KR20200116052A - Resin composition - Google Patents

Abstract

The present invention provides a resin composition in which a tack property is suppressed low while excellent flexibility is maintained. The resin composition contains (A) a thermosetting resin, (B) an inorganic filler, (C) an organic filler, and (D) an adhesive softening agent, wherein the content of the component (C) is 5 mass% or more when a nonvolatile component in the resin composition is 100 mass%.

Description

Resin composition {RESIN COMPOSITION}

The present invention relates to a resin composition containing a thermosetting resin and an inorganic filler.

BACKGROUND ART In recent years, there is a growing demand for thinner, lighter, and higher mounting density semiconductor components. In order to meet this demand, it is attracting attention to use a flexible substrate as a substrate substrate 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.

In general, it is necessary to blend a softening resin component in the insulating material of a flexible substrate, but when the softening resin component is blended, the tackiness (adhesiveness) increases and handling properties may be inferior. In this case, it is possible to suppress tackiness by blending the inorganic filler (Patent Document 1), but when the blending ratio of the inorganic filler increases, compatibility with flexibility becomes difficult.

Japanese Laid-Open Patent Publication No. 2014-95047

Accordingly, an object of the present invention is to provide a resin composition having low tackiness while maintaining excellent flexibility.

In order to achieve the subject of the present invention, the present inventors intensively studied, as a result, in the resin composition containing (A) a thermosetting resin, (D) an adhesive softener, and (B) an inorganic filler, 5% by mass or more (C) an organic filler By blending, it was found that the tackiness can be suppressed low while maintaining excellent flexibility, thereby completing the present invention.

That is, the present invention includes the following contents.

[1] As a resin composition containing (A) a thermosetting resin, (B) an inorganic filler, (C) an organic filler, and (D) an adhesive softening agent,

The resin composition, wherein the content of the component (C) is 5% by mass or more when the nonvolatile component in the resin composition is 100% by mass.

[2] The resin composition according to [1], wherein the content of the component (B) is 50% by mass or less when the nonvolatile component in the resin composition is 100% by mass.

[3] The resin composition according to [1] or [2], wherein the content of the component (C) is 10 mass% or less when the nonvolatile component in the resin composition is 100 mass%.

[4] Any of the above [1] to [3], wherein the component (D) is selected from the group consisting of a resin having a polybutadiene structure, a polyrotaxane resin, a polyimide resin, and a maleimide resin having a dimer acid skeleton. The resin composition according to one.

[5] The resin composition according to any one of [1] to [4], wherein the content of the component (D) is 1% by mass or more when the nonvolatile component in the resin composition is 100% by mass.

[6] (C) The resin composition according to any one of [1] to [5], wherein the organic filler is a core-shell graft copolymer particle.

[7] The resin composition according to [6] above, wherein the monomer component forming the shell portion of the core-shell graft copolymer particles is a (meth)acrylic acid ester.

[8] The resin composition according to [6] or [7], wherein the core particles of the core-shell graft copolymer particles contain a thermoplastic elastomer.

[9] The resin composition according to any one of [1] to [8], wherein the component (A) is an epoxy resin.

[10] (E) The resin composition according to any one of [1] to [9], further containing a curing agent.

[11] The resin composition according to [10], wherein the component (E) contains an active ester curing agent.

[12] The resin composition according to any one of [1] to [11], wherein the solid content fraction in the resin composition is 95% by mass or less.

[13] The resin composition according to any one of [1] to [12], which is for forming an insulating layer on a multilayer flexible substrate.

[14] A cured product of the resin composition according to any one of [1] to [13].

[15] A resin sheet comprising a support and a resin composition layer formed of the resin composition according to any one of [1] to [13], provided on the support.

[16] A multilayer flexible substrate comprising an insulating layer formed by curing the resin composition according to any one of [1] to [13].

[17] A semiconductor device comprising the multilayer flexible substrate according to [16].

By the resin composition of the present invention, it is possible to suppress the tackiness low while maintaining excellent flexibility.

Hereinafter, the present invention will be described in detail based on its preferred embodiment. However, the present invention is not limited to the following embodiments and examples, and can be carried out by arbitrarily changing the scope of the claims and the equivalent scope of the present invention.

<Resin composition>

The resin composition of the present invention contains (A) a thermosetting resin, (B) an inorganic filler, (C) an organic filler, and (D) an adhesive softening agent. The content of the component (C) is 5% by mass or more when the nonvolatile component in the resin composition is 100% by mass.

By using such a resin composition, tackiness can be suppressed low while maintaining excellent flexibility.

In addition to (A) a thermosetting resin, (B) an inorganic filler, (C) an organic filler, and (D) an adhesive softener, the resin composition of the present invention may further contain optional components. As an arbitrary component, (E) hardening agent, (F) hardening accelerator, (G) other additives, and (H) organic solvent are mentioned, for example. Hereinafter, each component contained in the resin composition will be described in detail.

<(A) Thermosetting resin>

The resin composition of the present invention contains (A) a thermosetting resin. (A) The thermosetting resin does not contain what corresponds to the component (D). (A) A known thermosetting resin may be used, and it is not particularly limited, but examples include polyester resin, polyurethane resin, polyester urethane resin, butyral resin, acrylic resin, cyanate resin, silicone resin, jade. Cetane resin, melamine resin, etc. are mentioned, Among these, an epoxy resin is preferable.

Examples of the 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 novolak type epoxy resin, phenol novolak type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidylamine type epoxy resin, glycy Dill ester type epoxy resin, cresol novolak type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring-containing epoxy resin, cyclohexane type epoxy resin, cyclohexanedimethanol Type epoxy resin, naphthylene ether type epoxy resin, trimethylol type epoxy resin, tetraphenylethane type epoxy resin, and the like. Epoxy resin may be used individually by 1 type, and may be used in combination of 2 or more types.

It is preferable that the resin composition contains an epoxy resin having two or more epoxy groups per molecule as an epoxy resin. From the viewpoint of remarkably obtaining the desired effect of the present invention, the ratio of the epoxy resin having two or more epoxy groups per molecule relative to 100% by mass of the nonvolatile component of the epoxy resin is preferably 50% by mass or more, more preferably It is 60 mass% or more, especially preferably 70 mass% or more.

Epoxy resins include 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”). have. The resin composition of the present invention may contain only a liquid epoxy resin, or may contain only a solid epoxy resin as an epoxy resin, but it is preferable to contain a liquid epoxy resin and a solid epoxy resin in combination.

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

Liquid epoxy resins 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, glycidylamine type epoxy resin, phenol novolak type epoxy resin. , An alicyclic epoxy resin having an ester skeleton, a cyclohexane type epoxy resin, a cyclohexanedimethanol type epoxy resin, and a glycidylamine type epoxy resin are preferable.

As a specific example of a liquid epoxy resin, "HP4032", "HP4032D", and "HP4032SS" (naphthalene type epoxy resin) manufactured by DIC Corporation; "828US", "828EL", "jER828EL", "825", "Epicoat 828EL" (bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical; "JER807" and "1750" manufactured by Mitsubishi Chemical (bisphenol F type epoxy resin); "JER152" manufactured by Mitsubishi Chemical (phenol novolak type epoxy resin); "630" and "630LSD" manufactured by Mitsubishi Chemical (glycidylamine type epoxy resin); "ZX1059" (a mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin) manufactured by Shinnittetsu Sumiking Chemical Co., Ltd.; "EX-721" manufactured by Nagase Chemtex (glyceryl ester type epoxy resin); "Ceroxide 2021P" manufactured by Daicel (alicyclic epoxy resin having an ester skeleton); "ZX1658" and "ZX1658GS" (liquid 1,4-glycidylcyclohexane type epoxy resin) manufactured by Shinnittetsu Sumiking Chemical Co., Ltd. are mentioned. These may be used individually by 1 type, and may be used in combination of 2 or more types.

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

Examples of the solid epoxy resin include bixylenol type epoxy resin, naphthalene type epoxy resin, naphthalene type tetrafunctional epoxy resin, cresol novolak type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, naphthol type epoxy resin, and Phenyl type epoxy resin, aphthylene 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.

As a specific example of a solid epoxy resin, "HP4032H" (naphthalene type epoxy resin) manufactured by DIC Corporation; "HP-4700" and "HP-4710" (naphthalene type tetrafunctional epoxy resin) manufactured by DIC Corporation; "N-690" (cresol novolak type epoxy resin) manufactured by DIC Corporation; "N-695" (cresol novolak type epoxy resin) manufactured by DIC Corporation; "HP-7200", "HP-7200HH", and "HP-7200H" (dicyclopentadiene type epoxy resin) manufactured by DIC Corporation; "EXA-7311", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", "HP6000" (naphthylene ether type epoxy resin) manufactured by DIC Corporation; "EPPN-502H" manufactured by Nihon Kayaku Co., Ltd. (trisphenol type epoxy resin); "NC7000L" manufactured by Nihon Kayaku Corporation (naphthol novolak type epoxy resin); "NC3000H", "NC3000", "NC3000L", "NC3100" (biphenyl type epoxy resin) manufactured by Nihon Kayaku Corporation; "ESN475V" (naphthol type epoxy resin) manufactured by Shinnittetsu Sumiking Chemical Co., Ltd.; "ESN485" (naphthol novolak type epoxy resin) manufactured by Shin-Nitetsu Sumiking Chemical Co., Ltd.; "YX4000H", "YX4000" and "YL6121" (biphenyl type epoxy resin) manufactured by Mitsubishi Chemical; "YX4000HK" manufactured by Mitsubishi Chemical Co., Ltd. (bixylenol type epoxy resin); "YX8800" manufactured by Mitsubishi Chemical (Anthracene-type epoxy resin); "YX7700" manufactured by Mitsubishi Chemical Corporation (novolac-type epoxy resin containing xylene structure); "PG-100" and "CG-500" manufactured by Osaka Gas Chemical Co., Ltd.; "YL7760" manufactured by Mitsubishi Chemical Corporation (bisphenol AF type epoxy resin); "YL7800" manufactured by Mitsubishi Chemical (fluorene type epoxy resin); "JER1010" manufactured by Mitsubishi Chemical (solid bisphenol A type epoxy resin); "JER1031S" (tetraphenyl ethane type epoxy resin) manufactured by Mitsubishi Chemical Corporation, etc. are mentioned. These may be used individually by 1 type, and may be used in combination of 2 or more types.

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

The epoxy equivalent of the epoxy resin is preferably 50 to 5,000 g/eq., more preferably 50 to 3,000 g/eq., more preferably 80 to 2,000 g/eq., even more preferably 110 to 1,000 g /eq. By being in this range, the crosslinking density of the cured product of the resin composition becomes sufficient, and an insulating layer having a small surface roughness can be produced. The epoxy equivalent is the mass ratio of the resin containing 1 equivalent of an epoxy group. This epoxy equivalent can be measured according to JIS K7236.

The weight average molecular weight (Mw) of the epoxy resin is preferably 100 to 5,000, more preferably 250 to 3,000, still more preferably 400 to 1,500 from the viewpoint of remarkably obtaining the desired effect of the present invention. The weight average molecular weight of a resin can be measured as a value in terms of polystyrene by gel permeation chromatography (GPC) method.

(A) The content of the thermosetting resin is not particularly limited, but when the nonvolatile component in the resin composition is 100% by mass, preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 15 It is mass% or more, particularly preferably 20 mass% or more. (A) The upper limit of the content of the thermosetting resin is not particularly limited, but when the nonvolatile component in the resin composition is 100% by mass, preferably 50% by mass or less, more preferably 40% by mass or less, further preferably Is 30 mass% or less, particularly preferably 25 mass% or less.

<(B) inorganic filler>

The resin composition of the present invention contains (B) an inorganic filler.

