CN112080126A

CN112080126A - Polyphenylene ether-containing resin composition

Info

Publication number: CN112080126A
Application number: CN202010534008.1A
Authority: CN
Inventors: 长田一人; 中村祥宇; 远藤正朗
Original assignee: Asahi Kasei Corp
Current assignee: Asahi Kasei Corp
Priority date: 2019-06-13
Filing date: 2020-06-12
Publication date: 2020-12-15
Anticipated expiration: 2040-06-12
Also published as: TW202102604A; TWI760763B; JP7308082B2; JP2020200432A; CN112080126B

Abstract

A resin composition containing polyphenylene ether. A resin composition containing polyphenylene ether (PPE) is required to have good compatibility with PPE, good coatability to substrates and the like, and excellent substrate characteristics when assembled into an electronic circuit substrate, and therefore, the present invention aims to satisfy these requirements. Provided is a resin composition comprising: (a) a polyphenylene ether component having a structure represented by the following formula (1) and a number average molecular weight of 500 to 8,000 [ wherein X, a, R⁵K, Y, n, A and L are as defined in the specification }; (b) a crosslinking agent; (c) an organic peroxide; and (d) at least 1 kind of thermoplastic resin selected from the group consisting of block copolymer of vinyl aromatic compound and alkene olefin compound and its hydrogenation product, and the homopolymer of the vinyl aromatic compound, and the weight average molecular weight is 150,000-800,000, and, the total mass of polyphenylene ether component A and cross-linking agent is 100 parts by mass as the benchmark, the content of the thermoplastic resin is 2 parts by mass-20 parts by mass. Formula (1)

Description

Polyphenylene ether-containing resin composition

Technical Field

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

Background

In recent years, with remarkable progress in information network technology and expansion of services using information networks, electronic devices are required to increase the capacity of information and increase the processing speed. In order to meet these requirements, a material for a substrate such as a printed wiring board is required to have a low dielectric constant and a low dielectric loss tangent in addition to the conventionally required properties such as flame retardancy, heat resistance, and peeling strength with a copper foil. Therefore, further improvements of resin compositions used for substrate materials such as printed wiring boards have been studied.

Among the materials for substrates, polyphenylene ether (PPE) has a low dielectric constant and a low dielectric loss tangent, and is therefore suitable as a material for printed wiring boards that can meet the above requirements. For example, in the polyphenylene ether-containing resin composition described in patent document 1, improvement of moldability, heat resistance, adhesiveness and electrical characteristics is attempted by controlling the average number of phenolic hydroxyl groups per 1 molecule of polyphenylene ether within a specific range or by specifying the content of a plurality of polyphenylene ethers having different molecular weights from each other.

Documents of the prior art

Patent document

Patent document 1: international publication No. 2012/081705

Disclosure of Invention

Problems to be solved by the invention

A resin composition containing polyphenylene ether (PPE) is required to have good compatibility with PPE, good coatability to substrates and the like, and excellent substrate characteristics when assembled into an electronic circuit substrate. The polyphenylene ether-containing resin composition described in patent document 1 has room for study from the viewpoint of satisfying all of these requirements.

Accordingly, an object of the present invention is to provide a polyphenylene ether-containing resin composition excellent in compatibility, coatability and substrate characteristics, and an electronic circuit substrate material, a resin film, a prepreg and a laminate formed using the same.

Means for solving the problems

The present inventors have made intensive studies to solve the above problems, and as a result, have found that: the present inventors have completed the present invention by defining the structure and molecular weight of polyphenylene ether, and the structure and molecular weight and content of thermoplastic resin in a resin composition comprising polyphenylene ether, a crosslinking agent, an organic peroxide and a thermoplastic resin, so that the compatibility, coatability and substrate characteristics are excellent. The following exemplifies embodiments of the present invention.

[1] A resin composition comprising:

(a) a polyphenylene ether component A having a structure represented by the following formula (1) and a number average molecular weight of 500 to 8,000;

(b) a crosslinking agent;

(c) an organic peroxide; and

(d) a thermoplastic resin having a weight average molecular weight of 150,000 to 800,000, which is at least 1 member selected from the group consisting of a block copolymer of a vinyl aromatic compound and an alkenyl olefin compound, a hydrogenated product thereof, and a homopolymer of the vinyl aromatic compound,

the content of the thermoplastic resin is 2 to 20 parts by mass based on 100 parts by mass of the total of the polyphenylene ether component A and the crosslinking agent.

Formula (1)

{ in the formula (I) { wherein,

x is an optional linking group of valency a, a is a number of 2.5 or more,

R⁵each independently is an optional substituent, each k is independently an integer of 1 to 4, and k R's are present⁵At least 1 of them comprises a partial structure represented by the following formula (2),

each Y is independently a divalent linking group having a structure represented by the following formula (3), n represents the number of repetitions of Y, each independently is an integer of 1 to 200,

l is any divalent linking group or single bond, and

a each independently represents a substituent containing a carbon-carbon double bond and/or an epoxy bond,

formula (2)

(in the formula, R¹¹Each independently is C_1-8Alkyl of R¹²Each independently is C_1-8B is each independently 0 or 1, R¹³Represents a hydrogen atom, C_1-8And the aforementioned alkyl, alkylene and phenyl group satisfy C_1-8Optionally having a substituent within the range of the conditions of (1)

Formula (3)

(in the formula，R²¹Each independently is C_1-6A saturated or unsaturated hydrocarbon group of R²²Each independently is a hydrogen atom or C_1-6And the aforementioned saturated or unsaturated hydrocarbon group satisfies C_1-6Optionally having a substituent) within the range of the condition(s).

[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 hydrogenated product thereof is 20% by mass or more and 70% by mass or less.

[3] The resin composition according to item 1 or 2, wherein the crosslinking agent has an average of 2 or more carbon-carbon unsaturated double bonds in 1 molecule, the number average molecular weight of the crosslinking agent is 4,000 or less, and the weight ratio of the polyphenylene ether component A to the crosslinking agent is 25:75 to 95: 5.

[4] The resin composition according to any one of items 1 to 3, wherein the crosslinking agent contains at least one compound selected from the group consisting of triallyl cyanurate, triallyl isocyanurate, and polybutadiene.

[5] The resin composition according to any one of items 1 to 4, wherein the organic peroxide has a 1-minute half-life temperature of 155 to 185 ℃.

[6] The resin composition according to any one of items 1 to 5, wherein the content of the organic peroxide is 0.05 to 5 parts by mass based on 100 parts by mass of the total of the polyphenylene ether component A and the crosslinking agent.

[7] The resin composition according to any one of items 1 to 6, wherein the resin composition further comprises a flame retardant, and the flame retardant is not compatible with other contained components in the resin composition after the resin composition is cured.

[8] An electronic circuit board material comprising the resin composition according to any one of items 1 to 7.

[9] A resin film comprising the resin composition according to any one of items 1 to 7.

[10] A prepreg which is a composite of a substrate and the resin composition described in any one of items 1 to 7.

[11] The prepreg according to item 10, wherein the substrate is a glass cloth.

[12] A laminate of a metal foil and the resin film according to item 9 or the cured product of the prepreg according to item 10 or 11.

ADVANTAGEOUS EFFECTS OF INVENTION

According to the present invention, the polyphenylene ether-containing resin composition is excellent in compatibility and coatability, and an electronic circuit substrate material, a resin film, a prepreg and a laminate excellent in substrate characteristics can be provided using the same.

Drawings

FIG. 1 shows a modified polyphenylene ether 1 (modified PPE1) obtained in production example 1¹H-NMR measurement results.

Detailed Description

Hereinafter, specific embodiments of the present invention (hereinafter, simply referred to as "the present embodiment") will be described in detail. The present invention is not limited to the following embodiments, and various modifications can be made within the scope of the present invention.

Resin composition

The PPE-containing resin composition of the present embodiment (hereinafter also simply referred to as "resin composition") contains a polyphenylene ether (PPE), a crosslinking agent, an organic peroxide, and a thermoplastic resin, and may further contain a flame retardant, other additives, a silica filler, a solvent, and the like as desired. The constituent elements of the resin composition of the present embodiment are explained below.

Polyphenylene Ether (PPE)

In general, polyphenylene ethers (PPE) have a repeating structure composed of substituted or unsubstituted phenylene ether units. In this specification, the term "polyphenylene ether" includes dimers, trimers, oligomers and polymers. The PPE may contain a copolymerization component unit other than the phenylene ether unit, and the amount of such a copolymerization component unit 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 with respect to the amount of the whole unit structure.

Typical PPE include, for example, poly (2, 6-dimethyl-1, 4-phenylene ether), poly (2-methyl-6-ethyl-1, 4-phenylene ether), poly (2-methyl-6-phenyl-1, 4-phenylene ether), poly (2, 6-dichloro-1, 4-phenylene ether), copolymers of 2, 6-dimethylphenol with other phenols (for example, 2,3, 6-trimethylphenol, 2-methyl-6-butylphenol, etc.), and PPE copolymers obtained by coupling 2, 6-dimethylphenol with a biphenol or a bisphenol.

