Method for producing organic-inorganic composite part

Abstract

To provide a method for producing an organic-inorganic composite part that enables continuous formation of a metal oxide film on a cured layer by an aerosol deposition method.SOLUTION: There is provided a method for producing an organic-inorganic composite part, the method including a step (A) of forming, by an aerosol deposition method, a metal oxide film having a thickness of 0.5 μm or more on a surface of a cured layer obtained by curing a resin composition, the resin composition containing an inorganic filler, and a content of the inorganic filler being 75 mass% or more when the non-volatile components of the resin composition are 100 mass%.SELECTED DRAWING: Figure 4

Description

[Technical Field]

[0001] The present invention relates to a method for producing an organic-inorganic composite part. [Background technology]

[0002] The aerosol deposition method (sometimes referred to as the "AD method") is known as a method for forming new films such as ceramic films and metal oxide films on a cured layer of a resin composition containing a resin material. Patent Document 1 discloses a method for forming a metal oxide film by the aerosol deposition method. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] International Publication No. 2018 / 194064 Summary of the Invention [Problem to be solved by the invention]

[0004] The aerosol deposition method has the advantage of being able to deposit a thick metal oxide film on a cured material layer. However, depending on the type of cured material layer, the aerosol deposition method may not be able to continuously form a metal oxide film, and there is a problem that the types of cured material layers that can be used are limited.

[0005] Methods other than aerosol deposition, such as atomic layer deposition (ALD), can also be considered for forming metal oxide films, but forming metal oxide films with thicknesses of 0.5 μm or more takes a long time and is therefore not practical.

[0006] The present invention has been made in view of the above circumstances, and aims to provide a method for producing an organic-inorganic composite part that is capable of continuously forming a metal oxide film on a cured material layer by an aerosol deposition method. [Means for solving the problem]

[0007] The present inventors have found that, in the aerosol deposition method, the resin material is scraped off by the collision of raw material powder particles, and therefore, depending on the type of cured material layer, a metal oxide film cannot be formed on the cured material layer. As a result of extensive research aimed at solving the above problem, the present inventors have found that, when the cured material layer is hard, a metal oxide film can be continuously formed by the aerosol deposition method, and have completed the present invention.

[0008] That is, the present invention includes the following. [1] (A) forming a metal oxide film having a thickness of 0.5 μm or more on the surface of a cured layer obtained by curing a resin composition by an aerosol deposition method, The resin composition contains an inorganic filler, A method for producing an organic-inorganic composite part, wherein the content of the inorganic filler is 75% by mass or more when the non-volatile components of the resin composition are taken as 100% by mass. [2] The method for producing an organic-inorganic composite part according to [1], wherein the cured layer has a tensile modulus of elasticity of 5 GPa or more. [3] The method for producing an organic-inorganic composite part according to [1] or [2], wherein the metal oxide film contains alumina. [4] The method for producing an organic-inorganic composite part according to any one of [1] to [3], wherein the inorganic filler is spherical. [5] The method for producing an organic-inorganic composite part according to any one of [1] to [4], wherein the content of the inorganic filler is 50% by volume or more when the non-volatile components of the resin composition are 100% by volume. [6] The method for producing an organic-inorganic composite part according to any one of [1] to [5], wherein the inorganic filler contains alumina. [7] The method for producing an organic-inorganic composite part according to any one of [1] to [6], wherein the inorganic filler and the metal oxide film both contain alumina. [8] The method for producing an organic-inorganic composite part according to any one of [1] to [7], comprising a step of forming a conductor layer on a cured material layer, in which a metal oxide film is formed on the surfaces of the cured material layer and the conductor layer in step (A). [9] The method for producing an organic-inorganic composite part according to any one of [1] to [8], wherein the organic-inorganic composite part is an insulating layer of a semiconductor package substrate.

[10] The method for producing an organic-inorganic composite part according to any one of [1] to [9], wherein the organic-inorganic composite part is used in a semiconductor device. [Effects of the Invention]

[0009] According to the present invention, it is possible to provide a method for producing an organic-inorganic composite part that is capable of continuously forming a metal oxide film on a cured material layer by an aerosol deposition method. [Brief explanation of the drawings]

[0010] [Figure 1] FIG. 1 is a cross-sectional view schematically showing an example of the state of a cured product layer. [Figure 2] FIG. 2 is a schematic diagram showing an example of a metal oxide film forming apparatus. [Figure 3] FIG. 3 is an enlarged cross-sectional view schematically illustrating an aerosol generator provided in the forming device. [Figure 4] FIG. 4 is a cross-sectional view schematically showing an example of an organic-inorganic composite part manufactured by the manufacturing method according to the first embodiment of the present invention. [Figure 5] FIG. 5 is a schematic cross-sectional view illustrating step (4) in the manufacturing method according to the second embodiment of the present invention. [Figure 6] FIG. 6 is a cross-sectional view schematically showing an example of an organic-inorganic composite part manufactured by the manufacturing method according to the second embodiment of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0011] The present invention will be described in detail below with reference to embodiments and examples. However, the present invention is not limited to the embodiments and examples described below, and can be implemented with any modifications within the scope of the claims of the present invention and their equivalents.

[0012] Before describing the method for producing an organic-inorganic composite part of the present invention in detail, a resin composition and a resin sheet that can be used in the method for producing an organic-inorganic composite part of the present invention will be described.

[0013] [Resin composition] The resin composition preferably has a hard cured product and, if necessary, insulating properties. Examples of such resin compositions include conventionally known components used in forming insulating layers of printed wiring boards, specifically compositions containing (a) an inorganic filler. Therefore, in one embodiment, the resin composition contains (a) an inorganic filler. The resin composition may further contain additives such as (b) a thermosetting resin, (c) a thermoplastic resin, (d) a curing accelerator, (e) other additives, and (f) a solvent, if necessary. The resin composition may be a thermosetting resin composition or a photocurable resin composition, and is preferably a thermosetting resin composition from the viewpoint of significantly achieving the effects of the present invention.

[0014] Hereinafter, each component that may be contained in the resin composition will be described. Here, "resin component" refers to the non-volatile components contained in the resin composition, excluding (a) inorganic filler. Furthermore, in the present invention, the content (mass%) of each component in the resin composition is a value when the non-volatile components in the resin composition are 100 mass%, unless otherwise specified, and the content (volume%) of each component in the resin composition is a value when the non-volatile components in the resin composition are 100 volume%, unless otherwise specified. The non-volatile components refer to all non-volatile components in the resin composition excluding the solvent.

[0015] <(a) Inorganic filler> The resin composition contains an inorganic filler (a) as component (a). By incorporating a predetermined amount of the inorganic filler (a) into the resin composition, a metal oxide film can be continuously formed on the cured product layer. The component (a) may be used alone or in combination of two or more.

[0016] From the viewpoint of continuously forming a metal oxide film on the cured product layer, the content (mass %) of the (a) inorganic filler is, when the non-volatile components in the resin composition are taken as 100 mass %, 75 mass % or more, preferably 78 mass % or more, more preferably 80 mass % or more, even more preferably 85 mass % or more, and is preferably 98 mass % or less, more preferably 95 mass % or less, even more preferably 95 mass % or less.

[0017] From the viewpoint of continuously forming a metal oxide film on the cured product layer, the content (volume %) of the (a) inorganic filler is preferably 50% by volume or more, more preferably 55% by volume or more, even more preferably 60% by volume or more, or 65% by volume or more, and is preferably 85% by volume or less, more preferably 80% by volume or less, and even more preferably 75% by volume or less, when the non-volatile components in the resin composition are taken as 100% by volume.

[0018] The (a) inorganic filler is usually contained in the resin composition in the form of particles. The shape of the (a) inorganic filler is not particularly limited, but from the viewpoint of highly loading the (a) inorganic filler in the resin composition, a spherical shape is preferred.

[0019] The (a) inorganic filler material is an inorganic compound. Examples of the (a) inorganic filler material include silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, barium titanate, barium titanate zirconate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate. Among these, alumina is preferred from the viewpoint of hardening the cured material layer, i.e., from the viewpoint of making the cured material layer have a tensile modulus of elasticity of 5 GPa or more.

[0020] (a) Examples of commercially available inorganic fillers include "SP60-05" and "SP507-05" manufactured by Nippon Steel Chemical & Material Co., Ltd.; "YC100C," "YA050C," "YA050C-MJE," "YA010C," "SC2500SQ," "SO-C4," "SO-C2," and "SO-C1" manufactured by Admatechs Co., Ltd.; "UFP-30," "DAW-03," and "FB-105FD" manufactured by Denka Company, Limited; "Silfil NSS-3N," "Silfil NSS-4N," and "Silfil NSS-5N" manufactured by Tokuyama Corporation; "CellSpheres" and "MGH-005" manufactured by Taiheiyo Cement Corporation; and "Sfereek" and "BA-1" manufactured by JGC Catalysts and Chemicals Co., Ltd.

[0021] The average particle size of the (a) inorganic filler is preferably 0.01 μm or more, more preferably 0.03 μm or more, even more preferably 0.05 μm, 0.1 μm, or 0.3 μm or more, and is preferably 20 μm or less, more preferably 15 μm or less, even more preferably 10 μm or less.

[0022] (a) The average particle size of an inorganic filler can be measured by a laser diffraction / scattering method based on Mie scattering theory. Specifically, a volumetric particle size distribution of the inorganic filler is created using a laser diffraction / scattering particle size distribution analyzer, and the median diameter is used as the average particle size. A measurement sample can be prepared by weighing 100 mg of inorganic filler and 10 g of methyl ethyl ketone into a vial and dispersing the mixture ultrasonically for 10 minutes. The volumetric particle size distribution of the inorganic filler is measured using a laser diffraction particle size distribution analyzer with blue and red light source wavelengths using a flow cell system, and the average particle size can be calculated as the median diameter from the particle size distribution obtained. Examples of laser diffraction particle size distribution analyzers include the LA-960 manufactured by Horiba, Ltd.

[0023] (a) The BET specific surface area of ​​the inorganic filler is preferably 0.1 m 2 / g or more, more preferably 0.5m 2 / g or more, more preferably 1m 2 / g or more, preferably 100m2 / g or less, more preferably 70m 2 / g or less, more preferably 40m 2 / g or less.

[0024] (a) The specific surface area of ​​an inorganic filler can be measured according to the BET method by adsorbing nitrogen gas onto the surface of the sample using a specific surface area measuring device (Macsorb HM-1210 manufactured by Mountech Co., Ltd.) and calculating the specific surface area using the BET multipoint method.

[0025] The (a) inorganic filler may be treated with a surface treatment agent to enhance moisture resistance and dispersibility. Examples of the surface treatment agent include fluorine-containing silane coupling agents, aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, silane coupling agents, alkoxysilanes, organosilazane compounds, and titanate coupling agents. One type of surface treatment agent may be used alone, or two or more types may be used in any combination.

[0026] Examples of commercially available surface treatment agents include Shin-Etsu Chemical Co., Ltd.'s "KBM403" (3-glycidoxypropyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd.'s "KBM803" (3-mercaptopropyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd.'s "KBE903" (3-aminopropyltriethoxysilane), Shin-Etsu Chemical Co., Ltd.'s "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd.'s "SZ-31" (hexamethyldisilazane), Shin-Etsu Chemical Co., Ltd.'s "KBM103" (phenyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd.'s "KBM-4803" (long-chain epoxy-type silane coupling agent), and Shin-Etsu Chemical Co., Ltd.'s "KBM-7103" (3,3,3-trifluoropropyltrimethoxysilane).

[0027] The degree of surface treatment with the surface treatment agent preferably falls within a specific 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 0.2% to 5% by mass of the surface treatment agent, more preferably with 0.2% to 3% by mass of the surface treatment agent, and even more preferably with 0.3% to 2% by mass of the surface treatment agent.

[0028] The degree of surface treatment with the surface treatment agent can be evaluated by the amount of carbon per unit surface area of ​​the inorganic filler. From the viewpoint of improving the dispersibility of the inorganic filler, the amount of carbon per unit surface area of ​​the inorganic filler is set to 0.02 mg / m 2 More than 0.1 mg / m is preferable. 2 More preferably, 0.2 mg / m or more 2 On the other hand, from the viewpoint of preventing an increase in the melt viscosity of the resin composition, it is more preferable that the content be 1.0 mg / m 2 Less than 0.8 mg / m is preferred 2 Less than 0.5 mg / m is more preferable. 2 The following is even more preferred:

[0029] (a) The amount of carbon per unit surface area of ​​an inorganic filler can be measured after the surface-treated inorganic filler is washed with a solvent (e.g., methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK as a solvent is added to the 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 amount of carbon per unit surface area of ​​the inorganic filler can be measured using a carbon analyzer. An "EMIA-320V" manufactured by Horiba, Ltd., or the like, can be used as the carbon analyzer.

