TWI836023B - resin composition - Google Patents

Abstract

The present invention provides a resin composition that can achieve both suppression of warpage of a cured product and excellent adhesion. A resin composition comprising (A) epoxy resin, (B) inorganic filler and (C) benzoxazine compound having at least one alicyclic structure in the molecule.

Description

Resin composition

The present invention relates to a resin composition containing an epoxy resin and a curing agent; a cured product of the above-mentioned resin composition; a sheet-like laminated material containing the above-mentioned resin composition; a resin sheet containing the above-mentioned resin composition; and printing containing the above-mentioned cured product. Wiring board; a semiconductor device including the above printed wiring board.

As a manufacturing technology of printed wiring boards, for example, a build-up manufacturing method in which insulating layers and conductive layers are alternately stacked is known. In the build-up manufacturing method, generally, the insulating layer is formed by hardening a resin composition.

Printed wiring boards are exposed to various environments such as high and low temperatures. Therefore, when the linear thermal expansion coefficient of the hardened material used for the insulating layer is high, the insulating layer repeatedly expands or contracts, deforming and causing cracks. As a method of reducing the coefficient of linear thermal expansion, for example, a method of using a relatively large amount of inorganic filler as a hardened material is known (Patent Document 1). However, when a relatively large amount of inorganic filler is blended into the hardened material, the elastic modulus becomes high, making it difficult to suppress warpage.

In addition, when the cured material contains a relatively large amount of inorganic filler, it is found that the adhesion between the conductor layer and the insulating layer of copper foil or the like decreases. Recently, there is a demand for smaller semiconductor chip packages, and therefore excellent adhesion is required.

Therefore, even when a relatively large amount of inorganic filler is used, a cured material that can suppress warpage due to a low elastic modulus and have excellent adhesion is required. [Prior technical literature] [Patent Document]

[Patent Document 1] Japanese Patent Application Publication No. 2016-27097

[The problem that the invention wants to solve]

An object of the present invention is to provide a resin composition that can achieve both suppression of warpage and excellent adhesion of the obtained cured product. [Means used to solve problems]

In order to achieve the object of the present invention, the present inventors have carefully examined and found that hardening can be reduced by including (C) a benzoxazine compound having one or more alicyclic structures in the molecule in the resin composition. Therefore, the elastic modulus of the material can be suppressed and excellent adhesion can be achieved, and the present invention is completed.

That is, the present invention includes the following contents. [1] A resin composition comprising (A) an epoxy resin, (B) an inorganic filler and (C) a benzoxazine compound having an alicyclic structure in the molecule. [2] The resin composition of [1] above, wherein the alicyclic structure of component (C) is a cyclohexane ring structure. [3] The resin composition of [1] or [2] above, wherein component (C) is of formula (2):

[In the formula, R ¹ and R ² each independently represent a substituent, and Y represents a bond, an alkylene group with 1 to 6 carbon atoms, -O-, -S-, -SO ₂ -, -NH-, - CO-, -CONH-, -NHCO-, -COO-, or -OCO-; s and t each independently represent an integer from 0 to 4, and u represents a compound represented by 0 or 1]. [4] The resin composition according to any one of the above [1] to [3], wherein the content of component (B) is 50 mass% or more when the total non-volatile components in the resin composition are 100 mass%. . [5] The resin composition according to any one of [1] to [4] above, wherein the average particle diameter of component (B) is 10 μm or less. [6] The resin composition according to any one of the above [1] to [5], further containing (D) elastomer. [7] The resin composition according to any one of [1] to [6] above, further containing (E) a hardener. [8] The resin composition according to any one of the above [1] to [7], which is used to form an insulating layer. [9] A cured product of the resin composition according to any one of the above [1] to [8]. [10] A sheet-like laminated material containing the resin composition according to any one of the above [1] to [8]. [11] A resin sheet having a support body and a resin composition layer provided on the support body and formed of the resin composition according to any one of the above [1] to [8]. [12] A printed wiring board provided with an insulating layer made of a cured product of the resin composition according to any one of [1] to [8] above. [13] A semiconductor device including the printed wiring board of [12] above. [Effects of the invention]

According to the present invention, it is possible to provide a resin composition that can achieve both suppression of warpage of the cured product and excellent adhesion by lowering the elastic modulus of the cured product. [Form of carrying out the invention]

Hereinafter, preferred embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments and examples, and can be arbitrarily modified and implemented within the scope of not departing from the patentable scope of the present invention and its equivalent scope.

<Resin composition> The resin composition of the present invention comprises (A) an epoxy resin, (B) an inorganic filler, and (C) a benzoxazine compound having an alicyclic structure in the molecule.

By using this resin composition, the elastic modulus of the cured product can be reduced, thereby achieving both suppression of warping and excellent adhesion.

The resin composition of the present invention may contain any other components in addition to (A) epoxy resin, (B) inorganic filler and (C) benzoxazine compound having alicyclic structure in the molecule. The optional components include, for example, (D) elastomer, (E) hardener, (F) hardening accelerator, (G) organic solvent and (H) other additives. The components contained in the resin composition are described in detail below.

＜(A) Epoxy resin＞ The resin composition of the present invention contains (A) epoxy resin.

(A) Epoxy resins include, for example, bisxylenol type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, and bisphenol AF type epoxy resin. , dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, naphthol novolak 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, glycidyl amine type epoxy resin, glycidyl ester type epoxy resin, cresol novolak epoxy resin, biphenyl type epoxy resin, Linear aliphatic epoxy resin, epoxy resin with butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, spirocyclic epoxy resin, cyclohexane-type epoxy resin, cyclohexane Dimethanol type epoxy resin, naphthylene ether type epoxy resin, trimethylol type epoxy resin, tetraphenylethane type epoxy resin, etc. Epoxy resin can be used alone or in combination of two or more types.

The resin composition preferably contains an epoxy resin having two or more epoxy groups per molecule as (A) the epoxy resin. From the viewpoint of clearly obtaining the desired effects of the present invention, the proportion of the epoxy resin having two or more epoxy groups per molecule is preferably 50% with respect to 100% by mass of the non-volatile component of the epoxy resin (A). % by mass or more, more preferably 60 mass % or more, particularly preferably 70 mass % or more.

Epoxy resins include epoxy resins that are liquid at a temperature of 20°C (hereinafter sometimes referred to as "liquid epoxy resins") and epoxy resins that are solid at a temperature of 20°C (hereinafter sometimes referred to as "solid epoxy resins"). like epoxy resin"). In one embodiment, the resin composition of the present invention contains a liquid epoxy resin as an epoxy resin. In one embodiment, the resin composition of the present invention contains a solid epoxy resin as an epoxy resin. The resin composition of the present invention may contain only a liquid epoxy resin or a solid epoxy resin as the epoxy resin, and preferably contains a combination of a liquid epoxy resin and a solid epoxy resin.

The liquid epoxy resin is preferably a liquid epoxy resin having two or more epoxy groups in one molecule.

Liquid epoxy resin, preferably bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, glycidyl Amine-type epoxy resin, phenol novolak-type epoxy resin, alicyclic epoxy resin with ester skeleton, cyclohexane-type epoxy resin, cyclohexanedimethanol-type epoxy resin, glycidylamine-type epoxy resin Oxygen resin, and epoxy resin with butadiene structure.

Specific examples of liquid epoxy resins include "HP4032", "HP4032D" and "HP4032SS" (naphthalene type epoxy resin) manufactured by DIC; "828US", "828EL" and "jER828EL" manufactured by Mitsubishi Chemical , "825", "Epikote828EL" (bisphenol A type epoxy resin); "jER807", "1750" (bisphenol F type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd.; "jER152" (phenol) manufactured by Mitsubishi Chemical Co., Ltd. Novolac type epoxy resin); "630" and "630LSD" (glycidylamine type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd.; "ZX1059" (bisphenol A type epoxy resin manufactured by Nippon Steel and Sumitomo Metal Chemical Co., Ltd. Mixed product with bisphenol F type epoxy resin); "EX-721" (glycidyl ester type epoxy resin) manufactured by Nagase Chemtex Co., Ltd.; "CELLOXID2021P" manufactured by DAICEL Co., Ltd. (alicyclic ring with ester skeleton) Oxygen resin); "PB-3600" made by DAICEL Co., Ltd., "JP-100" and "JP-200" (epoxy resin with butadiene structure) made by Nippon Soda Co., Ltd.; made by Nippon Steel and Sumitomo Metal Chemical Co., Ltd. "ZX1658", "ZX1658GS" (liquid 1,4-glycidylcyclohexane type epoxy resin), etc. One type of these may be used alone, or two or more types may be used in combination.

The solid epoxy resin is preferably a solid epoxy resin having three or more epoxy groups per molecule, and more preferably an aromatic solid epoxy having three or more epoxy groups per molecule. resin.

Solid epoxy resin, preferably bisxylenol type epoxy resin, naphthalene type epoxy resin, naphthalene type 4-functional epoxy resin, cresol novolak epoxy resin, dicyclopentadiene type epoxy resin, Trisphenol type epoxy resin, naphthol 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 , tetraphenylethane type epoxy resin.

Specific examples of the solid epoxy resin include "HP4032H" (naphthalene type epoxy resin) manufactured by DIC Corporation; "HP-4700" and "HP-4710" (naphthalene type tetrafunctional epoxy resin) manufactured by DIC Corporation ; "N-690" (cresol novolak epoxy resin) made by DIC; "N-695" (cresol novolak epoxy resin) made by DIC; "HP-7200" (two) made by DIC Cyclopentadiene type epoxy resin); "HP-7200HH", "HP-7200H", "EXA-7311", "EXA-7311-G3", "EXA-7311-G4", "EXA" manufactured by DIC Corporation -7311-G4S", "HP6000" (naphthylene ether type epoxy resin); "EPPN-502H" (trisphenol type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; "NC7000L" (naphthalene ether type epoxy resin) manufactured by Nippon Kayaku Co., Ltd. Phenol novolak type epoxy resin); "NC3000H", "NC3000", "NC3000L", "NC3100" (biphenyl type epoxy resin) manufactured by Nippon Chemical Co., Ltd.; "ESN475V" manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd. (naphthol-type epoxy resin); "ESN485" (naphthol-type epoxy resin) manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd.; "YX4000H", "YX4000", "YL6121" (biphenyl) manufactured by Mitsubishi Chemical Co., Ltd. Type epoxy resin); "YX4000HK" (bisxylenol type epoxy resin) made by Mitsubishi Chemical Co., Ltd.; "YX8800" (anthracene type epoxy resin) made by Mitsubishi Chemical Co., Ltd.; "YX7700" (made by Mitsubishi Chemical Co., Ltd. Novolak type epoxy resin containing xylene structure); "PG-100" and "CG-500" made by Osaka Gas Chemical Co., Ltd.; "YL7760" (bisphenol AF type epoxy resin) made by Mitsubishi Chemical Co., Ltd.; Mitsubishi "YL7800" made by Chemical Co., Ltd. (N-type epoxy resin); "jER1010" made by Mitsubishi Chemical Co., Ltd. (solid bisphenol A-type epoxy resin); "jER1031S" (tetraphenyl ethane type) made by Mitsubishi Chemical Co., Ltd. Epoxy resin) etc. One type of these may be used alone, or two or more types may be used in combination.

When the epoxy resin (A) is used in combination with a liquid epoxy resin and a solid epoxy resin, the quantitative ratio (liquid epoxy resin: solid epoxy resin), in terms of mass ratio, is preferably 1 :1~1:30, preferably 1:1~1:20, particularly preferably 1:1~1:10. By keeping the ratio of the liquid epoxy resin to the solid epoxy resin within this range, the desired effects of the present invention can be significantly obtained.

(A) The epoxy equivalent of the epoxy resin is preferably 50g/eq.~5000g/eq., more preferably 50g/eq.~3000g/eq., and even more preferably 80g/eq.~2000g/eq. , and preferably 110g/eq.~1000g/eq. By maintaining this range, the crosslinking density of the cured resin sheet becomes sufficient, and an insulating layer with small surface roughness can be provided. The epoxy equivalent weight is the mass of the resin containing 1 equivalent of epoxy groups. This epoxy equivalent can be measured in accordance with JIS K7236.

(A) The weight average molecular weight (Mw) of the epoxy resin is preferably 100 to 5000, more preferably 250 to 3000, and still more preferably 400 to 1500, in order to significantly obtain the desired effects of the present invention. The weight average molecular weight of the resin can be measured as a polystyrene-converted value by gel permeation chromatography (GPC).

