TW202300591A - resin composition - Google Patents

Abstract

The present invention addresses the problem of providing a resin composition in which the water absorption of a cured product is low. A resin composition containing (A) an epoxy resin, (B) a thiol compound, (C) a silane coupling agent, and (D) a silicone powder.

Description

resin composition

This invention relates to resin compositions.

Epoxy resin compositions using a thiol compound as a curing agent are used in various applications such as adhesives for assembling electronic devices due to their excellent low-temperature curability and rapid curability (see, for example, Patent Document 1). Electronic devices and the like are being miniaturized, mobile, and wearable, and are being used in more diverse environments than ever before. As a result, drop impact resistance and thermal shock resistance are sometimes required for adhesives used for electronic devices and the like. In order to realize these characteristics, the epoxy resin composition is required to have a low modulus of elasticity after curing. [Prior Art Literature] [Patent Document]

Patent Document 1: Japanese Patent Application Laid-Open No. 11-256013

[Problem to be Solved by the Invention]

However, in an epoxy resin composition containing a thiol compound, if the composition of the epoxy resin composition is designed so that the modulus of elasticity after curing becomes low, the water absorption after curing tends to increase. If the water absorption rate is high, the adhesiveness may decrease due to swelling or deterioration. For example, in the case of an electronic device application, the water absorption rate has a great influence on reliability. Therefore, an object of the present invention is to provide a technology capable of reducing the modulus of elasticity without increasing the water absorption in an epoxy resin composition having a thiol compound. [Means to solve the problem]

The inventors of the present invention conducted in-depth studies, and found that using a resin composition containing (A) epoxy resin, (B) thiol compound, (C) silane coupling agent, and (D) silicone powder , the above-mentioned problems can be solved, and the present invention has been completed. That is, the present invention includes the following matters. [1] A resin composition containing: (A) epoxy resin, (B) thiol compound, (C) silane coupling agent and (D) silicone powder. [2] The resin composition according to [1], which contains (E) a latent hardening accelerator. [3] The resin composition according to [1] or [2], which contains (F) a stabilizer. [4] The resin composition according to any one of [1] to [3], wherein the component (B) contains: (B-1) a thiol compound having three or more thiol groups in the molecule, and (B-2) a thiol compound having two thiol groups in the molecule. [5] The resin composition according to [4], wherein the component (B-1) has a ring skeleton in a molecule. [6] The resin composition according to [4] or [5], wherein the component (B-1) does not have an ester bond in the molecule. [7] The resin composition according to any one of [4] to [6], wherein the component (B-2) does not have a ring skeleton in the molecule. [8] The resin composition according to any one of [4] to [7], wherein the component (B-2) does not have an ester bond in the molecule. [9] The resin composition according to any one of [5] to [8], wherein the component (B-1) and the component (B-2) do not have a hydroxyl group. [10] The resin composition according to any one of [1] to [9], wherein the component (C) has an epoxy group. [11] The resin composition according to any one of [1] to [10], which contains 1 to 10% by mass of the component (C) relative to 100% by mass of non-volatile components of the resin composition. [12] The resin composition according to any one of [1] to [11], which contains 5 to 20% by mass of component (D) relative to 100% by mass of non-volatile components of the resin composition. [13] An adhesive comprising the resin composition according to any one of [1] to [12]. [14] A sealing material comprising the resin composition according to any one of [1] to [12]. [15] A cured product obtained by thermosetting the resin composition according to any one of [1] to [12]. [16] An electronic component comprising the cured product described in [15]. [Effect of the invention]

According to the present invention, it is possible to provide a technique for reducing the modulus of elasticity without increasing the water absorption in an epoxy resin composition having a thiol compound.

One embodiment of the present invention will be described below. The resin composition according to this embodiment contains (A) epoxy resin, (B) thiol compound, (C) silane coupling agent, and (D) silicone powder.

By employing the composition as described above, a resin composition having a low elastic modulus after curing and a low water absorption rate can be provided.

Each component of the resin composition will be described in detail below.

(A) epoxy resin The epoxy resin is not particularly limited as long as it has at least one epoxy group in the molecule. It is preferable to use an epoxy resin having an average of two or more epoxy groups per molecule as the epoxy resin.

As the epoxy resin, for example, polyhydric phenols such as bisphenol A, bisphenol F, bisphenol AD, catechol and resorcinol, glycerin, and polyhydric alcohols such as polyethylene glycol are mixed with epoxy chloride. Polyglycidyl ether obtained by reacting propane; glycidyl ether ester obtained by reacting hydroxycarboxylic acids such as p-hydroxybenzoic acid and β-hydroxynaphthoic acid with epichlorohydrin; making phthalic acid, terephthalic acid Polyglycidyl esters of polycarboxylic acids such as formic acid reacted with epichlorohydrin; epoxidized phenol novolac resins; epoxidized cresol novolak resins; epoxidized polyolefins; cycloaliphatic epoxy resins; other urethane-modified epoxy resin, etc., but not limited to these.

As the epoxy resin, from the viewpoint of maintaining high heat resistance and low moisture permeability, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac (phenol novolac) type epoxy resin, Biphenyl aralkyl type epoxy resin, phenol aralkyl type epoxy resin, aromatic glycidylamine type epoxy resin, epoxy resin with dicyclopentadiene structure, etc., more preferably bisphenol A type epoxy resin resin and bisphenol F epoxy resin.

The epoxy equivalent of the epoxy resin is, for example, 50 to 1000 g/eq, preferably 100 to 750 g/eq, more preferably 150 to 500 g/eq. Here, epoxy equivalent is the mass of the epoxy resin per epoxy group, and can measure based on JISK7236 (2009).

Epoxy resins can be either liquid or solid. In addition, both liquid resin and solid resin can also be used. Here, "liquid" and "solid" are states of the epoxy resin at room temperature. From the viewpoint of applicability, workability, and adhesiveness, it is preferable that at least 10 mass % or more of the entire epoxy resin used is in a liquid state. Specific examples of the liquid epoxy resin include liquid bisphenol A epoxy resin (Mitsubishi Chemical Corporation "jER828EL", Mitsubishi Chemical Corporation "jER827"), liquid bisphenol F epoxy resin (Mitsubishi Chemical Corporation "jER807" manufactured by DIC Corporation), naphthalene-type difunctional epoxy resins ("HP4032" and "HP4032D" manufactured by DIC Corporation), liquid bisphenol A epoxy resins/bisphenol F epoxy resins (" ZX1059"), and a hydrogenated epoxy resin ("jERYX8000" manufactured by Mitsubishi Chemical Corporation). Among them, "jER828EL" manufactured by Mitsubishi Chemical Corporation and "jER807" manufactured by Mitsubishi Chemical Corporation, which have high heat resistance and low viscosity, are preferable. In addition, specific examples of solid epoxy resins include naphthalene-type tetrafunctional epoxy resins ("HP4700" manufactured by DIC Corporation), dicyclopentadiene-type polyfunctional epoxy resins ("HP7200" manufactured by DIC Corporation), Naphthol-type epoxy resin ("ESN-475V" manufactured by Nippon Steel Chemicals Co., Ltd.), epoxy resin having a butadiene structure ("PB-3600" manufactured by Daicel Chemical Co., Ltd.), biphenyl resin Epoxy resins ("NC3000H" and "NC3000L" manufactured by Nippon Kayaku Co., Ltd., "jERYX4000" manufactured by Mitsubishi Chemical Corporation) and the like.

