CN111574817A

CN111574817A - Polyphenylene ether-containing resin composition

Info

Publication number: CN111574817A
Application number: CN202010096840.8A
Authority: CN
Inventors: 远藤正朗; 杉村昌治; 长田一人
Original assignee: Asahi Kasei Corp
Current assignee: Asahi Kasei Corp; Asahi Chemical Industry Co Ltd
Priority date: 2019-02-15
Filing date: 2020-02-17
Publication date: 2020-08-25
Also published as: TWI724783B; JP2020132716A; TW202035563A

Abstract

The present invention addresses the problem of providing a polyphenylene ether-containing resin composition that can provide a cured product that can achieve improved electrical properties, improved peel properties, and improved malleability. The solution is a resin composition comprising polyphenylene ether, a crosslinking agent and an organic peroxide, wherein the polyphenylene ether comprises: a polyphenylene ether component A having 1.5 to 5 functional groups containing carbon-carbon double bonds per 1 molecule on average and a number average molecular weight of 500 to 8,000 at the end of the main chain; and a polyphenylene ether component B having an average number of phenolic hydroxyl groups per 1 molecule of 1.2 or more and a number average molecular weight of more than 8,000.

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 PPE-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 PPE to a specific range, or by specifying the contents of a plurality of PPEs having different molecular weights.

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 cured product of a resin composition containing PPE is required to have improved strength against stress, deformation, and the like (improved toughness) in addition to excellent electrical characteristics and excellent peel strength. On the other hand, in patent document 1, there is room for study in order to satisfy all of these requirements.

Accordingly, the present invention provides a PPE-containing resin composition that can provide a cured product having improved electrical characteristics, improved peel strength, and improved toughness.

Further, the present invention has an object to provide an electronic circuit board material, a resin film, a prepreg and a laminate formed using such a PPE-containing resin composition.

Means for solving the problems

The present inventors have conducted extensive studies to solve the above problems, and as a result, have found that the above problems can be solved by using a resin composition comprising a PPE, a crosslinking agent and an organic peroxide in combination with a PPE component a (PPE-a) having a relatively low molecular weight and a specific structure and a PPE component B (PPE-B) having a relatively high molecular weight and another specific structure, respectively, and have completed the present invention. Namely, the present invention is as follows.

[1]

A resin composition comprising polyphenylene ether, a crosslinking agent and an organic peroxide,

the polyphenylene ether comprises:

a polyphenylene ether component A having 1.5 to 5 functional groups containing carbon-carbon double bonds per 1 molecule on average and a number average molecular weight of 500 to 8,000 at the end of the main chain;

the polyphenylene ether component B has an average number of phenolic hydroxyl groups of 1 molecule of 1.2 or more and a number average molecular weight of more than 8,000.

[2]

The resin composition according to [1], wherein the functional group at the end of the main chain of the polyphenylene ether component A comprises a structure represented by the following formula (1):

(wherein n represents an integer of 0 or 1, and R¹Is C_1～8And R is alkylene or alkenylene, and²is a hydrogen atom or C_1～8Alkylene or alkenylene groups of (ii).

[3]

The resin composition according to [1] or [2], wherein the polyphenylene ether component A contains a structure represented by the following formula (2-1):

{ in the formula (I) { wherein,

x is an optional linking group having a valence, a is a number of 2.0 or more;

R⁵each independently represents an arbitrary substituent, k is each independently an integer of 1 to 4, and k R' s⁵At least 1 of them comprises a partial structure represented by the following formula (2-2):

(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_1-8Any of the alkyl group or phenyl group of (2), and the aforementioned alkyl group, alkylene group and phenyl group satisfy C_1-8May contain a substituent within the range of the condition(s);

each Y is independently a 2-valent linking group having a structure represented by the following formula (2-3), n represents the number of repetitions of Y, and each is independently an integer of 1 to 200:

(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_1-6May have a substituent within the range of the condition(s);

l is any 2-valent connecting group or single bond; and is

Each A independently represents a substituent having a carbon-carbon double bond and/or an epoxy bond }.

[4]

The resin composition according to any one of [1] to [3], wherein the polyphenylene ether component B has a number average molecular weight of 50,000 or less.

[5]

The resin composition according to any one of [1] to [4], further comprising an isocyanate compound.

[6]

The resin composition according to any one of [1] to [5], wherein the crosslinking agent contains at least 1 selected from the group consisting of triallyl cyanurate, triallyl isocyanurate, and polybutadiene.

[7]

The resin composition according to any one of [1] to [6], 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 polyphenylene ether: the weight ratio of the crosslinking agent is 25: 75-95: 5.

[8]

the resin composition according to any one of [1] to [7], wherein the organic peroxide has a 1-minute half-life temperature of 155 ℃ to 185 ℃ inclusive,

the content of the organic peroxide is 0.05 to 0.9 mass% based on 100 mass% of the total mass of the polyphenylene ether and the crosslinking agent.

[9]

The resin composition according to any one of [1] to [8], further comprising a thermoplastic resin,

the thermoplastic resin 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, and a homopolymer of a vinyl aromatic compound,

the content of the unit derived from the vinyl aromatic compound in the block copolymer or the hydrogenated product thereof is 20% by mass or more.

[10]

The resin composition according to item [9], wherein the thermoplastic resin has a weight average molecular weight of 10,000 to 300,000.

[11]

The resin composition according to [9] or [10], wherein the polyphenylene ether and the crosslinking agent are added to the resin composition in an amount of 100% by mass in total,

the content of the thermoplastic resin is 2 to 20 mass%.

[12]

The resin composition according to any one of [1] to [11], further comprising a flame retardant, wherein the flame retardant is incompatible with other components contained in the resin composition after the resin composition is cured.

[13]

An electronic circuit board material comprising the resin composition according to any one of [1] to [12 ].

[14]

A resin film comprising the resin composition according to any one of [1] to [12 ].

[15]

A prepreg which is a composite of a substrate and the resin composition according to any one of [1] to [12 ].

[16]

The prepreg according to [15], wherein the aforementioned substrate is a glass cloth.

[17]

[14] The resin film or the laminate of the cured product of the prepreg according to [15] or [16] and a metal foil.

ADVANTAGEOUS EFFECTS OF INVENTION

According to the present invention, a PPE resin composition can be provided that can provide a cured product that can achieve improved electrical characteristics, improved peel strength, and improved toughness.

