丁基、異丁基、正戊基、2-戊基、3-戊基、環戊基、正己基、2-己基、3-己基、環己基。Regarding specific examples of the hydrocarbon group as Z, for example, the structure represented by the following formula or the like. [化16]

In the above formula, R ⁴ to R ¹⁰ may be the same or different, and represent hydrogen or a C _1-8 hydrocarbon group. In addition, R ³¹ to R ³³ may be the same or different, and represent hydrogen or a C _1-6 hydrocarbon group. j, k, l, and m may be the same or different, and are an integer of 0-4. Specific examples of R ⁴ to R ¹⁰ include hydrogen, methyl, ethyl, n-propyl, isopropyl n-butyl, isobutyl, tertiary butyl, n-pentyl, 2-pentyl, 3-pentyl, cyclopentyl, n-hexyl, 2-hexyl, 3-hexyl, cyclohexyl, n-heptyl, 2-heptyl, 3-heptyl, n-octyl, 2-ethylhexyl, etc. Specific examples of R ³¹ to R ³³ include hydrogen, methyl, ethyl, n-propyl, isopropyl n-butyl, isobutyl, n-pentyl, 2-pentyl, 3-pentyl, Cyclopentyl, n-hexyl, 2-hexyl, 3-hexyl, cyclohexyl.

於上述式中，R⁴ ～R¹⁰ 可相同亦可不同，表示氫或C_1-8 之烴基。j、k、l及m可相同亦可不同，為0～4之整數。作為R⁴ ～R¹⁰ 之具體例，可列舉：氫、甲基、乙基、正丙基、異丙基正丁基、異丁基、第三丁基、正戊基、2-戊基、3-戊基、環戊基、正己基、2-己基、3-己基、環己基、正庚基、2-庚基、3-庚基、正辛基、2-乙基己基等。In addition, a specific example of a hydrocarbon group containing one or more elements selected from the group consisting of nitrogen, phosphorus, silicon, and oxygen as Z is represented by the following formula. [化17]

In the above formula, R ⁴ to R ¹⁰ may be the same or different, and represent hydrogen or a C _1-8 hydrocarbon group. j, k, l, and m may be the same or different, and are an integer of 0-4. Specific examples of R ⁴ to R ¹⁰ include hydrogen, methyl, ethyl, n-propyl, isopropyl n-butyl, isobutyl, tertiary butyl, n-pentyl, 2-pentyl, 3-pentyl, cyclopentyl, n-hexyl, 2-hexyl, 3-hexyl, cyclohexyl, n-heptyl, 2-heptyl, 3-heptyl, n-octyl, 2-ethylhexyl, etc.

In addition, specific examples of groups including nitrogen, phosphorus, oxygen, etc. as Z are as follows. [化18]

[化20]

In the above-mentioned specific example, regarding the first one, if the structure of A is embodied, it becomes the structure of the following formula. In addition, the same is true in the case of 4 to 6 branches. In addition, R ³¹ , R ³² , s, and t in the following formula are as defined in the specific example of A. [化19]

[化20]

The number average molecular weight (Mn) of the polyphenylene ether component A is 500-8,000 in terms of the polystyrene conversion molecular weight using GPC (gel permeation chromatograph), in terms of fluidity, compatibility with other components, etc. From a viewpoint, it is preferably 700 to 6,000, and more preferably 900 to 4,500. In addition, from the same viewpoint, the molecular weight distribution of the polyphenylene ether component A is Mw (weight average molecular weight)/Mn, preferably in the range of 1.1-5, 1.4-4, or 1.5-3.

The modified polyphenylene ether having the structure of formula (1) in this embodiment can be produced, for example, by the following method: preparing polyphenylene ether by a redistribution reaction method using a higher molecular weight phenylene ether polymer, and The group A is introduced to the end. When the redistribution reaction is used to produce polyphenylene ether, it can be produced according to the conditions specified by the known reaction conditions. In this case, the molecular weight of the obtained polymer becomes lower than the phenylene ether polymer used as the raw material, so the ratio of the raw polyphenylene ether to the polyfunctional phenol compound can be adjusted according to the target molecular weight.

In addition, the method of introducing the substituent A in the formula (1), such as the functional groups represented by the formulas (4) to (7), to the end of the obtained polyphenylene ether polymer is not limited, and it depends on the type of the functional group. Various known methods are used. For example, when a functional group having a structure of formula (4), (6) or (7) is introduced, it can usually be based on the formation of ether bonds using the Williamson synthesis method. The introduction of the functional group with the structure of formula (5) is the formation reaction of the ester bond between the hydroxyl group at the end of the polyphenylene ether polymer and the carboxylic acid having a carbon-carbon double bond (hereinafter referred to as carboxylic acid), and a known ester can be used Key formation method.

Polyphenylene ether component A (PPE-A) has high curing reactivity, low dielectric properties, good fluidity, formability, and excellent heat resistance, so it can be suitably used as materials for various electrical and electronic equipment. In particular, it can be suitably used for the production of prepregs for electrical and electronic parts (printed wiring board substrates, etc.). PPE-A can be used as a single resin in the resin composition, can also be used in combination with polyphenylene ether with other structures, and can also be used in combination with various known additives. The content of PPE-A in the resin composition can be set to 0.5% by mass to 95% by mass, for example.

Polyphenylene ether component B (PPE-B) In addition to the polyphenylene ether component A with a number average molecular weight of 500 to 8,000 described above, the resin composition of this embodiment may also contain an average number of phenolic hydroxyl groups per molecule of 1.2 Polyphenylene ether component B with a number average molecular weight of 8,000 or more and less than 50,000. Since the polyphenylene ether component B is stable during its production process and has excellent dielectric properties and heat resistance, it tends to improve the electrical properties of the cured resin composition without inhibiting the polyphenylene ether component A.

