Resin composition

Abstract

The problem of the present invention is to provide a resin composition for obtaining a cured product having excellent flexibility, flame retardancy and reflow resistance. The solution of the present invention is a resin composition comprising (A) an epoxy resin, (B) silicone rubber particles and (C) an elastomer, wherein when the non-volatile component in the resin composition is set to 100% by mass, the content of the component (C) is 20% to 50% by mass.

Description

Technical Field

[0001] The present invention relates to a resin composition containing an epoxy resin and further to a cured product, a resin sheet, a multilayer flexible substrate and a semiconductor device obtained by using the resin composition. Background Art

[0002] In recent years, there has been an increasing demand for thinner and lighter semiconductor components with a higher mounting density. In order to meet this demand, a scheme using a flexible substrate as a base substrate used in a semiconductor component has attracted attention. Compared with a rigid substrate, a flexible substrate can be thinner and lighter. In addition, since a flexible substrate is soft and deformable, it can be bent and mounted.

[0003] Generally, in order to improve flexibility, it is necessary to add an elastomer to the insulating material of the flexible substrate, but if the elastomer addition rate is increased, there is a tendency for the flame retardancy to decrease. Therefore, it is generally known that it is difficult to achieve flexibility and flame retardancy at the same time. In addition, if the elastomer addition rate is increased, there is also the following problem: in the manufacturing process of the flexible substrate, expansion is likely to occur between the insulating layer and the conductor layer after the reflow process.

[0004] Conventionally, epoxy resin compositions containing silicone rubber particles are known (Patent Documents 1 and 2).

[0005] Prior art literature

[0006] Patent Literature

[0007] Patent Document 1: Japanese Patent No. 5146438

[0008] Patent document 2: Japanese Patent No. 5589363. Summary of the invention

[0009] Problems to be solved by the invention

[0010] An object of the present invention is to provide a resin composition for obtaining a cured product having excellent flexibility, flame retardancy, and reflow resistance.

[0011] Means for solving problems

[0012] In order to solve the problem of the present invention, the inventors conducted in-depth research and found that by using a resin composition containing (A) epoxy resin, (B) silicone rubber particles, and 20% to 50% by mass of (C) elastomer, a cured product with excellent flexibility, flame retardancy and reflow resistance can be obtained, thereby completing the present invention.

[0013] That is, the present invention includes the following contents:

[0014] [1] A resin composition comprising (A) an epoxy resin, (B) silicone rubber particles and (C) an elastomer, wherein the content of the component (C) is 20% to 50% by mass when the non-volatile component in the resin composition is 100% by mass;

[0015] [2] The resin composition according to [1] above, wherein the molar ratio of phenolic hydroxyl groups to epoxy groups in all components of the resin composition (phenolic hydroxyl groups / epoxy groups) is 1 or less;

[0016] [3] The resin composition according to [1] or [2] above, wherein component (A) is a solid epoxy resin, or a combination of a liquid epoxy resin and a solid epoxy resin,

[0017] When a liquid epoxy resin and a solid epoxy resin are combined, the mass ratio of the solid epoxy resin to the liquid epoxy resin (solid epoxy resin / liquid epoxy resin) is 1 or more;

[0018] [4] The resin composition according to any one of [1] to [3] above, wherein the content of the component (A) is 5% to 60% by mass, based on 100% by mass of the non-volatile component in the resin composition;

[0019] [5] The resin composition according to any one of [1] to [4] above, wherein the content of the component (B) is 35% by mass or less when the non-volatile component in the resin composition is 100% by mass;

[0020] [6] The resin composition according to [5] above, wherein the content of the component (B) is 25% by mass or less when the non-volatile component in the resin composition is 100% by mass;

[0021] [7] The resin composition according to any one of [1] to [6] above, wherein the component (C) is a resin having one or more structures selected from the group consisting of a polybutadiene structure, a polysiloxane structure, a poly(meth)acrylate structure, a polyalkylene structure, a polyalkyleneoxy structure, a polyisoprene structure, a polyisobutylene structure, and a polycarbonate structure;

[0022] [8] The resin composition according to [7] above, wherein the component (C) is a resin having a polybutadiene structure;

[0023] [9] The resin composition according to [8] above, wherein the component (C) comprises: a polybutadiene resin containing a phenolic hydroxyl group;

[0024]

[10] The resin composition according to any one of [1] to [9] above, further comprising (D) an inorganic filler;

[0025]

[11] The resin composition according to

[10] above, wherein the content of the component (D) is 50% by mass or less when the non-volatile component in the resin composition is 100% by mass;

[0026]

[12] The resin composition according to

[10] or

[11] above, wherein the mass ratio of the component (B) to the component (D) (component (B) / component (D)) is 1 or less;

[0027]

[13] The resin composition according to any one of [1] to

[12] above, further comprising (E) a flame retardant;

[0028]

[14] The resin composition according to

[13] above, wherein the component (E) comprises: a phosphorus-based flame retardant containing a phenolic hydroxyl group;

[0029]

[15] The resin composition according to

[13] or

[14] , wherein the content of the component (E) is 4% by mass or more when the non-volatile component in the resin composition is 100% by mass;

[0030]

[16] The resin composition according to any one of [1] to

[15] above, which is used to form an insulating layer of a multi-layer flexible substrate;

[0031]

[17] A cured product, which is a cured product of the resin composition described in any one of [1] to

[16] above;

[0032]

[18] A resin sheet comprising a support and a resin composition layer formed from the resin composition described in any one of [1] to

[16] above and disposed on the support;

[0033]

[19] A multi-layer flexible substrate comprising an insulating layer formed by curing the resin composition described in any one of [1] to

[16] above;

[0034]

[20] A semiconductor device comprising the multi-layer flexible substrate described in

[19] above.

[0035] Effects of the Invention

[0036] The resin composition of the present invention can provide a cured product having excellent flexibility, flame retardancy and reflow resistance. DETAILED DESCRIPTION

[0037] Hereinafter, the present invention will be described in detail according to its preferred embodiments. However, the present invention is not limited to the following embodiments and examples, and can be implemented with arbitrary changes within the scope of the claims of the present invention and their equivalents.

[0038] <Resin composition>

[0039] The resin composition of the present invention comprises (A) epoxy resin, (B) silicone rubber particles and (C) elastomer, and the content of (C) component is 20% to 50% by mass. By using such a resin composition, a cured product with excellent flexibility, flame retardancy and reflow resistance can be obtained. In addition, for such a resin composition, the tackiness can be suppressed at a low level, and / or the tensile properties, copper adhesion and / or insulation reliability of the cured product can be excellent.

[0040] The resin composition of the present invention may include any component in addition to (A) epoxy resin, (B) silicone rubber particles and (C) elastomer. As any component, for example, (D) inorganic filler, (E) flame retardant, (F) curing agent, (G) curing accelerator, (H) other additives and (I) organic solvent may be cited. Hereinafter, each component included in the resin composition is described in detail.

[0041] <(A) Epoxy resin>

[0042] The resin composition of the present invention contains (A) an epoxy resin. (A) The epoxy resin refers to a curable resin having an epoxy group.

[0043] Examples of the epoxy resin (A) include biphenylol epoxy resins, bisphenol A epoxy resins, bisphenol F epoxy resins, bisphenol S epoxy resins, bisphenol AF epoxy resins, dicyclopentadiene epoxy resins, trisphenol epoxy resins, naphthol novolac epoxy resins, phenol novolac epoxy resins, tert-butylcatechol epoxy resins, naphthalene epoxy resins, naphthol epoxy resins, anthracene epoxy resins, glycidylamine epoxy resins, glycidylester epoxy resins, cresol novolac epoxy resins, phenolaralkyl epoxy resins. Resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, epoxy resin having a butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring-containing epoxy resin, cyclohexane type epoxy resin, cyclohexanedimethanol type epoxy resin, naphthylene ether type epoxy resin, trimethylol type epoxy resin, tetraphenylethane type epoxy resin, isocyanurate type epoxy resin, phenolphthalimidine type epoxy resin, phenolphthalein type epoxy resin, etc. (A) Epoxy resins may be used alone or in combination of two or more.

[0044] The resin composition preferably contains an epoxy resin having two or more epoxy groups in one molecule as the epoxy resin (A). The proportion of the epoxy resin having two or more epoxy groups in one molecule is preferably 50% by mass or more, more preferably 60% by mass or more, and particularly preferably 70% by mass or more relative to 100% by mass of the nonvolatile component of the epoxy resin (A).

[0045] Epoxy resins include epoxy resins that are liquid at a temperature of 20°C (hereinafter, sometimes referred to as "liquid epoxy resins") and epoxy resins that are solid at a temperature of 20°C (hereinafter, sometimes referred to as "solid epoxy resins"). For the resin composition of the present invention, as an epoxy resin, only a liquid epoxy resin may be included, or only a solid epoxy resin may be included, or a liquid epoxy resin and a solid epoxy resin may be included in combination. The epoxy resin in the resin composition of the present invention is preferably a solid epoxy resin, or a combination of a liquid epoxy resin and a solid epoxy resin, and more preferably a solid epoxy resin.

[0046] As the liquid epoxy resin, a liquid epoxy resin having two or more epoxy groups in one molecule is preferred.

[0047] As liquid epoxy resins, preferred are bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol AF type epoxy resins, naphthalene type epoxy resins, glycidyl ester type epoxy resins, glycidyl amine type epoxy resins, phenol novolac type epoxy resins, alicyclic epoxy resins having an ester skeleton, cyclohexane type epoxy resins, cyclohexanedimethanol type epoxy resins, and epoxy resins having a butadiene structure.

[0048] Specific examples of liquid epoxy resins include "HP4032", "HP4032D", and "HP4032SS" (naphthalene-type epoxy resins) manufactured by DIC Corporation; "828US", "828EL", "jER828EL", "825", and "EPIKOTE "828EL" (bisphenol A type epoxy resin); "jER807", "1750" (bisphenol F type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER152" (phenol novolac type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "630", "630LSD", "604" (glycidylamine type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "ED-523T" (glycidyloxy (Glycirol) type epoxy resin) manufactured by ADEKA Corporation; "EP-3950L", "EP-3980S" (glycidylamine type epoxy resin) manufactured by ADEKA Corporation; "EP-4088S" (dicyclopentadiene type epoxy resin) manufactured by ADEKA Corporation; "ZX1059" (a mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin) manufactured by Nippon Steel & Sumitomo Metal Chemical Corporation; Nagase "EX-721" (glycidyl ester type epoxy resin) manufactured by ChemteX; "Celloxide 2021P" (alicyclic epoxy resin with ester skeleton) manufactured by Daicel; "PB-3600" manufactured by Daicel, "JP-100" and "JP-200" manufactured by Nippon Soda Co., Ltd. (epoxy resin with butadiene structure); "ZX1658" and "ZX1658GS" (liquid 1,4-glycidyl cyclohexane type epoxy resin) manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., etc. They can be used alone or in combination of two or more.

[0049] As the solid epoxy resin, a solid epoxy resin having three or more epoxy groups in one molecule is preferred, and an aromatic solid epoxy resin having three or more epoxy groups in one molecule is more preferred.

[0050] As solid epoxy resins, preferred are biphenylol-type epoxy resins, naphthalene-type epoxy resins, naphthalene-type tetrafunctional epoxy resins, naphthol novolac-type epoxy resins, cresol novolac-type epoxy resins, dicyclopentadiene-type epoxy resins, trisphenol-type epoxy resins, naphthol-type epoxy resins, biphenyl-type epoxy resins, naphthylene ether-type epoxy resins, anthracene-type epoxy resins, bisphenol A-type epoxy resins, bisphenol AF-type epoxy resins, phenol aralkyl-type epoxy resins, tetraphenylethane-type epoxy resins, phenol benzopyrrolidone-type epoxy resins, and phenolphthalein-type epoxy resins.

[0051] Specific examples of solid epoxy resins include "HP4032H" (naphthalene-type epoxy resin) manufactured by DIC Corporation; "HP-4700" and "HP-4710" (naphthalene-type tetrafunctional epoxy resin) manufactured by DIC Corporation; "N-690" (cresol novolac-type epoxy resin) manufactured by DIC Corporation; "N-695" (cresol novolac-type epoxy resin) manufactured by DIC Corporation; "HP-7200", "HP-7200HH", "HP-7200H", and "HP-7200L" (dicyclopentadiene-type epoxy resin) manufactured by DIC Corporation; "EXA- 7311", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", "HP6000" (naphthylene ether type epoxy resin); "EPPN-502H" (trisphenol type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; "NC7000L" (naphthol novolac type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; "NC3000H", "NC3000", "NC3000L", "NC3000FH", "NC3100" (biphenyl type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; NIPPON STEEL Chemical & Material "ESN475V" (naphthalene type epoxy resin) manufactured by ESN Co., Ltd.; "ESN485" (naphthol type epoxy resin) manufactured by Nippon Steel Chemical Materials Co., Ltd.; "ESN375" (dihydroxynaphthalene type epoxy resin) manufactured by Nippon Steel Chemical Materials Co., Ltd.; "YX4000H", "YX4000", "YX4000HK", "YL7890" (biphenyl type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YL6121" (biphenyl type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YX8800" (anthracene type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YX7700" (phenol aralkyl type epoxy resin) manufactured by Osaka Gas Chemical Co., Ltd.; "PG-100" and "CG-500" manufactured by Osaka Gas Chemical Co., Ltd.; "YL7760" (bisphenol AF type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd.; "YL7800" (fluorene type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd.; "jER1010" (bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd.; "jER1031S" (tetraphenylethane type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd.; "WHR991S" (phenol benzopyrrolone type epoxy resin) manufactured by Nippon Kayaku Co., Ltd., etc. These can be used alone or in combination of two or more.

[0052] When a liquid epoxy resin and a solid epoxy resin are used as component (A), the mass ratio of the solid epoxy resin to the liquid epoxy resin (solid epoxy resin / liquid epoxy resin) is not particularly limited, but is preferably 0.2 or more, more preferably 0.5 or more, further preferably 1 or more, further more preferably 5 or more, and particularly preferably 10 or more.

[0053] The epoxy equivalent of the epoxy resin (A) is preferably 50 g / eq. to 5,000 g / eq., more preferably 60 g / eq. to 2,000 g / eq., further preferably 70 g / eq. to 1,000 g / eq., and further more preferably 80 g / eq. to 500 g / eq. The epoxy equivalent is the mass of the resin per 1 equivalent of epoxy group. The epoxy equivalent can be measured in accordance with JIS K7236.

[0054] (A) The weight average molecular weight (Mw) of the epoxy resin is preferably 100 to 5,000, more preferably 250 to 3,000, and further preferably 400 to 1,500. The weight average molecular weight of the resin can be measured as a value in terms of polystyrene by gel permeation chromatography (GPC).

[0055] The content of the epoxy resin (A) in the resin composition is not particularly limited. When the non-volatile component in the resin composition is set to 100% by mass, it is preferably 60% by mass or less, more preferably 50% by mass or less, further preferably 40% by mass or less, and particularly preferably 35% by mass or less. The lower limit of the content of the epoxy resin (A) in the resin composition is not particularly limited. When the non-volatile component in the resin composition is set to 100% by mass, it is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 15% by mass or more, and particularly preferably 20% by mass or more.

[0056] The molar ratio of the phenolic hydroxyl group to the epoxy group in all the components of the resin composition (phenolic hydroxyl group / epoxy group) is not particularly limited, and is preferably less than 1.6, more preferably less than 1.3, further preferably less than 1, further more preferably less than 0.95, and particularly preferably less than 0.9. It is preferred that some components of the resin composition of the present invention have a phenolic hydroxyl group, and the lower limit of the molar ratio of the phenolic hydroxyl group to the epoxy group in all the components of the resin composition (phenolic hydroxyl group / epoxy group) is not particularly limited, and is preferably more than 0.1, more preferably more than 0.2, further preferably more than 0.3, further more preferably more than 0.4, and particularly preferably more than 0.45. It should be noted that the so-called phenolic hydroxyl group refers to a hydroxyl group bonded to an aromatic carbon atom.

