TW202116912A - Resin composition capable of lowering tackiness in spite of low blending of inorganic fillers - Google Patents

Abstract

This invention aims to provide a resin composition capable of lowering tackiness in spite of low blending of inorganic fillers, and obtaining a cured product having excellent flexibility and excellent insulation reliability. The solution is a resin composition containing (A) an epoxy resin, (B) an inorganic filler, and (C) a polyimide resin, characterized in that the component (A) contains (A-1) an epoxy resin containing a siloxane skeleton, and the content of the component (B) is 40% by mass or less when the nonvolatile component in the resin composition is 100% by mass.

Description

Resin composition

The present invention relates to a resin composition containing polyimide resin. Furthermore, it relates to a cured product, a resin sheet, a multilayer flexible substrate, and a semiconductor device obtained by using the resin composition.

In recent years, the demand for thinner, lighter, and high-density semiconductor components has been increasing. In order to meet this requirement, attention is being paid to the use of flexible substrates as substrate substrates used in semiconductor parts. Compared with rigid substrates, flexible substrates can be thinner and lighter. Furthermore, since the flexible substrate is soft and deformable, it can be bent and mounted.

Generally speaking, it is necessary to blend flexible resins such as polyimide resin in the insulating materials of flexible substrates. However, when blending polyimide resin, the viscosity (adhesiveness) is improved and the workability is improved. Deteriorating situation. Although it is possible to suppress viscosity by blending inorganic fillers (Patent Document 1), increasing the blending rate of inorganic fillers makes it difficult to achieve both flexibility. [Prior Technical Literature] [Patent Literature]

[Patent Document 1] JP 2014-95047 A

[The problem to be solved by the invention]

The subject of the present invention is to provide a resin composition or the like that can obtain a cured product having excellent flexibility and excellent insulation reliability even if the inorganic filler is low-blended, the viscosity can be suppressed to be low. [Means to solve the problem]

In order to achieve the subject of the invention, as a result of diligent research, the inventors found that by using a resin composition containing (A) epoxy resin, (B) inorganic filler, and (C) polyimide resin, and (A) Component is a resin composition containing (A-1) epoxy resin containing a silicone skeleton. When the content of (B) inorganic filler is 40% by mass or less, it can be blended at a low level. A cured product with low viscosity, excellent flexibility and excellent insulation reliability, and finally completed the present invention.

That is, the present invention includes the following contents. [1] A resin composition comprising (A) epoxy resin, (B) inorganic filler and (C) polyimide resin, characterized in that (A) component contains (A- 1) Epoxy resin containing silicone skeleton, (B) The content of the component is 40% by mass or less when the non-volatile content in the resin composition is 100% by mass. [2] The resin composition as described in [1] above, wherein the component (A-1) is an epoxy resin containing a cyclic siloxane skeleton. [3] The resin composition as described in [1] or [2] above, wherein the component (A-1) is a compound represented by formula (A1),

[In the formula, R ¹ each independently represents an epoxy alkyl group; R ² each independently represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted aryl group; R ³ and R ⁴ each independently Independently represent substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, or substituted or unsubstituted aryl, or R ³ and R ⁴ become together to show 1 -O- and bond to each other to form a ring Siloxane skeleton; s represents an integer greater than 1]. [4] The resin composition as described in any one of [1] to [3] above, wherein the molecular weight of the component (A-1) is 800 or less. [5] The resin composition as described in any one of [1] to [4] above, wherein the epoxy equivalent of the component (A-1) is 150 g/eq. to 250 g/eq. [6] The resin composition as described in any one of [1] to [5] above, wherein the content of the component (A-1) is when the non-volatile content in the resin composition is 100% by mass, It is 5% by mass or more. [7] The resin composition as described in any one of [1] to [6] above, wherein the content of the component (A-1) is when the non-volatile content in the resin composition is 100% by mass, It is 10% by mass or less. [8] The resin composition as described in any one of [1] to [7] above, wherein the average particle size of the component (B) is 1 μm or less. [9] The resin composition as described in any one of [1] to [8] above, wherein the component (B) is silica. [10] The resin composition as described in any one of [1] to [9] above, wherein the weight average molecular weight of the component (C) is 1,000 or more and 100,000 or less. [11] The resin composition as described in any one of [1] to [10] above, wherein the content of component (C) is 20 when the non-volatile content in the resin composition is 100% by mass Above mass%. [12] The resin composition as described in any one of [1] to [11] above, wherein the content of component (C) is 30 when the non-volatile content in the resin composition is 100% by mass Less than mass%. [13] The resin composition as described in any one of [1] to [12] above, which further contains (D) a curing agent. [14] The resin composition as described in [13] above, wherein the component (D) contains an active ester curing agent. [15] The resin composition as described in any one of [1] to [14] above, which is used for forming an insulating layer of a multilayer flexible substrate. [16] A cured product of the resin composition as described in any one of [1] to [15] above. [17] A resin sheet comprising a support and a resin composition layer formed of the resin composition described in any one of [1] to [15] above and provided on the support. [18] A multilayer flexible substrate comprising an insulating layer formed by curing the resin composition described in any one of [1] to [15] above. [19] A semiconductor device including the multilayer flexible substrate as described in [18] above. [Effects of the invention]

According to the resin composition of the present invention, even if the inorganic filler is low blended, it is possible to obtain a cured product with low viscosity, excellent flexibility and excellent insulation reliability.

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

＜Resin composition＞ The resin composition of the present invention is a resin composition containing (A) epoxy resin, (B) inorganic filler, and (C) polyimide resin, and is characterized in that (A) component contains (A-1) ) Epoxy resin containing silicone skeleton, the content of component (B) is 40% by mass or less. By using such a resin composition, even if the inorganic filler is blended at a low level, it is possible to obtain a cured product with excellent flexibility and excellent insulation reliability, with low viscosity and low viscosity.

In addition to (A) epoxy resin, (B) inorganic filler, and (C) polyimide resin, the resin composition of the present invention may further contain optional components. Examples of optional components include (D) curing agent, (E) curing accelerator, (F) other additives, and (G) organic solvent. Hereinafter, each component contained in the resin composition will be described in detail.

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

Although the content of (A) epoxy resin in the resin composition is not particularly limited, when the non-volatile content in the resin composition is 100% by mass, it is preferably 10% by mass or more, and more preferably 20% by mass % Or more, more preferably 25% by mass or more, particularly preferably 30% by mass or more. Although the upper limit of the content of (A) epoxy resin in the resin composition is not particularly limited, when the non-volatile content in the resin composition is 100% by mass, it is preferably 70% by mass or less, more preferably It is 60% by mass or less, more preferably 50% by mass or less, and particularly preferably 40% by mass or less.

＜(A-1) Epoxy resin containing silicone skeleton＞ (A) The epoxy resin contains (A-1) an epoxy resin containing a silicone skeleton. The so-called (A-1) epoxy resin containing a siloxane skeleton refers to a compound having two or more epoxy groups and a siloxane (Si-O-Si) bond.

(A-1) The epoxy resin containing a siloxane skeleton may be an epoxy resin containing a cyclic siloxane skeleton, or an epoxy resin containing a chain siloxane skeleton, but it is preferably an epoxy resin containing a cyclic siloxane skeleton Epoxy resin with siloxane skeleton.

(A-1) The number of silicon atoms forming the siloxane bond of the epoxy resin containing the siloxane skeleton is not particularly limited, but it is preferably 3 or more per molecule. It is 10 or less, more preferably 8 or less, still more preferably 6 or less, and still more preferably 5 or less. Especially preferred are 4.

(A-1) The number of epoxy groups in the epoxy resin containing a siloxane skeleton is not particularly limited, but it is preferably 3 or more, preferably 10 or less per molecule, and more Preferably it is 8 or less, more preferably 6 or less, and still more preferably 5 or less. Especially preferred are 4.

In (A-1) the silicon atom of the epoxy resin containing a siloxane skeleton, it is preferable that all the substitutable positions are substituted with a hydrocarbon group such as an alkyl group, an alkenyl group, and an aryl group with or without an epoxy group. The hydrocarbon group may have a substituent other than the epoxy group.

(A-1) Epoxy resin containing silicone skeleton, preferably a compound represented by formula (A1),

[In the formula, R ¹ each independently represents an epoxy alkyl group; R ² each independently represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted aryl group; R ³ and R ⁴ each independently Independently represent substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, or substituted or unsubstituted aryl, or R ³ and R ⁴ become together to show 1 -O- and bond to each other to form a ring Siloxane skeleton; s represents an integer greater than 1].

The "alkane (group)" refers to a linear, branched, and/or cyclic monovalent aliphatic saturated hydrocarbon group. The "alkane (group)" is preferably an alkyl group having 1 to 10 carbon atoms. Examples of "alk(yl)" include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, and neopentyl. Group, sec-pentyl, tert-pentyl, cyclopentyl, cyclohexyl, cyclopentylmethyl, 2-cyclohexylmethyl, 2-cyclopentylethyl, 2-cyclohexylethyl, etc.

The so-called "alkylene oxide" refers to a group in which two hydrogen atoms bonded to different carbon atoms of an alkyl group are replaced by one oxygen atom to form an oxirane (ethylene oxide) ring. The "epoxyalkyl group" is preferably an epoxyalkyl group having 2 to 10 carbon atoms. Examples of the "epoxyalkyl group" include straight-chain rings such as 2,3-epoxypropyl, 3,4-epoxybutyl, 4,5-epoxypentyl, and 5,6-epoxyhexyl. Oxyalkyl; 2,3-epoxy-2-methylpropyl, 3,4-epoxy-3-methylbutyl, etc. branched chain epoxyalkyl; 2,3-epoxycyclopentyl , 3,4-epoxycyclopentyl, 2,3-epoxycyclohexyl, 3,4-epoxycyclohexyl and other cyclic epoxy alkyl groups; 2,3-epoxycyclopentylmethyl, 3 ,4-Epoxycyclopentylmethyl, 2,3-epoxycyclohexylmethyl, 3,4-epoxycyclohexylmethyl, 2-(2,3-epoxycyclopentyl)ethyl, 2 -(3,4-epoxycyclopentyl)ethyl, 2-(2,3-epoxycyclohexyl)ethyl, 2-(3,4-epoxycyclohexyl)ethyl, 3-(2, 3-epoxycyclopentyl) propyl, 3-(3,4-epoxycyclopentyl) propyl, 3-(2,3-epoxycyclohexyl) propyl, 3-(3,4-ring Oxycyclohexyl) propyl, 4-(2,3-epoxycyclopentyl)butyl, 4-(3,4-epoxycyclopentyl)butyl, 4-(2,3-epoxycyclohexyl) ) Butyl, 4-(3,4-epoxycyclohexyl)butyl, etc. are linear alkyl groups whose ends are cyclic epoxyalkyl groups.

The "alkenyl (base)" refers to a linear, branched, and/or cyclic monovalent aliphatic unsaturated hydrocarbon group having at least one carbon-carbon double bond. The "alkenyl group" is preferably an alkenyl group having 2 to 10 carbon atoms. Examples of "alkenyl" include vinyl, 1-propenyl, 2-propenyl, 2-methyl-1-propenyl, 1-butenyl, 2-butenyl, and 3-butene. Group, 3-methyl-2-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 4-methyl-3-pentenyl, 1- Hexenyl, 3-hexenyl, 5-hexenyl, 2-cyclohexenyl and the like.

Although the substituents of the alkyl group in the "substituted or unsubstituted alkyl group" and the alkenyl group in the "substituted or unsubstituted alkenyl group" are not particularly limited, for example, halogen atoms, cyano groups, Nitro, alkyl-oxy, alkyl-carbonyl, alkyl-oxy-carbonyl, alkyl-carbonyl-oxy, alkenyl-oxy, alkenyl-carbonyl, alkenyl-oxy-carbonyl, alkenyl Group-carbonyl-oxy, aryl, aryl-oxy, aryl-carbonyl, aryl-oxy-carbonyl, aryl-carbonyl-oxy, etc., or a combination thereof. As the number of substituents, 1 to 3 are preferable, and one is more preferable.