Polyphenylene ether component A (PPE-A)

The resin composition of the present embodiment contains, as a polyphenylene ether component, a polyphenylene ether component A having a structure represented by the following formula (1) and a number average molecular weight of 500 to 8,000.

Formula (1)

In the formula (1), X is an arbitrary connecting group with a valence; a is a number of 2.5 or more, preferably an integer of 3 or more, more preferably an integer of 3 to 6. Specific examples of X include hydrocarbon groups; a hydrocarbon group containing one or more elements selected from nitrogen, phosphorus, silicon, or oxygen; or an element containing nitrogen, phosphorus, silicon or the like, or a group of these elements, or the like.

Furthermore, R⁵Is an optional substituent; k is an integer of 1 to 4, and when k is 2 or more, 2R are optionally selected⁵Are linked to form a ring, k R being present⁵At least 1 of them contains a partial structure represented by the following formula (2).

Formula (2)

In the formula (2), R¹¹Each independently is C_1-8Alkyl radical, R¹²Each independently is C_1-8Alkylene, b is independently 0 or 1, R¹³Represents a hydrogen atom, C_1-8Alkyl radicalOr a phenyl group, these alkyl, alkylene and phenyl groups satisfying C_1-8Optionally having a substituent within the range of the conditions of (1).

The partial structure represented by the formula (2) preferably has a secondary carbon and/or a tertiary carbon, and may have, for example, an isopropyl group, an isobutyl group, a sec-butyl group, a tert-pentyl group, a 2, 2-dimethylpropyl group, a structure having a phenyl group at the terminal thereof, or the like. The partial structure represented by the formula (2) is preferably the same as R in the formula (1)⁵The bonded benzene rings are directly bonded. Further, the partial structure represented by the formula (2) is preferably bonded to R in the formula (1)⁵The 2-and/or 6-position (ortho-position with respect to-O-) of the bonded benzene ring.

Regarding the following portions among the structures represented by formula (1):

preferably any of the following structures:

specific examples thereof include a structure in which all of the hydrogens of the terminal phenolic hydroxyl groups are removed 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, 3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 2,4, 6-tris (3 ', 5 ' -di-tert-butyl-4 ' -hydroxybenzyl) mesitylene, pentaerythrityl 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-triazine-2, 4,6(1H,3H,5H) -trione, 1,3, 5-tris [ [4- (1, 1-dimethylethyl) -3-hydroxy-2, 6-dimethylphenyl ] methyl ] -1,3, 5-triazine-2, 4,6(1H,3H,5H) -trione.

Each Y in formula (1) is independently a divalent linking group (substituted phenol unit) having a structure represented by formula (3), and each n in formula (1) represents the number of repetitions of Y, and is independently an integer of 0 to 200.

Formula (3)

In the formula (3), R²¹Independently is C_1-6The saturated or unsaturated hydrocarbon group of (3) is preferably a methyl group, an ethyl group, an n-propyl group, a vinyl group, an allyl group, an ethynyl group, a propargyl group, or the like, more preferably a methyl group or an ethyl group, and still more preferably a methyl group. R²²Independently is a hydrogen atom or C_1-6The saturated or unsaturated hydrocarbon group (2) is preferably a hydrogen atom, a methyl group, an ethyl group, an n-propyl group or the like, more preferably a hydrogen atom or a methyl group, and still more preferably a hydrogen atom. Here, the saturated or unsaturated hydrocarbon group satisfies C_1-6May have a substituent within the range of the condition(s).

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 formulae (4) to (8):

in the formulae (4) to (8), R³¹Each independently is hydrogen, hydroxy or C_1-30Alkyl, aryl, alkoxy, allyloxy, amino, or hydroxyalkyl. R³²Each independently is C_1-30A hydrocarbon group of (1). R³³Each independently is hydrogen, hydroxy or C_1-30Alkyl, aryl, alkoxy, allyloxy, amino, hydroxyalkyl, ethenyl or isopropenyl, R³³At least one of which is vinyl or isopropenyl. s and t are integers of 0-5.

As R³¹Specific examples of the hydrocarbon group of (3) 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-dimethylpropyl, 1-dimethylpropyl, n-hexyl, cyclohexyl, 1-ethylbutyl, 2-ethylbutyl, 3-ethylbutyl, tert-butyl, 2-ethylpropyl, 1-methylbutyl, 2-methylbutyl, pentyl, cyclopentyl, 2-dimethylbutyl, 2-ethylpropyl,1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1-dimethylbutylene, 2-dimethylbutylene, 3-dimethylbutyl, 1, 2-dimethylbutyl, 1, 3-dimethylbutyl, 2, 3-dimethylbutyl, n-heptyl, 1-methylhexyl, 2-methylhexyl, 3-methylhexyl, 4-methylhexyl, 5-methylhexyl, 1-ethylpentyl, 2-ethylpentyl, 3-ethylpentyl, 1-dimethylpentyl, 2-dimethylpentyl, 3-dimethylpentyl, 4-dimethylpentyl, 1, 2-dimethylpentyl, 1, 3-dimethylpentyl, 4-dimethylpentyl, 1, 4-dimethylpentyl group, 2, 3-dimethylpentyl group, 2, 4-dimethylpentyl group, 3, 4-dimethylpentyl group, 2-methyl-3, 3-dimethylbutyl group, 1,2, 3-trimethylbutyl group, 1, 3-dimethyl-2-pentyl group, 2-isopropylbutyl group, 2-methylcyclohexyl group, 3-methylcyclohexyl group, 4-methylcyclohexyl group, 1-cyclohexylmethyl group, 2-ethylcyclopentyl group, 3-ethylcyclopentyl group, 2, 3-dimethylcyclopentyl group, 2, 4-dimethylcyclopentyl group, 2-methylcyclopentylmethyl group, 2-cyclopentylethyl group, 1-cyclopentylethyl group, n-octyl group, 2-pentyl group, 3-octyl group, 4-octyl group, 2-methylheptyl group, 3-methylheptyl group, 4-methylheptyl group, 5-methylheptyl group, 6-methylheptyl group, 2-ethylhexyl group, 3-ethylhexyl group, 4-ethylhexyl group, 5-ethylhexyl group, 1-dimethylhexyl group, 2-dimethylhexyl group, 3-dimethylhexyl group, 4-dimethylhexyl group, 5-dimethylhexyl group, 1, 2-dimethylhexyl group, 1, 3-dimethylhexyl group, 1, 4-dimethylhexyl group, 1, 5-dimethylhexyl group, 2, 3-dimethylhexyl group, 2, 4-dimethylhexyl group, 2, 5-dimethylhexyl group, 1-ethylmethylpentyl group, 2-ethylmethylpentyl group, 2-dimethylheptyl group, 2-methylheptyl group, 3-dimethylhexyl group, 4-dimethylhexyl group, 3, 3-ethylmethylpentyl, 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-methylpentyl, 3-ethyl-2-methylpentyl, 4-ethyl-3-methylpentyl, 3-ethyl-4-methylpentyl, 4-ethyl-3-methylpentyl, 1- (2-methylpropyl) butyl, 2-ethyl-4-methylpentyl, 3-ethyl-3-methylpentyl, 4-ethyl-3-methylpentyl, 1- (2-methylpropyl) butyl, 2-methylpentyl, 2-ethyl-4-methylpentyl, 2, 1- (2-methylpropyl) -2-methylbutyl, 1- (2-methylpropyl) ethyl, 1- (2-methylpropyl) ethylpropyl, 1-diethylpropyl, 2-diethylpropyl, 1-ethylmethyl-2, 2-dimethylpropyl, 2-ethylmethyl-1, 1-dimethylpropyl group, 2-ethyl-1, 1-dimethylbutyl group, 2, 3-dimethylcyclohexyl group, 2, 5-dimethylcyclohexyl group, 2, 6-dimethylcyclohexyl group, 3, 5-dimethylcyclohexyl group, 2-methylcyclohexylmethyl group, 3-methylcyclohexylmethyl group, 4-methylcyclohexylmethyl group, 2-ethylcyclohexyl group, 3-ethylcyclohexyl group, 4-ethylcyclohexyl group, 2-cyclohexylethyl group, 1-cyclohexyl-2-ethylidene group, nonyl group, isononyl group, decyl group, isodecyl group, undecyl group, dodecyl group, benzyl group, 2-phenylethyl group, etc.

