JP2020075960A - Resin composition - Google Patents

Abstract

To provide a resin composition capable of providing a cured article having low roughness and high peel strength, and excellent in water resistance and flexibility.SOLUTION: There is provided a resin composition containing (A) an epoxy resin, (B) a curing agent, (C) a fluorine-based organic filler, and (D) a polyimide resin, and having content of the (D) component of 12 mass% or more based on 100 mass% of a nonvolatile component in the resin composition.SELECTED DRAWING: None

Description

  The present invention relates to a resin composition containing an epoxy resin and a curing agent; a cured product of the above resin composition; a resin sheet containing the above resin composition; a multilayer flexible substrate including an insulating layer formed from the above resin composition; The present invention relates to a semiconductor device including a multilayer flexible substrate.

  In recent years, there has been an increasing demand for semiconductor components that are thinner, lighter and have a higher packaging density. In order to meet this demand, attention has been paid to the use of flexible substrates as substrate substrates used for semiconductor components. The flexible substrate can be made thinner and lighter than the rigid substrate. Further, since the flexible substrate is flexible and deformable, it can be bent and mounted.

  The flexible substrate is generally formed by preparing a three-layer film made of a polyimide film, a copper foil and an adhesive, or a two-layer film made of a polyimide film and a conductor layer, and etching the conductor layer according to a subtractive method. Is formed by performing and. Conventionally, a three-layer film is often used because it can be produced relatively inexpensively. However, in a circuit board having high-density wiring, a two-layer film may be used to solve the problems of heat resistance and electrical insulation of the adhesive. However, the two-layer film has problems in cost and productivity. Therefore, in order to solve this problem, Patent Documents 1 to 3 disclose insulating materials for multilayer flexible substrates. Further, Patent Documents 4 and 5 describe a polyimide resin.

JP, 2006-37083, A JP, 2016-41797, A Patent No. 6387181 Japanese Patent No. 6240798 Japanese Patent No. 6240799

  The subject of the present invention includes a resin composition having a low roughness and a high peel strength and capable of obtaining a cured product excellent in water resistance and flexibility; a cured product of the above resin composition; and the above resin composition. It is to provide a resin sheet; a multilayer flexible substrate including an insulating layer formed of the resin composition; and a semiconductor device including the multilayer flexible substrate.

  In order to achieve the object of the present invention, as a result of intensive investigations by the present inventors, (A) an epoxy resin, (B) a curing agent, and (C) a fluorine-based organic filler are contained, and (D) a polyimide resin is included. By using a resin composition containing 12% by mass or more, it was found that a cured product having low roughness and high peel strength and excellent in water resistance and flexibility can be obtained, and the present invention has been completed. ..

That is, the present invention includes the following contents.
[1] A resin composition containing (A) an epoxy resin, (B) a curing agent, (C) a fluorine-based organic filler, and (D) a polyimide resin, wherein the content of the (D) component is a resin composition. The resin composition is 12% by mass or more when the non-volatile component in the product is 100% by mass.
[2] The resin composition according to the above [1], wherein the component (C) is a fluoropolymer particle.
[3] The resin composition according to the above [1] or [2], wherein the content of the component (C) is 10% by mass or more when the nonvolatile component in the resin composition is 100% by mass.
[4] The resin composition according to any one of the above [1] to [3], wherein the content of the component (D) is 40% by mass or less when the nonvolatile component in the resin composition is 100% by mass. object.
[5] The resin composition according to any one of the above [1] to [4], wherein the component (A) contains a fluorine-containing epoxy resin.
[6] The resin composition according to any one of the above [1] to [5], wherein the component (B) is selected from the group consisting of a phenol-based curing agent, a naphthol-based curing agent, and an active ester-based curing agent. ..
[7] Further, the content of the component (E) with or without the inorganic filler (E) is 60% by mass or less when the nonvolatile component in the resin composition is 100% by mass. ] The resin composition in any one of [6].
[8] The resin composition according to any one of the above [1] to [7], which is for forming an insulating layer of a multilayer flexible substrate.
[9] A cured product of the resin composition according to any one of [1] to [8].
[10] A resin sheet including a support and a resin composition layer formed of the resin composition according to any one of the above [1] to [8] provided on the support.
[11] A multilayer flexible substrate including an insulating layer formed by curing the resin composition according to any one of [1] to [8].
[12] A semiconductor device comprising the multilayer flexible substrate according to the above [11].

  According to the present invention, a resin composition having a low roughness and a high peel strength and capable of obtaining a cured product excellent in water resistance and flexibility; a cured product of the above resin composition; and the above resin composition are included. It is possible to provide a resin sheet; a multilayer flexible substrate including an insulating layer formed of the resin composition; and a semiconductor device including the multilayer flexible substrate.

  Hereinafter, the present invention will be described in detail with reference to its preferred embodiments. However, the present invention is not limited to the following embodiments and exemplifications, and may be implemented by being arbitrarily modified within the scope of the claims of the present invention and the scope of equivalents thereof.

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

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

  The resin composition of the present invention may further contain any component in addition to (A) epoxy resin, (B) curing agent, (C) fluorine-based organic filler, and (D) polyimide resin. Examples of the optional components include (E) inorganic filler, (F) curing accelerator, (G) organic solvent, and (H) other additives. 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) an epoxy resin.

  Examples of (A) epoxy resin include bixylenol type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type. Epoxy resin, naphthol novolac type epoxy resin, phenol novolac type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidyl amine type epoxy resin, glycidyl ester type epoxy resin , Cresol novolac type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, epoxy resin having butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring-containing epoxy resin, cyclohexane type epoxy resin, cyclohexane Examples thereof include dimethanol type epoxy resin, naphthylene ether type epoxy resin, trimethylol type epoxy resin, tetraphenylethane type epoxy resin and the like. The epoxy resin may be used alone or in combination of two or more kinds.

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

  The epoxy resin may be a liquid epoxy resin at a temperature of 20 ° C. (hereinafter sometimes referred to as “liquid epoxy resin”) and a solid epoxy resin at a temperature of 20 ° C. (hereinafter referred to as “solid epoxy resin”). ) There is. In one embodiment, the resin composition of the present invention contains a liquid epoxy resin as the epoxy resin. In one embodiment, the resin composition of the present invention contains a solid epoxy resin as the epoxy resin. The resin composition of the present invention may contain only a liquid epoxy resin as an epoxy resin or may contain only a solid epoxy resin, but contains a combination of a liquid epoxy resin and a solid epoxy resin. Preferably.

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

  Examples of the liquid epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, phenol novolac type epoxy resin, and ester skeleton. Preferred are alicyclic epoxy resins, cyclohexane-type epoxy resins, cyclohexanedimethanol-type epoxy resins, glycidylamine-type epoxy resins, and epoxy resins having a butadiene structure.

  Specific examples of the liquid epoxy resin include “HP4032”, “HP4032D” and “HP4032SS” (naphthalene type epoxy resin) manufactured by DIC; “828US”, “828EL”, “jER828EL” and “825” manufactured by Mitsubishi Chemical Corporation. , "Epicoat 828EL" (bisphenol A type epoxy resin); "jER807", "1750" (bisphenol F type epoxy resin) manufactured by Mitsubishi Chemical; "jER152" (phenol novolac type epoxy resin) manufactured by Mitsubishi Chemical; Mitsubishi Chemical's "630", "630LSD" (glycidylamine type epoxy resin); Nippon Steel & Sumikin Chemical's "ZX1059" (mixed product of bisphenol A type epoxy resin and bisphenol F type epoxy resin); Nagase Chemtex "EX-721" (glycidyl ester type epoxy resin) manufactured by Daicel Co., Ltd. "Celoxide 2021P" (cycloaliphatic epoxy resin having an ester skeleton) manufactured by Daicel Co., Ltd. "PB-3600" manufactured by Daicel Co., Ltd., manufactured by Nippon Soda Co., Ltd. “JP-100”, “JP-200” (epoxy resin having a butadiene structure); “ZX1658” and “ZX1658GS” (liquid 1,4-glycidylcyclohexane type epoxy resin) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. and the like. These may be used alone or in combination of two or more.

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

  As the solid epoxy resin, bixylenol type epoxy resin, naphthalene type epoxy resin, naphthalene type tetrafunctional epoxy resin, cresol novolac type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, naphthol type epoxy resin, biphenyl Type epoxy resin, naphthylene ether type epoxy resin, anthracene type epoxy resin, bisphenol A type epoxy resin, bisphenol AF type epoxy resin, and tetraphenylethane type epoxy resin are preferable.

  Specific examples of the solid epoxy resin include "HP4032H" (naphthalene type epoxy resin) manufactured by DIC; "HP-4700" and "HP-4710" (naphthalene type tetrafunctional epoxy resin) manufactured by DIC; DIC "N-690" (cresol novolac type epoxy resin) manufactured by DIC; "N-695" (cresol novolac type epoxy resin) manufactured by DIC; "HP-7200" (dicyclopentadiene type epoxy resin) manufactured by DIC; DIC "HP-7200HH", "HP-7200H", "EXA-7331", "EXA-7331-G3", "EXA-7331-G4", "EXA-7331-G4S", "HP6000" ( Naphthylene ether type epoxy resin); Nippon Kayaku Co., Ltd. "EPPN-502H" (trisphenol type epoxy resin); Nippon Kayaku Co., Ltd. "NC7000L" (naphthol novolac type epoxy resin); Nippon Kayaku Co., Ltd. "NC3000H", "NC3000", "NC3000L", "NC3100" (biphenyl type epoxy resin); "ESN475V" (Napthol type epoxy resin) made by Nippon Steel & Sumikin Chemical; "ESN485" (Naphthol novolak) made by Nippon Steel & Sumitomo Chemical Type epoxy resin); "YX4000H", "YX4000", and "YL6121" (biphenyl type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd .; "YX4000HK" (bixylenol type epoxy resin) manufactured by Mitsubishi Chemical Co .; YX8800 "(anthracene type epoxy resin); Mitsubishi Chemical" YX7700 "(xylene structure-containing novolac type epoxy resin); Osaka Gas Chemicals" PG-100 "," CG-500 "; Mitsubishi Chemical "YL7760" (bisphenol AF type epoxy resin); "YL7800" (fluorene type epoxy resin) manufactured by Mitsubishi Chemical; "jER1010" (solid bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical; "Made by Mitsubishi Chemical" jER1031S ”(tetraphenylethane type epoxy resin) and the like. These may be used alone or in combination of two or more.

  When a liquid epoxy resin and a solid epoxy resin are used in combination as the (A) epoxy resin, the quantity ratio thereof (liquid epoxy resin: solid epoxy resin) is preferably 1: 1 to 1:50 by mass ratio. , More preferably 1: 3 to 1:30, and particularly preferably 1: 5 to 1:20. When the amount ratio of the liquid epoxy resin and the solid epoxy resin is within such a range, the desired effect of the present invention can be remarkably obtained.

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

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

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

  Examples of preferable fluorine-containing epoxy resin include bisphenol AF type epoxy resin represented by the following formula (A).

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

  Among the bisphenol AF type epoxy resins represented by the formula (A), 4,4 ′-[2,2,2-trifluoro-1- (trifluoromethyl) ethylidene] bisphenol type epoxy is used as the fluorine-based epoxy resin. Resins are particularly preferred. With such a preferable fluorine-based epoxy resin, the desired effects of the present invention can be remarkably obtained.

