CN111662532A

CN111662532A - Resin composition

Info

Publication number: CN111662532A
Application number: CN202010142790.2A
Authority: CN
Inventors: 池平秀
Original assignee: Ajinomoto Co Inc
Current assignee: Ajinomoto Co Inc
Priority date: 2019-03-07
Filing date: 2020-03-04
Publication date: 2020-09-15
Also published as: JP2022179472A; TW202104424A; JP7124770B2; JP7338758B2; JP2020143239A

Abstract

The present invention addresses the problem of providing a resin composition that can simultaneously suppress warpage of a cured product and achieve 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 1 or more alicyclic structures in the molecule.

Description

Resin composition

Technical Field

The present invention relates to a resin composition comprising an epoxy resin and a curing agent; a cured product of the resin composition; a sheet-like laminate material comprising the above resin composition; a resin sheet comprising the above resin composition; a printed wiring board comprising the cured product; a semiconductor device comprising the printed wiring board.

Background

As a manufacturing technique of a printed wiring board, a build-up (build) method is known in which insulating layers and conductor layers are alternately stacked. In the build-up method, the insulating layer is generally formed by curing a resin composition.

Since printed wiring boards are exposed to various environments such as high temperature and low temperature, if the linear thermal expansion coefficient of a cured material used for an insulating layer is high, the insulating layer repeats expansion and contraction, and cracks are generated due to the deformation. As a method for suppressing the linear thermal expansion coefficient to a low level, a method of blending a relatively large amount of an inorganic filler into a cured material is known (patent document 1). However, when a relatively large amount of an inorganic filler is added to the cured material, the elastic modulus increases, and it becomes difficult to suppress warpage.

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

Therefore, even when a relatively large amount of inorganic filler is used, a cured material that can simultaneously suppress warpage due to a low elastic modulus and achieve excellent adhesion is required.

Documents of the prior art

Patent document

Patent document 1: japanese patent laid-open publication No. 2016-.

Disclosure of Invention

Problems to be solved by the invention

The present invention addresses the problem of providing a resin composition that can simultaneously achieve both suppression of warpage and excellent adhesion of the resulting cured product.

Means for solving the problems

As a result of intensive studies to achieve the object of the present invention, the present inventors have found that by containing (C) a benzoxazine compound having 1 or more alicyclic structures in the molecule in a resin composition, the elastic modulus of a cured product can be reduced, and thereby both suppression of warpage and excellent adhesion can be achieved, and have completed the present invention.

That is, the present invention includes the following,

[1] a resin composition comprising (a) an epoxy resin, (B) an inorganic filler, and (C) a benzoxazine compound having an alicyclic structure in a 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 according to the above [1] or [2], wherein the component (C) is a compound represented by the formula (2).

[ chemical formula 1]

。

[ in the formula, R¹And R²Each independently represents a substituent, Y represents a bond, an alkylene group having 1 to 6 carbon atoms, -O-, -S-, -SO₂-, -NH-, -CO-, -CONH-, -NHCO-, -COO-, or-OCO-, s and t each independently represent an integer of 0 to 4, and u represents 0 or 1. Angle (c)

[4] The resin composition according to any one of the above [1] to [3], wherein the content of the component (B) is 50% by mass or more, assuming that all nonvolatile components in the resin composition are 100% by mass;

[5] the resin composition according to any one of the above [1] to [4], wherein the average particle diameter of the component (B) is 10 μm or less;

[6] the resin composition according to any one of the above [1] to [5], further comprising (D) an elastomer;

[7] the resin composition according to any one of the above [1] to [6], further comprising (E) a curing agent;

[8] the resin composition according to any one of the above [1] to [7], which is used for forming an insulating layer;

[9] a cured product of the resin composition according to any one of the above [1] to [8 ];

[10] a sheet-like laminate comprising the resin composition according to any one of the above [1] to [8 ];

[11] a resin sheet comprising a support and, provided on the support, a resin composition layer formed of the resin composition according to any one of the above [1] to [8 ];

[12] a printed wiring board comprising an insulating layer formed from a cured product of the resin composition according to any one of [1] to [8 ];

[13] a semiconductor device comprising the printed wiring board according to [12 ].

ADVANTAGEOUS EFFECTS OF INVENTION

According to the present invention, a resin composition can be provided which can simultaneously suppress warpage of a cured product and achieve excellent adhesion by reducing the elastic modulus of the cured product.

Detailed Description

The present invention will be described in detail below with reference to preferred embodiments thereof. However, the present invention is not limited to the embodiments and examples described below, and can be implemented by arbitrarily changing the embodiments without departing from the scope of the claims and the equivalent scope thereof.

< resin composition >

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

By using such a resin composition, the elastic modulus of a cured product can be reduced, and thus warpage suppression and excellent adhesion can be achieved at the same time.

The resin composition of the present invention may contain any component in addition to the epoxy resin (a), the inorganic filler (B), and the benzoxazine compound (C) having an alicyclic structure in the molecule. Examples of the optional components include (D) an elastomer, (E) a curing agent, (F) a curing accelerator, (G) an organic solvent, and (H) other additives. Hereinafter, each component contained in the resin composition will be described in detail.

(A) epoxy resin

The resin composition of the present invention comprises (a) an epoxy resin.

Examples of the epoxy resin (A) include a biphenol-type epoxy resin, a bisphenol A-type epoxy resin, a bisphenol F-type epoxy resin, a bisphenol S-type epoxy resin, a bisphenol AF-type epoxy resin, a dicyclopentadiene-type epoxy resin, a trisphenol-type epoxy resin, a naphthol novolac-type epoxy resin, a phenol novolac-type epoxy resin, a tert-butyl-catechol-type epoxy resin, a naphthalene-type epoxy resin, a naphthol-type epoxy resin, an anthracene-type epoxy resin, a glycidyl amine-type epoxy resin, a glycidyl ester-type epoxy resin, a cresol novolac-type epoxy resin, a biphenyl-type epoxy resin, a linear aliphatic epoxy resin, an epoxy resin having a butadiene structure, an alicyclic epoxy resin, a heterocyclic-type epoxy resin, an epoxy resin containing a spiro ring, a cyclohexane-type epoxy resin, a cyclohexane dimethanol-type epoxy resin, a naphthylene ether-type epoxy resin, Trimethylol type epoxy resins, tetraphenylethane type epoxy resins, and the like. The epoxy resin may be used alone in 1 kind, or in combination of 2 or more kinds.

As the (a) epoxy resin, the resin composition preferably contains an epoxy resin having 2 or more epoxy groups in 1 molecule. From the viewpoint of remarkably obtaining the desired effect of the present invention, the proportion of the epoxy resin having 2 or more epoxy groups in 1 molecule is preferably 50% by mass or more, more preferably 60% by mass or more, and particularly preferably 70% by mass or more, relative to 100% by mass of the nonvolatile component of the epoxy resin (a).

The epoxy resin includes an epoxy resin which is liquid at a temperature of 20 ℃ (hereinafter, sometimes referred to as "liquid epoxy resin") and an epoxy resin which is solid at a temperature of 20 ℃ (hereinafter, sometimes referred to as "solid epoxy resin"). In one embodiment, the resin composition of the present invention comprises a liquid epoxy resin as the epoxy resin. In one embodiment, the resin composition of the present invention comprises a solid epoxy resin as the 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 as an epoxy resin, but preferably contains a liquid epoxy resin and a solid epoxy resin in combination as an epoxy resin.

As the liquid epoxy resin, a liquid epoxy resin having 2 or more epoxy groups in 1 molecule is preferable.

As the liquid epoxy resin, bisphenol a type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, phenol novolac type epoxy resin, alicyclic epoxy resin having an ester skeleton, cyclohexane type epoxy resin, cyclohexane dimethanol type epoxy resin, glycidyl amine type epoxy resin, and epoxy resin having a butadiene structure are preferable.

Specific examples of the liquid epoxy resin include "HP 4032", "HP 4032D" and "HP 4032 SS" (naphthalene type epoxy resin) manufactured by DIC corporation; "828 US", "828 EL", "jER 828 EL", "825", "EPIKOTE 828 EL" (bisphenol A type epoxy resin) manufactured by Mitsubishi chemical company; "jER 807" and "1750" (bisphenol F type epoxy resin) manufactured by Mitsubishi chemical corporation; "jER 152" (phenol novolac type epoxy resin) manufactured by mitsubishi chemical corporation; "630" and "630 LSD" (glycidyl amine type epoxy resins) manufactured by mitsubishi chemical corporation; "ZX 1059" (a mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin) manufactured by Nissian Ciki Kaisha; "EX-721" (glycidyl ester type epoxy resin) manufactured by Nagase ChemteX; "Celloxide 2021P" (alicyclic epoxy resin having an ester skeleton) manufactured by Dailuo corporation; "PB-3600" manufactured by Daxylonite, JP-100 "and JP-200" manufactured by Nippon Caoda (a butadiene-structured epoxy resin); "ZX 1658" and "ZX 1658 GS" (liquid 1, 4-glycidylcyclohexane-type epoxy resins) manufactured by Nippon iron and Japan chemical Co., Ltd. These can be used alone in 1 kind, also can be combined with more than 2 kinds.

The solid epoxy resin is preferably a solid epoxy resin having 3 or more epoxy groups in 1 molecule, and more preferably an aromatic solid epoxy resin having 3 or more epoxy groups in 1 molecule.

As the solid epoxy resin, a biphenol-type epoxy resin, a naphthalene-type tetrafunctional epoxy resin, a cresol novolak-type epoxy resin, a dicyclopentadiene-type epoxy resin, a trisphenol-type epoxy resin, a naphthol-type epoxy resin, a biphenyl-type epoxy resin, a naphthylene ether-type epoxy resin, an anthracene-type epoxy resin, a bisphenol a-type epoxy resin, a bisphenol AF-type epoxy resin, and a tetraphenylethane-type epoxy resin are preferable.

Specific examples of the solid epoxy resin include "HP 4032H" (naphthalene type epoxy resin) manufactured by DIC; "HP-4700" and "HP-4710" (naphthalene type tetrafunctional epoxy resins) manufactured by DIC; "N-690" (cresol novolac type epoxy resin) manufactured by DIC; "N-695" (cresol novolac type epoxy resin) manufactured by DIC; "HP-7200" (dicyclopentadiene type epoxy resin) manufactured by DIC; "HP-7200 HH", "HP-7200H", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S" and "HP 6000" (naphthylene ether type epoxy resins) manufactured by DIC; EPPN-502H (trisphenol type epoxy resin) manufactured by Nippon chemical Co., Ltd.; "NC 7000L" (naphthol novolac type epoxy resin) manufactured by japan chemicals); "NC 3000H", "NC 3000L" and "NC 3100" (biphenyl type epoxy resin) manufactured by japan chemical company; ESN475V (naphthol type epoxy resin) manufactured by Nippon iron and gold Chemicals; ESN485 (naphthol novolac type epoxy resin) manufactured by Nippon iron and gold Chemicals, Ltd; "YX 4000H", "YX 4000", "YL 6121" (biphenyl type epoxy resin) manufactured by Mitsubishi chemical company; "YX 4000 HK" (bisphenol type epoxy resin) manufactured by Mitsubishi chemical corporation; YX8800 (anthracene-based epoxy resin) available from Mitsubishi chemical corporation; "YX 7700" (novolac-type epoxy resin containing a xylene structure) manufactured by mitsubishi chemical corporation; PG-100 and CG-500 manufactured by Osaka gas chemical company; "YL 7760" (bisphenol AF type epoxy resin) manufactured by Mitsubishi chemical corporation; "YL 7800" (fluorene-based epoxy resin) manufactured by Mitsubishi chemical corporation; "jER 1010" (solid bisphenol a type epoxy resin) manufactured by mitsubishi chemical corporation; "jER 1031S" (tetraphenylethane-type epoxy resin) manufactured by Mitsubishi chemical corporation, and the like. These can be used alone in 1 kind, also can be combined with more than 2 kinds.

