JP2022001628A - Resin composition - Google Patents

Abstract

To provide a resin composition which can provide a cured product with a dielectric constant (Dk) and dielectric dissipation factor (Df) kept low.SOLUTION: Provided is a resin composition comprising (A) a polystyrene resin having ethylenic unsaturated bonds, (B) a crosslinking agent, and (C) inorganic filler.SELECTED DRAWING: None

Description

The present invention relates to a resin composition containing a polystyrene resin. Further, the present invention relates to a cured product obtained by using the resin composition, a sheet-like laminated material, a resin sheet, a printed wiring board, and a semiconductor device.

As a manufacturing technique for a printed wiring board, a manufacturing method by a build-up method in which insulating layers and conductor layers are alternately stacked is known. In the build-up manufacturing method, the insulating layer is generally formed by curing the resin composition. In recent years, as the frequency of signals has increased due to the progress of miniaturization and high performance of electronic devices, it is required to reduce the dielectric constant and dielectric loss tangent of the insulating layer of the multilayer printed wiring board.

So far, a resin composition containing a polystyrene resin containing a cyclic imino ether skeleton has been known (Patent Document 1).

Japanese Unexamined Patent Publication No. 2017-36353

An object of the present invention is to provide a resin composition for obtaining a cured product having a low relative permittivity (Dk) and a low dielectric loss tangent (Df).

As a result of diligent studies to achieve the object of the present invention, the present inventors have made a resin composition containing (A) a polystyrene resin having an ethylenically unsaturated bond, (B) a cross-linking agent, and (C) an inorganic filler. Surprisingly, it was found that a cured product having a low relative permittivity (Dk) and a low dielectric loss tangent (Df) can be obtained by using the above, and the present invention has been completed.

That is, the present invention includes the following contents.
[1] A resin composition containing (A) a polystyrene resin having an ethylenically unsaturated bond, (B) a cross-linking agent, and (C) an inorganic filler.
[2] The resin composition according to the above [1], wherein the component (A) contains a polystyrene resin having an ethylenically unsaturated bond in the side chain.
[3] The resin composition according to the above [2], wherein the side chain having an ethylenically unsaturated bond in the component (A) further has an ester bond.
[4] The resin composition according to the above [2] or [3], wherein the side chain having an ethylenically unsaturated bond in the component (A) further has an amide bond.
[5] The resin composition according to any one of the above [1] to [4], wherein the component (A) has an acryloyl group and / or a methacryloyl group.
[6] The ethylenically unsaturated bond equivalent of the component (A) is 1000 g / eq. 10,000 g / eq. The resin composition according to any one of the above [1] to [5].
[7] The resin composition according to any one of the above [1] to [6], wherein the weight average molecular weight (Mw) of the component (A) is 10,000 or more.
[8] The component (A) is the formula (1) :.

[In the formula, R ¹¹ , R ¹² and R ¹³ each independently indicate a hydrogen atom or a substituent; R ¹⁴ independently indicate a substituent; a is an integer of 0 to 5. show. ]
Repeat unit represented by, and equation (2):

[In the formula, R ²¹ , R ²² , R ²³ and R ²⁴ each independently indicate a hydrogen atom or a substituent; R ²⁵ indicates an ethylenically unsaturated bond-containing hydrocarbon group; X is a single bond. Indicates a bond or linking group; n represents an integer greater than or equal to 2. ]
The resin composition according to any one of the above [1] to [7], which comprises a resin having a repeating unit represented by.
[9] The repeating unit represented by the equation (2) is the equation (2') :.

[In the formula, R ²¹ , R ²² , R ²³ and R ²⁴ independently indicate a hydrogen atom or a substituent; R ²⁶ , R ²⁷ and R ²⁸ independently indicate a hydrogen atom or an alkyl group, respectively. ; X indicates a single bond or a linking group; n indicates an integer of 2 or more. ]
The resin composition according to the above [8], which is a repeating unit represented by.
[10] The above-mentioned [1] to [9], wherein the mass ratio of the component (B) to the component (A) (component (B) / component (A)) is 0.01 to 1. Resin composition.
[11] The above-mentioned [1] to [10], wherein the mass ratio of the component (C) to the component (A) (component (C) / component (A)) is 0.5 to 10. Resin composition.
[12] The content of the component (C) is 40% by mass to 75% by mass when the non-volatile component in the resin composition is 100% by mass, according to any one of the above [1] to [11]. Resin composition.
[13] The resin composition according to any one of the above [1] to [12], further comprising (D) an epoxy resin.
[14] Any of the above [1] to [13], wherein the dielectric loss tangent of the cured product (curing temperature 200 ° C.) of the resin composition is 0.004 or less when measured at 5.8 GHz and 23 ° C. The resin composition described.
[15] Any of the above [1] to [14], wherein the relative permittivity of the cured product (curing temperature 200 ° C.) of the resin composition is 3.0 or less when measured at 5.8 GHz and 23 ° C. The resin composition according to.
[16] The resin composition according to any one of the above [1] to [15] for forming an insulating layer of a printed wiring board.
[17] A cured product of the resin composition according to any one of the above [1] to [16].
[18] A sheet-like laminated material containing the resin composition according to any one of the above [1] to [16].
[19] A resin sheet having a support and a resin composition layer formed from the resin composition according to any one of the above [1] to [16] provided on the support.
[20] A printed wiring board provided with an insulating layer made of a cured product of the resin composition according to any one of the above [1] to [16].
[21] A semiconductor device including the printed wiring board according to the above [20].

According to the resin composition of the present invention, it is possible to obtain a cured product having a low relative permittivity (Dk) and a low dielectric loss tangent (Df).

Hereinafter, the present invention will be described in detail according to the preferred embodiment thereof. However, the present invention is not limited to the following embodiments and examples, and may be arbitrarily modified and implemented without departing from the scope of claims of the present invention and the equivalent scope thereof.

<Resin composition>
The resin composition of the present invention contains (A) a polystyrene resin having an ethylenically unsaturated bond, (B) a cross-linking agent, and (C) an inorganic filler. By using such a resin composition, it is possible to obtain a cured product in which the relative permittivity (Dk) and the dielectric loss tangent (Df) are suppressed to be low.

The resin composition of the present invention may further contain any component in addition to (A) a polystyrene resin having an ethylenically unsaturated bond, (B) a cross-linking agent, and (C) an inorganic filler. Optional components include, for example, (D) radical polymerization initiator, (E) epoxy resin, (F) epoxy curing agent, (G) epoxy curing accelerator, (H) other additives, and (I) organic. Examples include solvents. Hereinafter, each component contained in the resin composition will be described in detail.

<(A) Polystyrene resin having an ethylenically unsaturated bond>
The resin composition of the present invention contains (A) a polystyrene resin having an ethylenically unsaturated bond. The ethylenically unsaturated bond means a radically polymerizable carbon-carbon double bond. As the component (A), one type may be used alone, or two or more types may be used in any combination.

In one embodiment, the component (A) preferably has an ethylenically unsaturated bond in the side chain. Therefore, the component (A) preferably contains a polystyrene resin having an ethylenically unsaturated bond in the side chain. In one embodiment, the ethylenically unsaturated bond is preferably at the end of the side chain. Therefore, in one embodiment, the component (A) preferably contains a polystyrene resin having an ethylenically unsaturated bond at the end of the side chain.

The side chain having an ethylenically unsaturated bond preferably further has an ester bond (-COO-) in one embodiment. The side chain having an ethylenically unsaturated bond preferably further has an amide bond (-CONH-) in one embodiment. The side chain having an ethylenically unsaturated bond preferably further has both an ester bond and an amide bond in a particularly preferred embodiment.

The component (A) is not particularly limited in one embodiment, but is, for example, an allyl group, a 3-cyclohexenyl group, a p-vinylphenyl group, an m-vinylphenyl group, an o-vinylphenyl group and the like. Unsaturated hydrocarbon group; radical polymerization of α, β-unsaturated carbonyl group such as acryloyl group, methacryloyl group, maleimide group (2,5-dihydro-2,5-dioxo-1H-pyrrole-1-yl group) It preferably has an acryloyl group and / or a methacryloyl group, and in one embodiment, the side chain having an ethylenically unsaturated bond in the component (A) has an acryloyl group and / or a methacryloyl group. It is particularly preferable to have a side chain.

In one embodiment, the component (A) is preferably the formula (1) :.

[In the formula, R ¹¹ , R ¹² and R ¹³ each independently indicate a hydrogen atom or a substituent; R ¹⁴ independently indicate a substituent; a is an integer of 0 to 5. show. ]
Repeat unit represented by, and equation (2):

[In the formula, R ²¹ , R ²² , R ²³ and R ²⁴ each independently indicate a hydrogen atom or a substituent; R ²⁵ indicates an ethylenically unsaturated bond-containing hydrocarbon group; X is a single bond. Indicates a bond or linking group; n represents an integer greater than or equal to 2. ]
Includes resins with repeating units represented by.

The order and individual arrangement of the repeating unit represented by the formula (1) and the repeating unit represented by the formula (2) are arbitrary, and alternate copolymers, block copolymers, random copolymers, etc. may be used. include. Further, the repeating unit represented by the formula (1) and the repeating unit represented by the formula (2) may be the same or different for each unit. ^{The 2n R 24s} contained in the formula (2) are independently the same or different from each other.

The substituent is not particularly limited, but is, for example, an alkyl group, an alkenyl group, an aryl group, an alkyl-aryl group (an aryl group substituted with one or more alkyl groups), and an aryl-aryl group (1). Aryl group substituted with one or more aryl groups), aryl-alkyl group (alkyl group substituted with one or more aryl groups), alkyl-oxy group, alkenyl-oxy group, aryl-oxy group, alkyl-carbonyl Group, alkenyl-carbonyl group, aryl-carbonyl group, alkyl-oxy-carbonyl group, alkenyl-oxy-carbonyl group, aryl-oxy-carbonyl group, alkyl-carbonyl-oxy group, alkenyl-carbonyl-oxy group, aryl-carbonyl A monovalent substituent such as a −oxy group can be mentioned, and if substitutable, a divalent substituent such as an oxo group (= O) can also be included.

Alkyl (group) refers to a linear, branched and / or cyclic monovalent saturated hydrocarbon group. Unless otherwise specified, the alkyl (group) is preferably an alkyl (group) having 1 to 14 carbon atoms, more preferably 1 to 10 carbon atoms, and further preferably 1 to 6 carbon atoms. Examples of the alkyl (group) include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group and a nonyl group. Examples thereof include a group, a decyl group, a cyclopentyl group, a cyclohexyl group, a methylcyclohexyl group, a dimethylcyclohexyl group, a trimethylcyclohexyl group, a cyclopentylmethyl group, a cyclohexylmethyl group and the like. Alkenyl (group) refers to a linear, branched and / or cyclic monovalent aliphatic unsaturated hydrocarbon group having at least one carbon-carbon double bond. Unless otherwise specified, the alkenyl (group) is preferably an alkenyl (group) having 2 to 14 carbon atoms, more preferably 2 to 10 carbon atoms, and further preferably 2 to 6 carbon atoms. Examples of the alkenyl (group) include a vinyl group, a 1-propenyl group, a 2-propenyl group (allyl group), an isopropenyl group, a 2-methyl-2-propenyl group, a 1-butenyl group and a 2-butenyl group, 3 -Butenyl group, 2-pentenyl group, 3-pentenyl group, 4-pentenyl group, 1-methyl-1-butenyl group, 2-methyl-1-butenyl group, 2-methyl-2-butenyl group, 3-methyl- 2-butenyl group, 3-methyl-3-butenyl group, 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, 4-pentenyl group, 4-methyl-4-pentenyl group, 1-hexenyl group, 2- Hexenyl group, 3-hexenyl group, 4-hexenyl group, 5-hexenyl group, 1-cyclopentenyl group, 2-cyclopentenyl group, 3-cyclopentenyl group, 1-cyclohexenyl group, 2-cyclohexenyl group, 3- Cyclohexenyl groups and the like can be mentioned. Aryl (group) refers to a monovalent aromatic hydrocarbon group. The aryl (group) is preferably an aryl (group) having 6 to 14 carbon atoms. Examples of the aryl (group) include a phenyl group, a 1-naphthyl group, a 2-naphthyl group and the like.

The linking group is not particularly limited, but for example, an alkylene group, an alkenylene group, an arylene group, -O-, -CO-, -S-, -SO-, _{-SO 2-, -COO-,.} Examples thereof include -OCO-, -CONH-, -NHCO-, and combinations thereof. The number of atoms in the main chain of the linking group is not particularly limited, but may be, for example, 1 to 100, preferably 1 to 50, more preferably 1 to 20, and even more preferably 1 to 10.

The alkylene group refers to a linear, branched or cyclic divalent saturated hydrocarbon group. Unless otherwise specified, the alkylene group is preferably an alkylene group having 1 to 14 carbon atoms, more preferably 1 to 10 carbon atoms, and further preferably 1 to 6 carbon atoms. As the alkylene group, _{e.g., -CH 2 -, - CH 2} -CH 2 -, - CH (CH 3) -, - CH 2 -CH 2 -CH 2 -, - CH 2 -CH (CH 3) -, _{-CH (CH 3) -CH 2 -} , - C (CH 3) 2 -, - CH 2 -CH 2 -CH 2 -CH 2 - and the like. The alkenylene group refers to a linear, branched or cyclic divalent aliphatic unsaturated hydrocarbon group having at least one carbon-carbon double bond. Unless otherwise specified, the alkenylene group is preferably an alkenylene group having 2 to 14 carbon atoms, more preferably 2 to 10 carbon atoms, and further preferably 2 to 6 carbon atoms. Examples of the alkenylene group include −CH ₂ = CH ₂ −, −C (= CH ₂ ) −, −CH = _{CH −CH 2 −, −CH 2} −CH = CH −, and the like. The arylene group refers to a divalent aromatic hydrocarbon group. The arylene group is preferably an arylene group having 6 to 14 carbon atoms. Examples of the arylene group include a 1,4-phenylene group, a 1,3-phenylene group, a 2,4-naphthylene group and the like.

R ¹¹ , R ¹² and R ¹³ each independently represent a hydrogen atom or a substituent, preferably a hydrogen atom, an alkyl group or an aryl group, more preferably a hydrogen atom or an alkyl group, and further. It is preferably a hydrogen atom. Each of R ¹⁴ independently exhibits a substituent, preferably an alkyl group or an aryl group, more preferably an alkyl group, and further preferably a methyl group. a represents an integer of 0 to 5, preferably 0 to 2, and more preferably 0.

R ²¹ , R ²² and R ²³ each independently represent a hydrogen atom or a substituent, preferably a hydrogen atom, an alkyl group or an aryl group, more preferably a hydrogen atom or an alkyl group, and further. Preferably, R ²¹ and R ²² are hydrogen atoms and R ²³ is an alkyl group, and particularly preferably, R ²¹ and R ²² are hydrogen atoms and R ²³ is a methyl group.

