TWI853038B - Resin composition - Google Patents

Abstract

The subject of the present invention is to provide a resin composition which can obtain a cured product having excellent heat resistance and crack resistance. The solution is a resin composition comprising (A) an epoxy resin, (B) an inorganic filler and (C) a non-reactive diphosphine compound, wherein when the non-volatile component in the resin composition is 100% by mass, the content of the component (C) is 0.2% by mass to 1.0% by mass.

Description

Resin composition

The present invention relates to a resin composition containing an epoxy resin, and further relates to a cured product, a sheet-like laminate material, a resin sheet, a printed wiring board and a semiconductor device obtained by using the resin composition.

In the manufacturing technology of printed wiring boards, there is known a manufacturing method by an assembly method in which an insulating layer and a conductive layer are alternately stacked. In the manufacturing method by the assembly method, generally speaking, the insulating layer is formed by curing a resin composition.

Generally speaking, printed wiring boards are exposed to a wide range of temperature environments, from low temperature environments such as room temperature to high temperature environments. If the thermal expansion coefficient is high, the dimensional stability will be poor, and the resin material of the insulation layer will repeatedly expand and contract, causing distortion and cracks.

In addition, epoxy resin compositions containing a phosphino compound containing a phenolic hydroxyl group are known (Patent Documents 1 and 2). [Prior Art Document] [Patent Document]

[Patent Document 1] Japanese Patent Publication No. 2018-131619 [Patent Document 2] Japanese Patent Publication No. 2018-188624

[The problem that the invention wants to solve]

The subject of the present invention is to provide a resin composition that can obtain a hardened material having excellent heat resistance and crack resistance in a wide temperature environment. [Means for solving the subject]

In order to achieve the subject of the present invention, the inventors have devoted themselves to the review and found that by using a resin composition comprising (A) an epoxy resin, (B) an inorganic filler and 0.2 mass % to 1.0 mass % of (C) a non-reactive diphosphine compound, a cured product with excellent heat resistance and crack resistance can be obtained, and finally the present invention is completed.

That is, the present invention includes the following contents. [1] A resin composition comprising (A) an epoxy resin, (B) an inorganic filler and (C) a non-reactive azophosphine compound, wherein the content of the component (C) is 0.2% to 1.0% by mass when the non-volatile components in the resin composition are 100% by mass. [2] The resin composition of [1] above, wherein the component (B) is silicon oxide. [3] The resin composition of [1] or [2] above, wherein the content of the component (B) is 70% by mass or more when the non-volatile components in the resin composition are 100% by mass. [4] A resin composition as described in any one of [1] to [3] above, wherein the component (C) is a compound represented by the following formula (1):

[wherein n represents an integer of 1 to 20. ^R1 and ^R2 each independently represent an aryl group which may have 1 to 3 substituents selected from the group consisting of (a) to (e): (a) an alkyl group, (b) an alkoxy group, (c) a cyano group, (d) a halogen atom, or (e) a group of the formula ^-XR3 (wherein X represents a single bond, -(alkylene)-, -O-, -S-, -CO-, or _-SO2- . ^R3 represents an aryl group which may have 1 to 3 substituents selected from the group consisting of an alkyl group, an alkoxy group, a cyano group, and a halogen atom). [5] The resin composition as described in any one of [1] to [4] above, further comprising (D) a curing agent. [6] The resin composition as described in [5] above, wherein the component (D) comprises an active ester curing agent. [7] A cured product of the resin composition of any one of the above [1] to [6]. [8] A sheet-like laminate material comprising the resin composition of any one of the above [1] to [6]. [9] A resin sheet comprising a support and a resin composition layer formed from the resin composition of any one of the above [1] to [6] and disposed on the support. [10] A printed wiring board having an insulating layer formed from the cured product of the resin composition of any one of the above [1] to [6]. [11] A semiconductor device comprising the printed wiring board of the above [10]. [Effect of the Invention]

According to the resin composition of the present invention, a hardened material having excellent heat resistance and crack resistance can be obtained.

The present invention will be described in detail below according to its suitable embodiments. However, the present invention is not limited to the following embodiments and examples, and can be arbitrarily modified within the scope of the patent application of the present invention and its equivalents.

<Resin composition> The resin composition of the present invention comprises (A) epoxy resin, (B) inorganic filler and (C) non-reactive azophosphine compound. The content of (C) non-reactive azophosphine compound is 0.2 mass% to 1.0 mass%. By using such a resin composition, a cured product with excellent heat resistance and crack resistance can be obtained. In addition, one embodiment can obtain a cured product that can maintain excellent insulation for a long time even in an overly harsh environment. In addition, one embodiment can obtain a cured product with even better flame retardancy.

The resin composition of the present invention may further contain any component in addition to (A) epoxy resin, (B) inorganic filler and (C) non-reactive azophosphite compound. The optional component may include (D) hardener, (E) hardening accelerator, (F) other additives and (G) organic solvent. The following is a detailed description of each component contained in the resin composition.

<(A) Epoxy resin> The resin composition of the present invention includes (A) epoxy resin. The so-called (A) epoxy resin refers to a curable resin having an epoxy group.

(A) Epoxy resins include, for example, bis(xylenol) epoxy resins, bisphenol A epoxy resins, bisphenol F epoxy resins, bisphenol S epoxy resins, bisphenol AF epoxy resins, dicyclopentadiene epoxy resins, tautomer epoxy resins, naphthol novolac epoxy resins, phenol novolac epoxy resins, tert-butyl-benzene epoxy resins, naphthalene epoxy resins, naphthol epoxy resins, anthracene epoxy resins, glycidol. Amine type epoxy resins, glycidyl ester type epoxy resins, cresol novolac type epoxy resins, biphenyl type epoxy resins, linear aliphatic epoxy resins, epoxy resins having a butadiene structure, alicyclic epoxy resins, heterocyclic epoxy resins, spirocyclic epoxy resins, oxalic acid type epoxy resins, oxalic acid dimethanol type epoxy resins, naphthyl ether type epoxy resins, trihydroxymethyl type epoxy resins, tetraphenylethane type epoxy resins, isocyanurate type epoxy resins, etc. Among them, naphthalene-based epoxy resins and naphthol-based epoxy resins are particularly preferred. (A) The epoxy resin may be used alone or in combination of two or more.

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

Epoxy resins include epoxy resins that are liquid at 20°C (hereinafter referred to as "liquid epoxy resins") and epoxy resins that are solid at 20°C (hereinafter referred to as "solid epoxy resins"). The resin composition of the present invention may contain only liquid epoxy resin as the epoxy resin, or only solid epoxy resin, or may contain a combination of liquid epoxy resin and solid epoxy resin.

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

As liquid epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol AF type epoxy resins, naphthalene type epoxy resins, glycidyl ester type epoxy resins, glycidyl amine type epoxy resins, phenol novolac type epoxy resins, aliphatic epoxy resins having an ester skeleton, cyclohexane type epoxy resins, cyclohexanedimethanol type epoxy resins and epoxy resins having a butadiene structure are preferred, among which naphthalene type epoxy resins are particularly preferred.

Specific examples of liquid epoxy resins include "HP4032", "HP4032D", and "HP4032SS" (naphthalene-based epoxy resins) manufactured by DIC Corporation; "828US", "828EL", "jER828EL", "825", and "EPIKOTE" manufactured by Mitsubishi Chemical Corporation; "828EL" (bisphenol A type epoxy resin); "jER807" and "1750" (bisphenol F type epoxy resin) manufactured by Mitsubishi Chemical; "jER152" (phenol novolac type epoxy resin) manufactured by Mitsubishi Chemical; "630", "630LSD", and "604" (glycidylamine type epoxy resin) manufactured by Mitsubishi Chemical; "ED-52 3T" (glycyrrhizin type epoxy resin); "EP-3950L" and "EP-3980S" (glycidylamine type epoxy resin) manufactured by ADEKA; "EP-4088S" (dicyclopentadiene type epoxy resin) manufactured by ADEKA; "ZX1059" (a mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin) manufactured by Nippon Steel & Sumitomo Chemicals; Nagase "EX-721" (glycidyl ester type epoxy resin) manufactured by ChemteX; "CELLOXIDE2021P" (lipid epoxy resin with ester skeleton) manufactured by Daicel; "PB-3600" manufactured by Daicel, "JP-100" and "JP-200" (epoxy resin with butadiene structure) manufactured by Nippon Soda; "ZX1658" and "ZX1658GS" (liquid 1,4-glycidyl cyclohexane type epoxy resin) manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd. These can be used alone or in combination of two or more.

As the solid epoxy resin, a solid epoxy resin having 3 or more epoxy groups in one molecule is preferred, and an aromatic solid epoxy resin having 3 or more epoxy groups in one molecule is more preferred.