The so-called "aryl (group)" refers to a monovalent aromatic hydrocarbon group. "Aryl" is preferably an aryl group having 6 to 14 carbon atoms. Examples of the "aryl (group)" include phenyl, 1-naphthyl, 2-naphthyl, and the like.

As the substituent of the aryl group in the "substituted or unsubstituted aryl group", although it is not particularly limited, for example, a halogen atom, a cyano group, a nitro group, an alkyl group, an alkyl-oxy group, and an alkyl- Carbonyl, alkyl-oxy-carbonyl, alkyl-carbonyl-oxy, alkenyl, alkenyl-oxy, alkenyl-carbonyl, alkenyl-oxy-carbonyl, alkenyl-carbonyl-oxy, aryl , Aryl-alkyl, aryl-alkenyl, aryl-oxy, aryl-carbonyl, aryl-oxy-carbonyl, aryl-carbonyl-oxy, etc., or combinations thereof. As the number of substituents, 1 to 3 are preferable, and one is more preferable.

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

In formula (A1), R ¹ each independently represents an alkylene oxide group, preferably a linear alkyl group having a cyclic alkylene oxide group at the end, and more preferably a methyl group having a cyclic alkylene oxide group, or An ethyl group having a cyclic epoxyalkyl group at the end is particularly preferably a 2-(3,4-epoxycyclohexyl)ethyl group.

In formula (A1), R ² each independently represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted aryl group, preferably a substituted or unsubstituted alkyl group, more preferably The (unsubstituted) alkyl group is more preferably methyl, ethyl, propyl or isopropyl, particularly preferably methyl.

In formula (A1), R ³ and R ⁴ each independently represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted aryl group, or R ³ and R ⁴ become together to show 1 Each -O- is bonded to each other to form a cyclic siloxane skeleton. Preferably, R ³ and R ⁴ become one -O- together and are bonded to each other to form a cyclic siloxane skeleton.

In formula (A1), s represents an integer of 1 or more, preferably an integer of 2 or more. s is preferably an integer of 9 or less, more preferably an integer of 7 or less, still more preferably an integer of 5 or less, and still more preferably an integer of 4 or less. Especially preferably, s is 3.

As a specific example of (A-1) epoxy resin containing siloxane skeleton, 1,3,5-gin (2-(3,4-epoxycyclohexyl)ethyl)-1,1,3 ,5,5-Pentamethyltrisiloxane and other epoxy resins containing chain siloxane skeleton; 2,4,6,8-four (4-(3,4-epoxycyclopentyl)butyl Group)-2,4,6,8-tetramethylcyclotetrasiloxane, 2,4,6,8-four (3-(3,4-epoxycyclopentyl)propyl)-2,4 ,6,8-Tetramethylcyclotetrasiloxane, 2,4,6,8-4-(2-(3,4-epoxycyclohexyl)ethyl)-2,4,6,8-tetramethyl Cyclotetrasiloxane, 2,4,6,8,10-5-(2-(3,4-epoxycyclohexyl)ethyl)-2,4,6,8,10-pentamethylcyclopenta Silicone and other epoxy resins containing a cyclic silicone skeleton, of which 2,4,6,8-four (2-(3,4-epoxycyclohexyl)ethyl)-2, 4,6,8-Tetramethylcyclotetrasiloxane.

As a commercially available product of (A-1) epoxy resin containing a silicone skeleton, for example, "KR-470" manufactured by Shin-Etsu Chemical Co., Ltd. (main component: 2,4,6,8-four (2-( 3,4-epoxycyclohexyl) ethyl)-2,4,6,8-tetramethylcyclotetrasiloxane), "X-40-2667" (main ingredient: 1,3,5-see ( 2-(3,4-epoxycyclohexyl)ethyl)-1,1,3,5,5-pentamethyltrisiloxane) and the like.

(A-1) The molecular weight of the epoxy resin containing a silicone skeleton is preferably 2,000 or less, more preferably 1,500 or less, still more preferably 1,000 or less, particularly preferably 800 or less. The lower limit can be set to 200 or more, 400 or more, 600 or more, for example.

(A-1) The epoxy equivalent of the epoxy resin containing the siloxane skeleton is preferably 1,000 g/eq. or less, more preferably 500 g/eq. or less, still more preferably 300 g/eq. or less, particularly preferred Less than 250g/eq. The lower limit is preferably 50 g/eq. or more, more preferably 100 g/eq. or more, still more preferably 130 g/eq. or more, particularly preferably 150 g/eq. or more.

(A-1) The viscosity (25°C) of the epoxy resin containing the silicone skeleton is preferably 100mPa･s~10,000mPa･s, more preferably 1,000mPa･s~5,000mPa･s.

Although the content of (A-1) epoxy resin containing silicone skeleton in the resin composition is not particularly limited, when the non-volatile content in the resin composition is set to 100% by mass, it is preferably 1 Mass% or more, more preferably 3 mass% or more, still more preferably 4 mass% or more, particularly preferably 5 mass% or more. Although the upper limit of the content of (A-1) epoxy resin containing a silicone skeleton in the resin composition is not particularly limited, when the non-volatile content in the resin composition is set to 100% by mass, it is preferably 30% by mass or less, more preferably 20% by mass or less, still more preferably 15% by mass or less, particularly preferably 10% by mass or less.

＜Any epoxy resin other than (A-1) component＞ (A) The epoxy resin may further contain any other epoxy resins in addition to (A-1) epoxy resin containing a silicone skeleton.

As any epoxy resins other than the component (A-1), for example, bixylenol (bixylenol) type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type ring Oxygen resin, bisphenol AF type epoxy resin, dicyclopentadiene type epoxy resin, ginseng phenol type epoxy resin, naphthol novolac epoxy resin, phenol novolac epoxy resin, tert-butyl-o-benzene Diphenol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, epoxy propyl amine type epoxy resin, glycidyl ester type epoxy resin, cresol phenol type Epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, epoxy resin with butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring containing epoxy resin, Cyclohexane type epoxy resin, cyclohexane dimethanol type epoxy resin, naphthyl ether type epoxy resin, trimethylol type epoxy resin, tetraphenylethane type epoxy resin, isocyanuric acid Ester type epoxy resin, glycidyl cyclohexane type epoxy resin, etc. Any epoxy resin can be used alone or in combination of two or more types.

As any epoxy resin other than the component (A-1), the resin composition preferably contains an epoxy resin having two or more epoxy groups in one molecule. The ratio of epoxy resin having two or more epoxy groups in one molecule with respect to 100% by mass of non-volatile components of any epoxy resin other than the component (A-1) is preferably 50% by mass or more, more preferably It is 60% by mass or more, particularly preferably 70% by mass or more.

There are epoxy resins that are liquid at a temperature of 20°C (hereinafter, sometimes referred to as "liquid epoxy resins"), and epoxy resins that are solid at a temperature of 20°C (hereinafter, sometimes referred to as It is "solid epoxy resin"). The resin composition of the present invention, as any epoxy resin other than the component (A-1), may include only liquid epoxy resin or only solid epoxy resin, but preferably includes a combined liquid epoxy resin With solid epoxy 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, and butadiene type epoxy resin Epoxy resin with olefin structure.

Specific examples of liquid epoxy resins include "HP4032", "HP4032D", and "HP4032SS" (naphthalene type epoxy resin) manufactured by DIC; "828US", "828EL", and "jER828EL manufactured by Mitsubishi Chemical Corporation" ", "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 (Phenolic epoxy resin); "630", "630LSD", "604" (glycidylamine epoxy resin) manufactured by Mitsubishi Chemical Corporation; "ED-523T" (glycyrrhizol (glycyrrhizol ( Glycyrol) type epoxy resin); "EP-3950L" and "EP-3980S" (glycidylamine epoxy resin) manufactured by ADEKA; "EP-4088S" (dicyclopentadiene) manufactured by ADEKA Type epoxy resin); "ZX1059" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. (a mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin); "EX-721" manufactured by Nagase ChemteX ( Glycidyl ester type epoxy resin); "Celloxide2021P" (alicyclic epoxy resin with ester skeleton) manufactured by Daicel; "PB-3600" manufactured by Daicel, and "JP-100" manufactured by Soda Corporation of Japan ", "JP-200" (epoxy resin with butadiene structure); "ZX1658", "ZX1658GS" (cyclohexane type epoxy resin) manufactured by Nippon Steel & Sumitomo Chemical Corporation. These 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 a molecule, and more preferably an aromatic solid ring having 3 or more epoxy groups in a molecule Oxy resin.

The solid epoxy resin is preferably bixylenol type epoxy resin, naphthalene type epoxy resin, naphthalene type tetrafunctional epoxy resin, cresol novolac type epoxy resin, and dicyclopentadiene type epoxy resin. Epoxy resin, ginseng phenol type epoxy resin, naphthol type epoxy resin, biphenyl type epoxy resin, naphthyl ether type epoxy resin, anthracene type epoxy resin, bisphenol A type epoxy resin, bisphenol AF type epoxy resin, 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 ); "N-690" (cresol novolac epoxy resin) manufactured by DIC; "N-695" (cresol novolac epoxy resin) manufactured by DIC; "HP-7200" manufactured by DIC, "HP-7200HH", "HP-7200H" (dicyclopentadiene epoxy resin); "EXA-7311", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311", "EXA-7311-G3", "EXA-7311-G4" and " EXA-7311-G4S", "HP6000" (naphthyl ether type epoxy resin); "EPPN-502H" (ginseng phenol type epoxy resin) manufactured by Nippon Kayaku Corporation; "NC7000L" manufactured by Nippon Kayaku Corporation (Naphthol-type epoxy resin); "NC3000H", "NC3000", "NC3000L", "NC3000FH", "NC3100" (biphenyl epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; Nippon Steel Chemical & Materials Co., Ltd. "ESN475V" (naphthalene type epoxy resin) manufactured by Nippon Steel; "ESN485" (naphthol type epoxy resin) manufactured by Nippon Steel Chemical &Materials; "ESN375" (dihydroxynaphthalene type epoxy resin) manufactured by Nippon Steel Chemical & Materials Oxygen resin); "YX4000H", "YX4000", "YX4000HK", "YL7890" (bixylenol type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YL6121" (biphenyl type) manufactured by Mitsubishi Chemical Corporation Epoxy resin); "YX8800" manufactured by Mitsubishi Chemical Corporation (anthracene epoxy resin); "YX7700" manufactured by Mitsubishi Chemical Corporation (phenolic epoxy resin containing xylene structure); manufactured by Osaka Gas Chemical Corporation "PG-100", "CG-500"; "YL7760" (bisphenol AF type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YL7800" (茀-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; manufactured by Mitsubishi Chemical Corporation "JER1010" (solid bisphenol A type epoxy resin); "jER1031S" (tetraphenylethane type epoxy resin) manufactured by Mitsubishi Chemical Corporation, etc. These can be used in one type alone, or in combination of two or more types.

When a liquid epoxy resin and a solid epoxy resin are used together as an arbitrary epoxy resin other than the component (A-1), the mass ratio of these (liquid epoxy resin: solid epoxy resin) is preferable It is in the range of 100:1~1:100, more preferably in the range of 10:1~1:40, and even more preferably in the range of 1:1~1:20.

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

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

When the resin composition contains any epoxy resin other than the component (A-1), the content of any epoxy resin other than the component (A-1) in the resin composition is not particularly limited, but the content of the resin composition When the non-volatile content is set to 100% by mass, it is preferably 5 mass% or more, more preferably 10 mass% or more, still more preferably 15 mass% or more, and particularly preferably 20 mass% or more. Although the upper limit of the content of any epoxy resin other than the component (A-1) in the resin composition is not particularly limited, when the non-volatile content in the resin composition is 100% by mass, it is preferably 60% by mass % Or less, more preferably 50% by mass or less, still more preferably 40% by mass or less, particularly preferably 30% by mass or less.