(B) The material of the inorganic filler is not particularly limited, for example, 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, titanate, bismuth oxide, titanium oxide , Barium titanate, barium titanate zirconate, barium zirconate, calcium zirconate, zirconium phosphate, zirconium tungsten phosphate, and the like, and silica is particularly suitable. Examples of the silica include amorphous silica, fused silica, crystalline silica, synthetic silica, and hollow silica. Moreover, spherical silica is preferable as silica. (B) Inorganic fillers may be used alone or in combination of two or more.

(B) The average particle diameter of the inorganic filler is not particularly limited, but from the viewpoint of obtaining the desired effect of the present invention, preferably 10 μm or less, more preferably 5 μm or less, still more preferably 3 μm or less, further It is more preferably 2 µm or less, particularly preferably 1 µm or less. The lower limit of the average particle diameter of the inorganic filler is preferably 0.01 µm or more, more preferably 0.05 µm or more, still more preferably 0.1 µm or more, even more preferably 0.2 µm from the viewpoint of obtaining the desired effect of the present invention. Or more, particularly preferably 0.25 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 diameter distribution of an inorganic filler on a volume basis with a laser diffraction scattering type particle diameter distribution measuring device, and setting the median diameter to an average particle diameter. As a measurement sample, 100 mg of an inorganic filler and 10 g of methyl ethyl ketone were measured in a vial bottle, and the sample was dispersed for 10 minutes by ultrasonic waves. Using a laser diffraction type particle diameter distribution measuring device, the measurement sample was set to blue and red wavelengths of the light source, and the particle diameter distribution based on the volume of the inorganic filler was measured by a flow cell method, and the median diameter from the obtained particle diameter distribution The average particle diameter was calculated as. Examples of the laser diffraction type particle size distribution measuring device include "LA-960" manufactured by Horibasakusho Corporation.

(B) As a commercial item of an inorganic filler, For example, "UFP-30" manufactured by Denka Chemical Industry Co., Ltd.; "SP60-05" and "SP507-05" manufactured by Shin-Nitetsu Sumikin Materials Co., Ltd.; "YC100C", "YA050C", "YA050C-MJE", "YA010C" manufactured by Adomex Corporation; "UFP-30" manufactured by Denka Corporation; "Silpil NSS-3N", "silpil NSS-4N", and "silpil NSS-5N" manufactured by Tokuyama; "SC2500SQ", "SO-C4", "SO-C2", "SO-C1" manufactured by Adomatex Corporation; And the like.

(B) The inorganic filler is an aminosilane coupling agent, an epoxysilane coupling agent, a mercaptosilane coupling agent, an alkoxysilane compound, an organosilazane compound, and a titanate coupling agent from the viewpoint of improving moisture resistance and dispersibility. It is preferable to be treated with one or more surface treatment agents such as. As a commercial product of the surface treatment agent, for example, "KBM403" (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., and "KBM803" (3-mercaptopropyltrime) manufactured by Shin-Etsu Chemical Co., Ltd. Oxysilane), Shin-Etsu Chemical Co., Ltd. "KBE903" (3-aminopropyltriethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBM573" (N-phenyl-3-aminopropyl trimethoxysilane), Shin-Etsuga "SZ-31" (hexamethyldisilazane) manufactured by Kakugo, Shin-Etsu Chemical "KBM103" (phenyltrimethoxysilane), manufactured by Shin-Etsu Chemical Industries "KBM-7103" (3,3, 3-trifluoropropyltrimethoxysilane) etc. are mentioned.

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

The degree of surface treatment by the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the inorganic filler. The amount of carbon per unit surface area of the inorganic filler is preferably 0.02 mg/m 2 or more, more preferably 0.1 mg/m 2 or more, and still more preferably 0.2 mg/m 2 or more, from the viewpoint of improving the dispersibility of the inorganic filler. On the other hand, from the viewpoint of preventing an increase in the melt viscosity of the resin composition or the melt viscosity in the form of a sheet, 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 still more preferable. .

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

(B) The specific surface area of the inorganic filler 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. Although there is no particular limitation on the upper limit, it is preferably 50 m 2 /g or less, more preferably 20 m 2 /g or less. The specific surface area of the inorganic filler is obtained by adsorbing nitrogen gas on the surface of the sample using a specific surface area measuring device (Macsorb HM-1210 manufactured by Mountec Co., Ltd.) according to the BET method, and calculating the specific surface area using the BET multi-point method. .

(B) The content of the inorganic filler is preferably 70% by mass or less, more preferably 60% by mass or less from the viewpoint of obtaining a cured product having more excellent flexibility when the nonvolatile component in the resin composition is 100% by mass. , More preferably 50 mass% or less, particularly preferably 45 mass% or less. (B) The lower limit of the content of the inorganic filler is not particularly limited, but from the viewpoint of obtaining a cured product having sufficient mechanical strength, when the nonvolatile component in the resin composition is 100% by mass, preferably 20% by mass or more, It is more preferably 30% by mass or more, still more preferably 35% by mass or more, and particularly preferably 38% by mass or more.

<(C) Organic filler>

The resin composition of the present invention contains (C) an organic filler. (C) The organic filler does not contain what corresponds to the component (D). By including the component (C) in the resin composition, tackiness can be reduced, and handling properties can be improved.

(C) The organic filler exists in a particulate form in the resin composition. (C) Examples of the organic filler include rubber particles, polyamide fine particles, and silicone particles, and in the present invention, it is preferable to use rubber particles from the viewpoint of remarkably obtaining the desired effects of the present invention. Do.

Examples of the rubber component contained in the rubber particles include polybutadiene, polyisoprene, polychlorobutadiene, ethylene-vinyl acetate copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-isobutylene copolymer, Olefin-based thermoplastic elastomers such as acrylonitrile-butadiene copolymer, isoprene-isobutylene copolymer, isobutylene-butadiene copolymer, ethylene-propylene-diene terpolymer, and ethylene-propylene-butene terpolymer ; And thermoplastic elastomers such as acrylic thermoplastic elastomers such as poly(meth)acrylate propyl, poly(meth)acrylate, poly(meth)acrylate cyclohexyl, and poly(meth)acrylate octyl. Preferably, olefin-based It is a thermoplastic elastomer, More preferably, it is a styrene-butadiene copolymer. Further, a silicone rubber such as polyorganosiloxane rubber may be mixed with the rubber component. The rubber component contained in the rubber particles has a glass transition temperature of, for example, 0°C or less, preferably -10°C or less, more preferably -20°C or less, and still more preferably -30°C or less.

(C) The organic filler is preferably a core-shell particle from the viewpoint of remarkably obtaining the desired effect of the present invention. The core-shell type particles are particulate organic fillers comprising core particles containing a rubber component as enumerated above, and one or more shell portions covering the core particles. In addition, the core-shell type particle is a core-shell type graft copolymer particle comprising a core particle containing a rubber component as enumerated above, and a shell portion obtained by graft copolymerizing a monomer component copolymerizable with a rubber component contained in the core particle. It is desirable. The term "core-shell type" here does not necessarily mean that the core particles and the shell part can be clearly distinguished, and includes those in which the boundary between the core particles and the shell part is unclear, and the core particles do not need to be completely covered with the shell part. .

The rubber component is preferably contained in a core-shell type graft copolymer particle in an amount of 40% by mass or more, more preferably 50% by mass or more, and still more preferably 60% by mass or more. The upper limit of the content of the rubber component in the core-shell graft copolymer particles is not particularly limited, but from the viewpoint of sufficiently covering the core particles with the shell portion, for example, it is preferably 95% by mass or less and 90% by mass.

As a monomer component forming the shell portion of the core-shell graft copolymer particles, for example, methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, cyclohexyl (meth)acrylate, octyl (meth)acrylate And (meth)acrylic acid esters such as glycidyl (meth)acrylate; (Meth)acrylic acid; N-substituted maleimide such as N-methylmaleimide and N-phenylmaleimide; Maleimide; Α,β-unsaturated carboxylic acids such as maleic acid and itaconic acid; Aromatic vinyl compounds such as styrene, 4-vinyltoluene, and α-methylstyrene; (Meth)acrylonitrile, etc. are mentioned, (meth)acrylic acid ester is preferable, and methyl (meth)acrylate is more preferable.

As a commercial item of the core-shell type graft copolymer particle, For example, "CHT" manufactured by Cheil Industries; "B602" manufactured by UMGABS; ``Pararoid EXL2602'', ``Pararoid EXL2603'', ``Pararoid EXL2655'', ``Pararoid EXL2311'', ``Paraoid EXL2313'', ``Paraoid EXL2315'', ``Paraoid KM330'', `` Paraloid KM336P", "Paraoid KCZ201"; "Metablene C-223A", "Metablene E-901", "Metablene S-2001", "Metablene W-450A", "Metablene SRK-200" manufactured by Mitsubishi Rayon; “Carne Ace M-5800”, “Kane Ace M-600”, “Kane Ace M-400”, “Kane Ace M-580”, and “Kane Ace MR-01” manufactured by Kaneka are mentioned. These may be used individually by 1 type, and may be used in combination of 2 or more types.

The average particle diameter (average primary particle diameter) of the core-shell graft copolymer particles is not particularly limited, but is preferably 20 nm or more, more preferably 50 nm or more, still more preferably 80 nm or more, particularly preferably Preferably, it is 100 nm or more, preferably 5,000 nm or less, more preferably 2,000 nm or less, still more preferably 1,000 nm or less, and particularly preferably 500 nm or less. The average particle diameter (average primary particle diameter) of the core-shell graft copolymer particles can be measured using a zeta potential particle size distribution measuring device or the like.

(C) The content of the organic filler is 5.0% by mass or more when the nonvolatile component in the resin composition is 100% by mass, and the tackiness is suppressed as much as possible, and (B) the amount of use of the inorganic filler is suppressed as much as possible to make it more flexible. From the viewpoint of obtaining this highly cured product, it is preferably 5.5% by mass or more, more preferably 5.8% by mass or more, still more preferably 6.0% by mass or more, and particularly preferably 6.2% by mass or more. (C) The upper limit of the content of the organic filler is preferably 30% by mass or less, 20% by mass or less, more preferably when the nonvolatile component in the resin composition is 100% by mass from the viewpoint of suppressing the viscosity as low as possible. It is preferably 15% by mass or less, and from the viewpoint of reducing void defects and achieving a more excellent pattern embedding property, it is more preferably 10% by mass or less, and particularly preferably 8% by mass or less.

<(D) adhesive softening agent>

The resin composition of the present invention contains (D) an adhesive softening agent.

(D) The adhesive softening agent means a component having a property of increasing the adhesiveness of a cured product among softening agents that give flexibility to a cured product of a thermosetting resin. (D) As the adhesive softening agent, a known softening agent having a property of increasing the adhesion of a cured product can be widely used. (D) Examples of the adhesive softening agent include resins having a polybutadiene structure (hereinafter referred to as ``polybutadiene resins''), polyrotaxane resins, polyimide resins, and maleimide resins having a dimer acid skeleton. However, it is not limited to these.

The polybutadiene structure includes not only a structure formed by polymerizing butadiene, but also a structure formed by hydrogenating the structure. In addition, the butadiene structure may be hydrogenated only in part, and all may be hydrogenated. In addition, in the component (D), the polybutadiene structure may be included in the main chain or may be included in the side chain.

Preferable examples of the polybutadiene resin include hydrogenated polybutadiene skeleton-containing resin, hydroxy group-containing polybutadiene resin, phenolic hydroxyl group-containing polybutadiene resin, carboxy group-containing polybutadiene resin, acid anhydride group-containing polybutadiene resin, epoxy group-containing polybutadiene resin. , An isocyanate group-containing polybutadiene resin, a urethane group-containing polybutadiene resin, and a polyphenylene ether-polybutadiene resin. Here, the "hydrogenated polybutadiene skeleton-containing resin" refers to a resin in which at least a part of the polybutadiene skeleton is hydrogenated, and it is not necessarily a resin in which the polybutadiene skeleton has been completely hydrogenated. Examples of the hydrogenated polybutadiene skeleton-containing resin include a hydrogenated polybutadiene skeleton-containing epoxy resin. Moreover, as a phenolic hydroxyl group-containing polybutadiene resin, resin etc. which have a polybutadiene structure and have a phenolic hydroxyl group are mentioned.