[0057] <(B) Silicone rubber particles>

[0058] The resin composition of the present invention contains (B) silicone rubber particles. The (B) silicone rubber particles are contained in the resin composition in the form of particles. The (B) silicone rubber particles are preferably spherical. The (B) silicone rubber particles can be used alone or in combination of two or more in any ratio.

[0059] (B) The silicone rubber in the silicone rubber particles is not particularly limited, and examples thereof include silicone rubbers composed of the following polysiloxanes: polydialkylsiloxanes such as polydimethylsiloxane; polydiarylsiloxanes such as polydiphenylsiloxane; polyalkylarylsiloxanes such as polymethylphenylsiloxane; polydialkyl-diarylsiloxanes such as polydimethyl-diphenylsiloxane; polydialkyl-alkylarylsiloxanes such as polydimethyl-methylphenylsiloxane; polydiaryl-alkylarylsiloxanes such as polydiphenyl-methylphenylsiloxane, etc., among which silicone rubbers composed of polydialkylsiloxanes are preferred, and silicone rubbers composed of polydimethylsiloxanes are particularly preferred. The polysiloxanes constituting the silicone rubber are usually cross-linked. As cross-linked polysiloxanes, there are no particular restrictions, and examples thereof include polysiloxanes cross-linked by, for example, condensation reaction of silanol groups, reaction of mercaptosilyl groups with vinylsilyl groups, reaction of vinylsilyl groups with hydrogensilyl groups, and the like. Among them, polysiloxane cross-linked by reaction of a vinylsilyl group and a hydrosilyl group or the like is preferred.

[0060] The (B) silicone rubber particles may be surface treated. As the form of the surface treatment, for example, a form coated with a resin may be mentioned. As the silicone rubber particles coated with resin, there are no particular restrictions, and for example, silicone rubber particles coated with an acrylic resin, silicone rubber particles coated with an organosilicon resin, etc. may be mentioned, among which silicone rubber particles coated with an organosilicon resin are preferred. Here, the organosilicon resin may be a cured polyorganosilsesquioxane.

[0061] The average particle size of the silicone rubber particles (B) is not particularly limited, but is preferably 50 μm or less, more preferably 20 μm or less, further preferably 10 μm or less, further more preferably 5 μm or less, and particularly preferably 3 μm or less. The lower limit of the average particle size of the silicone rubber particles (B) is not particularly limited, but is preferably 0.05 μm or more, more preferably 0.1 μm or more, further preferably 0.3 μm or more, further more preferably 0.5 μm or more, and particularly preferably 0.7 μm or more. The average particle size of the silicone rubber particles (B) can be determined as a volume-based median particle size, for example, by measurement based on a laser diffraction method.

[0062] Specific examples of commercially available silicone rubber particles (B) include “KMP-600,” “KMP-601,” “KMP-602,” “KMP-605,” and “X-52-7030” (silicone rubber particles coated with a silicone resin) manufactured by Shin-Etsu Chemical Co., Ltd.; and “KMP-597,” “KMP-598,” “KMP-594,” and “X-52-875” (uncoated silicone rubber particles) manufactured by Shin-Etsu Chemical Co., Ltd.

[0063] The content of the silicone rubber particles (B) in the resin composition is not particularly limited. When the non-volatile component in the resin composition is set to 100% by mass, it is preferably 35% by mass or less, more preferably 30% by mass or less, and from the viewpoint of further improving insulation reliability, it is further preferably 25% by mass or less, further more preferably 20% by mass or less, and particularly preferably 15% by mass or less. The lower limit of the content of the silicone rubber particles (B) in the resin composition is not particularly limited. When the non-volatile component in the resin composition is set to 100% by mass, it is preferably 0.5% by mass or more, more preferably 1% by mass or more, further preferably 2% by mass or more, further more preferably 5% by mass or more, and particularly preferably 8% by mass or more.

[0064] <(C) Elastomer>

[0065] The resin composition of the present invention may contain (C) an elastomer as an optional component. By using the (C) elastomer, the flexibility of the cured product of the resin composition can be improved and the elastic modulus can be reduced.

[0066] In the present invention, (C) elastomer refers to a flexible resin, which is an amorphous resin component soluble in an organic solvent, and is preferably a resin having rubber elasticity or a resin that exhibits rubber elasticity by polymerization with other components. Examples of rubber elasticity include resins that exhibit an elastic modulus of 1 GPa or less when subjected to a tensile test at a temperature of 25° C. and a humidity of 40% RH according to Japanese Industrial Standards (JIS K7161).

[0067] In one embodiment, the component (C) is preferably a resin having one or more structures selected from the group consisting of a polybutadiene structure, a polysiloxane structure, a poly(meth)acrylate structure, a polyalkylene structure, a polyalkyleneoxy structure, a polyisoprene structure, a polyisobutylene structure, and a polycarbonate structure in the molecule. From the viewpoint of obtaining a flexible material, a resin having one or more structures selected from the group consisting of a polybutadiene structure and a polycarbonate structure is more preferred, and a resin having a polybutadiene structure is particularly preferred. It should be noted that the so-called "(meth)acrylate" refers to methacrylate and acrylate.

[0068] In another embodiment, component (C) is preferably one or more selected from a resin having a glass transition temperature (Tg) of 25°C or less and a resin that is liquid at 25°C or less. The glass transition temperature of the resin having a glass transition temperature (Tg) of 25°C or less is preferably 20°C or less, more preferably 15°C or less. The lower limit of the glass transition temperature is not particularly limited, and may generally be -15°C or more. In addition, as a resin that is liquid at 25°C or less, a resin that is liquid at 20°C or less is preferably a resin that is liquid at 15°C or less, and more preferably a resin that is liquid at 15°C or less.

[0069] As a more preferred embodiment, component (C) is preferably one or more selected from resins having a glass transition temperature of 25°C or less and being liquid at 25°C, and having in the molecule one or more structures selected from the group consisting of a polybutadiene structure, a polysiloxane structure, a poly(meth)acrylate structure, a polyalkylene structure, a polyalkyleneoxy structure, a polyisoprene structure, a polyisobutylene structure, and a polycarbonate structure.

[0070] The polybutadiene structure includes not only a structure formed by polymerizing butadiene, but also a structure formed by hydrogenating the structure. In addition, for the butadiene structure, only a part of it may be hydrogenated, or all of it may be hydrogenated. In addition, in the (C) component, the polybutadiene structure may be included in the main chain or in the side chain.

[0071] As preferred examples of polybutadiene resins, resins containing hydrogenated polybutadiene skeletons, polybutadiene resins containing hydroxyl groups, polybutadiene resins containing phenolic hydroxyl groups, polybutadiene resins containing carboxyl groups, polybutadiene resins containing acid anhydride groups, polybutadiene resins containing epoxy groups, polybutadiene resins containing isocyanate groups, polybutadiene resins containing carbamate groups, etc. can be cited. Among them, polybutadiene resins containing phenolic hydroxyl groups are further preferred. Here, the so-called "resin containing hydrogenated polybutadiene skeleton" refers to a resin in which at least a part of the polybutadiene skeleton is hydrogenated, and it is not necessarily a resin in which the polybutadiene skeleton is completely hydrogenated. As resins containing hydrogenated polybutadiene skeletons, for example, epoxy resins containing hydrogenated polybutadiene skeletons can be cited. In addition, "polybutadiene resins containing phenolic hydroxyl groups" are resins having a polybutadiene structure and having phenolic hydroxyl groups. (C) component preferably includes a polybutadiene resin containing phenolic hydroxyl groups.

[0072] Specific examples of the polybutadiene resin having a polybutadiene structure in the molecule include "Ricon 657" (epoxy-containing polybutadiene), "Ricon 130MA8", "Ricon 130MA13", "Ricon 130MA20", "Ricon 131MA5", "Ricon 131MA10", "Ricon 131MA17", "Ricon 131MA20", "Ricon 131MA51", "Ricon 131MA10", "Ricon 131MA17", "Ricon 131MA20", "Ricon 131MA52", "Ricon 131MA10", "Ricon 131MA17", "Ricon 131MA20", "Ricon 131MA51", "Ricon 131MA10", "Ricon 131MA17", "Ricon 131MA20", "Ricon 131MA 184MA6" (polybutadiene containing anhydride groups), "GQ-1000" (polybutadiene into which hydroxyl groups and carboxyl groups are introduced), "G-1000", "G-2000", "G-3000" (polybutadiene containing hydroxyl groups at both ends), "GI-1000", "GI-2000", "GI-3000" (hydrogenated polybutadiene containing hydroxyl groups at both ends), "PB3600", "PB4700" (polybutadiene skeleton epoxy compounds) manufactured by Daicel Corporation, "Epofriend A1005", "Epofriend A1010", "Epofriend A1020" (epoxy compounds of block copolymers of styrene, butadiene and styrene), "FCA-061L" (hydrogenated polybutadiene skeleton epoxy compound) manufactured by Nagase ChemteX Co., Ltd., "R-45EPT" (polybutadiene skeleton epoxy compound), etc.

[0073] In addition, as an example of a preferred polybutadiene resin, a linear polyimide (polyimide described in Japanese Unexamined Patent Publication No. 2006-37083 and International Publication No. 2008 / 153208) made of hydroxyl-terminated polybutadiene, a diisocyanate compound and a polyacid or its anhydride can also be cited. The content of the polybutadiene structure of the polyimide resin is preferably 60% to 95% by mass, and more preferably 75% to 85% by mass. The details of the polyimide resin can be referred to the records of Japanese Unexamined Patent Publication No. 2006-37083 and International Publication No. 2008 / 153208, and the contents are incorporated into this specification.

[0074] The number average molecular weight of the hydroxyl-terminated polybutadiene is preferably 500 to 5,000, more preferably 1,000 to 4,000. The hydroxyl equivalent of the hydroxyl-terminated polybutadiene is preferably 250 to 1,250 g / eq.

[0075] Examples of the diisocyanate compound include aromatic diisocyanates such as toluene-2,4-diisocyanate, toluene-2,6-diisocyanate, xylene diisocyanate, and diphenylmethane diisocyanate; aliphatic diisocyanates such as hexamethylene diisocyanate; and alicyclic diisocyanates such as isophorone diisocyanate. Among these, aromatic diisocyanates are preferred, and toluene-2,4-diisocyanate is more preferred.

[0076] Examples of the polybasic acid or its anhydride include ethylene glycol ditrimellitate, pyromellitic acid, benzophenonetetracarboxylic acid, biphenyltetracarboxylic acid, naphthalenetetracarboxylic acid, 5-(2,5-dioxotetrahydrofuranyl)-3-methyl-cyclohexene-1,2-dicarboxylic acid, 3,3'-4,4'-diphenylsulfonetetracarboxylic acid and other tetrabasic acids and their anhydrides, trimellitic acid, cyclohexanetricarboxylic acid and other tribasic acids and their anhydrides, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho(1,2-C)furan-1,3-dione and the like.

[0077] In addition, the resin having a polybutadiene structure may include a polystyrene structure having a structure obtained by polymerizing styrene.

[0078] Specific examples of polystyrene resins having a polystyrene structure in the molecule include styrene-butadiene-styrene block copolymers (SBS), styrene-isoprene-styrene block copolymers (SIS), styrene-ethylene-butylene-styrene block copolymers (SEBS), styrene-ethylene-propylene-styrene block copolymers (SEPS), styrene-ethylene-ethylene-propylene-styrene block copolymers (SEEPS), styrene-butadiene-butylene-styrene block copolymers (SBBS), styrene-butadiene diblock copolymers, hydrogenated styrene-butadiene block copolymers, hydrogenated styrene-isoprene block copolymers, hydrogenated styrene-butadiene random copolymers, and the like.

[0079] The polystyrene resin may be a commercially available product, for example, hydrogenated styrene-based thermoplastic elastomers "H1041", "Tuftec H1043", "Tuftec P2000", "Tuftec MP10" (manufactured by Asahi Kasei Corporation); epoxidized styrene-butadiene thermoplastic elastomers "Epofriend AT501", "CT310" (manufactured by Daicel Corporation); modified styrene-based elastomers "SEPTON HG252" (manufactured by Kuraray Corporation) having hydroxyl groups; modified styrene-based elastomers "Tuftec N503M" having carboxyl groups, modified styrene-based elastomers "Tuftec N501" having amino groups, and modified styrene-based elastomers "Tuftec M1913" having acid anhydride groups (manufactured by Asahi Kasei Chemicals Corporation); unmodified styrene-based elastomers "SEPTON S8104" (manufactured by Kuraray Corporation), etc. Component (C) may be used alone or in combination of two or more.

[0080] The polysiloxane structure is a structure including a siloxane bond, and is included in, for example, silicone rubber. The polysiloxane structure may be included in the main chain or in the side chain in the component (C).

[0081] Specific examples of the polysiloxane resin having a polysiloxane structure in the molecule include "SMP-2006", "SMP-2003PGMEA", "SMP-5005PGMEA" manufactured by Shin-Etsu Silicone Co., Ltd., amino-terminated polysiloxane, and linear polyimide made from a tetrabasic acid anhydride (International Publication No. 2010 / 053185).

[0082] The poly(meth)acrylate structure is a structure formed by polymerizing acrylic acid or acrylic acid ester, and also includes a structure formed by polymerizing methacrylic acid or methacrylic acid ester. The (meth)acrylate structure may be contained in the main chain or in the side chain in the component (C).

[0083] Preferred examples of the poly(meth)acrylate resin as a resin having a poly(meth)acrylate structure in the molecule include poly(meth)acrylate resins containing hydroxyl groups, poly(meth)acrylate resins containing phenolic hydroxyl groups, poly(meth)acrylate resins containing carboxyl groups, poly(meth)acrylate resins containing acid anhydride groups, poly(meth)acrylate resins containing epoxy groups, poly(meth)acrylate resins containing isocyanate groups, poly(meth)acrylate resins containing urethane groups, and the like.

[0084] Specific examples of poly(meth)acrylate resins include TEISANRESIN "SG-70L", "SG-708-6", "WS-023", "SG-700AS", "SG-280TEA" (carboxyl-containing acrylate copolymer resins, acid values ​​of 5 to 34 mgKOH / g, weight average molecular weights of 400,000 to 900,000, Tg of -30°C to 5°C), "SG-80H", "SG-80H-3", "SG-P3" (epoxy-containing acrylate copolymer resins, epoxy equivalents of 4761 to 14285 g / eq, weight average molecular weight of 350,000) manufactured by Nagase ChemteX Co., Ltd. ~850,000, Tg is 11°C~12°C), "SG-600TEA", "SG-790" (hydroxyl-containing acrylate copolymer resin, hydroxyl value is 20~40mgKOH / g, weight average molecular weight is 500,000~1.2 million, Tg is -37°C~-32°C), "ME-2000", "W-116.3" (carboxyl-containing acrylate copolymer resin), "W-197C" (hydroxyl-containing acrylate copolymer resin), "KG-25", "KG-3000" (epoxy-containing acrylate copolymer resin) made by Negami Industries, Ltd., etc.

[0085] The polyalkylene structure preferably has a predetermined number of carbon atoms. The specific number of carbon atoms in the polyalkylene structure is preferably 2 or more, more preferably 3 or more, particularly preferably 5 or more, preferably 15 or less, more preferably 10 or less, particularly preferably 6 or less. In addition, the polyalkylene structure may be included in the main chain or in the side chain in the component (C).

[0086] The polyalkyleneoxy structure preferably has a predetermined number of carbon atoms. The specific number of carbon atoms in the polyalkyleneoxy structure is preferably 2 or more, preferably 3 or more, more preferably 5 or more, preferably 15 or less, more preferably 10 or less, and particularly preferably 6 or less. The polyalkyleneoxy structure may be contained in the main chain or in the side chain in the component (C).

