TW202028357A - Resin composition capable of obtaining a cured product having low roughness, high peel strength, excellent water resistance and excellent flexibility - Google Patents

Abstract

Disclosed is a resin composition capable of obtaining a cured product having low roughness, high peel strength, excellent water resistance and excellent flexibility. The resin composition contains (A) an epoxy resin, (B) a curing agent, (C) a fluorine-based organic filler and (D) a polyimide resin, and is characterized in that the content of the component (D) is 12 mass% or more when the nonvolatile component in the resin composition is considered as 100 mass%.

Description

Resin composition

The present invention relates to: a resin composition containing an epoxy resin and a curing agent; a cured product of the above-mentioned resin composition; a resin sheet of the above-mentioned resin composition; a multilayer flexible substrate comprising an insulating layer formed of the above-mentioned resin composition; And a semiconductor device provided with the above-mentioned multilayer flexible substrate.

In recent years, the demand for thinner, lighter, and high-density semiconductor components has increased. In response to demand, people who use flexible substrates as base substrates for semiconductor components are attracting attention. The flexible substrate can be thinner and lighter than the rigid substrate. Furthermore, since the flexible substrate is soft and deformable, it can be bent and installed.

Flexible substrates are generally manufactured by: making a three-layer film made of polyimide film, copper foil and adhesive, or a two-layer film made of polyimide film and conductor layer , And in accordance with the subtractive method, etching the conductor layer to form a circuit. In the past, since it can be produced relatively cheaply, three-layer films are often used. However, in a circuit board with high-density wiring, in order to solve the problems of the heat resistance and electrical insulation of the adhesive, a two-layer film is sometimes used. However, the two-layer film has problems in cost and productivity. Therefore, in order to solve this problem, Patent Documents 1 to 3 disclose insulating materials for multilayer flexible substrates. In addition, Patent Documents 4 and 5 describe polyimide resins. [Prior Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Application Publication No. 2006-37083 [Patent Document 2] JP 2016-41797 A [Patent Document 3] Japanese Invention Patent No. 6387181 [Patent Document 4] Japanese Invention Patent No. 6240798 [Patent Document 5] Japanese Invention Patent No. 6240799

[The problem to be solved by the invention]

The subject of the present invention is to provide: a resin composition capable of obtaining a cured product having low roughness, high peel strength, and excellent water resistance and flexibility; a cured product of the above resin composition; a resin containing the above resin composition A sheet; a multilayer flexible substrate including an insulating layer formed by the above-mentioned resin composition; and a semiconductor device having the above-mentioned multilayer flexible substrate. [Means to solve the problem]

In order to achieve the subject of the invention, the inventors intensively reviewed and found that by using a 12% by mass containing (A) epoxy resin, (B) hardener and (C) fluorine-based organic filler The resin composition of the above (D) polyimide resin can obtain a cured product with low roughness and high peel strength, excellent water resistance and flexibility, and finally completed the present invention.

That is, the present invention includes the following contents. [1] A resin composition comprising (A) an epoxy resin, (B) a hardener, (C) a fluorine-based organic filler, and (D) a polyimide resin, When the non-volatile components in the resin composition are regarded as 100% by mass, the content of the component (D) is 12% by mass or more. [2] The resin composition according to the above [1], wherein the component (C) is fluorine-based polymer particles. [3] The resin composition according to [1] or [2] above, wherein when the non-volatile content in the resin composition is regarded as 100% by mass, the content of the component (C) is 10% by mass or more. [4] The resin composition as described in any one of [1] to [3] above, wherein when the non-volatile content in the resin composition is regarded as 100% by mass, the content of component (D) is 40% by mass or less . [5] The resin composition according to any one of [1] to [4] above, wherein the component (A) contains a fluorine-containing epoxy resin. [6] The resin composition according to any one of [1] to [5] above, wherein the component (B) is selected from the group consisting of phenol hardeners, naphthol hardeners, and active ester hardeners group. [7] The resin composition as described in any one of [1] to [6] above, which further contains or does not contain (E) an inorganic filler, and when the non-volatile content in the resin composition is regarded as 100% by mass , The content of (E) component is 60% by mass or less. [8] The resin composition as described in any one of [1] to [7] above, which is used for forming an insulating layer of a multilayer flexible substrate. [9] A cured product which is a cured product of the resin composition described in any one of [1] to [8] above. [10] A resin sheet comprising a support and a resin composition layer formed of the resin composition described in any one of [1] to [8] above provided on the support. [11] A multilayer flexible substrate comprising an insulating layer formed by curing the resin composition described in any one of [1] to [8] above. [12] A semiconductor device including the multilayer flexible substrate as described in [11] above. [Effects of the invention]

According to the present invention, it is possible to provide: a resin composition capable of obtaining a cured product having low roughness, high peel strength, and excellent water resistance and flexibility; a cured product of the above resin composition; a resin containing the above resin composition A sheet; a multilayer flexible substrate including an insulating layer formed by the above-mentioned resin composition; and a semiconductor device having the above-mentioned multilayer flexible substrate.

[The form of implementing the invention]

Hereinafter, the present invention will be explained in detail with suitable embodiments. However, the present invention is not limited by the following embodiments and exemplified materials, and can be implemented with arbitrarily changed without departing from the scope of the invention patent application of the present invention and its equivalent scope.

＜Resin composition＞ The resin composition of the present invention contains (A) epoxy resin, (B) curing agent, (C) fluorine-based organic filler, and (D) polyimide resin. When the non-volatile components in the resin composition are regarded as 100% by mass, the content of the component (D) is 12% by mass or more.

By using such a resin composition, a cured product having low roughness and high peel strength, and excellent water resistance and flexibility can be obtained.

In addition to (A) epoxy resin, (B) curing agent, (C) fluorine-based organic filler, and (D) polyimide resin, the resin composition of the present invention may further contain optional components. Examples of optional components include (E) inorganic fillers, (F) hardening accelerators, (G) organic solvents, and (H) other additives. Hereinafter, each component contained in the resin composition is explained in detail.

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

Examples of (A) epoxy resins include bixylenol type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, and bisphenol AF type epoxy resins. Oxygen resin, dicyclopentadiene type epoxy resin, triphenol type epoxy resin, naphthol novolak type epoxy resin, phenol novolak type epoxy resin, tertiary butylcatechol type epoxy resin, naphthalene Type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidylamine type epoxy resin, glycidyl ester type epoxy resin, cresol novolac type epoxy resin, biphenyl type Epoxy resin, linear aliphatic epoxy resin, epoxy resin with butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring-containing epoxy resin, cyclohexane epoxy resin Resin, cyclohexanedimethanol type epoxy resin, naphthyl ether type epoxy resin, trimethylol type epoxy resin, tetraphenylethane type epoxy resin, etc. The epoxy resin may be used alone or in combination of two or more types.

The resin composition preferably contains an epoxy resin having two or more epoxy groups in one molecule as the (A) epoxy resin. From the standpoint of remarkably obtaining the desired effect of the present invention, the ratio of epoxy resin having two or more epoxy groups in one molecule relative to 100% by mass of the non-volatile content of epoxy resin (A) It is preferably 50% by mass or more, more preferably 60% by mass or more, and particularly preferably 70% by mass or more.

Among epoxy resins, there are epoxy resins that are liquid at a temperature of 20°C (hereinafter also referred to as "liquid epoxy resins") and solid epoxy resins that are solid at a temperature of 20°C (hereinafter also referred to as "solid Epoxy resin"). In one embodiment, the resin composition of the present invention contains a liquid epoxy resin as the epoxy resin. In one embodiment, the resin composition of the present invention includes a solid epoxy resin as the epoxy resin. The resin composition of the present invention may include only liquid epoxy resin as the epoxy resin, or may include only solid epoxy resin as the epoxy resin, but it is preferably a combination of liquid epoxy resin and solid epoxy resin. It contains resin.

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

As the liquid epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, Glycidylamine type epoxy resin, phenol novolac type epoxy resin, alicyclic epoxy resin with ester skeleton, cyclohexane type epoxy resin, cyclohexane dimethanol type epoxy resin, epoxy propylene Amine type epoxy resin and epoxy resin with butadiene structure.

Specific examples of liquid epoxy resins include "HP4032", "HP4032D", and "HP4032SS" (naphthalene type epoxy resin) manufactured by DIC; and "828US", "828EL", and "Mitsubishi Chemical Corporation". "jER828EL", "825", "Epikote 828EL" (bisphenol A type epoxy resin); "jER807" and "1750" (bisphenol F type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER152" manufactured by Mitsubishi Chemical Corporation "(Phenol novolac type epoxy resin); "630" and "630LSD" (glycidylamine type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "ZX1059" (bisphenol A) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. Type epoxy resin and bisphenol F type epoxy resin); "EX-721" (glycidyl ester epoxy resin) manufactured by Nagase ChemteX; "Celloxide 2021P" manufactured by DAICEL (with ester Skeleton alicyclic epoxy resin); "PB-3600" manufactured by DAICEL, "JP-100" and "JP-200" manufactured by Soda Corporation of Japan (epoxy resin with butadiene structure); New Japan "ZX1658" and "ZX1658GS" (liquid 1,4-epoxypropyl cyclohexane type epoxy resin) manufactured by Tetsusumijin Chemical Co., Ltd. These systems can be used in one type alone or in combination of two or more types.

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

As the solid epoxy resin, dixylenol type epoxy resin, naphthalene type epoxy resin, naphthalene type tetrafunctional epoxy resin, cresol novolak type epoxy resin, and dicyclopentadiene type epoxy resin are preferred. Resin, triphenol type epoxy resin, naphthol type epoxy resin, biphenyl type epoxy resin, naphthyl ether type epoxy resin, anthracene type epoxy resin, bisphenol A type epoxy resin, bisphenol AF type Epoxy resin, tetraphenylethane type epoxy resin.

Specific examples of solid epoxy resins include "HP4032H" (naphthalene type epoxy resin) manufactured by DIC; "HP-4700" and "HP-4710" (naphthalene type tetrafunctional epoxy resin) manufactured by DIC Resin); "N-690" (cresol novolac epoxy resin) made by DIC; "N-695" (cresol novolak epoxy resin) made by DIC; "HP- 7200" (Dicyclopentadiene epoxy resin); "HP-7200HH", "HP-7200H", "EXA-7311", "EXA-7311-G3", "EXA-7311-G4" manufactured by DIC Corporation ", "EXA-7311-G4S", "HP6000" (naphthyl ether type epoxy resin); "EPPN-502H" (triphenol type epoxy resin) manufactured by Nippon Kayaku Co.; "NC7000L" (naphthol novolac type epoxy resin); "NC3000H", "NC3000", "NC3000L", "NC3100" (biphenyl type epoxy resin) manufactured by Nippon Kayaku Corporation; Nippon Steel & Sumikin Chemical Co., Ltd. "ESN475V" (naphthol type epoxy resin) manufactured by Nippon Steel & Sumitomo Chemical Corporation; "ESN485" (naphthol novolak type epoxy resin) manufactured by Nippon Steel & Sumitomo Chemical Corporation; "YX4000H", "YX4000", "Mitsubishi Chemical Corporation" "YL6121" (biphenyl type epoxy resin); "YX4000HK" (bixylenol type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YX8800" (anthracene type epoxy resin) manufactured by Mitsubishi Chemical Corporation; manufactured by Mitsubishi Chemical Corporation "YX7700" (novolac epoxy resin containing xylene structure); "PG-100" and "CG-500" manufactured by Osaka Gas Chemical Company; "YL7760" manufactured by Mitsubishi Chemical Company (bisphenol AF type ring Oxygen resin); "YL7800" manufactured by Mitsubishi Chemical Corporation (茀-type epoxy resin); "jER1010" manufactured by Mitsubishi Chemical Corporation (solid bisphenol A epoxy resin); "jER1031S" manufactured by Mitsubishi Chemical Corporation (fourth Phenylethane type epoxy resin) and so on. These systems can be used in one type alone or in combination of two or more types.

As the (A) epoxy resin, when a liquid epoxy resin and a solid epoxy resin are used in combination, the ratio of their amounts (liquid epoxy resin: solid epoxy resin) is expressed as a mass ratio, and is preferably 1:1~1:50, more preferably 1:3~1:30, particularly preferably 1:5~1:20. Since the amount ratio of the liquid epoxy resin to the solid epoxy resin is in such a range, the desired effect of the present invention can be significantly obtained.

In one embodiment, from the viewpoint of remarkably obtaining the desired effect of the present invention, the (A) epoxy resin preferably includes a fluorine-containing epoxy resin.

The fluorine-containing epoxy resin is an epoxy resin having fluorine atoms in the molecule. The number of fluorine atoms per molecule of the fluorine-containing epoxy resin is usually 1 or more, preferably 2 or more, and usually 30 or less, preferably 25 or less, and more preferably 20 or less. Since the number of fluorine atoms per molecule of the fluorine-containing epoxy resin is within the aforementioned range, the desired effect of the present invention can be remarkably obtained.

The fluorine-containing epoxy resin is preferably an aromatic epoxy resin. Here, the so-called aromatic epoxy resin is an epoxy resin whose molecule contains an aromatic skeleton. In addition, the so-called aromatic skeleton is a chemical structure generally defined as an aromatic, and includes not only a monocyclic structure such as a benzene ring, but also a polycyclic aromatic structure such as a naphthalene ring, and an aromatic heterocyclic structure.

