JP2020200434A - Polyphenylene ether-containing resin composition - Google Patents

Abstract

To provide a PPE resin composition capable of obtaining a cured product capable of realizing improvement in electric characteristics, heat resistance and toughness and having an excellent impregnation property into a substrate.SOLUTION: There is provided a resin composition which comprises a polyphenylene ether, a crosslinking agent and an organic peroxide, wherein the polyphenylene ether contains 2 mass% or more and less than 40 mass% of a polyphenylene ether component A having a structure represented by the following formula (provided that the content the total polyphenylene ether component is defined as 100 mass%) and more than 60 mass% and less than 98 mass% (the same as above) of a polyphenylene ether component B having 1.5 to 2.5 (meth)acryloyloxy groups in one molecule on average at a main chain terminal and a number average molecular weight of 1,000 or more and 4,500 or less.SELECTED DRAWING: Figure 1

Description

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

In recent years, with the remarkable progress of information network technology or the expansion of services utilizing information networks, electronic devices are required to have a large amount of information and a high processing speed. In order to meet these demands, substrate materials such as printed wiring boards have low dielectric constant and low dielectric constant in addition to the characteristics such as flame retardancy, heat resistance, and peel strength with copper foil, which have been conventionally required. Direct contact is required. Therefore, further improvement of the resin composition used for the material for the substrate such as the printed wiring board is being studied.

Among the materials for substrates, polyphenylene ether (PPE) has a relatively low dielectric constant and a relatively low dielectric loss tangent, and is therefore suitable as a material for printed wiring boards that can meet the above-mentioned requirements. For example, the PPE-containing resin composition described in Patent Document 1 controls the average number of phenolic hydroxyl groups per molecule of PPE within a specific range, or specifies the content of a plurality of PPEs having different molecular weights from each other. Attempts are made to improve moldability, heat resistance, adhesiveness, and electrical properties.

International Publication No. 2012/081705

A cured product of a resin composition containing PPE is required to have excellent heat resistance and strength against stress or deformation (improvement of toughness) in addition to excellent electrical characteristics. Further, the resin composition containing PPE is also required to be suitably dissolved in an organic solvent such as toluene and, by extension, to have excellent impregnation property on the substrate. On the other hand, in Patent Document 1, there is still room for examination from the viewpoint of responding to all these demands.

Therefore, the present invention provides a PPE resin composition which can obtain a cured product capable of improving electrical characteristics, heat resistance, and toughness, and has excellent impregnation property into a substrate. Is to provide.
Another object of the present invention to be solved is to provide an electronic circuit board material, a resin film, a prepreg, and a laminate formed by using such a PPE resin composition.

As a result of intensive research to solve the above problems, the present inventors have found that the resin composition containing PPE, a cross-linking agent, and an organic peroxide has a PPE component A (PPE-A) having a unique structure. , PPE component B (PPE-B) having a peculiar molecular weight and another peculiar structure, and then using both of them in combination and determining the content of each in the resin composition, as described above. It was found that the above problems could be solved, and the present invention was completed. That is, the present invention is as follows.
[1]
A resin composition containing a polyphenylene ether, a cross-linking agent, and an organic peroxide.
The polyphenylene ether has the following formula (1):
{In the formula,
X is an arbitrary linking group of a value, and a is a number of 2.5 or more.
R ⁵ is any substituent independently, k are each independently 1 to 4 integer, and at least one of the k is R ⁵ is represented by the following formula (2):
(In the formula, R ¹¹ is an alkyl group of C _1-8 independently, R ¹² is an alkylene group of C _1-8 independently, b is 0 or 1 independently, and R _{Reference numeral} ¹³ denotes a hydrogen atom, either an alkyl group or a phenyl group of C _1-8 , and the alkyl group, the alkylene group, and the phenyl group may contain a substituent to the extent that the condition of C _1-8 is satisfied. Good)
Including the partial structure represented by
Y is independently expressed by the following equation (3):
(In the formula, R ²¹ is an independently saturated or unsaturated hydrocarbon group of C _1-6 , and R ²² is an independently saturated or unsaturated hydrocarbon group of C _1-6. And the saturated or unsaturated hydrocarbon group may have a substituent as long as the condition of C _1-6 is satisfied).
It is a divalent linking group having a structure represented by, n represents the number of repetitions of Y, and each is an integer of 1 to 200 independently.
L is any divalent linking group or single bond, and A represents a substituent containing a carbon-carbon double bond and / or an epoxy bond, respectively}.
Polyphenylene ether component A containing the structure represented by
The following formula (4A): at the end of the main chain:
{Wherein, n is an integer of 0 or _1, ^{R 1} is a saturated alkyl group or unsaturated alkyl group of _{C 1-8,} and ^{R 2} is or a saturated alkyl group of a hydrogen atom or a _{C 1-8} Unsaturated alkyl group}
It contains a polyphenylene ether component B having an average of 1.5 to 2.5 functional groups represented by (1) and having a number average molecular weight of 1,000 or more and 4,500 or less.
Based on the total amount of 100% by mass of the polyphenylene ether, the content of the polyphenylene ether component A is 2% by mass or more and less than 40% by mass, and the content of the polyphenylene ether component B is more than 60% by mass and less than 98% by mass. The resin composition that is.
[2]
The resin composition according to [1], wherein the cross-linking agent comprises at least one selected from the group consisting of triallyl cyanurate, triallyl isocyanurate, and polybutadiene.
[3]
The cross-linking agent has an average of two or more carbon-carbon unsaturated double bonds in one molecule.
The resin composition according to [1] or [2], wherein the number average molecular weight of the cross-linking agent is 4,000 or less, and the mass ratio of the polyphenylene ether: the cross-linking agent is 25:75 to 95: 5. Stuff.
[4]
The one-minute half-life temperature of the organic peroxide is 155 ° C or higher and 185 ° C or lower.
[1] to [3], wherein the content of the organic peroxide is 0.05% by mass or more and 0.9% by mass or less based on the total mass of 100% by mass of the polyphenylene ether and the cross-linking agent. The resin composition according to any one of the items.
[5]
The resin composition further comprises a thermoplastic resin and
The thermoplastic resin is at least one selected from the group consisting of a block copolymer of a vinyl aromatic compound and an olefin-based alkene compound, a hydrogenated product thereof, and a homopolymer of the vinyl aromatic compound.
The resin composition according to any one of [1] to [4], wherein the content of the unit derived from the vinyl aromatic compound in the block copolymer or its hydrogenated product is 20% by mass or more.
[6]
The resin composition according to [5], wherein the thermoplastic resin has a weight average molecular weight of 30,000 to 300,000.
[7]
The content of the thermoplastic resin is
The resin composition according to [5] or [6], which is 2% by mass or more and 20% by mass or less based on a total of 100% by mass of the polyphenylene ether and the cross-linking agent.
[8]
Any of [1] to [7], wherein the resin composition further contains a flame retardant, and the flame retardant is incompatible with other contained components in the resin composition after curing of the resin composition. The resin composition according to item 1.
[9]
An electronic circuit board material containing the resin composition according to any one of [1] to [8].
[10]
A resin film containing the resin composition according to any one of [1] to [8].
[11]
A prepreg that is a composite of a base material and the resin composition according to any one of [1] to [9].
[12]
The prepreg according to [11], wherein the base material is glass cloth.
[13]
A laminate of the resin film according to [10] or the cured product of the prepreg according to [11] or [12] and a metal foil.

According to the present invention, a PPE resin composition capable of obtaining a cured product capable of improving electrical characteristics, heat resistance, and toughness, and having excellent impregnation property into a base material can be obtained. Can be provided.
Further, according to the present invention, it is possible to provide an electronic circuit board material, a resin film, a prepreg, and a laminate formed by using such a PPE resin composition.

It is a ¹ H-NMR measurement result of the modified polyphenylene ether 1 (modified PPE1) obtained in Production Example 1.

Hereinafter, embodiments for carrying out the present invention (hereinafter, simply referred to as “the present embodiment”) will be described. Since the following embodiments are one aspect of the present invention, the present invention is not limited to the following embodiments. Therefore, the following embodiments can be appropriately modified and implemented within the scope of the gist of the present invention. Further, "~" in the present 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. In the present specification, the upper limit value and the lower limit value of the numerical range can be arbitrarily combined.

[Resin composition]
The PPE-containing resin composition according to the present embodiment (hereinafter, also simply referred to as “resin composition”) contains PPE, a cross-linking agent, and an organic peroxide. Then, PPE has a polyphenylene ether component A (PPE-A) having a unique structure, and a polyphenylene ether component B (PPE-A) having another unique structure and having a number average molecular mass (Mn) of 1,000 or more and 4,500 or less. PPE-B) is included, and the content of PPE-A is 2% by mass or more and less than 40% by mass, and the content of PPE-B exceeds 60% by mass, based on 100% by mass of the total amount of PPE. It is less than 98% by mass.
According to such an embodiment, a cured product capable of improving electrical characteristics, heat resistance, and toughness can be obtained, and PPE is excellent in impregnation property into a base material. A resin composition can be provided.

The number average molecular weight of PPE can be obtained in terms of standard polystyrene from the relational expression between the molecular weight of the standard polystyrene sample measured under the same conditions and the elution time by gel permeation chromatography (GPC) measurement. For example, for each of PPE-A and PPE-B, a specific method for calculating the number average molecular weight can be referred to the method described in Examples.

The resin composition comprises (a) PPE, (b) a cross-linking agent, and (c) an organic peroxide, as well as (d) a thermoplastic resin, () (e) a flame retardant, and (f) silica, if desired. It may further contain a filler, (g) solvent and the like. Hereinafter, the elements that can form the resin composition will be described.

[(A) PPE]
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. As used herein, the term "polyphenylene ether" includes dimers, trimmers, oligomers, and polymers.
The PPE may also include other building blocks other than the phenylene ether unit. The amount of 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 total number of unit structures. However, the amount of other structural units may exceed 30% with respect to the total number of unit structures as long as the effects of the present invention are not impaired.

The PPE is preferably the following formula (3):
{In the formula, R ²¹ and R ²² each independently have a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, and a bromine atom), and an alkyl group which may have a substituent (for example, methyl). C _1-6 linear or branched alkyl groups such as groups, ethyl groups, propyl groups, isopropyl groups, butyl groups, isobutyl groups, and tert-butyl groups; C _6-10 cyclic groups such as cyclohexyl groups. Alkyl group), an alkoxy group which may have a substituent (for example, a C _1-6 alkoxy group such as a methoxy group, an ethoxy group, and a butoxy group), and an aryl group which may have a substituent (for example, an aryl group). It represents a phenyl group and a 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. } Includes repeating structural units.
More specifically, R ²¹ is an independently saturated or unsaturated hydrocarbon group of C _1-6 , and R ²² is an independently saturated or unsaturated hydrocarbon of C _1-6. The hydrocarbon group which is a group and is saturated or unsaturated thereof may contain a substituent as long as the condition of C _1-6 is satisfied.