Specific examples of the polybutadiene resin, which is a resin having a polybutadiene structure in its molecule, is ``BX360'', ``BX660'' (polyphenylene ether-polybutadiene resin) manufactured by Nihon Kayaku Corporation, and ``Ricon 657'' manufactured by Clay Valley (epoxy group). Polybutadiene), ``Ricon 130MA8'', ``Ricon 130MA13'', ``Ricon 130MA20'', ``Ricon 131MA5'', ``Ricon 131MA10'', ``Ricon 131Ma17'', ``Ricon 131MA20'', ``Ricon 184MA6'' (acid anhydride-containing poly Butadiene), ``GQ-1000'' (hydroxyl, carboxyl group-introduced polybutadiene), ``G-1000'', ``G-2000'', ``G-3000'' (polybutadiene at both ends), ``GI-1000'', `` GI-2000'', ``GI-3000'' (both terminal hydroxyl hydrogenated polybutadiene), Daicel's ``PB3600'', ``PB4700'' (polybutadiene skeleton epoxy compound), ``Epofriend A1005'', ``Epofriend A1010'', ``Epofriend A1020'' (epoxy compound of styrene, butadiene and styrene block copolymer), ``FCA-061L'' (hydrogenated polybutadiene skeletal epoxy compound), ``R-45EPT'' (polybutadiene skeletal epoxy compound) manufactured by Nagase Chemtex ), etc.

In addition, as an example of a preferred polybutadiene resin, a linear polyimide butadiene resin made from a hydroxyl group-terminated polybutadiene, a diisocyanate compound, and a polybasic acid or an anhydride thereof (Japanese Laid-Open Patent Publication No. 2006-37083, International Publication No. 2008/153208 The polyimide described in the issue) is also mentioned. The content rate of the polybutadiene structure of the polyimide butadiene resin is preferably 60 to 95% by mass, more preferably 75 to 85% by mass. For details of the polyimide butadiene resin, the description of Japanese Laid-Open Patent Publication No. 2006-37083 and International Publication No. 2008/153208 can be referred to, and the contents are incorporated herein.

The number average molecular weight of the hydroxyl group-terminated polybutadiene as a raw material of the polyimide butadiene resin is preferably 500 to 5,000, more preferably 1,000 to 3,000 from the viewpoint of exhibiting the desired effect of the present invention. The hydroxyl group equivalent of the hydroxyl group-terminated polybutadiene is preferably 250 to 1,250 from the viewpoint of exhibiting the desired effect of the present invention.

As a diisocyanate compound that is a raw material of the polyimide butadiene resin, for example, aromatic diisocyanates such as toluene-2,4-diisocyanate, toluene-2,6-diisocyanate, xylylene diisocyanate, and diphenylmethane diisocyanate. ; Aliphatic diisocyanates such as hexamethylene diisocyanate; Alicyclic diisocyanates, such as isophorone diisocyanate, are mentioned. Among these, aromatic diisocyanate is preferable, and toluene-2,4-diisocyanate is more preferable.

Examples of the polybasic acid or its anhydride as a raw material of the polyimide butadiene resin include ethylene glycol bistrimeric acid, pyromellitic acid, benzophenone tetracarboxylic acid, biphenyl tetracarboxylic acid, naphthalene tetracarboxylic acid (5-(2,5- Tetrabasic acids such as dioxotetrahydrofuryl)-3-methyl-cyclohexene-1,2-dicarboxylic acid, 3,3'-4,4'-diphenylsulfonetetracarboxylic acid, and anhydrides thereof, trimellitic acid, Tribasic acids such as cyclohexanetricarboxylic acid and anhydrides thereof, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho (1,2-C) furan-1,3-dione, etc. are mentioned.

The polyrotaxane resin is a resin having a structure having a plurality of cyclic molecules, a linear axial molecule that is enclosed so as to penetrate the cyclic molecule, and a blocking group in which the end of the axial molecule is blocked so that the cyclic molecule is not removed. The number of cyclic molecules (inclusion amount) in the polyrotaxane resin is not particularly limited as long as the number of cyclic molecules is within a range of two or more, but for example, one axial molecule penetrates a plurality of cyclic molecules. When enclosing in a state where the cyclic molecule is maximally enclosed to one axial molecule (maximum enclosing amount) is 100%, preferably 10% or more, more preferably 15% or more, even more preferably Is 20% or more, preferably 90% or less, more preferably 85% or less, and still more preferably 80% or less. The amount of inclusion can be determined by the length of the axial molecule and the thickness of the cyclic molecule. For example, when the axial molecule is polyethylene glycol and the cyclic molecule is an α-cyclodextrin molecule, the maximum inclusion amount is experimentally determined (see Macromolecules 1993, 26, 5698-5703).

As the axial molecule in the polysiloxane resin, a linear molecule having a molecular weight of 10,000 or more and capable of chemically modifying the terminal with a blocking group can be used. "Linear" indicates that the axial molecule is substantially straight, and the axial molecule may have a branched chain as long as the cyclic molecule through which the axial molecule passes can be rotated or moved. Examples of the axial molecule include polyvinyl alcohol, polyvinylpyrrolidone, poly(meth)acrylate cellulose resin, polyacrylamide, polyethylene oxide, polyethylene glycol, polypropylene glycol, polyvinyl acetal resin, and polyvinylmethyl Ether, polyamine, polyethyleneimine, casein, gelatin, starch, polyolefin, polyester, polyvinyl chloride, polystyrene, acrylonitrile-styrene copolymer and other copolymers, acrylic resins, polycarbonate, polyurethane, polyvinyl butyral, poly Isobutylene, polytetrahydrofuran, polyamide, polyimide, polydiene, polysiloxane, polyurea, polysulfide, polyphosphazene, polyketone, polyphenylene, polyhaloolefin and derivatives thereof, and the like. . Among these, a polyethylene glycol chain is suitably used. Two or more of these may be mixed in the polyrotaxane resin.

The length of the axial molecule is not particularly limited as long as the cyclic molecule can rotate or move. The length of the axial molecule can be expressed using the weight average molecular weight. As the weight average molecular weight of the axial molecule, it is preferably 3,000 or more, more preferably 4,000 or more, still more preferably 5,000 or more, preferably 100,000 or less, more preferably 90,000 or less, even more preferably 85,000 or less. The weight average molecular weight of the axial molecule is the weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC).

The axial molecule usually has a structure in which a molecule containing a main chain group reacts and bonds to an electric functional group of a molecule having a functional group at both ends. As a functional group, an amide group, a hydroxyl group, a carboxyl group, an acrylic group, a methacryl group, an epoxy group, a vinyl group, etc. are mentioned preferably, for example.

As the cyclic molecule in the polyrotaxane resin, a molecule having at least one reactive group (functional group) can be used, which is a cyclic molecule that can be encapsulated while passing through the axial molecule, and can react with the (E) curing agent. A cyclic molecule refers to a molecule that is substantially cyclic, and ``substantially cyclic'' means that it is not completely cyclized, and includes ones having an overlapping helical structure without one end and multistage of English ``C'' being bonded. Structure. Examples of the cyclic molecules include cyclodextrins, crown ethers, creep stands, large cyclic amines, calix arenes, and cyclophanes. Among these, cyclodextrins are preferred. Two or more of these may be mixed in the polyrotaxane resin.

Examples of cyclodextrins include α-cyclodextrin, β-cyclodextrin, γ-cyclodextrin, dimethylcyclodextrin and glucosylcyclodextrin, derivatives or modified products thereof, and the like.

It is preferred that the cyclic molecule contains a reactive group. Examples of the reactor include a hydroxyl group, a carboxyl group, an acrylic group, a methacrylic group, an epoxy group, and a vinyl group, and among them, a hydroxyl group is preferable. When the cyclic molecules have a reactive group, the cyclic molecules or the polyrotaxane resin and the thermosetting resin can be crosslinked through a curing agent. Further, the reactive group of one cyclic molecule and the reactive group of the other cyclic molecule may be crosslinked. One type of reactor may be used alone, or two or more types of reactors may be used.

The reactor does not need to be directly bonded to the cyclic molecule. For example, when the cyclic molecule is a cyclodextrin, the hydroxyl group present in the cyclodextrin itself is a reactive group, and when a hydroxypropyl group is added to the hydroxyl group, the hydroxyl group of the hydroxypropyl group is also a reactive group. Alternatively, when ring-opening polymerization of ε-caprolactone is carried out via a hydroxyl group of the hydroxypropyl group to have a caprolactone chain, the hydroxyl group located at the end opposite to the polyester moiety in the caprolactone chain is a reactive group.

The cyclic molecule may have one per cyclic molecule, and may have two or more.

The weight average molecular weight of the cyclic molecule is preferably 5,000 or more, more preferably 6,000 or more, still more preferably 7,000 or more, preferably 1,500,000 or less, more preferably 1,400,000 or less, and even more preferably 1,350,000 or less. The weight average molecular weight of a cyclic molecule is a weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC).

The blocking group in the polysiloxane resin is not particularly limited as long as it has a structure having a volume size such that cyclic molecules are not removed. As a blocking group, a cyclodextrin group, an adamantane group, a dinitrophenyl group, a trityl group, etc. are mentioned, for example. Among these, an adamantane group is preferable. These may be contained individually by 1 type in polyrotaxane resin, and may have 2 or more types.

The weight average molecular weight of the whole polyrotaxane resin is preferably 10,000 or more, more preferably 15,000 or more, still more preferably 20,000 or more, preferably 1,500,000 or less, more preferably 1,400,000 or less, even more preferably 1,350,000 or less to be. The weight average molecular weight of the polyrotaxane resin is the weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC).

The hydroxyl value of the polyrotaxane resin is preferably 45 mgKOH/g or more, more preferably 50 mgKOH/g or more, still more preferably 55 mgKOH/g or more, and preferably 120 mgKOH/g or less. , More preferably 115 mgKOH/g or less, still more preferably 110 mgKOH/g or less. The hydroxyl value can be measured according to JIS K0070.

Although the polyrotaxane resin may be in a liquid form, it is preferably contained in the resin composition in particulate form. The particulate polyrotaxane resin is easy to disperse, and can lower the viscosity of the resin composition.

The average particle diameter of the particulate polyrotaxane resin is preferably 100 nm or more, more preferably 500 nm or more, even more preferably 800 nm or more, preferably 50,000 nm or less, more preferably 40,000 nm or less, More preferably, it is 30,000 nm or less. The particulate polyrotaxane resin having such an average particle diameter is easily dispersed uniformly in the resin composition, and the viscosity of the resin composition is liable to decrease. The average particle diameter can be measured by the same method as the measurement of the average particle diameter in the inorganic filler.

Polyrotaxane resin can be synthesized, for example, by the method described in International Publication No. 01/83566, Japanese Unexamined Patent Publication No. 2005-154675, and Japanese Unexamined Patent Publication No. 4442633.

As for the polyrotaxane resin, a commercial item may be used. As a commercial item, "SH2400B-007", "SH1310P", "Serum Superpolymer A1000" and the like manufactured by Advanced Soft Materials Co., Ltd. can be used. These may be used alone or in combination of two or more.

Polyimide resin is a resin having an imide bond in a repeating unit. In general, the polyimide resin can contain a resin obtained by an imidization reaction of a diamine compound and a tetracarboxylic anhydride. Modified polyimide resins, such as a siloxane-modified polyimide resin, are also contained as a polyimide resin.

The polyimide resin may include, for example, a structure represented by Chemical Formula 1.

In Formula 1,

X ¹ represents a tetravalent group excluding two -CO-O-CO- from tetracarboxylic dianhydride,

X ² represents a divalent group excluding two -NH ₂ from a diamine compound,

n represents an integer of 2 or more.