As an example of a preferable fluorine-containing epoxy resin, the bisphenol AF type epoxy resin represented by following formula (A) is mentioned.

In formula (A), R ^A1 to R ^A8 each independently represent a group selected from a hydrogen atom, a fluorine atom, and an alkyl group; R ^A1 to R ^{A8 are} preferably hydrogen atoms.

Among the bisphenol AF type epoxy resins represented by the formula (A), the fluorine-based epoxy resin is particularly preferably 4,4'-[2,2,2-trifluoro-1-(trifluoromethyl ) Ethylene] bisphenol type epoxy resin. With such a preferred fluorine-based epoxy resin, the desired effect of the present invention can be significantly obtained.

As a specific example of the fluorine-containing epoxy resin, "YL7760" (bisphenol AF type epoxy resin) manufactured by Mitsubishi Chemical Corporation and the like can be cited. In addition, the fluorine-containing epoxy resin may be used alone or in combination of two or more types.

(A) The ratio of the fluorine-containing epoxy resin in the epoxy resin is preferably 10% by mass or more, more preferably 20% by mass or more, particularly preferably 30% by mass or more, and particularly preferably 40% by mass.

The epoxy equivalent of the epoxy resin is preferably 50g/eq.~5000g/eq., more preferably 50g/eq.~3000g/eq., particularly preferably 80g/eq.~2000g/eq., and more preferably 110g/eq.~1000g/eq.. Due to this range, the crosslink density of the cured resin sheet becomes sufficient, and an insulating layer with a small surface roughness can be provided. The epoxy equivalent is the mass of an epoxy resin containing 1 equivalent of epoxy groups. This epoxy equivalent can be measured in accordance with JIS K7236.

From the viewpoint of remarkably obtaining the desired effect of the present invention, the weight average molecular weight (Mw) of the (A) epoxy resin is preferably 100 to 5000, more preferably 250 to 3000, and particularly preferably 400 to 1500. The weight average molecular weight of the resin can be measured as a polystyrene conversion value by gel permeation chromatography (GPC).

When the non-volatile content in the resin composition is regarded as 100% by mass, the content of (A) epoxy resin is not particularly limited, but from the viewpoint of remarkably obtaining the desired effect of the present invention, it is preferably 5% by mass or more, more preferably 10% by mass or more, particularly preferably 15% by mass or more, and particularly preferably 20% by mass or more. From the viewpoint of remarkably obtaining the desired effect of the present invention, the upper limit thereof is preferably 50% by mass or less, more preferably 40% by mass or less, particularly preferably 30% by mass or less, and particularly preferably 25% by mass or less.

When the resin component in the resin composition is regarded as 100% by mass, the content of (A) epoxy resin is not particularly limited, but from the viewpoint of remarkably obtaining the desired effect of the present invention, it is preferably 5 mass% % Or more, more preferably 10% by mass or more, particularly preferably 15% by mass or more, and particularly preferably 20% by mass or more. From the viewpoint of remarkably obtaining the desired effect of the present invention, the upper limit is preferably 60% by mass or less, more preferably 50% by mass or less, particularly preferably 40% by mass or less, and particularly preferably 35% by mass or less.

The "resin component" in this specification means all components remaining after removing the inorganic filler from the resin composition. Therefore, the "resin component" may also include low molecular weight compounds.

＜(B) Hardener＞ The resin composition of the present invention contains (B) a curing agent.

The curing agent (B) is not particularly limited as long as it has the function of curing epoxy resin. Examples include phenol curing agents, naphthol curing agents, acid anhydride curing agents, active ester curing agents, benzene And 㗁𠯤 series hardener, cyanate ester hardener and carbodiimide hardener. The hardener system may be used alone or in combination of two or more kinds. The (B) hardener of the resin composition of the present invention is preferably selected from phenol hardeners, naphthol hardeners, and active ester hardeners from the viewpoint of remarkably obtaining the desired effect of the present invention. As a group of people.

As the phenol-based curing agent and the naphthol-based curing agent, from the viewpoint of heat resistance and water resistance, a phenol-based curing agent having a novolak structure or a naphthol-based curing agent having a novolak structure is preferable. In addition, from the viewpoint of adhesion to the attached body, a nitrogen-containing phenol-based hardener or a nitrogen-containing naphthol-based hardener is preferable, and a phenol-based hardener containing a tri-skeleton or a tri-containing hardener is more preferable. Naphthol-based hardener for the skeleton. Among them, from the viewpoint of highly satisfying heat resistance, water resistance, and adhesion, a phenol novolak resin containing a tri-skeleton is preferred. Specific examples of phenol-based hardeners and naphthol-based hardeners include "MEH-7700", "MEH-7810", and "MEH-7851" manufactured by Meiwa Chemical Co., Ltd., and "NHN" manufactured by Nippon Kayaku Co., Ltd. ", "CBN", "GPH", "SN-170", "SN-180", "SN-190", "SN-475", "SN-485", "SN -495", "SN-375", "SN-395", "LA-7052", "LA-7054", "LA-3018", "LA-3018-50P", "LA-1356" manufactured by DIC ", "TD2090", "TD-2090-60M", etc.

Examples of acid anhydride hardeners include hardeners having one or more acid anhydride groups in one molecule. Specific examples of acid anhydride hardeners include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, and methylhexahydrophthalic anhydride. Dicarboxylic anhydride, methyl nadic anhydride, hydrogenated methyl nadic anhydride, trialkyltetrahydrophthalic anhydride, dodecenyl succinic anhydride, 5-(2,5-dioxotetrahydro-3- (Furyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trimellitic anhydride, pyromellitic anhydride, diphenyl ketone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, naphthalene Tetracarboxylic dianhydride, oxydiphthalic dianhydride, 3,3'-4,4'-diphenyl tetracarboxylic dianhydride, 1,3,3a,4,5,9b-hexahydro -5-(Tetrahydro-2,5-dioxo-3-furyl)-naphtho[1,2-C]furan-1,3-dione, ethylene glycol bis(trimellitic anhydride), styrene and Maleic acid copolymerized into styrene, maleic acid resin and other polymer type acid anhydrides. Examples of commercially available products of acid anhydride hardeners include "HNA-100" and "MH-700" manufactured by Nippon Rika Corporation.

There are no special restrictions on the active ester curing agent. Generally, it is better to use phenol esters, thiophenol esters, N-hydroxyamine esters, heterocyclic hydroxyl compound esters, etc. The reactivity is high in 1 molecule Compounds with more than two ester groups. The active ester hardener is preferably obtained by a condensation reaction of a carboxylic acid compound and/or a thiocarboxylic acid compound and a hydroxyl compound and/or a thiol compound. Particularly from the viewpoint of improving heat resistance, an active ester curing agent derived from a carboxylic acid compound and a hydroxy compound is preferred, and an active ester curing agent derived from a carboxylic acid compound and a phenol compound and/or a naphthol compound is more preferred hardener. 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 the phenol compound or naphthol compound include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalein, methylated bisphenol A, methylated bisphenol F, methyl Alkylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-Dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucinol, benzenetriol, dicyclopentadiene type diphenol compounds, phenol Novolac, etc. The "dicyclopentadiene type diphenol compound" referred to here refers to a diphenol compound obtained by condensing two molecules of phenol with one molecule of dicyclopentadiene.

Specifically, it is preferably an active ester compound containing a dicyclopentadiene type diphenol structure, an active ester compound containing a naphthalene structure, an active ester compound containing an acetate of a phenol novolak, and a benzyl containing a phenol novolak. Among the active ester compounds of the acetate, the active ester compound containing a naphthalene structure and the active ester compound containing a dicyclopentadiene type diphenol structure are more preferable. The so-called "dicyclopentadiene-type diphenol structure" refers to a bivalent structural unit formed by phenylene-dicyclopentene-phenylene.

As a commercially available product of an active ester hardener, among active ester compounds containing a dicyclopentadiene-type diphenol structure, "EXB9451", "EXB9460", "EXB9460S", "HPC-8000", and " "HPC-8000H", "HPC-8000-65T", "HPC-8000H-65TM", "EXB-8000L", "EXB-8000L-65TM" (manufactured by DIC); among the active ester compounds containing naphthalene structure, Examples include "EXB9416-70BK" and "EXB-8150-65T" (manufactured by DIC Corporation); among the active ester compounds containing the acetate of phenol novolak, "DC808" (manufactured by Mitsubishi Chemical Corporation) can be cited; Among the active ester compounds containing phenol novolac benzoate, "YLH1026" (manufactured by Mitsubishi Chemical Corporation) can be cited; among the active ester hardeners of phenol novolak acetate, "DC808 "(Manufactured by Mitsubishi Chemical Corporation); among the active ester hardeners of phenol novolac benzoate, "YLH1026" (manufactured by Mitsubishi Chemical Corporation), "YLH1030" (manufactured by Mitsubishi Chemical Corporation), and "YLH1048" "(Mitsubishi Chemical Corporation) etc.

As specific examples of the benzoic hardener, "JBZ-OP100D" and "ODA-BOZ" manufactured by JFE Chemical Co., Ltd.; "HFB2006M" manufactured by Showa Polymer Co., Ltd. and "HFB2006M" manufactured by Shikoku Chemical Industry Co., Ltd. Pd", "Fa", etc.

Examples of cyanate ester curing agents include bisphenol A dicyanate, polyphenol cyanate (oligo(3-methylene-1,5-phenylene cyanate)), 4, 4'-methylene bis(2,6-dimethylphenyl cyanate), 4,4'-ethylene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2, 2-bis(4-cyanate ester)phenyl propane, 1,1-bis(4-cyanate ester phenylmethane), bis(4-cyanate ester-3,5-dimethylphenyl)methane, 1,3-bis(4-cyanate phenyl-1-(methylethylene))benzene, bis(4-cyanate phenyl)sulfide, and bis(4-cyanate phenyl) Difunctional cyanate ester resins such as ethers, polyfunctional cyanate ester resins derived from phenol novolacs and cresol novolacs, and prepolymers of these cyanate ester resins that have been partially tri-formed. Specific examples of cyanate ester curing agents include "PT30" and "PT60" (all-phenol novolak type polyfunctional cyanate resin) manufactured by LONZA Japan, "BA230", "BA230S75" (bisphenol A Part or all of the dicyanate is tripolymerized into a prepolymer, etc.

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

When the hardener is included, the ratio of the amount of epoxy resin to hardener is expressed by the ratio of [total number of epoxy groups of epoxy resin]: [total number of reactive groups of hardener], preferably 1:0.2~ The range of 1:2 is more preferably 1:0.3~1:1.5, and more preferably 1:0.4~1:1.2. Here, the so-called reactive groups of the hardener are active hydroxyl groups, active ester groups, etc., which differ depending on the type of hardener. In addition, the total number of epoxy groups in epoxy resins is the value obtained by dividing the mass of the non-volatile components of each epoxy resin by the epoxy equivalent. The total value of all epoxy resins is the value of the hardener The total number of reactive groups is the value obtained by dividing the mass of the non-volatile components of each hardener by the equivalent of the reactive groups, which is the sum of all hardeners. Since the ratio of the amount of epoxy resin to hardener is in such a range, the heat resistance of the obtained hardened product is further improved.

When the non-volatile content in the resin composition is regarded as 100% by mass, the content of (B) hardener is not particularly limited, but from the viewpoint of remarkably obtaining the desired effect of the present invention, it is preferably 0.1 Mass% or more, more preferably 1 mass% or more, particularly preferably 3 mass% or more, particularly preferably 5 mass% or more. From the standpoint of remarkably obtaining the desired effect of the present invention, the upper limit is preferably 30% by mass or less, more preferably 20% by mass or less, particularly preferably 15% by mass or less, and particularly preferably 8% by mass or less.

When the resin component in the resin composition is regarded as 100% by mass, the content of (B) hardener is not particularly limited, but from the viewpoint of remarkably obtaining the desired effect of the present invention, it is preferably 0.1% by mass The above is more preferably 1% by mass or more, particularly preferably 3% by mass or more, and particularly preferably 5% by mass or more. From the standpoint of remarkably obtaining the desired effect of the present invention, the upper limit is preferably 30% by mass or less, more preferably 20% by mass or less, particularly preferably 15% by mass or less, and particularly preferably 9% by mass or less.

＜(C)Fluorine-based organic filler＞ The resin composition of the present invention contains (C) a fluorine-based organic filler.

(C) The fluorine-based organic filler is an organic filler containing a fluorine atom-containing compound as a material. The fluorine-based organic filler is present as particles in the resin composition. Therefore, as the (C) fluorine-based organic filler, particles containing a fluorine atom-containing compound as a material are generally used.

(C) The material of the fluorine-based organic filler includes, for example, fluorine-based polymers and fluorine-based rubbers. Among them, fluorine-based polymers are preferred. Therefore, (C) the fluorine-based organic filler is preferably fluorine-based polymer particles.

Examples of fluorine-based polymers include polytetrafluoroethylene (PTFE), perfluoroalkoxy alkane (PFA), perfluoroethylene propylene copolymer (FEP), ethylene-tetrafluoroethylene copolymer (ETFE), tetrafluoroethylene Vinyl fluoride-perfluorodioxole copolymer (TFE/PDD), polyvinylidene fluoride (PVDF), polychlorotrifluoroethylene (PCTFE), ethylene-chlorotrifluoroethylene copolymer (ECTFE), poly Vinyl fluoride (PVF). These systems can be used in one type alone or in combination of two or more types.

