TW202115168A - Resin composition - Google Patents

Abstract

The present invention addresses the problem of providing a resin composition with which it is possible to obtain a cured product having excellent heat resistance and crack resistance. The resin composition comprises (A) an epoxy resin, (B) an inorganic filler and (C) a non-reactive phosphazene compound, wherein the content of the component (C) is 0.2-1.0 mass% when the content of non-volatile components in the resin composition is taken as 100 mass%.

Description

Resin composition

The present invention relates to a resin composition containing epoxy resin. Furthermore, it 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 terms of the manufacturing technology of the printed wiring board, a manufacturing method by an assembly method in which an insulating layer and a conductor layer are alternately laminated is known. In the manufacturing method of the assembly method, generally, the insulating layer is formed by curing a resin composition.

Printed wiring boards are generally exposed to a wide range of temperature environments from a low temperature environment such as room temperature to a high temperature environment. If the linear thermal expansion coefficient is high, the dimensional stability will be poor, and the resin material of the insulating layer will expand repeatedly. With shrinkage, cracks will occur due to the distortion.

In addition, epoxy resin compositions containing a phenol-based hydroxyl group-containing azo compound are known (Patent Documents 1 and 2). [Prior Technical Literature] [Patent Literature]

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

[The problem to be solved by the invention]

The subject of the present invention is to provide a resin composition that can obtain a cured product having excellent heat resistance and crack resistance in a wide temperature environment. [Means to solve the problem]

In order to achieve the subject of the invention, the present inventors devoted themselves to the results of the review and found that by using (A) epoxy resin, (B) inorganic filler and 0.2 mass% to 1.0 mass% (C) non-reactive The resin composition of the azo compound can obtain a cured product having excellent heat resistance and crack resistance, and the present invention has been completed.

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

[In the formula, n represents an integer of 1-20. R ¹ and R ² each independently represent an aryl group which may have 1 to 3 substituents selected from the group consisting of (a) to (e): (a) alkyl, (b) alkoxy , (C) cyano group, (d) halogen atom, (e) formula -XR ³ (where X represents a single bond, -(alkylene)-, -O-, -S-, -CO-, or -SO _{2 -.} R ³ represents a group represented by 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 according to any one of [1] to [4] above, which further contains (D) a hardener. [6] The resin composition according to the above [5], wherein the component (D) contains an active ester curing agent. [7] A cured product of the resin composition of any one of [1] to [6] above. [8] A sheet-like laminated material containing the resin composition of any one of [1] to [6] above. [9] A resin sheet having a support and a resin composition layer formed on the support and formed of the resin composition of any one of [1] to [6] above. [10] A printed wiring board provided with an insulating layer made of a cured product of the resin composition of any one of [1] to [6] above. [11] A semiconductor device including the printed wiring board of [10] above. [Effects of Invention]

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

Hereinafter, the present invention will be described in detail based on its suitable embodiments. However, the present invention is not limited to the following embodiments and exemplified materials, and can be modified and implemented arbitrarily within the scope of the present invention and its equivalent scope.

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

The resin composition of the present invention may further include arbitrary components in addition to (A) epoxy resin, (B) inorganic filler, and (C) non-reactive azo compound. The optional components include (D) curing agents, (E) curing accelerators, (F) other additives, and (G) organic solvents. Hereinafter, each component contained in the resin composition will be explained in detail.

＜(A) Epoxy resin＞ The resin composition of the present invention contains (A) epoxy resin. The (A) epoxy resin means a curable resin having an epoxy group.

(A) Epoxy resins include, for example, bisxylenol type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, and bisphenol AF type epoxy resins. Resin, dicyclopentadiene type epoxy resin, ginseng phenol type epoxy resin, naphthol novolak type epoxy resin, phenol novolak type epoxy resin, tert-butyl-benzenediol type epoxy resin, naphthalene Type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidylamine type epoxy resin, glycidyl ester type epoxy resin, cresol novolak type epoxy resin, biphenyl type epoxy resin , Linear aliphatic epoxy resin, epoxy resin with butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring containing epoxy resin, cyclohexane type epoxy resin, ring Hexane dimethanol type epoxy resin, naphthyl ether type epoxy resin, trimethylol type epoxy resin, tetraphenylethane type epoxy resin, isocyanurate type epoxy resin, etc. Among them, naphthalene type epoxy resins and naphthol type epoxy resins are particularly preferred. (A) Epoxy resin may be used individually by 1 type, and may be used in combination of 2 or more types.

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

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

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

For liquid epoxy resins, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, and glycidyl amine Type epoxy resin, phenol novolac type epoxy resin, alicyclic epoxy resin with ester skeleton, cyclohexane type epoxy resin, cyclohexane dimethanol type epoxy resin and epoxy resin with butadiene structure The resin is preferable, and the naphthalene type epoxy resin is particularly preferable.

Specific examples of liquid epoxy resins include "HP4032", "HP4032D", and "HP4032SS" (naphthalene type epoxy resin) manufactured by DIC; and "828US", "828EL", and "Mitsubishi Chemical Corporation" manufactured by Mitsubishi Chemical Corporation. "jER828EL", "825", "EPIKOTE 828EL" (bisphenol A type epoxy resin); "jER807" and "1750" (bisphenol F type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER152" manufactured by Mitsubishi Chemical Corporation "(Phenol novolac type epoxy resin); "630", "630LSD", "604" (glycidylamine type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "ED-523T" (glycyrrhizol type) manufactured by ADEKA Epoxy resin); "EP-3950L" and "EP-3980S" (glycidylamine epoxy resin) manufactured by ADEKA; "EP-4088S" (dicyclopentadiene epoxy resin) manufactured by ADEKA ; "ZX1059" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. (a mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin); "EX-721" manufactured by Nagase ChemteX (glycidyl ester type epoxy resin) Resin); "CELLOXIDE2021P" (alicyclic epoxy resin with ester skeleton) manufactured by Daicel; "PB-3600" manufactured by Daicel, "JP-100" and "JP-200" manufactured by Soda Corporation of Japan ( Epoxy resin with butadiene structure); "ZX1658" and "ZX1658GS" (liquid 1,4-glycidyl cyclohexane type epoxy resin) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. These can be used individually by 1 type, and can also be used in combination of 2 or more types.

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

For solid epoxy resin, bis-xylenol type epoxy resin, naphthalene type epoxy resin, naphthalene type tetrafunctional epoxy resin, cresol novolak type epoxy resin, dicyclopentadiene type epoxy resin , Phenol type epoxy resin, naphthol type epoxy resin, biphenyl type epoxy resin, naphthyl ether type epoxy resin, anthracene type epoxy resin, bisphenol A type epoxy resin, bisphenol AF type epoxy resin Resin and tetraphenylethane type epoxy resin are preferred, and naphthol type epoxy resin is particularly preferred.