[0087] Specific examples of the polyalkylene resin which is a resin having a polyalkylene structure in the molecule and the polyalkyleneoxy resin which is a resin having a polyalkyleneoxy structure in the molecule include "PTXG-1000" and "PTXG-1800" manufactured by Asahi Kasei Fibers Corporation, "YX-7180" (a resin containing an alkylene structure having an ether bond) manufactured by Mitsubishi Chemical Corporation, "EXA-4850-150", "EXA-4816" and "EXA-4822" manufactured by DIC Corporation, "EP-4000", "EP-4003", "EP-4010" and "EP-4011" manufactured by ADEKA Corporation, "BEO-60E" and "BPO-20E" manufactured by Shin Nippon Chemical Co., Ltd., and "YL7175" and "YL7410" manufactured by Mitsubishi Chemical Corporation.

[0088] The polyisoprene structure may be contained in the main chain or in the side chain of the component (C). Specific examples of the polyisoprene resin having a polyisoprene structure in the molecule include "KL-610" and "KL-613" manufactured by Kuraray Co., Ltd.

[0089] The polyisobutylene structure may be contained in the main chain or in the side chain in the component (C). Specific examples of the polyisobutylene resin having a polyisobutylene structure in the molecule include "SIBSTAR-073T" (styrene-isobutylene-styrene triblock copolymer) and "SIBSTAR-042D" (styrene-isobutylene diblock copolymer) manufactured by KANEKA Corporation.

[0090] The polycarbonate structure may be contained in the main chain or in the side chain in the component (C).

[0091] Preferred examples of polycarbonate resins as resins having a polycarbonate structure in the molecule include hydroxyl group-containing polycarbonate resins, phenolic hydroxyl group-containing polycarbonate resins, carboxyl group-containing polycarbonate resins, acid anhydride group-containing polycarbonate resins, epoxy group-containing polycarbonate resins, isocyanate group-containing polycarbonate resins, and urethane group-containing polycarbonate resins.

[0092] Specific examples of the polycarbonate resin include "T6002" and "T6001" (polycarbonate diol) manufactured by Asahi Kasei Chemicals Corporation, and "C-1090", "C-2090" and "C-3090" (polycarbonate diol) manufactured by Kuraray Corporation.

[0093] In addition, as an example of a preferred polycarbonate resin, a linear polyimide made of a hydroxyl-terminated polycarbonate, a diisocyanate compound, and a polyacid or its anhydride as a raw material can also be cited. The linear polyimide has a carbamate structure and a polycarbonate structure. The content of the polycarbonate structure of the polyimide resin is preferably 60% to 95% by mass, and more preferably 75% to 85% by mass. The details of the polyimide resin can be referred to the record of International Publication No. 2016 / 129541, and the content is incorporated into this specification.

[0094] In addition, as other preferred examples of polycarbonate resins, polycarbonate-based urethane (meth) acrylates made from hydroxyl-terminated polycarbonate, diisocyanate compounds, and (meth) acrylates containing hydroxyl groups can also be cited. Polycarbonate-based urethane (meth) acrylates not only have a urethane structure and a polycarbonate structure, but also have two or more (meth) acryloyl groups. As specific examples of polycarbonate-based urethane (meth) acrylates, "ART RESIN UN-5500" manufactured by Gengami Industries, Ltd. can be cited.

[0095] The (meth)acrylate containing a hydroxyl group is not particularly limited, and examples thereof include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, 3-chloro-2-hydroxypropyl (meth)acrylate, 2-(2-ethoxyethoxy)ethyl (meth)acrylate, 1,4-cyclohexanedimethanol mono(meth)acrylate, and 2-(meth)acryloyloxyethyl-2-hydroxyethyl-phthalate.

[0096] The number average molecular weight of the hydroxyl-terminated polycarbonate is preferably 500 to 50,000, more preferably 1,000 to 35,000. The weight average molecular weight of the hydroxyl-terminated polycarbonate is preferably 500 to 50,000, more preferably 1,000 to 35,000. The hydroxyl equivalent of the hydroxyl-terminated polycarbonate is preferably 250 to 1,250 g / eq.

[0097] The component (C) preferably further has an imide structure. The imide structure can improve the heat resistance of the component (C) and effectively improve the crack resistance.

[0098] The component (C) may have any structure of linear, branched, or cyclic, but is preferably linear.

[0099] The component (C) preferably has a functional group that can react with the component (A). The functional group also includes a reactive group that appears by heating. By making the component (C) have a functional group, the mechanical strength of the cured product of the resin composition can be improved.

[0100] As the functional group, there can be mentioned a carboxyl group, a hydroxyl group, an acid anhydride group, a phenolic hydroxyl group, an epoxy group, an isocyanate group, and a carbamate group, etc. Among them, from the viewpoint of significantly obtaining the effect of the present invention, as the functional group, it is preferred to have one or more functional groups selected from a hydroxyl group, an acid anhydride group, a phenolic hydroxyl group, an epoxy group, an isocyanate group, and a carbamate group, and a phenolic hydroxyl group is particularly preferred.

[0101] The component (C) may be used alone or in combination of two or more.

[0102] From the viewpoint of exhibiting flexibility, the component (C) preferably has a high molecular weight.

[0103] The specific number average molecular weight (Mn) of the component (C) is preferably 4,000 or more, more preferably 4,500 or more, further preferably 5,000 or more, particularly preferably 5,500 or more, and preferably 100,000 or less, more preferably 95,000 or less, particularly preferably 90,000 or less. The number average molecular weight Mn of the component (C) is a number average molecular weight measured by GPC (gel permeation chromatography) in terms of polystyrene.

[0104] In order to obtain flexibility, the specific weight average molecular weight (Mw) of the component (C) is preferably 5,500 to 100,000, more preferably 10,000 to 90,000, and even more preferably 15,000 to 80,000. The weight average molecular weight of the component (C) is a weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC).

[0105] When the component (C) has a functional group, the functional group equivalent of the component (C) is preferably 100 g / eq. or more, more preferably 200 g / eq. or more, further preferably 300 g / eq. or more, particularly preferably 400 g / eq. or more, preferably 50,000 g / eq. or less, more preferably 30,000 g / eq. or less, further preferably 10,000 g / eq. or less, particularly preferably 5,000 g / eq. or less. The functional group equivalent is the number of grams of the resin containing 1 gram equivalent of the functional group. For example, the epoxy equivalent can be measured in accordance with JIS K7236. In addition, for example, the hydroxyl equivalent can be calculated by dividing the molecular weight of KOH by the hydroxyl value measured in accordance with JIS K1557-1.

[0106] The glass transition temperature (Tg) of the component (C) is 30°C or lower, preferably 0°C or lower.

[0107] When the non-volatile component in the resin composition is 100% by mass, the content of the (C) elastomer in the resin composition is 50% by mass or less, and from the viewpoint of further improving the reflow resistance, it is preferably 45% by mass or less, more preferably 40% by mass or less, further preferably 35% by mass or less, and particularly preferably 33% by mass or less. When the non-volatile component in the resin composition is 100% by mass, the lower limit of the content of the (C) elastomer in the resin composition is 20% by mass or more.

[0108] <(D) Inorganic fillers>

[0109] The resin composition of the present invention may contain (D) an inorganic filler as an optional component. The (D) inorganic filler is contained in the resin composition in the form of particles.

[0110] As the material of (D) inorganic filler, inorganic compounds are used. As the material of (D) inorganic filler, for example, silicon dioxide, aluminum oxide, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, barium titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium phosphotungstate, etc., can be cited. Among these, silicon dioxide is particularly preferred. As silicon dioxide, for example, amorphous silicon dioxide, fused silica, crystalline silicon dioxide, synthetic silicon dioxide, hollow silica, etc. can be cited. In addition, as silicon dioxide, spherical silicon dioxide is preferred. (D) The inorganic filler may be used alone or in combination of two or more at any ratio.

[0111] (D) Commercially available products of the inorganic filler include, for example, "SP60-05" and "SP507-05" manufactured by Nippon Steel & Sumitomo Metal Materials Corporation; "YC100C", "YA050C", "YA050C-MJE", "YA010C", "SC2500SQ", "SO-C4", "SO-C2", and "SO-C1" manufactured by Admatechs Corporation; "Silfil NSS-3N", "Silfil NSS-4N", and "Silfil NSS-5N" manufactured by Tokuyama Co., Ltd.; "UFP-30", "DAW-03", and "FB-105FD" manufactured by DENKA Corporation; and "IMSIL A-8", "IMSIL A-10", "IMSIL A-15", and "IMSIL A-25" manufactured by Unimin Corporation.

[0112] (D) The average particle size of the inorganic filler is not particularly limited, preferably 40 μm or less, more preferably 10 μm or less, further preferably 5 μm or less, further more preferably 3 μm or less, and particularly preferably 2 μm or less. (D) The lower limit of the average particle size of the inorganic filler is not particularly limited, preferably 0.005 μm or more, more preferably 0.01 μm or more, further preferably 0.03 μm or more, further more preferably 0.05 μm or more, and particularly preferably 0.08 μm or more. (D) The average particle size of the inorganic filler can be measured by a laser diffraction-scattering method based on Mie scattering theory. Specifically, it can be measured in the following manner: using a laser diffraction scattering particle size distribution measuring device, a particle size distribution of the inorganic filler is prepared on a volume basis, and the median particle size is used as the average particle size. The sample can be measured using a sample obtained by the following method: 100 mg of inorganic filler and 10 g of methyl ethyl ketone are weighed into a vial and dispersed for 10 minutes using ultrasound. For the measurement sample, a laser diffraction particle size distribution measuring device is used, and the wavelength of the light source is set to blue and red, and the volume-based particle size distribution of the inorganic filler is measured in a flow cell manner, and the average particle size is calculated as the median particle size from the obtained particle size distribution. As a laser diffraction particle size distribution measuring device, for example, "LA-960" made by Horiba, Ltd., etc. can be cited.

[0113] (D) The specific surface area of ​​the inorganic filler is not particularly limited, but is preferably 0.1 m 2 / g or more, more preferably 0.5m 2 / g or more, more preferably 1m 2 / g or more, particularly preferably 5 m 2 The upper limit of the specific surface area of ​​the inorganic filler (D) is not particularly limited, but is preferably 50 m 2 / g or less, more preferably 30m 2 / g or less, more preferably 20m 2 / g or less, particularly preferably 15m 2 The specific surface area of ​​the inorganic filler can be obtained by adsorbing nitrogen on the surface of the sample using a specific surface area measuring device (Macsorb HM-1210 manufactured by Mountech Co., Ltd.) according to the BET method, and calculating the specific surface area by the BET multipoint method.

[0114] The (D) inorganic filler is preferably surface treated with an appropriate surface treatment agent. By performing the surface treatment, the moisture resistance and dispersibility of the (D) inorganic filler can be improved. Examples of the surface treatment agent include vinyl-based silane coupling agents such as vinyltrimethoxysilane and vinyltriethoxysilane; epoxy-based silane coupling agents such as 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyltriethoxysilane; styrene-based silane coupling agents such as styryltrimethoxysilane; 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyl Methacrylic silane coupling agents such as propyl trimethoxysilane, 3-methacryloxypropyl methyl diethoxy silane, and 3-methacryloxypropyl triethoxy silane; acrylic silane coupling agents such as 3-acryloxypropyl trimethoxy silane; N-2-(aminoethyl)-3-aminopropyl methyl dimethoxy silane, N-2-(aminoethyl)-3-aminopropyl trimethoxy silane, 3-aminopropyl trimethoxy silane, 3-aminopropyl triethoxy silane, 3-triethoxy silyl-N-(1,3-dimethyl-butylidene) Amino silane coupling agents such as propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-8-aminooctyltrimethoxysilane, and N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane; isocyanurate silane coupling agents such as tris(trimethoxysilylpropyl)isocyanurate; urea silane coupling agents such as 3-ureapropyltrialkoxysilane; mercapto silane coupling agents such as 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane; isocyanate silane coupling agents such as 3-isocyanatepropyltriethoxysilane Silane coupling agent; silane coupling agent such as anhydride silane coupling agent such as 3-trimethoxysilylpropyl succinic anhydride; methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, 1,6-bis(trimethoxysilyl)hexane, trifluoropropyltrimethoxysilane and other non-silane coupling-alkoxysilane compounds. Among them, amino-based silane coupling agents are preferred. The surface treatment agent may be used alone or in combination of two or more in any ratio.

[0115] Commercially available products of the surface treatment agent include, for example, "KBM-1003", "KBE-1003" (vinyl silane coupling agent); "KBM-303", "KBM-402", "KBM-403", "KBE-402", "KBE-403" (epoxy silane coupling agent); "KBM-1403" (styrene silane coupling agent); "KBM-502", "KBM-503", "KBE-502", "KBE-503" (methacrylic silane coupling agent); "KBM-5103" (acrylic silane coupling agent); "KBM-602", "KBM-603", "KBM-903", "KBE-903", "KBE-9103P", "KBM-573", "KBM-575" (ammonia silane coupling agent); "KBM-9659" (isocyanurate silane coupling agent); "KBE-585" (urea silane coupling agent); "KBM-802", "KBM-803" (mercapto silane coupling agent); "KBE-9007N" (isocyanate silane coupling agent); "X-12-967C" (anhydride silane coupling agent); "KBM-13", "KBM-22", "KBM-103", "KBE-13", "KBE-22", "KBE-103", "KBM-3033", "KBE-3033", "KBM-3063", "KBE-3063", "KBE-3083", "KBM-3103C", "KBM-3066", "KBM-7103" (non-silane coupling-alkoxysilane compound), etc.

[0116] From the viewpoint of improving the dispersibility of the inorganic filler, the degree of surface treatment based on the surface treatment agent is preferably within a specified range. Specifically, for 100% by mass of the inorganic filler, it is preferred that 0.2% by mass to 5% by mass of the surface treatment agent be used for surface treatment, more preferably 0.2% by mass to 3% by mass, and further preferably 0.3% by mass to 2% by mass.

[0117] The degree of surface treatment by the surface treatment agent can be evaluated by the amount of carbon per unit surface area of ​​the inorganic filler. From the viewpoint of improving the dispersibility of the inorganic filler, the amount of carbon per unit surface area of ​​the inorganic filler is preferably 0.02 mg / m 2 More preferably 0.1 mg / m 2 More preferably, 0.2 mg / m 2 On the other hand, from the viewpoint of preventing the increase in the melt viscosity of the resin composition and the melt viscosity in the form of a sheet, 1.0 mg / m 2Below, more preferably 0.8 mg / m 2 Below, more preferably 0.5 mg / m 2 the following.

[0118] (D) The amount of carbon per unit surface area of ​​the inorganic filler can be measured after washing the surface-treated inorganic filler with a solvent (e.g., methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK as a solvent can be added to the inorganic filler surface-treated with a surface treatment agent, and ultrasonic washing is performed at 25°C for 5 minutes. The supernatant is removed, the solid component is dried, and then the amount of carbon per unit surface area of ​​the inorganic filler is measured using a carbon analyzer. As a carbon analyzer, "EMIA-320V" manufactured by Horiba, Ltd., etc. can be used.

[0119] The content of (D) inorganic filler in the resin composition is not particularly limited. When the non-volatile component in the resin composition is set to 100% by mass, it is preferably 70% by mass or less, more preferably 60% by mass or less, from the viewpoint of obtaining more excellent flexibility, it is further preferably 50% by mass or less, and particularly preferably 45% by mass or less. The lower limit of the content of (D) inorganic filler in the resin composition is not particularly limited. When the non-volatile component in the resin composition is set to 100% by mass, for example, 0% by mass or more, 0.01% by mass or more, 0.1% by mass or more, from the viewpoint of achieving more excellent insulation reliability, it is preferably 1% by mass or more, more preferably 5% by mass or more, further preferably 10% by mass or more, and particularly preferably 15% by mass or more.

[0120] When the resin composition contains (D) an inorganic filler, the mass ratio of the (B) silicone rubber particles to the (D) inorganic filler ((B) silicone rubber particles / (D) inorganic filler) is not particularly limited, but is preferably 1 or less, more preferably 0.9 or less, further preferably 0.8 or less, and particularly preferably 0.7 or less from the viewpoint of obtaining better insulation reliability. The lower limit of the mass ratio of the (B) silicone rubber particles to the (D) inorganic filler ((B) silicone rubber particles / (D) inorganic filler) is not particularly limited, and may be, for example, 0.01 or more, 0.05 or more, 0.1 or more, etc.