As long as the polyphenylene ether component B (PPE-B) can be distinguished from the polyphenylene ether component A (PPE-A), and the average number of phenolic hydroxyl groups per molecule is 1.2 or more and the number average molecular weight is 8,000 to 50,000, it can be It is any polyphenylene ether (PPE). From the viewpoint of combined use with PPE-A, the number average molecular weight of PPE-B is preferably more than 8,000 and less than 50,000. When PPE-A and PPE-B are used together in a resin composition, from the viewpoint of the stability and heat resistance of the resin composition, the total mass of PPE-A and PPE-B is 100% by mass. Preferably, the content of PPE-A is 1% to 99.9% by mass and the content of PPE-B is 0.1% to 99% by mass, more preferably the content of PPE-A is 20% to 98% by mass and PPE- The content of B is 2% by mass to 80% by mass, and it is more preferable that the content of PPE-A is 40% to 95% by mass and the content of PPE-B is 5% to 60% by mass.

Cross-linking agent In this embodiment, any cross-linking agent that has the ability to cause or promote a cross-linking reaction can be used. The crosslinking agent preferably has a number average molecular weight of 4,000 or less. If the number average molecular weight of the crosslinking agent is 4,000 or less, the increase in the viscosity of the resin composition can be suppressed, and good resin fluidity during thermoforming can be obtained. The number average molecular weight should just be what is measured by the usual molecular weight measurement method, and specifically, the value measured using GPC etc. can be mentioned.

From the viewpoint of the crosslinking reaction, the crosslinking agent preferably has an average of 2 or more carbon-carbon unsaturated double bonds per molecule. The crosslinking agent may be composed of one type of compound, or may be composed of two or more types of compounds. The term "carbon-carbon unsaturated double bond" in this specification refers to a double bond located at the end of the main chain branch when the crosslinking agent is a polymer or oligomer. Examples of carbon-carbon unsaturated double bonds include 1,2-vinyl bonds in polybutadiene.

When the number average molecular weight of the crosslinking agent is less than 600, the number (average value) of carbon-carbon unsaturated double bonds per molecule of the crosslinking agent is preferably 2-4. When the number average molecular weight of the crosslinking agent is 600 to 1500, the number (average value) of carbon-carbon unsaturated double bonds per molecule of the crosslinking agent is preferably 4 to 26. When the number average molecular weight of the crosslinking agent is 1,500 to 4,000, the number (average value) of carbon-carbon unsaturated double bonds per molecule of the crosslinking agent is preferably 26-60. When the number average molecular weight of the crosslinking agent is within the above range, the reactivity of the crosslinking agent of the resin composition of this embodiment is further improved by making the number of carbon-carbon unsaturated double bonds more than a specific value. The crosslinking density of the cured product of the resin composition is further increased, and as a result, further excellent heat resistance can be imparted. On the other hand, when the number average molecular weight of the crosslinking agent is within the above range, by making the number of carbon-carbon unsaturated double bonds below a specific value, it is possible to impart further excellent resin fluidity during thermoforming.

As the crosslinking agent, for example, triallyl isocyanurate (TAIC) and other isocyanurate trienyl ester compounds, triallyl cyanurate (TAC) and other cyanurate trienyl ester compounds, which have Multifunctional methacrylate compounds with two or more methacrylic groups, multifunctional acrylate compounds with two or more acrylic groups in the molecule, polybutadiene, etc., multifunctional ethylene with two or more vinyl groups in the molecule Compounds, vinylbenzyl compounds such as divinylbenzene with a vinylbenzyl group in the molecule, 4,4'-bismaleimide diphenylmethane, etc. have more than 2 maleimide groups in the molecule Functional maleimide compounds, etc. These crosslinking agents can be used individually by 1 type or in combination of 2 or more types. The crosslinking agent preferably contains at least one compound selected from the group consisting of triallyl cyanurate, triallyl isocyanurate, and polybutadiene. When the crosslinking agent contains at least one or more of the compounds described above, the resin composition has better compatibility with PPE and coatability, and when it is adhered to an electronic circuit board, the substrate properties tend to be more excellent.

In terms of the compatibility of the crosslinking agent with PPE, the coating properties of the resin composition, and the characteristics of the electronic circuit board, the weight ratio of the PPE: crosslinking agent is preferably 25:75 to 95:5, more preferably It is 32:68～85:15. In addition, from the same viewpoint, the weight ratio of PPE-A: crosslinking agent is preferably 25:75 to 95:5, and more preferably 32:68 to 85:15.

Organic peroxide In this embodiment, any organic peroxide that has the ability to promote the polymerization reaction of a resin composition containing polyphenylene ether and a crosslinking agent can be used. Examples of organic peroxides include benzyl peroxide, cumene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, and 2,5-dimethyl- 2,5-Di(tertiary butylperoxy)hexyne-3, di-tertiary butyl peroxide, tertiary butyl cumyl peroxide, bis(2- tertiary butyl peroxide) Propyl)benzene, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, dicumyl peroxide, di-tert-butylperoxyisophthalate , Tert-butyl peroxybenzoate, 2,2-bis(tert-butylperoxy)butane, 2,2-bis(tert-butylperoxy)octane, 2,5-dimethyl Peroxides such as oxy-2,5-bis(benzylperoxy)hexane, bis(trimethylsilyl) peroxide, and trimethylsilyl triphenylsilyl peroxide. Furthermore, a radical generator such as 2,3-dimethyl-2,3-diphenylbutane can also be used as a reaction initiator for the resin composition. Among them, in terms of providing a cured product having excellent heat resistance and mechanical properties, and a lower dielectric constant and dielectric loss tangent, 2,5-dimethyl-2,5- Di(tertiary butylperoxy)hexyne-3, bis(2-peroxy tertiary butyl isopropyl)benzene, and 2,5-dimethyl-2,5-bis(tertiary butyl) Peroxy)hexane.

The 1-minute half-life temperature of the organic peroxide is preferably from 155°C to 185°C, more preferably from 160°C to 180°C or from 165°C to 175°C. In this specification, the one-minute half-life temperature is the temperature at which the organic peroxide decomposes and the amount of active oxygen becomes half the time for one minute. The one-minute half-life temperature is the value confirmed by the following method: the organic peroxide is dissolved in a solvent inert to free radicals, such as benzene, at a concentration of 0.05 mol/L to 0.1 mol/L, by The organic peroxide solution is thermally decomposed by nitrogen atmosphere.

