Resin composition and thermosetting adhesive sheet

Abstract

To provide a resin composition which can be formed into a sheet-like form, and can suppress warpage when base materials are bonded and an insulation layer is formed, especially, dissimilar base materials are bonded and an insulation layer is formed, and a thermosetting adhesive sheet having an adhesive layer formed from the resin composition.SOLUTION: A resin composition contains (A) a thermosetting resin, (B) a thermoplastic resin having a glass transition temperature of 50°C or higher, (C) a thermoplastic resin having a glass transition temperature of lower than 50°C, and (D) a curing agent.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a resin composition useful for adhesion between components and formation of an insulating layer in an electronic device such as lamination of semiconductors and adhesion of electronic components, and a thermosetting adhesive sheet having a resin composition layer formed from the resin composition.

Background Art

[0002] As a material used for adhesion between components and formation of an insulating layer in an electronic device such as lamination of semiconductors and adhesion of electronic components, a thermosetting adhesive sheet is known. For example, Patent Document 1 discloses a thermosetting adhesive film containing an epoxy resin, a specific curing agent, and a phenoxy resin. However, in the case of a thermosetting adhesive film, there has been a problem that warpage is likely to occur due to the difference in the coefficient of thermal expansion (CTE) of each material, particularly in adhesion between different materials and formation of an insulating layer.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] The present invention has been made paying attention to the above circumstances, and an object thereof is to provide a resin composition capable of forming a film in a sheet form as a thermosetting adhesive, and suppressing warpage during adhesion of a substrate and formation of an insulating layer, particularly during adhesion between different material substrates and formation of an insulating layer, and a thermosetting adhesive sheet having a resin composition layer formed from the resin composition.

Means for Solving the Problems

[0005] As a result of intensive studies to solve the above problems, the present inventors have found that, in a resin composition containing a thermosetting resin and a curing agent, by using in combination a thermoplastic resin having a glass transition temperature of 50°C or higher and a thermoplastic resin having a glass transition temperature of less than 50°C, warpage can be suppressed when bonding a substrate or forming an insulating layer, particularly when bonding different material substrates or forming an insulating layer between them, and thus the present invention has been completed.

[0006] That is, the present invention has the following features. [1] A resin composition containing (A) a thermosetting resin, (B) a thermoplastic resin having a glass transition temperature of 50°C or higher, (C) a thermoplastic resin having a glass transition temperature of less than 50°C, and (D) a curing agent. [2] The resin composition according to [1], wherein (A) the thermosetting resin contains a thermosetting resin having a glass transition temperature of 50°C or higher. [3] The resin composition according to [1] or [2], wherein (A) the thermosetting resin is an epoxy resin. [4] The resin composition according to any one of [1] to [3], wherein (B) the thermoplastic resin having a glass transition temperature of 50°C or higher is selected from a phenoxy resin and a polyester resin having a glass transition temperature of 50°C or higher. [5] The resin composition according to any one of [1] to [4], wherein (C) the thermoplastic resin having a glass transition temperature of less than 50°C is selected from a phenoxy resin and a polyester resin having a glass transition temperature of less than 50°C. [6] The resin composition according to any one of [1] to [5], wherein (D) the curing agent is one or more selected from an ionic liquid, an acid anhydride compound, an imidazole compound, a tertiary amine-based compound, and a dimethylurea compound. of the resin composition according to any one of the above items. [7] The resin composition according to any one of [1] to [6], wherein the content of (A) the thermosetting resin in the resin composition is 10 to 70% by mass based on 100% by mass of the non-volatile content of the resin composition. [8] The resin composition according to any one of [1] to [7], wherein the content of (B) the thermoplastic resin having a glass transition temperature of 50°C or higher in the resin composition is 3 to 50% by mass based on 100% by mass of the non-volatile content of the resin composition. [9] The content of the thermoplastic resin in the resin composition, where the (C) glass transition temperature is less than 50°C, is 10 to 60% by mass based on 100% by mass of the non-volatile content of the resin composition. The resin composition according to any one of [1] to [8].

[10] The mass ratio of the thermoplastic resin with a (B) glass transition temperature of 50°C or higher and the thermoplastic resin with a (C) glass transition temperature of less than 50°C in the resin composition is 1:20 to 1:0.2. The resin composition according to any one of [1] to [9].

[11] The content of the (D) curing agent in the resin composition is 0.1 to 40% by mass based on 100% by mass of the non-volatile content of the resin composition. The resin composition according to any one of [1] to

[10] .

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

[11] , further comprising an (E) curing accelerator.

[13] The content of the (E) curing accelerator in the resin composition is 0.05 to 10% by mass based on 100% by mass of the non-volatile content of the resin composition. The resin composition according to

[12] .

[14] A thermosetting adhesive sheet having a resin composition layer formed from the resin composition according to any one of [1] to

[13] .

[15] An electronic device having a cured product of the resin composition according to any one of [1] to

[13] .

Advantages of the Invention

[0007] According to the present invention, it is possible to provide a resin composition that can be formed into a sheet-like form as a thermosetting adhesive, and can suppress warping when adhering to a substrate or forming an insulating layer, particularly when adhering between different material substrates or forming an insulating layer, and a thermosetting adhesive sheet having a resin composition layer formed from the resin composition.

Embodiments for Carrying Out the Invention

[0008] Hereinafter, the present invention will be described with reference to its preferred embodiments. [Resin Composition] The resin composition of the present invention contains (A) a thermosetting resin, (B) a thermoplastic resin having a glass transition temperature of 50°C or higher, (C) a thermoplastic resin having a glass transition temperature of less than 50°C, and (D) a curing agent.

[0009] The glass transition temperature (Tg) of the thermosetting resin and the thermoplastic resin in the present invention can be measured by a differential scanning calorimeter (DSC) in accordance with JIS K 7121 (2012). Specifically, using X-DSC7000 (manufactured by SII) as the measuring device, a DSC measurement pan enclosing a sample of the thermosetting resin or the thermoplastic resin is set in this device, and the temperature is raised to 270°C at a rate of 5°C / min under a nitrogen atmosphere. Then, the temperature at the intersection of the straight line obtained by extending the baseline on the low-temperature side to the high-temperature side and the tangent line drawn at the point where the curvature of the stepped change portion of the glass transition is maximized is defined as the "glass transition temperature".

[0010] <(A) Thermosetting resin> The thermosetting resin used in the resin composition of the present invention is not particularly limited as long as the effects of the present invention are exhibited. For example, epoxy resins, cyanate ester resins, phenol resins, bismaleimide-triazine resins, polyimide resins, acrylic resins, vinylbenzyl resins, etc. may be mentioned. Among them, epoxy resins are preferable from the viewpoints of low-temperature curability, etc. These thermosetting resins may be used alone or in combination of two or more. When a thermosetting resin having a low glass transition temperature is used, warpage tends to be suppressed, but the reflow resistance of the cured product decreases. Therefore, it is preferable to use a thermosetting resin having a glass transition temperature of 50°C or higher. The glass transition temperature of the thermosetting resin is more preferably 55°C or higher, further preferably 60°C or higher, and particularly preferably 70°C or higher. The upper limit of the glass transition temperature of the above thermosetting resin is not particularly limited as long as the effects of the present invention are exhibited, but from the viewpoints of processability and handleability, it is preferably 400°C or lower, more preferably 350°C or lower, and further preferably 300°C or lower.

[0011] The content of the thermosetting resin having a glass transition temperature of 50°C or higher with respect to the entire thermosetting resin is preferably 60% by weight or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, and particularly preferably 90% by mass or more with respect to 100% by weight of the thermosetting resin used in the resin composition of the present invention.

[0012] The epoxy resin is not particularly limited as long as the effects of the present invention are exhibited, and those having two or more epoxy groups per molecule on average and having a high transmittance can be used. For example, hydrogenated epoxy resins (hydrogenated bisphenol A type epoxy resin, hydrogenated bisphenol F type epoxy resin, etc.), fluorine-containing epoxy resins, chain aliphatic type epoxy resins, cycloaliphatic type epoxy resins, bisphenol A type epoxy resins, biphenyl type epoxy resins, biphenyl aralkyl type epoxy resins, fluorene type epoxy resins, naphthol type epoxy resins, naphthalene type epoxy resins, bisphenol F type epoxy resins, epoxy resins containing a hydrocarbon chain as a main skeleton, phosphorus-containing epoxy resins, bisphenol S type epoxy resins, aromatic glycidylamine type epoxy resins (for example, tetraglycidyl diaminodiphenylmethane, triglycidyl-p-aminophenol, diglycidyl toluidine, diglycidyl aniline, etc.), alicyclic epoxy resins, phenol novolak type epoxy resins, alkylphenol type epoxy resins, cresol novolak type epoxy resins, bisphenol A novolak type epoxy resins, epoxy resins having a butadiene structure, diglycidyl ether compounds of bisphenols, diglycidyl ether compounds of naphthalenediols, diglycidyl ether compounds of phenols, and diglycidyl ether compounds of alcohols, and alkyl-substituted products of these epoxy resins, etc. may be mentioned.