Although it does not specifically limit as a diamine compound for preparing a polyimide resin, For example, an aliphatic diamine compound and an aromatic diamine compound are mentioned.

As the aliphatic diamine compound, for example, 1,2-diethyldiamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, 1,6-hexamethylenediamine, 1 Linear aliphatic diamine compounds such as ,5-diaminopentane and 1,10-diaminodecane; Branched-chain aliphatic diamine compounds such as 1,2-diamino-2-methylpropane, 2,3-diamino-2,3-butane, and 2-methyl-1,5-diaminopentane; Alicyclic diamines such as 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, 1,4-diaminocyclohexane, and 4,4'-methylenebis(cyclohexylamine) compound; Dimer acid type diamine (hereinafter also referred to as "dimer diamine"), and the like.

The dimer acid type diamine means a diamine compound obtained by substituting two terminal carboxylic acid groups (-COOH) of a dimer acid with an aminomethyl group (-CH ₂ -NH ₂ ) or an amino group (-NH ₂ ). Dimeric acid is an existing compound obtained by dimerizing an unsaturated fatty acid (preferably having 11 to 22 carbon atoms, particularly preferably having 18 carbon atoms), and its industrial production process is almost standardized in the industry. In particular, dimer acids can be easily obtained, particularly those containing as a main component a dimer acid having 36 carbon atoms obtained by dimerizing an unsaturated fatty acid having 18 carbon atoms such as oleic acid and linoleic acid, which is inexpensive and easy to obtain. In addition, the dimer acid may contain an arbitrary amount of monomeric acid, trimer acid, other polymerized fatty acids, and the like, depending on the production method, the degree of purification, and the like. In addition, although a double bond remains after the polymerization reaction of the unsaturated fatty acid, in the present specification, a hydrogenated substance obtained by further hydrogenation reaction to reduce the degree of unsaturation is also included in the dimer acid. The dimer acid type diamine is commercially available, and examples thereof include PRIAMINE 1073, PRIAMINE 1074, PRIAMINE 1075 manufactured by Croda Japan, and Basamine 551 and Basamine 552 manufactured by Cognis Japan.

As an aromatic diamine compound, a phenylenediamine compound, a naphthalenediamine compound, a dianiline compound, etc. are mentioned, for example.

The phenylenediamine compound means a compound consisting of a benzene ring having two amino groups, wherein the benzene ring may optionally have 1 to 3 substituents. Here, the substituent is not particularly limited. As a phenylenediamine compound, specifically, 1,4-phenylenediamine, 1,2-phenylenediamine, 1,3-phenylenediamine, 2,4-diaminotoluene, 2,6-diaminotoluene, 3 ,5-diaminobiphenyl, 2,4,5,6-tetrafluoro-1,4-phenylenediamine, and the like.

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

The dianiline compound means a compound containing two aniline structures in the molecule, and the two benzene rings in the two aniline structures may each further optionally have 1 to 3 substituents. Here, the substituent is not particularly limited. The two aniline structures in the dianiline compound are a direct bond and/or 1 to 100 (preferably 1 to 50, more preferably 1) selected from carbon atoms, oxygen atoms, sulfur atoms and nitrogen atoms. To 20) of skeletal atoms, and may be bonded through 1 or 2 divalent linking groups. The dianiline compound includes a thing in which two aniline structures are bonded at two places.

As the "divalent linking group" in the dianiline compound, 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 -,

,

(상기 화학식 중, *는 결합 부위를 나타낸다) 등을 들 수 있다. 「Ph」는 1,4-페닐렌기, 1,3-페닐렌기 또는 1,2-페닐렌기를 나타낸다.

,

(In the above formula, * represents a bonding site) and the like. "Ph" represents a 1,4-phenylene group, a 1,3-phenylene group, or a 1,2-phenylene group.

As a dianiline compound, specifically, 4,4'-diamino-2,2'-ditrifluoromethyl-1,1'-biphenyl, 3,4'-diaminodiphenyl ether, 4,4' -Diaminodiphenylether, 3,3'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfide, 4-aminophenyl4-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'-(hexafluoroisopropyridene)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-fluolenylidene)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, 4-aminobenzoic acid 5-amino-1,1'-biphenyl-2-yl, and the like, and preferably 5-(4- Aminophenoxy)-3-[4-(4-aminophenoxy)phenyl]-1,1,3-trimethylindan and 4-aminobenzoic acid 5-amino-1,1'-biphenyl-2-yl.

As the dimine compound, a commercially available one may be used, or one synthesized by a known method may be used. The diamine compounds may be used alone or in combination of two or more.

The tetracarboxylic anhydride for producing the polyimide resin is not particularly limited, and examples thereof include an aromatic tetracarboxylic dianhydride and an aliphatic tetracarboxylic dianhydride.

Examples of the aromatic tetracarboxylic dianhydride include benzene tetracarboxylic dianhydride, naphthalene tetracarboxylic dianhydride, anthracene tetracarboxylic dianhydride, and diphthalic dianhydride, and preferably diphthalic dianhydride.

Benzenetetracarboxylic dianhydride refers to a dianhydride of benzene having 4 carboxyl groups, wherein the benzene ring may optionally have 1 to 3 substituents. Here, the substituent is not particularly limited. Specific examples of the benzene tetracarboxylic dianhydride include pyromellitic dianhydride and 1,2,3,4-benzenetetracarboxylic dianhydride.

Naphthalenetetracarboxylic dianhydride refers to a dianhydride of naphthalene having 4 carboxyl groups, wherein the naphthalene ring may optionally have 1 to 3 substituents. Here, the substituent is not particularly limited. Specific examples of the naphthalene tetracarboxylic dianhydride include 1,4,5,8-naphthalene tetracarboxylic dianhydride and 2,3,6,7-anthracene tetracarboxylic dianhydride.

Anthracenetetracarboxylic dianhydride refers to an anthracene dianhydride having 4 carboxyl groups, wherein the anthracene ring may optionally have 1 to 3 substituents. Here, the substituent is not particularly limited. Specific examples of the anthracene tetracarboxylic dianhydride include 2,3,6,7-anthracene tetracarboxylic dianhydride and the like.

The diphthalic acid dianhydride means a compound containing two phthalic anhydrides in a molecule, and the two benzene rings in the two phthalic anhydrides may each optionally have 1 to 3 substituents. Here, the substituent is not particularly limited. The two phthalic anhydrides in the diphthalic acid dianhydride are direct bonds or 1 to 100 (preferably 1 to 50, more preferably 1 to 100) selected from carbon atoms, oxygen atoms, sulfur atoms and nitrogen atoms. 20) can be bonded via a divalent linking group having skeletal atoms.

As a divalent linking group, 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-, -SO2-, -Ph-, -O-Ph-O-, -O-Ph-SO ₂ -Ph-O-, -O-Ph-C(CH ₃ ) ₂ -Ph-O-, and the like.

As diphthalic acid dianhydride, specifically, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride, 3,3',4 ,4'-diphenylsulfonetetracarboxylic dianhydride, 3,3',4,4'biphenyltetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, 2,3,3 ',4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-benzophenonetetracarboxylic dianhydride, 2,3,3',4'-diphenylethertetracarboxylic dianhydride, 2,3 ,3',4'-diphenylsulfonetetracarboxylic acid dianhydride, 2,2'-bis(3,4-dicarboxyphenoxyphenyl)sulfone dianhydride, methylene-4,4'-diphthalic acid dianhydride, 1, 1-ethynylidene-4,4'-diphthalic dianhydride, 2,2-propylidene-4,4'-diphthalic dianhydride, 1,2-ethylene-4,4'-diphthalic dianhydride, 1,3-trimethylene-4,4'-diphthalic dianhydride, 1,4-tetramethylene-4,4'-diphthalic dianhydride, 1,5-pentamethylene-4,4'-diphthalic dianhydride , 1,3-bis(3,4-dicarboxyphenyl)benzene dianhydride, 1,4-bis(3,4-dicarboxyphenoxy)benzene dianhydride, 1,4-bis(3,4-dicarboxy Phenoxy)benzene dianhydride, 1,4-bis(3,4-dicarboxyphenoxy)benzene dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 2,2-bis( 3,4-dicarboxyphenyl)propane dianhydride, 4,4'-(4,4'-isopropylidenediphenoxy)bisphthalic acid dianhydride, and the like.

As aliphatic tetracarboxylic dianhydride, specifically, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, cyclohexane-1,2,3,4-tetracarboxylic dianhydride, cyclohexane -1,2,4,5-tetracarboxylic dianhydride, 3,3',4,4'-bicyclohexyltetracarboxylic dianhydride, carbonyl-4,4'-bis(cyclohexane-1,2-di Carboxylic acid) dianhydride, methylene-4,4'-bis (cyclohexane-1,2-dicarboxylic acid) dianhydride, 1,2-ethylene-4,4'-bis (cyclohexane-1,2-dicarboxylic acid) Dianhydride, oxy-4,4'-bis (cyclohexane-1,2-dicarboxylic acid) dianhydride, thio-4,4'-bis (cyclohexane-1,2-dicarboxylic acid) dianhydride, sulfonyl- 4,4'-bis (cyclohexane-1,2-dicarboxylic acid) dianhydride, etc. are mentioned.

As the tetracarboxylic dianhydride, a commercially available one may be used, or a compound synthesized by a known method or a method similar thereto may be used. Tetracarboxylic dianhydride may be used singly or in combination of two or more.

The content of the structure derived from the aromatic tetracarboxylic dianhydride with respect to the entire structure derived from the tetracarboxylic dianhydride constituting the polyimide resin is preferably 10 mol% or more, more preferably 30 mol% or more, and 50 mol% or more. It is more preferable that it is more preferably 70 mol% or more, still more preferably 90 mol% or more, and particularly preferably 100 mol%.

It is preferable that the weight average molecular weight of the polyimide resin is 1,000 to 100,000.

The maleimide resin having a dimer acid skeleton is, for example, a bismaleimide compound having a hydrocarbon skeleton derived from dimer acid. The maleimide resin having a dimer acid skeleton is, for example, a bismaleimide compound obtained by imidization reaction of at least a dimer acid type diamine and maleic anhydride, and furthermore, a dimer acid type diamine, tetracarboxylic dianhydride and maleic anhydride are already It contains a bismaleimide compound obtained by deforming reaction.

The maleimide resin having a dimer acid skeleton is, for example, a bismaleimide compound represented by the following formula (2).

In Chemical Formula 2,

Y ¹ and Y ³ each independently represent a divalent group excluding two -NH ₂ from dimer acid-type diamine,

Y ² represents a tetravalent group excluding two -CO-O-CO- from tetracarboxylic dianhydride,

m represents 0 or 1.

Specific examples of the maleimide resin having a dimer acid skeleton include "BMI689", "BMI1500", "BMI1700", and "BMI3000" manufactured by DESIGNER MOLECULES. These may be used individually by 1 type, and may be used in combination of 2 or more types.

(D) The content of the tacky softening agent is not particularly limited, but from the viewpoint of obtaining a cured product with more excellent flexibility, when the nonvolatile component in the resin composition is 100% by mass, preferably 1% by mass or more, more It is preferably 5% by mass or more, more preferably 10% by mass or more, and particularly preferably 15% by mass or more. (D) The upper limit of the content of the tacky softener is not particularly limited, but when the nonvolatile component in the resin composition is 100% by mass, preferably 50% by mass or less, more preferably 40% by mass or less, further preferably It is preferably 30% by mass or less, particularly preferably 25% by mass or less.

<(E) curing agent>

The resin composition of the present invention may contain (E) a curing agent as an optional component. (E) Curing agent has a function of curing (A) thermosetting resin.