[0030] The degree of surface treatment with a surface treatment agent can be evaluated by the amount of carbon per unit mass of the inorganic filler. The amount of carbon per unit mass of the inorganic filler is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and even more preferably 0.1% by mass or more, and is preferably 1.0% by mass or less, more preferably 0.8% by mass or less, and even more preferably 0.5% by mass or less. The amount of carbon per unit mass of (a) the inorganic filler can be measured using a carbon analyzer, just like the amount of carbon per unit surface area of ​​(a) the inorganic filler.

[0031] -(b)Thermosetting resin- The resin composition may further contain (b) a thermosetting resin as an optional component. The type of (b) thermosetting resin is not particularly limited as long as it can be cured by heat. One type of (b) thermosetting resin may be used alone, or two or more types may be used in combination.

[0032] (b) Examples of thermosetting resins include epoxy resins, phenolic resins, cyanate resins, active ester resins, carbodiimide resins, acid anhydride resins, amine resins, benzoxazine resins, and thiol resins.

[0033] The (b) thermosetting resin is preferably a combination of an epoxy resin and a resin capable of reacting with the epoxy resin to cure the resin composition. Hereinafter, a resin capable of reacting with an epoxy resin to cure the resin composition may be referred to as a "curing agent." Therefore, the (b) thermosetting resin preferably contains an epoxy resin and a curing agent. Examples of curing agents include phenolic resins, cyanate resins, active ester resins, carbodiimide resins, acid anhydride resins, amine resins, benzoxazine resins, and thiol resins. The curing agent preferably contains a phenolic resin. One type of curing agent may be used alone, or two or more types may be used in combination. In one embodiment, the thermosetting resin contains an epoxy resin and a phenolic resin.

[0034] The epoxy resin as component (b) is a thermosetting resin having an epoxy group. Examples of epoxy resins include bixylenol-type epoxy resins, bisphenol A-type epoxy resins, bisphenol F-type epoxy resins, bisphenol S-type epoxy resins, bisphenol AF-type epoxy resins, dicyclopentadiene-type epoxy resins, trisphenol-type epoxy resins, naphthol novolac-type epoxy resins, phenol novolac-type epoxy resins, tert-butyl-catechol-type epoxy resins, naphthalene-type epoxy resins, naphthol-type epoxy resins, anthracene-type epoxy resins, glycidylamine-type epoxy resins, glycidyl ester-type epoxy resins, glycidylcyclohexane-type epoxy resins, alkyl diglycidyl ether-type epoxy resins, cresol novolac-type epoxy resins, biphenyl-type epoxy resins, linear aliphatic epoxy resins, epoxy resins having a butadiene structure, alicyclic epoxy resins, heterocyclic epoxy resins, spiro ring-containing epoxy resins, cyclohexane-type epoxy resins, cyclohexane dimethanol-type epoxy resins, naphthylene ether-type epoxy resins, trimethylol-type epoxy resins, tetraphenylethane-type epoxy resins, and phenolphthalimidine-type epoxy resins. Among these, epoxy resins having an aromatic ring are preferred.

[0035] The (b) thermosetting resin preferably contains an epoxy resin having two or more epoxy groups per molecule, and the proportion of the epoxy resin having two or more epoxy groups per molecule is preferably 50% by mass or more, more preferably 60% by mass or more, and particularly preferably 70% by mass or more, relative to 100% by mass of the non-volatile components of the epoxy resin.

[0036] Epoxy resins include epoxy resins that are liquid at a temperature of 20°C (hereinafter sometimes referred to as "liquid epoxy resins") and epoxy resins that are solid at a temperature of 20°C (hereinafter sometimes referred to as "solid epoxy resins"). The resin composition may contain, as component (b), only a liquid epoxy resin, only a solid epoxy resin, or a combination of a liquid epoxy resin and a solid epoxy resin.

[0037] The liquid epoxy resin is preferably a liquid epoxy resin having two or more epoxy groups in one molecule.

[0038] Preferred liquid epoxy resins include glycerol-type epoxy resins, bisphenol A-type epoxy resins, bisphenol F-type epoxy resins, bisphenol AF-type epoxy resins, naphthalene-type epoxy resins, glycidyl ester-type epoxy resins, glycidyl amine-type epoxy resins, phenol novolac-type epoxy resins, alicyclic epoxy resins having an ester skeleton, cyclohexanedimethanol-type epoxy resins, cyclic aliphatic glycidyl ethers, and epoxy resins having a butadiene structure, dicyclopentadiene-type epoxy resins, alkyleneoxy-skeleton-containing epoxy resins, and fluorene-structure-containing epoxy resins.

[0039] Specific examples of liquid epoxy resins include "EX-992L" manufactured by Nagase ChemteX Corporation, "YX7400" manufactured by Mitsubishi Chemical Corporation, "HP4032", "HP4032D", and "HP4032SS" (naphthalene-type epoxy resins) manufactured by DIC Corporation; "828US", "jER828EL", "828EL", "825", and "Epikote 828EL" (bisphenol A-type epoxy resins) manufactured by Mitsubishi Chemical Corporation; and "jER807" and "1750" manufactured by Mitsubishi Chemical Corporation. " (bisphenol F type epoxy resin); "jER152" (phenol novolac type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "630", "630LSD", and "604" (glycidylamine type epoxy resins) manufactured by Mitsubishi Chemical Corporation; "ED-523T" (glycirol type epoxy resin) manufactured by ADEKA Corporation; "EP-3950L" and "EP-3980S" (glycidylamine type epoxy resins) manufactured by ADEKA Corporation; "EP-4088S" (dicyclopentadiene type epoxy resin) manufactured by ADEKA Corporation; "ZX1059" (mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin) manufactured by Nippon Steel Chemical & Material Co., Ltd.; "EX-721" (glycidyl ester type epoxy resin) manufactured by Nagase ChemteX Corporation; "EX-991L" (alkyleneoxy skeleton-containing epoxy resin) manufactured by Nagase ChemteX Corporation; "Celloxide 2021P" (alicyclic epoxy resin with ester skeleton) manufactured by Daicel Corporation; Examples include "PB-3600" manufactured by Daicel Corporation, "JP-100" and "JP-200" manufactured by Nippon Soda Co., Ltd. (epoxy resins having a butadiene structure); "ZX1658" and "ZX1658GS" (liquid 1,4-glycidylcyclohexane-type epoxy resins) manufactured by Nippon Steel Chemical & Material Co., Ltd.; "EG-280" (fluorene structure-containing epoxy resin) manufactured by Osaka Gas Chemicals Co., Ltd.; and "EX-201" (alicyclic glycidyl ether) manufactured by Nagase ChemteX Corporation. These may be used alone or in combination of two or more.

[0040] As the solid epoxy resin, a solid epoxy resin having two or more epoxy groups in one molecule is preferred, a solid epoxy resin having three or more epoxy groups in one molecule is more preferred, and an aromatic solid epoxy resin having three or more epoxy groups in one molecule is even more preferred.

[0041] Preferred solid epoxy resins include bixylenol-type epoxy resins, naphthalene-type epoxy resins, naphthalene-type tetrafunctional epoxy resins, cresol novolac-type epoxy resins, dicyclopentadiene-type epoxy resins, trisphenol-type epoxy resins, naphthol-type epoxy resins, biphenyl-type epoxy resins, naphthylene ether-type epoxy resins, anthracene-type epoxy resins, bisphenol A-type epoxy resins, bisphenol AF-type epoxy resins, and tetraphenylethane-type epoxy resins, with naphthalene-type epoxy resins and biphenyl-type epoxy resins being more preferred.

[0042] Specific examples of solid epoxy resins include "HP4032H" (naphthalene type epoxy resin), "HP-4700", "HP-4710" (naphthalene type tetrafunctional epoxy resin), "N-690" (cresol novolac type epoxy resin), "N-695" (cresol novolac type epoxy resin), "HP-7200", "HP-7200HH", "HP-7200H" (dicyclopentadiene type epoxy resin), "EXA-7311", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", "HP6000", "HP6000L" (naphthylene ether type epoxy resin), manufactured by DIC Corporation; "EPPN-502H" (trisphenol type epoxy resin), "NC7000L" (naphthol novolac type epoxy resin), "NC3000H", "NC3000", "NC3000L" manufactured by Nippon Kayaku Co., Ltd.; Examples include "NC3100" (biphenyl-type epoxy resin); "ESN475V" (naphthalene-type epoxy resin) and "ESN485" (naphthol novolac-type epoxy resin) manufactured by Nippon Steel Chemical & Material Co., Ltd.; "YX4000H", "YL6121" (biphenyl-type epoxy resin), "YX4000HK" (bixylenol-type epoxy resin), and "YX8800" (anthracene-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "PG-100" and "CG-500" manufactured by Osaka Gas Chemical Co., Ltd.; "YL7760" (bisphenol AF-type epoxy resin), "YL7800" (fluorene-type epoxy resin), "jER1010" (solid bisphenol A-type epoxy resin), and "jER1031S" (tetraphenylethane-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; and "WHR-991S" (phenolphthalimidine-type epoxy resin) manufactured by Nippon Kayaku Co., Ltd. These may be used alone or in combination of two or more.

[0043] When a liquid epoxy resin and a solid epoxy resin are used in combination as the epoxy resin, the ratio by mass between them (liquid epoxy resin:solid epoxy resin) is preferably 1:0.1 to 1:20, more preferably 1:0.15 to 1:10, and particularly preferably 1:0.2 to 1:5. When the ratio by mass between the liquid epoxy resin and the solid epoxy resin is within this range, the desired effects of the present invention can be significantly achieved.

[0044] The epoxy equivalent of the epoxy resin is preferably 50 g / eq to 5000 g / eq, more preferably 50 g / eq to 3000 g / eq, even more preferably 80 g / eq to 2000 g / eq, and even more preferably 110 g / eq to 1000 g / eq. The epoxy equivalent is the mass of an epoxy resin containing one equivalent of epoxy groups. This epoxy equivalent can be measured according to JIS K7236.

[0045] The weight average molecular weight (Mw) of the epoxy resin is preferably 100 to 5000, more preferably 150 to 3000, and even more preferably 200 to 1500. The weight average molecular weight of the epoxy resin is a weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC).

[0046] The content of the epoxy resin as component (b) is preferably 1% by mass or more, more preferably 2% by mass or more, and even more preferably 3% by mass or more, based on 100% by mass of the nonvolatile components in the resin composition, and the upper limit is preferably 15% by mass or less, more preferably 13% by mass or less, and even more preferably 10% by mass or less.

[0047] The phenolic resin may be a compound having one or more, preferably two or more, hydroxyl groups bonded to an aromatic ring such as a benzene ring or a naphthalene ring per molecule. When combined with an epoxy resin, the phenolic resin may react with the epoxy resin to harden the resin composition layer, and is therefore sometimes referred to as a "phenolic curing agent." From the viewpoint of achieving the remarkable effects of the present invention, the phenolic resin is preferably a phenolic resin having a novolac structure. Furthermore, from the viewpoint of adhesion, nitrogen-containing phenolic resins are preferred, and triazine skeleton-containing phenolic resins are more preferred. Of these, triazine skeleton-containing phenolic novolac resins are preferred from the viewpoint of achieving the remarkable effects of the present invention. Specific examples of phenolic resins include "MEH-7700," "MEH-7810," and "MEH-7851" manufactured by Meiwa Chemical Industry Co., Ltd.; "NHN," "CBN," and "GPH" manufactured by Nippon Kayaku Co., Ltd.; "SN-170," "SN-180," "SN-190," "SN-475," "SN-485," "SN-495," "SN-375," and "SN-395" manufactured by Nippon Steel Chemical & Material Co., Ltd.; and "LA-7052," "LA-7054," "LA-3018," "LA-3018-50P," "LA-1356," "TD2090," "TD-2090-60M," and "KA-1163" manufactured by DIC Corporation.

