TW202104424A - Resin composition - Google Patents

Abstract

The present invention addresses the problem of providing a resin composition capable of achieving both suppression of warpage of a cured product and excellent adhesion. The solution of the present invention is a resin composition comprising (A) an epoxy resin, (B) an inorganic filler, and (C) a benzoxazine compound having one or more alicyclic structures 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 resin composition; a sheet-like laminate material containing the above resin composition; a resin sheet containing the above resin composition; printing containing the above cured product Wiring board; a semiconductor device including the above-mentioned printed wiring board.

As a manufacturing technology of a printed wiring board, for example, a build-up method of stacking an insulating layer and a conductive layer alternately is known. In the manufacturing method of the build-up method, generally, the insulating layer is formed by curing a resin composition.

The printed wiring board is exposed to various environments such as high temperature and low temperature. Therefore, when the linear thermal expansion coefficient of the hardened material used in the insulating layer is high, the insulating layer repeatedly expands or contracts, and cracks occur due to its deformation. A method of reducing the linear thermal expansion coefficient, for example, a method of using a relatively large amount of inorganic filler as a hardening material is known (Patent Document 1). However, when a relatively large amount of inorganic filler is blended into the hardened material, the modulus of elasticity becomes high, and it becomes difficult to suppress warpage.

In addition, when a relatively large amount of inorganic filler is contained in the hardened material, it is found that the adhesion between the conductor layer and the insulating layer such as copper foil is reduced. Recently, a smaller semiconductor chip package is required, and therefore, excellent adhesion is required.

Therefore, even in the case of using a relatively large amount of inorganic fillers, a hardened material that can suppress warpage due to a low elastic modulus and excellent adhesion is required. [Prior Technical Literature] [Patent Literature]

[Patent Document 1] JP 2016-27097 A

[The problem to be solved by the invention]

The subject of the present invention is to provide a resin composition that can achieve both suppression of warpage of the obtained cured product and excellent adhesion. [Means to solve the problem]

In order to achieve the subject of the present invention, the inventors of the present invention conducted a careful review and found that by including (C) a benzoxazine compound having at least one alicyclic structure in the molecule, the hardening can be reduced. The modulus of elasticity of the object can therefore have both the suppression of warpage and excellent adhesion, and the present invention has been 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 according to the above [1], wherein the alicyclic structure of the component (C) is a cyclohexane ring structure. [3] The resin composition of the above [1] or [2], wherein the component (C) is the formula (2):

[In the formula, R ¹ and R ² each independently represent a substituent, Y represents a bonding 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 of any one of [1] to [3] above, wherein when all the non-volatile components in the resin composition are set to 100% by mass, the content of component (B) is 50% by mass or more . [5] The resin composition according to any one of [1] to [4] above, wherein the average particle size of the component (B) is 10 μm or less. [6] The resin composition according to any one of [1] to [5] above, which further contains (D) an elastomer. [7] The resin composition according to any one of [1] to [6] above, which further contains (E) a hardener. [8] The resin composition according to any one of [1] to [7] above, which is used for forming an insulating layer. [9] A cured product of the resin composition according to any one of [1] to [8] above. [10] A sheet-like laminated material containing the resin composition according to any one of [1] to [8] above. [11] A resin sheet having a support and a resin composition layer formed on the support and formed of the resin composition of any one of [1] to [8] above. [12] A printed wiring board provided with an insulating layer composed of a cured product of the resin composition as described in any one of [1] to [8] above. [13] A semiconductor device comprising the printed wiring board as described in [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 reducing the elastic modulus of the cured product. [The form of implementing 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 exemplified materials, and can be implemented with arbitrarily changed within a scope that does not deviate from the scope of the present invention and its equivalent scope.

＜Resin composition＞ The resin composition of the present invention includes (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 warpage and excellent adhesion.

The resin composition of the present invention may further contain arbitrary components in addition to (A) epoxy resin, (B) inorganic filler, and (C) benzoxazine compound having an alicyclic structure in the molecule. The optional components include (D) elastomers, (E) curing agents, (F) curing accelerators, (G) organic solvents, and (H) other additives. Hereinafter, each component contained in the resin composition will be explained in detail.

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

(A) Epoxy resins, for example, bisxylenol type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, and bisphenol AF type epoxy resins , Dicyclopentadiene type epoxy resin, triphenol type epoxy resin, naphthol novolak type epoxy resin, phenol novolak 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. One type of epoxy resin may be used alone, or two or more types may be used in combination.

The resin composition preferably contains an epoxy resin having two or more epoxy groups in one molecule as the epoxy resin (A). From the viewpoint of clearly obtaining the desired effect of the present invention, the ratio of epoxy resin having two or more epoxy groups per molecule relative to 100% by mass of the non-volatile content of the epoxy resin (A) is preferably 50 Mass% or more, more preferably 60% by mass or more, particularly preferably 70% by 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 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 as an epoxy resin, or may contain only a solid epoxy resin, and preferably contains a liquid epoxy resin and a solid epoxy resin in combination.

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, glycidol Amine type epoxy resin, phenol novolak type epoxy resin, alicyclic epoxy resin with ester skeleton, cyclohexane type epoxy resin, cyclohexane dimethanol type epoxy resin, glycidyl amine 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" and "1750" (bisphenol F type epoxy resin) manufactured by Mitsubishi Chemical; "jER152" (phenol Novolac epoxy resin); "630" and "630LSD" (glycidylamine epoxy resin) made by Mitsubishi Chemical; "ZX1059" (bisphenol A epoxy resin) made by Nippon Steel & Sumikin Chemical Co., Ltd. Mixture with bisphenol F epoxy resin); "EX-721" (glycidyl ester epoxy resin) made by nagase chemtex; "CELLOXID2021P" made by DAICEL (alicyclic ring with ester skeleton) Oxygen resin); "PB-3600" manufactured by DAICEL, "JP-100" and "JP-200" manufactured by Soda Corporation of Japan (epoxy resin with butadiene structure); manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. "ZX1658", "ZX1658GS" (liquid 1,4-glycidyl cyclohexane type epoxy resin), etc. These can be used in one type alone or in combination of two or more types.

The solid epoxy resin is preferably a solid epoxy resin having 3 or more epoxy groups in a molecule, and more preferably an aromatic solid epoxy resin having 3 or more epoxy groups in a molecule Resin.

The solid epoxy resin is preferably bis-xylenol type epoxy resin, naphthalene type epoxy resin, naphthalene type tetrafunctional epoxy resin, cresol novolak epoxy resin, dicyclopentadiene type epoxy resin, Triphenol 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 solid epoxy resins include "HP4032H" (naphthalene type epoxy resin) manufactured by DIC; "HP-4700" and "HP-4710" (naphthalene type tetrafunctional epoxy resin) manufactured by DIC ; "N-690" (cresol novolak epoxy resin) made by DIC; "N-695" (cresol novolak epoxy resin) made by DIC; "HP-7200" made by DIC (two Cyclopentadiene epoxy resin); "HP-7200HH", "HP-7200H", "EXA-7311", "EXA-7311-G3", "EXA-7311-G4", "EXA" manufactured by DIC -7311-G4S", "HP6000" (naphthylene ether type epoxy resin); "EPPN-502H" (triphenol type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; "NC7000L" (naphthalene type epoxy resin) manufactured by Nippon Kayaku Co., Ltd. Phenolic novolac type epoxy resin); "NC3000H", "NC3000", "NC3000L", "NC3100" (biphenyl type epoxy resin) manufactured by Nippon Kayaku Corporation; "ESN475V" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. (Naphthol type epoxy resin); "ESN485" (naphthol novolak type epoxy resin) manufactured by Nippon Steel & Sumikin Chemical Co.; "YX4000H", "YX4000", "YL6121" (biphenyl) manufactured by Mitsubishi Chemical Type epoxy resin); "YX4000HK" (bis-xylenol type epoxy resin) manufactured by Mitsubishi Chemical; "YX8800" (anthracene type epoxy resin) manufactured by Mitsubishi Chemical; "YX7700" manufactured by Mitsubishi Chemical ( Novolac epoxy resin containing xylene structure); "PG-100" and "CG-500" manufactured by Osaka Gas Chemical Company; "YL7760" (bisphenol AF epoxy resin) manufactured by Mitsubishi Chemical Company; Mitsubishi "YL7800" made by Mitsubishi Chemical Company (茀-type epoxy resin); "jER1010" made by Mitsubishi Chemical Company (solid bisphenol A epoxy resin); "jER1031S" made by Mitsubishi Chemical Company (tetraphenylethane type) Epoxy resin) and so on. These can be used in one type alone or in combination of two or more types.

As (A) the epoxy resin, when a liquid epoxy resin and a solid epoxy resin are used in combination, the ratio of their amounts (liquid epoxy resin: solid epoxy resin), in terms of mass ratio, is preferably 1 :1~1:30, more preferably 1:1~1:20, particularly preferably 1:1~1:10. When the ratio of the liquid epoxy resin to the solid epoxy resin is in this range, the desired effect of the present invention can be significantly obtained.

(A) The epoxy equivalent of epoxy resin is preferably 50g/eq.~5000g/eq., more preferably 50g/eq.~3000g/eq., and still more preferably 80g/eq.~2000g/eq. , And more preferably 110g/eq.~1000g/eq. With this range, the crosslinking density of the cured resin sheet becomes sufficient, and an insulating layer with a small surface roughness can be provided. The epoxy equivalent 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 even more preferably 400 to 1500 from the viewpoint of remarkably obtaining the desired effect of the present invention. The weight average molecular weight of the resin can be measured as a value in terms of polystyrene by gel permeation chromatography (GPC).