When a liquid epoxy resin and a solid epoxy resin are used in combination as the epoxy resin (a), the amount ratio thereof (liquid epoxy resin: solid epoxy resin) is preferably 1:1 to 1:30, more preferably 1:1 to 1:20, and particularly preferably 1:1 to 1:10 in terms of mass ratio. By setting the amount ratio of the liquid epoxy resin to the solid epoxy resin within the above range, the desired effects of the present invention can be remarkably obtained.

(A) The epoxy equivalent of the epoxy resin is preferably 50g/eq to 5000g/eq, more preferably 50g/eq to 3000g/eq, even more preferably 80g/eq to 2000g/eq, and even more preferably 110g/eq to 1000g/eq. By setting the above range, the crosslinking density of the cured product of the resin sheet becomes sufficient, and an insulating layer having a small surface roughness can be formed. The epoxy equivalent is the mass of the resin containing 1 equivalent of epoxy group. The epoxy equivalent can be measured according to JIS K7236.

The weight average molecular weight (Mw) of the epoxy resin (a) 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 a Gel Permeation Chromatography (GPC) method.

(A) The content of the epoxy resin is not particularly limited, and is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 15% by mass or more, and particularly preferably 20% by mass or more, from the viewpoint of remarkably obtaining the desired effect of the present invention, when the nonvolatile components other than the component (B) in the resin composition are set to 100% by mass. From the viewpoint of remarkably obtaining the desired effect of the present invention, the upper limit thereof is preferably 60% by mass or less, more preferably 50% by mass or less, further preferably 40% by mass or less, and particularly preferably 30% by mass or less.

(B) inorganic filler

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

(B) The material of the inorganic filler is not particularly limited, and examples thereof include silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, barium titanate zirconate, barium zirconate, calcium zirconate, zirconium phosphate tungstate, etc., and silica and alumina are particularly preferable. Examples of the silica include amorphous silica, fused silica, crystalline silica, synthetic silica, hollow silica and the like. In addition, as the silica, spherical silica is preferable. (B) The inorganic filler may be used alone in 1 kind, or may be used in combination in 2 or more kinds.

Examples of commercially available products of the inorganic filler (B) include "UFP-30" manufactured by DENKA chemical industries, Inc.; "SP 60-05" and "SP 507-05" manufactured by Nissi iron-alloy materials Corp; "YC 100C", "YA 050C", "YA 050C-MJE", "YA 010C" manufactured by Yadu Ma (Admatechs) of Kabushiki Kaisha; "UFP-30" manufactured by the electric chemical company; "Silfil (シルフィル) NSS-3N", "Silfil NSS-4N" and "Silfil NSS-5N" manufactured by Deshan, Kuyama, K.K.; "SC 2500 SQ", "SO-C4", "SO-C2", "SO-C1", "A23-SX-C1", manufactured by Yadu Ma K.K.; "DAW-03" and "FB-105 FD" manufactured by DENKA corporation, and the like.

(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, and particularly preferably 5 μm or less. The lower limit of the average particle size of the inorganic filler is not particularly limited, but is preferably 0.01 μm or more, more preferably 0.05 μm or more, further preferably 0.1 μm or more, further preferably 0.2 μm or more, further more preferably 0.3 μm or more, and particularly preferably 0.4 μm or more. The average particle diameter of the inorganic filler can be measured by a laser diffraction-scattering method based on Mie scattering theory. Specifically, it can be determined by: the particle size distribution of the inorganic filler was prepared on a volume basis by using a laser diffraction scattering particle size distribution measuring apparatus, and the median particle size was defined as an average particle size. The measurement sample may be a sample obtained by: 100mg of the inorganic filler and 10g of methyl ethyl ketone were weighed into a vial, and dispersed for 10 minutes by ultrasonic waves. For the measurement sample, the volume-based particle size distribution of the inorganic filler was measured by a flow cell (flow cell) method using a laser diffraction type particle size distribution measuring apparatus with the wavelength of the light source used being blue and red, and the average particle size was calculated from the obtained particle size distribution as the median particle size. Examples of the laser diffraction type particle size distribution measuring apparatus include "LA-960" manufactured by horiba, Ltd.

The inorganic filler (B) is preferably treated with 1 or more surface-treating agents such as an aminosilane-based coupling agent, an epoxysilane-based coupling agent, a mercaptosilane-based coupling agent, an alkoxysilane compound, an organosilazane compound, and a titanate-based coupling agent, from the viewpoint of improving moisture resistance and dispersibility. Examples of commercially available surface-treating agents include "KBM 403" (3-glycidoxypropyltrimethoxysilane) available from shin-Etsu chemical Co., Ltd, "KBM 803" (3-mercaptopropyltrimethoxysilane) available from shin-Etsu chemical Co., Ltd, "KBE 903" (3-aminopropyltriethoxysilane) available from shin-Etsu chemical Co., Ltd, "KBM 573" (N-phenyl-3-aminopropyltrimethoxysilane) available from shin-Etsu chemical Co., Ltd, "SZ-31" (hexamethyldisilazane) available from shin-Etsu chemical Co., Ltd, "KBM 103" (phenyltrimethoxysilane) available from shin-Etsu chemical Co., Ltd, "KBM-4803" (long-chain epoxy-type silane coupling agent) available from shin-Etsu chemical Co., Ltd, "KBM-7103" (3,3, 3-trifluoropropyltrimethoxysilane), KBM503 (3-methacryloxypropyltrimethoxysilane) manufactured by shin-Etsu chemical industries, KBM5783 manufactured by shin-Etsu chemical industries, and the like.

From the viewpoint of improving the dispersibility of the inorganic filler, it is preferable to control the degree of the surface treatment with the surface treatment agent to be within a predetermined range. Specifically, the inorganic filler is preferably surface-treated with 0.2 to 5 mass%, more preferably 0.2 to 3 mass%, and still more preferably 0.3 to 2 mass% of a surface-treating agent with respect to 100 mass% of the inorganic filler.

The degree of surface treatment with the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the inorganic filler. From the viewpoint of improving the dispersibility of the inorganic filler, the carbon amount per unit surface area of the inorganic filler is preferably 0.02mg/m²Above, more preferably 0.1mg/m²Above, more preferably 0.2mg/m²The above. On the other hand, from the viewpoint of preventing the melt viscosity of the resin composition and the melt viscosity in the form of a sheet from increasing, it is preferably 1mg/m²The concentration is more preferably 0.8mg/m or less²The concentration is more preferably 0.5mg/m or less²The following.

(B) The amount of carbon per unit surface area of the inorganic filler can be measured after the inorganic filler after the surface treatment is washed with a solvent (for example, Methyl Ethyl Ketone (MEK)). Specifically, a sufficient amount of MEK as a solvent may be added to the inorganic filler surface-treated with the surface treatment agent, and ultrasonic washing may be performed at 25 ℃ for 5 minutes. The supernatant liquid was removed, the solid components were dried, and then the amount of carbon per unit surface area of the inorganic filler was measured using a carbon analyzer. As the carbon analyzer, "EMIA-320V" manufactured by horiba, Ltd., can be used.

From the viewpoint of further improving the effect of the present invention, the specific surface area of the (B) inorganic filler is preferably 0.01m²A value of at least one per gram, more preferably 0.1m²A specific ratio of 0.2m or more per gram²More than g. The upper limit is not particularly limited, but is preferably 50m²A ratio of 20m or less per gram²10m below/g²Less than or equal to 5 m/g²The ratio of the carbon atoms to the carbon atoms is less than g. The specific surface area of the inorganic filler material can be obtained by: according to the BET method, a nitrogen gas was adsorbed to the surface of the sample using a specific surface area measuring apparatus (Macsorb HM-1210, manufactured by Mountech corporation), and the ratio was calculated by the BET multipoint methodSurface area.

(B) The content of the inorganic filler is not particularly limited, and is preferably 30% by mass or more, more preferably 50% by mass or more, further preferably 60% by mass or more, and particularly preferably 70% by mass or more, from the viewpoint of use for a specific application, when the nonvolatile content in the resin composition is 100% by mass. In general, a resin composition containing a large amount of an inorganic filler tends to have a large warpage, but the resin composition of the present invention containing a combination of components (a) to (C) can effectively suppress warpage even when the component (B) is large. On the other hand, the upper limit of the content of the (B) inorganic filler is not particularly limited, and may be, for example, 98 mass% or less, 95 mass% or less, 90 mass% or less, 85 mass% or less, or the like.

< (C) A benzoxazine compound having an alicyclic structure in the molecule

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

(C) The "benzoxazine compound" in the composition means: a compound having a 3, 4-dihydro-2H-1, 3-benzoxazine ring (hereinafter, may be simply referred to as "dihydrobenzoxazine ring"). In this compound, 2 or more dihydrobenzoxazine rings are preferably present in the molecule. (C) In the component (b), when 2 or more dihydrobenzoxazine rings are present, 2 or more dihydrobenzoxazine rings are preferably bonded to the nitrogen atom of the ring via a linking group. (C) In the component (b), the linking group preferably has an alicyclic structure. Each dihydrobenzoxazinyl ring may have a substituent.

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

[ chemical formula 2]

。

Wherein R independently represents a substituent, X represents a m-valent linking group having an alicyclic structure, m represents an integer of 2 or more, and n represents an integer of 0 to 4.

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

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

The "alkyl group" refers to a straight, branched or cyclic aliphatic saturated hydrocarbon group having a valence of 1. 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 the "alkyl group" include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, cyclopentyl, and cyclohexyl. The substituent of the alkyl group in the "substituted or unsubstituted alkyl group" is not particularly limited, and examples thereof include a halogen atom, a cyano group, an alkoxy group, an alkylcarbonyl group, an aryl group, a heteroaryl group, an aryloxy group, an arylcarbonyl group, an amino group, a nitro group, and a hydroxyl group. The number of substituents is preferably 1 to 3, more preferably 1.

The "alkoxy group" refers to a 1-valent group (alkyl-O-) in which an alkyl group is bonded 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. Examples of the "alkoxy group" include methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, and pentyloxy. The substituent of the alkoxy group in the "substituted or unsubstituted alkoxy group" is not particularly limited, and examples thereof include a halogen atom, a cyano group, an alkoxy group, an alkylcarbonyl group, an aryl group, a heteroaryl group, an aryloxy group, an arylcarbonyl group, an amino group, a nitro group, and a hydroxyl group. The number of substituents is preferably 1 to 3, more preferably 1.

By "alkenyl" is meant a straight, branched or cyclic, 1 valent unsaturated hydrocarbon group having at least 1 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. Examples of the "alkenyl group" include vinyl, 1-propenyl, 2-methyl-1-propenyl, 1-butenyl, 2-butenyl, 3-methyl-2-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-methyl-3-pentenyl, 1-hexenyl, 3-hexenyl, 5-hexenyl, 2-cyclohexenyl and the like. The substituent of the alkenyl group in the "substituted or unsubstituted alkenyl group" is not particularly limited, and examples thereof include a halogen atom, a cyano group, an alkoxy group, an alkylcarbonyl group, an aryl group, a heteroaryl group, an aryloxy group, an arylcarbonyl group, an amino group, a nitro group, a hydroxyl group, and the like. The number of substituents is preferably 1 to 3, more preferably 1.