When the non-volatile content of the resin composition is 100% by mass, the content of the epoxy resin is, for example, 5% by mass or more, preferably 10% by mass or more, more preferably 20% by mass or more, even more preferably 30% by mass or more, In particular, it is more preferably 40% by mass or more, particularly preferably 45% by mass or more. In addition, the content of the epoxy resin is, for example, 95% by mass or less, preferably 90% by mass or less, more preferably 85% by mass or less, still more preferably 80% by mass or less, even more preferably 75% by mass or less, particularly preferably 70% by mass. Mass% or less.

(式(1)和(2)中，X、X ₁和X ₂可以相同也可以不同，是在主骨架中包含4個以上的-(CH ₂)-的二價的非芳香族烴基，Ar、Ar1和Ar2可以相同也可以不同，是在主骨架中包含二價芳香族基的二價的含芳香族的烴基，n和m各自獨立地為1~20的整數) 此處，「主骨架」是指在兩末端具有環氧基的骨架中鏈長最長的骨架。 In one embodiment, an epoxy resin represented by the following formula (1) or (2) can be used as the epoxy resin.

(In formulas (1) and (2), X, _X1 and _X2 can be the same or different, and are divalent non-aromatic hydrocarbon groups containing more than 4 -(CH ₂ )- in the main skeleton, Ar , Ar1 and Ar2 may be the same or different, and are divalent aromatic-containing hydrocarbon groups containing divalent aromatic groups in the main skeleton, and n and m are each independently an integer of 1 to 20) Here, "the main skeleton "" means the skeleton with the longest chain length among the skeletons having epoxy groups at both ends.

Preferably, the "divalent non-aromatic hydrocarbon group containing 4 or more -(CH ₂ )- in the main skeleton" in X, X ₁ and X ₂ is selected from: (b1)-O-CH(- CH ₃ )-(O-(CH ₂ ) _p ) _q -O-CH(-CH ₃ )-, (b2)-(O-(CH ₂ ) _r ) _s -, (b3)-(O-CH ₂ -CH(-CH ₃ )) _t -, (b4)-O-CH ₂ -CH(-OH)-CH ₂ -(O-(CH ₂ ) _u ) _v -O-CH ₂ -CH(-OH) -CH ₂ -, (b5)-(O-(CH ₂ ) _w ) _y -O-CH ₂ -CH(-OH)-, and (b6)-(O-CH ₂ -CH(-CH ₃ )) zO—CH ₂ —CH(—OH)— (provided that p, q, r, s, t, u, v, w, y, and z are each independently an integer of 1 to 20).

In addition, in the "divalent aromatic-containing hydrocarbon group containing a divalent aromatic group in the main skeleton" in Ar, Ar1 and Ar2, examples of the aromatic group include phenylene, naphthyl, anthracenyl , Biphenyl. The phenylene group can be ortho, meta or para phenylene. Two or more of these aromatic groups may be included in the divalent aromatic-containing hydrocarbon group. When two or more aromatic groups are included, the aromatic groups may be directly bonded to each other, or via two carbons bonded by an alkylene group, an ether bond, an ester bond, an amide bond, a double bond, or a triple bond, etc. And bond. Examples of particularly preferable divalent aromatic-containing hydrocarbon groups include structures represented by the following formulas (3) and (4).

In another embodiment, as the epoxy resin, a modified bisphenol-type epoxy resin represented by the following formula (5) can be used.

Here, Y in the formula (5) is an aliphatic hydrocarbon, and Z represents CH ₂ or C(CH ₃ ). Moreover, n is the range of 0-10, Preferably it is 1-8. Specific examples of such an epoxy resin include, for example, YL7175-500 and YL7175-1000 (both are made by Japan Epoxy Resin Co., Ltd.).

In a preferred embodiment, two types of epoxy resins (first epoxy resin and second epoxy resin) are used as the epoxy resin.

The epoxy equivalent of the first epoxy resin is, for example, 300-1000 g/eq, preferably 300-700 g/eq, more preferably 350-600 g/eq. The viscosity of the first epoxy resin is, for example, 5,000 to 50,000 mPa·s at 25° C. (E-type viscometer), preferably 10,000 to 30,000 mPa·s. When the non-volatile content of the resin composition is 100% by mass, the content of the first epoxy resin is, for example, 5 to 40% by mass, preferably 10 to 30% by mass, more preferably 10 to 25% by mass, and even more preferably 10~20% by mass. As a specific example of a 1st epoxy resin, "EXA-4850-150" (made by DIC Corporation, epoxy equivalent 450g/eq) is mentioned.

The epoxy equivalent of the second epoxy resin is, for example, 50-300 g/eq, preferably 100-250 g/eq, more preferably 100-200 g/eq. The viscosity of the second epoxy resin is, for example, 500 to 5,000 mPa·s at 25°C (E-type viscometer), preferably 1,000 to 3,000 mPa·s. When the non-volatile content of the resin composition is 100% by mass, the content of the second epoxy resin is, for example, 10 to 60% by mass, preferably 20 to 50% by mass, more preferably 30 to 50% by mass, and even more preferably 30~45% by mass. As a specific example of a 2nd epoxy resin, "ZX-1059" (made by Nippon Steel Chemicals Co., Ltd., epoxy equivalent 165 g/eq) is mentioned, for example.

(B) Thiol compound The thiol compound is not particularly limited as long as it is a compound that is cross-linked or polymerized with an epoxy group. As the thiol compound, it is preferably a thiol compound having 2 to 6 (difunctional to hexafunctional) thiol groups in one molecule, and more preferably 2 to 5 (difunctional to hexafunctional) thiol groups in one molecule. Pentafunctional) thiol compounds.

For example, as the thiol compound, a group selected from trimethylolpropane tris (3-mercaptopropionate) (abbreviation: TMTP), pentaerythritol tetrakis (3-mercaptopropionate) (abbreviation: PEMP), dipentaerythritol hexa (3-mercaptopropionate) (abbreviation: DPMP), tris-[(3-mercaptopropionyloxy)-ethyl]-isocyanurate (abbreviation: TEMPIC), tris(3-mercaptopropyl) Isocyanurate (abbreviation: TMPIC), ethylene glycol bisthioglycolate (abbreviation: EGTG), trimethylolpropane trimercaptoglycolate (abbreviation: TMTG), pentaerythritol tetramercaptoethanol ester (abbreviation: PETG), pentaerythritol tetrakis(3-mercaptobutyrate), 1,4-bis(3-mercaptobutyryloxy)butane, 1,3,5-tris(3-mercaptobutyryloxy) ethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, trimethylolpropane tris(3-mercaptobutyrate) (abbreviation: TPMB), Trimethylolethane tris(3-mercaptobutyrate) (abbreviation: TEMB), 1,3,4,6-tetrakis(2-mercaptoethyl) glycoluril, and 4,4'-isopropylidene At least one of the group consisting of bis[(3-mercaptopropoxy)benzene].