R³¹The hydrocarbon group(s) is preferably a methyl group, an ethyl group, a n-propyl group, a 2-propyl group, a n-butyl group, an isobutyl group, a tert-butyl group, a n-pentyl group, a 1-ethylpropyl group, a 1-methylbutyl group, a 2-methylbutyl group, a 3-methylbutyl group, a pentyl group, a cyclopentyl group, a n-hexyl group, a cyclohexyl group, a 1-ethylbutyl group, a 2-ethylbutyl group, a 3-ethylbutyl group, a 1-methylpentyl group, a 2-methylpentyl group, a 3-methylpentyl group, a 4-methylpentyl group, a n-heptyl group, a 1-methylhexyl group, a 2-methylhexyl group, a 3-methylhexyl group, a 4-methylhexyl group, a 5-methylhexyl group, a 1-ethylpentyl group, 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 and the like, more preferably methyl, ethyl, n-propyl, 2-propyl, n-butyl, isobutyl, tert-butyl, n-pentyl, 1-ethylpropyl, 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 and the like, with methyl, ethyl, n-propyl, 2-propyl, n-butyl, isobutyl, tert-butyl, n-pentyl, cyclopentyl, n-hexyl, cyclohexyl, n-heptyl, n-octyl, 2-substitutedOctyl, 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 and the like.

As R³²Specific examples of the hydrocarbon group of (3) include: methylene, ethylene, trimethylene, 1, 2-propylene, tetramethylene, 2-methyl-1, 3-trimethylene, 1-dimethylethylene, pentamethylene, 1-ethyl-1, 3-propylene, 1-methyl-1, 4-butylene, 2-methyl-1, 4-butylene, 3-methyl-1, 4-butylene, 2-dimethyl-1, 3-propylene, 1, 2-cyclopentylene, 1, 3-cyclopentylene, 2-dimethyl-1, 3-propylene, 1-dimethyl-1, 3-propylene, 3-dimethyl-1, 3-propylene, hexamethylene, 1, 2-cyclohexylene, 1, 3-cyclohexylene, 1, 4-cyclohexylene, 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-methylpentylene, 1-dimethyl-1, 4-butylene, 2-dimethyl-1, 4-butylene, 3-dimethyl-1, 4-butylene, 1, 2-dimethyl-1, 4-butylene, 1, 3-dimethyl-1, 4-butylene, 2, 3-dimethyl-1, 4-butylene, 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, 1-dimethyl-1, 5-pentylene, 2-dimethyl-1, 5-pentylene, 3-dimethyl-1, 5-pentylene, 4-dimethyl-1, 5-pentylene, 1, 2-dimethyl-1, 5-pentylene, 1, 3-dimethyl-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, 1,2, 3-trimethyl-1, 4-butylene, and the like.

Further, as R³²Specific examples of the hydrocarbon group of (3) 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-cyclohexyleneA group, 1-cyclohexylmethylene group, 2-ethyl-1, 3-cyclopentylene group, 3-ethyl-1, 3-cyclopentylene group, 2, 3-dimethyl-1, 3-cyclopentylene group, 2, 4-dimethyl-1, 3-cyclopentylene group, 2-methyl-1, 3-cyclopentylmethylene group, 2-cyclopentylethylene group, 1-cyclopentylethylene group, octamethylene group, 1-methyl-1, 7-heptylene group, 1-ethyl-1, 6-hexylene group, 1-propyl-1, 5-pentylene group, 2-methyl-1, 7-heptylene group, 3-methyl-1, 7-heptylene group, 4-methyl-1, 7-heptylene group, a salt thereof, and a salt thereof, 5-methyl-1, 7-heptylene, 6-methyl-1, 7-heptylene, 2-ethyl-1, 6-hexylene, 3-ethyl-1, 6-hexylene, 4-ethyl-1, 6-hexylene, 5-ethyl-1, 6-hexylene, 1-dimethyl-1, 6-hexylene, 2-dimethyl-1, 6-hexylene, 3-dimethyl-1, 6-hexylene, 4-dimethyl-1, 6-hexylene, 5-dimethyl-1, 6-hexylene, 1, 2-dimethyl-1, 6-hexylene, 1, 3-dimethyl-1, 6-hexylene, 1, 4-dimethyl-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-ethylmethyl-1, 5-pentylene, 2-ethylmethyl-1, 5-pentylene, 3-ethylmethyl-1, 5-pentylene, 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-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, 2-ethyl-1-, 4-ethyl-3-methyl-1, 5-pentylene, and the like.

Further, as R³²Specific examples of the hydrocarbon group of (3) include: 1- (2-methylpropyl) -1, 4-butylene, 1- (2-methylpropyl) -2-methyl-1, 4-butylene, 1- (2-methylpropyl) ethylene, 1- (2-methylpropyl) ethyl-1, 3-propylene, 1-diethyl-1, 3-propylene, 2-diethyl-1, 3-propylene, 1-ethylmethyl-2, 2-dimethyl-1, 3-propylene, 2-ethylmethyl-1, 1-dimethyl-1, 3-propylene, 2-ethyl-1, 1-dimethyl-1, 4-butylene, 1-methyl-1, 3-propylene, 1-ethyl-1, 1-dimethyl-1, 4-butylene, 1-butylene, 2-methyl-1, 3-propylene, 1-butylene, 2-methyl-1, 2-ethyl-1, 2, 3-dimethyl-1, 4-cyclohexylene, 2, 5-dimethyl-1, 4-cyclohexylene, 2, 6-dimethyl-1, 4-cyclohexylene, 3, 5-dimethyl-1,4-cyclohexylene, 2-methyl-1, 4-cyclohexyl-1-methylene, 3-methyl-1, 4-cyclohexyl-1-methylene, 4-methyl-1, 4-cyclohexyl-1-methylene, 2-ethyl-1, 4-cyclohexylene, 3-ethyl-1, 4-cyclohexylene, 4-ethyl-1, 4-cyclohexylene, 2-cyclohexylethylene, 1-cyclohexyl-2-ethylene, nonylmethylene, 1-methyl-1, 8-octylene, decylmethylene, 1-methyl-1, 8-nonylene, undecylmethylene, dodecylmethylene, dimethylmethylene, dimethyl, 1, 4-phenylene, 1, 3-phenylene, 1, 2-phenylene, methylene-1, 4-phenylene-methylene, ethylene-1, 4-phenylene-ethylene, and the like.

R³²The hydrocarbon group of (A) is preferably a methylene group, an ethylene group, a trimethylene group, a 1, 2-propylene group, a tetramethylene group, a 2-methyl-1, 2-propylene group, a 1, 1-dimethylethylene group, a pentamethylene group, a 1-ethyl-1, 3-propylene group, a 1-methyl-1, 4-butylene group, a 2-methyl-1, 4-butylene group, a 3-methyl-1, 4-butylene group, a 2, 2-dimethyl-1, 3-propylene group, a 1, 3-cyclopentylene group, a 1, 6-hexamethylene group, a 1, 4-cyclohexylene group, a 1-ethyl-1, 4-butylene group, a 2-ethyl-1, 4-butylene group, a 3-ethyl-1, 4-butylene group, a, 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 group, 4-methyl-1, 4-cyclohexylene group, octamethylene group, 1-methyl-1, 7-heptylene group, 3-methyl-1, 7-heptylene group, 4-methyl-1, 7-heptylene group, 2-methyl-1, 7-heptylene group, 5-methyl-1, 7-heptylene group, 6-methyl-1, 7-heptylene group, 2-ethyl-1, 6-hexylene group, 3-ethyl-1, 6-hexylene group, 4-ethyl-1, 6-hexylene group, 5-ethyl-1, 6-hexylene group, nonylmethylene group, decylmethylene group, undecylmethylene group, dodecylmethylene group and the like are more preferred, and methylene group, dodecylmethylene group and the like are more preferred, Ethylene, trimethylene, 1, 2-propylene, tetramethylene, 2-methyl-1, 2-propylene, 1-dimethylethylene, pentamethylene, 1-ethyl-1, 3-propylene, 1-methyl-1, 4-butylene, 2-methyl-1, 4-butylene, 3-methyl-1, 4-butylene, 2-dimethyl-1, 3-propylene, 1, 3-cyclopentylene1, 6-hexamethylene, 1, 4-cyclohexylene, heptamethylene, octamethylene, 1-methyl-1, 7-heptylene, 3-methyl-1, 7-heptylene, 4-methyl-1, 7-heptylene, 2-methyl-1, 7-heptylene, 5-methyl-1, 7-heptylene, 6-methyl-1, 7-heptylene, 2-ethyl-1, 6-hexylene, 3-ethyl-1, 6-hexylene, 4-ethyl-1, 6-hexylene, 5-ethyl-1, 6-hexylene, nonylmethylene, decylmethylene, undecylmethylene, dodecylmethylene and the like are more preferable, and methylene, dodecylmethylene and the like are still more preferable, Ethylene, trimethylene, 1, 2-propylene, tetramethylene, 2-methyl-1, 2-propylene, 1-dimethylethylene, pentamethylene, 2-dimethyl-1, 3-propylene, 1, 3-cyclopentylene, 1, 6-hexamethylene, 1, 4-cyclohexylene, heptamethylene, octamethylene, 1-methyl-1, 7-heptylene, 3-methyl-1, 7-heptylene, 4-methyl-1, 7-heptylene, 2-methyl-1, 7-heptylene, 5-methyl-1, 7-heptylene, 6-methyl-1, 7-heptylene, 2-ethyl-1, 6-hexylene, hexamethylene, heptamethylene, octamethylene, 1-methyl-1, 7-heptamethylene, 2-methyl-1, 7-heptamethylene, 2-ethyl-1, 6-heptamethylene, 2-methyl-1, 3-ethyl-1, 6-hexylene, 4-ethyl-1, 6-hexylene, 5-ethyl-1, 6-hexylene, nonylmethylene, decylmethylene, undecylmethylene, dodecylmethylene, and the like.