R ²⁴ independently represents a hydrogen atom or a substituent, preferably a hydrogen atom, an alkyl group or an aryl group, more preferably a hydrogen atom or an alkyl group, and further preferably a hydrogen atom.

R ²⁵ represents an ethylenically unsaturated bond-containing hydrocarbon group. The ethylenically unsaturated bond-containing hydrocarbon group may contain an aromatic carbocycle. The number of carbon atoms of the ethylenically unsaturated bond-containing hydrocarbon group is not particularly limited, but is, for example, 2 to 100, preferably 2 to 50, more preferably 2 to 30, still more preferably 1 to 10. be. Examples of the ethylenically unsaturated bond-containing hydrocarbon group include (1) an alkenyl group, (2) an alkenyl group substituted with one or more aryl groups, and (3) a substituent substituted with one or more alkyl-aryl groups. Alkenyl groups, (4) alkenyl groups substituted with one or more aryl-aryl groups, (5) aryl groups substituted with one or more alkenyl groups, (6) one or more alkenyl groups and one. Aryl groups substituted with the above alkyl groups, (7) one or more alkenyl groups and one or more aryl groups substituted, (8) one or more alkenyl groups and one or more alkyl- Aryl groups substituted with aryl groups, (9) one or more alkenyl groups and one or more aryl-aryl groups substituted, (10) one or more alkenyl groups and one or more aryl- Aryl groups substituted with alkyl groups, (11) aryl-alkyl groups substituted with one or more alkenyl groups, (12) aryl-alkyl substituted with one or more alkenyl groups and one or more alkyl groups. Groups, (13) one or more alkenyl groups, aryl-alkyl groups substituted with one or more aryl groups, and the like. In one embodiment, the ethylenically unsaturated bond-containing hydrocarbon group preferably has an ethylenically unsaturated bond at the terminal.

R ²⁵ is preferably an alkenyl group, or an aryl group substituted with one or more alkenyl groups, more preferably, an alkenyl group, more preferably a vinyl group or an isopropenyl group.

X indicates a single bond or a linking group, preferably a single bond. n represents an integer of 2 or more, preferably an integer of 2 to 10, more preferably an integer of 2 to 5, still more preferably 2 or 3, and particularly preferably 2.

In one embodiment, as a specific example of the repeating unit represented by the formula (1), for example, the formula (1'):

The repeating unit represented by is mentioned.

(A) The number of repeating units represented by the formula (1) in one molecule of a polystyrene resin having an ethylenically unsaturated bond is not particularly limited, but is preferably 5 to 100,000, more preferably 5. It is 10000, more preferably 100-5000.

In one embodiment, the repeating unit represented by the formula (2) is preferably the formula (2') :.

[In the formula, R ²⁶ , R ²⁷ and R ²⁸ each independently indicate a hydrogen atom or an alkyl group; other symbols are the same as in formula (2). ]
It is a repeating unit represented by.

R ²⁶ represents a hydrogen atom or an alkyl group, preferably a hydrogen atom or a methyl group, and particularly preferably a methyl group. R ²⁷ and R ²⁸ each independently represent a hydrogen atom or an alkyl group, preferably a hydrogen atom or a methyl group, and particularly preferably a hydrogen atom.

In one embodiment, specific examples of the repeating unit represented by the formula (2) include, for example, formulas (2 ″ -1) to (2 ″ -12) :.

The repeating unit represented by is mentioned. Among them, in one embodiment, the repeating unit represented by the formula (2 ″ -1) or (2 ″ -7) is preferable, and the repeating unit represented by the formula (2 ″ -1) is particularly preferable.

(A) The number of repeating units represented by the formula (2) in one molecule of a polystyrene resin having an ethylenically unsaturated bond is not particularly limited, but is preferably 5 to 5000, more preferably 5. It is ~ 500, more preferably 10 to 100.

(A) Ratio of the number of repeating units represented by the formula (1) to the number of repeating units represented by the formula (2) in the polystyrene resin having an ethylenically unsaturated bond (formula (1) unit / formula). The (2) unit) is not particularly limited, but is preferably 3 to 500, more preferably 10 to 100, and even more preferably 20 to 60.

The resin having the repeating unit represented by the formula (1) and the repeating unit represented by the formula (2) is other than the repeating unit represented by the formula (1) and the repeating unit represented by the formula (2). It may further have any unit. The arbitrary unit is not particularly limited, and is, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, and tert-butyl. (Meta) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, norbornyl (meth) acrylate, isobornyl (meth) ) Acrylate, adamantyl (meth) acrylate, lauryl (meth) acrylate, tetradecyl (meth) acrylate, stearyl (meth) acrylate, isoboronyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol Di (meth) acrylate, triethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) Acrylate (meth) acrylic acid esters such as acrylates, dipentaerythritol penta (meth) acrylates and dipentaerythritol hexa (meth) acrylates; aromatic (meth) such as phenoxyethyl (meth) acrylates and phenoxydiethylene glycol (meth) acrylates. Acrylic acid ester; hydroxyl group-containing (meth) acrylic acid ester such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate; halogen-containing (meth) acrylate such as 2,2,2-trifluoroethyl (meth) acrylate ( Meta) acrylic acid ester; Ethylene unsaturated carboxylic acid such as cyano group-containing (meth) acrylic acid ester such as methyl cyano (meth) acrylate, ethyl cyano (meth) acrylate, propyl cyano (meth) acrylate, and isopropyl cyano (meth) acrylate. Estres; Ethyl unsaturated carboxylic acid amides such as (meth) acrylamide, maleimide, N-methylmaleimide, N-phenylmaleimide, N, N'-ethylenebis (meth) acrylamide; (meth) acrylic acid, maleic acid, fumal Ethylene unsaturated carboxylic acids such as acids and itaconic acids; ethylenically unsaturated such as maleic anhydride Anhydrous carboxylic acid; ethylenically unsaturated nitriles such as (meth) acrylonitrile; vinyl acetate, vinyl propionate, allyl acetate, allyl propionate, vinyl butyrate, vinyl benzoate, diallyl phthalate, triallyl isocyanurate, triallyl cyanurate, malein Olefin esters such as diallyl acid, divinyl adipate, divinyl glutarate; olefin ethers such as allyl ethyl ether, tetraallyloxyetane, diallyl ether; conjugated diolefins such as butadiene and isoprene; 2-isopropenyl-2-oxazoline, 2 A monomer unit derived from a monomer such as a cyclic iminoether skeleton-containing olefin such as −vinyl-2-oxazoline, 2-vinyl-5,6-dihydro-4H-1,3-oxadin (olefin addition polymerization unit). Can be mentioned. "(Meta) acrylate" includes acrylates and methacrylates. The same applies to "(meth) acrylic acid", "(meth) acrylamide", "(meth) acrylonitrile" and the like.

(A) The weight average molecular weight (Mw) of the polystyrene resin having an ethylenically unsaturated bond is not particularly limited, but is preferably 10,000 or more, more preferably 50,000 or more, and further preferably 100,000 or more. (A) The upper limit of the weight average molecular weight (Mw) of the polystyrene resin having an ethylenically unsaturated bond is not particularly limited, but is preferably 1,000,000 or less, more preferably 500,000 or less, still more preferably 300,000 or less. .. The weight average molecular weight of the component (A) can be measured as a polystyrene-equivalent value by a gel permeation chromatography (GPC) method.

(A) The ethylenically unsaturated bond content of the polystyrene resin having an ethylenically unsaturated bond is not particularly limited, but is preferably 0.03 mmol / g to 3.00 mmol / g, more preferably 0. 05 mmol / g to 1.50 mmol / g, more preferably 0.10 mmol / g. It is ~ 0.30 mmol / g. The ethylenically unsaturated bond content of the component (A) is the molar equivalent of the ethylenically unsaturated bond per 1 g of the component (A). (A) The ethylenically unsaturated bond equivalent of the polystyrene resin having an ethylenically unsaturated bond is not particularly limited, but is preferably 300 g / eq. ~ 30,000 g / eq. , More preferably 1000 g / eq. 10,000 g / eq. , More preferably 2000 g / eq. ~ 5000 g / eq. Is. The ethylenically unsaturated bond equivalent of the component (A) is the mass of the resin per one equivalent of the ethylenically unsaturated bond.

(A) The polystyrene resin having an ethylenically unsaturated bond is not particularly limited, but is not ethylenically compared to, for example, a cyclic imino ether skeleton-containing polystyrene resin having a skeleton such as an oxazoline ring or a dihydrooxazine ring. It can be easily synthesized by subjecting a carboxylic acid having a saturated bond to a ring-opening addition reaction. Examples of commercially available products of the polystyrene resin containing a cyclic imino ether skeleton include “Epocross RPS-1005” manufactured by Nippon Shokubai Co., Ltd.

The content of the (A) polystyrene resin having an ethylenically unsaturated bond in the resin composition is not particularly limited, but is desired by the present invention when the non-volatile component in the resin composition is 100% by mass. From the viewpoint of remarkably obtaining the effect of, it is preferably 80% by mass or less, more preferably 60% by mass or less, further preferably 50% by mass or less, still more preferably 40% by mass or less, and particularly preferably 35% by mass or less. .. The lower limit of the content of the (A) polystyrene resin having an ethylenically unsaturated bond in the resin composition is not particularly limited, but the present invention is based on the case where the non-volatile component in the resin composition is 100% by mass. From the viewpoint of remarkably obtaining the desired effect of, preferably 1% by mass or more, more preferably 5% by mass or more, still more preferably 10% by mass or more, still more preferably 15% by mass or more, and particularly preferably 20% by mass or more. Is.

<(B) Crosslinking agent>
The resin composition of the present invention contains (B) a cross-linking agent. (B) The cross-linking agent may be used alone or in any combination of two or more. The (B) cross-linking agent has a function of cross-linking the component (A).

(B) The cross-linking agent is, in one embodiment, a radically polymerizable cross-linking agent having an ethylenically unsaturated bond. The (B) cross-linking agent is not particularly limited, but for example, an allyl group, a 3-cyclohexenyl group, a 3-cyclopentenyl group, a p-vinylphenyl group, an m-vinylphenyl group, and an o-vinylphenyl group. Unsaturated hydrocarbon groups such as α, β-unsaturated carbonyl groups such as acryloyl group, methacryloyl group, maleimide group (2,5-dihydro-2,5-dioxo-1H-pyrrole-1-yl group) and the like. It may have a radically polymerizable group.

(B) The cross-linking agent is, in one embodiment, a benzocyclobutene-type cross-linking agent having a benzocyclobutene ring.

Examples of the (B) cross-linking agent include (B-1) (meth) acrylic cross-linking agent, (B-2) styrene-based cross-linking agent, (B-3) allyl-based cross-linking agent, and (B-4) maleimide-based cross-linking agent. It may be a cross-linking agent, a (B-5) benzocyclobutene-type cross-linking agent, or the like.

(B-1) The (meth) acrylic cross-linking agent is a compound having two or more acryloyl groups and / or methacryloyl groups. Examples of the (meth) acrylic cross-linking agent include cyclohexane-1,4-dimethanol di (meth) acrylate, cyclohexane-1,3-dimethanol di (meth) acrylate, and tricyclodecanedimethanol di (meth). Acrylate, neopentyl glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,8-octanediol di (meth) acrylate, 1,9 -Nonandiol di (meth) acrylate, 1,10-decanediol di (meth) acrylate Trimethylol propantri (meth) acrylate, trimethylol ethanetri (meth) acrylate, glycerintri (meth) acrylate, pentaerythritol tetra (meth) ) Acrylate (meth) acrylic acid ester compounds such as acrylates; dioxane glycol di (meth) acrylates, 3,6-dioxa-1,8-octanediol di (meth) acrylates, 3,6,9-trioxaundecane- 1,11-diol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, 9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene, ethoxylated bisphenol A di Ether-containing (meth) acrylic acid esters such as (meth) acrylates and propoxylated bisphenol A di (meth) acrylates; tris (3-hydroxypropyl) isocyanuratetri (meth) acrylates, tris (2-hydroxyethyl) isocyanuratetris. Examples thereof include isocyanurate-containing (meth) acrylic acid ester compounds such as (meth) acrylate and tri (meth) acrylate ethoxylated isocyanuric acid. Examples of commercially available (B-1) (meth) acrylic cross-linking agents include "A-DOG" (dioxane glycol diacrylate) manufactured by Shin Nakamura Chemical Industry Co., Ltd. and "DCP-A" manufactured by Kyoeisha Chemical Co., Ltd. (DCP-A). Tricyclodecanedimethanol diacrylate), "DCP" (tricyclodecanedimethanol dimethacrylate), "KAYARAD R-684" (tricyclodecanedimethanol diacrylate), "KAYARAD R-604" manufactured by Nippon Kayaku Co., Ltd. (Dioxane glycol diacrylate) and the like.

(B-2) The styrene-based cross-linking agent is a compound having two or more vinyl groups directly bonded to an aromatic carbon atom. Examples of the (B-2) styrene-based cross-linking agent include divinylbenzene, 2,4-divinyltoluene, 2,6-divinylnaphthalene, 1,4-divinylnaphthalene, 4,4'-divinylbiphenyl, 1,2-. Examples thereof include bis (4-vinylphenyl) ethane, 2,2-bis (4-vinylphenyl) propane, and bis (4-vinylphenyl) ether.

(B-3) The allyl-based cross-linking agent is a compound having two or more allyl groups. Examples of the (B-3) allyl-based cross-linking agent include diallyl diphenate, triallyl trimeritate, diallyl phthalate, diallyl isophthalate, diallyl terephthalate, diallyl 2,6-naphthalenedicarboxylate, and 2,3-naphthalene carboxylic acid. Aromatic carboxylic acid allyl ester compounds such as diallyl acid; isocyanuric acid allyl ester compounds such as 1,3,5-triallyl isocyanurate and 1,3-diallyl-5-glycidyl isocyanurate; 2,2-bis [3- Allyl-4- (glycidyloxy) phenyl] Epoxy-containing aromatic allyl compounds such as propane; bis [3-allyl-4- (3,4-dihydro-2H-1,3-benzoxazine-3-yl) phenyl] Examples thereof include benzoxazine-containing aromatic allyl compounds such as methane; ether-containing aromatic allyl compounds such as 1,3,5-triallyl etherbenzene; and allylsilane compounds such as diallyldiphenylsilane. (B-3) Commercially available allyl-based cross-linking agents include "TAIC" (1,3,5-triallyl isocyanurate) manufactured by Nihon Kasei Co., Ltd. and "DAD" (diallyl diphenate) manufactured by Nitto Technofine Chemical Co., Ltd. ), "TRIAM-705" manufactured by Wako Pure Chemical Industries, Ltd. (triallyl trimellitic acid), trade name "DAND" manufactured by Nihon Kasei Kogyo Co., Ltd. (diallyl 2,3-naphthalenecarboxylate), "ALP" manufactured by Shikoku Kasei Kogyo Co., Ltd. -D "(bis [3-allyl-4- (3,4-dihydro-2H-1,3-benzoxazine-3-yl) phenyl] methane)," RE-810NM "(2) manufactured by Nihon Kasei Co., Ltd. , 2-Bis [3-allyl-4- (glycidyloxy) phenyl] propane), "DA-MGIC" manufactured by Shikoku Kasei Co., Ltd. (1,3-diallyl-5-glycidyl isocyanurate) and the like.