By making the 1-minute half-life temperature of the organic peroxide in the range of 155°C to 185°C, the compatibility of the organic peroxide and PPE, the coating property of the resin composition, and the characteristics of the electronic circuit board are further improved The tendency.

Examples of organic peroxides whose one-minute half-life temperature is within the range of 155°C to 185°C include: peroxymonocarbonate O,O-third hexyl-O-isopropyl ester (155.0°C), peroxide- 3,5,5-Trimethylhexanoic acid tert-butyl ester (166.0℃), peroxylauric acid tert-butyl ester (159.4℃), peroxymonocarbonate O,O-tert-butyl-O-isopropyl Base ester (158.8℃), O,O-tert-butyl-O-2-ethylhexyl peroxycarbonate (161.4℃), tertiary hexyl peroxybenzoate (160.3℃), 2,5- Dimethyl-2,5-bis(benzylperoxy)hexane (158.2℃), tertiary butyl peroxyacetate (159.9℃), 2,2-bis(tertiary butylperoxy) ) Butane (159.9°C), tert-butyl peroxybenzoate (166.8°C), 4,4-bis(tert-butylperoxy) n-butyl valerate (172.5°C), bis(2- Tertiary butyl isopropyl peroxide) benzene (175.4°C), dicumyl peroxide (175.2°C), di-tertiary hexyl peroxide (176.7°C), 2,5-dimethyl-2 , 5-Di(tert-butylperoxy)hexane (179.8°C), and tert-butylcumyl peroxide (173.3°C), etc.

The content of the organic peroxide is based on 100 parts by mass of the total of PPE and the crosslinking agent. From the viewpoint that the compatibility of the organic peroxide and PPE and the coating properties of the resin composition are further superior, it is preferably 0.05 mass Parts or more, more preferably 0.5 parts by mass or more or 1 part by mass or more, and still more preferably 1.5 parts by mass or more. From the viewpoint of excellent substrate properties when the resin composition is adhered to an electronic circuit board, 5 parts by mass is preferred Parts or less, more preferably 4.5 parts by mass or less. Also, from the same viewpoint, the content of the organic peroxide is based on 100 parts by mass of the total of PPE-A and the crosslinking agent, preferably 0.05 parts by mass or more and 5 parts by mass or less, more preferably 0.5 parts by mass More than and 4.5 parts by mass or less, more preferably 1 part by mass or more and 4.5 parts by mass or less, or 1.5 parts by mass or more and 4.5 parts by mass or less.

Thermoplastic resin The thermoplastic resin of this embodiment is selected from block copolymers of vinyl aromatic compounds and olefin-based olefin compounds and their hydrogenated products (the resulting block copolymers of vinyl aromatic compounds and olefin-based olefin compounds are hydrogenated). At least one of the group consisting of hydrogenated block copolymers) and homopolymers of vinyl aromatic compounds, and has a weight average molecular weight of 150,000 to 800,000. If the resin composition contains PPE, crosslinking agent, organic peroxide, and thermoplastic resin of the type and weight average molecular weight described above, it will have compatibility between PPE and other components and coatability to substrates. It tends to become better, and the substrate characteristics are also excellent when assembled on an electronic circuit board. The weight average molecular weight can be obtained by the method described in the following examples.

The lower limit of the content of the vinyl aromatic compound-derived unit of the block copolymer or its hydrogenated product is preferably 20% by mass or more, more preferably 22% by mass or more, 24% by mass or more, and 26% by mass Above, 28% by mass or more, 30% by mass or more, or 32% by mass or more, and the upper limit is preferably 70% by mass or less, more preferably 69% by mass or less, 68% by mass or less, or 67% by mass or less. By increasing the content of the vinyl aromatic compound-derived unit of the block copolymer or its hydrogenated product from 20% by mass to 70% by mass, the compatibility with polyphenylene ether is further improved, and/or with metal The adhesion strength of the foil tends to increase further.

The vinyl aromatic compound should just have an aromatic ring and a vinyl group in the molecule, and for example, styrene can be mentioned. The olefin-based olefin compound may be an olefin having a linear or branched structure in the molecule, and examples thereof include ethylene, propylene, butene, isobutylene, butadiene, and isoprene. Among them, from the viewpoint that the compatibility between the thermoplastic resin and the polyphenylene ether is more excellent, it is preferably selected from the group consisting of styrene-butadiene block copolymers and styrene-ethylene-butadiene block copolymers. , Styrene-ethylene-butene block copolymer, styrene-butadiene-butene block copolymer, styrene-isoprene block copolymer, styrene-ethylene-propylene block copolymer, Styrene-isobutylene block copolymer, hydrogenated styrene-butadiene block copolymer, hydrogenated styrene-ethylene-butadiene block copolymer, styrene-butadiene-butene block At least one from the group consisting of hydrogenated copolymers, hydrogenated styrene-isoprene block copolymers, and homopolymers of styrene (polystyrene), more preferably selected from styrene -One or more of the group consisting of a butadiene block copolymer, a hydrogenated product of a styrene-butadiene block copolymer, and polystyrene.

The hydrogenation rate in the above-mentioned hydride is not particularly limited, and a part of the carbon-carbon unsaturated double bond derived from the olefin-based olefin compound may remain.

In terms of compatibility with PPE, resin fluidity, coating properties of the resin composition, and heat resistance during curing, the weight average molecular weight of the thermoplastic resin is preferably more than 150,000 and 780,000 or less, more preferably It is 155,000 to 750,000, more preferably 160,000 to 700,000.