Further, according to the present invention, an electronic circuit substrate material, a resin film, a prepreg, and a laminate formed using such a PPE resin composition can be provided.

Drawings

FIG. 1 is a drawing showing a modified polyphenylene ether 1 (modified PPE1) obtained in example 1¹H-NMR measurement results.

Detailed Description

Hereinafter, a specific embodiment of the present invention (hereinafter, simply referred to as "the present embodiment") will be described. The following embodiments are one aspect of the present invention, and therefore the present invention is not limited to the following embodiments. Therefore, the following embodiments can be implemented by being appropriately modified within the scope of the gist of the present invention. In addition, "to" in this specification means that the numerical values at both ends thereof are included as the upper limit value and the lower limit value unless otherwise specified.

[ resin composition ]

The PPE-containing resin composition of the present embodiment (hereinafter also simply referred to as "resin composition") contains PPE, a crosslinking agent, and an organic peroxide. And, the PPE comprises: a PPE-A having 1.5 to 5 functional groups containing a carbon-carbon double bond per 1 molecule on average and a number average molecular weight (Mn) of 500 to 8,000, and a PPE-B having 1.2 or more phenolic hydroxyl groups per 1 molecule on average and a number average molecular weight (Mn) of more than 8,000.

That is, the present embodiment was made focusing on the use of a combination of PPE-A having a specific structure and a PPE-B having a specific structure and a relatively high molecular weight. According to the present embodiment, a resin composition capable of obtaining a cured product having improved electrical characteristics, improved peel strength, and improved toughness can be provided.

The number average molecular weight of PPE was determined as follows: the molecular weight of a standard polystyrene sample was measured by Gel Permeation Chromatography (GPC) and the molecular weight was calculated in terms of standard polystyrene from the relationship between the molecular weight and the elution time of the standard polystyrene sample measured under the same conditions. For example, with respect to PPE-A and PPE-B, the specific methods for calculating the number average molecular weights of the respective PPE-A and PPE-B can be referred to the methods described in examples.

The resin composition may contain, in addition to the PPE (a), the crosslinking agent (b), and the organic peroxide (c), a thermoplastic resin (d), an isocyanate compound (e), a flame retardant (f), a silica filler (g), a solvent (h), and the like, as desired. Hereinafter, elements that can constitute the resin composition will be described.

[(a)PPE]

The PPE contains a phenylene ether unit as a repeating structural unit. The phenylene group in the phenylene ether unit may or may not have a substituent. In this specification, the term "polyphenylene ether" includes dimers, trimers, oligomers and polymers.

The PPE may contain other structural units in addition to the phenylene ether units. The amount of the other structural units is typically 30% or less, 25% or less, 20% or less, 15% or less, 10% or less, or 5% or less with respect to the number of the whole unit structure. However, the amount of the other structural units may exceed 30% with respect to the number of the entire unit structures within a range not to impair the effects of the present invention.

The PPE preferably contains a repeating structural unit represented by the following formula (2-3):

{ formula (II) wherein R²¹And R²²Each independently represents a hydrogen atom, a halogen atom (e.g., a fluorine atom, a chlorine atom and a bromine atom), an alkyl group which may have a substituent (e.g., C such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl and tert-butyl_1～6The linear or branched alkyl group of (1); c of cyclohexyl or the like_6～10Cyclic alkyl group of (2), alkoxy group which may have a substituent (e.g., methoxy group)C such as alkyl, ethoxy and butoxy_1～6Alkoxy group of (b), an aryl group which may have a substituent (e.g., phenyl group and naphthyl group), an amino group which may have a substituent, a nitro group which may have a substituent, or a carboxyl group which may have a substituent. }.

More specifically, 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_1-6May contain a substituent within the range of the condition(s).

Specific examples of PPE include 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), a copolymer of 2, 6-dimethylphenol and another phenol (e.g., 2,3, 6-trimethylphenol, 2-methyl-6-butylphenol, etc.), a PPE copolymer obtained by coupling 2, 6-dimethylphenol with a biphenol or a bisphenol, and a polyphenylene ether obtained by heating poly (2, 6-dimethyl-1, 4-phenylene ether) or the like in a toluene solvent in the presence of a bisphenol such as a bisphenol or a trisphenol compound and an organic peroxide to effect redistribution reaction The obtained PPE has a linear structure or a branched structure.

[PPE-A]

The PPE-A is a PPE having 1.5 to 5 functional groups containing a carbon-carbon double bond at the end of the main chain on average per 1 molecule and having a number average molecular weight of 500 to 8,000.

Among them, the number (average value) of terminal functional groups in 1 molecule of PPE-A is 1.5 to 5 from the viewpoint of exhibiting the effects of the present invention. Further, if the number of the terminal functional groups is 1.5 or more, sufficient heat resistance can be imparted to the resin composition when it is cured, and if the number of the terminal functional groups is 5 or less, sufficient resin fluidity can be imparted to the resin composition when it is heat molded. Therefore, the number of terminal functional groups in 1 molecule of PPE-A is more preferably 1.7 to 4.

The "number of terminal functional groups" referred to in the present specification is a numerical value representing an average value of functional groups per 1 molecule of the total PPE present in 1 mole of PPE. The number of terminal functional groups can be determined, for example, by measuring the number of remaining hydroxyl groups in the obtained PPE and calculating the number of hydroxyl groups that are decreased from the number of hydroxyl groups in the PPE before modification. The number of hydroxyl groups reduced from the number of hydroxyl groups of the PPE before modification is the number of terminal functional groups. The number of hydroxyl groups of PPE before and after modification was determined by adding a quaternary ammonium salt (tetraethylammonium hydroxide) associated with hydroxyl groups to a solution of PPE and measuring the UV absorbance of the mixed solution. Specific methods for calculating the number of terminal functional groups can be referred to the methods described in examples described later.

Here, from the viewpoint of more easily ensuring high heat resistance after curing the resin composition, the functional group at the end of the main chain of PPE-a (hereinafter also referred to as "end functional group") preferably has a structure represented by the following formula (1):

(wherein n represents an integer of 0 or 1, and R¹Is C_1～8Alkylene or alkenylene of, R²Is a hydrogen atom or C_1～8Alkylene or alkenylene groups of (ii).

Among them, the terminal functional group is more preferably a methacryl group and/or an acryl group from the viewpoint that the resin fluidity at the time of heat molding is more excellent.