[0013] The epoxy resin may be used alone or in combination of two or more. From the viewpoint of reactivity and the like, the epoxy equivalent of the epoxy resin is preferably 50 to 5,000, more preferably 50 to 3,000, still more preferably 80 to 2,000, and particularly preferably 100 to 1,500. Here, the "epoxy equivalent" is the number of grams of resin containing 1 gram equivalent of epoxy groups (g / eq), and is measured according to the method specified in JIS K 7236. The weight average molecular weight of the epoxy resin is preferably 5,000 or less.

[0014] The weight average molecular weight in the present invention is measured by gel permeation chromatography (GPC) method (polystyrene conversion). Specifically, the weight average molecular weight by the GPC method is measured at a column temperature of 40 °C using LC-9A / RID-6A manufactured by Shimadzu Corporation as the measuring device, Shodex K-800P / K-804L / K-804L manufactured by Showa Denko KK as the column, and chloroform or the like as the mobile phase, and can be calculated using the calibration curve of standard polystyrene.

[0015] The epoxy resin may be either liquid or solid, or a liquid epoxy resin and a solid epoxy resin may be used in combination. Here, "liquid" and "solid" refer to the state of the epoxy resin at normal temperature (25 °C) and normal pressure (1 atm). From the viewpoints of coatability, processability, and adhesiveness, it is preferable that 10% by mass or more of the total epoxy resin used is a liquid epoxy resin. From the viewpoint of varnish viscosity, it is particularly preferable to use a liquid epoxy resin and a solid epoxy resin in combination. The mass ratio of the liquid epoxy resin to the solid epoxy resin (liquid epoxy resin: solid epoxy resin) is preferably 1:2 to 1:0, and more preferably 1:1.5 to 1:0.

[0016] "Hydrogenated epoxy resin" means an epoxy resin obtained by hydrogenating an epoxy resin containing an aromatic ring. The hydrogenation rate of the hydrogenated epoxy resin is preferably 50% or more, more preferably 70% or more. "Chain aliphatic type epoxy resin" means an epoxy resin having a linear or branched alkyl chain or alkyl ether chain, and "cycloaliphatic type epoxy resin" means an epoxy resin having a cycloaliphatic skeleton, such as a cycloalkane skeleton, in the molecule. "Alkylphenol type epoxy resin" means an epoxy resin having a benzene ring skeleton having one or more alkyl groups and one or more hydroxy groups as substituents, and the hydroxy group is converted into a glycidyl ether group.

[0017] As the hydrogenated epoxy resin, hydrogenated bisphenol A type epoxy resin and hydrogenated bisphenol F type epoxy resin are preferable. As long as the effects of the present invention are exhibited, epoxy resins other than the above-mentioned suitable epoxy resins may be contained in the thermosetting resin.

[0018] Examples of the hydrogenated bisphenol A type epoxy resin include liquid hydrogenated bisphenol A type epoxy resin (for example, "YX8000" (manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: about 205), "Denacol EX-252" (manufactured by Nagase ChemteX Corporation, epoxy equivalent: about 213)), solid hydrogenated bisphenol A type epoxy resin (for example, "YX8040" (manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: about 1000)), and the like.

[0019] As the fluorine-containing epoxy resin, for example, the fluorine-containing epoxy resin described in WO2011 / 089947 can be used.

[0020] Examples of the chain aliphatic epoxy resin include polyglycerol polyglycidyl ether (e.g., "Denacol EX-512", "Denacol EX-521", manufactured by Nagase ChemteX Corporation), pentaerythritol polyglycidyl ether (e.g., "Denacol EX-411", manufactured by Nagase ChemteX Corporation), diglycerol polyglycidyl ether (e.g., "Denacol EX-421", manufactured by Nagase ChemteX Corporation), glycerol polyglycidyl ether (e.g., "Denacol EX-313", "Denacol EX-314", manufactured by Nagase ChemteX Corporation), trimethylolpropane polyglycidyl ether (e.g., "Denacol EX-321", manufactured by Nagase ChemteX Corporation), neopentyl glycol diglycidyl ether (e.g., "Denacol EX-211", manufactured by Nagase ChemteX Corporation), 1,6-hexanediol diglycidyl ether (e.g., "Denacol EX-212", manufactured by Nagase ChemteX Corporation), ethylene glycol diglycidyl ether (e.g., "Denacol EX-810", "Denacol EX-811", manufactured by Nagase ChemteX Corporation), diethylene glycol diglycidyl ether (e.g., "Denacol EX-850", "Denacol EX-851", manufactured by Nagase ChemteX Corporation), polyethylene glycol diglycidyl ether (e.g., "Denacol EX-821", "Denacol EX-830", "Denacol EX-832", "Denacol EX-841", "Denacol EX-861", manufactured by Nagase ChemteX Corporation), propylene glycol diglycidyl ether (e.g., "Denacol EX-911", manufactured by Nagase ChemteX Corporation), polypropylene glycol diglycidyl ether (e.g., "Denacol EX-941", "Denacol EX-920", "Denacol EX-931", manufactured by Nagase ChemteX Corporation), and the like.

[0021] Examples of the cycloaliphatic epoxy resin include "EHPE-3150" manufactured by Daicel Chemical Industries, Ltd.

[0022] Examples of the alkylphenol type epoxy resin include "HP-820" manufactured by DIC Corporation; "YDC-1312" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.; "EX-146" manufactured by Nagase ChemteX Corporation, etc.

[0023] The "biphenyl aralkyl type epoxy resin" means an epoxy resin having a main chain in which a novolak structure and a divalent biphenyl structure are bonded. The "fluorene type epoxy resin" means an epoxy resin having a fluorene skeleton. The "fluorine-containing aromatic type epoxy resin" means a fluorine-containing epoxy resin having an aromatic ring. For example, the fluorine-containing aromatic type epoxy resin described in WO2011 / 089947 can be used.

[0024] Examples of the bisphenol A type epoxy resin include "828EL", "1001" and "1004AF" manufactured by Mitsubishi Chemical Corporation; "840" and "850-S" manufactured by DIC Corporation; "YD-128" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., etc. Further, examples of the mixture of the liquid bisphenol A type epoxy resin and the liquid bisphenol F type epoxy resin include "ZX-1059" (epoxy equivalent: about 165) manufactured by Nippon Steel Chemical Co., Ltd.

[0025] Examples of the bisphenol F type epoxy resin include "807" manufactured by Mitsubishi Chemical Corporation; "830" manufactured by DIC Corporation; "YDF-170" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., etc.

[0026] Examples of commercially available epoxy resins containing a hydrocarbon chain as the main skeleton include "EP-4000S", "EP-4010S" (modified bisphenol type epoxy resin) manufactured by ADEKA Corporation; "YL7175-500", "YL7175-1000", "YL7410", "YX7105" (modified bisphenol type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "EXA-4850", "EXA-4850-150", "EXA-4816", "EXA-4822" (modified bisphenol type epoxy resin) manufactured by DIC Corporation; "EG-280" manufactured by Osaka Gas Chemical Co., Ltd.; "EX-830" (modified bisphenol type epoxy resin) manufactured by Nagase ChemteX Corporation; "YX7400" (polybutylene glycol diglycidyl ether) manufactured by Mitsubishi Chemical Corporation, and the like.

[0027] Examples of phenol novolac type epoxy resins include "N-730A", "N-740", "N-770" and "N-775" manufactured by DIC Corporation; "152" and "154" manufactured by Mitsubishi Chemical Corporation, and the like.

[0028] Examples of biphenyl aralkyl type epoxy resins include "NC-3000", "NC-3000L" and "NC-3100" manufactured by Nippon Kayaku Co., Ltd., and the like.

[0029] Examples of fluorene type epoxy resins include "OGSOL PG-100", "CG-500EG-200" and "EG-280" manufactured by Osaka Gas Chemical Co., Ltd., and the like.

[0030] From the viewpoint of imparting toughness to the resin composition, the content of the thermosetting resin in the resin composition of the present invention is preferably 10 to 70% by mass, more preferably 15 to 65% by mass, and still more preferably 20 to 60% by mass with respect to 100% by mass of the non-volatile content of the resin composition.