(E) Although it does not specifically limit as a curing agent, When (A) thermosetting resin is an epoxy resin, For example, a phenol type curing agent, a naphthol type curing agent, an acid anhydride type curing agent, an active ester curing agent, a benzoxazine type curing agent, a cyanate Ester-based curing agents and carbodiimide-based curing agents, and phenolic curing agents, naphthol-based curing agents, and active ester curing agents are preferred. (E) It is preferable that the curing agent contains an active ester curing agent. Hardeners may be used alone or in combination of two or more.

As the phenolic curing agent and the naphthol curing agent, from the viewpoint of heat resistance and water resistance, a phenolic curing agent having a novolac structure or a naphthol curing agent having a novolac structure is preferable. Further, from the viewpoint of adhesion to an 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 curing agent is more preferable. Among these, a triazine skeleton-containing phenol novolac resin is preferred from the viewpoint of highly satisfying heat resistance, water resistance, and adhesion. Specific examples of the phenolic curing agent and the naphthol curing agent include, for example, "MEH-7700", "MEH-7810", "MEH-7851" manufactured by Meiwa Kasei, "NHN", "CBN" manufactured by Nihon Kayaku Corporation. '', ``GPH'', ``SN-170'', ``SN-180'', ``SN-190'', ``SN-475'', ``SN-485'', ``SN-495'' manufactured by Shin-Nitetsu Sumiking Chemical Co., Ltd. "SN-375", "SN-395", "LA-7052", "LA-7054", "LA-3018", "LA-3018-50P", "LA-1356", "TD2090" manufactured by DIC Corporation ", "TA-2090-60M", etc. are mentioned.

Examples of the acid anhydride-based curing agent include a curing agent having at least one acid anhydride group in one molecule. Specific examples of the acid anhydride-based curing agent include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, hydrogenated methylnadic anhydride, trialkyltetrahydrophthalic anhydride , Dodecenyl succinic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trimellitic anhydride, pyromerite anhydride Acid, benzophenonetetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, naphthalene tetracarboxylic dianhydride, oxydiphthalic dianhydride, 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride, 1,3, 3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2-C]furan-1,3-dione, ethylene glycolbis (Anhydrotrimericate), and polymeric acid anhydrides such as styrene maleic acid resin in which styrene and maleic acid are copolymerized. As commercially available products of the acid anhydride-based curing agent, "HNA-100", "MH-700" and the like manufactured by Shinnihon Rika Corporation are mentioned.

The active ester curing agent is not particularly limited, but generally, there are two ester groups with high reactive activity such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds. Compounds having the above are preferably used. It is preferable that the said active ester curing agent is obtained by condensation reaction of a carboxylic acid compound and/or a thiocarboxylate compound, and a hydroxy compound and/or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester curing agent obtained from a carboxylic acid compound and a hydroxy compound is preferable, and an active ester curing agent obtained from a carboxylic acid compound, 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, pyromellitic acid, and the like. As a phenol compound or a naphthol compound, for example, hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthalin, 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, fluoroglucine, benzenetriol, dicyclopentadiene-type diphenol compound, phenol novolac, and the like. Here, the "dicyclopentadiene-type diphenol compound" refers to a diphenol compound obtained by condensing two molecules of phenol into one molecule of dicyclopentadiene.

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 a benzoylated product of phenol novolac. Active ester compounds are preferable, and among them, 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" refers to a divalent structural unit composed of phenylene-dicyclopentalene-phenylene.

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

As specific examples of the benzoxazine-based curing agent, "JBZ-OP100D" and "ODA-BOZ" manufactured by JFE Chemical Co., Ltd.; "HFB2006M" manufactured by Showa Kohunshi; "P-d" and "F-a" manufactured by Shikoku Chemical Co., Ltd. are mentioned.

As a cyanate ester curing agent, for example, bisphenol A dicyanate, polyphenol cyanate (oligo(3-methylene-1,5-phenylene cyanate)), 4,4'-methylenebis(2,6 -Dimethylphenyl cyanate), 4,4'-ethylidenediphenyldicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanate)phenylpropane, 1,1-bis(4 -Cyanatephenylmethane), bis(4-cyanate-3,5-dimethylphenyl)methane, 1,3-bis(4-cyanatephenyl-1-(methylethylidene))benzene, bis(4- Difunctional cyanate resins such as cyanate phenyl) thioether and bis (4-cyanate phenyl) ether, polyfunctional cyanate resins derived from phenol novolacs and cresol novolacs, and some of these cyanate resins are triazineized Prepolymers and the like are mentioned. As specific examples of the cyanate ester curing agent, ``PT30'' and ``PT60'' (both phenol novolak type polyfunctional cyanate ester resins) manufactured by Ronza Japan, ``BA230'', ``BA230S75'' (part of bisphenol A dicyanate) Or a prepolymer in which all of them are triazineized to become a trimer), and the like.

As specific examples of the carbodiimide-based curing agent, "V-03" and "V-07" manufactured by Nissei Bo Chemicals Co., Ltd. are mentioned.

When the resin composition contains (E) a curing agent, the amount ratio of (A) thermosetting resin and (E) curing agent is a ratio of [the total number of reactors of the thermosetting resin]: [the total number of reactors of the curing agent], 1: The range of 0.2 to 1:2 is preferable, 1:0.3 to 1:1.5 are more preferable, and 1:0.4 to 1:1.2 are more preferable. Here, the reactive group of the curing agent is an active hydroxyl group, an active ester group, and the like, and varies depending on the type of curing agent. The reactor of the thermosetting resin is an epoxy group or the like, and varies depending on the type of the thermosetting resin.

When the resin composition contains the curing agent (E), the content is not particularly limited, but when the nonvolatile component in the resin composition is 100% by mass, preferably 0.1% by mass or more, more preferably 1% by mass It is above, more preferably 3% by mass or more, and particularly preferably 4% by mass or more. (E) The upper limit of the content of the curing agent is not particularly limited, but when the nonvolatile component in the resin composition is 100% by mass, preferably 30% by mass or less, more preferably 20% by mass or less, further preferably It is 15% by mass or less, particularly preferably 10% by mass or less.

<(F) hardening accelerator>

The resin composition of the present invention may contain (F) a curing accelerator as an optional component. (F) The curing accelerator has a function of accelerating the curing rate of the (A) thermosetting resin.

(F) Although it does not specifically limit as a curing accelerator, (A) When the thermosetting resin is an epoxy resin, for example, a phosphorus curing accelerator, an amine curing accelerator, an imidazole curing accelerator, a guanidine curing accelerator, a metal curing accelerator And the like. Among these, a phosphorus-based curing accelerator, an amine-based curing accelerator, an imidazole-based curing accelerator, and a metallic curing accelerator are preferable, and an amine-based curing accelerator is more preferable. The hardening accelerator may be used individually by 1 type, and may be used in combination of 2 or more types.

Examples of phosphorus-based curing accelerators include triphenylphosphine, phosphonium borate compounds, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, (4-methylphenyl)triphenyl Phosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyl triphenylphosphonium thiocyanate, etc. are mentioned.

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

Examples of the imidazole-based curing accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, and 2-ethyl-4-methyl Imidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methyl Midazole, 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 trimeritate, 1-cyanoethyl-2-phenylimidazolium Trimeritate, 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-pyrroro[1,2-a ]Imidazole compounds such as benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, and 2-phenylimidazoline, and adducts of imidazole compounds and epoxy resins A sieve can be mentioned.

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

Examples of the guanidine-based curing accelerator include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, dimethylguanidine, and diphenylguanidine. , Trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo[4.4.0]deca-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-allyl biguanide, 1-phenyl biguanide, 1-(o-tolyl) biguanide, etc. are mentioned.

Examples of the metal-based curing accelerator include an organic metal complex or an organic metal salt of a metal such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of the organometallic 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. Organic zinc complexes, 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 organometallic salt include zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, zinc stearate, and the like.

When the resin composition contains (F) a curing accelerator, the content is not particularly limited, but when the nonvolatile component in the resin composition is 100% by mass, preferably 0.001% by mass or more, more preferably 0.01% by mass % Or more, more preferably 0.05% by mass or more, particularly preferably 0.1% by mass or more. (F) The upper limit of the content of the curing accelerator is not particularly limited, but when the nonvolatile component in the resin composition is 100% by mass, preferably 2% by mass or less, more preferably 1% by mass or less, further preferably Is 0.5% by mass or less, particularly preferably 0.3% by mass or less.

<(G) Other additives>

The resin composition of the present invention may further contain an optional additive as a nonvolatile component. Examples of such additives include phenoxy resins, polyvinyl acetal resins, polyolefin resins, polysulfone resins, polyethersulfone resins, polyphenylene ether resins, polycarbonate resins, polyether ether ketone resins, polyester resins, etc. Thermoplastic resin; Organometallic compounds such as organocopper compounds, organozinc compounds, and organocobalt compounds; Colorants such as phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium oxide, and carbon black; Polymerization inhibitors such as hydroquinone, catechol, pyrogarol, and phenothiadine; Leveling agents such as siloxane; Thickeners such as bentone and montmorillonite; Antifoaming agents such as silicone antifoam, acrylic antifoam, fluorine antifoam, and vinyl resin antifoam; Ultraviolet absorbers such as benzotriazole-based ultraviolet absorbers; Adhesion improving agents such as urea silane; Antioxidants such as a silane coupling agent, a triazole-based adhesive imparting agent, a hindered phenol-based antioxidant, and a hindered amine-based antioxidant; Adhesive imparting agents such as tetrazole-based adhesive imparting agents and triazine-based adhesive imparting agents; Optical brighteners such as stilbene derivatives; Flame retardants such as phosphorus-based flame retardants (for example, phosphoric acid ester compounds, phosphazene compounds, phosphinic acid compounds, red), nitrogen-based flame retardants (for example, melamine sulfate), halogen-based flame retardants, and inorganic flame retardants (for example, antimony trioxide), etc. Can be mentioned. Additives may be used singly or in combination of two or more at an arbitrary ratio. (G) The content of other additives can be appropriately set by those skilled in the art.

<(H) organic solvent>

The resin composition of the present invention may further contain an optional organic solvent as a volatile component in addition to the above nonvolatile component. (H) As an organic solvent, as long as it can dissolve at least part of a nonvolatile component, a well-known thing can be used suitably, and its kind is not specifically limited. (H) Examples of the organic solvent include ketone solvents such as anthone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; Ester solvents such as methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, isoamyl acetate, methyl propionate, ethyl propionate, and γ-butyrolactone; Ether solvents such as tetrahydropyran, tetrahydrofuran, 1,4-dioxane, diethyl ether, diisopropyl ether, dibutyl ether, and diphenyl ether; Alcohol solvents such as methanol, ethanol, propanol, butanol, and ethylene glycol; Ether ester solvents such as 2-ethoxyethyl acetate, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl diglycol acetate, γ-butyrolactone, and methyl methoxypropionate; Ester alcohol solvents such as methyl lactate, ethyl lactate, and methyl 2-hydroxyisobutyrate; Ether alcohol-based solvents such as 2-methoxypropanol, 2-methoxyethanol, 2-ethoxyethanol, propylene glycol monomotyl ether, and diethylene glycol monobutyl ether (butylcarbitol); Amide group solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone; Sulfoxide solvents such as dimethyl sulfoxide; Nitrile solvents such as acetonitrile and propionitrile; Aliphatic hydrocarbon solvents such as hexane, cyclopentane, cyclohexane, and methylcyclohexane; And aromatic hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, and trimethylbenzene. Organic solvents may be used alone or in combination of two or more in an arbitrary ratio.

(H) The content of the organic solvent is the mass ratio of the non-volatile component to the total mass of the resin composition, that is, the solid content, from the viewpoint of efficiently drying the resin composition, preferably 30% by mass or more, more preferably It may be set to be 35% by mass or more, more preferably 40% by mass or more, and particularly preferably 45% by mass or more. The upper limit of the solid content is not particularly limited, but from the viewpoint of handleability of the resin composition, preferably 100% by mass or less, more preferably 95% by mass or less, still more preferably 92% by mass or less, particularly preferably 90 It may be less than or equal to mass%.