(B-4) The maleimide-based cross-linking agent is a compound having two or more maleimide groups. (B-4) Examples of the maleimide-based cross-linking agent include aromatic maleimide compounds such as 2,2-bis [4- (4-maleimidephenoxy) phenyl] propane and biphenylaralkyl-type polymaleimide; N, N'-ethylene. Dimareimide, N, N'-tetramethylene dimaleimide, N, N'-hexamethylene dimaleimide, 1-maleimide-3-maleimidemethyl-3,5,5-trimethylcyclohexane (IPBM), 1,1'-( Cyclohexane-1,3-diylbismethylene) bis (1H-pyrrole-2,5-dione) (CBM), 1,1'-(4,4'-methylenebis (cyclohexane-4,1-diyl)) bis ( Examples thereof include aliphatic maleimide compounds such as 1H-pyrrole-2,5-dione) (MBCM) and dimeric acid skeleton-containing bismaleimide. (B-4) Commercially available maleimide-based cross-linking agents include "BMI-689" (bismaleimide containing dimer acid skeleton) manufactured by Designer Molecule's and "MIR-3000-70MT" manufactured by Nippon Kayaku Co., Ltd. ( Biphenyl aralkyl type polymaleimide) and the like.

(B-5) The benzocyclobutene type cross-linking agent is a compound having two or more benzocyclobutene rings. In one embodiment, the (B-5) benzocyclobutene crosslinker preferably further has an ethylenically unsaturated group. In one embodiment, the (B-5) benzocyclobutene-type cross-linking agent preferably further has an organosiloxane skeleton. (B-5) Examples of commercially available products of the benzocyclobutene type cross-linking agent include "CYCLOTENE3022" (divinylsiloxane bisbenzocyclobutene) manufactured by The Dow Chemical Company.

(B) The ethylenically unsaturated bond equivalent or the benzocyclobutene equivalent of the cross-linking agent is preferably 20 g / eq. ~ 1000 g / eq. , More preferably 50 g / eq. ~ 750 g / eq. , More preferably 100 g / eq. ~ 500 g / eq. , Particularly preferably 150 g / eq. ~ 400 g / eq. Is. The ethylenically unsaturated bond equivalent is the mass of the cross-linking agent per equivalent of the ethylenically unsaturated bond. Benzocyclobutene equivalent is the mass of cross-linking agent per equivalent of benzocyclobutene.

The content of the (B) cross-linking agent in the resin composition is not particularly limited, but when the non-volatile component in the resin composition is 100% by mass, it is preferably 50% by mass or less, more preferably 30. It is 0% by mass or less, more preferably 20% by mass or less, still more preferably 10% by mass or less, and particularly preferably 5% by mass or less. The lower limit of the content of the (B) cross-linking agent in the resin composition is not particularly limited, but when the non-volatile component in the resin composition is 100% by mass, it is preferably 0.01% by mass or more. It is more preferably 0.1% by mass or more, further preferably 0.5% by mass or more, still more preferably 1% by mass or more, and particularly preferably 3% by mass or more.

The mass ratio ((B) component / (A) component) of the (B) cross-linking agent to the (A) polystyrene resin having an ethylenically unsaturated bond in the resin composition is not particularly limited, but is preferable. It is 0.001 or more, more preferably 0.01 or more, still more preferably 0.05 or more, and particularly preferably 0.1 or more. The upper limit of the mass ratio ((B) component / (A) component) of the (B) cross-linking agent to the (A) polystyrene resin having an ethylenically unsaturated bond in the resin composition is not particularly limited. It is preferably 10 or less, more preferably 1 or less, still more preferably 0.5 or less, and particularly preferably 0.2 or less.

<(C) Inorganic filler>
The resin composition of the present invention contains (C) an inorganic filler. (C) The inorganic filler is contained in the resin composition in the form of particles.

(C) An inorganic compound is used as the material of the inorganic filler. Examples of the material of the inorganic filler (C) include silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, and water. Aluminum oxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide , Zirconium oxide, barium titanate, barium titanate, barium zirconate, calcium zirconate, zirconium phosphate, zirconium tungstate phosphate, ferrite, iron-based alloys and the like. Of these, silica is particularly suitable. Examples of silica include amorphous silica, fused silica, crystalline silica, synthetic silica, hollow silica and the like. Further, as silica, spherical silica is preferable. (C) The inorganic filler may be used alone or in combination of two or more at any ratio.

(C) Commercially available inorganic fillers include, for example, "UFP-30" manufactured by Denka Kagaku Kogyo Co., Ltd .; "SP60-05" and "SP507-05" manufactured by Nippon Steel & Sumikin Materials Co., Ltd .; "YC100C", "YA050C", "YA050C-MJE", "YA010C"; "UFP-30" manufactured by Denka Corporation; "Silfil NSS-3N", "Silfil NSS-4N", "Silfil NSS-" manufactured by Tokuyama Corporation. 5N ";" SC2500SQ "," SO-C4 "," SO-C2 "," SO-C1 "," SC2050-SXF "manufactured by Admatex;" DAW-03 "," FB-105FD "manufactured by Denka. "And so on.

The average particle size of the (C) inorganic filler is not particularly limited, but is preferably 10 μm or less, more preferably 5 μm or less, still more preferably 3 μm or less, still more preferably 2 μm or less, and particularly preferably 1 μm or less. Is. (C) The lower limit of the average particle size of the inorganic filler is not particularly limited, but is preferably 0.01 μm or more, more preferably 0.1 μm or more, still more preferably 0.3 μm or more, and particularly preferably 0. It is 5.5 μm or more. (C) The average particle size of the inorganic filler can be measured by a laser diffraction / scattering method based on the Mie scattering theory. Specifically, it can be measured by creating a particle size distribution of the inorganic filler on a volume basis by a laser diffraction / scattering type particle size distribution measuring device and using the median diameter as the average particle size. As the measurement sample, 100 mg of an inorganic filler and 10 g of methyl ethyl ketone can be weighed in a vial and dispersed by ultrasonic waves for 20 minutes. The measurement sample was measured using a laser diffraction type particle size distribution measuring device, the light source wavelengths used were blue and red, and the volume-based particle size distribution of the inorganic filler was measured by the flow cell method, and the obtained particle size distribution was used. The average particle size was calculated as the median diameter. Examples of the laser diffraction type particle size distribution measuring device include "SALD-2200" manufactured by Shimadzu Corporation.

(C) The specific surface area of the inorganic filler is not particularly limited, but is preferably 0.1 m ² / g or more, more preferably 0.5 m ² / g or more, still more preferably 1 m ² / g or more. Particularly preferably, it is 3 m ² / g or more. (C) The upper limit of the specific surface area of the inorganic filler is not particularly limited, but is preferably 100 m ² / g or less, more preferably 50 m ² / g or less, still more preferably 30 m ² / g or less, and particularly preferably. Is 10 m ² / g or less. For the specific surface area of the inorganic filler, nitrogen gas is adsorbed on the sample surface using a specific surface area measuring device (Macsorb HM-1210 manufactured by Mountech) according to the BET method, and the specific surface area is calculated using the BET multipoint method. It can be obtained by.

(C) The inorganic filler is preferably surface-treated with an appropriate surface treatment agent. By surface treatment, (C) the moisture resistance and dispersibility of the inorganic filler can be enhanced. Examples of the surface treatment agent include vinyl-based silane coupling agents such as vinyltrimethoxysilane and vinyltriethoxysilane; 2- (3,4-epyloxycyclohexyl) ethyltrimethoxysilane and 3-glycidoxypropylmethyldimethoxysilane. , 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane and other epoxy-based silane coupling agents; p-styryltrimethoxysilane and other styryl-based Silane coupling agents; methacrylic silane coupling agents such as 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane; Acrylic silane coupling agents such as 3-acryloxypropyltrimethoxysilane; N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane , 3-Aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N Amino-based silane coupling agents such as −phenyl-8-aminooctyltrimethoxysilane, N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane; tris- (trimethoxysilylpropyl) isocyanurate, etc. Isocyanurate-based silane coupling agent; ureido-based silane coupling agent such as 3-ureidopropyltrialkoxysilane; mercapto-based silane coupling agent such as 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane. An isocyanate-based silane coupling agent such as 3-isopropylpropyltriethoxysilane; an acid anhydride-based silane coupling agent such as 3-trimethoxysilylpropylsuccinic anhydride; a silane coupling agent such as; methyltrimethoxysilane, Dimethyldimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, hexyltrimeth Examples thereof include non-silane coupling-alkoxysilane compounds such as xysilane, hexyltriethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, 1,6-bis (trimethoxysilyl) hexane, and trifluoropropyltrimethoxysilane. Further, the surface treatment agent may be used alone or in combination of two or more at any ratio.

Examples of commercially available surface treatment agents include "KBM-1003" and "KBE-1003" (vinyl-based silane coupling agents) manufactured by Shin-Etsu Chemical Industry Co., Ltd .; "KBM-303", "KBM-402", and "KBM-402". KBM-403 "," KBE-402 "," KBE-403 "(epoxy-based silane coupling agent);" KBM-1403 "(styryl-based silane coupling agent);" KBM-502 "," KBM-503 " , "KBE-502", "KBE-503" (methacrylic silane coupling agent); "KBM-5103" (acrylic silane coupling agent); "KBM-602", "KBM-603", "KBM-" 903 ”,“ KBE-903 ”,“ KBE-9103P ”,“ KBM-573 ”,“ KBM-575 ”(amino silane coupling agent);“ KBM-9569 ”(isocyanurate-based silane coupling agent); "KBE-585" (ureido-based silane coupling agent); "KBM-802", "KBM-803" (mercapto-based silane coupling agent); "KBE-9007N" (isocyanate-based silane coupling agent); "X" -12-967C "(acid anhydride-based silane coupling agent);" KBM-13 "," KBM-22 "," KBM-103 "," KBE-13 "," KBE-22 "," KBE-103 ". , "KBM-3033", "KBE-3033", "KBM-3063", "KBE-3063", "KBE-3083", "KBM-3103C", "KBM-3066", "KBM-7103" ( Non-silane coupling-alkoxysilane compound) and the like.

The degree of surface treatment with the surface treatment agent is preferably within a predetermined range from the viewpoint of improving the dispersibility of the inorganic filler. Specifically, 100% by mass of the inorganic filler is preferably surface-treated with 0.2% by mass to 5% by mass of a surface treatment agent, and is surface-treated with 0.2% by mass to 3% by mass. It is more preferable that the surface is treated with 0.3% by mass to 2% by mass.

The degree of surface treatment with the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the inorganic filler. Carbon content per unit surface area of the inorganic filler, from the viewpoint of improving dispersibility of the inorganic filler is preferably 0.02 mg / ^{m 2} or more, 0.1 mg / ^{m 2} or more preferably, 0.2 mg / ^{m 2} The above is more preferable. On the other hand, from the viewpoint of preventing an increase in the melt viscosity at the melt viscosity or sheet form a resin composition, preferably from 1.0 mg / ^{m 2} or less, more preferably 0.8 mg / ^{m 2} or less, 0.5 mg / ^{m 2} The following is more preferable.

(C) The amount of carbon per unit surface area of the inorganic filler can be measured after the surface-treated inorganic filler is washed with a solvent (for example, methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK as a solvent is added to the inorganic filler surface-treated with the surface treatment agent, and ultrasonic cleaning is performed at 25 ° C. for 5 minutes. After removing the supernatant and drying the solid content, the amount of carbon per unit surface area of the inorganic filler can be measured using a carbon analyzer. As the carbon analyzer, "EMIA-320V" manufactured by HORIBA, Ltd. or the like can be used.

The content of the (C) inorganic filler in the resin composition is not particularly limited, but when the non-volatile component in the resin composition is 100% by mass, the desired effect of the present invention is remarkably obtained. From the viewpoint, it may be preferably 95% by mass or less, more preferably 90% by mass or less, still more preferably 85% by mass or less, still more preferably 80% by mass or less, and particularly preferably 75% by mass or less. The lower limit of the content of the (C) inorganic filler in the resin composition is not particularly limited, but when the non-volatile component in the resin composition is 100% by mass, for example, 1% by mass or more and 5 It is preferably 10% by mass or more, more preferably 30% by mass or more, still more preferably 40% by mass or more, still more preferably 50% by mass or more, from the viewpoint of significantly obtaining the desired effect of the present invention. , Particularly preferably 60% by mass or more.

The mass ratio ((C) component / (A) component) of the (C) inorganic filler to the (A) polystyrene resin having an ethylenically unsaturated bond in the resin composition is not particularly limited, but is preferable. Is 0.1 or more, more preferably 0.5 or more, still more preferably 0.8 or more, and particularly preferably 1 or more. The upper limit of the mass ratio ((C) component / (A) component) of the (C) inorganic filler to the (A) polystyrene resin having an ethylenically unsaturated bond in the resin composition is not particularly limited. It is preferably 20 or less, more preferably 10 or less, still more preferably 5 or less, and particularly preferably 4 or less.

<(D) Radical polymerization initiator>
The resin composition of the present invention may further contain (D) a radical polymerization initiator as an optional component. (D) The radical polymerization initiator can be, for example, a thermal polymerization initiator that generates free radicals when heated. (D) The radical polymerization initiator may be used alone or in any combination of two or more.

Examples of the (D) radical polymerization initiator include peroxide-based radical polymerization initiators, azo-based radical polymerization initiators, and the like. Of these, a peroxide-based radical polymerization initiator is preferable.

Examples of the peroxide radical polymerization initiator include hydroperoxide compounds such as 1,1,3,3-tetramethylbutylhydroperoxide; tert-butylcumyl peroxide, di-tert-butyl peroxide, and di-tert-butyl peroxide. -Tert-Hexyl peroxide, dicumyl peroxide, 1,4-bis (1-tert-butylperoxy-1-methylethyl) benzene, 2,5-dimethyl-2,5-bis (tert-butylperoxy) ) Dialkyl peroxide compounds such as hexane; diacyl peroxide compounds such as dilauroyl peroxide, didecanoyl peroxide, dicyclohexylperoxydicarbonate, bis (4-tert-butylcyclohexyl) peroxydicarbonate; tert-butylper. Oxyacetate, tert-butyl peroxybenzoate, tert-butyl peroxyisopropyl monocarbonate, tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxyneodecanoate, tert-hexyl peroxyisopropyl monocarbonate , Tert-Butyl peroxylaurate, (1,1-dimethylpropyl) 2-ethylperhexanoate, tert-butyl2-ethylperhexanoate, tert-butyl 3,5,5-trimethylperhexanoate , Tert-Butylperoxy-2-ethylhexyl monocarbonate, peroxyester compounds such as tert-butylperoxymaleic acid; and the like.