Specific examples of solid epoxy resins include "HP4032H" (naphthalene type epoxy resin) manufactured by DIC; "HP-4700" and "HP-4710" (naphthalene type tetrafunctional epoxy resin) manufactured by DIC Resin); "N-690" (cresol novolac type epoxy resin) manufactured by DIC; "N-695" (cresol novolak type epoxy resin) manufactured by DIC; "HP- 7200", "HP-7200HH", "HP-7200H" (dicyclopentadiene epoxy resin); "EXA-7311", "EXA-7311-G3", "EXA-7311-G4" manufactured by DIC Corporation ", "EXA-7311-G4S", "HP6000" (naphthyl ether type epoxy resin); "EPPN-502H" (ginseng phenol type epoxy resin) manufactured by Nippon Kayaku Corporation; "NC7000L" manufactured by Nippon Kayaku Corporation "(Naphthol novolac type epoxy resin); "NC3000H", "NC3000", "NC3000L", "NC3000FH", "NC3100" (biphenyl type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; Nippon Steel Chemical "ESN475V" (naphthol type epoxy resin) manufactured by ＆Materials; "ESN485" (naphthol type epoxy resin) manufactured by Nippon Steel Chemical & Materials Co., Ltd.; "ESN375" manufactured by Nippon Steel Chemical & Materials Co., Ltd. (2 Hydroxynaphthalene type epoxy resin); "YX4000H", "YX4000", "YL6121", "YL7890", "YX4000HK" (biphenyl type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YX8800" manufactured by Mitsubishi Chemical Corporation (Anthracene type epoxy resin); "YX7700" (novolac type epoxy resin containing xylene structure) manufactured by Mitsubishi Chemical Corporation; "PG-100" and "CG-500" manufactured by Osaka Gas Chemical Company; Mitsubishi Chemical Corporation "YL7760" (Bisphenol AF type epoxy resin) manufactured by the company; "YL7800" (Tea type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER1010" (solid bisphenol A epoxy resin) manufactured by Mitsubishi Chemical Corporation ); "jER1031S" (tetraphenylethane type epoxy resin) manufactured by Mitsubishi Chemical Corporation, etc. These can be used individually by 1 type, and can also be used in combination of 2 or more types.

(A) In terms of component, when liquid epoxy resin and solid epoxy resin are used together, the mass ratio of these (liquid epoxy resin: solid epoxy resin) is in the range of 100:1 to 1:100 Preferably, the range of 30:1~1:30 is even better, and the range of 10:1~1:10 is even better.

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

(A) The weight average molecular weight (Mw) of the epoxy resin is preferably 100 to 5,000, more preferably 250 to 3,000, and still 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 the gel permeation chromatography (GPC) method.

Although the content of (A) epoxy resin in the resin composition is not particularly limited, when the non-volatile content in the resin composition is 100% by mass, it is preferably 1% by mass or more, and more preferably 5% by mass or more. It is still more preferably 8% by mass or more, and particularly preferably 10% by mass or more. (A) Although the upper limit of the epoxy resin content is not particularly limited, when the non-volatile content in the resin composition is 100% by mass, it is preferably 50% by mass or less, more preferably 30% by mass or less, and still more It is preferably 20% by mass or less, and particularly preferably 15% by mass or less.

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

(B) As for the material of the inorganic filler, an inorganic compound is used. (B) In terms of materials for inorganic fillers, for example, silica, alumina, glass, vermilionite, 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, titanic acid Bismuth, titanium oxide, zirconium oxide, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate and zirconium tungstate phosphate, etc. Among these, silicon oxide is particularly suitable. Regarding silica, examples thereof include amorphous silica, molten silica, crystalline silica, synthetic silica, and hollow silica. In addition, for silica, spherical silica is preferred. (B) An inorganic filler may be used individually by 1 type, and may be used combining 2 or more types at arbitrary ratios.

(B) Commercial products of inorganic fillers include "UFP-30" manufactured by Denka Chemical Industry Co., Ltd.; "SP60-05" and "SP507-05" manufactured by Nippon Steel & Sumitomo Metal Materials Co., Ltd.; and "SP507-05" manufactured by Admatechs Co., Ltd. "YC100C", "YA050C", "YA050C-MJE", "YA010C"; "UFP-30" manufactured by Denka; "Silfil NSS-3N", "Silfil NSS-4N", "Silfil NSS" manufactured by TOKUYAMA -5N"; "SC2500SQ", "SO-C4", "SO-C2", "SO-C1" manufactured by Admatechs; "DAW-03", "FB-105FD" manufactured by Denka, etc.

(B) Although the average particle size of the inorganic filler is not particularly limited, it is preferably 40 μm or less, more preferably 10 μm or less, still more preferably 5 μm or less, still more preferably 3 μm or less, particularly preferably 1 μm or less. (B) Although the lower limit of the average particle size of the inorganic filler is not particularly limited, it is preferably 0.005 μm or more, more preferably 0.01 μm or more, still more preferably 0.05 μm or more, still more preferably 0.1 μm or more, and again It is more preferably 0.3 μm or more, particularly preferably 0.4 μm or more. (B) The average particle size of the inorganic filler can be measured by the laser diffraction and scattering method based on the Mie scattering theory. Specifically, with a laser diffraction scattering type particle size distribution measuring device, the particle size distribution of the inorganic filler can be created on a volume basis, and the median diameter can be measured as the average particle size. For the measurement sample system, 100 mg of inorganic filler and 10 g of methyl ethyl ketone can be weighed into a small glass bottle and dispersed by ultrasound for 10 minutes. Use a laser diffraction particle size distribution measuring device for the measurement sample, divide the wavelength of the light source into blue and red, measure the volume-based particle size distribution of the inorganic filler by the flow cell method, and calculate the average from the obtained particle size distribution The particle size is taken as the median diameter. Examples of laser diffraction particle size distribution measuring devices include "LA-960" manufactured by Horiba Manufacturing Co., Ltd., and the like.

(B) Although the specific surface area of the inorganic filler is not particularly limited, it 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) Although the upper limit of the specific surface area of the inorganic filler is not particularly limited, it 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 based on the BET method, using a specific surface area measuring device (Macsorb HM-1210 manufactured by Mountech) to adsorb nitrogen on the surface of the sample, and calculate the specific surface area by the BET multipoint method.

(B) Inorganic fillers are preferably those that have been surface-treated with a suitable surface treatment agent. By surface treatment, the moisture resistance and dispersibility of (B) inorganic filler can be improved. In terms of surface treatment agents, for example, vinyl-based silane coupling agents such as vinyl trimethoxy silane and vinyl triethoxy silane; 2-(3,4-epoxycyclohexyl) ethyl trimethoxy silane , 3-glycidoxymethyldimethoxysilane, 3-glycidoxytrimethoxysilane, 3-glycidoxymethyldiethoxysilane, 3-glycidoxypropoxy Epoxy silane coupling agent such as triethoxysilane; Styryl silane coupling agent such as p-styryltrimethoxysilane; 3-methacryloxypropylmethyldimethoxysilane , 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, etc. Methacrylic silane coupling agent; acrylic silane coupling agent such as 3-propenoxypropyltrimethoxysilane; N-2-(aminoethyl)-3-aminopropylmethyldimethoxy Silane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3- Triethoxysilyl-N-(1,3-dimethyl-butylene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-8-amino Amino-based silane coupling agents such as octyltrimethoxysilane, N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane, etc.; see -(trimethoxysilyl) Propyl) isocyanurate-based silane coupling agent such as isocyanurate; 3-ureidopropyl trialkoxysilane, etc. urea-based silane coupling agent; 3-mercaptopropyl methyl Mercapto-based silane coupling agents such as dimethoxysilane and 3-mercaptopropyl trimethoxysilane; isocyanate-based silane coupling agents such as 3-isocyanate propyl triethoxy silane; 3-trimethoxysilyl propyl Acid anhydrides such as succinic anhydride and other silane coupling agents; such as silane coupling agents; methyl trimethoxy silane, dimethyl dimethoxy silane, phenyl trimethoxy silane, methyl triethoxy silane, dimethyl Diethoxysilane, phenyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, octyltri Non-silane coupling-alkoxysilane compounds such as ethoxysilane, decyltrimethoxysilane, 1,6-bis(trimethoxysilyl)hexane, trifluoropropyltrimethoxysilane, etc. Moreover, a surface treatment agent may be used individually by 1 type, and may be used combining 2 or more types at arbitrary ratios.