The content of the epoxy resin (A) is not particularly limited. When the non-volatile components other than the component (B) in the resin composition are set to 100% by mass, the desired effect of the present invention can be significantly obtained. From the viewpoint of significantly obtaining the desired effect of the present invention, it is preferably 5 % by mass or more, more preferably 10 mass % or more, still more preferably 15 mass % or more, particularly preferably 20 mass % or more. The upper limit is preferably 60 mass% or less, more preferably 50 mass% or less, still more preferably 40 mass% or less, and particularly preferably 30 mass% or less, from the viewpoint of significantly obtaining the desired effects of the present invention.

<(B) Inorganic filler> The resin composition of the present invention contains (B) an inorganic filler.

(B) The material of the inorganic filler is not particularly limited, and examples thereof include silicon dioxide, alumina, glass, hyaline, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, and water. Talc, diaspore, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, titanium Magnesium oxide, bismuth titanate, titanium oxide, zirconium oxide, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium phosphotungstate, etc., especially silicon dioxide and alumina . Examples of silica include amorphous silica, fused silica, crystalline silica, synthetic silica, and hollow silica. Moreover, as for silica, spherical silica is preferable. (B) Inorganic fillers can be used alone or in combination of two or more types.

(B) Commercially available inorganic fillers include, for example, "UFP-30" manufactured by Denka Chemical Industry Co., Ltd.; "SP60-05" and "SP507-05" manufactured by NIPPON STEEL & SUMIKIN MATERIALS; and "SP507-05" manufactured by admatechs. "YC100C", "YA050C", "YA050C-MJE", "YA010C"; "UFP-30" made by Denka Co., Ltd.; "SilFile NSS-3N", "SilFile NSS-4N", "SilFile NSS" made by Tokuyama Co., Ltd. -5N"; "SC2500SQ", "SO-C4", "SO-C2", "SO-C1", "A23-SX-C1" made by admatechs; "DAW-03", "FB" made by Denka -105FD" etc.

(B) The average particle size of the inorganic filler is not particularly limited, but is preferably 40 μm or less, more preferably 30 μm or less, further preferably 20 μm or less, further preferably 10 μm or less, and particularly preferably 5 μm or less. 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 0.05 μm or more, further preferably 0.1 μm or more, further preferably 0.2 μm or more, further preferably 0.3 μm or more, and particularly preferably 0.4 μm or more. The average particle size of the inorganic filler can be measured by the laser diffraction scattering method based on the Mie scattering theory. Specifically, the particle size distribution of the inorganic filler is prepared on a volume basis by a laser diffraction scattering type particle size distribution measuring device, and the median particle size is measured as the average particle size. The sample to be measured can be 100 mg of inorganic filler and 10 g of methyl ethyl ketone weighed in a small glass bottle, and then dispersed by ultrasound for 10 minutes. The sample to be measured is measured using a laser diffraction particle size distribution measuring device, and the sample is measured using a light source wavelength of blue and red, and the volume-based particle size distribution of the inorganic filler is measured by a flow cell method. The obtained particle size distribution is used as the median particle size to calculate the average particle size. Examples of laser diffraction particle size distribution measuring devices include "LA-960" manufactured by Horiba, Ltd.

(B) Inorganic fillers, from the viewpoint of improving moisture resistance and dispersibility, include aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, alkoxysilane compounds, and organosilazane It is preferable to use one or more surface treatment agents such as chemical compounds and titanate coupling agents. Commercially available surface treatment agents include, for example, "KBM403" (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Industries, Ltd., "KBM803" (3-mercaptopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Industries, Ltd. Oxysilane), "KBE903" (3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical Industries, Ltd., "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Industries, Ltd. Silane), "SZ-31" (hexamethyldisilazane) manufactured by Shin-Etsu Chemical Industries, Ltd., "KBM103" (phenyltrimethoxysilane) manufactured by Shin-Etsu Chemical Industries, Ltd., "KBM-4803" manufactured by Shin-Etsu Chemical Industries, Ltd. (Long-chain epoxy silane coupling agent), "KBM-7103" (3,3,3-trifluoropropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Industries, Ltd., "KBM503" (3- Methacryloxypropyltrimethoxysilane), "KBM5783" manufactured by Shin-Etsu Chemical Industry Co., Ltd., etc.

From the viewpoint of improving the dispersibility of the inorganic filler, the degree of surface treatment by the surface treatment agent is preferably within a specific range. Specifically, 100% by mass of the inorganic filler is preferably surface-treated with a surface treatment agent of 0.2% to 5% by mass, more preferably 0.2% to 3% by mass, and still more preferably 0.3% by mass. Mass%~2 mass% for surface treatment.

The degree of surface treatment by the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the inorganic filler. From the perspective of improving the dispersibility of the inorganic filler, the amount of carbon per unit surface area of the inorganic filler is preferably 0.02 mg/ ^m2 or more, more preferably 0.1 mg/ ^m2 or more, and even more preferably 0.2 mg/ ^m2 or more. Furthermore, from the perspective of preventing the melt viscosity of the resin composition or the melt viscosity in the form of a sheet from increasing, it is preferably 1 mg/ ^m2 or less, more preferably 0.8 mg/ ^m2 or less, and even more preferably 0.5 mg/ ^m2 or less.

(B) The amount of carbon per unit surface area of the inorganic filler can be measured by washing the surface-treated inorganic filler 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 a 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. A carbon analyzer such as "EMIA-320V" manufactured by Horiba Manufacturing Co., Ltd. can be used.

From the viewpoint of improving the effect of the present invention, the specific surface area of (B) the inorganic filler is preferably 0.01 m ² /g or more, more preferably 0.1 m ² /g or more, particularly preferably 0.2 m ² /g or more. The upper limit is not particularly limited, but it is preferably 50 m ² /g or less, more preferably 20 m ² /g or less, 10 m ² /g or less, or 5 m ² /g or less. The specific surface area of the inorganic filler was calculated based on the BET method, using a specific surface area measuring device (Macsorb HM-1210 manufactured by MOUNTECH Corporation), adsorbing nitrogen gas on the surface of the sample, and calculating the specific surface area using the BET multi-point method.

The content of (B) inorganic filler is not particularly limited. When all non-volatile components in the resin composition are set to 100% by mass, from the perspective of use for specific purposes, it is preferably 30% by mass or more, more preferably 50% by mass or more, more preferably 60% by mass or more, and particularly preferably 70% by mass or more. Generally, resin compositions containing many inorganic fillers have a tendency to warp greatly. The resin composition of the present invention comprising a combination of components (A) to (C) can effectively suppress warp even when (B) is more. The upper limit of the content of (B) inorganic filler is not particularly limited. For example, it can be less than 98% by mass, less than 95% by mass, less than 90% by mass, less than 85% by mass, etc.

<(C) Benzoxazine compound having an alicyclic structure in the molecule> The resin composition of the present invention contains (C) a benzoxazine compound having an alicyclic structure in the molecule. By using component (C), the flexibility of the cured product of the resin composition can be improved and the elastic modulus can be reduced. In addition, excellent adhesion can be achieved.

The "benzoxazine compound" in the component (C) refers to a compound having a 3,4-dihydro-2H-1,3-benzoxazine ring (hereinafter sometimes referred to as "dihydrobenzoxazine ring") compound. In this compound, it is preferable that there are two or more dihydrobenzoxazine rings in the molecule. When the component (C) has two or more dihydrobenzoxazine rings, it is preferable that the two or more dihydrobenzoxazine rings are bonded via a linking group from the nitrogen atom of the ring. Among the components (C), it is preferable that the linking group has an alicyclic structure. In addition, each dihydrobenzoxazine ring may have a substituent.

Therefore, (C) a benzoxazine compound having an alicyclic structure in the molecule is preferably formula (1):

[In the formula, R each independently represents a substituent, X represents an m-valent linking group having an alicyclic structure, m represents an integer greater than 2, and n represents an integer from 0 to 4] compound represented by.

In formula (1), the "substituent" of R is not particularly limited as long as it does not hinder the function of component (C), and examples thereof include halogen atoms, cyano groups, amino groups, nitro groups, hydroxyl groups, substituted or unsubstituted alkyl groups, substituted or unsubstituted alkenyl groups, substituted or unsubstituted alkoxy groups, substituted or unsubstituted alkylcarbonyl groups, substituted or unsubstituted aryl groups, substituted or unsubstituted heteroaryl groups, substituted or unsubstituted aryloxy groups, substituted or unsubstituted arylcarbonyl groups, substituted or unsubstituted aralkyl groups, and the like.

Examples of the "halogen atom" include a fluorine atom, a chlorine atom, a bromine atom, and the like.

"Alkyl" refers to a linear, branched chain or cyclic monovalent aliphatic saturated hydrocarbon group. The "alkyl group" is preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms. Examples of "alkyl" include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, and cyclopentyl base, cyclohexyl, etc. The substituent of the alkyl group in the "substituted or unsubstituted alkyl group" is not particularly limited, and examples thereof include halogen atom, cyano group, alkoxy group, alkylcarbonyl group, aryl group, heteroaryl group, aryloxy group, aryl group, etc. Carbonyl group, amine group, nitro group, hydroxyl group, etc. The number of substituents is preferably 1 to 3, more preferably 1.

"Alkoxy" refers to a monovalent group formed by an alkyl group bonded to an oxygen atom (alkyl-O-). "Alkoxy" is preferably an alkoxy group having 1 to 6 carbon atoms, and more preferably an alkoxy group having 1 to 3 carbon atoms. "Alkoxy" includes, for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, pentyloxy, etc. The substituent of the alkoxy in "substituted or unsubstituted alkoxy" is not particularly limited, and includes, for example, a halogen atom, cyano, alkoxy, alkylcarbonyl, aryl, heteroaryl, aryloxy, arylcarbonyl, amino, nitro, hydroxyl, etc. The number of substituents is preferably 1 to 3, and more preferably 1.

"Alkenyl" refers to a linear, branched chain or cyclic monovalent unsaturated hydrocarbon group having at least one carbon-carbon double bond. "Alkenyl" is preferably an alkenyl group having 2 to 6 carbon atoms, more preferably an alkenyl group having 2 or 3 carbon atoms. Examples of "alkenyl" include vinyl, 1-propenyl, 2-propenyl, 2-methyl-1-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 3- Methyl-2-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 4-methyl-3-pentenyl, 1-hexenyl, 3-hexenyl, 5-hexenyl, 2-cyclohexenyl, etc. The substituent of the alkenyl group in the "substituted or unsubstituted alkenyl group" is not particularly limited, and examples thereof include halogen atom, cyano group, alkoxy group, alkylcarbonyl group, aryl group, heteroaryl group, aryloxy group, aryl group, etc. Carbonyl group, amine group, nitro group, hydroxyl group, etc. The number of substituents is preferably 1 to 3, more preferably 1.

"Alkylcarbonyl" refers to a monovalent group (alkyl-CO-) formed by an alkyl group bonded to a carbonyl group. "Alkylcarbonyl" is preferably an alkylcarbonyl group having 2 to 7 carbon atoms, and more preferably an alkylcarbonyl group having 2 to 4 carbon atoms. Examples of "alkylcarbonyl" include acetyl, propionyl, butyryl, 2-methylpropionyl, pentyl, 3-methylbutyryl, 2-methylbutyryl, 2,2-dimethylpropionyl, hexyl, heptyl, and the like. The substituent of the alkylcarbonyl in "substituted or unsubstituted alkylcarbonyl" is not particularly limited, and examples thereof include halogen atoms, cyano, alkoxy, alkylcarbonyl, aryl, heteroaryl, aryloxy, arylcarbonyl, amino, nitro, hydroxyl, and the like. The number of substituents is preferably 1 to 3, and more preferably 1.

"Aryl" refers to a monovalent aromatic hydrocarbon group. The "aryl group" is preferably an aryl group having 6 to 14 carbon atoms, more preferably an aryl group having 6 to 10 carbon atoms. Examples of the "aryl group" include phenyl, 1-naphthyl, 2-naphthyl and the like, and phenyl is preferred. The substituent of the aryl group in the "substituted or unsubstituted aryl group" is not particularly limited, and examples thereof include a halogen atom, a cyano group, an alkyl group, an alkoxy group, an alkylcarbonyl group, an aryl group, a heteroaryl group, and an aryloxy group. group, arylcarbonyl group, aralkyl group, amine group, nitro group, hydroxyl group, etc. The number of substituents is preferably 1 to 3, more preferably 1.