(A) The content of the epoxy resin 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 is remarkably obtained, and it is preferably 5 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, from the viewpoint of remarkably obtaining the desired effect of the present invention, it is preferably 60% by mass or less, more preferably 50% by mass or less, still more preferably 40% by mass or less, and particularly preferably 30% by mass or less.

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

(B) The material of the inorganic filler is not particularly limited. Examples include silica, alumina, glass, cyanite, silica, 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, especially silicon dioxide and alumina . Examples of silicon dioxide include amorphous silicon dioxide, fused silicon dioxide, crystalline silicon dioxide, synthetic silicon dioxide, and hollow silicon dioxide. In addition, silicon dioxide is preferably spherical silicon dioxide. (B) Inorganic fillers, one type may be used alone, or two or more types may be used in combination.

(B) Commercial products of 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" manufactured by Denka; "SilFile NSS-3N", "SilFile NSS-4N", "SilFile NSS" manufactured by Tokuyama -5N"; "SC2500SQ", "SO-C4", "SO-C2", "SO-C1", "A23-SX-C1" manufactured by admatechs; "DAW-03", "FB" manufactured by Denka -105FD" and so on.

(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, still more preferably 20 μm or less, still more preferably 10 μm or less, particularly preferably 5 μm or less. The lower limit of the average particle size of the inorganic filler is not particularly limited. It is preferably 0.01 μm or more, more preferably 0.05 μm or more, still more preferably 0.1 μm or more, still more preferably 0.2 μm or more, and still more preferably 0.3 μm Above, it is particularly preferably 0.4 μm or more. The average particle size of the inorganic filler can be measured by the laser diffraction and scattering method based on the Mie scattering theory. Specifically, by a laser diffraction scattering type particle size distribution measuring device, the particle size distribution of the inorganic filler is created on a volume basis, and the median particle size is measured as the average particle size. For the measurement sample, 100 mg of the inorganic filler and 10 g of methyl ethyl ketone can be weighed in a small glass bottle and dispersed by ultrasound for 10 minutes. Using a laser diffraction particle size distribution measuring device, the measurement sample uses the light source wavelength to be blue and red, and the volume-based particle size distribution of the inorganic filler is measured by the flow battery method. The obtained particle size distribution is used as the medium Calculate the average particle size from the value particle size. Examples of the laser diffraction particle size distribution measuring device include "LA-960" manufactured by Horiba Manufacturing Co., Ltd. and the like.

(B) Inorganic fillers, from the viewpoint of improving moisture resistance and dispersibility, aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, alkoxysilane compounds, organosilazanes One or more surface treatment agents such as compounds and titanate-based coupling agents are preferably treated. Commercially available surface treatment agents include, for example, "KBM403" (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., and "KBM803" (3-mercaptopropyltrimethyl) manufactured by Shin-Etsu Chemical Co., Ltd. Oxysilane), "KBE903" (3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., and "KBM573" (N-phenyl-3-aminopropyltrimethoxy) manufactured by Shin-Etsu Chemical Co., Ltd. Silane), "SZ-31" (hexamethyldisilazane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM103" (phenyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., and "KBM-4803" manufactured by Shin-Etsu Chemical Co., Ltd. (Long-chain epoxy-based silane coupling agent), "KBM-7103" (3,3,3-trifluoropropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM503" manufactured by Shin-Etsu Chemical Co., Ltd. (3- Methacryloxypropyltrimethoxysilane), "KBM5783" manufactured by Shin-Etsu Chemical 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 Surface treatment is carried out by mass% to 2% by mass.

The degree of surface treatment of the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the inorganic filler. From the viewpoint of improving the dispersibility of the inorganic filler, the carbon content per unit surface area of the inorganic filler is preferably 0.02 mg/m ² or more, more preferably 0.1 mg/m ² or more, and still more preferably 0.2 mg/m ² the above. In addition, from the viewpoint 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/m ² or less, more preferably 0.8 mg/m ² or less, and still more preferably 0.5 mg/m ² 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, in addition to adding a sufficient amount of MEK as a solvent to the inorganic filler surface-treated with a surface treatment agent, ultrasonic cleaning was performed at 25°C for 5 minutes. After removing the supernatant liquid and drying the solid content, use a carbon analyzer to measure the amount of carbon per unit surface area of the inorganic filler. For the carbon analyzer, "EMIA-320V" manufactured by Horiba Manufacturing Co., Ltd. can be used.

From the viewpoint of enhancing the effect of the present invention, the specific surface area of the (B) inorganic filler is preferably 0.01 m ² /g or more, more preferably 0.1 m ² /g or more, and particularly ^{preferably 0.2 m 2} /g or more. The upper limit is not particularly limited, but 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 is based on the BET method, using a specific surface area measuring device (Macsorb HM-1210 manufactured by MOUNTECH), adsorbing nitrogen on the sample surface, and calculating the specific surface area using the BET multipoint method.

(B) The content of the inorganic filler is not particularly limited. When all the non-volatile components in the resin composition are set to 100% by mass, from the viewpoint of being used 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, particularly preferably 70% by mass or more. Generally, resin compositions containing many inorganic fillers tend to warp. The resin composition of the present invention containing a combination of (A) to (C) components can be effective even when there are many (B) Suppress warpage. The upper limit of the content of (B) inorganic filler is not particularly limited. For example, it may be 98% by mass or less, 95% by mass or less, 90% by mass or less, 85% by mass or less.

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

(C) The "benzoxazine compound" in the component refers to a 3,4-dihydro-2H-1,3-benzoxazine ring (hereinafter sometimes referred to as "dihydrobenzoxazine ring") Compound. In this compound, the dihydrobenzoxazine ring preferably has two or more 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 via a nitrogen atom of the ring. In the component (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 with an alicyclic structure, m represents an integer of 2 or more, and n represents an integer of 0-4] Represents the compound.

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 include halogen atoms, cyano groups, amino groups, nitro groups, hydroxyl groups, substituted or unsubstituted ones Alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkoxy, substituted or unsubstituted alkylcarbonyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted Aryloxy, substituted or unsubstituted arylcarbonyl, substituted or unsubstituted aralkyl, etc.

The "halogen atom" includes, for example, a fluorine atom, a chlorine atom, and a bromine atom.

"Alkyl" refers to a linear, branched or cyclic monovalent aliphatic saturated hydrocarbon group. The "alkyl group" is preferably an alkyl group having 1 to 6 carbon atoms, and 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. Group, cyclohexyl, etc. The substituent of the alkyl group in the "substituted or unsubstituted alkyl group" is not particularly limited, and examples include a halogen atom, a cyano group, an alkoxy group, an alkylcarbonyl group, an aryl group, a heteroaryl group, an aryloxy group, and an aryl group. Carbonyl, amine, nitro, hydroxyl, etc. The number of substituents is preferably 1 to 3, more preferably 1.

"Alkoxy" refers to a monovalent group (alkyl-O-) formed by bonding an alkyl group to an oxygen atom. The "alkoxy group" 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, pentoxy Wait. The substituent of the alkoxy group in the "substituted or unsubstituted alkoxy group" is not particularly limited, and examples include halogen atoms, cyano groups, alkoxy groups, alkylcarbonyl groups, aryl groups, heteroaryl groups, and aryloxy groups. , Arylcarbonyl, amine, nitro, hydroxyl, etc. The number of substituents is preferably 1 to 3, more preferably 1.

"Alkenyl" refers to a linear, branched or cyclic monovalent unsaturated hydrocarbon group having at least one carbon-carbon double bond. The "alkenyl group" is preferably an alkenyl group having 2 to 6 carbon atoms, and more preferably an alkenyl group having 2 or 3 carbon atoms. "Alkenyl" includes, for example, 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 substituents of the alkenyl group in the "substituted or unsubstituted alkenyl group" are not particularly limited, and examples include halogen atoms, cyano groups, alkoxy groups, alkylcarbonyl groups, aryl groups, heteroaryl groups, aryloxy groups, and aryl groups. Carbonyl, amine, nitro, hydroxyl, etc. The number of substituents is preferably 1 to 3, more preferably 1.

"Alkylcarbonyl" refers to a monovalent group (alkyl-CO-) formed by bonding an alkyl group to a carbonyl group. The "alkylcarbonyl group" is preferably an alkylcarbonyl group having 2 to 7 carbon atoms, and more preferably an alkylcarbonyl group having 2 to 4 carbon atoms. "Alkylcarbonyl" includes, for example, acetyl, propionyl, butyryl, 2-methylpropionyl, pentanyl, 3-methylbutyryl, 2-methylbutyryl, 2,2-dimethylpropane醯基, hexyl, heptyl, etc. The substituent of the alkylcarbonyl group in the "substituted or unsubstituted alkylcarbonyl group" is not particularly limited, and examples include a halogen atom, a cyano group, an alkoxy group, an alkylcarbonyl group, an aryl group, a heteroaryl group, and an aryloxy group. , Arylcarbonyl, amine, nitro, hydroxyl, etc. The number of substituents is preferably 1 to 3, more preferably one.

"Aryl" refers to a monovalent aromatic hydrocarbon group. The "aryl group" is preferably an aryl group having 6 to 14 carbon atoms, and more preferably an aryl group having 6 to 10 carbon atoms. Examples of the "aryl group" include phenyl, 1-naphthyl, and 2-naphthyl, and phenyl is preferred. The substituent of the aryl group in the "substituted or unsubstituted aryl group" is not particularly limited, and examples 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 one.