When the resin composition contains any epoxy resin other than the component (A-1), the content of (A-1) epoxy resin containing silicone skeleton in (A) epoxy resin is not particularly limited, but When the total amount of (A) epoxy resin is 100% by mass, it is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 15% by mass or more, and particularly preferably 20% by mass or more. Although the upper limit of the content of (A-1) epoxy resin containing silicone skeleton in (A) epoxy resin is not particularly limited, when the total amount of (A) epoxy resin is set to 100% by mass, it is more It is preferably 50% by mass or less, more preferably 40% by mass or less, still more preferably 30% by mass or less, and particularly preferably 25% by mass or less.

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

(B) As the material of the inorganic filler, an inorganic compound is used. (B) Inorganic filler materials include, for example, silica, alumina, glass, cordierite, silica, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehm Stone, 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, titanium Bismuth, titanium oxide, zirconium oxide, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate and zirconium tungstate phosphate, etc. Among these, silicon dioxide is particularly suitable. Examples of silica include amorphous silica, fused silica, crystalline silica, synthetic silica, and hollow silica. In addition, as the silica, spherical silica is preferred. (B) Inorganic fillers may be used alone or in combination of two or more at any ratio.

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

(B) The average particle size of the inorganic filler is not particularly limited, but is preferably 40 μm or less, more preferably 10 μm or less, still more preferably 5 μm or less, still more preferably 3 μm or less, particularly preferably 1 μm or less. (B) The lower limit of the average particle diameter of the inorganic filler is not particularly limited, but it is preferably 0.005 μm or more, more preferably 0.01 μm or more, still more preferably 0.05 μm or more, still more preferably 0.1 μm or more, and It is still more preferably 0.2 μm or more, and particularly preferably 0.3 μm or more. (B) The average particle size of the inorganic filler can be measured by the laser diffraction/scattering method according to 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 determined as the average particle size for measurement. The measurement sample can be obtained by weighing 100 mg of the inorganic filler and 10 g of methyl ethyl ketone in a vial, and dispersing it for 10 minutes by ultrasonic waves. A laser diffraction particle size distribution measuring device is used for the measurement sample, and the wavelength of the light source is set to blue and red, and the volume-based particle size distribution of the inorganic filler is measured by the flow cell method. The obtained particle size distribution can be obtained The average particle diameter is calculated as the median diameter. As a laser diffraction type particle size distribution measuring device, for example, "LA-960" manufactured by Horiba Manufacturing Co., Ltd. can be cited.

(B) The specific surface area of the inorganic filler is not particularly limited, but it is preferably 0.1 m ² /g or more, more preferably 0.5 m ² /g or more, still more preferably 1 m ² /g or more, particularly preferably 5 m ² /g or more. (B) The upper limit of the specific surface area of the inorganic filler is not particularly limited, but it is preferably 50 m ² /g or less, more preferably 30 m ² /g or less, still more preferably 20 m ² /g or less, particularly preferably 15 m ² /g or less. The specific surface area of the inorganic filler was obtained by using a specific surface area measuring device (Macsorb HM-1210 manufactured by Mountech Corporation) based on the BET method, adsorbing nitrogen gas on the surface of the sample, and calculating the specific surface area using the BET multipoint method.

(B) The inorganic filler is preferably surface-treated with a suitable surface treatment agent. By surface treatment, the moisture resistance and dispersibility of (B) inorganic filler can be improved. Examples of surface treatment agents include vinyl-based silane coupling agents such as vinyl trimethoxy silane and vinyl triethoxy silane; 2-(3,4-epoxycyclohexyl) ethyl trimethoxy silane, 3-glycidoxy propyl methyl dimethoxy silane, 3-glycidoxy propyl trimethoxy silane, 3-glycidoxy propyl methyl diethoxy silane, 3- Epoxy silane coupling agent such as glycidoxy propyl triethoxy silane; Styryl silane coupling agent such as p-styryl trimethoxy silane; 3-methacryloxy propyl group Methyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyl Methacryl-based silane coupling agent such as triethoxysilane; 3-propenyloxypropyltrimethoxysilane, etc. acryl-based silane coupling agent; N-2-(aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3- Aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylene) propylamine, N-phenyl-3-aminopropyltrimethoxy Amino groups such as methyl silane, N-phenyl-8-aminooctyl trimethoxysilane, N-(vinylbenzyl)-2-aminoethyl-3-aminopropyl trimethoxysilane, etc. Silane coupling agent; isocyanurate silane coupling agent such as-(trimethoxysilyl propyl) isocyanurate; ureido system such as 3-ureidopropyl trialkoxysilane Silane coupling agent; mercapto-based silane coupling agent such as 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane; isocyanate-based silane coupling agent such as 3-isocyanate propyl triethoxy silane Mixture; 3-trimethoxysilylpropyl succinic anhydride and other acid anhydride silane coupling agents; and other silane coupling agents; methyl trimethoxy silane, dimethyl dimethoxy silane, phenyl trimethoxy silane, Methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, hexyltrimethoxysilane, Non-silane coupling of hexyltriethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, 1,6-bis(trimethoxysilyl)hexane, trifluoropropyltrimethoxysilane, etc. -Alkoxysilane compounds, etc. Among them, an amine-based silane coupling agent is preferred. A surface treatment agent may be used individually by 1 type, and may be used in combination of 2 or more types at arbitrary ratios.

Commercial products of surface treatment agents include, for example, "KBM-1003", "KBE-1003" (vinyl silane coupling agent) manufactured by Shin-Etsu Chemical Co., Ltd.; "KBM-303", "KBM-402", "KBM-403", "KBE-402", "KBE-403" (epoxy silane coupling agent); "KBM-1403" (styrene-based silane coupling agent); "KBM-502", "KBM- 503", "KBE-502", "KBE-503" (methacrylic silane coupling agent); "KBM-5103" (acrylic silane coupling agent); "KBM-602", "KBM- 603", "KBM-903", "KBE-903", "KBE-9103P", "KBM-573", "KBM-575" (amine-based silane coupling agent); "KBM-9659" (isocyanurea Acid ester silane coupling agent); "KBE-585" (ureido silane coupling agent); "KBM-802", "KBM-803" (mercapto silane coupling agent); "KBE-9007N" (isocyanate silane coupling agent) Coupling agent); "X-12-967C" (anhydride silane coupling agent); "KBM-13", "KBM-22", "KBM-103", "KBE-13", "KBE-22", " KBE-103", "KBM-3033", "KBE-3033", "KBM-3063", "KBE-3063", "KBE-3083", "KBM-3103C", "KBM-3066", "KBM- 7103" (non-silane coupling-alkoxysilane compound) and so on.

The degree of surface treatment by the surface treatment agent is preferably within a specified range from the viewpoint of enhancing the dispersibility of the inorganic filler. Specifically, it is preferable that 100% by mass of the inorganic filler is surface-treated with a surface treatment agent of 0.2% by mass to 5% by mass, more preferably 0.2% by mass to 3% by mass, and still more preferably 0.3% by mass. Surface treatment is carried out by mass% to 2% by mass.

The degree of surface treatment by the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the inorganic filler. 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 still more preferably 0.2 mg /m ² or more. On the other hand, from the viewpoint of preventing the melt viscosity of the resin composition or the melt viscosity in the sheet form from increasing, it is preferably 1.0 mg/m ² or less, more preferably 0.8 mg/m ² or less, and still more preferably 0.5mg/m ² or less.

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

The content of (B) inorganic filler in the resin composition is 40% by mass or less, preferably 38% by mass or less, more preferably 36% by mass when the non-volatile content in the resin composition is 100% by mass % Or less, more preferably 34% by mass or less, particularly preferably 32% by mass or less. Although the lower limit of the content of the (B) inorganic filler in the resin composition is not particularly limited, when the non-volatile content in the resin composition is 100% by mass, it is preferably 5% by mass or more, and more preferably 10% by mass or more, more preferably 20% by mass or more, particularly preferably 30% by mass or more.

＜(C) Polyimide resin＞ The resin composition of the present invention contains (C) polyimide resin. (C) The polyimide resin is a resin having an imine bond in the repeating unit. (C) Polyimide resin Generally speaking, it may include (1) a resin obtained by the imidization reaction of a diamine compound and tetracarboxylic anhydride, or (2) a resin obtained by a diisocyanate compound and tetracarboxylic anhydride The resin obtained by the imidization reaction. (C) Polyimide resins also include modified polyimide resins such as silicone modified polyimide resins.

(C) Although the polyimide resin is not particularly limited, it may include a structure represented by formula (C1), for example,

[In the formula, X ¹ represents the removal of 2 -CO-O-CO- tetravalent groups from tetracarboxylic dianhydride, for example, it may include 2 selected from carbon atoms, oxygen atoms, nitrogen atoms and sulfur atoms The above (for example, 2 to 3,000, 2 to 1,000, 2 to 100, 2 to 50) skeleton atoms are organic groups. X ² _{represents the removal of 2 divalent groups of -NH 2} from the diamine compound or the removal of 2 divalent groups of -NCO from the diisocyanate compound. For example, it can be selected from carbon atoms, oxygen atoms, nitrogen atoms and sulfur An organic group consisting of two or more atoms (for example, 2 to 3,000, 2 to 1,000, 2 to 100, 2 to 50) of the skeleton atoms. n represents an integer of 2 or more]. ^{The organic groups of X 1} and X ² in the formula (C1) are not particularly limited as long as they are within the range of a chemically stable structure, and are a structure appropriately selected by a person having ordinary knowledge in the field of the present invention, and may be, for example, known The structure of polyimide resin. (C) When the polyimide resin contains the structure represented by the formula (C1), it preferably contains 60% by mass or more of the structure represented by the formula (C1), more preferably contains 80% by mass or more, and more preferably contains 90% by mass or more. Mass% or more, and it is particularly preferable to include 95 mass% or more.

Although it is not specifically limited as a diamine compound for preparing (C) polyimide resin, for example, an aliphatic diamine compound and an aromatic diamine compound are mentioned.

As the aliphatic diamine compound, for example, 1,2-ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, 1,6- Straight-chain aliphatic diamine compounds such as Hexamethylenediamine, 1,5-diaminopentane, 1,10-diaminodecane, etc.; 1,2-diamino-2-methyl Branched chain aliphatic diamine compounds such as 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 type diamine (hereinafter also referred to as "dimer diamine") and so on.

The so-called dimer acid type diamine refers to the diamine compound obtained by substituting the two terminal carboxyl groups (-COOH) of the dimer acid by aminomethyl group (-CH ₂ -NH ₂ ) or amino group (-NH ₂₎ . Dimer acid is a compound obtained by dimerizing unsaturated fatty acid (preferably one with carbon number 11-22, particularly preferably one with carbon number 18), and its industrial manufacturing process is almost standardized in the industry. Dimer acid can be easily obtained by dimerizing particularly cheap and easy-to-obtain oleic acid, linoleic acid, and other unsaturated fatty acids with carbon number of 18, and dimer acid with carbon number of 36 as the main component. In addition, the dimer acid may contain any amount of monomer acid, trimer acid, other polymerized fatty acids, etc., depending on the manufacturing 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, the hydrogen additive that further undergoes the hydrogen addition reaction to lower the degree of unsaturation is also included in the dimer acid. The dimer acid type diamine is commercially available, and examples thereof include "PRIAMINE1073", "PRIAMINE1074", "PRIAMINE1075" manufactured by Croda Japan, "VERSAMINE551" and "VERSAMINE552" manufactured by Cognis Japan.