Commercial products of surface treatment agents include, for example, "KBM-1003", "KBE-1003" (vinyl silane coupling agent) manufactured by Shin-Etsu Chemical Co., Ltd.; "KBM-303", "KBM-402", "KBM-403", "KBE-402", "KBE-403" (epoxy silane coupling agent); "KBM-1403" (styrene-based silane coupling agent); "KBM-502", "KBM- 503", "KBE-502", "KBE-503" (methacrylic silane coupling agent); "KBM-5103" (acrylic silane coupling agent); "KBM-602", "KBM-603", " KBM-903", "KBE-903", "KBE-9103P", "KBM-573", "KBM-575" (amino-based silane coupling agent); "KBM-9659" (isocyanurate-based Silane coupling agent); "KBE-585" (ureido-based silane coupling agent); "KBM-802", "KBM-803" (mercapto-based silane coupling agent); "KBE-9007N" (isocyanate-based silane coupling agent) ; "X-12-967C" (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 coupling-alkoxysilane compound) and so on.

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

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. The amount of carbon per unit surface area of the inorganic filler, from the viewpoint of improving the dispersibility of the inorganic filler, is preferably 0.02 mg/m ² or more, more preferably 0.1 mg/m ² or more, and 0.2 mg/m ² or more. Better. On the other hand, from the viewpoint of preventing the melt viscosity of the resin composition or the melt viscosity in the sheet form from increasing, 1.0 mg/m ² or less is preferable, 0.8 mg/m ² or less is more preferable, and 0.5 mg/m ² or less Better yet.

(B) The amount of carbon per unit surface area of the inorganic filler can be measured by washing the surface-treated inorganic filler with a solvent (for example, methyl ethyl ketone (MEK)). Specifically, in terms of solvent, a sufficient amount of MEK is added to an inorganic filler that has been surface-treated with a surface treatment agent, and ultrasonic cleaning is performed at 25°C for 5 minutes. After removing the supernatant and drying the solid content, the carbon content per unit surface area of the inorganic filler can be measured using a carbon analyzer. For carbon analyzers, "EMIA-320V" manufactured by Horiba Manufacturing Co., Ltd. can be used.

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

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

The so-called (C) non-reactive azo compound refers to a compound having a structural unit represented by -P=N- as a basic skeleton and not having an epoxy-reactive group. The structural unit shown by -P=N- in the basic skeleton can be a continuous repeating unit. The epoxy-reactive group means a functional group that has a tendency to react directly or indirectly with the epoxy group of the epoxy resin (A), and may be, for example, a hydroxyl group, an amino group, a mercapto group, a carboxyl group, and the like.

(C) As regards the non-reactive azo compound, for example, a non-reactive cyclic azo compound having a cyclic structure formed by a structural unit represented by -P=N-, and a non-reactive cyclic azo compound having a structure consisting of -P=N- Shows non-reactive polyazo compounds with a chain structure formed by structural units. In the present invention, the (C) non-reactive azo compound is preferably a non-reactive cyclic azo compound.

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

[In the formula, n represents an integer from 1 to 20, and R ¹ and R ² each independently represent an aryl group that may have 1 to 3 substituents selected from the group consisting of the following (a) to (e): (a) alkyl group, (b) alkoxy group, (c) cyano group, (d) halogen atom, (e) formula -XR ³ (where X represents a single bond, -(alkylene)-,- O-, -S-, -CO-, or -SO ₂ -, R ³ represents an aromatic 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基) The shown basis].

The aryl group means a monovalent aromatic hydrocarbon group. The aryl group is preferably an aryl group with 6 to 14 carbon atoms, more preferably an aryl group with 6 to 10 carbon atoms. As for the aryl group, for example, phenyl, 1-naphthyl, 2-naphthyl, etc. are mentioned, and phenyl is preferred. The alkyl group means a linear or branched monovalent aliphatic saturated hydrocarbon group. The alkyl group is preferably an alkyl group with 1 to 6 carbon atoms, more preferably an alkyl group with 1 to 3 carbon atoms. Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, and the like. The alkoxy group means a monovalent group (alkyl-O-) formed by having an alkyl group bond to an oxygen atom. The alkoxy group is preferably an alkoxy group having 1 to 6 carbon atoms, and an alkoxy group having 1 to 3 carbon atoms is more preferable. In terms of alkoxy groups, for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, pentyloxy Wait. The so-called alkylene group means a linear or branched divalent aliphatic saturated hydrocarbon group. The alkylene group is preferably an alkylene having 1 to 6 carbon atoms, and an alkylene having 1 to 3 carbon atoms is more preferred. As for the alkylene group, for example, -CH ₂ -, -CH ₂ -CH ₂ -, -CH(CH ₃ )-, -CH ₂ -CH ₂ -CH ₂ -, -CH ₂ -CH(CH ₃ )- , -CH(CH ₃ )-CH ₂ -, -C(CH ₃ ) ₂ -, -CH ₂ -CH ₂ -CH ₂ -CH ₂ -, -CH ₂ -CH ₂ -CH(CH ₃ )-,- CH ₂ -CH(CH ₃ )-CH ₂ -, -CH(CH ₃ )-CH ₂ -CH ₂ -, -CH ₂ -C(CH ₃ ) ₂ -, -C(CH ₃ ) ₂ -CH _2- Wait. The halogen atom includes, for example, a fluorine atom, a chlorine atom, and a bromine atom.

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

(C) Specific examples of non-reactive azo compounds include compounds represented by the following formulae (2) to (4), but (C) non-reactive azo compounds are not limited to these Etc.

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

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

(C) Commercially available non-reactive azo compounds can be used, such as "SPS-100" manufactured by Otsuka Chemical Co., Ltd. (the compound represented by the above formula (2)), and "FP-" manufactured by Fushimi Pharmaceutical Co., Ltd. 100" (the compound represented by the above formula (2)), "FP-300" (the compound represented by the above formula (3)), "FP-390" (the compound represented by the above formula (4)), etc.

When the non-volatile content in the resin composition is 100% by mass, the content of the (C) non-reactive phosphorus nitrogen compound in the resin composition is 0.2% by mass or more. (C) The upper limit of the content of the non-reactive azo compound is 1.0% by mass or less when the non-volatile content in the resin composition is 100% by mass. From the viewpoint of further increasing the glass transition temperature, it is preferably It is 0.9% by mass or less, more preferably 0.7% by mass or less, and still more preferably 0.5% by mass or less.

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

The mass ratio ((C) component/(A) component) of the (C) non-reactive azo compound to the (A) epoxy resin in the resin composition is preferably 0.005 or more, more preferably 0.010 or more, especially Preferably, it is 0.015 or more. The upper limit of the mass ratio (component (C)/component (A)) is preferably 0.20 or less, more preferably 0.15 or less, and still more 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) a hardener. (D) Hardener has the function of hardening (A) epoxy resin.

(D) Hardeners are not particularly limited. Examples include phenol hardeners, naphthol hardeners, acid anhydride hardeners, active ester hardeners, benzoxazine hardeners, and cyanate ester hardeners. Hardener and carbodiimide hardener. The curing agent may be used singly or in combination of two or more kinds. (D) The hardener is preferably one containing a hardener selected from a phenol hardener, a naphthol hardener, an active ester hardener, and a carbodiimide hardener, especially those containing an active ester hardener good.

Regarding the phenol hardener and the naphthol hardener, from the viewpoint of heat resistance and water resistance, a phenol hardener with a novolak structure or a naphthol hardener with a novolak structure is preferable. In addition, from the viewpoint of adhesion to the adherend, nitrogen-containing phenol hardeners or nitrogen-containing naphthol hardeners are preferred. The triazine skeleton contains a phenol hardener or the triazine skeleton contains naphthol. The hardener is better. Among them, from the viewpoint of satisfying a high degree of heat resistance, water resistance, and adhesion, it is preferable that the triazine skeleton contains a phenol novolak resin. Specific examples of phenol hardeners and naphthol hardeners include "MEH-7700", "MEH-7810", and "MEH-7851" manufactured by Meiwa Chemical Co., Ltd., and "NHN" manufactured by Nippon Kayaku Co., Ltd. , "CBN", "GPH", "SN-170", "SN-180", "SN-190", "SN-475", "SN-485", "SN- 495", "SN-375", "SN-395", "LA-7052", "LA-7054", "LA-3018", "LA-3018-50P", "LA-1356" manufactured by DIC , "TD2090", "TD-2090-60M", etc.

