JP2020158704A - Resin composition - Google Patents

Abstract

To provide a resin composition that has a low tackiness while maintaining an excellent flexibility.SOLUTION: A resin composition, containing (A) a thermosetting resin, (B) an inorganic filler, (C) an organic filler, and (D) an adhesive softening agent, and in which, setting the non-volatile component in the resin composition as 100 mass%, the content of the (C) component is 5 mass% or more.SELECTED DRAWING: None

Description

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

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

Generally, it is necessary to add a softening resin component to the insulating material of the flexible substrate, but when the softening resin component is added, the tackiness (adhesiveness) may increase and the handleability may be inferior. In this case, it is possible to suppress the tackiness by blending the inorganic filler (Patent Document 1), but when the blending ratio of the inorganic filler is high, it becomes difficult to achieve both flexibility.

Japanese Unexamined Patent Publication No. 2014-95047

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

As a result of diligent studies to achieve the object of the present invention, the present inventors have found that a resin composition containing (A) a thermosetting resin, (D) an adhesive softening agent, and (B) an inorganic filler has been added. We have found that by blending 5% by mass or more of the (C) organic filler, it is possible to suppress the tackiness to a low level while maintaining excellent flexibility, and have completed the present invention.

That is, the present invention includes the following contents.
[1] A resin composition containing (A) a thermosetting resin, (B) an inorganic filler, (C) an organic filler, and (D) an adhesive softening agent.
A resin composition in which the content of the component (C) is 5% by mass or more when the non-volatile component in the resin composition is 100% by mass.
[2] The resin composition according to the above [1], wherein the content of the component (B) is 50% by mass or less when the non-volatile component in the resin composition is 100% by mass.
[3] The resin composition according to the above [1] or [2], wherein the content of the component (C) is 10% by mass or less when the non-volatile component in the resin composition is 100% by mass.
[4] The above-mentioned [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. Resin composition.
[5] The resin composition according to any one of [1] to [4] above, wherein the content of the component (D) is 1% by mass or more when the non-volatile component in the resin composition is 100% by mass. object.
[6] The resin composition according to any one of [1] to [5] above, wherein the organic filler is core-shell type graft copolymer particles.
[7] The resin composition according to the above [6], wherein the monomer component forming the shell portion of the core-shell type graft copolymer particles is a (meth) acrylic acid ester.
[8] The resin composition according to the above [6] or [7], wherein the core particles of the core-shell type graft copolymer particles contain a thermoplastic elastomer.
[9] The resin composition according to any one of the above [1] to [8], wherein the component (A) is an epoxy resin.
[10] The resin composition according to any one of the above [1] to [9], which further contains (E) a curing agent.
[11] The resin composition according to the above [10], wherein the component (E) contains an active ester curing agent.
[12] The resin composition according to any one of the above [1] to [11], wherein the solid content in the resin composition is 95% by mass or less.
[13] The resin composition according to any one of the above [1] to [12], which is used for forming an insulating layer of a multilayer flexible substrate.
[14] A cured product of the resin composition according to any one of the above [1] to [13].
[15] A resin sheet comprising a support and a resin composition layer provided on the support and formed of the resin composition according to any one of the above [1] to [13].
[16] A multilayer flexible substrate including an insulating layer formed by curing the resin composition according to any one of the above [1] to [13].
[17] A semiconductor device including the multilayer flexible substrate according to the above [16].

According to the resin composition of the present invention, tackiness can be suppressed low while maintaining excellent flexibility.

Hereinafter, the present invention will be described in detail according to the preferred embodiment thereof. However, the present invention is not limited to the following embodiments and examples, and may be arbitrarily modified and implemented without departing from the scope of claims of the present invention and the equivalent scope thereof.

<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 non-volatile component in the resin composition is 100% by mass.

By using such a resin composition, it is possible to suppress the tackiness to a low level while maintaining excellent flexibility.

The resin composition of the present invention further contains any component in addition to (A) thermosetting resin, (B) inorganic filler, (C) organic filler, and (D) adhesive softening agent. You may. Optional components include, for example, (E) curing agent, (F) curing accelerator, (G) other additives, and (H) organic solvent. 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. The thermosetting resin (A) does not include the one corresponding to the component (D). As the thermosetting resin (A), known ones can be used and are not particularly limited, but for example, polyester resin, polyurethane resin, polyester urethane resin, butyral resin, acrylic resin, cyanate resin, silicone resin, oxetane resin. , Melamine resin and the like, and epoxy resin is particularly preferable.

Examples of the epoxy resin include bixilenol 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, and trisphenol type epoxy resin. Naftor novolac type epoxy resin, phenol novolac type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidylamine type epoxy resin, glycidyl ester type epoxy resin, cresol novolac 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 Examples thereof include an epoxy resin, a trimethylol type epoxy resin, and a tetraphenylethane type epoxy resin. One type of epoxy resin may be used alone, or two or more types may be used in combination.

The resin composition preferably contains an epoxy resin having two or more epoxy groups in one molecule as the 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 in one molecule is preferably 50% by mass or more with respect to 100% by mass of the non-volatile component of the epoxy resin. It is more preferably 60% by mass or more, and particularly preferably 70% by mass or more.

The epoxy resin may be a liquid epoxy resin at a temperature of 20 ° C. (hereinafter sometimes referred to as "liquid epoxy resin") or a solid epoxy resin at a temperature of 20 ° C. (hereinafter referred to as "solid epoxy resin"). ). The resin composition of the present invention may contain only the liquid epoxy resin as the epoxy resin, or may contain only the solid epoxy resin, but contains a combination of the liquid epoxy resin and the solid epoxy resin. Is preferable.

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

Examples of the liquid epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, glycidylamine type epoxy resin, phenol novolac type epoxy resin, and ester skeleton. An alicyclic epoxy resin, a cyclohexane type epoxy resin, a cyclohexanedimethanol type epoxy resin, and a glycidylamine type epoxy resin are preferable.

Specific examples of the liquid epoxy resin include "HP4032", "HP4032D", and "HP4032SS" (naphthalene type epoxy resin) manufactured by DIC; "828US", "828EL", "jER828EL", and "825" manufactured by Mitsubishi Chemical Co., Ltd. , "Epicoat 828EL" (bisphenol A type epoxy resin); "jER807", "1750" (bisphenol F type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd .; "jER152" (phenol novolac type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd.; "630" and "630LSD" manufactured by Mitsubishi Chemical Co., Ltd. (glycidylamine type epoxy resin); "ZX1059" manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd. (mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin); Nagase ChemteX Corporation "EX-721" (glycidyl ester type epoxy resin); "Selokiside 2021P" (alicyclic epoxy resin having an ester skeleton) manufactured by Daicel; "ZX1658" and "ZX1658GS" (liquid) manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd. 1,4-Glysidylcyclohexane type epoxy resin) and the like. 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 preferable, and an aromatic solid epoxy resin having three or more epoxy groups in one molecule is more preferable.

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

Specific examples of the solid epoxy resin include "HP4032H" (naphthalene type epoxy resin) manufactured by DIC; "HP-4700" and "HP-4710" (naphthalene type tetrafunctional epoxy resin) manufactured by DIC; DIC. "N-690" (cresol novolac type epoxy resin); DIC "N-695" (cresol novolac type epoxy resin); DIC "HP-7200", "HP-7200HH", "HP" -7200H "(dicyclopentadiene type epoxy resin);" EXA-7311 "," EXA-7311-G3 "," EXA-7311-G4 "," EXA-7311-G4S "," HP6000 "(made by DIC) Naphthylene ether type epoxy resin); "EPPN-502H" (trisphenol type epoxy resin) manufactured by Nippon Kayakusha; "NC7000L" (naphthol novolac type epoxy resin) manufactured by Nihon Kayakusha; "NC3000H", "NC3000", "NC3000L", "NC3100" (biphenyl type epoxy resin); "ESN475V" (naphthol type epoxy resin) manufactured by Nippon Steel & Sumitomo Metal Corporation; "ESN485" (naphthol novolac) manufactured by Nippon Steel & Sumitomo Metal Corporation Type epoxy resin); "YX4000H", "YX4000", "YL6121" (biphenyl type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd .; "YX4000HK" (bixilenol type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd .; "YX8800" (anthracene type epoxy resin); "YX7700" (xylene structure-containing novolac type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd .; "PG-100" and "CG-500" manufactured by Osaka Gas Chemical Co., Ltd .; "YL7760" (bisphenol AF type epoxy resin); "YL7800" (fluorene type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd .; "jER1010" (solid bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd .; "jER1031S" (tetraphenylethane type epoxy resin) and the like can be 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. ~ 1:30, particularly preferably 1: 5 to 1:20. When the mass ratio of the liquid epoxy resin to the solid epoxy resin is in such a range, the desired effect of the present invention can be remarkably obtained.

The epoxy equivalent of the epoxy resin is preferably 50 g / eq. ~ 5,000 g / eq. , More preferably 50 g / eq. ~ 3,000 g / eq. , More preferably 80 g / eq. ~ 2,000 g / eq. , Even more preferably 110 g / eq. ~ 1,000 g / eq. Is. Within this range, the crosslink density of the cured product of the resin composition becomes sufficient, and an insulating layer having a small surface roughness can be provided. Epoxy equivalent is the mass of a 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 significantly obtaining the desired effect of the present invention. is there. The weight average molecular weight of the resin can be measured as a polystyrene-equivalent value by a gel permeation chromatography (GPC) method.