As the aromatic diamine compound, for example, 1,4-phenylenediamine (Phenylenediamine), 1,2-phenylenediamine, 1,3-phenylenediamine, 2,4-diaminotoluene, 2,6- Phenylenediamine compounds such as diaminotoluene, 3,5-diaminobiphenyl, 2,4,5,6-tetrafluoro-1,3-phenylenediamine; 1,5-diaminonaphthalene, 1 ,8-Diaminonaphthalene, 2,6-diaminonaphthalene, 2,3-diaminonaphthalene and other naphthalene diamine compounds; 4,4'-diamino-2,2'-ditrifluoromethyl -1,1'-biphenyl, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4 ,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 4-aminophenyl 4-aminobenzoate, 1,3-bis(3-amine Benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 2,2-bis(4-aminophenoxy)benzene Yl)propane, 4,4'-(hexafluoroisopropylidene)diphenylamine, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[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-fluorenylidene) 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'-diamino-2,2'-dimethyl-1,1'-biphenyl, 9,9'-bis(3-methyl- 4-aminophenyl) pyridium, 5-(4-aminophenoxy)-3-[4-(4-aminophenoxy)phenyl]-1,1,3-trimethyldihydro Diphenylamine compounds such as indene, 4-aminobenzoic acid 5-amino-1,1'-biphenyl-2-yl, etc.

As the diamine compound, a commercially available one can be used, and one synthesized by a known method can be used. A diamine compound may be used individually by 1 type, and may be used in combination of 2 or more types.

Although the diisocyanate compound used to prepare (C) polyimide resin is not particularly limited, for example, aliphatic diisocyanate compound, aromatic diisocyanate compound, and both-terminal isocyanate group polyurethane Acid esters and so on.

As the aliphatic diisocyanate compound, for example, linear aliphatic diisocyanate compounds such as tetramethylene diisocyanate, hexamethylene diisocyanate, octamethylene diisocyanate, dodecamethylene diisocyanate, etc. can be cited; Branched chains of 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 2,2-dimethylpentamethylene diisocyanate, etc. Aliphatic diisocyanate compound; isophorone diisocyanate (IPDI), 1,4-cyclohexylene diisocyanate (CHDI), 4-methyl-1,3-cyclohexylene diisocyanate, 2-methyl -1,3-cyclohexylene diisocyanate, 2-methyl-1,4-cyclohexylene diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, 1,3-bis(isocyanate methyl Base) cyclohexane, 3a,4,5,6,7,7a-hexahydro-4,7-methanol dihydroindene (methanoindan)-1,8-subunit (ylene) diisocyanate and other alicyclic two Isocyanate compound; dimer acid type diisocyanate, etc.

The so-called dimer acid diisocyanate refers to _{a diisocyanate compound obtained by substituting the amine group (-NH 2} ) of the dimer acid diamine described above with an isocyanate group (-NCO).

As the aromatic diisocyanate compound, for example, 1,4-phenylene diisocyanate, 1,3-phenylene diisocyanate, phenylene-2,6-diisocyanate, phenylene-2,4 -Diisocyanate, phenylmethylene-3,5-diisocyanate and other phenylene diisocyanate compounds; 1,3-naphthalenediyl diisocyanate, 1,6-naphthalenediyl diisocyanate, 1,7-naphthalene diisocyanate Naphthalene diisocyanate compounds such as methyl diisocyanate, 1,8-naphthalenediyl diisocyanate, 2,6-naphthalenediyl diisocyanate, 2,7-naphthalenediyl diisocyanate, etc.; 4,4'-diphenylmethane Diisocyanate benzene compounds such as isocyanate, 4,4'-diphenyl ether diisocyanate, etc.

Polyurethane with two-terminal isocyanate groups can be obtained by urethane reaction of aliphatic diisocyanate compound and/or aromatic diisocyanate compound with two-terminal hydroxyl polymer as listed above By. The two-terminal hydroxyl polymer may be, for example, two-terminal hydroxyl polybutadiene, two-terminal hydroxyl hydrogenated polybutadiene, two-terminal hydroxyl polyisoprene, two-terminal hydroxyl hydrogenated polyisoprene, and the like. Polyolefins; two-terminal hydroxy polyethers such as polyethylene glycol with two-terminal hydroxy groups, polypropylene glycol with two-terminal hydroxy groups, and polytetramethylene glycol with two-terminal hydroxy groups.

The number average molecular weight of the hydroxyl polymer at both ends is not particularly limited, but is preferably 500 or more, more preferably 1,000 or more, and still more preferably 2,000 or more. The upper limit of the number average molecular weight of the hydroxyl polymer at both ends is not particularly limited, but it is preferably 10,000 or less, and more preferably 8,000 or less. The number average molecular weight here is a value measured by the gel permeation chromatography (GPC) method (in terms of polystyrene).

Polyurethane with two-terminal isocyanate groups, for example, polyurethane with two-terminal isocyanate groups represented by formula (C2),

[In the formula, X ^2a each independently represents the removal of two -NCO divalent groups from an aliphatic diisocyanate compound or an aromatic diisocyanate compound. For example, it may include a carbon atom, an oxygen atom, a nitrogen atom, and a sulfur atom. It is an organic group composed of 2~50 skeleton atoms. X ^2b each independently represents the removal of two -OH divalent groups from the two terminal hydroxyl polymers. For example, it may contain two or more selected from carbon atoms and oxygen atoms (e.g., 2 to 1,000, 2 to 500) The skeleton atoms form the organic group. m represents an integer from 1 to 10].

The diisocyanate compound may be a commercially available one, or may be synthesized by a known method or a method based on this. A diisocyanate compound may be used individually by 1 type, and may be used in combination of 2 or more types.

Although not specifically limited as the tetracarboxylic anhydride for preparing (C) polyimide resin, aliphatic tetracarboxylic dianhydride and aromatic tetracarboxylic dianhydride are mentioned, for example.

As aliphatic tetracarboxylic dianhydride, specifically, 1,2,3,4-cyclobutane tetracarboxylic dianhydride, cyclopentane tetracarboxylic dianhydride, cyclohexane-1,2,3 ,4-tetracarboxylic 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) two Anhydride and so on.

As the aromatic tetracarboxylic dianhydride, for example, pyromellitic dianhydride, pyromellitic dianhydride such as pyromellitic dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, etc.; 1,4,5,8- Naphthalene tetracarboxylic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride and other naphthalene tetracarboxylic dianhydrides; 2,3,6,7-anthracene tetracarboxylic dianhydride and other anthracene tetracarboxylic acids Dianhydride; 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride, 3,3',4, 4'-diphenyl tetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, 2 ,3,3',4'-Biphenyltetracarboxylic dianhydride, 2,3,3',4'-benzophenonetetracarboxylic dianhydride, 2,3,3',4'-diphenyl Ether tetracarboxylic dianhydride, 2,3,3',4'-diphenyl tetracarboxylic dianhydride, 2,2'-bis(3,4-dicarboxyphenoxyphenyl) dianhydride, sub Methyl-4,4'-diphthalic dianhydride, 1,1-ethynylene (ethynylidene)-4,4'-diphthalic dianhydride, 2,2-propylene-4, 4'-diphthalic dianhydride, 1,2-ethylene-4,4'-diphthalic dianhydride, 1,3-trimethylene-4,4'-diphthalic acid 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-dicarboxyphenyl)propane dianhydride, 2,2-bis( 3,4-Dicarboxyphenyl) propane dianhydride, 4,4'-(4,4'-isopropylidene diphenoxy) diphthalic dianhydride, etc., diphthalic dianhydride, etc. .

The tetracarboxylic dianhydride may be commercially available, or may be synthesized by a known method or a method based on this. Tetracarboxylic dianhydride may be used singly or in combination of two or more kinds.

The content of the structure derived from aromatic tetracarboxylic dianhydride relative to the total structure derived from the tetracarboxylic dianhydride constituting (C) polyimide resin is preferably 10 mol% or more, more preferably 30 More than mol%, more preferably more than 50 mol%, more preferably 70 mol% or more for the upper layer, more preferably 90 mol% or more for the upper layer, and particularly preferably 100 mol%.

(C) The weight average molecular weight of the polyimide resin is not particularly limited, but is preferably 1,000 or more, more preferably 3,000 or more, still more preferably 5,000 or more, particularly preferably 7,000 or more. (C) The upper limit of the weight average molecular weight of the polyimide resin is not particularly limited, but it is preferably 100,000 or less, more preferably 80,000 or less, particularly preferably 60,000 or less, and particularly preferably 50,000 or less.

(C) The number average molecular weight of the polyimide resin is not particularly limited, but is preferably 1,000 or more, more preferably 3,000 or more, still more preferably 5,000 or more, particularly preferably 7,000 or more. (C) The upper limit of the number average molecular weight of the polyimide resin is not particularly limited, but it is preferably 100,000 or less, more preferably 80,000 or less, particularly preferably 60,000 or less, and particularly preferably 50,000 or less.

Although the content of (C) polyimide resin in the resin composition is not particularly limited, when the non-volatile content in the resin composition is set to 100% by mass, it is preferably 5% by mass or more, and more preferably 10% by mass or more, more preferably 15% by mass or more, and particularly preferably 20% by mass or more. Although the upper limit of the content of (C) polyimide resin in the resin composition is not particularly limited, when the non-volatile content in the resin composition is 100% by mass, it is preferably 50% by mass or less, and more It is preferably 40% by mass or less, more preferably 35% by mass or less, and particularly preferably 30% by mass or less.

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

The (D) curing agent is not particularly limited, but for example, phenolic curing agents, naphthol curing agents, acid anhydride curing agents, active ester curing agents, benzoxazine curing agents, cyanic acid Ester ester hardener and carbodiimide hardener. The curing agent may be used singly or in combination of two or more kinds. (D) The curing agent preferably contains a curing agent selected from the group consisting of a phenolic curing agent, a naphthol curing agent, and an active ester curing agent, and particularly preferably an active ester curing agent.

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 phenolic structure or a naphthol-based curing agent having a phenolic structure is preferable. In addition, from the viewpoint of adhesion to the adherend, a nitrogen-containing phenolic curing agent or a nitrogen-containing naphthol curing agent is preferred, and a phenolic curing agent containing a triazine skeleton or a triazine-containing curing agent is more preferred. The naphthol of the skeleton is a hardener. Among them, from the viewpoint of highly satisfying heat resistance, water resistance, and adhesion, a phenolic resin containing a triazine skeleton is preferred. Specific examples of phenolic curing agents and naphthol curing agents 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 the acid anhydride-based hardener include hardeners having one or more acid anhydride groups in one molecule, and hardeners having two or more acid anhydride groups in one molecule are preferred. Specific examples of acid anhydride hardeners include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, and methylhexahydrophthalic anhydride. Formic 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, benzophenonetetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, naphthalene tetracarboxylic acid anhydride Carboxylic 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(anhydrotrimellitic acid (Anhydro Trimellitate)), copolymerized styrene and maleic acid styrene, maleic acid resin and other polymeric acid anhydrides. Examples of commercially available products of acid anhydride hardeners include "HNA-100" and "MH-700" manufactured by Nippon Rika Corporation.

The active ester curing agent is not particularly limited, but in general, it is preferable to use one molecule of phenol esters, thiophenol esters, N-hydroxyamine esters, esters of heterocyclic hydroxy compounds, etc. A compound with more than two ester groups with high reactivity. The active ester curing agent is preferably obtained by a condensation reaction of a carboxylic acid compound and/or a thiocarboxylic acid compound and a hydroxy compound and/or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester curing agent derived from a carboxylic acid compound and a hydroxy compound is preferred, and an active ester curing agent derived from a carboxylic acid compound and a phenol compound and/or a naphthol compound is more preferred. hardener. Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. Examples of phenol compounds or naphthol compounds 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, Phloroglucin, benzenetriol, dicyclopentadiene type Diphenol compounds, phenolic aldehydes, etc. Here, the "dicyclopentadiene-type diphenol compound" 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 phenolic phenolic acetate, and a phenolic phenolic compound containing phenolic aldehyde Among the active ester compounds, more preferred are active ester compounds containing naphthalene structure and active ester compounds containing dicyclopentadiene-type diphenol structure. The "dicyclopentadiene-type diphenol structure" refers to a bivalent structural unit comprising phenylene-bicyclopentylene-phenylene.