[0031] <(B) Thermoplastic resin having a glass transition temperature of 50°C or higher> The thermoplastic resin having a glass transition temperature of 50°C or higher used in the resin composition of the present invention is not particularly limited as long as the effects of the present invention are exhibited. For example, a phenoxy resin, a polyvinyl acetal resin, a polyimide resin, a polyamideimide resin, a polyethersulfone resin, a polysulfone resin, a polyester resin, a (meth)acrylic polymer, etc. having a glass transition temperature of 50°C or higher can be mentioned. These thermoplastic resins may be used alone or in combination of two or more. The thermoplastic resin having a glass transition temperature of 50°C or higher By using it, it becomes possible to form a film into a sheet-like form.

[0032] From the viewpoint of giving the resin composition an appropriate rigidity, etc., the glass transition temperature of the above thermoplastic resin is preferably 55°C or higher, more preferably 60°C or higher, and still more preferably 70°C or higher. The upper limit of the glass transition temperature of the above thermoplastic resin is not particularly limited as long as the effects of the present invention are exhibited, but from the viewpoints of processability and handleability, it is preferably 500°C or lower, more preferably 400°C or lower, and still more preferably 300°C or lower.

[0033] From the viewpoints of imparting flexibility to the resin composition layer formed from the resin composition and the coatability (anti-repelling) of the resin composition varnish when preparing the adhesive sheet, etc., the weight average molecular weight of the thermoplastic resin having a glass transition temperature of 50°C or higher is preferably 15,000 or more, and more preferably 20,000 or more. However, if this weight average molecular weight is too large, there is a tendency such as a decrease in the compatibility between the thermoplastic resin having a glass transition temperature of 50°C or higher and the thermosetting resin (especially, an epoxy resin). Therefore, this weight average molecular weight is preferably 1,000,000 or less, and more preferably 800,000 or less.

[0034] As the thermoplastic resin having a glass transition temperature of 50°C or higher, a phenoxy resin having a glass transition temperature of 50°C or higher is preferable from the viewpoint of good compatibility with a thermosetting resin (especially an epoxy resin).

[0035] Phenoxy resins with a glass transition temperature of 50 °C or higher may also have epoxy groups, similar to epoxy resins which are thermosetting resins. The weight average molecular weight of the phenoxy resin with a glass transition temperature of 50 °C or higher is preferably 10,000 to 500,000, more preferably 20,000 to 300,000.

[0036] Suitable phenoxy resins with a glass transition temperature of 50 °C or higher include those having one or more skeletons selected from a bisphenol A skeleton, a bisphenol F skeleton, a bisphenol S skeleton, a bisphenol acetophenone skeleton, a novolac skeleton, a biphenyl skeleton, a fluorene skeleton, a dicyclopentadiene skeleton, and a norbornene skeleton. The phenoxy resin with a glass transition temperature of 50 °C or higher may be used alone or in combination of two or more.

[0037] Commercially available products of phenoxy resins with a glass transition temperature of 50 °C or higher include, for example, "YX7200B35" (manufactured by Mitsubishi Chemical Corporation: biphenyl skeleton-containing phenoxy resin), "1256" (manufactured by Mitsubishi Chemical Corporation: bisphenol A skeleton-containing phenoxy resin), "YX6954BH35" (manufactured by Mitsubishi Chemical Corporation: bisphenol acetophenone skeleton-containing phenoxy resin), "FX-293" (manufactured by Nippon Steel Chemical & Material Co., Ltd.: bisphenol A skeleton-containing resin), "FX-310" (manufactured by Nippon Steel Chemical & Material Co., Ltd.: bisphenol A skeleton-containing resin), and the like.

[0038] As thermoplastic resins with a glass transition temperature of 50 °C or higher, polyester resins with a glass transition temperature of 50 °C or higher are also preferable from the viewpoint of good compatibility with thermosetting resins (especially epoxy resins).

[0039] Examples of polyester resins with a glass transition temperature of 50 °C or higher include "UE-9200", "UE-3600", "UE-9800", "UE-9900", "UE-9820", "UE-3550", "UE-3380" (all manufactured by Unitika Ltd.: saturated copolymerized polyester resins), and the like.

[0040] The content of the thermoplastic resin having a glass transition temperature of 50°C or higher in the resin composition of the present invention is From the viewpoints of forming the resin composition into a sheet-like form and suppressing cracks in the cured product, it is preferably 3 to 50% by mass, more preferably 4 to 45% by mass, and still more preferably 5 to 40% by mass with respect to 100% by mass of the non-volatile content of the resin composition.

[0041] <(C) Thermoplastic resin having a glass transition temperature of less than 50°C> The thermoplastic resin having a glass transition temperature of less than 50°C used in the resin composition of the present invention is not particularly limited as long as the effects of the present invention are exhibited. For example, a phenoxy resin, a polyvinyl acetal resin, a polyimide resin, a polyamideimide resin, a polyethersulfone resin, a polysulfone resin, a polyester resin, a (meth)acrylic polymer, etc. having a glass transition temperature of less than 50°C can be mentioned. These thermoplastic resins may be used alone or in combination of two or more. The thermoplastic resin having a glass transition temperature of less than 50°C can suppress warping when used in combination with the thermoplastic resin having a glass transition temperature of 50°C or higher, particularly when forming an adhesive layer or an insulating layer between different material substrates.

[0042] From the viewpoint of warping suppression, the glass transition temperature of the above thermoplastic resin is preferably 45°C or lower, more preferably 40°C or lower, and still more preferably 30°C or lower. The lower limit of the glass transition temperature of the above thermoplastic resin is not particularly limited as long as the effects of the present invention are exhibited, but from the viewpoint of the heat resistance of the resin composition, it is preferably -50°C or higher, more preferably -40°C or higher, and still more preferably -30°C or higher.

[0043] From the viewpoints of imparting flexibility to a resin composition layer formed from a resin composition and coatability (anti-repellent property) of a resin composition varnish when preparing an adhesive sheet, etc., the weight average molecular weight of a thermoplastic resin having a glass transition temperature of less than 50°C is preferably 15,000 or more, more preferably 20,000 or more. However, if this weight average molecular weight is too large, there is a tendency such as a decrease in compatibility between a thermoplastic resin having a glass transition temperature of less than 50°C and a thermosetting resin (particularly, an epoxy resin). Therefore, this weight average molecular weight is preferably 1,000,000 or less, more preferably 800,000 or less.

[0044] As the thermoplastic resin having a glass transition temperature of less than 50°C, a phenoxy resin having a glass transition temperature of less than 50°C is preferable from the viewpoint of good compatibility with a thermosetting resin (particularly an epoxy resin).

[0045] A phenoxy resin having a glass transition temperature of less than 50°C may also have an epoxy group, similar to an epoxy resin which is a thermosetting resin. The weight average molecular weight of a phenoxy resin having a glass transition temperature of less than 50°C is preferably from 10,000 to 500,000, more preferably from 20,000 to 300,000.

[0046] Preferable phenoxy resins having a glass transition temperature of less than 50°C include those having one or more skeletons selected from a bisphenol A skeleton, a bisphenol F skeleton, a bisphenol S skeleton, a bisphenol acetophenone skeleton, a novolac skeleton, a biphenyl skeleton, a fluorene skeleton, a dicyclopentadiene skeleton, and a norbornene skeleton. A phenoxy resin having a glass transition temperature of less than 50°C may be used alone or in combination of two or more.

[0047] Examples of commercially available products of phenoxy resins having a glass transition temperature of less than 50°C include "YX7180BH40" (manufactured by Mitsubishi Chemical Corporation), etc.

[0048] As a thermoplastic resin having a glass transition temperature of less than 50°C, from the viewpoint of good compatibility with a thermosetting resin (especially an epoxy resin), etc., a poly ester resin is also preferable.

[0049] Examples of the polyester resin having a glass transition temperature of less than 50°C include "UE-3510", "UE-3400", "UE-3220", "UE-3500", "UE-9100" (all manufactured by Unitika Ltd.: saturated copolymerized polyester resins), etc.

[0050] The content of the thermoplastic resin having a glass transition temperature of less than 50°C in the resin composition of the present invention is preferably 10 to 60% by mass, more preferably 15 to 55% by mass, and still more preferably 20 to 50% by mass with respect to 100% by mass of the non-volatile content of the resin composition, from the viewpoints of warp suppression, suppression of the tack of the film when formed, and heat resistance of the cured product.

[0051] The mass ratio of the thermoplastic resin (B) having a glass transition temperature of 50°C or higher and the thermoplastic resin (C) having a glass transition temperature of less than 50°C in the resin composition of the present invention is preferably 1:20 to 1:0.2, more preferably 1:10 to 1:0.2, still more preferably 1:7 to 1:0.25, and even more preferably 1:5 to 1:0.3, from the viewpoints of warp suppression and film formation into a sheet-like form.

[0052] <(D) curing agent and (E) curing accelerator> The resin composition of the present invention contains a curing agent. The curing agent is not particularly limited as long as it has a function of curing a thermosetting resin. From the viewpoint of suppressing the amount of warpage and heat distortion generated, as the curing agent, one that can cure a thermosetting resin at a temperature of 140°C or lower (preferably 120°C or lower) (one that can be cured at a low temperature) is preferable. The curing agent may be used alone or in combination of two or more.