The content of the thermosetting resin (A) is not particularly limited, but when the non-volatile component in the resin composition is 100% by mass, it is preferably 5% by mass or more, more preferably 10% by mass or more. , More preferably 15% by mass or more, and particularly preferably 20% by mass or more. The upper limit of the content of the thermosetting resin (A) is not particularly limited, but when the non-volatile component in the resin composition is 100% by mass, it is preferably 50% by mass or less, more preferably 40% by mass. % Or less, more preferably 30% by mass or less, and particularly preferably 25% by mass or less.

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

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

The average particle size of the inorganic filler (B) is not particularly limited, but is preferably 10 μm or less, more preferably 5 μm or less, still more preferably 3 μm or less, and further, from the viewpoint of obtaining the desired effect of the present invention. It is more preferably 2 μm or less, and particularly preferably 1 μm or less. The lower limit of the average particle size 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, still more preferably 0, from the viewpoint of obtaining the desired effect of the present invention. .2 μm or more, particularly preferably 0.25 μm or more. The average particle size of the inorganic filler can be measured by a laser diffraction / scattering method based on the Mie scattering theory. Specifically, it can be measured by creating a particle size distribution of the inorganic filler on a volume basis with a laser diffraction / scattering type particle size distribution measuring device and using the median diameter as the average particle size. As the measurement sample, 100 mg of an inorganic filler and 10 g of methyl ethyl ketone can be weighed in a vial and dispersed by ultrasonic waves for 10 minutes. The measurement sample was measured using a laser diffraction type particle size distribution measuring device, the wavelengths of the light sources used were blue and red, and the volume-based particle size distribution of the inorganic filler was measured by the flow cell method, and the obtained particle size distribution was used. The average particle size was calculated as the median diameter. Examples of the laser diffraction type particle size distribution measuring device include "LA-960" manufactured by HORIBA, Ltd.

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

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

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

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

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

The specific surface area of the inorganic filler (B) 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. The upper limit is not particularly limited, but is preferably 50 m ² / g or less, more preferably 20 m ² / g or less. For the specific surface area of the inorganic filler, nitrogen gas is adsorbed on the sample surface using a specific surface area measuring device (Macsorb HM-1210 manufactured by Mountech) according to the BET method, and the specific surface area is calculated using the BET multipoint method. It can be obtained by.

The content of the inorganic filler (B) is preferably 70% by mass or less, more preferably 60, from the viewpoint of obtaining a cured product having more flexibility when the non-volatile component in the resin composition is 100% by mass. It is mass% or less, more preferably 50 mass% or less, and particularly preferably 45 mass% or less. (B) The lower limit of the content of the inorganic filler is not particularly limited, but when the non-volatile component in the resin composition is 100% by mass from the viewpoint of obtaining a cured product having sufficient mechanical strength. It is preferably 20% by mass or more, 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. The organic filler (C) does not include the one corresponding to the component (D). By including the component (C) in the resin composition, the tackiness can be reduced and the handleability can be improved.

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

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, and the like. Olefin-based thermoplastic elastomers such as acrylonitrile-butadiene copolymer, isoprene-isobutylene copolymer, isobutylene-butadiene copolymer, ethylene-propylene-diene ternary copolymer, ethylene-propylene-butene ternary copolymer; Examples thereof include thermoplastic elastomers such as acrylic thermoplastic elastomers such as propyl poly (meth) acrylate, butyl poly (meth) acrylate, cyclohexyl poly (meth) acrylate, and octyl poly (meth) acrylate. It is an olefin-based thermoplastic elastomer, more preferably a styrene-butadiene copolymer. Further, a silicone-based 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 lower, preferably −10 ° C. or lower, more preferably −20 ° C. or lower, still more preferably −30 ° C. or lower.

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

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

Examples of the monomer component forming the shell portion of the core-shell type graft copolymer particles include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and cyclohexyl (meth) acrylate. (Meta) acrylic acid esters such as octyl (meth) acrylate and glycidyl (meth) acrylate; (meth) acrylic acid; N-substituted maleimides such as N-methylmaleimide and N-phenylmaleimide; maleimide; maleic acid, itacon Α, β-unsaturated carboxylic acids such as acids; aromatic vinyl compounds such as styrene, 4-vinyltoluene and α-methylstyrene; (meth) acrylonitrile and the like, preferably (meth) acrylic acid esters, and (meth) acrylic acid esters. ) Methyl acrylate is more preferred.

Commercially available core-shell graft copolymer particles include, for example, "CHT" manufactured by Chail Industries, Ltd .; "B602" manufactured by UMG ABS; "Paraloid EXL2602" and "Paraloid EXL2603" manufactured by Dow Chemical Japan. , "Paraloid EXL2655", "Paraloid EXL2311", "Paraloid EXL2313", "Paraloid EXL2315", "Paraloid KM330", "Paraloid KM336P", "Paraloid KCZ201", "Metabren C-223A" manufactured by Mitsubishi Rayon, "Metabren" "E-901", "Metabren S-2001", "Metabren W-450A", "Metabren SRK-200", "Kaneka M-511", "Kaneka M-600", "Kaneace M-400", manufactured by Kaneka Corporation, Examples thereof include "Kaneka M-580" and "Kaneka MR-01". These may be used individually by 1 type, and may be used in combination of 2 or more types.

The average particle size (average primary particle size) of the core-shell type 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, and particularly preferably 80 nm or more. 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 size (average primary particle size) of the core-shell type graft copolymer particles can be measured using a zeta potential particle size distribution measuring device or the like.

The content of the organic filler (C) is 5.0% by mass or more when the non-volatile component in the resin composition is 100% by mass, the tackiness is suppressed as much as possible, and (B) the use of the inorganic filler is used. From the viewpoint of obtaining a cured product having higher flexibility by suppressing the amount as much as possible, 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. The upper limit of the content of the organic filler (C) is preferably 30% by mass or less, more preferably 20% by mass or less, when the non-volatile component in the resin composition is 100% by mass, from the viewpoint of suppressing the viscosity as low as possible. Is 15% by mass or less, more preferably 10% by mass or less, and particularly preferably 8% by mass or less, from the viewpoint of reducing void defects and achieving better pattern embedding property.

<(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 the cured product among the softening agents that impart flexibility to the cured product of the thermosetting resin. As the adhesive softening agent (D), a known softening agent having a property of increasing the adhesiveness of the cured product can be widely used. Examples of the adhesive softening agent (D) include, but are limited to, a resin having a polybutadiene structure (hereinafter referred to as "polybutadiene resin"), a polyrotaxane resin, a polyimide resin, and a maleimide resin having a dimer acid skeleton. It's not something.

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

Preferred examples of the polybutadiene resin are a hydride polybutadiene skeleton-containing resin, a hydroxy group-containing polybutadiene resin, a phenolic hydroxyl group-containing polybutadiene resin, a carboxy group-containing polybutadiene resin, an acid anhydride group-containing polybutadiene resin, an epoxy group-containing polybutadiene resin, and an isocyanate group. Examples thereof include a containing polybutadiene resin, a urethane group containing polybutadiene resin, and a polyphenylene ether-polybutadiene resin. Here, the "hydrogenated polybutadiene skeleton-containing resin" means a resin in which at least a part of the polybutadiene skeleton is hydrogenated, and the polybutadiene skeleton does not necessarily have to be a completely hydrogenated resin. Examples of the hydrogenated polybutadiene skeleton-containing resin include a hydrogenated polybutadiene skeleton-containing epoxy resin. Further, examples of the phenolic hydroxyl group-containing polybutadiene resin include a resin having a polybutadiene structure and having a phenolic hydroxyl group.

Specific examples of the polybutadiene resin, which is a resin having a polybutadiene structure in the molecule, include "BX360" and "BX660" (polyphenylene ether-polybutadiene resin) manufactured by Nippon Kayakusha, and "Ricon 657" (epoxy) manufactured by Clay Valley. Group-containing polybutadiene), "Ricon 130MA8", "Ricon 130MA13", "Ricon 130MA20", "Ricon 131MA5", "Ricon 131MA10", "Ricon 131MA17", "Ricon 131MA20", "Ricon 184MA6" (containing acid anhydride groups) Polybutadiene), "GQ-1000" (hydroxyl group, carboxyl group introduced polybutadiene), "G-1000", "G-2000", "G-3000" (both terminal hydroxyl group polybutadiene), "GI-1000", "GI- 2000 "," GI-3000 "(polybutadiene with hydroxylated hydroxyl groups at both ends)," 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 skeleton epoxy compound), "R-45EPT" (polybutadiene skeleton epoxy compound) manufactured by Nagase ChemteX, etc. Can be mentioned.

Further, as an example of a preferable polybutadiene resin, a linear polyimide butadiene resin using hydroxyl group-terminated polybutadiene, a diisocyanate compound and a polybasic acid or an anhydride thereof as raw materials (Japanese Patent Laid-Open No. 2006-37083, International Publication No. 2008/153208). The polyimide described in 1) is also mentioned. The content of the polybutadiene structure of the polyimide butadiene resin is preferably 60% by mass to 95% by mass, and more preferably 75% by mass to 85% by mass. For details of the polyimide butadiene resin, the description of JP-A-2006-37083 and International Publication No. 2008/153208 can be referred to, and the contents thereof are incorporated in the present specification.

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 exerting the desired effect of the present invention.