The "alkylcarbonyl group" refers to a 1-valent group (alkyl-CO-) in which an alkyl group is bonded 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. Examples of the "alkylcarbonyl group" include acetyl, propionyl, butyryl, 2-methylpropionyl, pentanoyl, 3-methylbutyryl, 2-dimethylpropionyl, hexanoyl, heptanoyl, and the like. The substituent of the alkylcarbonyl group in the "substituted or unsubstituted alkylcarbonyl group" is not particularly limited, and examples thereof include a halogen atom, a cyano group, an alkoxy group, an alkylcarbonyl group, an aryl group, a heteroaryl group, an aryloxy group, an arylcarbonyl group, an amino group, a nitro group, a hydroxyl group and the like. The number of substituents is preferably 1 to 3, more preferably 1.

The "aryl" refers to an aromatic hydrocarbon group having a valence of 1. 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 groups, and a phenyl group is preferable. The substituent of the aryl group in the "substituted or unsubstituted aryl group" is not particularly limited, and examples thereof include a halogen atom, a cyano group, an alkyl group, an alkoxy group, an alkylcarbonyl group, an aryl group, a heteroaryl group, an aryloxy group, an arylcarbonyl group, an aralkyl group, an amino group, a nitro group, and a hydroxyl group. The number of substituents is preferably 1 to 3, more preferably 1.

The "heteroaryl group" refers to a 1-valent aromatic heterocyclic group having 1 to 4 heteroatoms selected from an oxygen atom, a nitrogen atom and a sulfur atom in addition to a carbon atom as a ring-constituting atom. The "heteroaryl group" is preferably a monocyclic, bicyclic or tricyclic (preferably monocyclic) aromatic heterocyclic group of five-to twelve-membered (preferably five-or six-membered). Examples of the "heteroaryl group" include furyl, thienyl, pyrrolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, imidazolyl, pyrazolyl, 1,2, 3-oxadiazolyl, 1,2, 4-oxadiazolyl, 1,3, 4-oxadiazolyl, furazanyl, 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, triazinyl and the like. The substituent of the heteroaryl group in the "substituted or unsubstituted heteroaryl 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, an aryloxy group, an arylcarbonyl group, an aralkyl group, an amino group, a nitro group, and a hydroxyl group. The number of substituents is preferably 1 to 3, more preferably 1.

The "aryloxy group" refers to a group having a valence of 1 (aryl-O-) in which an aryl group is bonded 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 the "aryloxy group" include phenoxy, naphthoxy and the like. The substituent of the aryloxy group in the "substituted or unsubstituted aryloxy 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, an aryloxy group, an arylcarbonyl group, an aralkyl group, an amino group, a nitro group, a hydroxyl group, and the like. The number of substituents is preferably 1 to 3, more preferably 1.

The "arylcarbonyl group" refers to a group having a valence of 1 (aryl-CO-) wherein an aryl group is bonded 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. Examples of the "arylcarbonyl group" include a benzoyl group, a 1-naphthoyl group, and a 2-naphthoyl group. The substituent of the arylcarbonyl group in the "substituted or unsubstituted arylcarbonyl 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, an aryloxy group, an arylcarbonyl group, an aralkyl group, an amino group, a nitro group, a hydroxyl group, and the like. The number of substituents is preferably 1 to 3, more preferably 1.

The "aralkyl group" 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 the "aralkyl group" include a benzyl group, a phenethyl group, a 2-naphthylmethyl group 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, an aryloxy group, an arylcarbonyl group, an aralkyl group, an amino group, a nitro group, and a hydroxyl group. The number of substituents is preferably 1 to 3, more preferably 1.

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

In the formula (1), the "m-valent linking group having an alicyclic structure" of X is not particularly limited as long as it has at least 1 alicyclic structure. (C) The number of alicyclic structures in the component (A) is not particularly limited, but is preferably 1 to 5, more preferably 1 to 3, and further preferably 1 or 2. Examples of the ring structure of the alicyclic structure in the component (C) include a cycloalkane ring, a cycloalkene ring, and a compound obtained by substituting at least 1 of the skeleton carbon atoms in these rings with a group selected from-O-, -S-, -SO₂Aliphatic heterocycles derived from a heteroatom-containing group of- (Y-O) -, -NH-, -CO-, -CONH-, -NHCO-, -COO-, and-OCO-, etc., and among them, cycloalkane rings are preferable.

The term "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 the "cycloalkane ring" include monocycloparaffin rings such as cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, and cyclooctane ring; a bicycloalkane ring such as a decahydronaphthalene ring, a norbornane ring or the like; a spiroalkane ring such as a spirononane ring, and the like.

The "cycloalkene ring" refers to a monocyclic or polycyclic aliphatic saturated hydrocarbon ring having at least 1 carbon-carbon double bond. The "cycloolefin ring" is preferably a cycloolefin ring having 3 to 10 carbon atoms. Examples of the "cycloalkane ring" include monocyclic olefin rings such as a cyclobutene ring, a cyclopropene ring, a cyclohexene ring, a cyclohexadiene ring, a cycloheptene ring, and a cyclooctene ring; a bicycloalkene ring such as a norbornene ring or a norbornadiene ring; a spiroolefin ring such as a spirononene ring, and the like.

The number of backbone atoms of the "m-valent linking group having an alicyclic structure" is preferably 3 to 200, more preferably 3 to 100, still more preferably 3 to 50, and particularly preferably 3 to 20. The skeleton atom may be an atom 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 saturated aliphatic group containing a ring. Here, as the substituent of the ring-containing saturated aliphatic group in the "substituted or unsubstituted m-valent ring-containing saturated aliphatic group", the same group as that of the substituent of R can be mentioned, and it is preferably unsubstituted. "saturated aliphatic group containing a ring" includes: a saturated hydrocarbon group containing at least 1 cycloalkane ring (hereinafter referred to as "ring-containing saturated hydrocarbon group"); and replacement of at least 1 of its backbone carbon atoms by a group selected from-O-, -S-, -SO₂A group derived from a heteroatom-containing group of- (O-X-O) -, -NH-, -CO-, -CONH-, -NHCO-, -COO-, and-OCO- (hereinafter referred to as a "saturated hydrocarbon heteroatom-substituted group containing a ring").

In the formula (1), m represents an integer of 2 or more, preferably 2 or 3, and more preferably 2. Thus, in a more preferred embodiment where m is 2, X is preferably a substituted or unsubstituted 2-valent ring-containing saturated aliphatic group. The two terminal atoms of the "saturated aliphatic group having a 2-valent ring" are preferably arbitrary carbon atoms, and more preferably carbon atoms constituting the ring.

Specific examples of the "2-valent saturated aliphatic group containing a ring" in X of the formula (1) include-cHex-, -cPent-, -DECAL-, -NORBOR-, -cHex-cHex-, -cPent-cPent-, -cHex-CH₂-cHex-、-cPent-CH₂-cPent-、-cHex-CH₂-CH₂-cHex-、-cPent-CH₂-CH₂-cPent-、-cHex-CH₂-CH₂-CH₂-cHex-、-cPent-CH₂-CH₂-CH₂-cPent-、-cHex-CH(CH₃)-cHex-、-cPent-CH(CH₃)-cPent-、-cHex-CH(CH₂CH₃)-cHex-、-cPent-CH(CH₂CH₃)-cPent-、-cHex-C(CH₃)₂-cHex-、-cPent-C(CH₃)₂-cPent-、-cHex-C(CH₂CH₃)₂-cHex-、-cPent-C(CH₂CH₃)₂-cPent-and the like 2-valent saturated hydrocarbon radicals containing rings; -cHex-O-cHex-, -cPent-O-cPent-, -cHex-O-CH₂-CH₂-O-cHex-、-cPent-O-CH₂-CH₂-O-cPent-、-cHex-S-cHex-、-cPent-S-cPent-、-cHex-S-CH₂-CH₂-S-cHex-、-cPent-S-CH₂-CH₂-S-cPent-、-cHex-CO-cHex-、-cPent-CO-cPent-、-cHex-SO₂-cHex-、-cPent-SO₂A 2-valent saturated hydrocarbon heteroatom-containing substituent group such as-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 the like. Here, "cHex" represents a1, 4-cyclohexylene group, a1, 3-cyclohexylene group, or a1, 2-cyclohexylene group. "cPent" means 1, 3-cyclopentylene, 1, 2-cyclopentylene. "DECAL" represents a 2-valent decahydronaphthyl group, and includes 2, 6-bicyclo [4.4.0]Decylene (decylene), 2, 7-bicyclo [4.4.0]]Decylene, and the like. "NORBOR" represents a 2-valent norbornyl group, and includes 2, 5-bicyclo [2.2.1]Heptylene (heptylene), 2, 6-bicyclo [2.2.1 ]]Heptylene, and the like.

(C) The alicyclic structure of the component (A) is preferably a cyclohexane ring structure. Namely, (C) isIt is preferable that the molecule has 1 or more cyclohexane ring structures. The cyclohexane ring structure may be part of a bicycloalkane ring structure. In this case, preferable examples of the "saturated aliphatic group having a ring with a valence of 2" in X of the formula (1) include-cHex-, -DECAL-, -NORBOR-, -cHex-, -cHex-CH₂-cHex-、-cHex-CH₂-CH₂-cHex-、-cHex-CH₂-CH₂-CH₂-cHex-、-cHex-CH(CH₃)-cHex-、-cHex-CH(CH₂CH₃)-cHex-、-cHex-C(CH₃)₂-cHex-、-cHex-C(CH₂CH₃)₂-cHex-equivalent 2-valent saturated hydrocarbon radicals containing rings; -cHex-O-cHex-, -cHex-O-CH₂-CH₂-O-cHex-、-cHex-S-cHex-、-cHex-S-CH₂-CH₂-S-cHex-、-cHex-CO-cHex-、-cHex-SO₂A 2-valent saturated hydrocarbon heteroatom-containing substituent group having a ring such as-cHex-, -cHex-CONH-cHex-, -cHex-NHCO-cHex-, -cHex-COO-cHex-, -cHex-OCO-cHex-, and the like.

(C) The benzoxazine compound having an alicyclic structure in the molecule is particularly preferably a compound represented by formula (2).

[ chemical formula 3]

。

R¹And R²The "substituent(s)" of (b) is the same as the substituent(s) for R in the formula (1). s and t are each independently preferably 0 or 1, particularly preferably 0.

The term "alkylene group" refers to a linear, branched or cyclic aliphatic saturated hydrocarbon group having a valence of 2. The number of carbon atoms of the "alkylene group having 1 to 6 carbon atoms" is preferably 1 to 3. Examples of the "alkylene group having 1 to 6 carbon atoms" include, for example, -CH₂-、-CH₂-CH₂-、-CH(CH₃)-、-CH₂-CH₂-CH₂-、-CH₂-CH(CH₃)-、-CH(CH₃)-CH₂-、-C(CH₃)₂-、-CH₂-CH₂-CH₂-CH₂-、-CH₂-CH₂-CH(CH₃)-、-CH₂-CH(CH₃)-CH₂-、-CH(CH₃)-CH₂-CH₂-、-CH₂-C(CH₃)₂-、-C(CH₃)₂-CH₂-, -cHex-, etc.