  Specific examples of the fluorine-containing epoxy resin include "YL7760" (bisphenol AF type epoxy resin) manufactured by Mitsubishi Chemical Corporation. The fluorine-containing epoxy resin may be used alone or in combination of two or more.

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

  The epoxy equivalent of the epoxy resin is preferably 50 g / eq. ~ 5000 g / eq. , And more preferably 50 g / eq. ~ 3000 g / eq. , And more preferably 80 g / eq. ~ 2000 g / eq. , And even more preferably 110 g / eq. ~ 1000 g / eq. Is. Within this range, the crosslinked density of the cured product of the resin sheet becomes sufficient, and an insulating layer having a small surface roughness can be provided. Epoxy equivalent is the mass of resin containing 1 equivalent of epoxy groups. This epoxy equivalent can be measured according to JIS K7236.

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

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

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

  In the present specification, the "resin component" means all the components remaining after removing the inorganic filler from the resin composition. Therefore, the "resin component" may include a low molecular weight compound.

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

  The (B) curing agent is not particularly limited as long as it has a function of curing an epoxy resin, and examples thereof include a phenol curing agent, a naphthol curing agent, an acid anhydride curing agent, an active ester curing agent, and a benzoxazine curing agent. Examples include a curing agent, a cyanate ester-based curing agent, and a carbodiimide-based curing agent. The curing agents may be used alone or in combination of two or more. The (B) curing agent of the resin composition of the present invention is selected from the group consisting of a phenol-based curing agent, a naphthol-based curing agent, and an active ester-based curing agent from the viewpoint of remarkably obtaining the desired effect of the present invention. Those are preferable.

  As the phenol-based curing agent and the naphthol-based curing agent, a phenol-based curing agent having a novolac structure or a naphthol-based curing agent having a novolac structure is preferable from the viewpoint of heat resistance and water resistance. From the viewpoint of adhesion to the adherend, a nitrogen-containing phenol-based curing agent or a nitrogen-containing naphthol-based curing agent is preferable, and a triazine skeleton-containing phenolic curing agent or a triazine skeleton-containing naphthol-based curing agent is more preferable. Among them, the triazine skeleton-containing phenol novolac resin is preferable from the viewpoint of highly satisfying heat resistance, water resistance, and adhesion. Specific examples of the phenol-based curing agent and the naphthol-based curing agent include, for example, "MEH-7700", "MEH-7810", "MEH-7851" manufactured by Meiwa Kasei Co., Ltd., "NHN" manufactured by Nippon Kayaku Co., Ltd., "CBN", "GPH", "SN-170", "SN-180", "SN-190", "SN-475", "SN-485", "SN-495" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. "SN-375", "SN-395", "LA-7052", "LA-7054", "LA-3018", "LA-3018-50P", "LA-1356", "TD2090" manufactured by DIC. , "TD-2090-60M" and the like.

  Examples of the acid anhydride-based curing agent include a curing agent having one or more acid anhydride groups in one molecule. Specific examples of the acid anhydride-based curing agent include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic acid anhydride and hydrogenated methylnadic acid. Anhydride, trialkyltetrahydrophthalic anhydride, dodecenyl succinic anhydride, 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trianhydride Mellitic acid, pyromellitic dianhydride, benzophenonetetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, naphthalenetetracarboxylic dianhydride, oxydiphthalic dianhydride, 3,3'-4,4'- Diphenyl sulfone tetracarboxylic dianhydride, 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-C] furan-1 , 3-dione, ethylene glycol bis (anhydrotrimellitate), and polymer type acid anhydrides such as a styrene-maleic acid resin in which styrene and maleic acid are copolymerized. Examples of commercially available acid anhydride curing agents include "HNA-100" and "MH-700" manufactured by Shin Nippon Rika Co., Ltd.

  The active ester-based curing agent is not particularly limited, but in general, an ester group having a high reaction activity such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds is contained in one molecule. Compounds having two or more of them are preferably used. The active ester type curing agent is preferably obtained by a condensation reaction of a carboxylic acid compound and / or a thiocarboxylic acid compound with a hydroxy compound and / or a thiol compound. Particularly, from the viewpoint of improving heat resistance, an active ester type curing agent obtained from a carboxylic acid compound and a hydroxy compound is preferable, and an active ester type curing agent obtained from a carboxylic acid compound and a phenol compound and / or a naphthol compound is more preferable. 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 the phenol compound or naphthol compound include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthaline, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m- Cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, Examples thereof include benzenetriol, dicyclopentadiene type diphenol compound, and phenol novolac. Here, the "dicyclopentadiene type diphenol compound" means a diphenol compound obtained by condensing one molecule of dicyclopentadiene with two molecules of phenol.

  Specifically, an active ester compound containing a dicyclopentadiene type diphenol structure, an active ester compound containing a naphthalene structure, an active ester compound containing an acetylated product of phenol novolac, and an active ester compound containing a benzoylated product of phenol novolac are preferable. Of these, an active ester compound containing a naphthalene structure and an active ester compound containing a dicyclopentadiene type diphenol structure are more preferable. The “dicyclopentadiene type diphenol structure” represents a divalent structural unit composed of phenylene-dicyclopentalene-phenylene.

  Commercially available active ester curing agents include "EXB9451", "EXB9460", "EXB9460S", "HPC-8000", "HPC-8000H", and "EXB9451", "EXB9460", "HPC-8000H", and "HPC-8000H" as "active ester compounds containing dicyclopentadiene type diphenol structure" HPC-8000-65T "," HPC-8000H-65TM "," EXB-8000L "," EXB-8000L-65TM "(manufactured by DIC);" EXB9416-70BK "," EXB "as active ester compounds containing a naphthalene structure. -8150-65T "(manufactured by DIC);" DC808 "as an active ester compound containing an acetylated product of phenol novolac (manufactured by Mitsubishi Chemical Co.);" YLH1026 "as an active ester compound containing a benzoylated product of phenol novolak (Mitsubishi Chemical Co.) "DC808" (manufactured by Mitsubishi Chemical Corporation) as an active ester type curing agent which is an acetylated product of phenol novolac; "YLH1026" (manufactured by Mitsubishi Chemical Company) as an activated ester type curing agent which is a benzoylated product of phenol novolac. "YLH1030" (manufactured by Mitsubishi Chemical Co.), "YLH1048" (manufactured by Mitsubishi Chemical Co.); and the like.

  Specific examples of the benzoxazine-based curing agent include "JBZ-OP100D" and "ODA-BOZ" manufactured by JFE Chemical Co., Ltd., "HFB2006M" manufactured by Showa High Polymer Co., Ltd., and "Pd" manufactured by Shikoku Chemicals Co., Ltd., "F-a" etc. are mentioned.

  Examples of the cyanate ester-based curing agent include bisphenol A dicyanate, polyphenol cyanate (oligo (3-methylene-1,5-phenylene cyanate)), 4,4′-methylenebis (2,6-dimethylphenyl cyanate), 4, 4'-ethylidene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis (4-cyanate) phenyl propane, 1,1-bis (4-cyanate phenylmethane), bis (4-cyanate-3,5- Difunctional cyanate resins such as dimethylphenyl) methane, 1,3-bis (4-cyanatephenyl-1- (methylethylidene)) benzene, bis (4-cyanatephenyl) thioether, and bis (4-cyanatephenyl) ether. Examples thereof include polyfunctional cyanate resins derived from phenol novolac, cresol novolac, and the like, and prepolymers obtained by partially converting these cyanate resins into triazine. Specific examples of the cyanate ester-based curing agent include "PT30" and "PT60" (all are phenol novolac type polyfunctional cyanate ester resins) manufactured by Lonza Japan Co., Ltd., "BA230", "BA230S75" (part of bisphenol A dicyanate). Alternatively, a prepolymer in which all are triazined to form a trimer) and the like can be mentioned.

  Specific examples of the carbodiimide-based curing agent include "V-03" and "V-07" manufactured by Nisshinbo Chemical Inc.

  When the curing agent is included, the amount ratio of the epoxy resin and the curing agent is 1: 0.2 to 1: in the ratio of [total number of epoxy groups of epoxy resin]: [total number of reactive groups of curing agent]. The range of 2 is preferable, 1: 0.3 to 1: 1.5 is more preferable, and 1: 0.4 to 1: 1.2 is further preferable. Here, the reactive group of the curing agent is an active hydroxyl group, an active ester group or the like, and varies depending on the type of the curing agent. Further, the total number of epoxy groups of the epoxy resin is a value obtained by summing the value obtained by dividing the non-volatile component mass of each epoxy resin by the epoxy equivalent for all epoxy resins, and the total number of reactive groups of the curing agent is It is a value obtained by summing the values obtained by dividing the mass of the non-volatile components of each curing agent by the reaction group equivalent for all the curing agents. By setting the amount ratio of the epoxy resin and the curing agent within such a range, the heat resistance of the obtained cured product is further improved.

  When the content of the nonvolatile component in the resin composition is 100% by mass, the content of the (B) curing agent is not particularly limited, but is preferably 0 from the viewpoint of remarkably obtaining the desired effect of the present invention. 0.1 mass% or more, more preferably 1 mass% or more, further preferably 3 mass% or more, particularly preferably 5 mass% or more. The upper limit is preferably 30% by mass or less, more preferably 20% by mass or less, further preferably 15% by mass or less, and particularly preferably 8% by mass or less, from the viewpoint of remarkably obtaining the desired effect of the present invention.

  When the resin component in the resin composition is 100% by mass, the content of the (B) curing agent is not particularly limited, but is preferably 0 from the viewpoint of remarkably obtaining the desired effect of the present invention. 0.1 mass% or more, more preferably 1 mass% or more, further preferably 3 mass% or more, particularly preferably 5 mass% or more. The upper limit is preferably 30% by mass or less, more preferably 20% by mass or less, further preferably 15% by mass or less, and particularly preferably 9% by mass or less from the viewpoint of remarkably obtaining the desired effect of the present invention.

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

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

  Examples of the material of the fluorine-based organic filler (C) include fluorine-based polymers and fluorine-based rubbers. Of these, fluoropolymers are preferable. Therefore, as the (C) fluorine-based organic filler, fluorine-based polymer particles are preferable.

  Examples of the fluorine-based polymer include polytetrafluoroethylene (PTFE), perfluoroalkoxyalkane (PFA), perfluoroethylenepropene copolymer (FEP), ethylene / tetrafluoroethylene copolymer (ETFE), and tetrafluoroethylene-perfluorodio. Examples include xol copolymer (TFE / PDD), polyvinylidene fluoride (PVDF), polychlorotrifluoroethylene (PCTFE), ethylene-chlorotrifluoroethylene copolymer (ECTFE), polyvinyl fluoride (PVF). These may be used alone or in combination of two or more.

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

  The weight average molecular weight of the fluoropolymer is preferably 5,000,000 or less, more preferably 4,000,000 or less, and particularly preferably 3,000,000 or less, from the viewpoint of remarkably obtaining the desired effect of the present invention. Is.

  The average particle size of the (C) fluorine-based organic filler is preferably 0.05 μm or more, more preferably 0.08 μm or more, particularly preferably 0.10 μm or more, preferably 10 μm or less, more preferably 5 μm or less, Particularly preferably, it is 4 μm or less. When the average particle diameter of the (C) fluorine-based organic filler is within the above range, the desired effect of the present invention can be remarkably obtained. The average particle size of the (C) fluorine-based organic filler can be measured by a laser diffraction / scattering method based on the Mie scattering theory as in the case of the (E) inorganic filler described below.