<Production method of resin composition>

The resin composition of the present invention, for example, in an arbitrary reaction vessel (A) a thermosetting resin, (B) an inorganic filler, (C) an organic filler, (D) an adhesive softening agent, if necessary (E) a curing agent, required It can be produced by adding (F) a curing accelerator, optionally (G) other additives, and (H) an organic solvent, if necessary, in any order and/or at the same time in part or all of them and mixing. In addition, in the process of adding and mixing each component, the temperature can be appropriately set, and may be heated and/or cooled temporarily or continuously. Further, in the process of adding and mixing each component, stirring or shaking may be performed. Further, at the time of adding and mixing or after that, the resin composition may be stirred using a stirring device such as a mixer, and uniformly dispersed.

<Characteristics of resin composition>

The resin composition of the present invention is added to (A) a thermosetting resin, (D) an adhesive softener, and (B) an inorganic filler, and contains 5% by mass or more of (C) an organic filler, so that the tackiness is low while maintaining excellent flexibility. Can be suppressed.

Since the resin composition of the present invention contains (D) an adhesive softening agent, since it has sufficient flexibility, for example, a layered cured product of a resin composition having a thickness of 40 µm, a width of 15 mm, and a length of 110 mm is obtained from JIS In accordance with C-5016, the number of times the MIT cutting resistance test was performed by setting the load 2.5N, bending angle 90 degrees, bending speed 175 times/minute, and bending radius 1.0mm is preferably 3,000 times or more, more preferably It may be 5,000 or more, more preferably 7,000 or more, and particularly preferably 8,000 or more.

The resin composition of the present invention has a minimum melt viscosity of the resin composition measured under the conditions of, for example, an initiation temperature of 60°C to 200°C, a heating rate of 5°C/min, a frequency of 1 Hz, and a strain of 1 deg, preferably 40,000 poise. Hereinafter, it may be preferably 30,000 poise or less, preferably 20,000 poise or less, preferably 10,000 poise or less.

Since the resin composition of the present invention contains (C) an organic filler, for example, for a layered resin composition, using a probe tack tester, a probe φ 5 mm , a load of 1 kgf/cm 2, a contact speed of 0.5 mm/second, The tack force measured under the conditions of a tensile speed of 0.5 mm/sec, a holding time of 10 seconds, and a temperature of 80°C is preferably 2.0 N or less, more preferably 1.8 N or less, still more preferably 1.7 N or less, particularly preferably 1.6 It can be less than N.

In addition, the resin composition of the present invention has characteristics that void defects are suppressed and pattern embedding properties are more excellent, particularly when the content of the organic filler (C) is 10% by mass or less.

<Resin sheet>

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

The thickness of the resin composition layer is preferably 200 µm or less, more preferably 150 µm or less, still more preferably 100 µm or less, and particularly preferably 70 µm or less. The lower limit of the thickness of the resin composition layer is not particularly limited, but may usually be 1 µm or more, 1.5 µm or more, 2 µm or more, and the like.

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 is, for example, polyethylene terephthalate (hereinafter sometimes abbreviated as ``PET''), polyethylene naphthalate (hereinafter sometimes abbreviated as ``PEN''). ) Polyester, polycarbonate (hereinafter sometimes abbreviated as ``PC''), acrylic such as polymethyl methacrylate (PMMA), cyclic polyolefin, triacetylcellulose (TAC), polyether sulfide (PES), Polyether ketone, polyimide, and the like. Among these, polyethylene terephthalate and polyethylene naphthalate are preferred, and inexpensive polyethylene terephthalate is particularly preferred.

When using a metal foil as a support, as a metal foil, a copper foil, an aluminum foil, etc. are mentioned, for example, and a 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 other metals (e.g., tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) may be used. Also good.

The support may be subjected to a mat treatment, a corona treatment, or an antistatic treatment to the surface to be bonded to the resin composition layer.

Further, as the support, a support with a release layer having a release layer on the surface to be bonded to the resin composition layer may be used. As a releasing agent used for the releasing layer of the support with a releasing layer, for example, one or more releasing agents selected from the group consisting of alkyd resins, polyolefin resins, urethane resins, and silicone resins can be mentioned. As a support with a release layer, a commercial item may be used. For example, "SK-1", "AL-5", and "AL-" manufactured by Lintec, which are PET films having a release layer containing an alkyd resin-based release agent as a main component. 7", "Lumira T60" by Tore, "Purex" by Teijin, "Uni-Feel" by Unichika, etc. are mentioned.

Although it does not specifically limit as a thickness of a support body, the range of 5 to 75 micrometers is preferable, and the range of 10 to 60 micrometers is more preferable. Moreover, when using a support body with a release layer, it is preferable that the thickness of the whole support body with a release layer is the said range.

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

The resin sheet can be prepared by applying the resin composition as it is or by applying a resin varnish prepared by dissolving the resin composition in an organic solvent, for example, on a support using a die coater, and further drying to form a resin composition layer. have.

Examples of the organic solvent that can be used when applying on the support include those listed in the description of the organic solvent (H). Organic solvents may be used alone or in combination of two or more.

Drying may be performed by a known method such as heating and hot air spraying. Although drying conditions are not particularly limited, drying is performed so that the content of the organic solvent in the resin composition layer is 10% by mass or less, preferably 5% by mass or less. It also differs depending on the boiling point of the organic solvent in the resin composition or resin varnish, but, for example, when using a resin composition or resin varnish containing 30 to 60% by mass of an organic solvent, drying at 50 to 150°C for 3 to 10 minutes By doing so, a resin composition layer can be formed.

The resin sheet can be wound and stored in a roll shape. When a resin sheet has a protective film, it becomes usable by peeling a protective film.

<Laminated sheet>

The laminated sheet is a sheet produced by laminating and curing a plurality of resin composition layers. The laminated sheet includes a plurality of insulating layers as a cured product of the resin composition layer. Usually, in order to manufacture a laminated sheet, the number of layers of the resin composition to be laminated 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, and particularly preferably 10 or less.

A laminated sheet is a sheet that is bent and used so that one side thereof faces each other. The minimum bending radius of the bend of the laminated sheet is not particularly limited, but is preferably 0.1 mm or more, more preferably 0.2 mm or more, particularly preferably 0.3 mm or more, preferably 5 mm or less, more preferably It is 4 mm or less, and particularly preferably 3 mm or less.

Holes 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 a multilayer flexible substrate.

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

The conductor material used for the conductor layer is not particularly limited. In a suitable embodiment, the conductor layer contains at least one metal selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin and indium. do. The conductor material may be a single metal or an alloy. As an alloy, an alloy of two or more types of metals selected from the above group (for example, a nickel/chromium alloy, a copper/nickel alloy, and a copper/titanium alloy) can be mentioned. Among these, chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper as a single metal from the viewpoints of versatility, cost, and ease of patterning for forming a conductor layer; And alloys such as nickel-chromium alloy, copper-nickel alloy, and copper-titanium alloy; This is desirable. Among them, monometals of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper; And nickel-chromium alloys; This is more preferable, and a single metal of copper is even more preferable.

The conductor layer may have a single layer structure, or a multilayer structure including two or more single metal layers or alloy layers made of different types 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 a 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 to 35 µm, more preferably 5 to 30 µm, still more 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 2,000 µm or less, more preferably 1,000 µm or less, particularly preferably 500 µm Below.

<Method of manufacturing a laminated sheet>

The laminated sheet can be produced 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 composition layers using a resin sheet. The order of lamination and curing of the resin composition layer is arbitrary as long as a desired laminated sheet is obtained. For example, after laminating all of the plurality of resin composition layers, the laminated plurality of resin composition layers may be collectively cured. Further, for example, whenever another resin composition layer is laminated on a certain resin composition layer, the laminated resin composition layer may be cured.

Hereinafter, a preferred embodiment of the step (b) will be described. In the embodiments described below, for the purpose of discrimination, the resin composition layer is appropriately numbered as in the "first resin composition layer" and the "second resin composition layer", and further, insulation obtained by curing these resin composition layers Like the resin composition layer, the layer is also numbered and indicated as in the "first insulating layer" and "second insulating layer".

In one preferred embodiment, step (b) is

(II) curing the first resin composition layer to form a first insulating layer,

(VI) a step of laminating a second resin composition layer on the first insulating layer, and

(VII) Step of curing the second resin composition layer to form a second insulating layer

Includes. In addition, step (b), if necessary,

(I) the step of laminating the first resin composition layer on the sheet supporting substrate,

(III) step of perforating the first insulating layer,

(IV) step of applying a roughening treatment to the first insulating layer,

(V) Step of forming a conductor layer on the first insulating layer

Arbitrary processes, such as may be included. Hereinafter, each process is demonstrated.

Step (I) is a step of laminating a first resin composition layer on a sheet supporting substrate prior to step (II). The sheet supporting base material is a peelable member, for example, a plate-like, sheet-like, or film-like member is used.

Lamination of the sheet supporting substrate and the first resin composition layer may be performed by a vacuum lamination method. In the vacuum lamination method, the heating compression temperature is preferably in the range of 60 to 160°C, more preferably 80 to 140°C, and the heating compression pressure is preferably in the range of 0.098 to 1.77 MPa, more preferably 0.29 to 1.47 MPa And the heating and pressing time is preferably in the range of 20 to 400 seconds, more preferably 30 to 300 seconds. Lamination is preferably carried out under reduced pressure conditions of 26.7 hPa or less.

Lamination can be performed by a commercially available vacuum laminator. Examples of commercially available vacuum laminators include a vacuum pressurized laminator manufactured by Meiki Sesakusho Co., Ltd., a vacuum applicator manufactured by Nikko Materials Corporation, and a batch vacuum pressurized laminator.

In the case of using a resin sheet, the lamination of the sheet supporting substrate and the first resin composition layer is performed by, for example, pressing the resin sheet from the support side and heat-pressing the first resin composition layer of the resin sheet to the sheet supporting substrate. Can be done. As a member for heat-pressing the resin sheet to the sheet supporting substrate (hereinafter, it may be appropriately referred to as "heat-pressing member"), for example, a heated metal plate (SUS hard plate, etc.) or a metal roll (SUS roll), etc. I can. It is preferable to press through an elastic material such as heat-resistant rubber so that the first resin composition layer is sufficiently harvested in the surface irregularities of the sheet supporting substrate without directly pressing the heat-pressed member onto the resin sheet.

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

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

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

Before thermosetting the first resin composition layer, you may preheat the first resin composition layer at a temperature lower than the curing temperature. For example, prior to thermosetting the first resin composition layer, at a temperature of 50°C or more and less than 120°C (preferably 60°C or more and 115°C or less, more preferably 70°C or more and 110°C or less), the first You may preheat the resin composition layer for 5 minutes or more (preferably 5 to 150 minutes, more preferably 15 to 120 minutes, still more preferably 15 to 100 minutes).

Step (III) is a step of drilling the first insulating layer. Through this step (III), holes such as via holes and through holes can be formed in the first insulating layer. The perforation may be performed using, for example, a drill, a laser, or plasma, 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 applying a roughening treatment to the first insulating layer. Usually, smear is also removed in this step (IV). Therefore, the roughening process is also called a desmear process. Examples of the roughening treatment include a method of performing a swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralization treatment with a neutralizing liquid in this order.

Although it does not specifically limit as a swelling liquid, Alkali aqueous solutions, such as an aqueous sodium hydroxide solution and an aqueous potassium hydroxide solution, are mentioned. As a commercially available swelling liquid, "Swelling Deep Securigans P" and "Swelling Deep Securigans SBU" manufactured by Atotech Japan can be mentioned, for example. The swelling treatment with a swelling liquid can be performed, for example, by immersing the cured product in a swelling liquid of 30 to 90°C for 1 to 20 minutes. From the viewpoint of suppressing the swelling of the insulating layer resin to an appropriate level, it is preferable to immerse the insulating layer in a swelling liquid at 40 to 80°C for 5 to 15 minutes.