Specific examples of PPE include poly (2,6-dimethyl-1,4-phenylene ether), poly (2-methyl-6-ethyl-1,4-phenylene ether), and poly (2-methyl-6). -Phenyl-1,4-phenylene ether), poly (2,6-dichloro-1,4-phenylene ether), 2,6-dimethylphenol and other phenols (eg, 2,3,6-trimethylphenol, A copolymer with 2-methyl-6-butylphenol, etc.), a PPE copolymer obtained by coupling 2,6-dimethylphenol with biphenols or bisphenols, and poly (2,6-dimethyl). -1,4-phenylene ether) or the like is heated in a toluene solvent in the presence of a phenol compound such as bisphenol or trisphenol and an organic peroxide, and redistributed to obtain a linear structure or branch. It is a PPE having a structure.

[PPE-A]
PPE-A has the following formula (1):
Includes the structure represented by.

In the formula (1), X is an arbitrary linking group of a value, and a is a number of 2.5 or more, preferably an integer of 3 or more, and more preferably an integer of 3 to 6. Specific examples of X include, for example, a hydrocarbon group; a hydrocarbon group containing one or more elements selected from nitrogen, phosphorus, silicon or oxygen; or an element such as nitrogen, phosphorus, silicon or these. The group etc. can be mentioned.

Further, R ⁵ is an arbitrary substituent, k is an integer of 1 to 4, and when k is 2 or more, two R ^5s may be linked to form a ring. At least one of the k is R ⁵ is represented by the following formula (2):
Includes the partial structure represented by.

In formula (2), R ¹¹ is an independently C _1-8 alkyl group, R ¹² is an independent C _1-8 alkylene group, b is independently 0 or 1, and R is. _{Reference numeral} ¹³ indicates either a hydrogen atom, a C _1-8 alkyl group or a phenyl group, and these alkyl group, alkylene group and phenyl group contain a substituent to the extent that the condition of C _1-8 is satisfied. May be good.

The partial structure represented by the formula (2) preferably has secondary and / or tertiary carbons, for example, an isopropyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a tert-amyl group. , 2,2-Dimethylpropyl group or a structure having a phenyl group at the terminal thereof and the like. The partial structure represented by the formula (2) is preferably directly bonded to the benzene ring to which R ⁵ in the formula (1) is bonded. The partial structure represented by formula (2) is attached to the formula (1) 2-position of the benzene ring to which R ⁵ is bonded in, and / or 6-position (ortho to -O-) It is preferable to do so.

The following of the structures represented by the formula (1):
The part has one of the following structures:
Specific examples thereof include those obtained by removing all the hydrogen of the terminal phenolic hydroxyl group from the following compounds:
4,6-ditert-butylbenzene 1,2,3-triol, 2,6-bis (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenol, 1,1,3- Tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 2,4,6-tris (3', 5'-di-tert-butyl-4'-hydroxybenzyl) mecitylene, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 1,3,5-tris [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] Methyl] -1,3,5-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.

Y in the formula (1) is independently represented by the following formula (3):
It is a divalent linking group (phenolic unit having a substituent) containing the structure represented by, and n in the formula (1) represents the number of repetitions of Y, each independently being an integer of 0 to 200. ..

In formula (3), R ²¹ is an independently saturated or unsaturated hydrocarbon group of C _1-6 , preferably a methyl, ethyl group, n-propyl group, vinyl group, allyl group, ethynyl group, propargyl. It is a group or the like, more preferably a methyl group or an ethyl group, and even more preferably a methyl group. R ²² is independently a hydrogen atom or a saturated or unsaturated hydrocarbon group of C _1-6 , preferably a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, or the like, and more preferably a hydrogen atom. It is a methyl group, more preferably a hydrogen atom. Here, the saturated or unsaturated hydrocarbon group may have a substituent as long as the condition of C _1-6 is satisfied.

A in the formula (1) is a substituent containing a carbon-carbon double bond and / or an epoxy bond. Specific examples of A are notations (4) to (8):
expressed.

In formulas (4) to (8), R ³¹ is independently a hydrogen, a hydroxyl group or a C _1-30 hydrocarbon group, an aryl group, an alkoxy group, an aryloxy group, an amino group or a hydroxyalkyl group. R ³² is an independent C _1-30 hydrocarbon group. R ³³ is independently a hydrogen, a hydroxyl group or a C _1-30 hydrocarbon group, an aryl group, an alkoxy group, an aryloxy group, an amino group, a hydroxyalkyl group, a vinyl group or an isopropenyl group, and among R ³³ , At least one is a vinyl group or an isopropenyl group. s and t are integers from 0 to 5.

Specific examples of the hydrocarbon group of R ³¹ include methyl, ethyl, n-propyl, 2-propyl, n-butyl, isobutyl, t-butyl, n-pentyl, 1-ethylpropyl, 1-methylbutyl, and 2-methylbutyl. , 3-Methylbutyl, Amil, Cyclopentyl, 2,2-dimethylpropyl, 1,1-dimethylpropyl, n-hexyl, Cyclohexyl, 1-ethylbutyl, 2-ethylbutyl, 3-ethylbutyl, 1-methylpentyl, 2-methyl Pentyl, 3-methylpentylene, 4-methylpentylene, 1,1-dimethylbutylene, 2,2-dimethylbutylene, 3,3-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2 , 3-Dimethylbutyl, n-Heptyl, 1-methylhexyl, 2-methylhexyl, 3-methylhexyl, 4-methylhexyl, 5-methylhexyl, 1-ethylpentyl, 2-ethylpentyl, 3-Ethylpentyl, 1,1-dimethylpentyl, 2,2-dimethylpentyl, 3,3-dimethylpentyl, 4,4-dimethylpentyl, 1,2-dimethylpentyl, 1,3-dimethylpentyl, 1,4 -Dimethylpentyl, 2,3-dimethylpentyl, 2,4-dimethylpentyl, 3,4-dimethylpentyl, 2-methyl-3,3-dimethylbutyl, 1-methyl-3,3-dimethylbutyl, 1,2 , 3-trimethylbutyl, 1,3-dimethyl-2-pentyl, 2-isopropylbutyl, 2-methylcyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 1-cyclohexylmethyl, 2-ethylcyclopentyl, 3-ethylcyclopentyl , 2,3-Dimethylcyclopentyl, 2,4-dimethylcyclopentyl, 2-methylcyclopentylmethyl, 2-cyclopentylethyl, 1-cyclopentylethyl, n-octyl, 2-octyl, 3-octyl, 4-octyl, 2-methyl Heptyl, 3-methylheptyl, 4-methylheptyl, 5-methylheptyl, 6-methylheptyl, 2-ethylhexyl, 3-ethylhexyl, 4-ethylhexyl, 5-ethylhexyl, 1,1- To dimethylhexyl, 2,2-dimethylhexyl, 3,3-dimethylhexyl, 4,4-dimethylhexyl, 5,5-dimethylhexyl, 1,2-dimethylhexyl, 1,3-dimethyl Xyl, 1,4-dimethylhexyl, 1,5-dimethylhexyl, 2,3-dimethylhexyl, 2,4-di Methylhexyl, 2,5-dimethylhexyl, 1,1-ethylmethylpentyl, 2,2-ethylmethylpentyl, 3,3-ethylmethylpentyl, 4,4-ethylmethylpentyl, 1-ethyl-2- Methylpentyl, 1-ethyl-3-methylpentyl, 1-ethyl-4-methylpentyl, 2-ethyl-1-methylpentyl, 3-ethyl-1-methylpentyl, 4-ethyl-1-methylpentyl, 2- Ethyl-3-methylpentyl, 2-ethyl-4-methylpentyl, 3-ethyl-2-methylpentyl, 4-ethyl-3-methylpentyl, 3-ethyl-4-methylpentyl, 4-ethyl-3-methyl Pentyl, 1- (2-methylpropyl) butyl, 1- (2-methylpropyl) -2-methylbutyl, 1,1- (2-methylpropyl) ethyl, 1,1- (2-methylpropyl) ethylpropyl, 1,1-diethylpropyl, 2,2-diethylpropyl, 1,1-ethylmethyl-2,2-dimethylpropyl, 2,2-ethylmethyl-1,1-dimethylpropyl, 2-ethyl-1,1- Dimethylbutyl, 2,3-dimethylcyclohexyl, 2,3-dimethylcyclohexyl, 2,5-dimethylcyclohexyl, 2,6-dimethylcyclohexyl, 3,5-dimethylcyclohexyl, 2-methylcyclohexylmethyl, 3-methylcyclohexylmethyl, 4-Methylcyclohexylmethyl, 2-ethylcyclohexyl, 3-ethylcyclohexyl, 4-ethylcyclohexyl, 2-cyclohexylethyl, 1-cyclohexylethyl, 1-cyclohexyl-2-ethylene, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl , Benzyl, 2-phenylethyl and the like.

The hydrocarbon group of R ³¹ is preferably methyl, ethyl, n-propyl, 2-propyl, n-butyl, isobutyl, t-butyl, n-pentyl, 1-ethylpropyl, 1-methylbutyl, 2-methylbutyl, 3-Methylbutyl, amyl, cyclopentyl, n-hexyl, cyclohexyl, 1-ethylbutyl, 2-ethylbutyl, 3-ethylbutyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, n-heptyl , 1-Methylhexyl, 2-Methylhexyl, 3-Methylhexyl, 4-Methylhexyl, 5-Methylhexyl, 1-ethylpentyl, 2-ethylpentyl, 3-ethylpentyl, 2-methylcyclohexyl , 3-Methylcyclohexyl, 4-Methylcyclohexyl, n-octyl, 2-octyl, 3-octyl, 4-octyl, 2-methylheptyl, 3-methylheptyl, 4-methylheptyl, 5-methylheptyl, 6-methyl Heptyl, 2-ethylhexyl, 3-ethylhexyl, 4-ethylhexyl, 5-ethylhexyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, benzyl and the like, more preferably methyl and ethyl. , N-propyl, 2-propyl, n-butyl, isobutyl, t-butyl, n-pentyl, 1-ethylpropyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, amyl, 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-ethyl Xyl, 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, t-butyl, n-pentyl, amyl, 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, Dode Syl, benzyl, etc.