As solid epoxy resins, preferred are dixylenol type epoxy resins, naphthalene type epoxy resins, naphthalene type tetrafunctional epoxy resins, cresol novolac type epoxy resins, dicyclopentadiene type epoxy resins, trisphenol type epoxy resins, naphthol type epoxy resins, biphenyl type epoxy resins, naphthyl ether type epoxy resins, anthracene type epoxy resins, bisphenol A type epoxy resins, bisphenol AF type epoxy resins, and tetraphenylethane type epoxy resins, among which naphthol type epoxy resins are particularly preferred.

Specific examples of solid epoxy resins include "HP4032H" (naphthalene-type epoxy resin) manufactured by DIC Corporation; "HP-4700" and "HP-4710" (naphthalene-type tetrafunctional epoxy resin) manufactured by DIC Corporation; "N-690" (cresol novolac-type epoxy resin) manufactured by DIC Corporation; "N-695" (cresol novolac-type epoxy resin) manufactured by DIC Corporation; "HP-7200", "HP-7200HH" and "HP-7200H" (dicyclopentadiene-type epoxy resin) manufactured by DIC Corporation; "EXA-7311", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", "HP6000" (naphthyl ether type epoxy resin) manufactured by DIC; "EPPN-502H" (triphenylphenol type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; "NC7000L" (naphthol novolac type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; "NC3000H", "NC3000", "NC3000L", "NC3000FH", "NC3000" manufactured by Nippon Kayaku Co., Ltd. NC3100" (biphenyl type epoxy resin); "ESN475V" (naphthol type epoxy resin) made by Nippon Steel Chemicals & Materials Co., Ltd.; "ESN485" (naphthol type epoxy resin) made by Nippon Steel Chemicals & Materials Co., Ltd.; "ESN375" (dihydroxynaphthalene type epoxy resin) made by Nippon Steel Chemicals & Materials Co., Ltd.; "YX4000H", "YX4000", "YL6121", "YL7890", "YX4000HK" (biphenyl type epoxy resin) made by Mitsubishi Chemical Corporation; "YX8800" made by Mitsubishi Chemical Corporation "(Anthracene type epoxy resin); "YX7700" manufactured by Mitsubishi Chemical Corporation (phenolic varnish type epoxy resin containing xylene structure); "PG-100" and "CG-500" manufactured by Osaka Gas Chemical Co., Ltd.; "YL7760" manufactured by Mitsubishi Chemical Corporation (bisphenol AF type epoxy resin); "YL7800" manufactured by Mitsubishi Chemical Corporation (fluorene type epoxy resin); "jER1010" manufactured by Mitsubishi Chemical Corporation (solid bisphenol A type epoxy resin); "jER1031S" manufactured by Mitsubishi Chemical Corporation (tetraphenylethane type epoxy resin), etc. These can be used alone or in combination of two or more.

(A) In terms of ingredients, when liquid epoxy resin and solid epoxy resin are used together, the mass ratio (liquid epoxy resin: solid epoxy resin) is preferably in the range of 100:1 to 1:100, more preferably in the range of 30:1 to 1:30, and even more preferably in the range of 10:1 to 1:10.

(A) The epoxy equivalent of the epoxy resin is preferably 50 g/eq. to 5,000 g/eq., more preferably 60 g/eq. to 2,000 g/eq., still more preferably 70 g/eq. to 1,000 g/eq., and still more preferably 80 g/eq. to 500 g/eq. The epoxy equivalent is the mass of the resin per 1 equivalent of epoxy group. The epoxy equivalent can be measured according to JIS K7236.

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

The content of the epoxy resin (A) in the resin composition is not particularly limited, but when the non-volatile components in the resin composition are 100% by mass, it 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. The upper limit of the content of the epoxy resin (A) is not particularly limited, but when the non-volatile components in the resin composition are 100% by mass, it is preferably 50% 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.

<(B) Inorganic filler> The resin composition of the present invention contains (B) inorganic filler. (B) Inorganic filler is made of inorganic material and contained in the resin composition in the form of particles.

(B) Inorganic fillers are made of inorganic compounds. (B) Inorganic fillers include, for example, silicon oxide, aluminum oxide, glass, diatomite, silicate, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, barium titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate. Among these, silicon oxide is particularly suitable. Silicon oxide includes, for example, amorphous silicon oxide, molten silicon oxide, crystalline silicon oxide, synthetic silicon oxide, hollow silicon oxide, etc. Moreover, as for silicon oxide, spherical silicon oxide is preferred. (B) The inorganic filler may be used alone or in combination of two or more in any ratio.

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

(B) The average particle size of the inorganic filler is not particularly limited, but is preferably 40 μm or less, more preferably 10 μm or less, further preferably 5 μm or less, further more preferably 3 μm or less, and particularly preferably 1 μm or less. (B) The lower limit of the average particle size of the inorganic filler is not particularly limited, but is preferably 0.005 μm or more, more preferably 0.01 μm or more, further more preferably 0.05 μm or more, further more preferably 0.1 μm or more, further more preferably 0.3 μm or more, and particularly preferably 0.4 μm or more. (B) The average particle size of the inorganic filler can be measured by a laser diffraction and scattering method based on the Mie scattering theory. Specifically, the particle size distribution of the inorganic filler can be made on a volume basis by using a laser diffraction scattering particle size distribution measuring device, and the median diameter can be used as the average particle size for measurement. The measurement sample can be made by weighing 100 mg of inorganic filler and 10 g of methyl ethyl ketone into a small glass bottle and dispersing it with ultrasound for 10 minutes. The sample is measured using a laser diffraction particle size distribution measuring device, and the wavelength of the light source used is divided into blue and red. The volume-based particle size distribution of the inorganic filler is measured using a flow cell method, and the average particle size is calculated from the obtained particle size distribution as the median diameter. As for the laser diffraction particle size distribution measuring device, an example of which is the "LA-960" manufactured by Horiba, Ltd.

(B) The specific surface area of the inorganic filler is not particularly limited, but is preferably 0.1 m ² /g or more, more preferably 0.5 m ² /g or more, and particularly preferably 1 m ² /g or more. (B) The upper limit of the specific surface area of the inorganic filler is not particularly limited, but is preferably 50 m ² /g or less, more preferably 20 m ² /g or less, and particularly preferably 10 m ² /g or less. The specific surface area of the inorganic filler is calculated by the BET method using a specific surface area measuring device (Macsorb HM-1210 manufactured by Mountech) to adsorb nitrogen on the sample surface and by using the BET multipoint method.

The (B) inorganic filler is preferably surface treated with an appropriate surface treatment agent. The surface treatment can improve the moisture resistance and dispersibility of the (B) inorganic filler. As for the surface treatment agent, there can be mentioned vinyl-based silane coupling agents such as vinyl trimethoxy silane and vinyl triethoxy silane; epoxy-based silane coupling agents such as 2-(3,4-epoxycyclohexyl)ethyl trimethoxy silane, 3-glycidoxymethyl dimethoxy silane, 3-glycidoxy trimethoxy silane, 3-glycidoxymethyl diethoxy silane, 3-glycidoxy triethoxy silane; styrene-based silane coupling agents such as p-styrene trimethoxy silane; 3-methacryloxypropyl methyl dimethoxy silane, 3-methacryloxypropyl Methacrylic silane coupling agents such as trimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, etc.; acrylic silane coupling agents such as 3-acryloxypropyltrimethoxysilane; N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylene)propylamine, N-phenyl- Amine-based silane coupling agents such as 3-aminopropyltrimethoxysilane, N-phenyl-8-aminooctyltrimethoxysilane, and N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane; isocyanate-based silane coupling agents such as tris-(trimethoxysilylpropyl)isocyanate; urea-based silane coupling agents such as 3-ureapropyltrialkoxysilane; 3-butylpropylmethyldimethoxysilane, 3-butylpropyltrimethoxysilane; isocyanate-based silane coupling agents such as 3-isocyanatepropyltriethoxysilane silane coupling agent; anhydride-based silane coupling agent such as 3-trimethoxysilylpropylsuccinic anhydride; silane coupling agent such as methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, 1,6-bis(trimethoxysilyl)hexane, trifluoropropyltrimethoxysilane and other non-silane coupling-alkoxysilane compounds. In addition, the surface treatment agent may be used alone or in combination of two or more at an arbitrary ratio.