The content of the thermoplastic resin having the types and weight average molecular weight described above is based on the total of 100 parts by mass of the PPE and the crosslinking agent, and is 2 parts by mass to 20 parts by mass, preferably 3 parts by mass to 19 parts by mass, and more It is preferably 4 parts by mass to 18 parts by mass or 5 parts by mass to 17 parts by mass. By setting the content within the above-mentioned numerical range, the resin composition of the present embodiment has better compatibility with PPE and coatability, and when it is adhered to an electronic circuit board, the substrate properties tend to be more excellent. In addition, from the same viewpoint, the content of the thermoplastic resin is 2 parts by mass to 20 parts by mass, preferably 3 parts by mass to 19 parts by mass based on 100 parts by mass of the total of PPE-A and the crosslinking agent. More preferably, it is 4 parts by mass to 18 parts by mass or 5 parts by mass to 17 parts by mass.

Furthermore, the resin composition of this embodiment may contain thermoplastic resins other than the thermoplastic resin which has the kind and weight average molecular weight demonstrated above.

Flame Retardant The resin composition of this embodiment preferably contains a flame retardant. As a flame retardant, from the viewpoint of improving heat resistance, it is not particularly limited as long as it is not compatible with other components contained in the resin composition after the resin composition is cured. It is preferable that the flame retardant does not dissolve with the PPE and/or the crosslinking agent in the resin composition after the resin composition is cured. Examples of flame retardants include inorganic flame retardants such as antimony trioxide, aluminum hydroxide, magnesium hydroxide, and zinc borate; hexabromobenzene, decabromodiphenylethane, 4,4-dibromobiphenyl, Aromatic bromine compounds such as ethyl bis(tetrabromophthalimide); phosphorus-based flame retardants such as resorcinol phosphate bis-diphenyl ester, resorcinol phosphate bis-bis(xylene) ester, etc. Wait. These flame retardants can be used individually by 1 type or in combination of 2 or more types. Among them, the flame retardant is preferably decabromodiphenyl ethane in terms of the compatibility of the flame retardant with PPE, the coating property of the resin composition, and the characteristics of the electronic circuit board.

The content of the flame retardant is not particularly limited. From the viewpoint of maintaining the flame retardancy of the UL standard 94V-0 level, it is preferably 5 with respect to the total of 100 parts by mass of the polyphenylene ether (PPE) resin and the crosslinking agent. Parts by mass or more, more preferably 10 parts by mass or more, and still more preferably 15 parts by mass or more. In addition, from the viewpoint of maintaining low dielectric constant and dielectric loss tangent of the obtained cured product, the content of the flame retardant is preferably 50 parts by mass or less, more preferably 45 parts by mass or less, and still more preferably It is 40 parts by mass or less.

Silica filler The resin composition of this embodiment may also contain silica filler. Examples of silica fillers include natural silica, fused silica, synthetic silica, amorphous silica, Aerosil, and hollow silica. The content of the silica filler can be 10 parts by mass to 100 parts by mass relative to 100 parts by mass of the total of the polyphenylene ether (PPE) resin and the crosslinking agent. In addition, the silica filler may have its surface treated with a silane coupling agent or the like.

In addition to flame retardants and silica fillers, the resin composition of the present embodiment may further include heat stabilizers, antioxidants, UV (ultraviolet) absorbers, surfactants, lubricants and other additives, solvents, and the like. When the resin composition of this embodiment contains a solvent, it may be in the form of a varnish in which the solid components in the resin composition are dissolved or dispersed in the solvent. In addition, a resin film can be formed from the resin composition of this embodiment.

Solvent As the solvent, from the viewpoint of solubility, aromatic compounds such as toluene and xylene, methyl ethyl ketone (MEK), cyclopentanone, cyclohexanone, and chloroform are preferred. These solvents can be used individually by 1 type or in combination of 2 or more types.

Prepreg The prepreg of this embodiment includes a substrate and the resin composition of this embodiment impregnated or coated on the substrate. The prepreg can be obtained, for example, by impregnating the above-mentioned varnish in a substrate such as glass cloth, and then drying and removing the solvent component with a hot air dryer or the like.

Examples of substrates include: various glass cloths such as roving cloth, cloth, chopped strand mat, and surface mat; asbestos cloth, metal fiber cloth, and other synthetic or natural inorganic fiber cloth; Woven or non-woven fabric obtained from liquid crystal fibers such as aromatic polyester fiber and polybenzoxazole fiber; natural fiber cloth such as cotton, linen, and felt; carbon fiber cloth, kraft paper, cotton paper, cloth obtained from paper-glass blended yarn Such as natural cellulose-based substrates; porous polytetrafluoroethylene membranes, etc. These base materials can be used individually by 1 type or in combination of 2 or more types.

The ratio of the solid content of the resin composition of the present embodiment in the prepreg is preferably 30 to 80% by mass, more preferably 40 to 70% by mass. By setting the above ratio to 30% by mass or more, the insulation reliability tends to be more excellent when the prepreg is used for electronic substrates or the like. By setting the above ratio to 80% by mass or less, mechanical properties such as flexural modulus tend to be more excellent in applications such as electronic substrates.

Metal foil laminated sheet The metal foil laminated sheet of this embodiment is obtained by laminating the resin composition or resin film of this embodiment or the prepreg of this embodiment and metal foil and curing them. The metal foil laminated board preferably has a form in which a cured product of a prepreg (also referred to as a "cured product composite") and a metal foil are laminated and closely adhered, and can be suitably used as a material for electronic substrates. Examples of the metal foil include aluminum foil and copper foil. Among them, copper foil is preferred because of its low resistance. The hardened product composite body combined with the metal foil can be one sheet or multiple sheets, depending on the application, which can be processed into a laminated board by superimposing the metal foil on one or both sides of the composite body. As a manufacturing method of a laminated board, for example, the following method: forming a composite (for example, the above-mentioned prepreg) containing a thermosetting resin composition and a base material, stacking it with a metal foil, and making the thermosetting resin composition Hardening, thereby obtaining a laminated board in which a hardened product laminated body and a metal foil are laminated. One of the most preferred applications of the above-mentioned laminated board is a printed wiring board. In the printed wiring board, at least a part of the metal foil is preferably removed from the metal foil laminate.