Although it does not specifically limit as an oxidizing agent, For example, an alkaline permanganic acid solution obtained by dissolving permanganate in an aqueous sodium hydroxide solution and an aqueous potassium hydroxide solution can be mentioned. The concentration of permanganate in the alkaline permanganic acid solution is preferably 5 to 10% by mass. Examples of commercially available oxidizing agents include alkaline permanganic acid solutions such as ``Concentrate Compact P'' manufactured by Atotech Japan, ``Concentrate Compact CP'', and ``Dosing Solution Securigans P''. . The roughening treatment with an oxidizing agent can be performed by immersing the cured product in the oxidizing agent solution heated at 60 to 80°C for 10 to 30 minutes.

In addition, an acidic aqueous solution is used as the neutralizing liquid. As a commercial item, "Reduction Solution Securigant P" made by Atotech Japan is mentioned, for example. Treatment with the neutralizing liquid can be performed by immersing the cured product in the neutralizing liquid at 30 to 80°C for 5 to 30 minutes. From the viewpoint of workability and the like, it is preferable to immerse the cured product in a neutralizing solution at 40 to 70°C for 5 to 20 minutes.

The arithmetic mean roughness (Ra) of the surface of the first insulating layer after the roughening treatment is preferably 400 nm or less, more preferably 300 nm or less, and 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, and 50 nm or more.

Step (V) is a step of forming a conductor layer over the first insulating layer, if necessary. Examples of the method of forming the conductor layer include a plating method, a sputtering method, a vapor deposition method, and the like, and among them, a plating method is preferable. As a suitable example, a method of forming a conductor layer having a desired wiring pattern by plating the surface of the first insulating layer by a suitable method such as a semi-additive method and a full-additive method. Among these, the semi-additive method is preferable from the viewpoint of the simplicity of production.

Hereinafter, an example of forming a conductor layer by a semiadditive method is shown. First, a plating seed layer is formed on the surface of the first insulating layer by electroless plating. Subsequently, on the formed plating seed layer, a mask pattern for exposing a part of the plating seed layer corresponding to a desired wiring pattern is formed. On the exposed plating seed layer, a metal layer is formed by electrolytic plating, and then the mask pattern is removed. Thereafter, the unnecessary plating seed layer is removed by a process such as etching, so that a conductor layer having a desired wiring pattern can be formed.

A first insulating layer is obtained in step (II), and if necessary, step (III), step (IV), and step (V) are performed, and then step (VI) is performed. Step (VI) is a step of laminating a second resin composition layer on the first insulating layer. Lamination of the first insulating layer and the second resin composition layer can be performed in the same manner as the lamination of the sheet supporting substrate and the first resin composition layer in step (I).

However, in the case where the first resin composition layer is formed using a resin sheet, the support of the resin sheet is removed before the step (VI). Removal of the support may be performed between step (I) and step (II), may be performed between step (II) and step (III), may be performed between step (III) and step (IV), or step It may be performed between (IV) and step (V).

Step (VII) is carried out after step (VI). Step (VII) is a step of hardening the second resin composition layer to form a second insulating layer. The curing of the second resin composition layer can be performed in the same manner as the curing of the first resin composition layer in step (II). Thereby, a laminated sheet including a plurality of insulating layers such as a first insulating layer and a second insulating layer can be obtained.

Further, in the method according to the above embodiment, if necessary, (VIII) a step of drilling the second insulating layer, (IX) a step of applying a roughening treatment to the second insulating layer, and (X) a conductor on the second insulating layer. You may perform the process of forming a layer. The perforation of the second insulating layer in step (VIII) can be performed in the same manner as the perforation of the first insulating layer in step (III). In addition, the roughening treatment of the second insulating layer in the step (IX) can be performed in the same manner as the roughening treatment of the first insulating layer in the step (IV). In addition, the formation of the conductor layer over the second insulating layer in step (X) can be performed in the same manner as the formation of the conductor layer over the first insulating layer in step (V).

In the above embodiment, an embodiment in which a laminated sheet is produced by laminating and curing two layers of resin composition layers such as a first resin composition layer and a second resin composition layer has been described, but lamination and curing of three or more resin composition layers You may manufacture a laminated sheet by this. For example, in the method according to the above-described embodiment, lamination and curing of the resin composition layer by steps (VI) to (VII), and, if necessary, the insulating layer by steps (VIII) to (X). A laminated sheet may be produced by repeatedly performing perforation of, roughening treatment of the insulating layer, and formation of a conductor layer on the insulating layer. As a result, a laminated sheet including three or more insulating layers is obtained.

In addition, the method according to the above-described embodiment may include arbitrary steps other than the above-described steps. For example, when step (I) is performed, a step of removing the sheet supporting substrate may be performed.

<Multilayer Flexible Substrate>

The multilayer flexible substrate includes a laminated sheet. The multilayer flexible substrate may contain only the laminated sheet, or may contain any member according to the laminated sheet. As an arbitrary member, an electronic component, a coverlay film, etc. are mentioned, for example.

The multilayer flexible substrate can be manufactured by a manufacturing method including the method of manufacturing the laminated sheet described above. 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 composition layers using a resin sheet.

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

The electric multilayer flexible substrate can be generally bent so that one side of the laminated sheet included in the multilayer flexible substrate faces to face. For example, a multilayer flexible substrate is accommodated in a housing of a semiconductor device while being bent and reduced in size. Further, for example, in a semiconductor device having a bendable movable part, a multilayer flexible substrate is provided on the movable part.

<Semiconductor device>

The semiconductor device includes an electric multilayer flexible substrate. A 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 can be accommodated in a housing of the semiconductor device by bending one side of the laminated sheet included in the multilayer flexible substrate to face.

As semiconductor devices, for example, various semiconductors provided in electric products (for example, computers, mobile phones, digital cameras, televisions, etc.) and vehicles (for example, motorcycles, automobiles, tanks, ships and aircraft, etc.) Device.

The above-described semiconductor device includes, for example, a step of preparing a multilayer flexible substrate, a step of bending the multilayer flexible substrate so that one side of the laminate sheet faces, and a step of accommodating the bent multilayer flexible substrate in a housing. It can be manufactured by a manufacturing method.

[Example]

Hereinafter, examples of the present invention will be described in detail. However, the present invention is not limited to the following examples. In the following description, "parts" and "%" representing amounts mean "parts by mass" and "% by mass", respectively, unless otherwise specified. In addition, the operation described below was performed in an environment of room temperature and pressure unless otherwise specified.

<Synthesis Example 1: Synthesis of phenolic hydroxyl group-containing polybutadiene resin>

In the reaction vessel, 69 g of bifunctional hydroxy group-terminated polybutadiene ("G-3000" manufactured by Nippon Soda Co., Ltd., number average molecular weight = 3000, hydroxy group equivalent = 1800 g/eq), and an aromatic hydrocarbon-based mixed solvent (Idemitsu Seki "Ipsol 150" manufactured by Yugaku Corporation) 40 g and 0.005 g of dibutyltin laurate were put, mixed, and dissolved uniformly. When the temperature became uniform, the temperature was raised to 60° C., while stirring again, 8 g of isophorone diisocyanate ("IPDI" manufactured by Ebonic Degu Corporation, isocyanate group equivalent = 113 g/eq) was added, followed by reaction for about 3 hours.

Subsequently, 23 g of a cresol novolak resin ("KA-1160" manufactured by DIC Corporation, hydroxyl group equivalent -117 g/eq) and 60 g of ethyldiglycol acetate (manufactured by Daicel) were added to the reaction product, and the temperature was raised to 150°C while stirring, The reaction was carried out for about 10 hours. The disappearance of the NCO peak of 2250 cm ^-1 was confirmed by FT-IR. Confirmation of disappearance of the NCO peak was regarded as the reaction endpoint, and the reaction was allowed to warm to room temperature. Then, the reaction product was filtered through a 100 mesh filter cloth to obtain an elastomer having a butadiene structure and a phenolic hydroxyl group (phenolic hydroxyl group-containing polybutadiene resin: nonvolatile content 50% by mass). The number average molecular weight of the elastomer was 5900 and the glass transition temperature was -7°C.

<Synthesis Example 2: Synthesis of polyimide resin 1>

In a 500 ml separable flask equipped with a nitrogen introduction tube and a stirring device, 9.13 g (30 mmol) of 4-aminobenzoic acid 5-amino-1,1'-biphenyl-2-yl, 4,4'-(4, 4'-isopropylidenediphenoxy)bisphthalic acid dianhydride 15.61 g (30 mmol), N-methyl-2-pyrrolidone 94.64 g, pyridine 0.47 g (6 mmol), toluene 10 g, and nitrogen atmosphere Below, at 180 degreeC, the polyimide solution (non-volatile content 20 mass %) containing polyimide resin 1 was obtained by imidation reaction for 4 hours, removing toluene out of the system. In the polyimide solution, precipitation of the synthesized polyimide resin 1 did not appear.

<Synthesis Example 3: Synthesis of polyimide resin 2>

Aromatic tetracarboxylic dianhydride ("BisDA-1000", manufactured by SABIC Japan, 4,4'-(4,4'-isopropylidenedife) in a reaction vessel equipped with a stirrer, water fountain, thermometer, and nitrogen gas inlet tube. Noxy) bisphthalic acid dianhydride) 65.0g, cyclohexanone 266.5g, and methylcyclohexanone 44.4g were injected, and the solution was heated to 60°C. Subsequently, 43.7 g of dimerdiamine ("PRIAMINE 1075" manufactured by Kroda Japan) and 5.4 g of 1,3-bis(aminomethyl)cyclohexane were added dropwise, followed by imidization reaction at 140°C over 1 hour. Thereby, a polyimide solution (non-volatile content 30 mass%) containing polyimide resin 2 was obtained. In addition, the weight average molecular weight of polyimide resin 2 was 25,000.

<Synthesis Example 4: Synthesis of polyimide resin 3>

A 500 mL separable flask equipped with a water-quantifying device connected to a reflux condenser, a nitrogen introduction tube, and a stirrer was prepared. In this flask, 20.3 g of 4,4'-oxydiphthalic anhydride (ODPA), 200 g of γ-butyrolactone, 20 g of toluene, and 5-(4-aminophenoxy)-3-[4-(4-aminophenoxy) Si) phenyl]-1,1,3-trimethylindane 29.6 g was added, and the mixture was stirred at 45° C. for 2 hours under a nitrogen stream to react. Subsequently, the temperature of the reaction solution was raised and the condensed water was azeotropically removed with toluene under a nitrogen stream while maintaining at about 160°C. It was confirmed that a predetermined amount of water was filled in the water metering device, and that water outflow did not occur. After confirmation, the reaction solution was heated again and stirred at 200° C. for 1 hour. Then, it cooled and obtained the polyimide solution (non-volatile content 20 mass %) containing polyimide resin 3. 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). In addition, the weight average molecular weight of the above-described polyimide resin 3 was 12,000.