The "heteroaryl group" refers to a monovalent aromatic heterocyclic group having 1 to 4 heteroatoms selected from an oxygen atom, a nitrogen atom, and a sulfur atom as a ring constituent atom, in addition to a carbon atom. The "heteroaryl group" is preferably a monocyclic, bicyclic or tricyclic (preferably monocyclic) aromatic heterocyclic group with 5 to 12 members (preferably 5 or 6 members). "Heteroaryl" includes, for example, furyl, thienyl, pyrrolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, imidazolyl, pyrazolyl, 1,2,3-oxadiazolyl , 1,2,4-oxadiazolyl, 1,3,4-oxadiazolyl, furyl, 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 Base and so on. The substituent of the heteroaryl group in the "substituted or unsubstituted heteroaryl group" is not particularly limited, and examples include a halogen atom, a cyano group, an alkyl group, an alkoxy group, an alkylcarbonyl group, an aryl group, a heteroaryl group, Aryloxy, arylcarbonyl, aralkyl, amine, nitro, hydroxyl, etc. The number of substituents is preferably 1 to 3, more preferably one.

"Aryloxy" refers to a monovalent group (aryl-O-) formed by bonding an aryl group to an oxygen atom. The "aryloxy group" 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 group in the "substituted or unsubstituted aryloxy group" is not particularly limited, and examples include a halogen atom, a cyano group, an alkyl group, an alkoxy group, an alkylcarbonyl group, an aryl group, a heteroaryl group, Aryloxy, arylcarbonyl, aralkyl, amine, nitro, hydroxyl, etc. The number of substituents is preferably 1 to 3, more preferably one.

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

"Aralkyl" refers to an alkyl group substituted with 1 or 2 or more aryl groups. The "aralkyl group" 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, and the like. The substituent of the aralkyl group in the "substituted or unsubstituted aralkyl 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, Aryloxy, arylcarbonyl, aralkyl, amine, nitro, hydroxyl, etc. The number of substituents is preferably 1 to 3, more preferably one.

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

In formula (1), when 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, and is preferably 1 to 5, more preferably 1 to 3, and still more preferably 1 or 2. (C) The ring structure of the alicyclic structure in the component includes cycloalkane ring, cycloalkene ring, and at least one of their skeleton carbon atoms substituted with -O-, -S-, -SO _2- Aliphatic heterocycles of heteroatom-containing groups such as -NH-, -CO-, -CONH-, -NHCO-, -COO-, and -OCO-, among which cycloalkane rings are preferred.

The "cycloalkane 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, and cyclooctane ring; decahydronaphthalene ring, norbornane ring, etc. Bicycloalkane ring; Spiroalkane ring such as spirononane ring, etc.

"Cycloalkene ring" refers to a monocyclic or polycyclic aliphatic saturated hydrocarbon ring having at least one carbon-carbon double bond. The "cycloalkene ring" is preferably a cycloalkene ring having 3 to 10 carbon atoms. Examples of the "cycloalkene ring" include monocyclic olefin rings such as cyclobutene ring, cyclopropene ring, cyclohexene ring, cyclohexadiene ring, cycloheptene ring, and cyclooctene ring; norbornene ring, camphene ring Bicyclic ene ring such as ene ring; Spiro ene ring 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, particularly preferably 3 to 20. The skeleton atom may be selected from a carbon atom, an oxygen atom, a nitrogen atom, and a sulfur atom.

The "m-valent linking group having an alicyclic structure" of X in the formula (1) is preferably a substituted or unsubstituted m-valent ring-containing saturated aliphatic group. Here, the substituent of the ring-containing saturated aliphatic group in the "substituted or unsubstituted m-valent ring-containing saturated aliphatic group" includes the same substituents as those of R, and is 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 at least one of its skeleton carbon atoms is substituted to be selected from -O -, -S-, -SO ₂ -, -NH-, -CO-, -CONH-, -NHCO-, -COO-, and -OCO- groups containing heteroatoms (hereinafter referred to as "containing Saturated hydrocarbon heteroatom substituents of the ring").

In formula (1), m represents an integer of 2 or more, preferably 2 or 3, more preferably 2. Therefore, in the more preferable embodiment where m is 2, X is preferably a substituted or unsubstituted divalent ring-containing saturated aliphatic group. The atoms at both ends of the "divalent ring-containing saturated aliphatic group" are preferably any carbon atoms, and more preferably carbon atoms constituting the ring.

Examples of the "divalent ring-containing saturated aliphatic group" in X of the formula (1), specifically, -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 -CH ₂ -cHex-, -cPent-CH ₂ -CH ₂ -CH ₂ -cPent-, -cHex-CH(CH ₃ )-cHex-, -cPent-CH(CH ₃ )-cPent -, -cHex-CH(CH ₂ CH ₃ )-cHex-, -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- and other divalent ring-containing saturated hydrocarbon groups; -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 ₂ -S-cPent-, -cHex-CO-cHex-,- cPent-CO-cPent- _{, -cHex-SO 2} -cHex-, -cPent-SO ₂ -cPent-, -cHex-CONH-cHex-, -cPent-CONH-cPent-, -cHex-NHCO-cHex-,- cPent-NHCO-cPent-, -cHex-COO-cHex-, -cPent-COO-cPent-, -cHex-OCO-cHex-, -cPent-OCO-cPent- and other divalent ring-containing saturated hydrocarbon heteroatom substitution base. Here, "cHex" represents 1,4-cyclohexylene, 1,3-cyclohexylene, or 1,2-cyclohexylene. "CPent" means 1,3-cyclopentyl or 1,2-cyclopentyl. "DECAL" means divalent decalinyl, 2,6-bicyclo[4.4.0]decenyl, 2,7-bicyclo[4.4.0]decenyl, etc. "NORBOR" means a divalent norbornanyl group, and examples include 2,5-bicyclo[2.2.1]heptanyl, 2,6-bicyclo[2.2.1]heptanyl, and the like.

(C) The alicyclic structure of the component is preferably a cyclohexane ring structure. That is, the component (C) preferably has one or more cyclohexane ring structures in the molecule. The cyclohexane ring structure may also be a part of the bicycloalkane ring structure. In this case, preferred examples of the "divalent ring-containing saturated aliphatic group" in X of the 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- and other divalent ring-containing saturation Hydrocarbon heteroatom substituents.

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

[In the formula, R ¹ and R ² each independently represent a substituent, Y represents a bonding 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 independent of each other, preferably 0 or 1, particularly preferably 0.

"Alkylene" refers to a linear, branched or cyclic divalent aliphatic saturated hydrocarbon group. The number of carbon atoms of the "alkylene having 1 to 6 carbon atoms" is preferably 1 to 3. "Alkylene group having 1 to 6 carbon atoms" includes, for example, -CH ₂ -, -CH ₂ -CH ₂ -, -CH(CH ₃ )-, -CH ₂ -CH ₂ -CH ₂ -, -CH ₂ -CH(CH ₃ )-, -CH(CH ₃ )-CH ₂ -, -C(CH ₃ ) ₂ -, -CH ₂ -CH ₂ -CH ₂ -CH ₂ -, -CH ₂ -CH _2- CH(CH ₃ )-, -CH ₂ -CH(CH ₃ )-CH ₂ -, -CH(CH ₃ )-CH ₂ -CH ₂ -, -CH ₂ -C(CH ₃ ) ₂ -, -C( CH ₃ ) ₂ -CH ₂ -, -cHex-, etc.

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

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

(C) The content of the benzoxazine compound having an alicyclic structure in the molecule is not particularly limited. When the non-volatile components other than the (B) component in the resin composition are set to 100% by mass, it is significantly obtained by the present invention From the viewpoint of the desired effect, it 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. 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 (D) elastomer, the flexibility of the hardened resin composition can be improved and the modulus of elasticity can be reduced.

In the present invention, (D) elastic system refers to a resin with flexibility and an amorphous resin component that is insoluble in organic solvents. A resin with rubber elasticity or polymerized with other components is preferable. A resin exhibiting rubber elasticity is preferred. The rubber elasticity can be exemplified by a resin that shows an elastic modulus of 1 GPa or less when a tensile test is performed at a temperature of 25° C. and a humidity of 40% RH in accordance with the Japanese Industrial Standards (JIS K7161).

In one embodiment, the component (D) is in the molecule and has a polybutadiene structure, a polysiloxane structure, a poly(meth)acrylate structure, a polyalkylene structure, and a polyalkyleneoxy structure. , Polyisoprene structure, polyisobutylene structure, and polycarbonate structure are more than one type of resin, from the viewpoint of obtaining a flexible material, it is more preferable to have a structure selected from polybutadiene and One or more resins of polycarbonate structure. In addition, "(meth)acrylate" means methacrylate and acrylate.

In another embodiment, the component (D) is preferably one or more selected from resins having a glass transition temperature (Tg) of 25°C or less and resins having a liquid state of 25°C or less. The glass transition temperature (Tg) is the glass transition temperature of the resin below 25°C, preferably 20°C or less, more preferably 15°C or less. The lower limit of the glass transition temperature is not particularly limited, but it can usually be -15°C or higher. 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 preferable embodiment, the component (D) is preferably one or more selected from resins whose glass transition temperature is 25°C or lower and liquid at 25°C, and has a structure selected from polybutadiene and polybutadiene in the molecule. Silicone structure, poly(meth)acrylate structure, polyalkylene structure, polyalkylene oxide structure, polyisoprene structure, polyisobutylene structure, and polycarbonate structure. .