Specific examples of the substituent containing a carbon-carbon double bond for a in the formula (1) include: vinyl, allyl, isopropenyl, 1-butenyl, 1-pentenyl, p-vinylphenyl, p-isopropenylphenyl, m-vinylphenyl, m-isopropenylphenyl, o-vinylphenyl, o-isopropenylphenyl, p-vinylbenzyl, p-isopropenylbenzyl, m-vinylbenzyl, m-isopropenylbenzyl, o-vinylbenzyl, o-isopropenylbenzyl, p-vinylphenylethenyl, p-vinylphenylpropenyl, p-vinylphenylbutenyl, m-vinylphenylethenyl, m-vinylphenylbutenyl, o-vinylphenylethenyl, o-vinylphenylpropenyl, o-vinylphenylbutenyl, methacryloyl, acryloyl, 2-ethylacryloyl, 2-hydroxymethylacryloyl, and the like.

L in formula (1) is any divalent linking group or single bond (direct bond). When L is a single bond, the structure represented by formula (1) is represented by the following formula.

When L is an arbitrary divalent linking group, specific examples of L include a structure represented by the following formula:

{ in the formula, a, R⁵K, X, Y and n are as defined in the description of formula (1) }

The structure represented by formula (1) can have various branched structures depending on the value of the valence a of X. For example, when a is 3 in formula (1), a branched structure shown by the following formula may be mentioned.

{ wherein n represents the number of repetition of Y and is an integer of 0 to 200 }

Specific examples of the structure represented by formula (1) include the following structures.

In the above formula, Z is an arbitrary linking group corresponding to X in the formula (1).R¹Is a substituent group shown in a formula (2), and b is an integer of 1-4. In addition, R is¹Is not limited, R¹Any position may be taken. When b is 2 or more, a plurality of R¹The structures may be the same or different. As R¹Examples thereof include: isopropyl group, isobutyl group, sec-butyl group, tert-pentyl group, 2-dimethylpropyl group, or a structure having a phenyl group at the terminal thereof. A is a substituent containing a carbon-carbon double bond and/or an epoxy bond. R²Is hydrogen or a C1-C8 hydrocarbon group having a chain or ring structure. In the presence of a plurality of R²In the case of (3), the substituents may be the same or different. As R²Specific examples of (3) include: methyl, ethyl, n-propyl, n-butyl, n-pentyl, cyclopentyl, n-hexyl, cyclohexyl, n-heptyl, n-octyl, phenyl, benzyl, 2-ethylhexyl, and the like, and hydrogen, methyl, ethyl, n-propyl, n-butyl, n-pentyl, cyclopentyl, n-hexyl, cyclohexyl, n-heptyl, and n-octyl are preferable from the viewpoint of reactivity at the time of synthesis, and the like. However, R can be set appropriately²When reactivity at the time of synthesis is controlled by the position of (3) or the reaction conditions at the time of synthesis, R is²Is not limited to the structure of (1) in the case of satisfying C_1-8May have any configuration within the scope of the conditions of (1). Z is a hydrocarbyl group; a hydrocarbon group containing one or more elements selected from nitrogen, phosphorus, silicon, and oxygen; or elements such as nitrogen, phosphorus, and silicon, or groups containing them.

Specific examples of the hydrocarbon group as Z include, for example, the structures shown by the following formulae.

In the above formula, R⁴～R¹⁰May be the same or different and represents hydrogen or C_1-8A hydrocarbon group of (1). Furthermore, R³¹～R³³May be the same or different and represents hydrogen or C_1-6A hydrocarbon group of (1). j. k, l and m may be the same or different and are integers of 0 to 4. MakingIs R⁴～R¹⁰Specific examples of (3) include: hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-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, and the like. As R³¹～R³³Specific examples of (3) include: hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, 2-pentyl, 3-pentyl, cyclopentyl, n-hexyl, 2-hexyl, 3-hexyl, cyclohexyl.

Further, as Z, a specific example of a hydrocarbon group containing one or more elements selected from the group consisting of nitrogen, phosphorus, silicon, and oxygen is shown by the following formula.

In the above formula, R⁴～R¹⁰May be the same or different and represents hydrogen or C_1-8A hydrocarbon group of (1). j. k, l and m may be the same or different and are integers of 0 to 4. As R⁴～R¹⁰Specific examples of (3) include: hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-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, and the like.

Specific examples of the group containing nitrogen, phosphorus, oxygen, etc. as Z are shown below.

In the above specific example, when the structure of a is embodied in the first example, the structure is represented by the following formula. The same applies to the case of 4 to 6 branched chains, and R in the following formula³¹、R³²S and t are as defined in the specific example of A.

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

The modified polyphenylene ether having the structure of the formula (1) of the present embodiment can be produced, for example, by preparing a polyphenylene ether by a redistribution reaction method using a higher molecular weight phenylene ether polymer and introducing a group a to the terminal thereof. When a polyphenylene ether is produced by redistribution reaction, it can be produced under conditions defined by known reaction conditions. In this case, since the molecular weight of the obtained polymer is lowered as compared with the phenylene ether polymer as a raw material, the ratio of the raw material polyphenylene ether to the polyfunctional phenol compound can be adjusted in accordance with the target molecular weight.

The method for introducing the substituent A in the formula (1), for example, the functional groups represented by the formulae (4) to (7), into the end of the obtained polyphenylene ether polymer is not limited, and various known methods can be employed depending on the kind of the functional group. For example, the functional group having a structure of formula (4), (6) or (7) can be introduced into the reaction system according to an ether bond produced by Williamson synthesis. The functional group having the structure of formula (5) is introduced as an ester bond forming reaction between a hydroxyl group at the end of the polyphenylene ether polymer and a carboxylic acid having a carbon-carbon double bond (hereinafter referred to as carboxylic acid), and a known ester bond forming method can be used.

The polyphenylene ether component a (PPE-a) has high curing reactivity and low dielectric properties, as well as good fluidity, moldability and heat resistance, and therefore can be suitably used as a material for various electrical and electronic devices, and particularly, can be suitably used as a prepreg for producing electrical and electronic parts (such as printed circuit board substrates). The PPE-A may be used in the form of a single resin, in combination with polyphenylene ethers having other structures, or in combination with various known additives in the resin composition. The content of PPE-A in the resin composition may be, for example, 0.5 to 95% by mass.

Polyphenylene ether component B (PPE-B)

The resin composition of the present embodiment may further contain a polyphenylene ether component B having an average phenolic hydroxyl number of 1.2 or more and a number average molecular weight of 8,000 or more and 50,000 or less per 1 molecule in addition to the polyphenylene ether component a having a number average molecular weight of 500 to 8,000 described above. Polyphenylene ether component B is stable in its production process and excellent in dielectric properties and heat resistance, and therefore tends to improve the electrical characteristics of a cured product of the resin composition without interfering with polyphenylene ether component a.

The polyphenylene ether component B (PPE-B) may be any polyphenylene ether (PPE) as long as it is different from the polyphenylene ether component A (PPE-A) and satisfies the condition that the number of phenolic hydroxyl groups per 1 molecule is 1.2 or more and the number average molecular weight is 8,000 to 50,000. From the viewpoint of use in combination with PPE-A, the number average molecular weight of PPE-B is preferably more than 8,000 and 50,000 or less. In the case where PPE-A and PPE-B are used in combination in the resin composition, from the viewpoint of stability and heat resistance of the resin composition, the content of PPE-A is preferably from 1 to 99.9% by mass and the content of PPE-B is from 0.1 to 99% by mass, more preferably from 20 to 98% by mass and the content of PPE-B is from 2 to 80% by mass, still more preferably from 40 to 95% by mass and the content of PPE-B is from 5 to 60% by mass, based on 100% by mass of the total mass of PPE-A and PPE-B.

Crosslinking agent

In the present embodiment, any crosslinking agent having the ability to initiate or accelerate the crosslinking reaction may be used. The crosslinking agent preferably has a number average molecular weight of 4,000 or less. When the number average molecular weight of the crosslinking agent is 4,000 or less, the increase in viscosity of the resin composition can be suppressed, and good resin fluidity during thermoforming can be obtained. The number average molecular weight may be a value measured by a conventional molecular weight measurement method, and specifically, a value measured by GPC or the like may be used.