Examples of the diisocyanate compound as a raw material of the polyimide butadiene resin include aromatic diisocyanates such as toluene-2,4-diisocyanate, toluene-2,6-diisocyanate, xylylene diisocyanate, and diphenylmethane diisocyanate; and aliphatic diisocyanates such as hexamethylene diisocyanate. An alicyclic diisocyanate such as isophorone diisocyanate can be mentioned. Of these, aromatic diisocyanates are preferable, and toluene-2,4-diisocyanates are more preferable.

Examples of the polybasic acid or its anhydride as the raw material of the polyimide butadiene resin include ethylene glycol bistrimeric acid, pyromellitic acid, benzophenone tetracarboxylic acid, biphenyltetracarboxylic acid, naphthalenetetracarboxylic acid, 5- (2,5). -Dioxotetrahydrofuryl) -3-methyl-cyclohexene-1,2-dicarboxylic acid, tetrabasic acids such as 3,3'-4,4'-diphenylsulfonetetracarboxylic acid and their anhydrides, trimellitic acid, Tribasic acids such as cyclohexanetricarboxylic acid and their anhydrides, 1,3,3a,4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho (1,2-) C) Franc-1,3-dione and the like can be mentioned.

The polyrotaxane resin has a structure having a plurality of cyclic molecules, a linear shaft molecule that is included so as to penetrate the cyclic molecule, and a blocking group that blocks the end of the shaft molecule so that the cyclic molecule does not come off. Is. 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 the range of two or more, but for example, one axial molecule is penetrated through a plurality of cyclic molecules. When the amount of the cyclic molecule to be maximally included in one axial molecule (maximum inclusion amount) is 100%, it is preferably 10% or more, more preferably 15% or more, still more preferably 20%. The above is preferably 90% or less, more preferably 85% or less, 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 axis molecule is polyethylene glycol and the cyclic molecule is an α-cyclodextrin molecule, the maximum inclusion amount has been experimentally determined (see Macromolecules 1993, 26, 5698-5703).

As the shaft molecule in the polyrotaxane 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" means substantially straight, and the shaft molecule may have a branched chain as long as the cyclic molecule through which the shaft molecule penetrates can rotate or move. .. Examples of the shaft molecule include polyvinyl alcohol, polyvinylpyrrolidone, poly (meth) acrylic acid cellulose-based resin, polyacrylamide, polyethylene oxide, polyethylene glycol, polypropylene glycol, polyvinyl acetal-based resin, polyvinyl methyl ether, polyamine, polyethyleneimine, and casein. , Gelatin, starch, polyolefin, polyester, polyvinyl chloride, polystyrene, acrylonitrile-styrene copolymer and other copolymers, acrylic resin, polycarbonate, polyurethane, polyvinyl butyral, polyisobutylene, poly tetrahydrofuran, polyamide, polyimide, polydiene, poly Examples thereof include siloxane, polyurea, polysulfide, polyphosphazene, polyketone, polyphenylene, polyhaloolefin and derivatives thereof. Among these, polyethylene glycol chains are preferably 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 be rotated or moved. The length of the shaft molecule can be expressed using the weight average molecular weight. The weight average molecular weight of the shaft molecule 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, and further. It is preferably 85,000 or less. The weight average molecular weight of the shaft molecule is a polystyrene-equivalent weight average molecular weight measured by a gel permeation chromatography (GPC) method.

The shaft molecule usually has a structure in which a molecule containing a blocking group is reacted and bonded to the functional group of a molecule having functional groups at both ends. As the functional group, for example, an amide group, a hydroxyl group, a carboxyl group, an acrylic group, a methacryl group, an epoxy group, a vinyl group and the like are preferably mentioned.

The cyclic molecule in the polyrotaxane resin is a cyclic molecule that can be included in a state in which a shaft molecule is penetrated, and has at least one reactive group (functional group) so as to be able to react with (E) a curing agent. Can be used. A cyclic molecule means a molecule that is substantially cyclic, and "substantially cyclic" means that it includes a molecule that is not completely ring-closed, and one end of the letter "C" and multiple ends are combined. It is a concept that includes those having a spiral structure that does not overlap. Examples of the cyclic molecule include cyclodextrins, crown ethers, cryptands, macrocyclic amines, calixarenes, cyclophanes and the like. Among these, cyclodextrins are preferable. 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.

The cyclic molecule preferably contains a reactive group. Examples of the reactive group include a hydroxyl group, a carboxyl group, an acrylic group, a methacryl group, an epoxy group, a vinyl group and the like, and a hydroxyl group is preferable. When the cyclic molecule has a reactive group, the cyclic molecule can be crosslinked with each other or the polyrotaxane resin and the thermosetting resin via a curing agent. Further, the reactive group of one cyclic molecule and the reactive group of the other cyclic molecule may be crosslinked. The reaction group may have one type alone or two or more types.

The reactive group does not have to be directly attached to the cyclic molecule. For example, when the cyclic molecule is cyclodextrin, the hydroxyl group existing 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. Furthermore, when ring-opening polymerization of ε-caprolactone is carried out via the hydroxyl group of the hydroxypropyl group and the caprolactone chain is provided, the hydroxyl group located at the opposite end of the polyester moiety in the caprolactone chain is also a reactive group.

The cyclic molecule may have one reactive group per cyclic molecule, or may have two or more reactive groups.

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, It is 000 or less, more preferably 1,350,000 or less. The weight average molecular weight of the cyclic molecule is a polystyrene-equivalent weight average molecular weight measured by a gel permeation chromatography (GPC) method.

The blocking group in the polyrotaxane resin is not particularly limited as long as it has a structure having a bulk enough to prevent the cyclic molecules from coming off. Examples of the blocking group include a cyclodextrin group, an adamantane group, a dinitrophenyl group, a trityl group and the like. Of these, the adamantane group is preferable. These may be contained alone in the polyrotaxane resin, or may be contained in two or more types.

The overall weight average molecular weight of the 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, It is 400,000 or less, more preferably 1,350,000 or less. The weight average molecular weight of the polyrotaxane resin is a polystyrene-equivalent weight average molecular weight measured by a gel permeation chromatography (GPC) method.

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, preferably 120 mgKOH / g or less, more preferably 115 mgKOH / g or less, still more preferable. Is 110 mgKOH / g or less. The hydroxyl value can be measured according to JIS K0070.

The polyrotaxane resin may be liquid, but is preferably contained in the resin composition in the form of particles. The particulate polyrotaxane resin is easy to disperse and can further reduce the viscosity of the resin composition.

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

The polyrotaxane resin can be synthesized, for example, by the methods described in International Publication No. 01/83566, Japanese Patent Application Laid-Open No. 2005-154675, Japanese Patent No. 4482633, and the like.

As the polyrotaxane resin, a commercially available product may be used. As commercially available products, for example, "SH2400B-007", "SH1310P", "SELM Superpolymer A1000" manufactured by Advanced Soft Materials Co., Ltd. can be used. These may be used individually by 1 type, and may be used in combination of 2 or more type.

The polyimide resin is a resin having an imide bond in the repeating unit. The polyimide resin may generally contain a resin obtained by an imidization reaction of a diamine compound and a tetracarboxylic dianhydride. The polyimide resin also includes a modified polyimide resin such as a siloxane modified polyimide resin.

For the polyimide resin, for example, the formula (1):

[In the formula, X ¹ represents a tetravalent group obtained by removing two -CO-O-CO- from the tetracarboxylic dianhydride, and X ² means removing _two -NH ₂ from the diamine compound. It represents a divalent group, and n represents an integer of 2 or more. ]
It may include a structure represented by.

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

Examples of the aliphatic diamine compound include 1,2-ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, 1,6-hexamethylenediamine, and 1,5-diaminopentane. , 1,10-Diaminodecane and other linear aliphatic diamine compounds; 1,2-diamino-2-methylpropane, 2,3-diamino-2,3-butane, and 2-methyl-1,5- Branched chain aliphatic diamine compounds such as diaminopentane; 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, 1,4-diaminocyclohexane, 4,4'-methylenebis (cyclohexyl) An alicyclic diamine compound such as amine); a dimer acid type diamine (hereinafter, also referred to as “dimer diamine”) and the like can be mentioned.

The diamine acid type diamine is a diamine compound obtained by substituting two terminal carboxylic acid groups (-COOH) of dimer acid with an aminomethyl group (-CH _2- NH ₂ ) or an amino group (-NH ₂ ). means. Dimeric acid is a known compound obtained by dimerizing unsaturated fatty acids (preferably those having 11 to 22 carbon atoms, particularly preferably those having 18 carbon atoms), and its industrial production process is almost the same in the industry. It is standardized. As the dimer acid, 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 are particularly inexpensive and easily available, can be easily obtained. Further, 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 double bonds remain after the polymerization reaction of unsaturated fatty acids, in the present specification, hydrogenated substances whose degree of unsaturation is lowered by further hydrogenation reaction are also included in dimer acid. Commercially available products of the diamine acid type diamine are available, and examples thereof include PRIAMINE 1073, PRIAMINE 1074, and PRIAMINE 1075 manufactured by Croda Japan, and Versamine 551 and Versamine 552 manufactured by Cognis Japan.

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

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

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

The dianiline compound means a compound containing two aniline structures in the molecule, and each of the two benzene rings in the two aniline structures further optionally has 1 to 3 substituents. Can be. The substituent here is not particularly limited. The two aniline structures in the dianiline compound are directly bonded and / or 1 to 100 selected from carbon atoms, oxygen atoms, sulfur atoms and nitrogen atoms (preferably 1 to 50, more preferably 1 to 20). It can be attached via one or two divalent linking groups having a skeleton atom of. Dianiline compounds also include those in which two aniline structures are bonded in two places.