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

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

Examples of cyanate ester-based 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)phenylpropane, 1,1-bis(4-cyanatephenylmethane), bis(4-cyanate-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 such as phenol phenolic and cresol phenolic resins, prepolymers in which part of these cyanate ester resins are triazineized, etc. Specific examples of cyanate ester curing agents include "PT30" and "PT60" (both phenolic novolac type polyfunctional cyanate ester resin) manufactured by Lonza Japan, "BA230", and "BA230S75" (double Part or all of the phenol A dicyanate becomes the prepolymer of the triazine-treated trimer) and the like.

As specific examples of the carbodiimide-based hardener, "V-03" and "V-07" manufactured by Nisshinbo Chemical Co., Ltd. can be cited.

When the resin composition contains (D) hardener, the ratio of the amount of (A) epoxy resin to (D) hardener is [(A) epoxy group number of epoxy resin]: [(D) reaction base number of hardener] The ratio of is preferably 1:0.2~1:2, more preferably 1:0.3~1:1.5, and still more preferably 1:0.4~1:1.4. Here, the reactive group of (D) hardener is an aromatic hydroxyl group if it is a phenol hardener or a naphthol hardener, and if it is an active ester hardener, it is an active ester group, depending on the type of hardener Vary.

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

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

When the resin composition contains (D) hardener, the content of (D) hardener in the resin composition is not particularly limited, but when the non-volatile content in the resin composition is 100% by mass, it is preferably 1% by mass or more, more preferably 3% by mass or more, still more preferably 4% by mass or more, particularly preferably 5% by mass or more. Although the upper limit of the content of (D) hardener in the resin composition is not particularly limited, when the non-volatile content in the resin composition is 100% by mass, it is preferably 20% by mass or less, and more preferably 15 % By mass or less, more preferably 10% by mass or less, particularly preferably 8% by mass or less.

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

(E) Hardening accelerators are not particularly limited, but for example, phosphorus hardening accelerators, urea hardening accelerators, amine hardening accelerators, imidazole hardening accelerators, guanidine hardening accelerators, metal Department of hardening accelerator, etc. Among them, a phosphorus-based hardening accelerator, an amine-based hardening accelerator, an imidazole-based hardening accelerator, and a metal-based hardening accelerator are preferable, and an imidazole-based hardening accelerator is particularly preferable. One type of hardening accelerator may be used alone, or two or more types may be used in combination.

Examples of phosphorus-based hardening accelerators include tetrabutylphosphonium bromide, tetrabutylphosphonium chloride, tetrabutylphosphonium acetate, tetrabutylphosphonium decanoate, tetrabutylphosphonium laurate, bis( Tetrabutyl phosphonium) pyromellitic acid, tetrabutyl phosphonium hydrogen hexahydrophthalate, tetrabutyl phosphonium cresol phenolic trimer salt, di-tert-butyl methyl phosphonium tetraphenyl borate, etc. The aliphatic phosphonium salt; methyl triphenyl phosphonium bromide, ethyl triphenyl phosphonium bromide, propyl triphenyl phosphonium bromide, butyl triphenyl phosphonium bromide, benzyl triphenyl phosphonium bromide , Tetraphenylphosphonium bromide, p-tolyl triphenyl phosphonium tetra-p-tolyl borate, tetraphenyl phosphonium tetraphenyl borate, tetraphenyl phosphonium tetrap-tolyl borate, Triphenyl ethyl phosphonium tetraphenyl borate, ginseng (3-methylphenyl) ethyl phosphonium tetraphenyl borate, ginseng (2-methoxyphenyl) ethyl phosphonium tetraphenyl boronic acid Aromatic phosphonium salts such as esters, (4-methylphenyl) triphenyl phosphonium thiocyanate, tetraphenyl phosphonium thiocyanate, butyl triphenyl phosphonium thiocyanate, etc.; triphenyl phosphine･ Aromatic phosphine and borane complexes such as triphenylborane; aromatic phosphine and quinone addition reactants such as triphenylphosphine･p-benzoquinone addition reactants; tributylphosphine, tri-tert- Of butyl phosphine, trioctyl phosphine, di-tert-butyl (2-butenyl) phosphine, di-tert-butyl (3-methyl-2-butenyl) phosphine, tricyclohexyl phosphine, etc. Aliphatic phosphine; dibutylphenylphosphine, two-tert-butylphenylphosphine, methyldiphenylphosphine, ethyldiphenylphosphine, butyldiphenylphosphine, diphenylcyclohexylphosphine, three Phenylphosphine, tris-o-tolylphosphine, tris-m-tolylphosphine, tris-p-tolylphosphine, ginseng(4-ethylphenyl)phosphine, ginseng(4-propylphenyl)phosphine, Ginseng (4-isopropylphenyl) phosphine, ginseng (4-butylphenyl) phosphine, ginseng (4-tert-butylphenyl) phosphine, ginseng (2,4-dimethylphenyl) phosphine, Ginseng(2,5-dimethylphenyl)phosphine, ginseng(2,6-dimethylphenyl)phosphine, ginseng(3,5-dimethylphenyl)phosphine, ginseng(2,4,6- Trimethylphenyl)phosphine, ginseng(2,6-dimethyl-4-ethoxyphenyl)phosphine, ginseng(2-methoxyphenyl)phosphine, ginseng(4-methoxyphenyl) Phosphine, ginseng(4-ethoxyphenyl)phosphine, ginseng(4-tert-butoxyphenyl)phosphine, diphenyl-2-pyridylphosphine, 1,2-bis(diphenylphosphino) Ethane, 1,3-bis(diphenylphosphino)propane, 1,4-bis(diphenylphosphino)butane, 1,2-bis(diphenylphosphino)Acetylene, 2 , 2'-bis(diphenylphosphino) diphenyl ether and other aromatic phosphines.

Examples of urea-based hardening accelerators include 1,1-dimethylurea; 1,1,3-trimethylurea, 3-ethyl-1,1-dimethylurea, and 3-cyclohexyl-1 ,1-Dimethylurea, 3-cyclooctyl-1,1-dimethylurea and other aliphatic dimethylurea; 3-phenyl-1,1-dimethylurea, 3-(4- Chlorophenyl)-1,1-dimethylurea, 3-(3,4-dichlorophenyl)-1,1-dimethylurea, 3-(3-chloro-4-methylphenyl) -1,1-dimethylurea, 3-(2-methylphenyl)-1,1-dimethylurea, 3-(4-methylphenyl)-1,1-dimethylurea, 3-(3,4-Dimethylphenyl)-1,1-dimethylurea, 3-(4-isopropylphenyl)-1,1-dimethylurea, 3-(4-methyl Oxyphenyl)-1,1-dimethylurea, 3-(4-nitrophenyl)-1,1-dimethylurea, 3-[4-(4-methoxyphenoxy) Phenyl]-1,1-dimethylurea, 3-[4-(4-chlorophenoxy)phenyl]-1,1-dimethylurea, 3-[3-(trifluoromethyl) Phenyl]-1,1-dimethylurea, N,N-(1,4-phenylene) bis(N',N'-dimethylurea), N,N-(4-methyl- 1,3-phenylene) bis(N',N'-dimethylurea)[toluene dimethylurea] and other aromatic dimethylureas.

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

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

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

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

Examples of the metal-based hardening accelerator 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 acetyl acetate (II) and cobalt acetyl acetate (III), organic copper complexes such as copper acetyl acetate (II), Organic zinc complexes such as zinc (II) acetyl acetate, organic iron complexes such as iron (III) acetyl acetate, organic nickel complexes such as nickel (II) acetyl acetate, manganese acetyl acetate ( II) Organic manganese complexes and so on. Examples of the organic metal salt include zinc octoate, tin octoate, zinc naphthenate, cobalt naphthenate, tin stearate, zinc stearate, and the like.

When the resin composition contains (E) hardening accelerator, the content of (E) hardening accelerator in the resin composition is not particularly limited, but when the non-volatile content in the resin composition is set to 100% by mass, it is more It is preferably 0.001% by mass or more, more preferably 0.01% by mass or more, still more preferably 0.05% by mass or more, and particularly preferably 0.1% by mass or more. Although the upper limit of the content of (E) hardening accelerator in the resin composition is not particularly limited, when the non-volatile content in the resin composition is 100% by mass, it is preferably 5% by mass or less, more preferably 3% by mass or less, more preferably 1% by mass or less, particularly preferably 0.5% by mass or less.

＜(F) Other additives＞ The resin composition of the present invention may further contain optional additives as a non-volatile component. Examples of such additives include organic fillers such as rubber particles, polyamide microparticles, and polysiloxane particles; phenoxy resins, polyvinyl acetal resins, polyolefin resins, polycure resins, and polyether clumps. Thermoplastic resins such as resins, polyphenylene ether resins, polycarbonate resins, polyether ether ketone resins, polyester resins, etc.; organic copper compounds, organic zinc compounds, organic cobalt compounds, and other organic metal compounds; phthalocyanine blue, phthalocyanine Coloring agents for cyanine green, iodine green, diazo yellow, crystal violet, titanium oxide, carbon black, etc.; polymerization inhibitors for hydroquinone, catechol, pyrogallol, phenothiazine, etc.; Polysiloxane-based leveling agent, acryl-based polymer-based leveling agent, etc.; Benton, montmorillonite, etc. viscosity-increasing agent; silicone-based defoaming agent, acryl-based defoaming agent , Fluorine-based defoamers, defoamers of vinyl resin-based defoamers; UV absorbers such as benzotriazole-based UV absorbers; Adhesion enhancers such as urea silane; Triazole-based adhesion imparting agent , Adhesion imparting agents such as tetrazole-based adhesiveness imparting agents, triazine-based adhesiveness imparting agents, etc.; hindered phenol-based antioxidants, hindered amine-based antioxidants, and other antioxidants; stilbene (Stilbene) derivatives Fluorescent brighteners such as fluorine-based surfactants, silicone-based surfactants, etc.; phosphorus-based flame retardants (such as phosphate compounds, Phosphazene compounds, hypophosphorous acid compounds, Red phosphorus), nitrogen-based flame retardants (for example, melamine), halogen-based flame retardants, inorganic flame retardants (for example, antimony trioxide) and other flame retardants. Additives may be used alone or in combination of two or more at any ratio. (F) The content of other additives can be appropriately set by those with ordinary knowledge in the field of the invention.

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

＜Manufacturing method of resin composition＞ The resin composition of the present invention can be obtained by adding (A) epoxy resin, (B) inorganic filler, and (C) polyamide in any reaction vessel in any order, and/or part or all of them at the same time. Amine resin (preliminarily imidized), if necessary (D) hardener, if necessary (E) hardening accelerator, if necessary (F) other additives, and if necessary (G ) Organic solvents are mixed to manufacture. In addition, in the process of adding and mixing each component, the temperature can be appropriately set, and heating and/or cooling can be performed temporarily or from beginning to end. In addition, in the process of adding and mixing each component, stirring or shaking may be performed. In addition, during or after the addition and mixing, the resin composition may be stirred using a stirring device such as a mixer to uniformly disperse it.

＜Characteristics of resin composition＞ The resin composition of the present invention contains (A) epoxy resin, (B) inorganic filler and (C) polyimide resin, and (A) component contains (A-1) epoxy resin containing silicone skeleton Resin, it is possible to obtain (B) when the content of the inorganic filler is 40% by mass or less, even if it is low blended, the viscosity can be suppressed to a low level, and the cured product has excellent flexibility and excellent insulation reliability. The resin composition.

The cured product of the resin composition of the present invention has excellent flexibility. For example, as in Test Example 1 below, a layered cured product of a resin composition having a thickness of 40 μm, a width of 15 mm, and a length of 110 mm is set at a load of 2.5 in accordance with JIS C-5016. N. The bending angle is 90 degrees, the bending speed is 175 times/min, and the bending radius is 1.0mm. The number of times of bending resistance during the MIT bending endurance test is preferably more than 3,000 times, more preferably more than 5,000 times, and even better It can be more than 7,000 times, particularly preferably more than 8,000 times.