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

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

Specific examples of polybutadiene resins having a polybutadiene structure in the molecule include "Ricon 657" (polybutadiene containing epoxy groups) manufactured by Cray Valley, "Ricon 130MA8", and "Ricon 130MA13", "Ricon 130MA20", "Ricon 131MA5", "Ricon 131MA10", "Ricon 131MA17", "Ricon 131MA20", "Ricon 184MA6" (polybutadiene with acid anhydride group), "GQ-1000" (introduction Polybutadiene with hydroxyl and carboxyl groups), "G-1000", "G-2000", "G-3000" (polybutadiene with two terminal hydroxyl groups), "GI-1000", "GI-2000", " GI-3000" (hydrogenated polybutadiene with both terminal hydroxyl groups), "PB3600", "PB4700" (polybutadiene-based epoxy compound) manufactured by DAICEL, "Epofriend A1005", "Epofriend A1010", "Epofriend A1020" ”(Epoxy compound of styrene, butadiene and styrene block copolymer), “FCA-061L” (hydrogenated polybutadiene skeleton epoxy compound), “R-45EPT” (poly Butadiene skeleton epoxy compound) and so on.

In addition, examples of preferable polybutadiene resins include hydroxyl-terminated polybutadiene, linear polyimides made from diisocyanate compounds and polybasic acids or their anhydrides (Japanese Patent Laid-Open No. 2006-37083, Polyimide described in International Publication No. 2008/153208). The content of the polybutadiene structure of the polyimide resin is preferably 60% by mass to 95% by mass, more preferably 75% by mass to 85% by mass. For details of the polyimide resin, refer to the descriptions in Japanese Patent Application Laid-Open No. 2006-37083 and International Publication No. 2008/153208, and the contents are incorporated in this specification.

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

The diisocyanate compound includes, for example, aromatic diisocyanates such as toluene-2,4-diisocyanate, toluene-2,6-diisocyanate, xylylene diisocyanate, and diphenylmethane diisocyanate; hexamethylene diisocyanate Aliphatic diisocyanates such as isocyanate; Alicyclic diisocyanates such as isophorone diisocyanate. Among these, aromatic diisocyanate is preferred, and toluene-2,4-diisocyanate is more preferred.

The polybasic acid or its anhydride includes, for example, ethylene glycol bis trimellitic acid, pyromellitic acid, benzophenone tetracarboxylic acid, biphenyl tetracarboxylic acid, naphthalene tetracarboxylic acid, 5-(2,5- Dioxytetrahydrofuranyl)-3-methyl-cyclohexene-1,2-dicarboxylic acid, 3,3'-4,4'-diphenyl tetracarboxylic acid and other tetrabasic acid (tetrabasic acid) and These acid anhydrides, trimellitic acid, cyclohexanetricarboxylic acid and other tribasic acids and these acid anhydrides, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2, 5-Dioxo-3-furyl)-naphtho(1,2-C)furan-1,3-dione and the like.

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

Specific examples of polystyrene resins having a polystyrene structure in the molecule include styrene-butadiene-styrene block copolymer (SBS), 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-butene-styrene block copolymer (SBBS), styrene-butadiene diblock copolymer, hydrogenated styrene-butadiene block Copolymers, hydrogenated styrene-isoprene block copolymers, hydrogenated styrene-butadiene random copolymers, etc.

As a polystyrene resin, commercially available products can be used. Examples include hydrogenated styrene-based thermoplastic elastomers "H1041", "TAFTEC H1043", "TAFTEC P2000", and "TAFTEC MP10" (manufactured by Asahi Kasei Corporation); epoxidized styrene -Butadiene thermoplastic elastomers "Epofriend AT501" and "CT310" (made by DAICEL); modified styrene elastomer with hydroxyl group "SEPTON HG252" (made by Kuraray); modified styrene with carboxyl group Elastomer "TAFTEC N503M", modified styrene elastomer with amine group "TAFTECN501", modified styrene elastomer with acid anhydride group "TAFTEC M1913" (manufactured by Asahi Kasei Chemicals); unmodified styrene Elastomer "SEPTON S8104" (manufactured by Kuraray), etc. (C) A component may be used individually by 1 type, and may be used in combination of 2 or more types.

The polysiloxane structure is a structure containing siloxane bonds, for example, it is contained in silicone rubber. In the component (D), a polysiloxane structure may be contained in the main chain or a polysiloxane structure may be contained in the side chain.

Specific examples of polysiloxane resins having a polysiloxane structure in the molecule include "SMP-2006", "SMP-2003PGMEA", "SMP-5005PGMEA", and amino-terminated polysilicon manufactured by Shin-Etsu Silicones. Oxyane, linear polyimide using tetrabasic acid anhydride as a raw material (International Publication No. 2010/053185), etc.

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

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

Specific examples of poly(meth)acrylate resins include Teisanresin "SG-70L", "SG-708-6", "WS-023", "SG-700AS", and "SG-280TEA" manufactured by Nagase Chemtex. "(Acrylate copolymer resin containing carboxyl group, acid value 5~34mgKOH/g, weight average molecular weight 400,000~900,000, Tg-30℃~5℃), "SG-80H", "SG-80H-3" , "SG-P3" (epoxy-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 Kogyo Co., Ltd. ”, “W-116.3” (acrylate copolymer resin containing carboxyl group), “W-197C” (acrylate copolymer resin containing hydroxyl group), “KG-25”, “KG-3000” (containing epoxy group The acrylate copolymer resin) and so on.

The polyalkylene structure preferably has a specific number of carbon atoms. The specific number of carbon atoms of 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), a polyalkylene structure may be contained in the main chain or a polyalkylene structure may be contained in the side chain.

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

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

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

In the component (D), a polyisobutylene structure may be contained in the main chain or a polyisobutylene structure may be contained in the side chain. Specific examples of polyisobutylene resins having a polyisobutylene structure in the molecule include "SIBSTAR-073T" (styrene-isobutylene-styrene triblock copolymer), "SIBSTAR-042D" (styrene -Isobutylene diblock copolymer) and so on.

In the component (D), the polycarbonate structure may be contained in the main chain or the polycarbonate structure may be contained in the side chain.

Preferable examples of polycarbonate resins with resins having a polycarbonate structure in the molecule include polycarbonate resins containing hydroxyl groups, polycarbonate resins containing phenolic hydroxyl groups, polycarbonate resins containing carboxyl groups, and acid anhydride groups containing polycarbonate resins. Polycarbonate resin, epoxy-containing polycarbonate resin, isocyanate-containing polycarbonate resin, urethane-containing polycarbonate resin, etc.

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

In addition, examples of preferable polycarbonate resins include hydroxyl-terminated polycarbonates, linear polyimides made from diisocyanate compounds and polybasic acids or their anhydrides. 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% by mass to 95% by mass, more preferably 75% by mass to 85% by mass. For details of the polyimide resin, please refer to the record in International Publication No. 2016/129541, and the content is incorporated into this specification.

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

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

(D) The component may have any of linear, branched, and cyclic structures, and it is preferably linear.

It is preferable that the component (D) further 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 and 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 urethane group. Among them, from the viewpoint of remarkably obtaining the effects of the present invention, the functional group preferably has one or more functional groups selected from the group consisting of a hydroxyl group, an acid anhydride group, a phenolic hydroxyl group, an epoxy group, an isocyanate group, and a urethane group. It is preferably a phenolic hydroxyl group.

(D) A component may be used individually by 1 type, and may be used in combination of 2 or more types.

The component (D) is preferably a high molecular weight in terms of flexibility. (D) The specific number average molecular weight Mn of the component is preferably 4000 or more, more preferably 4500 or more, still more preferably 5000 or more, particularly preferably 5500 or more, preferably 100,000 or less, more preferably 95000 or less, especially Preferably, it is less than 90,000. (D) The number average molecular weight Mn of the component is a number average molecular weight in terms of polystyrene measured by GPC (Gel Permeation Chromatography).

In addition, from the viewpoint of obtaining flexibility, the specific weight average molecular weight of the component (D) is preferably 5,500 to 100,000, more preferably 10,000 to 90,000, and still more preferably 15,000 to 80,000. (D) The weight average molecular weight of the component is the weight average molecular weight in terms of polystyrene measured by the gel permeation chromatography (GPC) method.

When the component (D) has a functional group, the equivalent of the functional group of the component (D) is preferably 100 g/eq. or more, more preferably 200 g/eq. or more, still more preferably 1000 g/eq. or more, particularly preferably 2500 g /eq. or more, preferably 50000g/eq. or less, more preferably 30000g/eq. or less, still more preferably 10000g/eq. or less, particularly preferably 5000g/eq. or less. The functional group equivalent is the number of grams of the resin containing 1 gram equivalent of the functional group. For example, the epoxy equivalent can be measured in accordance with JIS K7236. Also, for example, the hydroxyl equivalent weight can be calculated by dividing the hydroxyl value measured by JIS K1557-1 by the molecular weight of KOH.

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

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, a more flexible viewpoint is obtained. It is preferably 10% by mass or more, more preferably 30% by mass or more, still more preferably 40% by mass or more, and particularly preferably 50% by mass or more. (D) The upper limit of the content of the elastomer, from the viewpoint of remarkably obtaining the desired effect of the present invention, is preferably 75% by mass or less, more preferably 70% by mass or less, still more preferably 65% by mass or less, and particularly preferably 60% by mass or less.