[0121] <(E) Flame retardant>

[0122] The resin composition of the present invention may contain (E) a flame retardant as an optional component.

[0123] As (E) flame retardants, phosphorus-based flame retardants such as phosphazene compounds, phosphates, phosphate esters, polyphosphates, phosphinates, phosphinates, phosphonates, and phosphonates can be cited; nitrogen-based flame retardants such as aliphatic amine compounds, aromatic amine compounds, nitrogen-containing heterocyclic compounds, and urea compounds; inorganic flame retardants such as antimony trioxide, antimony pentoxide, and sodium antimonate; halogen-based flame retardants such as chlorinated paraffin, brominated polycarbonate resin, brominated epoxy resin, brominated phenoxy resin, brominated polyphenylene ether resin, brominated polystyrene resin, and brominated benzyl polyacrylate resin can be cited, among which phosphorus-based flame retardants are preferred. (E) Flame retardants can be used alone or in combination of two or more.

[0124] Examples of the phosphazene compound include phenoxy cyclotriphosphazene compounds such as hexaphenoxy cyclotriphosphazene, tris(4-hydroxyphenoxy)triphenoxy cyclotriphosphazene, hexa(4-hydroxyphenoxy)cyclotriphosphazene, tris(4-methylphenoxy)triphenoxy cyclotriphosphazene, tris(4-cyanophenoxy)triphenoxy cyclotriphosphazene, hexa(4-aminophenoxy)cyclotriphosphazene, tris[4-(2-glycidyloxyethyl)phenoxy]triphenoxy cyclotriphosphazene and octaphenoxycyclotetraphosphazene.

[0125] Examples of the phosphate include ammonium phosphate and melamine phosphate.

[0126] Examples of the phosphoric acid ester include non-halogen aliphatic phosphoric acid esters such as trimethyl phosphate, triethyl phosphate, tributyl phosphate, and trioctyl phosphate; non-halogen aromatic phosphoric acid esters such as triphenyl phosphate, cresyl diphenyl phosphate, dicresyl phenyl phosphate, tricresyl phosphate, tris(4-isopropylphenyl) phosphate, hydroxyphenyl diphenyl phosphate, and octyl diphenyl phosphate; and halogen aliphatic phosphoric acid esters such as tris(1-chloro-2-propyl) phosphate, tris(1,3-dichloro-2-propyl) phosphate, and tris[3-bromo-2,2-bis(bromomethyl)propyl] phosphate.

[0127] Examples of the polyphosphate include ammonium polyphosphate and melamine polyphosphate.

[0128] Examples of the phosphinate include dialkyl phosphinates such as aluminum tris(diethylphosphinate), zinc bis(diethylphosphinate), aluminum tris(methylethylphosphinate), zinc bis(methylethylphosphinate), and titanium tetrakis(diethylphosphinate); and diaryl phosphinates such as zinc bis(diphenylphosphinate), and titanium tetrakis(diphenylphosphinate).

[0129] Examples of the phosphinate include acyclic diaryl phosphinates such as phenyl diphenylphosphinate, methyl diphenylphosphinate, and ethyl diphenylphosphinate; cyclic diaryl phosphinates such as 10-(2,5-dihydroxyphenyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(1,4-dihydroxy-2-naphthyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(2,5-dihydroxybiphenyl-4-yl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, and 10-[2,4-di(glycidyloxy)phenyl]-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide; and 9,10-dihydro-10-benzyl-9-oxa-10-phosphaphenanthrene-10-oxide, 10-[2,3-bis(2-hydroxyethoxycarbonyl)propyl]-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide or its polyether condensation product, 10-(2-cyanoethyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-[2-(3,4-epoxycyclohexyl)ethyl]-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(3-glycidyloxypropyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and the like.

[0130] Examples of the phosphonate include zinc methanephosphonate, zinc ethylphosphonate, zinc butylphosphonate, zinc phenylphosphonate, and the like.

[0131] Examples of the phosphonic acid ester include diphenyl methanephosphonate, diethyl phenylphosphonate, dibutyl butylphosphonate, and diethyl ethylphosphonate.

[0132] (E) The flame retardant preferably includes a phosphorus-based flame retardant containing a phenolic hydroxyl group, and particularly preferably includes a phosphonate containing a phenolic hydroxyl group. The phenolic hydroxyl equivalent of the phosphorus-based flame retardant containing a phenolic hydroxyl group is not particularly limited, but is preferably 80 g / eq. to 1,000 g / eq., more preferably 100 g / eq. to 500 g / eq., further preferably 110 g / eq. to 300 g / eq., further more preferably 120 g / eq. to 200 g / eq., and preferably 130 g / eq. to 180 g / eq. The phenolic hydroxyl equivalent is the mass of the phosphorus-based flame retardant relative to 1 equivalent of phenolic hydroxyl groups.

[0133] Specific examples of the flame retardant (E) include, for example, "SPH-100", "SPS-100", "SPB-100", "SPE-100" (phosphazene compounds) manufactured by Otsuka Chemical Co., Ltd.; "FP-100", "FP-110", "FP-300", "FP-400" (phosphazene compounds) manufactured by Fushimi Pharmaceutical Co., Ltd.; "HCA-NQ", "HCA-HQ", "HCA-HQ-HST" (phosphinates (containing phenolic hydroxyl groups)) manufactured by Sanko Co., Ltd.; "PX-200", "PX-201", "PX-202", "CR-733S", "CR-741", "CR-747" (phosphate esters) manufactured by Daihachi Chemical Industry Co., Ltd., etc.

[0134] The content of (E) flame retardant in the resin composition is not particularly limited. When the non-volatile component in the resin composition is set to 100% by mass, it is preferably 30% by mass or less, more preferably 20% by mass or less, further preferably 15% by mass or less, further more preferably 10% by mass or less, and particularly preferably 8% by mass or less. The lower limit of the content of (E) flame retardant in the resin composition is not particularly limited. When the non-volatile component in the resin composition is set to 100% by mass, for example, 0% by mass or more, 0.01% by mass or more, from the viewpoint of achieving more excellent flame retardancy, it is preferably 0.1% by mass or more, more preferably 1% by mass or more, further preferably 2% by mass or more, further more preferably 3% by mass or more, and particularly preferably 4% by mass or more.

[0135] <(F) Curing agent>

[0136] The resin composition of the present invention may further contain (F) a curing agent. The (F) curing agent has a function of curing the (A) epoxy resin. The (F) curing agent here is a component that does not belong to the (A) component to the (E) component.

[0137] The (F) curing agent is not particularly limited, and examples thereof include phenolic curing agents, naphthol curing agents, anhydride curing agents, active ester curing agents, benzoxazine curing agents, cyanate curing agents, and carbodiimide curing agents. The curing agent may be used alone or in combination of two or more. The (F) curing agent preferably includes a curing agent selected from phenolic curing agents, naphthol curing agents, and active ester curing agents, and particularly preferably includes an active ester curing agent.

[0138] As phenolic curing agent and naphthol curing agent, from the viewpoint of heat resistance and water resistance, preferably, phenolic curing agent with novolac structure or naphthol curing agent with novolac structure is used. In addition, from the viewpoint of adhesion with adherend, preferably, nitrogen-containing phenolic curing agent or nitrogen-containing naphthol curing agent is used, more preferably, phenolic curing agent containing triazine skeleton or naphthol curing agent containing triazine skeleton is used. Among them, from the viewpoint of highly satisfying heat resistance, water resistance, and adhesion, preferably, phenolic novolac resin containing triazine skeleton is used. Specific examples of phenol-based curing agents and naphthol-based curing agents include "MEH-7700", "MEH-7810", and "MEH-7851" manufactured by Meiwa Chemicals, "NHN", "CBN", and "GPH" manufactured by Nippon Kayaku Co., Ltd., "SN-170", "SN-180", "SN-190", "SN-475", "SN-485", "SN-495", "SN-375", and "SN-395" manufactured by Nippon Steel Chemicals Co., Ltd., and "LA-7052", "LA-7054", "LA-3018", "LA-3018-50P", "LA-1356", "TD2090", and "TD-2090-60M" manufactured by DIC Corporation.

[0139] As the acid anhydride curing agent, there can be mentioned a curing agent having one or more acid anhydride groups in one molecule, preferably a curing agent having two or more acid anhydride groups in one molecule. Specific examples of the acid anhydride curing agent include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, hydrogenated methylnadic anhydride, trialkyltetrahydrophthalic anhydride, dodecenylsuccinic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trimellitic anhydride, pyromellitic anhydride, dicarboxylic anhydride, and the like. Benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, naphthalene tetracarboxylic dianhydride, oxydiphthalic dianhydride, 3,3'-4,4'-diphenylsulfone tetracarboxylic dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2-C]furan-1,3-dione, ethylene glycol bis(trimellitic anhydride ester), styrene-maleic acid resin obtained by copolymerization of styrene and maleic acid, etc. Examples of commercially available acid anhydride curing agents include "HNA-100" and "MH-700" manufactured by Shin Nippon Rika Co., Ltd.

[0140] As active ester curing agent, there is no particular restriction, usually, preferably use phenolic esters, thiophenolic esters, N-hydroxylamine esters, heterocyclic hydroxy compounds and other esters with ester groups having more than 2 high reactive activities in 1 molecule. The active ester curing agent is preferably obtained by the condensation reaction of carboxylic acid compounds and / or thiocarboxylic acid compounds with hydroxy compounds and / or thiol compounds. Especially from the viewpoint of improving heat resistance, preferably the active ester curing agent obtained by carboxylic acid compounds and hydroxy compounds, more preferably the active ester curing agent obtained by carboxylic acid compounds and phenolic compounds and / or naphthol compounds. As carboxylic acid compounds, for example benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid etc. can be mentioned. Examples of the phenol compound or naphthol compound include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalein, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucinol, pyrogallol, dicyclopentadiene-type diphenol compounds, phenol novolac resins, etc. Here, the so-called "dicyclopentadiene-type diphenol compound" refers to a diphenol compound obtained by condensing two molecules of phenol on one molecule of dicyclopentadiene.

[0141] Specifically, active ester compounds containing a dicyclopentadiene-type diphenol structure, active ester compounds containing a naphthalene structure, active ester compounds containing acetylated products of phenol novolac, and active ester compounds containing benzoylated products of phenol novolac are preferred, and active ester compounds containing a naphthalene structure and active ester compounds containing a dicyclopentadiene-type diphenol structure are more preferred. The so-called "dicyclopentadiene-type diphenol structure" refers to a divalent structural unit composed of phenylene-dicyclopentalene-phenylene.

[0142] Commercially available active ester curing agents include "EXB9451", "EXB9460", "EXB9460S", "HPC-8000", "HPC-8000H", "HPC-8000-65T", "HPC-8000H-65TM", "EXB-8000L", "EXB-8000L-65M", and "EXB-8000L-65TM" (manufactured by DIC Corporation), which are active ester compounds containing a dicyclopentadiene-type diphenol structure; "EXB-9416-70BK", "EXB-8150-65T", "EXB-8100L-65T", "EXB-8150L-65T" (manufactured by DIC Corporation); "DC808" (manufactured by Mitsubishi Chemical Corporation), which is an active ester curing agent for acetylated phenol novolac; "YLH1026" (manufactured by Mitsubishi Chemical Corporation), "YLH1030" (manufactured by Mitsubishi Chemical Corporation), "YLH1048" (manufactured by Mitsubishi Chemical Corporation), which are active ester curing agents for benzoylated phenol novolac; and the like.

[0143] Specific examples of the benzoxazine-based curing agent include “JBZ-OP100D” and “ODA-BOZ” manufactured by JFE Chemical Co., Ltd.; “HFB2006M” manufactured by Showa High Molecular Co., Ltd.; and “Pd” and “Fa” manufactured by Shikoku Chemical Industry Co., Ltd.

[0144] Examples of the cyanate curing agent include difunctional cyanate resins such as bisphenol A dicyanate, polyphenol cyanate (oligo(3-methylene-1,5-phenylene cyanate)), 4,4′-methylenebis(2,6-dimethylphenylcyanate), 4,4′-ethylenediphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanate)phenylpropane, 1,1-bis(4-cyanatephenylmethane), bis(4-cyanate-3,5-dimethylphenyl)methane, 1,3-bis(4-cyanatephenyl-1-(methylethylene))benzene, bis(4-cyanatephenyl)sulfide, and bis(4-cyanatephenyl)ether; polyfunctional cyanate resins derived from phenol novolac resins and cresol novolac resins; and prepolymers obtained by partially triazinizing these cyanate resins. Specific examples of cyanate curing agents include "PT30" and "PT60" manufactured by Lonza Japan Co., Ltd. (both are phenol novolac-type multifunctional cyanate resins), "BA230", "BA230S75" (prepolymers obtained by triazine-forming a part or all of bisphenol A dicyanate to form a trimer), etc.

[0145] Specific examples of the carbodiimide-based curing agent include "V-03" and "V-07" manufactured by Nisshinbo Chemical Co., Ltd.

[0146] When the resin composition contains (F) a curing agent, the amount ratio of the (A) epoxy resin to the (F) curing agent is preferably 1:0.2 to 1:2, more preferably 1:0.3 to 1:1.5, and even more preferably 1:0.4 to 1:1.4 in terms of the ratio of [number of epoxy groups of the (A) epoxy resin]: [number of reactive groups of the (F) curing agent]. Here, regarding the reactive group of the (F) curing agent, for example, when the curing agent is a phenol-based curing agent or a naphthol-based curing agent, the reactive group is an aromatic hydroxyl group; when the curing agent is an active ester-based curing agent, the reactive group is an active ester group; the reactive group varies depending on the type of the curing agent.

[0147] (F) The reactive group equivalent of the curing agent is preferably 50 g / eq. to 3,000 g / eq., more preferably 100 g / eq. to 1,000 g / eq., further preferably 100 g / eq. to 500 g / eq., and particularly preferably 100 g / eq. to 300 g / eq. The reactive group equivalent is the mass of the curing agent per 1 equivalent of reactive groups.

[0148] When the (F) curing agent includes an active ester curing agent, the content thereof is not particularly limited. When the total amount of the (F) curing agent is set to 100 mass %, it is preferably 10 mass % or more, more preferably 20 mass % or more, further preferably 30 mass % or more, and particularly preferably 40 mass % or more.

[0149] The content of (F) curing agent in the resin composition is not particularly limited. When the non-volatile component in the resin composition is set to 100 mass %, it is preferably less than 40 mass %, more preferably less than 30 mass %, further preferably less than 20 mass %, and particularly preferably less than 10 mass %. The lower limit of the content of (F) curing agent in the resin composition is not particularly limited. When the non-volatile component in the resin composition is set to 100 mass %, for example, it can be more than 0 mass %, more than 0.1 mass %, more than 1 mass %, more than 3 mass %, more than 5 mass %, etc. From the viewpoint of obtaining excellent reflow resistance, the content of (F) curing agent in the resin composition is preferably 0 mass %.

[0150] <(G) Curing accelerator>

[0151] The resin composition of the present invention may contain (G) a curing accelerator as an optional component. The (G) curing accelerator has a function of accelerating the curing of the (A) epoxy resin.

[0152] (G) curing accelerator is not particularly limited, and examples thereof include phosphorus curing accelerators, urea curing accelerators, amine curing accelerators, imidazole curing accelerators, guanidine curing accelerators, and metal curing accelerators. Among them, phosphorus curing accelerators, amine curing accelerators, imidazole curing accelerators, and metal curing accelerators are preferred, and amine curing accelerators and imidazole curing accelerators are particularly preferred. One curing accelerator may be used alone, or two or more may be used in combination.