[0048] As the active ester resin, compounds having two or more highly reactive ester groups per molecule, such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds, are generally preferred. When combined with an epoxy resin, active ester resins can react with the epoxy resin to cure the resin composition layer, and are therefore sometimes referred to as "active ester curing agents." The active ester resin is preferably one obtained by the condensation reaction of a carboxylic acid compound and / or a thiocarboxylic acid compound with a hydroxy compound and / or a thiol compound. In particular, from the viewpoint of improving resistance to high-temperature reflow blistering, active ester resins obtained from a carboxylic acid compound and a hydroxy compound are preferred, and active ester resins obtained from a carboxylic acid compound and a phenol compound and / or a naphthol compound are more preferred. Examples of carboxylic acid compounds include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. Examples of phenol compounds or naphthol compounds include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalene, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol, dicyclopentadiene-type diphenol compounds, and phenol novolak. Here, "dicyclopentadiene-type diphenol compounds" refers to diphenol compounds obtained by condensing one dicyclopentadiene molecule with two phenol molecules.

[0049] Specifically, the active ester resin is preferably a dicyclopentadiene-type active ester resin, a naphthalene-type active ester resin containing a naphthalene structure, an active ester resin containing an acetylated product of phenol novolac, or an active ester resin containing a benzoylated product of phenol novolac, and among these, at least one selected from a dicyclopentadiene-type active ester resin and a naphthalene-type active ester resin is more preferred. As the dicyclopentadiene-type active ester resin, an active ester resin containing a dicyclopentadiene-type diphenol structure is preferred.

[0050] Commercially available active ester resins include, for example, activated ester resins containing a dicyclopentadiene-type diphenol structure such as "EXB9451", "EXB9460", "EXB9460S", "EXB-8000L", "EXB-8000L-65M", "EXB-8000L-65TM", "HPC-8000L-65TM", "HPC-8000L-65T", "HPC-8000", "HPC-8000-65T", "HPC-8000H", and "HPC-8000H-65TM" (manufactured by DIC Corporation); activated ester resins containing a naphthalene structure such as "HP-B-8151-62T", "EXB-8100L-65T", and "EXB-8150-60T"; Examples of such active ester resins include "EXB-8150-62T," "EXB-9416-70BK," "HPC-8150-60T," "HPC-8150-62T," and "EXB-8" (manufactured by DIC Corporation); "EXB9401" (manufactured by DIC Corporation) as a phosphorus-containing active ester resin; "DC808" (manufactured by Mitsubishi Chemical Corporation) as an active ester resin which is an acetylated product of phenol novolac; "YLH1026," "YLH1030," and "YLH1048" (manufactured by Mitsubishi Chemical Corporation) as active ester resins which are benzoylated products of phenol novolac; and "PC1300-02-65MA" (manufactured by Air Water Inc.) as an active ester resin containing a styryl group and a naphthalene structure.

[0051] The cyanate resin may be a compound having one or more, preferably two or more, cyanate groups in one molecule. When combined with an epoxy resin, the cyanate resin reacts with the epoxy resin to harden the resin composition layer, and therefore is sometimes called a "cyanate-based curing agent." Examples of cyanate resins include bifunctional cyanate resins such as bisphenol A dicyanate, polyphenol cyanate (oligo(3-methylene-1,5-phenylene cyanate)), 4,4'-methylenebis(2,6-dimethylphenyl cyanate), 4,4'-ethylidene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanate)phenylpropane, 1,1-bis(4-cyanatephenylmethane), bis(4-cyanate-3,5-dimethylphenyl)methane, 1,3-bis(4-cyanatephenyl-1-(methylethylidene))benzene, bis(4-cyanatephenyl)thioether, and bis(4-cyanatephenyl)ether; multifunctional cyanate resins derived from phenol novolac and cresol novolac; and prepolymers in which these cyanate resins are partially converted to triazine. Specific examples of cyanate resins include "PT30" and "PT60" manufactured by Arxada (both phenol novolac type multifunctional cyanate resins), "BA230" and "BA230S75" (prepolymers in which part or all of bisphenol A dicyanate has been triazine converted to a trimer).

[0052] As the carbodiimide resin, a compound having one or more, preferably two or more, carbodiimide structures in one molecule can be used. When combined with an epoxy resin, the carbodiimide resin can react with the epoxy resin to harden the resin composition layer, and therefore is sometimes called a "carbodiimide-based curing agent." Specific examples of carbodiimide resins include aliphatic biscarbodiimides such as tetramethylene-bis(t-butylcarbodiimide) and cyclohexane-bis(methylene-t-butylcarbodiimide); aromatic biscarbodiimides such as phenylene-bis(xylylcarbodiimide); aliphatic polycarbodiimides such as polyhexamethylenecarbodiimide, polytrimethylhexamethylenecarbodiimide, polycyclohexylenecarbodiimide, poly(methylenebiscyclohexylenecarbodiimide), and poly(isophoronecarbodiimide); poly(phenylenecarbodiimide), poly(naphthalenecarbodiimide); Examples of polycarbodiimides include aromatic polycarbodiimides such as poly(methylenediphenylenecarbodiimide), poly(tolylenecarbodiimide), poly(methyldiisopropylphenylenecarbodiimide), poly(triethylphenylenecarbodiimide), poly(diethylphenylenecarbodiimide), poly(triisopropylphenylenecarbodiimide), poly(diisopropylphenylenecarbodiimide), poly(xylylenecarbodiimide), poly(tetramethylxylylenecarbodiimide), poly(methylenediphenylenecarbodiimide), and poly[methylenebis(methylphenylene)carbodiimide]. Commercially available carbodiimide resins include, for example, "Carbodilite V-02B," "Carbodilite V-03," "Carbodilite V-04K," "Carbodilite V-07," and "Carbodilite V-09" manufactured by Nisshinbo Chemical Inc.; and "Stavaxol P," "Stavaxol P400," and "Hykasil 510" manufactured by Lanxess AG.

[0053] As the acid anhydride resin, a compound having one or more, preferably two or more, acid anhydride groups in one molecule can be used. When combined with an epoxy group, the acid anhydride resin can react with the epoxy resin to harden the resin composition layer, and therefore is sometimes called an "acid anhydride curing agent." Specific examples of acid anhydride resins include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, hydrogenated methylnadic anhydride, trialkyltetrahydrophthalic anhydride, dodecenyl succinic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trimellitic anhydride, pyromellitic anhydride, and benzophenonetetracarboxylic anhydride. Examples of suitable anhydrides include hydrates, biphenyltetracarboxylic dianhydride, naphthalenetetracarboxylic dianhydride, oxydiphthalic dianhydride, 3,3'-4,4'-diphenylsulfonetetracarboxylic dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2-C]furan-1,3-dione, ethylene glycol bis(anhydrotrimellitate), and polymeric anhydrides such as styrene-maleic acid resin, which is a copolymer of styrene and maleic acid. Commercially available acid anhydride resins include, for example, "HNA-100," "MH-700," "MTA-15," "DDSA," and "OSA" manufactured by New Japan Chemical Co., Ltd.; "YH-306" and "YH-307" manufactured by Mitsubishi Chemical Corporation; "HN-2200" and "HN-5500" manufactured by Resonac Corporation; and "EF-30," "EF-40," "EF-60," and "EF-80" manufactured by Cray Valley Chemical Industries, Ltd.

[0054] The amine resin may be a compound having one or more, preferably two or more, amino groups in one molecule. When combined with an epoxy group, the amine resin may react with the epoxy resin to harden the resin composition layer, and is therefore sometimes referred to as an "amine-based curing agent." Examples of the amine resin include aliphatic amines, polyether amines, alicyclic amines, and aromatic amines, with aromatic amines being preferred. The amine resin is preferably a primary amine or secondary amine, with primary amines being more preferred. Specific examples of amine resins include 4,4'-methylenebis(2,6-dimethylaniline), 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, m-phenylenediamine, m-xylylenediamine, diethyltoluenediamine, 4,4'-diaminodiphenyl ether, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dihydroxybenzidine, and 2,2-bis(3-amino-4-hydroxyphenyl)propionate. Examples of suitable bis(4-aminophenoxy)benzene include bis(4-aminophenyl)propane, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethanediamine, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-(4-aminophenoxy)phenyl)propane, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, bis(4-(4-aminophenoxy)phenyl)sulfone, and bis(4-(3-aminophenoxy)phenyl)sulfone. Commercially available amine resins include, for example, "SEIKACURE-S" manufactured by Seika Corporation; "KAYABOND C-200S," "KAYABOND C-100," "KAYAHARD AA," "KAYAHARD AB," and "KAYAHARD AS" manufactured by Nippon Kayaku Co., Ltd.; "Epicure W" manufactured by Mitsubishi Chemical Corporation; and "DTDA" manufactured by Sumitomo Seika Chemicals Co., Ltd.

[0055] Benzoxazine resins, when combined with epoxy resins, can react with the epoxy resin to cure the resin composition layer, and are therefore sometimes referred to as "benzoxazine-based curing agents." Specific examples of benzoxazine resins include "JBZ-OP100D" and "ODA-BOZ" manufactured by JFE Chemical Corporation; "HFB2006M" manufactured by Showa Polymer Co., Ltd.; and "Pd" and "Fa" manufactured by Shikoku Chemicals Corporation.

[0056] Thiol resins, when combined with epoxy resins, can react with the epoxy resin to harden the resin composition layer, and are therefore sometimes referred to as "thiol-based curing agents." Examples of thiol resins include trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptobutyrate), and tris(3-mercaptopropyl)isocyanurate.

[0057] The active group equivalent of the curing agent as component (b) is preferably 50 g / eq. to 3000 g / eq., more preferably 100 g / eq. to 1000 g / eq., even more preferably 100 g / eq. to 500 g / eq., and particularly preferably 100 g / eq. to 300 g / eq. The active group equivalent is the mass of the curing agent per equivalent of the active group.

[0058] When the number of epoxy groups is taken as 1, the number of active groups in the curing agent is preferably 0.01 or more, more preferably 0.05 or more, even more preferably 0.1 or more, and preferably 10 or less, more preferably 5 or less, and even more preferably 3 or less. The "number of epoxy groups in the epoxy resin" refers to the total value obtained by dividing the mass of the non-volatile components of the epoxy resin present in the resin composition layer by the epoxy equivalent. Furthermore, the "number of active groups in the curing agent" refers to the total value obtained by dividing the mass of the non-volatile components of the curing agent present in the resin composition layer by the active group equivalent.

[0059] The content of the curing agent as component (b) is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1% by mass or more, and is preferably 5% by mass or less, more preferably 4% by mass or less, and even more preferably 3% by mass or less, assuming that the non-volatile components in the resin composition are 100% by mass.

[0060] The content of component (b) is preferably 1.1% by mass or more, more preferably 2.5% by mass or more, and even more preferably 3% by mass or more, based on 100% by mass of the nonvolatile components in the resin composition. The upper limit is preferably 10% by mass or less, more preferably 8% by mass or less, and even more preferably 5.5% by mass or less.

[0061] <(c) Thermoplastic resin> The resin composition may further contain a (c) thermoplastic resin as an optional component. The (c) thermoplastic resin as component (c) does not include those corresponding to the above-mentioned components (a) and (b). The (c) thermoplastic resin may be used alone or in combination of two or more.

[0062] (c) Examples of thermoplastic resins include phenoxy resins, acrylic resins, polyimide resins, polyvinyl acetal resins, polyolefin resins, polybutadiene resins, polyamideimide resins, polyetherimide resins, polysulfone resins, polyethersulfone resins, polyphenylene ether resins, polycarbonate resins, polyetheretherketone resins, and polyester resins.

[0063] Examples of phenoxy resins include phenoxy resins having one or more skeletons selected from the group consisting of bisphenol A, bisphenol F, bisphenol S, bisphenolacetophenone, novolac, biphenyl, fluorene, dicyclopentadiene, norbornene, naphthalene, anthracene, adamantane, terpene, and trimethylcyclohexane. The terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group or an epoxy group. Specific examples of phenoxy resins include "1256" and "4250" manufactured by Mitsubishi Chemical Corporation (both of which are phenoxy resins containing a bisphenol A skeleton); "YX8100" manufactured by Mitsubishi Chemical Corporation (phenoxy resin containing a bisphenol S skeleton); "YX6954" manufactured by Mitsubishi Chemical Corporation (phenoxy resin containing a bisphenol acetophenone skeleton); "FX280" and "FX293" manufactured by Nippon Steel Chemical & Material Co., Ltd.; "YL7500BH30," "YX6954BH30," "YX7553," "YX7553BH30," "YL7769BH30," "YL6794," "YL7213," "YL7290," "YL7482," and "YL7891BH30" manufactured by Mitsubishi Chemical Corporation; and the like.