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

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

(C) The content of the benzoxazine compound having an alicyclic structure in the molecule is not particularly limited, and is preferably 0.1% by mass or more, more preferably 1% by mass or more, further 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, when the nonvolatile components other than the component (B) in the resin composition are 100% by mass. From the viewpoint of remarkably obtaining the desired effect of the present invention, the upper limit thereof is preferably 30% by mass or less, more preferably 20% by mass or less, further 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) an elastomer as an optional component. By using the elastomer (D), the flexibility of the cured product of the resin composition can be improved, and the elastic modulus can be reduced.

In the present invention, the elastomer (D) is a resin having flexibility, and is an amorphous resin component dissolved in an organic solvent, and is preferably a resin having rubber elasticity or a resin exhibiting rubber elasticity by polymerizing with other components. Examples of the rubber elasticity include: a resin exhibiting an elastic modulus of 1GPa or less when subjected to a tensile test at a temperature of 25 ℃ and a humidity of 40% RH in accordance with Japanese Industrial standards (JIS K7161).

In one embodiment, the component (D) is preferably a resin having 1 or more structures selected from a polybutadiene structure, a polysiloxane structure, a poly (meth) acrylate structure, a polyalkylene structure, a polyalkyleneoxy structure, a polyisoprene structure, a polyisobutylene structure, and a polycarbonate structure in a molecule, and more preferably a resin having 1 or more structures selected from a polybutadiene structure and a polycarbonate structure from the viewpoint of obtaining a material having flexibility. The "(meth) acrylate" means methacrylate and acrylate.

In another embodiment, component (D) is preferably 1 or more selected from the group consisting of a resin having a glass transition temperature (Tg) of 25 ℃ or lower and a resin that is liquid at 25 ℃ or lower. The glass transition temperature (Tg) of the resin is preferably 20 ℃ or lower, more preferably 15 ℃ or lower. The lower limit of the glass transition temperature is not particularly limited, and may be usually-15 ℃ or higher. The resin that is liquid at 25 ℃ is preferably a resin that is liquid at 20 ℃ or lower, and more preferably a resin that is liquid at 15 ℃ or lower.

In a more preferred embodiment, the component (D) is 1 or more selected from the group consisting of resins having a glass transition temperature of 25 ℃ or lower and being liquid at 25 ℃, and has 1 or more structures selected from the group consisting of a polybutadiene structure, a polysiloxane structure, a poly (meth) acrylate structure, a polyalkylene structure, a polyalkyleneoxy structure, a polyisoprene structure, a polyisobutylene structure, and a polycarbonate structure in a molecule.

The polybutadiene structure includes not only a structure obtained by polymerizing butadiene but also a structure obtained by hydrogenating the structure. In addition, the butadiene structure may be partially hydrogenated or entirely hydrogenated. In addition, the polybutadiene structure may be contained in the main chain or may be contained in the side chain in the component (D).

Preferred examples of the polybutadiene resin include resins having a hydrogenated polybutadiene skeleton, polybutadiene resins having hydroxyl groups, polybutadiene resins having phenolic hydroxyl groups, polybutadiene resins having carboxyl groups, polybutadiene resins having acid anhydride groups, polybutadiene resins having epoxy groups, polybutadiene resins having isocyanate groups, and polybutadiene resins having urethane groups. Among these, polybutadiene resins containing phenolic hydroxyl groups are more preferable. Here, the "resin having a hydrogenated polybutadiene skeleton" refers to a resin in which at least a part of the polybutadiene skeleton is hydrogenated, and is not necessarily a resin in which the polybutadiene skeleton is completely hydrogenated. Examples of the resin having a hydrogenated polybutadiene skeleton include epoxy resins having a hydrogenated polybutadiene skeleton. Examples of the polybutadiene resin containing a phenolic hydroxyl group include resins having a polybutadiene structure and a phenolic hydroxyl group.

Specific examples of the polybutadiene resin having a polybutadiene structure in the molecule include "Ricon 657" (polybutadiene containing an epoxy group), "Ricon 130MA 8", "Ricon 130MA 13", "Ricon 130MA 20", "Ricon 131MA 5", "Ricon 131MA 10", "Ricon 131MA 17", "Ricon 131MA 20", "Ricon 184MA 6" (polybutadiene containing an acid anhydride group), "GQ-1000" (polybutadiene containing a hydroxyl group or a carboxyl group introduced), "G-1000", "G-2000", "G-3000" (both-terminal hydroxyl polybutadiene), "GI-1000", "GI-2000", "GI-3000" (both-terminal hydroxyl-hydrogenated polybutadiene), and "PB 0", "PB 4700" (polybutadiene epoxy compound), and "Epofriend a", "1005 and" Epofriend a1010 ", which are available from Cray Valley corporation, "Epofriend A1020" (epoxy compound of block copolymer of styrene and butadiene with styrene), "FCA-061L" (hydrogenated polybutadiene skeleton epoxy compound) manufactured by Nagase ChemteX, and "R-45 EPT" (polybutadiene skeleton epoxy compound).

Further, as a preferred example of the polybutadiene resin, there is also mentioned a linear polyimide made from hydroxyl-terminated polybutadiene, a diisocyanate compound and a polybasic acid or an anhydride thereof (polyimide described in jp 2006-a-37083 and international publication No. 2008/153208). The content of the polybutadiene structure in the polyimide resin is preferably 60 to 95% by mass, and more preferably 75 to 85% by mass. The details of the polyimide resin can be found in Japanese patent application laid-open No. 2006-37083 and International publication No. 2008/153208, which are incorporated herein by reference.

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 weight of the hydroxyl-terminated polybutadiene is preferably 250 to 1,250.

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

Examples of the polybasic acid or anhydride thereof include ethylene glycol ditrimellitic acid, pyromellitic acid, benzophenone tetracarboxylic acid, biphenyl tetracarboxylic acid, naphthalene tetracarboxylic acid, tetrabasic acids such as 5- (2, 5-dioxotetrahydrofuryl) -3-methyl-cyclohexene-1, 2-dicarboxylic acid and 3,3 '-4, 4' -diphenylsulfone tetracarboxylic acid, anhydrides thereof, tribasic acids such as trimellitic acid and cyclohexanetricarboxylic acid, anhydrides thereof, and 1,3,3a,4,5,9 b-hexahydro-5- (tetrahydro-2, 5-dioxo-3-furanyl) -naphtho (1,2-C) furan-1, 3-dione.

The resin having a polybutadiene structure may contain a polystyrene structure having a structure obtained by polymerizing styrene.

As a specific example of the polystyrene resin which is a resin having a polystyrene structure in the molecule, examples thereof include a styrene-butadiene-styrene block copolymer (SBS), a styrene-isoprene-styrene block copolymer (SIS), a styrene-ethylene-butylene-styrene block copolymer (SEBS), a styrene-ethylene-propylene-styrene block copolymer (SEPS), a styrene-ethylene-propylene-styrene block copolymer (SEEPS), a styrene-butadiene-butylene-styrene block copolymer (SBBS), a styrene-butadiene diblock copolymer, a hydrogenated styrene-butadiene block copolymer, a hydrogenated styrene-isoprene block copolymer, and a hydrogenated styrene-butadiene random copolymer.

As the polystyrene resin, commercially available products can be used, and examples thereof include hydrogenated styrene-based thermoplastic elastomers "H1041", "Tuftec H1043", "Tuftec P2000", "Tuftec MP 10" (manufactured by Asahi Kasei corporation); epoxidized styrene-butadiene thermoplastic elastomers "Epofriend AT 501" and "CT 310" (manufactured by celluloid corporation); a modified styrene elastomer "SEPTON HG 252" (manufactured by clony corporation) having a hydroxyl group; a modified styrene-based elastomer "Tuftec N503M" having a carboxyl group, a modified styrene-based elastomer "Tuftec N501" having an amino group, and a modified styrene-based elastomer "Tuftec M1913" having an acid anhydride group (manufactured by asahi chemicals); an unmodified styrene-based elastomer "SEPTON S8104" (manufactured by Coly corporation), and the like. (C) The components can be used singly or in combination of 2 or more.

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

Specific examples of the silicone resin as a resin having a polysiloxane structure in the molecule include "SMP-2006", "SMP-2003 PGMEA", "SMP-5005 PGMEA" manufactured by shinylen silicone corporation, and linear polyimide (international publication No. 2010/053185) using an amino-terminated silicone and a tetrabasic acid anhydride as raw materials.

The poly (meth) acrylate structure is a structure obtained by polymerizing acrylic acid or acrylic acid ester, and includes a structure obtained by polymerizing methacrylic acid or methacrylic acid ester. The (meth) acrylate structure may be contained in the main chain or may be contained in the side chain in the component (D).

Preferable examples of the poly (meth) acrylate resin as the resin having a poly (meth) acrylate structure in the molecule include a hydroxyl group-containing poly (meth) acrylate resin, a phenolic hydroxyl group-containing poly (meth) acrylate resin, a carboxyl group-containing poly (meth) acrylate resin, an acid anhydride group-containing poly (meth) acrylate resin, an epoxy group-containing poly (meth) acrylate resin, an isocyanate group-containing poly (meth) acrylate resin, a urethane group-containing poly (meth) acrylate resin, and the like.

Specific examples of the poly (meth) acrylate resin include TEISANRESIN ' SG-70L ', SG-708-6 ', WS-023 ', SG-700AS ', SG-280TEA ' manufactured by Nagase ChemteX, having an acid value of 5 to 34mgKOH/g, a weight average molecular weight of 40 to 90 ten thousand, and a Tg of-30 to 5 deg.C, ' SG-80H ', SG-80H-3 ', and SG-P3 ' (an epoxy group-containing acrylate copolymer resin having an epoxy equivalent of 4761 to 14285g/eq, a weight average molecular weight of 35 to 85 ten thousand, and a Tg of 11 to 12 deg.C), ' SG-600TEA ' and SG-790 ' (a hydroxyl group-containing acrylate copolymer resin having a hydroxyl group of 20 to 40mgKOH/g, and a weight average molecular weight of 50 to 120 ten thousand, tg of-37 ℃ to-32 ℃), "ME-2000", "W-116.3" (carboxyl group-containing acrylate copolymer resin), "W-197C" (hydroxyl group-containing acrylate copolymer resin), "KG-25" and "KG-3000" (epoxy group-containing acrylate copolymer resin) manufactured by Kogyo industries, Ltd.

The polyalkylene structure preferably has a predetermined 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, and particularly preferably 6 or less. In addition, the polyalkylene structure may be contained in the main chain or in the side chain in the component (D).

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

Specific examples of the polyalkylene resin as a resin having a polyalkylene structure in the molecule and the polyalkylene oxide resin as a resin having a polyalkylene oxide structure in the molecule include "PTXG-1000", "PTXG-1800" manufactured by Asahi chemical fibers, and "YX-7180" (a resin having an alkylene structure having an ether bond) manufactured by Mitsubishi chemical corporation, "EXA-4850-.

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

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

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

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

Specific examples of the polycarbonate resin include "T6002" and "T6001" (polycarbonate diols) manufactured by Asahi Kasei Chemicals, and "C-1090", "C-2090" and "C-3090" (polycarbonate diols) manufactured by Colorado.

Further, as a preferable example of the polycarbonate resin, there can be mentioned a linear polyimide obtained from a hydroxyl-terminated polycarbonate, a diisocyanate compound and a polybasic acid or an acid anhydride thereof. The linear polyimide has a urethane structure and a polycarbonate structure. The content of the polycarbonate structure in the polyimide resin is preferably 60 to 95% by mass, and more preferably 75 to 85% by mass. The details of the polyimide resin can be found in International publication No. 2016/129541, which is incorporated herein.