As for the acid anhydride-based curing agent, a curing agent having one or more acid anhydride groups in one molecule is mentioned, and one having two or more acid anhydride groups in one molecule is preferable. Specific examples of acid anhydride hardeners include anhydrous phthalic acid, tetrahydro anhydrous phthalic acid, hexahydro anhydrous phthalic acid, methyl tetrahydro anhydrous phthalic acid, methyl hexahydro anhydrous phthalic acid, methane Kinadic anhydride, hydrogenated methyl nadic anhydride, trialkyltetrahydro anhydrous phthalic acid, dodecenyl anhydrous succinic acid, 5-(2,5-di-side oxytetrahydro-3-yl)- 3-Methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, anhydrous trimellitic acid, anhydrous pyromellitic acid, benzophenone tetracarboxylic acid anhydride, biphenyl tetracarboxylic acid anhydrous , Naphthalenetetracarboxylic acid two anhydrate, oxydiphthalic acid two anhydrate, 3,3'-4,4'-diphenyl tetracarboxylic acid two anhydrate, 1,3,3a,4,5 ,9b-Hexahydro-5-(tetrahydro-2,5-dioxo-3-yl)-naphtho[1,2-C]furan-1,3-dione, ethylene glycol bis( Trimellitic anhydride ester), styrene and maleic acid copolymerized styrene, maleic acid resin and other polymer type acid anhydrides. Commercial products of acid anhydride hardeners include "HNA-100" and "MH-700" manufactured by Nippon Rika Corporation.

There are no particular restrictions on the active ester curing agent, but generally speaking, phenol esters, thiophenol esters, N-hydroxy amine esters, heterocyclic hydroxy compound esters, etc. are used in one molecule with 2 Compounds with more than one ester group with high reactivity are preferred. The active ester hardener is preferably obtained by the condensation reaction of a carboxylic acid compound and/or a thiocarboxylic acid compound and a hydroxyl compound and/or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester curing agent derived from a carboxylic acid compound and a hydroxy compound is preferred, and an active ester curing agent derived from a carboxylic acid compound, a phenol compound and/or a naphthol compound is more preferred . The carboxylic acid compound includes, for example, benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid, and the like. In terms of phenol compounds or naphthol compounds, for example, hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalein, methylated bisphenol A, methylated bisphenol F, methyl Bisphenol S, phenol, o-cresol, m-cresol, p-cresol, hydroquinone, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxyl Naphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, 1,3,5-benzenetriol, 1,2,4-benzenetriol, bicyclic Pentadiene type diphenol compounds, phenol novolacs, etc. Here, the "dicyclopentadiene-type diphenol compound" means a diphenol compound obtained by condensing two molecules of phenol in one molecule of dicyclopentadiene.

Specifically, it is an active ester compound containing a dicyclopentadiene type diphenol structure, an active ester compound containing a naphthalene structure, an active ester compound containing an acetyl compound of a phenol novolak, and a benzyl containing a phenol novolak. Active ester compounds of acyl compounds are preferred, and among them, active ester compounds containing naphthalene structure and active ester compounds containing dicyclopentadiene-type diphenol structure are more preferred. The so-called "dicyclopentadiene-type diphenol structure" means a bivalent structural unit formed by phenylene-dicyclopentene-phenylene.

As for the commercially available active ester hardeners, examples of active ester compounds containing dicyclopentadiene-type diphenol structure include "EXB9451", "EXB9460", "EXB9460S", "HPC-8000", and "HPC- 8000H", "HPC-8000-65T", "HPC-8000H-65TM", "EXB-8000L", "EXB-8000L-65M", "EXB-8000L-65TM" (manufactured by DIC); as a naphthalene-containing structure Examples of active ester compounds include "EXB-9416-70BK", "EXB-8150-65T", "EXB-8100L-65T", "EXB-8150L-65T" (manufactured by DIC Corporation); The active ester-based hardener of the acyl compound includes "DC808" (manufactured by Mitsubishi Chemical Corporation); the active ester-based hardener of the benzyl compound of the phenol novolak includes "YLH1026" (manufactured by Mitsubishi Chemical Corporation) , "YLH1030" (manufactured by Mitsubishi Chemical Corporation), "YLH1048" (manufactured by Mitsubishi Chemical Corporation), etc.

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

Regarding the cyanate ester curing agent, for example, bisphenol A dicyanate, polyphenol cyanate (oligo(3-methylene-1,5-phenylene cyanate)), 4, 4'-methylene bis(2,6-dimethylphenyl cyanate), 4,4'-ethylene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2, 2-bis(4-cyanate ester)phenyl propane, 1,1-bis(4-cyanate ester phenylmethane), bis(4-cyanate ester-3,5-dimethylphenyl)methane, 1,3-bis(4-cyanate phenyl-1-(methyl ethylene))benzene, bis(4-cyanate phenyl)sulfide and bis(4-cyanate phenyl)ether Such as bifunctional cyanate resins, polyfunctional cyanate resins derived from phenol novolacs and cresol novolacs, and partially triazineized prepolymers of these cyanate resins. Specific examples of cyanate ester curing agents include "PT30" and "PT60" (both phenol novolak type polyfunctional cyanate resin) manufactured by Lonza Japan, "BA230", and "BA230S75" (double Part or all of the phenol A dicyanate is triazineized to form a three-weight prepolymer) and so on.

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

When the resin composition contains (D) hardener, the ratio of the amount of (A) epoxy resin to (D) hardener is [(A) epoxy group number of epoxy resin]: [(D) reaction base number of hardener] In terms of the ratio, 1:0.2~1:2 is better, 1:0.3~1:1.5 is better, and 1:0.4~1:1.4 is even better. Here, (D) the reactive group of the hardener, for example, if it is a phenol-based hardener or a naphthol-based hardener, it is an aromatic hydroxyl group, if it is an active ester-based hardener, it is an active ester group, depending on the hardener The type varies.

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

(D) When the active ester-based hardener is contained in the hardener, its content is not particularly limited, but when the total amount of (D) hardener is 100% by mass, it is preferably 10% by mass or more, more preferably 20 % By mass or more, more preferably 30% by mass or more, particularly preferably 40% by mass or more.

When the resin composition contains (D) hardener, the content of (D) hardener in the resin composition is not particularly limited, but when the non-volatile content in the resin composition is 100% by mass, it is preferably 1 mass % Or more, more preferably 3% by mass or more, still more preferably 7% by mass or more, particularly preferably 10% by mass or more. (D) Although the upper limit of the content of the hardener is not particularly limited, when the non-volatile content in the resin composition is 100% by mass, it is preferably 70% by mass or less, more preferably 50% by mass or less, and even more preferably It is 30% by mass or less, particularly preferably 20% by mass or less.

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

(E) Hardening accelerators are not particularly limited, but examples include phosphorus-based hardening accelerators, urea-based hardening accelerators, amine-based hardening accelerators, imidazole-based hardening accelerators, guanidine-based hardening accelerators, and metal-based hardening accelerators. Hardening accelerator, etc. Among them, phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, and metal-based curing accelerators are more preferable, and imidazole-based curing accelerators are particularly preferable. A hardening accelerator may be used individually by 1 type, and may be used in combination of 2 or more types.