Specific examples of the "divalent linking group" in the dianiline compound include -NHCO-, -CONH-, -OCO-, -COO-, -CH _2- , -CH ₂ CH _2- , -CH ₂ CH _2. CH _2- , -CH ₂ CH ₂ CH ₂ CH _2- , -CH ₂ CH ₂ CH ₂ CH ₂ CH _2- , -CH (CH ₃ )-, -C (CH ₃ ) _2- , -C (CF ₃₎ ) _2- , -CH = CH-, -O-, -S-, -CO-, -SO _2- , -NH-, -Ph-, -Ph-Ph-, -C (CH ₃ ) ₂ -Ph -C (CH ₃ ) _2- , -O-Ph-O-, -O-Ph-Ph-O-, -O-Ph-SO ₂ --Ph-O-, -O-Ph-C (CH ₃ ) _2- Ph-O-, -C (CH ₃ ) _2- Ph-C (CH ₃ ) _2- ,

(In the formula, * indicates the binding site.)
And so on. "Ph" represents a 1,4-phenylene group, a 1,3-phenylene group or a 1,2-phenylene group.

Specific examples of the dianiline compound include 4,4'-diamino-2,2'-ditrifluoromethyl-1,1'-biphenyl, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3, 3'-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-fluorenylidene) dianiline, 2,2 -Bis (3-methyl-4-aminophenyl) propane, 2,2-bis (3-methyl-4-aminophenyl) benzene, 4,4'-diamino-3,3'-dimethyl-1,1'- Biphenyl, 4,4'-diamino-2,2'-dimethyl-1,1'-biphenyl, 9,9'-bis (3-methyl-4-aminophenyl) fluorene, 5- (4-aminophenoxy)- Examples thereof include 3- [4- (4-aminophenoxy) phenyl] -1,1,3-trimethylindan, 5-amino-1,1'-biphenyl-2-yl 4-aminobenzoate, and the like, preferably. 5- (4-Aminophenoxy) -3- [4- (4-Aminophenoxy) phenyl] -1,1,3-trimethylindan, and 4-aminobenzoate 5-amino-1,1'-biphenyl-2 -Il.

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

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

Examples of the aromatic tetracarboxylic dianhydride include benzenetetracarboxylic dianhydride, naphthalenetetracarboxylic dianhydride, anthracenetetracarboxylic dianhydride, diphthalic acid dianhydride and the like, and preferred examples thereof. It is a diphthalic dianhydride.

The benzenetetracarboxylic dianhydride means a benzene dianhydride having 4 carboxy groups, and the benzene ring here may optionally have 1 to 3 substituents. Here, the substituent is not particularly limited. Specific examples of the benzenetetracarboxylic dianhydride include pyromellitic dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride and the like.

The naphthalenetetracarboxylic dianhydride means a naphthalene dianhydride having 4 carboxy groups, and the naphthalene ring here may optionally have 1 to 3 substituents. Here, the substituent is not particularly limited. Specific examples of the naphthalenetetracarboxylic dianhydride include 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride and the like.

The anthracene tetracarboxylic dianhydride means an anthracene dianhydride having 4 carboxy groups, and the anthracene ring here 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.

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

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-, -SO _2- , -Ph-, -O-Ph-O-, -O -Ph-SO ₂ -Ph-O-, -O-Ph-C (CH ₃ ) ₂ -Ph-O- and the like can be mentioned.

Specific examples of the diphthalic acid dianhydride include 3,3', 4,4'-benzophenonetetracarboxylic dianhydride, 3,3', 4,4'-diphenylethertetracarboxylic dianhydride, 3,. 3', 4,4'-diphenylsulfonetetracarboxylic dianhydride, 3,3', 4,4'-biphenyltetracarboxylic dianhydride, 2,2', 3,3'-biphenyltetracarboxylic dianhydride Anhydroide, 2,3,3', 4'-biphenyltetracarboxylic dianhydride, 2,3,3', 4'-benzophenonetetracarboxylic dianhydride, 2,3,3', 4'-diphenyl ether Tetetracarboxylic dianhydride, 2,3,3', 4'-diphenylsulfonetetracarboxylic dianhydride 2,2'-bis (3,4-dicarboxyphenoxyphenyl) sulfonate dianhydride, methylene-4, 4'-diphthalic acid dianhydride, 1,1-ethinilidene-4,4'-diphthalic acid dianhydride, 2,2-propylidene-4,4'-diphthalic acid dianhydride, 1,2-ethylene-4 , 4'-Diphthalic dianhydride, 1,3-trimethylethylene-4,4'-diphthalic dianhydride, 1,4-tetramethylene-4,4'-diphthalic dianhydride, 1,5-penta Methylene-4,4'-diphthalic dianhydride, 1,3-bis (3,4-dicarboxyphenyl) benzene dianhydride, 1,4-bis (3,4-dicarboxyphenyl) benzene dianhydride , 1,3-bis (3,4-dicarboxyphenoxy) benzene dianhydride, 1,4-bis (3,4-dicarboxyphenoxy) benzene dianhydride, 2,2-bis (2,3-di) Carboxiphenyl) propane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 4,4'-(4,5pyridenediphenoxy) bisphthalic dianhydride, etc. Can be mentioned.

Specific examples of the aliphatic tetracarboxylic dianhydride include 1,2,3,4-cyclobutanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, and cyclohexane-1,2,3,4-. Tetetracarboxylic dianhydride, cyclohexane-1,2,4,5-tetracarboxylic dianhydride, 3,3',4,54'-bicyclohexyltetracarboxylic dianhydride, carbonyl-4,4'- Bis (cyclohexane-1,2-dicarboxylic acid) dianhydride, methylene-4,4'-bis (cyclohexane-1,2-dicarboxylic acid) dianhydride, 1,2-ethylene-4,4'-bis ( Cyclohexane-1,2-dicarboxylic dianhydride, oxy-4,4'-bis (cyclohexane-1,2-dicarboxylic acid) dianhydride, thio-4,4'-bis (cyclohexane-1,2-bis) Examples thereof include (dicarboxylic acid) dianhydride and sulfonyl-4,4'-bis (cyclohexane-1,2-dicarboxylic acid) dianhydride.

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

The content of the structure derived from the aromatic tetracarboxylic dianhydride with respect to the total structure derived from the tetracarboxylic dianhydride constituting the polyimide resin is preferably 10 mol% or more, preferably 30 mol% or more. More preferably, it is more preferably 50 mol% or more, further preferably 70 mol% or more, even more preferably 90 mol% or more, and particularly preferably 100 mol%. ..

The weight average molecular weight of the polyimide resin is preferably 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 imidizing at least a dimer acid type diamine and a maleic anhydride, and further, a dimer acid type diamine and a tetracarboxylic acid dianhydride. It contains a bismaleimide compound obtained by imidizing with a maleic anhydride.

The maleimide resin having a dimer acid skeleton is, for example, the following formula (2):

[In the formula, Y ¹ and Y ³ each independently represent a divalent group obtained by removing two -NH ₂ from the diamine-type diamine, and Y ² is ^two from the tetracarboxylic dianhydride. Indicates a tetravalent group excluding −CO—O—CO−, where m represents 0 or 1. ]
It is a bismaleimide compound represented by.

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

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

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

The (E) curing agent is not particularly limited, but when the (A) thermosetting resin is an epoxy resin, for example, a phenol-based curing agent, a naphthol-based curing agent, an acid anhydride-based curing agent, and an activity. Examples thereof include ester-based curing agents, benzoxazine-based curing agents, cyanate ester-based curing agents and carbodiimide-based curing agents, and phenol-based curing agents, naphthol-based curing agents, and active ester-based curing agents are preferable. The curing agent (E) preferably contains an active ester-based curing agent. The curing agent may be used alone or in combination of two or more.

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

Examples of the acid anhydride-based curing agent include a curing agent having one or more acid anhydride groups in one molecule. Specific examples of the acid anhydride-based curing agent include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic acid anhydride, and methylnadic hydride. Anhydride, trialkyltetrahydrophthalic anhydride, succinic anhydride, 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, trihydride Merit acid, pyromellitic anhydride, benzophenone tetracarboxylic acid dianhydride, biphenyltetracarboxylic acid dianhydride, naphthalenetetracarboxylic acid dianhydride, oxydiphthalic acid dianhydride, 3,3'-4,4'- Diphenylsulfone tetracarboxylic dianhydride, 1,3,3a,4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-franyl) -naphtho [1,2-C] furan-1 , 3-Dione, ethylene glycol bis (anhydrotrimeritate), polymer-type acid anhydrides such as styrene / maleic acid resin in which styrene and maleic acid are copolymerized, and the like. Examples of commercially available acid anhydride-based curing agents include "HNA-100" and "MH-700" manufactured by New Japan Chemical Co., Ltd.

The active ester-based curing agent is not particularly limited, but generally contains an ester group having high reactive activity such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds in one molecule. A compound having two or more esters is preferably used. The active ester-based curing agent is preferably obtained by a condensation reaction between a carboxylic acid compound and / or a thiocarboxylic acid compound and a hydroxy compound and / or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester-based curing agent obtained from a carboxylic acid compound and a hydroxy compound is preferable, and an active ester-based curing agent obtained from a carboxylic acid compound and a phenol compound and / or a naphthol compound is more preferable. Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid and the like. Examples of the phenol compound or naphthol compound include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthaline, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-. Cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenol, trihydroxybenzophenol, tetrahydroxybenzophenone, fluoroglusin, Examples thereof include benzenetriol, dicyclopentadiene-type diphenol compounds, and phenol novolac. Here, the "dicyclopentadiene-type diphenol compound" refers to a diphenol compound obtained by condensing two phenol molecules with one dicyclopentadiene molecule.