Printed wiring board In the printed wiring board of this embodiment, a part of the metal foil is removed from the metal foil laminate. The printed wiring board of this embodiment can typically be formed by a method of pressurizing and heating molding using the prepreg of the present invention described above. As a base material, the same thing as mentioned above can be mentioned about a prepreg. The printed wiring board of the present embodiment has excellent heat resistance and electrical properties (low dielectric constant and low dielectric loss tangent) by including the resin composition of the present embodiment, and can suppress changes in electrical properties due to environmental changes , And has excellent insulation reliability and mechanical properties. [Example]

Hereinafter, examples are given to describe the present embodiment in detail, but the present embodiment is not limited to the examples.

The synthesis reaction of polyphenylene ether is carried out under an inert gas atmosphere. The solvent used in the reaction is a commercially available reagent. The raw materials and reagents used are as follows.

1. Solvent: Toluene: Use Wako Pure Chemical's special grade reagent directly. Methyl ethyl ketone: Use Wako Pure Chemical's special grade reagent directly. Methanol: Use the special grade reagents produced by Wako Pure Chemicals directly. 2. Initiator: Nyper BMT: Directly use Japanese oil products. 3. Raw material polyphenylene ether S202A (polystyrene conversion number average molecular weight 16,000): directly use Asahi Kasei Co., Ltd. products. S202A has the following structure. [化21]

4. Raw material phenol (multifunctional/difunctional phenol) 4-1. Phenols containing the valence a (a=3～6) of the partial structure of formula (2) 1,1,3-tris(2-methyl- 4-Hydroxy-5-tert-butylphenyl)butane: ADEKA Co., Ltd. product (Adekastab AO-30) was used directly.

4-2. Phenols of valence 3 that do not contain the partial structure of formula (2) Tris (4-hydroxyphenyl) ethane: Asahi Organics products are used directly.

5. Modified base material methacrylic anhydride: use Aldrich reagents directly. Dimethylaminopyridine: Use Aldrich reagents directly.

Identification and analysis of polyphenylene ether 1. Determination of number average molecular weight The number average molecular weight was determined by GPC in chloroform solvent. The number average molecular weight is based on the calibration curve using standard polystyrene, and is calculated by the polystyrene conversion algorithm. 2. NMR measurement Dissolve the sample in deuterated chloroform so as to have a concentration of 5 mass%, and perform NMR measurement. The progress of the reaction is confirmed by the reduction of the hydroxyl peak based on the ratio of the aromatic peak of the polyfunctional phenol unit to the proton peak of the hydroxyl group. 3. Melt viscosity Add 200 ml of a 20% by mass methyl ethyl ketone solution of the sample to a beaker, and measure the viscosity with a B-type rotary viscometer at 25°C at a rotation speed of 30 rpm.

4. Average number of terminal functional groups Use the following method to find the average number of terminal functional groups per molecule of PPE. That is, according to the method described in "Polymer Essays, vol.51, No.7 (1994), page 480", the UV-Vis spectrophotometer is used to measure by adding tetramethylhydroxide to the dichloromethane solution of PPE. The absorbance change of the sample obtained from the base ammonium solution at a wavelength of 318 nm. Based on the measured value, the number of phenolic hydroxyl groups before and after the end modification of the PPE is determined. In addition, the number average molecular weight of PPE and the mass of PPE obtained by the method 1 above are used to determine the number of PPE molecules (number average number of molecules). According to these values and the following formula (1), find the average number of phenolic hydroxyl groups per molecule of PPE before and after modification: Average number of phenolic hydroxyl groups per molecule = Number of phenolic hydroxyl groups/number of average molecules Number (1) The average number of terminal functional groups after modification is based on the following formula (2) to obtain the average number of terminal functional groups after modification: average number of terminal functional groups per molecule = average phenolic hydroxyl groups before modification Number-average number of phenolic hydroxyl groups after modification (2)

{式中，l、m及n為以滿足下述數量平均分子量之方式所任意選擇之數}所表示之結構之聚苯醚(以下，稱為PPE1)。GPC測定之結果為，所獲得之PPE1之以聚苯乙烯換算計之分子量為Mn＝1,500。又，PPE1之20%甲基乙基酮溶劑中之溶液黏度為125 cPoise。Production Example 1 Synthesis of Polyphenylene Ether 1 (PPE1) A three-way stopcock was installed in a 500 ml three-necked flask, and a Dai's condenser and an equal pressure dropping funnel were installed. After replacing the flask with nitrogen, 100 g of raw material polyphenylene ether S202A, 200 g of toluene, and 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylbenzene, which is a polyfunctional phenol, were added Base) butane 12.8 g. A thermometer was set in the flask, and while stirring with a magnetic stirrer, the flask was heated to 90°C with an oil bath to dissolve the raw material polyphenylene ether. Dilute 37.5 g of a 40% m-xylene solution (NOF: Nyper BMT) of a mixture of benzyl peroxide, m-methylbenzyl peroxide, and m-toluyl peroxide as a starting agent In 87.5 g of toluene, add to the isobaric dropping funnel. After the temperature in the flask was lowered to 80°C, the initiator solution was dropped into the flask to start the reaction. The initiator was added dropwise for 2 hours, after the dropwise addition, the temperature was raised to 90° C. again, and stirring was continued for 4 hours. After the reaction, the polymer solution was dropped into methanol, and after reprecipitation, it was separated from the solution by filtration, and the polymer was recovered. After that, it was dried under vacuum at 100°C for 3 hours. By ¹ H-NMR, it was confirmed that the low-molecular-weight phenol was absorbed into the polymer, and the peak of the hydroxyl group disappeared. According to the ¹ H-NMR measurement result, it was confirmed that the obtained polymer has the following formula: [Chemical Formula 22]

{Wherein, l, m, and n are numbers arbitrarily selected to satisfy the following number average molecular weight} polyphenylene ether (hereinafter referred to as PPE1) represented by the structure. As a result of GPC measurement, the molecular weight of the obtained PPE1 in terms of polystyrene was Mn=1,500. In addition, the viscosity of the solution in 20% methyl ethyl ketone solvent of PPE1 is 125 cPoise.