The above-mentioned thiol compound can be synthesized by a known method, and a commercially available product can be used. Tris(3-mercaptopropyl) isocyanurate (abbreviation: TMPIC), 4,4'-isopropylidene bis[(3-mercaptopropoxy)benzene] can be used, for example, Japanese Patent Application No. 2012-153794 It was synthesized by the method described in the gazette and International Publication No. 2001/00698. Examples of commercially available products include: PEMP manufactured by SC Organic Chemicals, OTG, EGTG, TMTG, PETG, 3-MPA, TMTP, PETP manufactured by SC Organic Chemicals Co., Ltd., TEMP manufactured by Sakai Chemical Industry Co., Ltd., PEMP, TEMPIC, DPMP, Showa Denko PE-1 (pentaerythritol tetrakis (3-mercaptobutyrate)), BD-1 (1,4-bis (3-mercaptobutyryloxy) butane), NR-1 (1 ,3,5-tris(3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione), TPMB, TEMB, Shikoku TS-G (1,3,4,6-tetrakis(2-mercaptoethyl)glycoluril) manufactured by Kasei Kogyo Co., Ltd., etc.

In a preferred embodiment, (B-1) a thiol compound having three or more thiol groups in the molecule (hereinafter referred to as a polyfunctional thiol compound) and (B-2) can be used as the thiol compound. A combination of thiol compounds (difunctional thiol compounds) having two thiol groups in the molecule.

(B-1) Multifunctional thiol compound The polyfunctional thiol compound is not particularly limited as long as it is a compound having three or more thiol groups (trifunctional or more) in the molecule. The polyfunctional thiol compound is preferably tri-hexafunctional, more preferably tri-tetrafunctional, and most preferably trifunctional.

The molecular weight of the polyfunctional thiol compound is, for example, 200-700, preferably 250-500, more preferably 300-400.

The thiol group equivalent (functional group equivalent) of the polyfunctional thiol compound is, for example, 50 to 300 g/eq, preferably 70 to 200 g/eq, and more preferably 80 to 150 g/eq. It should be noted that the thiol group equivalent is a value representing the mass of the thiol compound per one thiol group, and is a value obtained by dividing the molecular weight of the thiol compound by the number of thiol groups contained in one molecule of the compound. .

Preferably, the polyfunctional thiol compound does not have an ester bond in the molecule. In the present invention, an ester bond means a bond represented by "-C(=O)O-".

Preferably, the polyfunctional thiol compound does not have a hydroxyl group in the molecule. When there is no hydroxyl group in the molecule, it tends to be easy to obtain a good pot life, and it is easy to achieve both the life of the resin composition and the rapid hardening property.

Preferable polyfunctional thiol compounds are compounds having a ring skeleton. The ring skeleton may be any of an alicyclic skeleton, an aromatic ring skeleton, a heteroaromatic skeleton, and a heterocyclic skeleton, preferably an aromatic ring skeleton, a heteroaromatic skeleton, or a heterocyclic skeleton, and more preferably a heterocyclic skeleton. In the case of having a ring skeleton, the shear adhesion improves. Examples of such a compound having a heterocyclic skeleton include monocyclic or bicyclic compounds having a 5- to 8-membered ring and containing at least one nitrogen atom as a ring atom. More specifically, examples of the compound having a heterocyclic skeleton include compounds containing an isocyanuric acid ring skeleton or a glycoluril skeleton.

上式(6)中，R ₁、R ₂和R ₃各自獨立地表示碳數1~6，優選碳數1~5的直鏈或支鏈的二價烴基。烴基中可以進一步包含1個以上的下述(6a)~(6c)所示的二價基。

作為上述式所示的多官能硫醇化合物，具體可舉出三(3-巰基丙基)異氰脲酸酯。 For example, the compound represented by following formula (6) is mentioned as a suitable polyfunctional thiol compound.

In the above formula (6), R ₁ , R ₂ and R ₃ each independently represent a linear or branched divalent hydrocarbon group having 1 to 6 carbons, preferably 1 to 5 carbons. The hydrocarbon group may further contain one or more divalent groups shown in the following (6a) to (6c).

Specific examples of the polyfunctional thiol compound represented by the above formula include tris(3-mercaptopropyl)isocyanurate.

The content of the (B-1) polyfunctional thiol compound in the resin composition is not particularly limited, and can be adjusted according to the type of epoxy resin, (B-2) bifunctional thiol compound, and the like. For example, when the content of (A) epoxy resin is set as 100 parts by mass, the content of (B-1) polyfunctional thiol compound is preferably 0.1 to 100 parts by mass, more preferably 1 to 60 parts by mass, even more preferably 10~50 parts by mass. In addition, when the sum of the number of thiol groups of the (B-1) polyfunctional thiol compound contained in the resin composition and the number of thiol groups of the (B-2) bifunctional thiol compound is set to "1", ( B-1) The proportion of the number of thiol groups in multifunctional thiol compounds (the total number of thiol groups in the B-1 component/(the total thiol group number in the B-1 component+the total thiol group in the B-2 component The number)) is, for example, 0.1 to 0.9, preferably 0.2 to 0.8, more preferably 0.3 to 0.7. Here, the number of thiol groups represents a value obtained by dividing the mass parts of thiol compounds contained in the composition by the thiol equivalent (mass parts of thiol/thiol equivalent). In addition, when the composition contains multiple types of thiol compounds as the B-1 component or the B-2 component, it means the sum of the values obtained by dividing the mass parts of each thiol by the equivalent weight of each thiol group.

(B-2) Difunctional thiol compound The difunctional thiol compound is not particularly limited as long as it contains two thiol groups in the molecule.

From the viewpoint of suppressing odor, the molecular weight of the difunctional thiol compound is preferably 130 or more, more preferably 140 or more, still more preferably 150 or more, and most preferably 160 or more. In addition, the molecular weight of the difunctional thiol compound is, for example, 1,000 or less, preferably 500 or less, more preferably 300 or less, and still more preferably 230 or less, from the viewpoint of obtaining good rapid hardening properties. In addition, the molecular weight of the difunctional thiol compound may be in a range selected from the above upper and lower limits, for example, 130 to 1000, preferably 140 to 500, more preferably 150 to 300, most preferably 160 or more And below 230.

The thiol equivalent of the difunctional thiol compound is, for example, 70 to 300 g/eq, preferably 80 to 200 g/eq, more preferably 85 to 150 g/eq.

Preferably, the difunctional thiol compound does not have a hydroxyl group in the molecule. When there is no hydroxyl group in the molecule, it tends to be easy to obtain a good pot life, and it is easy to achieve both the longevity and the rapid curing property of the resin composition.