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

(E) The curing agent is not particularly limited as long as it has the function of curing epoxy resin. Examples include phenolic curing agents, naphthol curing agents, acid anhydride curing agents, active ester curing agents, and benzoxazines. Series hardeners, cyanate ester hardeners and carbodiimide hardeners. The curing agent may be used alone or in combination of two or more kinds. The (E) hardener of the resin composition of the present invention is preferably selected from the group consisting of phenol hardeners, naphthol hardeners, and active ester hardeners from the viewpoint of remarkably obtaining the desired effect of the present invention Those in the group. Moreover, in one embodiment, (E) the hardening agent preferably contains an active ester hardening agent.

The phenolic hardener and the naphthol hardener are preferably a phenol hardener having a novolak structure or a naphthol hardener having a novolak structure from the viewpoint of heat resistance and water resistance. Also, from the viewpoint of adhesion to adherends, nitrogen-containing phenolic hardeners or nitrogen-containing naphthol hardeners are preferred, and phenolic hardeners containing triazine skeletons or those containing triazine skeletons are more preferred. Naphthol hardener. Among them, from the viewpoint of highly satisfying heat resistance, water resistance, and adhesion, a phenol novolak resin containing a triazine skeleton is preferred. Specific examples of phenolic hardeners and naphthol hardeners include "MEH-7700", "MEH-7810", "MEH-7851", and "MEH-8000H" manufactured by Meiwa Chemical Co., Ltd.; Nippon Kayaku Co., Ltd. "NHN", "CBN", "GPH" manufactured by Nippon Steel & Sumitomo Chemical Corporation; "SN-170", "SN-180", "SN-190", "SN-475", and "SN-485" manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd. ”, “SN-495”, “SN-495V”, “SN-375”, “SN-395”; DIC’s “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"; "GDP-6115L", "GDP-6115H", "ELPC75", etc. manufactured by Qunrong Chemical Company.

The acid anhydride-based curing agent includes a curing agent having one or more acid anhydride groups in one molecule. Specific examples of acid anhydride hardeners include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, and methylhexahydrophthalic anhydride Acid anhydride, methyl nadic anhydride, hydrogenated methyl nadic anhydride, trialkyltetrahydrophthalic anhydride, dodecenyl succinic anhydride, 5-(2,5-dioxtetrahydro-3-furanyl )-3-Methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, Naphthalene tetracarboxylic dianhydride, oxygen diphthalic anhydride, 3,3'-4,4'-diphenyl tetracarboxylic dianhydride, 1,3,3a,4,5,9b-hexahydro- 5-(Tetrahydro-2,5-dioxo-3-furyl)-naphtho[1,2-C]furan-1,3-dione, ethylene glycol bis(trimellitic anhydride), styrene and maleic acid Polymeric acid anhydrides such as styrene and maleic acid resin copolymerized by acid. Commercially available acid anhydride hardeners include "HNA-100" and "MH-700" manufactured by Nippon Rika Corporation.

The active ester curing agent is not particularly limited. Generally, it is preferable to use phenol esters, thiophenol esters, N-hydroxyamine esters, esters of heterocyclic hydroxy compounds, etc. having two or more in one molecule. Highly reactive ester-based compound. The active ester curing agent is preferably obtained by the condensation reaction of a carboxylic acid compound and/or a thiocarboxylic acid compound and 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 hydroxy compound is preferable, and an active ester curing agent obtained from a carboxylic acid compound and a phenol compound and/or a naphthol compound is more preferable. 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. Phenol compounds or naphthol compounds, for example, hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalein, methylated bisphenol A, methylated bisphenol F, methylated bisphenol Phenol 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 diphenol compound, phenol phenolic aldehyde Varnish etc. Here, the "dicyclopentadiene-type diphenol compound" refers to a diphenol compound obtained by condensing one molecule of dicyclopentadiene and two molecules of phenol.

Specifically, it is preferably an active ester compound containing a dicyclopentadiene type diphenol structure, an active ester compound containing a naphthalene structure, an active ester compound containing an acetate of phenol novolak, and a benzyl containing phenol novolak. Among the active ester compounds of the acyl compounds, active ester compounds containing a naphthalene structure and active ester compounds containing a dicyclopentadiene-type diphenol structure are more preferred. The "dicyclopentadiene-type diphenol structure" means a bivalent structural unit composed of phenylene-dicyclopentene-phenylene.

Commercially available active ester hardeners, including active ester compounds with a dicyclopentadiene type diphenol structure, such as "EXB9451", "EXB9460", "EXB9460S", "HPC-8000", and "HPC-8000H" , "HPC-8000-65T", "HPC-8000H-65TM", "EXB-8000L", "EXB-8000L-65TM" (manufactured by DIC Corporation); active ester compounds containing naphthalene structure, including "EXB9416-70BK ", "EXB-8150-65T" (manufactured by DIC Corporation); active ester compounds containing phenol novolac acetate, including "DC808" (manufactured by Mitsubishi Chemical Corporation); containing phenol novolac benzoate Examples of active ester compounds include "YLH1026" (manufactured by Mitsubishi Chemical Co., Ltd.); active ester-based hardeners for acetone phenol novolacs, including "DC808" (manufactured by Mitsubishi Chemical Co., Ltd.); benzyl phenolic novolacs Examples of the active ester-based hardeners include "YLH1026" (manufactured by Mitsubishi Chemical Co., Ltd.), "YLH1030" (manufactured by Mitsubishi Chemical Co., Ltd.), and "YLH1048" (manufactured by Mitsubishi Chemical Co., Ltd.); and the like.

Specific examples of benzoxazine-based hardeners include "JBZ-OP100D" and "ODA-BOZ" manufactured by JFE Chemical; "HFB2006M" manufactured by Showa Polymer Corporation; and "Pd" manufactured by Shikoku Chemical Industry Co., Ltd. , "Fa", etc.

The cyanate ester curing agent includes, for example, bisphenol A dicyanate, polyphenol cyanate (oligo(3-methylene-1,5-phenylene cyanate)), 4,4'- Methylene bis(2,6-dimethylphenyl cyanate), 4,4'-ethylene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis (4-cyanate ester) phenylpropane, 1,1-bis(4-cyanate phenylmethane), bis(4-cyanate-3,5-dimethylphenyl)methane, 1,3 -Bis (4-cyanate phenyl-1-(methyl ethylene)) benzene, bis (4-cyanate phenyl) sulfide, and bis (4-cyanate phenyl) ether, etc. Polyfunctional cyanate resins derived from bifunctional cyanate resins, phenol novolacs and cresol novolacs, and prepolymers in which a part of these cyanate resins are triazineized, etc. Specific examples of cyanate ester curing agents include "PT30" and "PT60" (both phenol novolak type polyfunctional cyanate resin) manufactured by Lonza Japan, "BA230", and "BA230S75" (bisphenol A Part or all of the dicyanate is triazineized to become a trimer (prepolymer) and the like.

Specific examples of the carbodiimide hardener include "V-03" and "V-07" manufactured by Nisshinbo Chemical.

When the hardener is included, the ratio of the amount of epoxy resin to hardener is based on the ratio of [total number of epoxy groups of epoxy resin]: [total number of reactive groups of hardener], preferably 1:0.2~1 The range of :2 is more preferably 1:0.3~1:1.5, and even more preferably 1:0.4~1:1.2. Here, the reactive groups of the hardener refer to active hydroxyl groups, active ester groups, etc., which vary depending on the type of hardener. In addition, the total number of epoxy groups of epoxy resin refers to the total value of all epoxy resins by dividing the mass of the non-volatile components of each epoxy resin by the epoxy equivalent, and the total number of reactive groups of the hardener is Refers to the value of the non-volatile content of each hardener divided by the equivalent of the reactive base as the total value of all hardeners. Setting the ratio of the amount of epoxy resin to hardener to this range can further improve the heat resistance of the resulting hardened product.

When (E) hardener is contained, the content of (E) hardener is not particularly limited. When the non-volatile components other than component (B) in the resin composition are set to 100% by mass, it is preferably 1% by mass or more , More preferably 5% by mass or more, still more preferably 8% by mass or more, particularly preferably 10% by mass or more. (E) The upper limit of the content of the hardener is preferably 40% by mass or less, more preferably 30% by mass or less, still more preferably 20% by mass or less, 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 hardening accelerators, amine hardening accelerators, imidazole hardening accelerators, guanidine hardening accelerators, metal hardening accelerators, and the like. Among them, a phosphorus-based hardening accelerator, an amine-based hardening accelerator, an imidazole-based hardening accelerator, and a metal-based hardening accelerator are preferable, and an amine-based hardening accelerator, an imidazole-based hardening accelerator, and a metal-based hardening accelerator are more preferable. 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, triphenyl phosphine, phosphonium borate compounds, tetraphenyl phosphonium tetraphenyl borate, n-butyl phosphonium tetraphenyl borate, tetrabutyl phosphonium decanoate, (4- (Methylphenyl) triphenyl phosphonium thiocyanate, tetraphenyl phosphonium thiocyanate, butyl triphenyl phosphonium thiocyanate, etc.

Amine-based hardening accelerators include, for example, 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.

The imidazole-based 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-undecylimidazolium trimellitate, 1-cyanoethyl-2-benzene Imidazolium 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'-methylimidazole -(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine isotriazine Polycyanic acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethyl Imidazole, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methyl Imidazole compounds such as imidazoline and 2-phenylimidazoline and adducts of imidazole compounds and epoxy resin.