  (C) Examples of commercially available fluorine-based organic fillers include, for example, "LUBRON L-2", "LUBRON L-5", and "LUBRON L-5F" manufactured by Daikin Industries Ltd .; "FluonPTFE L-" manufactured by Asahi Glass Co., Ltd. 170JE "," FluonPTFE-172JE "," FluonPTFE L-173JE ";" KTL-500F "," KTL-2N "," KTL-1N "manufactured by Kitamura Co .;" TLP10F-1 "manufactured by Mitsui-Kemers Fluoro Products Co., Ltd. ]; And the like.

  The (C) fluorine-based organic filler may be surface-treated. For example, the (C) fluorine-based organic filler may be surface-treated with an arbitrary surface-treating agent. Examples of the surface treatment agent include surfactants such as nonionic surfactants, amphoteric surfactants, cationic surfactants and anionic surfactants; inorganic fine particles; From the viewpoint of affinity, it is preferable to use a fluorine-based surfactant as the surface treatment agent. Specific examples of the fluorine-based surfactant include "Surflon S-243" (perfluoroalkyl ethylene oxide adduct) manufactured by AGC Seimi Chemical Co .; "MegaFac F-251" and "MegaFac F-" manufactured by DIC. "477", "Megafuck F-553", "Megafuck R-40", "Megafuck R-43", "Megafuck R-94"; "FTX-218" and "Futtergent 610FM" manufactured by Neos. ; Are mentioned.

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

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

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

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

  Examples of the aliphatic diamine compound include 1,2-ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, 1,6-hexamethylenediamine, 1,5-diaminopentane. , Linear aliphatic diamine compounds such as 1,10-diaminodecane; 1,2-diamino-2-methylpropane, 2,3-diamino-2,3-butane, and 2-methyl-1,5- Branched-chain aliphatic diamine compounds such as diaminopentane; 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, 1,4-diaminocyclohexane, 4,4′-methylenebis (cyclohexyl) Examples thereof include alicyclic diamine compounds such as amines; dimer acid type diamines (hereinafter, also referred to as “dimer diamines”) and the like, and among them, dimer acid type diamines are preferable.

The dimer acid type diamine, the two terminal carboxylic acid groups of dimer acid (-COOH) is a diamine compound obtained is substituted into aminomethyl group _{(-CH 2} -NH 2) or an amino group (-NH ₂₎ means. Dimer acid is a known compound obtained by dimerizing an unsaturated fatty acid (preferably having a carbon number of 11 to 22, particularly preferably having a carbon number of 18), and its industrial production process is almost the same in the industry. It is standardized. As the dimer acid, one mainly containing dimer acid having a carbon number of 36, which is obtained by dimerizing an unsaturated fatty acid having a carbon number of 18 such as oleic acid and linoleic acid, which are inexpensive and easily available, can be easily obtained. Further, the dimer acid may contain an arbitrary amount of monomer acid, trimer acid, other polymerized fatty acid or the like depending on the production method, the degree of purification and the like. Further, although a double bond remains after the polymerization reaction of unsaturated fatty acid, in the present specification, a dimer acid also includes a hydrogenated product which is further hydrogenated to reduce the degree of unsaturation. The dimer acid type diamine is commercially available, and examples thereof include PRIAMINE 1073, PRIAMINE 1074, PRIAMINE 1075 manufactured by Croda Japan Co., Ltd., Versamine 551 and Versamine 552 manufactured by Cognis Japan.

  Examples of the aromatic diamine compound include a phenylenediamine compound, a naphthalenediamine compound, a dianiline compound, and the like.

  The phenylenediamine compound means a compound composed of a benzene ring having two amino groups, and the benzene ring here may optionally have 1 to 3 substituents. The substituent here is not particularly limited. Specific examples of the phenylenediamine compound include 1,4-phenylenediamine, 1,2-phenylenediamine, 1,3-phenylenediamine, 2,4-diaminotoluene, 2,6-diaminotoluene and 3,5-diamino. Examples thereof include biphenyl and 2,4,5,6-tetrafluoro-1,3-phenylenediamine.

  The naphthalenediamine compound means a compound composed of a naphthalene ring having two amino groups, and the naphthalene ring here may optionally have 1 to 3 substituents. The substituent here is not particularly limited. Specific examples of the naphthalenediamine compound include 1,5-diaminonaphthalene, 1,8-diaminonaphthalene, 2,6-diaminonaphthalene, and 2,3-diaminonaphthalene.

  The dianiline compound means a compound containing two aniline structures in the molecule, and each of the two benzene rings in each of the two aniline structures further has 1 to 3 substituents. You can The substituent here is not particularly limited. The two aniline structures in the dianiline compound are directly bonded and / or bonded via one or two linker structures having 1 to 100 skeletal atoms selected from carbon atom, oxygen atom, sulfur atom and nitrogen atom. You can The dianiline compound also includes a compound in which two aniline structures are bound by two bonds.

The "linker structure" in dianiline compounds, specifically, -NHCO -, - CONH -, - OCO -, - COO -, - CH 2 -, - CH 2 CH 2 -, - CH 2 CH 2 CH 2 - _{, -CH 2 CH 2 CH 2 CH} 2 -, - CH 2 CH 2 CH 2 CH 2 CH 2 -, - CH (CH 3) -, - C (CH 3) 2 -, - C (CF 3) 2 - _{, -CH = CH -, - O} -, - S -, - CO -, - SO 2 -, - NH -, - Ph -, - Ph-Ph -, - C (CH 3) 2 -Ph-C ( _{CH 3) 2 -, - O} -Ph-O -, - O-Ph-Ph-O -, - O-Ph-SO 2 -Ph-O -, - O-Ph-C (CH 3) 2 -Ph _{-O -, - C (CH 3} ) 2 -Ph-C (CH 3) 2 -,

Etc. In the present specification, "Ph" represents a 1,4-phenylene group, a 1,3-phenylene group or a 1,2-phenylene group.

  In one embodiment, specific examples of the dianiline compound include 4,4′-diamino-2,2′-ditrifluoromethyl-1,1′-biphenyl, 3,4′-diaminodiphenyl ether, 4,4′- Diaminodiphenyl ether, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfide, 4-aminophenyl 4-aminobenzoate, 1,3-bis (3-aminophenoxy) Benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 2,2-bis (4-aminophenyl) propane, 4,4 ′-(hexafluoroisopropyl) Ridene) dianiline, 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) Dianiline, 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) fluorene, 5- (4 -Aminophenoxy) -3- [4- (4-aminophenoxy) phenyl] -1,1,3-trimethylindane and the like, and preferably 5- (4-aminophenoxy) -3- [4- ( 4-aminophenoxy) phenyl] -1,1,3-trimethylindane.

In another embodiment, the dianiline compound includes, for example:
Formula (1) below:

[In the formula,
R ^{1 to} R ⁸ each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, -X ⁹ -R ⁹ or -X ¹⁰ -R ¹⁰ .
At least one of R ^{1 to} R ⁸ is —X ¹⁰ —R ¹⁰ ,
X ⁹ are each independently a single ^{bond, -NR 9 '-, - O} -, - S -, - CO -, - SO 2 -, - NR 9' CO -, - CONR 9 '-, - OCO -Or -COO- is shown,
R ^9's each independently represent a substituted or unsubstituted alkyl group, or a substituted or unsubstituted alkenyl group,
R ^{9 ′} each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted alkenyl group,
X ¹⁰ are each independently a single bond, - (substituted or unsubstituted alkylene group) -, - NH -, - O -, - S -, - CO -, - SO 2 -, - NHCO -, - Represents CONH-, -OCO-, or -COO-,
R ^10's each independently represent a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group. ]
And a diamine compound represented by the following.

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

  In the present specification, the “alkyl group” refers to a linear, branched or cyclic monovalent aliphatic saturated hydrocarbon group. An alkyl group having 1 to 6 carbon atoms is preferable, and an alkyl group having 1 to 3 carbon atoms is more preferable. Examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, an isopentyl group, a neopentyl group, a cyclopentyl group and a cyclohexyl group. The substituent of the alkyl group in the “substituted or unsubstituted alkyl group” is not particularly limited, but for example, a halogen atom, a cyano group, an alkoxy group, an amino group, a nitro group, a hydroxy group, a carboxy group, Examples thereof include a sulfo group. The number of substituents is preferably 1 to 3, and more preferably 1.

  In the present specification, the “alkoxy group” refers to a monovalent group (alkyl-O—) formed by binding an alkyl group to an oxygen atom. An alkoxy group having 1 to 6 carbon atoms is preferable, and an alkoxy group having 1 to 3 carbon atoms is more preferable. Examples thereof include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, a sec-butoxy group, a tert-butoxy group and a pentyloxy group.

  In the present specification, the “alkenyl group” refers to a linear, branched or cyclic monovalent unsaturated hydrocarbon group having at least one carbon-carbon double bond. An alkenyl group having 2 to 6 carbon atoms is preferable, and an alkenyl group having 2 or 3 carbon atoms is more preferable. For example, vinyl group, 1-propenyl group, 2-propenyl group, 2-methyl-1-propenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 3-methyl-2-butenyl group, 1- Pentenyl group, 2-pentenyl group, 3-pentenyl group, 4-pentenyl group, 4-methyl-3-pentenyl group, 1-hexenyl group, 3-hexenyl group, 5-hexenyl group, 2-cyclohexenyl group and the like. Be done. The substituent of the alkenyl group in the "substituted or unsubstituted alkenyl group" is not particularly limited, and examples thereof include a halogen atom, a cyano group, an alkoxy group, an aryl group, a heteroaryl group, an amino group and a nitro group. , A hydroxy group, a carboxy group, a sulfo group and the like. The number of substituents is preferably 1 to 3, and more preferably 1.

In the present specification, the “alkylene group” refers to a linear, branched or cyclic divalent saturated aliphatic hydrocarbon group. An alkylene group having 1 to 6 carbon atoms is preferable, and an alkylene group having 1 to 3 carbon atoms is more preferable. For _{example, -CH 2 -, - CH 2} -CH 2 -, - CH (CH 3) -, - CH 2 -CH 2 -CH 2 -, - CH 2 -CH (CH 3) -, - CH (CH 3 _{) -CH 2 -, - C (} CH 3) 2 -, - CH 2 -CH 2 -CH 2 -CH 2 -, - CH 2 -CH 2 -CH (CH 3) -, - CH 2 -CH (CH _{3) -CH 2 -, - CH} (CH 3) -CH 2 -CH 2 -, - CH 2 -C (CH 3) 2 -, - C (CH 3) 2 -CH 2 - and the like. The substituent of the alkylene group in the "substituted or unsubstituted alkylene group" is not particularly limited, and examples thereof include a halogen atom, a cyano group, an alkoxy group, an aryl group, a heteroaryl group, an amino group, and a nitro group. , A hydroxy group, a carboxy group, a sulfo group and the like. The number of substituents is preferably 1 to 3, and more preferably 1.

  In the present specification, the “aryl group” refers to a monovalent aromatic hydrocarbon group. An aryl group having 6 to 14 carbon atoms is preferable, and an aryl group having 6 to 10 carbon atoms is more preferable. Examples thereof include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, and the like, and a phenyl group is preferable. The substituent of the aryl group in the “substituted or unsubstituted aryl group” is not particularly limited, and examples thereof include a halogen atom, a cyano group, an alkyl group, an alkoxy group, an aryl group, a heteroaryl group, and an amino group. , Nitro group, hydroxy group, carboxy group, sulfo group and the like. The number of substituents is preferably 1 to 3, and more preferably 1.