Preferably, the difunctional thiol compound does not have an ester bond in the molecule. In the absence of an ester bond, hydrolysis due to the ester bond does not occur, so moisture resistance can be improved, and reliability can be further improved.

Preferably, the difunctional thiol compound does not have a ring skeleton in the molecule. When not having a ring skeleton, the skeleton becomes soft, and a resin composition having further excellent peel strength can be obtained.

應予說明，式(7)中，R ₄表示碳數3~16，優選碳數4~12的直鏈或支鏈的二價烴基。烴基中可以包含1個以上的下述(7a)~(7c)所示的二價基。R ₄優選為直鏈的烴基、或包含1個以上的下述(7a)所示的二價基的直鏈的烴基。

Examples of suitable difunctional thiol compounds include compounds represented by the following formula (7).

It should be noted that in the formula (7), R ₄ represents a straight-chain or branched divalent hydrocarbon group with 3 to 16 carbons, preferably 4 to 12 carbons. One or more divalent groups shown in the following (7a) to (7c) may be included in the hydrocarbon group. R ₄ is preferably a straight-chain hydrocarbon group or a straight-chain hydrocarbon group containing one or more divalent groups represented by the following (7a).

Specific examples of the difunctional thiol compound represented by the above formula (7) include 1,4-butanedithiol, 1,6-hexanedithiol, 1,8-octanedithiol, and 1 , 10-decanedithiol and 3,6-dioxa-1,8-octanedithiol and bis-2-mercaptoethyl sulfide, etc., preferably 1,8-octanedithiol and 1,10 -Decanedithiol and 3,6-dioxa-1,8-octanedithiol.

The content of the (B-2) difunctional thiol compound in the resin composition is not particularly limited. For example, when the content of (A) epoxy resin is set as 100 parts by mass, the content of (B-2) difunctional thiol compound is preferably 0.1 to 100 parts by mass, more preferably 1 to 60 parts by mass, even more preferably 5~30 parts by mass.

In addition, in the resin composition according to the present embodiment, the ratio of "the total number of thiol groups of component B" to "the number of epoxy groups of component A" (total number of thiol groups of component B/total number of epoxy groups of component A) The number of oxygen groups) is preferably 0.2 to 2.0, more preferably 0.6 to 1.2. Here, the number of epoxy groups represents a value obtained by dividing the mass parts of epoxy resin contained in the composition by the epoxy group equivalent (mass part of epoxy group/epoxy group equivalent). In addition, when the composition contains the epoxy resin of multiple types of A component, the number of epoxy groups shows the sum of the value which divided the mass part of each epoxy resin by each epoxy group equivalent.

(C) Silane coupling agent The silane coupling agent used in this embodiment is not particularly limited. Examples of silane coupling agents include: alkoxysilane compounds, aminosilane coupling agents, epoxy silane coupling agents, methacrylsilane coupling agents, vinyl silane coupling agents, benzene Vinyl silane coupling agent, acryl silane coupling agent, isocyanurate silane coupling agent, ureido silane coupling agent, mercapto silane coupling agent, and silane coupling agent in isocyanate silane coupling agent. Among these, silane coupling agents selected from the group consisting of aminosilane coupling agents, epoxysilane coupling agents, and methacrylsilane coupling agents are preferred. One type of silane coupling agent may be used alone, or two or more types may be used in combination.

The alkoxysilane compound refers to R _a SiX _4-a (wherein, R represents (i) a hydrogen atom; (ii) an alkyl group which may have a substituent selected from an alkoxy group and a halogen atom; and (iii) An aryl group that may have a substituent selected from an alkyl group, an alkoxy group, and a halogen atom, X represents an alkoxy group, and a represents an integer of 0 to 3.) The silane compound represented by, for example: methyl trimethyl Oxysilane (for example, Shin-Etsu Chemical Co., Ltd. "KBM-13"), dimethyldimethoxysilane (for example, Shin-Etsu Chemical Co., Ltd. "KBM-22"), phenyltrimethoxysilane (for example, Shin-Etsu Chemical Co., Ltd. "KBM103"), methyltriethoxysilane (for example, Shin-Etsu Chemical Co., Ltd. "KBE-13"), dimethyldiethoxysilane (for example, Shin-Etsu Chemical Co., Ltd. "KBE-13"-22"), phenyltriethoxysilane (for example, Shin-Etsu Chemical Co., Ltd. "KBE-103"), n-propyltrimethoxysilane (for example, Shin-Etsu Chemical Co., Ltd. "KBM-3033"), n- Propyltriethoxysilane (for example, Shin-Etsu Chemical Co., Ltd. "KBE-3033"), hexyltrimethoxysilane (for example, Shin-Etsu Chemical Co., Ltd. "KBM-3063"), hexyltriethoxysilane (for example, , Shin-Etsu Chemical Co., Ltd. "KBE-3063"), octyltriethoxysilane (for example, Shin-Etsu Chemical Co., Ltd. "KBE-3083"), decyltrimethoxysilane (for example, Shin-Etsu Chemical Co., Ltd. "KBE-3083"), decyltrimethoxysilane (for example, Shin-Etsu Chemical Co., Ltd. "KBM-3103C"), 1,6-bis(trimethoxysilyl)hexane (for example, "KBM-3066" manufactured by Shin-Etsu Chemical Co., Ltd.), 3,3,3-trifluoropropyltrimethoxysilane ( For example, "KBM-7103" manufactured by Shin-Etsu Chemical Co., Ltd.) and the like.

Aminosilane-based coupling agents refer to alkoxysilane compounds with amino groups, for example: N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane (for example, Shin-Etsu Chemical Co., Ltd. "KBM-602"), N-2-(aminoethyl)-3-aminopropyltrimethoxysilane (for example, Shin-Etsu Chemical Co., Ltd. "KBM-603"), 3- Aminopropyltrimethoxysilane (for example, Shin-Etsu Chemical Co., Ltd. "KBM-903"), 3-aminopropyltriethoxysilane (for example, Shin-Etsu Chemical Co., Ltd. "KBE-903"), 3 - Triethoxysilyl-N-(1,3-dimethyl-butylene) propylamine (for example, "KBE-9103" manufactured by Shin-Etsu Chemical Co., Ltd.), N-phenyl-3-aminopropyltrimethyl Oxysilane (for example, "KBM-573" manufactured by Shin-Etsu Chemical Co., Ltd.), N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride (for example, Shin-Etsu Chemical Co., Ltd. "KBM-575") and the like.