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

Guanidine-based hardening accelerators include, for example, dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, and dimethylguanidine. 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-methyl biguanide, 1-ethyl biguanide, 1-n-butyl biguanide, 1-n-octadecyl biguanide, 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 organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of organometallic complexes include organic cobalt complexes such as cobalt acetone (II) and cobalt acetone (III), organic copper complexes such as copper acetone (II), and Organic zinc complexes such as zinc acetone (II), organic iron complexes such as iron acetone (III), organic nickel complexes such as nickel acetone (II), manganese acetone (II) ) And other organic manganese complexes. Examples of organic metal salts include zinc octoate, tin octoate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.

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

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

Organic solvents include, for example, ketone solvents such as acetone, methyl ethyl ketone and cyclohexanone; ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, carbitol ethyl Ester solvents such as acid esters, ethyl diethylene glycol acetate, and γ-butyrolactone; carbitol solvents such as cellosolve and butyl carbitol; benzene, toluene, xylene, ethylbenzene , Trimethylbenzene and other aromatic hydrocarbon solvents; dimethylformamide, dimethylacetamide (DMAc) and N-methylpyrrolidone and other amine solvents; methanol, ethanol, 2-methoxy Alcohol-based solvents such as methyl propanol; hydrocarbon-based solvents such as cyclohexane and methylcyclohexane. An organic solvent may be used individually by 1 type, and may be used combining 2 or more types in arbitrary ratios.

＜(H) Other additives＞ In addition to the above-mentioned components, the resin composition may further contain other additives as optional components. Examples of such additives include organic fillers, thickeners, defoamers, flattening agents, adhesion imparting agents, polymerization initiators, flame retardants, and the like. These additives can be used alone or in combination of two or more types. The respective content can be appropriately set by those who are familiar with the art.

＜Manufacturing method of resin composition＞ In one embodiment, the resin composition of the present invention can be manufactured by a method including the following steps. For example, in a reaction vessel, (A) epoxy resin, (B) inorganic filler, and (C) intramolecular A benzoxazine compound with more than one alicyclic structure, if necessary (D) elastomer, if necessary, (E) hardener, if necessary, (F) hardening accelerator, if necessary, (G) organic A method in which the solvent and, if necessary, (H) other additives are added in an arbitrary order and/or part or all of them at the same time to perform the steps of mixing to obtain a resin composition.

In the above steps, the temperature of the process of adding each component can be appropriately set. During the process of adding each component, heating and/or cooling can be performed temporarily or all the time. During the process of adding each ingredient, stirring or shaking can be carried out. Furthermore, after the above steps, it is preferable to further include a step of stirring the resin composition using a stirring device such as a mixer to uniformly disperse it.

＜Characteristics of resin composition＞ The resin composition of the present invention contains (A) epoxy resin, (B) inorganic filler, and (C) a benzoxazine compound having at least one alicyclic structure in the molecule, thereby reducing the elasticity of the cured product Modulus, so the suppression of warpage and excellent adhesion can be achieved.

In one embodiment, the cured product of the resin composition of the present invention has a tensile modulus of elasticity (GPa) at 23°C measured in accordance with JIS K7127. The point of view is to reduce warpage and relax the stress generated during thermal curing. It is preferably 15 Gpa or less, more preferably 12 Gpa or less, still more preferably 11 Gpa or less, and particularly preferably 10.5 Gpa or less.

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

In one embodiment, the amount of warpage of the resin composition layer (thickness 100μm) 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 4mm or less, more preferably 3mm Below, it is more preferably 2.5 mm or less, particularly preferably 2.3 mm or less, 2.2 mm or less, 2.1 mm or less, or 2 mm or less.

＜Use of resin composition＞ The resin composition of the present invention is suitable as a resin composition for insulating applications, and 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 the insulating layer (resin composition for forming a conductive layer) for forming a conductive layer (including a rewiring layer) formed on an insulating layer. In addition, 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 (a resin composition for forming an insulating layer of a printed wiring board). The resin composition of the present invention can also be used for sheet-like build-up materials such as resin sheets, prepregs, solder resists, underfill materials, die-bonding materials, semiconductor packaging materials, buried-hole resins, parts-embedded resins, etc., A wide range of uses of the resin composition is required.

In addition, 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 ( Used as a resin composition for forming a rewiring forming layer and a resin composition for encapsulating a semiconductor wafer (resin composition for encapsulating a semiconductor wafer). When semiconductor chip packaging is manufactured, a rewiring layer can be formed on the packaging layer. (1) The step of temporarily fixing the film by layering on the substrate, (2) The step of temporarily fixing the semiconductor wafer on the temporary fixing film, (3) The step of forming an encapsulation layer on the semiconductor wafer, (4) The step of peeling the substrate and the temporary fixing film from the semiconductor wafer, (5) A step of forming a rewiring forming layer as an insulating layer on the surface where the substrate of the semiconductor wafer and the temporary fixing film are peeled off, and (6) Step of forming a rewiring layer as a conductor layer on the rewiring forming layer

In addition, the resin composition of the present invention can provide an insulating layer with good parts embedding, so it can be applied to the case where the printed wiring board is a circuit board with a built-in part.

＜Sheet-like laminated materials＞ The resin composition of the present invention can be applied and used in a varnish state, and industrially, it is generally preferably used in the form of a sheet-like laminated material containing the resin composition.

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

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

The thickness of the resin composition layer, in terms of the thickness reduction of the printed wiring board and the viewpoint that even if the cured product of the resin composition is a thin film, a cured product with excellent insulation properties can be provided, preferably 50 μm or less, more preferably 40 μm or less . The lower limit of the thickness of the resin composition layer is not particularly limited, but it can usually be 5 μm or more, 10 μm or more.

Examples of the support include a film made of a plastic material, metal foil, and release paper, and a film made of a plastic material or metal foil is preferred.

When a film made of a plastic material is used as the support, the plastic material may include, for example, polyethylene terephthalate (hereinafter sometimes referred to as "PET"), polyethylene naphthalate (hereinafter sometimes referred to as "PEN") and other polyester, polycarbonate (hereinafter sometimes referred to as "PC"), polymethylmethacrylate (PMMA) and other acrylic, cyclic polyolefin, triacetyl cellulose (TAC) , Polyether sulfide (PES), polyether ketone, 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 a support, examples of the metal foil include copper foil and aluminum foil, and copper foil is preferred. As the copper foil, a foil composed of a single metal of copper can be used, or an alloy composed of copper and other metals (for example, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) can be used Foil.

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

Moreover, as a support body, the support body with a mold release layer which has a mold release layer on the surface joined with a resin composition layer can also be used. The mold release agent used for the mold release layer of the support with the mold release layer includes, for example, one or more selected from the group consisting of alkyd resins, polyolefin resins, urethane resins, and silicone resins. Release agent. For the support with a release layer, commercially available products can be used. Examples include "SK-1" and "AL-" made by Lintec, which have PET films with a release layer mainly composed of alkyd resin-based release agents. 5", "AL-7", "lumirrorT60" 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, more preferably in the range of 10 μm to 60 μm. In addition, when a support with a release layer is used, the thickness of the entire support with a release layer is preferably within the above-mentioned range.

In one embodiment, the resin sheet may further include an arbitrary layer if necessary. Examples of the optional layer include a support-based protective film provided on the surface of the resin composition layer that is not bonded to the support (that is, the surface on the opposite side of the support). The thickness of the protective film is not particularly limited, and is, for example, 1 μm to 40 μm. The laminated protective film can prevent the adhesion of dirt on the surface of the resin composition layer or inhibit scars.

For the resin sheet, for example, by directly applying a liquid resin composition or preparing a resin varnish in which the resin composition is dissolved in an organic solvent, the resin varnish is applied to the support by using a die coater or the like to make It is manufactured by drying to form a resin composition layer.

Organic solvents include, for example, ketones such as acetone, methyl ethyl ketone (MEK) and cyclohexanone; ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbamide Acetates such as alcohol acetate; carbitols such as cellosolve and butyl carbitol; aromatic hydrocarbons such as toluene and xylene; dimethylformamide, dimethylacetamide (DMAc) and N-methylpyrrolidone and other amide-based solvents. The organic solvent may be used alone or in combination of two or more kinds.

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

The resin sheet can be wound into a roll for storage. When the resin sheet has a protective film, it is used by peeling off the protective film.

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

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

The prepreg can be manufactured by a conventional method such as a hot melt method and a solvent method.

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

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

The sheet-like laminated material of the present invention can be used for the formation of the insulating layer of printed wiring boards (for the insulating layer of printed wiring boards), and can be more suitable for the formation of interlayer insulating layers of printed wiring boards (for the interlayer insulating layers of printed wiring boards). use).

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

The printed wiring board can be manufactured by a method including the following steps (I) and (II) using the above-mentioned resin sheet, for example. (I) The 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) The step of thermally curing (for example, thermal curing) the resin composition layer to form an insulating layer

The "inner substrate" used in step (I) is a member that becomes the substrate of the printed wiring board. Examples include glass epoxy substrates, metal substrates, polyester substrates, polyimide substrates, BT resin substrates, and thermosetting poly Phenyl ether substrate, etc. In addition, one or both sides of the substrate may have a conductive layer, and the conductive layer may also be patterned. An inner substrate with a conductor layer (circuit) formed on one or both sides of the substrate is sometimes referred to as an "inner circuit substrate". In addition, when manufacturing a printed wiring board, an intermediate product in which an insulating layer and/or a conductor layer is further formed is also included in the so-called "inner layer substrate" in the present invention. When the printed wiring board is a circuit board with built-in parts, an inner-layer substrate with built-in parts can also be used.