  In the present specification, the “heteroaryl group” refers to an aromatic heterocyclic group having 1 to 4 heteroatoms selected from oxygen atom, nitrogen atom and sulfur atom. A 5- to 12-membered (preferably 5- or 6-membered) monocyclic, bicyclic or tricyclic (preferably monocyclic) aromatic heterocyclic group is preferred. For example, furyl group, thienyl group, pyrrolyl group, oxazolyl group, isoxazolyl group, thiazolyl group, isothiazolyl group, imidazolyl group, pyrazolyl group, 1,2,3-oxadiazolyl group, 1,2,4-oxadiazolyl group, 1,3 , 4-oxadiazolyl group, flazanyl group, 1,2,3-thiadiazolyl group, 1,2,4-thiadiazolyl group, 1,3,4-thiadiazolyl group, 1,2,3-triazolyl group, 1,2,4 -Triazolyl group, tetrazolyl group, pyridyl group, pyridazinyl group, pyrimidinyl group, pyrazinyl group, triazinyl group and the like. The substituent of the heteroaryl group in the "substituted or unsubstituted heteroaryl group" is not particularly limited, but for example, a halogen atom, a cyano group, an alkyl group, an alkoxy group, an aryl group, a heteroaryl group, Examples thereof include an amino group, a nitro group, a hydroxy group, a carboxy group and a sulfo group. The number of substituents is preferably 1 to 3, and more preferably 1.

R ¹ to R ⁸ each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, ^-X 9 -R ^9, or ^-X 10 ^{-R 10.} R ^{1 to} R ⁸ are preferably each independently a hydrogen atom or —X ¹⁰ —R ¹⁰ .

At least one of R ^{1 to} R ⁸ is —X ¹⁰ —R ¹⁰ . Preferably, one or two of R ^{1 to} R ⁸ are -X ¹⁰ -R ¹⁰ , and more preferably one or two of R ^{5 to} R ⁸ are -X ¹⁰ -R ¹⁰ , and Preferably, one or two of R ⁵ and R ⁷ are -X ¹⁰ -R ¹⁰ .

In one embodiment, preferably one or two of R ^{1 to} R ⁸ are -X ¹⁰ -R ¹⁰ and the other of R ^{1 to} R ⁸ is a hydrogen atom, and more preferably R ⁵ one or two of to R ⁸ is a ^-X 10 ^{-R 10,} and among the ^R 1 to R ⁸ other is hydrogen atom, more preferably, one or two of ^{R 5} and ^{R 7} one is a ^-X 10 ^{-R 10,} and among the ^R 1 to R ⁸ other is hydrogen atom.

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

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

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

R ^10's each independently represent a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group. R ¹⁰ is preferably a substituted or unsubstituted aryl group.

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

[In the formula, R ^{1 to} R ⁶ and R ⁸ each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, or —X ⁹ —R ⁹ , and other symbols are the same as those in the formula (1). Is. ]
And more preferably a compound represented by the following formula (1 ″):

Is a compound represented by (5-amino-1,1'-biphenyl-2-yl 4-aminobenzoate).

  As the diamine compound, a commercially available one may be used, or one synthesized by a known method may be used. For example, the diamine compound represented by the formula (1) can be synthesized by the synthesis method described in Japanese Patent No. 6240798 or a method analogous thereto. The diamine compounds may be used alone or in combination of two or more.

  The acid anhydride for preparing the (D) polyimide resin is not particularly limited, but in a preferred embodiment, it is an aromatic tetracarboxylic dianhydride. Examples of the aromatic tetracarboxylic dianhydride, for example, benzenetetracarboxylic dianhydride, naphthalenetetracarboxylic dianhydride, anthracene tetracarboxylic dianhydride, diphthalic dianhydride, and the like, preferably, It is diphthalic dianhydride.

The benzenetetracarboxylic dianhydride means a benzene dianhydride having four carboxy groups, and further, the benzene ring here may optionally have 1 to 3 substituents. Here, as the substituent, a halogen atom, a cyano group, and ^-X 13 ^{-R 13} those selected from (as defined by the following formula (2)) are preferred. Specific examples of the benzenetetracarboxylic dianhydride include pyromellitic dianhydride and 1,2,3,4-benzenetetracarboxylic dianhydride.

The naphthalene tetracarboxylic acid dianhydride means a naphthalene dianhydride having four carboxy groups, and further, the naphthalene ring here may optionally have 1 to 3 substituents. Here, as the substituent, a halogen atom, a cyano group, and ^-X 13 ^{-R 13} those selected from (as defined by the following formula (2)) are preferred. Specific examples of the naphthalenetetracarboxylic dianhydride include 1,4,5,8-naphthalenetetracarboxylic dianhydride and 2,3,6,7-naphthalenetetracarboxylic dianhydride.

Anthracene tetracarboxylic acid dianhydride means an anthracene dianhydride having 4 carboxy groups, and further, the anthracene ring herein may optionally have 1 to 3 substituents. Here, as the substituent, a halogen atom, a cyano group, and ^-X 13 ^{-R 13} those selected from (as defined by the following formula (2)) are preferred. Specific examples of the anthracene tetracarboxylic dianhydride include 2,3,6,7-anthracene tetracarboxylic dianhydride.

Diphthalic dianhydride means a compound containing two phthalic anhydrides in the molecule, and two benzene rings in two phthalic anhydrides are each optionally 1 to 3 benzene rings. It may have a substituent. Here, as the substituent, a halogen atom, a cyano group, and ^-X 13 ^{-R 13} those selected from (as defined by the following formula (2)) are preferred. The two phthalic anhydrides in the diphthalic dianhydride may be bonded directly or via a linker structure having 1 to 100 skeletal atoms selected from carbon atom, oxygen atom, sulfur atom and nitrogen atom.

  Examples of the diphthalic dianhydride include those represented by the formula (2):

[In the formula,
R ¹¹ and R ¹² each independently represent a halogen atom, a cyano group, a nitro group, or —X ¹³ —R ¹³ .
X ¹³ are each independently a single ^{bond, -NR 13 '-, - O} -, - S -, - CO -, - SO 2 -, - NR 13' CO -, - CONR 13 '-, - OCO -Or -COO- is shown,
R ^13's each independently represent a substituted or unsubstituted alkyl group, or a substituted or unsubstituted alkenyl group,
R ^{13 ′} each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted alkenyl group,
Y represents a single bond or a linker structure having 1 to 100 skeleton atoms selected from carbon atom, oxygen atom, sulfur atom and nitrogen atom,
n and m each independently represent an integer of 0 to 3. ]
The compound represented by

  Y is preferably a linker structure having 1 to 100 skeleton atoms selected from carbon atom, oxygen atom, sulfur atom and nitrogen atom. n and m are preferably 0.

The “linker structure” in Y has 1 to 100 skeleton atoms selected from carbon atom, oxygen atom, sulfur atom and nitrogen atom. The "linker structure" is preferably-[A-Ph] _a -A- [Ph-A] _b- [In the formula, A is independently a single bond,-(substituted or unsubstituted alkylene group. ) -, - O -, - S -, - CO -, - SO 2 -, - CONH -, - NHCO -, - COO-, or -OCO- indicates, a and b are each independently 0 It shows the integer (preferably 0 or 1) of -2. ] It is a divalent group represented by.

"Linker structure" in Y, _{specifically, -CH 2 -, - CH 2} CH 2 -, - CH 2 CH 2 CH 2 -, - CH 2 CH 2 CH 2 CH 2 -, - CH 2 CH 2 CH _{2 CH 2 CH 2 -, -} CH (CH 3) -, - C (CH 3) 2 -, - O -, - CO -, - SO 2 -, - Ph -, - O-Ph-O -, - _{O-Ph-SO 2 -Ph-} O -, - O-Ph-C (CH 3) 2 -Ph-O- , and the like.

  Specific examples of the diphthalic dianhydride include 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride, and 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride. 3 ', 4,4'-diphenylsulfone tetracarboxylic dianhydride, 3,3', 4,4'-biphenyltetracarboxylic dianhydride, 2,2 ', 3,3'-biphenyltetracarboxylic dianhydride Anhydride, 2,3,3 ', 4'-biphenyltetracarboxylic dianhydride, 2,3,3', 4'-benzophenone tetracarboxylic dianhydride, 2,3,3 ', 4'-diphenyl ether Tetracarboxylic acid dianhydride, 2,3,3 ′, 4′-diphenylsulfone Tetracarboxylic acid dianhydride 2,2′-bis (3,4-dicarboxyphenoxyphenyl) sulfone dianhydride, methylene-4 4'-diphthalic acid dianhydride, 1,1-ethynylidene-4,4'-diphthalic acid dianhydride, 2,2-propylidene-4,4'-diphthalic acid dianhydride, 1,2-ethylene-4 , 4'-diphthalic acid dianhydride, 1,3-trimethylene-4,4'-diphthalic acid dianhydride, 1,4-tetramethylene-4,4'-diphthalic acid dianhydride, 1,5-penta Methylene-4,4′-diphthalic dianhydride, 1,3-bis (3,4-dicarboxyphenyl) benzene dianhydride, 1,4-bis (3,4-dicarboxyphenyl) benzene dianhydride 1,3-bis (3,4-dicarboxyphenoxy) benzene dianhydride, 1,4-bis (3,4-dicarboxyphenoxy) benzene dianhydride, 2,2-bis (2,3-di) Carboxyphenyl) propane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 4,4 ′-(4,4′-isopropylidenediphenoxy) bisphthalic acid dianhydride, etc. Can be mentioned.

  As the aromatic tetracarboxylic dianhydride, a commercially available one may be used, or one synthesized by a known method or a method analogous thereto may be used. The aromatic tetracarboxylic dianhydrides may be used alone or in combination of two or more.

  In one embodiment, the acid anhydride for producing the (D) polyimide resin may contain other acid anhydride in addition to the aromatic tetracarboxylic dianhydride.

  Specific examples of other acid anhydrides include 1,2,3,4-cyclobutanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, and cyclohexane-1,2,3,4-tetracarboxylic acid. Dianhydride, 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) Aliphatic tetracarboxylic acid dianhydrides such as dianhydride and sulfonyl-4,4′-bis (cyclohexane-1,2-dicarboxylic acid) dianhydride can be mentioned.

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

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

  The (D) polyimide resin can be prepared by a conventionally known method. Known methods include, for example, a method in which a mixture of a diamine compound, an acid anhydride, and a solvent is heated and reacted. The amount of the diamine compound mixed can be, for example, usually 0.5 to 1.5 molar equivalents, preferably 0.9 to 1.1 molar equivalents, relative to the acid anhydride.