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

Commercially available active ester-based curing agents include active ester compounds containing a dicyclopentadiene-type diphenol structure, 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", "EXB-8150-65T" (manufactured by DIC); "DC808" (manufactured by Mitsubishi Chemical Co., Ltd.) as an active ester compound containing an acetylated product of phenol novolac; an active ester compound containing a benzoylated product of phenol novolac. As "YLH1026" (manufactured by Mitsubishi Chemical Co., Ltd.); "DC808" (manufactured by Mitsubishi Chemical Co., Ltd.) as an active ester-based curing agent which is an acetylated product of phenol novolac; "YLH1026" as an active ester-based curing agent which is a benzoylated product of phenol novolac. (Made by Mitsubishi Chemical Co., Ltd.), "YLH1030" (manufactured by Mitsubishi Chemical Co., Ltd.), "YLH1048" (manufactured by Mitsubishi Chemical Co., Ltd.); etc.

Specific examples of the benzoxazine-based curing agent include "JBZ-OP100D" and "ODA-BOZ" manufactured by JFE Chemicals; "HFB2006M" manufactured by Showa Polymer Co., Ltd., and "P-d" manufactured by Shikoku Chemicals Corporation. Examples include "FA".

Examples of the cyanate ester-based curing agent include bisphenol A disicianate, polyphenol cyanate (oligo (3-methylene-1,5-phenylencyanate)), 4,4'-methylenebis (2,6-dimethylphenylcyanate), 4, 4'-Etilidendidiphenyl disianate, hexafluorobisphenol A disyanate, 2,2-bis (4-cyanate) phenylpropane, 1,1-bis (4-cyanate phenylmethane), bis (4-cyanate-3,5-) Bifunctional cyanate resins such as dimethylphenyl) methane, 1,3-bis (4-cyanatephenyl-1- (methylethylidene)) benzene, bis (4-cyanatephenyl) thioether, and bis (4-cyanatephenyl) ether, Examples thereof include polyfunctional cyanate resins derived from phenol novolac, cresol novolak and the like, and prepolymers in which these cyanate resins are partially triazined. Specific examples of the cyanate ester-based curing agent include "PT30" and "PT60" (both are phenol novolac type polyfunctional cyanate ester resins), "BA230", and "BA230S75" (part of bisphenol A disocyanate) manufactured by Lonza Japan. Alternatively, a prepolymer in which all of them are triazined to form a trimer) and the like can be mentioned.

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

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

When the resin composition contains the (E) curing agent, the content thereof is not particularly limited, but is preferably 0.1% by mass when the non-volatile component in the resin composition is 100% by mass. As mentioned above, it is more preferably 1% by mass or more, further preferably 3% by mass or more, and particularly preferably 4% by mass or more. The upper limit of the content of the curing agent (E) is not particularly limited, but when the non-volatile component in the resin composition is 100% by mass, it is preferably 30% by mass or less, more preferably 20% by mass or less. It is more preferably 15% by mass or less, and 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. The (F) curing accelerator has a function of accelerating the curing rate of the (A) thermosetting resin.

The (F) curing accelerator is not particularly limited, but (A) when the thermosetting resin is an epoxy resin, for example, a phosphorus-based curing accelerator, an amine-based curing accelerator, or an imidazole-based curing accelerator. , Guanidine-based curing accelerator, metal-based curing accelerator and the like. Among them, a phosphorus-based curing accelerator, an amine-based curing accelerator, an imidazole-based curing accelerator, and a metal-based curing accelerator are preferable, and an amine-based curing accelerator is more preferable. The curing accelerator may be used alone or in combination of two or more.

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

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

Examples of the imidazole-based curing accelerator include 2-methylimidazole, 2-undecyl imidazole, 2-heptadecyl imidazole, 1,2-dimethyl imidazole, 2-ethyl-4-methyl imidazole, 1,2-dimethyl imidazole, and the like. 2-Ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-Cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimerite, 1-cyanoethyl- 2-Phenylimidazolium trimerite, 2,4-diamino-6- [2'-methylimidazolyl- (1')]-ethyl-s-triazine, 2,4-diamino-6- [2'-undecyl Imidazolyl- (1')]-ethyl-s-triazine, 2,4-diamino-6- [2'-ethyl-4'-methylimidazolyl- (1')]-ethyl-s-triazine, 2,4- Diamino-6- [2'-methylimidazolyl- (1')]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2- Phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo [1,2-a] benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline , 2-Imidazole compounds such as phenylimidazolin and adducts of imidazole compounds and epoxy resins can be mentioned.

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

Examples of the guanidine-based curing accelerator include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1- (o-tolyl) guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, and the like. 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-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1,1-dimethylbiguanide, 1,1-diethylbiguanide, 1-cyclohexylbiguanide, 1 -Allyl biguanide, 1-phenylbiguanide, 1- (o-tolyl) biguanide and the like can be mentioned.

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

When the resin composition contains the (F) curing accelerator, the content thereof is not particularly limited, but is preferably 0.001% by mass when the non-volatile component in the resin composition is 100% by mass. % Or more, more preferably 0.01% by mass or more, still more preferably 0.05% by mass or more, and particularly preferably 0.1% by mass or more. The upper limit of the content of the (F) curing accelerator is not particularly limited, but when the non-volatile component in the resin composition is 100% by mass, it is preferably 2% by mass or less, more preferably 1% by mass. Below, it is more preferably 0.5% by mass or less, and particularly preferably 0.3% by mass or less.

<(G) Other additives>
The resin composition of the present invention may further contain any additive as a non-volatile component. Examples of such additives include thermoplastic resins such as phenoxy resins, polyvinyl acetal resins, polyolefin resins, polysulfone resins, polyether sulfone resins, polyphenylene ether resins, polycarbonate resins, polyether ether ketone resins, and polyester resins; organic. Organic metal compounds such as copper compounds, organic zinc compounds, and organic cobalt compounds; colorants such as phthalocyanine blue, phthalocyanine green, iodin green, diazo yellow, crystal violet, titanium oxide, carbon black; hydroquinone, catechol, pyrogallol, phenothiazine, etc. Polymer retardants; Leveling agents such as siloxane; Thickeners such as Benton and Montmorillonite; Silicone-based defoaming agents, Acrylic-based defoaming agents, Fluorine-based defoaming agents, Vinyl resin-based defoaming agents Ultraviolet absorbers such as triazole-based ultraviolet absorbers; Adhesive improvers such as ureasilane; Adhesion-imparting agents such as silane coupling agents, triazole-based adhesion-imparting agents, tetrazole-based adhesion-imparting agents, and triazine-based adhesion-imparting agents Agents; Antioxidants such as hindered phenolic antioxidants and hindered amine antioxidants; Fluorescent whitening agents such as stelvene derivatives; Phosphorus flame retardants (eg phosphoric acid ester compounds, phosphazene compounds, phosphinic acid compounds, red phosphorus) ), Nitrogen-based flame retardants (for example, melamine sulfate), halogen-based flame retardants, inorganic flame retardants (for example, antimony trioxide) and other flame retardants. As the additive, one type may be used alone, or two or more types may be used in combination at an arbitrary ratio. The content of (G) 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 arbitrary organic solvent as a volatile component in addition to the above-mentioned non-volatile component. As the organic solvent (H), known ones can be appropriately used as long as at least a part of the non-volatile component can be dissolved, and the type thereof is not particularly limited. Examples of the organic solvent (H) include ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, isoamyl acetate, methyl propionate, ethyl propionate, and γ-. Ester-based solvents such as butyrolactone; ether-based solvents such as tetrahydropyran, tetrahydrofuran, 1,4-dioxane, diethyl ether, diisopropyl ether, dibutyl ether and diphenyl ether; alcohol-based 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, methyl methoxypropionate; methyl lactate, ethyl lactate, 2-hydroxyisobutyric acid Ester alcohol solvents such as methyl; ether alcohol solvents such as 2-methoxypropanol, 2-methoxyethanol, 2-ethoxyethanol, propylene glycol monomethyl ether, diethylene glycol monobutyl ether (butyl carbitol); N, N-dimethylformamide, Amid solvents such as N, N-dimethylacetamide and N-methyl-2-pyrrolidone; Sulfoxide solvents such as dimethylsulfoxide; Nitrile solvents such as acetonitrile and propionitrile; hexane, cyclopentane, cyclohexane, methylcyclohexane and the like. An aliphatic hydrocarbon solvent; an aromatic hydrocarbon solvent such as benzene, toluene, xylene, ethylbenzene, and trimethylbenzene can be mentioned. The organic solvent may be used alone or in combination of two or more in any ratio.

The content of the organic solvent (H) is preferably 30% by mass or more, more preferably the mass ratio of the non-volatile component to the total mass of the resin composition, that is, the solid content ratio, from the viewpoint of efficiently drying the resin composition. Can 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, it is preferably 100% by mass or less, more preferably 95% by mass or less, still more preferably 92% by mass or less, particularly. It can be preferably 90% by mass or less.