Commercially available surface treatment agents include, for example, "KBM-1003", "KBE-1003" (vinyl silane coupling agents); "KBM-303", "KBM-402", "KBM-403", "KBE-402", "KBE-403" (epoxy silane coupling agents); "KBM-1403" (styrene silane coupling agent ... M-502", "KBM-503", "KBE-502", "KBE-503" (methacrylic silane coupling agent); "KBM-5103" (acrylic silane coupling agent); "KBM-602", "KBM-603", "KBM-903", "KBE-903", "KBE-9103P", "KBM-573", "KBM-575" (amino "KBM-9659" (isocyanurate silane coupling agent); "KBE-585" (urea silane coupling agent); "KBM-802", "KBM-803" (methylene silane coupling agent); "KBE-9007N" (isocyanate silane coupling agent); "X-12-967C" (anhydride silane coupling agent); "KBM-13", "KBM-22 "KBM-103", "KBE-13", "KBE-22", "KBE-103", "KBM-3033", "KBE-3033", "KBM-3063", "KBE-3063", "KBE-3083", "KBM-3103C", "KBM-3066", "KBM-7103" (non-silane coupled-alkoxysilane compounds), etc.

From the perspective of improving the dispersibility of the inorganic filler, the degree of surface treatment by the surface treatment agent is preferably within a predetermined range. Specifically, 100% by mass of the inorganic filler is preferably treated with 0.2% to 5% by mass of the surface treatment agent, more preferably 0.2% to 3% by mass, and even more preferably 0.3% to 2% by mass.

The degree of surface treatment by the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the inorganic filler. From the perspective of improving the dispersibility of the inorganic filler, the amount of carbon per unit surface area of the inorganic filler is preferably 0.02 mg/ ^m2 or more, more preferably 0.1 mg/ ^m2 or more, and even more preferably 0.2 mg/ ^m2 or more. On the other hand, from the perspective of preventing the melt viscosity of the resin composition or the melt viscosity of the sheet form from rising, it is preferably 1.0 mg/ ^m2 or less, more preferably 0.8 mg/ ^m2 or less, and even more preferably 0.5 mg/ ^m2 or less.

(B) The amount of carbon per unit surface area of the inorganic filler can be measured by washing the surface-treated inorganic filler with a solvent (e.g., methyl ethyl ketone (MEK)). Specifically, the solvent is to add a sufficient amount of MEK to the inorganic filler that has been surface-treated with the surface treatment agent, and then ultrasonically wash it at 25°C for 5 minutes. After removing the supernatant and drying the solid components, the amount of carbon per unit surface area of the inorganic filler can be measured using a carbon analyzer. For the carbon analyzer, the "EMIA-320V" manufactured by Horiba, Ltd. can be used.

The content of the (B) inorganic filler in the resin composition is not particularly limited, but when the non-volatile components in the resin composition are 100% by mass, it is preferably 20% by mass or more, more preferably 40% by mass or more, further preferably 60% by mass or more, and particularly preferably 70% by mass or more. The upper limit of the content of the (B) inorganic filler is not particularly limited, but when the non-volatile components in the resin composition are 100% by mass, it is preferably 98% by mass or less, more preferably 95% by mass or less, further preferably 90% by mass or less, and particularly preferably 80% by mass or less.

<(C) Non-reactive azophosphine compound> The resin composition of the present invention comprises (C) a non-reactive azophosphine compound.

The so-called (C) non-reactive azophosphine compound refers to a compound having a structural unit represented by -P=N- as a basic skeleton and having no epoxy reactive group. The structural unit represented by -P=N- in the basic skeleton may be a continuous repeating unit. The so-called epoxy reactive group refers to a functional group having a tendency to react directly or indirectly with the epoxy group of the (A) epoxy resin, for example, a hydroxyl group, an amine group, a hydroxyl group, a carboxyl group, etc.

As for the (C) non-reactive azophosphine compound, for example, there can be mentioned a non-reactive cyclic azophosphine compound having a ring structure formed by a structural unit represented by -P=N-, a non-reactive polyazophosphine compound having a chain structure formed by a structural unit represented by -P=N-, etc. In the present invention, the (C) non-reactive azophosphine compound is preferably a non-reactive cyclic azophosphine compound.

In the present invention, the non-reactive azophosphorus compound (C) is particularly preferably a compound represented by the following formula (1):

[In the formula, n represents an integer of 1 to 20, ^R1 and ^R2 each independently represent an aryl group which may have 1 to 3 substituents selected from the group consisting of the following (a) to (e): (a) an alkyl group, (b) an alkoxy group, (c) a cyano group, (d) a halogen atom, (e) a group represented by the formula ^-XR3 (in the formula, X represents a single bond, -(alkylene)-, -O-, -S-, -CO-, or _-SO2- , and ^R3 represents an aryl group which may have 1 to 3 substituents selected from the group consisting of an alkyl group, an alkoxy group, a cyano group, and a halogen atom)].

The so-called aryl group refers to a monovalent aromatic hydrocarbon group. The aryl group is preferably an aryl group with 6 to 14 carbon atoms, and more preferably an aryl group with 6 to 10 carbon atoms. As for the aryl group, for example, phenyl, 1-naphthyl, 2-naphthyl, etc., preferably phenyl. The so-called alkyl group refers to a monovalent aliphatic saturated hydrocarbon group in a straight chain or branched chain. The alkyl group is preferably an alkyl group with 1 to 6 carbon atoms, and more preferably an alkyl group with 1 to 3 carbon atoms. As for the alkyl group, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, etc. The so-called alkoxy group refers to a monovalent group formed by an alkyl group bonded to an oxygen atom (alkyl-O-). 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 so-called alkylene group refers to a straight chain or branched chain divalent aliphatic saturated hydrocarbon group. The alkylene group is preferably an alkylene group having 1 to 6 carbon atoms, and more preferably an alkylene group having 1 to 3 carbon atoms. Examples of the alkylene group include _-CH2- , -CH2-CH2-, _-CH ( _CH3 )-, -CH2- _CH2 -CH2-, _-CH2 -CH _{( CH3} )-, _-CH ( _{CH3 )} -CH2-, -C(CH3)2-, -CH2- _CH2 -CH2 _{- CH2-} , -CH2-CH2-CH( _CH3 )-, -CH2-CH _{( CH3} )-, _-CH2 -CH( _{CH2- ,} -CH( _CH3 )-CH2-, _-CH2 -CH( _CH3 ) _- , _-CH2 -CH( _CH2 - _CH2- , _-CH2 -C( _CH3 ) _2- , and -C( _CH3 ) ₂ - _CH2- . Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom.

n is preferably an integer of 1 to 10, more preferably an integer of 1 to 5, further preferably 1 or 2, and particularly preferably 1.

Specific examples of the (C) non-reactive azophosphine compound include compounds represented by the following formulae (2) to (4), but the (C) non-reactive azophosphine compound is not limited thereto.

(In the formula, n is the same as above.)

(C) The molecular weight of the non-reactive azophosphine compound is preferably 600-3,000, more preferably 600-2,000, and even more preferably 600-1,000.

(C) The non-reactive azophosphine compounds may be commercially available products, for example, "SPS-100" manufactured by Otsuka Chemical Co., Ltd. (the compound represented by the above formula (2)), "FP-100" manufactured by Fushimi Pharmaceutical Co., Ltd. (the compound represented by the above formula (2)), "FP-300" (the compound represented by the above formula (3)), and "FP-390" (the compound represented by the above formula (4)).

When the non-volatile components in the resin composition are 100% by mass, the content of the (C) non-reactive aphosphino compound in the resin composition is 0.2% by mass or more. The upper limit of the content of the (C) non-reactive aphosphino compound is 1.0% by mass or less when the non-volatile components in the resin composition are 100% by mass, and is preferably 0.9% by mass or less, more preferably 0.7% by mass or less, and even more preferably 0.5% by mass or less from the viewpoint of further increasing the glass transition temperature.

When the non-volatile components other than the inorganic filler (B) in the resin composition are 100% by mass, the content of the non-reactive azophosphino compound (C) in the resin composition is preferably 0.3% by mass or more, more preferably 0.5% by mass or more, still more preferably 0.6% by mass or more, and particularly preferably 0.7% by mass or more. The upper limit of the content of the non-reactive azophosphino compound (C) is preferably 10% by mass or less, more preferably 7% by mass or less, still more preferably 5% by mass or less, and still more preferably 4% by mass or less, and particularly preferably 3% by mass or less, 2% by mass or less, or 1% by mass or less from the viewpoint of further increasing the glass transition temperature.

The mass ratio of the (C) non-reactive azophosphine compound to the (A) epoxy resin in the resin composition ((C) component/(A) component) is preferably 0.005 or more, more preferably 0.010 or more, and particularly preferably 0.015 or more. The upper limit of the mass ratio ((C) component/(A) component) is preferably 0.20 or less, more preferably 0.15 or less, and further preferably 0.10 or less. From the viewpoint of further increasing the glass transition temperature, it may be particularly preferably 0.09 or less, 0.07 or less, or 0.05 or less.

<(D) Hardener> The resin composition of the present invention may contain (D) hardener. (D) Hardener has the function of hardening (A) epoxy resin.