Examples of the azo-based radical polymerization initiator include 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2. '-Azobisisobutyronitrile, 2,2'-azobis (2-methylbutyronitrile), 1,1'-azobis (cyclohexane-1-carbonitrile), 1-[(1-cyano-1-methyl) Azobisisobuty compound such as ethyl) azo] formamide, 2-phenylazo-4-methoxy-2,4-dimethyl-valeronitrile; 2,2'-azobis [2-methyl-N- [1,1-bis (hydroxymethyl)) -2-Hydroxyethyl] propionamide], 2,2'-azobis [2-methyl-N- [1,1-bis (hydroxymethyl) ethyl] propionamide], 2,2'-azobis [2-methyl- N- [2- (1-hydroxybutyl)]-propionamide], 2,2'-azobis [2-methyl-N- (2-hydroxyethyl) -propionamide], 2,2'-azobis (2-) Methylpropionamide) dihydrate, 2,2'-azobis [N- (2-propenyl) -2-methylpropionamide], 2,2'-azobis (N-butyl-2-methylpropionamide), 2,2' Azobisisobuty compounds such as -azobis (N-cyclohexyl-2-methylpropionamide); alkylazos such as 2,2'-azobis (2,4,4-trimethylpentane) and 2,2'-azobis (2-methylpropane). Compounds; and the like.

Examples of commercially available products of the radical polymerization initiator (D) include "Perbutyl C", "Perbutyl A", "Perbutyl P", "Perbutyl L", "Perbutyl O", and "Perbutyl ND" manufactured by NOF CORPORATION. "Perbutyl Z", "Perbutyl I", "Park Mill P", "Park Mill D", "Perhexil D", "Perhexil A", "Perhexil I", "Perhexil Z", "Perhexyl ND", "Perhexyl O", Examples thereof include "perhexyl PV" and "perhexyl O".

The content of the (D) radical polymerization initiator in the resin composition is not particularly limited, but when the non-volatile component in the resin composition is 100% by mass, the desired effect of the present invention is remarkable. From the viewpoint of obtaining, preferably 5% by mass or less, more preferably 1% by mass or less, still more preferably 0.5% by mass or less, still more preferably 0.3% by mass or less, and particularly preferably 0.2% by mass or less. possible. The lower limit of the content of the (D) radical polymerization initiator in the resin composition is not particularly limited, but when the non-volatile component in the resin composition is 100% by mass, for example, 0% by mass or more. 0.00001% by mass or more, 0.0001% by mass or more, preferably 0.001% by mass or more, more preferably 0.005% by mass or more, still more preferably 0.01% by mass or more, still more preferably 0. It can be 0.05% by mass or more, particularly preferably 0.1% by mass or more.

<(E) Epoxy resin>
The resin composition of the present invention may contain (E) epoxy resin as an optional component. The resin composition of the present invention preferably contains (E) an epoxy resin from the viewpoint of further improving the copper adhesion. (E) The epoxy resin means a curable resin having an epoxy group.

Examples of the epoxy resin include bixilenol type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, dicyclopentadiene type epoxy resin, and trisphenol type. Epoxy resin, naphthol novolac type epoxy resin, phenol novolac type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidylamine type epoxy resin, glycidyl ester type epoxy resin , Cresol novolak type epoxy resin, phenol aralkyl type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, epoxy resin having a butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring-containing epoxy resin, Cyclohexane type epoxy resin, cyclohexanedimethanol type epoxy resin, naphthylene ether type epoxy resin, trimethylol type epoxy resin, tetraphenylethane type epoxy resin, isocyanurate type epoxy resin, phenolphthalimidine type epoxy resin, phenolphthaline Examples include type epoxy resins. (E) One type of epoxy resin may be used alone, or two or more types may be used in combination.

In one embodiment, the epoxy resin in the resin composition of the present invention preferably contains a fluorine-containing epoxy resin and / or an alicyclic skeleton-containing epoxy resin from the viewpoint of suppressing the relative permittivity and the dielectric loss tangent to be lower.

The resin composition preferably contains, as the (E) epoxy resin, an epoxy resin having two or more epoxy groups in one molecule. (E) The ratio of the epoxy resin having two or more epoxy groups in one molecule to 100% by mass of the non-volatile component of the epoxy resin is preferably 50% by mass or more, more preferably 60% by mass or more, and particularly preferably. Is 70% by mass or more.

The epoxy resin may be a liquid epoxy resin at a temperature of 20 ° C. (hereinafter, may be referred to as “liquid epoxy resin”) or a solid epoxy resin at a temperature of 20 ° C. (hereinafter, “solid epoxy resin”). ). The resin composition of the present invention may contain only the liquid epoxy resin or only the solid epoxy resin as the epoxy resin, or may contain the liquid epoxy resin and the solid epoxy resin in combination. You may be.

In one embodiment, the epoxy resin in the resin composition of the present invention may be a solid epoxy resin, a liquid epoxy resin, or a combination thereof, but is liquid from the viewpoint of further improving copper adhesion. It is preferably only an epoxy resin or a combination of a liquid epoxy resin and a solid epoxy resin.

As the liquid epoxy resin, a liquid epoxy resin having two or more epoxy groups in one molecule is preferable.

Examples of the liquid epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, glycidylamine type epoxy resin, phenol novolac type epoxy resin, and ester skeleton. An alicyclic epoxy resin having an alicyclic epoxy resin, a cyclohexane type epoxy resin, a cyclohexanedimethanol type epoxy resin, and an epoxy resin having a butadiene structure are preferable.

Specific examples of the liquid epoxy resin include "HP4032", "HP4032D", and "HP4032SS" (naphthalene type epoxy resin) manufactured by DIC; "828US", "828EL", "jER828EL", and "825" manufactured by Mitsubishi Chemical Co., Ltd. , "Epicoat 828EL" (bisphenol A type epoxy resin); "jER807", "1750" (bisphenol F type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd .; "jER152" (phenol novolak type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd.; Mitsubishi Chemical's "630", "630LSD", "604" (glycidylamine type epoxy resin); ADEKA's "ED-523T" (glycilol type epoxy resin); ADEKA's "EP-3950L", "EP-3980S" (glycidylamine type epoxy resin); "EP-4088S" (dicyclopentadiene type epoxy resin) manufactured by ADEKA; "ZX1059" (bisphenol A type epoxy resin and bisphenol) manufactured by Nittetsu Chemical & Materials Co., Ltd. Mixture of F-type epoxy resin); "EX-721" (glycidyl ester type epoxy resin) manufactured by Nagase ChemteX Co., Ltd .; "Selokiside 2021P" (alicyclic epoxy resin having an ester skeleton) manufactured by Daicel Co., Ltd .; "PB-3600" manufactured by Nippon Soda, "JP-100", "JP-200" (epoxy resin having a butadiene structure); "ZX1658", "ZX1658GS" manufactured by Nittetsu Chemical & Materials Co., Ltd. (liquid) 1,4-Glysidylcyclohexane type epoxy resin) and the like. These may be used individually by 1 type, or may be used in combination of 2 or more types.

As the solid epoxy resin, a solid epoxy resin having three or more epoxy groups in one molecule is preferable, and an aromatic solid epoxy resin having three or more epoxy groups in one molecule is more preferable.

Examples of the solid epoxy resin include bixilenol type epoxy resin, naphthalene type epoxy resin, naphthalene type tetrafunctional epoxy resin, naphthol novolac type epoxy resin, cresol novolac type epoxy resin, dicyclopentadiene type epoxy resin, and trisphenol type epoxy resin. Naftor type epoxy resin, biphenyl type epoxy resin, naphthylene ether type epoxy resin, anthracene type epoxy resin, bisphenol A type epoxy resin, bisphenol AF type epoxy resin, phenol aralkyl type epoxy resin, tetraphenylethane type epoxy resin, phenol phthali Midin type epoxy resin and phenol phthalein type epoxy resin are preferable.

Specific examples of the solid epoxy resin include "HP4032H" (naphthalene type epoxy resin) manufactured by DIC; "HP-4700" and "HP-4710" (naphthalen type tetrafunctional epoxy resin) manufactured by DIC; DIC. "N-690" (cresol novolac type epoxy resin); DIC "N-695" (cresol novolac type epoxy resin); DIC "HP-7200", "HP-7200HH", "HP" -7200H "," HP-7200L "(dicyclopentadiene type epoxy resin);" EXA-7311 "," EXA-7311-G3 "," EXA-7311-G4 "," EXA-7311-G4S "manufactured by DIC. , "HP6000" (naphthylene ether type epoxy resin); "EPPN-502H" (trisphenol type epoxy resin) manufactured by Nippon Kayaku Co., Ltd .; "NC7000L" (naphthol novolac type epoxy resin) manufactured by Nihon Kayaku Co., Ltd.; "NC3000H", "NC3000", "NC3000L", "NC3000FH", "NC3100" (biphenyl type epoxy resin) manufactured by Nippon Kayaku Co., Ltd .; "ESN475V" (naphthalene type epoxy resin) manufactured by Nittetsu Chemical & Materials Co., Ltd.; "ESN485" (naphthol type epoxy resin) manufactured by Nittetsu Chemical &Materials; "ESN375" (dihydroxynaphthalene type epoxy resin) manufactured by Nittetsu Chemical &Materials; "YX4000H", "YX4000", manufactured by Mitsubishi Chemical Co., Ltd. "YX4000HK", "YL7890" (bixilenol type epoxy resin); "YL6121" (biphenyl type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd .; "YX8800" (anthracen type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd. "YX7700" (phenol aralkyl type epoxy resin); "PG-100" and "CG-500" manufactured by Osaka Gas Chemical Co., Ltd .; "YL7760" (bisphenol AF type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd .; "YL7800" (fluorene type epoxy resin); "jER1010" manufactured by Mitsubishi Chemical Co., Ltd. (bisphenol A type epoxy resin); "jER1031S" manufactured by Mitsubishi Chemical Co., Ltd. (tetraphenylethane type epoxy resin); WHR991S ”(phenol phthalimidine type epoxy resin) and the like can be mentioned. These may be used individually by 1 type, or may be used in combination of 2 or more types.

(E) When a liquid epoxy resin and a solid epoxy resin are used in combination as the epoxy resin, the amount ratio (liquid epoxy resin: solid epoxy resin) thereof is a mass ratio, preferably 1: 1 to 1: 1. 20, more preferably 1: 1.5 to 1:15, and particularly preferably 1: 2 to 1:10. When the quantitative ratio of the liquid epoxy resin and the solid epoxy resin is in such a range, the desired effect of the present invention can be remarkably obtained. Further, usually, when used in the form of a resin sheet, moderate adhesiveness is provided. Further, when used in the form of a resin sheet, sufficient flexibility is usually obtained and handleability is improved. Further, usually, a cured product having sufficient breaking strength can be obtained.

The epoxy equivalent of the (E) epoxy resin is preferably 50 g / eq. ~ 5,000 g / eq. , More preferably 60 g / eq. ~ 1,000 g / eq. , More preferably 80 g / eq. ~ 500 g / eq. , Even more preferably 100 g / eq. ~ 300 g / eq. Is. Epoxy equivalent is the mass of resin per equivalent of epoxy group. This epoxy equivalent can be measured according to JIS K7236.

(E) The weight average molecular weight (Mw) of the epoxy resin is preferably 100 to 5,000, more preferably 250 to 3,000, and even more preferably 400 to 1,500. The weight average molecular weight of the resin can be measured as a polystyrene-equivalent value by a gel permeation chromatography (GPC) method.

The content of the (E) epoxy resin in the resin composition is not particularly limited, but when the non-volatile component in the resin composition is 100% by mass, it is preferably 50% by mass or less, more preferably 30. It is 0% by mass or less, more preferably 20% by mass or less, still more preferably 10% by mass or less, and particularly preferably 7% by mass or less. The lower limit of the content of the (E) epoxy resin in the resin composition is not particularly limited, but when the non-volatile component in the resin composition is 100% by mass, for example, 0% by mass or more, 0. It may be 01% by mass or more, 0.1% by mass or more, 1% by mass or more, 2% by mass or more, 4% by mass or more, and the like.

<(F) Epoxy curing agent>
When the resin composition of the present invention contains (E) an epoxy resin, it may further contain (F) an epoxy curing agent as an optional component. The (F) epoxy curing agent described here can react with (E) an epoxy resin (for example, an addition reaction). (F) The epoxy curing agent may be used alone or in combination of two or more.

The (F) epoxy curing agent is not particularly limited, but for example, (E-1) active ester-based curing agent, (F-2) carbodiimide-based curing agent, and (F-3) phenol-based curing agent. , (F-4) Acid Anhydrous Curing Agent, (F-5) Amine Curing Agent, (F-6) Benzoxazine Curing Agent, (F-7) Cyanate Ester Curing Agent, (F-8) Examples include thiol-based curing agents. In one embodiment, it is particularly preferable that the (E) epoxy curing agent contains (E-1) an active ester-based curing agent.

(E-1) As the active ester-based curing agent, generally, an ester group having high reaction activity such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds is contained in one molecule. A compound having two or more esters is preferably used.

The (E-1) active ester-based curing agent is preferably obtained by a condensation reaction between a carboxylic acid compound and / or a thiocarboxylic acid compound and a hydroxy compound and / or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester-based curing agent obtained from a carboxylic acid compound and a hydroxy compound is preferable, and an active ester-based curing agent obtained from a carboxylic acid compound and a phenol compound and / or a naphthol compound is more preferable.

Examples of the (E-1) active ester-based curing agent include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid and the like. Examples of the phenol compound or naphthol compound include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthaline, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-. Cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, fluoroglucin, Examples thereof include benzenetriol, dicyclopentadiene-type diphenol compound, and phenol novolac. Here, the "dicyclopentadiene-type diphenol compound" refers to a diphenol compound obtained by condensing two phenol molecules with one dicyclopentadiene molecule.

Specifically, the (E-1) active ester-based curing agent includes a dicyclopentadiene-type active ester-based curing agent, a naphthalene-type active ester-based curing agent containing a naphthalene structure, and an active ester-based curing agent containing an acetylated product of phenol novolac. An active ester-based curing agent containing a curing agent and a benzoylated product of phenol novolac is preferable, and at least one selected from a dicyclopentadiene-type active ester-based curing agent and a naphthalene-type active ester-based curing agent is more preferable. A dicyclopentadiene-type active ester-based curing agent is more preferable. As the dicyclopentadiene-type active ester-based curing agent, an active ester-based curing agent containing a dicyclopentadiene-type diphenol structure is preferable. The "dicyclopentadiene-type diphenol structure" represents a divalent structural unit consisting of phenylene-dicyclopentylene-phenylene.