From the viewpoint of crosslinking reaction, the crosslinking agent preferably has an average of 2 or more carbon-carbon unsaturated double bonds in 1 molecule. The crosslinking agent may be composed of 1 kind of compound, or may be composed of 2 or more kinds of compounds. The term "carbon-carbon unsaturated double bond" as used herein means a double bond located at the end branching from the main chain when the crosslinking agent is a polymer or oligomer. Examples of the carbon-carbon unsaturated double bond include a 1, 2-vinyl bond 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 1 molecule of the crosslinking agent is preferably 2 to 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 1 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 1 molecule of the crosslinking agent is preferably 26 to 60. When the number average molecular weight of the crosslinking agent is within the above range, the reactivity of the crosslinking agent in the resin composition of the present embodiment is further improved by setting the number of carbon-carbon unsaturated double bonds to a predetermined value or more, and the crosslinking density of the cured product of the resin composition is further improved, and as a result, more 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, more excellent resin fluidity can be imparted during heat molding by setting the number of carbon-carbon unsaturated double bonds to a predetermined value or less.

Examples of the crosslinking agent include: a triallyl isocyanurate compound such as triallyl isocyanurate (TAIC), a triallyl cyanurate compound such as triallyl cyanurate (TAC), a polyfunctional methacrylate compound having 2 or more methacryloyl groups in the molecule, a polyfunctional acrylate compound having 2 or more acryloyl groups in the molecule, a polyfunctional vinyl compound having 2 or more vinyl groups in the molecule such as polybutadiene, a vinylbenzyl compound such as divinylbenzene having a vinylbenzyl group in the molecule, a polyfunctional maleimide compound having 2 or more maleimide groups in the molecule such as 4, 4' -bismaleimide diphenylmethane, and the like. These crosslinking agents may be used alone in 1 kind or in combination of 2 or more kinds. Crosslinking agent of these, it is preferable to contain at least 1 compound selected from the group consisting of triallyl cyanurate, triallyl isocyanurate, and polybutadiene. When the crosslinking agent contains at least 1 or more of the compounds described above, the resin composition is more excellent in compatibility with PPE and coating properties, and tends to be more excellent in substrate characteristics when mounted on an electronic circuit substrate.

The weight ratio of the PPE to the crosslinking agent is preferably 25:75 to 95:5, more preferably 32:68 to 85:15, from the viewpoint of excellent compatibility between the crosslinking agent and the PPE, coatability of the resin composition, and properties of the electronic circuit board. From the same viewpoint, the weight ratio of PPE-A to the crosslinking agent is preferably 25:75 to 95:5, more preferably 32:68 to 85: 15.

Organic peroxides

In the present embodiment, any organic peroxide having the ability to accelerate the polymerization reaction of the resin composition containing polyphenylene ether and the crosslinking agent may be used. Examples of the organic peroxide include: benzoyl peroxide, cumene hydroperoxide, 2, 5-dimethylhexane-2, 5-dihydroperoxide, 2, 5-dimethyl-2, 5-di (t-butylperoxy) hexyne-3, di-t-butyl peroxide, t-butylcumyl peroxide, di (2-t-butylperoxyisopropyl) benzene, 2, 5-dimethyl-2, 5-di (t-butylperoxy) hexane, peroxides such as dicumyl peroxide, di-tert-butyl peroxyisophthalate, tert-butyl peroxybenzoate, 2-bis (tert-butylperoxy) butane, 2-bis (tert-butylperoxy) octane, 2, 5-dimethyl-2, 5-bis (benzoylperoxy) hexane, bis (trimethylsilyl) peroxide, and trimethylsilyl triphenylsilyl peroxide. A radical generator such as 2, 3-dimethyl-2, 3-diphenylbutane can be used as a reaction initiator for the resin composition. Among them, 2, 5-dimethyl-2, 5-di (t-butylperoxy) hexyne-3, di (2-t-butylperoxyisopropyl) benzene and 2, 5-dimethyl-2, 5-di (t-butylperoxy) hexane are preferable from the viewpoint of providing a cured product which is excellent in heat resistance and mechanical properties and further has a low dielectric constant and dielectric loss tangent.

The organic peroxide preferably has a 1-minute half-life temperature of 155 ℃ or more and 185 ℃ or less, more preferably 160 ℃ to 180 ℃ or 165 ℃ to 175 ℃. In the present specification, the 1-minute half-life temperature is a temperature at which the decomposition of the organic peroxide takes place and the time at which the amount of active oxygen reaches half is 1 minute. The 1-minute half-life temperature is a value confirmed by a method of dissolving an organic peroxide in a solvent inactive to radicals, for example, benzene to a concentration of 0.05 to 0.1mol/L and thermally decomposing the organic peroxide solution in a nitrogen atmosphere.

When the 1-minute half-life temperature of the organic peroxide is in the range of 155 to 185 ℃, the compatibility of the organic peroxide with PPE, the coatability of the resin composition, and the characteristics of the electronic circuit board tend to be more excellent.

Examples of the organic peroxide having a 1-minute half-life temperature in the range of 155 to 185 ℃ include: t-butyl peroxyisopropyl monocarbonate (155.0 ℃), t-butyl peroxy-3, 5, 5-trimethylhexanoate (166.0 ℃), t-butyl peroxylaurate (159.4 ℃), t-butyl peroxyisopropyl monocarbonate (158.8 ℃), t-butyl peroxy 2-ethylhexyl monocarbonate (161.4 ℃), t-hexyl peroxybenzoate (160.3 ℃), 2, 5-dimethyl-2, 5-di (benzoylperoxy) hexane (158.2 ℃), t-butyl peroxyacetate (159.9 ℃), 2-di- (t-butylperoxy) butane (159.9 ℃), t-butyl peroxybenzoate (166.8 ℃), n-butyl 4, 4-di- (t-butylperoxy) valerate (172.5 ℃), di (2-t-butylperoxyisopropyl) benzene (175.4 ℃), dicumyl peroxide (175.2 ℃), di-t-hexyl peroxide (176.7 deg.C), 2, 5-dimethyl-2, 5-di (t-butylperoxy) hexane (179.8 deg.C), t-butylcumyl peroxide (173.3 deg.C), etc.

The content of the organic peroxide is preferably 0.05 parts by mass or more, more preferably 0.5 parts by mass or more or 1 part by mass or more, and even more preferably 1.5 parts by mass or more, from the viewpoint of more excellent compatibility between the organic peroxide and PPE and coatability of the resin composition, and is preferably 5 parts by mass or less, and more preferably 4.5 parts by mass or less, from the viewpoint of excellent substrate characteristics when the resin composition is mounted on an electronic circuit substrate, based on 100 parts by mass of the total of the PPE and the crosslinking agent. From the same viewpoint, the content of the organic peroxide is preferably 0.05 to 5 parts by mass, more preferably 0.5 to 4.5 parts by mass, even more preferably 1 to 4.5 parts by mass, or 1.5 to 4.5 parts by mass, based on 100 parts by mass of the total of the PPE-a and the crosslinking agent.

Thermoplastic resin

The thermoplastic resin of the present embodiment is at least 1 selected from the group consisting of a block copolymer of a vinyl aromatic compound and an olefin compound, a hydrogenated product thereof (a hydrogenated block copolymer obtained by hydrogenating a block copolymer of a vinyl aromatic compound and an olefin compound), and a homopolymer of a vinyl aromatic compound, and has a weight average molecular weight of 150,000 to 800,000. When the resin composition contains PPE, a crosslinking agent, and an organic peroxide, and contains a thermoplastic resin having the kind and weight average molecular weight described above, the compatibility of PPE with other components contained therein and the coating property to a base material and the like tend to be good, and further, the substrate characteristics when assembled into an electronic circuit substrate may be excellent. The weight average molecular weight is determined by the method described in the examples below.

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

The vinyl aromatic compound may have an aromatic ring and a vinyl group in the molecule, and examples thereof include styrene. The alkene-based olefin compound may be an olefin having a linear or branched structure in the molecule, and examples thereof include: ethylene, propylene, butylene, isobutylene, butadiene and isoprene. Of these, from the viewpoint of more excellent compatibility with polyphenylene ether, the thermoplastic resin is preferably at least 1 selected from the group consisting of a styrene-butadiene block copolymer, a styrene-ethylene-butylene block copolymer, a styrene-butadiene-butylene block copolymer, a styrene-isoprene block copolymer, a styrene-ethylene-propylene block copolymer, a styrene-isobutylene block copolymer, a hydrogenated product of a styrene-butadiene block copolymer, a hydrogenated product of a styrene-ethylene-butadiene block copolymer, a hydrogenated product of a styrene-butadiene-butylene block copolymer, a hydrogenated product of a styrene-isoprene block copolymer, and a homopolymer of styrene (polystyrene), more preferably 1 or more selected from the group consisting of a styrene-butadiene block copolymer, a hydrogenated product of a styrene-butadiene block copolymer, and polystyrene.