  As the solvent used for preparing the component (D), amide solvents such as N, N-dimethylacetamide, N, N-diethylacetamide, N, N-dimethylformamide, N-methyl-2-pyrrolidone; acetone, methyl ethyl ketone Examples include ketone solvents such as (MEK) and cyclohexanone; ester solvents such as γ-butyrolactone; and hydrocarbon solvents such as cyclohexane and methylcyclohexane. Moreover, you may use an imidization catalyst, an azeotropic dehydration solvent, an acid catalyst etc. for preparation of (D) component as needed. Examples of the imidization catalyst include tertiary amines such as triethylamine, triisopropylamine, triethylenediamine, N-methylpyrrolidine, N-ethylpyrrolidine, N, N-dimethyl-4-aminopyridine and pyridine. Examples of the azeotropic dehydration solvent include toluene, xylene, ethylcyclohexane and the like. Examples of the acid catalyst include acetic anhydride and the like. Those skilled in the art can appropriately set the amounts of the imidization catalyst, the azeotropic dehydration solvent, the acid catalyst and the like to be used. The reaction temperature for preparing the component (D) is usually 100 to 250 ° C.

  When the nonvolatile component in the resin composition is 100% by mass, the content of the (D) polyimide resin is 12% by mass or more, and preferably 14% by mass from the viewpoint of remarkably obtaining the desired effect of the present invention. The amount is more preferably 16% by mass or more, further preferably 18% by mass or more, particularly preferably 20% by mass or more. The upper limit is preferably 40 mass% or less, more preferably 35 mass% or less, further preferably 30 mass% or less, and particularly preferably 25 mass% or less, from the viewpoint of remarkably obtaining the desired effect of the present invention.

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

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

  The material of the inorganic filler (E) is not particularly limited, and examples thereof include silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, Boehmite, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate. , Titanium oxide, zirconium oxide, barium titanate, barium titanate zirconate, barium zirconate, calcium zirconate, zirconium phosphate, zirconium phosphate tungstate, and the like, with silica being particularly preferred. Examples of silica include amorphous silica, fused silica, crystalline silica, synthetic silica, hollow silica, and the like. Spherical silica is preferable as the silica. The inorganic filler (E) may be used alone or in combination of two or more.

  (E) Commercially available inorganic fillers include, for example, "UFP-30" manufactured by Denka Kagaku Kogyo Co., Ltd .; "SP60-05", "SP507-05" manufactured by Nippon Steel & Sumikin Materials Co., Ltd .; manufactured by Admatechs Co., Ltd. "YC100C", "YA050C", "YA050C-MJE", "YA010C"; Denka's "UFP-30"; Tokuyama's "Silfill NSS-3N", "Silfill NSS-4N", "Silfill NSS-" 5N ";" SC2500SQ "," SO-C4 "," SO-C2 "," SO-C1 "manufactured by Admatechs Co., Ltd. and the like.

  The average particle diameter of the (E) inorganic filler is not particularly limited, but from the viewpoint of obtaining the desired effect of the present invention, it is preferably 20 μm or less, more preferably 10 μm or less, further preferably 8 μm or less, It is more preferably 6 μm or less, and particularly preferably 5 μm or less. The lower limit of the average particle diameter of the inorganic filler is preferably 0.1 μm or more, more preferably 1 μm or more, still more preferably 2 μm or more, still more preferably 3 μm or more, particularly preferably from the viewpoint of obtaining the desired effect of the present invention. Is 4 μm or more. The average particle diameter of the inorganic filler can be measured by a laser diffraction / scattering method based on Mie scattering theory. Specifically, it can be measured by creating a particle size distribution of the inorganic filler on a volume basis with a laser diffraction / scattering particle size distribution measuring device and setting the median size as the average particle size. As the measurement sample, an inorganic filler (100 mg) and methyl ethyl ketone (10 g) can be weighed in a vial and dispersed by ultrasonic waves for 10 minutes. Using a laser diffraction particle size distribution measuring device, the measurement sample was set to a blue and red light source wavelength, and the volume-based particle size distribution of the inorganic filler was measured by the flow cell method. The average particle diameter was calculated as the median diameter. Examples of the laser diffraction particle size distribution measuring device include “LA-960” manufactured by Horiba Ltd.

  (E) The inorganic filler is an aminosilane-based coupling agent, an epoxysilane-based coupling agent, a mercaptosilane-based coupling agent, an alkoxysilane compound, an organosilazane compound, and a titanate-based coupling from the viewpoint of improving moisture resistance and dispersibility. It is preferably treated with one or more surface treatment agents such as agents. Examples of commercially available surface treatment agents include "KBM403" (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM803" (3-mercaptopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., Shin-Etsu Chemical Industry "KBE903" (3-aminopropyltriethoxysilane), Shin-Etsu Chemical Industry "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane), Shin-Etsu Chemical Industry "SZ-31" ( Hexamethyldisilazane), Shin-Etsu Chemical Co., Ltd. "KBM103" (phenyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBM-4803" (long-chain epoxy type silane coupling agent), Shin-Etsu Chemical Co., Ltd. "KBM-" 7103 ”(3,3,3-trifluoropropyltrimethoxysilane) and the like.

  The degree of surface treatment with the surface treatment agent is preferably within a predetermined range from the viewpoint of improving the dispersibility of the inorganic filler. Specifically, 100% by mass of the inorganic filler is preferably surface-treated with 0.2% by mass to 5% by mass of a surface treatment agent, and is surface treated with 0.2% by mass to 3% by mass. Is preferable, and it is preferable that the surface treatment is performed at 0.3% by mass to 2% by mass.

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

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

The specific surface area of the inorganic filler (E) is preferably 1 m ² / g or more, more preferably 2 m ² / g or more, and particularly preferably 3 m ² / g or more, from the viewpoint of further improving the effect of the present invention. The upper limit is not particularly limited, but is preferably 50 m ² / g or less, more preferably 20 m ² / g or less, 10 m ² / g or less, or 5 m ² / g or less. The specific surface area of the inorganic filler is calculated according to the BET method by using a specific surface area measuring device (Macsorb HM-1210 manufactured by Mountech Co., Ltd.) to adsorb nitrogen gas on the sample surface and using the BET multipoint method. It can be obtained.

  The content of the inorganic filler (E) is preferably 60% by mass or less, more preferably 50% by mass from the viewpoint of remarkably obtaining the desired effect of the present invention when the nonvolatile component in the resin composition is 100% by mass. The content is less than or equal to mass%, more preferably less than or equal to 40 mass%, particularly preferably less than or equal to 30 mass%. When the inorganic filler (E) is contained, the lower limit of the content is not particularly limited, but is, for example, 10% by mass or more, 15% by mass or more, 20% by mass or more, 25% by mass or more. obtain.

<(F) Curing accelerator>
The resin composition of the present invention may contain (F) a curing accelerator as an optional component.

  Examples of the curing accelerator (F) include a phosphorus curing accelerator, an amine curing accelerator, an imidazole curing accelerator, a guanidine curing accelerator, and a metal curing accelerator. Of these, phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators and metal-based curing accelerators are preferable, and amine-based curing accelerators, imidazole-based curing accelerators and metal-based curing accelerators are more preferable. The curing accelerator may be used alone or in combination of two or more.

  Examples of phosphorus-based curing accelerators include triphenylphosphine, phosphonium borate compounds, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, (4-methylphenyl) triphenylphosphonium thiocyanate. , Tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate and the like.

  Examples of the amine-based curing accelerator include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine (DMAP), benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) phenol, 1, 8-diazabicyclo (5,4,0) -undecene and the like can be mentioned, and 4-dimethylaminopyridine is preferable.

  Examples of the imidazole-based curing accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 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'-undecyl Imidazolyl- (1 ')]-ethyl-s-triazine, 2,4-diamino-6- [2'-ethyl-4'-methylimidazolyl- (1')]-ethyl-s-triazine, 2,4- Diamino-6- [2'-methylimidazolyl- (1 ')]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2- Phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo [1,2-a] benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline Examples include imidazole compounds such as 2-phenylimidazoline and adducts of imidazole compounds and epoxy resins.

  As the imidazole-based curing accelerator, a commercially available product may be used, and examples thereof include "P200-H50" manufactured by Mitsubishi Chemical Corporation.

  Examples of the guanidine-based curing accelerator include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1- (o-tolyl) guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, Tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo [4.4.0] dec-5-ene, 7-methyl-1,5,7-triazabicyclo [4.4.0] Deca-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 -Aryl biguanide, 1-phenyl biguanide, 1- (o-tolyl) biguanide and the like.

  Examples of the metal-based curing accelerator include organic metal complexes or organic metal salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of the organic metal complex include organic cobalt complexes such as cobalt (II) acetylacetonate and cobalt (III) acetylacetonate, organic copper complexes such as copper (II) acetylacetonate, and zinc (II) acetylacetonate. And the like, organic iron complexes such as iron (III) acetylacetonate, organic nickel complexes such as nickel (II) acetylacetonate, and organic manganese complexes such as manganese (II) acetylacetonate. Examples of the organic metal salt include zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, zinc stearate and the like.

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

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

  Examples of the organic solvent include ketone solvents such as acetone, methyl ethyl ketone, and cyclohexanone; ester solvents such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, carbitol acetate, ethyl diglycol acetate, and γ-butyrolactone. Carbitol solvents such as cellosolve and butyl carbitol; aromatic hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, trimethylbenzene; amide solvents such as dimethylformamide, dimethylacetamide (DMAc) and N-methylpyrrolidone; Examples thereof include alcohol solvents such as methanol, ethanol and 2-methoxypropanol; hydrocarbon solvents such as cyclohexane and methylcyclohexane. The organic solvent may be used alone, or two or more kinds may be used in combination at an arbitrary ratio.

<(H) Other additives>
The resin composition may further contain other additives as optional components in addition to the components described above. Examples of such additives include organic fillers other than fluorine, thickeners, defoamers, leveling agents, adhesion promoters, polymerization initiators, flame retardants and the like. These additives may be used alone or in combination of two or more. Those skilled in the art can appropriately set the respective contents.

<Method for producing resin composition>
In one embodiment, the resin composition of the present invention is, for example, (A) epoxy resin, (B) curing agent, (C) fluorine-based organic filler, (D) polyimide resin (preliminarily imidized) in a reaction vessel. A), if necessary (E) an inorganic filler, if necessary (F) a curing accelerator, if necessary (G) an organic solvent, and if necessary (H) other additives, It can be produced by a method including a step of adding a resin composition in an arbitrary order and / or a part or all of them at the same time and mixing them (hereinafter referred to as step (1)).

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

  Step (1) includes (A) epoxy resin, (D) polyimide resin (preliminarily imidized) in the reaction vessel, if necessary, especially when (A) epoxy resin contains solid epoxy resin. (G) an organic solvent, and optionally (H) other additives in any order and / or partly or all at the same time, mixed and heated to obtain a mixture, and The mixed mixture is cooled, and (B) a curing agent, (C) a fluorine-based organic filler, (E) an inorganic filler as needed, (F) a curing accelerator as needed, and optionally ( It is preferable that G) an organic solvent and, if necessary, (H) other additives are added in any order and / or at least partly at the same time and mixed to obtain a resin composition in two stages. ..

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

<Characteristics of resin composition>
Since the resin composition of the present invention contains (A) an epoxy resin, (B) a curing agent, and (D) a polyimide resin, it has low roughness and high peel strength, and is cured with excellent water resistance and flexibility. You can get things.

  Regarding the excellent water resistance which is one of the characteristics of the resin composition of the present invention, for example, when a resin composition having a thickness of 50 μm is cured and the obtained cured product is exposed to pure water in a boiling state for 1 hour. In, the amount of mass change (water absorption) (%) before and after exposure is preferably 1.0% or less, more preferably 0.9% or less, still more preferably 0.8% or less, and particularly preferably 0.7%. It is below.