[0153] Phosphorus curing accelerators include, for example, tetrabutylphosphonium bromide, tetrabutylphosphonium chloride, tetrabutylphosphonium acetate, tetrabutylphosphonium decanoate, tetrabutylphosphonium laurate, bis(tetrabutylphosphonium)pyromellitic acid salt, tetrabutylphosphonium hexahydrophthalic acid hydrogen salt, tetrabutylphosphonium cresol novolac resin trimer salt, di-tert-butylmethylphosphonium tetraphenylborate and other aliphatic phosphonium salts; methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, propyltriphenylphosphonium bromide, butyltriphenylphosphonium bromide, benzyltriphenylphosphonium chloride, tetraphenylphosphonium bromide, p-tolyltriphenylphosphonium tetra-p-tolylborate, Aromatic phosphonium salts such as tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium tetra-p-tolylborate, triphenylethylphosphonium tetraphenylborate, tris(3-methylphenyl)ethylphosphonium tetraphenylborate, tris(2-methoxyphenyl)ethylphosphonium tetraphenylborate, (4-methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, and butyltriphenylphosphonium thiocyanate; aromatic phosphine-borane complexes such as triphenylphosphine-triphenylborane; aromatic phosphine-quinone addition reactants such as triphenylphosphine-p-benzoquinone addition reactants; tributylphosphine, tri-tert-butylphosphine, trioctylphosphine, di-tert-butyl(2-butenyl)phosphine, Aliphatic phosphines such as di-tert-butyl (3-methyl-2-butenyl) phosphine and tricyclohexyl phosphine; dibutylphenyl phosphine, di-tert-butylphenyl phosphine, methyldiphenyl phosphine, ethyldiphenyl phosphine, butyldiphenyl phosphine, diphenylcyclohexyl phosphine, triphenyl phosphine, tri-o-tolyl phosphine, tri-m-tolyl phosphine, tri-p-tolyl phosphine, tri(4-ethylphenyl)phosphine, tri(4-propylphenyl)phosphine, tri(4-isopropylphenyl)phosphine, tri(4-butylphenyl)phosphine, tri(4-tert-butylphenyl)phosphine, tri(2,4-dimethylphenyl)phosphine, tri(2,5-dimethylphenyl)phosphine, tri(2,6-dimethylphenyl)phosphine Aromatic phosphines such as phosphine, tri(3,5-dimethylphenyl)phosphine, tri(2,4,6-trimethylphenyl)phosphine, tri(2,6-dimethyl-4-ethoxyphenyl)phosphine, tri(2-methoxyphenyl)phosphine, tri(4-methoxyphenyl)phosphine, tri(4-ethoxyphenyl)phosphine, tri(4-tert-butoxyphenyl)phosphine, diphenyl-2-pyridylphosphine, 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane, 1,4-bis(diphenylphosphino)butane, 1,2-bis(diphenylphosphino)acetylene, and 2,2'-bis(diphenylphosphino)diphenyl ether, etc.

[0154] Examples of the urea curing accelerator include 1,1-dimethylurea; aliphatic dimethylureas such as 1,1,3-trimethylurea, 3-ethyl-1,1-dimethylurea, 3-cyclohexyl-1,1-dimethylurea, and 3-cyclooctyl-1,1-dimethylurea; 3-phenyl-1,1-dimethylurea, 3-(4-chlorophenyl)-1,1-dimethylurea, 3-(3,4-dichlorophenyl)-1,1-dimethylurea, 3-(3-chloro-4-methylphenyl)-1,1-dimethylurea, 3-(2-methylphenyl)-1,1-dimethylurea, 3-(4-methylphenyl)-1,1-dimethylurea, 3-(3,4-dimethylphenyl)-1,1 -dimethylurea, 3-(4-isopropylphenyl)-1,1-dimethylurea, 3-(4-methoxyphenyl)-1,1-dimethylurea, 3-(4-nitrophenyl)-1,1-dimethylurea, 3-[4-(4-methoxyphenoxy)phenyl]-1,1-dimethylurea, 3-[4-(4-chlorophenoxy)phenyl]-1,1-dimethylurea, 3-[3-(trifluoromethyl)phenyl]-1,1-dimethylurea, N,N-(1,4-phenylene)bis(N',N'-dimethylurea), N,N-(4-methyl-1,3-phenylene)bis(N',N'-dimethylurea) [toluenebisdimethylurea] and the like.

[0155] Examples of the amine curing accelerator include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine (DMAP), benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, and 1,8-diazabicyclo(5,4,0)-undecene, and 4-dimethylaminopyridine is preferred.

[0156] Examples of the imidazole curing accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole trimellitate, 1-cyanoethyl-2-phenylimidazole trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1') imidazole compounds such as 2,4-diamino-6-[2'-undecylimidazolyl-(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, 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, and 2-phenylimidazoline, and adducts of imidazole compounds with epoxy resins.

[0157] As the imidazole-based curing accelerator, a commercially available item may be used, and examples thereof include "P200-H50" manufactured by Mitsubishi Chemical Corporation.

[0158] Examples of the guanidine-based curing accelerator include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, 1-methylbiguanidine, 1-ethylbiguanidine, 1-n-butylbiguanidine, 1-n-octadecylbiguanidine, 1,1-dimethylbiguanidine, 1,1-diethylbiguanidine, 1-cyclohexylbiguanidine, 1-allylbiguanidine, 1-phenylbiguanidine, and 1-(o-tolyl)biguanidine.

[0159] As metal curing accelerators, organic metal complexes or organic metal salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin can be cited. As specific examples of organic metal complexes, organic cobalt complexes such as cobalt acetylacetonate (II), cobalt acetylacetonate (III), organic copper complexes such as copper acetylacetonate (II), organic zinc complexes such as zinc acetylacetonate (II), organic iron complexes such as iron acetylacetonate (III), organic nickel complexes such as nickel acetylacetonate (II), and organic manganese complexes such as manganese acetylacetonate (II) can be cited. As organic metal salts, for example, zinc octoate, tin octoate, zinc naphthenate, cobalt naphthenate, tin stearate, zinc stearate, etc. can be cited.

[0160] The content of the (G) curing accelerator in the resin composition is not particularly limited. When the non-volatile component in the resin composition is set to 100% by mass, it is preferably 5% by mass or less, more preferably 2% by mass or less, further preferably 1% by mass or less, and particularly preferably 0.5% by mass or less. The lower limit of the content of the (G) curing accelerator in the resin composition is not particularly limited. When the non-volatile component in the resin composition is set to 100% by mass, it can be, for example, 0% by mass or more, 0.0001% by mass or more, 0.001% by mass or more, 0.01% by mass or more, 0.1% by mass or more, etc.

[0161] <(H) Other additives>

[0162] The resin composition of the present invention may further contain any additive as a non-volatile component. Examples of such additives include: organic fillers other than silicone rubber particles such as polyamide microparticles; thermoplastic resins such as phenoxy resins, polyvinyl acetal resins, polyolefin resins, polysulfone resins, polyethersulfone resins, polyphenylene ether resins, polyetheretherketone resins, polyester resins; organic metal compounds such as organic copper compounds, organic zinc compounds, and organic cobalt compounds; colorants such as phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium oxide, and carbon black; polymerization inhibitors such as hydroquinone, catechol, pyrogallol, and phenothiazine; silicone-based leveling agents, acrylic polymer-based Leveling agents such as leveling agents; thickeners such as bentonite and montmorillonite; defoamers such as silicone defoamers, acrylic defoamers, fluorine defoamers, and vinyl resin defoamers; UV absorbers such as benzotriazole UV absorbers; adhesion enhancers such as urea silane; adhesion imparting agents such as triazole adhesion imparting agents, tetrazole adhesion imparting agents, and triazine adhesion imparting agents; antioxidants such as hindered phenol antioxidants and hindered amine antioxidants; fluorescent whitening agents such as stilbene derivatives; surfactants such as fluorine surfactants and silicone surfactants, etc. The additives can be used alone or in combination of two or more in any ratio. (H) The content of other additives can be appropriately set by those skilled in the art.

[0163] <(I) Organic solvent>

[0164] For the resin composition of the present invention, in addition to the above-mentioned non-volatile components, as a volatile component, it sometimes contains any organic solvent. As (I) organic solvent, a known organic solvent can be used appropriately, and its type is not particularly limited. As (I) organic solvent, for example, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.; ester solvents such as methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, isoamyl acetate, methyl propionate, ethyl propionate, γ-butyrolactone, etc.; ether solvents such as tetrahydropyran, tetrahydrofuran, 1,4-dioxane, diethyl ether, diisopropyl ether, dibutyl ether, diphenyl ether, etc.; alcohol solvents such as methanol, ethanol, propanol, butanol, ethylene glycol, etc.; 2-ethoxyethyl acetate, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, carbitol acetate (ethyl diglycol Ether ester solvents such as acetate, γ-butyrolactone, and methyl methoxypropionate; ester alcohol solvents such as methyl lactate, ethyl lactate, and methyl 2-hydroxyisobutyrate; ether alcohol solvents such as 2-methoxypropanol, 2-methoxyethanol, 2-ethoxyethanol, propylene glycol monomethyl ether, and diethylene glycol monobutyl ether (butyl carbitol); amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone; sulfoxide solvents such as dimethyl sulfoxide; nitrile solvents such as acetonitrile and propionitrile; aliphatic hydrocarbon solvents such as hexane, cyclopentane, cyclohexane, and methylcyclohexane; aromatic hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, and trimethylbenzene. (I) The organic solvent may be used alone or in combination of two or more in any ratio.

[0165] <Method for producing resin composition>

[0166] The resin composition of the present invention can be manufactured, for example, in the following manner: in any reaction vessel, in any order and / or part or all of the same time, add (A) epoxy resin, (B) silicone rubber particles, (C) elastomer, (D) inorganic filler as required, (E) flame retardant as required, (F) curing agent as required, (G) curing accelerator as required, (H) other additives as required, and (I) organic solvent as required, and mix. In addition, in the process of adding each component and mixing, the temperature can be appropriately set, and heating and / or cooling can be performed temporarily or throughout. In addition, in the process of adding each component and mixing, stirring or vibration can be performed. In addition, when adding and mixing or subsequently, for example, a stirring device such as a mixer can be used to stir the resin composition so that it is evenly dispersed.

[0167] <Characteristics of resin composition>

[0168] The resin composition of the present invention comprises (A) an epoxy resin, (B) silicone rubber particles and (C) an elastomer, wherein the content of the component (C) is 20% to 50% by mass, and thus a cured product having excellent flexibility, flame retardancy and reflow resistance can be obtained. In addition, for such a resin composition, the viscosity can be suppressed to a low level, and / or the cured product thereof has excellent tensile properties, copper adhesion and / or insulation reliability.

[0169] The cured product of the resin composition of the present invention has excellent flexibility. Therefore, for example, the number of folding times in the MIT folding test as described in Test Example 2 below is preferably 3,000 times or more, more preferably 5,000 times or more, further preferably 8,000 times or more, and particularly preferably 10,000 times or more.

[0170] The cured product of the resin composition of the present invention has excellent reflow resistance. Therefore, for example, when the expansion in the reflow process is evaluated as in Test Example 3 below, the abnormal number can be preferably 4 or less, more preferably 2 or less, further preferably 1 or less, and particularly preferably 0.

[0171] The cured product of the resin composition of the present invention has excellent flame retardancy. Therefore, when subjected to a UL94 vertical flame retardancy test as in Test Example 4 below, the flammability classification is preferably V-0 or V-1, and particularly preferably V-0.

[0172] The cured product of the resin composition of the present invention can have excellent tensile properties. For example, the tensile elastic modulus measured according to JIS K7127 as in the following Test Example 1 can be preferably less than 5 GPa, more preferably less than 4 GPa, further preferably less than 3 GPa, further more preferably less than 2 GPa, and particularly preferably less than 1 GPa. In addition, the elongation at break measured according to JIS K7127 as in the following Test Example 1 can be preferably 5% or more, more preferably 10% or more, further preferably 15% or more, and particularly preferably 20% or more.

[0173] The copper adhesion of the cured product of the resin composition of the present invention can be excellent, therefore, for example, the peel strength before HAST obtained by measuring according to JIS C6481 as described in the following Test Example 5 can be preferably 0.2kgf / cm or more, more preferably 0.3kgf / cm or more, further preferably 0.4kgf / cm or more, further more preferably 0.5kgf / cm or more, and particularly preferably 0.6kgf / cm or more. In addition, the peel strength after HAST obtained by measuring according to JIS C6481 as described in the following Test Example 5 can be preferably 0.1kgf / cm or more, more preferably 0.2kgf / cm or more, further preferably 0.3kgf / cm or more, further more preferably 0.4kgf / cm or more, and particularly preferably 0.5kgf / cm or more.

[0174] The resin composition of the present invention can suppress viscosity to a low level. Therefore, for example, the probe viscosity (adhesive force) measured as in the following Test Example 6 can be preferably less than 0.6N, particularly preferably less than 0.4N.

[0175] The cured product of the resin composition of the present invention can have excellent insulation reliability. Therefore, for example, the insulation resistance value of the insulation layer of the evaluation laminate measured by the method of Test Example 7 below can be preferably 1.00×10 7 Ω or more, more preferably 1.00×10 8 Ω or more, more preferably 1.00×10 9 Ω or more, particularly preferably 1.00×10 10 Ω or more.

[0176] <Application of resin composition>

[0177] The resin composition of the present invention can be used in a wide range of applications such as insulating materials such as printed wiring boards and multilayer flexible substrates, solder resists, underfill materials, chip bonding materials, semiconductor sealing materials, hole filling resins, and component embedding resins. Printed wiring boards, multilayer flexible substrates, etc. can be manufactured using sheet-like laminated materials such as resin sheets and prepregs.

[0178] <Resin Sheet>

[0179] The resin sheet of the present invention includes a support and a resin composition layer formed from the resin composition of the present invention and provided on the support.

[0180] The thickness of the resin composition layer is preferably 200 μm or less, more preferably 150 μm or less, further 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, and can usually be 1 μm or more, 1.5 μm or more, 2 μm or more, etc.

[0181] Examples of the support include films made of plastic materials, metal foils, and release papers, and films made of plastic materials and metal foils are preferred.

[0182] When a film formed of a plastic material is used as a support, the plastic material includes polyesters such as polyethylene terephthalate (hereinafter, sometimes referred to as "PET") and polyethylene naphthalate (hereinafter, sometimes referred to as "PEN"), polycarbonate (hereinafter, sometimes referred to as "PC"), acrylic polymers such as polymethyl methacrylate (PMMA), cyclic polyolefins, triacetyl cellulose (TAC), polyether sulfide (PES), polyether ketone, polyimide, etc. Among them, polyethylene terephthalate and polyethylene naphthalate are preferred, and inexpensive polyethylene terephthalate is particularly preferred.

[0183] When a metal foil is used as a support, examples of the metal foil include copper foil and aluminum foil, preferably copper foil. The copper foil may be a foil made of a single metal such as copper or an alloy of copper and other metals (e.g., tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.).

[0184] The surface of the support to be in contact with the resin composition layer may be subjected to matte treatment, corona treatment, or antistatic treatment.

[0185] In addition, as a support, a support with a release layer having a release layer on the surface bonded to the resin composition layer can be used. As a release agent used in the release layer of a support with a release layer, for example, one or more release agents selected from the group consisting of alkyd resins, polyolefin resins, polyurethane resins, and silicone resins can be cited. The support with a release layer can use a commercial product, for example, a PET film having a release layer with an alkyd resin-based release agent as the main component, i.e., "SK-1", "AL-5", "AL-7" made by Lintec, "Lumirror T60" made by Toray, "Purex" made by Teijin, "Unipeel" made by UNITIKA, etc.

[0186] The thickness of the support is not particularly limited, but is preferably in the range of 5 μm to 75 μm, more preferably in the range of 10 μm to 60 μm. When a support with a release layer is used, the thickness of the entire support with a release layer is preferably in the above range.

[0187] In one embodiment, the resin sheet may further include other layers as needed. As the other layers, for example, a protective film selected according to the support and provided on the surface of the resin composition layer that is not bonded to the support (i.e., the surface on the opposite side of the support) can be cited. The thickness of the protective film is not particularly limited, for example, 1 μm to 40 μm. By laminating the protective film, dust and the like can be prevented from adhering to the surface of the resin composition layer or from being damaged on the surface of the resin composition layer.