However, the terminal functional group is not limited to the above examples. The terminal functional group may be a functional group other than a methacryl group or an acryl group, for example, a functional group such as a benzyl group, an allyl group, a propynyl group, a glycidyl group, an epoxy group, and a vinylphenyl group, within a range not to impair the effects of the present invention.

In addition, the PPE-A has a number average molecular weight of 500 to 8,000 or less from the viewpoint of exhibiting the effects of the present invention. By including PPE-A in such a low molecular range, reduction in dielectric constant and dielectric loss tangent can be achieved in the cured form of the resin composition.

The number average molecular weight of PPE-A is preferably 800 or more, more preferably 1,200 or more, and still more preferably 1,400 or more, from the viewpoint of achieving a reduction in dielectric constant and dielectric loss tangent, and further from the viewpoint of fluidity, compatibility with other components, and the like. From the same viewpoint, the number average molecular weight of PPE-A is preferably 7,000 or less, more preferably 6,000 or less, and still more preferably 5,000 or less.

From the same viewpoint, the molecular weight distribution of PPE-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.

Hereinafter, a particularly preferred example of the PPE component A will be described.

The PPE component A preferably has a structure represented by the following formula (2-1):

in the formula (2-1), X is an optional linking group having a valence, and a is a number of 2.0 or more, preferably a number of 2.5 or more, more preferably an integer of 3 or more, and further preferably an integer of 3 to 6. Specific examples of X include: a hydrocarbyl 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.

Furthermore, R⁵Is an optional substituent, k is an integer of 1 to 4, and when k is 2 or more, 2R' s⁵Can be linked to form a ring, k R⁵At least 1 of them comprises a partial structure represented by the following formula (2-2):

in the formula (2-2), R¹¹Each independently is C_1-8Alkyl radical, R¹²Each independently is C_1-8Alkylene, b is independently 0 or 1, R¹³Represents a hydrogen atom, C_1-8Any of alkyl or phenyl, these alkyl, alkylene and phenyl satisfying C_1-8May contain a substituent within the range of the condition(s).

Formula (2-2)The partial structure shown 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 (2-2) is preferably the same as R in the formula (2-1)⁵The bonded benzene rings are directly bonded. Furthermore, the partial structure represented by the formula (2-2) is preferably bonded to R in the formula (2-1)⁵The 2-and/or 6-position (ortho-position with respect to-O-) of the bonded benzene ring.

Regarding the following portions in the structure represented by the formula (2-1):

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-butyl-1, 2, 3-benzenetriol, 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 (2-1) is independently a 2-valent linking group (substituted phenol unit) comprising the structure represented by formula (3):

in the formula (2-1), n represents the number of repetitions of Y, and each n is independently an integer of 0 to 200.

In the formula (2-3), 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 (2-1) is a substituent containing a carbon-carbon double bond and/or an epoxy bond. Specific examples of A are represented by the above formula (1), more specifically, by the following formulae (2-4) to (2-8):

in the formulae (2-4) to (2-8), 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 (1) 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, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1-dimethylbutylene, 2-dimethylbutylene, 3-dimethylbutyl, 1, 2-dimethylbutyl, 1, 3-dimethylbutylA phenyl group, a 2, 3-dimethylbutyl group, an 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, a 2-ethylpentyl group, a 3-ethylpentyl group, a 1, 1-dimethylpentyl group, a 2, 2-dimethylpentyl group, a 3, 3-dimethylpentyl group, a 4, 4-dimethylpentyl group, a 1, 2-dimethylpentyl group, a 1, 3-dimethylpentyl group, a 1, 4-dimethylpentyl group, a 2, 3-dimethylpentyl group, a 2, 4-dimethylpentyl group, a 3, 4-dimethylpentyl group, a 2-methyl-3, 3-dimethylbutyl group, a 1-methyl-3, 3, 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, 2-methylcyclopentylmethyl, 2-cyclopentylethyl, 1-cyclopentylethyl, 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, 1-dimethylhexyl, 2-methylcyclohexyl, 2-methylcyclopentyl, 2-cyclopentylethyl, 1-cyclohexylmethyl, 3-octyl, 4-octyl, 2,2, 2-dimethylhexyl, 3-dimethylhexyl, 4-dimethylhexyl, 5-dimethylhexyl, 1, 2-dimethylhexyl, 1, 3-dimethylhexyl, 1, 4-dimethylhexyl, 1, 5-dimethylhexyl, 2, 3-dimethylhexyl, 2, 4-dimethylhexyl, 2, 5-dimethylhexyl, 1-ethylmethylpentyl, 2-ethylmethylpentyl, 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-dimethylhexyl, 1, 5-dimethylhexyl, 2, 1, 2-dimethylhexyl, 1, 3-ethyl-1-methylpentyl, 2, 3-ethyl-1-, 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, 1- (2-methylpropyl) -2-methylbutyl, 1- (2-methylpropyl) ethyl, 1- (2-methylpropyl) ethylpropyl, 1-diethylpropyl, 2-diethylpropyl, 1-ethylmethyl-2, 2-dimethylpropyl, methyl-ethyl-2-methyl-ethyl-propyl, methyl-ethyl-4-methylpentyl, methyl-ethyl-1-methylpropyl, methyl-ethyl-2-propyl, 2, 2-ethylmethyl-1, 1-dimethylpropyl, 2-ethyl-1, 1-dimethylbutyl, 2, 3-dimethylcyclohexyl, 2, 5-dimethylcyclohexyl, 2, 6-dimethylcyclohexyl, 3, 5-dimethylcyclohexyl, 2-methylcyclohexylCyclohexylmethyl 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 and the like.

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-octyl, 3-octyl, 4-octyl, 2-methylheptyl, 3-methylheptyl, 4-methylheptyl, 5-methylheptyl, 6-methylheptyl, 2-ethylhexyl, 3-ethylhexyl, 4-ethylhexyl, 5-ethylhexyl, 2-ethylhexyl, 3-ethylhexyl, 2-ethylhexyl, 5-ethylhexyl, benzyl and the like being more preferred, NoneAlkyl, isononyl, decyl, isodecyl, undecyl, dodecyl, benzyl, and the like.