The (D) hardener is not particularly limited, and examples thereof include phenol hardeners, naphthol hardeners, acid anhydride hardeners, active ester hardeners, benzoxazine hardeners, cyanate hardeners, and carbodiimide hardeners. A single hardener may be used alone, or two or more hardeners may be used in combination. The (D) hardener is preferably a hardener selected from the group consisting of phenol hardeners, naphthol hardeners, active ester hardeners, and carbodiimide hardeners, and is particularly preferably an active ester hardener.

As for phenolic hardeners and naphthol hardeners, phenolic hardeners with a novolac structure or naphthol hardeners with a novolac structure are preferred from the viewpoint of heat resistance and water resistance. Furthermore, nitrogen-containing phenolic hardeners or nitrogen-containing naphthol hardeners are preferred from the viewpoint of adhesion to the adherend, and triazine skeleton-containing phenolic hardeners or triazine skeleton-containing naphthol hardeners are more preferred. Among them, triazine skeleton-containing phenol novolac resins are preferred from the viewpoint of highly satisfying heat resistance, water resistance and adhesion. Specific examples of the phenol-based hardener and the naphthol-based hardener include "MEH-7700", "MEH-7810", and "MEH-7851" manufactured by Meiwa Chemicals, "NHN", "CBN", and "GPH" manufactured by Nippon Kayaku, "SN-170", "SN-180", "SN-190", "SN-475", "SN-485", "SN-495", "SN-375", and "SN-395" manufactured by Nippon Steel Chemicals & Materials, and "LA-7052", "LA-7054", "LA-3018", "LA-3018-50P", "LA-1356", "TD2090", and "TD-2090-60M" manufactured by DIC Corporation.

As for the acid anhydride curing agent, there can be mentioned a curing agent having one or more acid anhydride groups in one molecule, and preferably a curing agent having two or more acid anhydride groups in one molecule. As for specific examples of the acid anhydride curing agent, there can be mentioned anhydrous phthalic acid, anhydrous tetrahydrophthalic acid, anhydrous hexahydrophthalic acid, anhydrous methyltetrahydrophthalic acid, anhydrous methylhexahydrophthalic acid, methylnadic anhydride, hydrogenated methylnadic anhydride, anhydrous trialkyltetrahydrophthalic acid, anhydrous dodecenylsuccinic acid, 5-(2,5-dioxotetrahydro-3-pyranyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, anhydrous trimellitic acid, anhydrous pyromellitic acid, benzophenone Tetracarboxylic acid dianhydrous, biphenyltetracarboxylic acid dianhydrous, naphthalenetetracarboxylic acid dianhydrous, oxydiphthalic acid dianhydrous, 3,3'-4,4'-diphenylsulfonatetetracarboxylic acid dianhydrous, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxy-3-pyranyl)-naphtho[1,2-c]furan-1,3-dione, ethylene glycol bis(trimellitic anhydride), styrene-maleic acid resin obtained by copolymerization of styrene and maleic acid, etc. Polymer-type acid anhydrides, etc. Commercially available products of acid anhydride-based hardeners include "HNA-100" and "MH-700" manufactured by Shin Nippon Chemical Co., Ltd.

As for the active ester curing agent, although there is no particular limitation, in general, it is preferred to use a compound having two or more highly reactive ester groups in one molecule, such as phenol esters, thiophenol esters, N-hydroxylamine esters, and esters of heterocyclic hydroxyl compounds. The active ester curing agent is preferably obtained by a condensation reaction of a carboxylic acid compound and/or a thiocarboxylic acid compound with a hydroxyl compound and/or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester curing agent obtained from a carboxylic acid compound and a hydroxyl compound is preferred, and an active ester curing agent obtained from a carboxylic acid compound and a phenol compound and/or a naphthol compound is more preferred. As for the carboxylic acid compound, for example, benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid, and the like can be cited. As for the phenol compound or naphthol compound, for example, hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalein, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, hydroquinone, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, 1,3,5-benzenetriol, 1,2,4-benzenetriol, dicyclopentadiene-type diphenol compounds, phenol novolac, etc. can be mentioned. Here, the "dicyclopentadiene-type diphenol compound" refers to a diphenol compound obtained by condensing two phenol molecules into one dicyclopentadiene molecule.

Specifically, active ester compounds containing dicyclopentadiene-type diphenol structures, active ester compounds containing naphthalene structures, active ester compounds containing acetylated products of phenol novolacs, and active ester compounds containing benzoylated products of phenol novolacs are preferred, among which active ester compounds containing naphthalene structures and active ester compounds containing dicyclopentadiene-type diphenol structures are more preferred. The so-called "dicyclopentadiene-type diphenol structure" refers to a divalent structural unit composed of phenylene-dicyclopentene-phenylene.

As for commercially available products of active ester curing agents, as active ester compounds containing dicyclopentadiene-type diphenol structures, there are "EXB9451", "EXB9460", "EXB9460S", "HPC-8000", "HPC-8000H", "HPC-8000-65T", "HPC-8000H-65TM", "EXB-8000L", "EXB-8000L-65M", "EXB-8000L-65TM" (manufactured by DIC Corporation); as active ester compounds containing naphthalene structures, there are "EXB-8000L-65M", "EXB-8000L-65TM" (manufactured by DIC Corporation); Examples of the active ester hardeners include "EXB-9416-70BK", "EXB-8150-65T", "EXB-8100L-65T", and "EXB-8150L-65T" (manufactured by DIC Corporation); examples of the active ester hardeners of the acetylated products of phenol novolac include "DC808" (manufactured by Mitsubishi Chemical Corporation); examples of the active ester hardeners of the benzoylated products of phenol novolac include "YLH1026" (manufactured by Mitsubishi Chemical Corporation), "YLH1030" (manufactured by Mitsubishi Chemical Corporation), and "YLH1048" (manufactured by Mitsubishi Chemical Corporation).

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

As for the cyanate curing agent, for example, bisphenol A dicyanate, polyphenol cyanate (oligo (3-methylene-1,5-phenylene cyanate)), 4,4'-methylenebis (2,6-dimethylphenyl cyanate), 4,4'-ethylenediphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis (4-cyanate) phenyl propane, 1,1-bis (4-cyanate) phenyl propane, The cyanate curing agent includes bifunctional cyanate resins such as bis(4-cyanate-3,5-dimethylphenyl)methane, 1,3-bis(4-cyanatephenyl-1-(methylethylidene))benzene, bis(4-cyanatephenyl)sulfide and bis(4-cyanatephenyl)ether, polyfunctional cyanate resins derived from phenol novolac and cresol novolac, and prepolymers of these cyanate resins partially triazinated. Specific examples of cyanate curing agents include "PT30" and "PT60" manufactured by Lonza Japan (both are phenol novolac type polyfunctional cyanate resins), "BA230", "BA230S75" (prepolymers of bisphenol A dicyanate partially or completely triazinated to form trimers), etc.

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

When the resin composition contains (D) a hardener, the amount ratio of (A) an epoxy resin to (D) a hardener is preferably 1:0.2 to 1:2, more preferably 1:0.3 to 1:1.5, and even more preferably 1:0.4 to 1:1.4, in terms of [number of epoxy groups of (A) an epoxy resin]:[number of reactive groups of (D) a hardener] Here, the reactive group of (D) a hardener is, for example, an aromatic hydroxyl group in the case of a phenol-based hardener or a naphthol-based hardener, and an active ester group in the case of an active ester-based hardener, depending on the type of the hardener.

(D) The reactive group equivalent of the hardener is preferably 50 g/eq. to 3,000 g/eq., more preferably 100 g/eq. to 1,000 g/eq., still more preferably 100 g/eq. to 500 g/eq., and particularly preferably 100 g/eq. to 300 g/eq. The reactive group equivalent is the mass of the hardener per 1 equivalent of the reactive group.

When the (D) hardener contains an active ester hardener, the content thereof is not particularly limited, but when the total amount of the (D) hardener is 100% by mass, it is preferably 10% by mass or more, more preferably 20% by mass or more, further preferably 30% by mass or more, and particularly preferably 40% by mass or more.

When the resin composition contains the (D) hardener, the content of the (D) hardener in the resin composition is not particularly limited, but is preferably 1% by mass or more, more preferably 3% by mass or more, further preferably 7% by mass or more, and particularly preferably 10% by mass or more, based on 100% by mass of the non-volatile components in the resin composition. The upper limit of the content of the (D) hardener is not particularly limited, but is preferably 70% by mass or less, more preferably 50% by mass or less, further preferably 30% by mass or less, and particularly preferably 20% by mass or less, based on 100% by mass of the non-volatile components in the resin composition.

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

(E) The curing accelerator is not particularly limited, but examples thereof include phosphorus-based curing accelerators, urea-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, guanidine-based curing accelerators, and metal-based curing accelerators. Among them, phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, and metal-based curing accelerators are preferred, and imidazole-based curing accelerators are particularly preferred. The curing accelerators may be used alone or in combination of two or more.