Among these, polytetrafluoroethylene is preferred as the fluorine-based polymer. Therefore, as the (C) fluorine-based organic filler, polytetrafluoroethylene particles containing polytetrafluoroethylene particles are preferable.

From the viewpoint of remarkably obtaining the desired effect of the present invention, the weight average molecular weight of the fluorine-based polymer is preferably 5,000,000 or less, more preferably 4,000,000 or less, and particularly preferably 3,000,000 or less.

(C) The average particle size of the fluorine-based organic filler is preferably 0.05 μm or more, more preferably 0.08 μm or more, particularly preferably 0.10 μm or more, and preferably 10 μm or less, more preferably 5 μm or less, particularly preferably 4 μm the following. Since (C) the average particle size of the fluorine-based organic filler is within the aforementioned range, the desired effect of the present invention can be remarkably obtained. (C) The average particle size of the fluorine-based organic filler is the same as the (E) inorganic filler described below, and can be measured by the laser diffraction and scattering method based on the Mie scattering theory.

(C) Commercial products of fluorine-based organic fillers include, for example, "Lubron L-2", "Lubron L-5", and "Lubron L-5F" manufactured by Daikin Industry Co.; and "F1uon" manufactured by Asahi Glass Co., Ltd. PTFE L-170JE", "Fluon PTFE L-172JE", "F1uon PTFE L-173JE"; "KTL-500F", "KTL-2N", "KTL-1N" manufactured by Kitamura; manufactured by Chemours-Mitsui Fluoroproducts "TLP10F-1" and so on.

(C) Fluorine-based organic fillers can be surface-treated. For example, (C) the fluorine-based organic filler can be surface-treated with any surface treatment agent. Examples of surface treatment agents include nonionic surfactants, amphoteric surfactants, cationic surfactants, anionic surfactants, and other surfactants; inorganic fine particles. From the viewpoint of affinity, it is preferable to use a fluorine-based surfactant as the surface treatment agent. As specific examples of fluorine-based surfactants, "Surflon S-243" (perfluoroalkyl ethylene oxide adduct) manufactured by AGC Seimi Chemical Company; "Megafac F-251" and "Megafac" manufactured by DIC "F-477", "Megafac F-553", "Megafac R-40", "Megafac R-43", "Megafac R-94"; "FTX-218" and "Ftergent 610FM" manufactured by NEOS.

When the non-volatile component in the resin composition is regarded as 100% by mass, the content of (C) fluorine-based organic filler is not particularly limited, but from the viewpoint of remarkably obtaining the desired effect of the present invention, it is preferred It is 10% by mass or more, more preferably 15% by mass or more, particularly preferably 20% by mass or more, and particularly preferably 25% by mass or more. From the viewpoint of remarkably obtaining the desired effect of the present invention, the upper limit is preferably 80% by mass or less, more preferably 70% by mass or less, particularly preferably 60% by mass or less, and particularly preferably 55% by mass or less.

When the resin component in the resin composition is regarded as 100% by mass, the content of (C) fluorine-based organic filler is not particularly limited, but from the viewpoint of remarkably obtaining the desired effect of the present invention, it is preferably 10% by mass or more, more preferably 20% by mass or more, particularly preferably 25% by mass or more, and particularly preferably 30% by mass or more. From the viewpoint of remarkably obtaining the desired effect of the present invention, the upper limit is preferably 80% by mass or less, more preferably 70% by mass or less, particularly preferably 60% by mass or less, and particularly preferably 55% by mass or less.

＜(D) Polyimide resin＞ The resin composition of the present invention contains (D) polyimide resin. (D) The polyimide resin is not particularly limited as long as it is a resin having an imine bond in the repeating unit. (D) Polyimide resins generally include those obtained by an imidization reaction of a diamine compound and an acid anhydride. (D) Polyimide resin also includes modified polyimide resin such as silicone modified polyimide resin.

The diamine compound used for preparing (D) polyimide resin is not particularly limited, and examples thereof include aliphatic diamine compounds and aromatic diamine compounds.

As the aliphatic diamine compound, for example, 1,2-ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, 1,6 -Linear aliphatic diamine compounds such as hexamethylene diamine, 1,5-diaminopentane, 1,10-diaminodecane, etc.; 1,2-diamino-2-methan Branched chain aliphatic diamine compounds such as methyl propane, 2,3-diamino-2,3-butane and 2-methyl-1,5-diaminopentane; 1,3-bis( Aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, 1,4-diaminocyclohexane, 4,4'-methylenebis(cyclohexylamine), etc. The alicyclic diamine compound; dimer acid diamine (hereinafter also referred to as "dimer diamine"), etc., of which dimer acid diamine is preferred.

The so-called dimer acid type diamine means that the two terminal carboxylic acid groups (-COOH) of the dimer acid are substituted with aminomethyl (-CH ₂ -NH ₂ ) or amino (-NH ₂ ). The diamine compound obtained. Dimer acid is a known compound obtained by dimerizing unsaturated fatty acids (preferably those with 11 to 22 carbons, and particularly preferably those with 18 carbons). The industrial process is generally in the industry. On standardization. In particular, dimer acid can be easily obtained by dimerizing an unsaturated fatty acid having 18 carbon atoms, such as oleic acid and linoleic acid, which is cheap and easy to obtain, and the dimer acid having 36 carbon atoms is obtained as the main component. In addition, the dimer acid system may contain any amount of monomer acid, trimer acid, other polymerized fatty acids, etc., depending on the production method, the degree of purification, and the like. In addition, although the double bond remains after the polymerization reaction of the unsaturated fatty acid, in this specification, a hydride system in which the degree of unsaturation is reduced by further hydrogenation reaction is also included in the dimer acid. The dimer acid-type diamine is commercially available, and examples thereof include PRIAMINE 1073, PRIAMINE 1074, PRIAMINE 1075 manufactured by CRODA Japan, and Versamine 551 and Versamine 552 manufactured by COGINS Japan.

As an aromatic diamine compound, a phenylene diamine compound, a naphthalene diamine compound, a diphenylamine compound, etc. are mentioned, for example.

The so-called phenylenediamine compound refers to a compound formed from a benzene ring having two amino groups, and the benzene ring system therein may optionally have 1 to 3 substituents. The substituent system is not particularly limited. Specific examples of the phenylenediamine compound include 1,4-phenylenediamine, 1,2-phenylenediamine, 1,3-phenylenediamine, 2,4-diaminotoluene, 2,6-diaminotoluene, Aminotoluene, 3,5-diaminobiphenyl, 2,4,5,6-tetrafluoro-1,3-phenylenediamine, etc.

The so-called naphthalene diamine compound refers to a compound formed from a naphthalene ring having two amino groups, and the naphthalene ring system can optionally have 1 to 3 substituents. The substituent system is not particularly limited. Specific examples of the naphthalenediamine compound include 1,5-diaminonaphthalene, 1,8-diaminonaphthalene, 2,6-diaminonaphthalene, 2,3-diaminonaphthalene, and the like.

The so-called diphenylamine compound refers to a compound containing two aniline structures in the molecule, and each of the two benzene rings in the two aniline structures may further optionally have 1 to 3 substituents. The substituent system is not particularly limited. The two aniline structures in the diphenylamine compound can be directly bonded and/or bonded through 1 or 2 connection structures with 1 to 100 skeleton atoms selected from carbon atoms, oxygen atoms, sulfur atoms, and nitrogen atoms . In the diphenylamine compound, two aniline structures are bonded by two bonds.

Specific examples of the "connection structure" in the diphenylamine compound include -NHCO-, -CONH-, -OCO-, -COO-, -CH ₂ -, -CH ₂ CH ₂ -, -CH ₂ CH ₂ CH ₂ -, -CH ₂ CH ₂ CH ₂ CH ₂ -, -CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ -, -CH(CH ₃ )-, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -CH=CH-, -O-, -S-, -CO-, -SO ₂ -, -NH-, -Ph-, -Ph-Ph-, -C(CH ₃ ) ₂ -Ph -C(CH ₃ ) ₂ -, -O-Ph-O-, -O-Ph-Ph-O-, -O-Ph-SO ₂ -Ph-O-, -O-Ph-C(CH ₃ ) ₂ -Ph-O-, -C(CH ₃ ) ₂ -Ph-C(CH ₃ ) ₂ -, etc.

In this specification, "Ph" means 1,4-phenylene, 1,3-phenylene or 1,2-phenylene.

In one embodiment, specific examples of the diphenylamine compound include 4,4'-diamino-2,2'-bistrifluoromethyl-1,1'-phenyl, 3,4'- Diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 4,4 '-Diaminodiphenyl sulfide, 4-aminophenyl 4-aminobenzoate, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4- Aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 2,2-bis(4-aminophenyl)propane, 4,4'-(hexafluoroisopropylene Yl)diphenylamine, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, α,α-bis[4-(4-aminophenoxy)phenyl]-1,3-diisopropylbenzene, α,α-bis[4-(4-aminophenoxy)phenyl ]-1,4-Diisopropylbenzene, 4,4'-(9-phenylene)diphenylamine, 2,2-bis(3-methyl-4-aminophenyl)propane, 2,2 -Bis(3-methyl-4-aminophenyl)benzene, 4,4'-diamino-3,3'-dimethyl-1,1'-biphenyl, 4,4'-diamine -2,2'-dimethyl-1,1'-biphenyl, 9,9'-bis(3-methyl-4-aminophenyl) stilbene, 5-(4-aminophenoxy) )-3-[4-(4-aminophenoxy)phenyl]-1,1,3-trimethylindan, etc., preferably 5-(4-aminophenoxy)-3- [4-(4-Aminophenoxy)phenyl]-1,1,3-trimethylindan.

In another embodiment, as the diphenylamine compound, for example, a diamine compound represented by the following formula (1) and the like can be given,

[In the formula, R ¹ to R ⁸ each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, -X ⁹ -R ⁹ or -X ¹⁰ -R ¹⁰ , at least one of R ¹ to R ⁸ -X ¹⁰ -R ^10, X ⁹ each independently represent a single ^{bond, -NR 9 '-, - O} -, - S -, - CO -, - SO 2 -, - NR 9' CO -, - CONR 9 ' -, - OCO- or -COO-, R ⁹ each independently represent a substituted or unsubstituted alkyl group, or a substituted or unsubstituted alkenyl group, R ^{9 'each} independently represents a hydrogen atom, a substituted or unsubstituted alkyl , Or substituted or unsubstituted alkenyl, X ¹⁰ each independently represents a single bond, -(substituted or unsubstituted alkylene)-, -NH-, -O-, -S-, -CO-, -SO ₂ -, -NHCO-, -CONH-, -OCO- or -COO-, R ¹⁰ each independently represents a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group].

In the present specification, examples of the "halogen atom" include a fluorine atom, a chlorine atom, and a bromine atom.

In this specification, the "alkyl" refers to a linear, branched, or cyclic monovalent aliphatic saturated hydrocarbon group. It is preferably an alkyl group having 1 to 6 carbon atoms, and more preferably an alkyl group having 1 to 3 carbon atoms. For example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, second butyl, tertiary butyl, pentyl, isopentyl, neopentyl, cyclopentyl, Cyclohexyl etc. The substituent of the alkyl group in the "substituted or unsubstituted alkyl group" is not particularly limited, but for example, halogen atom, cyano group, alkoxy group, amine group, nitro group, hydroxyl group, carboxyl group, sulfonate Base etc. The number of substituents is preferably 1 to 3, more preferably 1.

In this specification, the "alkoxy" refers to a monovalent group (alkyl-O-) formed by bonding an alkyl group to an oxygen atom. It is preferably an alkoxy group having 1 to 6 carbon atoms, and more preferably an alkoxy group having 1 to 3 carbon atoms. For example, methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, second butoxy, tertiary butoxy, pentoxy and the like can be mentioned.

In this specification, the "alkenyl group" refers to a linear, branched or cyclic monovalent unsaturated hydrocarbon group having at least one carbon-carbon double bond. It is preferably an alkenyl group having 2 to 6 carbon atoms, and more preferably an alkenyl group having 2 or 3 carbon atoms. For example, vinyl, 1-propenyl, 2-propenyl, 2-methyl-1-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 3-methyl -2-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 4-methyl-3-pentenyl, 1-hexenyl, 3- Hexenyl, 5-hexenyl, 2-cyclohexenyl, etc. The substituent of the alkenyl group in the "substituted or unsubstituted alkenyl group" is not particularly limited, but examples include halogen atoms, cyano groups, alkoxy groups, aryl groups, heteroaryl groups, amino groups, and nitro groups. Group, hydroxyl group, carboxyl group, sulfo group, etc. The number of substituents is preferably 1 to 3, more preferably 1.