Specific examples of the hydrocarbon group of R ³² include methylene, ethylene, trimethylene, 1,2-propylene, tetramethylene, 2-methyl-1,3-trimethylene, 1,1-dimethylethylene, pentamethylene and 1-ethyl. -1,3-propylene, 1-methyl-1,4-butylene, 2-methyl-1,4-butylene, 3-methyl-1,4-butylene, 2,2-dimethyl-1,3-propylene, 1 , 2-Cyclopentylene, 1,3-Cyclopentylene, 2,2-dimethyl-1,3-propylene, 1,1-dimethyl-1,3-propylene, 3,3-dimethyl-1,3-propylene , Hexamethylene, 1,2-cyclohexylene, 1,3-cyclohexylene, 1,4-cyclohexylene, 1-ethyl-1,4-butylene, 2-ethyl-1,4-butylene, 3-ethyl-1 , 4-Methyl-1,5-pentylene, 2-methyl-1,5-pentylene, 3-methyl-1,5-pentylene, 4-methylpentylene, 1,1-dimethyl-1,4 -Butylene, 2,2-dimethyl-1,4-butylene, 3,3-dimethyl-1,4-butylene, 1,2-dimethyl-1,4-butylene, 1,3-dimethyl-1,4-butylene , 2,3-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, 1,1 -Dimethyl-1,5-pentylene, 2,2-dimethyl-1,5-pentylene, 3,3-dimethyl-1,5-pentylene, 4,4-dimethyl-1,5-pentylene, 1,2-dimethyl -1,5-pentylene, 1,3-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-methyl-3,3-dimethyl-1,4-butylene, 1 , 2,3-Trimethyl-1,4-butylene and the like.

Specific examples of the hydrocarbon group of R ³² include 1,3-dimethyl-1,4-pentylene, 2-isopropyl-1,4-butylene, 2-methyl-1,4-cyclohexylene, and 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-Cyclopentylmethylene, 2-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, 1,1-dimethyl-1,6-hexylene, 2,2-dimethyl-1,6-hexylene, 3,3-dimethyl- 1,6-Hexylene, 4,4-dimethyl-1,6-hexylene, 5,5-dimethyl-1,6-hexylene, 1,2-dimethyl-1,6-hexylene, 1,3-dimethyl-1, 6-Hexylene, 1,4-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, 1,1-ethylmethyl-1,5-pentylene, 2,2-ethylmethyl-1,5-pentylene, 3,3-ethylmethyl-1,5 -Pentylene, 4,4-ethylmethyl-1,5-pentylene, 1-ethyl-2-methyl-1,5-pentylene, 1-ethyl-3-methyl-1,5-pentylene, 1-ethyl-4- Methyl-1,5-pentylene, 2-ethyl-1-methyl-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- Examples thereof include 4-methyl-1,5-pentylene and 4-ethyl-3-methyl-1,5-pentylene.

Further, specific examples of the hydrocarbon group of R ³² include 1- (2-methylpropyl) -1,4-butylene, 1- (2-methylpropyl) -2-methyl-1,4-butylene, 1, 1- (2-methylpropyl) ethylene, 1,1- (2-methylpropyl) ethyl-1,3-propylene, 1,1-diethyl-1,3-propylene, 2,2-diethyl-1,3- Propropylene, 1,1-ethylmethyl-2,2-dimethyl-1,3-propylene, 2,2-ethylmethyl-1,1-dimethyl-1,3-propylene, 2-ethyl-1,1-dimethyl- 1,4-butylene, 2,3-dimethyl-1,4-cyclohexylene, 2,3-dimethyl-1,4-cyclohexylene, 2,5-dimethyl-1,4-cyclohexylene, 2,6-dimethyl -1,4-Cyclohexylene, 3,5-dimethyl-1,4-cyclohexylene, 2-methyl-1,4-cyclohexyl-1-methylene, 3-methyl-1,4-cyclohexyl-1-methylene, 4 -Methyl-1,4-cyclohexyl-1-methylene, 2-ethyl-1,4-cyclohexylene, 3-ethyl-1,4-cyclohexylene, 4-ethyl-1,4-cyclohexylene, 2-cyclohexylethylene , 1-cyclohexylethylene, 1-cyclohexyl-2-ethylene, nonylmethylene, 1-methyl-1,8-octylene, decylmethylene, 1-methyl-1,8-nonylene, undecylmethylene, dodecylmethylene, 1,4 Examples thereof include −phenylene, 1,3-phenylene, 1,2-phenylene, methylene-1,4-phenylene-methylene, ethylene-1,4-phenylene-ethylene and the like.

The hydrocarbon group of R ³² is preferably methylene, ethylene, trimethylene, 1,2-propylene, tetramethylene, 2-methyl-1,2-propylene, 1,1-dimethylethylene, pentamethylene, 1-ethyl-. 1,3-propylene, 1-methyl-1,4-butylene, 2-methyl-1,4-butylene, 3-methyl-1,4-butylene, 2,2-dimethyl-1,3-propylene, 1, 3-Cyclopentylene, 1,6-hexamethylene, 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-methyl-1,5-pentylene, heptamethylylene, 1-methyl-1,6- Hexylene, 2-methyl-1,6-hexylene, 3-methyl-1,6-hexylene, 4-methyl-1,6-hexylene, 5-methyl-1,6-hexylene, 1-ethyl-1,5- Pentylene, 2-ethyl-1,5-pentylene, 3-ethyl-1,5-pentylene, 2-methyl-1,4-cyclohexylene, 3-methyl-1,4-cyclohexylene, 4-methyl-1, 4-Cyclohexylene, Octamethylene, 1-Methyl-1,7-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, more preferably methylene, ethylene, trimethylene, 1,2-propylene, tetramethylene, 2-methyl-1,2. -Propylene, 1,1-dimethylethylene, pentamethylene, 1-ethyl-1,3-propylene, 1-methyl-1,4-butylene, 2-methyl-1,4-butylene, 3-methyl-1,4 -Butylene, 2,2-dimethyl-1,3-propylene, 1,3-cyclopentylene, 1,6-hexamethylene, 1,4-cyclohexylene, heptamethylylene, octamethylene, 1-methyl-1,7- Heptylene, 3-Methyl-1,7-Heptylene, 4-Methyl-1,7-Heptylene, 2-Methyl-1,7-Heptylene, 5-Methyl Chill-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, more preferably methylene, ethylene, trimethylene, 1,2-propylene, tetramethylene, 2-methyl-1,2. -Propylene, 1,1-dimethylethylene, pentamethylene, 2,2-dimethyl-1,3-propylene, 1,3-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, etc.

Regarding A in the formulas (1) and (1'), specific examples of the substituent containing a carbon-carbon double bond include a vinyl group, an allyl group, an isopropenyl group, a 1-butenyl group, and a 1-pentenyl group. Group, p-vinylphenyl group, p-isopropenylphenyl group, m-vinylphenyl group, m-isopropenylphenyl group, o-vinylphenyl group, o-isopropenylphenyl group, p-vinylbenzyl group, p-iso Propenylbenzyl group, m-vinylbenzyl group, m-isopropenylbenzyl group, o-vinylbenzyl group, o-isopropenylbenzyl group, p-vinylphenylethenyl group, p-vinylphenylpropenyl group, p-vinylphenylbu Tenyl group, m-vinylphenylethenyl group, m-vinylphenylpropenyl group, m-vinylphenylbutenyl group, o-vinylphenylethenyl group, o-vinylphenylpropenyl group, o-vinylphenylbutenyl group, methacryl Examples thereof include a group, an acrylic group, a 2-ethyl acrylic group and a 2-hydroxymethyl acrylic group.

L in the formula (1) is an arbitrary divalent linking group or a single bond (direct bond). When L is a single bond, the equation (1) is expressed as the following equation.
Further, when L is an arbitrary divalent linking group, a specific example of such L is, for example, the following formula:
{In the equation, a, R ⁵ , k, X, Y, and n are as defined in the description of equation (1)}
It has a structure represented by.

The structure represented by the formula (1) can have various branched structures depending on the value of the valence a of X. For example, when a = 3 in the equation (1), the following equation:
{In the formula, n represents the number of repetitions of Y and is an integer from 0 to 200}
The branch structure represented by is mentioned.

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

In the formula, Z is an arbitrary linking group corresponding to X in the formula (1). R ¹ is a substituent represented by the formula (2), and b is an integer of 1 to 4. The position of R ¹ is not limited, and R ¹ may take any position. Also, if b is 2 or more, each of the plurality of R ¹ is, take the same structure may take a different structure. Examples of R ¹ include an isopropyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a tert-amyl group, a 2,2-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. R ² is a hydrocarbon group having a chain or cyclic structure of hydrogen or C _1-8 . When there are a plurality of R ² , the substituents may be the same or different. Specific examples of R ² include, for example, methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, cyclopentyl group, n-hexyl group, cyclohexyl group, n-heptyl group, n-octyl. Examples include a group, a phenyl group, a benzyl group, a 2-ethylhexyl group, and the like, and from the viewpoint of reactivity during synthesis, hydrogen, methyl, ethyl, n-propyl group, n-butyl group, n-pentyl group, cyclopentyl group and the like. , N-hexyl group, cyclohexyl group, n-heptyl group, and n-octyl group are preferable. However, if the reactivity at the time of synthesis can be controlled by appropriately setting the position of R ² or the reaction conditions at the time of synthesis, the structure of R ² is not limited and the condition of C _1-8 is satisfied. Any structure may be used within the range. Z is a hydrocarbon group; a hydrocarbon group selected from nitrogen, phosphorus, silicon, oxygen and containing one or more elements; or an element such as nitrogen, phosphorus, silicon or a group containing these.

A specific example of the hydrocarbon group as Z is, for example, a structure represented by the following formula.
In the formula, R ^{4 to} R ¹⁰ may be the same or different and indicate hydrogen or a hydrocarbon group of C _1-8 . Further, R ^{31 to} R ³³ may be the same or different, and represent hydrogen or a hydrocarbon group of C _1-6 . j, k, l, and m may be the same or different, and are integers from 0 to 4. Specific examples of R ^{4 to} R ¹⁰ include hydrogen, methyl group, ethyl group, n-propyl group, isopropyl n-butyl group, isobutyl group, t-butyl group, n-pentyl group, 2-pentyl group, 3-. Pentyl group, cyclopentyl group, n-hexyl group, 2-hexyl group, 3-hexyl group, cyclohexyl group, n-heptyl group, 2-heptyl group, 3-heptyl group, n-octyl group, 2-ethylhexyl group, etc. Can be mentioned. Specific examples of R ^{31 to} R ³³ include hydrogen, methyl group, ethyl group, n-propyl group, isopropyl n-butyl group, isobutyl group, n-pentyl group, 2-pentyl group, 3-pentyl group and cyclopentyl group. , N-hexyl group, 2-hexyl group, 3-hexyl group, cyclohexyl group and the like.