As R³²Specific examples of the hydrocarbon group of (1) 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 (1) 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-cyclopentylene, 3-ethyl-1, 3-cyclopentylene, 2, 3-dimethyl-1, 3-cyclopentylene, 2, 4-dimethyl-1, 3-cyclopentylene, 2-methyl-1, 3-cyclopentylmethylenemethylene2-cyclopentylethylene, 1-cyclopentylethylene, octamethylene, 1-methyl-1, 7-heptylene, 1-ethyl-1, 6-hexylene, 1-propyl-1, 5-pentylene, 2-methyl-1, 7-heptylene, 3-methyl-1, 7-heptylene, 4-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, 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, 4-ethyl-3-methyl-1, 5-pentylene, and the like.

Further, as R³²Specific examples of the hydrocarbon group of (1) 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-cyclohexylene4-ethyl-1, 4-cyclohexylene, 2-cyclohexylethylene, 1-cyclohexyl-2-ethylene, nonylmethylene, 1-methyl-1, 8-octylene, decylmethylene, 1-methyl-1, 8-nonylene, undecylmethylene, dodecylmethylene, 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-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-methyl1, 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, with methylene, 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, 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 (2-1) 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, methacryl, acryloyl, 2-ethylacryloyl, 2-hydroxymethylacryloyl, and the like.

L in the formula (2-1) is an arbitrary linking group having a valence of 2 or a single bond (direct bond). When L is a single bond, the formula (2-1) is represented by the following formula.

In addition, in the case where L is an arbitrary linking group having a valence of 2, specific examples of L have, for example, a structure represented by the following formula:

{ in the formula, a, R⁵K, X, Y and n are as defined in the description of formula (2-1).

The structure represented by the formula (2-1) may have various branched structures depending on the value of the valence a of X. For example, when a is 3 in the formula (2-1), a branched structure represented by the following formula may be mentioned:

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

Specific examples of the structure represented by the formula (2-1) include the following structures.

In the above formula, Z is an arbitrary linking group corresponding to X in the formula (2-1). R¹Is a substituent represented by the formula (2-2), and b is an integer of 1 to 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 C_1～8The hydrocarbon group having a chain or ring structure of (1). 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, for example: methyl, ethyl, n-propyl, n-butyl, n-pentyl, cyclopentyl, n-hexyl, cycloHexyl group, n-heptyl group, n-octyl group, phenyl group, benzyl group, 2-ethylhexyl group and the like, and from the viewpoint of reactivity at the time of synthesis and the like, hydrogen, methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, cyclopentyl group, n-hexyl group, cyclohexyl group, n-heptyl group and n-octyl group are preferable. 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 of Z include the structures represented 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. 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. 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, specific examples of the hydrocarbon group containing one or more elements selected from the group consisting of nitrogen, phosphorus, silicon, and oxygen are 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 Z include elements such as nitrogen, phosphorus, and silicon, and groups containing these elements.

In the above specific example, the structure of a is embodied as the following formula in the first example. 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 number average molecular weight of PPE-A described above is 500 to 8,000 in terms of polystyrene equivalent molecular weight using GPC as described above.

The modified PPE having the structure of formula (2-1) according to the present embodiment can be produced, for example, by preparing PPE by a redistribution reaction method using a higher molecular PPE polymer and introducing a (for example, a terminal functional group including the structure represented by formula (1)) into the terminal thereof. When PPE 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 reduced to be lower than that of PPE as a raw material, the ratio of the raw material PPE 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 (2-1), for example, the functional groups represented by the formulae (2-4) to (2-7), into the ends of the obtained PPE 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 (2-4), (2-6) or (2-7) can be introduced into the reaction system according to an ether bond produced by Williamson synthesis. The functional group having the structure of formula (2-5) is introduced by an ester bond formation reaction between a hydroxyl group at the end of the PPE polymer and a carboxylic acid having a carbon-carbon double bond (hereinafter referred to as carboxylic acid), and a known ester bond formation method can be used.

Since PPE-a has high curing reactivity and low dielectric properties, as well as good fluidity, moldability, and heat resistance, PPE-a 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 (e.g., printed circuit board substrates).

In the resin composition, the prescribed PPE-A may be used alone or a plurality of different PPE-As may be used in combination.

[PPE-B]

PPE-B is a PPE in which the average number of phenolic hydroxyl groups per 1 molecule is 1.2 or more and the number average molecular weight exceeds 8,000.

Among them, the PPE has a number average molecular weight of more than 8,000 from the viewpoint of exerting the effect of the present invention. By including PPE-B in such a high molecular weight range, the toughness can be improved in the cured form of the resin composition. Further, since PPE-B is stable in the production process and excellent in dielectric properties and heat resistance, it tends to improve electrical characteristics of a cured product of the resin composition without hindering PPE-A.

The number average molecular weight of PPE-B is preferably 8,500 or more, more preferably 8,700 or more, and still more preferably 9,000 or more, from the viewpoint of more easily improving the toughness of the resin composition in the cured form. From the same viewpoint, the number average molecular weight of PPE-B is preferably 50,000 or less, more preferably 40,000 or less, and still more preferably 30,000 or less.

The PPE-B may be any PPE as long as it is different from PPE-A and satisfies the condition that the average number of phenolic hydroxyl groups per 1 molecule is 1.2 or more and the number average molecular weight exceeds 8,000.

Of course, if the average number of phenolic hydroxyl groups per 1 molecule in PPE-B is 1.2 or more, the main chain end of PPE-B is not limited to a hydroxyl group, and may contain a terminal functional group other than a hydroxyl group. Specific examples of the terminal functional group are as described above.

In PPE-B, the average number of phenolic hydroxyl groups per 1 molecule is 1.2 or more and the number average molecular weight exceeds 8,000, whereby the adhesiveness between the PPE resin layer and the substrate (various glass cloths and the like) and the adhesiveness between the PPE resin layer and the metal foil (copper foil and the like) can be improved, and thus the peel strength can be improved.

In the resin composition, the prescribed PPE-B may be used alone or a plurality of different PPE-B may be used in combination.

[ Combined use of PPE-A and PPE-B ]

In the present embodiment, the PPE-A and the PPE-B are used in combination, from the viewpoint of exhibiting the effects of the present invention.

In the present embodiment, a plurality of PPEs having different structural molecular weights are not simply used in combination, but a combination of a PPE component a (PPE-a) having a specific structure and a PPE component B (PPE-B) having a specific structure and a relatively high molecular weight is focused on. When these specific two compounds are used in combination, it is preferable to further use an isocyanate compound described later in combination from the viewpoint of easily ensuring heat resistance (high Tg).