[0188] The resin sheet can be produced by directly coating the resin composition on a support using a die coater or the like, or by preparing a resin varnish by dissolving the resin composition in an organic solvent and coating it on a support using a die coater or the like, followed by drying to form a resin composition layer.

[0189] Examples of the organic solvent that can be used when coating the support include the same organic solvents as those listed in the description of the organic solvent as a component of the resin composition. The organic solvent may be used alone or in combination of two or more.

[0190] Drying can be carried out by known methods such as heating and blowing hot air. The drying conditions are not particularly limited, and the drying is carried out in a manner such that the content of the organic solvent in the resin composition layer is 10% by mass or less, preferably 5% by mass or less. Although it varies depending on the boiling point of the organic solvent in the resin composition or resin varnish, for example, in the case of using a resin composition or resin varnish containing 30% by mass to 60% by mass of an organic solvent, the resin composition layer can be formed by drying at 50° C. to 150° C. for 3 minutes to 10 minutes.

[0191] The resin sheet can be stored in a roll. When the resin sheet has a protective film, the protective film can be peeled off before use.

[0192] <Laminated Sheet>

[0193] The laminated sheet is a sheet made by laminating and curing multiple layers of resin composition. The laminated sheet contains multiple layers of insulating layers as a cured product of the resin composition layer. Usually, the number of resin composition layers laminated to make the laminated sheet is consistent with the number of insulating layers contained in the laminated sheet. The number of specific insulating layers per laminated sheet is usually more than 2, preferably more than 3, particularly preferably more than 5, preferably less than 20, more preferably less than 15, and particularly preferably less than 10.

[0194] The laminated sheet can be a sheet used by bending one side thereof relative to the other. The minimum bending radius of the laminated sheet is not particularly limited, and is preferably 0.1 mm or more, more preferably 0.2 mm or more, further preferably 0.3 mm or more, preferably 5 mm or less, more preferably 4 mm or less, and particularly preferably 3 mm or less.

[0195] Each insulating layer included in the laminated sheet may have a hole formed therein, and the hole can function as a through hole or a through hole in the multilayer flexible substrate.

[0196] For the laminated sheet, in addition to the insulating layer, any element may be further included. For example, the laminated sheet may have a conductor layer as an arbitrary element. The conductor layer is usually formed partially on the surface of the insulating layer or between the insulating layers. The conductor layer usually functions as a wiring in the multilayer flexible substrate.

[0197] The conductor material used in the conductor layer is not particularly limited. In a preferred embodiment, the conductor layer includes one or more metals selected from gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin and indium. The conductor material may be a single metal or an alloy. As an alloy, for example, an alloy of two or more metals selected from the above metals (for example, nickel-chromium alloy, copper-nickel alloy and copper-titanium alloy) can be mentioned. Among them, from the viewpoint of versatility, cost, ease of patterning, etc. of the formation of the conductor layer, chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper as a single metal is preferred; and alloys such as nickel-chromium alloy, copper-nickel alloy, and copper-titanium alloy. Among them, single metals of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper are more preferred; and nickel-chromium alloy, and single metal of copper is further preferred.

[0198] The conductor layer may be a single-layer structure or a multi-layer structure including two or more single metal layers or alloy layers formed of different types of metals or alloys. When the conductor layer is a multi-layer structure, the layer in contact with the insulating layer is preferably a single metal layer of chromium, zinc or titanium, or an alloy layer of a nickel-chromium alloy.

[0199] In order to make the conductor layer function as wiring, it can be patterned.

[0200] The thickness of the conductor layer depends on the design of the multi-layer flexible substrate, and is preferably 3 μm to 35 μm, more preferably 5 μm to 30 μm, further preferably 10 μm to 20 μm, and particularly preferably 15 μm to 20 μm.

[0201] The thickness of the laminated sheet is preferably 100 μm or more, more preferably 150 μm or more, particularly preferably 200 μm or more, and is preferably 2,000 μm or less, more preferably 1,000 μm or less, particularly preferably 500 μm or less.

[0202] <Method for producing laminated sheet>

[0203] The laminated sheet can be manufactured using a manufacturing method comprising the following steps: (a) a step of preparing a resin sheet, and (b) a step of using a resin sheet and laminating and curing a resin composition layer. The order of laminating and curing the resin composition layer is arbitrary, as long as the desired laminated sheet can be obtained. Depending on the components contained in the resin composition, for example, after all the multi-layer resin composition layers are laminated, the laminated multi-layer resin composition layers can be cured together. In addition, for example, each time other resin composition layers are laminated on a certain resin composition layer, the laminated resin composition layer can be cured.

[0204] A preferred embodiment of step (b) is described below. In the embodiments described below, for the purpose of distinction, the resin composition layers are appropriately numbered as "first resin composition layer" and "second resin composition layer", and further, similarly to the resin composition layers, the insulating layers obtained by curing these resin composition layers are also numbered as "first insulating layer" and "second insulating layer".

[0205] In a preferred embodiment, step (b) comprises the following steps:

[0206] (II) a step of curing the first resin composition layer to form a first insulating layer,

[0207] (VI) a step of laminating a second resin composition layer on the first insulating layer, and

[0208] (VII) a step of curing the second resin composition layer to form a second insulating layer. In addition, step (b) may include any of the following steps as required:

[0209] (I) a step of laminating a first resin composition layer on a sheet-like supporting substrate,

[0210] (III) a step of opening a hole in the first insulating layer,

[0211] (IV) a step of roughening the first insulating layer,

[0212] (V) forming a conductive layer on the first insulating layer;

[0213] Hereinafter, each step will be described.

[0214] Step (I) is a step of laminating the first resin composition layer on the sheet-like supporting substrate before step (II). The sheet-like supporting substrate is a removable member, and for example, a plate-like, sheet-like, or film-like member can be used.

[0215] The lamination of the sheet-like support substrate and the first resin composition layer can be implemented by vacuum lamination. In the vacuum lamination method, the heating and pressing temperature is preferably 60°C to 160°C, more preferably in the range of 80°C to 140°C, the heating and pressing pressure is preferably 0.098MPa to 1.77MPa, more preferably in the range of 0.29MPa to 1.47MPa, and the heating and pressing time is preferably 20 seconds to 400 seconds, more preferably in the range of 30 seconds to 300 seconds. The lamination is preferably implemented under reduced pressure conditions with a pressure of 26.7hPa or less.

[0216] Lamination can be performed using a commercially available vacuum laminator. Examples of commercially available vacuum laminators include a vacuum pressure laminator manufactured by Meiki Mfg. Co., Ltd., a vacuum applicator manufactured by Nikko-Materials Co., Ltd., and a batch vacuum pressure laminator.

[0217] When using a resin sheet, the lamination of the sheet-like support substrate and the first resin composition layer can be performed, for example, by pressing the resin sheet from the support body side, and the first resin composition layer of the resin sheet is heated and pressed to the sheet-like support substrate. As a member for heating and pressing the resin sheet to the sheet-like support substrate (hereinafter sometimes appropriately referred to as a "heating and pressing member"), for example, a heated metal plate (SUS end plate, etc.) or a metal roller (SUS roller) can be cited. Preferably, the heating and pressing member is not directly pressed to the resin sheet, but is pressed through an elastic material such as heat-resistant rubber so that the first resin composition layer fully follows the surface unevenness of the sheet-like support substrate.

[0218] After lamination, by pressing at normal pressure (under atmospheric pressure), for example, with a heating and pressing member, the first resin composition layer can be smoothed. For example, when a resin sheet is used, the first resin composition layer of the resin sheet can be smoothed by pressing the resin sheet with a heating and pressing member from the support side. The pressing conditions of the smoothing treatment can be set to the same conditions as the heating and pressing conditions of the above-mentioned lamination. The smoothing treatment can be performed using a commercially available laminator. The lamination and smoothing treatment can be performed continuously using the above-mentioned commercially available vacuum laminator.

[0219] Step (II) is a step of curing the first resin composition layer to form a first insulating layer. The curing conditions of the first resin composition layer are not particularly limited, and the conditions used when forming the insulating layer of the printed wiring board can be arbitrarily applied. The first resin composition layer can be cured by thermal curing.

[0220] Generally, specific heat curing conditions vary depending on the type of resin composition. For example, the curing temperature is preferably 120°C to 240°C, more preferably 150°C to 220°C, and further preferably 170°C to 210°C. In addition, the curing time is preferably 5 minutes to 120 minutes, more preferably 10 minutes to 110 minutes, and further preferably 20 minutes to 100 minutes.

[0221] The first resin composition layer may be preheated at a temperature lower than the curing temperature before the first resin composition layer is thermally cured. For example, the first resin composition layer may be preheated 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) for 5 minutes or more (preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes, and further preferably 15 minutes to 100 minutes) before the first resin composition layer is thermally cured.

[0222] Step (III) is a step of opening a hole in the first insulating layer. Through this step (III), holes such as through holes and through holes can be formed in the first insulating layer. For opening a hole, for example, a drill, laser, plasma, etc. can be used, depending on the composition of the resin composition. The size and shape of the hole can be appropriately set according to the design of the multilayer flexible substrate.

[0223] Step (IV) is a step of roughening the first insulating layer. Usually, smear removal is also performed in step (IV). Therefore, the roughening treatment is sometimes referred to as desmear treatment. Examples of the roughening treatment include a swelling treatment using a swelling solution, a roughening treatment using an oxidizing agent, and a neutralization treatment using a neutralizing solution.

[0224] There are no particular restrictions on the swelling liquid, and examples include alkaline aqueous solutions such as sodium hydroxide aqueous solution and potassium hydroxide aqueous solution. Examples of commercially available swelling liquids include "Swelling DipSecuriganth P" and "Swelling DipSecuriganth SBU" manufactured by Atotech Japan. The swelling treatment using the swelling liquid can be performed, for example, by immersing the cured body in a swelling liquid at 30°C to 90°C for 1 minute to 20 minutes. From the viewpoint of suppressing the swelling of the resin of the insulating layer to an appropriate level, it is preferred to immerse the insulating layer in a swelling liquid at 40°C to 80°C for 5 minutes to 15 minutes.

[0225] As the oxidant, there is no particular limitation, and an alkaline permanganate solution formed by dissolving permanganate in an aqueous sodium hydroxide solution or an aqueous potassium hydroxide solution can be cited. The concentration of permanganate in the alkaline permanganate solution is preferably 5% by mass to 10% by mass. As commercially available oxidants, alkaline permanganate solutions such as "Concentrate Compact P", "Concentrate Compact CP", and "Dosing Solution Securiganth P" manufactured by Atotech Japan Co., Ltd. can be cited. The roughening treatment using the oxidant can be carried out by immersing the cured body in an oxidant solution heated to 60°C to 80°C for 10 minutes to 30 minutes.

[0226] In addition, an acidic aqueous solution can be used as a neutralizing solution. As a commercially available product, for example, "Reduction Solution Securiganth P" manufactured by Atotech Japan Co., Ltd. can be cited. The treatment with the neutralizing solution can be carried out by immersing the solidified body in a neutralizing solution at 30°C to 80°C for 5 minutes to 30 minutes. In consideration of operability, etc., it is preferred to immerse the solidified body in a neutralizing solution at 40°C to 70°C for 5 minutes to 20 minutes.

[0227] The arithmetic mean roughness (Ra) of the surface of the roughened first insulating layer is preferably 400 nm or less, more preferably 300 nm or less, and further preferably 200 nm or less. The lower limit is not particularly limited and may be 30 nm or more, 40 nm or more, or 50 nm or more.

[0228] Step (V) is a step of forming a conductor layer on the first insulating layer as needed. Regarding the method for forming the conductor layer, for example, a plating method, a sputtering method, a vapor deposition method, etc. can be cited, among which a plating method is preferred. As a preferred example, a method of plating on the surface of the first insulating layer using an appropriate method such as a semi-additive method and a full-additive method to form a conductor layer having a desired wiring pattern can be cited. Among them, from the viewpoint of simplicity of production, a semi-additive method is preferred.

[0229] The following is an example of forming a conductor layer using a semi-additive method. First, a plating seed layer is formed on the surface of a first insulating layer by electroless plating. Next, a mask pattern is formed on the formed plating seed layer to expose a portion of the plating seed layer corresponding to a desired wiring pattern. A metal layer is formed on the exposed plating seed layer by electrolytic plating, and then the mask pattern is removed. Then, the unnecessary plating seed layer is removed by etching or other treatments to form a conductor layer having a desired wiring pattern.

[0230] In step (II), the first insulating layer is obtained, and if necessary, after step (III), step (IV), and step (V), step (VI) is performed. 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-like supporting substrate and the first resin composition layer in step (I).

[0231] However, when the first resin composition layer is formed using a resin sheet, the support of the resin sheet is removed before step (VI). The support may be removed between step (I) and step (II), between step (II) and step (III), between step (III) and step (IV), or between step (IV) and step (V).

[0232] After step (VI), step (VII) is performed. 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 by the same method as the curing of the first resin composition layer in step (II). Thus, a laminated sheet including a multilayer insulating layer such as a first insulating layer and a second insulating layer can be obtained.

[0233] In addition, in the method according to the aforementioned embodiment, as necessary, a step (VIII) of opening a hole in the second insulating layer, a step (IX) of roughening the second insulating layer, and a step (X) of forming a conductor layer on the second insulating layer may be performed. The opening of the second insulating layer in step (VIII) may be performed by the same method as the opening of the first insulating layer in step (III). In addition, the roughening of the second insulating layer in step (IX) may be performed by the same method as the roughening of the first insulating layer in step (IV). Furthermore, the formation of the conductor layer on the second insulating layer in step (X) may be performed by the same method as the formation of the conductor layer on the first insulating layer in step (V).

[0234] In the aforementioned embodiment, the embodiment of manufacturing a laminated sheet by laminating and curing two layers of resin composition layers such as the first resin composition layer and the second resin composition layer is described, but a laminated sheet can also be manufactured by laminating and curing more than three layers of resin composition layers. For example, in the method related to the aforementioned embodiment, the laminating and curing of the resin composition layer based on process (VI) to process (VII), and the opening of the insulating layer based on process (VIII) to process (X) as needed, the roughening treatment of the insulating layer, and the formation of the conductor layer on the insulating layer can be repeatedly implemented to manufacture a laminated sheet. Thus, a laminated sheet comprising more than three insulating layers can be obtained.

[0235] Furthermore, the method according to the above-mentioned embodiment may further include any steps other than the above-mentioned steps. For example, when step (I) is performed, a step of removing the sheet-like supporting substrate may be performed.

[0236] <Multilayer flexible substrate>

[0237] The multilayer flexible substrate includes a laminated sheet. The multilayer flexible substrate may include only the laminated sheet, or may include an arbitrary member in combination with the laminated sheet. Examples of the arbitrary member include electronic components and cover films.

[0238] The multilayer flexible substrate can be manufactured using a manufacturing method including the above-mentioned method for manufacturing a laminated sheet. Therefore, the multilayer flexible substrate can be manufactured using a manufacturing method including the following steps: (a) a step of preparing a resin sheet, and (b) a step of using the resin sheet to laminate and cure a plurality of resin composition layers.

[0239] The method for manufacturing a multilayer flexible substrate may include not only the aforementioned steps but also any other steps. For example, the method for manufacturing a multilayer flexible substrate having an electronic component may include the step of bonding the electronic component to a laminated sheet. The bonding conditions between the laminated sheet and the electronic component may be any conditions that can connect the terminal electrodes of the electronic component to the conductor layer as wiring provided on the laminated sheet. In addition, for example, the method for manufacturing a multilayer flexible substrate having a cover film may include the step of laminating the laminated sheet and the cover film.

[0240] The aforementioned multi-layer flexible substrate can usually be used by being bent in a manner that one surface of the laminated sheet included in the multi-layer flexible substrate faces each other. For example, the multi-layer flexible substrate is accommodated in a housing of a semiconductor device in a state where the multi-layer flexible substrate is bent and reduced in size. In addition, for example, in a semiconductor device having a bendable movable portion, the multi-layer flexible substrate is provided in the movable portion.