"Heteroaryl group" refers to a monovalent aromatic heterocyclic group having 1 to 4 heteroatoms selected from oxygen atoms, nitrogen atoms and sulfur atoms as ring constituent atoms in addition to carbon atoms. "Heteroaryl" is preferably a monocyclic, bicyclic or tricyclic (preferably monocyclic) aromatic heterocyclic group with 5 to 12 members (preferably 5 or 6 members). Examples of the "heteroaryl group" include furyl, thienyl, pyrrolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, imidazolyl, pyrazolyl, and 1,2,3-oxadiazolyl. , 1,2,4-oxadiazolyl, 1,3,4-oxadiazolyl, furoxanyl, 1,2,3-thiadiazolyl, 1,2,4-thiadiazolyl, 1 ,3,4-thiadiazolyl, 1,2,3-triazolyl, 1,2,4-triazolyl, tetrazolyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazine Key et al. The substituent of the heteroaryl group in the "substituted or unsubstituted heteroaryl group" is not particularly limited, and examples thereof include halogen atom, cyano group, alkyl group, alkoxy group, alkylcarbonyl group, aryl group, heteroaryl group, Aryloxy group, arylcarbonyl group, aralkyl group, amine group, nitro group, hydroxyl group, etc. The number of substituents is preferably 1 to 3, more preferably 1.

"Aryloxy" refers to a monovalent group formed by an aryl group bonded to an oxygen atom (aryl-O-). "Aryloxy" is preferably an aryloxy group having 6 to 14 carbon atoms, and more preferably an aryloxy group having 6 to 10 carbon atoms. Examples of "aryloxy" include phenoxy and naphthoxy. The substituent of the aryloxy in "substituted or unsubstituted aryloxy" is not particularly limited, and examples thereof include halogen atoms, cyano, alkyl, alkoxy, alkylcarbonyl, aryl, heteroaryl, aryloxy, arylcarbonyl, aralkyl, amino, nitro, and hydroxyl. The number of substituents is preferably 1 to 3, and more preferably 1.

"Arylcarbonyl" refers to a monovalent group (aryl-CO-) formed by the bonding of an aryl group to a carbonyl group. "Arylcarbonyl" is preferably an arylcarbonyl group having 7 to 15 carbon atoms, and more preferably an arylcarbonyl group having 7 to 11 carbon atoms. Examples of "arylcarbonyl" include benzyl, 1-naphthyl, 2-naphthyl, etc. The substituent of the arylcarbonyl in the "substituted or unsubstituted arylcarbonyl" is not particularly limited, and examples thereof include a halogen atom, cyano, alkyl, alkoxy, alkylcarbonyl, aryl, heteroaryl, aryloxy, arylcarbonyl, aralkyl, amino, nitro, hydroxyl, etc. The number of substituents is preferably 1 to 3, and more preferably 1.

"Aralkyl" refers to an alkyl group substituted with 1 or more aryl groups. "Aralkyl" is preferably an aralkyl group having 7 to 15 carbon atoms, and more preferably an aralkyl group having 7 to 11 carbon atoms. Examples of "aralkyl" include benzyl, phenethyl, 2-naphthylmethyl, etc. The substituent of the aralkyl group in "substituted or unsubstituted aralkyl" is not particularly limited, and examples thereof include halogen atoms, cyano groups, alkyl groups, alkoxy groups, alkylcarbonyl groups, aryl groups, heteroaryl groups, aryloxy groups, arylcarbonyl groups, aralkyl groups, amino groups, nitro groups, hydroxyl groups, etc. The number of substituents is preferably 1 to 3, and more preferably 1.

In formula (1), n represents an integer from 0 to 4, preferably 0 or 1, more preferably 0. That is, the dihydrobenzoxazine ring is more preferably unsubstituted.

In formula (1), if the "m-valent linking group having an alicyclic structure" of X has at least one alicyclic structure, it is not particularly limited. (C) The number of alicyclic structures in the component is not particularly limited, but is preferably 1 to 5, more preferably 1 to 3, and still more preferably 1 or 2. The ring structure of the alicyclic structure in the component (C) can include cycloalkane ring, cycloalkene ring, and at least one of the skeleton carbon atoms of them is substituted with -O-, -S-, -SO ₂ - , -NH-, -CO-, -CONH-, -NHCO-, -COO-, and -OCO- -aliphatic heterocycles containing heteroatom groups, among which cycloalkane rings are preferred.

"Naphthenic ring" refers to a monocyclic or polycyclic saturated aliphatic hydrocarbon ring. The "cycloalkane ring" is preferably a cycloalkane ring having 3 to 10 carbon atoms. Examples of "cycloalkane ring" include monocycloalkane rings such as cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, etc.; decalin ring, norbornane ring, etc. Bicycloalkane ring; spirononane ring, spiroalkane ring, etc.

"Cycloolefin ring" refers to a monocyclic or polycyclic aliphatic saturated hydrocarbon ring having at least one carbon-carbon double bond. "Cycloolefin ring" is preferably a cycloolefin ring having 3 to 10 carbon atoms. "Cycloolefin ring" includes, for example, monocyclic olefin rings such as cyclobutene ring, cyclopropene ring, cyclohexene ring, cyclohexadiene ring, cycloheptene ring, cyclooctene ring, etc.; bicyclic olefin rings such as norbornene ring, camphene ring, etc.; helical olefin rings such as spirononene ring, etc.

The number of skeleton atoms of the "m-valent linking group having an alicyclic structure" is preferably 3 to 200, more preferably 3 to 100, still more preferably 3 to 50, and particularly preferably 3 to 20. The skeleton atoms may be selected from carbon atoms, oxygen atoms, nitrogen atoms, and sulfur atoms.

The "m-valent linking group having an alicyclic structure" of X in formula (1) is preferably a substituted or unsubstituted m-valent ring-containing saturated aliphatic group. Here, the substituents of the ring-containing saturated aliphatic group in the "substituted or unsubstituted m-valent ring-containing saturated aliphatic group" may be the same as the substituents of R, and are preferably unsubstituted. The "ring-containing saturated aliphatic group" includes: a saturated hydrocarbon group containing at least one cycloalkane ring (hereinafter referred to as a "ring-containing saturated hydrocarbon group"); and a group in which at least one of its backbone carbon atoms is substituted with a group containing a heteroatom selected from -O-, -S-, _-SO2- , -NH-, -CO-, -CONH-, -NHCO-, -COO-, and -OCO- (hereinafter referred to as a "ring-containing saturated hydrocarbon heteroatom substituent").

In formula (1), m represents an integer greater than or equal to 2, preferably 2 or 3, and more preferably 2. Therefore, in the embodiment in which m is more preferably 2, X is preferably a substituted or unsubstituted divalent ring-containing saturated aliphatic group. The two terminal atoms of the "divalent ring-containing saturated aliphatic group" are preferably any carbon atoms, and more preferably carbon atoms constituting a ring.

Specific examples of the "divalent ring-containing saturated aliphatic group" in X of formula (1) include -cHex-, -cPent-, -DECAL-, -NORBOR-, -cHex-cHex-, -cPent-cPent-, -cHex-CH 2 -cHex-, -cPent-CH ₂ -cPent-, -cHex-CH 2 -CH ₂ -cHex-, -cPent-CH _{2 -CH 2 -cPent-, -cHex-CH 2 -CH 2 -cPent-, -cHex-CH 2 -CH 2 -CH 2 -cHex-, -cPent-CH 2 -CH 2 -cPent- , -cHex - CH} (CH ₃ )-cHex-, -cPent-CH(CH ₃ )-cPent-, -cHex-CH(CH ₂ CH ₃ )-cHex-, a divalent saturated ring-containing hydrocarbon group such as -cPent-CH(CH ₂ CH ₃ )-cPent-, -cHex-C(CH ₃ ) ₂ -cHex-, -cPent-C(CH ₃ ) ₂ -cPent-, -cHex-C(CH ₂ CH ₃ ) 2 -cHex-, -cPent _- C(CH ₂ CH ₃ ) ₂ -cPent-; -cHex-O-cHex-, -cPent-O-cPent-, -cHex-O-CH ₂ -CH ₂ -O-cHex-, -cPent-O-CH ₂ -CH ₂ -O-cPent-, -cHex-S-cHex-, -cPent-S-cPent-, -cHex-S-CH ₂ -CH ₂ -S-cHex-, -cPent-S-CH ₂ -CH _Here , "cHex" represents a _1,4 -cyclohexylene group, a _1,3 -cyclohexylene group, or a 1,2-cyclohexylene group. "cPent" represents 1,3-cyclopentylene and 1,2-cyclopentylene. "DECAL" represents a divalent decahydronaphthyl, 2,6-bicyclo[4.4.0]decylene, 2,7-bicyclo[4.4.0]decylene, etc. "NORBOR" represents a divalent norbornyl, examples of which include 2,5-bicyclo[2.2.1]heptylene and 2,6-bicyclo[2.2.1]heptylene.

(C) The alicyclic structure of the component is preferably a cyclohexane ring structure. That is, component (C) preferably has one or more cyclohexane ring structures in the molecule. The cyclohexane ring structure can also be part of the bicycloalkane ring structure. In this case, preferred examples of the "divalent ring-containing saturated aliphatic group" in X in formula (1) include -cHex-, -DECAL-, -NORBOR-, -cHex-cHex-, -cHex- CH ₂ -cHex-, -cHex-CH ₂ -CH ₂ -cHex-, -cHex-CH ₂ -CH ₂ -CH ₂ -cHex-, -cHex-CH(CH ₃ )-cHex-, -cHex-CH( CH ₂ CH ₃ )-cHex-, -cHex-C(CH ₃ ) ₂ -cHex-, -cHex-C(CH ₂ CH ₃ ) ₂ -cHex- and other divalent ring-containing saturated hydrocarbon groups; -cHex-O -cHex-, -cHex-O-CH ₂ -CH ₂ -O-cHex-, -cHex-S-cHex-, -cHex-S-CH ₂ -CH ₂ -S-cHex-, -cHex-CO-cHex -, -cHex-SO ₂ -cHex-, -cHex-CONH-cHex-, -cHex-NHCO-cHex-, -cHex-COO-cHex-, -cHex-OCO-cHex-, etc. saturated divalent rings Hydrocarbon heteroatom substituents.

(C) A benzoxazine compound having an alicyclic structure in the molecule, preferably a compound of formula (2):

[In the formula, R ¹ and R ² each independently represent a substituent, and Y represents a bond, an alkylene group with 1 to 6 carbon atoms, -O-, -S-, -SO ₂ -, -NH-, - CO-, -CONH-, -NHCO-, -COO-, or -OCO-; s and t each independently represent an integer from 0 to 4, and u represents a compound represented by 0 or 1]. The "substituents" of R ¹ and R ² are the same as the substituents of R in formula (1). s and t are each independent, preferably 0 or 1, particularly preferably 0.

"Alkylene" refers to a straight chain, branched chain or cyclic divalent aliphatic saturated hydrocarbon group. The number of carbon atoms in "alkylene having 1 to 6 carbon atoms" is preferably 1 to 3. Examples of the “alkylene group having 1 to 6 carbon atoms” include _-CH2- , _{-CH2- CH2-} , -CH( _CH3 )-, -CH2-CH2- _CH2- , _{-CH2 -} CH(CH3)-, -CH(CH3) _{-CH2-, -C(CH3)2- , -CH2 - CH2 -} CH2-CH2-, -CH2- _CH2 -CH( _CH3 )-, _-CH2 - _{CH2 -} CH _{(CH3)-, -CH2-CH(CH3)-CH2-, -CH(CH3)-CH2- , -CH2 - CH ( CH2} )-, -CH( _CH3 )-CH2-CH2-, _-CH2 -C( _CH3 ) _2- , -C( _CH3 ) _{2 -} CH2-, and -cHex-.

(C) Specific examples of benzoxazine compounds having an alicyclic structure in the molecule include 1,4-bis(3,4-dihydro-2H-1,3-benzoxazin-3-yl)cyclohexane, bis[4-(3,4-dihydro-2H-1,3-benzoxazin-3-yl)cyclohexyl]methane, 1,2-bis[4-(3,4-dihydro-2H-1,3-benzoxazin-3-yl)cyclohexyl]methane, bis[4-(3,4-dihydro-2H-1,3-benzoxazin-3-yl)cyclohexyl]ethane, 2,2-bis[4-(3,4-dihydro-2H-1,3-benzoxazin-3-yl)cyclohexyl]propane, bis[4-(3,4-dihydro-2H-1,3-benzoxazin-3-yl)cyclohexyl]ether, bis[4-(3,4-dihydro-2H-1,3-benzoxazin-3-yl)cyclohexyl]sulfone, and the like.

The molecular weight of the component (C) is not particularly limited, but is preferably 5,000 or less, more preferably 3,000 or less, further preferably 2,000 or less, and particularly preferably 1,000 or less from the viewpoint of remarkably obtaining the desired effect of the present invention.