{式中，l、m及n為以滿足下述數量平均分子量之方式所任意選擇之數}所表示之結構之改性聚苯醚(以下，稱為低分子量、改性PPE1)。  又，GPC測定之結果為，所獲得之低分子量、改性PPE1之以聚苯乙烯換算計之分子量為Mn＝1,600。又，低分子量、改性PPE1之平均末端官能基數依據上述數式(2)，算出為2.5以上。進而，改性PPE1於20%甲基乙基酮溶劑中之溶液黏度為131 cPoise。Synthesis of modified polyphenylene ether 1 (low molecular weight, modified PPE1) 80 g of toluene and 26 g of PPE1 synthesized above were mixed and heated to about 85°C. 0.55 g of dimethylaminopyridine was added to the heated mixture. At the point in time when all the solids were considered to be dissolved, 4.9 g of methacrylic anhydride was slowly added to the dissolved matter. While continuously mixing the obtained solution, the temperature was maintained at 85°C for 3 hours. Next, the solution was cooled to room temperature to obtain a toluene solution of methacrylate modified polyphenylene ether. A part of the solution was collected, dried and then subjected to ¹ H-NMR measurement. The progress of the reaction is judged based on the disappearance of the peak derived from the hydroxyl group of the polyphenylene ether, and it is moved to the purification operation. Over 30 minutes, 120 g of the toluene solution of the above methacrylate modified polyphenylene ether was added dropwise to 360 g of methanol vigorously stirred in a 1 L beaker with a magnetic stirrer. The obtained precipitate was filtered under reduced pressure with a membrane filter and dried to obtain 38 g of polymer. ^{The 1} H-NMR measurement result of the dried polymer is shown in FIG. 1. It was confirmed that the peak derived from the hydroxyl group of polyphenylene ether at around 4.5 ppm disappeared, and the peak derived from the methacrylic olefin at around 5.75 ppm was confirmed to appear. In addition, by GC measurement, the peaks derived from dimethylaminopyridine, methacrylic anhydride, and methacrylic acid almost disappeared. From this, it is judged that the peaks derived from methacrylic acid groups in NMR are bonded to the end of polyphenylene ether. The knot of methacrylic acid base. According to the results, it was confirmed that the obtained polymer has the following formula: [Chemical Formula 23]

{Wherein, l, m, and n are arbitrarily selected numbers to satisfy the following number average molecular weight} modified polyphenylene ether (hereinafter referred to as low molecular weight, modified PPE1) represented by the structure. In addition, as a result of GPC measurement, the molecular weight of the obtained low molecular weight, modified PPE1 in terms of polystyrene was Mn=1,600. In addition, the average number of terminal functional groups of the low molecular weight, modified PPE1 is calculated to be 2.5 or more based on the above-mentioned formula (2). Furthermore, the solution viscosity of modified PPE1 in 20% methyl ethyl ketone solvent is 131 cPoise.

The material used for the formation of the resin composition and its hardened product PPE The low molecular weight, modified polyphenylene ether 1 obtained in the above (low molecular weight, modified PPE1)

Crosslinking agent TAIC (manufactured by Nippon Kasei Co., Ltd., molecular weight: 249.7, number of unsaturated double bonds: 3)

Organic peroxide Bis(1-tert-butylperoxy-1-methylethyl)benzene ``Product name PERBUTYL P'' (manufactured by NOF Corporation)

Thermoplastic resin · SEBS N525: product name "Tuftec N525", manufactured by Asahi Kasei Co., Ltd., Mw: 200,000, styrene unit content: 67% by mass · SEBS N504: product name "Tuftec N504", manufactured by Asahi Kasei Co., Ltd., Mw: 200,000, styrene unit content rate: 32 mass% SEBS N516: product name "Tuftec N516", manufactured by Asahi Kasei Co., Ltd., Mw: 160,000, styrene unit content rate: 40 mass% SEBS N517: product Name "Tuftec N517", manufactured by Asahi Kasei Co., Ltd., Mw: 400,000, styrene unit content: 40% by mass ・SEBS H1041: Product name "Tuftec H1041", manufactured by Asahi Kasei Co., Ltd., Mw: 57,000, styrene Unit content rate: 31 mass% ・SEBS H1221: Product name "Tuftec H1221", manufactured by Asahi Kasei Co., Ltd., Mw: 120,000, styrene unit content rate: 12 mass%

Flame retardant Decabromodiphenyl ethane "product name SAYTEX8010" (manufactured by Albemarle)

Filler・Spherical silica (manufactured by Longsen)

Base material L glass cloth (manufactured by Asahi-Schwebel, model: 2116)

Evaluation method 1. The number average molecular weight of PPE and the weight average molecular weight of thermoplastic resin are analyzed by GPC, and the number average molecular weight of PPE and the weight average molecular weight of thermoplastic resin are calculated by comparing with the dissolution time of standard polystyrene with known molecular weight. . Specifically, after preparing a measurement sample with a sample concentration of 0.2 w/vol% (solvent: chloroform), the measuring device uses HLC-8220GPC (manufactured by Tosoh Co., Ltd.) on the column: Shodex GPC KF-405L HQ×3 (Manufactured by Showa Denko Co., Ltd.), lysate: chloroform, injection volume: 20 μL, flow rate: 0.3 mL/min, column temperature: 40°C, and detector: RI.