The epoxysilane-based coupling agent refers to a silane compound having an epoxy group, preferably an alkoxysilane compound having an epoxy group. Examples of epoxysilane-based coupling agents include 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (for example, "KBM-303" manufactured by Shin-Etsu Chemical Co., Ltd.), 3-epoxycyclohexyl Propoxypropylmethyldimethoxysilane (for example, "KBM-402" manufactured by Shin-Etsu Chemical Co., Ltd.), 3-glycidoxypropyltrimethoxysilane (for example, "KBM-402" manufactured by Shin-Etsu Chemical Co., Ltd. -403"), 3-glycidoxypropylmethyldiethoxysilane (for example, "KBE-402" manufactured by Shin-Etsu Chemical Co., Ltd.), 3-glycidoxypropyltriethoxysilane (for example, Shin-Etsu Chemical Co., Ltd. "KBE-403"), 8-glycidoxyoctyltrimethoxysilane (for example, Shin-Etsu Chemical Co., Ltd. "KBM-4083"), epoxy-modified alkoxy Oligomer type silane coupling agent (for example, "KR-517" manufactured by Shin-Etsu Chemical Co., Ltd.), glycidoxyoctyltrimethoxysilane (for example, "KBM-4803" manufactured by Shin-Etsu Chemical Co., Ltd.), and the like.

Methacryl silane coupling agent refers to alkoxysilane compounds with methacryl groups, for example: 3-methacryloxypropylmethyldimethoxysilane (for example, Shin-Etsu Chemical Industry Co., Ltd. "KBM-502"), 3-methacryloxypropyltrimethoxysilane (for example, Shin-Etsu Chemical Co., Ltd. "KBM-503"), 3-methacryloxypropyl Methyldiethoxysilane (for example, Shin-Etsu Chemical Co., Ltd. "KBE-502"), 3-methacryloxypropyl triethoxysilane (for example, Shin-Etsu Chemical Co., Ltd. "KBE-503" )wait.

Vinylsilane-based coupling agents refer to alkoxysilane compounds having a vinyl group, for example, vinyltrimethoxysilane (for example, "KBM-1003" manufactured by Shin-Etsu Chemical Co., Ltd.), vinyltriethoxysilane Silane (eg, "KBE-1003" manufactured by Shin-Etsu Chemical Co., Ltd.) and the like. The styrylsilane-based coupling agent refers to an alkoxysilane compound having a styryl group, and examples thereof include p-styryltrimethoxysilane (for example, "KBM-1403" manufactured by Shin-Etsu Chemical Co., Ltd.). The acrylsilane-based coupling agent refers to an alkoxysilane compound having an acryl group, for example, 3-acryloxypropyltrimethoxysilane (for example, "KBM-5103" manufactured by Shin-Etsu Chemical Co., Ltd.) wait.

The isocyanurate silane coupling agent refers to an alkoxysilane compound having an isocyanurate structure, such as tris(trimethoxysilylpropyl)isocyanurate (for example, Shin-Etsu Chemical Co., Ltd. "KBM-9659" made by the company), etc. The ureidosilane-based coupling agent refers to an alkoxysilane compound having a ureido group, and examples thereof include 3-ureidopropyltrialkoxysilane (for example, "KBE-585" manufactured by Shin-Etsu Chemical Co., Ltd.). The mercaptosilane-based coupling agent refers to an alkoxysilane compound having a mercapto group, for example, 3-mercaptopropylmethyldimethoxysilane (for example, "KBM-802" manufactured by Shin-Etsu Chemical Co., Ltd.), 3-mercapto Propyltrimethoxysilane (for example, "KBM-803" manufactured by Shin-Etsu Chemical Co., Ltd.) and the like. The isocyanate-based silane coupling agent is an alkoxysilane compound having an isocyanate structure, and examples thereof include 3-isocyanatopropyltriethoxysilane (for example, "KBE-9007N" manufactured by Shin-Etsu Chemical Co., Ltd.).

Among the above, a preferable silane coupling agent is an epoxy silane-based coupling agent. As an epoxysilane-based coupling agent, more preferably: 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane , 3-Glycidoxypropyltrimethoxysilane, 3-Glycidoxypropylmethyldiethoxysilane, 3-Glycidoxypropyltriethoxysilane, 8-cyclo Oxypropoxyoctyltrimethoxysilane, and an oligomer-type coupling agent with alkoxysilyl and epoxy groups.

The content of the silane coupling agent is, for example, 1 to 10% by mass, preferably 2 to 8% by mass, more preferably 4 to 6% by mass based on 100% by mass of non-volatile components of the resin composition.

(D) Organosilicon powder Organosilicon powder refers to a powdered organosilicon compound. Examples of the silicone powder include silicone rubber powder, silicone resin powder, and silicone composite powder. Silicone rubber powder is powder of a compound obtained by cross-linking linear molecules (for example, linear organopolysiloxane). Silicone resin powder is a powder of organosilicon compounds cross-linked into a three-dimensional network structure. Specific examples include: polyorganic polycarbonates having a three-dimensional network structure shown by siloxane bonds cross-linked into (RSiO _3/2 ) _n (R represents a substituted or unsubstituted monovalent hydrocarbon group, n is 1 to 18.) Silsesquioxane hardening micropowder, etc. The silicone composite powder is a powder having a structure in which the particle surface of the silicone rubber powder is coated with a silicone resin. Preferably, a silicone composite powder is used as the silicone powder.

The average particle size of the silicone powder is, for example, 0.05 μm or more, preferably 0.1 μm or more, more preferably 0.5 μm or more. In addition, the average particle size of the silicone powder is, for example, 100 μm or less, preferably 50 μm or less, more preferably 30 μm or less.

The content of the silicone powder is, for example, 5 to 25% by mass, preferably 5 to 20% by mass, more preferably 5 to 15% by mass based on 100% by mass of non-volatile components of the resin composition.

Specific examples of silicone powder include, for example, KMP-600 (manufactured by Shin-Etsu Chemical Co., Ltd.), KMP-601 (manufactured by Shin-Etsu Chemical Co., Ltd.), KMP-602 (manufactured by Shin-Etsu Chemical Co., Ltd.), KMP-605 (manufactured by Shin-Etsu Chemical Co., Ltd. Shin-Etsu Chemical Co., Ltd.), X-52-7030 (Shin-Etsu Chemical Co., Ltd.), etc.

(E) Latent Hardening Accelerator Preferably, the resin composition according to this embodiment contains a latent hardening accelerator. The latent hardening accelerator is an additive that does not contribute to the hardening of the epoxy resin at room temperature (20°C±15°C (JISZ8703), but has a function of accelerating the hardening of the epoxy resin when heated.

It is preferable to use a solid dispersion type latent hardening accelerator as the latent hardening accelerator. The solid-dispersed latent hardening accelerator is a solid that is insoluble in epoxy resin at room temperature, but is soluble by heating and functions as a hardening accelerator for epoxy resin. Examples of solid-dispersed latent curing accelerators include imidazole compounds that are solid at room temperature and solid-dispersed amine adduct-based latent curing accelerators, but are not limited thereto. Among these, solid-dispersed amine adduct-based latent hardening accelerators are preferable.

Examples of the aforementioned imidazole compounds that are solid at room temperature include: 2-heptadecylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-undecylimidazole, 2- Phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl-4-benzyl-5-hydroxymethylimidazole, 2,4-diamino-6-(2-methylimidazolyl- (1))-Ethyl-s-triazine, 2,4-diamino-6-(2'-methylimidazolyl-(1)')-ethyl-s-triazine・Isocyanuric acid addition 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole -trimellitate, 1-cyanoethyl-2-phenylimidazole-trimellitate, N-(2-methylimidazolyl-1-ethyl)-urea, N,N'-( 2-methylimidazolyl-(1)-ethyl)-adipamide, etc., but not limited to these.