In the resin composition, as described above, a predetermined PPE-A may be used alone, or a plurality of different PPE-As may be used in combination, or a predetermined PPE-B may be used alone, or a plurality of different PPE-B may be used in combination. Further, in the resin composition, PPE other than PPE-A and PPE-B may be contained as long as the effect of the present invention is not impaired. When only PPE-A and PPE-B are used as PPE, 100% by mass or 100 parts by mass of PPE corresponds to 100% by mass or 100 parts by mass of the total of PPE-A and PPE-B in the resin composition. On the other hand, when the resin composition contains PPE other than PPE-A and PPE-B, 100% by mass or 100 parts by mass of PPE corresponds to 100% by mass or 100 parts by mass of the total of PPE-A, PPE-B and PPE.

The resin composition may contain a resin other than PPE as long as the effects of the present invention are not impaired.

From the viewpoint of stability and heat resistance of the resin composition, it is preferable that the content of PPE-A is 20% by mass or more and less than 90% by mass and the content of PPE-B is 10% by mass or more and less than 80% by mass based on 100% by mass of PPE.

However, depending on the type of PPE and various conditions, the content of PPE-A may be less than 20% by mass, or may be 90% by mass or more, and the content of PPE-B may be less than 10% by mass, or may be 20% by mass or more, based on 100% by mass in total.

When PPE-A is used in combination with PPE-B, PPE-B may be added to PPE-A or PPE-A may be added to PPE-B. Thus, for example, a device may be designed in a line of PPE-A or similar PPE in a manner that PPE-B is added, and a device may also be designed in a line of PPE-B or similar PPE in a manner that PPE-A is added. For example, PPE-A and PPE-B may be added simultaneously or one may be added in the presence of the other at the stage of preparing a varnish by adding a solvent (organic solvent) to the resin composition. In either case, when PPE-A and PPE-B are used in combination, the known production line can be effectively used without any major change.

[ (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 and the crosslinking density of the cured product of the resin composition is further improved by setting the number of carbon-carbon unsaturated double bonds to a specific value or more, 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 specific 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 methacryl 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 crosslinking density during the curing reaction (crosslinking reaction) is further increased, and thus the heat resistance of the cured product of the resin composition tends to be further improved.

From the viewpoint of achieving a low dielectric constant upon curing and a balance between a low dielectric loss tangent and a crosslinking density of a crosslinked structure, PPE: the weight ratio of the crosslinking agent is preferably 25: 75-95: 5, more preferably 32: 68-85: 15.

[ (c) organic peroxide ]

In the present embodiment, any organic peroxide having the ability to promote the polymerization reaction of the resin composition containing PPE 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 155 ℃ or more, the PPE-containing resin composition is subjected to heat and pressure molding, and then the PPE is sufficiently melted and then starts to react with the crosslinking agent, so that the molding property tends to be excellent. On the other hand, when the 1-minute half-life temperature of the organic peroxide is 185 ℃ or less, the decomposition rate of the organic peroxide under ordinary hot press molding conditions (for example, at a maximum temperature of 200 ℃) is sufficient, and therefore, the crosslinking reaction with the crosslinking agent can be efficiently and slowly carried out, and a cured product having good electrical characteristics (in particular, dielectric loss tangent) can be formed.

Examples of the organic peroxide having a 1-minute half-life temperature in the range of 155 to 185 ℃ include: for example, t-hexyl peroxyisopropylmonocarbonate (155.0 ℃), t-butyl peroxy-3, 5, 5-trimethylhexanoate (166.0 ℃), t-butyl peroxylaurate (159.4 ℃), t-butyl peroxyisopropylmonocarbonate (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 further preferably 1.5 parts by mass or more, based on 100 parts by mass (total mass 100%) of the PPE and the crosslinking agent in total, and is preferably 5 parts by mass or less, and more preferably 4.5 parts by mass or less, from the viewpoint of enabling the reaction rate to be improved, and from the viewpoint of enabling the dielectric constant and the dielectric loss tangent of the resulting cured product to be kept low.

[ (d) thermoplastic resin ]

The resin composition preferably contains a thermoplastic resin. The thermoplastic resin is preferably at least 1 selected from the group consisting of a block copolymer of a vinyl aromatic compound and an olefin compound and 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. The content of the unit derived from the vinyl aromatic compound in the block copolymer or the hydrogenated product thereof is preferably 20% by mass or more, and may be 99% by mass or less. When the content of the unit derived from the vinyl aromatic compound in the block copolymer or the hydrogenated product thereof is 20% by mass or more, the compatibility with PPE tends to be further improved, and the adhesion strength to a 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 PPE, 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 styrene-butadiene block copolymers, hydrogenated products of styrene-butadiene block copolymers, and polystyrene.

The hydrogenation ratio in the above hydride is not particularly limited, and some of the carbon-carbon unsaturated double bonds derived from the olefin compound may remain.

The weight average molecular weight of the thermoplastic resin is preferably 10,000 to 300,000, more preferably 20,000 to 290,000, and still more preferably 30,000 to 280,000. When the weight average molecular weight is 10,000 or more, the resin composition of the present embodiment tends to have more excellent heat resistance after curing. By setting the weight average molecular weight to 300,000 or less, the resin composition of the present embodiment tends to have more favorable resin flowability during thermoforming. The weight average molecular weight is determined by the method described in the examples below.

The content of the thermoplastic resin is preferably 2 to 20 parts by mass based on 100 parts by mass of the total of the PPE-A and the crosslinking agent. When the content is 2 parts by mass or more, the resin composition of the present embodiment tends to have more excellent low dielectric constant property, low dielectric loss tangent property and adhesion to a metal foil after curing. When the content is 20 parts by mass or less, the resin composition of the present embodiment tends to have more excellent resin fluidity during heat molding.

[ (e) isocyanate Compound ]

As described above, when PPE-A and PPE-B are used in combination, it is preferable to use an isocyanate compound in combination from the viewpoint of easily securing heat resistance (high Tg). That is, when PPE-B having a relatively high molecular weight and having a hydroxyl group at the end of the molecule is used, the lowering of the glass transition temperature (Tg) of the cured product of the crosslinking agent compatible with PPE-B can be easily prevented by further using an isocyanate compound in combination. The reason for this is not clear, but it is presumed that the isocyanate compound acts on the hydroxyl group at the end of the main chain of PPE-B to form a longer chain chemical structure.