Further, a specific example of a hydrocarbon group containing one or more elements selected from the group consisting of nitrogen, phosphorus, silicon, and oxygen as Z is represented by the following formula.
In the formula, R ^{4 to} R ¹⁰ may be the same or different and indicate hydrogen or a hydrocarbon group of C _1-8 . j, k, l, and m may be the same or different, and are integers from 0 to 4. Specific examples of R ^{4 to} R ¹⁰ include hydrogen, methyl group, ethyl group, n-propyl group, isopropyl n-butyl group, isobutyl group, t-butyl group, n-pentyl group, 2-pentyl group, 3-. Pentyl group, cyclopentyl group, n-hexyl group, 2-hexyl group, 3-hexyl group, cyclohexyl group, n-heptyl group, 2-heptyl group, 3-heptyl group, n-octyl group, 2-ethylhexyl group, etc. Can be mentioned.

Specific examples of Z as an element such as nitrogen, phosphorus, silicon, or a group containing these elements are as follows.

If the structure of A is specified for the first of the above specific examples, the structure is as shown in the following formula. The same applies to the case of 4 to 6 branches, and R ³¹ , R ³² , s, and t in the following equation are as defined in the specific example of A.

The number average molecular weight of PPE-A described above is preferably 500 to 8,000 in terms of polystyrene-equivalent molecular weight using GPC.
The number average molecular weight of PPE-A is preferably 700 or more, more preferably 900 or more, still more preferably 1,100, from the viewpoint of making it easier to reduce the dielectric constant and the dielectric loss tangent in the cured form of the resin composition. That is all. On the other hand, from the viewpoint of fluidity, compatibility with other components, etc., the number average molecular weight of PPE-A is preferably 7,000 or less, more preferably 6,000 or less, still more preferably 4,500 or less. ..
The modified PPE having the structure of the formula (1) in the present embodiment can be produced, for example, by preparing PPE by a redistribution reaction method using a higher polymer PPE polymer and introducing A at the terminal thereof. it can. In the case of producing PPE by a redistribution reaction, it is possible to produce PPE according to the conditions defined in the known reaction conditions. In this case, since the obtained polymer has a lower molecular weight than the raw material PPE, the ratio of the raw material PPE to the polyfunctional phenol compound may be adjusted according to the target molecular weight.

Further, there is no limitation on the method of introducing the substituent A in the formula (1) or (1') into the obtained PPE polymer terminal, for example, the functional groups represented by the formulas (4) to (7). , Various known methods may be employed depending on the type of functional group. For example, the introduction of a functional group having the structure of the formula (4), (6) or (7) can generally follow the formation of an ether bond by the Williamson synthetic method. The introduction of the functional group having the structure of the formula (5) is a reaction of forming an ester bond between the hydroxyl group at the terminal of the PPE polymer and a carboxylic acid having a carbon-carbon double bond (hereinafter referred to as carboxylic acid), and is a known ester bond. A forming method can be used.

PPE-A has high curing reactivity, low dielectric properties, good fluidity and moldability, and excellent heat resistance, so that it can be suitably used as a material for various electric and electronic devices, and in particular, electricity. -It can be suitably used for manufacturing prepregs for electronic parts (printed wiring board base materials, etc.).
In the resin composition, the predetermined PPE-A may be used alone, or a plurality of different PPE-A may be used in combination.

[PPE-B]
PPE-B has the following formula (4A): at the end of its main chain.
{Wherein, n is an integer of 0 or _1, ^{R 1} is a saturated alkyl group or unsaturated alkyl group of _{C 1-8,} and ^{R 2} is or a saturated alkyl group of a hydrogen atom or a _{C 1-8} Unsaturated alkyl group}
It is a PPE having an average of 1.5 to 2.5 functional groups represented by (1) in one molecule and having a number average molecular weight of 1,000 or more and 4,500 or less. In the present specification, the functional group at the end of the main chain of PPE-B is also referred to as "terminal functional group".
Of these, the number average molecular weight of PPE is 1,000 or more and 4,500 or less from the viewpoint of exerting the action and effect of the present invention. By including PPE-B having such a low molecular weight range together with PPE-A, which also has a preferable low molecular weight range, an increase in the viscosity of the resin composition can be suppressed, so that the coating property of the resin composition on the substrate can be improved. It can be improved. By improving the coatability of the resin composition on the base material, it is possible to improve various properties required for the resin composition or a cured product thereof.
The term "low molecular weight" as used herein means, for example, a low molecular weight as compared with PPE having a number average molecular weight of more than 8,000. Therefore, "small molecule" for PPE-B does not mean to limit that PPE-B has a lower number average molecular weight than PPE-A, and similarly, "small molecule" for PPE-A means PPE. It is not intended to limit -A to having a lower number average molecular weight than PPE-B. The number average molecular weight of PPE-B may be higher or lower than the number average molecular weight of PPE-A.

The number average molecular weight of PPE-B is preferably 1,000 or more, more preferably 1,200 or more, from the viewpoint of making it easier to improve the resin fluidity and various properties required for the cured product of the resin composition. , More preferably 1,500 or more. From the same viewpoint, the number average molecular weight of PPE-B is preferably 4,500 or less, more preferably 4,000 or less, still more preferably 3,500 or less.

In addition, PPE-B can be distinguished from PPE-A.
In the resin composition, the predetermined PPE-B may be used alone, or a plurality of different PPE-Bs may be used in combination.

Then, PPE-B has an average of 1.5 to 2.5 terminal functional groups represented by the formula (4A) in one molecule at the end of its main chain. As a result, it becomes easy to suppress a large increase in the molecular weight, and an increase in the viscosity of the resin composition can be suppressed, so that the coatability of the resin composition to the base material can be improved.

From the viewpoint of further excellent resin fluidity during heat molding, the terminal functional group represented by the formula (4A) is more preferably a methacrylic group and / or an acrylic group.
However, the terminal functional group is a functional group other than a methacryl group or an acrylic group, for example, a benzyl group, an allyl group, a propagyl group, a glycidyl group, an epoxy group, and a vinyl, as long as it does not inhibit the action and effect of the present invention. It may be a functional group such as a benzene group.

[Combination of PPE-A and PPE-B]
In the present embodiment, the above PPE-A and the above PPE-B are used in combination from the viewpoint of exerting the effects of the present invention.
Rather than simply using multiple PPEs that are different from each other, PPE-A having a unique structure and PPE-B having a unique molecular weight and another unique structure are identified, and then both are identified. The present embodiment focuses on determining the content of each of the resin compositions together with the combined use.

In the resin composition, the predetermined PPE-A may be used alone, a plurality of different PPE-A may be used in combination, or the predetermined PPE-B may be used alone. , A plurality of different PPE-Bs may be used in combination, as described above.
Further, the resin composition may contain other PPEs other than PPE-A and PPE-B as long as the effects of the present invention are not impaired. Other PPEs include PPE having a number average molecular weight included in a preferable number average molecular weight range in PPE-A, PPE having a number average molecular weight included in a number average molecular weight range in PPE-B, and a number average molecular weight of 8,000. High molecular weight PPE exceeding the above. Among these, examples of high molecular weight PPE include PPE having an average number of phenolic hydroxyl groups per molecule of 1.2 or more and a number average molecular weight of more than 8,000. However, as described above, the resin composition of the present embodiment does not have to contain other PPE.
When only PPE-A and PPE-B are used as PPE, 100% by mass or 100 parts by mass of PPE in the resin composition corresponds to 100% by mass or 100 parts by mass of PPE-A and PPE-B in total. .. On the other hand, when the resin composition contains PPE-A and PPE other than PPE-B, 100% by mass of PPE or 100 parts by mass of PPE is 100% by mass of PPE-A, PPE-B, and other PPE in total. It corresponds to 100 parts by mass in total.
The resin composition may contain a resin other than PPE as long as it does not interfere with the action and effect of the present invention.

From the viewpoint of exerting the effects of the present invention, the content of PPE-A is 2% by mass or more and less than 40% by mass, and the content of PPE-B exceeds 60% by mass, based on 100% by mass of the total amount of PPE. It is less than 98% by mass.
First, when the lower limit of the content of PPE-A is the above value, the ratio of PPE-A to the resin composition can be secured. On the other hand, if the upper limit of the content of PPE-A is the above value, the ratio of PPE-B to the resin composition can be secured. Similarly, when the lower limit of the content of PPE-B is the above value, the ratio of PPE-B to the resin composition can be secured. On the other hand, if the upper limit of the content of PPE-B is the above value, the ratio of PPE-A to the resin composition can be secured.
Then, by combining PPE-A and PPE-B in the above-mentioned specific ratio, various properties required for the resin composition or its cured product can be improved, and in particular, the cured product of the resin composition can be improved. It is possible to secure an excellent glass transition temperature (Tg) and improve the electrical characteristics (for example, reduce the dielectric loss tangent (Df)) in a well-balanced manner.

Therefore, from the viewpoint of exerting the action and effect of the present invention, the content of PPE-A preferably exceeds 2% by mass, more preferably 3% by mass or more, still more preferably 5% by mass, based on the total amount of PPE of 100% by mass. % Or more. From the same viewpoint, the content of PPE-A is preferably 39% by mass or less, more preferably 35% by mass or less, still more preferably 30% by mass or less.
Further, from the viewpoint of exerting the effects of the present invention, the content of PPE-B is preferably 61% by mass or more, more preferably 65% by mass or more, still more preferably 70% by mass, based on the total amount of PPE of 100% by mass. % Or more. From the same viewpoint, the content of PPE-B is preferably 97% by mass or less, more preferably less than 97% by mass, and further preferably less than 95% by mass.

When PPE-A and PPE-B are used in combination, PPE-B may be added to PPE-A, or PPE-A may be added to PPE-B. Thus, for example, the equipment may be designed to add PPE-B in the PPE-A or similar PPE production line, or in the PPE-B or similar PPE production line, PPE-A. The equipment may be designed to add. Further, for example, at the stage of producing a varnish by adding a solvent (organic solvent) to the resin composition, PPE-A and PPE-B may be added at the same time or in the presence of one of them. In any case, when PPE-A and PPE-B are used in combination, it is possible to effectively utilize the PPE-A and PPE-B without major changes from the known production line.