The content of the benzoxazine compound having an alicyclic structure in the molecule (C) is not particularly limited, but is preferably 0.1% by mass or more, more preferably 1% by mass or more, still more preferably 3% by mass or more, and particularly preferably 5% by mass or more, based on 100% by mass of the non-volatile components other than the component (B) in the resin composition, from the viewpoint of remarkably obtaining the desired effect of the present invention. From the viewpoint of remarkably obtaining the desired effect of the present invention, the upper limit is preferably 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.

＜(D) Elastomer＞ The resin composition of the present invention may contain (D) elastomer as an optional component. By using the (D) elastomer, the flexibility of the cured product of the resin composition can be improved and the elastic modulus can be reduced.

In the present invention, (D) elastomer refers to a flexible resin and an amorphous resin component that is insoluble in an organic solvent. A resin having rubber elasticity or a resin that exhibits rubber elasticity after polymerization with other components is preferred. The rubber elasticity may be, for example, a resin that exhibits an elastic modulus of 1 GPa or less in a tensile test at 25°C and 40%RH according to Japanese Industrial Standards (JIS K7161).

In one embodiment, the component (D) is preferably a resin having one or more structures selected from the group consisting of polybutadiene structure, polysiloxane structure, poly(meth)acrylate structure, polyalkylene structure, polyalkoxyene structure, polyisoprene structure, polyisobutylene structure, and polycarbonate structure in the molecule. From the viewpoint of obtaining a flexible material, a resin having one or more structures selected from the group consisting of polybutadiene structure and polycarbonate structure is more preferred. In addition, "(meth)acrylate" refers to methacrylate and acrylate.

In another embodiment, component (D) is preferably one or more selected from a resin having a glass transition temperature (Tg) of 25°C or less and a resin that is liquid at 25°C or less. The glass transition temperature of the resin having a glass transition temperature (Tg) of 25°C or less is preferably 20°C or less, and more preferably 15°C or less. The lower limit of the glass transition temperature is not particularly limited, and can usually be -15°C or more. In addition, the resin that is liquid at 25°C is preferably a resin that is liquid at 20°C or less, and more preferably a resin that is liquid at 15°C or less.

In a more preferred embodiment, component (D) is preferably at least one resin selected from the group consisting of resins with a glass transition temperature of 25°C or lower and liquid at 25°C, and has an intramolecule structure selected from the group consisting of polybutadiene structure and polyethylene resin. Resin containing one or more structures of siloxane structure, poly(meth)acrylate structure, polyalkylene structure, polyalkyleneoxy structure, polyisoprene structure, polyisobutylene structure and polycarbonate structure .

The polybutadiene structure is not only a structure formed by polymerizing butadiene, but also includes a structure formed by hydrogenating this structure. In addition, only a part of the butadiene structure may be hydrogenated, or the entire butadiene structure may be hydrogenated. In addition, the polybutadiene structure in component (D) may include a polybutadiene structure in the main chain or a polybutadiene structure in a side chain.

Preferable examples of the polybutadiene resin include a hydrogenated polybutadiene skeleton-containing resin, a hydroxyl group-containing polybutadiene resin, a phenolic hydroxyl group-containing polybutadiene resin, and a carboxyl group-containing polybutadiene resin. , polybutadiene resin containing acid anhydride groups, polybutadiene resin containing epoxy groups, polybutadiene resin containing isocyanate groups, polybutadiene resin containing urethane groups, etc. Among them, polybutadiene resin containing phenolic hydroxyl groups is more preferred. Here, "resin containing a hydrogenated polybutadiene skeleton" refers to a resin in which at least part of the polybutadiene skeleton is hydrogenated, and does not necessarily require a resin in which the polybutadiene skeleton is completely hydrogenated. Examples of the resin containing a hydrogenated polybutadiene skeleton include epoxy resins containing a hydrogenated polybutadiene skeleton. Examples of the polybutadiene resin containing a phenolic hydroxyl group include a resin having a polybutadiene structure and a phenolic hydroxyl group.

Specific examples of polybutadiene resins having a polybutadiene structure in the molecule include "Ricon 657" (polybutadiene containing an epoxy group), "Ricon 130MA8", "Ricon 130MA13", "Ricon 130MA20", "Ricon 131MA5", "Ricon 131MA10", "Ricon 131MA17", "Ricon 131MA20", "Ricon 184MA6" (polybutadiene with anhydride groups), "GQ-1000" (polybutadiene with hydroxyl and carboxyl groups introduced), "G-1000", "G-2000", "G-3000" (polybutadiene with hydroxyl groups at both ends), "GI-1000", "GI-2000", "GI-3000" (polybutadiene with hydroxyl groups at both ends), "PB3600", "PB4700" (polybutadiene skeleton epoxy compounds) manufactured by DAICEL, "Epofriend A1005", "Epofriend A1010", "Epofriend A1020" (epoxy compounds of styrene, butadiene and styrene block copolymers), nagase "FCA-061L" (hydrogenated polybutadiene skeleton epoxy compound) and "R-45EPT" (polybutadiene skeleton epoxy compound) manufactured by Chemtex.

In addition, examples of preferred polybutadiene resins include hydroxyl-terminated polybutadiene, linear polyimide made of diisocyanate compounds and polyacids or their anhydrides (polyimide described in Japanese Patent Publication No. 2006-37083 and International Publication No. 2008/153208). The content of the polybutadiene structure in the polyimide resin is preferably 60% to 95% by mass, and more preferably 75% to 85% by mass. The details of the polyimide resin can be found in Japanese Patent Publication No. 2006-37083 and International Publication No. 2008/153208, the contents of which are incorporated into this specification.

The number average molecular weight of the hydroxyl-terminated polybutadiene is preferably 500-5,000, more preferably 1,000-3,000. The hydroxyl equivalent weight of the hydroxyl-terminated polybutadiene is preferably 250-1,250.

Examples of diisocyanate compounds include aromatic diisocyanates such as toluene-2,4-diisocyanate, toluene-2,6-diisocyanate, xylylene diisocyanate, and diphenylmethane diisocyanate; aliphatic diisocyanates such as hexamethylene diisocyanate; and alicyclic diisocyanates such as isophorone diisocyanate. Among these, aromatic diisocyanates are preferred, and toluene-2,4-diisocyanate is more preferred.

Examples of the polybasic acid or its anhydride include ethylene glycol ditrimellitate, pyromellitic acid, benzophenonetetracarboxylic acid, biphenyltetracarboxylic acid, naphthalenetetracarboxylic acid, 5-(2,5-dioxotetrahydrofuranyl)-3-methyl-cyclohexene-1,2-dicarboxylic acid, 3,3'-4,4'-diphenylsulfonatetetracarboxylic acid and the like tetrabasic acids and their anhydrides, trimellitic acid, cyclohexanetricarboxylic acid and the like tribasic acids and their anhydrides, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho(1,2-C)furan-1,3-dione and the like.

Furthermore, the resin having a polybutadiene structure may include a polystyrene structure having a structure obtained by polymerizing styrene.

Specific examples of the polystyrene resin, which is a resin having a polystyrene structure in the molecule, include styrene-butadiene-styrene block copolymer (SBS) and styrene-isoprene-styrene block copolymer. (SIS), styrene-ethylene-butylene-styrene block copolymer (SEBS), styrene-ethylene-propylene-styrene block copolymer (SEPS), styrene-ethylene-ethylene-propylene-benzene Ethylene block copolymer (SEEPS), styrene-butadiene-butylene-styrene block copolymer (SBBS), styrene-butadiene diblock copolymer, hydrogenated styrene-butadiene block Copolymers, hydrogenated styrene-isoprene block copolymers, hydrogenated styrene-butadiene random copolymers, etc.

The polystyrene resin may be a commercially available product, for example, hydrogenated styrene-based thermoplastic elastomer "H1041", "TAFTEC H1043", "TAFTEC P2000", "TAFTEC MP10" (manufactured by Asahi Kasei Corporation); epoxidized styrene-butadiene thermoplastic elastomer "Epofriend AT501", "CT310" (manufactured by DAICEL Corporation); modified styrene-based elastomer with a hydroxyl group "SEPTON HG252" (manufactured by Kuraray Corporation); modified styrene-based elastomer with a carboxyl group "TAFTEC N503M", modified styrene-based elastomer with an amine group "TAFTEC N501", modified styrene-based elastomer with an acid anhydride group "TAFTEC M1913" (produced by Asahi Kasei Chemicals Co., Ltd.); unmodified styrene elastomer "SEPTON S8104" (produced by Kuraray Co., Ltd.), etc. Component (C) may be used alone or in combination of two or more.

The polysiloxane structure is a structure containing a siloxane bond, and is contained in, for example, silicone rubber. The component (D) may contain the polysiloxane structure in the main chain or in the side chain.

Specific examples of the polysiloxane resin, which is a resin having a polysiloxane structure in the molecule, include "SMP-2006", "SMP-2003PGMEA", "SMP-5005PGMEA" and amino-terminated polysilica manufactured by Shin-Etsu SILICONES Co., Ltd. Oxane, linear polyimide using tetrabasic acid anhydride as raw material (International Publication No. 2010/053185), etc.

The poly(meth)acrylate structure includes a structure formed by polymerizing acrylic acid or acrylic acid ester, and a structure formed by polymerizing methacrylic acid or methacrylic acid ester. (Meth)acrylate structure: Component (D) may contain a (meth)acrylate structure in the main chain or a (meth)acrylate structure in a side chain.

Preferred examples of the poly(meth)acrylate resin having a poly(meth)acrylate structure in the molecule include poly(meth)acrylate resins containing a hydroxyl group, poly(meth)acrylate resins containing a phenolic hydroxyl group, poly(meth)acrylate resins containing a carboxyl group, poly(meth)acrylate resins containing anhydride groups, poly(meth)acrylate resins containing epoxy groups, poly(meth)acrylate resins containing isocyanate groups, poly(meth)acrylate resins containing urethane groups, and the like.

Specific examples of the poly(meth)acrylate resin include Teisanresin "SG-70L", "SG-708-6", "WS-023", "SG-700AS", and "SG-280TEA" manufactured by Nagase Chemtex Corporation "(Acrylate copolymer resin containing carboxyl groups, acid value 5~34mgKOH/g, weight average molecular weight 400,000~900,000, Tg-30℃~5℃), "SG-80H", "SG-80H-3" , "SG-P3" (epoxy group-containing acrylate copolymer resin, epoxy equivalent 4761~14285g/eq, weight average molecular weight 350,000~850,000, Tg11℃~12℃), "SG-600TEA", " SG-790" (hydroxyl-containing acrylate copolymer resin, hydroxyl value 20~40mgKOH/g, weight average molecular weight 500,000~1.2 million, Tg-37℃~-32℃), "ME-2000" manufactured by Negami Industrial Co., Ltd. ”, “W-116.3” (acrylate copolymer resin containing carboxyl groups), “W-197C” (acrylate copolymer resin containing hydroxyl groups), “KG-25”, “KG-3000” (containing epoxy groups acrylate copolymer resin), etc.

The polyalkylene structure preferably has a specific number of carbon atoms. The specific number of carbon atoms in the polyalkylene structure is preferably 2 or more, more preferably 3 or more, particularly preferably 5 or more, preferably 15 or less, more preferably 10 or less, particularly preferably 6 or less. In addition, in the component (D), the polyalkylene structure may be contained in the main chain or in the side chain.

The polyalkyleneoxy structure preferably has a specific number of carbon atoms. The specific number of carbon atoms in the polyalkyleneoxy structure is preferably 2 or more, preferably 3 or more, more preferably 5 or more, preferably 15 or less, more preferably 10 or less, and particularly preferably 6 or less. The polyalkyleneoxy structure in component (D) may contain a polyalkyleneoxy structure in the main chain, or may contain a polyalkyleneoxy structure in a side chain.

Specific examples of the polyalkylene resin having a polyalkylene structure in the molecule and the polyalkylene oxide resin having a polyalkylene oxide structure in the molecule include "PTXG-1000" and "PTXG-1800" manufactured by Asahi Kasei Fibers Corporation, "YX-7180" (a resin containing an alkylene oxide structure having an ether bond) manufactured by Mitsubishi Chemical Co., Ltd., "EXA-4850-150", "EXA-4816", and "EXA-4822" manufactured by DIC Corporation, "EP-4000", "EP-4003", "EP-4010", and "EP-4011" manufactured by ADEKA Corporation, "BEO-60E" and "BPO-20E" manufactured by Shin Nippon Chemical Co., Ltd., and "BPO-700" manufactured by Mitsubishi Chemical Corporation. "YL7175" and "YL7410" manufactured by Chemical Company.