In the present specification, the "alkylene group" refers to a linear, branched or cyclic divalent aliphatic saturated hydrocarbon group. It is preferably an alkylene having 1 to 6 carbon atoms, and more preferably an alkylene having 1 to 3 carbon atoms. For example, -CH ₂ -, -CH ₂ -CH ₂ -, -CH(CH ₃ )-, -CH ₂ -CH ₂ -CH ₂ -, -CH ₂ -CH(CH ₃ )-, -CH (CH ₃ ) -CH ₂ -, -C(CH ₃ ) ₂ -, -CH ₂ -CH ₂ -CH ₂ -CH ₂ -, -CH ₂ -CH ₂ -CH(CH ₃ )-, -CH _2- CH(CH ₃ ) -CH ₂ -, -CH(CH ₃ ) -CH ₂ -CH ₂ -, -CH ₂ -C(CH ₃ ) ₂ -, -C(CH ₃ ) ₂ -CH ₂ -, etc. The substituent of the alkylene group in the "substituted or unsubstituted alkylene group" is not particularly limited, but examples include halogen atoms, cyano groups, alkoxy groups, aryl groups, heteroaryl groups, and amino groups. , Nitro, hydroxyl, carboxyl, sulfo, etc. The number of substituents is preferably 1 to 3, more preferably 1.

In this specification, the "aryl group" refers to a monovalent aromatic hydrocarbon group. It is preferably an aryl group having 6 to 14 carbon atoms, and more preferably an aryl group having 6 to 10 carbon atoms. For example, phenyl, 1-naphthyl, 2-naphthyl, etc. are mentioned, and phenyl is preferred. The substituent of the aryl group in the "substituted or unsubstituted aryl group" is not particularly limited, but examples include halogen atoms, cyano groups, alkyl groups, alkoxy groups, aryl groups, heteroaryl groups, and amines. Group, nitro group, hydroxyl group, carboxyl group, sulfo group, etc. The number of substituents is preferably 1 to 3, more preferably 1.

In the present specification, the "heteroaryl group" refers to an aromatic heterocyclic group having 1 to 4 heteroatoms selected from oxygen atoms, nitrogen atoms, and sulfur atoms. Preferably, it is a monocyclic, bicyclic or tricyclic (preferably monocyclic) aromatic heterocyclic group with 5 to 12 members (preferably 5 or 6 members). For example, furyl, thienyl, pyrrolyl, azolyl, isothiazolyl, thiazolyl, isothiazolyl, imidazolyl, pyrazolyl, 1,2,3-oxadiazolyl, 1, 2,4-oxadiazolyl, 1,3,4-oxadiazolyl, furazanyl, 1,2,3-thiadiazolyl, 1,2,4-thiadiazolyl, 1,3, 4-thiadiazolyl, 1,2,3-triazolyl, 1,2,4-triazolyl, tetrazolyl, pyridyl, titanyl, pyrimidinyl, pyridine, triazolyl, etc. The substituent of the heteroaryl group in the "substituted or unsubstituted heteroaryl group" is not particularly limited, but examples include halogen atoms, cyano groups, alkyl groups, alkoxy groups, aryl groups, and heteroaryl groups. , Amine, nitro, hydroxyl, carboxyl, sulfo, etc. The number of substituents is preferably 1 to 3, more preferably 1.

R ¹ to R ⁸ each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, -X ⁹ -R ⁹ or -X ¹⁰ -R ¹⁰ . Preferably, R ¹ to R ⁸ each independently represent a hydrogen atom or -X ¹⁰ -R ¹⁰ .

At least one of R ¹ to R ⁸ is -X ¹⁰ -R ¹⁰ . Preferably, one or two of R ¹ to R ⁸ are -X ¹⁰ -R ¹⁰ , more preferably one or two of R ⁵ to R ⁸ are -X ¹⁰ -R ¹⁰ , especially R One or two of ⁵ and R ⁷ are -X ¹⁰ -R ¹⁰ .

In one embodiment, one or two of R ¹ to R ⁸ are preferably -X ¹⁰ -R ¹⁰ , and the other hydrogen atoms in R ¹ to R ⁸ are more preferably R ⁵ to R ⁸ One or two of them are -X ¹⁰ -R ¹⁰ , and the other hydrogen atoms in R ¹ ~R ⁸ are preferably one or two of R ⁵ ~R ⁷ are -X ¹⁰ -R ¹⁰ , And the rest of R ¹ to R ⁸ are hydrogen atoms.

X ⁹ each independently represent a single ^{bond, -NR 9 '-, - O} -, - S -, - CO -, - SO 2 -, - NR 9' CO -, - CONR 9 '-, - OCO- or - COO-. R ⁹ each independently represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted alkenyl group. X ^{9 is} preferably a single bond.

R ^{9 'each} independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted alkenyl group. R ^{9 is} preferably a substituted or unsubstituted alkyl group.

X ¹⁰ each independently represents a single bond,-(substituted or unsubstituted alkylene) -, -NH-, -O-, -S-, -CO-, -SO ₂ , -NHCO-, -CONH-, -OCO- or -COO-. X ^{10 is} preferably a single bond.

R ¹⁰ each independently represents a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group. R ^{10 is} preferably a substituted or unsubstituted aryl group.

In one embodiment, the diamine compound represented by formula (1) is preferably the following formula (1'):

[In the formula, R ¹ to R ⁶ and R ⁸ each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, -X ⁹ -R ⁹ , and other symbol systems are the same as those of the formula (1)] ; More preferably, the following formula (1”):

The compound shown (4-aminobenzoic acid 5-amino-1,1'-biphenyl-2-yl).

A commercially available diamine compound may be used, or a compound synthesized by a well-known method may be used. For example, the diamine compound represented by the formula (1) can be synthesized by the synthesis method described in Japanese Patent No. 6240798 or a method based thereon. The diamine compound system may be used individually by 1 type, and may be used in combination of 2 or more types.

The acid anhydride used for preparing (D) polyimide resin is not particularly limited, but in a preferred embodiment, it is an aromatic tetracarboxylic dianhydride. As the aromatic tetracarboxylic dianhydride, for example, pyromellitic dianhydride, naphthalene tetracarboxylic dianhydride, anthracene tetracarboxylic dianhydride, diphthalic dianhydride, etc. may be mentioned, and diphthalic dianhydride is preferred. Formic acid dianhydride.

The so-called benzene tetracarboxylic dianhydride refers to benzene dianhydride having 4 carboxyl groups, and the benzene ring system therein may optionally have 1 to 3 substituents. Here, the substituent is preferably selected from a halogen atom, a cyano group, and -X ¹³ -R ¹³ (the same as the definition of the following formula (2)). Specific examples of pyromellitic dianhydride include pyromellitic dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, and the like.

The so-called naphthalene tetracarboxylic dianhydride means naphthalene dianhydride having 4 carboxyl groups, and the naphthalene ring system therein may optionally have 1 to 3 substituents. Here, the substituent is preferably selected from a halogen atom, a cyano group, and -X ¹³ -R ¹³ (the same as the definition of the following formula (2)). Specific examples of naphthalenetetracarboxylic dianhydride include 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, and the like.

The so-called anthracene tetracarboxylic dianhydride means an anthracene dianhydride having 4 carboxyl groups, and the anthracene ring system therein may optionally have 1 to 3 substituents. Here, the substituent is preferably selected from a halogen atom, a cyano group, and -X ¹³ -R ¹³ (the same as the definition of the following formula (2)). As anthracene tetracarboxylic dianhydride, 2,3,6,7-anthracene tetracarboxylic dianhydride etc. are mentioned specifically,.

The so-called diphthalic dianhydride refers to a compound containing two phthalic anhydrides in the molecule. Furthermore, each of the two benzene rings in the two phthalic anhydrides may optionally have 1~ 3 substituents. Here, the substituent is preferably selected from a halogen atom, a cyano group, and -X ¹³ -R ¹³ (the same as the definition of the following formula (2)). The two phthalic anhydrides in diphthalic dianhydride can be directly bonded or bonded through a connection structure with 1 to 100 skeleton atoms selected from carbon atoms, oxygen atoms, sulfur atoms, and nitrogen atoms Knot.

Examples of diphthalic dianhydride include compounds represented by formula (2),

[In the formula, R ¹¹ and R ¹² each independently represent a halogen atom, a cyano group, a nitro group, or -X ¹³ -R ¹³ , and X ¹³ each independently represents a single bond, -NR ^13' -, -O-, -S -, -CO-, -SO ₂ -, -NR ^13' CO-, -CONR ^13' -, -OCO- or -COO-, R ¹³ each independently represents a substituted or unsubstituted alkyl group, or substituted or unsubstituted A substituted alkenyl group, R ^13' each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted alkenyl group, Y represents a single bond or has a carbon atom, an oxygen atom, a sulfur atom, and a nitrogen atom The selected connection structure of 1-100 skeleton atoms, n and m each independently represent an integer of 0-3].

Y preferably has a connection structure of 1 to 100 skeleton atoms selected from carbon atoms, oxygen atoms, sulfur atoms, and nitrogen atoms. n and m are preferably zero.

The "connection structure" in Y has 1 to 100 skeleton atoms selected from carbon atoms, oxygen atoms, sulfur atoms, and nitrogen atoms. The "connection structure" is preferably -[A-Ph] _a -A-[Ph-A] _b- [wherein, A each independently represents a single bond,-(substituted or unsubstituted alkylene) -,- O-, -S-, -CO-, -SO ₂ -, -CONH-, -NHCO-, -COO- or -OCO-, a and b each independently represent an integer of 0 to 2 (preferably 0 or 1)] The divalent group shown.

Specifically, the "connection structure" in Y includes -CH ₂ -, -CH ₂ CH ₂ -, -CH ₂ CH ₂ CH ₂ -, -CH ₂ CH ₂ CH ₂ CH ₂ -, -CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ -, -CH(CH ₃ )-, -C(CH ₃ ) ₂ -, -O-, -CO-, -SO ₂ -, -Ph-, -O-Ph-O-, -O-Ph-SO ₂ -Ph-O-, -O-Ph-C(CH ₃ ) ₂ -Ph-O-, etc.

Specific examples of the diphthalic dianhydride include 3,3',4,4'-diphenyl ketone tetracarboxylic dianhydride, 3,3',4,4'-diphenyl ether tetra Carboxylic dianhydride, 3,3',4,4'-diphenyl tetracarboxylic dianhydride, 3,3',4,4'-biphenyl tetracarboxylic dianhydride, 2,2',3 ,3'-biphenyl tetracarboxylic dianhydride, 2,3,3',4'-biphenyl tetracarboxylic dianhydride, 2,3,3',4'-diphenyl ketone tetracarboxylic dianhydride Anhydride, 2,3,3',4'-diphenyl ether tetracarboxylic dianhydride, 2,3,3',4'-diphenyl tetracarboxylic dianhydride, 2,2'-bis(3 ,4-Dicarboxyphenoxyphenyl) dianhydride, methylene-4,4'-diphthalic dianhydride, 1,1-ethylene-4,4'-diphthalic acid Dianhydride, 2,2-propylene-4,4'-diphthalic dianhydride, 1,2-ethylene-4,4'-diphthalic dianhydride, 1,3-triethylene Methyl-4,4'-diphthalic dianhydride, 1,4-tetramethylene-4,4'-diphthalic dianhydride, 1,5-pentamethylene-4,4' -Diphthalic dianhydride, 1,3-bis(3,4-dicarboxyphenyl)phthalic anhydride, 1,4-bis(3,4-dicarboxyphenyl)phthalic anhydride, 1,3 -Bis(3,4-dicarboxyphenoxy)phthalic anhydride, 1,4-bis(3,4-dicarboxyphenoxy)phthalic anhydride, 2,2-bis(2,3-dicarboxybenzene) Base) propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 4,4'-(4,4'-isopropylidene diphenoxy) bisphthalic acid Dianhydride and so on.

As the aromatic tetracarboxylic dianhydride, commercially available ones can be used, or those synthesized by well-known methods or methods based on them can be used. The aromatic tetracarboxylic dianhydride system may be used individually by 1 type, and may be used in combination of 2 or more types.

In one embodiment, the acid anhydride system used to produce (D) polyimide resin may contain other acid anhydrides in addition to aromatic tetracarboxylic dianhydride.

Specific examples of other acid anhydrides include 1,2,3,4-cyclobutanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, and cyclohexane-1,2,3,4-tetracarboxylic acid dianhydride. Carboxylic dianhydride, cyclohexane-1,2,4,5-tetracarboxylic dianhydride, 3,3',4,4'-bicyclohexyltetracarboxylic dianhydride, carbonyl-4,4'-bis( Cyclohexane-1,2-dicarboxylic acid) dianhydride, methylene-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, 1,2-ethylene-4 ,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, oxy-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, thio-4 ,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, sulfonyl-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, etc. Tetracarboxylic dianhydride.

The content of the structure derived from the aromatic tetracarboxylic dianhydride in the entire structure derived from the acid anhydride constituting the polyimide resin (D) is preferably 10 mol% or more, more preferably 30 mol% or more, and particularly preferably 50 mol% or more, more preferably 70 mol% or more, even more preferably 90 mol% or more, and particularly preferably 100 mol%.

In one embodiment, the weight average molecular weight of (D) polyimide resin is preferably 1,000 to 100,000.

(D) The polyimide resin system can be prepared by a conventional method. As a well-known method, the method of heating the mixture of a diamine compound, an acid anhydride, and a solvent, and making it react is mentioned, for example. The mixing amount of the diamine compound, for example, relative to the acid anhydride, may generally be 0.5 to 1.5 molar equivalents, preferably 0.9 to 1.1 molar equivalents.