[(B) Crosslinking agent]
In this embodiment, any cross-linking agent having the ability to cause or promote a cross-linking reaction can be used. The cross-linking agent preferably has a number average molecular weight of 4,000 or less. When the number average molecular weight of the cross-linking agent is 4,000 or less, an increase in the viscosity of the resin composition can be suppressed, and good resin fluidity during heat molding can be obtained. The number average molecular weight may be any one measured by a general molecular weight measuring method, and specific examples thereof include a value measured by using GPC.

From the viewpoint of the cross-linking reaction, the cross-linking agent preferably has two or more carbon-carbon unsaturated double bonds in one molecule on average. The cross-linking agent may be composed of one kind of compound or two or more kinds of compounds. The "carbon-carbon unsaturated double bond" as used herein means a double bond located at the end branched from the main chain when the cross-linking agent is a polymer or an 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 cross-linking agent is less than 600, the number of carbon-carbon unsaturated double bonds (average value) per molecule of the cross-linking agent is preferably 2 to 4. When the number average molecular weight of the cross-linking agent is 600 to 1500, the number of carbon-carbon unsaturated double bonds (average value) per molecule of the cross-linking agent is preferably 4 to 26. Number of cross-linking agents When the average molecular weight is 1,500 to 4,000, the number of carbon-carbon unsaturated double bonds (average value) per molecule of the cross-linking agent is preferably 26 to 60. .. When the number average molecular weight of the cross-linking agent is within the above range, the number of carbon-carbon unsaturated double bonds is equal to or more than a specific value, so that the resin composition according to the present embodiment has the reactivity of the cross-linking agent. Further, the crosslink density of the cured product of the resin composition is further improved, and as a result, more excellent heat resistance can be imparted. On the other hand, when the number average molecular weight of the cross-linking agent is within the above range, the number of carbon-carbon unsaturated double bonds is not more than a specific value, so that more excellent resin fluidity can be imparted during heat molding. ..

Examples of the cross-linking agent include a trialkenyl isocyanurate compound such as triallyl isocyanurate (TAIC), a trialkenyl cyanurate compound such as triallyl cyanurate (TAC), and a polyfunctional methacrylate having two or more methacryl groups in the molecule. Compounds, polyfunctional acrylate compounds having two or more acrylic groups in the molecule, polyfunctional vinyl compounds having two or more vinyl groups in the molecule such as polybutadiene, vinylbenzyl compounds such as divinylbenzene having a vinylbenzyl group in the molecule , 4,4'-Bismaleimide diphenylmethane and the like, which include polyfunctional maleimide compounds having two or more maleimide groups in the molecule. These cross-linking agents may be used alone or in combination of two or more. Among these, the cross-linking agent preferably contains at least one compound selected from the group consisting of triallyl cyanurate, triallyl isocyanurate, and polybutadiene. When the cross-linking agent contains at least one compound described above, the cross-linking density becomes higher during the curing reaction (cross-linking reaction), whereby the heat resistance of the cured product of the resin composition is further improved. There is a tendency.

The mass ratio of PPE: cross-linking agent is preferably 25:75 to 95: 5 from the viewpoint of balancing the low dielectric constant at the time of curing and the low dielectric loss tangent and the cross-linking density of the cross-linked structure, which is more preferable. Is 32:68 to 85:15.

[(C) Organic peroxide]
In this embodiment, PPE and any organic peroxide having an ability to accelerate the polymerization reaction of the resin composition containing a cross-linking agent can be used. Examples of the organic peroxide include benzoyl peroxide, cumene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, and 2,5-dimethyl-2,5-di (t-butylper). Oxy) hexin-3, di-t-butyl peroxide, t-butyl cumyl peroxide, di (2-t-butyl peroxyisopropyl) benzene, 2,5-dimethyl-2,5-di (t-butyl peroxy) ) Hexane, dicumyl peroxide, di-t-butylperoxyisophthalate, t-butylperoxybenzoate, 2,2-bis (t-butylperoxy) butane, 2,2-bis (t-butylperoxy) ) Octane, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, di (trimethylsilyl) peroxide, trimethylsilyltriphenylsilyl peroxide and other peroxides. A radical generator such as 2,3-dimethyl-2,3-diphenylbutane can also be used as a reaction initiator for the resin composition. Above all, from the viewpoint of being able to provide a cured product having excellent heat resistance and mechanical properties, a lower dielectric constant, and a dielectric loss tangent, 2,5-dimethyl-2,5-di (t-butyl). Peroxy) hexin-3, di (2-t-butylperoxyisopropyl) benzene, and 2,5-dimethyl-2,5-di (t-butylperoxy) hexane are preferred.

The 1-minute half-life temperature of the organic peroxide is preferably 155 ° C. or higher and 185 ° C. or lower, and more preferably 160 ° C. to 180 ° C. or 165 ° C. to 175 ° C. In the present specification, the 1-minute half-life temperature is a temperature at which the time during which the organic peroxide is decomposed and the amount of active oxygen thereof is halved is 1 minute. For the 1-minute half-life temperature, an organic peroxide solution is dissolved in a radical-inactive solvent such as benzene so as to have a concentration of 0.05 mol / L to 0.1 mol / L. It is a value confirmed by the method of thermally decomposing the material in a nitrogen atmosphere.

When the 1-minute half-life temperature of the organic peroxide is 155 ° C. or higher, when the PPE-containing resin composition is subjected to heat and pressure molding, the reaction with the cross-linking agent is started after the PPE is sufficiently melted. Therefore, it tends to be excellent in moldability. On the other hand, since the one-minute half-life temperature of the organic peroxide is 185 ° C. or lower, the decomposition rate of the organic peroxide under normal heat and pressure molding conditions (for example, the maximum ultimate temperature of 200 ° C.) is sufficient. Since the cross-linking reaction with the cross-linking agent can proceed efficiently and slowly, it is possible to form a cured product having good electrical characteristics (particularly dielectric positive contact).

Examples of organic peroxides having a 1-minute half-life temperature in the range of 155 ° C to 185 ° C include t-hexylperoxyisopropyl monocarbonate (155.0 ° C) and t-butylperoxy-3,5,5. -Trimethylhexanoate (166.0 ° C), t-butylperoxylaurate (159.4 ° C), t-butylperoxyisopropylmonocarbonate (158.8 ° C), t-butylperoxy2-ethylhexylmonocarbonate (161.4 ° C), t-hexyl peroxybenzoate (160.3 ° C), 2,5-dimethyl-2,5-di (benzoylperoxy) hexane (158.2 ° C), t-butyl peroxyacetate (159.9 ° C), 2,2-di- (t-butylperoxy) butane (159.9 ° C), t-butylperoxybenzoate (166.8 ° C), n-butyl 4,4-di- (T-Butylperoxy) Valerate (172.5 ° C), Di (2-t-Butylperoxyisopropyl) benzene (175.4 ° C), Dicumyl peroxide (175.2 ° C), Di-t-hexylper Oxide (176.7 ° C), 2,5-dimethyl-2,5-di (t-butylperoxy) hexane (179.8 ° C), t-butylcumyl peroxide (173.3 ° C) and the like. Be done.

The content of the organic peroxide is preferably 0.05% by mass or more, more preferably 0.5, from the viewpoint that the reaction rate can be increased based on the total mass of PPE and the cross-linking agent of 100% by mass. It is preferably 5% by mass or more, more preferably 1.5% by mass or more, and more preferably 5% by mass or less, from the viewpoint of being able to keep the dielectric constant and the dielectric tangent of the obtained cured product low. It is preferably 4.5% by mass or less, more preferably 0.9% by mass or less.

[(D) Thermoplastic resin]
The resin composition preferably contains a thermoplastic resin. The thermoplastic resin is water obtained by hydrogenating a block copolymer of a vinyl aromatic compound and an olefin-based alkene compound and a hydrogenated product thereof (a block copolymer of a vinyl aromatic compound and an olefin-based alkene compound). It is preferably at least one selected from the group consisting of hydrogenated block copolymers) and homopolymers of vinyl aromatic compounds. The content of the unit derived from the vinyl aromatic compound of the block copolymer or its hydrogenated product is preferably 20% by mass or more, and can be 99% by mass or less. When the content of the unit derived from the vinyl aromatic compound of the block copolymer or its hydrogenated product is 20% by mass or more, the compatibility with PPE is further improved, and the adhesion strength with the metal leaf is further improved. Tend to do.

The vinyl aromatic compound may have an aromatic ring and a vinyl group in the molecule, and examples thereof include styrene. The olefin-based alkene compound may be an alkene having a linear or branched structure in the molecule, and examples thereof include ethylene, propylene, butylene, isobutylene, butadiene, and isoprene. Among these, the thermoplastic resin is a styrene-butadiene block copolymer, a styrene-ethylene-butadiene block copolymer, a styrene-ethylene-butylene block copolymer, and a styrene-from the viewpoint of being more excellent in compatibility with PPE. Butadiene-butylene block copolymer, styrene-isoprene block copolymer, styrene-ethylene-propylene block copolymer, styrene-isobutylene block copolymer, hydrogenated product of styrene-butadiene block copolymer, styrene-ethylene- Selected from the group consisting of butadiene block copolymer hydrogenated products, styrene-butadiene-butylene block copolymer hydrogenated products, styrene-isoprene block copolymer hydrogenated products, and styrene homopolymers (polystyrene). It is preferably at least one kind selected from the group consisting of a styrene-butadiene block copolymer, a hydrogenated additive of a styrene-butadiene block copolymer, and polystyrene.

The hydrogenation rate of the hydrogenated product is not particularly limited, and a carbon-carbon unsaturated double bond derived from an olefin-based alkene compound may partially remain.

The weight average molecular weight of the thermoplastic resin is preferably 30,000 to 300,000, more preferably 31,000 to 290,000. When the weight average molecular weight is 30,000 or more, the resin composition of the present embodiment tends to be more excellent in heat resistance when cured. Since the weight average molecular weight is 300,000 or less, the resin composition of the present embodiment tends to have better resin fluidity at the time of heat molding. The weight average molecular weight is determined by the method described in Examples described later.

The content of the thermoplastic resin is preferably 2 parts by mass to 20 parts by mass based on a total of 100 parts by mass of PPE and the cross-linking agent. When the content is 2 parts by mass or more, the resin composition of the present embodiment tends to be more excellent in low dielectric constant, low dielectric loss tangent property, and adhesion to the metal leaf when cured. When the content is 20 parts by mass or less, the resin composition of the present embodiment tends to have more excellent resin fluidity at the time of heat molding.