<Example 1>

5 parts of bixylenol-type epoxy resin (``YX4000HK'' manufactured by Mitsubishi Chemical Co., Ltd., epoxy equivalent of about 185 g/eq), 5 parts of naphthalene-type epoxy resin (``ESN475V'' manufactured by Shinnittetsu Sumiking Chemical Company, approximately 332 g/eq, epoxy equivalent) 5 Parts, bisphenol AF-type epoxy resin (``YL7760'' manufactured by Mitsubishi Chemical Co., Ltd., epoxy equivalent of about 238 g/eq) 10 parts, cyclohexane-type epoxy resin (``ZX1658GS" manufactured by Mitsubishi Chemical Company, approximately 135 g/eq epoxy equivalent) 2 Parts, 40 parts of the phenolic hydroxyl group-containing polybutadiene resin (non-volatile component 50% by mass) obtained in Synthesis Example 1 and 10 parts of cyclohexanone were heated and dissolved in a mixed solvent while stirring. After cooling to room temperature, there is a triazine skeleton-containing cresol novolak-based curing agent ("LA-3018-50P" manufactured by DIC Corporation, a hydroxyl equivalent of about 151, a 2-methoxypropanol solution of 50% of a nonvolatile component) 4 Part, active ester curing agent ("EXB-8000L-65M" manufactured by DIC, an active group equivalent of about 220, a MEK solution of 65% by mass of a non-volatile component) 6 parts, spherical silica ("SC2500SQ" manufactured by Adomatex, average particle diameter) 0.5 μm, specific surface area 11.2 m 2 /g, 40 parts of N-phenyl-3-aminopropyltrimethoxysilane (surface-treated with 1 part of Shin-Etsu Chemical Co., KBM573) per 100 parts of silica, core-shell type Graft copolymer rubber particles ("EXL2655" manufactured by Dow Chemical Nihon Co., Ltd.) 6 parts and 0.2 parts of an amine-based curing accelerator (4-dimethylaminopyridine (DMAP)) were mixed, uniformly dispersed in a high-speed rotary mixer, and then a cartridge filter ( ROKITECHNO (manufactured by "SHP020") was filtered to prepare a resin composition.

<Example 2>

Instead of using 40 parts of the phenolic hydroxyl group-containing polybutadiene resin (nonvolatile component 50% by mass) obtained in Synthesis Example 1, the same as in Example 1 except that 100 parts of the polyimide solution obtained in Synthesis Example 2 (20% by mass nonvolatile component) was used. The same operation was performed to prepare a resin composition.

<Example 3>

Example 1 and Example 1 except that 66.7 parts of the polyimide solution obtained in Synthesis Example 3 (30% by mass nonvolatile component) was used instead of 40 parts of the phenolic hydroxyl group-containing polybutadiene resin (nonvolatile component 50% by mass) obtained in Synthesis Example 1. The same operation was performed to prepare a resin composition.

<Example 4>

Instead of using 40 parts of the phenolic hydroxyl group-containing polybutadiene resin (non-volatile component 50% by mass) obtained in Synthesis Example 1, the same as in Example 1 except that 100 parts of the polyimide solution obtained in Synthesis Example 4 (20% by mass non-volatile component) was used. The same operation was performed to prepare a resin composition.

<Example 5>

Instead of using 40 parts of the phenolic hydroxyl group-containing polybutadiene resin (non-volatile component 50% by mass) obtained in Synthesis Example 1, a polybutadiene structure-containing resin (manufactured by Nihon Kayaku Corporation, ``BX360'', block copolymer of polyphenylene ether and polybutadiene) A resin composition was prepared in the same manner as in Example 1, except that 40 parts of coalescence and a 50% by mass of a nonvolatile component) were used.

<Example 6>

The same operation as in Example 1 except for using 20 parts of bismaleimide resin (manufactured by DM, ``BMI689'') instead of using 40 parts of the phenolic hydroxyl group-containing polybutadiene resin (non-volatile component 50% by mass) obtained in Synthesis Example 1 To prepare a resin composition.

<Example 7>

Instead of using 40 parts of the phenolic hydroxyl group-containing polybutadiene resin (non-volatile component 50% by mass) obtained in Synthesis Example 1, a polyrotaxane resin (manufactured by Advanced Softmaterials, 40% solution of methyl ethyl ketone of ``SH1310P'', A resin composition was prepared in the same manner as in Example 1 except that 50 parts of the axial molecule contained a polyethylene glycol chain and the cyclic molecule contained cyclodextrins).

<Example 8>

A resin composition was prepared in the same manner as in Example 1 except that the amount of the core-shell graft copolymer rubber particles of Example 1 ("EXL2655" manufactured by Dow Chemical Nihon Co., Ltd.) was changed from 6 parts to 12 parts.

<Comparative Example 1>

The use of the spherical silica of Example 1 ("SC2500SQ" manufactured by Adomatex, surface-treated) was changed from 40 parts to 70 parts, and the core-shell type graft copolymer rubber particles ("EXL2655" manufactured by Dow Chemical Nihon) ") was changed from 6 parts to 5 parts, and the same operation as in Example 1 was carried out to prepare a resin composition.

<Comparative Example 2>

A resin composition was prepared in the same manner as in Example 1 except that 6 parts of the core-shell graft copolymer rubber particles of Example 1 ("EXL2655" manufactured by Dow Chemical Nihon Co., Ltd.) were not used.

<Comparative Example 3>

Example 1 except for using 42 parts of a phenoxy resin (``YX7553BH30'' manufactured by Mitsubishi Chemical, 30% by mass solid content) instead of using 40 parts of a phenolic hydroxyl group-containing polybutadiene resin (non-volatile component 50% by mass) obtained in Synthesis Example 1 The same operation as that was performed to prepare a resin composition.

<Test Example 1: Evaluation of flexibility (MIT cutting resistance)>

After drying the resin composition of each Example and Comparative Example on the release treatment surface of a PET film (thickness 38㎛) treated with an alkyd release agent, the resin composition layer was evenly coated with a die coater so that the thickness of the resin composition layer was 40㎛, and 80 to 120 It dried for 6 minutes at degreeC (average 100 degreeC), and obtained the resin sheet.

The obtained resin sheet was laminated to a polyimide film (Ubekosan Co., Ltd. product, UPIREX S) using a batch-type vacuum pressurized laminator ("MVLP-500" manufactured by Meiki Sesakusho Co., Ltd.). The laminate was decompressed for 30 seconds and the atmospheric pressure was 13 hPa or less, and then pressed at 120° C. for 30 seconds at a pressure of 0.74 MPa to obtain a resin sheet with a protective film. Thereafter, the PET film was peeled from the resin sheet with a protective film, the resin composition was cured under curing conditions at 190° C. for 90 minutes, and the polyimide film was peeled to obtain a cured product sample.

The obtained cured product sample was cut into a test piece having a width of 15 mm and a length of 110 mm, and using an MIT test apparatus (manufactured by Toyo Seiki Seakusho Co., Ltd., MIT-breaking fatigue tester "MIT-DA"), JIS C- In accordance with 5016, the number of internal fractures to fracture of the hardened body was measured under the measurement conditions of a load of 2.5N, a bending angle of 90 degrees, a bending radius of 1.0 mm, and a bending speed of 175 times/min. In addition, the measurement was performed for 5 samples, and the average value of the upper 3 points was calculated. A case where the number of internal cuts was less than 8,000 was evaluated as "x", and a case of 8,000 or more was evaluated as "○".

<Test Example 2: Evaluation of pattern embedding property and flatness>

<Test Example 2-1: Measurement of the lowest melt viscosity>

With respect to the resin composition layer of the resin sheet obtained in Test Example 1, the lowest melt viscosity was measured using a dynamic viscoelasticity measuring device ("Rheosol-G3000" manufactured by U.P.M.). About 1 g of the sample resin composition collected from the resin composition layer, using a parallel plate having a diameter of 18 mm, the temperature was raised from the starting temperature of 60°C to 200°C at a heating rate of 5°C/min, and the measurement temperature interval was 2.5°C, the frequency of 1 Hz, The dynamic viscoelastic modulus was measured under the measurement conditions of the modification 1deg, and the lowest melt viscosity (poise) was measured.

<Test Example 2-2: Measurement of tack force>

The protective film was peeled off from the resin sheet with a protective film obtained in Test Example 1, and the resin composition layer was loaded with a glass probe having a diameter of 5 mm using a probe tack tester (manufactured by Tester Sangyo Co., Ltd., "TE-6002"). The tack force (N) at 1 kgf/cm 2, a contact speed of 0.5 mm/sec, a tensile rate of 0.5 mm/sec, a holding time of 10 seconds, and a temperature of 80°C was measured. The case where the tack force exceeded 1.6N was evaluated as "x", and the case of 1.6N or less was evaluated as "○".

<Test Example 2-3: Evaluation of pattern embedding property and void>

As an inner circuit board, a glass cloth-based epoxy resin double-sided copper-clad laminate (copper foil thickness of 18 μm, substrate thickness of 0.15 mm) having circuit conductors (copper) formed with a wiring pattern of 1 mm square (59% residual ratio) on both sides , "HL832NSF LCA" manufactured by Mitsubishi Gas Chemical Co., Ltd., 255*340mm size) was prepared. Both surfaces of the inner circuit board were subjected to a roughening treatment (copper etching amount of 0.5 µm) on the copper surface with "CZ8201" manufactured by MEC.

The resin sheet obtained in Test Example 1 was subjected to a batch-type vacuum pressurized laminator (manufactured by Nikko-Materials Co., Ltd., a two-stage build-up laminator, CVP700), so that the resin composition layer was in contact with the inner-layer circuit board. It was laminated on both sides of the substrate. Lamination was carried out by decompressing for 30 seconds, making the atmospheric pressure 13 hPa or less, and compressing at 130°C and 0.74 MPa for 45 seconds. Subsequently, a heat press was performed at 120°C and a pressure of 0.5 MPa for 75 seconds.

The inner circuit board on which the resin sheet was laminated was placed in an oven at 100° C. for 30 minutes, and then transferred to an oven at 180° C. at a temperature of 180° C. for 30 minutes, and then thermally cured to an insulating layer. Formed. This is referred to as the "evaluation substrate".

The support was peeled from the evaluation substrate, and the surface of the insulating layer was observed with a micro-optical microscope. The pattern embedding property was evaluated as "(circle)" for the case where it was clearly embedded, and "x" for the case where the embedding was insufficient. For voids, the case where no void was generated was evaluated as "○" and the case where the void occurred was evaluated as "x".

Table 1 shows the amount of nonvolatile components used in the resin compositions of Examples and Comparative Examples, and the measurement results and evaluation results of the Test Examples.

By using a resin composition containing (A) a thermosetting resin, (B) an inorganic filler, 5% by mass or more of (C) an organic filler, and (D) an adhesive softening agent, it is possible to maintain excellent flexibility and low tackiness. And it was found. In particular, it was found that when the (C) organic filler was 10% by mass or less, void defects were suppressed and the pattern embedding property was excellent.

Claims (17)

As a resin composition containing (A) a thermosetting resin, (B) an inorganic filler, (C) an organic filler, and (D) an adhesive softening agent,
The resin composition, wherein the content of the component (C) is 5% 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 content of the component (B) is 50% by mass or less when the nonvolatile component in the resin composition is 100% by mass. The resin composition according to claim 1, wherein the content of the component (C) is 10% by mass or less when the nonvolatile component in the resin composition is 100% by mass. The resin composition according to claim 1, wherein the component (D) is selected from the group consisting of a resin having a polybutadiene structure, a polyrotaxane resin, a polyimide resin, and a maleimide resin having a dimer acid skeleton. The resin composition according to claim 1, wherein the content of the component (D) is 1% by mass or more when the nonvolatile component in the resin composition is 100% by mass. The resin composition according to claim 1, wherein (C) the organic filler is a core-shell type graft copolymer particle. The resin composition according to claim 6, wherein the monomer component forming the shell portion of the core-shell graft copolymer particles is a (meth)acrylic acid ester. The resin composition according to claim 6, wherein the core particles of the core-shell graft copolymer particles contain a thermoplastic elastomer. The resin composition according to claim 1, wherein the component (A) is an epoxy resin. The resin composition according to claim 1, further comprising (E) a curing agent. The resin composition according to claim 10, wherein the component (E) contains an active ester curing agent. The resin composition according to claim 1, wherein the solid content fraction in the resin composition is 95% by mass or less. The resin composition according to claim 1, which is for forming an insulating layer of a multilayer flexible substrate. A cured product of the resin composition according to any one of claims 1 to 13. A resin sheet comprising a support and a resin composition layer formed of the resin composition according to any one of claims 1 to 13 provided on the support. A multilayer flexible substrate comprising an insulating layer formed by curing the resin composition according to any one of claims 1 to 13. A semiconductor device comprising the multilayer flexible substrate according to claim 16.