[0064] Examples of acrylic resins include resins containing a (meth)acrylate structure. The acrylic resin may contain the (meth)acrylate structure in the main chain or in a side chain. Here, the term "(meth)acrylate structure" encompasses both acrylate and methacrylate structures. Specific examples of acrylic resins include Teisan Resin "SG-70L," "SG-708-6," "WS-023," "SG-700AS," "SG-280TEA," "SG-80H," "SG-80H-3," "SG-P3," "SG-600TEA," and "SG-790" manufactured by Nagase ChemteX Corporation; "ME-2000," "W-116.3," "W-197C," "KG-25," and "KG-3000" manufactured by Negami Chemical Industrial Co., Ltd.; and "ARUFON UH-2000" manufactured by Toagosei Co., Ltd.

[0065] Specific examples of polyimide resins include "SLK-6100" manufactured by Shin-Etsu Chemical Co., Ltd., and "Rikacoat SN20" and "Rikacoat PN20" manufactured by New Japan Chemical Co., Ltd. Specific examples of polyimide resins also include modified polyimides such as linear polyimides obtained by reacting bifunctional hydroxyl group-terminated polybutadiene, a diisocyanate compound, and a tetrabasic acid anhydride (polyimides described in JP-A No. 2006-37083), and polysiloxane skeleton-containing polyimides (polyimides described in JP-A Nos. 2002-12667 and 2000-319386).

[0066] Examples of polyvinyl acetal resins include polyvinyl formal resins and polyvinyl butyral resins, with polyvinyl butyral resins being preferred. Specific examples of polyvinyl acetal resins include S-LEC BH series, BX series (e.g., BX-5Z), KS series (e.g., KS-1), BL series, and BM series manufactured by Sekisui Chemical Co., Ltd.

[0067] Examples of polyolefin resins include ethylene copolymer resins such as low-density polyethylene, very low-density polyethylene, high-density polyethylene, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, and ethylene-methyl acrylate copolymer; and polyolefin polymers such as polypropylene and ethylene-propylene block copolymer.

[0068] Examples of polybutadiene resins include hydrogenated polybutadiene skeleton-containing resins, hydroxy group-containing polybutadiene resins, phenolic hydroxy group-containing polybutadiene resins, carboxy group-containing polybutadiene resins, acid anhydride group-containing polybutadiene resins, epoxy group-containing polybutadiene resins, isocyanate group-containing polybutadiene resins, urethane group-containing polybutadiene resins, polyphenylene ether-polybutadiene resins, etc. Part or all of the polybutadiene structure of the polybutadiene resin may be hydrogenated. Specific examples of polybutadiene resins include "Ricon 130MA8," "Ricon 130MA13," "Ricon 130MA20," "Ricon 131MA5," "Ricon 131MA10," "Ricon 131MA17," "Ricon 131MA20," and "Ricon 184MA6" (polybutadienes containing acid anhydride groups) manufactured by Cray Valley Corporation; "GQ-1000" (polybutadiene having hydroxyl and carboxyl groups introduced therein), "G-1000," "G-2000," and "G-3000" (polybutadienes having hydroxyl groups at both ends), "GI-1000," "GI-2000," and "GI-3000" (hydrogenated polybutadiene having hydroxyl groups at both ends) manufactured by Nippon Soda Co., Ltd.; and "FCA-061L" (an epoxy resin with a hydrogenated polybutadiene backbone) manufactured by Nagase ChemteX Corporation. Specific examples of polybutadiene resins include polyimide resins having a polybutadiene structure, a urethane structure, and an imide structure in the molecule. The polyimide resin can be produced as a linear polyimide resin (polyimides described in JP 2006-37083 A and WO 2008 / 153208 A) using hydroxyl-terminated polybutadiene, a diisocyanate compound, and a tetrabasic acid anhydride as raw materials. The content of the butadiene structure in the polyimide resin is preferably 60% to 95% by mass, more preferably 75% to 85% by mass. For details of the polyimide resin, please refer to the descriptions in JP 2006-37083 A and WO 2008 / 153208 A, the contents of which are incorporated herein by reference.

[0069] Specific examples of polyamide-imide resins include "Vylomax HR11NN" and "Vylomax HR16NN" manufactured by Toyobo Co., Ltd. Specific examples of polyamide-imide resins also include modified polyamide-imides such as "KS9100" and "KS9300" (polysiloxane skeleton-containing polyamide-imides) manufactured by Hitachi Chemical Co., Ltd.

[0070] A specific example of the polyetherimide resin is "Ultem" manufactured by GE.

[0071] Specific examples of polysulfone resins include polysulfones "P1700" and "P3500" manufactured by Solvay Advanced Polymers.

[0072] A specific example of the polyethersulfone resin is "PES5003P" manufactured by Sumitomo Chemical Co., Ltd.

[0073] Specific examples of polyphenylene ether resins include "NORYL SA90" manufactured by SABIC and oligophenylene ether-styrene resin "OPE-2St 1200" manufactured by Mitsubishi Gas Chemical Company, Inc.

[0074] Examples of polycarbonate resins include hydroxyl group-containing carbonate resins, phenolic hydroxyl group-containing carbonate resins, carboxyl group-containing carbonate resins, acid anhydride group-containing carbonate resins, isocyanate group-containing carbonate resins, and urethane group-containing carbonate resins. Specific examples of polycarbonate resins include "FPC0220" manufactured by Mitsubishi Gas Chemical Company, Inc., "T6002" and "T6001" (polycarbonate diols) manufactured by Asahi Kasei Corporation, and "C-1090," "C-2090," and "C-3090" (polycarbonate diols) manufactured by Kuraray Co., Ltd. Specific examples of polycarbonate resins include polyimide resins having imide structures, urethane structures, and polycarbonate structures within the molecule. Such polyimide resins can be produced as linear polyimide resins using hydroxyl group-terminated polycarbonate, a diisocyanate compound, and a tetrabasic acid anhydride as raw materials. The content of the carbonate structure in the polyimide resin is preferably 60% by mass to 95% by mass, more preferably 75% by mass to 85% by mass. For details of the polyimide resin, please refer to the description in WO 2016 / 129541, the contents of which are incorporated herein by reference.

[0075] A specific example of the polyether ether ketone resin is "Sumiploy K" manufactured by Sumitomo Chemical Co., Ltd.

[0076] Examples of polyester resins include polyethylene terephthalate resin, polyethylene naphthalate resin, polybutylene terephthalate resin, polybutylene naphthalate resin, polytrimethylene terephthalate resin, polytrimethylene naphthalate resin, and polycyclohexane dimethyl terephthalate resin.

[0077] From the viewpoint of significantly achieving the effects of the present invention, the weight average molecular weight (Mw) of the (c) thermoplastic resin is preferably 5,000 or more, more preferably 8,000 or more, even more preferably 10,000 or more, and particularly preferably 20,000 or more, and is preferably 100,000 or less, more preferably 70,000 or less, even more preferably 60,000 or less, and particularly preferably 50,000 or less.

[0078] The content of (c) thermoplastic resin is preferably 1% by mass or more, more preferably 2% by mass or more, and even more preferably 3% by mass or more, and is preferably 10% by mass or less, more preferably 8% by mass or less, and even more preferably 5% by mass or less, assuming that the non-volatile components in the resin composition are 100% by mass.

[0079] <(d) Curing accelerator> The resin composition may further contain a (d) curing accelerator as an optional component. The (d) curing accelerator as component (d) does not include those corresponding to the above-mentioned components (a) to (c). The (d) curing accelerator functions as a curing catalyst that accelerates the curing of the (d) epoxy resin. The (d) component may be used alone or in combination of two or more.

[0080] Examples of the (d) curing accelerator include phosphorus-based curing accelerators, urea-based curing accelerators, guanidine-based curing accelerators, imidazole-based curing accelerators, metal-based curing accelerators, and amine-based curing accelerators. Of these, it is preferable to use either a phosphorus-based curing accelerator or an imidazole-based curing accelerator. One type of (d) curing accelerator may be used alone, or two or more types may be used in combination.

[0081] Examples of the phosphorus-based curing accelerator include aliphatic phosphonium salts such as tetrabutylphosphonium bromide, tetrabutylphosphonium chloride, tetrabutylphosphonium acetate, tetrabutylphosphonium decanoate, tetrabutylphosphonium laurate, bis(tetrabutylphosphonium)pyromellitate, tetrabutylphosphonium hydrogenhexahydrophthalate, tetrabutylphosphonium 2,6-bis[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenolate, and di-tert-butyldimethylphosphonium tetraphenylborate; methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, propyltriphenylphosphonium bromide, butyltriphenylphosphonium bromide, benzyltriphenylphosphonium chloride, tetraphenylphosphonium bromide, p-tolyltriphenylphosphonium tetra-p-tolylborate, and tetraphenylphosphonium tetra-p-tolylborate. aromatic phosphonium salts such as tetraphenylborate, tetraphenylphosphonium tetra-p-tolylborate, triphenylethylphosphonium tetraphenylborate, tris(3-methylphenyl)ethylphosphonium tetraphenylborate, tris(2-methoxyphenyl)ethylphosphonium tetraphenylborate, (4-methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, and butyltriphenylphosphonium thiocyanate; aromatic phosphine-borane complexes such as triphenylphosphine-triphenylborane; aromatic phosphine-quinone adducts such as triphenylphosphine-p-benzoquinone adduct; aliphatic phosphines such as tributylphosphine, tri-tert-butylphosphine, trioctylphosphine, di-tert-butyl(2-butenyl)phosphine, di-tert-butyl(3-methyl-2-butenyl)phosphine, and tricyclohexylphosphine;Dibutylphenylphosphine, di-tert-butylphenylphosphine, methyldiphenylphosphine, ethyldiphenylphosphine, butyldiphenylphosphine, diphenylcyclohexylphosphine, triphenylphosphine, tri-o-tolylphosphine, tri-m-tolylphosphine, tri-p-tolylphosphine, tris(4-ethylphenyl)phosphine, tris(4-propylphenyl)phosphine, tris(4-isopropylphenyl)phosphine, tris(4-butylphenyl)phosphine, tris(4-tert-butylphenyl)phosphine, tris(2,4-dimethylphenyl)phosphine, tris(2,5-dimethylphenyl)phosphine, tris(2,6-dimethylphenyl)phosphine aromatic phosphines such as benzene, tris(3,5-dimethylphenyl)phosphine, tris(2,4,6-trimethylphenyl)phosphine, tris(2,6-dimethyl-4-ethoxyphenyl)phosphine, tris(2-methoxyphenyl)phosphine, tris(4-methoxyphenyl)phosphine, tris(4-ethoxyphenyl)phosphine, tris(4-tert-butoxyphenyl)phosphine, diphenyl-2-pyridylphosphine, 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane, 1,4-bis(diphenylphosphino)butane, 1,2-bis(diphenylphosphino)acetylene, and 2,2'-bis(diphenylphosphino)diphenyl ether;

[0082] Examples of the urea-based curing accelerator include 1,1-dimethylurea; aliphatic dimethylureas such as 1,1,3-trimethylurea, 3-ethyl-1,1-dimethylurea, 3-cyclohexyl-1,1-dimethylurea, and 3-cyclooctyl-1,1-dimethylurea; 3-phenyl-1,1-dimethylurea, 3-(4-chlorophenyl)-1,1-dimethylurea, 3-(3,4-dichlorophenyl)-1,1-dimethylurea, 3-(3-chloro-4-methylphenyl)-1,1-dimethylurea, 3-(2-methylphenyl)-1,1-dimethylurea, 3-(4-methylphenyl)-1,1-dimethylurea, and 3-(3,4-dimethylphenyl)-1,1-dimethylurea. aromatic dimethylureas such as toluene bis(dimethylurea), 3-(4-isopropylphenyl)-1,1-dimethylurea, 3-(4-methoxyphenyl)-1,1-dimethylurea, 3-(4-nitrophenyl)-1,1-dimethylurea, 3-[4-(4-methoxyphenoxy)phenyl]-1,1-dimethylurea, 3-[4-(4-chlorophenoxy)phenyl]-1,1-dimethylurea, 3-[3-(trifluoromethyl)phenyl]-1,1-dimethylurea, N,N-(1,4-phenylene)bis(N',N'-dimethylurea), and N,N-(4-methyl-1,3-phenylene)bis(N',N'-dimethylurea) [toluene bisdimethylurea].

[0083] Examples of guanidine curing accelerators include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1,1-dimethylbiguanide, 1,1-diethylbiguanide, 1-cyclohexylbiguanide, 1-allylbiguanide, 1-phenylbiguanide, and 1-(o-tolyl)biguanide.