The cured product of the resin composition of the present invention has excellent insulation reliability. For example, the insulation resistance value of the insulation layer of the evaluation substrate measured by the method of Test Example 3 below is preferably 1.00×10 ⁷ Ω or more, and more It is preferably 1.00×10 ⁸ Ω or more, still more preferably 1.00×10 ⁹ Ω or more, and particularly ^{preferably 1.00×10 10} Ω or more.

Since the resin composition of the present invention can suppress the viscosity to a low level, for example, as in the following test example 2, the diameter of the glass probe is 5 mm, the load is 1 kgf/cm ² , the contact speed is 0.5 mm/sec, and the stretching speed is 0.5 The adhesive force measured under the conditions of mm/sec, holding time of 10 seconds, and temperature of 80°C is preferably 1.8N or less, more preferably 1.6N or less, still more preferably 1.4N or less, and particularly preferably 1.2N or less.

＜Use of resin composition＞ The resin composition of the present invention can be used in a wide range of insulating materials such as printed wiring boards, multilayer flexible substrates, solder resists, underfill materials, die bonding materials, semiconductor sealing materials, cavity filling resins, and part embedding resins. range. Printed wiring boards, multilayer flexible substrates, etc., can be manufactured using, for example, sheet-like laminate materials such as resin sheets and prepregs.

＜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.

The thickness of the resin composition layer is preferably 200 μm or less, more preferably 150 μm or less, still more preferably 100 μm or less, particularly preferably 70 μm or less. Although the lower limit of the thickness of the resin composition layer is not particularly limited, it can usually be set to 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 can be cited, and a film made of a plastic material, and a metal foil are preferred.

When a film containing a plastic material is used as a support, as the plastic material, for example, polyethylene terephthalate (hereinafter sometimes referred to as "PET"), polyethylene naphthalate (hereinafter Sometimes abbreviated as "PEN") such as polyester, polycarbonate (hereinafter sometimes referred to as "PC"), polymethylmethacrylate (PMMA) and other acryl, cyclic polyolefin, triacetin Base cellulose (TAC), polyether sulfide (PES), polyether ketone, polyimide, etc. Among them, polyethylene terephthalate and polyethylene naphthalate are preferred, and inexpensive polyethylene terephthalate is particularly preferred.

When a metal foil is used as a support, 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 containing 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 may be subjected to matting treatment, corona treatment, and antistatic treatment on the surface joined to the resin composition layer.

In addition, as the support, a support with a mold release layer having a mold release layer on the surface to be bonded to the resin composition layer can be used. As the mold release agent used in the mold release layer of the support with the mold release layer, for example, one may be selected from the group consisting of alkyd resin, polyolefin resin, urethane resin, and silicone resin. One or more release agents. Commercially available products can be used for the support with a release layer. Examples include PET films with a release layer based on an alkyd resin-based release agent, namely "SK-1" and "AL -5", "AL-7", "Lumirror T60" manufactured by Toray, "Purex" manufactured by Teijin, "Unipiel" manufactured by Unitika, etc.

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

In one embodiment, the resin sheet may further include other layers if necessary. As this other layer, for example, it is provided on the surface which is not joined to the support of the resin composition layer (that is, the surface on the opposite side to the support), the protective film according to the support, and the like. Although the thickness of the protective film is not particularly limited, it is, for example, 1 μm to 40 μm. By laminating the protective film, it is possible to suppress adhesion or scratches of dust and the like on the surface of the resin composition layer.

The resin sheet can be prepared by directly dissolving the resin composition or, for example, the resin composition in an organic solvent, and coating the resin varnish on the support using a die coater, and then drying to form the resin composition Material layer to manufacture.

As an organic solvent which can be used when apply|coating to a support body, the same thing as the thing mentioned in the description of the organic solvent which is a component of a resin composition can be mentioned, for example. An organic solvent may be used individually by 1 type, and may be used in combination of 2 or more types.

Drying can be performed by a well-known method such as heating and hot air blowing. Although the drying conditions are not particularly limited, the drying is performed so that the content of the organic solvent in the resin composition layer becomes 10% by mass or less, preferably 5% by mass or less. Although it varies with the boiling point of the organic solvent in the resin composition or resin varnish, for example, when a resin composition or resin varnish containing 30% to 60% by mass of organic solvent is used, it can be carried out by 50°C to 150°C. It dries for 10 minutes to 10 minutes to form a resin composition layer.

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

＜Laminated sheet＞ The laminated sheet is a sheet made by laminating and hardening a plurality of resin composition layers. The laminated sheet is a plurality of insulating layers including a cured product of the resin composition layer. Generally, the number of resin composition layers laminated in order to manufacture the laminated sheet is the same as the number of insulating layers included 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, preferably 20 or less, more preferably 15 or less, particularly preferably 10 or less.

The laminated sheet can be used by bending so that one side of the sheet faces each other. The minimum bending radius of the laminated sheet is not particularly limited, but is preferably 0.1 mm or more, more preferably 0.2 mm or more, still more preferably 0.3 mm or more, preferably 5 mm or less, more preferably 4 mm or less, Particularly preferred is 3mm or less.

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

In addition to the insulating layer, the laminated sheet may further contain any elements. For example, the laminated sheet may be provided with a conductor layer as an optional element. The conductor layer is usually partially formed on the surface of the insulating layer or between the insulating layers. This conductor layer is usually used as wiring in a multilayer flexible substrate system.

The conductor material used in the conductor layer is not particularly limited. In a suitable embodiment, the conductor layer includes one selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin, and indium Above the metal. The conductor material can be a single metal or an alloy. As the alloy, for example, an alloy 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 versatility, cost, and ease of patterning of the conductor layer, 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, more preferred are single metals of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper; and nickel and chromium alloys; and even more preferred are single metals of copper.

The conductor layer can be a single-layer structure or a multi-layer structure. The multi-layer structure includes two or more single metal layers or alloy layers composed of different types of metals or alloys. When the conductor layer is a multi-layer structure, the layer in contact with the insulating layer is preferably a single metal layer of chromium, zinc or titanium or an alloy layer of nickel-chromium alloy.

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

Although the thickness of the conductor layer varies depending on the design of the multilayer flexible substrate, it is preferably 3 μm to 35 μm, more preferably 5 μm to 30 μm, still more preferably 10 μm to 20 μm, particularly preferably 15 μm to 20 μm.

The thickness of the laminated sheet is preferably 100 μm or more, more preferably 150 μm or more, particularly preferably 200 μm or more, preferably 2,000 μm or less, more preferably 1,000 μm or less, particularly preferably 500 μm or less.

＜Manufacturing method of 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 using a resin sheet, laminating a plurality of layers, and curing the resin composition layer. The order of lamination and curing of the resin composition layer is arbitrary as long as the desired laminated sheet can be obtained. Depending on the components contained in the resin composition, for example, after all the plural resin composition layers are laminated, the laminated plural resin composition layers can be cured at one time. In addition, for example, it is possible to perform curing of the resin composition layer to the extent that another resin composition layer is laminated on a certain resin composition layer.

Hereinafter, a preferred embodiment of step (b) will be described. In the embodiment described below, in order to distinguish, it is appropriate to the resin composition layer, such as the "first resin composition layer" and "second resin composition layer" with numbers, and further, to make these resins The insulating layer obtained by curing the composition layer is also the same as the resin composition layer, and is indicated by numbers like "first insulating layer" and "second insulating layer".

In a preferred embodiment, step (b) includes: (II) The step of hardening the first resin composition layer to form the first insulating layer, and (VI) the step of laminating the second resin composition layer on the first insulating layer, and (VII) A step of hardening the second resin composition layer to form a second insulating layer. Furthermore, step (b) may include if necessary: (I) The step of laminating the first resin composition layer on the sheet supporting substrate, (III) The step of drilling holes in the first insulating layer, (IV) The step of roughening the first insulating layer, (V) Step of forming a conductor layer on the first insulating layer And so on any steps. The following describes each step.

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

The lamination of the sheet supporting substrate and the first resin composition layer can be performed by a vacuum lamination method. In the vacuum lamination method, the heating and pressing temperature is preferably 60°C to 160°C, more preferably in the range of 80°C to 140°C, and the heating and pressing pressure is preferably 0.098MPa to 1.77MPa, more preferably 0.29MPa to 1.47 In the range of MPa, the heating and pressing 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 can be performed by a commercially available vacuum laminator. As a commercially available vacuum laminator, for example, a vacuum pressurized laminator manufactured by Meiji Seisakusho Co., Ltd., a vacuum applicator manufactured by Nikko & Material Co., Ltd., a batch vacuum pressurized laminator, etc. can be cited.

When using a resin sheet, the sheet supports the lamination of the base material and the first resin composition layer. For example, by pressing the resin sheet from the support side, the first resin composition layer of the resin sheet can be heated and pressed on the sheet support base材进行。 Material progress. As a member that heats and presses the resin sheet on the sheet supporting substrate (hereinafter, it may also be referred to as a "heat press member" as appropriate), for example, a heated metal plate (SUS mirror plate, etc.) or a metal roll (SUS Roller) and so on. It is preferable not to press the heating and pressing member directly on the resin sheet, but to press through an elastic material such as heat-resistant rubber so that the unevenness of the surface of the sheet support substrate is sufficiently followed by the first resin composition layer.

After lamination, the first resin composition layer can be smoothed by pressing under normal pressure (under atmospheric pressure), for example, by heating and pressing the member. For example, when a resin sheet is used, the first resin composition layer of the resin sheet can be smoothed by pressing the resin sheet from the support side with a heating and pressing member. The pressing conditions of the smoothing treatment can be set to the same conditions as the heating and pressing conditions of the above-mentioned lamination. The smoothing treatment can be carried out by a commercially available laminator. The lamination and smoothing treatment can be continuously performed using the above-mentioned commercially available vacuum laminator.

Step (II) is a step of hardening the first resin composition layer to form a first insulating layer. The curing conditions of the first resin composition layer are not particularly limited, and the conditions used when forming the insulating layer of the printed wiring board can be arbitrarily applied. The first resin composition layer can be cured by thermal curing, for example.

Generally, 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 even more preferably 170°C to 210°C. In addition, the curing time is preferably 5 minutes to 120 minutes, more preferably 10 minutes to 110 minutes, and still more preferably 20 minutes to 100 minutes.

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

Step (III) is a step of drilling the first insulating layer. Through this step (III), holes such as through holes and through holes can be formed in the first insulating layer. Drilling can be performed according to the composition of the resin composition, for example, using a drilling machine, laser, plasma, etc. The size and shape of the hole can be appropriately set according to the design of the multilayer flexible substrate.

Step (IV) is a step of roughening the first insulating layer. Usually in this step (IV), the removal of scum is also carried out. Therefore, roughening treatment is sometimes referred to as desmear treatment. As an example of the roughening treatment, a method of performing a swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralization treatment with a neutralization liquid in this order can be cited.

Although it does not specifically limit as a swelling liquid, alkali aqueous solutions, such as a sodium hydroxide aqueous solution and potassium hydroxide aqueous solution, are mentioned. Examples of commercially available swelling fluids include "Swelling Dip Securiganth P" and "Swelling Dip Securiganth SBU" manufactured by Atotech Japan. The swelling treatment of the swelling liquid is carried out, for example, by immersing the hardened body in the swelling liquid at 30 to 90°C for 1 to 20 minutes. From the viewpoint of suppressing the swelling of the resin of the insulating layer to an appropriate level, it is preferable to impregnate the insulating layer with a swelling solution at 40°C to 80°C for 5 minutes to 15 minutes.

Although it does not specifically limit as an oxidizing agent, for example, sodium hydroxide aqueous solution, potassium hydroxide aqueous solution, the alkaline permanganic acid solution which melt|dissolved permanganate is mentioned. The concentration of permanganate in the alkaline permanganic acid solution is preferably 5 mass% to 10 mass %. Examples of commercially available oxidants include alkaline permanganic acid solutions such as "Concentrate･Compact P", "Concentrate･Compact CP", and "Dosing solution･Securiganth P" manufactured by Atotech Japan. The roughening treatment by the oxidant can be carried out by immersing the hardened body in an oxidant solution heated to 60°C to 80°C for 10 minutes to 30 minutes.