Phosphorus-based hardening accelerators include aliphatic phosphonium salts such as tetrabutylphosphonium bromide, tetrabutylphosphonium chloride, tetrabutylphosphonium acetate, tetrabutylphosphonium decanoate, tetrabutylphosphonium laurate, di(tetrabutylphosphonium) pyruvate, tetrabutylphosphonium hydrohexahydrophthalic acid, tetrabutylphosphonium cresol novolac trihydrate, and di-tert-butylmethylphosphonium tetraphenylborate; methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, propyltriphenylphosphonium bromide, butyltriphenylphosphonium bromide, benzyltriphenylphosphonium chloride, tetraphenylphosphonium bromide, p-tolyltriphenylphosphonium tetra-p-tolylborate, tetraphenylphosphonium tetraphenyl Aromatic phosphonium salts such as borate, tetraphenylphosphonium tetra-p-tolylborate, triphenylethylphosphonium tetraphenylborate, tris(3-methylphenyl)ethylphosphonium tetraphenylborate, tris(2-methoxyphenyl)ethylphosphonium tetraphenylborate, (4-methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate; aromatic phosphine-borane complexes such as triphenylphosphine and triphenylborane; aromatic phosphine-quinone addition products such as triphenylphosphine-p-benzoquinone addition products; tributylphosphine, tri-tert-butylphosphine, trioctylphosphine, di-tert-butyl(2-butenyl)phosphine aliphatic phosphines such as di-tert-butyl(3-methyl-2-butenyl)phosphine and tricyclohexylphosphine; dibutylphenylphosphine, di-tert-butylphenylphosphine, methyldiphenylphosphine, ethyldiphenylphosphine, butyldiphenylphosphine, diphenylcyclohexylphosphine, triphenylphosphine, tri-o-tolylphosphine, tri-m-tolylphosphine, tri-p-tolylphosphine, tris(4-ethylphenyl)phosphine, tris(4-propylphenyl)phosphine, tris(4-isopropylphenyl)phosphine, tris(4-butylphenyl)phosphine, tris(4-tert-butylphenyl)phosphine, tris(2,4-dimethylphenyl)phosphine, tris(2,5-dimethylphenyl)phosphine, tris(4-ethylphenyl)phosphine, tris(4-propylphenyl)phosphine, tris(4-isopropylphenyl)phosphine, tris(4-butylphenyl)phosphine, tris(4-tert-butylphenyl)phosphine, tris(2,4-dimethylphenyl)phosphine, tris(2,5-dimethylphenyl)phosphine, tris(4- Aromatic phosphines such as (2,6-dimethylphenyl)phosphine, (3,5-dimethylphenyl)phosphine, (2,4,6-trimethylphenyl)phosphine, (2,6-dimethyl-4-ethoxyphenyl)phosphine, (2-methoxyphenyl)phosphine, (4-methoxyphenyl)phosphine, (4-ethoxyphenyl)phosphine, (4-tert-butoxyphenyl)phosphine, diphenyl-2-pyridylphosphine, 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane, 1,4-bis(diphenylphosphino)butane, 1,2-bis(diphenylphosphino)acetylene, and 2,2'-bis(diphenylphosphino)diphenyl ether.

As for the urea-based hardening accelerator, there can be mentioned, for example, 1,1-dimethylurea; aliphatic dimethylureas such as 1,1,3-trimethylurea, 3-ethyl-1,1-dimethylurea, 3-cyclohexyl-1,1-dimethylurea, 3-cyclooctyl-1,1-dimethylurea; 3-phenyl-1,1-dimethylurea, 3-(4-chlorophenyl)-1,1-dimethylurea, 3-(3,4-dichlorophenyl)-1,1-dimethylurea, 3-(3-chloro-4-methylphenyl)-1,1-dimethylurea, 3-(2-methylphenyl)-1,1-dimethylurea, 3-(4-methylphenyl)-1,1-dimethylurea, 3-(3,4-dimethylphenyl)-1,1 -dimethylurea, 3-(4-isopropylphenyl)-1,1-dimethylurea, 3-(4-methoxyphenyl)-1,1-dimethylurea, 3-(4-nitrophenyl)-1,1-dimethylurea, 3-[4-(4-methoxyphenoxy)phenyl]-1,1-dimethylurea, 3-[4-(4-chlorophenoxy)phenyl]-1,1-dimethylurea, 3-[3-(trifluoromethyl)phenyl]-1,1-dimethylurea, N,N-(1,4-phenylene)bis(N’,N’-dimethylurea), N,N-(4-methyl-1,3-phenylene)bis(N’,N’-dimethylurea) [toluenebis-dimethylurea] and the like.

As for the amine-based hardening accelerator, there can be mentioned trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine (DMAP), benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, 1,8-diazabicyclo(5,4,0)-undecene, etc., and 4-dimethylaminopyridine is preferred.

As for the imidazole hardening accelerator, for example, 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole trimellitate, 1-cyanoethyl-2-phenylimidazole trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl 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, cyanuric acid adduct of 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2-phenylimidazole Imidazole compounds such as cyanuric acid adducts, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, 2-phenylimidazoline, and adducts of imidazole compounds with epoxy resins.

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

As for the guanidine-based hardening accelerator, for example, cyanamide, 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-methylbiguanidine, 1-ethylbiguanidine, 1-n-butylbiguanidine, 1-n-octadecylbiguanidine, 1,1-dimethylbiguanidine, 1,1-diethylbiguanidine, 1-cyclohexylbiguanidine, 1-allylbiguanidine, 1-phenylbiguanidine, 1-(o-tolyl)biguanidine, and the like can be cited.

As the metal hardening accelerator, there can be mentioned metals, organic metal complexes or organic metal salts such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of the organometallic complex include organic cobalt complexes such as cobalt (II) acetylacetonate compounds and cobalt (III) acetylacetonate compounds, organic copper complexes such as copper (II) acetylacetonate compounds, organic zinc complexes such as zinc (II) acetylacetonate compounds, organic iron complexes such as iron (III) acetylacetonate compounds, organic nickel complexes such as nickel (II) acetylacetonate compounds, and organic manganese complexes such as manganese (II) acetylacetonate compounds. As for the organic metal salt, for example, zinc octylate, tin octylate, zinc cycloalkanoate, cobalt cycloalkanoate, tin stearate, zinc stearate, etc. can be mentioned.

When the resin composition contains the (E) hardening accelerator, the content of the (E) hardening accelerator in the resin composition is not particularly limited, but is preferably 0.0001% by mass or more, more preferably 0.001% by mass or more, further preferably 0.005% by mass or more, and particularly preferably 0.01% by mass or more, based on 100% by mass of the non-volatile components in the resin composition. The upper limit of the content of the (E) hardening accelerator is not particularly limited, but is preferably 5% by mass or less, more preferably 1% by mass or less, further preferably 0.1% by mass or less, and particularly preferably 0.05% by mass or less, based on 100% by mass of the non-volatile components in the resin composition.

<(F) Other additives> The resin composition of the present invention may further include any additives in terms of non-volatile components. Examples of such additives include organic fillers such as rubber particles, polyamide particles, and polysilicone particles; thermoplastic resins such as phenoxy resins, polyvinyl acetal resins, polyolefin resins, polysulfone resins, polyethersulfone resins, polyphenylene ether resins, polycarbonate resins, polyetheretherketone resins, and polyester resins; organic copper compounds, organic zinc compounds, and organic zinc compounds. Compounds, organic cobalt compounds and other organic metal compounds; phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium oxide, carbon black and other colorants; hydroquinone, diphenol, pyrogallol, phenothiazine and other polymerization inhibitors; silicone leveling agents, acrylic polymer leveling agents and other leveling agents; bentonite, montmorillonite and other viscosity enhancers; silicone disinfectants Foaming agents, acrylic defoaming agents, fluorine defoaming agents, vinyl resin defoaming agents; UV absorbers such as benzotriazole UV absorbers; adhesion enhancers such as urea silane; adhesion enhancers such as triazole adhesion enhancers, tetrazole adhesion enhancers, triazine adhesion enhancers; hindered phenol antioxidants, hindered amine Antioxidants such as antioxidants; fluorescent whitening agents such as diphenylethylene derivatives; surfactants such as fluorine-based surfactants and polysilicone-based surfactants; flame retardants other than non-reactive diphosphonitrile compounds such as phosphate-based flame retardants, nitrogen-based flame retardants (such as melamine sulfate), halogen-based flame retardants, and inorganic-based flame retardants (such as antimony trioxide). The additives may be used alone or in combination of two or more in any ratio. (F) The content of other additives may be appropriately set by a person familiar with the field.