As the solvent used for the preparation of component (D), N,N-dimethylacetamide, N,N-diethylacetamide, N,N-dimethylformamide, N- Amine solvents such as methyl-2-pyrrolidone; ketone solvents such as acetone, methyl ethyl ketone (MEK) and cyclohexanone; ester solvents such as γ-butyrolactone; cyclohexane, Hydrocarbon solvents such as methylcyclohexane. In addition, in the preparation of the component (D), an imidization catalyst, azeotropic dehydration solvent, acid catalyst, etc. can also be used as necessary. As the imidization catalyst, for example, triethylamine, triisopropylamine, triethylenediamine, N-methylpyrrolidine, N-ethylpyrrolidine, N,N-dimethyl-4- Tertiary amines such as aminopyridine and pyridine. Examples of the azeotropic dehydration solvent include toluene, xylene, and ethylcyclohexane. As an acid catalyst, acetic anhydride etc. are mentioned, for example. The amount of use of the imidization catalyst, azeotropic dehydration solvent, acid catalyst, etc. can be set appropriately as long as it is a professional. (D) The reaction temperature for the preparation of the component is usually 100 to 250°C.

When the non-volatile component in the resin composition is regarded as 100% by mass, the content of (D) polyimide resin is 12% by mass or more. From the viewpoint of remarkably obtaining the desired effect of the present invention, it is preferable It is 14% by mass or more, more preferably 16% by mass or more, particularly preferably 18% by mass or more, and particularly preferably 20% by mass or more. From the viewpoint of remarkably obtaining the desired effect of the present invention, the upper limit thereof is preferably 40% by mass or less, more preferably 35% by mass or less, particularly preferably 30% by mass or less, and particularly preferably 25% by mass or less.

When the resin component in the resin composition is regarded as 100% by mass, from the viewpoint of remarkably obtaining the desired effect of the present invention, the content of (D) polyimide resin is preferably 16% by mass or more, more preferably It is 18% by mass or more, particularly preferably 20% by mass or more. From the standpoint of remarkably obtaining the desired effect of the present invention, the upper limit is preferably 50% by mass or less, more preferably 40% by mass or less, particularly preferably 35% by mass or less, and particularly preferably 30% by mass or less.

＜(E) Inorganic fillers＞ The resin composition of the present invention may include (E) an inorganic filler as an optional component.

(E) The material of the inorganic filler is not particularly limited, and examples include silica, alumina, glass, cordierite, silica, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, Hydrotalcite, diaspore, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, Magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate and zirconium tungstate phosphate, etc., particularly preferably silicon dioxide. Examples of the silicon dioxide include amorphous silicon dioxide, fused silicon dioxide, crystalline silicon dioxide, synthetic silicon dioxide, and hollow silicon dioxide. In addition, as the silica, spherical silica is preferred. (E) The inorganic filler system may be used individually by 1 type, and may be used in combination of 2 or more types.

(E) Commercial products of inorganic fillers include, for example, "UFP-30" manufactured by Denka Chemical Industry Co., Ltd.; "SP60-05" and "SP507-05" manufactured by Nippon Steel & Sumitomo Metal Materials Co., Ltd.; and ADMATECHS "YC100C", "YA050C", "YA050C-MJE", "YA010C" manufactured by DENKA; "UFP-30" manufactured by DENKA; "Silfill NSS-3N", "Silfill NSS-4N", "Silfill" manufactured by TOKUYAMA NSS-5N"; "SC2500SQ", "SO-C4", "SO-C2", "SO-C1", etc. manufactured by ADMATECHS.

(E) The average particle size of the inorganic filler is not particularly limited, but from the viewpoint of obtaining the desired effect of the present invention, it is preferably 20 μm or less, more preferably 10 μm or less, particularly preferably 8 μm or less, and even more It is preferably 6 μm or less, and particularly preferably 5 μm or less. The lower limit of the average particle size of the inorganic filler, from the viewpoint of obtaining the desired effect of the present invention, is preferably 0.1 μm or more, more preferably 1 μm or more, particularly preferably 2 μm or more, and particularly preferably 3 μm or more. It is 4μm or more. The average particle size of the inorganic filler can be measured by the laser diffraction and scattering method based on the Mie scattering theory. Specifically, the particle size distribution of the inorganic filler can be created on a volume basis by a laser diffraction scattering particle size distribution measuring device, and the median diameter can be measured as the average particle size. For the measurement sample, 100 mg of the inorganic filler and 10 g of methyl ethyl ketone can be weighed in a vial and dispersed by ultrasonic for 10 minutes. For the sample to be measured, a laser diffraction type particle size distribution measuring device is used. The wavelength of the light source used is blue and red. The volume-based particle size distribution of the inorganic filler is measured by a flow cell method. The diameter distribution is used as the median diameter to calculate the average particle diameter. As a laser diffraction particle size distribution measuring device, for example, "LA-960" manufactured by Horiba Manufacturing Co., Ltd. can be cited.

From the standpoint of improving moisture resistance and dispersibility, (E) the inorganic filler is preferably aminosilane coupling agent, epoxysilane coupling agent, mercaptosilane coupling agent, alkoxysilane compound, Treated with one or more surface treatment agents such as organosilazane compound and titanate coupling agent. Commercial products of surface treatment agents include, for example, "KBM403" (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., and "KBM803" (3-mercaptopropane) manufactured by Shin-Etsu Chemical Co., Ltd. Trimethoxysilane), "KBE903" (3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., and "KBM573" (N-phenyl-3-aminopropyl trimethyl) manufactured by Shin-Etsu Chemical Co., Ltd. Oxysilane), "SZ-31" (hexamethylsilazane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM103" (phenyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., and KBM-4803 manufactured by Shin-Etsu Chemical Co., Ltd. "(Long-chain epoxy silane coupling agent), "KBM-7103" (3,3,3-trifluoropropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., etc.

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

The degree of surface treatment by the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the inorganic filler. The amount of carbon per unit surface area of the inorganic filler, from the viewpoint of improving the dispersibility of the inorganic filler, is preferably 0.02 mg/m ² or more, more preferably 0.1 mg/m ² or more, and particularly preferably 0.2 mg/ m ² or more. On the other hand, from the viewpoint of preventing the melt viscosity of the resin varnish and the melt viscosity of the sheet form from increasing, it is preferably 1 mg/m ² or less, more preferably 0.8 mg/m ² or less, and particularly preferably 0.5 mg/m ² or less.

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

(E) a specific surface area of the inorganic filler, from the viewpoint of further improving the effect of the present invention, the view is preferably 1m ² / g or more, more preferably 2m ² / g or more, particularly preferably 3m ² / g or more. The upper limit is not particularly limited, but it is preferably 50 m ² /g or less, more preferably 20 m ² /g or less, 10 m ² /g or less, or 5 m ² /g or less. The specific surface area of the inorganic filler is based on the BET method, using a specific surface area measuring device (Macsorb HM-1210 manufactured by MOUNTECH), adsorbing nitrogen on the sample surface, and calculating the specific surface area using the BET multipoint method.

When the non-volatile content in the resin composition is regarded as 100% by mass, from the viewpoint of remarkably obtaining the desired effect of the present invention, the content of (E) inorganic filler is preferably 60% by mass or less, more preferably It is 50% by mass or less, particularly preferably 40% by mass or less, and particularly preferably 30% by mass or less. When the (E) inorganic filler is contained, the lower limit of the content is not particularly limited, but for example, it may be 10% by mass or more, 15% by mass or more, 20% by mass or more, 25% by mass or more.

＜(F) Hardening accelerator＞ The resin composition of the present invention may include (F) a hardening accelerator as an optional component.

(F) Hardening accelerators include, for example, phosphorus hardening accelerators, amine hardening accelerators, imidazole hardening accelerators, guanidine hardening accelerators, metal hardening accelerators, and the like. Among them, phosphorus-based hardening accelerators, amine-based hardening accelerators, imidazole-based hardening accelerators, and metal-based hardening accelerators are preferred, and amine-based hardening accelerators, imidazole-based hardening accelerators, and metal-based hardening accelerators are more preferred. The hardening accelerator system may be used alone or in combination of two or more types.

Examples of phosphorus-based hardening accelerators include triphenylphosphine, borate phosphonium compounds, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, (4 -Methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyl triphenylphosphonium thiocyanate.

Examples of amine-based hardening accelerators include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine (DMAP), benzyldimethylamine, 2,4,6, -Ginseng (dimethylaminomethyl)phenol, 1,8-diazabicyclo(5,4,0)-undecene, etc., preferably 4-dimethylaminopyridine.

Examples of imidazole-based hardening accelerators include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, and 2-ethyl-4-methylimidazole , 1,2-Dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1 -Benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4 -Methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazole Onium trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-tris, 2,4-diamino-6- [2'-Undecylimidazolyl-(1')]-ethyl-s-tris, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-( 1')]-ethyl-s-tris, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-tris isocyanuric acid Adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-Dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, 2 -Imidazole compounds such as phenylimidazoline and adducts of imidazole compounds and epoxy resin.

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

Examples of guanidine-based hardening accelerators include cyanoguanidine, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, and dimethylguanidine. Guanidine, diphenylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-methyl-1, 5,7-Triazabicyclo[4.4.0]dec-5-ene, 1-methyl biguanide, 1-ethyl biguanide, 1-n-butyl biguanide, 1-n-octadecyl biguanide, 1,1- Dimethyl biguanide, 1,1-diethyl biguanide, 1-cyclohexyl biguanide, 1-allyl biguanide, 1-phenyl biguanide, 1-(o-tolyl) biguanide, etc.

Examples of metal-based hardening accelerators include organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of organometallic complexes include organic cobalt complexes such as cobalt acetone (II) and cobalt acetone (III), and organic copper complexes such as copper acetone (II). , Organic zinc complexes such as zinc acetone (II), organic iron complexes such as iron (III) acetone, organic nickel complexes such as nickel (II) acetone, manganese acetone (II) and other organic manganese complexes. Examples of organic metal salts include zinc octoate, tin octoate, zinc naphthenate, cobalt naphthenate, tin stearate, zinc stearate, and the like.

When the curing accelerator (F) is contained, its content is not particularly limited, but when the non-volatile content in the resin composition is regarded as 100% by mass, from the viewpoint of remarkably obtaining the desired effect of the present invention, it is more It is preferably 0.001 mass% or more, more preferably 0.01 mass% or more, particularly preferably 0.05 mass% or more, and particularly preferably 0.1 mass% or more. From the viewpoint of remarkably obtaining the desired effect of the present invention, the upper limit is preferably 2% by mass or less, more preferably 1% by mass or less, particularly preferably 0.5% by mass or less, and particularly preferably 0.3% by mass or less.

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

Examples of organic solvents include ketone solvents such as acetone, methyl ethyl ketone, and cyclohexanone; ethyl acetate, butyl acetate, serosol acetate, propylene glycol monomethyl ether acetate, carbohydrate Ester solvents such as hexyl acetate, ethyl diethylene glycol acetate, γ-butyrolactone, etc.; carbitol solvents such as Celosul and butyl carbitol; benzene, toluene, xylene, ethyl Aromatic hydrocarbon solvents such as methylbenzene and trimethylbenzene; Amine solvents such as dimethylformamide, dimethylacetamide (DMAc) and N-methylpyrrolidone; methanol, ethanol, Alcohol-based solvents such as 2-methoxypropanol; hydrocarbon-based solvents such as cyclohexane and methylcyclohexane. The organic solvent system may be used singly or in combination of two or more types at any ratio.

＜(H) Other additives＞ In addition to the above-mentioned components, the resin composition system may further contain other additives as optional components. Examples of such additives include organic fillers other than fluorine, thickeners, defoamers, leveling agents, adhesion imparting agents, polymerization initiators, flame retardants, and the like. These additives can be used alone or in combination of two or more types. The content of each can be set appropriately as long as it belongs to the industry.

＜Manufacturing method of resin composition＞ In one embodiment, the resin composition of the present invention can be manufactured, for example, by a method comprising: in a reaction vessel, (A) epoxy resin, (B) curing agent, (C) fluorine-based organic Filling material, (D) polyimide resin (pre-imidized), if necessary (E) inorganic filler, if necessary (F) hardening accelerator, if necessary (G) organic solvent and If necessary (H) other additives are added and mixed in any order and/or part or all at the same time to obtain a resin composition (hereinafter referred to as step (1)).

In step (1), the temperature of the process of adding each component can be appropriately set, and during the process of adding each component, heating and/or cooling can be temporarily or consistently. The specific temperature of the process of adding each component is not particularly limited, but may be, for example, 0°C to 150°C. In the process of adding each ingredient, stirring or shaking can be carried out.

In step (1), especially when solid epoxy resin is contained in (A) epoxy resin, it is preferable to combine (A) epoxy resin and (D) polyimide resin (preliminarily The step of adding, mixing, and heating in any order and/or part or all of them simultaneously to obtain a mixture, and (G) organic solvents and (H) other additives as required, in any order and/or at the same time. The resulting mixture is cooled, and (B) hardener, (C) fluorine-based organic filler, (E) inorganic filler, if necessary (F) hardening accelerator, and (G) organic solvent if necessary And if necessary (H) other additives are added and mixed in any order and/or part or all at the same time to obtain the second stage of the step of obtaining a resin composition.

Furthermore, after step (1), it is preferable to further include a step of stirring the resin composition to uniformly disperse it (hereinafter referred to as step (2)) using a stirring device such as a rotary mixer. Furthermore, after step (1), preferably after step (2), it is preferable to further include, for example, a step of filtering the resin composition using a cassette filter.