The isocyanate compound means a compound having 1 or 2 or more isocyanate groups (-CNO). Specific examples of the isocyanate compound are not particularly limited, and examples thereof include: methyl isocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, isophorone diisocyanate, phenethylisocyanate, methylene diphenyl diisocyanate, hexamethylene diisocyanate, and the like. The isocyanate compound may be used alone in 1 kind or in combination of 2 or more kinds.

In the cured form of the resin composition, the amount of the isocyanate compound is preferably 0.2 parts by mass or more, more preferably 0.5% by mass or more, and still more preferably 0.7% by mass or more per 100 parts by mass of PPE, from the viewpoint of more easily ensuring high heat resistance. From the same viewpoint, the amount of the isocyanate compound to be compounded is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and still more preferably 3 parts by mass or less, per 100 parts by mass of PPE.

In the case of using an isocyanate compound in combination, a catalyst may be further used in combination in order to accelerate the reaction (cure acceleration) based on the isocyanate compound. Examples of catalysts that can be used in combination include: dibutyltin dilaurate, dibutyltin dioctoate, dibutyltin dilaurate, triethylamine, diethanolamine, p-toluenesulfonic acid, dodecylbenzenesulfonic acid, dinonylnaphthalenesulfonic acid, and the like. The amount of such a catalyst to be blended is preferably 0.1 part by mass or less, more preferably 0.05% by mass or less, and further preferably 0.01% by mass or more, per 100 parts by mass of PPE.

[ (f) flame retardant ]

The resin composition preferably contains a flame retardant. The flame retardant is preferably 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 from the viewpoint that the low dielectric constant property and the low dielectric loss tangent property after curing the resin composition are more excellent.

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 PPE and the crosslinking agent, from the viewpoint of maintaining the flame retardancy at the 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.

[ (g) silica Filler ]

The resin composition 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 based on 100 parts by mass of the total of the PPE and the crosslinking agent. The silica filler may be a silica filler whose surface is surface-treated with a silane coupling agent or the like.

The resin composition may contain, in addition to the above additives, additives such as a heat stabilizer, an antioxidant, a UV absorber, a surfactant, and a lubricant, and a solvent. When the resin composition contains a solvent, the solid content in the resin composition may be dissolved or dispersed in the solvent to form a varnish.

[ (h) solvent ]

The solvent is preferably an aromatic compound such as toluene or xylene, methyl ethyl ketone, 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.

In many cases, PPE-B has a low solubility in a solvent relative to PPE-A. The solvent is preferably a solvent for an aromatic compound such as toluene, for example, a toluene/methyl ethyl ketone mixed solvent, a toluene/cyclohexane mixed solvent, or a toluene/cyclopentanone mixed solvent, from the viewpoint of dissolving PPE-B in the solvent appropriately and easily ensuring appropriate fluidity of the resin composition even at room temperature or thereabouts.

[ electronic Circuit Board Material ]

The electronic circuit board material of the present embodiment is formed using the varnish. The electronic circuit board material is specifically a resin film, an impregnated composite of a base material and a resin (also referred to as "prepreg" in the present invention), a resin-attached metal foil, or a laminate containing at least 1 of these.

[ resin film ]

The resin film of the present embodiment can be obtained by coating the varnish alone or on a support such as a support film, and then drying and removing the organic solvent in the resin varnish to form a film.

Examples of the support include: polyolefins such as polyethylene, polypropylene, and polyvinyl chloride; polyesters such as polyethylene terephthalate and polyethylene naphthalate; a polycarbonate; a polyimide; metal foils such as copper foil and aluminum foil; release paper, and the like. The support may be subjected to chemical or physical treatment such as roughening treatment, corona treatment, and mold release treatment.

The resin film of the present embodiment can be suitably used as an interlayer insulation sheet, an adhesive film, or the like of a laminate such as a multilayer printed wiring board.

[ 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 the varnish into a base material such as glass cloth 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 laminates ]

The metal-clad laminate of the present embodiment is obtained by laminating and curing the resin composition of the present embodiment or the prepreg of the present embodiment and a 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, and can be suitably used as a material for an electronic circuit board. 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 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 laminate in which a cured product laminate and the metal foil are laminated. One of the particularly preferred uses of the aforementioned laminate is in printed circuit boards. 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. However, the present embodiment is not limited to the examples.

(synthetic reaction of PPE)

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 grade product manufactured by Wako pure chemical industries, Ltd.

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

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

2. Initiator

NYPER BMT: the product of Nippon fat and oil Co., Ltd was used as it was.

3. Raw material PPE

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 a (a: 2-6) comprising a partial structure of formula (2-1)

1,1, 3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane: the product of ADEKA (ADK STAB AO-30) from Kabushiki Kaisha was used as it was.

5. Modified radical raw material

Methacrylic anhydride: aldrich reagent product was used directly.

Dimethylaminopyridine: aldrich reagent product was used directly.

(identification and analysis of PPE)

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 equation (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 PPE1(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 nitrogen gas was purged from the flask, 202A 100g of PPE S202, 200g of toluene, and 12.8g of 1,1, 3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane as a polyfunctional phenol were added. 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 raw material PPE. As an initiator, 37.5g of a 40% m-xylene solution (NYPERBMT, manufactured by Nichikoku K.K.) 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 PPE (hereinafter referred to as "PPE 1") 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 of the obtained PPE1 was 1,500 (Mn) in terms of polystyrene. In addition, the PPE1 had a solution viscosity of 125 cps in 20% methyl ethyl ketone solvent.

(Synthesis of 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. Next, the solution was cooled to room temperature to obtain a toluene solution of the methacrylate-modified PPE.

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 PPE, and the operation was shifted to purification. 120g of the above-mentioned toluene solution of methacrylate-modified PPE was added dropwise over 30 minutes to 360g of methanol vigorously stirred in a 1L beaker with a magnetic stirrer. The resulting precipitate was filtered under reduced pressure through a membrane filter and then dried to obtain 38g of a polymer. Of the polymer to be dried¹The results of H-NMR measurement are shown in FIG. 1. It was confirmed that the peak of the hydroxyl group derived from PPE at around 4.5ppm disappeared and the peak of the alkene derived from the methacryl 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 peaks derived from the methacryl group by NMR were peaks of the methacryl group bonded to the PPE terminal. From the results, it was confirmed that the obtained polymer was a modified PPE (hereinafter referred to as modified PPE1) having a structure represented by the following formula:

Further, as a result of GPC measurement, the molecular weight of the resulting modified PPE1 was 1,600 in terms of polystyrene. The average number of terminal functional groups of the modified PPE1 was calculated to be 2.0 or more according to the above equation (2). Further, the solution viscosity of the modified PPE1 was 131 cps in 20% methyl ethyl ketone solvent.