The hydrogenation rate in the hydrogenated product is not particularly limited, and a part of carbon-carbon unsaturated double bonds derived from the olefin compound may be optionally left.

The weight average molecular weight of the thermoplastic resin is preferably more than 150,000 and 780,000 or less, more preferably 155,000 to 750,000, and even more preferably 160,000 to 700,000, from the viewpoint of further excellence in compatibility with PPE, resin flowability, coatability of the resin composition, heat resistance during curing, and the like.

The content of the thermoplastic resin having the kind and weight average molecular weight described above is 2 to 20 parts by mass, preferably 3 to 19 parts by mass, more preferably 4 to 18 parts by mass or 5 to 17 parts by mass based on 100 parts by mass of the total of the PPE and the crosslinking agent. When the content is within the above numerical range, the resin composition of the present embodiment is more excellent in compatibility with PPE and coatability, and tends to be more excellent in substrate characteristics when mounted on an electronic circuit substrate. From the same viewpoint, the content of the thermoplastic resin is 2 to 20 parts by mass, preferably 3 to 19 parts by mass, more preferably 4 to 18 parts by mass or 5 to 17 parts by mass, based on 100 parts by mass of the total of the PPE-a and the crosslinking agent.

The resin composition of the present embodiment may contain a thermoplastic resin other than the thermoplastic resins having the types and weight average molecular weights described above.

Flame retardant

The resin composition of the present embodiment preferably contains a flame retardant. The flame retardant is not particularly limited as long as it is incompatible with other components contained in the resin composition after curing of the resin composition, from the viewpoint of improving heat resistance. Preferably, the flame retardant is incompatible with the PPE and/or the crosslinker in the resin composition after curing of the resin composition. Examples of the flame retardant include: inorganic flame retardants such as antimony trioxide, aluminum hydroxide, magnesium hydroxide, and zinc borate; aromatic bromine compounds such as hexabromobenzene, decabromodiphenylethane, 4-dibromobiphenyl, and ethylenebis (tetrabromophthalimide); and phosphorus flame retardants such as resorcinol bis (diphenyl phosphate) and resorcinol bis (dixylyl phosphate). These flame retardants may be used alone in 1 kind or in combination of 2 or more kinds. Among these, decabromodiphenylethane is preferable as the flame retardant from the viewpoint of further improving the compatibility of the flame retardant with PPE, the coatability of the resin composition, and the characteristics of the electronic circuit board.

The content of the flame retardant is not particularly limited, but is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and still more preferably 15 parts by mass or more, per 100 parts by mass of the total of the polyphenylene ether (PPE) resin and the crosslinking agent, from the viewpoint of maintaining flame retardancy at a level of 94V-0 in UL standard. 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 40 parts by mass or less, from the viewpoint of keeping the dielectric constant and the dielectric loss tangent of the resulting cured product low.

Silica filler

The resin composition of the present embodiment may contain a 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 may be 10 to 100 parts by mass with respect to 100 parts by mass of the total of the polyphenylene ether (PPE) resin and the crosslinking agent. The surface of the silica filler may be surface-treated with a silane coupling agent or the like.

The resin composition of the present embodiment may contain additives such as a heat stabilizer, an antioxidant, a UV absorber, a surfactant, and a lubricant, a solvent, and the like, in addition to the flame retardant and the silica filler. When the resin composition of the present embodiment contains a solvent, the solid content in the resin composition may be dissolved or dispersed in the solvent to form a varnish. Further, a resin film may be formed from the resin composition of the present embodiment.

Solvent(s)

The solvent is preferably an aromatic compound such as toluene or xylene, Methyl Ethyl Ketone (MEK), cyclopentanone, cyclohexanone, or chloroform, from the viewpoint of solubility. These solvents may be used alone in 1 kind or in combination of 2 or more kinds.

Prepreg

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

Examples of the base material include: various glass cloths such as roving cloth, chopped strand mat, surface mat and the like; asbestos cloth, metal fiber cloth and other synthetic or natural inorganic fiber cloth; woven or nonwoven fabrics obtained from liquid crystal fibers such as wholly aromatic polyamide fibers, wholly aromatic polyester fibers, and polybenzoxazole fibers; cotton cloth, linen cloth, felt, and other natural fiber cloth; natural cellulose base materials such as carbon fiber cloth, kraft paper, cotton paper, and cloth obtained from paper-glass hybrid yarn; polytetrafluoroethylene porous films, and the like. These substrates may be used alone in 1 kind or in combination of 2 or more kinds.

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

Metal-clad laminated board

The metal-clad laminate of the present embodiment is obtained by laminating and curing the resin composition or the resin film of the present embodiment or the prepreg of the present embodiment and the metal foil. The metal-clad laminate 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 to each other, and can be suitably used as a material for an electronic substrate. Examples of the metal foil include aluminum foil and copper foil, and among these, copper foil is preferred because of its low electrical resistance. The cured product composite combined with the metal foil may be 1 sheet or a plurality of sheets, and the metal foil is laminated on one surface or both surfaces of the composite according to the application and processed into a laminate. Examples of the method for producing the laminate include the following methods: a composite (for example, the prepreg described above) composed of a thermosetting resin composition and a substrate is formed, and after the composite is laminated with a metal foil, the thermosetting resin composition is cured to obtain a laminated sheet in which a cured product laminate and a metal foil are laminated. One of the particularly preferred uses of the aforementioned laminate is a printed circuit board. The printed circuit board preferably removes at least a portion of the metal foil from the metal clad laminate.

Printed circuit board

In the printed wiring board of the present embodiment, a part of the metal foil is removed from the metal-clad laminate. The printed wiring board of the present embodiment can be typically formed by a press-and-heat molding method using the prepreg of the present invention. Examples of the base material include those similar to those described above with respect to the prepreg. The printed wiring board of the present embodiment has excellent heat resistance and electrical characteristics (low dielectric constant and low dielectric loss tangent) by including the resin composition of the present embodiment, and further can suppress the change in electrical characteristics with environmental changes, and also has excellent insulation reliability and mechanical characteristics.

Examples

The present embodiment will be described in detail below with reference to examples, but the present embodiment is not limited to the examples.

Synthesis reaction of polyphenylene ether

The following reaction was carried out under an inert gas atmosphere. The solvent used for the reaction is a commercially available reagent. The kinds of raw materials and reagents used are as follows.

1. Solvent(s)

Toluene: the reagent special grade product manufactured by Wako pure chemical industries, Ltd.

Methyl ethyl ketone: the reagent special grade product manufactured by Wako pure chemical industries, Ltd.

Methanol: the reagent special grade product manufactured by Wako pure chemical industries, Ltd.

2. Initiator:

NYPER BMT: the product of Nippon grease was used as it is.

3. Polyphenylene ether S202A (polystyrene equivalent number average molecular weight 16,000): the product manufactured by Asahi Kasei corporation was used as it is.

S202A has the following structure.

4. Starting material phenol (polyfunctional/bifunctional phenol)

4-1. phenols having a valence of a (a-3 to 6) and comprising a partial structure of formula (2)

1,1, 3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane: the product (ADEKASTAB AO-30) was used as it was.

4-2 phenols not containing part of the structure of formula (2) and having a valence of 3

Tris (4-hydroxyphenyl) ethane: the product of Asahi organic materials company was used as it is.

5. Modified radical raw material

Methacrylic anhydride: aldrich reagent was used directly.

Dimethylaminopyridine: aldrich reagent was used directly.

Identification/analysis of polyphenylene ethers

1. Number average molecular weight measurement

The number average molecular weight was measured by GPC in a chloroform solvent. The number average molecular weight was determined by a polystyrene conversion method from a calibration curve using standard polystyrene.

NMR measurement

The sample was dissolved in deuterated chloroform to a concentration of 5% by mass, and then NMR measurement was performed. The progress of the reaction was confirmed by the decrease in the peak of hydroxyl groups from the ratio of the peak of aromatic groups of the polyfunctional phenol units to the peak of protons of hydroxyl groups.

3. Melt viscosity

A20 mass% methyl ethyl ketone solution (200 ml) of the sample was poured into a beaker, and the viscosity was measured at 25 ℃ at 30rpm using a type B rotational viscometer.

4. Average number of terminal functional groups

The average number of terminal functional groups per molecule of PPE was determined by the following method. That is, the change in absorbance at a wavelength of 318nm of a sample obtained by adding a tetramethylammonium hydroxide solution to a methylene chloride solution of PPE was measured by a UV-visible absorptiometer according to the method described in "thesis of Polymer (Japanese: Nature Co., Ltd., Polymer ), vol.51, No.7(1994), p.480". From the measured values, the number of phenolic hydroxyl groups before and after the modification of the PPE at the terminal was determined. The number average molecular weight of PPE and the mass of PPE obtained by the method 1 were used to determine the number of molecules of PPE (number average molecular number).