＜Characteristics of resin composition＞ Since the resin composition of the present invention contains (A) epoxy resin, (B) hardener, and (D) polyimide resin, it can be obtained with low roughness and high peel strength, as well as water resistance and flexibility Excellent hardening material.

Regarding the excellent water resistance, which is one of the characteristics of the resin composition of the present invention, for example, after curing a resin composition with a thickness of 50 μm and exposing the resulting cured product to boiling pure water for 1 hour, the amount of mass change before and after exposure ( The water absorption (%) is preferably 1.0% or less, more preferably 0.9% or less, particularly preferably 0.8% or less, and particularly preferably 0.7% or less.

Regarding the excellent flexibility, which is one of the characteristics of the resin composition of the present invention, for example, a resin composition having a thickness of 40 μm is cured, and the resulting cured product is set at a load of 2.5N, a bending angle of 90 degrees, and bending according to JIS K7127. The speed is 175 times per minute, and the bending radius is 1.0mm. The number of times of bending resistance during the MIT bending endurance test is preferably 6,000 times or more, more preferably 7,000 times or more, particularly preferably 8,000 times or more, particularly preferably 9,000 times or more .

Regarding the low roughness, which is one of the characteristics of the resin composition of the present invention, for example, the resin composition is cured to form an insulating layer, and the arithmetic average roughness (Ra) of the insulating layer surface after roughening the insulating layer surface It is preferably 240 nm or less, more preferably 220 nm or less, and particularly preferably 200 nm or less. The lower limit is not particularly limited, but may be 30 nm or more, 40 nm or more, or 50 nm or more. The arithmetic average roughness (Ra) of the surface of the insulating layer can be measured with a non-contact surface roughness meter.

With regard to the high peel strength, which is one of the characteristics of the resin composition of the present invention, for example, the resin composition is cured to form an insulating layer, the surface of the insulating layer is roughened, and the conductive layer and the insulating layer obtained by plating have higher peel strengths. It is preferably 0.3 kgf/cm or more, more preferably 0.35 kgf/cm or more, and particularly preferably 0.4 kgf/cm or more. The upper limit is not particularly limited, but may be 1.5 kgf/cm or less, 1.2 kgf/cm or less, 1.0 kgf/cm or less. The measurement of the peel strength between the insulating layer and the conductor layer can be performed in accordance with the Japanese Industrial Standards (JIS C6481).

When measuring water absorption, MIT folding resistance, arithmetic average roughness (Ra) or peel strength, the curing temperature for obtaining the insulating layer (cured material) is not particularly limited, but it is preferably 120°C to 240°C , More preferably 150℃~220℃, especially preferably 170℃~210℃. In addition, the curing time is not particularly limited, but it is preferably 5 minutes to 120 minutes, more preferably 10 minutes to 110 minutes, and particularly preferably 20 minutes to 100 minutes. In addition, when measuring the arithmetic average roughness (Ra) or peeling strength, it is preferable to preliminarily heat before thermal curing. For example, the preheating temperature is not particularly limited, but is preferably 60°C or higher and 115°C or lower, and more preferably 70°C or higher and 110°C or lower. In addition, the preheating time is not particularly limited, but it is preferably 5 minutes to 150 minutes, more preferably 5 minutes to 120 minutes, and particularly preferably 5 minutes to 100 minutes.

The method of the roughening treatment when measuring the arithmetic average roughness (Ra) or the peel strength is not particularly limited, but a wet roughening treatment is preferred, and a swelling treatment of a swelling liquid is more preferred. For example, it can be obtained by immersing in a swelling solution at 60°C for 10 minutes, then in an oxidizer solution at 80°C for 20 minutes, and finally immersing in a neutralizing solution at 40°C for 5 minutes, and then drying at 80°C for 15 minutes. Carry out roughening treatment.

＜Resin sheet＞ The resin sheet of the present invention includes a support and a resin composition layer formed of the resin composition of the present invention provided on the support.

From the viewpoint of providing a cured product with excellent insulating properties even with thinner printed wiring boards and thin films, the thickness of the resin composition layer is preferably 15μm or less, more preferably 13μm or less, and particularly preferably 10μm or less or 8μm or less . The lower limit of the thickness of the resin composition layer is not particularly limited, but it can generally be 1 μm or more, 1.5 μm or more, 2 μm or more.

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

When using a film made of a plastic material as a support, as the plastic material, for example, polyethylene terephthalate (hereinafter also referred to as "PET"), polyethylene naphthalate (hereinafter also referred to as " PEN”) and other polyester, polycarbonate (hereinafter referred to as “PC”), polymethylmethacrylate (PMMA) and other acrylic, cyclic polyolefin, triacetyl cellulose (TAC), polyether vulcanization (PES), polyether ketone, polyether ketone, polyimide, etc. Among them, polyethylene terephthalate and polyethylene naphthalate are preferred, and inexpensive polyethylene terephthalate is particularly preferred.

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

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

Moreover, as a support body, you may use the support body with a mold release layer which has a mold release layer on the surface joined with a resin composition layer. As the mold release agent used in the mold release layer of the support with the mold release layer, for example, one selected from the group consisting of alkyd resin, polyolefin resin, urethane resin and silicone resin More than one release agent. Commercial products can also be used for the support with a release layer. For example, "SK-1" and "AL" made by LINTEC, a PET film with a release layer mainly composed of an alkyd resin-based release agent, can be used. -5", "AL-7", "Lumirror T60" manufactured by Toray, "Purex" manufactured by Teijin, "Unipeel" manufactured by UNITIKA, etc.

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

In one embodiment, the resin sheet may further include other layers as necessary. Examples of the other layer include a support-aligned protective film provided on a surface of the resin composition layer that is not bonded to the support (that is, the surface on the opposite side of the support). The thickness of the protective film is not particularly limited, but is, for example, 1 μm to 40 μm. By laminating the protective film, it is possible to prevent dust and the like from adhering to or damaging the surface of the resin composition layer.

The resin sheet can be manufactured, for example, by preparing a resin varnish in which a resin composition is dissolved in an organic solvent, coating the resin varnish on a support using a die coater or the like, and drying it to form a resin composition layer.

Examples of organic solvents include ketones such as acetone, methyl ethyl ketone (MEK), and cyclohexanone; ethyl acetate, butyl acetate, serosol acetate, and propylene glycol monomethyl ether acetate Acetate esters such as carbitol acetate; Carbitols such as Celosine and butyl carbitol; Aromatic hydrocarbons such as toluene and xylene; Dimethylformamide, dimethyl Amine solvents such as acetamide (DMAc) and N-methylpyrrolidone. An organic solvent system may be used individually by 1 type, and may be used in combination of 2 or more types.

The drying system can be performed by well-known methods such as heating and hot air blowing. The drying conditions are not particularly limited, but the organic solvent in the resin composition layer is dried so that the content of the organic solvent is 10% by mass or less, preferably 5% by mass or less. Although it also varies with the boiling point of the organic solvent in the resin varnish, for example, when a resin varnish containing 30% to 60% by mass of organic solvent is used, by drying at 50°C to 150°C for 3 minutes to 10 minutes, A resin composition layer can be formed.

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

＜Laminated sheet＞ The laminated sheet is a sheet produced by laminating and curing a plurality of resin sheets. Therefore, the laminated sheet includes a plurality of insulating layers as hardened resin sheets. Generally, in order to manufacture a laminated sheet, the number of resin sheets laminated is the same as the number of insulating layers contained in the laminated sheet. The number of specific insulating layers per laminated sheet is usually 2 or more, preferably 3 or more, particularly preferably 5 or more, and preferably 20 or less, more preferably 15 or less, particularly preferably 10 or less.

The laminated sheet is a sheet that is used by bending with one side facing each other. The minimum bending radius of the laminated sheet is not particularly limited, but it is preferably 0.1 mm or more, more preferably 0.2 mm or more, particularly preferably 0.3 mm or more, and preferably 5 mm or less, more preferably 4 mm or less , Particularly preferably below 3mm.

Holes can be formed in each insulating layer included in the laminated sheet. The hole can function as a through hole or a through hole in the multilayer flexible substrate.

The laminated sheet system may further include arbitrary elements in addition to the insulating layer. For example, the laminated sheet may have a conductor layer as an arbitrary element. The conductor layer is usually partially formed on the surface of the insulating layer or between the insulating layers. This conductor layer usually has a function as wiring in a multilayer flexible substrate.

The conductor material used for the conductor layer is not particularly limited. In a suitable embodiment, the conductor layer includes at least one selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin, and indium Of metal. The conductor material can be a single metal or an alloy. Examples of alloys include alloys of two or more metals selected from the above-mentioned group (for example, nickel-chromium alloy, copper-nickel alloy, and copper-titanium alloy). Among them, from the viewpoints of the versatility of conductor layer formation, cost, ease of patterning, etc., chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper as a single metal is preferred; and , Nickel-chromium alloy, copper-nickel alloy, copper-titanium alloy and other alloys. Among them, a single metal of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper is more preferred; and a nickel-chromium alloy, and a single metal of copper is particularly preferred.

The conductor layer may have a single-layer structure, or a multiple-layer structure including a single metal layer made of different types of metals or alloys, or two or more alloy layers. When the conductor layer has a multi-layer structure, the layer in contact with the insulating layer is preferably a single metal layer of chromium, zinc, or titanium, or a nickel-chromium alloy alloy layer.

The conductor layer can be patterned in order to function as wiring.

The thickness of the conductor layer depends on the design of the multilayer flexible substrate, but is preferably 3μm~35μm, more preferably 5μm~30μm, particularly preferably 10~20μm, particularly preferably 15~20μm.

The thickness of the laminated sheet is preferably 100 μm or more, more preferably 150 μm or more, particularly preferably 200 μm or more, and preferably 600 μm or less, more preferably 500 μm or less, particularly preferably 400 μm or less.

<Method of manufacturing laminated sheet> The laminated sheet can be manufactured by a manufacturing method including (a) a step of preparing a resin sheet and (b) a step of laminating and curing a plurality of resin sheets. The order of laminating and curing the resin sheet is arbitrary as long as the desired laminated sheet can be obtained. For example, after all the plural resin sheets are laminated, the laminated plural resin sheets can be cured together. Also, for example, each time another resin sheet is laminated on a certain resin sheet, the laminated resin sheet may be cured.

Hereinafter, a preferred embodiment of step (b) will be described. In the embodiments described below, in order to distinguish, it is appropriate to attach numbers such as "the first resin sheet" and "the second resin sheet" to the resin sheet. Furthermore, it is necessary to harden the resin sheet. The obtained insulating layer is also attached with numbers such as "first insulating layer" and "second insulating layer" in the same way as the resin sheet.

In a preferred embodiment, step (b) may include the following steps: (II) The step of hardening the first resin sheet to form the first insulating layer, (VI) A step of laminating a second resin sheet on the first insulating layer, and (VII) A step of curing the second resin sheet to form a second insulating layer. Furthermore, step (b) may include any of the following steps as necessary: (I) The step of laminating the first resin sheet on the sheet supporting substrate, (III) The step of opening holes in the first insulating layer, (IV) The step of roughening the first insulating layer, and (V) A step of forming a conductor layer on the first insulating layer. The steps are described below.

Step (I) is a step of laminating the first resin sheet on the sheet supporting substrate, optionally before step (II). The sheet supporting substrate is a peelable member, and for example, a plate-shaped, sheet-shaped, or film-shaped member can be used.

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

The lamination system can be carried out by a commercially available vacuum laminator. As a commercially available vacuum laminator, for example, a vacuum pressure laminator manufactured by Mingji Seisakusho Co., Ltd., a vacuum applicator manufactured by NICHIGO Materials Co., Ltd., a batch vacuum pressure laminator, and the like can be cited.

When a sheet-like laminate material is used, the sheet supporting base material and the first resin sheet are laminated. For example, the first resin sheet of the sheet-like laminate material can be heated by pressing the sheet-like laminate material from the support side Pressure bonding is performed on the sheet supporting substrate. As a member for heating and pressing the sheet-like laminate material to the sheet supporting substrate (hereinafter, also referred to as "heating and pressing member" as appropriate), for example, a heated metal plate (SUS mirror plate, etc.) or a metal roll (SUS roller) etc. It is preferable not to directly press the heat-compression bonding member on the sheet-like laminate material, but to press the first resin sheet through an elastic material such as heat-resistant rubber so that the first resin sheet fully follows the uneven surface of the sheet support substrate .

After lamination, the first resin sheet can be smoothed by applying pressure under normal pressure (under atmospheric pressure), for example, with a heating and pressing member. For example, when a sheet-like laminate material is used, the first resin sheet of the sheet-like laminate material can be smoothed by pressing the sheet-like laminate material with a heating and pressure bonding member from the support side. The pressurization conditions of the smoothing treatment can be the same conditions as the heat and pressure bonding conditions of the above-mentioned lamination. The smoothing treatment can be performed by a commercially available laminator. The lamination and smoothing treatment can also be continuously performed using the above-mentioned commercially available vacuum laminator.

Step (II) is a step of curing the first resin sheet to form a first insulating layer. The thermosetting conditions of the first resin sheet are not particularly limited, and the conditions used when forming the insulating layer of the printed wiring board can be arbitrarily used.

Generally, the specific thermosetting conditions vary depending on the type of resin composition. For example, the curing temperature is preferably 120°C to 240°C, more preferably 150°C to 220°C, and particularly preferably 170°C to 210°C. Furthermore, the curing time is preferably 5 minutes to 120 minutes, more preferably 10 minutes to 110 minutes, and particularly preferably 20 minutes to 100 minutes.