[0241] <Semiconductor devices>

[0242] The semiconductor device includes the aforementioned multi-layer flexible substrate. The semiconductor device includes, for example, a multi-layer flexible substrate and a semiconductor chip mounted on the multi-layer flexible substrate. In most semiconductor devices, the multi-layer flexible substrate can be bent in a manner such that one surface of the laminated sheet included in the multi-layer flexible substrate faces each other and is accommodated in a housing of the semiconductor device.

[0243] Examples of the semiconductor device include various semiconductor devices that can be used in electrical products (eg, computers, mobile phones, digital cameras, and televisions) and vehicles (eg, motorcycles, cars, trains, ships, and airplanes).

[0244] The semiconductor device described above can be manufactured, for example, using a manufacturing method including the steps of preparing a multilayer flexible substrate, bending the multilayer flexible substrate so that one surface of a laminated sheet faces each other, and housing the bent multilayer flexible substrate in a housing.

[0245] Example

[0246] The present invention is specifically described below by way of examples. The present invention is not limited to these examples. It should be noted that, below, unless otherwise clearly stated, "parts" and "%" indicating amounts represent "parts by mass" and "% by mass", respectively. In addition, unless otherwise clearly stated, the operations described below are performed under normal temperature and pressure (25°C, 1 atm).

[0247] <Synthesis Example 1: Synthesis of polybutadiene resin containing phenolic hydroxyl group>

[0248] 69 g of difunctional hydroxy-terminated polybutadiene ("G-3000" manufactured by Nippon Soda Co., Ltd., number average molecular weight = 3000, hydroxyl equivalent = 1800 g / eq.), 40 g of aromatic hydrocarbon mixed solvent ("Ipsol 150" manufactured by Idemitsu Petrochemical Co., Ltd.), and 0.005 g of dibutyltin laurate were placed in a reaction container and mixed to uniformly dissolve. After becoming uniform, the temperature was raised to 60° C., and 8 g of isophorone diisocyanate ("IPDI" manufactured by Evonik Degussa Japan Co., Ltd., isocyanate equivalent = 113 g / eq.) was added while stirring, and the reaction was carried out for about 3 hours.

[0249] Next, 23 g of cresol novolac resin ("KA-1160" manufactured by DIC Corporation, hydroxyl equivalent = 117 g / eq.) and 60 g of ethyl diglycol acetate (manufactured by Daicel Corporation) were added to the reactants, and the mixture was heated to 150°C while being stirred, and the reaction was carried out for about 10 hours. The reaction was observed by FT-IR at 2250 cm -1 The disappearance of the NCO peak was confirmed. Based on the confirmation of the disappearance of the NCO peak, the reaction was regarded as the end point, and the reactants were cooled to room temperature. Then, the reactants were filtered with a 100-mesh filter cloth to obtain an elastomer having a butadiene structure and phenolic hydroxyl groups (butadiene resin containing phenolic hydroxyl groups: non-volatile components are 50% by mass). The number average molecular weight of the elastomer is 5900, and the glass transition temperature is -7°C.

[0250] <Example 1>

[0251] 20 parts of a biphenyl epoxy resin ("NC-3000-L" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent of about 269 g / eq.), 5 parts of a phenolbenzopyrrolidone epoxy resin ("WHR-991S" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent of about 265 g / eq.), 50 parts of a polybutadiene resin containing a phenolic hydroxyl group obtained in Synthesis Example 1 (phenolic hydroxyl group equivalent of about 467 g / eq., solid content of 50% by mass), 15 parts of spherical silica ("UFP-30" manufactured by DENKA Co., Ltd., average particle size of 0.1 μm, surface treated with an aminosilane coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.), 10 parts of silicone rubber particles ("KMP-605" manufactured by Shin-Etsu Chemical Co., Ltd., with an average particle size of 2.0 μm), 5 parts of a flame retardant ("HCA-HQ-HST" manufactured by Sanko Co., Ltd., 10-(2,5-dihydroxyphenyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, with an average particle size of 1.5 μm and a phenolic hydroxyl equivalent of about 162 g / eq.), 2 parts of a curing accelerator (a methyl ethyl ketone solution having a solid content of 10% by mass of 1-benzyl-2-phenylimidazole ("1B2PZ" manufactured by Shikoku Chemical Industry Co., Ltd.)), and 25 parts of methyl ethyl ketone were mixed and uniformly dispersed using a high-speed rotary mixer to prepare a resin composition.

[0252] <Example 2>

[0253] A resin composition was prepared in the same manner as in Example 1 except that the amount of spherical silica ("UFP-30" manufactured by DENKA, average particle size 0.1 μm, surface treated with an aminosilane coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.)) was changed from 15 parts to 50 parts.

[0254] <Example 3>

[0255] A resin composition was prepared in the same manner as in Example 1, except that the amount of biphenyl type epoxy resin ("NC-3000-L" manufactured by Nippon Kayaku Co., Ltd., with an epoxy equivalent of approximately 269 g / eq.) was changed from 20 parts to 12 parts, and the amount of phenol benzopyrrolidone type epoxy resin ("WHR-991S" manufactured by Nippon Kayaku Co., Ltd., with an epoxy equivalent of approximately 265 g / eq.) was changed from 5 parts to 3 parts.

[0256] <Example 4>

[0257] A resin composition was prepared in the same manner as in Example 1, except that 15 parts of spherical silica ("UFP-30" manufactured by DENKA, with an average particle size of 0.1 μm, surface-treated with an aminosilane coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.)) were replaced with 15 parts of crystalline silica ("IMSILA-8" manufactured by Unimin Co., Ltd., with an average particle size of 1.38 μm, surface-treated with 3-methacryloxypropyltrimethoxysilane ("KBM503" manufactured by Shin-Etsu Chemical Co., Ltd.)), and 10 parts of silicone rubber particles ("KMP-605" manufactured by Shin-Etsu Chemical Co., Ltd., with an average particle size of 2.0 μm) were replaced with 10 parts of silicone rubber particles ("X-52-7030" manufactured by Shin-Etsu Chemical Co., Ltd., with an average particle size of 0.8 μm).

[0258] <Example 5>

[0259] A resin composition was prepared in the same manner as in Example 1, except that 2 parts of the curing accelerator (a methyl ethyl ketone solution having a solid content of 10% by mass of 1-benzyl-2-phenylimidazole ("1B2PZ" manufactured by Shikoku Chemical Industry Co., Ltd.)) was replaced with 4 parts of the curing accelerator (a methyl ethyl ketone solution having a solid content of 5% by mass of 4-dimethylaminopyridine (DMAP).

[0260] <Example 6>

[0261] A resin composition was prepared in the same manner as in Example 1, except that 20 parts of a biphenyl-type epoxy resin ("NC-3000-L" manufactured by Nippon Kayaku Co., Ltd., with an epoxy equivalent of approximately 269 g / eq.) was replaced with 20 parts of a naphthalene-type epoxy resin ("HP-4032SS" manufactured by DIC Corporation, with an epoxy equivalent of approximately 144 g / eq.).

[0262] <Example 7>

[0263] A resin composition was prepared in the same manner as in Example 1 except that the amount of biphenyl epoxy resin ("NC-3000-L" manufactured by Nippon Kayaku Co., Ltd., with an epoxy equivalent of approximately 269 g / eq.) was changed from 20 parts to 10 parts, and 10 parts of liquid bisphenol A epoxy resin ("jER828EL" manufactured by Mitsubishi Chemical Corporation, with an epoxy equivalent of approximately 180 g / eq.) was used.

[0264] <Example 8>

[0265] A resin composition was prepared in the same manner as in Example 1, except that the amount of biphenyl epoxy resin ("NC-3000-L" manufactured by Nippon Kayaku Co., Ltd., with an epoxy equivalent of approximately 269 g / eq.) was changed from 20 parts to 10 parts, and 10 parts of bisphenol AF epoxy resin ("YX7760" manufactured by Mitsubishi Chemical Corporation, with an epoxy equivalent of approximately 238 g / eq.) was used.

[0266] <Example 9>

[0267] A resin composition was prepared in the same manner as in Example 1, except that the amount of biphenyl epoxy resin ("NC-3000-L" manufactured by Nippon Kayaku Co., Ltd., with an epoxy equivalent of approximately 269 g / eq.) was changed from 20 parts to 10 parts, and 10 parts of dicyclopentadiene epoxy resin ("HP-7200L" manufactured by DIC Corporation, with an epoxy equivalent of approximately 250 g / eq.) was used.

[0268] <Example 10>

[0269] The resin composition was prepared in the same manner as in Example 1 except that the amount of biphenyl type epoxy resin ("NC-3000-L" manufactured by Nippon Kayaku Co., Ltd., with an epoxy equivalent of approximately 269 g / eq.) was changed from 20 parts to 10 parts, and 8 parts of xylene type epoxy resin ("YX7700" manufactured by Mitsubishi Chemical Corporation, with an epoxy equivalent of 270 g / eq.) and 2 parts of naphthalene type multifunctional epoxy resin ("HP-4710" manufactured by DIC Corporation, with an epoxy equivalent of approximately 170 g / eq.) were used.

[0270] <Example 11>

[0271] A resin composition was prepared in the same manner as in Example 1 except that the amount of biphenyl type epoxy resin ("NC-3000-L" manufactured by Nippon Kayaku Co., Ltd., with an epoxy equivalent of approximately 269 g / eq.) was changed from 20 parts to 10 parts, and 5 parts of dicyclopentadiene type epoxy resin ("HP-7200L" manufactured by DIC Corporation, with an epoxy equivalent of approximately 250 g / eq.) and 5 parts of naphthylene ether type epoxy resin ("HP-6000" manufactured by DIC Corporation, with an epoxy equivalent of approximately 250 g / eq.) were used.

[0272] <Example 12>

[0273] The resin composition was prepared in the same manner as in Example 1 except that the amount of the flame retardant ("HCA-HQ-HST" manufactured by Sanko Co., Ltd., 10-(2,5-dihydroxyphenyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, average particle size of 1.5 μm, phenolic hydroxyl equivalent of approximately 162 g / eq.) was changed from 5 parts to 3 parts, and 2 parts of the flame retardant ("SPS-100" manufactured by Otsuka Chemical Co., Ltd.) was used.

[0274] <Example 13>

[0275] A resin composition was prepared in the same manner as in Example 1 except that 4 parts of an active ester compound (“HPC-8000-65T” manufactured by DIC Corporation, an active group equivalent of approximately 223, a toluene solution with a solid content of 65% by mass) and 4 parts of a phenol-based curing agent containing a triazine skeleton (“LA-3018-50P” manufactured by DIC Corporation, a phenolic hydroxyl equivalent of approximately 151 g / eq., a 2-methoxypropanol solution with a solid content of 50% by mass) were used.

[0276] <Example 14>

[0277] A resin composition was prepared in the same manner as in Example 13 except that 50 parts of the polybutadiene resin containing phenolic hydroxyl groups (phenolic hydroxyl group equivalent of about 467 g / eq., solid content of 50 mass%) was replaced with 75 parts of a styrene-butadiene resin (a toluene solution of "Tuftec (registered trademark) P2000" manufactured by Asahi Kasei Corporation having a non-volatile component of 33.3 wt %), and 25 parts of methyl ethyl ketone were not added.

[0278] <Example 15>

[0279] A resin composition was prepared in the same manner as in Example 13, except that 50 parts of the polybutadiene resin containing phenolic hydroxyl groups (phenolic hydroxyl group equivalent of approximately 467 g / eq., solid content of 50 mass%) obtained in Synthesis Example 1 was replaced with 50 parts of a polycarbonate-based urethane acrylate ("ARTRESIN UN-5500" manufactured by Negami Industries, a methyl ethyl ketone solution with a non-volatile content of 50 mass%).

[0280] <Example 16>

[0281] A resin composition was prepared in the same manner as in Example 1, except that 15 parts of spherical silica ("UFP-30" manufactured by DENKA Corporation, with an average particle size of 0.1 μm, surface-treated with an aminosilane coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.)) was not used, and the amount of silicone rubber particles ("KMP-605" manufactured by Shin-Etsu Chemical Co., Ltd., with an average particle size of 2.0 μm) was changed from 10 parts to 20 parts.

[0282] <Comparative Example 1>

[0283] A resin composition was prepared in the same manner as in Example 1, except that 10 parts of silicone rubber particles ("KMP-605" manufactured by Shin-Etsu Chemical Co., Ltd., with an average particle size of 2.0 μm) were replaced with 10 parts of rubber particles ("IM401-4-14" manufactured by AICA Industries, Ltd., core-shell type rubber particles having a core of polybutadiene and a shell of a copolymer of styrene and divinylbenzene).

[0284] <Comparative Example 2>

[0285] A resin composition was prepared in the same manner as in Example 1 except that 10 parts of silicone rubber particles ("KMP-605" manufactured by Shin-Etsu Chemical Co., Ltd., average particle size: 2.0 μm) were not used.

[0286] <Comparative Example 3>

[0287] A resin composition was prepared in the same manner as in Example 1 except that the amount of spherical silica ("UFP-30" manufactured by Denki Kagaku Kogyo Co., Ltd., average particle size 0.1 μm, surface-treated with an aminosilane coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.)) was changed from 15 parts to 80 parts.

[0288] <Comparative Example 4>

[0289] A resin composition was prepared in the same manner as in Example 1 except that the amount of the phenolic hydroxyl group-containing polybutadiene resin (phenolic hydroxyl group equivalent: about 467 g / eq., solid content: 50 mass %) obtained in Synthesis Example 1 was changed from 50 parts to 120 parts.

[0290] <Comparative Example 5>

[0291] A resin composition was prepared in the same manner as in Example 1, except that 10 parts of silicone rubber particles ("KMP-605" manufactured by Shin-Etsu Chemical Co., Ltd., with an average particle size of 2.0 μm) were replaced with 12 parts of epoxy-modified silicone resin ("ES-1002T" manufactured by Shin-Etsu Chemical Co., Ltd., a toluene solution with a non-volatile content of 60% by mass).

[0292] <Comparative Example 6>

[0293] A resin composition was prepared in the same manner as in Example 1, except that 10 parts of silicone rubber particles ("KMP-605" manufactured by Shin-Etsu Chemical Co., Ltd., with an average particle size of 2.0 μm) were replaced with 10 parts of a rubber-based silicone resin ("KR-114B" manufactured by Shin-Etsu Chemical Co., Ltd., a petroleum ether (ligroin) solution with a non-volatile content of 30% by mass).

[0294] <Test Example 1: Evaluation of tensile properties>

[0295] (1) Preparation of Cured Material for Evaluation

[0296] On the surface of the PET film (“501010” manufactured by Lintec, 50 μm thick, 240 mm square) that has been treated with a release agent, a glass cloth-based epoxy resin double-sided copper-clad laminate (“R5715ES” manufactured by Panasonic, 0.7 mm thick, 255 mm square) is overlapped and fixed on all four sides with polyimide tape (10 mm wide) (hereinafter sometimes referred to as “fixed PET film”).

[0297] The resin composition prepared in the examples and comparative examples was applied onto the release-treated surface of the "fixed PET film" using a die coater so that the thickness of the resin composition layer after drying was 40 μm, and dried at 80° C. to 120° C. (100° C. on average) for 10 minutes to obtain a resin sheet.

[0298] Next, the resin composition layer was thermally cured under curing conditions of placing in an oven at 180° C. and thermally curing for 90 minutes.

[0299] After thermal curing, the polyimide tape was peeled off, and the cured product was removed from the glass cloth substrate epoxy resin double-sided copper-clad laminate, and the PET film ("501010" manufactured by Lintec) was also peeled off to obtain a sheet-like cured product. The obtained cured product is referred to as "cured product for evaluation".

[0300] (2) Determination of tensile strength

[0301] The cured product for evaluation was cut into a dumbbell No. 1 shape to obtain a test piece. For the test piece, the tensile strength was measured using a tensile testing machine "RTC-1250A" manufactured by Orientec, and the tensile modulus and elongation at break at 23°C were determined. The measurement was carried out in accordance with JIS K7127. This operation was performed 5 times. The case where the average value of the 5 tensile moduli was less than 5 GPa was evaluated as "○", and the case where it was more than 5 GPa was evaluated as "×"; the case where the average value of the elongation at break was more than 5% was evaluated as "○", and the case where it was less than 5% was evaluated as "×". The results are shown in Table 1 below. The numerical values ​​in Table 1 below represent the average values ​​of 5 times.