<Manufacturing method of resin composition>
The resin composition of the present invention can be used in any reaction vessel, for example, (A) thermosetting resin, (B) inorganic filler, (C) organic filler, (D) adhesive softening agent, if necessary. (E) curing agent, (F) curing accelerator if necessary, (G) other additives if necessary, (H) organic solvent if necessary, in any order and / or partly or It can be manufactured by adding and mixing all at the same time. Further, in the process of adding and mixing each component, the temperature can be appropriately set, and heating and / or cooling may be performed temporarily or from beginning to end. Further, stirring or shaking may be performed in the process of adding and mixing each component. Further, the resin composition may be stirred at the time of additional mixing or thereafter using a stirring device such as a mixer to uniformly disperse the resin composition.

<Characteristics of resin composition>
Since the resin composition of the present invention contains (C) an organic filler in an amount of 5% by mass or more in addition to (A) a thermosetting resin, (D) an adhesive softening agent, and (B) an inorganic filler. Tackiness can be kept low while maintaining excellent flexibility.

Since the resin composition of the present invention contains (D) an adhesive softening agent, it has sufficient flexibility. Therefore, 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. When the MIT fold resistance test is performed by setting the load to 2.5 N, the bending angle to 90 degrees, the bending speed to 175 times / minute, and the bending radius to 1.0 mm in accordance with JIS C-5016, the number of fold resistance is It can be preferably 3,000 times or more, more preferably 5,000 times or more, further preferably 7,000 times or more, and particularly preferably 8,000 times or more.

The resin composition of the present invention preferably has a minimum melt viscosity of the resin composition measured under the conditions of, for example, a starting 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. It can be 40,000 poise or less, 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, a probe φ5 mm, a load of 1 kgf / cm ² , and a contact speed of 0.5 mm are used using a probe tack tester. The tack force measured under the conditions of / sec, tensile speed 0.5 mm / sec, holding time 10 seconds, and temperature 80 ° C. is preferably 2.0 N or less, more preferably 1.8 N or less, still more preferably 1.7 N or less. , Especially preferably 1.6 N or less.

Further, the resin composition of the present invention is characterized in that void defects are suppressed and the pattern embedding property is more excellent, especially 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 be usually 1 μm or more, 1.5 μm or more, 2 μm or more, or the like.

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

When a film made of a plastic material is used as the support, the plastic material may be, for example, polyethylene terephthalate (hereinafter abbreviated as "PET") or polyethylene naphthalate (hereinafter abbreviated as "PEN"). ) Etc., polyester, polycarbonate (hereinafter sometimes abbreviated as "PC"), acrylic such as polymethylmethacrylate (PMMA), cyclic polyolefin, triacetylcellulose (TAC), polyethersulfide (PES), polyether. Examples thereof include ketones and polyimides. Of these, polyethylene terephthalate and polyethylene naphthalate are preferable, and inexpensive polyethylene terephthalate is particularly preferable.

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

The surface of the support to be joined to the resin composition layer may be matted, corona-treated, or antistatic-treated.

Further, as the support, a support with a release layer having a release layer on the surface to be joined with the resin composition layer may be used. Examples of the release agent used for the release layer of the support with the release layer include one or more release agents selected from the group consisting of alkyd resin, polyolefin resin, urethane resin, and silicone resin. .. As the support with a release layer, a commercially available product may be used. For example, "SK-1" and "SK-1" manufactured by Lintec Corporation, which are PET films having a release layer containing an alkyd resin-based release agent as a main component. Examples thereof include "AL-5" and "AL-7", "Lumirror T60" manufactured by Toray Industries, Inc., "Purex" manufactured by Teijin Corporation, and "Unipee" manufactured by Unitika.

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

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

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

Examples of the organic solvent that can be used when coating on the support include the same organic solvents as those mentioned in the above description of the organic solvent (H). The organic solvent may be used alone or in combination of two or more.

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

The resin sheet can be rolled up and stored. When the resin sheet has a protective film, it can be used by peeling off the protective film.

<Laminated sheet>
The laminated sheet is a sheet produced by laminating and curing a plurality of resin composition layers. The laminated sheet contains a plurality of insulating layers as a cured product of the resin composition layer. Usually, the number of resin composition layers laminated to produce a laminated sheet corresponds to the number of insulating layers contained 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. ..

The laminated sheet is a sheet used by bending so that one of the surfaces faces each other. The minimum bending radius for bending the laminated sheet is not particularly limited, but is preferably 0.1 mm or more, more preferably 0.2 mm or more, still more preferably 0.3 mm or more, and preferably 5 mm or less. It is preferably 4 mm or less, 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 the multilayer flexible substrate.

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

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

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

The conductor layer may be patterned to function as wiring.

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

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

<Manufacturing method of 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 the resin sheet. The order of laminating and curing the resin composition layer is arbitrary as long as a desired laminated sheet can be obtained. For example, after all the plurality of resin composition layers are laminated, the laminated plurality of resin composition layers may be cured at once. Further, for example, each time another resin composition layer is laminated on one resin composition layer, the laminated resin composition layer may be cured.

Hereinafter, a preferred embodiment of step (b) will be described. In the embodiments described below, for the sake of distinction, the resin composition layers are appropriately numbered such as "first resin composition layer" and "second resin composition layer", and further, they are indicated. The insulating layer obtained by curing the resin composition layer of No. 1 is also numbered like "first insulating layer" and "second insulating layer" in the same manner as the resin composition layer.

In one preferred embodiment, step (b) is
(II) A step of 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,
(VII) A step of curing the second resin composition layer to form a second insulating layer,
including. Further, in step (b), if necessary,
(I) Step of laminating the first resin composition layer on the sheet support base material,
(III) The process of drilling holes in the first insulating layer,
(IV) Step of roughening the first insulating layer,
(V) It may include an arbitrary step such as a step of forming a conductor layer on the first insulating layer. Hereinafter, each step will be described.

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

Lamination of the sheet support base material and the first resin composition layer may be carried out by a vacuum laminating method. In the vacuum laminating method, the heat crimping temperature is preferably in the range of 60 ° C. to 160 ° C., more preferably 80 ° C. to 140 ° C., and the heat crimping pressure is preferably 0.098 MPa to 1.77 MPa, more preferably 0. It is in the range of .29 MPa to 1.47 MPa, and the heat crimping time is preferably in the range of 20 seconds to 400 seconds, more preferably 30 seconds to 300 seconds. Lamination is preferably carried out under reduced pressure conditions at a pressure 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 pressurizing laminator manufactured by Meiki Co., Ltd., a vacuum applicator manufactured by Nikko Materials, and a batch type vacuum pressurizing laminator.

When a resin sheet is used, the laminating of the sheet supporting base material and the first resin composition layer is performed, for example, by pressing the resin sheet from the support side and using the first resin composition layer of the resin sheet as the sheet supporting base material. This can be done by heat crimping. Examples of the member for heat-pressing the resin sheet to the sheet support base material (hereinafter, also appropriately referred to as “heat-bonding member”) include a heated metal plate (SUS end plate or the like) or a metal roll (SUS roll). And so on. Rather than pressing the heat-bonded member directly onto the resin sheet, it is preferable to press the member through an elastic material such as heat-resistant rubber so that the first resin composition layer sufficiently follows the surface irregularities of the sheet-supporting base material.

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

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

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

The first resin composition layer may be preheated at a temperature lower than the curing temperature before the first resin composition layer is thermosetting. For example, prior to thermosetting the first resin composition layer, the first resin is at a temperature of 50 ° C. or higher and lower than 120 ° C. (preferably 60 ° C. or higher and 115 ° C. or lower, more preferably 70 ° C. or higher and 110 ° C. or lower). The composition layer may be preheated for 5 minutes or longer (preferably 5 to 150 minutes, more preferably 15 to 120 minutes, even more preferably 15 to 100 minutes).

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

Step (IV) is a step of roughening the first insulating layer. Usually, smear removal is also performed in this step (IV). Therefore, the roughening treatment is sometimes called a desmear treatment. 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.

The swelling liquid is not particularly limited, and examples thereof include alkaline aqueous solutions such as sodium hydroxide aqueous solution and potassium hydroxide aqueous solution. Examples of commercially available swelling liquids include "Swelling Dip Security SBU" and "Swelling Dip Security SBU" manufactured by Atotech Japan. The swelling treatment with the swelling liquid can be performed, for example, by immersing the cured product in the swelling liquid at 30 to 90 ° C. for 1 to 20 minutes. From the viewpoint of suppressing the swelling of the resin of the insulating layer to an appropriate level, it is preferable to immerse the insulating layer in a swelling liquid at 40 ° C. to 80 ° C. for 5 minutes to 15 minutes.

The oxidizing agent is not particularly limited, and examples thereof include an alkaline permanganate solution in which a permanganate solution is dissolved in a sodium hydroxide aqueous solution or a potassium hydroxide aqueous solution. The concentration of permanganate in the alkaline permanganate solution is preferably 5% by mass to 10% by mass. Examples of commercially available oxidizing agents include alkaline permanganic acid solutions such as "Concentrate Compact P", "Concentrate Compact CP", and "Dosing Solution Security P" manufactured by Atotech Japan. .. The roughening treatment with an oxidizing agent can be performed by immersing the cured product in an oxidizing agent solution heated to 60 ° C. to 80 ° C. for 10 minutes to 30 minutes.

An acidic aqueous solution is used as the neutralizing solution. Examples of commercially available products include "Reduction Solution Security P" manufactured by Atotech Japan. The treatment with the neutralizing solution can be performed by immersing the cured product in the neutralizing solution at 30 ° C. 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 ° C. 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, 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.

The step (V) is a step of forming a conductor layer on the first insulating layer, if necessary. Examples of the method for forming the conductor layer include a plating method, a sputtering method, and a vapor deposition method, and the plating method is particularly preferable. Preferable examples include a method of plating the surface of the first insulating layer by an appropriate method such as a semi-additive method or a full-additive method to form a conductor layer having a desired wiring pattern. Above all, the semi-additive method is preferable from the viewpoint of ease of production.