The component (D) may contain a polyisoprene structure in the main chain or a polyisoprene structure in the side chain. Specific examples of the polyisoprene resin, which is a resin having a polyisoprene structure in the molecule, include "KL-610" and "KL-613" manufactured by Kuraray Corporation.

The component (D) may contain a polyisobutylene structure in the main chain or in the side chain. Specific examples of the polyisobutylene resin having a polyisobutylene structure in the molecule include "SIBSTAR-073T" (styrene-isobutylene-styrene triblock copolymer) and "SIBSTAR-042D" (styrene-isobutylene diblock copolymer) manufactured by Kaneka Corporation.

The component (D) may contain a polycarbonate structure in the main chain or in the side chain.

Preferred examples of the polycarbonate resin having a polycarbonate structure in the molecule include a polycarbonate resin containing a hydroxyl group, a polycarbonate resin containing a phenolic hydroxyl group, a polycarbonate resin containing a carboxyl group, a polycarbonate resin containing an acid anhydride group, a polycarbonate resin containing an epoxy group, a polycarbonate resin containing an isocyanate group, a polycarbonate resin containing a urethane group, and the like.

Specific examples of polycarbonate resins include "T6002" and "T6001" (polycarbonate diol) manufactured by Asahi Kasei Chemicals, and "C-1090", "C-2090", and "C-3090" (polycarbonate diol) manufactured by Kuraray.

Preferable examples of the polycarbonate resin include hydroxyl-terminated polycarbonate and linear polyimide using a diisocyanate compound and a polybasic acid or anhydride thereof as raw materials. The linear polyimide has a urethane structure and a polycarbonate structure. The content rate of the polycarbonate structure of the polyimide resin is preferably 60 mass% to 95 mass%, and more preferably 75 mass% to 85 mass%. For details of the polyimide resin, please refer to the records of International Publication No. 2016/129541, the content of which is incorporated into this specification.

The number average molecular weight of the hydroxyl-terminated polycarbonate is preferably 500-5,000, more preferably 1,000-3,000. The hydroxyl equivalent weight of the hydroxyl-terminated polycarbonate is preferably 250-1,250.

It is preferable that the component (D) has an amide imine structure. By having an amide imine structure, the heat resistance of component (D) can be improved, and the crack resistance can be effectively improved.

The component (D) may have a linear chain structure, a branched structure, or a ring structure, but a linear chain structure is preferred.

The component (D) preferably has a functional group that can react with the component (A). This functional group also includes a reactive group that appears by heating. The component (D) has a functional group that can improve the mechanical strength of the cured product of the resin composition.

Examples of the functional group include a carboxyl group, a hydroxyl group, an acid anhydride group, a phenolic hydroxyl group, an epoxy group, an isocyanate group, and a carbamate group. Among them, from the viewpoint of significantly obtaining the effect of the present invention, the functional group is preferably a functional group having one or more selected from a hydroxyl group, an acid anhydride group, a phenolic hydroxyl group, an epoxy group, an isocyanate group, and a carbamate group, and a phenolic hydroxyl group is particularly preferred.

The component (D) may be used alone or in combination of two or more.

From the viewpoint of flexibility, component (D) is preferably of high molecular weight. The specific number average molecular weight Mn of the component (D) is preferably 4,000 or more, more preferably 4,500 or more, still more preferably 5,000 or more, particularly preferably 5,500 or more, preferably 100,000 or less, more preferably 95,000 or less, especially The best value is less than 90,000. (D) The number average molecular weight Mn of the component is the number average molecular weight in terms of polystyrene measured using GPC (gel permeation chromatography).

From the viewpoint of obtaining softness, the specific weight average molecular weight of the component (D) is preferably 5500 to 100000, more preferably 10000 to 90000, and even more preferably 15000 to 80000. The weight average molecular weight of the component (D) is the weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC).

When component (D) has a functional group, the functional group equivalent of component (D) is preferably 100g/eq. or more, more preferably 200g/eq. or more, still more preferably 1000g/eq. or more, particularly preferably 2500g /eq. or more, preferably 50,000g/eq. or less, more preferably 30,000g/eq. or less, still more preferably 10,000g/eq. or less, particularly preferably 5,000g/eq. or less. Functional group equivalent weight is the number of grams of resin containing 1 gram equivalent of functional group. For example, the epoxy group equivalent can be measured in accordance with JIS K7236. For example, the hydroxyl equivalent can be calculated by dividing the hydroxyl value measured by JIS K1557-1 by the molecular weight of KOH.

The glass transition temperature (Tg) of the component (D) is 20°C or lower, preferably 0°C or lower.

When the (D) elastomer is contained, the content of the (D) elastomer is not particularly limited. When the non-volatile components other than the (B) component in the resin composition are set to 100% by mass, greater flexibility will be obtained. The content is preferably 10 mass% or more, more preferably 30 mass% or more, still more preferably 40 mass% or more, and particularly preferably 50 mass% or more. (D) The upper limit of the elastomer content is preferably 75 mass% or less, more preferably 70 mass% or less, and still more preferably 65 mass% or less, in order to significantly obtain the desired effect of the present invention. 60% by mass or less.

<(E) Hardener> The resin composition of the present invention may contain (E) hardener as an optional component. By containing (E) hardener, (A) epoxy resin can be easily hardened.

The (E) hardener is not particularly limited as long as it has the function of hardening the epoxy resin, and examples thereof include phenolic hardeners, naphthol hardeners, acid anhydride hardeners, active ester hardeners, benzoxazine hardeners, cyanate hardeners, and carbodiimide hardeners. The hardener may be used alone or in combination of two or more. The (E) hardener of the resin composition of the present invention is preferably selected from the group consisting of phenolic hardeners, naphthol hardeners, and active ester hardeners in order to significantly achieve the desired effect of the present invention. In one embodiment, the (E) hardener preferably includes an active ester hardener.

Phenol hardeners and naphthol hardeners are preferably phenol hardeners having a novolac structure or naphthol hardeners having a novolac structure from the viewpoint of heat resistance and water resistance. Also, nitrogen-containing phenol hardeners or nitrogen-containing naphthol hardeners are preferred from the viewpoint of adhesion to the adherend, and phenol hardeners containing a triazine skeleton or naphthol hardeners containing a triazine skeleton are more preferred. Among them, phenol novolac resins containing a triazine skeleton are preferred from the viewpoint of highly satisfying heat resistance, water resistance and adhesion. Specific examples of phenolic hardeners and naphthol hardeners include "MEH-7700", "MEH-7810", "MEH-7851", and "MEH-8000H" manufactured by Meiwa Chemicals; "NHN", "CBN", and "GPH" manufactured by Nippon Kayaku Co., Ltd.; "SN-170", "SN-180", "SN-190", "SN-475", "SN-485", "SN-495", "SN-495V", "SN-375", and "SN-475" manufactured by Nippon Steel & Sumitomo Metal Industries, Ltd. "SN-395" manufactured by DIC Corporation; "TD-2090", "TD-2090-60M", "LA-7052", "LA-7054", "LA-1356", "LA-3018", "LA-3018-50P", "EXB-9500", "HPC-9500", "KA-1160", "KA-1163", "KA-1165" manufactured by Qun Rong Chemical Corporation; "GDP-6115L", "GDP-6115H", "ELPC75" and so on.

The acid anhydride curing agent includes a curing agent having one or more acid anhydride groups in one molecule. Specific examples of the acid anhydride curing agent include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, hydrogenated methylnadic anhydride, trialkyltetrahydrophthalic anhydride, dodecenylsuccinic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trimellitic anhydride, pyromellitic anhydride, Benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, naphthalene tetracarboxylic dianhydride, oxydiphthalic anhydride, 3,3'-4,4'-diphenylsulfonate tetracarboxylic dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2-C]furan-1,3-dione, ethylene glycol bis(trimellitic anhydride), styrene-maleic acid resin copolymerized with maleic acid, and other polymer-type acid anhydrides. Commercially available products of acid anhydride-based hardeners include "HNA-100" and "MH-700" manufactured by Shin Nippon Rika Co., Ltd.

The active ester curing agent is not particularly limited. Generally, it is preferred to use a compound having two or more highly reactive ester groups in one molecule such as phenol esters, thiophenol esters, N-hydroxylamine esters, and esters of heterocyclic hydroxyl compounds. The active ester curing agent is preferably obtained by a condensation reaction of a carboxylic acid compound and/or a thiocarboxylic acid compound with a hydroxyl compound and/or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester curing agent obtained from a carboxylic acid compound and a hydroxyl compound is preferred, and an active ester curing agent obtained from a carboxylic acid compound and a phenol compound and/or a naphthol compound is more preferred. Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. Examples of the phenolic compound or naphthol compound include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalein, 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, phloroglucinol, benzenetriol, dicyclopentadiene-type diphenolic compounds, phenol novolac, etc. Here, "dicyclopentadiene-type diphenolic compounds" refer to diphenolic compounds obtained by condensation of one dicyclopentadiene molecule and two phenolic molecules.

Specifically, preferred are active ester compounds containing a dicyclopentadiene diphenol structure, active ester compounds containing a naphthalene structure, active ester compounds containing acetylated phenol novolacs, and active ester compounds containing benzoylated phenol novolacs, among which active ester compounds containing a naphthalene structure and active ester compounds containing a dicyclopentadiene diphenol structure are more preferred. "Dicyclopentadiene diphenol structure" refers to a divalent structural unit composed of phenylene-dicyclopentalene-phenylene.

Commercially available active ester curing agents include active ester compounds of dicyclopentadiene-type diphenol structures, such as "EXB9451", "EXB9460", "EXB9460S", "HPC-8000", "HPC-8000H", "HPC-8000-65T", "HPC-8000H-65TM", "EXB-8000L", and "EXB-8000L-65TM" (manufactured by DIC Corporation); active ester compounds of naphthalene structures, such as "EXB9416-70BK" and "EXB-8150-65T" (manufactured by DIC Corporation); active ester compounds of acetylated phenol novolacs, such as "DC808" (manufactured by Mitsubishi Chemical Company); active ester compounds of phenol novolac benzoyl compounds, such as "YLH1026" (Mitsubishi Chemical Company); active ester hardeners of phenol novolac acetylation compounds, such as "DC808" (Mitsubishi Chemical Company); active ester hardeners of phenol novolac benzoyl compounds, such as "YLH1026" (Mitsubishi Chemical Company), "YLH1030" (Mitsubishi Chemical Company), and "YLH1048" (Mitsubishi Chemical Company); etc.

Specific examples of benzoxazine-based hardeners include "JBZ-OP100D" and "ODA-BOZ" manufactured by JFE Chemical, "HFB2006M" manufactured by Showa High Polymer, and "P-d" and "F-a" manufactured by Shikoku Chemical Industries.

Examples of cyanate curing agents include bifunctional cyanate resins such as bisphenol A dicyanate, polyphenol cyanate (oligo(3-methylene-1,5-phenylene cyanate)), 4,4'-methylenebis(2,6-dimethylphenylcyanate), 4,4'-ethylenediphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanate)phenylpropane, 1,1-bis(4-cyanatephenylmethane), bis(4-cyanate-3,5-dimethylphenyl)methane, 1,3-bis(4-cyanatephenyl-1-(methylethylene))benzene, bis(4-cyanatephenyl)sulfide, and bis(4-cyanatephenyl)ether, polyfunctional cyanate resins derived from phenol novolac and cresol novolac, and prepolymers of these cyanate resins partially triazinated. Specific examples of cyanate-based curing agents include "PT30" and "PT60" manufactured by Lonza Japan (both are phenol novolac-type multifunctional cyanate resins), "BA230", and "BA230S75" (prepolymers in which bisphenol A dicyanate is partially or completely triazinated to become trimer).

Specific examples of carbodiimide-based hardeners include "V-03" and "V-07" manufactured by Nisshinbo Chemical Co., Ltd.

When a hardener is included, the amount ratio of the epoxy resin to the hardener is a ratio of [the total number of epoxy groups of the epoxy resin]: [the total number of reactive groups of the hardener], preferably in the range of 1:0.2 to 1:2, more preferably 1:0.3 to 1:1.5, and even more preferably 1:0.4 to 1:1.2. Here, the reactive group of the hardener refers to an active hydroxyl group, an active ester group, etc., which varies depending on the type of the hardener. In addition, the total number of epoxy groups of epoxy resin refers to the total value of all epoxy resins obtained by dividing the mass of non-volatile components of each epoxy resin by the epoxy equivalent, and the total number of reactive groups of hardener refers to the total value of all hardeners obtained by dividing the mass of non-volatile components of each hardener by the reactive group equivalent. When the amount ratio of epoxy resin to hardener is within this range, the heat resistance of the obtained hardened material can be further improved.