Examples of solid-dispersed amine adduct-based latent hardening accelerators include reaction products of amine compounds and epoxy compounds (amine-epoxy adduct systems), and combinations of amine compounds and isocyanate compounds or urea compounds. Reaction products (urea-type adduct system), etc.

Regarding the epoxy compound used as one of the raw materials for the production of the aforementioned solid-dispersed amine adduct-based latent hardening accelerator (amine-epoxy adduct-based), for example, bisphenol A, bisphenol F, polyglycidyl ethers obtained by reacting polyphenols such as catechol and resorcinol, or polyols such as glycerin and polyethylene glycol with epichlorohydrin; make p-hydroxybenzoic acid, β-hydroxy Glycidyl ether esters obtained by reacting hydroxycarboxylic acids such as naphthoic acid with epichlorohydrin; polyglycidol obtained by reacting polycarboxylic acids such as phthalic acid and terephthalic acid with epichlorohydrin esters; 4,4'-diaminodiphenylmethane or m-aminophenol and other glycidylamine compounds reacted with epichlorohydrin; and epoxidized phenol novolak resin, epoxidized cresol novolac resin, Polyfunctional epoxy compounds such as epoxidized polyolefin, or monofunctional epoxy compounds such as butyl glycidyl ether, phenyl glycidyl ether, glycidyl methacrylate, etc., but not limited to these.

The amine compound used as the raw material for the production of the aforementioned solid-dispersed amine adduct-based latent hardening accelerator has at least one active hydrogen capable of addition reaction with an epoxy group in the molecule, and at least The amine compound may have one or more functional groups selected from primary amino groups, secondary amino groups, and tertiary amino groups in the molecule. Such amine compounds include, for example, diethylenetriamine, triethylenetetramine, n-propylamine, 2-hydroxyethylaminopropylamine, cyclohexylamine, 4,4'-diamino- Aliphatic amines such as dicyclohexylmethane; aromatic amine compounds such as 4,4'-diaminodiphenylmethane and 2-methylaniline; 2-ethyl-4-methylimidazole, 2-ethyl Heterocyclic compounds containing nitrogen atoms such as 4-methylimidazoline, 2,4-dimethylimidazoline, piperidine, piperazine, etc., but not limited to these.

In addition, among them, compounds having a tertiary amino group in the molecule are raw materials for providing latent hardening accelerators having excellent hardening accelerating ability, and examples of such compounds include, for example, dimethylaminopropylamine , diethylaminopropylamine, di-n-propylaminopropylamine, dibutylaminopropylamine, dimethylaminoethylamine, diethylaminoethylamine, N-methylpiperazine and other amine compounds, or 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole and other imidazole compounds such as primary or secondary amines with tertiary amino groups in the molecule; 2-Dimethylaminoethanol, 1-methyl-2-dimethylaminoethanol, 1-phenoxymethyl-2-dimethylaminoethanol, 2-diethylaminoethanol, 1 -Butoxymethyl-2-dimethylaminoethanol, 1-(2-hydroxy-3-phenoxypropyl)-2-methylimidazole, 1-(2-hydroxy-3-phenoxy Propyl)-2-ethyl-4-methylimidazole, 1-(2-hydroxy-3-butoxypropyl)-2-methylimidazole, 1-(2-hydroxy-3-butoxypropyl base)-2-ethyl-4-methylimidazole, 1-(2-hydroxy-3-phenoxypropyl)-2-phenylimidazoline, 1-(2-hydroxy-3-butoxypropyl base)-2-methylimidazoline, 2-(dimethylaminomethyl)phenol, 2,4,6-tris(dimethylaminomethyl)phenol, N-β-hydroxyethylmorpholine , 2-Dimethylaminoethanethiol, 2-Mercaptopyridine, 2-Benzimidazole, 2-Mercaptobenzimidazole, 2-Mercaptobenzothiazole, 4-Mercaptopyridine, N,N-Dimethylamine Benzoic acid, N,N-dimethylglycine, niacin, isonicotinic acid, picolinic acid, N,N-dimethylglycine hydrazide, N,N-dimethylpropionyl Alcohols, phenols, mercaptans, carboxylic acids, and hydrazines having a tertiary amino group in the molecule, such as hydrazine, nicotinic acid hydrazine, and isonicotinic acid hydrazine; and the like.

When the latent hardening accelerator is produced by addition-reacting the said epoxy compound and an amine compound, the active hydrogen compound which has 2 or more active hydrogens in a molecule|numerator may further be added. Examples of such active hydrogen compounds include bisphenol A, bisphenol F, bisphenol S, hydroquinone, catechol, resorcinol, pyrogallol, and phenol novolac resins. ) and other polyphenols, trimethylolpropane and other polyols, adipic acid, phthalic acid and other polycarboxylic acids, 1,2-dimercaptoethane, 2-mercaptoethanol, 1-mercapto-3-benzene Oxy-2-propanol, thioglycolic acid, anthranilic acid, lactic acid, etc., but not limited to these.

For the isocyanate compound used as the raw material for the aforementioned solid-dispersed amine adduct-based latent hardening accelerator, monofunctional compounds such as n-butyl isocyanate, isopropyl isocyanate, phenyl isocyanate, and benzyl isocyanate can also be used. Isocyanate compounds; hexamethylene diisocyanate, toluene diisocyanate, 1,5-naphthalene diisocyanate, diphenylmethane-4,4'-diisocyanate, isophorone diisocyanate, xylylene diisocyanate, Polyfunctional isocyanate compounds such as p-phenylene diisocyanate, 1,3,6-hexamethylene triisocyanate, and biscycloheptane triisocyanate; and terminal isocyanate groups obtained by reacting these polyfunctional isocyanate compounds with active hydrogen compounds compounds; and so on. Examples of such compounds containing terminal isocyanate groups include: addition compounds having terminal isocyanate groups obtained by the reaction of toluene diisocyanate and trimethylolpropane; compounds obtained by the reaction of toluene diisocyanate and pentaerythritol; Addition compounds having a terminal isocyanate group, etc., but are not limited to these.

In addition, examples of the urea compound used as a raw material for the production of the solid-dispersed amine adduct-based latent hardening accelerator include urea, thiourea, and the like, but are not limited thereto.

The solid-dispersed latent hardening accelerator can be easily obtained, for example, by mixing the above-mentioned production raw materials appropriately, reacting them at a temperature from room temperature to 200°C, cooling and hardening, and then pulverizing them, or by It is reacted in a solvent such as ethyl ethyl ketone, dioxane, tetrahydrofuran, etc., and after removing the solvent, the solid content is pulverized.