Phosphorus-based hardening accelerators include, for example, tetrabutylphosphonium bromide, tetrabutylphosphonium chloride, tetrabutylphosphonium acetate, tetrabutylphosphonium decanoate, tetrabutylphosphonium laurate, bis( (Tetrabutyl phosphonium) pyruvate, tetrabutyl phosphonium hydrogen hexahydrophthalic acid, tetrabutyl phosphonium cresol novolac 3-weight body salt, di-tert-butyl methyl phosphonium tetraphenyl borate and other aliphatic Phosphonium salt; methyl triphenyl phosphonium bromide, ethyl triphenyl phosphonium bromide, propyl triphenyl phosphonium bromide, butyl triphenyl phosphonium bromide, benzyl triphenyl phosphonium chloride, tetraphenyl Phosphonium bromide, p-tolyl triphenyl phosphonium tetra-p-tolyl borate, tetraphenyl phosphonium tetraphenyl borate, tetraphenyl phosphonium tetra p-tolyl borate, triphenyl ethyl phosphonium Tetraphenyl borate, ginseng (3-methylphenyl) ethyl phosphonium tetraphenyl borate, ginseng (2-methoxyphenyl) ethyl phosphonium tetraphenyl borate, (4-methylphenyl) ) Aromatic phosphonium salts such as triphenyl phosphonium thiocyanate, tetraphenyl phosphonium thiocyanate, butyl triphenyl phosphonium thiocyanate, etc.; triphenyl phosphine, triphenyl borane, etc. Aromatic phosphine and borane complex; triphenylphosphine, p-benzoquinone addition reactant and other aromatic phosphine and quinone addition reactants; tributyl phosphine, tri-tert-butyl phosphine, three Aliphatic phosphines such as octyl phosphine, di-tert-butyl (2-butenyl) phosphine, di-tert-butyl (3-methyl-2-butenyl) phosphine, tricyclohexyl phosphine, etc.; two Butylphenylphosphine, two-tert-butylphenylphosphine, methyldiphenylphosphine, ethyldiphenylphosphine, butyldiphenylphosphine, diphenylcyclohexylphosphine, triphenylphosphine, triphenylphosphine -o-tolylphosphine, tris-m-tolylphosphine, tris-p-tolylphosphine, ginseng(4-ethylphenyl)phosphine, ginseng(4-propylphenyl)phosphine, ginseng(4-iso Propylphenyl) phosphine, ginseng (4-butylphenyl) phosphine, ginseng (4-tert-butylphenyl) phosphine, ginseng (2,4-dimethylphenyl) phosphine, ginseng (2,5 -Dimethylphenyl)phosphine, ginseng(2,6-dimethylphenyl)phosphine, ginseng(3,5-dimethylphenyl)phosphine, ginseng(2,4,6-trimethylphenyl) )Phosphine, ginseng (2,6-dimethyl-4-ethoxyphenyl) phosphine, ginseng (2-methoxyphenyl) phosphine, ginseng (4-methoxyphenyl) phosphine, ginseng (4 -Ethoxyphenyl)phosphine, ginseng (4-tert-butoxyphenyl)phosphine, diphenyl-2-pyridylphosphine, 1,2-bis(diphenylphosphine)ethane, 1,3 -Bis(diphenylphosphine)propane, 1,4-bis(diphenylphosphine)butane, 1,2-bis(diphenylphosphine)acetylene, 2,2'-bis(diphenylphosphine)bis Aromatic phosphines such as phenyl ethers, etc.

Examples of urea-based hardening accelerators include 1,1-dimethylurea; 1,1,3-trimethylurea, 3-ethyl-1,1-dimethylurea, and 3-cyclohexyl-1 ,1-Dimethylurea, 3-cyclooctyl-1,1-dimethylurea and other aliphatic 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-methyl) (Oxyphenyl)-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)[toluene bis-dimethylurea] and other aromatic dimethylureas.

Examples of amine curing accelerators include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine (DMAP), benzyldimethylamine, 2,4,6 ,-(Dimethylaminomethyl)phenol, 1,8-diazabicyclo(5,4,0)-undecene, etc., and 4-dimethylaminopyridine is preferred.

Examples of imidazole-based hardening accelerators include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methyl Imidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl -4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2- Phenylimidazolium trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino -6-[2'-Undecylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methyl Imidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine Polycyanic acid adduct, 2-phenylimidazole cyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethyl Imidazole, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazole Imidazole compounds such as morpholine and 2-phenylimidazoline, and adducts of imidazole compounds and epoxy resin.

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

Regarding guanidine-based hardening accelerators, for example, dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, metformin Guanidine, diphenylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-methyl-1 ,5,7-Triazabicyclo[4.4.0]dec-5-ene, 1-methyl biguanide, 1-ethyl biguanide, 1-n-butyl biguanide, 1-n-octadecyl biguanide, 1,1-Dimethyl biguanide, 1,1-diethyl biguanide, 1-cyclohexyl biguanide, 1-allyl biguanide, 1-phenyl biguanide, 1-(o-tolyl) biguanide, etc.

As for the metal-based hardening accelerator, for example, metals such as cobalt, copper, zinc, iron, nickel, manganese, tin, organometallic complexes, or organometallic salts can be mentioned. Specific examples of organometallic complexes include organic cobalt complexes such as cobalt (II) acetone acetone compounds, cobalt (III) acetone acetone compounds, and organic copper such as copper (II) acetone acetone compounds. Complexes, organic zinc complexes such as zinc (II) acetone compounds, organic iron complexes such as iron (III) acetone compounds, and organic nickel complexes such as nickel (II) acetone compounds Organic manganese complexes such as manganese (II) acetone compounds, etc. The organic metal salt includes, for example, zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, zinc stearate, and the like.

When the resin composition contains (E) a hardening accelerator, the content of (E) hardening accelerator in the resin composition is not particularly limited, but when the non-volatile content in the resin composition is 100% by mass, it is preferably 0.0001% by mass or more, more preferably 0.001% by mass or more, still more preferably 0.005% by mass or more, particularly preferably 0.01% by mass or more. (E) Although the upper limit of the content of the hardening accelerator is not particularly limited, when the non-volatile content in the resin composition is 100% by mass, it is preferably 5% by mass or less, more preferably 1% by mass or less, and still more It is preferably 0.1% by mass or less, and particularly preferably 0.05% by mass or less.

＜(F) Other additives＞ The resin composition of the present invention may further include arbitrary additives in terms of non-volatile components. Examples of such additives include organic fillers such as rubber particles, polyamide particles, and silicone particles; phenoxy resins, polyvinyl acetal resins, polyolefin resins, polyether resins, and polyether resins. , Polyphenylene ether resin, polycarbonate resin, polyether ether ketone resin, polyester resin and other thermoplastic resins; organic copper compounds, organic zinc compounds, organic cobalt compounds and other organic metal compounds; phthalocyanine blue, phthalocyanine Coloring agents for cyanine green, iodine green, diazonium yellow, crystal violet, titanium oxide, carbon black, etc.; polymerization inhibitors for hydroquinone, benzenediol, benzenetriol, phenothiazine, etc.; polysiloxane-based leveling agent , Acrylic polymer-based leveling agents, etc.; tackifiers such as bentonite, montmorillonite, etc.; polysiloxane-based defoamers, acrylic defoamers, fluorine-based defoamers, vinyl Antifoaming agent for resin-based defoamers; UV absorbers such as benzotriazole-based ultraviolet absorbers; Adhesive upward agents such as urea silane; Triazole-based adhesiveness imparting agent, tetrazole-based adhesiveness imparting agent 、Adhesion imparting agents such as triazine-based adhesiveness imparting agents; antioxidants such as hindered phenol-based antioxidants and hindered amine-based antioxidants; fluorescent brighteners such as stilbene derivatives; fluorine-based interfacial activity Surfactants, silicone-based surfactants, etc.; phosphate ester-based flame retardants, nitrogen-based flame retardants (e.g. melamine sulfate), halogen-based flame retardants, inorganic flame retardants (e.g. triacid antimony) Flame retardants other than non-reactive phosphorus azo compounds. An additive may be used individually by 1 type, and may be used combining 2 or more types at arbitrary ratios. (F) The content of other additives can be set appropriately if it is an industry familiar with the field.