The lamination of the inner layer substrate and the resin sheet can be performed, for example, by heating and pressing the resin sheet to the inner layer substrate from the support side. The member for heat-compressing the resin sheet to the inner substrate (hereinafter also referred to as "heat-compression bonding member") includes, for example, a heated metal plate (SUS mirror plate, etc.) or metal roller (SUS roller). In addition, instead of pressing the heating and pressing member directly on the resin sheet, the resin sheet sufficiently follows the surface irregularities of the inner substrate and is preferably pressed through an elastic material such as heat-resistant rubber.

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

Laminating can be performed by a commercially available vacuum laminator. Commercially available vacuum laminators include, for example, vacuum pressurized laminators manufactured by Meike Manufacturing Co., Ltd., vacuum coaters manufactured by Nikko-materials, and batch vacuum pressurized laminators.

After the lamination, under normal pressure (atmospheric pressure), for example, by pressing the heating and pressing member from the support side, the layered resin sheet can also be smoothed. The pressing conditions of the smoothing treatment may be the same conditions as the heating and pressing conditions of the above-mentioned build-up. The smoothing process can be performed by a commercially available laminate machine. In addition, the layering and smoothing treatment can also be performed continuously using the above-mentioned commercially available vacuum layering machine.

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

In the step (II), the resin composition layer is thermally cured (e.g., thermally 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 when forming the insulating layer of the printed wiring board, the conditions generally used can be used.

For example, the thermal curing conditions of the resin composition layer vary depending on the type of resin composition, etc. 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 still more preferably 15 minutes to 100 minutes.

Before thermally curing the resin composition layer, the resin composition layer may be preheated at a temperature lower than the curing temperature. For example, before the resin composition layer is thermally cured, the resin composition is usually heated at a temperature above 50°C and below 120°C, preferably above 60°C and below 115°C, and more preferably above 70°C and below 110°C. The layer is preheated for more than 5 minutes, preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes, and still more preferably 15 minutes to 100 minutes.

When manufacturing a printed wiring board, (III) a step of making holes in the insulating layer, (IV) a step of roughening the insulating layer, and (V) a step of forming a conductor layer may be further implemented. These steps (III) to (V) can be implemented in accordance with various methods known to those skilled in the art used in the manufacture of printed wiring boards. In addition, when the support is removed after step (II), the support can be removed between step (II) and step (III), step (III) and step (IV), or step (IV) Implemented between step (V). In addition, if necessary, the formation of the insulating layer and the conductor layer of step (II) to step (V) can be repeated to form a multilayer wiring board.

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

Step (III) is a step of making holes in the insulating layer, whereby holes such as via holes and through holes can be formed in the insulating layer. Step (III) can be implemented in accordance with the composition of the resin composition used in the formation of the insulating layer, for example, using a drill, a laser, and a plasma. 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 well-known order and conditions generally used when forming the insulating layer of a printed wiring board can be adopted. For example, the swelling treatment with a swelling liquid, the roughening treatment with an oxidizing agent, and the neutralization treatment with a neutralization liquid can be carried out in order, and the insulating layer can be roughened.

The swelling liquid used in the roughening treatment is not particularly limited, and an alkali solution, a surfactant solution, etc. may be mentioned, and an alkali solution is preferred, and the alkali solution is more preferably a sodium hydroxide solution or a potassium hydroxide solution. Examples of commercially available swelling fluids include "Swelling Dip Securiganth P" and "Swelling Dip Securiganth SBU" manufactured by atotech Japan. The swelling treatment by the swelling solution is not particularly limited. For example, the swelling treatment can be performed by immersing the insulating layer in a swelling solution at 30°C to 90°C for 1 minute to 20 minutes. From the viewpoint of suppressing the swelling of the resin of the insulating layer to an appropriate level, it is preferable to immerse the insulating layer in a swelling solution at 40°C to 80°C for 5 minutes to 15 minutes.

The oxidizing agent used in the roughening treatment is not particularly limited, and examples include an alkaline permanganic acid solution in which potassium permanganate or sodium permanganate is dissolved in an aqueous solution of sodium hydroxide. The roughening treatment by 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. Examples of commercially available oxidants include alkaline permanganic acid solutions such as "Concentrate Compact CP" and "Dosing Solution Securiganth P" manufactured by Atotech Japan.

In addition, the neutralizing liquid 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 neutralization liquid can be performed by immersing the treated surface roughened with an oxidizing agent in a neutralization liquid at 30°C to 80°C for 5 minutes to 30 minutes. From the viewpoint of workability and the like, a method of immersing an object roughened with an oxidizing agent in a neutral solution at 40°C to 70°C for 5 minutes to 20 minutes is preferred.

In one embodiment, the arithmetic average roughness (Ra) of the surface of the insulating layer after the roughening treatment is not particularly limited, and 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 may be preferably 0.5 nm or more, more preferably 1 nm or more. In addition, the root mean square roughness (Rq) of the insulating layer surface after the 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 may be preferably 0.5 nm or more, more preferably 1 nm or more. The arithmetic average roughness (Ra) and root mean square roughness (Rq) of the insulating layer surface can be measured with a non-contact surface roughness meter.

Step (V) is a step of forming a conductor layer, forming a conductor layer on the insulating layer. The conductor material used in the conductor layer is not particularly limited. In a preferred embodiment, the conductor layer includes at least one selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin, and indium Metal. The conductor layer may be a single metal layer or an alloy layer; the alloy layer may be, for example, an alloy made of two or more metals selected from the above group (for example, nickel･chromium alloy, copper･nickel alloy, and copper･titanium alloy) The formed layer. Among them, from the viewpoints of versatility, cost, and ease of patterning of the conductor layer formation, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or nickel is preferred. ･Cr alloy, copper, nickel alloy, copper and titanium alloy layer, more preferably a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or a nickel and chromium alloy layer , And more preferably a single metal layer of copper.

The conductor layer may have a single-layer structure, or a multi-layer structure in which two or more layers of single metal layers or alloys made of different types of metals or alloys are laminated. When the conductor layer is a multilayer 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 printed wiring board design, and is generally 3 μm to 35 μm, preferably 5 μm to 30 μm.

In one embodiment, the conductive layer can be formed by plating. For example, by plating on the surface of the insulating layer by a conventionally known technique such as a semi-additive method and a full-additive method, a conductor layer with a desired wiring pattern can be formed. From the viewpoint of ease of manufacture, by The semi-additive method is better. The following shows an example of forming the conductor layer by the semi-additive method.

First, a shield layer is formed on the surface of the insulating layer by electroless plating. Next, on the formed plating protection layer, a mask pattern corresponding to the desired wiring pattern is formed so that a part of the plating protection layer is exposed. After the metal layer is formed by electroplating on the exposed plating protection layer, the mask pattern is removed. Then, by removing the unnecessary plating protection layer by etching or the like, a conductor layer having a desired wiring pattern can be formed.

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

The metal foil can be produced by a conventional method such as an electrolysis method and a rolling method. Commercially available metal foils include, for example, HLP foil, JXUT-III foil, 3EC-III foil, TP-III foil produced by JX Nikkei Nippon Oil Metals Co., Ltd., Mitsui Metal Mining Co., Ltd., and the like.

When using the resin composition of the present invention containing a combination of the (A) component, (B) component, and (C) component in a specific content, when manufacturing a printed wiring board, no matter whether the conductor layer is formed by plating or metal foil is used to form the conductor The 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.

Examples of semiconductor devices include various semiconductor devices for supplying electrical products (for example, computers, mobile phones, digital cameras, televisions, etc.) and vehicles (for example, motorcycles, automobiles, trams, ships, and aircrafts, etc.).

[Example]

Hereinafter, the present invention will be described in detail with examples. However, the present invention is not limited to these embodiments. In addition, in the following description, the "parts" and "%" indicating the amount indicate "parts by mass" and "% by mass", unless otherwise specified.

<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% polyoxymethylene were each heated in toluene at a molar ratio of 1:2:4.1 to perform the reaction. After the toluene was distilled off, the target compound was obtained. In the purity measurement by GPC, the purity as a monomer is 65%. Although it contains a polymer as a by-product, it can be used directly in the examples.

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

The 1,4-cyclohexanediamine, phenol, and 92% polyformaldehyde were each heated to reflux in toluene at a molar ratio of 1:2:4.1 to perform the reaction. After the toluene was distilled off, the target compound was obtained. In the purity measurement by GPC, the purity as a monomer is 60%. Although it contains a polymer as a by-product, it can be used directly in the examples.