[0053] Examples of the curing agent will be given for a curing agent for an epoxy resin, which is preferable as a thermosetting resin. For example, ionic liquids, acid anhydride compounds, imidazole compounds, tertiary amine compounds, dimethylurea compounds, amine adduct compounds, organic acid dihydrazide compounds, organic phosphine compounds, dicyandiamide compounds, primary and secondary amine compounds, and the like can be mentioned.

[0054] The curing agent is preferably at least one selected from ionic liquids, acid anhydride compounds, imidazole compounds, tertiary amine compounds, dimethylurea compounds, and amine adduct compounds, and more preferably at least one selected from ionic liquids, acid anhydride compounds, imidazole compounds, tertiary amine compounds, and dimethylurea compounds.

[0055] In particular, as the curing agent in the present invention, an ionic liquid capable of curing a thermosetting resin (especially an epoxy resin) at a temperature of 140°C or lower (preferably 120°C or lower), that is, a salt that can melt in a temperature range of 140°C or lower (preferably 120°C or lower) and has a curing action on a thermosetting resin (especially an epoxy resin) is preferable. The ionic liquid is preferably used in a state of being uniformly dissolved in the thermosetting resin (especially an epoxy resin).

[0056] In addition to the curing agent, the resin composition of the present invention may contain a (E) curing accelerator for the purpose of adjusting the curing time and the like. Only one kind of curing accelerator may be used, or two or more kinds may be used in combination. Examples of the curing accelerator will be given for a curing accelerator for an epoxy resin, which is preferable as a thermosetting resin. For example, imidazole compounds, tertiary amine compounds, dimethylurea compounds, amine adduct compounds, and the like can be mentioned. The curing accelerator is preferably at least one selected from imidazole compounds, tertiary amine compounds, and dimethylurea compounds.

[0057] Examples of the cation constituting the ionic liquid as the curing agent in the present invention include imidazolium ions, piperidinium ions, pyrrolidinium ions, pyrazonium ions, guani Ammonium cations such as guinium ions and pyridinium ions; phosphonium cations such as tetraalkylphosphonium cations (e.g., tetrabutylphosphonium ions, tributylhexylphosphonium ions, etc.); sulfonium cations such as triethylsulfonium ions, etc. are exemplified.

[0058] As anions constituting the ionic liquid as a curing agent in the present invention, halide anions such as fluoride ions, chloride ions, bromide ions, iodide ions; alkyl sulfate anions such as methanesulfonate ions; fluorine-containing compound anions such as trifluoromethanesulfonate ions, hexafluorophosphonate ions, trifluorotris(pentafluoroethyl)phosphonate ions, bis(trifluoromethanesulfonyl)imide ions, trifluoroacetate ions, tetrafluoroborate ions; phenol anions such as phenol ions, 2-methoxyphenol ions, 2,6-di-tert-butylphenol ions; acidic amino acid anions such as aspartate ions, glutamate ions; neutral amino acid anions such as glycine ions, alanine ions, phenylalanine ions; N-acylamino acid anions represented by the following general formula (1) such as N-benzoylalanine ions, N-acetylphenylalanine ions, N-acetylglycine ions; carboxylic acid anions such as formate ions, acetate ions, decanoate ions, 2-pyrrolidone-5-carboxylate ions, α-lipoic acid ions, lactate ions, tartrate ions, hippurate ions, N-methylhippurate ions, benzoate ions are exemplified.

[0059]

Chemical formula

[0060] (However, R is a linear or branched alkyl group having 1 to 5 carbon atoms, or a substituted or unsubstituted phenyl group, and X represents the side chain of an amino acid.)

[0061] Examples of the amino acid in the formula (1) include, for example, aspartic acid, glutamic acid, glycine, alanine, phenylalanine, etc. Among them, glycine is preferable.

[0062] Among the above, the cation is preferably an ammonium-based cation or a phosphonium-based cation, and more preferably an imidazolium ion or a phosphonium ion. More specifically, the imidazolium ion is, for example, 1-ethyl-3-methylimidazolium ion, 1-butyl-3-methylimidazolium ion, 1-propyl-3-methylimidazolium ion, etc.

[0063] The anion is preferably a phenolic anion, an N-acyl amino acid ion represented by the general formula (1) or a carboxylic acid-based anion, and more preferably an N-acyl amino acid ion or a carboxylic acid-based anion.

[0064] Specific examples of the phenolic anion include 2,6-di-tert-butylphenol ion. Specific examples of the carboxylic acid-based anion include acetate ion, decanoate ion, 2-pyrrolidone-5-carboxylate ion, formate ion, α-lipoic acid ion, lactate ion, tartrate ion, hippurate ion, N-methylhippurate ion, etc. Among them, acetate ion, 2-pyrrolidone-5-carboxylate ion, formate ion, lactate ion, tartrate ion, hippurate ion, N-methylhippurate ion are preferable, and acetate ion, decanoate ion, N-methylhippurate ion, formate ion are particularly preferable. Specific examples of the N-acyl amino acid ion represented by the general formula (1) include N-benzoylalanine ion, N-acetylphenylalanine ion, aspartic acid ion, glycine ion, N-acetylglycine ion, etc. Among them, N-benzoylalanine ion, N-acetylphenylalanine ion, N-acetylglycine ion are preferable, and N-acetylglycine ion is particularly preferable.

[0065] Specific ionic liquids include, for example, 1-butyl-3-methylimidazolium lactate, tetrabutylphosphonium-2-pyrrolidone-5-carboxylate, tetrabutylphosphonium acetate, tetrabutylphosphonium decanoate, tetrabutylphosphonium trifluoroacetate, tetrabutylphosphonium α-lipoate, tetrabutylphosphonium formate salt, tetrabutylphosphonium lactate, bis(tetrabutylphosphonium) tartrate salt, tetrabutylphosphonium hippurate salt, N-methyltetrabutylphosphonium hippurate salt, tetrabutylphosphonium benzoyl-DL-alaninate salt, N-acetylphenylalanine tetrabutylphosphonium salt, 2,6-di-tert-butylphenol tetrabutylphosphonium salt, L-aspartic acid monotetrabutylphosphonium salt, glycine tetrabutylphosphonium salt, N-acetylglycine tetrabutylphosphonium salt, 1-ethyl-3-methylimidazolium lactate, 1-ethyl-3-methylimidazolium acetate, 1-ethyl-3-methylimidazolium formate salt, 1-ethyl-3-methylimidazolium hippurate salt, N-methyltetrabutylphosphonium 1-ethyl-3-methylimidazolium hippurate salt, bis(1-ethyl-3-methylimidazolium) tartrate salt, N-acetylglycine 1-ethyl-3-methylimidazolium salt are preferred, and tetrabutylphosphonium decanoate, N-acetylglycine tetrabutylphosphonium salt, 1-ethyl-3-methylimidazolium acetate, 1-ethyl-3-methylimidazolium formate salt, 1-ethyl-3-methylimidazolium hippurate salt, N-methyltetrabutylphosphonium 1-ethyl-3-methylimidazolium hippurate salt are particularly preferred.

[0066] As the method for synthesizing the ionic liquid, for example, there are an anion exchange method in which a precursor composed of a cation moiety such as alkylimidazolium, alkylpyridinium, alkylammonium, and alkylsulfonium ions and an anion moiety containing halogen is reacted with NaBF4, NaPF6, CF3SO3Na, LiN(SO2CF3)2, etc., an acid ester method in which an amine-based substance and an acid ester are reacted to introduce an alkyl group while the organic acid residue becomes a counter anion, and a neutralization method in which amines are neutralized with an organic acid to obtain a salt, etc., but it is not limited thereto. In the neutralization method using an anion, a cation, and a solvent, the anion and the cation can be used in equal amounts, and the solvent in the obtained reaction solution can be distilled off and used as it is, or an organic solvent (methanol, toluene, ethyl acetate, acetone, etc.) can be added to concentrate the solution.

[0067] Examples of the acid anhydride compound as the curing agent in the present invention include tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, dodecenyl succinic anhydride, etc. Specific examples of the acid anhydride compound include Likacid TH, TH-1A, HH, MH, MH-700, MH-700G (all manufactured by Shin Nippon Rika Co., Ltd.), etc.