  Regarding the excellent flexibility which is one of the characteristics of the resin composition of the present invention, for example, a resin composition having a thickness of 40 μm is cured and the obtained cured product is subjected to a load of 2. The number of folding endurances when the MIT folding endurance test is conducted under the conditions of 5 N, bending angle 90 degrees, bending speed 175 times / min, and bending radius 1.0 mm is preferably 6,000 times or more, more preferably It is 7,000 times or more, more preferably 8,000 times or more, and particularly preferably 9,000 times or more.

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

  Regarding the high peel strength which is one of the characteristics of the resin composition of the present invention, for example, a conductor obtained by curing the resin composition to form an insulating layer, roughening the surface of the insulating layer, and plating. The peel strength between the layer and the insulating layer is preferably 0.3 kgf / cm or more, more preferably 0.35 kgf / cm or more, and particularly preferably 0.4 kgf / cm or more. The upper limit is not particularly limited, but may be 1.5 kgf / cm or less, 1.2 kgf / cm or less, 1.0 kgf / cm or less, and the like. The peel strength of the insulating layer and the conductor layer can be measured according to Japanese Industrial Standards (JIS C6481).

  The curing temperature for obtaining the insulating layer (cured product) when measuring the water absorption rate, MIT folding endurance, arithmetic mean roughness (Ra) or peel strength is not particularly limited, but is preferably 120 ° C to 240 ° C. The temperature is more preferably 150 ° C to 220 ° C, still more preferably 170 ° C to 210 ° C. The curing time is not particularly limited, but is preferably 5 minutes to 120 minutes, more preferably 10 minutes to 110 minutes, and further preferably 20 minutes to 100 minutes. Further, when measuring the arithmetic average roughness (Ra) or the peel strength, it is preferable to preheat before the thermosetting. For example, the preheating temperature is not particularly limited, but is preferably 60 ° C. or higher and 115 ° C. or lower, more preferably 70 ° C. or higher and 110 ° C. or lower. The preheating time is not particularly limited, but is preferably 5 minutes to 150 minutes, more preferably 5 minutes to 120 minutes, and further preferably 5 minutes to 100 minutes.

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

<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 on the support.

  The thickness of the resin composition layer is preferably 15 μm or less, more preferably 13 μm or less, and further preferably from the viewpoint that a printed wiring board can be thinned and a cured product excellent in insulating property can be provided even if it is a thin film. It is 10 μm or less, or 8 μm or less. The lower limit of the thickness of the resin composition layer is not particularly limited, but may be usually 1 μm or more, 1.5 μm or more, 2 μm or more.

  Examples of the support include a film made of a plastic material, a metal foil and a release paper, and a film made of a plastic material and a metal foil are preferable.

  When a film made of a plastic material is used as the support, the plastic material may be, for example, polyethylene terephthalate (hereinafter sometimes abbreviated as “PET”) or polyethylene naphthalate (hereinafter sometimes referred to as “PEN”). .) And the like, polycarbonate (hereinafter sometimes abbreviated as “PC”), acrylic such as polymethylmethacrylate (PMMA), cyclic polyolefin, triacetyl cellulose (TAC), polyether sulfide (PES), polyether. Examples include ketones and polyimides. Among them, polyethylene terephthalate and polyethylene naphthalate are preferable, and inexpensive polyethylene terephthalate is particularly preferable.

  When a metal foil is used as the support, examples of the metal foil include copper foil and aluminum foil, and copper foil is preferable. As the copper foil, a foil made of a single metal of copper may be used, and a foil made of an alloy of copper and another metal (for example, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium) is used. You may use.

  The support may have a matte treatment, a corona treatment, or an antistatic treatment on the surface to be joined to the resin composition layer.

  Further, as the support, a support with a release layer having a release layer on the surface to be joined with the resin composition layer may be used. Examples of the release agent used in the release layer of the support with release layer include one or more release agents selected from the group consisting of alkyd resin, polyolefin resin, urethane resin, and silicone resin. .. As the support with a release layer, a commercially available product may be used, for example, “SK-1” manufactured by Lintec Co., Ltd., which is a PET film having a release layer containing an alkyd resin-based release agent as a main component. Examples include AL-5, AL-7, Toray's "Lumirror T60", Teijin's "Purex", and Unitika's "Unipeal".

  The thickness of the support is not particularly limited, but is preferably in the range of 5 μm to 75 μm, more preferably in the range of 10 μm to 60 μm. When the support with release layer is used, the thickness of the support with release layer as a whole is preferably within the above range.

  In one embodiment, the resin sheet may further include other layers, if necessary. Examples of such other layer include a protective film provided on the surface of the resin composition layer that is not bonded to the support (that is, the surface opposite to the support), which is similar to the support. Be done. The thickness of the protective film is not particularly limited, but is, for example, 1 μm to 40 μm. By laminating the protective film, it is possible to suppress the adhesion of dust or the like to the surface of the resin composition layer and the scratches.

  For the resin sheet, for example, a resin varnish prepared by dissolving a resin composition in an organic solvent is prepared, and the resin varnish is applied onto a support using a die coater or the like, and further dried to form a resin composition layer. It can be manufactured.

  Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone (MEK) and cyclohexanone; acetic acid esters such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate and carbitol acetate; cellosolve and butyl carbitol. Carbitols; aromatic hydrocarbons such as toluene and xylene; amide solvents such as dimethylformamide, dimethylacetamide (DMAc) and N-methylpyrrolidone. The organic solvent may be used alone or in combination of two or more.

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

  The resin sheet can be rolled up and stored. 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 manufactured by laminating and curing a plurality of resin sheets. Therefore, the laminated sheet includes a plurality of insulating layers as a cured product of the resin sheet. Usually, the number of resin sheets laminated to manufacture a laminated sheet corresponds to the number of insulating layers included in the laminated sheet. The specific number of 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 is a sheet that is bent and used so that its one surface faces each other. The minimum bending radius for bending 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, and preferably 5 mm or less. It is preferably 4 mm or less, particularly preferably 3 mm or less.

  A hole may be formed in each insulating layer included in the laminated sheet. This hole can function as a via hole or a through hole in the multilayer flexible substrate.

  The laminated sheet may further include an optional element in addition to the insulating layer. For example, the laminated sheet may include 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 usually functions as a wiring in the multilayer flexible substrate.

  The conductor material used for the conductor layer is not particularly limited. In a preferred embodiment, the conductor layer is one or more selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin and indium. Including metal. The conductor material may be a single metal or an alloy. Examples of the alloy include alloys of two or more kinds of metals selected from the above group (for example, nickel-chromium alloy, copper-nickel alloy and copper-titanium alloy). Among them, from the viewpoints of versatility of forming a conductor layer, cost, easiness of patterning, etc., chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper as a single metal; and nickel-chromium alloy, copper -Alloys such as nickel alloys and copper-titanium alloys are preferred. Among them, single metals of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper; and nickel-chromium alloys are more preferable, and single metals of copper are more preferable.

  The conductor layer may have a single-layer structure or a multi-layer structure including two or more single metal layers or alloy layers made of different kinds of metals or alloys. When the conductor layer has a multilayer 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 may be patterned in order to function as a wiring.

  The thickness of the conductor layer depends on the design of the multilayer flexible substrate, but is preferably 3 μm to 35 μm, more preferably 5 μm to 30 μm, further preferably 10 to 20 μm, and particularly preferably 15 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 600 μm or less, more preferably 500 μm or less, particularly preferably 400 μm or less.

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

  Hereinafter, a preferred embodiment of the step (b) will be described. In the embodiments described below, for the sake of distinction, the resin sheets are appropriately numbered and indicated as “first resin sheet” and “second resin sheet”, and the resin sheets are cured. Similarly to the resin sheet, the obtained insulating layer is also numbered as "first insulating layer" and "second insulating layer".

In a preferred embodiment, step (b) comprises
(II) a step of curing the first resin sheet to form a first insulating layer,
(VI) a step of laminating a second resin sheet on the first insulating layer,
(VII) a step of curing the second resin sheet to form a second insulating layer,
including. In addition, the step (b), if necessary,
(I) a step of laminating the first resin sheet on the sheet supporting base material,
(III) A step of making a hole in the first insulating layer,
(IV) a step of subjecting the first insulating layer to a roughening treatment,
(V) Any step such as a step of forming a conductor layer on the first insulating layer may be included. Hereinafter, each step will be described.

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

  The lamination of the sheet supporting base material and the first resin sheet may be performed by a vacuum laminating method. In the vacuum laminating method, the thermocompression bonding temperature is preferably in the range of 60 ° C. to 160 ° C., more preferably 80 ° C. to 140 ° C., and the thermocompression bonding pressure is preferably 0.098 MPa to 1.77 MPa, more preferably 0. It is in the range of 0.29 MPa to 1.47 MPa, and the thermocompression bonding time is preferably in the range of 20 seconds to 400 seconds, more preferably 30 seconds to 300 seconds. Lamination is preferably performed under reduced pressure conditions with a pressure of 26.7 hPa or less.

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

  When using the sheet-like laminating material, the sheet supporting base material and the first resin sheet are laminated, for example, by pressing the sheet-like laminating material from the support side to form the first resin sheet of the sheet-like laminating material. This can be performed by thermocompression bonding to the sheet supporting base material. Examples of a member (hereinafter, also referred to as “thermocompression bonding member” as appropriate) for thermocompression bonding the sheet-shaped laminating material to the sheet supporting substrate include, for example, a heated metal plate (SUS end plate, etc.) or a metal roll ( SUS roll) and the like. It is preferable that the thermocompression bonding member is not directly pressed onto the sheet-shaped laminating material, but is pressed via an elastic material such as heat-resistant rubber so that the first resin sheet sufficiently follows the surface irregularities of the sheet supporting base material. .

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

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

  Usually, the specific thermosetting conditions differ 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 further preferably 170 ° C to 210 ° C. The curing time is preferably 5 minutes to 120 minutes, more preferably 10 minutes to 110 minutes, and further preferably 20 minutes to 100 minutes.

  Before thermosetting the first resin sheet, the first resin sheet may be preheated at a temperature lower than the curing temperature. For example, prior to thermosetting the first resin sheet, the first resin sheet is treated at a temperature of 50 ° C or higher and lower than 120 ° C (preferably 60 ° C or higher and 115 ° C or lower, more preferably 70 ° C or higher and 110 ° C or lower). Preheating may be performed for 5 minutes or more (preferably 5 minutes to 150 minutes, more preferably 5 minutes to 120 minutes, further preferably 5 minutes to 100 minutes).

  Step (III) is a step of making a hole in the first insulating layer, if necessary. By this step (III), holes such as via holes and through holes can be formed in the first insulating layer. Drilling may be performed using, for example, a drill, a laser, plasma or the like, depending on the composition of the resin composition. The size and shape of the hole may be appropriately set according to the design of the multilayer flexible substrate.

  Step (IV) is a step of subjecting the first insulating layer to a roughening treatment, if necessary. Usually, smear is also removed in this step (IV). Therefore, the roughening process is sometimes called a desmear process. As the roughening treatment, either dry or wet roughening treatment may be performed. Examples of the dry roughening treatment include plasma treatment and the like. As an example of the wet roughening treatment, there is a method of performing swelling treatment with a swelling liquid, roughening treatment with an oxidizing agent, and neutralization treatment with a neutralizing liquid in this order.