(E-1) Commercially available products of the active ester-based curing agent include "EXB9451", "EXB9460", "EXB9460S", "EXB-8000L", as active ester-based curing agents containing a dicyclopentadiene-type diphenol structure. "EXB-8000L-65M", "EXB-8000L-65TM", "HPC-8000L-65TM", "HPC-8000", "HPC-8000-65T", "HPC-8000H", "HPC-8000H-65TM" , (Manufactured by DIC); "EXB-8100L-65T", "EXB-8150-60T", "EXB-8150-62T", "EXB-9416-70BK", as active ester-based curing agents containing a naphthalene structure. "HPC-8150-60T", "HPC-8150-62T" (manufactured by DIC); "EXB9401" (manufactured by DIC) as a phosphorus-containing active ester-based curing agent, an active ester-based acetylated product of phenol novolac. "DC808" (manufactured by Mitsubishi Chemical Co., Ltd.) as a curing agent, "YLH1026", "YLH1030", "YLH1048" (manufactured by Mitsubishi Chemical Co., Ltd.) as an active ester-based curing agent which is a benzoylated product of phenol novolac, a styryl group and a naphthalene structure. Examples of the active ester-based curing agent contained include "PC1300-02-65MA" (manufactured by Air Water Co., Ltd.) and the like.

Examples of the (F-2) carbodiimide-based curing agent include curing agents having one or more, preferably two or more carbodiimide structures in one molecule, and examples thereof include tetramethylene-bis (t-butylcarbodiimide). Aliphatic biscarbodiimides such as cyclohexanebis (methylene-t-butylcarbodiimide); biscarbodiimides such as aromatic biscarbodiimides such as phenylene-bis (xysilylcarbodiimide); polyhexamethylenecarbodiimide, polytrimethylhexamethylenecarbodiimide, polycyclohexylene. An aliphatic polycarbodiimide such as carbodiimide, poly (methylenebiscyclohexylenecarbodiimide), poly (isophoroncarbodiimide); poly (phenylenecarbodiimide), poly (naphthylenecarbodiimide), poly (trilencarbodiimide), poly (methyldiisopropylphenylenecarbodiimide) , Poly (triethylphenylene carbodiimide), poly (diethylphenylene carbodiimide), poly (triisopropylphenylene carbodiimide), poly (diisopropylphenylene carbodiimide), poly (xylylene carbodiimide), poly (tetramethylxylylene carbodiimide), poly (methylenediimide) Examples thereof include polycarbodiimides such as aromatic polycarbodiimides such as phenylene carbodiimide) and poly [methylenebis (methylphenylene) carbodiimide].

(F-2) Commercially available products of the carbodiimide-based curing agent include, for example, "carbodilite V-02B", "carbodilite V-03", "carbodilite V-04K", "carbodilite V-07" manufactured by Nisshinbo Chemical Co., Ltd. "Carbodilite V-09"; "Stavaxol P", "Stavaxol P400", "Hikazil 510", etc. manufactured by Rheinchemy Co., Ltd. may be mentioned.

The (F-3) phenol-based curing agent is not particularly limited, but a biphenyl-type curing agent, a naphthalene-type curing agent, a phenol novolac-type curing agent, a naphthylene ether-type curing agent, and a triazine skeleton-containing phenol-based curing agent are preferable. Specifically, the biphenyl type curing agents "MEH-7700", "MEH-7810", "MEH-7851" (manufactured by Meiwa Kasei Co., Ltd.), and the naphthalene type curing agents "NHN", "CBN", "GPH" (Manufactured by Nippon Kayaku Co., Ltd.), "SN170", "SN180", "SN190", "SN475", "SN485", "SN495", "SN375", "SN395" (manufactured by DIC Corporation), "EXB9500" (Made by DIC), "TD2090" (manufactured by DIC), a phenol novolac type curing agent, "EXB-6000" (manufactured by DIC), a naphthylene ether type curing agent, and the like. Specific examples of the triazine skeleton-containing phenolic curing agent include "LA3018", "LA7052", "LA7054", "LA1356" (manufactured by DIC Corporation) and the like. In particular, naphthalene-type curing agents and triazine skeleton-containing phenol-based curing agents are more preferable.

Examples of the (F-4) acid anhydride-based curing agent include a curing agent having one or more acid anhydride groups in one molecule, and having two or more acid anhydride groups in one molecule. Hardeners are preferred. Specific examples of the (F-3) acid anhydride-based curing agent include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrohydride phthalic acid, methylhexahydrohydride phthalic acid, and methylnadic acid anhydride. Methylnadic hydride anhydride, trialkyltetrahydrohydride phthalic acid, dodecenyl anhydride succinic acid, 5- (2,5-dioxotetrahydro-3-franyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid Anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic acid dianhydride, biphenyltetracarboxylic acid dianhydride, naphthalenetetracarboxylic acid dianhydride, oxydiphthalic acid dianhydride, 3,3'- 4,4'-Diphenylsulfone tetracarboxylic acid dianhydride, 1,3,3a,4,5,9b-hexahydro-5 (tetrahydro-2,5-dioxo-3-franyl) -naphtho [1,2- C] Examples include polymer-type acid anhydrides such as furan-1,3-dione, ethylene glycol bis (anhydrotrimeritate), and styrene / maleic acid resin in which styrene and maleic acid are copolymerized. (F-4) Commercially available acid anhydride-based curing agents include "HNA-100", "MH-700", "MTA-15", "DDSA", "OSA", and Mitsubishi manufactured by Shin Nihon Rika Co., Ltd. Examples thereof include "YH-306" and "YH-307" manufactured by Chemical Corporation, and "HN-2200" and "HN-5500" manufactured by Hitachi Chemical Co., Ltd.

Examples of the (F-5) amine-based curing agent include curing agents having one or more, preferably two or more amino groups in one molecule, and examples thereof include aliphatic amines, polyether amines, and fats. Examples thereof include cyclic amines and aromatic amines. Among them, aromatic amines are preferable from the viewpoint of exhibiting the desired effect of the present invention. As the (F-5) amine-based curing agent, a primary amine or a secondary amine is preferable, and a primary amine is more preferable. Specific examples of the (F-5) amine-based curing agent include 4,4'-methylenebis (2,6-dimethylaniline), 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, 3,3. '-Diaminodiphenylsulfone, m-phenylenediamine, m-xylylenediamine, diethyltoluenediamine, 4,4'-diaminodiphenylether, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl -4,4'-diaminobiphenyl, 3,3'-dihydroxybenzidine, 2,2-bis (3-amino-4-hydroxyphenyl) propane, 3,3-dimethyl-5,5-diethyl-4,4- Diphenylmethanediamine, 2,2-bis (4-aminophenyl) propane, 2,2-bis (4- (4-aminophenoxy) phenyl) propane, 1,3-bis (3-aminophenoxy) benzene, 1,3 -Bis (4-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 4,4'-bis (4-aminophenoxy) biphenyl, bis (4- (4-aminophenoxy) phenyl) sulfone , Bis (4- (3-aminophenoxy) phenyl) sulfone, and the like. (F-5) A commercially available product may be used as the amine-based curing agent. For example, "SEIKACURE-S" manufactured by Seika Co., Ltd., "KAYABOND C-200S" manufactured by Nippon Kayaku Co., Ltd., "KAYABOND C-100", "KAYABOND C-100", " Examples thereof include "Kayahard A-A", "Kayahard AB", "Kayahard AS", and "Epicure W" manufactured by Mitsubishi Chemical Corporation.

(F-6) Specific examples of the benzoxazine-based curing agent include "JBZ-OP100D" and "ODA-BOZ" manufactured by JFE Chemical Co., Ltd .; "HFB2006M" manufactured by Showa High Polymer Co., Ltd .; "HFB2006M" manufactured by Shikoku Chemicals Corporation. Examples include "P-d" and "F-a".

Examples of the (F-7) cyanate ester-based curing agent include bisphenol A dicyanate, polyphenol cyanate (oligo (3-methylene-1,5-phenylencianate)), and 4,4'-methylenebis (2,6-dimethylphenyl). Cyanate), 4,4'-Etilidene diphenyl cyanate, hexafluorobisphenol A cyanate, 2,2-bis (4-cyanate) phenylpropane, 1,1-bis (4-cyanate phenylmethane), bis (4-cyanate) -3,5-dimethylphenyl) methane, 1,3-bis (4-cyanatephenyl-1- (methylethylidene)) benzene, bis (4-cyanatephenyl) thioether, bis (4-cyanatephenyl) ether, etc. Examples thereof include bifunctional cyanate resins, polyfunctional cyanate resins derived from phenol novolac, cresol novolak and the like, and prepolymers in which these cyanate resins are partially triazined. Specific examples of the (F-7) cyanate ester-based curing agent include "PT30" and "PT60" (both phenol novolac type polyfunctional cyanate ester resins), "BA230", and "BA230S75" (bisphenols) manufactured by Lonza Japan. A prepolymer in which a part or all of the dicyanate is triazined to form a trimer) and the like can be mentioned.

Examples of the (F-8) thiol-based curing agent include trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate), tris (3-mercaptopropyl) isocyanurate and the like. Be done.

(F) The reaction group equivalent of the epoxy curing agent is preferably 50 g / eq. ~ 3000 g / eq. , More preferably 100 g / eq. ~ 1000 g / eq. , More preferably 100 g / eq. ~ 500 g / eq. , Particularly preferably 100 g / eq. ~ 300 g / eq. Is. The reaction group equivalent is the mass of the curing agent per reaction group equivalent.

The content of the (F) epoxy curing agent in the resin composition is not particularly limited, but when the non-volatile component in the resin composition is 100% by mass, it is preferably 50% by mass or less, more preferably 50% by mass or less. It is 30% by mass or less, more preferably 20% by mass or less, still more preferably 10% by mass or less, and particularly preferably 8% by mass or less. The lower limit of the content of the (F) epoxy curing agent in the resin composition is not particularly limited, but when the non-volatile component in the resin composition is 100% by mass, for example, 0% by mass or more, 0. It can be 1% by mass or more, 1% by mass or more, 3% by mass or more, 5% by mass or more, and the like.

<(G) Epoxy curing accelerator>
When the resin composition of the present invention contains (E) an epoxy resin, it may further contain (G) an epoxy curing accelerator as an optional component. In one embodiment, the (G) epoxy curing accelerator may have a function as a catalyst for promoting the reaction of the (E) epoxy resin.

Examples of the (G) epoxy curing accelerator include (G-1) an imidazole-based curing accelerator.
(G-2) Amine-based curing accelerator, (G-3) Phosphorus-based curing accelerator, (G-4) Urea-based curing accelerator, (G-5) Guanidine-based curing accelerator, (G-6) Metal Examples include system curing accelerators. In one embodiment, the (G) epoxy curing accelerator preferably contains an epoxy curing accelerator selected from (G-1) imidazole-based curing accelerator and (G-2) amine-based curing accelerator. (G) The epoxy curing accelerator may be used alone or in combination of two or more.

Examples of the (G-1) imidazole-based curing accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1, 2-Dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl- 2-Methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate , 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino-6- [2'-methylimidazolyl- (1')]-ethyl-s-triazine, 2,4-diamino-6- [ 2'-Undecylimidazolyl- (1')] -ethyl-s-triazine, 2,4-diamino-6- [2'-ethyl-4'-methylimidazolyl- (1')]-ethyl-s-triazine , 2,4-Diamino-6- [2'-methylimidazolyl- (1')]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxy Methylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo [1,2-a] benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride , 2-Methylimidazoline, 2-phenylimidazoline and other imidazole compounds, and imidazole compounds and epoxy resins are adducts.

(G-1) As the imidazole-based curing accelerator, a commercially available product may be used, for example, "1B2PZ", "2MZA-PW", "2PHZ-PW" manufactured by Shikoku Chemicals Corporation, and manufactured by Mitsubishi Chemical Corporation. Examples thereof include "P200-H50".

Examples of the (G-2) amine-based curing accelerator include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6, -tris (dimethylaminomethyl) phenol, and the like. 1,8-diazabicyclo (5,4,0) -undecene and the like can be mentioned.

As the (G-2) amine-based curing accelerator, a commercially available product may be used, and examples thereof include “MY-25” manufactured by Ajinomoto Fine-Techno.

Examples of the (G-3) phosphorus-based curing accelerator include tetrabutylphosphonium bromide, tetrabutylphosphonium chloride, tetrabutylphosphonium acetate, tetrabutylphosphonium decanoate, tetrabutylphosphonium laurate, and bis (tetrabutylphosphonium) pyromeritate. , Triphenylphosphinehydrogen hexahydrophthalate, tetrabutylphosphonium 2,6-bis [(2-hydroxy-5-methylphenyl) methyl] -4-methylphenorate, di-tert-butylmethylphosphonium tetraphenylborate, etc. Aliphatic phosphonium salts; methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, propyltriphenylphosphonium bromide, butyltriphenylphosphonium bromide, benzyltriphenylphosphonium chloride, tetraphenylphosphonium bromide, p-triltriphenylphosphonium tetra-p- Triphenylphosphine, tetraphenylphosphonium tetraphenylphosphine, tetraphenylphosphine tetrap-trilborate, triphenylethylphosphonium tetraphenylborate, tris (3-methylphenyl) ethylphosphonium tetraphenylborate, tris (2-methoxyphenyl) ethylphosphonium tetra Arophenylphosphine salts such as phenylphosphine, (4-methylphenyl) triphenylphosphonium thiocineate, tetraphenylphosphine thiosianate, butyltriphenylphosphonium thiosianate; aromatic phosphine-boran complex such as triphenylphosphine / triphenylborane; triphenyl Arophenylphosphine-quinone addition reactants such as phosphine-p-benzosphine addition reactants; tributylphosphine, tri-tert-butylphosphine, trioctylphosphine, di-tert-butyl (2-butenyl) phosphine, di-tert-butyl (3-Methyl-2-butenyl) aliphatic phosphine such as phosphine, tricyclophenylphosphine; dibutylphenylphosphine, di-tert-butylphenylphosphine, methyldiphenylphosphine, ethyldiphenylphosphine, butyldiphenylphosphine, diphenylcyclohexinephosphine, triphenyl Tri-o-triphenylphosphine, tri-m-trilphosphine, tri-p -Trill phosphine, tris (4-ethylphenyl) phosphine, tris (4-propylphenyl) phosphine, tris (4-isopropylphenyl) phosphine, tris (4-butylphenyl) phosphine, tris (4-tert-butylphenyl) phosphine , Tris (2,4-dimethylphenyl) phosphine, Tris (2,5-dimethylphenyl) phosphine, Tris (2,6-dimethylphenyl) phosphine, Tris (3,5-dimethylphenyl) phosphine, Tris (2,4) , 6-trimethylphenyl) phosphine, tris (2,6-dimethyl-4-ethoxyphenyl) phosphine, tris (2-methoxyphenyl) phosphine, tris (4-methoxyphenyl) phosphine, tris (4-ethoxyphenyl) phosphine, Tris (4-tert-butoxyphenyl) phosphine, diphenyl-2-pyridylphosphine, 1,2-bis (diphenylphosphine) ethane, 1,3-bis (diphenylphosphine) propane, 1,4-bis (diphenylphosphine) Examples thereof include aromatic phosphines such as fino) butane, 1,2-bis (diphenylphosphino) acetylene, and 2,2'-bis (diphenylphosphino) diphenyl ether.