[0068] Examples of the imidazole compound as the curing agent and the curing accelerator in the present invention include 1H-imidazole, 2-methyl-imidazole, 2-phenyl-4-methylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-ethyl-4-methyl-imidazole, 2-undecylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 2,4 -Diamino-6-(2'-undecylimidazolyl-(1'))-ethyl-s-triazine, 2-phenyl-4,5-bis(hydroxymethyl)-imidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 2-phenyl-imidazole, 2-dodecyl-imidazole, 2-heptadecylimidazole, 1,2-dimethyl-imidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,4-diamino-6-(2'-methylimidazolyl-(1')-ethyl-s-triazine, 2,4-diamino-6-(2'-methylimidazolyl-(1'))-ethyl-s-triazine isocyanuric acid adduct, and the like. Specific examples of the imidazole compound include Curezol 2MZ, 2P4MZ, 2E4MZ, 2E4MZ-CN, C11Z, C11Z-CN, C11Z-CNS, C11Z-A, 2PHZ, 1B2MZ, 1B2PZ, 2PZ, C17Z, 1.2DMZ, 2P4MHZ-PW, 2MZ-A, 2MA-OK (all manufactured by Shikoku Kasei Kogyo Co., Ltd.), and the like.

[0069] Specific examples of the tertiary amine compound as the curing agent and curing accelerator in the present invention include DBN (1,5-diazabicyclo[4.3.0]non-5-ene), DBU (1,8-diazabicyclo[5.4.0]undeca-7-ene), 2-ethylhexanoate of DBU, phenolate of DBU, p-toluenesulfonate of DBU, U-CAT SA 102 (manufactured by San-Apro Ltd.: octylate of DBU), DBU-organic acid salts such as formate of DBU, and tris(dimethylaminomethyl)phenol (TAP), and the like.

[0070] Specific examples of the dimethylurea compound as the curing agent and curing accelerator in the present invention include aromatic dimethylureas such as DCMU (3-(3,4-dichlorophenyl)-1,1-dimethylurea) and U-CAT3512T (manufactured by San-Apro Ltd.), and aliphatic dimethylureas such as U-CAT3503N (manufactured by San-Apro Ltd.). Among them, aromatic dimethylureas are preferably used from the viewpoint of curability.

[0071] Examples of the amine adduct compound as a curing agent and a curing accelerator in the present invention include epoxy adduct compounds obtained by stopping the addition reaction of a tertiary amine to an epoxy resin halfway. Specific examples of the amine adduct compound include Amicure PN-23, Amicure MY-24, Amicure PN-D, Amicure MY-D, Amicure PN-H, Amicure MY-H, Amicure PN-31, Amicure PN-40, Amicure PN-40J (all manufactured by Ajinomoto Fine-Techno Co., Inc.).

[0072] Specific examples of the organic acid dihydrazide compound as a curing agent in the present invention include Amicure VDH-J, Amicure UDH, Amicure LDH (all manufactured by Ajinomoto Fine-Techno Co., Inc.).

[0073] Examples of the organic phosphine compound as a curing agent and a curing accelerator in the present invention include triphenylphosphine, tetraphenylphosphonium tetra-p-tolylborate, tetraphenylphosphonium tetraphenylborate, tri-tert-butylphosphonium tetraphenylborate, (4-methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate, triphenylphosphine triphenylborane, etc. Specific examples of the organic phosphine compound include TPP, TPP-MK, TPP-K, TTBuPK, TPP-SCN, TPP-S (manufactured by Hokko Chemical Industry Co., Ltd.).

[0074] Examples of the dicyandiamide compound as a curing agent in the present invention include dicyandiamide. Specific examples of the dicyandiamide compound include DICY7 and DICY15 which are finely pulverized products of dicyandiamide (both manufactured by Mitsubishi Chemical Corporation).

[0075] Examples of the primary / secondary amine compounds as curing agents in the present invention include aliphatic amines such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine, trimethylhexamethylenediamine, 2-methylpentamethylenediamine, 1,3-bis(aminomethyl)cyclohexane, dipropylenediamine, diethylaminopropylamine, bis(4-aminocyclohexyl)methane, norbornenediamine, 1,2-diaminocyclohexane, etc.; alicyclic amines such as N-aminoethylpiperazine, 1,4-bis(3-aminopropyl)piperazine, etc.; and aromatic amines such as diaminodiphenylmethane, m-phenylenediamine, m-xylenediamine, metaphenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, diethyltoluenediamine, etc. Specific examples of the primary / secondary amine compounds include Kayahard A-A (manufactured by Nippon Kayaku Co., Ltd.: 4,4'-diamino-3,3'-dimethyldiphenylmethane), etc.

[0076] The content of the curing agent in the resin composition of the present invention is preferably 0.1 to 40% by mass, more preferably 0.5 to 38 parts by mass, and still more preferably 1 to 35 parts by mass with respect to 100% by mass of the non-volatile content of the resin composition. If this content is less than 0.1% by mass, sufficient curability may not be obtained, and if this content is more than 40% by mass, the storage stability of the resin composition may be impaired. When an ionic liquid is used as the curing agent, the amount of the ionic liquid is preferably 0.1 to 20% by mass, more preferably 0.5 to 18% by mass, and still more preferably 1 to 15% by mass with respect to 100% by mass of the non-volatile content of the resin composition.

[0077] When the resin composition of the present invention contains a curing accelerator, its content is preferably 0.05 to 10% by mass, more preferably 0.1 to 8% by mass, and still more preferably 0.5 to 5% by mass with respect to 100% by mass of the non-volatile content of the resin composition. If this content is less than 0.05% by mass, curing tends to be slow and the thermosetting time tends to be long, and if it exceeds 10% by mass, the storage stability of the resin composition tends to decrease.

[0078] The resin composition in the present invention is preferably used by combining a curing agent and a curing accelerator. As the combination of the curing agent and the curing accelerator, two or more selected from ionic liquids, acid anhydride compounds, imidazole compounds, tertiary amine-based compounds, dimethylurea compounds, and amine adduct compounds are preferred.

[0079] <(F) Inorganic filler> In the resin composition of the present invention, an inorganic filler can be further contained within the range where the effects of the present invention are exhibited. Examples of such inorganic fillers include unfired hydrotalcite, semi-fired hydrotalcite, fired hydrotalcite, talc, silica, alumina, barium sulfate, clay, mica, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, boron nitride, aluminum borate, barium titanate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, barium zirconate, calcium zirconate, silicate, etc. The inorganic filler may be used alone or in combination of two or more. The particle size of the primary particles of the inorganic filler is preferably 5 μm or less, more preferably 3 μm or less. For example, those having a primary particle size of 0.001 to 3 μm, more preferably 0.005 to 2 μm can be used.

[0080] The particle form of the inorganic filler is not particularly limited, and substantially spherical, rectangular parallelepiped, plate-like, linear shapes like fibers, and branched shapes can be used. The inorganic filler is preferably talc, silica, zeolite, titanium oxide, alumina, zirconium oxide, silicate, mica, magnesium hydroxide, aluminum hydroxide, etc., more preferably talc and silica, and particularly preferably talc. As the silica, amorphous silica, fused silica, crystalline silica, synthetic silica, wet silica, dry silica, colloidal silica (aqueous dispersion type, organic solvent dispersion type, fumed silica, etc.) are preferred. From the viewpoint of being difficult to precipitate and settle and being easily compounded with the resin, organosilica sol (organic solvent dispersion type colloidal silica) is particularly preferred.

[0081] As the inorganic filler, those surface-treated with a surface treatment agent can be used. As the surface treatment agent used for surface treatment, for example, higher fatty acids, alkyl silanes, silane coupling agents, etc. can be used. Among them, higher fatty acids and alkyl silanes are preferable. Only one kind of surface treatment agent may be used, or two or more kinds may be used in combination.

[0082] Examples of the higher fatty acids include higher fatty acids having 18 or more carbon atoms such as stearic acid, montanic acid, myristic acid, and palmitic acid. Among them, stearic acid is preferable. These may be used alone or in combination of two or more.

[0083] Examples of the alkyl silanes include methyltrimethoxysilane, ethyltrimethoxysilane, hexyltrimethoxysilane, octyltrimethoxysilane, decyltrimethoxysilane, octadecyltrimethoxysilane, dimethyldimethoxysilane, octyltriethoxysilane, n-octadecyldimethyl(3-(trimethoxysilyl)propyl)ammonium chloride, etc. These may be used alone or in combination of two or more.