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 weight of the hydroxyl-terminated polycarbonate is preferably 250 to 1,250.

(D) The component (B) preferably further has an imide structure. By having an imide structure, the heat resistance of the component (D) can be improved, and the crack resistance can be effectively improved.

(D) The component (C) may have any of a linear, branched and cyclic structure, but is preferably linear.

(D) Component (a) preferably further has a functional group reactive with component (a). The functional group also includes a reactive group that appears upon heating. By providing component (D) with a functional group, the mechanical strength of the cured product of the resin composition can be improved.

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 these, from the viewpoint of remarkably obtaining the effect of the present invention, the functional group preferably has 1 or more functional groups selected from a hydroxyl group, an acid anhydride group, a phenolic hydroxyl group, an epoxy group, an isocyanate group and a carbamate group, and particularly preferably has a phenolic hydroxyl group.

(D) The components can be used singly or in combination of 2 or more.

From the viewpoint of exhibiting flexibility, the component (D) is preferably high in molecular weight. (D) The specific number average molecular weight Mn of the component (a) is preferably 4000 or more, more preferably 4500 or more, further preferably 5000 or more, particularly preferably 5500 or more, preferably 100000 or less, more preferably 95000 or less, and particularly preferably 90000 or less. (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).

From the viewpoint of flexibility, the specific weight average molecular weight of the component (D) is preferably 5500 to 100000, more preferably 10000 to 90000, and still more preferably 15000 to 80000. (D) The weight average molecular weight of the component (a) is a weight average molecular weight in terms of polystyrene measured by a Gel Permeation Chromatography (GPC) method.

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

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

When the elastomer (D) is contained, the content of the elastomer (D) is not particularly limited, and when the nonvolatile components other than the component (B) in the resin composition are 100 mass%, from the viewpoint of further obtaining flexibility, the content is preferably 10 mass% or more, more preferably 30 mass% or more, further preferably 40 mass% or more, and particularly preferably 50 mass% or more. From the viewpoint of remarkably obtaining the desired effect of the present invention, the upper limit of the content of the (D) elastomer is preferably 75% by mass or less, more preferably 70% by mass or less, further preferably 65% by mass or less, and particularly preferably 60% by mass or less.

(E) curing agent

The resin composition of the present invention may contain (E) a curing agent as an optional component. The epoxy resin (a) can be easily cured by containing the curing agent (E).

The curing agent (E) is not particularly limited as long as it has a function of curing an epoxy resin, and examples thereof include phenol-based curing agents, naphthol-based curing agents, acid anhydride-based curing agents, active ester-based curing agents, benzoxazine-based curing agents, cyanate ester-based curing agents, and carbodiimide-based curing agents. The curing agent may be used alone in 1 kind, or in combination of 2 or more kinds. The curing agent (E) of the resin composition of the present invention is preferably selected from the group consisting of phenol-based curing agents, naphthol-based curing agents, and active ester-based curing agents, from the viewpoint of remarkably obtaining the desired effects of the present invention. In one embodiment, the curing agent (E) preferably contains an active ester curing agent.

As the phenol curing agent and the naphthol curing agent, a phenol curing agent having a novolac structure or a naphthol curing agent having a novolac structure is preferable from the viewpoint of heat resistance and water resistance. From the viewpoint of adhesion to an adherend, a nitrogen-containing phenol curing agent or a nitrogen-containing naphthol curing agent is preferable, and a triazine skeleton-containing phenol curing agent or a triazine skeleton-containing naphthol curing agent is more preferable. Among them, a phenol novolac resin containing a triazine skeleton is preferable from the viewpoint of satisfying heat resistance, water resistance, and adhesion at a high level. Specific examples of the phenol-based curing agent and the naphthol-based curing agent include "MEH-7700", "MEH-7810", "MEH-7851" and "MEH-8000H" manufactured by Minghu Kaisha corporation; "NHN", "CBN" and "GPH" manufactured by Nippon chemical Co., Ltd.; "SN-170", "SN-180", "SN-190", "SN-475", "SN-485", "SN-495V", "SN-375", "SN-395", manufactured by Xinri Cingjin chemical company; "TD-2090", "TD-2090-60M", "LA-7052", "LA-7054", "LA-1356", "LA-3018-50P", "EXB-9500", "HPC-9500", "KA-1160", "KA-1163", "KA-1165", manufactured by DIC; GDP-6115L, GDP-6115H, ELPC75, etc., manufactured by Rongche chemical Co.

Examples of the acid anhydride-based curing agent include a curing agent having 1 or more acid anhydride groups in 1 molecule. Specific examples of the acid anhydride curing agent include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, hydrogenated methylnadic anhydride, trialkyltetrahydrophthalic anhydride, dodecenylsuccinic anhydride, 5- (2, 5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1, 2-dicarboxylic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, naphthalene tetracarboxylic dianhydride, oxydiphthalic dianhydride, 3,3 '-4, 4' -diphenylsulfone tetracarboxylic dianhydride, 1,3,3a,4,5,9 b-hexahydro-5- (tetrahydro-2, 5-dioxo-3-furyl) -naphtho [1,2-C ] furan-1, 3-dione, ethylene glycol bis (trimellitic anhydride ester), styrene-maleic acid resin obtained by copolymerizing styrene with maleic acid, and other polymer-type acid anhydrides. As commercially available products of the acid anhydride-based curing agent, "HNA-100" and "MH-700" manufactured by Nissan chemical and chemical Co., Ltd.

The active ester-based curing agent is not particularly limited, and compounds having 2 or more ester groups having high reactivity in 1 molecule, such as phenol esters, thiophenol esters, N-hydroxylamine esters, and esters of heterocyclic hydroxy compounds, can be preferably used. The active ester curing agent is preferably obtained by a condensation reaction of a carboxylic acid compound and/or a thiocarboxylic acid compound with a hydroxyl compound and/or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester-based curing agent obtained from a carboxylic acid compound and a hydroxyl compound is preferable, and an active ester-based curing agent obtained from a carboxylic acid compound and a phenol compound and/or a naphthol compound is more preferable. Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. Examples of the phenol compound or naphthol compound include hydroquinone, resorcinol, bisphenol a, bisphenol F, bisphenol S, phenolphthalin, methylated bisphenol a, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α -naphthol, β -naphthol, 1, 5-dihydroxynaphthalene, 1, 6-dihydroxynaphthalene, 2, 6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucinol, benzenetriol, dicyclopentadiene type diphenol compound, phenol novolak and the like. Here, the "dicyclopentadiene type diphenol compound" refers to a diphenol compound obtained by condensing 2 molecules of phenol on1 molecule of dicyclopentadiene.

Specifically, an active ester compound containing a dicyclopentadiene type diphenol structure, an active ester compound containing a naphthalene structure, an active ester compound containing an acetyl compound of phenol novolac, and an active ester compound containing a benzoyl compound of phenol novolac are preferable, and among them, an active ester compound containing a naphthalene structure and an active ester compound containing a dicyclopentadiene type diphenol structure are more preferable. The "dicyclopentadiene type diphenol structure" refers to a 2-valent structural unit formed from phenylene-dicyclopentanalene-phenylene.

As the commercially available product of the active ester-based curing agent, there may be mentioned "EXB 9451", "EXB 9460S", "HPC-8000H", "HPC-8000-65T", "HPC-8000H-65 TM", "EXB-8000L-65 TM" (manufactured by DIC Co., Ltd.) as an active ester compound having a dicyclopentadiene type diphenol structure; "EXB 9416-70 BK" and "EXB 8150-65T" (manufactured by DIC) as active ester compounds having a naphthalene structure; "DC 808" (manufactured by mitsubishi chemical corporation) which is an active ester compound containing an acetylate of phenol novolac; "YLH 1026" (manufactured by mitsubishi chemical corporation) which is an active ester compound including a benzoyl compound of phenol novolac; "DC 808" (manufactured by mitsubishi chemical corporation) as an active ester-based curing agent which is an acetylated product of phenol novolac; "YLH 1026" (manufactured by mitsubishi chemical corporation), "YLH 1030" (manufactured by mitsubishi chemical corporation), and "YLH 1048" (manufactured by mitsubishi chemical corporation), which are active ester-based curing agents for benzoylates of phenol novolak; and so on.

Specific examples of the benzoxazine-based curing agent include "JBZ-OP 100D" and "ODA-BOZ" manufactured by JFE chemical company; "HFB 2006M" available from Showa Polymer Co; "P-d" and "F-a" manufactured by four national chemical industries, Inc.

Examples of the cyanate ester curing agent include bifunctional cyanate ester resins such as bisphenol a dicyanate, polyphenol cyanate ester (oligo (3-methylene-1, 5-phenylene cyanate)), 4 '-methylenebis (2, 6-dimethylphenyl cyanate), 4' -ethylenediphenyldicyanate, hexafluorobisphenol a dicyanate, 2-bis (4-cyanate) phenylpropane, 1-bis (4-cyanate phenylmethane), bis (4-cyanate-3, 5-dimethylphenyl) methane, 1, 3-bis (4-cyanate-phenyl-1- (methylethylidene)) benzene, bis (4-cyanate-phenyl) sulfide, and bis (4-cyanate-phenyl) ether, and polyfunctional cyanate ester resins derived from phenol novolac, cresol novolac, and the like, Prepolymers obtained by partially triazinating these cyanate ester resins, and the like. Specific examples of the cyanate ester-based curing agent include "PT 30" and "PT 60" (both of which are phenol novolac type polyfunctional cyanate ester resins), "BA 230" and "BA 230S 75" (prepolymers obtained by triazinating a part or all of bisphenol a dicyanate ester to form a trimer), which are manufactured by Lonza Japan.

Specific examples of the carbodiimide-based curing agent include "V-03" and "V-07" manufactured by Nisshinbo chemical Co.

In the case where the curing agent is contained, the amount ratio of the epoxy resin to the curing agent is represented by [ total number of epoxy groups of epoxy resin ]: the ratio of [ total number of reactive groups of the curing agent ] is preferably in the range of 1:0.2 to 1:2, more preferably 1:0.3 to 1:1.5, and further preferably 1:0.4 to 1: 1.2. Here, the reactive group of the curing agent means an active hydroxyl group, an active ester group, and the like, and varies depending on the kind of the curing agent. The total number of epoxy groups in the epoxy resin is a value obtained by summing the values obtained by dividing the mass of the nonvolatile components of the respective epoxy resins by the epoxy equivalent weight for all the epoxy resins, and the total number of reactive groups in the curing agent is a value obtained by dividing the mass of the nonvolatile components of the respective curing agents by the equivalent weight of the reactive groups for all the curing agents. When the amount ratio of the epoxy resin to the curing agent is in the above range, the heat resistance of the obtained cured product is further improved.

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

(F) curing Accelerator

The resin composition of the present invention may contain (F) a curing accelerator as an optional component. (F) The curing accelerator has a function of accelerating curing of the epoxy resin (a).

Examples of the curing accelerator (F) include phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, guanidine-based curing accelerators, and metal-based curing accelerators. Among them, preferred are phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators and metal-based curing accelerators, and more preferred are amine-based curing accelerators, imidazole-based curing accelerators and metal-based curing accelerators. The curing accelerator may be used alone in 1 kind, or in combination of 2 or more kinds.

Examples of the phosphorus-based curing accelerator include triphenylphosphine, a phosphonium borate compound, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, (4-methylphenyl) triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate and the like.