In addition, as the neutralizing liquid, an acidic aqueous solution was used. As a commercially available product, for example, "Reduction solution･Securigant P" manufactured by Atotech Japan can be cited. The treatment of the neutralization solution can be carried out by immersing the hardened body in the neutralization solution at 30°C to 80°C for 5 minutes to 30 minutes. From the viewpoint of workability and the like, it is preferable to immerse the hardened body in a neutralizing solution at 40°C to 70°C for 5 minutes to 20 minutes.

The arithmetic average roughness (Ra) of the surface of the first insulating layer after the roughening treatment is preferably 400 nm or less, more preferably 300 nm or less, and even more preferably 200 nm or less. Although the lower limit is not particularly limited, it 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 if necessary. The method of forming the conductor layer includes, for example, a plating method, a sputtering method, and a vapor deposition method. Among them, the plating method is preferred. As a suitable example, a suitable method such as a semi-additive method and a full additive method may be used to plate the surface of the first insulating layer to form a conductor layer with a desired wiring pattern. Methods. Among them, from the viewpoint of ease of manufacture, the semi-additive method is preferred.

The following shows an example in which the conductor layer is formed 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), if necessary, after performing step (III), step (IV), and step (V), perform step (VI). Step (VI) is a step of laminating the second resin composition layer on the first insulating layer. The lamination of the first insulating layer and the second resin composition layer can be performed in the same manner as the lamination of the sheet support substrate and the first resin composition layer in step (I).

However, when a resin sheet is used to form the first resin composition layer, the support of the resin sheet is removed earlier than 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 hardening the second resin composition layer to form a second insulating layer. The curing of the second resin composition layer can be performed in the same way as the curing of the first resin composition layer in step (II). Thereby, a laminated sheet including a plurality of insulating layers including the first insulating layer and the second insulating layer can be obtained.

In addition, in the method related to the foregoing embodiment, if necessary, (VIII) the step of drilling the second insulating layer, (IX) the step of roughening the second insulating layer, and (X) The step of forming a conductor layer on the second insulating layer. The drilling of the second insulating layer in step (VIII) can be performed in the same way as the drilling of the first insulating layer in step (III). In addition, the roughening treatment of the second insulating layer in step (IX) can be performed in the same way 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 in the same way as the formation of the conductor layer on the first insulating layer in step (V).

In the foregoing embodiment, although the first resin composition layer and the second resin composition layer are laminated and hardened so-called two-layer resin composition layers to produce a laminated sheet, it is also possible to use Lamination and curing of three or more resin composition layers to produce a laminated sheet. For example, in the method related to the aforementioned embodiment, the lamination and curing of the resin composition layer from step (VI) to step (VII) and, if necessary, step (VIII) to step (X ) The insulating layer is drilled, the insulating layer is roughened, and the conductor layer on the insulating layer is formed to produce a laminated sheet. Thereby, a laminated sheet including three or more insulating layers is 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 be performed.

＜Multilayer flexible substrate＞ The multilayer flexible substrate includes a laminated sheet. The multi-layer flexible substrate may include only the laminate sheet, or may include arbitrary members in combination with the laminate sheet. As optional members, for example, electronic parts, cover films, etc. can be cited.

The multilayer flexible substrate can be manufactured by a manufacturing method including the method of 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 using a resin sheet, laminating a plurality of layers, and curing the resin composition layer.

The manufacturing method of the multilayer flexible substrate can be combined with the aforementioned steps, and further includes any steps. For example, a method of manufacturing a multilayer flexible substrate with electronic components may include the step of bonding the electronic components with the laminated sheet. The bonding conditions of the laminate sheet and the electronic component can be any conditions of the terminal electrode of the electronic component that can be connected by a conductor and the conductor layer as the wiring provided on the laminate sheet. In addition, for example, a method for 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 is usually used by bending one side of the laminated sheet included in the multi-layer flexible substrate in such a way that they face each other. For example, a multilayer flexible substrate is housed in a housing of a semiconductor device in a state of being bent and reduced in size. In addition, for example, a semiconductor device having a flexible movable portion of a multilayer flexible substrate is provided at the movable portion.

＜Semiconductor device＞ The semiconductor device is equipped with 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 multilayer flexible substrate can be placed in the housing of the semiconductor device, and one side of the laminated sheet included in the multilayer flexible substrate can be bent so as to face each other to be accommodated.

Examples of semiconductor devices include various semiconductor devices used in electrical products (for example, computers, mobile phones, digital cameras, televisions, etc.) and vehicles (for example, motorcycles, automobiles, trams, ships, and airplanes).

The aforementioned semiconductor device can be prepared, for example, by including a step of preparing a multilayer flexible substrate, a step of bending the multilayer flexible substrate so that one side of the laminated sheet faces each other, and a step of bending the multilayer The flexible substrate is manufactured by the manufacturing method of the step where the flexible substrate is housed in the frame. [Example]

Hereinafter, the present invention will be specifically described with examples. The present invention is not limited to these embodiments. . However, in the following, it means "parts" and "%" of the quantity, unless otherwise specified, they mean "parts by mass" and "% by mass" respectively. In addition, unless otherwise specified, the operations described below are performed in an environment of normal temperature and pressure (25°C, 1 atm).

<Synthesis example 1: Synthesis of polyimide resin 1> G-3000 (bifunctional hydroxyl-terminated polybutadiene, number average molecular weight = 5,047 (GPC method), hydroxyl equivalent = 1,798 g/eq. , Solid content 100% by mass: 50 g of Nippon Soda Co., Ltd., 23.5 g of Ipsol 150 (aromatic hydrocarbon-based mixed solvent: manufactured by Idemitsu Petrochemical Co., Ltd.), and 0.005 g of dibutyltin laurate and uniformly dissolved. When it became uniform, the temperature was raised to 50°C, and 4.8 g of toluene-2,4-diisocyanate (isocyanate group equivalent=87.08 g/eq.) was added while stirring, and the reaction was performed for about 3 hours. Next, after cooling the reactant to room temperature, 8.96 g of benzophenone tetracarboxylic dianhydride (anhydride equivalent = 161.1 g/eq.), 0.07 g of triethylenediamine, and ethyl acetate were added to this. 40.4 g of diethylene glycol acetate (manufactured by Daicel) was heated to 130°C while stirring, and the reaction was carried out for about 4 hours. It was confirmed by FTIR that the NCO peak ^{at 2250 cm -1 disappeared.} The confirmation of the disappearance of the NCO peak is regarded as the end of the reaction. After the reactant is cooled to room temperature, it is filtered with a filter cloth of 100 meshes to obtain an imine skeleton, a urethane skeleton, and a butadiene skeleton. The polyimide resin 1. Viscosity: 7.5Pa･s (25°C, E-type viscometer) Acid value: 16.9mgKOH/g Solid content: 50% by mass Number average molecular weight: 13,723 Glass transition temperature: -10°C Polybutadiene structural part content: 50/(50+4.8+8.96)×100=78.4 mass%

<Synthesis example 2: Synthesis of polyimide resin 2> Put 9.13g (30 millimoles) of 4-aminobenzoic acid 5-amino-1,1'-biphenyl-2-yl, 4,4' into a 500ml separable flask equipped with a nitrogen introduction tube and a stirring device -(4,4'-isopropylidene diphenoxy) bisphthalic dianhydride 15.61g (30 millimoles), N-methyl-2-pyrrolidone 94.64g, pyridine 0.47g (6 millimoles) Ears), 10g of toluene, in a nitrogen environment, at 180°C, while spying toluene outside the system during the process, the toluene was reacted for 4 hours to obtain a polyimide solution containing polyimide resin 2 ( Non-volatile content 20% by mass). In the polyimide solution, no precipitation of the synthesized polyimide resin 2 was observed. The weight average molecular weight of the polyimide resin 2 is 45,000.

<Synthesis Example 3: Synthesis of Polyimide Resin 3> Place the aromatic tetracarboxylic dianhydride (“BisDA-1000” manufactured by SABIC Japan Co., Ltd., 4,4'-(4,4'-iso Propylene diphenoxy) diphthalic dianhydride) 65.0 g, cyclohexanone 266.5 g, and methylcyclohexane 44.4 g, and the solution was heated to 60°C. Next, 43.7 g of dimer diamine ("PRIAMINE 1075" manufactured by Croda Japan) and 5.4 g of 1,3-bis(aminomethyl)cyclohexane were dropped, and the imidization was carried out at 140°C for 1 hour. reaction. Thereby, a polyimide solution (non-volatile content 30% by mass) containing polyimide resin 3 was obtained. In addition, the weight average molecular weight of the polyimide resin 3 was 25,000.

<Synthesis Example 4: Synthesis of Polyimide Resin 4> Prepare a 500mL separable flask equipped with a moisture quantitative receiver connected to a circulating cooler, a nitrogen introduction tube, and a stirrer. Add 4,4'-oxydiphthalic anhydride (ODPA) 20.3g, γ-butyrolactone 200g, toluene 20g and 5-(4-aminophenoxy)-3-(4- (4-Aminophenoxy)phenyl]-1,1,3-trimethylindene 29.6 g, stirred at 45°C for 2 hours under a nitrogen stream, and reacted. Next, the temperature of the reaction solution was raised, while maintaining the temperature at about 160°C, the condensation water was azeotropically removed with toluene under a nitrogen stream. Confirm that the specified amount of water accumulates in the moisture quantitative receiver until no outflow of water is observed. After confirmation, the reaction solution was further heated, and stirred at 200°C for 1 hour. Then, it cooled, and obtained the polyimide solution (non-volatile content 20 mass %) containing the polyimide resin 4 which has a 1,1,3-trimethylindene skeleton. The obtained polyimide resin 4 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 4 is 12,000.

<Example 1: Preparation of resin composition 1> 5 parts of bixylenol type epoxy resin ("YX4000HK" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of about 185 g/eq.) and naphthalene type epoxy resin (Nippon Steel & Sumitomo Metal Chemical Corporation "ESN475V", epoxy equivalent: about 332g/eq.) 5 parts, bisphenol AF type epoxy resin (Mitsubishi Chemical Corporation "YL7760", epoxy equivalent: about 238g/eq.) 10 Parts, 2 parts of cyclohexane type epoxy resin (Mitsubishi Chemical Corporation "ZX1658GS", epoxy equivalent about 135g/eq.), and polyimide resin 1 (non-volatile content 50% by mass) obtained in Synthesis Example 1 ) 40 parts, while stirring 10 parts of cyclohexanone, heat and dissolve it. After cooling to room temperature, mix it with a cresol phenolic hardener containing a triazine skeleton ("LA3018-50P" manufactured by DIC Corporation, with a hydroxyl equivalent of about 151 g/eq., and a non-volatile content of 50% 2-methoxypropane). Alcohol solution) 4 parts, active ester hardener (DIC company "EXB-8000L-65TM", active base equivalent of about 220g/eq., non-volatile content 65% by mass MEK solution) 6 parts, spherical silica ( Admatechs company "SC2500SQ", average particle diameter of 0.5 m, a specific surface area 11.2m ² / g, silicon dioxide with respect to 100 parts of N- phenyl-3-aminopropyl trimethoxy Silane (by Shin-Etsu chemical Co., Ltd. , KBM573) 1 part after surface treatment) 25 parts, epoxy resin containing silicone skeleton (manufactured by Shin-Etsu Chemical Co., Ltd., "KR470", epoxy equivalent about 200g/eq.) 6 parts, amine hardening accelerator After 0.2 part of (4-dimethylaminopyridine (DMAP)) was uniformly dispersed with a high-speed rotary mixer, it was filtered with a cartridge filter ("SHP020" manufactured by ROKITECHNO) to prepare a resin composition 1.