From these values, the average number of phenolic hydroxyl groups per 1 molecule of PPE before and after modification was determined according to the following equation (1).

Average number of phenolic hydroxyl groups per 1 molecule

Number of phenolic hydroxyl groups/number average molecular number … (1)

The average number of terminal functional groups after modification was determined according to the following formula (2).

Average number of terminal functional groups per 1 molecule

Average number of phenolic hydroxyl groups before modification-average number of phenolic hydroxyl groups after modification … (2)

Production example 1

Synthesis of polyphenylene Ether 1(PPE1)

A three-way cock was fitted to a 500ml 3-neck flask, and a serpentine condenser tube and an isobaric dropping funnel were further provided. After the flask was purged with nitrogen, 100g of polyphenylene ether S202A 100, 200g of toluene as a raw material, and 12.8g of 1,1, 3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane as a polyfunctional phenol were charged. A thermometer was placed in the flask, and the flask was heated to 90 ℃ in an oil bath with stirring by a magnetic stirrer to dissolve the polyphenylene ether as a raw material. As an initiator, 37.5g of a 40% m-xylene solution (NYPER BMT, manufactured by Nichikoku Co., Ltd.) of a mixture of benzoyl peroxide, benzoyl-m-methylbenzoyl peroxide and m-toluoyl peroxide was diluted with 87.5g of toluene, and the diluted solution was poured into an isobaric dropping funnel. After the temperature in the flask was lowered to 80 ℃, the initiator solution was added dropwise to the flask to start the reaction. The initiator was added dropwise over 2 hours, after which time the temperature was again raised to 90 ℃ and stirring was continued for 4 hours. After the reaction, the polymer solution was added dropwise to methanol to reprecipitate, and then the solution was filtered off to recover the polymer. Then, it was dried under vacuum at 100 ℃ for 3 hours. By passing¹H-NMR confirmed that low-molecular phenol was introduced into the polymer and the peak of hydroxyl group had disappeared. According to the above¹As a result of H-NMR measurement, it was confirmed that the obtained polymer was a polyphenylene ether (hereinafter referred to as PPE1) having a structure represented by the following formula.

{ wherein l, m and n are numbers arbitrarily selected so as to satisfy the following number average molecular weight }

As a result of GPC measurement, the molecular weight Mn of the obtained PPE1 was 1,500 in terms of polystyrene. In addition, the PPE1 had a solution viscosity of 125cPoise in 20% methyl ethyl ketone solvent.

Synthesis of modified polyphenylene ether 1 (Low molecular weight modified PPE1)

Toluene 80g was mixed with the synthesized PPE 126 g described above and heated to about 85 ℃. To the heated mixture was added 0.55g of dimethylaminopyridine. At the point when the solid was considered to have completely dissolved, 4.9g of methacrylic anhydride was slowly added to the dissolved matter. The resulting solution was maintained at 85 ℃ for 3 hours while continuously mixing. Subsequently, the solution was cooled to room temperature to obtain a toluene solution of methacrylate-modified polyphenylene ether.

Taking a part of the solution, drying, and performing¹H-NMR measurement. The reaction was judged to have proceeded by the disappearance of the peak derived from the hydroxyl group of the polyphenylene ether, and the operation was shifted to purification. 120g of the above-mentioned toluene solution of methacrylate-modified polyphenylene ether was added dropwise over 30 minutes to 360g of methanol vigorously stirred with a magnetic stirrer in a 1L beaker. The resulting precipitate was filtered under reduced pressure through a membrane filter and then dried to obtain 38g of a polymer. Of the dried polymer¹The results of H-NMR measurement are shown in FIG. 1. It was confirmed that the peak of hydroxyl group derived from polyphenylene ether at around 4.5ppm disappeared and the peak of alkene derived from methacryloyl group appeared at around 5.75 ppm. Further, it was judged by GC measurement that the peaks derived from dimethylaminopyridine, methacrylic anhydride and methacrylic acid were almost disappeared, and the peak derived from methacryloyl group by NMR was the peak of methacryloyl group bonded to the end of polyphenylene ether. From these results, it was confirmed that the obtained polymer was a modified polyphenylene ether (hereinafter referred to as low molecular weight modified PPE1) having a structure represented by the following formula.

Further, as a result of GPC measurement, the molecular weight Mn of the obtained low molecular weight modified PPE1 in terms of polystyrene was 1,600. The average number of terminal functional groups of the low molecular weight modified PPE1 was calculated to be 2.5 or more according to the above equation (2). Further, the solution viscosity of the modified PPE1 in 20% methyl ethyl ketone solvent was 131 cPoise.

Material for forming resin composition and cured product thereof

PPE

Low molecular weight modified polyphenylene ether 1 (Low molecular weight modified PPE1) obtained as described above

Crosslinking agent

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

Organic peroxides

Bis (1-tert-butylperoxy-1-methylethyl) benzene

"product name: PERBUTYL P (manufactured by Nichio oil Co., Ltd.)

Thermoplastic resin

SEBS N525: product name "TUFTEC N525", manufactured by asahi chemicals corporation, Mw: 20 ten thousand, styrene unit content: 67% by mass

SEBS N504: product name "TUFTEC N504", manufactured by asahi chemicals corporation, Mw: 20 ten thousand, styrene unit content: 32% by mass

SEBS N516: product name "TUFTEC N516", manufactured by Asahi Kasei corporation, Mw: 16 ten thousand, styrene unit content: 40% by mass

SEBS N517: product name "TUFTEC N517", manufactured by asahi chemicals corporation, Mw: 40 ten thousand, styrene unit content: 40% by mass

SEBS H1041: product name "TUFTEC H1041", manufactured by asahi chemicals corporation, Mw: 5.7 ten thousand, styrene unit content: 31 mass%

SEBS H1221: product name "TUFTEC H1221", manufactured by asahi chemicals corporation, Mw: 12 ten thousand, styrene unit content: 12% by mass

Flame retardant

Decabromodiphenylethane "product name SAYTEX 8010" (manufactured by ALBEMARLE corporation)

Filler

Spherical silica (manufactured by Longsen Co., Ltd.)

Base material

L glass cloth

(model 2116 manufactured by Asahi-Schwebel Co., Ltd.)

Evaluation method

Number average molecular weight of PPE, weight average molecular weight of thermoplastic resin

The number average molecular weight of PPE and the weight average molecular weight of the thermoplastic resin were determined by GPC analysis and by comparison with the elution time of standard polystyrene having a known molecular weight. Specifically, after preparing a measurement sample having a sample concentration of 0.2 w/vol% (solvent: chloroform), the measurement apparatus used was HLC-8220GPC (manufactured by Tosoh Corp.) and the column was: shodex GPCKF-405 LHQ.times.3 (manufactured by Showa Denko K.K.), eluent: chloroform, injection amount: 20 μ L, flow rate: 0.3 mL/min, column temperature: 40 ℃, detector: RI was measured under the conditions described above.

2. Viscosity of varnish

A resin varnish (solid content: 53% by mass) prepared from each resin composition and toluene was poured into a beaker in an amount of 200ml, and the viscosity was measured at 25 ℃ for 30 seconds at a rotation speed of 30rpm using a type B rotational viscometer. The measured viscosity was evaluated in 5 grades.

5: more than 50 mPas and not more than 150 mPas

4: more than 150 mPas and not more than 200 mPas

3: more than 200 mPas and less than 300 mPas

2: more than 300 mPas and not more than 500 mPas

1: more than 500 mPas and not more than 1000 mPas

3. Impregnation property

A resin varnish (solid content: 53 mass%) prepared from each resin composition and toluene was poured into a pot, and an L-shaped glass cloth (Asahi-Schwebel Co., Ltd., model 2116) cut into a 50mm square was placed thereon, and the impregnation of the glass cloth with the resin varnish was visually observed. The impregnation of the resin varnish into the glass cloth was evaluated on a 5-point scale.

5: the resin varnish was impregnated into the entire glass cloth within 1 minute

4: the resin varnish was impregnated into the entire glass cloth within 2 minutes

3: the resin varnish was impregnated into the entire glass cloth within 3 minutes

2: the resin varnish impregnated into the entire glass cloth within 5 minutes

1: after 5 minutes, the impregnation was not completed

4. Dispersibility

The components shown in table 1 and the solvent were mixed and stirred, and the state of the mixture after the stirring was stopped was visually observed, and evaluated according to the following criteria.

Good: the good stirring is stopped, and the insoluble substance is uniformly dispersed without sedimentation for more than 2 hr.

X: the insoluble substance is precipitated within 1hr after the poor stirring is stopped.