Before thermally curing the first resin sheet, the first resin sheet may be preliminarily heated at a temperature lower than the curing temperature. For example, before the first resin sheet is thermally cured, the first resin can be heated at a temperature above 50°C and below 120°C (preferably 60°C or more and 115°C or less, more preferably 70°C or more and 110°C or less). The slices are preheated for more than 5 minutes (preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes, and particularly preferably 15 minutes to 100 minutes).

Step (III) is a step of opening holes in the first insulating layer as necessary. Through this step (III), holes such as through holes and through holes can be formed in the first insulating layer. The opening system can be implemented according to the composition of the resin composition, for example, using a drill, a laser, or a plasma. The size or shape of the hole can be appropriately determined according to the design of the multilayer flexible substrate.

Step (IV) is a step of roughening the first insulating layer as needed. Usually, in this step (IV), the glue residue is also removed. In this way, the roughening treatment is also referred to as scum removal treatment. As the roughening treatment, either dry or wet roughening treatment can be performed. As an example of dry roughening treatment, plasma treatment etc. are mentioned. In addition, as an example of the wet roughening treatment, a method of performing the swelling treatment of the swelling liquid, the roughening treatment of the oxidizing agent, and the neutralization treatment of the neutralization liquid in this order can be mentioned.

The arithmetic average roughness (Ra) of the surface of the first insulating layer after the roughening treatment is preferably 240 nm or less, more preferably 220 nm or less, and particularly preferably 200 nm or less. The lower limit is not particularly limited, but may be 30 nm or more, 40 nm or more, or 50 nm or more.

Step (V) is a step of forming a conductor layer on the first insulating layer as necessary. The method of forming the conductor layer includes, for example, a plating method, a sputtering method, and an evaporation method. Among them, the plating method is preferred. As a suitable example, a method of forming a conductor layer with a desired wiring pattern by plating on the surface of the first insulating layer by an appropriate method such as a semi-additive method and a full-additive method can be cited. Among them, from the viewpoint of ease of manufacture, the semi-additive method is preferred.

The following shows an example of forming the conductor layer by the semi-additive method. First, on the surface of the first insulating layer, a plating seed layer is formed by electroless plating. Next, on the formed plating seed layer, corresponding to the desired wiring pattern, a mask pattern is formed that exposes a part of the plating seed layer. After forming a metal layer by electrolytic plating on the exposed plating seed layer, the mask pattern is removed. Then, the unnecessary plating seed layer is removed by processing such as etching, and a conductor layer having a desired wiring pattern can be formed.

After the first insulating layer is obtained in step (II), and after steps (III) to (V) are performed as necessary, step (VI) is performed. Step (VI) is a step of laminating a second resin sheet on the first insulating layer. The lamination system of the first insulating layer and the second resin sheet can be carried out by the same method as the lamination of the sheet supporting substrate and the first resin sheet in step (I).

However, when the first insulating layer is formed using a sheet-like laminate material, the support of the sheet-like laminate is removed before step (VI). The removal of the support can be performed between step (I) and step (II), between step (II) and step (III), or between step (III) and step (IV) It can also be carried out between step (IV) and step (V).

After step (VI), proceed to step (VII). Step (VII) is a step of curing the second resin sheet to form a second insulating layer. The curing of the second resin sheet can be performed by the same method as the curing of the first resin sheet in step (II). Thereby, a laminated sheet including a plurality of insulating layers such as a first insulating layer and a second insulating layer can be obtained.

Furthermore, in the method of the foregoing embodiment, (VIII) the step of opening a hole in the second insulating layer, (IX) the step of roughening the second insulating layer, and (X) the step of Two steps of forming a conductor layer on the insulating layer. The opening of the second insulating layer in step (VIII) can be performed by the same method as the opening of the first insulating layer in step (III). Moreover, the roughening treatment of the second insulating layer in step (IX) can be performed by the same method as the roughening treatment of the first insulating layer in step (IV). Furthermore, the formation of the conductor layer on the second insulating layer in step (X) can be performed by the same method as the formation of the conductor layer on the first insulating layer in step (V).

In the foregoing embodiment, the first resin sheet and the second resin sheet are laminated and cured to produce a laminated sheet. However, it is also possible to use 3 or more resin sheets. Laminate and harden to produce a laminated sheet. For example, in the method of the foregoing embodiment, the laminating and curing of the resin sheet of step (VI) to step (VII), and the opening of the insulating layer of step (VIII) to step (X), if necessary, are repeated. The roughening treatment of the insulating layer and the formation of a conductor layer on the insulating layer can produce laminated sheets. Thereby, a laminated sheet including three or more insulating layers can be obtained.

Furthermore, the method of the aforementioned embodiment may include any steps other than the above-mentioned steps. For example, in the case of performing step (I), a step of removing the sheet supporting substrate may also be performed.

＜Multilayer flexible substrate＞ The multilayer flexible substrate includes a laminated sheet. Therefore, the multilayer flexible substrate includes an insulating layer formed by curing the resin composition of the present invention. The multi-layer flexible substrate may include only the laminate sheet, or may include any components, combined with the laminate sheet. As an arbitrary member, an electronic component, a cover film, etc. are mentioned, for example.

The multilayer flexible substrate can be manufactured by a manufacturing method including the method for manufacturing the above-mentioned laminated sheet. Therefore, the multilayer flexible substrate can be manufactured by a manufacturing method including (a) a step of preparing a resin sheet and (b) a step of laminating and hardening the resin sheet in plural.

The manufacturing method of the multilayer flexible substrate may further include any steps, combined with the foregoing steps. For example, a method for manufacturing a multilayer flexible substrate with electronic components may include the step of bonding the electronic components to the laminate sheet. The bonding conditions between the laminate sheet and the electronic component can be any conditions that can connect the terminal electrodes of the electronic component and the conductor layer as wiring provided on the laminate sheet. In addition, for example, a method of manufacturing a multilayer flexible substrate provided with a cover film may include a step of laminating a laminate sheet and a cover film.

The aforementioned multi-layer flexible substrate can usually be bent and used in such a way that one of the laminated sheets included in the multi-layer flexible substrate faces each other. For example, the multi-layer flexible substrate can be folded to reduce the size and housed in the housing of the semiconductor device. In addition, for example, a multilayer flexible substrate is provided in a semiconductor device having a movable portion that can be bent.

＜Semiconductor device＞ The semiconductor device includes the aforementioned multilayer flexible substrate. The semiconductor device includes, for example, a multilayer flexible substrate and a semiconductor chip mounted on the multilayer flexible substrate. In most semiconductor devices, the multi-layer flexible substrate can be bent in such a way that one of the laminated sheets included in the multi-layer flexible substrate faces each other to be housed in the housing of the semiconductor device.

Examples of semiconductor devices include various semiconductor devices such as power supply products (such as computers, mobile phones, digital cameras, and televisions) and vehicles (such as locomotives, automobiles, trams, ships, and airplanes).

The aforementioned semiconductor device can be manufactured, for example, by a manufacturing method including the following steps, including: preparing a multilayer flexible substrate, bending the multilayer flexible substrate with one side of the laminated sheet facing each other, and The step of storing the folded multilayer flexible substrate in the housing. [Example]

Hereinafter, the present invention will be explained in more detail with examples. The present invention is not limited by these embodiments. In addition, in the following, the "parts" and "%" that indicate the amount respectively mean "parts by mass" and "% by mass" unless otherwise specified.

<Synthesis example 1: Synthesis of polyimide resin 1> Put 4-aminobenzoic acid 5-amino-1,1'-biphenyl-2-yl (compound of formula (l")) into a 500ml separable flask equipped with a nitrogen inlet pipe and a stirring device. 9.13 g (30 millimoles), 4,4'-(4,4'-isopropylidene diphenoxy) bisphthalic dianhydride 15.61g (30 millimoles), N-methyl-2 -94.64 g of pyrrolidone, 0.47 g (6 millimoles) of pyridine, and 10 g of toluene, in a nitrogen atmosphere, at 180°C, by removing toluene from the system while removing toluene from the system and reacting for 4 hours at the same time, A polyimide solution (non-volatile content 20%) containing polyimide resin 1 was obtained. In the polyimide solution, no precipitation of the synthesized polyimine resin 1 was seen.

<Synthesis example 2: Synthesis of polyimide resin 2> Add a commercially available aromatic tetracarboxylic dianhydride ("BisDA-1000" manufactured by SABIC Japan Co., Ltd., 4,4'-(4,4') to a reaction vessel equipped with a stirrer, a water trap, a thermometer, and a nitrogen introduction tube. -Isopropylidene diphenoxy) diphthalic dianhydride) 65.0 g, 266.5 g of cyclohexanone, and 44.4 g of methylcyclohexane, and the solution was heated to 60°C. Next, after dropping 43.7 g of a commercially available dimer diamine ("PRIAMINE 1075" manufactured by CRODA Japan Co., Ltd.) and 5.4 g of 1,3-bisaminomethylcyclohexane, it was heated at 140°C for 1 hour. Amination reaction. Thereby, a polyimide solution (non-volatile content 30%) containing polyimide resin 2 was obtained. In addition, the weight average molecular weight of the polyimide resin 2 is 25,000.

<Synthesis example 3: Synthesis of polyimide resin 3> A 500 mL separable flask was prepared, which was equipped with a moisture quantitative receiver connected to a reflux cooler, a nitrogen introduction tube, and a stirrer. In this flask, add 4,4'-oxydiphthalic anhydride (ODPA) 20.3g, γ-butyrolactone 200g, toluene 20g and 5-(4-aminophenoxy)-3-[ 29.6 g of 4-(4-aminophenoxy)phenyl]-1,1,3-trimethylindane was stirred at 45°C for 2 hours under a nitrogen stream to perform the reaction. Next, the temperature of the reaction solution was raised, and while maintaining the temperature at about 160°C, the condensation water was azeotropically removed with toluene under a nitrogen stream. Make sure that a certain amount of water is accumulated in the moisture quantitative receiver and that no water flows out. After confirmation, the reaction solution was further heated, and stirred at 200°C for 1 hour. Then, cooling was performed to obtain a polyimine solution (non-volatile content of 20% by mass), which contained polyimine resin 3 having a 1,1,3-trimethylindan skeleton. The obtained polyimide resin 3 has a repeating unit represented by the following formula (X1) and a repeating unit represented by the following formula (X2). In addition, the weight average molecular weight of the aforementioned polyimide resin 3 is 12,000.

<Example 1: Preparation of resin composition 1> 5 parts of xylenol type epoxy resin ("YX4000HK" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of about 185), naphthalene type epoxy resin (Nippon Steel & Sumikin Chemical Company "ESN475V", epoxy equivalent of about 332) 5 parts, bisphenol AF type epoxy resin (Mitsubishi Chemical Corporation "YL7760", epoxy equivalent of about 238) 10 parts, cyclohexane type epoxy resin (Mitsubishi Chemical The company’s "ZX1658GS", epoxy equivalent is about 135) 2 parts, 100 parts of the polyimide solution (non-volatile content 20%) obtained in Synthesis Example 1 and 10 parts of cyclohexanone are heated and dissolved in a mixed solvent while stirring. After cooling to room temperature, mix it with a cresol novolac hardener containing a tri-skeleton ("LA3018-50P" manufactured by DIC Corporation, a 2-methoxypropanol solution with a hydroxyl equivalent of about 151 and a solid content of 50%). 4 parts, active ester hardener (DIC company "EXB-8000L-65M", active base equivalent of about 220, non-volatile content 65% by mass MEK solution) 6 parts, spherical silica (ADMATECHS company "SC2500SQ" , Average particle size 0.5μm, specific surface area 11.2m ² /g, N-phenyl-3-aminopropyltrimethoxysilane ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.) relative to 100 parts of silica 1 part of the surface treated person) 25 parts, 25 parts of polytetrafluoroethylene particles ("Lubron L-2" manufactured by Daikin Industry Co., Ltd., average particle size 3μm), 25 parts of amine curing accelerator (4-dimethylaminopyridine ( DMAP)) 0.2 part, uniformly dispersed with a high-speed rotating mixer, and filtered with a cassette filter ("SHP020" manufactured by ROKITECHNO) to prepare a resin composition 1.

<Example 2: Preparation of resin composition 2> Except for 25 parts of polytetrafluoroethylene particles (“Lubron L-2” manufactured by DAIKIN Industry Co., Ltd., average particle size 3μm) used instead of 50 parts, and not used Spherical silica ("SC2500SQ" manufactured by ADMATECHS, Inc., with an average particle size of 0.5μm, a specific surface area of 11.2m ² /g, and N-phenyl-3-aminopropyltrimethoxyl per 100 parts of silica Except for silane (KBM573 manufactured by Shin-Etsu Chemical Co., Ltd., which is surface-treated with 1 part), the same operation as in Example 1 was performed to prepare a resin composition 2.