<(G) Organic solvent> The resin composition of the present invention may contain any organic solvent as a volatile component in addition to the above-mentioned non-volatile component. (G) As for the organic solvent, any well-known organic solvent may be used appropriately, and its type is not particularly limited. (G) As for the organic solvent, there may be mentioned ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.; ester solvents such as methyl anhydride, ethyl anhydride, butyl anhydride, isobutyl anhydride, isoamyl anhydride, methyl propionate, ethyl propionate, γ-butyrolactone, etc.; ether solvents such as tetrahydropyran, tetrahydrofuran, 1,4-dioxane, diethyl ether, diisopropyl ether, dibutyl ether, diphenyl ether, etc.; alcohol solvents such as methanol, ethanol, propanol, butanol, ethylene glycol, etc.; 2-ethoxyethyl anhydride, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol acetate, γ-butyrolactone, methoxypropyl Ether ester solvents such as methyl lactate, ethyl lactate, 2-hydroxyisobutyric acid methyl ester, etc.; ester alcohol solvents such as 2-methoxypropanol, 2-methoxyethanol, 2-ethoxyethanol, propylene glycol monomethyl ether, diethylene glycol monobutyl ether (butyl carbitol), etc.; amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, etc.; sulfoxide solvents such as dimethyl sulfoxide; nitrile solvents such as acetonitrile and propionitrile; aliphatic hydrocarbon solvents such as hexane, cyclopentane, cyclohexane, methylcyclohexane, etc.; aromatic hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, trimethylbenzene, etc. (G) The organic solvent may be used alone or in combination of two or more at any ratio.

<Manufacturing method of resin composition> The resin composition of the present invention can be manufactured by adding and mixing (A) epoxy resin, (B) inorganic filler, (C) non-reactive azophosphine compound, (D) hardener as required, (E) hardening accelerator as required, (F) other additives as required, and (G) organic solvent as required in any reaction container in any order and/or at the same time. In addition, during the process of adding and mixing the components, the temperature can be appropriately set, and heating and/or cooling can be maintained temporarily or continuously. In addition, during the process of adding and mixing the components, stirring or shaking can also be performed. Furthermore, during or after the addition and mixing, the resin composition may be stirred using a stirring device such as a stirrer to be uniformly dispersed.

<Characteristics of resin composition> The resin composition of the present invention contains (A) epoxy resin, (B) inorganic filler and a predetermined amount of (C) non-reactive diphosphine compound, and can obtain a cured product with excellent heat resistance and crack resistance. In addition, one embodiment can obtain a cured product that can maintain excellent insulation for a long time even in an overly harsh environment. In addition, one embodiment can obtain a cured product with excellent flame retardancy.

The cured product of the resin composition of the present invention has heat resistance. For example, the glass transition temperature measured by thermomechanical analysis (TMA) is preferably 130°C or higher, more preferably 140°C or higher, further preferably 145°C or higher, further preferably 150°C or higher, and particularly preferably 155°C or higher.

The cured product of the resin composition of the present invention has excellent crack resistance. After the circuit substrate is manufactured and roughened as in the following Test Example 2, when the copper pads of 100 circuit substrates are observed, the number of cracks is preferably 10 or less.

One embodiment is that the cured product of the resin composition of the present invention can maintain excellent insulation for a long time even in an extremely harsh environment. Therefore, when a circuit substrate is obtained by laminating a layer of the resin composition of the present invention (thickness 40μm) on a polyimide substrate with a comb-shaped wiring pattern of L/S=15/15 and curing it, and then irradiating it for 200 hours at 130°C, 98% humidity, and an applied voltage of 3.3V, the insulation resistance value is preferably above ^1x10-10Ω .

One embodiment is a cured product of the resin composition of the present invention, which has excellent flame retardancy and can preferably obtain a rating of "V0" or above when evaluated according to the UL flame retardancy test specification (UL-94).

<Use of resin composition> The resin composition of the present invention is suitable for use as a resin composition for insulation, in particular, as a resin composition for forming an insulating layer. Specifically, it can be suitably used as a resin composition for forming an insulating layer (resin composition for forming an insulating layer for forming a conductive layer), wherein the insulating layer is formed on the conductive layer (including a redistribution layer). Furthermore, in the printed wiring board described later, it can be suitably used as a resin composition for forming an insulating layer of a printed wiring board (resin composition for forming an insulating layer of a printed wiring board). The resin composition of the present invention can be widely used in applications that require a resin composition, such as resin sheets, prepregs, and other sheet-shaped laminate materials, solder resists, primer filling materials, chip bonding materials, semiconductor sealing materials, hole embedding resins, and component embedding resins.

Furthermore, for example, when a semiconductor chip package is manufactured through the following steps (1) to (6), the resin composition of the present invention can be applied to a resin composition for a redistribution forming layer (resin composition for forming a redistribution forming layer) as an insulating layer for forming a redistribution layer and a resin composition for sealing a semiconductor chip (resin composition for sealing a semiconductor chip). When the semiconductor chip package is manufactured, a redistribution layer can be further formed on the sealing layer. (1) a step of laminating a temporary fixing film on a substrate, (2) a step of temporarily fixing a 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 substrate and the temporary fixing film from the semiconductor chip, (5) a step of forming a redistribution layer as an insulating layer on the surface of the semiconductor chip from which the substrate and the temporary fixing film have been peeled, and (6) a step of forming a redistribution layer as a conductive layer on the redistribution layer

Furthermore, the resin composition of the present invention is also suitable for use when the printed wiring board is a component-embedded circuit board because it provides an insulating layer with good component embedding properties.

<Flake-like laminated material> The resin composition of the present invention can also be used in a painted state, but in general, it is preferably used in the form of a flaky laminated material containing the resin composition in industry.

As for the sheet-like laminate material, the resin sheets and prepreg materials shown below are preferred.

One embodiment is a resin sheet, comprising a support and a resin composition layer disposed on the support, wherein the resin composition layer is formed by the resin composition of the present invention.

The thickness of the resin composition layer is preferably 50 μm or less, and more preferably 40 μm or less, from the viewpoint of providing a cured product with excellent insulation even when the printed wiring board is thinned and 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 is usually 5 μm or more, 10 μm or more, etc.

As for the support, there can be mentioned, for example, a film made of a plastic material, a metal foil, and a release paper, with a film made of a plastic material and a metal foil being preferred.

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

When a metal foil is used as a support, the metal foil may be, for example, copper foil, aluminum foil, etc., with copper foil being preferred. The copper foil may be a foil made of copper alone, or a foil made of an alloy of copper and other metals (e.g., tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.).

The support system may be subjected to matte treatment, corona treatment, and antistatic treatment on the surface that is bonded to the resin composition layer.

In addition, the support may be a support having a release layer on the surface bonded to the resin composition layer. As the release agent used for the release layer of the support having the release layer, for example, one or more release agents selected from the group consisting of alkyd resins, polyolefin resins, urethane resins and silicone resins may be mentioned. The support to which the release layer is attached may be a commercially available product, for example, a PET film having a release layer having an alkyd resin-based release agent as a main component, such as "SK-1", "AL-5", and "AL-7" manufactured by LINTEC, "Lumirror T60" manufactured by Toray, "Purex" manufactured by Teijin, and "unipeel" manufactured by UNITIKA.

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

One embodiment is a resin sheet, which may include any layer as required. The arbitrary layer may be, for example, a protective film that is provided on the surface of the resin composition layer that is not bonded to the support (i.e., the surface opposite to the support) and is in contact with the support. The thickness of the protective film is not particularly limited, for example, 1 μm to 40 μm. By laminating the protective film, the adhesion or scratching of dust on the surface of the resin composition layer can be suppressed.

The resin sheet can be produced, for example, by directly applying a liquid resin composition or preparing a resin paint prepared by dissolving the resin composition in an organic solvent, applying the resin paint on a support using a die coater, and then drying the resin composition to form a resin composition layer.

As the organic solvent, the same ones as those explained as the components of the resin composition can be cited. The organic solvent may be used alone or in combination of two or more.

Drying can be carried out by a well-known method such as heating or blowing hot air. The drying conditions are not particularly limited, and the resin composition layer is dried in such a manner that the content of the organic solvent is 10% by mass or less, preferably 5% by mass or less. Although it varies depending on the boiling point of the organic solvent in the resin composition or resin paint, for example, when a resin composition or resin paint containing 30% to 60% by mass of an organic solvent is used, the resin composition layer can be formed by drying it at 50°C to 150°C for 3 minutes to 10 minutes.

The resin sheet can be stored by rolling it into a roll. If the resin sheet has a protective film, it can be used by peeling off the protective film.