[(E) Flame Retardant]
The resin composition preferably contains a flame retardant. From the viewpoint of improving heat resistance, the flame retardant is preferably one that is incompatible with other components in the resin composition after curing. Preferably, the flame retardant is incompatible with the PPE and / or the cross-linking agent 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; hexabromobenzene, decabromodiphenylethane, 4,4-dibromobiphenyl, ethylenebistetrabromophthalimide and the like. Aromatic bromine compounds of the above; phosphorus-based flame retardants such as resorcinol bis-diphenyl phosphate and resorcinol bis-dixylenyl phosphate. These flame retardants may be used alone or in combination of two or more. Among these, the flame retardant is preferably decabromodiphenylethane from the viewpoint of further excellent low dielectric constant and low dielectric loss tangent when the resin composition is cured.

The content of the flame retardant is not particularly limited, but from the viewpoint of maintaining the flame retardancy of UL standard 94V-0 level, it is preferably 5 parts by mass or more with respect to a total of 100 parts by mass of PPE and the cross-linking agent. It is more preferably 10 parts by mass or more, still more preferably 15 parts by mass or more. Further, from the viewpoint that the dielectric constant of the obtained cured product and the dielectric loss tangent can be kept low, the content of the flame retardant is preferably 50 parts by mass or less, more preferably 45 parts by mass or less, and further preferably 40 parts by mass or less. is there.

[(F) Silica filler]
The resin composition may contain a silica filler. Examples of the silica filler include natural silica, fused silica, synthetic silica, amorphous silica, Aerosil, and hollow silica. The content of the silica filler can be 10 to 100 parts by mass with respect to 100 parts by mass of the total of PPE and the cross-linking agent. Further, the silica filler may have its surface treated with a silane coupling agent or the like.

In addition to the above additives, the resin composition may further contain additives such as heat stabilizers, antioxidants, UV absorbers, surfactants, lubricants, solvents and the like. When the resin composition contains a solvent, the resin composition can be in the form of a varnish in which the solid components in the resin composition are dissolved or dispersed in the solvent.

[(G) solvent]
From the viewpoint of solubility, the solvent is preferably an aromatic compound such as toluene or xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, and chloroform. These solvents may be used alone or in combination of two or more.
From the viewpoint of suitably dissolving PPE in the solvent and facilitating the securing of suitable fluidity of the resin composition even at about room temperature, the solvent is preferably a solvent of an aromatic compound such as toluene, for example. , Toluene / methyl ethyl ketone mixed solvent, toluene / cyclohexane mixed solvent, toluene / cyclopentanone mixed solvent and the like are preferable. Further, in the case of the resin composition of the present embodiment, even if the solvent is toluene alone, it dissolves suitably in such a solvent, and by extension, the substrate is excellent in impregnation property. Therefore, a solvent using toluene alone is also preferable.

[Electronic circuit board material]
The electronic circuit board material according to this embodiment is formed by using the above varnish. Specifically, the electronic circuit board material is a resin film, an impregnated composite of a base material and a resin (also referred to as "prepreg" in the present disclosure), a metal leaf with a resin, or a laminate containing at least one of them. The body.

[Resin film]
The resin film according to the present embodiment can be obtained by applying 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; polycarbonate; polyimide; metal foils such as copper foil and aluminum foil; and release paper. The support may be subjected to chemical or physical treatment such as mud treatment, corona treatment, and mold release treatment.

The resin film according to this embodiment can be suitably used as an interlayer insulating sheet, an adhesive film, or the like of a laminated body such as a multilayer printed wiring board.

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

As the base material, various glass cloths such as roving cloths, cloths, chopped mats, and surface mats; asbestos cloths, metal fiber cloths, and other synthetic or natural inorganic fiber cloths; all aromatic polyamide fibers, all aromatic polyesters. Woven or non-woven fabrics obtained from liquid crystal fibers such as fibers and polybenzoxazole fibers; natural fiber fabrics such as cotton cloth, linen cloth and felt; carbon fiber cloth, kraft paper, cotton paper, cloth obtained from paper-glass mixed fiber yarn, etc. Natural cellulose-based base material; polytetrafluoroethylene porous film and the like can be mentioned. These base materials may be used alone or in combination of two or more.

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

[Metal-clad laminate (laminate)]
The metal-clad laminate (laminate) according to 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 adhered to each other, and is preferably 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 preferable because it has low electrical resistance. The cured product composite to be combined with the metal foil may be one or more, and the metal foil is laminated on one side or both sides of the composite depending on the application and processed into a laminated plate. As a method for producing a laminated board, for example, a composite composed of a thermosetting resin composition and a base material (for example, the above-mentioned prepreg) is formed, and after laminating this with a metal foil, a thermosetting resin is produced. Examples thereof include a method of obtaining a laminated plate in which a cured product laminate and a metal foil are laminated by curing the composition. One of the particularly preferable uses of the laminated board is a printed wiring board. The printed wiring board preferably has at least a part of the metal foil removed from the metal-clad laminate.

[Printed circuit board]
In the printed wiring board according to 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 typically be formed by a method of pressure heating molding using the prepreg of the present embodiment described above. Examples of the base material include the same materials as those described above for 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 containing the resin composition of the present embodiment, and further, electricity due to environmental changes. It is possible to suppress fluctuations in characteristics, and it also has excellent insulation reliability and mechanical properties.

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

(PPE synthesis reaction)
The following reaction was carried out in an atmosphere of an inert gas. The solvent used in the reaction is a commercially available reagent. The raw materials and reagents used are as follows.

1. 1. Solvent Toluene: A special grade reagent manufactured by Wako Pure Chemical Industries, Ltd. was used as it was.
Methyl ethyl ketone: A special grade reagent manufactured by Wako Pure Chemical Industries, Ltd. was used as it was.
Methanol: A special grade reagent manufactured by Wako Pure Chemical Industries, Ltd. was used as it was.
2. 2. Initiator NOF BMT: NOF products were used as they were.
3. 3. Raw material PPE
S202A (polystyrene equivalent number average molecular weight 16,000): A product manufactured by Asahi Kasei Corporation was used as it was.
Each of S202A has the following structure.

4. Raw material phenol (polyfunctional / bifunctional phenol)
4-1. Phenols 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane having a valence of a (a = 3 to 6) containing a partial structure of the formula (2): ADEKA CORPORATION The product (ADEKA STAB AO-30) was used as it was.

4-2. Phenols of valence 2 not including the partial structure of the formula (2) Bisphenol A: Aldrich reagent product was used as it was.

5. Denatured group raw material Methacrylic anhydride: Aldrich reagent product was used as it was.
Dimethylaminopyridine: The Aldrich reagent product was used as it was.

(Identification and analysis of PPE)
1. 1. Number average molecular weight measurement The number average molecular weight was measured by GPC under chloroform solvent. The number average molecular weight was determined by the polystyrene conversion method based on the calibration curve using standard polystyrene.
2. 2. NMR measurement A sample was dissolved in deuterated chloroform to a concentration of 5% by mass, and NMR measurement was performed. The progress of the reaction was confirmed by the decrease of the hydroxyl group peak from the ratio of the aromatic peak of the polyfunctional phenol unit to the proton peak of the hydroxyl group.
3. 3. Melt Viscosity 200 ml of a 20 mass% methyl ethyl ketone solution of a sample was placed in a beaker, and the viscosity was measured at 25 ° C. and a rotation speed of 30 rpm using a B-type 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, a sample obtained by adding a tetramethylammonium hydroxide solution to a methylene chloride solution of PPE in accordance with the method described in "Polymer Papers, vol.51, No. 7 (1994), p. 480". The change in absorbance at a wavelength of 318 nm was measured with an ultraviolet-visible absorptiometer. From this measured value, the number of phenolic hydroxyl groups before and after the terminal modification of PPE was determined. Further, the number of molecules of PPE (number average number of molecules) was determined by using the number average molecular weight of PPE obtained by the above method 1 and the mass of PPE.
From these values, the average number of phenolic hydroxyl groups per PPE molecule before and after denaturation was determined according to the following mathematical formula (1). :
Average number of phenolic hydroxyl groups per molecule = number of phenolic hydroxyl groups / number average number of molecules ... (1)
For the average number of terminal functional groups after modification, the average number of terminal functional groups after modification was determined according to the following mathematical formula (2). :
Average number of terminal functional groups per molecule = average number of phenolic hydroxyl groups before modification-average number of phenolic hydroxyl groups after modification ... (2)

(Manufacturing Example 1)
Synthesis of PPE1 A 500 ml three-necked flask was provided with a three-way cock, and a Dimroth and an isobaric dropping funnel were further installed. After replacing the inside of the flask with nitrogen, 100 g of the raw material PPE S202A, 200 g of toluene, and 12.8 g of 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane as a polyfunctional phenol were added. .. A thermometer was installed in the flask, and the flask was heated to 90 ° C. in an oil bath while stirring with a magnetic stirrer to dissolve the raw material PPE. As an initiator, 37.5 g of a 40% metaxylene solution (Nippon Oil Co., Ltd .: Niper BMT) of a mixture of benzoyl peroxide, benzoyl m-methylbenzoyl peroxide, and m-toluyl peroxide was diluted to 87.5 g of toluene and added dropwise at isobaric pressure. I put it in the funnel. After lowering the temperature inside the flask to 80 ° C., the initiator solution was started dropping into the flask to start the reaction. The initiator was added dropwise over 2 hours, and after the addition, the temperature was raised to 90 ° C. again, and stirring was continued for 4 hours. After the reaction, the polymer solution was added dropwise to methanol, reprecipitated, and then filtered off from the solution to recover the polymer. Then, this was dried under vacuum at 100 ° C. for 3 hours. ¹ It was confirmed by ¹ H-NMR that low molecular weight phenol was incorporated into the polymer and the peak of the hydroxyl group disappeared. The polymer obtained from this ^{1 1} H-NMR measurement result has the following formula:
{In the formula, l, m, and n are numbers arbitrarily selected to satisfy the following number average molecular weights}
It was confirmed that the PPE has a structure as represented by (hereinafter referred to as PPE1). As a result of GPC measurement, the molecular weight of the obtained PPE1 in terms of polystyrene was Mn = 1,500. The solution viscosity of PPE1 in a 20% methyl ethyl ketone solvent was 125 cPoise.