(G-4) As the urea-based curing accelerator, for example, 1,1-dimethylurea; 1,1,3-trimethylurea, 3-ethyl-1,1-dimethylurea, 3-cyclohexyl-1,1- Alibo dimethylurea such as dimethylurea, 3-cyclooctyl-1,1-dimethylurea; 3-phenyl-1,1-dimethylurea, 3- (4-chlorophenyl) -1,1-dimethylurea, 3-( 3,4-Dichlorophenyl) -1,1-dimethylurea, 3- (3-chloro-4-methylphenyl) -1,1-dimethylurea, 3- (2-methylphenyl) -1,1-dimethylurea, 3- (4-Methylphenyl) -1,1-dimethylurea, 3- (3,4-dimethylphenyl) -1,1-dimethylurea, 3- (4-isopropylphenyl) -1,1-dimethylurea, 3- (4-methoxyphenyl) -1,1-dimethylurea, 3- (4-nitrophenyl) -1,1-dimethylurea, 3- [4- (4-methoxyphenoxy) phenyl] -1,1- Dimethylurea, 3- [4- (4-chlorophenoxy) phenyl] -1,1-dimethylurea, 3- [3- (trifluoromethyl) phenyl] -1,1-dimethylurea, N, N- (1) , 4-Phenylene) bis (N', N'-dimethylurea), N, N- (4-methyl-1,3-phenylene) bis (N', N'-dimethylurea) [toluenebis dimethylurea], etc. Fragrant dimethylurea and the like.

Examples of the (G-5) guanidine-based curing accelerator include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1- (o-tolyl) guanidine, dimethylguanidine, and diphenyl. Guanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo [4.4.0] deca-5-ene, 7-methyl-1,5,7-triazabicyclo [4] 4.0] Deca-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1,1-dimethylbiguanide, 1,1-diethylbiguanide, 1 -Cyclohexylbiguanide, 1-allylbiguanide, 1-phenylbiguanide, 1- (o-tolyl) biguanide and the like can be mentioned.

Examples of the (G-6) metal-based curing accelerator include organic metal complexes or organic metal salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of the organometallic complex include organic cobalt complexes such as cobalt (II) acetylacetonate and cobalt (III) acetylacetonate, organic copper complexes such as copper (II) acetylacetonate, and zinc (II) acetylacetonate. Examples thereof include an organic zinc complex such as iron (III) acetylacetonate, an organic nickel complex such as nickel (II) acetylacetonate, and an organic manganese complex such as manganese (II) acetylacetonate. Examples of the organic metal salt include zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, zinc stearate and the like.

The content of the (G) epoxy curing accelerator in the resin composition is not particularly limited, but when the non-volatile component in the resin composition is 100% by mass, it is preferably 10% by mass or less, more preferably. Is 5% by mass or less, more preferably 1% by mass or less, and particularly preferably 0.5% by mass or less. The lower limit of the content of the (G) epoxy curing accelerator in the resin composition is not particularly limited, but when the non-volatile component in the resin composition is 100% by mass, for example, 0% by mass or more. It can be 0.001% by mass or more, 0.01% by mass or more, 0.1% by mass or more, and the like.

<(H) Other additives>
The resin composition of the present invention may further contain any additive as a non-volatile component. Examples of such additives include thermoplastic resins such as polyvinyl acetal resin, polyolefin resin, polysulfone resin, polyether sulfone resin, polyphenylene ether resin, polycarbonate resin, polyether ether ketone resin, and polyester resin; epoxy acrylate resin, Thermo-curable resins other than epoxy resins such as urethane acrylate resin, urethane resin, cyanate resin, polyimide resin, benzoxazine resin, unsaturated polyester resin, phenol resin, melamine resin, silicone resin, phenoxy resin; organic filling of rubber particles, etc. Materials: Organic metal compounds such as organic copper compounds, organic zinc compounds, and organic cobalt compounds; Colorants such as phthalocyanine blue, phthalocyanine green, iodin green, diazo yellow, crystal violet, titanium oxide, and carbon black; hydroquinone, catechol, and pyrogallol. , Phenothiazine and other polymerization inhibitors; Silicone-based leveling agents, acrylic polymer-based leveling agents and other leveling agents; Benton, montmorillonite and other thickeners; Silicone-based defoaming agents, acrylic-based defoaming agents, fluorine-based defoaming agents, Defoaming agents such as vinyl resin-based defoaming agents; UV absorbers such as benzotriazole-based ultraviolet absorbers; Adhesive improvers such as ureasilane; Triazole-based adhesion-imparting agents, tetrazole-based adhesion-imparting agents, triazine-based adhesion Adhesion-imparting agents such as sex-imparting agents; Antioxidants such as hindered phenol-based antioxidants and hindered amine-based antioxidants; Fluorescent whitening agents such as stilben derivatives; Fluorine-based surfactants, silicone-based surfactants, etc. Surface active agents; phosphorus-based flame retardants (eg phosphoric acid ester compounds, phosphazene compounds, phosphinic acid compounds, red phosphorus), nitrogen-based flame retardants (eg melamine sulfate), halogen-based flame retardants, inorganic flame retardants (eg trioxidation). Anti-flame retardants such as Antimon); Dispersants such as phosphate ester dispersants, polyoxyalkylene dispersants, acetylene dispersants, silicone dispersants, anionic dispersants, cationic dispersants; borate stabilizers, Examples thereof include stabilizers such as titanate-based stabilizers, aluminate-based stabilizers, zirconate-based stabilizers, isocyanate-based stabilizers, carboxylic acid-based stabilizers, and carboxylic acid anhydride-based stabilizers. (H) As the other additives, one type may be used alone, or two or more types may be used in combination at any ratio. (H) The content of other additives can be appropriately set by those skilled in the art.

<(I) Organic solvent>
The resin composition of the present invention may further contain an arbitrary organic solvent as a volatile component in addition to the above-mentioned non-volatile component. (I) As the organic solvent, known ones can be appropriately used as long as at least a part of the non-volatile component can be dissolved, and the type thereof is not particularly limited. (I) Examples of the organic solvent include ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, isoamyl acetate, methyl propionate, ethyl propionate and γ-. Ester-based solvents such as butyrolactone; ether-based solvents such as tetrahydropyran, tetrahydrofuran, 1,4-dioxane, diethyl ether, diisopropyl ether, dibutyl ether and diphenyl ether; alcohol-based solvents such as methanol, ethanol, propanol, butanol and ethylene glycol; Ether ester solvents such as 2-ethoxyethyl acetate, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl diglycol acetate, γ-butyrolactone, methyl methoxypropionate; methyl lactate, ethyl lactate, 2-hydroxyisobutyric acid Ester alcohol solvents such as methyl; ether alcohol solvents such as 2-methoxypropanol, 2-methoxyethanol, 2-ethoxyethanol, propylene glycol monomethyl ether, diethylene glycol monobutyl ether (butyl carbitol); N, N-dimethylformamide, Amido-based solvents such as N, N-dimethylacetamide and N-methyl-2-pyrrolidone; Sulfoxide-based solvents such as dimethylsulfoxide; Nitrile-based solvents such as acetonitrile and propionitrile; hexane, cyclopentane, cyclohexane, methylcyclohexane and the like. An aliphatic hydrocarbon solvent; an aromatic hydrocarbon solvent such as benzene, toluene, xylene, ethylbenzene, trimethylbenzene and the like can be mentioned. (I) The organic solvent may be used alone or in combination of two or more at any ratio. (I) When using the organic solvent, one type may be used alone, or two or more types may be used in combination at any ratio.

In one embodiment, the content of (I) the organic solvent is not particularly limited, but when all the components in the resin composition are 100% by mass, for example, 60% by mass or less and 40% by mass or less. , 30% by mass or less, 20% by mass or less, 15% by mass or less, 10% by mass or less, and the like.

<Manufacturing method of resin composition>
The resin composition of the present invention is, for example, in an arbitrary preparation container, in which (A) a polystyrene resin having an ethylenically unsaturated bond, (B) a cross-linking agent, (C) an inorganic filler, and (D) a radical if necessary. Polymerization initiator, (E) epoxy resin as needed, (F) epoxy curing agent as needed, and (G) epoxy curing accelerator as needed, in any order and / or in part or in whole. It can be manufactured by adding and mixing at the same time. Further, in the process of adding and mixing each component, the temperature can be appropriately set, and heating and / or cooling may be performed temporarily or from beginning to end. Further, the resin composition may be uniformly dispersed by stirring or shaking using, for example, a stirring device such as a mixer or a shaking device in the process of adding and mixing, or thereafter. Further, at the same time as stirring or shaking, defoaming may be performed under low pressure conditions such as under vacuum.

<Characteristics of resin composition>
The resin composition of the present invention contains (A) a polystyrene resin having an ethylenically unsaturated bond, (B) a cross-linking agent, and (C) an inorganic filler. By using such a resin composition, it is possible to obtain a cured product in which the relative permittivity (Dk) and the dielectric loss tangent (Df) are suppressed to be low. Further, in one embodiment, by using such a resin composition, a cured product having excellent copper adhesion can be obtained.

The cured product of the resin composition of the present invention may have a feature of low dielectric loss tangent (Df). Therefore, in one embodiment, the dielectric positive contact (Df) of the cured product (curing temperature 200 ° C.) of the resin composition when measured at 5.8 GHz and 23 ° C. as in Test Example 1 below is preferably 0.020. Below, it may be 0.010 or less, more preferably 0.008 or less, 0.007 or less, still more preferably 0.006 or less, 0.005 or less, and particularly preferably 0.004 or less, 0.003 or less.

The cured product of the resin composition of the present invention may have a feature of having a low relative permittivity (Dk). Therefore, in one embodiment, the relative permittivity (Dk) of the cured product (curing temperature 200 ° C.) of the resin composition when measured at 5.8 GHz and 23 ° C. as in Test Example 1 below is preferably 5. It can be 0 or less, more preferably 4.0 or less, even more preferably 3.5 or less, even more preferably 3.2 or less, 3.0 or less, and particularly preferably 2.9 or less, 2.8 or less.

In one embodiment, the cured product of the resin composition of the present invention may have excellent copper adhesion. Therefore, in one embodiment, the copper foil peeling strength calculated from the load when the copper foil is peeled in the vertical direction from the cured product (curing temperature 200 ° C.) laminated with the copper foil as in Test Example 2 below is obtained. , Preferably 0.1 kgf / cm or more, more preferably 0.2 kgf / cm or more, still more preferably 0.3 kgf / cm or more, still more preferably 0.4 kgf / cm or more, particularly preferably 0.45 kgf / cm or more. Can be. The upper limit is not particularly limited, but may be, for example, 10 kgf / cm or less.

<Use of resin composition>
The resin composition of the present invention can be suitably used as a resin composition for insulating use, particularly as a resin composition for forming an insulating layer. Specifically, a resin composition for forming the insulating layer for forming the conductor layer (including the rewiring layer) formed on the insulating layer (resin for forming the insulating layer for forming the conductor layer). It can be suitably used as a composition). Further, in a printed wiring board described later, it can be suitably used as a resin composition for forming an insulating layer of a printed wiring board (resin composition for forming an insulating layer of a printed wiring board). The resin composition of the present invention also requires a resin composition such as a resin sheet, a sheet-like laminated material such as a prepreg, a solder resist, an underfill material, a die bonding material, a semiconductor encapsulant, a hole filling resin, and a component embedding resin. Can be used in a wide range of applications.

Further, for example, when the semiconductor chip package is manufactured through the following steps (1) to (6), the resin composition of the present invention is for a rewiring forming layer as an insulating layer for forming the rewiring layer. Can also be suitably used as a resin composition (resin composition for forming a rewiring forming layer) and a resin composition for encapsulating a semiconductor chip (resin composition for encapsulating a semiconductor chip). When the semiconductor chip package is manufactured, a rewiring layer may be further formed on the sealing layer.
(1) Step of laminating a temporary fixing film on a base material,
(2) A process of temporarily fixing a semiconductor chip on a temporary fixing film,
(3) Step of forming a sealing layer on a semiconductor chip,
(4) Step of peeling the base material and the temporary fixing film from the semiconductor chip,
(5) A step of forming a rewiring forming layer as an insulating layer on the surface from which the base material and the temporary fixing film of the semiconductor chip are peeled off, and (6) a rewiring layer as a conductor layer is formed on the rewiring forming layer. Forming process

Further, since the resin composition of the present invention provides an insulating layer having good component embedding property, it can be suitably used even when the printed wiring board is a component built-in circuit board.

<Sheet-like laminated material>
The resin composition of the present invention can be applied and used in a varnished state, but industrially, it is generally preferable to use the resin composition in the form of a sheet-like laminated material containing the resin composition.

As the sheet-shaped laminated material, the following resin sheets and prepregs are preferable.

In one embodiment, the resin sheet comprises a support and a resin composition layer provided on the support, and the resin composition layer is formed from the resin composition of the present invention.

The thickness of the resin composition layer is preferably 50 μm or less from the viewpoint of reducing the thickness of the printed wiring board and providing a cured product having excellent insulating properties even if the cured product of the resin composition is a thin film. It is preferably 40 μm or less. The lower limit of the thickness of the resin composition layer is not particularly limited, but may be usually 5 μm or more, 10 μm or more, or the like.

Examples of the support include a film made of a plastic material, a metal foil, and a release paper, and a film made of a plastic material and a metal foil are preferable.

When a film made of a plastic material is used as the support, the plastic material may be, for example, polyethylene terephthalate (hereinafter abbreviated as "PET") or polyethylene naphthalate (hereinafter abbreviated as "PEN"). ) And other polyesters, polycarbonate (hereinafter sometimes abbreviated as "PC"), acrylics such as polymethylmethacrylate (PMMA), cyclic polyolefins, triacetylcellulose (TAC), polyethersulfide (PES), polyethers. Examples thereof include ketones and polyimides. Of these, polyethylene terephthalate and polyethylene naphthalate are preferable, and inexpensive polyethylene terephthalate is particularly preferable.

When a metal foil is used as the support, examples of the metal foil include copper foil, aluminum foil, and the like, and copper foil is preferable. As the copper foil, a foil made of a single metal of copper may be used, and a foil made of an alloy of copper and another metal (for example, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) may be used. You may use it.

The support may be matted, corona-treated, or antistatic-treated on the surface to be joined to the resin composition layer.

Further, as the support, a support with a release layer having a release layer on the surface to be joined to the resin composition layer may be used. Examples of the release agent used for the release layer of the support with the release layer include one or more release agents selected from the group consisting of alkyd resin, polyolefin resin, urethane resin, and silicone resin. .. As the support with a release layer, a commercially available product may be used. For example, "SK-1" and "SK-1" manufactured by Lintec Corporation, which are PET films having a release layer containing an alkyd resin-based mold release agent as a main component. Examples include "AL-5", "AL-7", "Lumilar T60" manufactured by Toray Industries, "Purex" manufactured by Teijin Ltd., and "Unipee" manufactured by Unitika Ltd.

The thickness of the support is not particularly limited, but is preferably in the range of 5 μm to 75 μm, and more preferably in the range of 10 μm to 60 μm. When a support with a release layer is used, the thickness of the entire support with a release layer is preferably in the above range.