2. Varnish viscosity Add 200 ml of the resin varnish (solid content 53% by mass) prepared from each resin composition and toluene into a beaker, using a type B rotary viscometer, at 25°C at 30 rpm for 30 seconds Determine the viscosity under the conditions. For the measured viscosity, it is evaluated in 5 levels. 5: More than 50 mPa·s and less than 150 mPa·s 4: More than 150 mPa·s and less than 200 mPa·s 3: More than 200 mPa·s and less than 300 mPa·s 2: More than 300 mPa·s and 500 mPa· s or less 1: more than 500 mPa·s and less than 1000 mPa·s

3. Impregnation. Add the resin varnish (53 mass% solid content) prepared from each resin composition and toluene into the tank, and place a 50 mm square L glass cloth (manufactured by Asahi-Schwebel, model number) on it. : 2116), visually observe the condition of the resin varnish impregnated in the glass cloth. According to the impregnation of the resin varnish to the glass cloth, it is evaluated in 5 grades. 5: The resin varnish is impregnated into the entire glass cloth within 1 minute 4: The resin varnish is impregnated into the entire glass cloth within 2 minutes 3: The resin varnish is impregnated into the entire glass cloth within 3 minutes 2: The resin varnish is impregnated within 5 minutes In the overall situation of the glass cloth 1: Even after 5 minutes, the impregnation has not been completed

4. Dispersibility Mix and stir the ingredients and solvents shown in Table 1, and visually observe the state of the mixture after the stirring is stopped, and evaluate it based on the following criteria. ○: Good The insoluble matter has not precipitated and is evenly dispersed for more than 2 hours after the stirring is stopped. ×: Poor Insoluble matter precipitates within 1 hr after the stirring is stopped.

5. The dielectric constant and dielectric loss tangent of the laminated board (electrical characteristics) Use the cavity resonance method to measure the dielectric constant and the dielectric loss tangent of the laminated board at 10 GHz. As a measurement device, a network analyzer (N5230A, manufactured by Agilent Technologies) and a cavity resonator (Cavity Resornator CP series) manufactured by Kanto Electronics Application Development Co., Ltd. were used for measurement. Cut the laminated board with a thickness of about 0.5 mm made by the following method into a size of about 2 mm in width and 50 mm in length with the warp of the glass cloth as the long sides. Next, put it in an oven at 105℃±2℃ to dry for 2 hours, then let it stand for 96±5 hours at 23℃ with a relative humidity of 50±5%. After that, the above-mentioned measuring device was used under an environment of 23°C and a relative humidity of 50±5% to measure the dielectric constant and the dielectric loss tangent, and evaluate them in 5 levels. 5: The dielectric constant is above 3.0 and below 3.3, and the dielectric loss tangent exceeds 0.0020 and below 0.0024. 4: The dielectric constant is above 3.0 and below 3.3, and the dielectric loss tangent exceeds 0.0024 and below 0.0026. 3: The dielectric constant is above 3.0 and below 3.3. And the dielectric loss tangent is more than 0.0026 and less than 0.0030 2: The dielectric constant is above 3.0 and less than 3.3, and the dielectric loss tangent is more than 0.0030 and less than 0.0035 1: The dielectric constant is more than 3.3, and the dielectric loss tangent is more than 0.0035

6. The glass transition temperature (Tg) of the laminated plate The dynamic viscoelasticity of the laminated plate is measured, and the temperature at which tanδ becomes the maximum is calculated as the glass transition temperature (Tg). The measuring device used a dynamic viscoelastic device (RHEOVIBRON model DDV-01FP, manufactured by ORIENTEC). The laminated board with a thickness of about 0.3 mm made by the following method is cut into a length of about 35 mm and a width of about 5 mm with the warp of the glass cloth as the long side to make a test piece. In the stretching mode, the frequency: 10 Measure under the condition of rad/s. According to the value of Tg, it is evaluated in 5 levels. 5: Over 200°C 4: Over 190°C and below 200°C 3: Over 180°C and below 190°C 2: Over 170°C and below 180°C 1: Over 160°C and below 170°C

7. Heat resistance of laminated board The prepregs obtained in the 8 examples and comparative examples are overlapped, and the laminated board produced by the following method is cut into 50 mm squares. Next, the cut sample is placed to 105 After drying in an oven at ℃±2℃ for 2 hours, perform the pressure cooker test under the conditions of 2 atmospheres and 4 hours. The heat resistance test is to visually evaluate the laminated board after the water absorption acceleration test based on the following criteria. ○: Good When the laminated board after the water absorption acceleration test is immersed in a solder bath at 288°C for 20 seconds, no bulging, peeling, and whitening are observed. ×: Poor When the laminated board after the water absorption acceleration test was immersed in a solder bath at 288°C for 20 seconds, any one of bulging, peeling, and whitening was observed.

8. The peeling strength of the copper foil of the laminate (peel strength N/mm) Measure the stress when the copper foil of the copper laminate is peeled off at a certain speed. Cut the copper foil laminated board using 35 μm thick copper foil (GTS-MP foil manufactured by Furukawa Electric Co., Ltd.) made by the following method into a size of 15 mm in width x 150 mm in length, and use Autograph (AG -5000D, manufactured by Shimadzu Corporation), measure the average value of the load when the copper foil is peeled off at an angle of 90°C with respect to the removal surface at a speed of 50 mm/min, and obtain the average value of 5 measurements to 5 levels to evaluate. 5: more than 1. N/mm 4: more than 0.80 N/mm and less than 1.0 N/mm 3: more than 0.70 N/mm and less than 0.80 N/mm 2: more than 0.5 N/mm and less than 0.70 N/mm 1: 0.5 N/mm or less

Example 1 According to the composition shown in Table 1, to 287 parts by mass of toluene, a thermoplastic resin was added, stirred and dissolved, and then flame retardant, spherical silica, and low molecular weight, modified PPE1 were added separately. Continue stirring until the low molecular weight, modified PPE1 is dissolved (solid content concentration 53% by mass). Then, a crosslinking agent and an organic peroxide are added to the dissolved matter, and the mixture is sufficiently stirred to obtain a varnish. After the varnish is impregnated in the L glass cloth, it is passed through a specific slit to scrape off the excess varnish, and dried in a drying oven at 105° C. for a specific time to remove toluene, thereby obtaining a prepreg. The prepreg was cut into a specific size, and its weight was compared with the weight of the glass cloth of the same size to calculate the solid content of the resin composition in the prepreg. The result was 58% by mass. A specific number of the prepregs are overlapped, and then copper foils (manufactured by Furukawa Electric Co., Ltd., thickness 35 μm, GTS-MP foil) are overlapped on both sides of the overlapped prepregs, and vacuum pressure is applied to this Obtained copper foil laminated board. In the step of vacuum pressurization, firstly, heating is performed from room temperature at a heating rate of 3°C/min while using a pressure of 10 kg/cm ² ; secondly, after reaching 130°C, a heating rate of 3°C/min is being used at the same time. When heating in min, the pressure is 40 kg/cm ² . After the temperature reaches 200°C, the pressure is 40 kg/cm ² and the time is 60 minutes while maintaining the temperature at 200°C. Next, the copper foil is removed from the above-mentioned copper foil laminated board by etching, thereby obtaining a laminated board.