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

  Step (V) is a step of forming a conductor layer on the first insulating layer, if necessary. Examples of the method for forming the conductor layer include a plating method, a sputtering method, a vapor deposition method, and the like, and the plating method is preferable. A preferable example is a method of forming a conductor layer having a desired wiring pattern by plating on the surface of the first insulating layer by an appropriate method such as a semi-additive method or a full-additive method. Among them, the semi-additive method is preferable from the viewpoint of ease of production.

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

  After obtaining the first insulating layer in step (II) and performing steps (III) to (V) as necessary, step (VI) is performed. Step (VI) is a step of laminating the second resin sheet on the first insulating layer. The lamination of the first insulating layer and the second resin sheet can be performed by the same method as the lamination of the sheet supporting base material and the first resin sheet in the step (I).

  However, when the first insulating layer is formed using the sheet-shaped laminating material, the support of the sheet-shaped laminated body is removed before the step (VI). The removal of the support may be performed between step (I) and step (II), between step (II) and step (III), and between step (III) and step (IV). ) Or between step (IV) and step (V).

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

  Further, in the method according to the above-described embodiment, (VIII) a step of boring the second insulating layer, (IX) a step of roughening the second insulating layer, and (X) a second insulating layer, if necessary. A step of forming a conductor layer on the layer may be performed. The drilling of the second insulating layer in the step (VIII) can be performed by the same method as the drilling of the first insulating layer in the step (III). The roughening treatment of the second insulating layer in the step (IX) can be performed by the same method as the roughening treatment of the first insulating layer in the step (IV). Further, the formation of the conductor layer on the second insulating layer in the step (X) can be performed by the same method as the formation of the conductor layer on the first insulating layer in the step (V).

  In the above-described embodiment, the embodiment in which the laminated sheet is manufactured by laminating and curing the two resin sheets, that is, the first resin sheet and the second resin sheet, is described. However, the laminating sheet is laminated by laminating and curing three or more resin sheets. The sheet may be manufactured. For example, in the method according to the above-described embodiment, the resin sheets are laminated and cured by the steps (VI) to (VII), and if necessary, the insulating layer is perforated and insulated by the steps (VIII) to (X). The layered sheet may be manufactured by repeatedly performing the layer roughening treatment and the formation of the conductor layer on the insulating layer. Thereby, a laminated sheet including three or more insulating layers is obtained.

  Furthermore, the method according to the above embodiment may include any step other than the steps described above. For example, when the step (I) is performed, the step of removing the sheet supporting base material may be performed.

<Multilayer flexible substrate>
The multilayer flexible substrate includes a laminated sheet. Therefore, the multilayer flexible substrate includes an insulating layer formed by curing the resin composition of the present invention. The multilayer flexible substrate may include only the laminated sheet, or may include any member in combination with the laminated sheet. Examples of the optional member include an electronic component and a coverlay film.

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

  The method for manufacturing a multilayer flexible substrate may further include any step in combination with the above steps. For example, the method for manufacturing a multilayer flexible substrate including an electronic component may include a step of joining the electronic component to the laminated sheet. As a joining condition between the laminated sheet and the electronic component, any condition can be adopted in which the terminal electrode of the electronic component and the conductor layer as the wiring provided on the laminated sheet can be conductor-connected. Further, for example, the method for producing a multilayer flexible substrate including a coverlay film may include a step of laminating a laminated sheet and a coverlay film.

  The multilayer flexible substrate may be usually used by bending so that one surface of a laminated sheet included in the multilayer flexible substrate faces each other. For example, the multilayer flexible substrate is housed in the housing of the semiconductor device in a state of being folded and reduced in size. Further, for example, the multilayer flexible substrate is provided in a movable portion of a semiconductor device having a bendable movable portion.

<Semiconductor device>
A semiconductor device includes the above-mentioned multilayer flexible substrate. The semiconductor device includes, for example, a multilayer flexible substrate and a semiconductor chip mounted on the multilayer flexible substrate. In many semiconductor devices, the multilayer flexible substrate may be folded and housed in a housing of the semiconductor device such that one surface of a laminated sheet included in the multilayer flexible substrate faces each other.

  Examples of the semiconductor device include various semiconductor devices provided for electric products (for example, computers, mobile phones, digital cameras and televisions) and vehicles (for example, motorcycles, automobiles, trains, ships and aircrafts). Be done.

  The semiconductor device, for example, a step of preparing a multilayer flexible substrate, a step of bending the multilayer flexible substrate so that one surface of the laminated sheet faces, a step of housing the folded multilayer flexible substrate in a housing, Can be manufactured by a manufacturing method including.

  Hereinafter, the present invention will be specifically described with reference to examples. The invention is not limited to these examples. In the following, “parts” and “%” representing amounts mean “parts by mass” and “mass%”, respectively, unless otherwise specified.

<Synthesis Example 1: Synthesis of polyimide resin 1>
In a 500 ml separable flask equipped with a nitrogen introducing tube and a stirrer, 5-amino-1,1′-biphenyl-2-yl 4-aminobenzoate (compound of formula (1 ″)) 9.13 g (30 mmol) ), 4,4 '-(4,4'-isopropylidene diphenoxy) bisphthalic dianhydride 15.61 g (30 mmol), N-methyl-2-pyrrolidone 94.64 g, pyridine 0.47 g (6 mmol). Then, 10 g of toluene was added, and a polyimide solution (nonvolatile content: 20% by mass) containing polyimide resin 1 was obtained by performing an imidization reaction at 180 ° C. in a nitrogen atmosphere for 4 hours while excluding toluene from the system on the way. No precipitation of the synthesized polyimide resin 1 was observed in the polyimide solution.

<Synthesis example 2: Synthesis of polyimide resin 2>
Aromatic tetracarboxylic acid dianhydride (“BisDA-1000”, 4,4 ′-(4,4 ′, manufactured by SABIC Japan Co., Ltd.) -Isopropylidene diphenoxy) bisphthalic acid dianhydride) 65.0 g, cyclohexanone 266.5 g, and methylcyclohexane 44.4 g were charged, and the solution was heated to 60 ° C. Then, 43.7 g of dimer diamine (“PRIAMINE 1075” manufactured by Croda Japan Co., Ltd.) and 5.4 g of 1,3-bis (aminomethyl) cyclohexane were dropped, and then an imidization reaction was performed at 140 ° C. for 1 hour. As a result, a polyimide solution containing the polyimide resin 2 (nonvolatile content: 30% by mass) was obtained. The weight average molecular weight of the polyimide resin 2 was 25,000.

<Synthesis Example 3: Synthesis of polyimide resin 3>
A 500 mL separable flask equipped with a moisture quantitative receiver connected with a reflux condenser, a nitrogen introducing tube, and a stirrer was prepared. In this flask, 4,4'-oxydiphthalic anhydride (ODPA) 20.3 g, γ-butyrolactone 200 g, toluene 20 g, and 5- (4-aminophenoxy) -3- [4- (4-aminophenoxy) were added. Phenyl] -1,1,3-trimethylindane (29.6 g) was added, and the mixture was stirred under a nitrogen stream at 45 ° C. for 2 hours to carry out a reaction. Next, the temperature of this reaction solution was raised, and while maintaining the temperature at about 160 ° C., the condensed water was azeotropically removed together with toluene under a nitrogen stream. It was confirmed that a predetermined amount of water had accumulated in the moisture quantitative receiver and that no outflow of water was observed. After confirmation, the reaction solution was further heated and stirred at 200 ° C. for 1 hour. Then, it cooled and the polyimide solution (nonvolatile content 20 mass%) containing the polyimide resin 3 which has a 1,1,3-trimethyl indane skeleton was obtained. The obtained polyimide resin 3 had a repeating unit represented by the following formula (X1) and a repeating unit represented by the following formula (X2). The weight average molecular weight of the polyimide resin 3 was 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), 5 parts of naphthalene type epoxy resin (“ESN475V” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., epoxy equivalent of about 332), bisphenol AF type epoxy resin ( Mitsubishi Chemical "YL7760", epoxy equivalent of about 238) 10 parts, cyclohexane type epoxy resin (Mitsubishi Chemical "ZX1658GS", epoxy equivalent of about 135) 2 parts, the polyimide solution obtained in Synthesis Example 1 (nonvolatile component 20 mass %) 100 parts, and cyclohexanone 10 parts in a mixed solvent with heating and stirring. After cooling to room temperature, 4 parts of a triazine skeleton-containing cresol novolac-based curing agent ("LA3018-50P" manufactured by DIC, hydroxyl equivalent of 151, 2-methoxypropanol solution with solid content of 50%), active ester system Curing agent ("EXB-8000L-65M" manufactured by DIC, active group equivalent weight about 220, MEK solution of non-volatile component 65 mass%) 6 parts, spherical silica ("SC2500SQ" manufactured by Admatechs Co., Ltd., average particle size 0.5 µm, 25 parts of a specific surface area of 11.2 m ² / g, 25 parts of N-phenyl-3-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM573) surface-treated with 100 parts of silica, polytetrafluoro 25 parts of ethylene particles (“Lublon L-2” manufactured by Daikin Industries, Ltd., average particle diameter 3 μm) and 0.2 part of an amine-based curing accelerator (4-dimethylaminopyridine (DMAP)) were mixed, and uniformly mixed with a high-speed rotating mixer. And then filtered through a cartridge filter (“SHP020” manufactured by ROKITECHNO) to prepare a resin composition 1.

<Example 2: Preparation of resin composition 2>
Instead of using 25 parts of polytetrafluoroethylene particles (“Lubron L-2” manufactured by Daikin Industries, Ltd., average particle size 3 μm), 50 parts were used, and spherical silica (“SC2500SQ” manufactured by Admatex Co., average particles) Diameter 0.5 μm, specific surface area 11.2 m ² / g, 100 parts of silica with N-phenyl-3-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM573, surface-treated with 1 part) is used. A resin composition 2 was prepared in the same manner as in Example 1 except that the resin composition 2 was not used.

<Example 3: Preparation of resin composition 3>
Instead of using 5 parts of bixylenol type epoxy resin (“YX4000HK” manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of about 185), 10 parts were used, naphthalene type epoxy resin (“ESN475V” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., epoxy equivalent weight) Instead of using 5 parts of 332), 10 parts were used, and instead of using 25 parts of polytetrafluoroethylene particles (“Lublon L-2” manufactured by Daikin Industries, Ltd., average particle diameter 3 μm), 50 parts were used. Bisphenol AF type epoxy resin (“YL7760” manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of about 238) and spherical silica (“SC2500SQ” manufactured by Admatechs Co., Ltd., average particle diameter 0.5 μm, specific surface area 11.2 m ² / g, The same operation as in Example 1 except that N-phenyl-3-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM573) was not used for 100 parts of silica each. Then, a resin composition 3 was prepared.

<Example 4: Preparation of resin composition 4>
Instead of using 100 parts of the polyimide solution (non-volatile component 20% by mass) obtained in Synthesis Example 1, 66.7 parts of the polyimide solution (non-volatile component 30% by mass) obtained in Synthesis Example 2 was used, polytetrafluoro Instead of using 25 parts of ethylene particles (“LUBRON L-2” manufactured by Daikin Industries, Ltd., average particle size 3 μm), 50 parts were used, and spherical silica (“SC2500SQ” manufactured by Admatechs Co., Ltd., average particle size 0. 5 μm, specific surface area 11.2 m ² / g, N-phenyl-3-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM573) surface-treated with 1 part per 100 parts of silica was not used. Except for the above, the same operation as in Example 1 was performed to prepare a resin composition 4.