<Example 2: Preparation of resin composition 2> In addition to replacing 40 parts of polyimide resin 1 (non-volatile content 50% by mass) obtained in Synthesis Example 1, 100 parts of polyimide resin 2 (non-volatile content 20% by mass) obtained in Synthesis Example 2 was used instead Otherwise, the same operations as in Example 1 were performed to prepare a resin composition 2.

<Example 3: Preparation of resin composition 3> In addition to replacing 40 parts of polyimide resin 1 (non-volatile content 50% by mass) obtained in Synthesis Example 1, 66.7 parts of polyimide resin 3 (non-volatile content 30% by mass) obtained in Synthesis Example 3 was used instead Otherwise, the same operations as in Example 1 were performed to prepare a resin composition 3.

<Example 4: Preparation of resin composition 4> In addition to replacing 40 parts of polyimide resin 1 (non-volatile content 50% by mass) used in Synthesis Example 1, 100 parts of polyimide resin 4 (non-volatile content 20% by mass) obtained in Synthesis Example 4 was used instead. Otherwise, the same operations as in Example 1 were performed to prepare a resin composition 4.

<Comparative example 1: Preparation of resin composition 5> Except that 6 parts of epoxy resin containing silicone skeleton (manufactured by Shin-Etsu Chemical Co., Ltd., "KR470", epoxy equivalent approximately 200g/eq.) were not used, the other operations were the same as in Example 1 to prepare the resin composition物5.

<Comparative example 2: Preparation of resin composition 6> Except for replacing 40 parts of polyimide resin 1 (50% by mass of non-volatile content) used in Synthesis Example 1, 66 parts of phenoxy resin (“YX7553BH30” manufactured by Mitsubishi Chemical Corporation, 30% by mass of solid content) was used instead. Otherwise, the same operations as in Example 1 were performed to prepare a resin composition 6.

<Test Example 1: Evaluation of Flexibility (MIT Folding Resistance)> On the release-treated surface of the PET film (thickness 38μm) treated with the resin composition of the resin composition of each of the Examples and Comparative Examples (thickness 38μm), the thickness of the resin composition layer after drying became 40μm. The coating machine applied uniformly, and dried at 80-120 degreeC (average 100 degreeC) for 6 minutes, and the resin sheet 1 was obtained.

The obtained resin sheet 1 was laminated on a polyimide film (manufactured by Ube Industries Co., Ltd., UPILEX S ) To obtain a resin sheet with a protective film. After the lamination system was pressure-reduced for 30 seconds and the air pressure was set to 13 hPa or less, it was pressed at 120° C. for 30 seconds under a pressure of 0.74 MPa. Then, the PET film was peeled off, the resin composition was cured under curing conditions of 190°C for 90 minutes, and the polyimide film was peeled off to obtain a cured product sample.

The obtained hardened product sample 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"), in accordance with JIS C-5016, Under the measurement conditions of a load of 2.5N, a bending angle of 90 degrees, a bending radius of 1.0mm, and a bending speed of 175 times/min, the number of times the hardened body can withstand breaking is measured. Still, the measurement 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 2: Evaluation of Tack (Adhesiveness)> From the resin sheet with protective film obtained in Test Example 1, the protective film was peeled off, and the resin composition layer was tested using a probe tack tester (TESTER Sangyo Co., Ltd. Manufacture, "TE-6002"), detect the glass with a diameter of 5mm ^{, and measure the adhesion at a temperature of 80℃ with a load of 1kgf/cm 2} , a contact speed of 0.5mm/sec, a stretching speed of 0.5mm/sec, and a holding time of 10 seconds. force. The case where the adhesive force exceeds 1.6N is evaluated as "×", and the case where the adhesive force is less than 1.6N is evaluated as "○".

<Test Example 3: Evaluation of Insulation Reliability> (1) Base treatment of inner circuit board As the inner layer circuit board, a glass cloth base epoxy resin double-sided copper-clad laminate with a circuit conductor (copper) formed in the wiring pattern of L/S=10μm/10μm is prepared on both sides (the thickness of the copper foil is 3μm) , Substrate thickness 0.15mm, "HL832NSF LCA" manufactured by Mitsubishi Gas Chemical Corporation, 255×340mm size). Both sides of the inner layer circuit board were treated with an organic coating on the copper surface in "FlatBOND-FT" manufactured by MEC Corporation.

(2) Laminating of resin sheet From the resin sheet with protective film obtained in Test Example 1, peel off the protective film, and use a batch-type vacuum press laminator (manufactured by Nikko Materials Co., Ltd., 2-stage stacking laminator, CVP700) to layer the resin composition with The contact method of the inner circuit board is laminated on both sides of the inner circuit board. The lamination is carried out by performing pressure reduction for 30 seconds, setting the air pressure to 13 hPa or less, and pressing at 130° C., pressure 0.74 MPa, and 45 seconds. Next, hot stamping was performed at 120°C and a pressure of 0.5 MPa for 75 seconds.

(3) Thermal curing of resin composition layer Put the inner circuit board of the laminated resin sheet into an oven at 100°C for 30 minutes, then transfer it to an oven at 180°C for 30 minutes, then heat it to form an insulating layer, and peel off the release PET.

(4) Roughening treatment The inner circuit substrate where the insulating layer is formed is subjected to a desmear treatment as a roughening treatment. Still, as a desmear treatment, the following wet desmear treatment is implemented. Wet slag removal treatment: It was immersed in a swelling solution ("Swelling Dip Securigant P" manufactured by Atotech Japan, an aqueous solution of diethylene glycol monobutyl ether and sodium hydroxide) at 60°C for 5 minutes, and then in an oxidizing agent solution ("Concentrate" manufactured by Atotech Japan) ･Compact CP", an aqueous solution of potassium permanganate concentration of about 6% and sodium hydroxide concentration of about 4%), immersed at 80°C for 10 minutes, and finally in a neutralization solution ("Reduction solution･Securigant P" manufactured by Atotech Japan, Sulfuric acid aqueous solution), immersed at 40°C for 5 minutes, and dried at 80°C for 15 minutes. Let this be "roughened substrate A".

(5) Conductor layer formation (5-1) Electroless plating In order to form a conductor layer on the roughened surface of the roughened substrate A, a plating step including the following steps 1 to 6 (a copper plating step using a chemical solution manufactured by Atotech Japan) is performed to form a conductor Floor.

1. Alkaline cleaning (cleaning and charge adjustment of the surface of the insulating layer) The surface of the roughened substrate A was washed at 60°C for 5 minutes using Cleaning Cleaner Securiganth 902 (trade name). 2. Soft etching (cleaning inside the through hole) The surface of the roughened substrate A was treated with a sulfuric acid acid sodium peroxodisulfate aqueous solution at 30°C for 1 minute. 3. Pre-dip (for adjustment of the charge on the surface of the insulating layer given by Pd) The surface of the roughened substrate A was treated with Pre. Dip Neoganth B (trade name) at room temperature for 1 minute. 4. Application of activator (application of Pd to the surface of the insulating layer) The surface of the roughened substrate A was treated at 35°C for 5 minutes using Activator Neoganth 834 (trade name). 5. Reduction (reduction of Pd imparted by the insulating layer) The surface of the roughened substrate A was treated with a mixture of Reducer Neoganth WA (trade name) and Reducer Acceralator 810 mod. (trade name) at 30°C for 5 minutes. 6. Electroless copper plating (precipitating Cu out of the surface of the insulating layer (Pd surface)) Use a mixture of Basic Solution Printganth MSK-DK (trade name), Copper solution Printganth MSK (trade name), Stabilizer Printganth MSK-DK (trade name), and Reducer Cu (trade name) to roughen the substrate A The surface was treated at 35°C for 20 minutes to form an electroless copper plating layer. The thickness of the formed electroless copper plating layer was 0.8 μm.

(5-2) Electrolytic plating Next, using a chemical solution manufactured by Atotech Japan, an electrolytic copper plating step was performed under the condition that copper was filled in the through hole. Then, as a resist pattern for patterning by etching, a land pattern with a diameter of 1 mm that is connected to the lower conductor and a circular conductor pattern with a diameter of 10 mm that is not connected to the lower conductor are used. On the surface of the insulating layer, a conductor layer with a land and a conductor pattern is formed with a thickness of 10 μm. Next, annealing treatment was performed at 200°C for 90 minutes. This board is designated as "evaluation board A".

(6) Evaluation of the insulation reliability of the insulating layer. The 10mm diameter circular conductor side of the evaluation substrate A is set as the + electrode, and the grid circuit conductor (copper) side of the inner circuit board connected to the 1mm diameter land Set as-electrode, use a highly accelerated life test device ("PM422" made by ETAC company, under the conditions of 110°C, 85% relative humidity, and 20V DC voltage applied, the insulation resistance value after 100 hours is measured in the electrochemical migration tester ("ECM-100" manufactured by J-RAS) measurement. This measurement is performed 6 times, and the resistance value of all the test pieces at 6 points is 1.00×10 ⁸ Ω or more as "○", even if it is 1 If it is less than 1.00×10 ⁸ Ω, it is regarded as "×". The evaluation result and insulation resistance value are shown in the following table. The insulation resistance value of the test piece with the insulation resistance value described in Table 1 below is 6 points The lowest value.

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

It is understood that by using a resin composition containing (A) epoxy resin, (B) inorganic filler and (C) polyimide resin, and (A) component contains (A-1) containing silicone The resin composition of the epoxy resin of the skeleton can be obtained (B) When the content of the inorganic filler is 40% by mass or less, even if it is low blended, the viscosity can be suppressed to a low level, and it has excellent flexibility and superiority. The hardened material of insulation reliability.

Claims (19)

A resin composition comprising (A) epoxy resin, (B) inorganic filler and (C) polyimide resin, characterized by: (A) Component contains (A-1) epoxy resin containing silicone skeleton, (B) The content of the component is 40% by mass or less when the non-volatile content in the resin composition is 100% by mass. The resin composition of claim 1, wherein the component (A-1) is an epoxy resin containing a cyclic silicone skeleton. Such as the resin composition of claim 1, wherein the component (A-1) is a compound represented by formula (A1),

[In the formula, R ¹ each independently represents an epoxy alkyl group; R ² each independently represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted aryl group; R ³ and R ⁴ each independently Independently represent substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, or substituted or unsubstituted aryl, or R ³ and R ⁴ become together to show 1 -O- and bond to each other to form a ring Siloxane skeleton; s represents an integer greater than 1]. The resin composition of claim 1, wherein the molecular weight of the component (A-1) is 800 or less. Such as the resin composition of claim 1, wherein the epoxy equivalent of the component (A-1) is 150 g/eq. to 250 g/eq. The resin composition of claim 1, wherein the content of the component (A-1) is 5% by mass or more when the non-volatile content in the resin composition is 100% by mass. The resin composition of claim 1, wherein the content of the component (A-1) is 10% by mass or less when the non-volatile content in the resin composition is 100% by mass. The resin composition of claim 1, wherein the average particle size of the component (B) is 1 μm or less. Such as the resin composition of claim 1, wherein the component (B) is silica. The resin composition of claim 1, wherein the weight average molecular weight of the component (C) is 1,000 or more and 100,000 or less. The resin composition of claim 1, wherein the content of component (C) is 20% by mass or more when the non-volatile content in the resin composition is 100% by mass. The resin composition of claim 1, wherein the content of the component (C) is 30% by mass or less when the non-volatile content in the resin composition is 100% by mass. Such as the resin composition of claim 1, which further contains (D) a hardener. The resin composition of claim 13, wherein the component (D) contains an active ester hardener. The resin composition of claim 1, which is used for forming an insulating layer of a multilayer flexible substrate. A cured product of the resin composition described in any one of claims 1-15. A resin sheet comprising a support and a resin composition layer formed from the resin composition described in any one of claims 1 to 15 provided on the support. A multilayer flexible substrate comprising an insulating layer formed by curing the resin composition described in any one of claims 1-15. A semiconductor device provided with a multilayer flexible substrate as described in claim 18.