[0084] Examples of the imidazole curing accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, and 1-benzyl-2-methylimidazole. Phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino-6-[2'-methylimidazolyl -(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-undecylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct Examples of imidazole compounds include 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, and 2-phenylimidazoline, as well as adducts of imidazole compounds with epoxy resins. Commercially available imidazole curing accelerators include "1B2PZ," "2E4MZ," "2MZA-PW," "2MZ-OK," "2MA-OK," "2MA-OK-PW," "2PHZ," "2PHZ-PW," "Cl1Z," "Cl1Z-CN," "Cl1Z-CNS," and "C11Z-A" manufactured by Shikoku Chemicals Corporation; and "P200-H50" manufactured by Mitsubishi Chemical Corporation.

[0085] Examples of metal-based curing accelerators include organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of organometallic complexes include organic cobalt complexes such as cobalt(II) acetylacetonate and cobalt(III) acetylacetonate, organic copper complexes such as copper(II) acetylacetonate, organic zinc complexes such as zinc(II) acetylacetonate, organic iron complexes such as iron(III) acetylacetonate, organic nickel complexes such as nickel(II) acetylacetonate, and organic manganese complexes such as manganese(II) acetylacetonate. Examples of organometallic salts include zinc octoate, tin octoate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.

[0086] Examples of the amine curing accelerator include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, 1,8-diazabicyclo(5,4,0)-undecene, etc. Commercially available amine curing accelerators may be used, such as "MY-25" manufactured by Ajinomoto Fine-Techno Co., Inc.

[0087] The content of (d) the curing accelerator is preferably 0.01% by mass or more, more preferably 0.02% by mass or more, even more preferably 0.03% by mass or more, and is preferably 0.5% by mass or less, more preferably 0.3% by mass or less, even more preferably 0.1% by mass or less, when the non-volatile components of the resin composition are taken as 100% by mass.

[0088] <(e) Optional Additives> The resin composition may contain (e) an optional additive as an optional component. Examples of the optional additive (e) include organic fillers such as rubber particles; elastomers (excluding those corresponding to component (c)); organometallic compounds such as organocopper compounds, organozinc compounds, and organocobalt compounds; colorants such as phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium oxide, and carbon black; polymerization inhibitors such as hydroquinone, catechol, pyrogallol, and phenothiazine; leveling agents such as silicone-based leveling agents and acrylic polymer-based leveling agents; thickeners such as bentone and montmorillonite; antifoaming agents such as silicone-based antifoaming agents, acrylic-based antifoaming agents, fluorine-based antifoaming agents, and vinyl resin-based antifoaming agents; ultraviolet absorbers such as benzotriazole-based ultraviolet absorbers; adhesion improvers such as urea silane; triazole-based adhesion promoters, tetrazole-based antifoaming agents, and the like. Examples of the additives include adhesion promoters such as phenol-based adhesion promoters and triazine-based adhesion promoters; antioxidants such as hindered phenol-based antioxidants; fluorescent brighteners such as stilbene derivatives; surfactants such as fluorine-based surfactants and silicone-based surfactants; flame retardants such as phosphorus-based flame retardants (e.g., phosphate ester compounds, phosphazene compounds, phosphinic acid compounds, and red phosphorus), nitrogen-based flame retardants (e.g., melamine sulfate), halogen-based flame retardants, and inorganic flame retardants (e.g., antimony trioxide); dispersants such as phosphate ester-based dispersants, polyoxyalkylene-based dispersants, acetylene-based dispersants, silicone-based dispersants, anionic dispersants, and cationic dispersants; and stabilizers such as borate-based stabilizers, titanate-based stabilizers, aluminate-based stabilizers, zirconate-based stabilizers, isocyanate-based stabilizers, carboxylic acid-based stabilizers, and carboxylic anhydride-based stabilizers. (e) Optional additives may be used alone or in combination of two or more.

[0089] <(f) Solvent> The resin composition may further contain (f) a solvent as an optional volatile component in addition to the non-volatile components (a) to (e) described above. The (f) solvent is typically an organic solvent. Examples of the organic solvent include ketone-based solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ester-based solvents such as methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, isoamyl acetate, methyl propionate, ethyl propionate, and γ-butyrolactone; ether-based solvents such as tetrahydropyran, tetrahydrofuran, 1,4-dioxane, diethyl ether, diisopropyl ether, dibutyl ether, diphenyl ether, and anisole; alcohol-based solvents such as methanol, ethanol, propanol, butanol, and ethylene glycol; 2-ethoxyethyl acetate, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl diglycol acetate, γ-butyrolactone, and methyl methoxypropionate. Examples of suitable solvents include ether ester solvents such as ethyl acetate; ester alcohol solvents such as methyl lactate, ethyl lactate, and methyl 2-hydroxyisobutyrate; ether alcohol solvents such as 2-methoxypropanol, 2-methoxyethanol, 2-ethoxyethanol, propylene glycol monomethyl ether, and diethylene glycol monobutyl ether (butyl carbitol); amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone; sulfoxide solvents such as dimethyl sulfoxide; nitrile solvents such as acetonitrile and propionitrile; aliphatic hydrocarbon solvents such as hexane, cyclopentane, cyclohexane, and methylcyclohexane; and aromatic hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, and trimethylbenzene. (f) The solvent may be used alone or in combination of two or more.

[0090] The amount of (f) solvent is not particularly limited, but may be, for example, 60% by mass or less, 40% by mass or less, 30% by mass or less, 20% by mass or less, 15% by mass or less, 10% by mass or less, or even 0% by mass, relative to 100% by mass of all components of the resin composition.

[0091] The resin composition can be produced, for example, by mixing the above-mentioned components. Some or all of the above-mentioned components may be mixed simultaneously, or they may be mixed sequentially. In the process of mixing each component, the temperature may be appropriately set, and thus heating and / or cooling may be performed temporarily or throughout. Furthermore, stirring or shaking may be performed in the process of mixing each component.

[0092] [Resin sheet] The resin sheet includes a support and a resin composition layer formed from a resin composition provided on the support. The resin composition layer may be two or more layers, but is preferably one layer from the viewpoint of significantly obtaining the effects of the present invention.

[0093] The thickness of the resin composition layer is preferably 300 μm or less, more preferably 200 μm or less, and even more preferably 100 μm or less. The lower limit of the thickness of the resin composition layer is not particularly limited, but can usually be 5 μm or more.

[0094] Examples of the support include films made of plastic materials, metal foils, and release papers, with films made of plastic materials and metal foils being preferred, and films made of plastic materials being more preferred.

[0095] When a film made of a plastic material is used as the support, examples of the plastic material include polyesters such as polyethylene terephthalate (hereinafter sometimes abbreviated as "PET") and polyethylene naphthalate (hereinafter sometimes abbreviated as "PEN"), polycarbonate (hereinafter sometimes abbreviated as "PC"), acrylics such as polymethyl methacrylate (PMMA), cyclic polyolefins, triacetyl cellulose (TAC), polyether sulfide (PES), polyether ketone, polyimide, etc. Among these, polyethylene terephthalate and polyethylene naphthalate are preferred, with inexpensive polyethylene terephthalate being particularly preferred.

[0096] When a metal foil is used as the support, examples of the metal foil include copper foil and aluminum foil, with copper foil being preferred. The copper foil may be a foil made of a single metal, copper, or an alloy of copper and another metal (e.g., tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.).

[0097] The surface of the support that is to be bonded to the resin composition layer may be subjected to a matte treatment, a corona treatment, or an antistatic treatment.

[0098] The support may also be a support with a release layer, which has a release layer on the surface that bonds to the resin composition layer. Examples of the release agent used in the release layer of the support with a release layer include one or more release agents selected from the group consisting of alkyd resins, polyolefin resins, urethane resins, and silicone resins. Commercially available products may also be used as the support with a release layer, including, for example, "SK-1," "AL-5," and "AL-7" manufactured by Lintec Corporation, "Lumirror T60" manufactured by Toray Industries, Inc., "Purex" manufactured by Teijin Limited, and "Uni-Peel" manufactured by Unitika Limited, which are PET films having a release layer primarily composed of an alkyd resin-based release agent.

[0099] The thickness of the support is not particularly limited, but is preferably in the range of 5 μm to 75 μm, more preferably 10 μm to 60 μm. When a support with a release layer is used, it is preferable that the thickness of the entire support with a release layer is in the above range.

[0100] In one embodiment, the resin sheet may further include other layers as necessary. Examples of such other layers include a protective film conforming to the support and provided on the surface of the resin composition layer that is not bonded to the support (i.e., the surface opposite the support). The thickness of the protective film is not particularly limited, but is, for example, 1 μm to 40 μm. By laminating the protective film, adhesion of dust and the like to the surface of the resin composition layer and scratches can be suppressed.

[0101] The resin sheet can be produced, for example, by preparing a resin varnish by dissolving a resin composition in a solvent, applying the resin varnish to a support using a die coater or the like, and then drying the applied resin varnish to form a resin composition layer. The solvent is as described above.

[0102] Drying may be carried out by known methods such as heating or hot air blowing. Drying conditions are not particularly limited, but drying is carried out so that the solvent content in the resin composition layer becomes 10% by mass or less, preferably 5% by mass or less. Although this varies depending on the boiling point of the solvent in the resin varnish, for example, when a resin varnish containing 30% by mass to 60% by mass of solvent is used, the resin composition layer can be formed by drying at 50°C to 150°C for 3 to 10 minutes.

[0103] The resin sheet can be stored in a rolled state. When the resin sheet has a protective film, it can be used by peeling off the protective film.

[0104] [Method of manufacturing organic-inorganic composite parts] The method for producing an organic-inorganic composite part of the present invention comprises the steps of: (A) forming a metal oxide film having a thickness of 0.5 μm or more on the surface of a cured material layer obtained by curing a resin composition by aerosol deposition. As mentioned above, in the past, it was difficult to form a metal oxide film on the surface of a cured material layer by aerosol deposition, depending on the type of cured material layer. However, in the present invention, a cured product of a resin composition having an inorganic filler content of 75% by mass or more, relative to 100% by mass of the nonvolatile components of the resin composition, is used as the cured material layer. Therefore, the cured material layer is hard, making it possible to form a metal oxide film by aerosol deposition. Furthermore, because the metal oxide film is formed by aerosol deposition, it is possible to achieve a thickness of 0.5 μm or more.

[0105] The method for producing an organic-inorganic composite part of the present invention will be described below in two separate embodiments: a first embodiment and a second embodiment. In the second embodiment, the description of the same content as in the first embodiment may be omitted.

[0106] First Embodiment In the first embodiment of the method for producing an organic-inorganic composite part of the present invention, before carrying out step (A), (1) preparing a substrate; (2) preparing a resin sheet including a support and a resin composition layer provided on the support; and (3) A step of laminating a resin sheet on a substrate and curing the resin composition layer to obtain a cured product layer may be carried out.

[0107] Examples of the substrate in step (1) include silicon wafers; glass wafers; glass substrates; metal substrates such as copper, titanium, stainless steel, and cold-rolled steel sheets (SPCC); substrates such as FR-4 substrates in which glass fibers are impregnated with epoxy resin or the like and then thermoset; and substrates made of bismaleimide triazine resins such as BT resin.

[0108] The substrate may also be an inner layer substrate. An inner layer substrate is a member that serves as the substrate of a wiring board, and examples thereof include a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, and a thermosetting polyphenylene ether substrate. The substrate may have a conductor layer on one or both sides, and this conductor layer may be patterned. An inner layer substrate having a conductor layer (circuit) formed on one or both sides of the substrate may be referred to as an "inner layer circuit board." In addition, an intermediate product on which an insulating layer and / or a conductor layer is to be further formed during the production of a wiring board is also included in the inner layer substrate of the present invention. For example, when the printed wiring board is a circuit board with built-in components, an inner layer substrate with built-in components may be used.

[0109] The arithmetic mean roughness (Ra) of the main surface of the substrate is preferably 1000 nm or less, more preferably 750 nm or less, and even more preferably 600 nm or less, or 500 nm or less. By keeping the arithmetic mean roughness (Ra) of the main surface of the substrate within this range, it is possible to prevent the insulating layer formed on the main surface from penetrating deep into the substrate, thereby improving the processability of via holes. There is no particular lower limit, but it is preferably 0.01 nm or more, more preferably 0.1 nm or more, and even more preferably 1 nm or more. The arithmetic mean roughness (Ra) of the main surface of the substrate is a value measured in accordance with ISO 25178 and can be measured using a non-contact surface roughness meter. The main surface of the substrate refers to the surface of the substrate on which the insulating layer is provided. In addition, when the arithmetic mean roughness (Ra) is not constant on the main surface, it is sufficient that the arithmetic mean roughness (Ra) of the main surface in the area where the insulating layer is formed is within the above-mentioned range, and it is preferable that the arithmetic mean roughness (Ra) of the main surface in the area where the recess is formed is within the above-mentioned range.