<Example 5: Preparation of resin composition 5>
Instead of using 100 parts of the polyimide solution (non-volatile component 20% by mass) obtained in Synthesis Example 1, 100 parts of the polyimide solution (non-volatile component 20% by mass) obtained in Synthesis Example 3 was used, polytetrafluoroethylene particles. (Daikin Industries Co., Ltd. "Lublon L-2", average particle diameter 3 μm), instead of using 25 parts, spherical silica (Admatex "SC2500SQ", average particle diameter 0.5 μm, Specific surface area 11.2 m ² / g, except that 100 parts of silica did not use N-phenyl-3-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM573) 1 part in surface treatment). A resin composition 5 was prepared in the same manner as in Example 1.

<Comparative Example 1: Preparation of resin composition 6>
A resin composition 6 was prepared by performing the same operation as in Example 1 except that 50 parts of the polyimide solution obtained in Synthesis Example 1 (20% by mass of nonvolatile components) was used instead of 100 parts.

<Comparative Example 2: Preparation of resin composition 7>
Spherical silica (“SC2500SQ” manufactured by Admatechs Co., Ltd., average particle size 0.5 μm, specific surface area 11.2 m ² / g, N-phenyl-3-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) per 100 parts of silica. , KBM573) surface-treated with 1 part), 50 parts were used instead of 25 parts, and polytetrafluoroethylene particles (“LUBRON L-2” manufactured by Daikin Industries, Ltd., average particle diameter 3 μm) were used. A resin composition 7 was prepared in the same manner as in Example 1 except that the resin composition 7 was not used.

<Comparative Example 3: Preparation of resin composition 8>
The same operation as in Example 1 was performed, except that the polyimide solution (non-volatile component 20% by mass) obtained in Synthesis Example 1 was not used, and 18 parts of phenoxy resin (“YX7553BH30” manufactured by Mitsubishi Chemical Corporation) was used. Thus, a resin composition 8 was prepared.

<Measurement of average particle size of inorganic filler>
100 mg of the inorganic filler and 10 g of methyl ethyl ketone were weighed in a vial and dispersed by ultrasonic waves for 10 minutes. Using a laser diffraction type particle size distribution measuring device (“LA-960” manufactured by Horiba Ltd.), the light source wavelengths used were blue and red, and the particle size distribution of the inorganic filler was measured on a volume basis by a flow cell method. From the obtained particle size distribution, the average particle size of the inorganic filler was calculated as the median size.

<Measurement of specific surface area of inorganic filler>
Using a BET fully automatic specific surface area measuring device (Macsorb HM-1210 manufactured by Mountech Co., Ltd.), nitrogen gas is adsorbed on the sample surface, and the specific surface area of the inorganic filler is calculated by calculating the specific surface area using the BET multipoint method. Was measured.

<Test Example 1: Evaluation of water resistance (water absorption)>
A polyethylene terephthalate film (“PET501010” manufactured by Lintec Co., Ltd.) having a surface subjected to a release treatment was prepared. On this polyethylene terephthalate film, the resin compositions of Examples and Comparative Examples were uniformly applied using a die coater so that the thickness of the dried resin composition layer would be 50 μm. The applied resin composition was dried at 80 ° C to 110 ° C (average 95 ° C) for 6 minutes to obtain a resin composition layer. Then, the resin composition layer was heat-treated at 200 ° C. for 90 minutes to be cured, and the support was peeled off to obtain a cured product film formed of the cured product of the resin composition.

The obtained cured product film was cut into 40 mm square test pieces, and the test pieces were dried at 130 ° C. for 30 minutes and then weighed (this weighed mass is defined as W ₀ (g)). The test piece was immersed in boiled ion-exchanged water for 1 hour. Then, the test piece was immersed in ion-exchanged water at room temperature (25 ° C.) for 1 minute, and the test piece was wiped off with a clean wiper (manufactured by Clarke Flex Co., Ltd.) and weighed (weighed this). The mass is W ₁ (g)). The boiling water absorption W _A of each of the five test pieces was determined from the following formula, and the average value was calculated. When the water absorption rate was 1.0% or more, it was evaluated as "x", and when it was less than 1.0%, it was evaluated as "○".

_{W A (%) = ((} W 1 -W 0) / W 0) × 100
W ₀ : Mass of evaluation sample before water absorption (g)
W ₁ : Mass (g) of the evaluation sample after absorbing water

<Test Example 2: Evaluation of flexibility (MIT folding endurance)>
The cured product film obtained in Test Example 1 is cut into a test piece having a width of 15 mm and a length of 110 mm, and a MIT test device (MIT Folding fatigue tester “MIT-DA” manufactured by Toyo Seiki Seisaku-sho, Ltd.) is used. Then, in accordance with JIS C-5016, the number of folding endurance up to breakage of the cured product is measured under the conditions of a load of 2.5 N, a bending angle of 90 degrees, a bending radius of 1.0 mm, and a bending speed of 175 times / min. did. The measurement was performed on 5 samples, and the average value of the top 3 points was calculated. When the folding endurance was less than 8,000 times, it was evaluated as “x”, and when it was 8,000 times or more, it was evaluated as “◯”.

<Test Example 3: Measurement and evaluation of peel strength>
A 38 μm-thick PET film (“AL5” manufactured by Lintec Corporation) was prepared as a support. The resin composition of each of Examples and Comparative Examples was uniformly applied onto the support with a die coater, and the coating film was dried at 80 to 120 ° C. (average 100 ° C.) for 3 minutes to give each on the support. A smooth surface side of a polypropylene cover film (“ALFAN MA-411” manufactured by Oji F-TEX Co., Ltd.) having a thickness of 15 μm on the resin surface on which a layer (thickness 25 μm) formed of the resin compositions of Examples and Comparative Examples was formed. Were bonded together to prepare a resin sheet having a structure of support (38 μm PET film) / resin composition layer / protective film (MA-411).

(1) Copper-clad laminate As a copper-clad laminate, a glass cloth-based epoxy resin double-sided copper-clad laminate with copper foil layers laminated on both sides (copper foil thickness 3 μm, substrate thickness 0.15 mm, Mitsubishi Gas Chemical Co., Inc. "HL832NSF LCA" (255 x 340 mm size) manufactured by the manufacturer was prepared.

(2) Lamination of resin sheet The protective film is peeled off from the resin sheet, and the resin composition layer is a copper-clad laminate using a batch-type vacuum pressure laminator (manufactured by Nikko Materials, two-stage build-up laminator, CVP700). It was laminated on both sides of the copper clad laminate so as to contact with. Lamination was carried out by reducing the pressure for 30 seconds so that the atmospheric pressure was 13 hPa or less, and then performing pressure bonding for 45 seconds at 130 ° C. and a pressure of 0.74 MPa. Then, hot pressing was performed for 75 seconds at 120 ° C. and a pressure of 0.5 MPa.

(3) Thermosetting of Resin Composition Layer The copper clad laminate laminated with the resin sheet is placed in an oven at 100 ° C. for 30 minutes, and then transferred to an oven at 180 ° C. for 30 minutes, followed by heat curing for insulation. Layers were formed. This is a cured substrate A.

(4) Step of Performing Roughening Treatment After removing the support of the via-processed substrate A in which the laser via was formed in the insulating layer of the cured substrate A, desmear treatment was performed as the following roughening treatment.

  Swelling liquid (Atotech Japan "Swelling Dip Securigant P", diethylene glycol monobutyl ether and sodium hydroxide aqueous solution) at 60 ° C for 10 minutes, and then an oxidizer solution (Atotech Japan "Concentrate Compact CP") , Potassium permanganate concentration of about 6%, sodium hydroxide concentration of about 4%) at 80 ° C for 20 minutes, and finally to a neutralizing solution (Atotech Japan's "Reduction Solution Securigant P", sulfuric acid aqueous solution) After soaking at 40 ° C. for 5 minutes, it was dried at 80 ° C. for 15 minutes. This is referred to as a roughened substrate A.

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

(6) Measurement of Peel Strength of Plated Conductor Layer The peel strength of the insulating layer and the conductor layer was measured for the evaluation board B in accordance with Japanese Industrial Standards (JIS C6481). Specifically, a rectangular portion having a width of 10 mm and a length of 100 mm is cut into the conductor layer of the evaluation board B, and one end in the length direction of the rectangular portion is peeled off to obtain a grip (made by TS E Co., Ltd.). Autocom type tester "AC-50CSL"), and a peeling test in which the conductor layer is peeled in the direction perpendicular to the surface of the evaluation substrate B at room temperature at a speed of 50 mm / min. The peel strength was measured by measuring the load (kgf / cm) when peeled off. For the measurement, the peel strength value was evaluated as “◯” when the peel strength was 0.39 kgf / cm or more, and was evaluated as “x” when the peel strength value was less than 0.39 kgf / cm.

<Test Example 4: Measurement of arithmetic average roughness (Ra)>
The surface of the roughened substrate A obtained in (4) of Test Example 3 was measured with a non-contact surface roughness meter ("WYKO NT3300" manufactured by Becoin Instruments Co., Ltd.) in VSI mode with a 50x lens. The arithmetic mean roughness (nm) was determined by the numerical value obtained as 121 μm × 92 μm. For each roughened substrate A, an average value of 10 points randomly selected was calculated.

  Table 1 below shows the amounts of the non-volatile components used in the resin compositions of Examples and Comparative Examples, and the measurement results and evaluation results of Test Examples.

  As described above, when using a resin composition containing (A) epoxy resin, (B) curing agent, (C) fluorine-based organic filler, and 12% by mass or more of (D) polyimide resin, arithmetic operation is performed. It can be seen that it is possible to obtain a cured product having characteristics such as low average roughness and high peel strength, and excellent water resistance and flexibility.

Claims (12)

A resin composition comprising (A) epoxy resin, (B) curing agent, (C) fluorine-based organic filler, and (D) polyimide resin,
The resin composition in which the content of the component (D) is 12% by mass or more when the nonvolatile component in the resin composition is 100% by mass.   The resin composition according to claim 1, wherein the component (C) is a fluoropolymer particle.   The resin composition according to claim 1 or 2, wherein the content of the component (C) is 10% by mass or more when the nonvolatile component in the resin composition is 100% by mass.   The resin composition according to any one of claims 1 to 3, wherein the content of the component (D) is 40% by mass or less when the nonvolatile component in the resin composition is 100% by mass.   The resin composition according to any one of claims 1 to 4, wherein the component (A) contains a fluorine-containing epoxy resin.   The resin composition according to any one of claims 1 to 5, wherein the component (B) is selected from the group consisting of a phenol-based curing agent, a naphthol-based curing agent, and an active ester-based curing agent.   Furthermore, the content of the component (E) with or without the inorganic filler (E) is 60% by mass or less when the non-volatile component in the resin composition is 100% by mass. The resin composition according to any one of items.   The resin composition according to claim 1, which is used for forming an insulating layer of a multilayer flexible substrate.   A cured product of the resin composition according to claim 1.   A resin sheet comprising a support and a resin composition layer formed on the support and formed of the resin composition according to any one of claims 1 to 8.   A multilayer flexible substrate, comprising an insulating layer formed by curing the resin composition according to claim 1.   A semiconductor device comprising the multilayer flexible substrate according to claim 11.