＜(G)Organic solvent＞ In addition to the above-mentioned non-volatile components, the resin composition of the present invention may further contain an arbitrary organic solvent as a volatile component. (G) As for the organic solvent, well-known ones can be used appropriately, and the kind is not particularly limited. (G) Organic solvents include, for example, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; methyl acetic acid, ethyl acetic acid, butyl acetic acid, and acetic acid Ester solvents such as isobutyl ester, isopentyl acetic acid, methyl propionate, ethyl propionate, γ-butyrolactone, etc.; tetrahydropyran, tetrahydrofuran, 1,4-dioxan, Ether solvents such as diethyl ether, diisopropyl ether, dibutyl ether, and diphenyl ether; alcohol solvents such as methanol, ethanol, propanol, butanol, ethylene glycol, etc.; acetic acid 2-ethoxy Ethyl ester, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol acetate, γ-butyrolactone, methyl methoxypropionate Ether ester solvents such as methyl lactate, ethyl lactate, methyl 2-hydroxyisobutyrate, etc.; 2-methoxypropanol, 2-methoxyethanol, 2-ethyl Ether alcohol solvents such as oxyethanol, propylene glycol monomethyl ether, diethylene glycol monobutyl ether (butyl carbitol); N,N-dimethylformamide, N,N-di Amine-based solvents such as methyl acetamide and N-methyl-2-pyrrolidone; sulfenic solvents such as dimethyl sulfide; nitrile solvents such as acetonitrile and propionitrile; hexane, cyclopentane, etc. Aliphatic hydrocarbon solvents such as cyclohexane and methylcyclohexane; aromatic hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, trimethylbenzene, etc. (G) An organic solvent may be used individually by 1 type, and may be used in combination of 2 or more types at arbitrary ratios.

＜Manufacturing method of resin composition＞ The resin composition of the present invention, for example, can be added and mixed partially or completely in any reaction container in any order and/or at the same time (A) epoxy resin, (B) inorganic filler, (C) non-reactive The azo compound, the required (D) hardening agent, the required (E) hardening accelerator, the required (F) other additives, and the required (G) organic solvent are manufactured by this method. In addition, during the process of adding and mixing each component, the temperature may be appropriately set, and heating and/or cooling may be maintained temporarily or all the time. In addition, in the process of adding and mixing each component, stirring or shaking may be performed. In addition, during or after the addition and mixing, the resin composition may be stirred using a stirring device such as a stirrer to uniformly disperse it.

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

Since 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, and still more preferably 145°C Above, it is more preferably 150°C or higher, and particularly preferably 155°C or higher.

Since the cured product of the resin composition of the present invention has excellent crack resistance, after the circuit board is produced and roughened as in the following test example 2, when the copper pads of 100 circuit boards are observed, the cracks are 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 a harsh environment. Therefore, the wiring is formed into a tooth-like shape with L/S=15/15 The resin composition layer (thickness 40μm) of the present invention is laminated on the polyimide substrate of the present invention to harden the circuit substrate, and the circuit substrate is exposed to 130°C, 98% humidity, and applied voltage 3.3V for 200 hours. The insulation is measured In the case of the resistance value, the insulation resistance value may preferably be 1× ^{10 -10} Ω or more.

One embodiment is that the cured product of the resin composition of the present invention has excellent flame retardancy. When evaluated in accordance with the UL flame retardancy test standard (UL-94), it is preferable to obtain an evaluation of "V0" or higher.

＜Use of resin composition＞ The resin composition of the present invention can be suitably used as a resin composition for insulation purposes, particularly 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) for forming a conductive layer formed on an insulating layer (including re- Wiring layer). In addition, in the printed wiring board described later, a resin composition for forming an insulating layer of the printed wiring board (resin composition for forming an insulating layer of a printed wiring board) can be suitably used. The resin composition of the present invention can also be used in sheet-like laminate materials such as resin sheets, prepregs, solder resists, primer fillers, die bonding materials, semiconductor sealing materials, hole-buried resins, parts-buried resins, etc. It must have the purpose of the resin composition and be widely used.

Also, for example, when a semiconductor chip package is manufactured through the following steps (1) to (6), the resin composition of the present invention can be suitably used as a resin composition for a rewiring forming layer of an insulating layer for forming a rewiring layer (A resin composition for forming a rewiring forming layer) and a resin composition for sealing a semiconductor wafer (a resin composition for sealing a semiconductor wafer). When the semiconductor chip package is manufactured, a rewiring layer can be further formed on the sealing layer. (1) The step of laminating a temporary fixing film on the substrate, (2) The step of temporarily fixing the semiconductor wafer on the temporary fixing film, (3) The step of forming a sealing layer on the semiconductor wafer, (4) The step of peeling the substrate and the temporary fixing film from the semiconductor wafer, (5) A step of forming a rewiring forming layer as an insulating layer on the surface where the substrate of the semiconductor wafer and the temporary fixing film have been peeled off, and (6) Step of forming a rewiring layer as a conductor layer on the rewiring forming layer

Furthermore, since the resin composition of the present invention provides an insulating layer with good part embedding properties, it is also very suitable when the printed wiring board is a circuit board with a built-in part.

＜Sheet-like laminated materials＞ Although the resin composition of the present invention can also be applied in a lacquered state, it is generally industrially preferred to be used in the form of a sheet-like laminated material containing the resin composition.

As for sheet-like laminate materials, the following resin sheets and prepregs are preferred.

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

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

As for the support, for example, a film made of plastic material, metal foil, and release paper, preferably a film made of plastic material, or metal foil.

When a film made of a plastic material is used as a support, the plastic material includes, for example, polyethylene terephthalate (hereinafter referred to as "PET"), polyethylene naphthalate (hereinafter referred to as "PEN") Polyester, polycarbonate (hereinafter referred to as "PC"), polymethylmethacrylate (PMMA) and other acrylics, cyclic polyolefins, triacetyl cellulose (TAC), polyether sulfide (PES), polyetherketone, polyimide, etc. Among them, polyethylene terephthalate and polyethylene naphthalate are more preferred, and cheap polyethylene terephthalate is particularly preferred.

When a metal foil is used as a support, examples of the metal foil include copper foil and aluminum foil, and copper foil is preferred. Regarding copper foil, foils made of a single metal of copper can be used, or foils made of alloys of copper and other metals (for example, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) can be used.

The support system can be subjected to matting treatment, corona treatment, and antistatic treatment on the surface joined with the resin composition layer.

In addition, as for the support, it can also be used for a support with a release layer having a release layer on the surface to be bonded to the resin composition layer. The release agent used in the release layer of the support with release layer includes, for example, one or more selected from the group consisting of alkyd resins, polyolefin resins, urethane resins, and silicone resins. The release agent. The support with a release layer can also use commercially available products. For example, a PET film with a release layer mainly composed of an alkyd resin-based release agent, such as "SK-1" and "AL" manufactured by LINTEC. -5", "AL-7", "Lumirror T60" manufactured by Toray, "Purex" manufactured by Teijin, "unipeel" manufactured by UNITIKA, etc.

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

According to one embodiment, the resin sheet may include any layers as required. The optional layer includes, for example, a protective film that is provided on the surface that is not bonded to the support of the resin composition layer (that is, the surface opposite to the support) conforms to the support. Although the thickness of the protective film is not particularly limited, it is, for example, 1 μm to 40 μm. With the laminated protective film, the adhesion or scratches of dust and the like on the surface of the resin composition layer can be suppressed.

For the resin sheet, for example, the liquid resin composition can be directly or prepared into a resin paint prepared by dissolving the resin composition in an organic solvent, and this can be applied to the support using a die coater or the like to further make it Drying forms the resin composition layer, and manufactures it thereby.