[0110] In step (2), a resin sheet is prepared that includes a support and a resin composition layer provided on the support. The resin sheet is as described above.

[0111] In step (3), a resin composition layer is laminated on a substrate, and the resin composition layer is thermally cured to form an insulating layer.

[0112] The substrate and the resin sheet can be laminated, for example, by thermocompression bonding the resin sheet to the substrate from the support side. Examples of the member for thermocompression bonding the resin sheet to the substrate (hereinafter also referred to as "thermocompression bonding member") include a heated metal plate (such as a SUS end plate) or a metal roll (such as a SUS roll). It is preferable to press the thermocompression bonding member not directly onto the resin sheet, but via an elastic material such as heat-resistant rubber so that the resin sheet can sufficiently conform to the surface irregularities of the substrate.

[0113] The substrate and the resin sheet may be laminated by a vacuum lamination method. In the vacuum lamination method, the thermocompression temperature is preferably in the range of 60°C to 160°C, more preferably 80°C to 140°C, the thermocompression pressure is preferably in the range of 0.098MPa to 1.77MPa, more preferably 0.29MPa to 1.47MPa, and the thermocompression time is preferably in the range of 20 seconds to 400 seconds, more preferably 30 seconds to 300 seconds. The lamination is preferably carried out under reduced pressure conditions of 26.7hPa or less.

[0114] The lamination can be performed using a commercially available vacuum laminator, such as a vacuum pressure laminator manufactured by Meiki Seisakusho Co., Ltd., a vacuum applicator manufactured by Nikko Materials Co., Ltd., or a batch vacuum pressure laminator.

[0115] After lamination, the laminated resin sheets may be smoothed under normal pressure (atmospheric pressure), for example, by pressing a thermocompression member from the support side. The pressing conditions for the smoothing treatment may be the same as the thermocompression conditions for lamination. The smoothing treatment may be performed using a commercially available laminator. Note that lamination and smoothing treatment may be performed consecutively using the commercially available vacuum laminator.

[0116] The support may be removed between step (2) and step (3), or may be removed after step (3).

[0117] The resin composition contained in the resin composition layer is preferably a thermosetting resin composition. Therefore, the resin composition layer is usually cured by thermal curing. Specific curing conditions for the resin composition layer may be the conditions usually employed when forming an insulating layer of a printed wiring board. Furthermore, as described above, the resin composition layer is preferably a single layer. Therefore, the cured product layer is also preferably a single layer.

[0118] For example, the thermal curing conditions for the resin composition layer vary depending on the types of components contained in the resin composition layer, but in one embodiment, the curing temperature is preferably 120° C. to 240° C., more preferably 150° C. to 220° C., and even more preferably 170° C. to 210° C. The curing time is preferably 5 minutes to 120 minutes, more preferably 10 minutes to 100 minutes, and even more preferably 15 minutes to 100 minutes.

[0119] Before thermally curing the resin composition layer, the resin composition layer may be preheated at a temperature lower than the curing temperature. For example, prior to thermally curing the resin composition layer, the resin composition layer may be preheated at a temperature of 50°C to 150°C, preferably 60°C to 140°C, more preferably 70°C to 130°C for 5 minutes or more, preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes, and even more preferably 15 minutes to 100 minutes.

[0120] Instead of steps (2) and (3), a step of forming a resin composition layer by applying a resin composition to a substrate and drying it, and then thermally curing the resin composition layer to form an insulating layer may be performed. The resin composition can be applied using an appropriate application device such as a die coater. The resin composition layer may be dried by heating, blowing hot air, or other methods. The drying conditions are not particularly limited, but the resin composition is usually dried so that the solvent content in the resin composition is 10% by mass or less, preferably 5% by mass or less. For example, when a resin composition containing 30% by mass to 60% by mass of solvent is applied, the resin composition layer can be formed by drying at 50°C to 150°C for 3 to 10 minutes, although this varies depending on the boiling point of the solvent in the resin composition. The conditions for thermally curing the resin composition layer are the same as those in step (3).

[0121] After the cured layer is formed, the substrate may be removed as necessary.

[0122] The cured material layer is hard because it contains a large amount of inorganic filler. Therefore, a metal oxide film can be continuously formed by aerosol deposition. The hardness of the cured material layer results in a high tensile modulus. The tensile modulus of the cured material layer is preferably 5 GPa or more, more preferably 8 GPa or more, and even more preferably 10 GPa or more. There is no particular upper limit, but it can be 50 GPa or less, 25 GPa or less, etc. The tensile modulus can be measured by the method described in the examples below.

[0123] <Process (A)> In step (A), a metal oxide film having a thickness of 0.5 μm or more is formed by aerosol deposition on the surface of a cured layer obtained by curing a resin composition. The metal oxide film is formed by aerosol deposition. Aerosol deposition is a technique in which raw material powder aerosolized by gas is sprayed onto a target component to form a coating on the surface of the target component. This aerosol deposition generally utilizes the room-temperature impact consolidation phenomenon to form a coating on the surface of the target component. Specifically, the kinetic energy of raw material powder particles accelerated by gas is converted into localized thermal energy upon impact with the surface of the target component, forming bonds between the component and the particles and between the particles themselves, which is thought to be how the metal oxide film is formed.

[0124] FIG. 1 is a cross-sectional view showing an example of a cured material layer before step (A) is performed. The cured material layer 110 contains a cured product of a resin composition, preferably only a cured product of the resin composition. The cured material layer 110 contains an inorganic filler 111 and a resin component 112, and the inorganic filler 111 is contained in an amount of 75% by mass or more when the non-volatile components of the resin composition are taken as 100% by mass. As a result of extensive research, the inventors have found that, because the aerosol deposition method requires that the kinetic energy of raw material powder particles be converted into thermal energy through collision, a metal oxide film is easily formed on a hard surface, but is difficult to form on a soft surface. The cured material layer 110 contains the inorganic filler 111 so that the content is 75% by mass or more when the non-volatile components of the resin composition are taken as 100% by mass. Therefore, the cured material layer 110 typically has a high hardness, with a tensile modulus of elasticity of 5 GPa or more. Therefore, the surface 110S of the cured material layer 110 formed from the resin composition is hard. Therefore, it becomes possible to form a metal oxide film having a thickness of 0.5 μm or more uniformly and continuously on the surface 110S of the cured material layer 110 by the aerosol deposition method.

[0125] In detail, step (A) is performed by aerosol deposition using a metal oxide powder as a raw material powder, thereby forming a metal oxide film on the surface 110S of the cured layer 110, thereby obtaining an organic-inorganic composite part. An example of step (A), i.e., a method for forming a metal oxide film by aerosol deposition, will be described below with reference to the drawings. However, the mechanism of the aerosol deposition method does not limit the technical scope of the present invention.

[0126] Fig. 2 is a schematic diagram showing an example of a metal oxide film forming apparatus 10. Fig. 3 is an enlarged cross-sectional view showing an aerosol generator 40 included in the forming apparatus 10. As shown in Fig. 2, the metal oxide film forming apparatus 10 according to this example includes a chamber 20 capable of accommodating a pre-treatment substrate 100 such as a cured material layer, an exhaust pump 30 capable of evacuating the chamber 20, the aerosol generator 40 provided outside the chamber 20, and a gas cylinder 50 as a supply source of a winding gas and a carrier gas.

[0127] The chamber 20 is provided with a stage 21 on which the unprocessed substrate 100 can be placed, and a nozzle 22 capable of spraying an aerosol gas onto the unprocessed substrate 100 placed on the stage 21. The stage 21 is typically provided so that its position can be adjusted so that the relative positional relationship between the unprocessed substrate 100 placed on the stage 21 and the nozzle 22 can be adjusted. The nozzle 22 is also connected to the aerosol generator 40 via a transfer pipe 51 so that the aerosol gas can be supplied from the aerosol generator 40. The nozzle 22 is typically provided to face the stage 21. For example, the aperture diameter of the nozzle 22 is preferably 1.0 mm to 200 mm in width and 0.1 mm to 2.0 mm in height, more preferably 50 mm to 100 mm in width and 0.1 mm to 0.5 mm in height. If necessary, a mask (not shown) may be provided between the stage 21 and the nozzle 22. When the aerosol gas is sprayed from the nozzle 22 onto the unprocessed substrate 100 on the stage 21 through the mask, it is possible to selectively spray the aerosol onto an area on the unprocessed substrate 100 according to the shape of the mask.

[0128] The untreated substrate that can be placed on the stage may be only a cured material layer, a laminate including a cured material layer and a substrate, or a laminate including a cured material layer and other layers such as a conductor layer.

[0129] 3, a metal oxide powder 41 is stored as a raw material powder inside an aerosol generator 40. A carrier pipe 52 capable of introducing a winding gas from a gas cylinder 50 into the aerosol generator 40, and a carrier pipe 53 capable of introducing a carrier gas from the gas cylinder 50 into the aerosol generator 40 are connected to the aerosol generator 40.

[0130] The conveying pipe 52 is inserted into the metal oxide powder 41 accumulated in the aerosol generator 40 so that the metal oxide powder 41 can be stirred up by the stirring gas introduced into the aerosol generator 40 through the conveying pipe 52. In this embodiment, an example will be described in which a diffusion member 54 capable of diffusing the stirring gas introduced through the conveying pipe 52 is attached to the tip of the conveying pipe 52. The aerosol generator 40 is provided so that the stirring gas can stir up the metal oxide powder 41 to generate an aerosol gas.

[0131] The carrier pipe 53 is connected to the top of the metal oxide powder 41 deposited in the aerosol generator 40 so that the aerosol gas can be transported by a carrier gas introduced into the aerosol generator 40 through the carrier pipe 53. In this embodiment, an example in which the carrier pipe 53 is connected to the top surface of the aerosol generator 40 will be described.

[0132] The aerosol generator 40 is connected to the transfer pipe 51, which is connected to the nozzle 22. The transfer pipe 51 is connected to the upper part of the metal oxide powder 41 deposited in the aerosol generator 40 so that the aerosol gas generated in the aerosol generator 40 can be discharged. The flow rate of the aerosol gas discharged through the transfer pipe 51 is generally controlled by two systems: the flow rate of the uplift gas and the flow rate of the carrier gas. In this case, the transfer pipes 51, 52, and 53 are preferably arranged in the aerosol generator 40 in a positional relationship that does not interfere with the flow rate of the aerosol gas as much as possible. Specifically, it is preferable to install the transfer pipe 52 for the uplift gas and the transfer pipe 53 for the carrier gas away from the transfer pipe 51 connected to the nozzle 22 so as not to interfere with the flow rate of the generated aerosol gas.

[0133] As the metal oxide powder 41, particles of a metal oxide to be contained in a metal oxide film to be formed on the surface of the pre-treatment base material (the surface 110S of the cured material layer 110 in the first embodiment) can be used. Examples of metal oxides include alumina (aluminum oxide), zinc oxide, silicon oxide, magnesium oxide, calcium oxide, zirconium oxide, yttrium oxide, nickel oxide, iron oxide, titanium oxide, tantalum oxide, tin oxide, vanadium oxide, cerium oxide, and chromium oxide; titanates such as aluminum titanate, barium titanate, calcium titanate, strontium titanate, zinc titanate, bismuth titanate, and strontium bismuth titanate; zirconates such as calcium zirconate, strontium zirconate, and barium zirconate; and ferrites such as Mg-Zn ferrite, Mn-Zn ferrite, Mn-Mg ferrite, Cu-Zn ferrite, Mg-Mn-Sr ferrite, Ni-Zn ferrite, Ni-Cu-Zn ferrite, Ni-Cu-Zn-Mg ferrite, and Ba ferrite. One or more types of metal oxides may be used.

[0134] In one example, the metal oxide is preferably a highly insulating oxide. A highly insulating oxide has a volume resistivity of 1.0×10 at room temperature. 8 Ω m~1.0×10 17 This refers to an oxide having a resistivity in the range of Ω·m. Examples of highly insulating oxides include alumina, silicon oxide, magnesium oxide, and calcium oxide. Among these, alumina is preferred as the metal oxide. Therefore, it is preferable to use a powder containing alumina as the metal oxide powder 41. Therefore, it is preferable that both the inorganic filler and the metal oxide film contain alumina.

[0135] The range of the average particle size of the particles of the metal oxide powder 41 is preferably larger than 0.50 μm and preferably smaller than 1.5 μm, where the average particle size of the particles of the metal oxide powder 41 represents the median diameter on a volume basis.