Examples of the amine-based curing accelerator include trialkylamines such as triethylamine and tributylamine, 4-Dimethylaminopyridine (DMAP), benzyldimethylamine, 2,4, 6-tris (dimethylaminomethyl) phenol, and 1, 8-diazabicyclo (5,4,0) -undecene, with 4-dimethylaminopyridine being preferred.

Examples of the imidazole-based curing accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1, 2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 2-heptadecylimidazole, 1, 2-dimethylimidazole, 2-ethylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 2-cyanoethyl-2, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2, 4-diamino-6- [2 ' -methylimidazolyl- (1 ') ] -ethyl-s-triazine, 2, 4-diamino-6- [2 ' -undecylimidazolyl- (1 ') ] -ethyl-s-triazine, 2, 4-diamino-6- [2 ' -ethyl-4 ' -methylimidazolyl- (1 ') ] -ethyl-s-triazine, 2, 4-diamino-6- [2 ' -methylimidazolyl- (1 ') ] -ethyl-s-triazine isocyanuric acid adduct, and mixtures thereof, Imidazole compounds such as 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4, 5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2, 3-dihydro-1H-pyrrolo [1,2-a ] benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline and 2-phenylimidazoline, and adducts of imidazole compounds with epoxy resins.

As the imidazole-based curing accelerator, commercially available products can be used, and examples thereof include "P200-H50" manufactured by Mitsubishi chemical corporation.

Examples of the guanidine-based curing accelerator include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1- (o-tolyl) guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5, 7-triazabicyclo [4.4.0] dec-5-ene, 7-methyl-1, 5, 7-triazabicyclo [4.4.0] dec-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1-dimethylbiguanide, 1-diethylbiguanide, 1-cyclohexylbiguanide, 1-allylbiguanide, 1-phenylbiguanide, 1- (o-tolyl) biguanide and the like.

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

When the (F) curing accelerator is contained, the content of the (F) curing accelerator is not particularly limited, and is preferably 0.001 mass% or more, more preferably 0.01 mass% or more, further preferably 0.05 mass% or more, and particularly preferably 0.1 mass% or more, based on 100 mass% of nonvolatile components other than the component (B) in the resin composition. (F) The upper limit of the content of the curing accelerator is preferably 5% by mass or less, more preferably 2% by mass or less, further preferably 1% by mass or less, and 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.

Examples of the organic solvent include ketone solvents such as acetone, methyl ethyl ketone, and cyclohexanone; ester solvents such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, carbitol acetate, diethylene glycol monoethyl ether acetate, and γ -butyrolactone; cellosolve and carbitol solvents such as butyl carbitol; aromatic hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, and trimethylbenzene; amide solvents such as dimethylformamide, dimethylacetamide (DMAc), and N-methylpyrrolidone; alcohol solvents such as methanol, ethanol, and 2-methoxypropanol; hydrocarbon solvents such as cyclohexane and methylcyclohexane. The organic solvent may be used alone in 1 kind, or may be used in combination in 2 or more kinds at an arbitrary ratio.

< (H) other additives

The resin composition may contain other additives as optional components in addition to the above components. Examples of such additives include organic fillers, thickeners, defoaming agents, leveling agents, adhesion imparting agents, polymerization initiators, and flame retardants. These additives may be used alone in 1 kind, or in combination of 2 or more kinds. The respective contents may be appropriately set by those skilled in the art.

< method for producing resin composition >

In one embodiment, the resin composition of the present invention can be produced, for example, by a method comprising the steps of: the resin composition is obtained by adding and mixing (a) an epoxy resin, (B) an inorganic filler, (C) a benzoxazine compound having 1 or more alicyclic structures in the molecule, (D) an elastomer used as needed, (E) a curing agent used as needed, (F) a curing accelerator used as needed, (G) an organic solvent used as needed, and (H) other additives used as needed, in a reaction vessel in an arbitrary order and/or partially or completely at the same time.

In the above-mentioned step, the temperature in the process of adding each component may be appropriately set, and heating and/or cooling may be performed temporarily or throughout the process of adding each component. During the addition of the ingredients, stirring or shaking may be performed. Further, it is preferable that the method further comprises, after the step, the step of: the resin composition is stirred and uniformly dispersed by using a stirring device such as a mixer.

< Property of resin composition >

The resin composition of the present invention contains (a) an epoxy resin, (B) an inorganic filler, and (C) a benzoxazine compound having 1 or more alicyclic structures in the molecule, and therefore, the elastic modulus of a cured product can be reduced, and thus, warpage suppression and excellent adhesion can be simultaneously achieved.

In one embodiment, the tensile elastic modulus (GPa) at 23 ℃ measured according to JIS K7127 of a cured product of the resin composition of the present invention is preferably 15GPa or less, more preferably 12GPa or less, further preferably 11GPa or less, and particularly preferably 10.5GPa or less, from the viewpoint of relaxing stress generated at the time of heat curing for reducing warpage.

In one embodiment, the peel strength (peelingstrength) between the cured product of the resin composition of the present invention and the copper foil may be preferably 0.25kgf/cm or more, more preferably 0.3kgf/cm or more, even more preferably 0.35kgf/cm or more, and particularly preferably 0.38kgf/cm or more, when the peel strength is measured at room temperature under a load of 35mm when peeled at a speed of 50 mm/min in the vertical direction in accordance with JIS C6481, for example.

In one embodiment, the warpage amount in the case of a substrate formed of the resin composition layer (thickness of 100 μm) of the present invention and a 12-inch silicon wafer heat-treated at 180 ℃ for 90 minutes may be preferably 4mm or less, more preferably 3mm or less, still more preferably 2.5mm or less, and particularly preferably 2.3mm or less, 2.2mm or less, 2.1mm or less, or 2mm or less.

< use of resin composition >

The resin composition of the present invention can be suitably used as a resin composition for insulation applications, particularly a resin composition for forming an insulation layer. Specifically, the resin composition (resin composition for forming an insulating layer for forming a conductor layer) for forming the insulating layer for forming a conductor layer (the conductor layer is formed on the insulating layer, and the conductor layer includes a rewiring layer) can be suitably used. In addition, in the printed wiring board described later, the resin composition for forming an insulating layer of the printed wiring board (resin composition for forming an insulating layer of the printed wiring board) can be suitably used. The resin composition of the present invention can be used in a wide range of applications requiring a resin composition, such as a resin sheet, a sheet-like laminate material such as a prepreg, a solder resist, an underfill material, a die bonding material, a semiconductor sealing material, a hole filling resin, and a component embedding resin.

For example, when a semiconductor chip package is manufactured through the following steps (1) to (6), the resin composition of the present invention can be suitably used as a resin composition for forming a "rewiring formation layer as an insulating layer for forming a rewiring layer" (a resin composition for forming a rewiring formation layer) and a resin composition for sealing a semiconductor chip (a resin composition for sealing a semiconductor chip). In manufacturing the semiconductor chip package, a rewiring layer may be further formed on the sealing layer;

(1) a step of laminating a temporary fixing film on the base material,

(2) a step of temporarily fixing the semiconductor chip on the temporary fixing film,

(3) a step of forming a sealing layer on the semiconductor chip,

(4) a step of peeling the base material and the temporary fixing film from the semiconductor chip,

(5) a step of forming a rewiring formation layer as an insulating layer on the surface of the semiconductor chip from which the base material and the temporary fixing film are peeled, and

(6) and forming a rewiring layer as a conductor layer on the rewiring-forming layer.

Further, the resin composition of the present invention can be suitably used also in the case where a printed wiring board is a component-embedded circuit board, since it forms an insulating layer having good component embeddability.

< sheet-like laminated Material >

The resin composition of the present invention can be used by coating in the form of varnish, but it is generally preferable to use the resin composition in the form of a sheet-like laminate containing the resin composition industrially.

As the sheet-like laminate, a resin sheet and a prepreg as shown below are preferable.

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

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

When a film made of a plastic material is used as the support, examples of the plastic material include polyesters such as polyethylene terephthalate (hereinafter, sometimes simply referred to as "PET"), polyethylene naphthalate (hereinafter, sometimes simply referred to as "PEN"), acrylic polymers such as polycarbonate (hereinafter, sometimes simply referred to as "PC"), polymethyl methacrylate (PMMA), cyclic polyolefins, triacetyl cellulose (TAC), polyether sulfide (PES), polyether ketone, and polyimide. Among them, polyethylene terephthalate and polyethylene naphthalate are preferable, and particularly, inexpensive polyethylene terephthalate is preferable.

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

The surface of the support to be bonded to the resin composition layer may be subjected to matting treatment, corona treatment, or antistatic treatment.

In addition, as the support, a support with a release layer having a release layer on a surface to be bonded to the resin composition layer can be used. Examples of the release agent used for the release layer of the support with a release layer include 1 or more release agents selected from the group consisting of alkyd resins, polyolefin resins, polyurethane resins, and silicone resins. As the support having a release layer, commercially available products can be used, and examples thereof include "SK-1", "AL-5" and "AL-7" manufactured by Linekaceae, which are PET films having a release layer containing an alkyd resin-based release agent as a main component, "Lumiror T60" manufactured by Toray, manufactured by Ditika, and "Unipel" manufactured by Unitika.

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

In one embodiment, the resin sheet may further include an arbitrary layer, as necessary. Examples of the optional layer include a protective film provided on a surface of the resin composition layer not bonded to the support (i.e., a surface opposite to the support) and selected for the support. The thickness of the protective film is not particularly limited, and is, for example, 1 μm to 40 μm. By laminating the protective film, it is possible to suppress adhesion of dust or the like to the surface of the resin composition layer or generation of damage on the surface of the resin composition layer.

The resin sheet can be produced, for example, by: the resin composition layer is formed by directly applying a liquid resin composition onto a support using a die coater or the like, or by preparing a resin varnish in which a resin composition is dissolved in an organic solvent, applying the resin varnish onto a support using a die coater or the like, and drying the resin varnish.

Examples of the organic solvent include ketones such as acetone, Methyl Ethyl Ketone (MEK), and cyclohexanone; acetates such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate and carbitol acetate; carbitols such as cellosolve and butyl carbitol; aromatic hydrocarbons such as toluene and xylene; amide solvents such as dimethylformamide, dimethylacetamide (DMAc) and N-methylpyrrolidone. The organic solvent may be used alone in 1 kind, or may be used in combination of 2 or more kinds.

The drying can be carried out by a known method such as heating or blowing hot air. The drying conditions are not particularly limited, and drying is performed so that the content of the organic solvent in the resin composition layer is 10 mass% or less, preferably 5 mass% or less. The drying conditions vary depending on the boiling point of the organic solvent in the resin varnish, and for example, when a resin varnish containing 30 to 60 mass% of the organic solvent is used, the resin composition layer can be formed by drying at50 to 150 ℃ for 3 to 10 minutes.

The resin sheet may be wound into a roll and stored. When the resin sheet has a protective film, the protective film can be peeled off and used.

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

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

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

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

In the present invention using a resin composition containing a combination of the component (a), the component (B) and the component (C) in a specific content, a sheet-like laminate material which is extremely useful in the production of a printed wiring board and which brings a cured product having a high glass transition temperature, a low dielectric loss tangent and good adhesion to a conductor layer can be realized.

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

< printed wiring board >

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

The printed wiring board can be produced, for example, by a method including the steps (I) and (II) below using the above resin sheet;

(I) laminating a resin sheet on the inner substrate so that the resin composition layer of the resin sheet is bonded to the inner substrate,

(II) a step of forming an insulating layer by curing (for example, thermosetting) the resin composition layer.