With respect to the organic solvent, the same organic solvent as the organic solvent explained as the component of the resin composition can be mentioned. An organic solvent may be used individually by 1 type, and may be used in combination of 2 or more types.

The drying system can be performed by well-known methods such as heating and blowing hot air. The drying conditions are not particularly limited, and the resin composition layer is dried so that the content of the organic solvent in the resin composition layer is 10% by mass or less, preferably 5% by mass or less. Although it differs depending on the boiling point of the organic solvent in the resin composition or resin paint, for example, when using a resin composition or resin paint containing 30% to 60% by mass of organic solvent, it can be reduced by 50°C to 150°C. It is dried for 3 minutes to 10 minutes to form a resin composition layer.

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

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

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

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

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

The sheet-like laminate material of the present invention is suitable for forming the insulating layer of a printed wiring board (for the insulating layer of a printed wiring board), and is suitable for forming the interlayer insulating layer of a printed wiring board (for the interlayer insulating layer of a printed wiring board) .

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

The printed wiring board can be manufactured by a method including the following steps (I) and (II) using the above-mentioned resin sheet, for example. (I) The step of laminating the resin sheet on the inner substrate by bonding the resin composition layer of the resin sheet to the inner substrate (II) The step of hardening (e.g. thermal hardening) the resin composition layer to form an insulating layer

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

The lamination of the inner layer substrate and the resin sheet can be performed, for example, by heating and pressing the resin sheet to the inner layer substrate from the support side. The member for heating and pressing the resin sheet on the inner substrate (hereinafter referred to as "heating and pressing member") includes, for example, a heated metal plate (SUS mirror plate, etc.) or metal roller (SUS roller). In addition, it is not that the heating and pressing member is directly pressurized on the resin sheet, but it is preferable that the resin sheet sufficiently follows the irregularities on the surface of the inner layer substrate and pressurizes through an elastic material such as heat-resistant rubber.

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

Laminating can be performed by a commercially available vacuum laminator. Commercially available vacuum laminators include, for example, a vacuum pressure laminator manufactured by Meike Manufacturing Co., Ltd., a vacuum applicator manufactured by NIKKO Materials Co., Ltd., and a batch vacuum pressure laminator.

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

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

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

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

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

When manufacturing a printed wiring board, (III) a step of opening a hole in the insulating layer, (IV) a step of roughening the insulating layer, and (V) a step of forming a conductor layer can be further implemented. These steps (III) and (V) can be implemented according to various methods well known to those skilled in the field used in the manufacture of printed wiring boards. In addition, when the support is removed after step (II), the support can be removed between step (II) and step (III), between step (III) and step (IV), or between step (IV) and step (IV). Implemented between steps (V). In addition, according to needs, the formation of the insulating layer and the conductor layer of steps (II) to (V) can be repeated to form a multilayer wiring board.

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

Step (III) is a step of opening a hole in the insulating layer, whereby vias such as vias and vias can be formed in the insulating layer. Step (III) can be carried out using, for example, drilling, laser, plasma, etc. because of the composition of the resin composition applied to the formation of 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 in this step (IV), stain removal will also be carried out. The procedure and conditions of the roughening treatment are not particularly limited, and well-known procedures and conditions generally used when forming the insulating layer of the printed wiring board can be adopted. For example, by sequentially performing swelling treatment by the swelling liquid, roughening treatment by the oxidizing agent, and neutralization treatment by the neutralization liquid, the insulating layer can be roughened.

The swelling liquid used in the roughening treatment is not particularly limited. Examples include alkaline solutions and surfactant solutions. Alkaline solutions are preferred. For the alkaline solution, sodium hydroxide solution or potassium hydroxide solution is more preferred. . Examples of commercially available swelling fluids 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. For example, the insulating layer can be immersed in the swelling liquid at 30°C to 90°C for 1 minute to 20 minutes. From the viewpoint of suppressing the swelling of the resin of the insulating layer to a moderate level, it is better to immerse the insulating layer in a swelling solution at 40°C to 80°C for 5 minutes to 15 minutes.

The oxidizing agent used in the roughening treatment is not particularly limited, and, for example, an alkaline permanganic acid solution obtained by dissolving potassium permanganate or sodium permanganate in an aqueous solution of sodium hydroxide can be mentioned. The roughening treatment by an oxidant such as an alkaline permanganic acid solution is preferably performed by immersing the insulating layer in an oxidant 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% to 10% by mass. Examples of commercially available oxidants include alkaline permanganic acid solutions such as "Concentrate Compact CP" and "Dosing solution Securiganth P" manufactured by Atotech Japan.

In addition, as for the neutralization liquid used in the roughening treatment, an acidic aqueous solution is preferred. As for a commercially available product, for example, "Reduction solution Securiganth P" manufactured by Atotech Japan can be mentioned.

The treatment by the neutralization liquid can be performed by immersing the treated surface roughened with an oxidizing agent in a neutralization liquid at 30°C to 80°C for 5 minutes to 30 minutes. From the viewpoint of workability, etc., the method of immersing the object subjected to the roughening treatment by the oxidizing agent in a neutralization solution at 40°C to 70°C for 5 minutes to 20 minutes is preferable.

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

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

The conductor layer may have a single-layer structure, a single metal layer made of different types of metals or alloys, or a multiple-layer structure formed by stacking two or more alloy layers. When the conductor layer has 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.

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

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

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

In other embodiments, the conductor layer can also be formed using metal foil. When a metal foil is used to form the conductor layer, step (V) is preferably implemented between step (I) and step (II). For example, after step (I), the support is removed, and a metal foil is layered on the surface area of the exposed resin composition layer. The lamination of the resin composition layer and the metal foil can be implemented by a vacuum lamination method. The conditions for the build-up may be the same as the conditions explained in step (I). Next, step (II) is performed to form an insulating layer. After that, the metal foil on the insulating layer can be used to form a conductor layer having a desired wiring pattern by a conventionally well-known technique such as a reduction method and a modified semi-additive method.

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

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

Semiconductor devices include various semiconductor devices for electrical products (for example, computers, mobile phones, digital cameras, televisions, etc.) and riding tools (for example, motorcycles, automobiles, trams, ships, and aircrafts, etc.). [Example]

Hereinafter, the present invention will be specifically explained with examples. The present invention is not limited to these embodiments. In addition, in the following examples, "parts" and "%" indicating quantities mean "parts by mass" and "% by mass", unless otherwise stated.

<Example 1> Make 7 parts of epoxy resin ("HP-4032-SS" manufactured by DIC Corporation, epoxy equivalent about 144), 3 parts of epoxy resin ("ESN-475V" manufactured by Nistetsu Chemical & Materials Co., Ltd., epoxy equivalent 332), 0.2 part of a non-reactive azo compound (“FP-100” manufactured by Fushimi Pharmaceutical Co., Ltd.) was dissolved in 10 parts of MEK. 70 parts of spherical silica (average particle size 0.77μm, "SO-C2" manufactured by Admatechs), surface-treated with an amine-based alkoxysilane compound ("KBM573" manufactured by Shin-Etsu Chemical Industry Co., Ltd.), active ester Compound (DIC company "HPC-8000-65T", solid content 65% by mass toluene solution) 21 parts, triazine-containing cresol novolac (DIC product "LA-3018-50P", solid content 50 mass% of formaldehyde Oxypropanol solution) 2 parts, carbodiimide resin (Nisshinbo Chemical Co. "V03", solid content 50% by mass toluene solution) 1 part, imidazole compound (Shikoku Kasei company "1B2PZ") 0.02 parts , Disperse uniformly with a high-speed rotating homogenizer to prepare a resin composition.