[0084] Examples of silane coupling agents include epoxy-based silane coupling agents such as 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyl(dimethoxy)methylsilane, and 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane; mercapto-based silane coupling agents such as 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, and 11-mercaptoundecyltrimethoxysilane; amino-based silane coupling agents such as 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyldimethoxymethylsilane, N-phenyl-3-aminopropyltrimethoxysilane, N-methylaminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, and N-(2-aminoethyl)-3-aminopropyldimethoxymethylsilane; ureido-based silane coupling agents such as 3-ureidopropyltriethoxysilane, vinyl-based silane coupling agents such as vinyltrimethoxysilane, vinyltriethoxysilane, and vinylmethyldiethoxysilane; styryl-based silane coupling agents such as p-styryltrimethoxysilane; acrylate-based silane coupling agents such as 3-acryloxypropyltrimethoxysilane and 3-methacryloxypropyltrimethoxysilane; isocyanate-based silane coupling agents such as 3-isocyanatopropyltrimethoxysilane; sulfide-based silane coupling agents such as bis(triethoxysilylpropyl)disulfide and bis(triethoxysilylpropyl)tetrasulfide; phenyltrimethoxysilane, methacryloxypropyltrimethoxysilane, imidazole silane, triazine silane, and the like. These may be used alone or in combination of two or more.

[0085] The surface treatment of the inorganic filler can be carried out, for example, by adding and spraying a surface treatment agent while stirring and dispersing the inorganic filler at room temperature in a mixer and stirring for 5 to 60 minutes. As the mixer, a known mixer can be used, for example, blenders such as V blender, ribbon blender, bubble cone blender, mixers such as Henschel mixer and concrete mixer, ball mill, cutter mill and the like. Further, when pulverizing the inorganic filler with a ball mill or the like, the above-mentioned higher fatty acid, alkyl silanes or silane coupling agent can be added for surface treatment. The amount of the surface treatment agent used varies depending on the type of the inorganic filler or the type of the surface treatment agent, etc., but 1 to 10 parts by mass is preferable with respect to 100 parts by mass of the inorganic filler that has not been surface-treated. In the present invention, the surface-treated inorganic filler is also included in the "inorganic filler" in the present invention. It is preferably 1 to 10 parts by mass with respect to 100 parts by mass of the material.

[0086] Commercially available products can be used as the inorganic filler. Examples of talc include "FG-15" (average particle size 1.4 μm), "D-1000" (average particle size 1.0 μm), "D-600" (average particle size 0.6 μm), etc. manufactured by Nippon Talc Co., Ltd. Examples of commercially available spherical fused silica include the true spherical silica "Admafine Series" (such as "SO-C2; average particle size 0.5 μm", "SC2500-SQ; average particle diameter 0.5 μm, silane coupling treatment", etc.) manufactured by Admatechs Co., Ltd. Examples of fumed silica include the "Aerosil Series" (such as "A-200: primary particle size 5 to 40 nm", etc.) manufactured by Nippon Aerosil Co., Ltd. Examples of organosol-dispersed colloidal silica include "MEK-EC-2130Y" (amorphous silica particle size 10 to 15 nm, non-volatile content 30% by mass, MEK solvent), "PGM-AC-2140Y" (silica particle size 10 to 15 nm, non-volatile content 40% by mass, PGM (propylene glycol monomethyl ether) solvent), "MIBK-ST" (silica particle size 10 to 15 nm, non-volatile content 30% by mass, MIBK (methyl isobutyl ketone) solvent), and colloidal silica sol "PL-2L-MEK" (silica particle size 15 to 20 nm, non-volatile content 20% by mass, MEK (methyl ethyl ketone) solvent) manufactured by Fuso Chemical Industry Co., Ltd., etc.

[0087] When an inorganic filler is blended into the resin composition of the present invention, warpage tends to be suppressed. However, when highly filled, the toughness of the resin composition layer before curing may decrease, and the adhesion and embedability to the adhesive substrate may also decrease. In addition, the transparency of the resin composition decreases due to the addition of the inorganic filler. Therefore, when it is desired to obtain a resin composition with excellent transparency, it is preferable not to blend the inorganic filler or to limit the blending amount of the inorganic filler to a range where the desired transparency can be obtained. From the viewpoint of the transparency of the resin composition, the content of the inorganic filler in the resin composition of the present invention is preferably 0 to 30% by mass, more preferably 0 to 20% by mass, and even more preferably 0 to 10% by mass based on 100% by mass of the non-volatile content of the resin composition.

[0088] <Coupling agent> The resin composition of the present invention may contain a coupling agent. Examples of the coupling agent include silane coupling agents, aluminate coupling agents, and titanate coupling agents. Examples of the silane coupling agent include epoxy-based silane coupling agents such as 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyl(dimethoxy)methylsilane, and 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane; mercapto-based silane coupling agents such as 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, and 11-mercaptoundecyltrimethoxysilane; amino-based silane coupling agents such as 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyldimethoxymethylsilane, N-phenyl-3-aminopropyltrimethoxysilane, N-methylaminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, and N-(2-aminoethyl)-3-aminopropyldimethoxymethylsilane; ureido-based silane coupling agents such as 3-ureidopropyltriethoxysilane; vinyl-based silane coupling agents such as vinyltrimethoxysilane, vinyltriethoxysilane, and vinylmethyldiethoxysilane; styryl-based silane coupling agents such as p-styryltrimethoxysilane; acrylate-based silane coupling agents such as 3-acryloxypropyltrimethoxysilane and 3-methacryloxypropyltrimethoxysilane; isocyanate-based silane coupling agents such as 3-isocyanatopropyltrimethoxysilane; sulfide-based silane such as bis(triethoxysilylpropyl)disulfide and bis(triethoxysilylpropyl)tetrasulfide Coupling agents; examples include phenyltrimethoxysilane, methacryloxypropyltrimethoxysilane, imidazole silane, triazine silane, etc. Among these, vinyl silane coupling agents and epoxy silane coupling agents are preferred, and epoxy silane coupling agents are particularly preferred. Examples of aluminate coupling agents include alkyl acetoacetate aluminum diisopropylate (e.g., "Prenact AL-M" manufactured by Ajinomoto Fine-Techno Co., Inc.). Specific examples of titanate coupling agents include Prenact TTS, Prenact 46B, Prenact 55, Prenact 41B, Prenact 38S, Prenact 138S, Prenact 238S, Prenact 338X, Prenact 44, Prenact 9SA (all manufactured by Ajinomoto Fine-Techno Co., Inc.), etc. The coupling agent may be used alone or in combination of two or more.

[0089] The content of the coupling agent in the resin composition of the present invention is preferably 0 to 15% by mass, more preferably 0.5 to 10% by mass, based on 100% by mass of the non-volatile content of the resin composition.

[0090] <Other Additives> The resin composition of the present invention may further contain other additives different from the above components as long as the effects of the present invention can be exhibited. Examples of such additives include organic fillers such as rubber particles, silicone powder, nylon powder, fluororesin powder; thickeners such as orben and bentonite; defoaming agents or leveling agents of silicone-based, fluorine-based, and polymer-based; adhesion-imparting agents such as triazole compounds, thiazole compounds, triazine compounds, and porphyrin compounds; flame retardants such as phosphorus-based compounds and metal hydroxides; etc.

[0091] [Manufacturing Method of Resin Composition] The manufacturing method of the resin composition of the present invention is not particularly limited, and examples include a method of adding the above-mentioned compounding components and, if necessary, a solvent or the like, and mixing them using a kneading roller or a rotary mixer.

[0092] [Thermosetting Adhesive Sheet] For example, the resin composition of the present invention made into a varnish by blending an organic solvent is applied onto a support, and the obtained coating film is dried by heating or blowing hot air or the like to form a resin composition layer (adhesive layer) on the support. Further, a protective film is laminated on the resin composition layer (adhesive layer) to obtain a thermosetting adhesive sheet. Alternatively, the resin composition of the present invention made into a varnish by blending an organic solvent is applied onto a protective film, and the obtained coating film is dried by heating or blowing hot air or the like to form a resin composition layer (adhesive layer) on the protective film. Further, a support is laminated on the resin composition layer (adhesive layer) to obtain a thermosetting adhesive sheet as well.

[0093] Examples of the support used for the thermosetting adhesive sheet include plastic films such as polyolefins like polyethylene, polypropylene, and polyvinyl chloride, cycloolefin polymers, polyesters such as polyethylene terephthalate (hereinafter sometimes abbreviated as "PET"), and polyethylene naphthalate, polycarbonate, and polyimide. As the plastic film, PET is particularly preferred. The support may also be a metal foil such as aluminum foil, stainless steel foil, or copper foil. The support may be subjected to a release treatment, a mat treatment, a corona treatment, etc. with a silicone resin-based release agent, an alkyd resin-based release agent, a fluororesin-based release agent, etc. In the present invention, when the support has a release layer, the release layer is also regarded as a part of the support. The thickness of the support is not particularly limited, but from the viewpoint of handleability and the like, it is preferably 20 to 200 μm, more preferably 20 to 125 μm.