As a representative example commercially available as a solid dispersion type latent hardening accelerator, for example, as an amine-epoxy adduct system (amine adduct system), "Ajicure PN-F" (Ajinomoto Fine-Techno Co., Ltd. manufacturer), "Ajicure PN-23" (product name of Ajinomoto Fine-Techno Corporation), "Ajicure PN-H" (product name of Ajinomoto Fine-Techno Corporation), "Novacure HX-3742" (product name of Asahi Kasei Corporation) name), "Novacure HX-3721" (trade name manufactured by Asahi Kasei Co., Ltd.), and "Fujicure FXR-1020" (trade name manufactured by Fuji Chemical Co., Ltd.), "Fujicure FXR- 1030" (trade name manufactured by Fuji Chemical Co., Ltd.), etc., but not limited to these.

When the content of the epoxy resin (component A) is 100 parts by mass, the content of the latent hardening accelerator (component E) is preferably 0.1 to 100 parts by mass, more preferably 1 to 60 parts by mass, and even more preferably 5 to 60 parts by mass. 30 parts by mass.

(F) Stabilizer In order to achieve excellent storage stability, the resin composition according to this embodiment preferably further contains a compound selected from borate compounds, titanate compounds, aluminate compounds, zirconate compounds, isocyanate compounds, carboxylic acids, acid anhydrides, and mercapto groups. One or more stabilizers (component F) among organic acids.

Examples of the borate ester compound include trimethyl borate, triethyl borate, tri-n-propyl borate, triisopropyl borate, tri-n-butyl borate, tripentyl borate, and triallyl borate. , trihexyl borate, tricyclohexyl borate, trioctyl borate, trinonyl borate, tridecyl borate, tridodecyl borate, trihexadecyl borate, tri( octadecyl) ester, tris(2-ethylhexyloxy)borane, bis(1,4,7,10-tetraoxaundecyl)(1,4,7,10,13-penta Oxatetradecyl)(1,4,7-trioxaundecyl)borane, Tribenzyl borate, Triphenyl borate, Tri-o-cresyl borate, Tri-m-cresyl borate, Triethanolamine boric acid Esters etc.

Examples of the titanate compound include tetraethyl titanate, tetrapropyl titanate, tetraisopropyl titanate, tetrabutyl titanate, and tetraoctyl titanate.

As said aluminate compound, triethyl aluminate, tripropyl aluminate, triisopropyl aluminate, tributyl aluminate, trioctyl aluminate etc. are mentioned, for example.

As said zirconate compound, tetraethyl zirconate, tetrapropyl zirconate, tetraisopropyl zirconate, tetrabutyl zirconate, etc. are mentioned, for example.

Examples of the isocyanate compound include n-butyl isocyanate, isopropyl isocyanate, 2-chloroethyl isocyanate, phenyl isocyanate, p-chlorophenyl isocyanate, benzyl isocyanate, hexamethylene diisocyanate, 2- Ethylphenyl isocyanate, 2,6-dimethylphenyl isocyanate, 2,4-toluene diisocyanate, toluene diisocyanate, 2,6-toluene diisocyanate, 1,5-naphthalene diisocyanate, diphenylmethane- 4,4'-diisocyanate, benzylidine diisocyanate, isophorone diisocyanate, xylylene diisocyanate, p-phenylene diisocyanate, dicyclohetane triisocyanate, etc.

Examples of the aforementioned carboxylic acid include saturated aliphatic monobasic acids such as formic acid, acetic acid, propionic acid, butyric acid, caproic acid, and octanoic acid; unsaturated aliphatic monobasic acids such as acrylic acid, methacrylic acid, and crotonic acid; Halogenated fatty acids such as acetic acid and dichloroacetic acid; monobasic oxyacids such as glycolic acid and lactic acid; aliphatic aldehyde acids and keto acids such as glyoxylic acid and gluconic acid; aliphatic acids such as oxalic acid, malonic acid, succinic acid and maleic acid Polyacids; aromatic monobasic acids such as benzoic acid, halogenated benzoic acid, methylbenzoic acid, phenylacetic acid, cinnamic acid, mandelic acid; aromatic polybasic acids such as phthalic acid and trimesic acid, etc.

Examples of the acid anhydride include succinic anhydride, dodecenyl succinic anhydride, maleic anhydride, an adduct of methylcyclopentadiene and maleic anhydride, hexahydrophthalic anhydride, methyltetrahydro Aliphatic or aliphatic polybasic acid anhydrides such as phthalic anhydride, etc.; aromatic polybasic anhydrides such as phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, etc.

Examples of the aforementioned mercapto organic acid include mercapto aliphatic monocarboxylic acids such as mercaptoacetic acid, mercaptopropionic acid, mercaptobutyric acid, mercaptosuccinic acid, and dimercaptosuccinic acid. The obtained mercapto aliphatic monocarboxylic acid, mercapto aromatic monocarboxylic acid such as mercaptobenzoic acid, and the like.

As component F, among these, boric acid ester compounds are preferable from the viewpoint of high versatility, high safety, and improved storage stability, and triethyl borate, tri-n-propyl borate, triisopropyl borate, boric acid Tri-n-butyl, more preferably triethyl borate. The content of the F component is not particularly limited as long as the storage stability of the resin can be improved. When the content of the epoxy resin of the A component is 100 parts by mass, the content of the F component is preferably 0.001 to 50 parts by mass, more preferably 0.001 to 50 parts by mass. Preferably it is 0.05-30 mass parts, More preferably, it is 0.1-10 mass parts.

As a method of blending the component F into the resin composition, besides blending the components A to E at the same time, the latent hardening accelerator of the component E and the component F may be mixed in advance. As a mixing method at this time, it can be performed by bringing both into contact in a solvent such as methyl ethyl ketone or toluene, or in a liquid epoxy resin, or in the absence of a solvent.

(G) Other ingredients In the resin composition of this embodiment, fillers (for example, fumed silica), diluents, solvents, pigments, flexibility-imparting agents, coupling agents, and antioxidants commonly used in the field of the present invention can be added as needed. , Various additives such as thixotropy-imparting agents and dispersants.

There is no particular difficulty in preparing the resin composition according to this embodiment using the components A to D described above and components E to G as optional components as raw materials, and it can be performed based on conventionally known methods. For example, the components can be mixed with a mixer such as a Henschel mixer to prepare a resin composition.

The resin composition according to the present embodiment can be provided and used as a one-component resin composition. That is, the resin composition can be cured by applying heat or the like by applying the resin composition. Heating is suitable as follows: for example, heating at a temperature of 70-150° C., preferably 75-120° C., more preferably 80-100° C., for 1-60 minutes, preferably 3-45 minutes. The resin composition is preferably used as an adhesive for assembling electronic components.

This embodiment also includes a cured resin product obtained by heating the above-mentioned resin composition, and also includes a functional product including the cured resin product. Examples of functional products include adhesives, casting agents, encapsulants, sealants, resins for fiber reinforcement, coating agents, and paints. [Example]

Hereinafter, the present invention will be more specifically described based on examples, but the present invention is not limited to the following examples.