Resin composition and material for forming cured product thereof

PPE

Modified polyphenylene ether 1 (modified PPE1) obtained as described above

end-Methylpropenyl-modified PPE "product name SA 9000"

(manufactured by SABIC Innovative Plastics IP BV, Mn: 2756, number of terminal functional groups: 2.0)

"PPE S202A" (manufactured by Asahi Kasei Co., Ltd., Mn: 16,000)

Crosslinking agent

TAIC (molecular weight: 249.7, number of unsaturated double bonds: 3, manufactured by Nippon Kabushiki Kaisha)

Polybutadiene "product name B-1000"

(Mn: 1200, number of unsaturated double bonds: 18.4, manufactured by Nippon Caoda Co., Ltd.)

Organic peroxides

Bis (2-tert-butylperoxyisopropyl) benzene

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

Thermoplastic resin

Hydrogenated styrenic thermoplastic resin "product name TUFTEC H1053"

(manufactured by Asahi Kasei corporation, Mw: 5.5 ten thousand, styrene unit content: 29% by mass)

Hydrogenated styrenic thermoplastic resin "product name TUFTEC M1911"

(manufactured by Asahi Kasei corporation, Mw: 4.8 ten thousand, styrene unit content: 30% by mass)

Isocyanate compound

Hexamethylene diisocyanate "product name TPA-100" (manufactured by Asahi Kasei Co., Ltd.)

Phenethylisocyanate (manufactured by Tokyo chemical industry Co., Ltd.)

Hexamethylene diisocyanate (manufactured by FUJIFILM Wako Pure Chemical Corporation)

Catalyst and process for preparing same

Dibutyltin dilaurate "product name NEOSTANN U-100" (manufactured by Nidoku Kabushiki Kaisha)

Flame retardant

Decabromodiphenylethane "product name SAYTEX 8010" (manufactured by ALBEMARLE JAPAN CORPORATION)

Filler

Spherical silica (manufactured by Lorson, K.K.)

Base material

L glass cloth

(Asahi-Schwebel Co., Ltd.; model 2116)

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. Dielectric constant and dielectric loss tangent (electric characteristics, 10GHz)

The dielectric constant and the dielectric loss tangent at 10GHz were measured by the cavity resonance method. As a measuring apparatus, a network analyzer (N5230A, manufactured by Agilent Technologies, inc.) and a Cavity resonator (Cavity resonator CP series) manufactured by kanto electronic application development of japan ltd.

The prepregs obtained in examples and comparative examples were stacked in 8 sheets, while being raised from room temperatureHeating at a temperature of 3 deg.C/min under a pressure of 5kg/cm²Vacuum pressing under the condition of (1), heating at a temperature rising rate of 3 ℃/min and a pressure of 40kg/cm after reaching 130 DEG C²Vacuum pressing under the condition of (1), and maintaining the temperature at 200 deg.C and the pressure at 40kg/cm²And vacuum pressing was performed for 60 minutes, thereby manufacturing a laminate.

The laminate was cut into a size of about 2mm in width and 50mm in length with the warp of the glass cloth as the long side, and used as a sample for measuring the dielectric constant and the dielectric loss tangent.

The sample for measurement 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%.

3. Glass transition temperature (Tg) of the laminate

The dynamic viscoelasticity was measured, and the temperature at which tan reached the maximum was determined as the glass transition temperature (Tg). The measurement device used was a dynamic viscoelasticity device (RHEOVIBRON model DDV-01FP, ORIENTEC co., ltd., manufactured by laboratory: length about 35mm, width about 12.5mm and thickness about 0.3mm, stretch mode, frequency: the measurement was performed under the condition of 10 rad/s.

The prepregs obtained in examples and comparative examples were stacked in 2 sheets, and copper foils (GTS-MP foils, manufactured by Kogawa electric industries, Ltd.) having a thickness of 35 μm were stacked on the prepregs, and then the prepregs were subjected to a final arrival temperature of 200 ℃ and a final arrival pressure of 40kg/cm²After obtaining a double-sided copper clad laminate by vacuum pressing under the conditions of (1), the copper foil is removed by etching to prepare the copper clad laminate.

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

The stress at which the copper foil of the copper-clad laminate was peeled off at a constant speed was measured in accordance with JIS C6481, a test method for copper-clad laminates for printed wiring boards.

The prepregs obtained in examples and comparative examples were stacked in 2 sheets, and copper foils (thickness: 35 μm, GTS) were stacked on the prepregsMP foil, manufactured by Kogawa electric industries Co., Ltd.), and then heated from room temperature at a heating rate of 3 ℃ per minute under a pressure of 5kg/cm²Vacuum pressing under the condition of (1), heating at a temperature rising rate of 3 ℃/min and a pressure of 40kg/cm after reaching 130 DEG C²Vacuum pressing under the condition of (1), and maintaining the temperature at 200 deg.C and the pressure at 40kg/cm²And vacuum pressing was performed for 60 minutes, thereby producing a double-sided copper-clad laminate.

The copper-clad laminate thus obtained was cut into a size of 15mm in width × 150mm in length, and 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 the 5 measurements was determined.

5. Cross-sectional observation of the laminate after weld Heat resistance and Heat resistance test

The prepregs obtained in examples and comparative examples were stacked in 8 sheets, and copper foils (FV-WS foils, manufactured by guhe electric industries, ltd.) having a thickness of 12 μm and a surface roughness rz2.0 μm were further stacked on both sides thereof. Next, while heating from room temperature at a temperature rise rate of 3 ℃/min, the mixture was heated under a pressure of 5kg/cm²Vacuum pressing under the condition of (1), heating at a temperature rising rate of 3 ℃/min and a pressure of 40kg/cm after reaching 130 DEG C²Vacuum pressing under a condition of (1), and after reaching 200 ℃, keeping the temperature at 200 ℃ and a pressure of 40kg/cm²And vacuum pressing was performed for 60 minutes, thereby producing a copper-clad laminate.

Only one side of the copper foil was removed by etching, and a heat resistance test was performed. Heat resistance test A test piece was cut into a 50mm square, dried in an oven at 105 ℃ for 2 hours, and subjected to a pressure cooker test under 2 atmospheres for 4 hours. Then, a heat resistance test was performed in which the test was repeated 30 times with the solder bath immersed at 260 ℃ or 288 ℃ for 20 seconds. The interval between the impregnations was set to 20 seconds.