<Example 3: Preparation of resin composition 3> Except that 5 parts of dixylenol type epoxy resin ("YX4000HK" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of about 185) was used instead of 10 parts, it will be used 5 parts of naphthalene type epoxy resin ("ESN475V" manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd., epoxy equivalent of about 332) is changed to 10 parts, and 25 parts of polytetrafluoroethylene particles (made by Daikin Industrial Co., Ltd. "Lubron L-2", an average particle size of 3μm) is changed to 50 parts, and bisphenol AF type epoxy resin ("YL7760" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of about 238) and spherical silica (ADMATECHS) are not used "SC2500SQ", average particle size 0.5μm, specific surface area 11.2m ² /g, N-phenyl-3-aminopropyltrimethoxysilane (Shin-Etsu Chemical Industry Co., Ltd.) relative to 100 parts of silica KBM573) except that 1 part was surface-treated), the same operation as in Example 1 was performed to prepare a resin composition 3.

<Example 4: Preparation of resin composition 4> Except that 100 parts of the polyimide solution (non-volatile content 20% by mass) obtained in Synthesis Example 1 was used, 66.7 parts of the polyimide solution obtained in Synthesis Example 2 was used Amine solution (non-volatile content 30% by mass), using 25 parts of polytetrafluoroethylene particles (“Lubron L-2” manufactured by Daikin Industrial Co., Ltd., average particle size 3μm) to use 50 parts, and not using spherical particles Silicon oxide ("SC2500SQ" manufactured by ADMATECHS, with an average particle size of 0.5μm, a specific surface area of 11.2m ² /g, and N-phenyl-3-aminopropyltrimethoxysilane ( The same operation as in Example 1 was performed except that KBM573 manufactured by Shin-Etsu Chemical Industry Co., Ltd. (KBM573) was surface-treated), and a resin composition 4 was prepared.

<Example 5: Preparation of resin composition 5> Except that 100 parts of the polyimide solution (non-volatile content 20% by mass) obtained in Synthesis Example 1 was used instead of 100 parts of the polyimide solution obtained in Synthesis Example 3 Amine solution (non-volatile content 20% by mass), 25 parts of polytetrafluoroethylene particles (“Lubron L-2” manufactured by Daikin Industrial Co., Ltd., average particle size 3μm) used instead of 50 parts, and non-use and spherical Silicon dioxide ("SC2500SQ" manufactured by ADMATECHS, with an average particle size of 0.5μm, a specific surface area of 11.2m ² /g, and N-phenyl-3-aminopropyltrimethoxysilane relative to 100 parts of silicon dioxide (KBM573 manufactured by Shin-Etsu Chemical Industry Co., Ltd.), except that 1 part was surface-treated), the same operation as in Example 1 was performed to prepare a resin composition 5.

<Comparative example 1: Preparation of resin composition 6> Except that 100 parts of the polyimide solution (non-volatile content 20% by mass) obtained in Synthesis Example 1 was used to use 50 parts, the same operation as in Example 1 was performed to prepare a resin composition 6.

<Comparative Example 2: Preparation of Resin Composition 7> Except that 25 parts of spherical silica ("SC2500SQ" manufactured by ADMATECHS Co., Ltd., with an average particle diameter of 0.5 μm and a specific surface area of 11.2 m ² /g) was used, it was compared with silica For 100 parts, N-phenyl-3-aminopropyl trimethoxysilane (KBM573 manufactured by Shin-Etsu Chemical Co., Ltd.) is changed to 50 parts, and no polytetrafluoroethylene particles are used. Except for "Lubron L-2" manufactured by Daikin Industrial Co., Ltd., with an average particle size of 3 μm), the same operation as in Example 1 was performed to prepare a resin composition 7.

<Comparative example 3: Preparation of resin composition 8> Except that the polyimide solution (non-volatile content 20% by mass) obtained in Synthesis Example 1 was not used, and 18 parts of phenoxy resin ("YX7553BH30" manufactured by Mitsubishi Chemical Corporation) was used, the same operation as in Example 1 was performed. Prepare resin composition 8.

＜Measurement of the average particle size of inorganic fillers＞ Weigh 100 mg of inorganic filler and 10 g of methyl ethyl ketone in a vial, and disperse by ultrasonic for 10 minutes. A laser diffraction particle size distribution measuring device (“LA-960” manufactured by Horiba Manufacturing Co., Ltd.) was used. The wavelength of the light source used was blue and red. The particle size of the inorganic filler was measured on a volume basis using a flow cell method. Diameter distribution. From the obtained particle size distribution, the average particle size of the inorganic filler was calculated as the median diameter.

＜Measurement of the specific surface area of inorganic fillers＞ Using a BET automatic specific surface area measuring device (Macsorb HM-1210 manufactured by MOUNTECH), nitrogen was adsorbed on the surface of the sample, and the specific surface area was calculated using the BET multipoint method to measure the specific surface area of the inorganic filler.

<Test Example 1: Evaluation of Water Resistance (Water Absorption)> Prepare a polyethylene terephthalate film (“PET501010” manufactured by LINTEC Corporation) with a release treatment applied to the surface. On this polyethylene terephthalate film, the resin composition of each example and comparative example was uniformly coated using a die coater so that the thickness of the resin composition layer after drying became 50 micrometers. The applied resin composition was dried at 80°C to 110°C (average 95°C) for 6 minutes to obtain a resin composition layer. Then, the resin composition layer is heat-treated at 200° C. for 90 minutes to be cured, and the support is peeled off to obtain a cured product film formed of a cured product of the resin composition.

The obtained cured film was cut into test pieces of 40 mm square, and the test pieces were dried at 130°C for 30 minutes, and then weighed (the weighed mass was regarded as W ₀ (g)). The test piece was immersed in the boiled ion exchange water for 1 hour. Then, the test piece was immersed in ion-exchanged water at room temperature (25°C) for 1 minute. For the test piece, wipe the water droplets on the surface of the test piece with a cleaning cloth (manufactured by KURAFLEX (stock)), and weigh the test piece (equal the measured mass to Make W ₁ (g)). The boiling water absorption rate W _{A of} the five test pieces was calculated from the following equation, and the average value was calculated. The case where the water absorption rate is 1.0% or more is evaluated as "×", and the case where the water absorption rate is less than 1.0% is evaluated as "○".

W _A (%)=((W ₁ －W ₀ )/W ₀ )×100 W ₀ : the mass of the evaluation sample before water absorption (g) W ₁ : the mass of the evaluation sample after water absorption (g)

<Test Example 2: Evaluation of Flexibility (MIT Folding Resistance)> The cured film obtained in Test Example 1 was cut into test pieces with a width of 15 mm and a length of 110 mm, using the MIT testing device (manufactured by Toyo Seiki Seisakusho Co., Ltd., MIT bending fatigue testing machine "MIT-DA"), according to JIS C -5016, under the measuring conditions of 2.5N load, 90 degree bending angle, 1.0mm bending radius, and 175 times per minute bending speed, the number of times of bending resistance until the hardened body breaks is measured. In addition, the measurement system was performed on 5 samples, and the average value of the upper 3 points was calculated. The case where the number of folds is less than 8,000 times is evaluated as "×", and the case of more than 8,000 times is evaluated as "○".

<Test Example 3: Measurement and Evaluation of Peeling Strength> As a support, a PET film (“AL5” manufactured by LINTEC Corporation) with a thickness of 38 μm was prepared. On the support, the resin compositions of the respective examples and comparative examples were uniformly coated with a die coater, and the coating film was dried at 80-120°C (average 100°C) for 3 minutes to form on the support The layer (thickness 25μm) formed from the resin composition of each example and comparative example, and a 15μm thick polypropylene cover film ("Arufun MA-411" manufactured by Oji F-TEX Co., Ltd.) is laminated on the resin surface for smoothness On the surface side, a resin sheet composed of support (38 μm PET film)/resin composition layer/protective film (MA-411) was produced.

(1) Copper clad laminate As a copper clad laminate, a glass cloth base epoxy resin double-sided copper clad laminate with copper foil layers laminated on both sides (copper foil thickness 3μm, substrate thickness 0.15mm, Mitsubishi Gas Chemical Corporation "HL832NSF LCA", 255×340mm size).

(2) Laminating of resin sheet Peel the protective film from the resin sheet and use a batch-type vacuum press laminator (manufactured by NICHIGO Materials Co., Ltd., 2-stage build-up laminator, CVP700) to connect the resin composition layer with the copper-clad laminate , Laminated on both sides of the copper clad laminate. The lamination system was pressure-reduced for 30 seconds to bring the air pressure to 13 hPa or less, and it was performed by pressure bonding at 130°C and a pressure of 0.74 MPa for 45 seconds. Next, hot pressing was performed at 120°C and a pressure of 0.5 MPa for 75 seconds.

(3) Thermal curing of resin composition layer The copper-clad laminate on which the resin sheet was laminated was put into an oven at 100°C for 30 minutes, and then moved to an oven at 180°C for 30 minutes, and cured by heat to form an insulating layer. Take this as hardened substrate A.

(4) Steps for roughening treatment After the support of the through-hole processed substrate A with a through hole formed by a laser in the insulating layer of the hardened substrate A is peeled off, as a roughening treatment, a desmear treatment is performed as follows.

In a swelling solution (ATOTECH Japan "Swelling Dip Securiganth P", an aqueous solution of diethylene glycol monobutyl ether and sodium hydroxide) at 60°C for 10 minutes, and then an oxidizing agent solution (ATOTECH Japan Co., Ltd.) "Concentrate Compact CP", potassium permanganate concentration of about 6%, sodium hydroxide concentration of about 4% in aqueous solution at 80 ℃ for 20 minutes, and finally in the neutralization solution (ATOTECH Japan Co., Ltd. "Reduction Solution Securigand P" , Sulfuric acid aqueous solution) was immersed in 40°C for 5 minutes, and then dried at 80°C for 15 minutes. Take this as the roughened substrate A.

(5) The formation of the conductor layer follows the semi-additive method to form a conductor layer on the roughened surface of the insulating layer. That is, the roughened substrate was immersed in an electroless plating solution containing PdCl ₂ at 40°C for 5 minutes, and then immersed in an electroless copper plating solution at 25°C for 20 minutes. Then, after heating at 150° C. for 30 minutes to perform annealing treatment, an etching resist is formed, and a pattern is formed by etching. Then, copper sulfate electroplating was performed to form a conductor layer with a thickness of 25 μm, and an annealing treatment was performed at 180° C. for 30 minutes. The obtained substrate is referred to as evaluation substrate B.

(6) Measurement of the peel strength of the plated conductor layer The measurement of the peel strength between the insulating layer and the conductor layer was performed on the evaluation substrate B in accordance with the Japanese Industrial Standards (JIS C6481). Specifically, in the conductor layer of the evaluation substrate B, a slit of a rectangular portion with a width of 10 mm and a length of 100 mm was introduced, and one end of the rectangular portion in the longitudinal direction was peeled off, and a jig (Autocom type testing machine "AC-50CSL manufactured by TSE) ") Grasp, at room temperature, at a speed of 50mm/min, in a direction perpendicular to the surface of the evaluation substrate B, conduct a tear test to tear the conductor layer, and measure the load when the length of 35mm is torn (kgf /cm) to obtain the peel strength. In the measurement, the value of the peel strength was 0.39 kgf/cm or more as "○", and the value less than 0.39 kgf/cm was evaluated as "x".

<Test Example 4: Measurement of Arithmetic Average Roughness (Ra)> For the surface of the roughened substrate A obtained in (4) of Test Example 3, a non-contact type surface roughness meter (“WYKO NT3300” manufactured by VEECO Instruments Co., Ltd.) was used to set the measurement range in VSI mode with a 50x lens 121μm×92μm, calculate the arithmetic average roughness (nm) from the obtained value. For each roughened substrate A, an average value of 10 randomly selected points was calculated.

The following Table 1 shows the usage amount of the non-volatile components of the resin composition of the examples and comparative examples, and the measurement results and evaluation results of the test examples.

From the above results, it can be seen that when a resin composition containing (A) epoxy resin, (B) hardener, (C) fluorine-based organic filler, and (D) polyimide resin is used A hardened product is obtained which has the characteristics of low arithmetic average roughness, high peel strength, and excellent water resistance and flexibility.

Claims (12)

A resin composition comprising (A) epoxy resin, (B) hardener, (C) fluorine-based organic filler and (D) polyimide resin, When the non-volatile components in the resin composition are regarded as 100% by mass, the content of the component (D) is 12% by mass or more. The resin composition of claim 1, wherein the component (C) is fluorine-based polymer particles. Such as the resin composition of claim 1, wherein when the non-volatile content in the resin composition is regarded as 100% by mass, the content of component (C) is 10% by mass or more. Such as the resin composition of claim 1, wherein when the non-volatile content in the resin composition is regarded as 100% by mass, the content of component (D) is 40% by mass or less. The resin composition of claim 1, wherein the component (A) contains a fluorine-containing epoxy resin. The resin composition of claim 1, wherein component (B) is selected from the group consisting of phenol hardeners, naphthol hardeners, and active ester hardeners. Such as the resin composition of claim 1, which further contains or does not contain (E) inorganic filler, and when the non-volatile content in the resin composition is regarded as 100% by mass, the content of the (E) component is 60% by mass or less. The resin composition of claim 1, which is used for forming the insulating layer of a multilayer flexible substrate. A cured product, which is a cured product of the resin composition of any one of claims 1 to 8. A resin sheet comprising a support and a resin composition layer formed on the support and formed of the resin composition according to any one of claims 1 to 8. A multilayer flexible substrate comprising an insulating layer formed by curing the resin composition of any one of claims 1 to 8. A semiconductor device provided with a multilayer flexible substrate as claimed in claim 11.