[0094] In order to improve the moisture resistance of the thermosetting adhesive sheet, a plastic film having a barrier layer may be used as a support. Examples of the barrier layer include nitrides such as silicon nitride, oxides such as aluminum oxide, stainless steel foils, and metal foils such as aluminum foils. Examples of the plastic film include the above-described plastic films. A commercially available plastic film having a barrier layer may be used. Alternatively, a film obtained by laminating a metal foil and a plastic film may be used. For example, commercially available products of polyethylene terephthalate films with aluminum foils include "PET with AL1N30" manufactured by Tokai-Toyo Aluminum Sales Co., Ltd., "PET with AL3025" manufactured by Fukuda Metal Co., Ltd., "Alpet" manufactured by Panac Co., Ltd., and the like.

[0095] Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone (hereinafter also abbreviated as "MEK"), and cyclohexanone; acetate esters such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol acetate; carbitols such as cellosolve and butyl carbitol; aromatic hydrocarbons such as toluene and xylene; dimethylformamide, dimethylacetamide, N-methylpyrrolidone, and the like. The organic solvent may be used alone or in combination of two or more.

[0096] The drying conditions are not particularly limited, but usually a temperature of about 50 to 100°C for about 3 to 15 minutes is suitable.

[0097] The thickness of the resin composition layer (adhesive layer) after drying is usually in the range of 3 μm to 200 μm, preferably 5 μm to 100 μm, and more preferably 5 μm to 50 μm.

[0098] The resin composition layer (adhesive layer) may be protected by a protective film. By protecting with a protective film, it is possible to prevent the adhesion of dust or the like and scratches on the surface of the resin composition layer (adhesive layer). It is preferable to use a plastic film similar to the support as the protective film. Further, the protective film may be subjected to a release treatment in addition to a matte treatment or a corona treatment. The thickness of the protective film is not particularly limited, but is usually in the range of 1 to 150 μm, preferably 10 to 100 μm.

[0099] When the resin composition of the present invention has transparency, the total light transmittance of D65 light of the resin composition layer of the adhesive sheet is preferably 80% or more, more preferably 85% or more, and still more preferably 90% or more regardless of the thickness of the resin composition layer. The total light transmittance can be measured, for example, in accordance with JIS K7361-1 "Plastics - Test method for total light transmittance of transparent materials - Part 1: Single beam method".

[0100] The average value of the total light transmittance of D65 light of the cured product layer having a thickness of 20 μm obtained by curing the resin composition layer (adhesive layer) formed from the resin composition of the present invention is preferably 80% or more, more preferably 85% or more, and still more preferably 90% or more.

[0101] [Use] The thermosetting adhesive sheet having the resin composition of the present invention and the resin composition layer formed from the resin composition can be used for adhesion between components and formation of an insulating layer in electronic devices such as lamination of semiconductors and adhesion of electronic components (between the same materials and between different materials), specifically, adhesion between metal foils such as copper foils or between a metal foil and a substrate (adhesion between copper and a substrate in a copper-clad laminate (CCL), etc.) (including post-processing such as plating) and as a material for forming an insulating layer. It can also be applied to adhesion and sealing applications of optical devices that require transparency.

[0102] For example, for the adhesion application, the protective film of the thermosetting adhesive sheet is peeled off, and the exposed tree A grease composition layer (adhesive layer) is laminated on one side of an object to be adhered (e.g., a semiconductor, an electronic component, etc.). The lamination method may be a batch type or a continuous type using a roll. After lamination, the support of the thermosetting adhesive sheet is peeled off, and the other side of the object to be adhered (e.g., a semiconductor, an electronic component, etc.) is laminated on the exposed resin composition layer (adhesive layer). After lamination, the resin composition layer (adhesive layer) is cured. The curing of the resin composition layer (adhesive layer) is usually carried out by heat curing. As the means, for example, a hot air circulation oven, an infrared heater, a heat gun, a high-frequency induction heating device, heating by pressure bonding with a heat tool, etc. can be mentioned. From the viewpoint of adhering the cured resin composition layer (cured product layer) to the object to be adhered with a sufficiently satisfactory adhesive strength, the curing temperature is preferably 50 °C or higher, more preferably 55 °C or higher, the curing time is preferably 10 minutes or longer, and more preferably 20 minutes or longer. In this way, with the thermosetting adhesive sheet of the present invention, lamination of a semiconductor and adhesion of electronic components (between the same kind of materials and between different kinds of materials) in an electronic device can be carried out. The cured product layer of the resin composition can also function as an insulating layer.

[0103] Alternatively, for example, for a sealing application, the protective film of the thermosetting adhesive sheet is peeled off, and the exposed resin composition layer is laminated on an object to be sealed (e.g., an electronic device, etc.). The lamination method may be a batch type or a continuous type using a roll. After lamination, the support of the thermosetting adhesive sheet is peeled off, or when the support is incorporated into the object to be sealed as a barrier film or the like, it is not peeled off, and the resin composition layer is cured. The curing of the resin composition layer is usually carried out by heat curing. The means are as described for the above adhesion application. In this way, an object to be sealed (e.g., an electronic device, etc.) sealed with the thermosetting adhesive sheet of the present invention (including the cured product layer of the resin composition of the present invention) can be manufactured. The cured product layer of the resin composition can also function as an insulating layer.

Examples

[0104] Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited by the following examples, and it is also possible to appropriately modify and implement within the range that conforms to the above and below gists, and all of them are included in the technical scope of the present invention. In addition, "parts" and "%" in the amount of components mean "parts by mass" and "mass %" respectively unless otherwise specified.

[0105] <Component> The components used in the examples and comparative examples are shown below. (A) Thermosetting resin: · Mixture of liquid bisphenol A type epoxy resin and liquid bisphenol F type epoxy resin ("ZX-1059" manufactured by Nippon Steel Chemical Co., Ltd., epoxy equivalent: about 165, Tg: 155 °C) · Ultra-flexible epoxy resin ("YX7105" manufactured by Mitsubishi Chemical Corporation, Tg: 31 °C) (B) Thermoplastic resin having a glass transition temperature of 50 °C or higher: · Phenoxy resin solution ("YX7200B35" manufactured by Mitsubishi Chemical Corporation, solvent: MEK, non-volatile content: 35%, Tg: 156 °C) · Phenoxy resin ("FX-293" manufactured by Nippon Steel Chemical & Material Co., Ltd., Tg: 158 °C) · Phenoxy resin ("FX-310" manufactured by Nippon Steel Chemical & Material Co., Ltd., Tg: 108 °C) · Polyester resin ("UE-9820" manufactured by Unitika Ltd., Tg: 52 °C) (C) Thermoplastic resin having a glass transition temperature of less than 50 °C: · Phenoxy resin solution ("YX7180BH40" manufactured by Mitsubishi Chemical Corporation, solvent: mixed solvent of MEK and cyclohexanone, non-volatile content: 40%, Tg: 15 °C) · Polyester resin ("UE-3400" manufactured by Unitika Ltd., Tg: -20 °C) (D) Curing agent: · "2E4MZ" manufactured by Shikoku Kasei Kogyo Co., Ltd. (E) Curing accelerator: · "U-CAT3512T" manufactured by San-Apro Ltd. · "Salicylic acid" manufactured by Wako Pure Chemical Industries, Ltd.

[0106] <Example 1> Varnishes with the compounding ratios shown in the following table were prepared by the following procedure, and a thermosetting adhesive sheet was prepared using the obtained varnishes. The amounts (parts) of each component described in the following table indicate the amounts of non-volatile components of each component in the varnish. Specifically, a mixture of a liquid bisphenol A type epoxy resin and a liquid bisphenol F type epoxy resin (「ZX-1059」manufactured by Nippon Steel Chemical Co., Ltd.), a phenoxy resin solution (「YX7200B35」manufactured by Mitsubishi Chemical Corporation), and a phenoxy resin solution (「YX7180BH40」manufactured by Mitsubishi Chemical Corporation) were blended, and a mixture uniformly dispersed by a high-speed rotary mixer was obtained. Further, a curing accelerator (「U-CAT3512T」manufactured by San-Apro Ltd. and 「salicylic acid」manufactured by Wako Pure Chemical Industries, Ltd.) and a curing agent (「2E4MZ」manufactured by Shikoku Kasei Kogyo Co., Ltd.) were blended and uniformly dispersed by a high-speed rotary mixer to obtain a varnish of the resin composition.

[0107] The obtained varnish was uniformly applied onto the release surface of a support (a polyethylene terephthalate film treated with a silicone-based release agent, thickness 38 μm, hereinafter abbreviated as 「release PET film」) with a die coater so that the thickness of the dried resin composition layer would be 20 μm, dried at 80°C for 10 minutes, and then a release PET film was placed as a protective film on the surface of the obtained resin composition layer such that the release surface was in contact with the resin composition layer, to obtain a thermosetting adhesive sheet.

[0108] <Example 2> A thermosetting adhesive sheet with a resin composition layer thickness of 20 μm was prepared in the same manner as in Example 1, except that the phenoxy resin solution (「YX7200B35」manufactured by Mitsubishi Chemical Corporation) was changed to a phenoxy resin (「FX-293」manufactured by Nippon Steel Chemical & Material Co., Ltd.).