(Synthesis of modified PPE1)
80 g of toluene and 26 g of PPE1 synthesized above were mixed and heated to about 85 ° C. 0.55 g of dimethylaminopyridine was added to the heated mixture. When all the solids seemed to be dissolved, 4.9 g of methacrylic anhydride was gradually added to the lysate. The resulting solution was maintained at 85 ° C. for 3 hours with continuous mixing. The solution was then cooled to room temperature to give a toluene solution of methacrylate-modified PPE.
A part of the solution was collected, dried, and then ¹ H-NMR measurement was carried out. Since the peak derived from the hydroxyl group of PPE had disappeared, it was judged that the reaction was proceeding, and the purification operation was started. 120 g of the toluene solution of the methacrylate-modified PPE was added dropwise to 360 g of methanol vigorously stirred with a magnetic stirrer in a 1 L beaker over 30 minutes. The obtained precipitate was filtered under reduced pressure with a membrane filter and then dried to obtain 38 g of a polymer. The ¹ H-NMR measurement result of the dried polymer is shown in FIG. It was confirmed that the peak derived from the hydroxyl group of PPE around 4.5 ppm disappeared, and the peak derived from the olefin of the methacrylic group was expressed around 5.75 ppm. In addition, since the peaks derived from dimethylaminopyridine, methacrylic anhydride, and methacrylic acid have almost disappeared by GC measurement, it is judged that the peaks derived from the methacrylic group of NMR are those of the methacrylic group bonded to the PPE terminal. did. From this result, the obtained polymer has the following formula:
{In the formula, l, m, and n are numbers arbitrarily selected to satisfy the following number average molecular weights}
It was confirmed that the modified PPE has a structure as represented by (hereinafter referred to as modified PPE1).
As a result of GPC measurement, the molecular weight of the modified PPE1 obtained in terms of polystyrene was Mn = 1,600. Further, the average number of terminal functional groups of the modified PPE1 was calculated to be 2.5 or more according to the above formula (2). Further, the solution viscosity of the modified PPE1 in a 20% methyl ethyl ketone solvent was 131 cPoise.

Material PPE used to form the resin composition and its cured product
-Modified polyphenylene ether 1 (modified PPE1) obtained above.
-Terminal methacrylic acid modified PPE "Product name SA9000"
(Manufactured by Sabic Innovative Plastics, Mn: 2756, number of terminal functional groups: 2.0)
・ "PPE S203A" (manufactured by Asahi Kasei Corporation, Mn: 10,000)

Crosslinker-TAIC (manufactured by Nihon Kasei Co., Ltd., molecular weight: 249.7, number of unsaturated double bonds: 3)
-Polybutadiene "Product name B-2000"
(Made by Nippon Soda, Mn: 2100, number of unsaturated double bonds: 34.4)

Organic peroxide ・ Bis (1-tert-butylperoxy-1-methylethyl) benzene "Product name Perbutyl P" (manufactured by NOF CORPORATION)

Thermoplastic Resin-Hydrogenated Styrene-based Thermoplastic Resin (SEBS) "Product Name Tough Tech H1041"
(Made by Asahi Kasei Corporation, Mw: 49,000, styrene unit content: 30% by mass) -Hydrogenated styrene-based thermoplastic resin (SEBS) "Product name Tough Tech H1051"
(Made by Asahi Kasei Corporation, Mw: 49,000, styrene unit content: 30% by mass)
-Hydrogenated styrene-based thermoplastic resin (SEBS) "Product name Tough Tech N504"
(Made by Asahi Kasei Corporation, Mw: 200,000, styrene unit content: 32% by mass)

Flame Retardant ・ Decabromodiphenylethane "Product name SAYTEX8010" (manufactured by Albemarle)

Filler ・ Spherical silica (manufactured by Ryumori Co., Ltd.)

Base material ・ L glass cloth (manufactured by Asahi Schebel, style: 2116)

Evaluation method 1. Number average molecular weight of PPE, weight average molecular weight of thermoplastic resin Using GPC analysis, the number average molecular weight of PPE and the weight average molecular weight of the thermoplastic resin were determined 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), HLC-8220 GPC (manufactured by Tosoh Corporation) is used as a measuring device, and a column: Shodex GPC KF-405L HQ × Measured under the conditions of 3 (manufactured by Showa Denko Co., Ltd.), eluent: chloroform, injection amount: 20 μL, flow rate: 0.3 mL / min, column temperature: 40 ° C., detector: RI.

2. 2. Permittivity and dielectric loss tangent (electrical characteristics, 10 GHz)
The permittivity at 10 GHz and the dielectric loss tangent were measured by the cavity resonance method. The measurement was performed using a network analyzer (N5230A, manufactured by Agilent Technologies) and a cavity resonator (Cavity Resonator CP series) manufactured by Kanto Electronics Applied Development Co., Ltd. as a measuring device.
Eight prepregs obtained in Examples and Comparative Examples were stacked and vacuum pressed at a pressure of 5 kg / cm ² while heating from room temperature at a temperature rise rate of 3 ° C./min. When the temperature reached 130 ° C., the temperature rise rate was reached. Vacuum press under the condition of pressure 40 kg / cm ² while heating at 3 ° C./min, and when reaching 200 ° C., perform vacuum press under the condition of pressure 40 kg / cm ² and 60 minutes while maintaining the temperature at 200 ° C. By doing so, a laminated board was produced.
The laminated plate was cut into a size of about 2 mm in width and 50 mm in length so that the warp of the glass cloth had a long side, and used as a sample for measuring the dielectric constant and the dielectric loss tangent.
The measurement sample was placed in an oven at 105 ° C. ± 2 ° C. and dried for 2 hours, and then allowed to stand in an environment at 23 ° C. and a relative humidity of 50 ± 5% for 96 ± 5 hours. Then, the permittivity and the dielectric loss tangent were measured and measured by using the above measuring device in an environment of 23 ° C. and a relative humidity of 50 ± 5%, and evaluated in 5 steps.
5: Permittivity 3.0 to 3.4 and dielectric loss tangent 0.0024 or less, exceeding 0.0020 4: Permittivity 3.0 to 3.4 and dielectric loss tangent 0.0026 or less, 0.0024 More than 3: Dielectric constant 3.0 to 3.4 and dielectric loss tangent 0.0030 or less, more than 0.0026 2: Dielectric constant 3.0 to 3.4 and dielectric loss tangent 0.0035 or less, 0 More than .0030 1: Permittivity exceeds 3.4 and dielectric loss tangent exceeds 0.0035

3. 3. Copper foil peeling strength of laminated board (peeling strength, N / mm)
The stress when peeling the copper foil of the copper-clad laminate at a constant speed was measured in accordance with JIS C 6481, a standard dedicated to the test of copper-clad laminates for printed wiring boards.
Two prepregs obtained in Examples and Comparative Examples were laminated, and copper foil (thickness 35 μm, GTS-MP foil, manufactured by Furukawa Denki Kogyo Co., Ltd.) was laminated on top of and below the prepreg, and the temperature was raised from room temperature to 3 ° C. Vacuum press under the condition of pressure 5 kg / cm ² while heating at / min, and when reaching 130 ° C, perform vacuum press under the condition of pressure 40 kg / cm ² while heating at a heating rate of 3 ° C / min, and then perform vacuum press at 200 ° C. When the temperature reached 200 ° C., a double-sided copper-clad laminate was produced by vacuum pressing under the conditions of a pressure of 40 kg / cm ² and 60 minutes while maintaining the temperature at 200 ° C.
The obtained copper-clad laminate was cut into a size of 15 mm in width × 150 mm in length, and the copper foil was removed at an angle of 90 ° C. with respect to the removal surface using an autograph (AG-5000D, manufactured by Shimadzu Corporation) at an angle of 50 mm / The load when peeled off at a speed of 1 minute was measured, and the average value of 5 measurements was calculated.
5: Over 1.0 N / mm 4: Over 0.80 N / mm Over 1.0 N / mm 3: Over 0.70 N / mm Over 0.80 N / mm 2: Over 0.5 N / mm Over 0.70 N / mm 1: 0.5 N / mm or less

4. Laminated glass transition temperature (Tg, ° C)
The dynamic viscoelasticity was measured, and the temperature at which tan δ was maximized was determined as the glass transition temperature (Tg). Using a dynamic viscoelastic device (RHEOVIBRON model DDV-01FP, manufactured by ORIENTEC) as the measuring device, test piece: length about 35 mm, width about 12.5 mm, thickness about 0.3 mm, pulling mode, frequency: 10 rad The measurement was performed under the condition of / s.
Two prepregs obtained in Examples and Comparative Examples were stacked, and a copper foil (GTS-MP foil, manufactured by Furukawa Denki Kogyo Co., Ltd.) with a thickness of 35 μm was laminated on top of and below the prepreg, and the final temperature reached 200 ° C. It was prepared by vacuum pressing under the condition of an ultimate pressure of 40 kg / cm ² to obtain a double-sided copper-clad laminate, and then removing the copper foil by etching.
It was evaluated on a 5-point scale according to the value of Tg.
5: Over 200 ° C 4: Over 190 ° C and below 200 ° C 3: Over 180 ° C and below 190 ° C 2: Over 170 ° C and below 180 ° C 1: Over 160 ° C and below 170 ° C

5. Solder heat resistance of laminated plates and cross-section observation after heat resistance test Eight prepregs obtained in Examples and Comparative Examples were stacked, and copper foils with a thickness of 12 μm and a surface roughness of Rz of 2.0 μm were placed on both sides thereof. FV-WS foil, manufactured by Furukawa Electric) was layered. Next, vacuum press is performed under the condition of a pressure of 5 kg / cm ² while heating at a heating rate of 3 ° C./min from room temperature, and when the temperature reaches 130 ° C., the pressure is 40 kg / cm ² while heating at a heating rate of 3 ° C./min. A copper-clad laminate was produced by vacuum pressing under the conditions, and when the temperature reached 200 ° C., the pressure was 40 kg / cm ² and the pressure was 40 kg / cm ² for 60 minutes while maintaining the temperature at 200 ° C.
The copper foil on only one side was removed by etching, and a heat resistance test was carried out. In the heat resistance test, the test piece was cut into 50 mm squares, then placed in an oven at 105 ° C. and dried for 2 hours, and then a pressure cooker test was carried out under the conditions of 2 atm and 4 hours. Then, a heat resistance test was carried out in which the test of dipping in a solder bath at 260 ° C. or 288 ° C. for 20 seconds was repeated 30 times. The dip interval was 20 seconds.
In the heat resistance test, evaluation was made based on the following by visual observation.
⊚: Laminated plate in which no swelling, peeling, or whitening was confirmed under the condition of 288 ° C. 〇: Laminated plate in which none of swelling, peeling, or whitening was confirmed under the condition of 260 ° C. Under the conditions, either swelling, peeling, or whitening occurred)
X: Laminated plate in which any of swelling, peeling, and whitening occurred under the condition of 260 ° C.