[Preparation of resin composition] Each component was mixed in the blending composition shown in Table 1, and the resin composition concerning Examples 1-5 and Comparative Examples 1-2 was prepared. The compounding quantity of each component in Table 1 is a mass part. The "tiol/epoxy column" in Table 1 represents the number of thiol groups/the number of epoxy groups. In addition, Table 2 shows the compounding quantity (mass part) of each component when the non-volatile content of a resin composition is made into 100 mass parts. In Table 3, the compounding quantity (mass part) of each component when an epoxy resin is made into 100 mass parts is shown.

Specifically, the epoxy resin, filler and silicone powder in the amounts shown in Table 1 were weighed into a dedicated plastic container. Then, they were thoroughly mixed at 2000 rpm for about 30 seconds to 1 minute at a room temperature of 25°C using a self-rotating and revolving mixer defoaming Sentaro (manufactured by THINKY Co., Ltd.; ARE-310), and kneaded with a three-roller mill to make them uniform. Disperse to obtain a roll dispersion. A silane coupling agent, a storage stabilizer, a hardening accelerator, and a mercaptan compound were added to this roll dispersion, and they were thoroughly mixed for about 30 seconds to 1 minute at 2000 rpm at a room temperature of 25° C. using a rotary revolution mixer. Finally, using an automatic revolution stirring defoamer HM-200W manufactured by Kyoritsu Seiki Co., Ltd., defoaming was carried out under vacuum (→ set to pressure 0), 900 rpm, and 2 minutes to obtain the target resin composition.

In addition, the details of the materials used are as follows. [A component epoxy resin] EXA-4850-150: Manufactured by DIC Corporation, epoxy equivalent 450g/eq, viscosity 15,000 (25°C, E-type viscometer, mPa・S), molecular weight 900 ZX-1059: bisphenol A type (BPA type)/bisphenol F type (BPF type) epoxy resin, epoxy equivalent 165g/eq, viscosity 1,900~2,600(mPa・s)

[B Component Thiol] TMPIC: manufactured by Ajinomoto Fine-Techno Co., Ltd., tris(3-mercaptopropyl)isocyanurate, functional group equivalent weight of thiol: 117g/eq

MR-93: Made by Daito Sangyo Co., Ltd., 3,6-dioxa-1,8-octanedithiol, thiol functional group equivalent weight 91g/eq

BD-1: Manufactured by Showa Denko Co., Ltd., 1,4-bis(3-mercaptobutyryloxy)butane, functional group equivalent of thiol 147g/eq

[C component modified silane coupling agent] KR-517: Shin-Etsu Chemical Co., Ltd., epoxy-modified alkoxy oligomer type silane coupling agent KBM-4803: Shin-Etsu Chemical Co., Ltd., glycidoxyoctyltrimethoxysilane

[Component D silicone powder] KMP-601: Shin-Etsu Chemical Co., Ltd., silicone composite powder, average particle size 12 μm KMP-605: Made by Shin-Etsu Chemical Co., Ltd., silicone composite powder, average particle size 2 μm

[E component hardening accelerator] PN-F: Ajinomoto Fine-Techno Co., Ltd., amine-epoxy adduct hardener

[F component storage stability improver] TEB: Tokyo Kasei Co., Ltd., triethyl borate

[Inorganic Filler] AEROSIL200: manufactured by Japan AEROSIL Corporation, fumed silicon dioxide

[Evaluation of modulus of elasticity] Each of the resin compositions obtained in Examples and Comparative Examples was coated on a release PET film (NS-80A: manufactured by Toray Corporation) by bar coating, and each was heated at 80° C. for 30 minutes to obtain cured products. The resulting cured product with a thickness of 100 μm was punched with a Dumbbell (trade name "Super Dumbbell Cutter (Model: SDMK-5889-01)", manufactured by Dumbbell Co., Ltd.), and a tensile strength measurement was prepared. Audition. The PET film was peeled off from the test piece. Under the conditions of a temperature of 25° C., a humidity of 50%, and a tensile speed of 5 mm/min, a tensile test was performed using a Tensilon universal testing machine (manufactured by Orientec, RTM-500), and the modulus of elasticity (MPa) was measured.

[Evaluation of water absorption] 2.8 ml of each resin composition obtained in Examples and Comparative Examples was put into an aluminum container with a diameter of 4 cm and a height of 6 mm, and heated at 60° C. for 4 hours to obtain hardened products with a diameter of 4 cm and a thickness of 2 mm. The weight of the obtained cured product was measured with a precision balance ("XS-205" manufactured by Mettler Toledo Co., Ltd.), and boiled in boiling water for 1 hour. After 1 hour, the hardened product was taken out and the moisture on the surface was removed, and then the weight was measured with a precision balance, and the water absorption (%) was calculated as follows. [Water absorption]=[[Weight after test]-[Initial weight]]×100/[Initial weight]

[Examination of evaluation results] Table 1 shows the results of the above evaluations.

When comparing Comparative Example 1 with Comparative Example 2, Comparative Example 1 has a smaller elastic modulus and a larger water absorption. That is, it is clear that if silicone powder is used in an epoxy resin composition containing a thiol compound, although the elastic modulus can be reduced, the water absorption rate will increase.

On the other hand, Examples 1-5 have a smaller elastic modulus than Comparative Examples 1 and 2. In addition, compared with Comparative Example 2, the water absorption of Examples 1 to 5 did not increase. That is, it is clear that the elastic modulus can be lowered without increasing the water absorption rate by using silicone powder and silane coupling agent together.

Claims (16)

A resin composition comprising: (A) epoxy resin, (B) Thiol compounds, (C) silane coupling agent, and (D) Silicone powder. The resin composition according to claim 1, which contains (E) a latent hardening accelerator. The resin composition according to claim 1 or 2, which contains (F) a stabilizer. The resin composition according to any one of claims 1 to 3, wherein component (B) includes: (B-1) a thiol compound having 3 or more thiol groups in the molecule, and (B-2) A thiol compound having two thiol groups in the molecule. The resin composition according to claim 4, wherein the component (B-1) has a ring skeleton in the molecule. The resin composition according to claim 4 or 5, wherein component (B-1) has no ester bond in the molecule. The resin composition according to any one of claims 4 to 6, wherein component (B-2) does not have a ring skeleton in the molecule. The resin composition according to any one of claims 4 to 7, wherein component (B-2) does not have an ester bond in the molecule. The resin composition according to any one of claims 5 to 8, wherein component (B-1) and component (B-2) do not have hydroxyl groups. The resin composition according to any one of claims 1 to 9, wherein component (C) has an epoxy group. The resin composition according to any one of claims 1 to 10, wherein the component (C) is contained in an amount of 1 to 10% by mass relative to 100% by mass of non-volatile components of the resin composition. The resin composition according to any one of claims 1 to 11, wherein the component (D) is contained in an amount of 5 to 20% by mass relative to 100% by mass of non-volatile components of the resin composition. An adhesive comprising the resin composition according to any one of claims 1-12. A sealing material comprising the resin composition according to any one of claims 1-12. A cured product obtained by thermosetting the resin composition according to any one of claims 1 to 12. An electronic component comprising the hardened product according to claim 15.