[0109] <Example 3> A thermosetting adhesive sheet with a resin composition layer thickness of 20 μm was prepared in the same manner as in Example 1, except that the phenoxy resin solution (「YX7200B35」manufactured by Mitsubishi Chemical Corporation) was changed to a phenoxy resin (「FX-310」manufactured by Nippon Steel Chemical & Material Co., Ltd.).

[0110] <Example 4> A thermosetting adhesive sheet with a resin composition layer thickness of 20 μm was produced in the same manner as in Example 1, except that the mixture of liquid bisphenol A type epoxy resin and liquid bisphenol F type epoxy resin (「ZX-1059」manufactured by Nippon Steel Chemical Co., Ltd.) was changed to a super-flexible epoxy resin (「YX7105」manufactured by Mitsubishi Chemical Corporation).

[0111] <Example 5> A thermosetting adhesive sheet with a resin composition layer thickness of 20 μm was produced in the same manner as in Example 1, except that the usage amount of the phenoxy resin solution (「YX7200B35」manufactured by Mitsubishi Chemical Corporation) was changed from 5 parts to 10 parts, and the usage amount of the phenoxy resin solution (「YX7180BH40」manufactured by Mitsubishi Chemical Corporation) was changed from 15 parts to 10 parts.

[0112] <Example 6> A thermosetting adhesive sheet with a resin composition layer thickness of 20 μm was produced in the same manner as in Example 1, except that the usage amount of the phenoxy resin solution (「YX7200B35」manufactured by Mitsubishi Chemical Corporation) was changed from 5 parts to 15 parts, and the usage amount of the phenoxy resin solution (「YX7180BH40」manufactured by Mitsubishi Chemical Corporation) was changed from 15 parts to 5 parts.

[0113] <Example 7> A thermosetting adhesive sheet with a resin composition layer thickness of 20 μm was produced in the same manner as in Example 6, except that the phenoxy resin solution (「YX7200B35」manufactured by Mitsubishi Chemical Corporation) was changed to a polyester resin (「UE-9820」manufactured by Unitika Ltd.), and the phenoxy resin solution (「YX7180BH40」manufactured by Mitsubishi Chemical Corporation) was changed to a polyester resin (「UE-3400」manufactured by Unitika Ltd.).

[0114] <Comparative Example 1> An attempt was made to produce a thermosetting adhesive sheet in the same manner as in Example 1, except that the formulation was changed to exclude the phenoxy resin solution (「YX7200B35」manufactured by Mitsubishi Chemical Corporation).

[0115] <Comparative Example 2> A thermosetting adhesive sheet with a resin composition layer thickness of 20 μm was produced in the same manner as in Example 1, except that the formulation was changed to exclude the phenoxy resin solution (「YX7180BH40」manufactured by Mitsubishi Chemical Corporation).

[0116] Regarding the thermosetting adhesive sheets obtained in the examples and comparative examples, the film properties (whether the formation as a thermosetting adhesive sheet was good or not), and warpage were evaluated by the following methods. Whether the formation as a thermosetting adhesive sheet was good or not, and warpage were evaluated by the following methods.

[0117] <Evaluation of film properties> The states of the thermosetting adhesive sheets prepared in the examples and comparative examples were evaluated according to the following criteria. 〇 (Good): Film formation was good and it could be used as a thermosetting adhesive sheet × (Bad): Film formation was possible, but the tackiness was strong and it could not be used as a thermosetting adhesive sheet, or film formation was impossible

[0118] <Evaluation of warpage> The varnish of the resin composition prepared in the example or comparative example was applied onto a PET film (「Lumirror Film 188μm」manufactured by AS ONE Corporation) with a die coater so that the thickness of the resin composition layer after drying would be 20 μm, and dried at 80 °C for 10 minutes to obtain a resin sheet having a laminated structure of 「PET film / resin composition layer」.

[0119] The obtained resin sheet was cut into a 5 cm square, and two adjacent sides out of the four sides were taped to a flat substrate, and the resin composition layer was thermoset by heating in an oven at 100 °C for 60 minutes to obtain a laminate having a laminated structure of 「PET film / cured product layer」. After taking out the laminate from the oven and allowing it to cool, the height at which the corner not in contact with the tape warped up was measured and evaluated according to the following criteria. ○ (Good): The warpage height was less than 5 mm × (Bad): The warpage height was 5 mm or more

[0120] <Measurement of total light transmittance> The resin composition layer of the thermosetting adhesive sheet produced in the examples and comparative examples was laminated onto a glass plate (a microslide glass with a length of 76 mm, a width of 26 mm, and a thickness of 1.2 mm (White Slide Glass S1112 Edge Grinding No. 2 manufactured by Matsunami Glass Industry Co., Ltd.)) using a batch-type vacuum laminator (V-160 manufactured by Nichigo-Morton Co., Ltd.) such that the resin composition layer was in contact with the glass plate. The lamination conditions were a temperature of 80°C, a decompression time of 30 seconds, and then a pressure of 0.3 MPa for 30 seconds of pressurization. Thereafter, the PET film was peeled off, and the light transmittance spectrum of the exposed resin composition layer was measured using a haze meter HZ-V3 (halogen lamp) manufactured by Suga Test Instruments Co., Ltd. in accordance with JIS K7361-1, and the total light transmittance (%) of D65 light was calculated and shown in the following table.

[0121]

Table 1

[0122] From the results in Table 1, it can be seen that the thermosetting adhesive sheet of the example of the present invention has good evaluations in terms of film properties and warpage. It is found to be favorable.

Industrial Applicability

[0123] The resin composition of the present invention can be formed into a sheet-like form, and can suppress warpage when bonding between base materials or forming an insulating layer, particularly when bonding between base materials of different materials or forming an insulating layer. Therefore, the resin composition and the thermosetting adhesive sheet having a resin composition layer formed from the resin composition are useful for bonding between components and forming an insulating layer in electronic devices.

Claims

1. A resin composition comprising (A) a thermosetting resin, (B) a thermoplastic resin having a glass transition temperature of 50°C or higher, (C) a thermoplastic resin having a glass transition temperature of less than 50°C, and (D) a curing agent.

2. The resin composition according to claim 1, wherein (A) the thermosetting resin includes a thermosetting resin having a glass transition temperature of 50°C or higher.

3. The resin composition according to claim 1 or 2, wherein (A) the thermosetting resin is an epoxy resin.

4. The resin composition according to any one of claims 1 to 3, wherein (B) the thermoplastic resin having a glass transition temperature of 50°C or higher is selected from a phenoxy resin and a polyester resin having a glass transition temperature of 50°C or higher.

5. The resin composition according to any one of claims 1 to 4, wherein (C) the thermoplastic resin having a glass transition temperature of less than 50°C is selected from a phenoxy resin and a polyester resin having a glass transition temperature of less than 50°C.

6. The resin composition according to any one of claims 1 to 5, wherein (D) the curing agent is one or more selected from an ionic liquid, an acid anhydride compound, an imidazole compound, a tertiary amine-based compound, and a dimethylurea compound.

7. The resin composition according to any one of claims 1 to 6, wherein the content of (A) the thermosetting resin in the resin composition is 10 to 70% by mass based on 100% by mass of the non-volatile content of the resin composition.

8. The resin composition according to any one of claims 1 to 7, wherein the content of (B) the thermoplastic resin having a glass transition temperature of 50°C or higher in the resin composition is 3 to 50% by mass based on 100% by mass of the non-volatile content of the resin composition.

9. The resin composition according to any one of claims 1 to 8, wherein the content of (C) the thermoplastic resin having a glass transition temperature of less than 50°C in the resin composition is 10 to 60% by mass based on 100% by mass of the non-volatile content of the resin composition.

10. The resin composition according to any one of claims 1 to 9, wherein the mass ratio of (B) the thermoplastic resin having a glass transition temperature of 50°C or higher to (C) the thermoplastic resin having a glass transition temperature of less than 50°C in the resin composition is 1:20 to 1:0.

2.

11. The resin composition according to any one of claims 1 to 10, wherein the content of (D) the curing agent in the resin composition is 0.1 to 40% by mass based on 100% by mass of the non-volatile content of the resin composition.

12. The resin composition according to any one of claims 1 to 11, further comprising (E) a curing accelerator.

13. The resin composition according to claim 12, wherein the content of the (E) curing accelerator in the resin composition is 0.05 to 10% by mass based on 100% by mass of the nonvolatile content of the resin composition.

14. A thermosetting adhesive sheet having a resin composition layer formed from the resin composition according to any one of claims 1 to 13.

15. An electronic device having a cured product of the resin composition according to any one of claims 1 to 13.

Images