When the (E) curing agent is contained, the content of the (E) curing agent is not particularly limited, but is preferably 1% by mass or more, more preferably 5% by mass or more, further preferably 8% by mass or more, and particularly preferably 10% by mass or more, based on 100% by mass of the non-volatile components other than the (B) component in the resin composition. The upper limit of the content of the (E) curing agent is preferably 40% by mass or less, more preferably 30% by mass or less, further preferably 20% by mass or less, and particularly preferably 15% by mass or less.

＜(F) Hardening accelerator＞ The resin composition of the present invention may contain (F) a hardening accelerator as an optional component. (F) The hardening accelerator has the function of accelerating the hardening of (A) epoxy resin.

(F) Hardening accelerators include, for example, phosphorus-based hardening accelerators, amine-based hardening accelerators, imidazole-based hardening accelerators, guanidine-based hardening accelerators, and metal-based hardening accelerators. Among them, phosphorus-based hardening accelerators, amine-based hardening accelerators, imidazole-based hardening accelerators, and metal-based hardening accelerators are preferred, and amine-based hardening accelerators, imidazole-based hardening accelerators, and metal-based hardening accelerators are more preferred. One type of hardening accelerator may be used alone, or two or more types may be used in combination.

Phosphorus-based hardening accelerators include, for example, triphenylphosphine, phosphonium borate compounds, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, (4-methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate, and the like.

Amine-based hardening accelerators include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine (DMAP), benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, 1,8-diazabicyclo(5,4,0)-undecene, etc., preferably 4-dimethylaminopyridine.

Imidazole hardening accelerators include, for example, 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-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole trimellitate, 1-cyanoethyl-2-phenylimidazole 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 Imidazole compounds such as isocyanuric acid adducts, 2-phenyl-4,5-dihydroxymethylimidazole, 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 adducts of imidazole compounds with epoxy resins.

As the imidazole-based hardening accelerator, a commercially available product may be used, for example, "P200-H50" manufactured by Mitsubishi Chemical Co., Ltd.

Guanidine-based hardening accelerators include, for example, dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, and dimethyl Guanidine, diphenylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-methyl-1,5 ,7-triazabicyclo[4.4.0]dec-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1,1 -Dimethyl biguanide, 1,1-diethyl biguanide, 1-cyclohexyl biguanide, 1-allyl biguanide, 1-phenyl biguanide, 1-(o-tolyl) biguanide, etc.

Examples of metal hardening accelerators include organic metal complexes or organic metal salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of organic metal complexes include organic cobalt complexes such as cobalt (II) acetylacetonate and cobalt (III) acetylacetonate, organic copper complexes such as copper (II) acetylacetonate, organic zinc complexes such as zinc (II) acetylacetonate, organic iron complexes such as iron (III) acetylacetonate, organic nickel complexes such as nickel (II) acetylacetonate, and organic manganese complexes such as manganese (II) acetylacetonate. Examples of the organic metal salt include zinc octylate, tin octylate, zinc cycloalkanoate, cobalt cycloalkanoate, tin stearate, zinc stearate, and the like.

When the (F) hardening accelerator is contained, the content of the (F) hardening accelerator is not particularly limited. When the non-volatile components other than the (B) component in the resin composition are taken as 100 mass %, it is preferably 0.001 mass %. It is more preferably 0.01 mass % or more, still more preferably 0.05 mass % or more, and particularly preferably 0.1 mass % or more. (F) The upper limit of the content of the hardening accelerator is preferably 5 mass% or less, more preferably 2 mass% or less, still more preferably 1 mass% or less, particularly preferably 0.5 mass% or less.

＜(G) Organic solvent＞ The resin composition of the present invention may further contain (G) organic solvent as an optional volatile component.

Examples of organic solvents include ketone solvents such as acetone, methyl ethyl ketone, and cyclohexanone; ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol ethyl Ester solvents such as acid esters, ethyl diethylene glycol acetate, γ-butyrolactone, etc.; carbitol solvents such as cellulose and butyl carbitol; benzene, toluene, xylene, ethylbenzene , trimethylbenzene and other aromatic hydrocarbon solvents; dimethylformamide, dimethylacetamide (DMAc) and N-methylpyrrolidone and other amide solvents; methanol, ethanol, 2-methoxy Alcohol-based solvents such as propanol; hydrocarbon-based solvents such as cyclohexane and methylcyclohexane. One type of organic solvent may be used alone, or two or more types may be used in combination at any ratio.

＜(H) Other additives＞ In addition to the above-mentioned components, the resin composition may also contain other additives as optional components. Such additives include, for example, organic fillers, thickeners, defoamers, leveling agents, adhesion-imparting agents, polymerization initiators, flame retardants, etc. These additives may be used alone or in combination of two or more. The content of each can be appropriately set by those familiar with the technology.

＜Manufacturing method of resin composition＞ In one embodiment, the resin composition of the present invention can be produced by a method including the following steps, for example, in a reaction vessel, (A) epoxy resin, (B) inorganic filler, (C) intramolecular filler Benzoxazine compound with one or more alicyclic structures, if necessary (D) elastomer, if necessary, (E) hardener, if necessary, (F) hardening accelerator, if necessary, (G) organic The solvent, and if necessary (H) other additives, are added in any order and/or partially or entirely simultaneously to perform the step of mixing to obtain a resin composition.

In the above steps, the temperature of the process of adding each component can be appropriately set, and heating and/or cooling can be performed temporarily or permanently during the process of adding each component. Stirring or shaking can be performed during the process of adding each component. In addition, after the above steps, it is preferred to further include a step of stirring the resin composition using a stirring device such as a mixer to uniformly disperse it.

<Characteristics of the resin composition> The resin composition of the present invention comprises (A) an epoxy resin, (B) an inorganic filler, and (C) a benzoxazine compound having one or more alicyclic structures in the molecule, thereby reducing the elastic modulus of the cured product, thereby achieving suppression of warping and excellent adhesion.

In one embodiment, the tensile elastic coefficient (GPa) of the cured product of the resin composition of the present invention at 23°C measured in accordance with JIS K7127 is relatively low from the viewpoint of reducing warpage and easing the stress generated during thermal curing. Preferably it is below 15Gpa, more preferably below 12Gpa, still more preferably below 11Gpa, particularly preferably below 10.5Gpa.

In one embodiment, the peeling strength (peeling strength) of the cured resin composition of the present invention from the copper foil is, for example, the load when peeling 35 mm in the vertical direction at a speed of 50 mm/min at room temperature. , when measured in accordance with JIS C6481, it is preferably 0.25kgf/cm or more, more preferably 0.3kgf/cm or more, further preferably 0.35kgf/cm or more, and particularly preferably 0.38kgf/cm or more.

In one embodiment, the warp of the resin composition layer (thickness 100 μm) of the present invention and a substrate composed of a 12-inch silicon wafer when heat-treated at 180° C. for 90 minutes is preferably less than 4 mm, more preferably less than 3 mm, even more preferably less than 2.5 mm, particularly preferably less than 2.3 mm, less than 2.2 mm, less than 2.1 mm, or less than 2 mm.

<Use of resin composition> The resin composition of the present invention is suitable as a resin composition for insulating purposes, and is particularly suitable for use as a resin composition for forming an insulating layer. Specifically, it is suitable for use as a resin composition for forming an insulating layer (resin composition for forming an insulating layer for forming a conductive layer) formed on an insulating layer. Furthermore, in the printed wiring board described later, it is suitable for use 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 can also be used for resin sheets, prepreg and other thin-sheet lamination materials, solder resists, bottom filling materials, die attach materials, semiconductor packaging materials, buried hole resins, component embedding resins, etc., and the resin composition has a wide range of uses.

Furthermore, for example, when a semiconductor chip package is manufactured through the following steps (1) to (6), the resin composition of the present invention can also be suitably used as a resin composition for a rewiring forming layer of an insulating layer for forming a rewiring layer ( Resin compositions for forming rewiring formation layers) and resin compositions for encapsulating semiconductor wafers (resin compositions for encapsulating semiconductor wafers) are used. During semiconductor chip packaging manufacturing, a rewiring layer can be formed on the packaging layer. (1) The step of laminating a temporary fixing film on the base material, (2) The step of temporarily fixing the semiconductor wafer on the temporary fixing film, (3) The steps of forming the packaging layer on the semiconductor wafer, (4) The step of peeling off the base material and the temporary fixing film from the semiconductor wafer, (5) The step of forming a rewiring formation layer as an insulating layer on the surface of the semiconductor wafer from which the base material and the temporary fixing film are peeled off, and (6) Step of forming a rewiring layer as a conductor layer on the rewiring formation layer

Furthermore, the resin composition of the present invention can provide an insulating layer with good component embedding properties, and thus can be applied to the case where the printed wiring board is a component-embedded circuit board.

<Flake-like laminated material> The resin composition of the present invention can be applied in a varnish state. In industry, it is generally preferred to use the resin composition in the form of a flaky laminated material.

The sheet-like laminate material is preferably a resin sheet or prepreg as shown below.

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

The thickness of the resin composition layer is preferably 50 μm or less, and more preferably 40 μm or less, from the viewpoint of thinning the printed wiring board and providing a cured product with excellent insulation even if the cured product of the resin composition is a thin film. The lower limit of the thickness of the resin composition layer is not particularly limited, and can usually be 5 μm or more, 10 μm or more, etc.

Examples of the support include films made of plastic materials, metal foils, and release papers, preferably films made of plastic materials and metal foils.

When a film made of a plastic material is used as the support, examples of the plastic material include polyethylene terephthalate (hereinafter sometimes referred to as "PET"), polyethylene naphthalate (hereinafter sometimes referred to as "PET"), polyethylene naphthalate (hereinafter sometimes referred to as "PET"), Polyesters such as "PEN"), polycarbonates (hereinafter sometimes referred to as "PC"), acrylics such as polymethyl methacrylate (PMMA), cyclic polyolefins, and triacetyl cellulose (TAC) , polyether sulfide (PES), polyetherketone, polyimide, etc. Among them, polyethylene terephthalate and polyethylene naphthalate are preferred, and inexpensive polyethylene terephthalate is particularly preferred.

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 preferred. As the copper foil, a foil composed of copper as a single metal may be used, or an alloy composed of copper and other metals (for example, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) may be used. foil.

The surface of the support that is joined to the resin composition layer can be subjected to matting treatment, corona treatment, or antistatic treatment.

Furthermore, as the support, a support with a release layer having a release layer on the surface bonded to the resin composition layer may be used. The release agent used for the release layer of the support with a release layer may be, for example, one or more release agents selected from the group consisting of alkyd resins, polyolefin resins, urethane resins, and silicone resins. The support body with a release layer can use commercially available products, for example, PET film having a release layer with an alkyd resin release agent as the main component, such as "SK-1", "AL-5", and "AL-7" manufactured by Lintec, "Lumirror T60" manufactured by Toray, "Purex" manufactured by Teijin, "unipeel" manufactured by Unitika, etc.

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. Moreover, when using the support body with a release layer, it is preferable that the thickness of the whole support body with a release layer falls within the said range.

In one embodiment, the resin sheet may further include an arbitrary layer if necessary. This arbitrary layer may be, for example, a protective film provided on the surface of the resin composition layer that is not bonded to the support (i.e., the surface opposite to the support). The thickness of the protective film is not particularly limited, and is, for example, 1 μm to 40 μm. By laminating the protective film, it is possible to prevent dirt from adhering to the surface of the resin composition layer or suppress scratches.

The resin sheet is prepared by directly applying a liquid resin composition or by preparing a resin varnish in which the resin composition is dissolved in an organic solvent. The resin varnish is coated on the support using a die coater or the like. It is produced by drying to form a resin composition layer.

Examples of organic solvents include ketones such as acetone, methyl ethyl ketone (MEK), and cyclohexanone; ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbide Acetate esters such as alcohol acetate; carbitols such as cellosolve and butylcarbitol; aromatic hydrocarbons such as toluene and xylene; dimethylformamide, dimethylacetamide (DMAc) and amide solvents such as N-methylpyrrolidone. One type of organic solvent may be used alone, or two or more types may be used in combination.

Drying can be performed by conventional methods such as heating and blowing hot air. Drying conditions are not particularly limited, but drying is performed until the content of the organic solvent in the resin composition layer becomes 10 mass% or less, preferably 5 mass% or less. It also depends on the boiling point of the organic solvent in the resin varnish. For example, when using a resin varnish containing 30% to 60% by mass of organic solvent, it can be formed by drying at 50°C to 150°C for 3 to 10 minutes. Resin composition layer.

The resin sheet can be stored in a roll. If the resin sheet has a protective film, the protective film can be peeled off before use.