[0136] The shape of the particles of the metal oxide powder 41 is not particularly limited, but a flat shape is preferable. When the particles of the metal oxide powder 41 have a flat shape, the aerosolized particles of the metal oxide powder 41 are more likely to deposit on the surface of the untreated substrate 100, thereby increasing the rate at which the metal oxide film is formed. Specifically, the particles of the metal oxide powder 41 preferably have a flat shape with an aspect ratio greater than 1.3 and less than 100. The aspect ratio of the particles of the metal oxide powder 41 is expressed as "D50 / t," where t is the thickness of the particle and D50 is the average particle size of the particle.

[0137] In the method for forming a metal oxide film using the forming apparatus 10, a winding gas and a carrier gas supplied from a gas cylinder 50 are introduced into an aerosol generator 40 to generate an aerosol gas, which is then sprayed from a nozzle 22 onto the untreated substrate 100 to form a metal oxide film.

[0138] 2, the unprocessed substrate 100 is placed on a stage 21 in a chamber 20. At this time, the unprocessed substrate 100 is set so as to face a nozzle 22 so that an aerosol gas can be sprayed onto the unprocessed substrate 100. Then, the chamber 20 is evacuated by an exhaust pump 30 as necessary to adjust the pressure inside the chamber 20. The pressure inside the chamber 20 may be set appropriately within a range that allows the formation of a metal oxide film, and may be, for example, 0.01 kPa to 10 kPa.

[0139] Thereafter, a stirring gas is introduced from the gas cylinder 50 through the carrier pipe 52 into the aerosol generator 40. Examples of the stirring gas include argon gas, helium gas, and nitrogen gas. The stirring gas stirs up the metal oxide powder 41, generating an aerosol gas within the aerosol generator 40. The flow rate of the stirring gas may be appropriately set within a range that allows the formation of a metal oxide film, and is preferably 20 SLM to 120 SLM, and more preferably 40 SLM to 60 SLM. Unless otherwise specified, "SLM" means "Standard Litter per Minutes" and represents the flow rate (liters) at 1 atm and 0°C.

[0140] If necessary, a carrier gas is introduced into the aerosol generator 40 from a gas cylinder 50 through a carrier pipe 53. The carrier gas is usually the same as the winding gas. The winding gas and the carrier gas send the aerosol gas generated in the aerosol generator 40 to the nozzle 22 through a carrier pipe 51. The flow rate of the carrier gas may be appropriately set within a range that allows the formation of a metal oxide film, and is preferably 0 SLM to 30 SLM, and more preferably 20 SLM to 30 SLM. The ratio of the carrier gas flow rate to the winding gas flow rate (carrier gas flow rate:winding gas flow rate) is preferably 1:1.5 to 1:7, and more preferably 1:1.5 to 1:5.5.

[0141] The aerosol gas sent to the nozzle 22 through the transfer pipe 51 is sprayed from the nozzle 22 onto the unprocessed substrate 100 on the stage 21. The metal oxide powder contained in the sprayed aerosol gas collides with the surface of the unprocessed substrate 100, forming a metal oxide film (see reference numeral 140 in FIG. 4). The metal oxide film formed may be a dense coating in which particles of the metal oxide powder 41 are bonded together.

[0142] The aerosol gas may be sprayed by causing the nozzle 22 to scan the unprocessed substrate 100. For example, the nozzle 22 may be fixed and the stage 21 may be moved to move the nozzle 22 relative to the unprocessed substrate 100, causing the nozzle 22 to scan the unprocessed substrate 100. Alternatively, for example, the nozzle 22 may be moved while the stage 21 is fixed, causing the nozzle 22 to scan the unprocessed substrate 100. In this case, the scanning speed of the nozzle 22 is preferably 200 mm / min to 400 mm / min, and more preferably 250 mm / min to 350 mm / min. The nozzle 22 may scan only once, or may scan two or more times.

[0143] Fig. 4 is a schematic cross-sectional view showing an example of an organic-inorganic composite part 1 after step (A) of the first embodiment has been performed. The cured material layer 110, which is the untreated substrate 100, usually has a high hardness, with a tensile modulus of elasticity of 5 GPa or more, and therefore the surface 110S of the cured material layer 110 is hard. As a result, as shown in an example in Fig. 4, it is possible to obtain an organic-inorganic composite part 1 in which a metal oxide film 140 is continuously formed on the surface 110S of the cured material layer 110 by the aerosol deposition method.

[0144] The thickness of the metal oxide film 140 is 0.5 μm or more, preferably 0.6 μm or more, more preferably 0.7 μm or more, and even more preferably 0.8 μm or more. The upper limit is preferably 15 μm or less, more preferably 10 μm or less, and even more preferably 8 μm or less.

[0145] Furthermore, if necessary, the steps (2), (3) and (A) may be repeated to form a multilayer organic-inorganic composite part.

[0146] Second Embodiment In a second embodiment of the method for producing an organic-inorganic composite part of the present invention, before performing step (A), (1) preparing a substrate; (2) A step of preparing a resin sheet including a support and a resin composition layer provided on the support; (3) laminating a resin sheet on a substrate and curing the resin composition layer to obtain a cured layer; and (4) A step of forming a conductive layer on the cured product layer may be carried out.

[0147] The second embodiment may be the same manufacturing method as the first embodiment except for the step (4). Steps (1) to (3) are the same as steps (1) to (3) of the first embodiment, as described above. Furthermore, the substrate may be removed as necessary, as in the first embodiment.

[0148] In step (4), a conductor layer 120 is formed on the cured material layer 110, as shown in an example in Fig. 5. If necessary, before forming the conductor layer 120 on the cured material layer 110, either a step of drilling holes in the cured material layer 110 or a step of roughening the cured material layer 110 may be performed.

[0149] By performing a step of drilling holes in the cured material layer, holes such as via holes and through holes can be formed in the cured material layer. The step of drilling holes in the cured material layer may be performed using, for example, a drill, a laser, plasma, or the like, depending on the composition of the resin composition layer used to form the cured material layer. The dimensions and shape of the holes may be determined appropriately depending on the design of the organic-inorganic composite part.

[0150] By performing a roughening treatment on the cured material layer, the surface roughness of the cured material layer can be increased. The roughening treatment procedure and conditions are not particularly limited, and appropriate procedures and conditions that can be used when forming an insulating layer of a printed wiring board can be adopted. For example, the cured material layer can be roughened by performing a swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralization treatment with a neutralizing liquid in this order.

[0151] Examples of swelling liquids used in the roughening treatment include alkaline solutions and surfactant solutions, with alkaline solutions being preferred. Examples of the alkaline solution include sodium hydroxide solution and potassium hydroxide solution. Examples of commercially available swelling liquids include "Swelling Dip Securigance P" and "Swelling Dip Securigance SBU" manufactured by Atotech Japan. Swelling treatment with a swelling liquid can be performed, for example, by immersing the cured material layer in the swelling liquid at 30°C to 90°C for 1 to 20 minutes. From the viewpoint of suppressing swelling of the resin in the cured material layer to an appropriate level, it is preferable to immerse the cured material layer in the swelling liquid at 40°C to 80°C for 5 to 15 minutes.

[0152] Examples of oxidizing agents used in the roughening treatment include alkaline permanganate solutions prepared by dissolving potassium permanganate or sodium permanganate in an aqueous solution of sodium hydroxide. Roughening treatment using an oxidizing agent such as alkaline permanganate solution is preferably carried out by immersing the cured material layer in an oxidizing agent solution heated to 60°C to 100°C for 10 to 30 minutes. The concentration of permanganate in the alkaline permanganate solution is preferably 5% by mass to 10% by mass. Commercially available oxidizing agents include alkaline permanganate solutions such as "Concentrate Compact CP" and "Dosing Solution Securigance P" manufactured by Atotech Japan.

[0153] The neutralizing solution used in the roughening treatment is preferably an acidic aqueous solution, and a commercially available product such as "Reduction Solution Securigant P" manufactured by Atotech Japan can be cited. Treatment with a neutralizing solution can be carried out by immersing the surface that has been roughened with an oxidizing agent in a neutralizing solution at 30°C to 80°C for 5 to 30 minutes. From the standpoint of workability, a preferred method is to immerse the object that has been roughened with an oxidizing agent in a neutralizing solution at 40°C to 70°C for 5 to 20 minutes.

[0154] The method for forming the conductor layer is not particularly limited, but plating is preferred. When plating is employed, the surface 110S of the cured layer 110 can be plated using a known technique such as a semi-additive method or a full-additive method to form the conductor layer 120 having a desired wiring pattern. From the viewpoint of ease of production, the conductor layer 120 is preferably formed by a semi-additive method. An example of forming the conductor layer 120 by a semi-additive method will be described below.

[0155] First, a plating seed layer is formed on the surface of the cured material layer by electroless plating. Next, a mask pattern is formed on the formed plating seed layer, exposing a portion of the plating seed layer corresponding to the desired wiring pattern. After forming a plating conductor layer on the exposed plating seed layer by electrolytic plating, the mask pattern is removed. Thereafter, unnecessary plating seed layer is removed by a removal method such as etching, thereby forming a conductor layer having the desired wiring pattern.

[0156] The thickness of the conductor layer is preferably 0.5 μm or more, more preferably 1 μm or more, and even more preferably 2 μm or more, and the upper limit is preferably 35 μm or less, more preferably 20 μm or less, and even more preferably 15 μm or less.

[0157] In the second embodiment, after forming a conductor layer in step (4), a metal oxide film is formed on the surfaces of the cured product layer and the conductor layer in step (A). Step (A) in the second embodiment may be the same as step (A) in the first embodiment.

[0158] Fig. 6 is a schematic cross-sectional view showing an example of an organic-inorganic composite part after step (A) of the second embodiment has been performed. The cured material layer 110 and the conductor layer 120 usually have a high hardness, with a tensile modulus of elasticity of 5 GPa or more, so the surface 110S of the cured material layer 110 and the surface 120S of the conductor layer 120 are hard. As a result, as shown in Fig. 6 as an example, it is possible to obtain an organic-inorganic composite part 1' in which a metal oxide film 140 is continuously formed on the surface 110S of the cured material layer 110 and the surface 120S of the conductor layer 120 by the aerosol deposition method. The thickness of the metal oxide film is the same as in the first embodiment.

[0159] The organic-inorganic composite parts obtained by the manufacturing methods of the first and second embodiments are useful for insulating layers in semiconductor chip packages, glazing glass to replace inorganic glass, hard coatings for various housings, hard coatings to improve the abrasion resistance of transparent resin plates, etc. Therefore, the organic-inorganic composite parts are suitable in technical fields such as semiconductor devices, automobile bodies, safety parts, glass, housings and display surfaces of mobile phones, etc. [Example]

[0160] The present invention will be specifically described below with reference to examples. However, the present invention is not limited to the following examples. In the following description, "parts" and "%" representing amounts mean "parts by mass" and "% by mass", respectively, unless otherwise specified. Furthermore, the operations described below were carried out in an environment of normal temperature and pressure, unless otherwise specified.

[0161] <Synthesis Example 1: Synthesis of Elastomer 1> A reaction vessel was charged with 69 g of G-3000 (difunctional hydroxyl-terminated polybutadiene, number average molecular weight = 5047 (GPC method), hydroxyl group equivalent = 1798 g / eq., solids content 100% by mass; manufactured by Nippon Soda Co., Ltd.), 40 g of Ipsol 150 (aromatic hydrocarbon-based mixed solvent; manufactured by Idemitsu Petrochemical Co., Ltd.), and 0.005 g of dibutyltin laurate, which were mixed and dissolved uniformly. Once the mixture was homogeneous, the temperature was raised to 50°C, and 8 g of isophorone diisocyanate (IPDI; manufactured by Evonik Degussa Japan Co., Ltd., isocyanate group equivalent = 113 g / eq.) was added with further stirring, and the reaction was carried out for approximately 3 hours. Next, after cooling the reaction mixture to room temperature, 23 g of cresol novolak resin (KA-1160, manufactured by DIC Corporation, hydroxyl group equivalent weight = 117 g / eq.) and 60 g of ethyl diglycol acetate (manufactured by Daicel Corporation) were added thereto, and the mixture was heated to 80°C with stirring and reacted for about 4 hours. -1 The disappearance of the NCO peak was confirmed. The disappearance of the NCO peak was considered to be the end of the reaction, and the reaction mixture was cooled to room temperature and filtered through a 100-mesh filter cloth to obtain Elastomer 1 (non-volatile content 50% by mass) having a polybutadiene structure and phenolic hydroxyl groups. The number average molecular weight was 5,500.