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

The first insulating layer is obtained in the step (II), and the step (III), the step (IV), and the step (V) are performed as necessary, and then the step (VI) is performed. The step (VI) is a step of laminating the second resin composition layer on the first insulating layer. The lamination of the first insulating layer and the second resin composition layer can be performed by the same method as the lamination of the sheet support base material and the first resin composition layer in the step (I).

However, when the first resin composition layer is formed using the resin sheet, the support of the resin sheet is removed before the step (VI). The removal of the support may be performed between the steps (I) and the step (II), between the steps (II) and the step (III), and between the steps (III) and the step (IV). ), Or between step (IV) and step (V).

After the step (VI), the step (VII) is performed. The step (VII) is a step of curing 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 the 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-described embodiment, (VIII) a step of drilling a hole in the second insulating layer, (IX) a step of roughening the second insulating layer, and (X) a second insulating layer, as necessary. A step of forming a conductor layer on the layer may be performed. The drilling of the second insulating layer in the step (VIII) can be performed in the same manner as the drilling of the first insulating layer in the step (III). Further, the roughening treatment of the second insulating layer in the step (IX) can be performed by the same method as the roughening treatment of the first insulating layer in the step (IV). Further, the formation of the conductor layer on the second insulating layer in the step (X) can be performed in the same manner as the formation of the conductor layer on the first insulating layer in the step (V).

In the above-described embodiment, an embodiment in which a laminated sheet is produced by laminating and curing two resin composition layers, that is, a first resin composition layer and a second resin composition layer, has been described, but a resin composition of three or more layers has been described. A laminated sheet may be manufactured by laminating and curing a material layer. For example, in the method according to the above-described embodiment, the resin composition layer is laminated and cured by steps (VI) to (VII), and the insulating layer is drilled by steps (VIII) to (X) if necessary. , The roughening treatment of the insulating layer and the formation of the conductor layer on the insulating layer may be repeatedly carried out to produce a laminated sheet. As a result, a laminated sheet containing three or more insulating layers can be obtained.

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

<Multilayer flexible substrate>
The multilayer flexible substrate includes a laminated sheet. The multilayer flexible substrate may include only a laminated sheet, or may include an arbitrary member in combination with the laminated sheet. Examples of the optional member include an electronic component, a coverlay film, and the like.

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

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

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

<Semiconductor device>
The semiconductor device includes the multilayer flexible substrate described above. The semiconductor device includes, for example, a multilayer flexible substrate and a semiconductor chip mounted on the multilayer flexible substrate. In many semiconductor devices, the multilayer flexible substrate can be stored in the housing of the semiconductor device by being bent so that one surface of the laminated sheet included in the multilayer flexible substrate faces each other.

Examples of semiconductor devices include various semiconductor devices used in electric products (for example, computers, mobile phones, digital cameras, televisions, etc.) and vehicles (for example, motorcycles, automobiles, trains, ships, aircraft, etc.). Be done.

The semiconductor device includes, for example, a step of preparing a multilayer flexible substrate, a step of bending the multilayer flexible substrate so that one surface of the laminated sheet faces each other, and a step of storing the bent multilayer flexible substrate in a housing. It can be manufactured by a manufacturing method including.

Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to the following examples. In the following description, "parts" and "%" representing quantities mean "parts by mass" and "% by mass", respectively, unless otherwise specified. In addition, the operations described below were performed in an environment of normal temperature and pressure unless otherwise specified.

<Synthesis Example 1: Synthesis of Polyimide Butadiene Resin>
In a 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 mixed solvent (Idemitsu Petrochemical) 40 g of “Ipsol 150” manufactured by Chemical Co., Ltd.) and 0.005 g of dibutyltin laurate were added, mixed and uniformly dissolved. When the temperature became uniform, the temperature was raised to 60 ° C., and 8 g of isophorone diisocyanate (“IPDI” manufactured by Evonik Degussa Japan Co., Ltd., isocyanate group equivalent = 113 g / eq.) Was added with further stirring, and the reaction was carried out for about 3 hours.

Next, 23 g of cresol novolak resin (“KA-1160” manufactured by DIC, 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 increased to 150 ° C. with stirring. The temperature was raised and 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 the disappearance of the NCO peak was regarded as the end point of the reaction, and the temperature of the reaction product was lowered to room temperature. Then, the reaction product was filtered with a 100-mesh filter cloth to obtain an elastomer having a butadiene structure and a phenolic hydroxyl group (phenolic hydroxyl group-containing butadiene resin: 50% by mass of non-volatile component). 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>
9.13 g (30 mmol) of 4-aminobenzoate 5-amino-1,1'-biphenyl-2-yl, 4,4'-(4,) in a 500 ml separable flask equipped with a nitrogen introduction tube and a stirrer. 4'-Isopropyridene diphenoxy) Bisphthalic acid dianhydride 15.61 g (30 mmol), N-methyl-2-pyrrolidone 94.64 g, pyridine 0.47 g (6 mmol), toluene 10 g were added, and under a nitrogen atmosphere. A polyimide solution containing the polyimide resin 1 (nonvolatile content: 20% by mass) was obtained by performing an imidization reaction at 180 ° C. for 4 hours while peeping toluene out of the system. No precipitation of the synthesized polyimide resin 1 was observed in the polyimide solution.

<Synthesis Example 3: Synthesis of Polyimide Resin 2>
Aromatic tetracarboxylic dianhydride ("BisDA-1000" manufactured by SABIC Japan, 4,4'-(4,4') in a reaction vessel equipped with a stirrer, a water divider, a thermometer and a nitrogen gas introduction tube. -Isopropyridenediphenoxy) bisphthalic acid dianhydride) 65.0 g, cyclohexanone 266.5 g, and methylcyclohexane 44.4 g were charged, and the solution was heated to 60 ° C. Next, 43.7 g of dimer diamine (“PRIAMINE 1075” manufactured by Croda Japan) and 5.4 g of 1,3-bis (aminomethyl) cyclohexane were added dropwise, and then an imidization reaction was carried out at 140 ° C. for 1 hour. As a result, a polyimide solution containing the polyimide resin 2 (nonvolatile content: 30% by mass) was obtained. The weight average molecular weight of the polyimide resin 2 was 25,000.

<Synthesis Example 4: Synthesis of Polyimide Resin 3>
A 500 mL separable flask equipped with a moisture metering receiver connected to a reflux condenser, a nitrogen introduction pipe, 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) Phenyl] -1,1,3-trimethylindan 29.6 g was added, and the reaction was carried out by stirring at 45 ° C. for 2 hours under a nitrogen stream. The reaction solution was then heated to about 160 ° C. and the condensed water was azeotropically removed with toluene under a nitrogen stream. It was confirmed that a predetermined amount of water had accumulated in the moisture metering receiver and that no outflow of water was observed. After confirmation, the reaction solution was further heated and stirred at 200 ° C. for 1 hour. Then, it cooled to obtain a polyimide solution (nonvolatile content 20% by mass) containing the 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). The weight average molecular weight of the polyimide resin 3 was 12,000.

<Example 1>
Bixylenol type epoxy resin (Mitsubishi Chemical Corporation "YX4000HK", epoxy equivalent about 185g / eq.) 5 parts, Naphthalene type epoxy resin (Nippon Steel & Sumitomo Metal Corporation "ESN475V", epoxy equivalent about 332g / eq.), 5 parts, Bisphenol AF type epoxy resin (Mitsubishi Chemical Corporation "YL7760", epoxy equivalent about 238 g / eq.) 10 parts, cyclohexane type epoxy resin (Mitsubishi Chemical Corporation "ZX1658GS", epoxy equivalent about 135 g / eq.), Synthetic It was dissolved by heating in a mixed solvent of 40 parts of the epoxy butadiene resin (50% by mass of the non-volatile component) obtained in Example 1 and 10 parts of cyclohexanone while stirring. After cooling to room temperature, there, 4 parts of a triazine skeleton-containing cresol novolac-based curing agent (“LA-3018-50P” manufactured by DIC, hydroxyl group equivalent of about 151, 2-methoxypropanol solution having a non-volatile content of 50%), activity. Ester-based curing agent ("EXB-8000L-65M" manufactured by DIC, MEK solution with active group equivalent of about 220, 65% by mass of non-volatile component), spherical silica ("SC2500SQ" manufactured by Admatex, average particle size 0. 5 μm, specific surface area 11.2 m ² / g, 40 parts of N-phenyl-3-aminopropyltrimethoxysilane (surface-treated with 1 part of KBM573 manufactured by Shinetsu Chemical Industry Co., Ltd.) for 100 parts of silica, core- 6 parts of shell-type graft copolymer rubber particles (“EXL2655” manufactured by Dow Chemical Japan Co., Ltd.) and 0.2 parts of amine-based curing accelerator (4-dimethylaminopyridine (DMAP)) are mixed and uniformed with a high-speed rotation mixer. The resin composition was prepared by filtering the mixture with a cartridge filter (“SHP020” manufactured by ROKITECHNO).

<Example 2>
Example 1 except that 100 parts of the polyimide solution (20% by mass of the non-volatile component) obtained in Synthesis Example 2 was used instead of 40 parts of the polyimide butadiene resin (50% by mass of the non-volatile component) obtained in Synthesis Example 1. The same operation as in the above was carried out to prepare a resin composition.