In one embodiment, the resin sheet may further contain any layer, if desired. Examples of such an arbitrary layer include a protective film similar to the support provided on a surface of the resin composition layer that is not bonded to the support (that is, a surface opposite to the support). Be done. The thickness of the protective film is not particularly limited, but is, for example, 1 μm to 40 μm. By laminating the protective film, it is possible to suppress the adhesion and scratches of dust and the like on the surface of the resin composition layer.

For the resin sheet, for example, a resin varnish prepared by dissolving the resin composition as it is in a liquid resin composition or in an organic solvent is applied onto a support using a die coater or the like, and further dried. It can be produced by forming a resin composition layer.

Examples of the organic solvent include the same organic solvents as those described as the components of the resin composition. The organic solvent may be used alone or in combination of two or more.

Drying may be carried out by a known method such as heating or blowing hot air. The drying conditions are not particularly limited, but the resin composition layer is dried so that the content of the organic solvent is 10% by mass or less, preferably 5% by mass or less. Depending on the boiling point of the organic solvent in the resin composition or resin varnish, for example, when a resin composition or resin varnish containing 30% by mass to 60% by mass of an organic solvent is used, the temperature is 50 ° C to 150 ° C for 3 minutes to 10 minutes. The resin composition layer can be formed by drying for a minute.

The resin sheet can be rolled up and stored. If the resin sheet has a protective film, it can be used by peeling off the protective film.

In one embodiment, the prepreg is formed by impregnating a sheet-like fiber substrate with the resin composition of the present invention.

The sheet-shaped fiber base material used for the prepreg is not particularly limited, and those commonly used as the base material for the prepreg such as glass cloth, aramid non-woven fabric, and liquid crystal polymer non-woven fabric can be used. From the viewpoint of reducing the thickness of the printed wiring board, the thickness of the sheet-shaped fiber base material is preferably 50 μm or less, more preferably 40 μm or less, still more preferably 30 μm or less, and particularly preferably 20 μm or less. The lower limit of the thickness of the sheet-shaped fiber base material is not particularly limited. Usually, it is 10 μm or more.

The prepreg can be produced by a known method such as a hot melt method or a solvent method.

The thickness of the prepreg may be in the same range as the resin composition layer in the above-mentioned resin sheet.

The sheet-shaped laminated material of the present invention can be suitably used for forming an insulating layer of a printed wiring board (for an insulating layer of a printed wiring board), and for forming an interlayer insulating layer of a printed wiring board (printed). It can be more preferably used for the interlayer insulating layer of the wiring board).

<Printed wiring board>
The printed wiring board of the present invention includes an insulating layer made of a cured product obtained by curing the resin composition of the present invention.

The printed wiring board can be manufactured, for example, by using the above-mentioned resin sheet by a method including the following steps (I) and (II).
(I) A step of laminating a resin sheet on an inner layer substrate so that the resin composition layer of the resin sheet is bonded to the inner layer substrate (II) The resin composition layer is cured (for example, thermosetting) to form an insulating layer. Process to do

The "inner layer board" used in the step (I) is a member that becomes a board of a printed wiring board, for example, a glass epoxy board, a metal board, a polyester board, a polyimide board, a BT resin board, and a thermosetting polyphenylene ether board. And so on. Further, the substrate may have a conductor layer on one side or both sides thereof, and the conductor layer may be patterned. An inner layer board in which a conductor layer (circuit) is formed on one side or both sides of the board may be referred to as an "inner layer circuit board". Further, an intermediate product in which an insulating layer and / or a conductor layer should be formed when the printed wiring board is manufactured is also included in the "inner layer substrate" in the present invention. When the printed wiring board is a circuit board with built-in components, an inner layer board containing built-in components may be used.

The inner layer substrate and the resin sheet can be laminated, for example, by heat-pressing the resin sheet to the inner layer substrate from the support side. Examples of the member for heat-pressing the resin sheet to the inner layer substrate (hereinafter, also referred to as “heat-bonding member”) include a heated metal plate (SUS end plate or the like) or a metal roll (SUS roll). It is preferable not to press the heat-bonded member directly onto the resin sheet, but to press it through an elastic material such as heat-resistant rubber so that the resin sheet sufficiently follows the surface irregularities of the inner layer substrate.

The inner layer substrate and the resin sheet may be laminated by a vacuum laminating method. In the vacuum laminating method, the heat crimping temperature is preferably in the range of 60 ° C. to 160 ° C., more preferably 80 ° C. to 140 ° C., and the heat crimping pressure is preferably 0.098 MPa to 1.77 MPa, more preferably 0. It is in the range of .29 MPa to 1.47 MPa, and the heat crimping time is preferably in the range of 20 seconds to 400 seconds, more preferably 30 seconds to 300 seconds. Lamination can be carried out under reduced pressure conditions preferably with a pressure of 26.7 hPa or less.

Lamination can be performed by a commercially available vacuum laminator. Examples of the commercially available vacuum laminator include a vacuum pressurizing laminator manufactured by Meiki Co., Ltd., a vacuum applicator manufactured by Nikko Materials, and a batch type vacuum pressurizing laminator.

After laminating, the laminated resin sheet may be smoothed by pressing under normal pressure (under atmospheric pressure), for example, from the support side. The press conditions for the smoothing treatment can be the same as the heat-bonding conditions for the above-mentioned lamination. The smoothing process can be performed by a commercially available laminator. The laminating and smoothing treatment may be continuously performed using the above-mentioned commercially available vacuum laminator.

The support may be removed between steps (I) and step (II) or after step (II).

In step (II), the resin composition layer is cured (for example, thermosetting) to form an insulating layer made of a cured product of the resin composition. The curing conditions of the resin composition layer are not particularly limited, and the conditions usually adopted when forming the insulating layer of the printed wiring board may be used.

For example, the thermosetting conditions of the resin composition layer differ depending on the type of the resin composition and the like, but in one embodiment, the curing temperature is preferably 120 ° C. to 250 ° C., more preferably 150 ° C. to 240 ° C., still more preferable. Is 170 ° C to 230 ° C. The curing time can be preferably 5 minutes to 120 minutes, more preferably 10 minutes to 100 minutes, and even more preferably 15 minutes to 100 minutes.

Before the resin composition layer is thermally cured, the resin composition layer may be preheated at a temperature lower than the curing temperature. For example, prior to thermosetting the resin composition layer, the resin composition layer is heated at a temperature of 50 ° C. to 120 ° C., preferably 60 ° C. to 115 ° C., more preferably 70 ° C. to 110 ° C. for 5 minutes or more. Preheating may be preferably 5 to 150 minutes, more preferably 15 to 120 minutes, still more preferably 15 to 100 minutes.

In manufacturing the printed wiring board, (III) a step of drilling a hole in the insulating layer, (IV) a step of roughening the insulating layer, and (V) a step of forming a conductor layer may be further carried out. These steps (III) to (V) may be carried out according to various methods known to those skilled in the art used for manufacturing a printed wiring board. When the support is removed after the step (II), the support may be removed between the steps (II) and the step (III), between the steps (III) and the step (IV), or the step ( It may be carried out between IV) and step (V). Further, if necessary, the formation of the insulating layer and the conductor layer in steps (II) to (V) may be repeated to form a multilayer printed wiring board.

In another embodiment, the printed wiring board of the present invention can be manufactured using the above-mentioned prepreg. The manufacturing method is basically the same as when a resin sheet is used.

The step (III) is a step of drilling holes in the insulating layer, whereby holes such as via holes and through holes can be formed in the insulating layer. The step (III) may be carried out by using, for example, a drill, a laser, a plasma, or the like, depending on the composition of the resin composition used for forming the insulating layer. The dimensions and shape of the holes may be appropriately determined according to the design of the printed wiring board.

Step (IV) is a step of roughening the insulating layer. Usually, in this step (IV), smear removal is also performed. The procedure and conditions for the roughening treatment are not particularly limited, and known procedures and conditions usually used for forming the insulating layer of the printed wiring board can be adopted. For example, the insulating layer can be roughened by performing a swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralization treatment with a neutralizing liquid in this order.

The swelling solution used for the roughening treatment is not particularly limited, and examples thereof include an alkaline solution and a surfactant solution, preferably an alkaline solution, and the alkaline solution is more preferably a sodium hydroxide solution or a potassium hydroxide solution. preferable. Examples of commercially available swelling liquids include "Swelling Dip Security Guns P" and "Swelling Dip Security Guns SBU" manufactured by Atotech Japan. The swelling treatment with the swelling liquid is not particularly limited, but can be performed, for example, by immersing the insulating layer in the swelling liquid at 30 ° C. to 90 ° C. for 1 minute to 20 minutes. From the viewpoint of suppressing the swelling of the resin of the insulating layer to an appropriate level, it is preferable to immerse the insulating layer in a swelling liquid at 40 ° C to 80 ° C for 5 to 15 minutes.

The oxidizing agent used for the roughening treatment is not particularly limited, and examples thereof include an alkaline permanganate solution in which potassium permanganate or sodium permanganate is dissolved in an aqueous solution of sodium hydroxide. The roughening treatment with an oxidizing agent such as an alkaline permanganate solution is preferably performed by immersing the insulating layer in an oxidizing agent solution heated to 60 ° C to 100 ° C for 10 to 30 minutes. The concentration of permanganate in the alkaline permanganate solution is preferably 5% by mass to 10% by mass. Examples of commercially available oxidizing agents include alkaline permanganate solutions such as "Concentrate Compact CP" and "Dozing Solution Security P" manufactured by Atotech Japan.

The neutralizing solution used for the roughening treatment is preferably an acidic aqueous solution, and examples of commercially available products include "Reduction Solution Security Gant P" manufactured by Atotech Japan.

The treatment with the neutralizing solution can be performed by immersing the treated surface that has been roughened with the oxidizing agent in the neutralizing solution at 30 ° C. to 80 ° C. for 5 to 30 minutes. From the viewpoint of workability and the like, a method of immersing the object roughened with an oxidizing agent in a neutralizing solution at 40 ° C to 70 ° C for 5 to 20 minutes is preferable.

In one embodiment, the arithmetic mean roughness (Ra) of the surface of the insulating layer after the roughening treatment is not particularly limited, but is preferably 500 nm or less, more preferably 400 nm or less, still more preferably 300 nm or less. .. The lower limit is not particularly limited and may be, for example, 1 nm or more and 2 nm or more. The root mean square roughness (Rq) of the surface of the insulating layer after the roughening treatment is preferably 500 nm or less, more preferably 400 nm or less, and further preferably 300 nm or less. The lower limit is not particularly limited and may be, for example, 1 nm or more and 2 nm or more. The arithmetic mean roughness (Ra) and the root mean square roughness (Rq) of the insulating layer surface can be measured using a non-contact surface roughness meter.

The step (V) is a step of forming a conductor layer, and a conductor layer is formed on the insulating layer. The conductor material used for the conductor layer is not particularly limited. In a preferred embodiment, the conductor layer is one or more selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin and indium. Contains metal. The conductor layer may be a single metal layer or an alloy layer, and the alloy layer may be, for example, an alloy of two or more metals selected from the above group (for example, nickel-chromium alloy, copper, etc.). Examples include layers formed from nickel alloys and copper-titanium alloys). Among them, from the viewpoint of versatility, cost, ease of patterning, etc. for forming a conductor layer, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or a nickel-chromium alloy, copper, etc. A nickel alloy, a copper-titanium alloy alloy layer is preferable, a chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper single metal layer, or a nickel-chromium alloy alloy layer is more preferable, and a copper single metal layer is preferable. A metal layer is more preferred.

The conductor layer may have a single-layer structure, a single metal layer made of different types of metals or alloys, or a multi-layer structure in which two or more alloy layers are laminated. When the conductor layer has a multi-layer structure, the layer in contact with the insulating layer is preferably a single metal layer of chromium, zinc or titanium, or an alloy layer of a nickel-chromium alloy.

The thickness of the conductor layer is generally 3 μm to 35 μm, preferably 5 μm to 30 μm, depending on the desired printed wiring board design.

In one embodiment, the conductor layer may be formed by plating. For example, a conductor layer having a desired wiring pattern can be formed by plating the surface of an insulating layer by a conventionally known technique such as a semi-additive method or a full additive method, and the semi-additive can be manufactured from the viewpoint of ease of manufacture. It is preferably formed by the method. Hereinafter, an example of forming the conductor layer by the semi-additive method will be shown.

First, a plating seed layer is formed on the surface of the insulating layer by electroless plating. Next, a mask pattern that exposes a part of the plating seed layer corresponding to a desired wiring pattern is formed on the formed plating seed layer. After forming a metal layer by electrolytic plating on the exposed plating seed layer, the mask pattern is removed. After that, the unnecessary plating seed layer can be removed by etching or the like to form a conductor layer having a desired wiring pattern.

In other embodiments, the conductor layer may be formed using metal leaf. When the conductor layer is formed using the metal foil, it is preferable that the step (V) is carried out between the steps (I) and the step (II). For example, after step (I), the support is removed and a metal leaf is laminated on the surface of the exposed resin composition layer. The laminating of the resin composition layer and the metal foil may be carried out by a vacuum laminating method. The laminating conditions may be the same as the conditions described for step (I). Then, step (II) is carried out to form an insulating layer. After that, the metal foil on the insulating layer can be used to form a conductor layer having a desired wiring pattern by a conventionally known technique such as a subtractive method or a modified semi-additive method.

The metal foil can be produced by a known method such as an electrolysis method or a rolling method. Examples of commercially available metal foils include HLP foils and JXUT-III foils manufactured by JX Nippon Mining & Metals Co., Ltd., 3EC-III foils and TP-III foils manufactured by Mitsui Mining & Smelting Co., Ltd.

<Semiconductor device>
The semiconductor device of the present invention includes the printed wiring board of the present invention. The semiconductor device of the present invention can be manufactured by using the printed wiring board of the present invention.

Examples of semiconductor devices include various semiconductor devices used in electric products (for example, computers, mobile phones, digital cameras, televisions, etc.) and vehicles (for example, motorcycles, automobiles, trains, ships, aircraft, etc.).

Hereinafter, the present invention will be specifically described with reference to Examples. The present invention is not limited to these examples. In the following, "parts" and "%" representing quantities mean "parts by mass" and "% by mass", respectively, unless otherwise specified. When no temperature is specified, the temperature condition is room temperature (25 ° C.). When no particular pressure is specified, the pressure condition is atmospheric pressure (1 atm).