The "inner layer substrate" used in the step (I) is a member to be a substrate of a printed wiring board, and examples thereof include a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, a thermosetting polyphenylene ether substrate, and the like. In addition, the substrate may have a conductive layer on one surface or both surfaces thereof, and the conductive layer may be patterned. An inner layer substrate having a conductor layer (circuit) formed on one surface or both surfaces of a substrate is sometimes referred to as an "inner layer circuit substrate". In addition, an intermediate manufactured product in which an insulating layer and/or a conductor layer is to be further formed when manufacturing a printed wiring board is also included in the so-called "inner layer substrate" in the present invention. When the printed wiring board is a component-embedded circuit board, an inner layer substrate in which components are embedded may be used.

The lamination of the inner layer substrate and the resin sheet can be performed, for example, by heating and pressure-bonding the resin sheet to the inner layer substrate from the support side. Examples of the member for heat-pressure bonding the resin sheet to the inner layer substrate (hereinafter also referred to as "heat-pressure bonding member") include a heated metal plate (such as SUS end plate) and a metal roll (SUS roll). It is preferable that the thermocompression bonding member is not directly pressed against the resin sheet, but is pressed via an elastic material such as heat-resistant rubber so that the resin sheet sufficiently follows the surface irregularities of the inner layer substrate.

The lamination of the inner substrate and the resin sheet may be performed by a vacuum lamination method. In the vacuum lamination method, the heating and pressure bonding temperature is preferably 60 to 160 ℃, more preferably 80 to 140 ℃, the heating and pressure bonding pressure is preferably 0.098 to 1.77MPa, more preferably 0.29 to 1.47MPa, and the heating and pressure bonding time is preferably 20 to 400 seconds, more preferably 30 to 300 seconds. The lamination is preferably performed under a reduced pressure of 26.7hPa or less.

The lamination can be carried out by means of a commercially available vacuum laminator. Examples of commercially available vacuum laminators include a vacuum pressure laminator manufactured by Nikko Co., Ltd, a vacuum applicator (vacuumapplicator) manufactured by Nikko-Materials, and a batch vacuum pressure laminator.

After the lamination, the thermocompression bonding member is pressed at normal pressure (atmospheric pressure), for example, from the support side, whereby the smoothing treatment of the laminated resin sheets can be performed. The pressing conditions for the smoothing treatment may be set to the same conditions as the above-described conditions for the heat and pressure bonding of the laminate. The smoothing treatment may be performed by a commercially available laminator. The lamination and smoothing processes can be continuously performed using a commercially available vacuum laminator as described above.

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

In the step (II), the resin composition layer is cured (for example, thermally cured) to form an insulating layer formed of a cured product of the resin composition. The curing conditions of the resin composition layer are not particularly limited, and conditions generally employed in forming an insulating layer of a printed wiring board can be used.

For example, the heat curing conditions of the resin composition layer vary depending on the kind of the resin composition, and the curing temperature is preferably 120 to 240 ℃, more preferably 150 to 220 ℃, and still more preferably 170 to 210 ℃. The curing time may be preferably 5 minutes to 120 minutes, more preferably 10 minutes to 100 minutes, and still more preferably 15 minutes to 100 minutes.

The resin composition layer may be preheated at a temperature lower than the curing temperature before the resin composition layer is thermally cured. For example, before the resin composition layer is thermally cured, the resin composition layer is preheated at a temperature of 50 ℃ or higher and lower than 120 ℃, preferably 60 ℃ or higher and lower than 115 ℃, more preferably 70 ℃ or higher and lower than 110 ℃ for 5 minutes or longer, preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes, and still more preferably 15 minutes to 100 minutes.

In the production of the printed wiring board, (III) a step of forming a hole in the insulating layer, (IV) a step of roughening the insulating layer, and (V) a step of forming a conductor layer may be further performed. The steps (III) to (V) can be performed by various methods known to those skilled in the art, which can be used for manufacturing a printed wiring board. When the support is removed after the step (II), the support may be removed between the steps (II), (III), (IV), or (V). If necessary, the insulating layer and the conductor layer may be formed by repeating the steps (II) to (V) to form a multilayer wiring board.

In another embodiment, the printed wiring board of the present invention can be manufactured using the prepreg described above. The manufacturing method is basically the same as the case of using the resin sheet.

In the step (III), a hole such as a via hole or a through hole can be formed in the insulating layer by forming the hole in the insulating layer. The step (III) can be performed using, for example, a drill, a laser, plasma, or the like, depending on the composition of the resin composition used for forming the insulating layer. The size and shape of the hole may be determined as appropriate according to the design of the printed wiring board.

The step (IV) is a step of roughening the insulating layer. In general, in this step (IV), the removal of the scum is also performed. The step and conditions of the roughening treatment are not particularly limited, and known steps and conditions generally used for forming an insulating layer of a printed wiring board can be used. For example, the roughening treatment may be performed on the insulating layer by sequentially performing a swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralizing treatment with a neutralizing liquid.

The swelling solution used for the roughening treatment is not particularly limited, and examples thereof include an alkali solution and a surfactant solution, and the alkali solution is preferably an alkali solution, and a sodium hydroxide solution and a potassium hydroxide solution are more preferably used as the alkali solution. Examples of commercially available Swelling liquids include "spinning Dip securigranthP" and "spinning Dip securigranth SBU" manufactured by ATOTECH JAPAN. The swelling treatment with the swelling solution is not particularly limited, and may be performed, for example, by immersing the insulating layer in the swelling solution at 30 to 90 ℃ for 1 to 20 minutes. From the viewpoint of suppressing swelling of the resin of the insulating layer to an appropriate level, the insulating layer is preferably immersed in a swelling solution at 40 to 80 ℃ for 5 to 15 minutes.

The oxidizing agent used in the roughening treatment is not particularly limited, and examples thereof include an alkaline permanganic acid solution obtained by dissolving potassium permanganate or sodium permanganate in an aqueous solution of sodium hydroxide. The roughening treatment with 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 to 100 ℃ for 10 to 30 minutes. The concentration of permanganate in the alkaline permanganate solution is preferably 5 to 10% by mass. Examples of commercially available oxidizing agents include alkaline permanganic acid solutions such as "Concentrate Compact CP" and "Dosing solution securigant P" manufactured by amett japan.

The neutralizing Solution used for the roughening treatment is preferably an acidic aqueous Solution, and examples of commercially available products include "Reduction Solution securigant P" manufactured by anmant japan.

The treatment with the neutralizing solution may be performed by immersing the treated surface on which the roughening treatment with the oxidizing agent is performed in the neutralizing solution at 30 to 80 ℃ for 5 to 30 minutes. From the viewpoint of workability, the object after the roughening treatment with the oxidizing agent is preferably immersed in a neutralizing solution at 40 to 70 ℃ for 5 to 20 minutes.

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

Step (V) is a step of forming a conductor layer, and the conductor layer is formed on the insulating layer. The conductor material used in the conductor layer is not particularly limited. In a preferred embodiment, the conductor layer contains 1 or more metals selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin, and indium. The conductor layer may be a single metal layer or an alloy layer, and examples of the alloy layer include layers formed of an alloy of 2 or more metals selected from the above-described group (for example, a nickel-chromium alloy, a copper-nickel alloy, and a copper-titanium alloy). Among them, from the viewpoint of versatility of conductor layer formation, cost, ease of patterning, and the like, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or an alloy layer of a nickel-chromium alloy, a copper-nickel alloy, or a copper-titanium alloy is preferable, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or an alloy layer of a nickel-chromium alloy is more preferable, and a single metal layer of copper is further preferable.

The conductor layer may have a single-layer structure, or may have a multilayer structure in which 2 or more layers of single metal layers or alloy layers made of different metals or alloys are stacked. When the conductor layer has 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 a nickel-chromium alloy.

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

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

First, a plating seed layer is formed on the surface of the insulating layer by electroless plating. Next, a mask pattern for exposing a part of the plating seed layer is formed on the formed plating seed layer in accordance with a desired wiring pattern. On the exposed plating seed layer, a metal layer is formed by electrolytic plating, and then the mask pattern is removed. Then, the unnecessary plating seed layer is removed by etching or the like, and a conductor layer having a desired wiring pattern can be formed.

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

The metal foil can be produced by a known method such as an electrolytic method or a rolling method. As commercially available products of the metal foil, for example, HLP foil, JXUT-III foil, 3EC-III foil, TP-III foil, and the like, available from JX Nikki Stone Metal Co., Ltd.

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

< 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 the semiconductor device include various semiconductor devices used in electric products (for example, computers, mobile phones, digital cameras, televisions, and the like) and vehicles (for example, motorcycles, automobiles, electric trains, ships, airplanes, and the like).

Examples

The present invention will be specifically described below with reference to examples. The present invention is not limited by these examples. In the following, unless otherwise explicitly stated, "part" and "%" representing amounts represent "part by mass" and "% by mass", respectively.

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

[ chemical formula 4]

。

4, 4' -methylenebis (cyclohexylamine), phenol and 92% paraformaldehyde (paraformaldehyde) were reacted in toluene at a molar ratio of 1:2:4.1 by heating under reflux. After toluene was distilled off, the objective compound was obtained. The purity of the monomer was measured by GPC, which was 65%. Although polymers were included as by-products, they were used directly in the examples.

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

[ chemical formula 5]

。

1, 4-cyclohexanediamine, phenol and 92% paraformaldehyde were reacted by heating under reflux in toluene at a molar ratio of 1:2:4.1, respectively. After toluene was distilled off, the objective compound was obtained. The purity of the monomer was measured by GPC, and the purity was 60%. Although polymers were included as by-products, they were used directly in the examples.

< Synthesis example 3: synthesis of elastomer

In a reaction vessel, 69G of bifunctional hydroxyl-terminated polybutadiene ("G-3000" manufactured by japan caokada corporation, number average molecular weight =3000, hydroxyl equivalent =1800G/eq.), 40G of an aromatic hydrocarbon-based mixed solvent ("Ipzole (イプゾール) 150" manufactured by lekushin petrochemical corporation), and 0.005G of dibutyltin laurate were charged and mixed to be uniformly dissolved. After the mixture became homogeneous, the temperature was raised to 60 ℃, 8g of isophorone diisocyanate (IPDI manufactured by Evonik Degussa Japan, isocyanate group equivalent =113g/eq.) was added while stirring, and the reaction was carried out for about 3 hours.

Then, 23g of cresol novolak resin ("KA-1160" manufactured by DIC corporation and hydroxyl equivalent =117g/eq.) and 60g of diethylene glycol monoethyl ether acetate (manufactured by xylonite corporation) were added to the reaction product, and the temperature was raised to 150 ℃ with stirring, and the reaction was carried out for about 10 hours. By FT-IR pair 2250cm^-1The disappearance of the NCO peak of (2) was confirmed. The time point at which disappearance of NCO peak was confirmed was regarded as the end point of the reaction, and the reaction was cooled to room temperature. Then, the reaction product was filtered through a 100-mesh filter cloth to obtain an elastomer having a butadiene structure and a phenolic hydroxyl group (phenolic hydroxyl group-containing butadiene resin: 50% by mass of nonvolatile matter). The number average molecular weight of the elastomer was 5900 and the glass transition temperature was-7 ℃.