In the heat resistance test, evaluation was performed based on the following by visual observation.

Very good: laminate with no evidence of swelling, peeling and whitening at 288 deg.C

Good: laminate in which neither swelling, peeling nor whitening was observed under 260 ℃

(any of swelling, peeling and whitening occurred at 288 ℃ C.)

X: laminate in which any of swelling, peeling and whitening occurs at 260 DEG C

Further, the test piece after the heat resistance test was observed in cross section by SEM.

In the cross-sectional observation, evaluation was performed based on the following by visual observation.

There is no problem: cracking such as cracking or breaking was not observed

There is a problem: cracking such as cracking or breaking was confirmed

(example 1)

According to the composition and solvent shown in Table 1,200 parts by mass of toluene was added with a thermoplastic resin and stirred to dissolve the thermoplastic resin, and then the flame retardant, spherical silica (silica filler) and modified PPE1 were added thereto, respectively, and stirring was continued until the modified PPE1 was dissolved. Subsequently, the crosslinking agent and the organic peroxide are added to the dissolved matter, respectively, and sufficiently stirred to obtain a varnish.

After the L-glass cloth was impregnated with the varnish, excess varnish was scraped off by passing it through a predetermined slit, and the resultant was 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.

(examples 2 to 9 and comparative examples 1 to 2)

Resin compositions, varnishes and prepregs were obtained in examples 2 to 9 and comparative examples 1 to 2, respectively, and evaluated in the same manner as in example 1 except that the resin composition and/or the base material were changed as shown in table 1.

[ Table 1]

As shown in Table 1, examples 1 to 9 were evaluated as "no problem" in cross-sectional observation after the heat resistance test, unlike comparative examples 1 to 2. Thus, it was confirmed that the prepregs of examples 1 to 9 achieved an improvement in strength (an improvement in toughness) against stress, deformation, and the like, as compared with comparative examples 1 to 2. In addition, it was confirmed that the dielectric constants and dielectric loss tangents of examples 1 to 9 were equal to or lower than those of comparative example 2, and thus the electrical characteristics were improved. Further, it was confirmed that examples 1 to 9 also achieved an improvement in peel strength as compared with comparative examples 1 to 2. It was thus confirmed that in examples 1 to 9, the electrical characteristics, the peel strength and the toughness were improved as compared with those of comparative examples 1 to 2.

Claims

1. A resin composition comprising polyphenylene ether, a crosslinking agent and an organic peroxide,

the polyphenylene ether comprises:

a polyphenylene ether component A having 1.5 to 5 functional groups containing carbon-carbon double bonds per 1 molecule on average and a number average molecular weight of 500 to 8,000 at the end of the main chain; and

2. The resin composition according to claim 1, wherein the functional group at the end of the main chain of the polyphenylene ether component A comprises a structure represented by the following formula (1):

in the formula (1), n represents an integer of 0 or 1, R¹Is C_1～8And R is alkylene or alkenylene, and²is a hydrogen atom or C_1～8Alkylene or alkenylene groups of (a).

3. The resin composition according to claim 1 or 2, wherein the polyphenylene ether component a comprises a structure represented by the following formula (2-1):

in the formula (2-1),

x is an optional linking group having a valence, a is a number of 2.0 or more;

R⁵each independently represents an arbitrary substituent, k is each independently an integer of 1 to 4, and k R' s⁵At least 1 of them comprises a partial structure represented by the following formula (2-2);

each Y is independently a 2-valent linking group having a structure represented by the following formula (2-3), n represents the number of repetitions of Y, and each is independently an integer of 1 to 200;

l is any 2-valent connecting group or single bond; and is

Each A independently represents a substituent containing a carbon-carbon double bond and/or an epoxy bond;

in the formula (2-2), 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 comprises a substituent within the scope of the conditions of (a);

in the formula (2-3), R²¹Each independently is C_1-6A saturated or unsaturated hydrocarbon group of R²²Each independently is a hydrogen atom or C_1-6A saturated or unsaturated hydrocarbon group ofThe saturated or unsaturated hydrocarbon group satisfies C_1-6Optionally having a substituent within the range of the conditions of (1).

4. The resin composition according to any one of claims 1 to 3, wherein the polyphenylene ether component B has a number average molecular weight of 50,000 or less.

5. The resin composition according to any one of claims 1 to 4, further comprising an isocyanate compound.

6. The resin composition according to any one of claims 1 to 5, wherein the crosslinking agent comprises at least 1 selected from the group consisting of triallyl cyanurate, triallyl isocyanurate, and polybutadiene.

7. The resin composition according to any one of claims 1 to 6, 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 polyphenylene ether: the weight ratio of the cross-linking agent is 25: 75-95: 5.

8. the resin composition according to any one of claims 1 to 7, wherein the organic peroxide has a 1-minute half-life temperature of 155 ℃ or more and 185 ℃ or less,

9. The resin composition according to any one of claims 1 to 8, further comprising a thermoplastic resin,

the thermoplastic resin is at least 1 selected from the group consisting of a block copolymer of a vinyl aromatic compound and an olefin compound and a hydrogenated product thereof, and a homopolymer of the vinyl aromatic compound,

the block copolymer or the hydrogenated product thereof has a content of a unit derived from a vinyl aromatic compound of 20 mass% or more.

10. The resin composition according to claim 9, wherein the weight average molecular weight of the thermoplastic resin is 10,000 to 300,000.

11. The resin composition according to claim 9 or 10, wherein the polyphenylene ether and the crosslinking agent are contained in the resin composition in an amount of 100% by mass in total,

the content of the thermoplastic resin is 2 to 20 mass%.

12. The resin composition according to any one of claims 1 to 11, further comprising a flame retardant, and the flame retardant is incompatible with other contained components in the resin composition after the resin composition is cured.

13. An electronic circuit substrate material comprising the resin composition according to any one of claims 1 to 12.

14. A resin film comprising the resin composition according to any one of claims 1 to 12.

15. A prepreg which is a composite of a substrate and the resin composition according to any one of claims 1 to 12.

16. The prepreg of claim 15, wherein the substrate is a glass cloth.

17. A laminate of a metal foil and the resin film according to claim 14 or the cured product of the prepreg according to claim 15 or 16.