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

The sheet-like fiber substrate used for the prepreg is not particularly limited, and glass cloth, aramid non-woven fabric, liquid crystal polymer non-woven fabric, etc., which are commonly used as prepreg substrates, can be used. From the perspective of thinning the printed wiring board, the thickness of the sheet-like fiber substrate is preferably 50 μm or less, more preferably 40 μm or less, more preferably 30 μm or less, and particularly preferably 20 μm or less. There is no particular lower limit to the thickness of the sheet-like fiber substrate. It is usually 10 μm or more.

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

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

The sheet-shaped laminated material of the present invention is suitable for forming an insulating layer of a printed wiring board (for insulating layer of a printed wiring board) and is suitable for forming an interlayer insulating layer of a printed wiring board (for insulating layer of a printed wiring board).

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

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

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

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

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

Lamination can be performed using a commercially available vacuum laminator. Examples of commercially available vacuum laminators include the vacuum pressure laminator manufactured by Meiki Seisakusho Co., Ltd., the vacuum applicator manufactured by NIKKO Materials Co., Ltd., and the batch vacuum pressure laminator.

After lamination, the laminated resin sheet can be smoothed by, for example, applying pressure to the heat-pressing member from the support side under normal pressure (atmospheric pressure). The pressurizing conditions for the smoothing treatment can be the same as the heat-pressing conditions for the lamination described above. The smoothing treatment can be performed by a commercially available laminator. In addition, the lamination and smoothing treatment can also be performed continuously using the commercially available vacuum laminator described above.

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

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

For example, the heat curing conditions of the resin composition layer vary depending on the type of the resin composition, but the curing temperature is preferably 120°C to 240°C, more preferably 150°C to 220°C, and even more preferably 170°C to 210°C. The curing time is preferably 5 minutes to 120 minutes, more preferably 10 minutes to 100 minutes, and even more preferably 15 minutes to 100 minutes.

Before the resin composition layer is heat-hardened, the resin composition layer may be pre-heated at a temperature lower than the hardening temperature. For example, before the resin composition layer is heat-hardened, the resin composition layer may be pre-heated at a temperature of 50°C to 120°C, preferably 60°C to 115°C, more preferably 70°C to 110°C, for more than 5 minutes, preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes, and even more preferably 15 minutes to 100 minutes.

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

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

Step (III) is a step of opening a hole in the insulating layer, thereby forming a via hole, a through hole, etc. in the insulating layer. Step (III) can be implemented by, for example, drilling, laser, plasma, etc., depending on the composition of the resin composition used to form the insulating layer. The size or shape of the through hole can be appropriately determined according to the design of the printed wiring board.

Step (IV) is a step of roughening the insulating layer. Usually, stains are also removed in this step (IV). The roughening process and conditions are not particularly limited, and the generally known processes and conditions used when forming the insulating layer of the printed wiring board can be adopted. For example, the insulating layer can be roughened by sequentially performing swelling treatment with a swelling liquid, roughening treatment with an oxidizing agent, and neutralization treatment with a neutralizing liquid.

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

There is no particular limitation on the oxidizing agent used in the roughening treatment, and an alkaline permanganic acid solution formed by dissolving potassium permanganate or sodium permanganate in an aqueous solution of sodium hydroxide can be cited. The roughening treatment using an oxidizing agent such as an alkaline permanganic acid solution is preferably carried out by immersing the insulating layer in the oxidizing agent solution heated to 60°C to 100°C for 10 minutes to 30 minutes. In addition, the concentration of permanganate in the alkaline permanganic acid solution is preferably 5% by mass to 10% by mass. As for commercially available oxidizing agents, alkaline permanganic acid solutions such as "Concentrate Compact CP" and "Dosing solution Securiganth P" manufactured by Atotech Japan can be cited.

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

The treatment with the neutralizing solution can be performed by immersing the surface roughened with the oxidizing agent in the neutralizing solution at 30°C to 80°C for 5 to 30 minutes. From the perspective of workability, it is preferred to immerse the surface roughened with the oxidizing agent in the neutralizing solution at 40°C to 70°C for 5 to 20 minutes.

One embodiment is that the arithmetic mean roughness (Ra) of the insulating layer surface after the roughening treatment is not particularly limited, but is preferably less than 500nm, more preferably less than 400nm, and more preferably less than 300nm. Although there is no particular limitation on the lower limit, for example, it can be greater than 1nm or greater than 2nm. In addition, the root mean square roughness (Rq) of the insulating layer surface after the roughening treatment is preferably less than 500nm, more preferably less than 400nm, and more preferably less than 300nm. Although there is no particular limitation on the lower limit, for example, it can be greater than 1nm or greater than 2nm. The arithmetic mean roughness (Ra) and root mean square roughness (Rq) of the insulating layer surface can be measured using a non-contact surface roughness meter.

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

The conductive layer may be a single layer structure or a multiple layer structure consisting of two or more single metal layers or alloy layers formed of different types of metals or alloys. When the conductive layer is a multiple layer structure, the layer in contact with the insulating layer is preferably a single metal layer of chromium, zinc or titanium, or an alloy layer of nickel-chromium alloy.

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

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

First, a coating seed layer is formed on the surface of the insulating layer by electroless plating. Then, on the formed coating seed layer, a portion of the coating seed layer is exposed corresponding to the desired wiring pattern to form a mask pattern. After a metal layer is formed on the exposed coating seed layer by electrolytic plating, the mask pattern is removed. Thereafter, the unnecessary coating seed layer is removed by etching, etc., and a conductor layer having a desired wiring pattern can be formed.

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

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

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

In terms of semiconductor devices, various semiconductor devices for electrical products (e.g., computers, mobile phones, digital cameras, and televisions) and vehicles (e.g., two-wheeled vehicles, automobiles, trains, ships, and aircrafts) can be cited. [Example]

The present invention is specifically described below by way of examples. The present invention is not limited to these examples. In addition, in the following examples, "parts" and "%" indicating quantities mean "parts by mass" and "% by mass" respectively unless otherwise specified.

<Example 1> 7 parts of epoxy resin ("HP-4032-SS" manufactured by DIC Corporation, epoxy equivalent of about 144), 3 parts of epoxy resin ("ESN-475V" manufactured by Nippon Steel Chemical & Materials Co., Ltd., epoxy equivalent of 332), and 0.2 parts of non-reactive azophosphite compound ("FP-100" manufactured by Fushimi Pharmaceutical Co., Ltd.) were dissolved in 10 parts of MEK. To this, 70 parts of spherical silica (average particle size 0.77 μm, Admatechs "SO-C2") surface-treated with an amine-based alkoxysilane compound ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.), 21 parts of an active ester compound ("HPC-8000-65T" manufactured by DIC Corporation, a toluene solution having a solid content of 65% by mass), 2 parts of a triazine-containing cresol novolac ("LA-3018-50P" manufactured by DIC Corporation, a methoxypropanol solution having a solid content of 50% by mass), 1 part of a carbodiimide resin ("V03" manufactured by Nisseibo Chemical Co., Ltd., a toluene solution having a solid content of 50% by mass), and 0.02 parts of an imidazole compound ("1B2PZ" manufactured by Shikoku Chemical Co., Ltd.) were uniformly dispersed using a high-speed rotary homogenizer to prepare a resin composition.

<Example 2> The resin composition was prepared in the same manner as in Example 1 except that the amount of the non-reactive azophosphite compound ("FP-100" manufactured by Fushimi Pharmaceutical Co., Ltd.) was changed from 0.2 parts to 0.4 parts.

<Example 3> The resin composition was prepared in the same manner as in Example 1 except that the amount of the non-reactive azophosphite compound ("FP-100" manufactured by Fushimi Pharmaceutical Co., Ltd.) was changed from 0.2 parts to 0.6 parts.

<Example 4> The resin composition was prepared in the same manner as in Example 1 except that the amount of the non-reactive azophosphite compound ("FP-100" manufactured by Fushimi Pharmaceutical Co., Ltd.) was changed from 0.2 parts to 0.9 parts.

<Comparative Example 1> The resin composition was prepared in the same manner as in Example 1 except that the amount of the non-reactive azophosphite compound ("FP-100" manufactured by Fushimi Pharmaceutical Co., Ltd.) was changed from 0.2 parts to 0.1 parts.

<Comparative Example 2> The resin composition was prepared in the same manner as in Example 1 except that the amount of the non-reactive azophosphite compound ("FP-100" manufactured by Fushimi Pharmaceutical Co., Ltd.) was changed from 0.2 parts to 1.1 parts.

<Comparative Example 3> The resin composition was prepared in the same manner as in Example 1 except that 0.4 parts of a phenolic hydroxyl group-containing azophosphine compound ("SPH-100" manufactured by Otsuka Chemical Co., Ltd.) was used instead of 0.2 parts of a non-reactive azophosphine compound ("FP-100" manufactured by Fushimi Pharmaceutical Co., Ltd.).