[0162] <Preparation of Resin Varnish 1> Four parts of high-resilience epoxy resin ("YX7400" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 440 g / eq.), three parts of liquid epoxy resin ("ZX1059" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., a 1:1 mixture (by mass) of bisphenol A epoxy resin and bisphenol F epoxy resin, epoxy equivalent: 169 g / eq.), and two parts of bixylenol epoxy resin ("YX4000HK" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 185 g / eq.) were dissolved in 10 parts of cyclohexanone, and spherical alumina (average particle size: 4.2 μm, specific surface area: 0.8 m) was added. 2 / g, specific gravity 3.9g / cm 3 ), 215 parts of Elastomer 1 (solid content 50% by mass, number average molecular weight 5500), 20 parts of a solid naphthol-based curing agent ("SN485" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., hydroxyl group equivalent 215 g / eq., MEK solution with a solid content of 50%), 6 parts of a curing accelerator (4-dimethylaminopyridine (DMAP), MEK solution with a solid content of 5% by mass), and 15 parts of methyl ethyl ketone were mixed and uniformly dispersed using a high-speed rotating mixer to prepare Resin Varnish 1.

[0163] <Preparation of Resin Varnish 2> In the preparation of resin varnish 1, spherical alumina (average particle size 4.2 μm, specific surface area 0.8 m) was used. 2 / g, specific gravity 3.9g / cm 3 The amount of aluminum nitride powder (surface treated with phenylaminosilane, average particle size: 0.9 μm to 1.4 μm, specific surface area: 2.3 to 2.9 m) was changed from 215 parts to 65 parts. 2 / g, specific gravity 3.26g / cm 3 Resin Varnish 2 was prepared in the same manner as Resin Varnish 1, except for the above points.

[0164] <Preparation of Resin Varnish 3> In the preparation of resin varnish 1, spherical alumina (average particle size 4.2 μm, specific surface area 0.8 m) was used. 2 / g, specific gravity 3.9g / cm 3 ), 215 parts of spherical copper powder (“Cu-HWQ7.5” manufactured by Fukuda Metal Powder Industry Co., Ltd., average particle size 7.5 μm, specific surface area 0.2 m 2 / g, specific gravity 4.7g / cm 3Resin Varnish 3 was prepared in the same manner as Resin Varnish 1, except for the above-mentioned changes.

[0165] <Preparation of Resin Varnish 4> In the preparation of resin varnish 1, spherical alumina (average particle size 4.2 μm, specific surface area 0.8 m) was used. 2 / g, specific gravity 3.9g / cm 3 ) 215 parts of silica (average particle diameter 0.5 μm, specific surface area 5.8 m 2 / g, specific gravity 2.2g / cm 3 Resin Varnish 4 was prepared in the same manner as Resin Varnish 1, except for the above-mentioned changes.

[0166] <Preparation of Resin Varnish 5> In the preparation of resin varnish 1, spherical alumina (average particle size 4.2 μm, specific surface area 0.8 m) was used. 2 / g, specific gravity 3.9g / cm 3 ) was changed from 215 parts to 34 parts. Resin Varnish 5 was prepared in the same manner as Resin Varnish 1, except for the above-mentioned changes.

[0167] [Example 1] <Fabrication of organic-inorganic composite parts> (1) Surface treatment of inner layer circuit board Both sides of a glass cloth-based epoxy resin double-sided copper-clad laminate (copper foil thickness 18 μm, substrate thickness 0.3 mm, Panasonic R5715ES) with an inner layer circuit formed on it were immersed in MEC CZ8100 to roughen the copper surface.

[0168] (2) Preparation of resin sheet Resin varnish 1 was applied using a die coater onto a PET film (Toray Industries, Inc.'s "Lumirror R80", thickness 38 μm, softening point 130°C, hereinafter sometimes referred to as the "support") that had been release-treated with an alkyd resin-based release agent (Lintec Corporation's "AL-5") so that the thickness of the resin composition layer after drying would be 50 μm, and the film was dried at 80°C to 100°C (average 90°C) for 7 minutes to obtain a resin sheet.

[0169] (3) Laminating resin sheets The prepared resin sheet was laminated on both sides of an inner layer circuit board using a batch-type vacuum pressure laminator (Nikko Materials Co., Ltd., two-stage build-up laminator "CVP700") so that the resin composition layer was bonded to the inner layer circuit board. Lamination was performed by reducing the pressure to 13 hPa or less for 30 seconds, followed by pressure bonding at 120°C and a pressure of 0.74 MPa for 30 seconds. Next, a heat press was performed at 120°C and a pressure of 0.5 MPa for 60 seconds.

[0170] (4) Curing of the resin composition layer After lamination, the PET film was peeled off, and the resin composition layer was cured at 180° C. for 90 minutes.

[0171] (5) Alumina film formation by aerosol deposition method An alumina coating film as a metal oxide film is formed on the surface of the first conductive layer of the untreated base material according to Example 2 of JP 2016-130350 A. Specifically, the following operations are carried out.

[0172] Al2O3 powder was prepared as the material for the metal oxide film. This Al2O3 powder was a flat powder whose average particle size D50 was adjusted by a pulverization method. The average particle size D50 of the powder particles was 0.52 μm, and the aspect ratio D50 / t was 0.52 μm / 0.079 μm. The average particle size of the powder particles was determined by measuring the volumetric particle size distribution using a particle size distribution analyzer (DT1200, manufactured by Disperion Technology). The average particle size was then determined as the median diameter from the particle size distribution. The thickness t of the powder particles was measured by embedding the powder in acrylic resin, polishing the sample, and observing the resulting cross-sectional images with a scanning electron microscope (SEM). The aspect ratio was calculated from the average value measured for 30 randomly selected powder particles.

[0173] To remove residual moisture and impurities, the Al2O3 powder is heat-treated at 300°C for 24 hours. Then, the Al2O3 powder is introduced into the aerosol generator. N2 gas (flow rate: 20 SLM) is used as the carrier gas, and N2 gas (flow rate: 40 SLM) is used as the lift-up gas. The nozzle scanning speed is 300 mm / min, and the vacuum chamber pressure is 1.0 × 10 -2 Under conditions of 100 Pa and a nozzle diameter of 100 mm x 0.3 mm, aerosol gas containing Al2O3 powder was sprayed 10 times onto the surface of the first conductor layer of the untreated substrate. The spraying of the aerosol gas formed an alumina coating (1.5 μm thick) as a metal oxide film on the surface of the first conductor layer at a deposition rate of 0.23 μm / min. The formation of the alumina coating resulted in the production of wiring board A, a printed wiring board with an alumina coating covering the surface of the first conductor layer that was not in contact with the first insulating layer.

[0174] The film density (relative density) of the formed alumina film is 3.3 g / cm 3 The film density of the alumina coating is calculated from the amount of powder added and the weight change of the workpiece due to the formation of the alumina coating (i.e., the weight difference between the untreated substrate before the formation of the alumina coating and the wiring board A after the formation of the alumina coating).

[0175] The volume resistivity of the formed alumina film is 2.78 x 10 10 The volume resistivity of the alumina coating is measured using a circular electrode formed by forming an alumina coating on a separate Si wafer under the same conditions and then forming an approximately 200 nm thick Ag counter electrode (φ=2.0 mm) by sputtering. The volume resistivity is measured using a Hewlett Packard High Resistance Meter (4339B) at an applied voltage of 100 mV to 10 V.

[0176] <Cross-section SEM observation of organic-inorganic composite parts> The cross-section of the sample was observed using a FIB-SEM composite device (Hitachi High-Tech Science Corporation's "ETHOS NX5000") and evaluated according to the following criteria. ◯: Alumina is continuously coated on the surface of the hardened material layer. △: Partial loss of alumina and unevenness occurred. ×: No alumina film was formed.

[0177] <Measurement of elastic modulus> A release PET film ("501010" manufactured by Lintec Corporation, 38 μm thick, 240 mm square) was placed on a glass cloth-based epoxy resin double-sided copper-clad laminate ("R5715ES" manufactured by Panasonic Electric Works, Ltd., 0.7 mm thick, 255 mm square) so that the untreated surface of the release PET film was in contact with the laminate, and the four sides of the release PET film were fixed with polyimide adhesive tape (10 mm wide).

[0178] The resin sheet prepared in (2) was cut into a 167 x 107 mm square and centrally laminated using a batch-type vacuum pressure laminator (Nikko Materials Co., Ltd., two-stage build-up laminator, CVP700) so that the resin composition layer was in contact with the release surface of a release PET film. The lamination was performed by reducing the pressure to 13 hPa or less for 30 seconds, followed by pressure bonding at 100°C and a pressure of 0.74 MPa for 30 seconds. The support was peeled off, and the resin composition layer was cured at 180°C for 90 minutes to obtain a cured product for evaluation. The cured product for evaluation was cut into a dumbbell-shaped test piece. The tensile strength of this test piece was measured using a tensile tester (Orientec Co., Ltd., "RTC-1250A") to determine the tensile modulus at 23°C. Measurements were performed in accordance with JIS K7127. This procedure was performed three times, and the average values ​​are shown in the table below.

[0179] [Example 2] In Example 1, Resin Varnish 1 was changed to Resin Varnish 2. Except for the above, the tensile modulus and the like were evaluated in the same manner as in Example 1.

[0180] [Example 3] In Example 1, Resin Varnish 1 was changed to Resin Varnish 3. Except for the above, the tensile modulus and the like were evaluated in the same manner as in Example 1.

[0181] [Comparative Example 1] In Example 1, Resin Varnish 1 was changed to Resin Varnish 4. Except for the above, the tensile modulus and the like were evaluated in the same manner as in Example 1.

[0182] Comparative Example 2 In Example 1, Resin Varnish 1 was changed to Resin Varnish 5. Except for the above, the tensile modulus and the like were evaluated in the same manner as in Example 1.

[0183] [Table 1]

[0184] In Examples 1 to 3, the content of inorganic filler in the cured product layer was 75 mass% or more, and therefore it was shown that an inorganic oxide film having a thickness of 0.5 μm or more could be continuously formed by the aerosol deposition method. On the other hand, in Comparative Examples 1 and 2, in which the content of inorganic filler was less than 75 mass% when the nonvolatile components of the resin composition were taken as 100 mass%, the resin component was higher than in the Examples, and therefore it was shown that an inorganic oxide film could not be continuously coated on the cured product layer. [Explanation of symbols]

[0185] 10 Forming device 20 Chamber 21 Stages 22 nozzles 30 Exhaust pump 40 Aerosol Generator 41 Metal oxide powder 50 gas cylinders 51 Conveyor pipe 52 Conveyor pipe 53 Conveyor pipe 54 Diffusion material 100 Untreated substrate 110 Cured material layer 110S Surface of the hardened layer 111 Inorganic fillers 112 Resin component 120 Conductor layer 120S Conductor layer surface 140 Metal oxide film

Claims

1. (A) forming a metal oxide film having a thickness of 0.5 μm or more on a surface of a cured product layer obtained by curing a resin composition by an aerosol deposition method, The resin composition contains an inorganic filler, A method for producing an organic-inorganic composite part, wherein the content of the inorganic filler is 75% by mass or more when the non-volatile components of the resin composition are 100% by mass.

2. The method for producing an organic-inorganic composite part according to claim 1 , wherein the cured product layer has a tensile modulus of elasticity of 5 GPa or more.

3. The method for producing an organic-inorganic composite part according to claim 1 , wherein the metal oxide film contains alumina.

4. The method for producing an organic-inorganic composite part according to claim 1 , wherein the inorganic filler is spherical.

5. 2. The method for producing an organic-inorganic composite part according to claim 1, wherein the content of the inorganic filler is 50% by volume or more when the non-volatile components of the resin composition are taken as 100% by volume.

6. The method for producing an organic-inorganic composite part according to claim 1 , wherein the inorganic filler contains alumina.

7. The method for producing an organic-inorganic composite part according to claim 1 , wherein both the inorganic filler and the metal oxide film contain alumina.

8. 2. The method for producing an organic-inorganic composite part according to claim 1, further comprising a step of forming a conductor layer on the cured material layer, wherein in step (A), a metal oxide film is formed on the surfaces of the cured material layer and the conductor layer.

9. The method for producing an organic-inorganic composite part according to claim 1 , wherein the organic-inorganic composite part is an insulating layer of a semiconductor package substrate.

10. The method for producing an organic-inorganic composite part according to claim 1 , wherein the organic-inorganic composite part is used in a semiconductor device.

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