<Synthesis example 1>
0.1 g of trifluoromethanesulfonic acid was uniformly dissolved in 200 g of toluene in a reaction vessel, and an oxazoline skeleton-containing polystyrene resin (“Epocross RPS-1005” manufactured by Nippon Catalyst Co., Ltd., weight average molecular weight = 160,000, oxazoline group amount = 0. 27 mmol / g) 100 g was added, and the reaction was carried out at 90 ° C. for about 1 hour. Then, 2.32 g of methacrylic acid (manufactured by Mitsubishi Chemical Corporation) was added to this reaction product, and the mixture was reacted at 70 ° C. overnight. Then, the temperature was returned to room temperature, an aqueous potassium carbonate solution was added, and the mixture was filtered, and the obtained solution was dried under vacuum at 70 ° C. to synthesize a vinyl resin. 10 mg of this resin was dissolved in 1 ml of deuterated dimethyl sulfoxide (manufactured by Kanto Chemical Co., Ltd., deuterated rate of 99.9%), and an NMR device (manufactured by Bruker Biospin Co., Ltd., superconducting NMR device "AVHD400") was used. When ^{1 1} H NMR was measured, the peak derived from the oxazoline group contained in the oxazoline skeleton-containing polystyrene resin (“Epocross RPS-1005” manufactured by Nippon Catalyst Co., Ltd.) disappeared, and a new peak derived from methacryl ( ¹ HNMR (DMSO-)) was observed. d6) δppm: 1.91 (s, 3H, CH3-C (= CH ₂ )-), 5.58 (s, 1H, -C = CH ₂ ), 6.06 (s, 1H, -C = CH _{Since 2} )) was detected, it was confirmed that the desired vinyl resin represented by the following formula (X) could be synthesized.

<Example 1>
50 parts of the vinyl resin synthesized in Synthesis Example 1 was heated and dissolved in 30 parts of MEK and 50 parts of toluene while stirring.

After cooling to room temperature, 6 parts of (meth) acrylic non-solid cross-linking agent (“NK ester A-DOG” manufactured by Shin-Nakamura Chemical Industry Co., Ltd., molecular weight 326), peroxide-based radical polymerization initiator (Nichiyu Co., Ltd.) Spherical surface-treated with 1.5 parts of "Perhexyl D" (MEK solution having a solid content of 20% by mass) and N-phenyl-8-aminooctyl-trimethoxysilane (Med. Shinetsu Chemical Industry Co., Ltd., molecular weight 325.2). 100 parts of silica ("SC2050-SXF" manufactured by Admatex, specific surface area 5.9 m ² / g, average molecular weight 0.77 μm) is mixed and uniformly dispersed by a high-speed rotary mixer, and then a cartridge filter (manufactured by ROKITECHNO). Filtered with "SHP020") to prepare a resin composition.

<Example 2>
Bisphenol A type epoxy resin ("828US" manufactured by Mitsubishi Chemical Co., Ltd., epoxy equivalent approx. 180) 6 parts, bixylenol type epoxy resin ("YX4000H", manufactured by Mitsubishi Chemical Co., Ltd., epoxy equivalent approx. 190 g / eq.) 6 parts, active ester 20 parts of a system curing agent (“HPC-8000-65T” manufactured by DIC, an active group equivalent of about 223 g / eq., A toluene solution having a solid content of 65% by mass), and a curing accelerator (4-dimethylaminopyridine (DMAP), 6 parts of MEK solution with 5% by mass of solid content) was added, and benzo was used instead of 6 parts of (meth) acrylic non-solid cross-linking agent (“NK ester A-DOG” manufactured by Shin-Nakamura Chemical Industry Co., Ltd., molecular weight 326). Using 13 parts of an oxadin ring-containing allyl-based non-solid cross-linking agent (“ALP-d” manufactured by Shikoku Kasei Kogyo Co., Ltd., MEK solution having a solid content of 65%), N-phenyl-8-aminooctyl-trimethoxysilane (Shinetsu). 100 parts of spherical silica (“SC2050-SXF” manufactured by Admatex, specific surface area 5.9 m ² / g, average particle size 0.77 μm) surface-treated with a molecular weight 325.2) manufactured by Kagaku Kogyo Co., Ltd. A resin composition was prepared in the same manner as in Example 1 except that the amount was changed from 150 parts to 150 parts.

<Example 3>
(Meta) Acrylic non-solid cross-linking agent ("NK ester A-DOG" manufactured by Shin-Nakamura Chemical Industry Co., Ltd., molecular weight 326) Instead of 6 parts, benzocyclobutene resin ("CYCLOTENE3022" manufactured by Dow Chemical Industry Co., Ltd.) 8.5 Spherical silica ("SC2050-SXF" manufactured by Admatex Co., Ltd., specific surface area 5) surface-treated with N-phenyl-8-aminooctyl-trimethoxysilane (manufactured by Shin-Etsu Chemical Industry Co., Ltd., molecular weight 325.2). A resin composition was prepared in the same manner as in Example 1 except that the amount used (9.9 ^{m 2 / g, average particle size 0.77 μm) was changed from 100 parts to 150 parts.}

<Example 4>
(Meta) Acrylic non-solid cross-linking agent ("NK ester A-DOG" manufactured by Shin-Nakamura Chemical Industry Co., Ltd., molecular weight 326) Instead of 6 parts, biphenyl aralkyl type maleimide resin ("MIR-3000-70MT" manufactured by Nippon Kayaku Co., Ltd. , Maleimide group equivalent: 275 g / eq, non-volatile content 70% MEK / toluene mixed solution) using 12.1 parts, N-phenyl-8-aminooctyl-trimethoxysilane (manufactured by Shinetsu Chemical Industry Co., Ltd., molecular weight 325). Except for changing the usage amount of spherical silica (“SC2050-SXF” manufactured by Admatex Co., Ltd., specific surface area 5.9 m ² / g, average molecular weight 0.77 μm) surface-treated in 2) from 100 parts to 150 parts. Prepared a resin composition in the same manner as in Example 1.

<Comparative Example 1>
Instead of 50 parts of the vinyl resin synthesized in Synthesis Example 1, 77 parts of a styrene-modified polyphenylene ether resin (“OPE-2St 1200” manufactured by Mitsubishi Gas Chemicals, a toluene solution having a non-volatile content of 65%) was used, and a (meth) acrylic system was used. Epoxy group-containing allyl-based non-solid cross-linking agent ("RE-810NM" manufactured by Nippon Kayaku Co., Ltd.) instead of 6 parts of non-solid cross-linking agent ("NK ester A-DOG" manufactured by Shin-Nakamura Chemical Industry Co., Ltd., molecular weight 326), A resin composition was prepared in the same manner as in Example 1 except that 6 parts of the epoxy equivalent 220) were used.

<Comparative Example 2>
Example 2 except that 77 parts of a styrene-modified polyphenylene ether resin (“OPE-2St 1200” manufactured by Mitsubishi Gas Chemical Company, a toluene solution having a non-volatile content of 65%) was used instead of 50 parts of the vinyl resin synthesized in Synthesis Example 1. The resin composition was prepared in the same manner as in the above.

<Measurement of average particle size of inorganic filler>
100 mg of an inorganic filler, 0.1 g of a dispersant (“SN9228” manufactured by San Nopco Ltd.), and 10 g of methyl ethyl ketone were weighed in a vial and dispersed by ultrasonic waves for 20 minutes. Using a laser diffraction type particle size distribution measuring device (“SALD-2200” manufactured by Shimadzu Corporation), the particle size distribution was measured by the batch cell method, and the average particle size based on the median diameter was calculated.

<Test Example 1: Measurement of relative permittivity and dielectric loss tangent>
As a support, a polyethylene terephthalate film ("Lumilar R80" manufactured by Toray Industries, Inc., thickness 38 μm, softening point 130 ° C.) subjected to a mold release treatment with an alkyd resin-based mold release agent ("AL-5" manufactured by Lintec Corporation) was prepared. ..

The resin compositions prepared in Examples and Comparative Examples were uniformly applied on a support with a die coater so that the thickness of the dried resin composition layer was 40 μm, and the temperature was 70 ° C to 95 ° C for 3 minutes. By drying, a resin composition layer was formed on the support. Next, a rough surface of a polypropylene film (“Alfan MA-411” manufactured by Oji F-Tex Co., Ltd., thickness 15 μm) was bonded to the surface of the resin composition layer that was not bonded to the support. As a result, a resin sheet having a support, a resin composition layer, and a protective film in this order was obtained.

The protective film was peeled off from the obtained resin sheet, and the resin composition layer was thermally cured by heating at 200 ° C. for 90 minutes, and then the support was peeled off to obtain a cured product.

The obtained cured product was cut into test pieces having a width of 2 mm and a length of 80 mm. With respect to the test piece, the relative permittivity and the dielectric loss tangent were measured at a measurement frequency of 5.8 GHz and a measurement temperature of 23 ° C. by a cavity resonance perturbation method using "HP8632B" manufactured by Azilent Technologies. Measurements were made on the three test pieces, and the average value was calculated. When the relative permittivity was 3.0 or less and the dielectric loss tangent was 0.004 or less, it was evaluated as "◯", and in other cases, it was evaluated as "x".

<Test Example 2: Measurement of copper foil peeling strength (copper foil adhesion strength)>
(1) Base treatment of copper foil The glossy surface of "3EC-III" (electric field copper foil, 35 μm) manufactured by Mitsui Mining & Smelting Co., Ltd. is etched by 1 μm with a micro-etching agent (“CZ8101” manufactured by Mech Co., Ltd.) on the copper surface. A roughening treatment was performed, and then a rust preventive treatment (CL8300) was performed. Further, a heat treatment was performed in an oven at 130 ° C. for 30 minutes. This copper foil is called a CZ copper foil.

(2) Preparation of inner layer substrate Both sides of the glass cloth base material epoxy resin double-sided copper-clad laminate (copper foil thickness 18 μm, substrate thickness 0.4 mm, Panasonic “R1515A”) on which the inner layer circuit is formed are microscopic. The copper surface was roughened by etching 1 μm with an etching agent (“CZ8101” manufactured by MEC).

(3) Lamination of Copper Foil and Formation of Insulating Layer The protective film was peeled off from each resin sheet obtained in Test Example 1 to expose the resin composition layer. Using a batch type vacuum pressure laminator (2-stage build-up laminator "CVP700" manufactured by Nikko Materials Co., Ltd.), the resin composition layer was laminated on both sides of the inner layer substrate so as to be in contact with the inner layer substrate. Laminating was carried out by reducing the pressure for 30 seconds, adjusting the atmospheric pressure to 13 hPa or less, and then crimping at 120 ° C. and a pressure of 0.74 MPa for 30 seconds. Then, heat pressing was performed at 100 ° C. and a pressure of 0.5 MPa for 60 seconds. The treated surface of the CZ copper foil was laminated on the resin composition layer under the same conditions as described above. Then, the resin composition layer was cured under the curing conditions of 200 ° C. for 90 minutes to form an insulating layer, thereby producing an evaluation substrate.

(4) Measurement of Copper Foil Peeling Strength The produced evaluation substrate was cut into small pieces of 150 × 30 mm. Make a notch in the copper foil part of a small piece with a width of 10 mm and a length of 100 mm using a cutter, peel off one end of the copper foil and grab it with a gripper, and at room temperature, in the vertical direction at a speed of 50 mm / min. The load (kgf / cm) when the 35 mm was peeled off was measured, and the peeling strength was determined. A tensile tester (“AC-50C-SL” manufactured by TSE) was used for the measurement. The measurement was performed in accordance with the Japanese Industrial Standards (JIS C6481). When the copper foil peeling strength was 0.4 kgf / cm or more, it was evaluated as “◯”, and in other cases, it was evaluated as “x”.

Table 1 below shows the amounts of the non-volatile components used in the resin compositions of Examples and Comparative Examples, the measurement results and the determination results of the Test Examples.

Based on the above, by using a resin composition containing (A) a polystyrene resin having an ethylenically unsaturated bond, (B) a cross-linking agent, and (C) an inorganic filler, the relative permittivity (Dk) and the dielectric loss tangent (Dk) can be obtained. It was found that a cured product having a low Df) and excellent copper adhesion can be obtained.

Claims (21)

A resin composition containing (A) a polystyrene resin having an ethylenically unsaturated bond, (B) a cross-linking agent, and (C) an inorganic filler. The resin composition according to claim 1, wherein the component (A) contains a polystyrene resin having an ethylenically unsaturated bond in the side chain. The resin composition according to claim 2, wherein the side chain having an ethylenically unsaturated bond in the component (A) further has an ester bond. The resin composition according to claim 2 or 3, wherein the side chain having an ethylenically unsaturated bond in the component (A) further has an amide bond. The resin composition according to any one of claims 1 to 4, wherein the component (A) has an acryloyl group and / or a methacryloyl group. The ethylenically unsaturated bond equivalent of the component (A) is 1000 g / eq. 10,000 g / eq. The resin composition according to any one of claims 1 to 5. (A) The resin composition according to any one of claims 1 to 6, wherein the weight average molecular weight (Mw) of the component is 10,000 or more. The component (A) is the formula (1) :.

[In the formula, R ¹¹ , R ¹² and R ¹³ each independently indicate a hydrogen atom or a substituent; R ¹⁴ independently indicate a substituent; a is an integer of 0 to 5. show. ]
Repeat unit represented by, and equation (2):

[In the formula, R ²¹ , R ²² , R ²³ and R ²⁴ each independently indicate a hydrogen atom or a substituent; R ²⁵ indicates an ethylenically unsaturated bond-containing hydrocarbon group; X is a single bond. Indicates a bond or linking group; n represents an integer greater than or equal to 2. ]
The resin composition according to any one of claims 1 to 7, which comprises a resin having a repeating unit represented by. The repeating unit represented by the formula (2) is the formula (2'):

[In the formula, R ²¹ , R ²² , R ²³ and R ²⁴ independently indicate a hydrogen atom or a substituent; R ²⁶ , R ²⁷ and R ²⁸ independently indicate a hydrogen atom or an alkyl group, respectively. ; X indicates a single bond or a linking group; n indicates an integer of 2 or more. ]
The resin composition according to claim 8, which is a repeating unit represented by. The resin composition according to any one of claims 1 to 9, wherein the mass ratio of the component (B) to the component (A) (component (B) / component (A)) is 0.01 to 1. The resin composition according to any one of claims 1 to 10, wherein the mass ratio of the component (C) to the component (A) (component (C) / component (A)) is 0.5 to 10. The resin composition according to any one of claims 1 to 11, wherein the content of the component (C) is 40% by mass to 75% by mass when the non-volatile component in the resin composition is 100% by mass. .. The resin composition according to any one of claims 1 to 12, further comprising (D) an epoxy resin. The resin composition according to any one of claims 1 to 13, wherein the dielectric loss tangent of the cured product (curing temperature 200 ° C.) of the resin composition is 0.004 or less when measured at 5.8 GHz and 23 ° C. thing. The resin according to any one of claims 1 to 14, wherein the relative permittivity of the cured product (curing temperature of 200 ° C.) of the resin composition is 3.0 or less when measured at 5.8 GHz and 23 ° C. Composition. The resin composition according to any one of claims 1 to 15, for forming an insulating layer of a printed wiring board. The cured product of the resin composition according to any one of claims 1 to 16. A sheet-like laminated material containing the resin composition according to any one of claims 1 to 16. A resin sheet comprising a support and a resin composition layer formed from the resin composition according to any one of claims 1 to 16 provided on the support. A printed wiring board provided with an insulating layer made of a cured product of the resin composition according to any one of claims 1 to 16. A semiconductor device comprising the printed wiring board according to claim 20.