<Synthesis example 3: Synthesis of elastomer> In the reaction vessel, add 69 g of bifunctional hydroxyl-terminated polybutadiene ("G-3000" manufactured by Soda, Japan, number average molecular weight = 3000, hydroxyl equivalent = 1800 g/eq.), and aromatic hydrocarbon-based mixed solvent (Idemitsu 40 g of "Ipsol 150" manufactured by Petrochemical Corporation and 0.005 g of dibutyltin laurate were mixed to dissolve uniformly. When it becomes uniform, the temperature is raised to 60°C, and 8 g of isophorone diisocyanate ("IPDI" manufactured by Evonik Degussa Japan Co., Ltd., isocyanate group equivalent = 113 g/eq.) is added while stirring, and the reaction is carried out 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) were added to the reactant, and stirred The temperature was raised to 150°C, and the reaction was carried out for about 10 hours. By FT-IR, it was confirmed that the NCO peak at ^{2250 cm -1 disappeared.} To confirm the disappearance of the NCO peak, it was regarded as the end of the reaction, and the reactant was cooled to room temperature. Furthermore, the reactant was filtered with 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: 50% by mass of non-volatile content). The number average molecular weight of the elastomer is 5900, and the glass transition temperature is -7°C.

<Example 1> Combine 5 parts of biphenyl type epoxy resin (Nippon Kayaku Corporation "NC3000", epoxy equivalent 276g/eq.), bisphenol type epoxy resin (Nippon Steel & Sumikin Chemical Co., "ZX1059", bisphenol A type 1:1 mixture with bisphenol F type, epoxy equivalent 169g/eq.) 2 parts, spherical bismuth surface treated with 0.5% by mass of an amine-based alkoxysilane compound ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.) 70 parts of silicon oxide ("SO-C2" manufactured by Admatechs, 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, cresol novolac resin ( DIC Corporation "KA-1160", phenolic hydroxyl equivalent: 117g/eq) 3 parts, hardening accelerator (Shikoku Kasei Corporation "1B2PZ", 1-benzyl-2-phenylimidazole) 0.1 part and methyl 15 parts of 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> Except for the use of 115 parts of spherical alumina (DAW-03 manufactured by Denka, average particle size 3.7μm) after surface treatment of 0.5% by mass of an amine-based alkoxysilane compound ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.), instead 70 parts of spherical silica ("SO-C2" manufactured by Admatechs, average particle size 0.5μm) after surface treatment of 0.5% by mass of amine-based alkoxysilane compound ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.), and In Example 1, a resin composition was prepared in the same manner.

<Example 4> Except for the use of spherical alumina (average particle size 1.5μm, specific surface area 2.0m ² /g, Maximum particle size 5μm) 115 parts of spherical silicon dioxide ("SO-C2" made by Admatechs Co., Ltd., "SO-C2" made by Admatechs Co., Ltd., and average particle size after 0.5% by mass surface treatment of amine alkoxysilane compound ("KBM573" made by Shin-Etsu Chemical Co., Ltd.) 0.5 μm), except for 70 parts, a resin composition was prepared in the same manner as in Example 1.

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

＜Comparative example 2＞ In addition to the use of commercially available benzoxazine compounds ("Pd-type benzoxazine" manufactured by Shikoku Chemical Industry Co., Ltd., bis[4-(3,4-dihydro-2H-1,3-benzoxazine-3) -Yl)phenyl]methane) 2 parts of the benzoxazine compound obtained in Synthesis Example 1 was substituted for 2 parts, and a resin composition was prepared in the same manner as in Example 1.

<Test Example 1: Measurement and Evaluation of Tensile Elasticity Coefficient> On the untreated surface of the PET film treated with the release agent (“501010” made by Lindeco, thickness 38μm, 240mm square), the glass cloth substrate ring is fixed with a polyimide adhesive tape (width 10mm) Oxygen resin double-sided copper-clad laminates ("R5715ES" made by Panasonic, thickness 0.7mm, 255mm square) overlap on four sides (hereinafter sometimes referred to as "fixed PET film").

The resin composition prepared in the examples and comparative examples was coated on the mold release treatment surface of the above-mentioned "fixed PET film" using a die coater, so that the thickness of the resin composition layer after drying became 50μm, and the temperature was 80°C~ It was dried 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 cured under curing conditions for 90 minutes. After thermal curing, the polyimide adhesive tape is peeled off, the cured product is removed from the glass cloth base epoxy resin double-sided copper-clad laminate, and the PET film (“501010” manufactured by Lindeke Co., Ltd.) is peeled off to obtain a thin sheet. Hardened object. The obtained cured product is called "evaluation cured product".

The hardened product for evaluation was cut into a dumbbell-shaped No. 1 shape to obtain a test piece. The tensile strength of the test piece was measured using a tensile testing machine "RTC-1250A" manufactured by ORIENTEC, and the elastic modulus at 23°C was determined. The measurement is implemented in accordance with JIS K7127. This operation was performed 3 times, and the average value is shown in the following table. In order to reduce the warpage, when considering the relaxation of the stress generated during thermal hardening, the lower the tensile elastic modulus, the better. In consideration of this, a coefficient of tensile elasticity of 10.5 GPa or less was evaluated as "o", and a coefficient of greater than 10.5 GPa was evaluated as "x".

<Test Example 2: Measurement and Evaluation of Peeling Strength> Prepare a glass cloth base epoxy resin with copper foil on the surface as an inner layer of a copper-clad laminate on both sides (the thickness of the copper foil is 18μm, the thickness of the substrate is 0.8mm, "R1515A" made by Panasonic). All the copper foil on the surface of the inner substrate is etched and removed. Then, drying was performed at 190°C for 30 minutes.

The resin composition obtained in the above-mentioned Examples and Comparative Examples was used in a batch-type vacuum pressure laminator (2-stage build-up laminator "CVP700" manufactured by nikko-materials) to make the resin composition layer and the aforementioned inner layer substrate The bonding method is laminated on both sides of the inner substrate. This layered layer was depressurized for 30 seconds to make the pressure less than 13 hPa, and then pressure-bonded at a temperature of 100° C. and a pressure of 0.74 MPa for 30 seconds. Next, the laminated resin sheet was smoothed by hot pressing at 100°C and a pressure of 0.5 MPa for 60 seconds under atmospheric pressure. Then, after the support is peeled off, an "intermediate multilayer body I" including a resin composition layer, an inner substrate, and a resin composition layer in this order is obtained.

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 etched with a copper etching amount of 1 μm using a micro-etching agent ("CZ8101" manufactured by MEC Corporation) and roughened. The copper foil thus obtained is called "roughened copper foil".

This roughened copper foil is laminated on both sides of the intermediate multilayer body I by joining the roughened surface of the roughened copper foil and the resin composition layer of the intermediate multilayer body I. This lamination is carried out under the same conditions as the lamination of the resin sheet of the aforementioned inner substrate. Thereby, an "intermediate composite II" including a roughened copper foil, a resin composition layer, an inner substrate, a resin composition layer, and a 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 thermal curing of the resin composition layer is performed, and the insulating layer which is the cured product of the resin composition layer, the inner substrate, the insulating layer which is the cured product of the resin composition layer, and the roughened copper foil in this order are obtained. The "evaluation substrate" of chemical copper foil. In this evaluation substrate, the roughened copper foil corresponds to the conductor layer.

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

<Test Example 3: Evaluation of Warpage> Prepare a polyethylene terephthalate film with a release layer as a support ("AL5" made by Lindeco, thickness 38μm). On the release layer of the support, the resin composition obtained in the above-mentioned Examples and Comparative Examples was uniformly coated so that the thickness of the resin composition layer after drying became 50 μm. Then, the resin varnish was dried at 80 to 120°C (average 100°C) for 6 minutes to obtain a resin sheet including a support and a resin composition layer.

Next, on the entire single side of a 12-inch wafer (thickness 775μm), the above-mentioned resin sheet is 50μm thick using a batch-type vacuum pressure laminator (Nikko-Materials Co., Ltd. 2-stage build-up laminator "CVP700") Layers were laminated, and two layers were laminated to form a resin composition layer with a thickness of 100 μm. The obtained silicon wafer with a resin composition layer is heat-treated in an oven at 180° C. for 90 minutes to form a silicon wafer with a cured resin composition layer (that is, an insulating layer). The end of the obtained wafer with an insulating layer is pressed against the stage, and the distance between the end of the wafer on the opposite side of the pressing position and the stage is measured as the amount of warpage. Those with a warpage of 0 to 2 mm were evaluated as "○", and those with a warpage greater than 2 mm were evaluated as "×".

The non-volatile components of the resin compositions of the examples and comparative examples and 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 (C) a benzoxazine compound having one or more alicyclic structures in the molecule is used, both suppression of warpage and excellent adhesion can be achieved.

Claims (13)

A resin composition comprising (A) an epoxy resin, (B) an inorganic filler, and (C) a benzoxazine compound having an alicyclic structure in the molecule. The resin composition of claim 1, wherein the alicyclic structure of component (C) is a cyclohexane ring structure. Such as the resin composition of claim 1, wherein the component (C) is formula (2):

[In the formula, R ¹ and R ² each independently represent a substituent, Y represents a bonding 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]. As in the resin composition of claim 1, when all the non-volatile components in the resin composition are set to 100% by mass, the content of the component (B) is 50% by mass or more. The resin composition of claim 1, wherein the average particle size of the component (B) is 10 μm or less. Such as the resin composition of claim 1, which further contains (D) elastomer. Such as the resin composition of claim 1, which further contains (E) a hardener. Such as the resin composition of claim 1, which is used for forming an insulating layer. A hardened product of the resin composition according to any one of claims 1 to 8. A sheet-like laminated material, which contains the resin composition according to any one of claims 1 to 8. A resin sheet having a support body and a resin composition layer formed on the support body and formed of the resin composition according to any one of claims 1 to 8. A printed wiring board is provided with an insulating layer composed of a hardened resin composition according to any one of claims 1 to 8. A semiconductor device including the printed wiring board as claimed in claim 12.