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

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

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

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

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

<Comparative Example 3> Except for using 0.4 part of phenol-based hydroxyl-containing azo compound ("SPH-100" manufactured by Otsuka Chemical Co., Ltd.) instead of 0.2 part of non-reactive azo compound ("FP-100" manufactured by Fushimi Pharmaceutical Co., Ltd.), the rest The resin composition was prepared in the same manner as in Example 1.

<Comparative Example 4> Except that 0.4 part of phenol-based hydroxyl-containing cyclic phosphorus compound (manufactured by Sanko "HCA-HQ") is used instead of 0.2 part of non-reactive azo compound (manufactured by Fushimi Pharmaceutical Co., Ltd. "FP-100"), the rest are compatible with In Example 1, a resin composition was prepared in the same manner.

<Production example 1: Resin sheet with a thickness of 40μm> As for the support, a polyethylene terephthalate film (“AL5” manufactured by LINTEC Corporation, thickness 38μm) equipped with a release layer was prepared. On the release layer of this support, the resin compositions obtained in the examples and comparative examples were uniformly applied so that the thickness of the resin composition layer after drying became 40 μm. After that, the resin composition was dried at 80° C. to 100° C. (an average of 90° C.) for 4 minutes to obtain a resin sheet containing a support and a resin composition layer.

<Production example 2: 25μm thick resin sheet> In the same manner as in Production Example 1, the resin compositions obtained in the Examples and Comparative Examples were uniformly coated so that the thickness of the resin composition layer after drying became 25 μm, and was applied at 70°C to 80°C (average 75°C) It was dried for 2.5 minutes to obtain a resin sheet containing a support and a resin composition layer.

<Test example 1: Measurement of glass transition temperature by thermomechanical analysis (TMA)> The resin sheet having a thickness of 40 μm obtained in Production 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. This hardened product was cut out to have a length of 20 mm and a width of 6 mm as evaluation samples. For this evaluation sample, the glass transition temperature (Tg) was measured from 25°C to 250°C using a TMA device manufactured by Rigaku Corporation at a temperature increase rate of 5°C/min. 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 Production Example 2 was formed into a round copper pad with a diameter of 350μm (copper thickness 35μm) into a grid-like core material with 400μm intervals (Hitachi Chemical Co., Ltd.) so that the copper residual rate was 60%. "E705GR", thickness 400μm) on both sides, using a batch-type vacuum pressure laminator (NIKKO Materials Co., Ltd. 2-stage assembly laminator "CVP700"), the resin composition layer and the aforementioned inner substrate The bonding method is laminated on both sides of the inner substrate. This lamination is carried out by performing pressure reduction for 30 seconds to make the air pressure 13 hPa or less, and then pressing at a temperature of 100°C and a pressure of 0.74 MPa for 30 seconds. This was put into an oven at 130°C and heated for 30 minutes, and then moved to an oven at 170°C and heated for 30 minutes. Then, the support layer was peeled off, and the obtained circuit board was immersed in Swelling Dip Securiganth P of Atotech Japan (stock) as a swelling liquid at 60°C for 10 minutes. Next, it was immersed for 30 minutes in Concentrate Compact P (KMnO4: 60 g/L, NaOH: 40 g/L aqueous solution) of Atotech Japan Co., Ltd. which is a roughening liquid at 80 degreeC. Finally, the neutralizer was immersed in Reduction solution Securiganth P of Atotech Japan (stock) at 40°C for 5 minutes. Observe 100 copper pads of the circuit board after the roughening process to confirm the presence or absence of cracks in the resin composition layer. If there were 10 or less cracks, it was evaluated as "o", 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 base epoxy resin laminated board [copper foil etching product, substrate thickness 0.2mm, halogen-free core material, 679FG manufactured by Hitachi Chemical Co., Ltd.], a batch-type vacuum pressure laminator ( The 2-platform assembly laminator "CVP700" manufactured by NIKKO Materials Co., Ltd.) laminates the resin sheet with a thickness of 40 μm obtained in Production Example 1 on both sides of the laminate. The lamination was performed by reducing the pressure for 30 seconds so that the air pressure was 13 hPa or less, and then applying pressure at 100° C. and 0.74 MPa for 30 seconds. After peeling the PET film from the laminated resin sheet, the same resin sheet is further laminated thereon under the same conditions. The PET film was peeled from the resin sheet of the outermost layer, and the resin composition was cured under curing conditions of 190°C for 90 minutes. After that, it was cut into a size of 12.7mm×127mm for UL flame retardancy test, and the end surface was polished with sandpaper (#1200 and #2800) to produce a substrate thickness of 0.2mm, and a flammability test with an insulating layer of 80μm on one side. Use test pieces. After that, the "V0" and "V1" were evaluated according to the UL flame retardancy test standard (UL-94). In addition, when there is no sample remaining after burning for 10 seconds, it is evaluated as "×".

<Test Example 4: Evaluation of Insulation> The resin sheet with a thickness of 40 μm obtained in Example 1 was formed using a batch-type vacuum pressure laminator (2-platform assembly laminator "CVP700" manufactured by NIKKO Materials Co., Ltd.) L/S=15/15 on the polyimide substrate of comb-tooth-shaped wiring, the resin composition layer and the aforementioned inner substrate are bonded to both sides of the inner substrate. This layering is carried out by pressing for 30 seconds under the conditions of a temperature of 100°C and a pressure of 0.74 MPa after the pressure is reduced for 30 seconds to make the air pressure less than 13 hPa. This was put into an oven at 130°C and heated for 30 minutes, then moved to an oven at 170°C and heated for 30 minutes, and then the support was peeled off and heated at 190°C for 90 minutes to obtain a circuit board laminated with a resin composition. Expose this for 200 hours under conditions of 130°C, 98% humidity, and applied voltage of 3.3V. After that, the insulation resistance value is measured at 3.3V. If the insulation resistance value is 1x10 ^-10 Ω or more, it is evaluated as "〇" and not reached. 1x10 ^-10 Ω is evaluated as "×".

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

It can be seen from this that by using a resin composition containing (A) epoxy resin, (B) inorganic filler, and 0.2% by mass to 1.0% by mass (C) non-reactive azo compound, it is possible to obtain excellent Hardened material with heat resistance and crack resistance. In addition, it is known that a cured product can be obtained that has more excellent flame retardancy and can maintain excellent insulation for a long time even in an excessively severe environment.

Claims (11)

A resin composition comprising (A) epoxy resin, (B) inorganic filler and (C) non-reactive azo compound, wherein When the non-volatile content in the resin composition is 100% by mass, the content of the component (C) is 0.2% by mass to 1.0% by mass. Such as the resin composition of claim 1, wherein the component (B) is silica. The resin composition of claim 1, wherein when the non-volatile content in the resin composition is 100% by mass, the content of the component (B) is 70% by mass or more. The resin composition of claim 1, wherein the component (C) is a compound represented by the following formula (1),

[In the formula, n represents an integer from 1 to 20; R ¹ and R ² each independently represent an aryl group that may have 1 to 3 substituents selected from the group consisting of the following (a) to (e): (a) alkyl group, (b) alkoxy group, (c) cyano group, (d) halogen atom, (e) formula -XR ³ (where X represents a single bond, -(alkylene)-,- O-, -S-, -CO-, or -SO ₂ -, R ³ represents an aromatic group which may have 1 to 3 substituents selected from the group consisting of alkyl, alkoxy, cyano and halogen atoms基) The shown basis]. The resin composition of claim 1, which further contains (D) a hardener. The resin composition according to claim 5, wherein the component (D) contains an active ester hardener. A hardened product of the resin composition according to any one of claims 1 to 6. A sheet-like laminated material containing the resin composition according to any one of claims 1 to 6. A resin sheet having a support, and a resin composition layer formed on the support and formed of the resin composition according to any one of claims 1 to 6. A printed wiring board provided with an insulating layer made of a hardened resin composition according to any one of claims 1 to 6. A semiconductor device including the printed wiring board as claimed in claim 10.