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

The sheet-like fiber base material used for the prepreg is not particularly limited, and those commonly used as base materials for prepregs such as glass cloth, aromatic polyamide nonwoven fabric, liquid crystal polymer nonwoven fabric, etc. can be used. From the viewpoint of thinning the printed wiring board, the thickness of the sheet-like fiber base material is preferably 50 μm or less, more preferably 40 μm or less, still more preferably 30 μm or less, particularly preferably 20 μm or less. The lower limit of the thickness of the sheet-like fiber base material is not particularly limited. Usually above 10μm.

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 that of the resin composition layer in the above-mentioned resin sheet.

The present invention using a resin composition containing a combination of components (A), (B) and (C) in a specific content can achieve high glass transition temperature, low dielectric tangent and good adhesion to the conductor layer. It is a good hardened material and is very useful as a sheet-like laminate material when manufacturing printed wiring boards.

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

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

A printed wiring board can be produced, for example, using the above-mentioned resin sheet by a method comprising the following steps (I) and (II). (I) A step of bonding the resin composition layer of the resin sheet to the inner substrate and laminating the resin sheet on the inner substrate (II) A step of thermally curing (e.g., thermosetting) the resin composition layer to form an insulating layer

The "inner substrate" used in step (I) is a component that becomes the substrate of the printed wiring board, and examples thereof include glass epoxy substrates, metal substrates, polyester substrates, polyimide substrates, BT resin substrates, thermosetting polyphenylene ether substrates, etc. Furthermore, one or both sides of the substrate may also have a conductive layer, and this conductive layer may also be patterned. An inner substrate having a conductive layer (circuit) formed on one or both sides of the substrate is sometimes referred to as an "inner circuit substrate." Furthermore, when manufacturing a printed wiring board, an intermediate product further having an insulating layer and/or a conductive layer formed thereon is also included in the so-called "inner substrate" of the present invention. When the printed wiring board is a circuit board with built-in components, an inner substrate with built-in components may also be used.

The inner substrate and the resin sheet can be laminated, for example, by heating and pressing the resin sheet to the inner substrate from the side of the support. The component for heating and pressing the resin sheet to the inner substrate (hereinafter also referred to as "heating and pressing component") can be, for example, a heated metal plate (SUS mirror plate, etc.) or a metal roller (SUS roller). In addition, the heating and pressing component is not directly pressed onto the resin sheet, but the resin sheet is preferably pressed through an elastic material such as heat-resistant rubber so that it fully follows the surface unevenness of the inner substrate.

The lamination of the inner substrate and the resin sheet can be performed by vacuum lamination. In the vacuum lamination, the heating and pressing temperature is preferably in the range of 60°C to 160°C, more preferably in the range of 80°C to 140°C, the heating and pressing pressure is preferably in the range of 0.098MPa to 1.77MPa, more preferably in the range of 0.29MPa to 1.47MPa, and the heating and pressing time is preferably in the range of 20 seconds to 400 seconds, more preferably in the range of 30 seconds to 300 seconds. Lamination is preferably performed under reduced pressure conditions with a pressure of less than 26.7hPa.

Lamination can be performed by a commercially available vacuum laminator. Commercially available vacuum laminators include, for example, a vacuum pressurized laminator manufactured by Meiki Seisakusho Co., Ltd., a vacuum coater manufactured by Nikko-Materials, and a batch-type vacuum pressurized laminator.

After lamination, the laminated resin sheets may be smoothed under normal pressure (atmospheric pressure), for example, by pressing a heating and crimping member from the support side. The pressing conditions for the smoothing treatment may be the same as those for the heat-pressing bonding of the above-described laminate. Smoothing treatment can be performed by a commercially available laminating machine. In addition, the lamination and smoothing treatment can also be performed continuously using the above-mentioned commercially available vacuum laminator.

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

In step (II), the resin composition layer is thermally cured (e.g., heat cured) to form an insulating layer composed of a cured product of the resin composition. The curing conditions of the resin composition layer are not particularly limited, and the conditions commonly used when forming an insulating layer of a printed wiring board can be used.

For example, the heat curing conditions of the resin composition layer vary depending on the type of the resin composition, and the curing temperature is preferably 120°C to 240°C, more preferably 150°C to 220°C, and even more preferably 170°C to 210°C. The curing time is 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 heat-cured, the resin composition layer may be pre-heated at a temperature lower than the curing temperature. For example, before the resin composition layer is heat-cured, the resin composition layer is pre-heated at a temperature of usually 50°C or higher and lower than 120°C, preferably 60°C or higher and lower than 115°C, and more preferably 70°C or higher and lower than 110°C for 5 minutes or more, preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes, and even more preferably 15 minutes to 100 minutes.

When manufacturing a printed wiring board, the step (III) of opening holes in the insulating layer, the step (IV) of roughening the insulating layer, and the step (V) of forming a conductive layer may be further performed. These steps (III) to (V) may be performed according to various methods known to those skilled in the art for manufacturing printed wiring boards. Furthermore, when the support is removed after step (II), the removal of the support may be performed between step (II) and step (III), between step (III) and step (IV), or between step (IV) and step (V). Furthermore, if necessary, the formation of the insulating layer and the conductive layer in steps (II) to (V) may be repeated to form a multi-layer wiring board.

In other embodiments, the printed wiring board of the present invention can be produced using the above prepreg. The manufacturing method is basically the same as in the case of using a resin sheet.

Step (III) is a step of opening a hole in the insulating layer, thereby forming a via hole, a through hole, etc. in the insulating layer. Step (III) can be performed, for example, using a drill, a laser, or plasma, depending on the composition of the resin composition used to form the insulating layer. The size or shape of the hole can 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), the residue is also removed. The order and conditions of the roughening treatment are not particularly limited, and the known order and conditions commonly used when forming the insulating layer of the printed wiring board can be adopted. For example, the insulating layer can be roughened in the order of swelling treatment with a swelling liquid, roughening treatment with an oxidizing agent, and neutralization treatment with a neutralizing liquid.

The swelling liquid used for the roughening treatment is not particularly limited, and can be an alkaline solution, a surfactant solution, etc., preferably an alkaline solution, and the alkaline solution is more preferably a sodium hydroxide solution, a potassium hydroxide solution. Commercially available swelling liquids include, for example, "Swelling Dip Securiganth P" and "Swelling Dip Securiganth SBU" manufactured by Atotech Japan. The swelling treatment using the swelling liquid is not particularly limited, and can be performed, for example, by immersing the insulating layer in a swelling liquid at 30°C to 90°C for 1 minute to 20 minutes. From the perspective of suppressing the swelling of the resin of the insulating layer to an appropriate level, it is preferred to immerse the insulating layer in a swelling liquid at 40°C to 80°C for 5 minutes to 15 minutes.

The oxidizing agent used for the roughening treatment is not particularly limited, and examples thereof include alkaline permanganic acid solutions in which potassium permanganate or sodium permanganate is dissolved in an aqueous solution of sodium hydroxide. The roughening treatment using an oxidizing agent such as an alkaline permanganic acid solution is preferably performed by immersing the insulating layer in an oxidizing agent solution heated to 60°C to 100°C for 10 minutes to 30 minutes. In addition, the concentration of permanganate in the alkaline permanganic acid solution is preferably 5% by mass to 10% by mass. Commercially available oxidizing agents include alkaline permanganic acid solutions such as "Concentrate Compact CP" and "Dosing Solution Securiganth P" manufactured by Atotech Japan (Co., Ltd.).

The neutralizing solution used in the roughening treatment is preferably an acidic aqueous solution, and commercially available products include, for example, "Reduction solution Securiganth P" manufactured by Atotech Japan.

The treatment with the neutralizing liquid can be performed by immersing the treated surface roughened with the oxidizing agent in the neutralizing liquid 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 liquid at 40°C to 70°C for 5 to 20 minutes is preferred.

In one embodiment, the arithmetic mean roughness (Ra) of the surface of the insulating layer after roughening is not particularly limited, but is preferably 500 nm or less, more preferably 400 nm or less, and still more preferably 300 nm or less. The lower limit is not particularly limited, but preferably it is 0.5 nm or more, more preferably 1 nm or more, etc. In addition, the root mean square roughness (Rq) of the surface of the insulating layer after roughening treatment is preferably 500 nm or less, more preferably 400 nm or less, and still more preferably 300 nm or less. The lower limit is not particularly limited, but preferably it is 0.5 nm or more, more preferably 1 nm or more, etc. The arithmetic mean roughness (Ra) and root mean square roughness (Rq) of the insulation layer surface can be measured using a non-contact surface roughness meter.

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

The conductor layer may be a single-layer structure, or may be a multi-layer structure in which a single metal layer made of different types of metals or alloys or 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 nickel-chromium alloy.

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

In one embodiment, the conductive layer can be formed by plating. For example, a conductive layer having a desired wiring pattern can be formed by plating on the surface of the insulating layer by a conventionally known technique such as a semi-additive method or a full-additive method. From the perspective of simplicity of manufacturing, it is preferably formed by a semi-additive method. The following shows an example of forming a conductive layer by a semi-additive method.

First, a shield layer is formed on the surface of the insulating layer by electroless plating. Then, a mask pattern is formed on the formed shield layer to expose a portion of the shield layer corresponding to the desired wiring pattern. A metal layer is formed on the exposed shield layer by electroplating, and the mask pattern is removed. Then, the unnecessary shield layer is removed by etching, etc., and a conductive layer having the desired wiring pattern can be formed.

In other embodiments, the conductive layer may be formed using a metal foil. When the conductive layer is formed using a metal foil, it is preferred to perform step (V) between step (I) and step (II). For example, after step (I), the support is removed and a metal foil is laminated on the surface of the exposed resin composition layer. The lamination of the resin composition layer and the metal foil may be performed by a vacuum lamination method. The lamination conditions may be the same as those described in step (I). Next, step (II) is performed to form an insulating layer. Then, using the metal foil on the insulating layer, a conductive layer having a desired wiring pattern can be formed by conventionally known techniques such as a subtractive process and an analog semi-additive process.

The metal foil can be produced by conventional methods such as electrolysis and calendering. Commercially available metal foils include, for example, HLP foil and JXUT-III foil manufactured by JX Nippon Mining & Metals Co., Ltd., 3EC-III foil and TP-III foil manufactured by Mitsui Metal Mining Co., Ltd., and the like.

When manufacturing a printed wiring board using the resin composition of the present invention containing a combination of (A) component, (B) component, and (C) component in a specific content, whether the conductor layer is formed by plating or the conductor is formed using metal foil layer, can significantly improve the adhesion between the conductor layer and the insulating layer.

<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 using the printed wiring board of the present invention.

Semiconductor devices include various semiconductor devices supplied to electrical products (such as computers, mobile phones, digital cameras, and televisions) and vehicles (such as motorcycles, automobiles, trains, ships, and aircraft).

[Example]

Hereinafter, the present invention will be explained in detail through examples. However, the present invention is not limited to these Examples. In addition, in the following description, "parts" and "%" indicating amounts refer to "parts by mass" and "% by mass" respectively, unless otherwise stated.

<Synthesis Example 1: Synthesis of bis[4-(3,4-dihydro-2H-1,3-benzoxazin-3-yl)cyclohexyl]methane>

4,4'-methylenebis(cyclohexylamine), phenol and 92% polyformaldehyde were heated and refluxed in toluene at a molar ratio of 1:2:4.1 to react. After toluene was distilled off, the target compound was obtained. In the purity measurement by GPC, the purity as a monomer was 65%. Although polymer is contained as a by-product, it can be used as it is in Examples.

<Synthesis Example 2: Synthesis of 1,4-bis(3,4-dihydro-2H-1,3-benzoxazin-3-yl)cyclohexane>

1,4-cyclohexanediamine, phenol and 92% polyoxymethylene were heated and refluxed in toluene at a molar ratio of 1:2:4.1. After distilling off the toluene, the target compound was obtained. The purity as a monomer was 60% as determined by GPC. Although a polymer was contained as a by-product, it can be used directly in the embodiment.

<Synthesis Example 3: Synthesis of Elastomer> In a reaction vessel, add 69 g of bifunctional hydroxyl-terminated polybutadiene ("G-3000" manufactured by Nippon Soda Co., Ltd., number average molecular weight = 3000, hydroxyl equivalent = 1800 g/eq.), 40 g of aromatic hydrocarbon mixed solvent ("Ipsol150" manufactured by Idemitsu Petrochemical Co., Ltd.) and 0.005 g of dibutyltin laurate, and mix and dissolve uniformly. When it becomes uniform, raise the temperature to 60°C, and then add 8 g of isophorone diisocyanate ("IPDI" manufactured by Evonik Degussa Japan Co., Ltd., isocyanate equivalent = 113 g/eq.) while stirring, and react for about 3 hours.