Further, the test piece after the heat resistance test was cross-sectionally observed using SEM.
In the cross-sectional observation, the evaluation was made based on the following by visual observation.
No problem: No cracks such as cracks were confirmed Problem: Cracks such as cracks or cracks were confirmed

6. Varnish Viscosity 200 ml of a resin varnish (solid content 53% by mass) prepared with each resin composition and toluene was placed in a beaker, and the viscosity was measured using a B-type rotational viscometer at 25 ° C. at a rotation speed of 30 rpm for 30 seconds. .. The measured viscosity was evaluated on a 5-point scale.
5: 50 mPa ・ s or more and less than 150 mPa ・ s 4: 150 mPa ・ s or more and less than 200 mPa ・ s 3: 200 mPa ・ s or more and less than 300 mPa ・ s 2: 300 mPa ・ s or more and less than 500 mPa ・ s 1: 500 mPa ・ s or more and 1000 mPa ・ s or less

7. Impregnation property A resin varnish (solid content 53% by mass) prepared with each resin composition and toluene is put in a bat, and an L glass cloth (manufactured by Asahi Schebel Co., Ltd., style: 2116) cut into 50 mm squares is placed on it. The appearance of the resin varnish impregnating the glass cloth was visually observed. The evaluation was made on a 5-point scale according to the impregnation property of the resin varnish into the glass cloth.
5: 1 When the entire glass cloth is impregnated with resin varnish within 4: 2 minutes When the entire glass cloth is impregnated with resin varnish 3: When the entire glass cloth is impregnated with resin varnish within 3 minutes 2: When the entire glass cloth is impregnated with resin varnish within 5 minutes 1: When impregnation is not completed even after 5 minutes

(Example 1)
According to the composition and solvent shown in Table 1, a thermoplastic resin was added to parts by mass of toluene, stirred and dissolved, and then a flame retardant, spherical silica (silica filler), and modified PPE1 were added and modified. Stirring was continued until PPE1 was dissolved. Next, a cross-linking agent and an organic peroxide were added to the lysate, and the mixture was sufficiently stirred to obtain a varnish. After impregnating this varnish with L glass cloth, excess varnish was scraped off by passing it through a predetermined slit, dried in a drying oven at 105 ° C. for a predetermined time, and toluene was removed to obtain a prepreg. .. The solid content of the resin composition in the prepreg was calculated by cutting out the prepreg to a predetermined size and comparing the mass of the glass cloth with the mass of the glass cloth, which was 58% by mass. A predetermined number of these prepregs are stacked, and copper foil (manufactured by Furukawa Electric Co., Ltd., thickness 35 μm, GTS-MP foil) is laminated on both sides of the stacked prepregs, and then vacuum pressed to perform copper tensioning. A laminated board was obtained. In this vacuum pressing process, first, the condition of a pressure of 10 kg / cm ² is adopted while heating from room temperature at a heating rate of 3 ° C./min, and then after reaching 130 ° C., the heating rate is 3 ° C./min. The condition of pressure 40 kg / cm ² was adopted while heating. After the temperature reached 200 ° C., the conditions of a pressure of 40 kg / cm ² and a time of 60 minutes were adopted while maintaining the temperature at 200 ° C. Next, a laminated plate was obtained by removing the copper foil from the copper-clad laminate by etching.

(Examples 2 to 8 and Comparative Examples 1 to 5)
The resin compositions, varnishes, and prepregs were obtained and evaluated in Examples 2 to 8 and Comparative Examples 1 to 5, respectively, according to the same method as in Example 1 except that the resin composition was changed as shown in Table 1.

As shown in Table 1, in all of Examples 1 to 8, the evaluation of electrical characteristics was "5", the evaluation of peel strength was "4" or higher, the evaluation of Tg was "5", and the evaluation of heat resistance was "◎". , The evaluation of viscosity was "5", and the evaluation of impregnation property was "5".
Specifically, in Examples 1 to 8, an increase in the viscosity of the resin composition can be suitably suppressed as compared with Comparative Examples (Comparative Examples 1, 2, and 5) in which the evaluation of the viscosity is "4" or less. confirmed. By suitably suppressing the increase in the viscosity of the resin composition, it is possible to improve the coatability of the resin composition on the base material.
Further, in Examples 1 to 8, the dielectric constant and the dielectric loss tangent (Df) can be reduced as compared with Comparative Examples 1 to 5 in which either the evaluation of the electrical characteristics or the evaluation of Tg is "4" or less, and further. It was confirmed that the heat resistance can be improved. Here, in the evaluation items of Tg, although the same evaluation of "5" was obtained in Comparative Examples 1, 2, and 5 and Examples 1 to 8, when looking at the evaluation items of heat resistance, Examples. It was confirmed that the values were "◎" in 1 to 8 but remained "○" in Comparative Examples 1 to 5. Therefore, it was confirmed that Examples 1 to 8 were excellent in heat resistance as compared with Comparative Examples 1, 2 and 5 in which "5" was obtained in the evaluation item of Tg.
Further, in Examples 1 to 8, unlike Comparative Examples 1 to 2 and 5, it was evaluated as "no problem" in the cross-sectional observation after the heat resistance test. Therefore, it was confirmed that the prepregs of Examples 1 to 8 were improved in strength against stress or deformation (improvement of toughness) as compared with Comparative Examples 1 to 2 and 5.
Further, it was confirmed that Examples 1 to 8 were superior in the evaluation result of invasiveness as compared with Comparative Examples 1, 2 and 5. Then, it was confirmed that the evaluation results of the peel strength of Examples 1 to 8 were the same or superior to those of Comparative Examples 1 to 5. As described above, in Examples 1 to 8, as compared with Comparative Examples 1 to 5, the electrical characteristics are improved (dielectric constant is reduced and the dielectric loss tangent is reduced), the peel strength is improved, the toughness is improved, and the heat resistance is improved. It was confirmed that both the above and the improvement of the impregnation to the substrate were feasible.

Claims (13)

A resin composition containing a polyphenylene ether, a cross-linking agent, and an organic peroxide.
The polyphenylene ether has the following formula (1):
{In the formula,
X is an arbitrary linking group of a value, and a is a number of 2.5 or more.
R ⁵ is any substituent independently, k are each independently 1 to 4 integer, and at least one of the k is R ⁵ is represented by the following formula (2):
(In the formula, R ¹¹ is an alkyl group of C _1-8 independently, R ¹² is an alkylene group of C _1-8 independently, b is 0 or 1 independently, and R _{Reference numeral} ¹³ denotes a hydrogen atom, either an alkyl group or a phenyl group of C _1-8 , and the alkyl group, the alkylene group, and the phenyl group may contain a substituent to the extent that the condition of C _1-8 is satisfied. Good)
Including the partial structure represented by
Y is independently expressed by the following equation (3):
(In the formula, R ²¹ is an independently saturated or unsaturated hydrocarbon group of C _1-6 , and R ²² is an independently saturated or unsaturated hydrocarbon group of C _1-6. And the saturated or unsaturated hydrocarbon group may have a substituent as long as the condition of C _1-6 is satisfied).
It is a divalent linking group having a structure represented by, n represents the number of repetitions of Y, and each is an integer of 1 to 200 independently.
L is any divalent linking group or single bond, and A represents a substituent containing a carbon-carbon double bond and / or an epoxy bond, respectively}.
Polyphenylene ether component A containing the structure represented by
The following formula (4A): at the end of the main chain:
{Wherein, n is an integer of 0 or _1, ^{R 1} is a saturated alkyl group or unsaturated alkyl group of _{C 1-8,} and ^{R 2} is or a saturated alkyl group of a hydrogen atom or a _{C 1-8} Unsaturated alkyl group}
It contains a polyphenylene ether component B having an average of 1.5 to 2.5 functional groups represented by (1) and having a number average molecular weight of 1,000 or more and 4,500 or less.
Based on the total amount of the polyphenylene ether of 100% by mass, the content of the polyphenylene ether component A is 2% by mass or more and less than 40% by mass, and the content of the polyphenylene ether component B is more than 60% by mass and less than 98% by mass. The resin composition that is. The resin composition according to claim 1, wherein the cross-linking agent comprises at least one selected from the group consisting of triallyl cyanurate, triallyl isocyanurate, and polybutadiene.
The cross-linking agent has an average of two or more carbon-carbon unsaturated double bonds in one molecule.
The resin composition according to claim 1 or 2, wherein the number average molecular weight of the cross-linking agent is 4,000 or less, and the mass ratio of the polyphenylene ether: the cross-linking agent is 25:75 to 95: 5.
The one-minute half-life temperature of the organic peroxide is 155 ° C or higher and 185 ° C or lower.
Any of claims 1 to 3, wherein the content of the organic peroxide is 0.05% by mass or more and 0.9% by mass or less based on the total mass of 100% by mass of the polyphenylene ether and the cross-linking agent. The resin composition according to item 1.
The resin composition further comprises a thermoplastic resin and
The thermoplastic resin is at least one selected from the group consisting of a block copolymer of a vinyl aromatic compound and an olefin-based alkene compound, a hydrogenated product thereof, and a homopolymer of the vinyl aromatic compound.
The resin composition according to any one of claims 1 to 4, wherein the content of the unit derived from the vinyl aromatic compound in the block copolymer or its hydrogenated product is 20% by mass or more.
The resin composition according to claim 5, wherein the thermoplastic resin has a weight average molecular weight of 30,000 to 300,000.
The content of the thermoplastic resin is
The resin composition according to claim 5 or 6, wherein the total amount of the polyphenylene ether and the cross-linking agent is 100% by mass or more and 2% by mass or more and 20% by mass or less.
Any one of claims 1 to 7, wherein the resin composition further contains a flame retardant, and the flame retardant is incompatible with other contained components in the resin composition after curing of the resin composition. The resin composition according to.
An electronic circuit board material containing the resin composition according to any one of claims 1 to 8.
A resin film containing the resin composition according to any one of claims 1 to 8.
A prepreg that is a composite of a base material and the resin composition according to any one of claims 1 to 9.
The prepreg according to claim 11, wherein the base material is glass cloth.
A laminate of the resin film according to claim 10 or the cured product of the prepreg according to claim 11 or 12 and a metal foil.