5. Dielectric constant and dielectric loss tangent (electrical characteristics) of the laminate

The dielectric constant and dielectric loss tangent of the laminate were measured at 10GHz by the cavity resonance method. As the measuring apparatus, measurement was performed using a network analyzer (N5230A, manufactured by Agilent Technologies, inc.) and a Cavity resonator (Cavity resonator CP series) manufactured by kanto electronic application development corporation. A laminated sheet having a thickness of about 0.5mm prepared by a method described later was cut into a size of about 2mm in width and 50mm in length with the warp of the glass cloth as a long side. Then, the mixture was dried in an oven at 105. + -. 2 ℃ for 2 hours and then allowed to stand at 23 ℃ under a relative humidity of 50. + -. 5% for 96. + -.5 hours. Then, the dielectric constant and the dielectric loss tangent were measured by using the above-mentioned measuring apparatus under an environment of 23 ℃ and a relative humidity of 50. + -. 5%, and evaluated on a scale of 5.

5: a dielectric constant of 3.0 to 3.3 inclusive, and a dielectric loss tangent of more than 0.0020 to 0.0024 inclusive

4: a dielectric constant of 3.0 to 3.3 inclusive, and a dielectric loss tangent of more than 0.0024 to 0.0026 inclusive

3: a dielectric constant of 3.0 to 3.3 inclusive, and a dielectric loss tangent of more than 0.0026 to 0.0030 inclusive

2: a dielectric constant of 3.0 to 3.3 inclusive, and a dielectric loss tangent of more than 0.0030 to 0.0035 inclusive

1: a dielectric constant of more than 3.3 and a dielectric loss tangent of more than 0.0035

6. Glass transition temperature (Tg) of the laminate

The dynamic viscoelasticity of the laminate was measured, and the temperature at which tan reached the maximum was determined as the glass transition temperature (Tg). The measurement apparatus used was a dynamic viscoelasticity apparatus (RHEOVIBRON model DDV-01FP, ORIENTEC Co., Ltd.). A laminated sheet having a thickness of about 0.3mm, which was produced by the method described below, was cut into a length of about 35mm and a width of about 5mm with the warp of the glass cloth as a long side to prepare a test piece, and the length and the frequency were measured in the following manner: the measurement was performed under the condition of 10 rad/s.

Evaluation was performed on 5 grades based on the value of Tg.

5: above 200 deg.C

4: over 190 ℃ and below 200 ℃

3: over 180 ℃ and below 190 ℃

2: over 170 ℃ and below 180 DEG C

1: over 160 ℃ and below 170 DEG C

7. Heat resistance of laminated sheet

A laminated plate prepared by stacking 8 prepregs obtained in examples and comparative examples and using a method described later was cut into a 50mm square, and then the cut sample was dried in an oven at 105 ℃ ± 2 ℃ for 2 hours, followed by performing a pressure cooker test under conditions of 2 atmospheres and 4 hours. Heat resistance test the laminated sheet after the water absorption acceleration test was visually evaluated according to the following criteria.

Good: when the laminate after the water absorption acceleration test was well immersed in a solder bath at 288 ℃ for 20 seconds, neither expansion nor peeling nor whitening was observed.

X: failure when the laminated plate after the water absorption acceleration test was immersed in a solder bath at 288 ℃ for 20 seconds, any of swelling, peeling, and whitening was observed.

8. Copper foil peel strength (peel strength N/mm) of laminate

The stress at the time of peeling the copper foil of the copper-clad laminate at a constant speed was measured. The copper-clad laminate using a 35 μm thick copper foil (GTS-MP foil, manufactured by guchuan electrical industries, ltd.) produced by the method described later was cut into a size of 15mm in width × 150mm in length, and the average value of the load when the copper foil was peeled at an angle of 90 ℃ to the removal surface at a speed of 50 mm/min was measured using Autograph (AG-5000D, manufactured by shimadzu corporation), and the average value of 5 measurements was determined and evaluated on 5-grade basis.

5: more than 1.0N/mm

4: more than 0.80N/mm and not more than 1.0N/mm

3: more than 0.70N/mm and not more than 0.80N/mm

2: more than 0.5N/mm and not more than 0.70N/mm

1: is less than 0.5N/mm

Example 1

According to the composition shown in table 1, a thermoplastic resin was added to toluene 287 parts by mass and dissolved by stirring, and then a flame retardant, spherical silica and low molecular weight modified PPE1 were added, respectively, and stirring was continued until low molecular weight modified PPE1 was dissolved (solid content concentration 53 mass%). Subsequently, the crosslinking agent and the organic peroxide are added to the dissolved matter, respectively, and sufficiently stirred to obtain a varnish. After the varnish was impregnated with L-glass cloth, excess varnish was scraped off by passing it through a predetermined slit, and dried in a drying oven at 105 ℃ for a predetermined time to remove toluene, thereby obtaining a prepreg. The prepreg was cut into a predetermined size, and the solid content of the resin composition in the prepreg was calculated by comparing the weight of the prepreg with the weight of a glass cloth having the same size, and found to be 58% by mass. The prepregs were laminated in a predetermined number, and copper foils (GTS-MP foils having a thickness of 35 μm, manufactured by guchuan electrical industries, inc.) were further laminated on both sides of the laminated prepregs, and vacuum-pressed in this state, thereby obtaining a copper-clad laminate. In the vacuum press step, first, the press was heated from room temperature at a temperature rise rate of 3 ℃ per minute with a pressure of 10kg/cm²Conditions of (1) thenAfter reaching 130 ℃, the mixture was heated at a temperature rise rate of 3 ℃/min while using a pressure of 40kg/cm²The conditions of (1). After the temperature reached 200 ℃, the pressure was 40kg/cm while maintaining the temperature at 200 ℃²And time 60 minutes. Next, the copper foil is removed from the copper-clad laminate by etching, thereby obtaining a laminate.

Examples 2 to 6 and comparative examples 1 to 4

Resin compositions, varnishes, prepregs, copper-clad laminates, and laminates were obtained in examples 2 to 6 and comparative examples 1 to 4, respectively, and evaluated in the same manner as in example 1, except that the compositions were changed as shown in table 1.

[ Table 1]

Claims

1. A resin composition comprising:

(b) a crosslinking agent;

(c) an organic peroxide; and

(d) a thermoplastic resin having a weight average molecular weight of 150,000 to 800,000, which is at least 1 selected from the group consisting of a block copolymer of a vinyl aromatic compound and an alkenyl olefin compound, a hydrogenated product thereof, and a homopolymer of the vinyl aromatic compound,

and the content of the thermoplastic resin is 2 to 20 parts by mass based on 100 parts by mass of the total of the polyphenylene ether component A and the crosslinking agent,

formula (1)

In the formula (1), the reaction mixture is,

x is an optional linking group of valency a, a is a number of 2.5 or more,

l is any divalent linking group or single bond, and

formula (2)

In the formula (2), R¹¹Each independently is C_1-8Alkyl of R¹²Each independently is C_1-8B is each independently 0 or 1, R¹³Represents a hydrogen atom, C_1-8And the alkyl, alkylene and phenyl group satisfy C_1-8Optionally having a substituent within the range of the condition(s),

formula (3)

In the formula (3), R²¹Each independently is C_1-6A saturated or unsaturated hydrocarbon group of R²²Each independently is a hydrogen atom or C_1-6And the saturated or unsaturated hydrocarbon group satisfies C_1-6Optionally having a substituent within the range of the conditions of (1).

2. The resin composition according to claim 1, wherein a content of the unit derived from the vinyl aromatic compound in the block copolymer or hydrogenated product thereof is 20 mass% or more and 70 mass% or less.

3. The resin composition according to claim 1 or 2, wherein the crosslinking agent has an average of 2 or more carbon-carbon unsaturated double bonds in 1 molecule, the number average molecular weight of the crosslinking agent is 4,000 or less, and the weight ratio of the polyphenylene ether component A to the crosslinking agent is 25:75 to 95: 5.

4. The resin composition according to any one of claims 1 to 3, wherein the crosslinking agent comprises at least one compound selected from the group consisting of triallyl cyanurate, triallyl isocyanurate, and polybutadiene.

5. The resin composition according to any one of claims 1 to 4, wherein the organic peroxide has a 1-minute half-life temperature of 155 ℃ to 185 ℃.

6. The resin composition according to any one of claims 1 to 5, wherein the content of the organic peroxide is 0.05 to 5 parts by mass based on 100 parts by mass of the total of the polyphenylene ether component A and the crosslinking agent.

7. The resin composition according to any one of claims 1 to 6, wherein the resin composition further comprises a flame retardant, and the flame retardant is not compatible with other contained components in the resin composition after the resin composition is cured.

8. An electronic circuit substrate material comprising the resin composition according to any one of claims 1 to 7.

9. A resin film comprising the resin composition according to any one of claims 1 to 7.

10. A prepreg which is a composite of a substrate and the resin composition according to any one of claims 1 to 7.

11. The prepreg of claim 10, wherein the substrate is a glass cloth.

12. A laminate comprising a metal foil and the resin film according to claim 9 or the cured product of the prepreg according to claim 10 or 11.