Next, 23 g of cresol novolac resin ("KA-1160" manufactured by DIC Corporation, hydroxyl equivalent = 117 g/eq.) and 60 g of ethyl diethylene glycol acetate (manufactured by DAICEL Corporation) were added to the reaction product while stirring. While heating to 150°C, the reaction takes about 10 hours. Through FT-IR, it was confirmed that the NCO peak at 2250cm ^-1 disappeared. To confirm that the NCO peak disappears, it is regarded as the end point of the reaction, and the reactant is cooled to room temperature. Furthermore, the reaction product was filtered through a 100-mesh filter cloth to obtain an elastomer having a butadiene structure and a phenolic hydroxyl group (butadiene resin containing a phenolic hydroxyl group: non-volatile content 50% by mass). The number average molecular weight of the elastomer is 5900, and the glass transition temperature is -7°C.

<Example 1> 5 parts of biphenyl epoxy resin ("NC3000" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 276 g/eq.), 2 parts of bisphenol epoxy resin ("ZX1059" manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., a 1:1 mixture of bisphenol A and bisphenol F, epoxy equivalent 169 g/eq.), 0.5% by mass surface-treated spherical silica (manufactured by Admatechs Co., Ltd.) 70 parts of "SO-C2", average particle size 0.5μm), 30 parts of the elastomer obtained in Synthesis Example 3, 2 parts of the benzoxazine compound obtained in Synthesis Example 1, 3 parts of cresol novolac resin ("KA-1160" manufactured by DIC Corporation, phenolic hydroxyl equivalent: 117g/eq), 0.1 parts of a curing accelerator ("1B2PZ" manufactured by Shikoku Chemical Industry Co., Ltd., 1-benzyl-2-phenylimidazole) and 15 parts of methyl ethyl ketone were mixed and uniformly dispersed using a high-speed rotary mixer to prepare a resin composition.

<Example 2> A resin composition was prepared in the same manner as in Example 1, except that 2 parts of the benzoxazine compound obtained in Synthesis Example 2 was used instead of 2 parts of the benzoxazine compound obtained in Synthesis Example 1.

<Example 3> In addition to using 115 parts of spherical alumina ("DAW-03" manufactured by Denka Corporation, average particle size 3.7 μm) surface-treated with 0.5% by mass of an amine alkoxysilane compound ("KBM573" manufactured by Shin-Etsu Chemical Industry Co., Ltd.), instead In addition to 70 parts of spherical silica ("SO-C2" manufactured by admatechs, average particle size 0.5 μm) surface-treated with 0.5% by mass of an amine alkoxysilane compound ("KBM573" manufactured by Shin-Etsu Chemical Industry Co., Ltd.), and A resin composition was prepared in the same manner as in Example 1.

<Example 4> In addition to using spherical alumina (average particle diameter 1.5 μm, specific surface area 2.0 m ² /g) surface-treated with 0.5% by mass of an amine alkoxysilane compound ("KBM573" manufactured by Shin-Etsu Chemical Industry Co., Ltd.), Maximum particle size: 5 μm) 115 parts of substituted amine alkoxysilane compound ("KBM573" manufactured by Shin-Etsu Chemical Industry Co., Ltd.) 0.5% by mass surface treatment of spherical silica ("SO-C2" manufactured by admatechs Co., Ltd., average particle size 0.5 μm), a resin composition was prepared in the same manner as in Example 1, except for 70 parts.

＜Comparative example 1＞ Except for not using 2 parts of the benzoxazine compound obtained in Synthesis Example 1 and changing the usage amount of cresol novolak resin (DIC Corporation "KA-1160", phenolic hydroxyl equivalent: 117g/eq) from 3 parts to 5 parts Except for this, a resin composition was prepared in the same manner as in Example 1.

＜Comparative example 2＞ In addition to using commercially available benzoxazine compounds ("P-d-type benzoxazine" manufactured by Shikoku Chemical Industry Co., Ltd., bis[4-(3,4-dihydro-2H-1,3-benzoxazine-3) A resin composition was prepared in the same manner as in Example 1, except that 2 parts of the benzoxazine compound obtained in Synthesis Example 1 was substituted with 2 parts of -(yl)phenyl]methane).

<Test Example 1: Determination and Evaluation of Tensile Elastic Modulus> On the release agent-untreated side of a release agent-treated PET film ("501010" manufactured by Lintec, thickness 38μm, 240mm square), a glass cloth-based epoxy resin double-sided copper laminate ("R5715ES" manufactured by Panasonic, thickness 0.7mm, 255mm square) was fixed with polyimide adhesive tape (width 10mm) on the four sides (hereinafter sometimes referred to as "fixed PET film").

The resin compositions prepared in the Examples and Comparative Examples were coated on the release-processed surface of the above-mentioned "fixed PET film" using a die coater, so that the thickness of the dried resin composition layer became 50 μm. Dry at 120°C (average 100°C) for 6 minutes to obtain a resin sheet. Next, after putting it into an oven at 180° C., the resin composition layer was thermally hardened under hardening conditions for 90 minutes. After thermal hardening, the polyimide adhesive tape was peeled off, the hardened product was removed from the glass cloth base epoxy resin laminate with copper on both sides, and the PET film ("501010" manufactured by Lintec Co., Ltd.) was peeled off to obtain a thin sheet. hardened matter. The obtained hardened material is called "hardened material for evaluation."

The hardened material for evaluation is cut into dumb bell No. 1 shape to obtain a test piece. The tensile strength of the test piece is measured using the tensile testing machine "RTC-1250A" manufactured by ORIENTEC, and the elastic modulus at 23°C is obtained. The measurement is carried out in accordance with JIS K7127. This operation is performed 3 times, and the average value is shown in the following table. In order to reduce warping, the lower the tensile modulus is, the better, considering the stress generated during thermal hardening. Considering this, the tensile modulus of elasticity below 10.5 GPa is evaluated as "0", and the tensile modulus of elasticity greater than 10.5 GPa is evaluated as "×".

<Test Example 2: Determination and Evaluation of Peel Strength> Prepare a glass cloth-based epoxy resin double-sided copper laminate with copper foil on the surface as the inner substrate (copper foil thickness 18μm, substrate thickness 0.8mm, "R1515A" made by Panasonic). Etch away all the copper foil on the surface of this inner substrate. Then, dry at 190℃ for 30 minutes.

The resin composition obtained in the above-mentioned embodiment and comparative example was laminated on both sides of the inner substrate by using a batch vacuum pressure laminator (Nikko-materials Co., Ltd. double-stage layer-building laminator "CVP700") to bond the resin composition layer to the inner substrate. The lamination was performed by reducing the pressure for 30 seconds to make the air pressure below 13hPa, and then pressing for 30 seconds at a temperature of 100°C and a pressure of 0.74MPa. Then, the laminated resin sheet was smoothed by hot pressing for 60 seconds at atmospheric pressure, 100°C, and a pressure of 0.5MPa. Then, after the support body is peeled off, an "intermediate complex body I" is obtained, which sequentially includes a resin composition layer, an inner substrate and a resin composition layer.

In addition, a copper foil with a glossy surface (thickness 35 μm, "3EC-III" manufactured by Mitsui Metals Co., Ltd.) was prepared. The glossy surface of this copper foil was roughened by etching with a copper etching amount of 1 μm using a micro-etching agent ("CZ8101" manufactured by MEC Corporation). The copper foil obtained in this way is called "roughened copper foil".

This roughened copper foil is laminated on both sides of the intermediate multilayer body I in such a manner that the roughened surface of the roughened copper foil is joined to the resin composition layer of the intermediate multilayer body I. This lamination is performed under the same conditions as the lamination of the resin sheets of the inner substrate. In this way, the "intermediate multilayer body II" including the roughened copper foil, the resin composition layer, the inner substrate, the resin composition layer and the roughened copper foil in this order is obtained.

This intermediate multilayer body II was put into an oven at 180° C. and heated for an additional 90 minutes. Thereby, the resin composition layer is thermally cured to obtain a roughened copper foil, an insulating layer that is a cured product of the resin composition layer, an inner substrate, an insulating layer that is a cured product of the resin composition layer, and a roughened copper foil. "Evaluation substrate" of copper foil. In this evaluation substrate, the roughened copper foil corresponds to the conductor layer.

Using the aforementioned evaluation substrate, the peeling strength of the roughened copper foil and the insulating layer was measured. The peel strength was measured in accordance with JIS C6481. Specifically, the peel strength was measured by the following operation. On the roughened copper foil of the evaluation substrate, a rectangular portion with a width of 10 mm and a length of 100 mm was cut. One end of this rectangular part is peeled off and grasped with a gripper (Autocom type testing machine "AC-50C-SL" manufactured by T.S.E.). A range of 35 mm in length of the aforementioned rectangular portion was pulled and peeled in the vertical direction, and the load (kgf/cm) during the pulling and peeling was measured as the peeling strength. The aforementioned peeling was performed at room temperature at a speed of 50 mm/min. Those with a peel strength of 0.39kgf/cm or more were evaluated as "0"; those with a peel strength of more than 0.39kgf/cm were evaluated as "×".

<Test Example 3: Evaluation of Warp> A polyethylene terephthalate film ("AL5" manufactured by Lintec Corporation, thickness 38μm) with a release layer was prepared as a support. The resin composition obtained in the above-mentioned embodiment and comparative example was evenly coated on the release layer of the support so that the thickness of the resin composition layer after drying became 50μm. Then, the resin varnish was dried at 80℃~120℃ (average 100℃) for 6 minutes to obtain a resin sheet including a support and a resin composition layer.

Next, the above-mentioned resin sheet with a thickness of 50 μm was laminated on the entire surface of one side of a 12-inch wafer (thickness 775 μm) using a batch vacuum pressure laminator (Nikko-materials Co., Ltd. double-stage laminator "CVP700") to form a resin composition layer with a thickness of 100 μm. The obtained silicon wafer with the resin composition layer was heat-treated in an oven at 180°C for 90 minutes to form a silicon wafer with a cured resin composition layer (i.e., an insulating layer). The end of the wafer with the insulating layer is pressed against the stage, and the distance between the end of the wafer on the opposite side of the pressing point and the stage is measured as the warp. The warp of 0 to 2 mm is evaluated as "0", and the warp greater than 2 mm is evaluated as "×".

The non-volatile components of the resin compositions of the Examples and Comparative Examples, their usage amounts, and the evaluation results of the test examples are shown in Table 1 below.

From the above results, it is known that when a benzoxazine compound having one or more alicyclic structures in the molecule (C) is used, both suppression of warpage and excellent adhesion can be achieved.

Claims (10)

A resin composition comprising (A) epoxy resin, (B) inorganic filler, (C) benzoxazine compound having an alicyclic structure in the molecule and (D) elastomer, wherein (C) The component is a compound represented by formula (2):

[In the formula, R ¹ and R ² each independently represent a halogen atom, a cyano group, an amine group, a nitro group, a hydroxyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkoxy group , substituted or unsubstituted alkylcarbonyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted aryloxy, substituted or unsubstituted arylcarbonyl or substituted or unsubstituted Aralkyl group, Y represents a bond, an alkylene group with 1 to 6 carbon atoms, -O-, -S-, -SO ₂ -, -NH-, -CO-, -CONH-, -NHCO-, -COO-, or -OCO-; s and t each independently represent an integer from 0 to 4, u represents 0 or 1], (D) component is selected from resins with a glass transition temperature (Tg) below 25°C and 25°C The following are more than one type of liquid resin, and the molecule has a polybutadiene structure, a polysiloxane structure, a poly(meth)acrylate structure, a polyalkylene structure, and a polyalkyleneoxy structure. , a resin with one or more structures of polyisoprene structure, polyisobutylene structure, and polycarbonate structure, and has a functional group that can react with component (A). The resin composition of claim 1, wherein the resin composition When the total non-volatile components in the product are 100% by mass, the content of component (B) is 50% by mass or more. In the resin composition of claim 1, the average particle size of component (B) is less than 10 μm. The resin composition of claim 1 further comprises (E) a hardener. The resin composition of claim 1 is used to form an insulating layer. A hardened product of the resin composition according to any one of claims 1 to 5. A sheet-like laminated material containing the resin composition according to any one of claims 1 to 5. A resin sheet having a support body and a resin composition layer provided on the support body and formed of the resin composition according to any one of claims 1 to 5. A printed wiring board provided with an insulating layer composed of a cured product of the resin composition according to any one of claims 1 to 5. A semiconductor device comprising a printed wiring board as claimed in claim 9.