< example 1 >

5 parts of a biphenyl type epoxy resin ("NC 3000" manufactured by Nippon chemical Co., Ltd., epoxy equivalent of 276g/eq.), 2 parts of a bisphenol type epoxy resin ("ZX 1059" manufactured by Nippon Steel chemical Co., Ltd., a 1:1 mixture of bisphenol A and bisphenol F, epoxy equivalent of 169g/eq.), 70 parts of a spherical silica (SO-C2 "manufactured by Yado corporation, average particle diameter of 0.5 μm) surface-treated with 0.5% by mass of an amine type alkoxysilane compound (" KBM573 "manufactured by shin-Etsu chemical Co., Ltd.), 30 parts of an elastomer obtained in Synthesis example 3, 2 parts of a benzoxazine compound obtained in Synthesis example 1,3 parts of a cresol novolak resin (" KA-1160 "manufactured by DIC Co., Ltd., phenolic hydroxyl equivalent of 117g/eq), and 0.1 part of a curing accelerator (" 1B2PZ "manufactured by Quaternary chemical Co., 1-benzyl-2-phenylimidazole), And 15 parts of methyl ethyl ketone, and uniformly dispersing the mixture by 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 >

A resin composition was prepared in the same manner as in example 1 except that 70 parts of spherical silica (SO-C2, average particle size 0.5 μm, manufactured by Yamadama, Ltd.) surface-treated with 0.5 mass% of an amine-based alkoxysilane compound (KBM 573, manufactured by shin chemical industries Co., Ltd.) and 115 parts of spherical alumina (DAW-03, manufactured by DENKA, average particle size 3.7 μm) surface-treated with 0.5 mass% of an amine-based alkoxysilane compound (KBM 573, manufactured by shin chemical industries Co., Ltd.) were used in place of 70 parts of the spherical silica surface-treated with 0.5 mass% of an amine-based alkoxysilane compound (KBM 573, manufactured by shin chemical industries Co., Ltd.).

< example 4 >

Instead of 70 parts of spherical silica (SO-C2, average particle size 0.5 μm, manufactured by Yadu Ma Co., Ltd.) surface-treated with 0.5 mass% of an amine-based alkoxysilane compound ("KBM 573", manufactured by shin-Etsu chemical Co., Ltd.), 0.5 mass% of spherical alumina (average particle size 1.5 μm, specific surface area 2.0 m) surface-treated with an amine-based alkoxysilane compound ("KBM 573", manufactured by shin-Etsu chemical Co., Ltd.) was used²A resin composition was prepared in the same manner as in example 1, except that the maximum particle diameter was 5 μm) was changed to 115 parts.

< comparative example 1 >

A resin composition was prepared in the same manner as in example 1 except that 2 parts of the benzoxazine compound obtained in Synthesis example 1 was not used, and the amount of the cresol novolak resin (KA-1160, phenolic hydroxyl group equivalent: 117g/eq, manufactured by DIC) used was changed from 3 parts to 5 parts.

< comparative example 2 >

A resin composition was prepared in the same manner as in example 1, except that 2 parts of a commercially available benzoxazine compound ("P-d type benzoxazine" manufactured by four kingdom chemical industry corporation, bis [4- (3, 4-dihydro-2H-1, 3-benzoxazin-3-yl) phenyl ] methane) was used instead of 2 parts of the benzoxazine compound obtained in synthesis example 1.

< test example 1: measurement and evaluation of tensile elastic modulus

On the release agent-untreated surface of the release agent-treated PET film ("501010" manufactured by linke corporation, 38 μm thick, 240mm square), a glass cloth base epoxy resin double-sided copper-clad laminate ("R5715 ES" manufactured by panasonic corporation, 0.7mm thick, 255mm square) was laminated, and four sides thereof were fixed with a polyimide tape (width 10mm) (hereinafter, sometimes referred to as "fixed PET film").

The resin compositions prepared in examples and comparative examples were applied to the release-treated surface of the "fixed PET film" by a die coater so that the thickness of the dried resin composition layer became 50 μm, and dried at 80 to 120 ℃ (average 100 ℃) for 6 minutes to obtain a resin sheet. Next, the resultant was put into an oven at 180 ℃, and then, the resin composition layer was thermally cured under curing conditions of 90 minutes. After thermosetting, the polyimide tape was peeled off, and the cured product was taken off from both surfaces of the glass cloth substrate epoxy resin copper-clad laminate, and further a PET film ("501010" manufactured by ledebacaceae) was peeled off to obtain a sheet-like cured product. The resulting cured product was referred to as "cured product for evaluation".

The cured product for evaluation was cut into a dumbbell No. 1 shape to obtain a test piece. The tensile strength of the test piece was measured using a tensile tester "RTC-1250A" manufactured by Orientec, and the elastic modulus at 23 ℃ was determined. The measurement was carried out in accordance with JIS K7127. This operation was carried out 3 times, and the average value thereof is shown in the following table. In order to reduce warpage, the tensile modulus is preferably low in consideration of relaxation of stress generated during heat curing. In view of this, the tensile modulus of elasticity of 10.5GPa or less was evaluated as "good", and the tensile modulus of elasticity of more than 10.5GPa was evaluated as "X".

< test example 2: measurement and evaluation of peeling Strength

As the inner layer substrate, a glass cloth substrate epoxy resin double-sided copper-clad laminate having a copper foil on the surface thereof was prepared (the thickness of the copper foil was 18 μm, the thickness of the substrate was 0.8mm, manufactured by Sonar corporation as "R1515A"). The copper foil on the surface of the inner layer substrate is entirely removed by etching. Then, drying was carried out at 190 ℃ for 30 minutes.

The resin compositions obtained in the above examples and comparative examples were laminated on both surfaces of the inner layer substrate using a batch vacuum press laminator (2-stage build-up laminator "CVP 700" manufactured by Nikko Materials) so that the resin composition layer was bonded to the inner layer substrate. The lamination is carried out by: the pressure was reduced to 13hPa or less for 30 seconds, and then pressure-bonded for 30 seconds at 100 ℃ and a pressure of 0.74 MPa. Next, the laminated resin sheet was subjected to hot pressing at 100 ℃ for 60 seconds under atmospheric pressure and a pressure of 0.5MPa to smooth it. Then, the support was peeled off to obtain an "intermediate multilayer body I" including the resin composition layer, the inner layer substrate, and the resin composition layer in this order.

On the other hand, a copper foil having a glossy surface (thickness: 35 μm, "3 EC-III" manufactured by Mitsui metals Co., Ltd.) was prepared. The glossy surface of the copper foil was etched with a copper etching amount of 1 μm using a microetching agent ("CZ 8101" by MEC) to perform roughening treatment. The copper foil obtained in the above manner is referred to as "roughened copper foil".

The roughened copper foil is laminated on both surfaces of the intermediate multilayer body I so that the roughened surface of the roughened copper foil is bonded to the resin composition layer of the intermediate multilayer body I. This lamination was performed under the same conditions as the aforementioned lamination of the resin sheet to the inner layer substrate. Thus, an "intermediate multilayer body II" was obtained which successively contained the roughened copper foil, the resin composition layer, the inner substrate, the resin composition layer, and the roughened copper foil.

The intermediate multilayer body II was put into an oven at 180 ℃ and heated for an additional 90 minutes. Thus, the resin composition layer was thermally cured to obtain an "evaluation substrate" comprising the roughened copper foil, the insulating layer as a cured product of the resin composition layer, the inner substrate, the insulating layer as a cured product of the resin composition layer, and the roughened copper foil in this order. In this evaluation substrate, the roughened copper foil corresponds to the conductor layer.

The peel strength between the roughened copper foil and the insulating layer was measured using the above-described evaluation substrate. The peel strength was measured according to JIS C6481. Specifically, the peel strength was measured by the following procedure. A cut was formed on the roughened copper foil of the evaluation substrate so as to surround a rectangular portion having a width of 10mm and a length of 100 mm. One end of the rectangular portion was peeled off and held by a jig (AUTO COM model test machine "AC-50C-SL" manufactured by t.s.e). The rectangular portion was peeled in the vertical direction in a range of 35mm in length, and the peel strength was measured as the load (kgf/cm) at the time of peeling. The aforementioned peeling was performed at room temperature at a rate of 50 mm/min. The case where the peel strength was 0.39kgf/cm or more was evaluated as "O", and the case where the peel strength was less than 0.39kgf/cm was evaluated as "X".

< test example 3: evaluation of warpage

As a support, a polyethylene terephthalate film (AL 5, manufactured by Lindelco) having a release layer was prepared, and the thickness thereof was 38 μm. The resin compositions obtained in the above examples and comparative examples were uniformly applied to the release layer of the support so that the thickness of the dried resin composition layer became 50 μm. Then, the resin varnish was dried at 80 to 120 ℃ (average 100 ℃) for 6 minutes to obtain a resin sheet including a support and a resin composition layer.

Then, the resin sheets were laminated in a thickness of 50 μm on the entire surface of a 12-inch silicon wafer (having a thickness of 775 μm) by using a batch vacuum press laminator (2-stage build-up laminator "CVP 700" manufactured by Nikko Materials Co., Ltd.), thereby forming 2 layers, and a resin composition layer having a thickness of 100 μm was formed. The resulting silicon wafer with the resin composition layer was subjected to heat treatment in an oven at 180 ℃ for 90 minutes to form a silicon wafer with a cured resin composition layer (i.e., an insulating layer). The end of the obtained wafer with the insulating layer was pressed against the stage, and the distance between the end of the wafer on the opposite side of the pressed position and the stage was measured as the warpage amount. The case where the warpage amount was 0 to 2mm was evaluated as "O", and the case where the warpage amount was more than 2mm was evaluated as "X".

The nonvolatile components and the amounts thereof used in the resin compositions of examples and comparative examples, and the evaluation results of the test examples are shown in table 1 below.

[ Table 1]

。

From the above results, it is understood that when (C) a benzoxazine compound having 1 or more alicyclic structures in the molecule is used, both suppression of warpage and excellent adhesion can be achieved.

Claims

1. A resin composition comprising: (A) an epoxy resin, (B) an inorganic filler, and (C) a benzoxazine compound having an alicyclic structure in its molecule.

2. The resin composition according to claim 1, wherein the alicyclic structure of the component (C) is a cyclohexane ring structure.

3. The resin composition according to claim 1, wherein the component (C) is a compound represented by the formula (2),

in the formula, R¹And R²Each independently represents a substituent, Y represents a bond, an alkylene group having 1 to 6 carbon atoms, -O-, -S-, -SO₂-, -NH-, -CO-, -CONH-, -NHCO-, -COO-or-OCO-, s and t each independently represent an integer of 0 to 4, and u represents 0 or 1.

4. The resin composition according to claim 1, wherein the content of the component (B) is 50% by mass or more, assuming that all nonvolatile components in the resin composition are 100% by mass.

5. The resin composition according to claim 1, wherein the average particle diameter of the component (B) is 10 μm or less.

6. The resin composition of claim 1, further comprising (D) an elastomer.

7. The resin composition according to claim 1, further comprising (E) a curing agent.

8. The resin composition according to claim 1, which is used for forming an insulating layer.

9. A cured product of the resin composition according to any one of claims 1 to 8.

10. A sheet-like laminate comprising the resin composition according to any one of claims 1 to 8.

11. A resin sheet having: a support, and a resin composition layer formed of the resin composition according to any one of claims 1 to 8 provided on the support.

12. A printed wiring board comprising an insulating layer formed from a cured product of the resin composition according to any one of claims 1 to 8.

13. A semiconductor device comprising the printed wiring board of claim 12.