<Comparative Example 4> The resin composition was prepared in the same manner as in Example 1 except that 0.4 parts of a phenolic hydroxyl-containing cyclic phosphorus compound ("HCA-HQ" manufactured by Sanko Co., Ltd.) was used instead of 0.2 parts of a non-reactive azophosphine compound ("FP-100" manufactured by Fushimi Pharmaceutical Co., Ltd.).

<Production Example 1: Resin sheet with a thickness of 40 μm> For the support, a polyethylene terephthalate film ("AL5" manufactured by LINTEC, thickness 38 μm) with a release layer was prepared. On the release layer of this support, the resin composition obtained in the embodiment and the comparative example was uniformly applied in such a manner that the thickness of the resin composition layer after drying became 40 μm. Thereafter, the resin composition was dried at 80°C to 100°C (average 90°C) for 4 minutes to obtain a resin sheet containing a support and a resin composition layer.

<Preparation Example 2: Resin sheet with a thickness of 25 μm> Similar to Preparation Example 1, the resin composition obtained in the embodiment and the comparative example was uniformly applied in such a manner that the thickness of the resin composition layer after drying became 25 μm, and dried at 70°C to 80°C (average 75°C) for 2.5 minutes to obtain a resin sheet containing a support and a resin composition layer.

<Test Example 1: Determination of glass transition temperature by thermomechanical analysis (TMA)> The resin sheet with a thickness of 40 μm obtained in Preparation Example 1 was cured in an oven at 190°C for 90 minutes and then peeled off from the support to obtain a cured film. The cured product was cut into pieces with a length of 20 mm and a width of 6 mm as evaluation samples. The glass transition temperature (Tg) of this evaluation sample was measured from 25°C to 250°C at a heating rate of 5°C/min using a TMA device manufactured by Rigaku Corporation. The same test piece was measured twice, and the second value was recorded.

<Test Example 2: Evaluation of cracks after electroless copper plating (roughening treatment)> The 25μm thick resin sheet obtained in Preparation Example 2 was laminated on both sides of a core material ("E705GR", 400μm thick, manufactured by Hitachi Chemical Co., Ltd.) in which circular copper pads with a diameter of 350μm (copper thickness 35μm) were formed into a grid pattern with a spacing of 400μm so as to achieve a residual copper rate of 60%. The resin composition layer was bonded to the aforementioned inner substrate using a batch vacuum pressure laminator ("CVP700", 2-platform assembly laminator, manufactured by NIKKO Materials Co., Ltd.). This layering is carried out by reducing the pressure for 30 seconds to below 13hPa, and then pressing at a temperature of 100°C and a pressure of 0.74MPa for 30 seconds. This is placed in an oven at 130°C and heated for 30 minutes, and then moved to an oven at 170°C and heated for 30 minutes. Next, the support layer is peeled off, and the resulting circuit board is immersed in Swelling Dip Securiganth P of Atotech Japan (Co., Ltd.) as a swelling liquid for 10 minutes at 60°C. Then, it is immersed in Concentrate Compact P (aqueous solution of KMnO4: 60g/L, NaOH: 40g/L) of Atotech Japan (Co., Ltd.) as a roughening liquid for 30 minutes at 80°C. Finally, the substrate was immersed in Reduction solution Securiganth P of Atotech Japan (Co., Ltd.) as a neutralizing solution at 40°C for 5 minutes. 100 copper pads of the roughened circuit substrate were observed to check for cracks in the resin composition layer. If there were 10 or fewer cracks, it was evaluated as "0", and if there were more than 10 cracks, it was evaluated as "×".

<Test Example 3: Evaluation of Flame Retardancy> On both sides of a glass cloth-based epoxy resin laminate [copper foil etched product, substrate thickness 0.2mm, halogen-free core material, Hitachi Chemical Co., Ltd. 679FG], a batch vacuum pressure laminator (Nikko Materials Co., Ltd. 2-platform assembly laminator "CVP700") was used to laminate the 40μm thick resin sheet obtained in Preparation Example 1 on both sides of the laminate. Lamination was performed by decompressing the air pressure for 30 seconds to a pressure of 13hPa or less, and then pressurizing for 30 seconds at 100°C and a pressure of 0.74MPa. After peeling off the PET film from the laminated resin sheet, the same resin sheet is further laminated on it under the same conditions. The PET film is peeled off from the outermost resin sheet and the resin composition is cured under the curing conditions of 190°C and 90 minutes. After that, for the UL flame retardancy test, it is cut into a size of 12.7mm×127mm, and the end surface is polished with sandpaper (#1200 then #2800) to make a test piece for the flammability test with a base material thickness of 0.2mm and an insulating layer of 80μm laminated on one side. After that, it is evaluated as "V0" and "V1" according to the UL flame retardancy test specification (UL-94). In addition, when no sample remains after 10 seconds of burning, the evaluation is "×".

<Test Example 4: Evaluation of Insulation> The resin sheet with a thickness of 40 μm obtained in Preparation Example 1 was laminated on both sides of the inner substrate by using a batch vacuum pressure laminator (Nikko Materials Co., Ltd. 2-platform assembly laminator "CVP700") on a polyimide substrate with a comb-shaped wiring of L/S = 15/15, in such a way that the resin composition layer was bonded to the inner substrate mentioned above. This lamination was carried out by depressurizing the pressure for 30 seconds to a pressure of 13 hPa or less, and then pressing for 30 seconds at a temperature of 100°C and a pressure of 0.74 MPa. This was placed in an oven at 130°C for 30 minutes, then moved to an oven at 170°C for 30 minutes, and then the support was peeled off and heated at 190°C for 90 minutes to obtain a circuit substrate with a resin composition layered thereon. This was exposed to light at 130°C, 98% humidity, and 3.3V applied voltage for 200 hours, and then the insulation resistance was measured at 3.3V. If the insulation resistance was 1x10 ^-10 Ω or more, it was evaluated as "0", and if it was less than 1x10 ^-10 Ω, it was evaluated as "×".

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

It is known that by using a resin composition comprising (A) an epoxy resin, (B) an inorganic filler and 0.2 mass% to 1.0 mass% of (C) a non-reactive azophosphine compound, a cured product having excellent heat resistance and crack resistance can be obtained. In addition, it is known that a cured product having even better flame retardancy and being able to maintain excellent insulation for a long time even in an extremely harsh environment can be obtained.

Claims (13)

A resin composition comprising (A) an epoxy resin, (B) an inorganic filler, (C) an azophosphine compound having no epoxy-reactive group, and (D) a hardener, wherein the average particle size of the component (B) is less than 10 μm, the component (D) comprises a carbodiimide-based hardener, and when the non-volatile component in the resin composition is 100% by mass, the content of the component (C) is 0.2% to 1.0% by mass, and the glass transition temperature of the hardened resin composition is above 150°C. A resin composition comprising (A) an epoxy resin, (B) an inorganic filler, (C) an azophosphine compound having no epoxy-reactive group, and (D) a hardener, wherein the average particle size of the component (B) is less than 10 μm, the component (D) comprises a carbodiimide-based hardener, and the content of the component (B) is 70% by mass or more when the non-volatile component in the resin composition is 100% by mass, and the content of the component (C) is 0.2% by mass to 1.0% by mass when the non-volatile component in the resin composition is 100% by mass. The resin composition of claim 1 or 2, wherein component (B) is silicon oxide. The resin composition of claim 1, wherein the content of component (B) is 70% by mass or more when the non-volatile components in the resin composition are 100% by mass. The resin composition of claim 1 or 2, wherein the component (C) is a compound represented by the following formula (1):

[wherein n represents an integer of 1 to 20; R ¹ and R ² each independently represent an aryl group which may have 1 to 3 substituents selected from the group consisting of the following (a) to (e): (a) an alkyl group, (b) an alkoxy group, (c) a cyano group, (d) a halogen atom, (e) a group represented by the formula -XR ³ (wherein X represents a single bond, -(alkylene)-, -O-, -S-, -CO-, or -SO ₂ -, and R ³ represents an aryl group which may have 1 to 3 substituents selected from the group consisting of an alkyl group, an alkoxy group, a cyano group, and a halogen atom)]. The resin composition of claim 1 or 2, wherein component (D) comprises an active ester hardener. The resin composition of claim 1 or 2, wherein component (D) comprises either or both of a phenolic hardener and a naphthol hardener. The resin composition of claim 1 or 2 is a resin composition used to form an insulating layer of a printed wiring board. A cured product of a resin composition as described in any one of claims 1 to 8. A lamellar laminate material comprising a resin composition as described in any one of claims 1 to 8. A resin sheet having a support and a resin composition layer formed by a resin composition as described in any one of claims 1 to 8 and disposed on the support. A printed wiring board having an insulating layer formed by a cured product of a resin composition as described in any one of claims 1 to 8. A semiconductor device comprising a printed wiring board as claimed in claim 12.