In Examples 2 to 6 and Comparative Examples 1 to 4, the composition was changed as shown in Table 1. Other than that, according to the same method as in Example 1, the resins were obtained in Examples 2 to 6 and Comparative Examples 1 to 4, respectively. The composition, varnish, prepreg, copper foil laminated board and laminated board are evaluated.

[Table 1] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4 composition PPE Low molecular weight, modified PPE1 80 80 80 80 80 80 80 80 80 80 Crosslinking agent TAIC 20 20 20 20 20 20 20 20 20 20 Organic peroxide PERBUTYL P 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 Thermoplastic resin SEBS N525 9 20 5 25 1 SEBS N504 9 SEBS N516 9 SEBS N517 9 SEBS H1041 9 SEBS H1221 9 Flame retardant SAYTEX8010 24.5 24.5 24.5 24.5 24.5 24.5 24.5 24.5 24.5 24.5 Silicon dioxide Spherical silica 66 66 66 66 66 66 66 66 66 66 Assessment Electrical characteristics 5 5 4 5 5 5 4 4 5 3 Peel strength 5 4 5 5 5 5 3 3 3 4 Tg 5 4 5 4 4 4 4 4 3 4 Heat resistance ○ ○ ○ ○ ○ ○ X X X ○ Dispersion ○ ○ ○ ○ ○ ○ X X ○ ○ Varnish viscosity 5 4 5 5 5 5 5 5 3 5 Impregnation 5 4 5 5 5 5 3 3 3 5

^{Figure 1 shows the 1} H-NMR (nuclear magnetic resonance) measurement results of the modified polyphenylene ether 1 (modified PPE1) obtained in Production Example 1.

Claims (12)

A resin composition comprising: (a) polyphenylene ether component A, which has the following formula (1): [化1]

{Where X is an arbitrary linking group with a valence, a is a number greater than 2.5, R ^{5 is} each independently an arbitrary substituent, k is each independently an integer from 1 to 4, and at least one of ^{k R 5 includes the following} Formula (2): [化2]

(In the formula, R ^{11 is} each independently a C _1-8 alkylene group, R ^{12 is} each independently a C _1-8 alkylene group, b is each independently 0 or 1, R ¹³ represents a hydrogen atom, C _1-8 Either an alkyl group or a phenyl group, and the above-mentioned alkyl group, alkylene group, and phenyl group _{may have a substituent within the limit of satisfying the condition of C 1-8} ), and Y each independently has the following formula (3): [化3]

(In the formula, R ^{21 is} independently a saturated or unsaturated hydrocarbon group _{of C 1-6} ^{, and R 22 is} independently a hydrogen atom or a _{saturated or unsaturated hydrocarbon group of C 1-6} , and the above saturated or unsaturated hydrocarbon is based on satisfying C _{1 The} divalent linking group of the structure represented by the condition of -6 may have a substituent), n represents the repeating number of Y, each independently an integer of 1 to 200, and L is any divalent linking group or a single bond, And A each independently represents a structure represented by a substituent containing a carbon-carbon double bond and/or an epoxy bond}, and the number average molecular weight is 500 to 8,000; (b) crosslinking agent; (c) organic peroxide; And (d) a thermoplastic resin, which is at least 1 selected from the group consisting of block copolymers of vinyl aromatic compounds and olefin-based olefin compounds and their hydrogenated products, and homopolymers of the aforementioned vinyl aromatic compounds And the weight average molecular weight is 150,000 to 800,000; and the content of the thermoplastic resin is 2 parts by mass to 20 parts by mass based on 100 parts by mass of the total mass of the polyphenylene ether component A and the crosslinking agent. The resin composition according to claim 1, wherein the content of the unit derived from the vinyl aromatic compound in the block copolymer or its hydrogenated product is 20% by mass or more and 70% by mass or less. The resin composition of claim 1 or 2, wherein the above-mentioned cross-linking agent has an average of 2 or more carbon-carbon unsaturated double bonds in one molecule, the number-average molecular weight of the above-mentioned cross-linking agent is 4,000 or less, and the above-mentioned polyphenylene ether Component A: The weight ratio of the above-mentioned crosslinking agent is 25:75 to 95:5. The resin composition according to any one of claims 1 to 3, wherein the crosslinking agent comprises at least one selected from the group consisting of triallyl cyanurate, triallyl isocyanurate, and polybutadiene A compound. The resin composition according to any one of claims 1 to 4, wherein the one-minute half-life temperature of the organic peroxide is 155°C to 185°C. The resin composition according to any one of claims 1 to 5, wherein the content of the organic peroxide is 0.05 parts by mass to 5 parts by mass based on 100 parts by mass of the total mass of the polyphenylene ether component A and the crosslinking agent Mass parts. The resin composition according to any one of claims 1 to 6, wherein the resin composition further contains a flame retardant, and the flame retardant does not interact with other components in the resin composition after the resin composition is cured. Miscible. An electronic circuit substrate material comprising the resin composition according to any one of claims 1 to 7. A resin film comprising the resin composition according to any one of claims 1 to 7. A prepreg, which is a composite of a substrate and the resin composition according to any one of claims 1 to 7. The prepreg according to claim 10, wherein the substrate is glass cloth. A laminated body which is a laminated body of a resin film as claimed in claim 9 or a hardened product of a prepreg as claimed in claim 10 or 11 and a metal foil.

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