<Example 3>
Except for using 66.7 parts of the polyimide solution (30% by mass of non-volatile component) obtained in Synthesis Example 3 instead of using 40 parts of the polyimide butadiene resin (50% by mass of non-volatile component) obtained in Synthesis Example 1. The same operation as in Example 1 was carried out to prepare a resin composition.

<Example 4>
Example 1 except that 100 parts of the polyimide solution (20% by mass of the non-volatile component) obtained in Synthesis Example 4 was used instead of 40 parts of the polyimide butadiene resin (50% by mass of the non-volatile component) obtained in Synthesis Example 1. The same operation as in the above was carried out to prepare a resin composition.

<Example 5>
Instead of using 40 parts of the polyimide butadiene resin (50% by mass of non-volatile component) obtained in Synthesis Example 1, a polybutadiene structure-containing resin (manufactured by Nippon Kayaku Co., Ltd., "BX360", a block copolymer of polyphenylene ether and polybutadiene, non-volatile A resin composition was prepared by performing the same operation as in Example 1 except that 40 parts of a toluene solution having a component of 50% by mass was used.

<Example 6>
The same operation as in Example 1 except that 20 parts of bismaleimide resin (manufactured by DM, "BMI689") was used instead of 40 parts of the polyimide butadiene resin (50% by mass of non-volatile component) obtained in Synthesis Example 1. Was carried out to prepare a resin composition.

<Example 7>
Instead of using 40 parts of the polyimide butadiene resin (50% by mass of non-volatile component) obtained in Synthesis Example 1, a polyrotaxan resin (manufactured by Advanced Soft Materials Co., Ltd., a 40% solution of "SH1310P" in methyl ethyl ketone, the axis molecule is a polyethylene glycol chain. The cyclic molecule contains cyclodextrins.) The resin composition was prepared by carrying out the same operation as in Example 1 except that 50 parts were used.

<Example 8>
The same operation as in Example 1 was performed, except that the amount of the core-shell type graft copolymer rubber particles (“EXL2655” manufactured by Dow Chemical Japan, Ltd.) used in Example 1 was changed from 6 parts to 12 parts. A resin composition was prepared.

<Comparative example 1>
The amount of spherical silica (“SC2500SQ” manufactured by Admatex Co., Ltd., surface-treated) of Example 1 was changed from 40 parts to 70 parts, and core-shell type graft copolymer rubber particles (Dow Chemical Japan Co., Ltd.). The resin composition was prepared by performing the same operation as in Example 1 except that the amount of the product "EXL2655") used was changed from 6 parts to 5 parts.

<Comparative example 2>
The resin composition was prepared by performing the same operation as in Example 1 except that 6 parts of the core-shell type graft copolymer rubber particles (“EXL2655” manufactured by Dow Chemical Japan, Inc.) of Example 1 were not used. did.

<Comparative example 3>
Implemented except that 42 parts of phenoxy resin (“YX7553BH30” manufactured by Mitsubishi Chemical Corporation, solid content 30% by mass) was used instead of 40 parts of the polyimide butadiene resin (50% by mass of non-volatile component) obtained in Synthesis Example 1. The same operation as in Example 1 was carried out to prepare a resin composition.

<Test Example 1: Evaluation of flexibility (MIT folding resistance)>
The thickness of the resin composition layer after drying is 40 μm on the release-treated surface of the PET film (thickness 38 μm) obtained by treating the resin compositions of each Example and Comparative Example with an alkyd-based mold release agent. , Was uniformly applied with a die coater and dried at 80 to 120 ° C. (average 100 ° C.) for 6 minutes to obtain a resin sheet.

The obtained resin sheet was laminated on a polyimide film (UPILEX S, manufactured by Ube Industries, Ltd.) using a batch type vacuum pressurizing laminator (“MVLP-500” manufactured by Meiki Seisakusho Co., Ltd.). The laminate was depressurized for 30 seconds to reduce the atmospheric pressure to 13 hPa or less, and then pressure-bonded at 120 ° C. for 30 seconds at a pressure of 0.74 MPa to obtain a resin sheet with a protective film. Then, the PET film was peeled off from the resin sheet with the protective film, the resin composition was cured under the curing conditions of 190 ° C. for 90 minutes, and the polyimide film was peeled off to obtain a cured product sample.

The obtained cured product sample was cut into test pieces having a width of 15 mm and a length of 110 mm, and a MIT tester (MIT-DA), a MIT folding fatigue tester manufactured by Toyo Seiki Seisakusho Co., Ltd. According to JIS C-5016, the number of folding resistances until the cured product was broken was measured under the measurement conditions of a load of 2.5 N, a bending angle of 90 degrees, a bending radius of 1.0 mm, and a bending speed of 175 times / minute. The measurement was performed on 5 samples, and the average value of the top 3 points was calculated. When the number of times of folding was less than 8,000, it was evaluated as "x", and when it was 8,000 or more, it was evaluated as "○".

<Test Example 2: Evaluation of pattern embedding property and flatness>
<Test Example 2-1: Measurement of minimum melt viscosity>
The minimum melt viscosity of the resin composition layer of the resin sheet obtained in Test Example 1 was measured using a dynamic viscoelasticity measuring device (“Rheosol-G3000” manufactured by UBM). 1 g of the sample resin composition collected from the resin composition layer was heated from a starting temperature of 60 ° C. to 200 ° C. at a heating rate of 5 ° C./min using a parallel plate having a diameter of 18 mm, and the measurement temperature interval was 2. The dynamic viscoelasticity was measured under the measurement conditions of 5 ° C., frequency 1 Hz, and strain 1 deg, and the minimum melt viscosity (poise) was measured.

<Test Example 2-2: Measurement of tack force>
The protective film was peeled off from the resin sheet with the 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 , contact speed 0.5 mm / sec, tensile speed 0.5 mm / sec, holding time 10 seconds, and temperature 80 ° C. was measured. When the tack force exceeded 1.6 N, it was evaluated as “x”, and when it was 1.6 N or less, it was evaluated as “◯”.

<Test Example 2-3: Evaluation of pattern embedding property and void>
As an inner layer circuit board, a glass cloth base material epoxy resin double-sided copper-clad laminate (copper foil thickness) having circuit conductors (copper) formed on both sides with a wiring pattern of 1 mm square lattice (remaining copper ratio 59%). 18 μm, substrate thickness 0.15 mm, “HL832NSF LCA” manufactured by Mitsubishi Gas Chemicals Co., Ltd., 255 * 340 mm size) were prepared. Both sides of the inner layer circuit board were roughened (copper etching amount 0.5 μm) on the copper surface with “CZ8201” manufactured by MEC COMPANY Ltd.

The resin sheet obtained in Test Example 1 was subjected to a batch type vacuum pressure laminator (manufactured by Nikko Materials Co., Ltd., 2-stage build-up laminator, CVP700) so that the resin composition layer was in contact with the inner layer circuit board. , Laminated on both sides of the inner layer circuit board. Lamination was carried out by reducing the pressure for 30 seconds to a pressure of 13 hPa or less, and crimping at 130 ° C. and a pressure of 0.74 MPa for 45 seconds. Then, heat pressing was performed at 120 ° C. and a pressure of 0.5 MPa for 75 seconds.

The inner layer circuit board on which the resin sheet is laminated is heat-cured for 30 minutes after being placed in an oven at 100 ° C. under a temperature condition of 100 ° C., and then transferred to an oven at 180 ° C. for 30 minutes at a temperature condition of 180 ° C. To form an insulating layer. This is referred to as an "evaluation substrate".

The support was peeled off from the evaluation substrate, and the surface of the insulating layer was observed with a micro optical microscope. Regarding the pattern embedding property, the case where the pattern was firmly embedded was evaluated as "○", and the case where the embedding was insufficient was evaluated as "×". Regarding voids, the case where no voids were generated was evaluated as "○", and the case where voids were generated was evaluated as "x".

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

Excellent flexibility 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 was found that the tackiness can be suppressed to a low level while maintaining the above. In particular, it was found that when the organic filler (C) was 10% by mass or less, void defects were suppressed and the pattern embedding property was excellent.

Claims (17)

A resin composition containing (A) a thermosetting resin, (B) an inorganic filler, (C) an organic filler, and (D) an adhesive softening agent.
A resin composition in which the content of the component (C) is 5% by mass or more when the non-volatile 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 non-volatile component in the resin composition is 100% by mass. The resin composition according to claim 1 or 2, wherein the content of the component (C) is 10% by mass or less when the non-volatile component in the resin composition is 100% by mass. The resin composition according to any one of claims 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 any one of claims 1 to 4, wherein the content of the component (D) is 1% by mass or more when the non-volatile component in the resin composition is 100% by mass. (C) The resin composition according to any one of claims 1 to 5, wherein the organic filler is core-shell type graft copolymer particles. The resin composition according to claim 6, wherein the monomer component forming the shell portion of the core-shell type graft copolymer particles is a (meth) acrylic acid ester. The resin composition according to claim 6 or 7, wherein the core particles of the core-shell type graft copolymer particles contain a thermoplastic elastomer. The resin composition according to any one of claims 1 to 8, wherein the component (A) is an epoxy resin. The resin composition according to any one of claims 1 to 9, 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 any one of claims 1 to 11, wherein the solid content in the resin composition is 95% by mass or less. The resin composition according to any one of claims 1 to 12, which is used for forming an insulating layer of a multilayer flexible substrate. The 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 provided on the support and formed of the resin composition according to any one of claims 1 to 13. A multilayer flexible substrate including 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.