[0302] <Test Example 2: Evaluation of flexibility (MIT folding resistance)>

[0303] The evaluation cured product obtained in Test Example 1 was cut into test pieces with a width of 15 mm and a length of 110 mm, and a bending test was performed using an MIT test device (manufactured by Toyo Seiki Seisaku-sho, Ltd., MIT bending fatigue tester "MIT-DA") 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 case where the number of bends until the evaluation cured product breaks is 10,000 times or more is evaluated as "○", and the case where it is less than 10,000 times is evaluated as "×". The results are shown in Table 1 below.

[0304] <Test Example 3: Evaluation of Reflow Resistance>

[0305] (1) Lamination of copper foil sheets with resin

[0306] The resin composition prepared in the examples and comparative examples was applied to a copper foil (JDLC manufactured by JX Metal Co., Ltd., with a thickness of 12 μm and a square of 240 mm) using a die coater so that the thickness of the dried resin composition layer was 40 μm, and dried at 80°C to 120°C (average 100°C) for 10 minutes to obtain a copper foil sheet with resin. The copper foil sheet with resin was laminated using an intermittent vacuum press laminator (MVLP-500 manufactured by Meiki Co., Ltd.) so that the resin composition layer was in contact with both sides of the laminate. Lamination was performed in the following manner: decompression was performed for 30 seconds to make the air pressure below 13 hPa, and then pressing was performed at 100°C and a pressure of 0.74 MPa for 30 seconds.

[0307] (2) Curing of the resin composition layer

[0308] The resin composition layer was cured under the curing conditions of 180° C. and 30 minutes on the laminated board formed by laminating the copper foil sheets with resin to form an insulating layer. This is referred to as an “evaluation substrate”.

[0309] (3) Expansion evaluation during the reflow process

[0310] The evaluation substrate was cut into small pieces of 100 mm×50 mm and passed through a reflow apparatus (HAS-6116 manufactured by ANTOM Japan) that reproduced a solder reflow temperature with a peak temperature of 260° C. 10 times (reflow temperature profile conformed to IPC / JEDEC J-STD-020C).

[0311] Evaluation was performed using two small pieces, and by visual observation, the case where there were 5 or more abnormal expansions on the conductor layer was judged as "×", the case where there were 1 to 4 abnormal expansions on the conductor layer was judged as "△", and the case where there were no abnormalities on all the small pieces was judged as "○". The results are shown in Table 1 below.

[0312] <Test Example 4: Evaluation of flame retardancy>

[0313] The resin composition prepared in the examples and comparative examples was applied to the release treated surface of the above-mentioned "fixed PET film" using a die coater so that the thickness of the resin composition layer after drying was 40 μm, and dried at 80°C to 120°C (average 100°C) for 10 minutes to obtain a resin sheet. The resin sheet was laminated on both sides of the substrate obtained by etching away the copper foil of a copper-clad laminate ("MCL-E-700G" manufactured by Hitachi Chemical Co., Ltd.) with a substrate thickness of 0.2 mm using an intermittent vacuum pressurizing laminator MVLP-500 (trade name manufactured by Meiki Co., Ltd.). The lamination was performed by reducing the pressure for 30 seconds to make the air pressure below 13 hPa, and then pressing at 100°C and 0.74 MPa for 30 seconds. After peeling off the PET film of the support, a resin sheet with a thickness of 40 μm was laminated on both sides again under the same conditions. Then, the PET film was peeled off and thermally cured at 180°C for 90 minutes to obtain a sample for flame retardancy test. It was cut into a width of 12.7 mm and a length of 127 mm, and the cut surface was grinded with a grinder (made by Struers, RotoPol-22). The above 5 samples were taken as a group and flame retardancy test was carried out according to the UL94 vertical flame retardancy test. The case where the evaluation result was equivalent to V-0 was evaluated as "○", the case where it was equivalent to V-1 was evaluated as "△", and the case other than that was evaluated as "×". The results are shown in Table 1 below.

[0314] <Test Example 5: Evaluation of copper adhesion (before and after HAST test)>

[0315] A cut with a width of 10 mm and a length of 100 mm was formed on the evaluation substrate obtained in Test Example 3, and one end was peeled off and clamped with a clamp (AUTO COM type tester "AC-50C-SL" manufactured by TSE Co., Ltd.). At room temperature, 20 mm was peeled off in the vertical direction at a speed of 50 mm / min. The load (kgf / cm) at this time was measured according to JIS C6481 to obtain the peel strength before HAST. For the measured samples, a highly accelerated life tester ("PM422" manufactured by Kusumoto Chemical Co., Ltd.) was used to perform an accelerated environmental test (HAST test) for 100 hours under the conditions of 130°C and 85% RH. Then, the peel strength after HAST was obtained by measuring the initial peel strength in the same manner. For the peel strength before HAST, the case of 0.4kgf / cm or more was evaluated as "0", and the case of less than 0.4kgf / cm was evaluated as "×"; for the peel strength after HAST, the case of 0.3kgf / cm or more was evaluated as "0", the case of 0.2kgf / cm or more and less than 0.3kgf / cm was evaluated as "△", and the case of less than 0.2kgf / cm was evaluated as "×". The results are shown in Table 1 below.

[0316] <Test Example 6: Evaluation of low viscosity>

[0317] The resin composition prepared in the examples and comparative examples is applied to the release treated surface of the above-mentioned "fixed PET film" using a die coater in such a manner that the thickness of the resin composition layer after drying becomes 40 μm, and dried at 80°C to 120°C (average 100°C) for 10 minutes to obtain a resin sheet. The adhesion is measured using a probe adhesion tester (TE-6002) with a constant temperature bath manufactured by TESTER Industries. A 5 mm φ cylindrical probe made of SUS is brought into contact with the resin sheet placed in a constant temperature bath at 25°C at a contact speed of 0.5 cm / sec. The temperature is then increased by 1000 gf / cm 2 After holding for 1 second under a load of , the peeling force when the probe is pulled apart at 0.5 cm / second is measured as the probe viscosity (adhesion). Three measurements are performed on one sample to find the average value in each measurement. The case where the average value of the probe viscosity (adhesion) is less than 0.4N is evaluated as "0", the case where it is greater than 0.4N and less than 0.6N is evaluated as "△", and the case where it is greater than 0.6N is evaluated as "×". The results are shown in Table 1 below.

[0318] <Test Example 7: Evaluation of insulation reliability>

[0319] The resin composition prepared in the examples and comparative examples was applied to the release treated surface of the above-mentioned "fixed PET film" using a die coater in such a manner that the thickness of the dried resin composition layer was 40 μm, and dried at 80° C. to 120° C. (average 100° C.) for 10 minutes to obtain a resin sheet. An intermittent vacuum pressurizing laminator MVLP-500 (trade name manufactured by Meiki Co., Ltd.) was used to laminate on an imide film formed with comb-shaped electrodes (line width / line spacing = 15 μm / 15 μm) in such a manner that the resin composition layer of the resin sheet was in contact with the surface of the copper circuit. Lamination was performed in the following manner: decompression was performed for 30 seconds to make the air pressure below 13 hPa, and then pressing was performed at 100° C. at a pressure of 0.74 MPa for 30 seconds. After the PET film of the support was peeled off, thermal curing was performed at 180° C. for 90 minutes to obtain a laminate for insulation reliability evaluation. The evaluation laminate was placed in a highly accelerated life tester ("PM422" manufactured by Kusumoto Chemicals Co., Ltd.), and a voltage of 3.3 V was applied under the conditions of 130°C and 85% RH. The insulation resistance value of the evaluation laminate was measured after 100 hours in this state. The insulation resistance value was 1.0×10 8 The case with a value of Ω or above is evaluated as "○", and the case with a value of less than 1.0×10 8 The case of Ω was evaluated as "×". The results are shown in Table 1 below.

[0320] The amounts of nonvolatile components used in the resin compositions of Examples and Comparative Examples, the measurement results of Test Examples, the evaluation results, and the like are shown in Table 1 below.

[0321] [Table 1]

[0322]

[0323] It is known that by using the following resin composition, a cured product having excellent flexibility, flame retardancy and reflow resistance can be obtained; the resin composition is a resin composition comprising (A) epoxy resin, (B) silicone rubber particles and (C) elastomer, and the content of component (C) is 20% to 50% by mass. It is also known that for such a resin composition, the viscosity can be suppressed to a low level, and the tensile properties, copper adhesion and insulation reliability of the cured product are excellent.

Claims

1. A resin composition comprising (A) an epoxy resin, (B) silicone rubber particles, (C) an elastomer and (D) an inorganic filler, in, (C) component comprises a polybutadiene resin containing a phenolic hydroxyl group, The weight average molecular weight (Mw) of the component (C) is 5,500 or more, The molar ratio of the phenolic hydroxyl group to the epoxy group in all the components of the resin composition, that is, the phenolic hydroxyl group / epoxy group is 1 or less. When the nonvolatile components in the resin composition are set to 100% by mass, the content of the component (B) is 15% by mass or less. When the nonvolatile components in the resin composition are 100 mass %, the content of the component (C) is 20 to 50 mass %, and when the nonvolatile components in the resin composition are 100 mass %, the content of the component (D) is 50 mass % or less.

2. A resin composition comprising (A) an epoxy resin, (B) silicone rubber particles and (C) an elastomer, in, Component (A) comprises a phenol benzopyrrolidone type epoxy resin, (C) component comprises a polybutadiene resin containing a phenolic hydroxyl group, The weight average molecular weight (Mw) of the component (C) is 5,500 or more, The molar ratio of the phenolic hydroxyl group to the epoxy group in all the components of the resin composition, that is, the phenolic hydroxyl group / epoxy group is 1 or less. When the nonvolatile matter in the resin composition is 100 mass %, the content of the component (C) is 20 mass % to 50 mass %.

3. The resin composition according to claim 1 or 2, in, The molar ratio of the phenolic hydroxyl group to the epoxy group in all the components of the resin composition, that is, the phenolic hydroxyl group / epoxy group is 0.9 or less.

4. The resin composition according to claim 1 or 2, in, The molar ratio of the phenolic hydroxyl group to the epoxy group in all the components of the resin composition, that is, the phenolic hydroxyl group / epoxy group is 0.4 or more.

5. The resin composition according to claim 1 or 2, in, Component (A) is a solid epoxy resin, or a combination of a liquid epoxy resin and a solid epoxy resin, When a liquid epoxy resin and a solid epoxy resin are combined, the mass ratio of the solid epoxy resin to the liquid epoxy resin, that is, solid epoxy resin / liquid epoxy resin, is 1 or more.

6. The resin composition according to claim 1 or 2, in, When the nonvolatile matter in the resin composition is 100 mass %, the content of the component (A) is 5 mass % to 60 mass %.

7. The resin composition according to claim 1 or 2, in, When the nonvolatile matter in the resin composition is 100 mass %, content of the component (A) is 10 mass % to 50 mass %.

8. The resin composition according to claim 1 or 2, in, When the nonvolatile matter in the resin composition is 100 mass %, the content of the component (A) is 20 mass % to 35 mass %.

9. The resin composition according to claim 1 or 2, in, The average particle size of the component (B) is 0.05 μm to 50 μm.

10. The resin composition according to claim 1 or 2, in, The average particle size of the component (B) is 0.7 μm to 3 μm.

11. The resin composition according to claim 2, in, When the nonvolatile matter in the resin composition is 100% by mass, the content of the component (B) is 35% by mass or less.

12. The resin composition according to claim 2, in, When the nonvolatile matter in the resin composition is 100% by mass, the content of the component (B) is 25% by mass or less.

13. The resin composition according to claim 2, in, When the nonvolatile matter in the resin composition is 100% by mass, the content of the component (B) is 15% by mass or less.

14. The resin composition according to claim 1 or 2, in, When the nonvolatile matter in the resin composition is 100% by mass, the content of the component (B) is 0.5% by mass or more.

15. The resin composition according to claim 1 or 2, in, When the nonvolatile matter in the resin composition is 100% by mass, the content of the component (B) is 5% by mass or more.

16. The resin composition according to claim 1 or 2, in, When the nonvolatile matter in the resin composition is 100% by mass, the content of the component (B) is 8% by mass or more.

17. The resin composition according to claim 1 or 2, in, The component (C) is one or more selected from the group consisting of a resin having a glass transition temperature (Tg) of 25° C. or lower and a resin that is liquid at 25° C. or lower.

18. The resin composition according to claim 1 or 2, in, The component (C) is one or more selected from the group consisting of a resin having a glass transition temperature (Tg) of 15° C. or lower and a resin that is liquid at 15° C. or lower.

19. The resin composition according to claim 1 or 2, in, When the nonvolatile matter in the resin composition is 100 mass %, the content of the component (C) is 20 mass % to 40 mass %.

20. The resin composition according to claim 1 or 2, in, When the nonvolatile matter in the resin composition is 100 mass %, the content of the component (C) is 20 mass % to 33 mass %. 21 . The resin composition according to claim 2 , further comprising (D) an inorganic filler.

22. The resin composition according to claim 21, in, When the nonvolatile matter in the resin composition is 100% by mass, the content of the component (D) is 70% by mass or less.

23. The resin composition according to claim 21, in, When the nonvolatile matter in the resin composition is 100% by mass, the content of the component (D) is 50% by mass or less.

24. The resin composition according to claim 1 or 21, in, When the nonvolatile matter in the resin composition is 100 mass %, content of the component (D) is 45 mass % or less.

25. The resin composition according to claim 1 or 21, in, When the nonvolatile matter in the resin composition is 100 mass %, the content of the component (D) is 1 mass % or more.

26. The resin composition according to claim 1 or 21, in, When the nonvolatile matter in the resin composition is 100% by mass, the content of the component (D) is 15% by mass or more.

27. The resin composition according to claim 1 or 21, in, The mass ratio of the component (B) to the component (D), that is, the component (B) / component (D) is 1 or less.

28. The resin composition according to claim 1 or 21, in, The mass ratio of the component (B) to the component (D), that is, the component (B) / component (D) is 0.7 or less.

29. The resin composition according to claim 1 or 21, in, The mass ratio of the component (B) to the component (D), that is, the component (B) / component (D) is 0.01 or more. 30 . The resin composition according to claim 1 , further comprising (E) a flame retardant.

31. The resin composition according to claim 30, in, The component (E) includes a phosphorus-based flame retardant containing a phenolic hydroxyl group.

32. The resin composition according to claim 30, in, When the nonvolatile matter in the resin composition is 100 mass %, the content of the component (E) is 30 mass % or less.

33. The resin composition according to claim 30, in, When the nonvolatile matter in the resin composition is 100% by mass, the content of the component (E) is 10% by mass or less.

34. The resin composition according to claim 30, in, When the nonvolatile matter in the resin composition is 100 mass %, content of the component (E) is 8 mass % or less.

35. The resin composition according to claim 30, in, When the nonvolatile matter in the resin composition is 100% by mass, the content of the component (E) is 0.01% by mass or more.

36. The resin composition according to claim 30, in, When the nonvolatile matter in the resin composition is 100 mass %, the content of the component (E) is 0.1 mass % or more.

37. The resin composition according to claim 30, in, When the nonvolatile matter in the resin composition is 100 mass %, content of the (E) component is 4 mass % or more.

38. The resin composition according to claim 1 or 2, which is used for forming an insulating layer of a multi-layer flexible substrate.

39. A cured product, which is a cured product of the resin composition according to any one of claims 1 to 38.

40. A resin sheet comprising: Support body, and A resin composition layer formed from the resin composition according to any one of claims 1 to 38 and provided on the support. 41 . A multi-layer flexible substrate comprising an insulating layer formed by curing the resin composition according to claim 1 . A semiconductor device comprising the multi-layer flexible substrate according to claim 41 .

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