JP2012177013A - Epoxy resin composition and insulating adhesive - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an epoxy resin composition for low-elastic thermosetting resin, wherein the resin composition is used as an insulating adhesive having high glass transition temperature (Tg) and is excellent in features such as low elasticity (stress-relieving properties) and low coefficient of thermal expansion; and to provide the insulating adhesive suitably used for electric components.SOLUTION: The epoxy resin composition is obtained by containing an epoxy resin (A), a core-shell type low-elastic filler (B), and a polyamide resin (C). The thermosetting insulating adhesive contains the resin composition. The content of the polyamide resin (C) is 50-150 pts.mass based on 100 pts.mass of the epoxy resin (A); and the content of the core-shell type low-elastic filler (B) is 20-50 mass% of all formulations.

Description

  The present invention relates to an epoxy resin composition and an insulating adhesive, and in particular, contains an appropriate amount of an epoxy resin, a low elastic filler and a polyamide resin, and is suitable as an insulating adhesive and an insulating adhesive obtained from the composition. It relates to the agent.

  Low elastic thermosetting resin not only has excellent shock absorption, but also has high adhesion to various adherends because it can relieve strain caused by external forces and strain in cured products due to its stress relaxation ability. It is known to express force. In particular, low elastic thermosetting resins are suitably used as adhesives for structures that are susceptible to distortion, such as impact tests and thermal cycle tests. There was a disadvantage that Tg) was low.

  For example, a low-elastic thermosetting resin that is an epoxy resin composition containing a liquid crystalline polymer, an epoxy resin, and a curing agent has already been proposed (Patent Document 1), but the resin obtained here has a thermal expansion property. There was a drawback that it was not low enough. Further, in the case of a low elastic modulus thermosetting resin composition (Patent Document 2) containing an epoxy resin, crosslinked fine particles and a curing agent, not only the heat resistance is insufficient but also the thermal expansibility is sufficiently low. There was a drawback of not. Furthermore, in the case of an insulating resin composition (Patent Document 3) comprising an epoxy resin, an epoxy resin curing agent, a curing accelerator, and a core-shell structure cross-linked rubber, the requirement for low elasticity and sufficiently low thermal expansion is satisfied. Not.

JP-A-9-194687 JP 2005-36136 A JP 2001-123044 A

Accordingly, a first object of the present invention is to provide an epoxy resin composition for low elastic thermosetting resin suitable as an insulating adhesive.
The second object of the present invention is to provide an insulating adhesive having excellent properties such as low elastic modulus (stress relaxation), high glass transition temperature (Tg), and low thermal expansion coefficient.

  As a result of intensive studies to achieve the above-mentioned objects, the present inventors have achieved the above-mentioned object by an epoxy resin composition containing a predetermined amount of an epoxy resin, a core-shell type low elastic filler and a polyamide resin. The present invention has been found.

  That is, the present invention is an epoxy resin composition obtained by containing (A) an epoxy resin, (B) a core-shell type low elastic filler and (C) a polyamide resin, wherein the content of the polyamide resin (C) is 50 to 150 parts by mass with respect to 100 parts by mass of the epoxy resin (A), and the content of the core-shell type low elastic filler (B) is 20 to 50% by mass in the total formulation. And an insulating adhesive containing the composition.

  The epoxy resin composition of the present invention not only has a low elastic modulus (stress relaxation), but also has a high glass transition temperature (Tg) and a low coefficient of thermal expansion, and thus has high reliability against thermal stress. In addition, since it has sufficient adhesion to silicon wafers and exhibits good insulation properties, it can be used as an insulating adhesive for electronic components that require thermal cycling tests and impact tests. It is suitably used for applications such as an electronic substrate as an insulating layer.

Hereinafter, the epoxy resin composition of the present invention will be described in detail.
Examples of the epoxy resin that is the component (A) used in the present invention include polyglycidyl ether compounds of mononuclear polyhydric phenol compounds such as hydroquinone, resorcin, pyrocatechol, and phloroglucinol; dihydroxynaphthalene, biphenol, methylene Bisphenol (bisphenol F), methylene bis (orthocresol), ethylidene bisphenol, isopropylidene bisphenol (bisphenol A), isopropylidene bis (orthocresol), tetrabromobisphenol A, 1,3-bis (4-hydroxycumylbenzene), 1,4-bis (4-hydroxycumylbenzene), 1,1,3-tris (4-hydroxyphenyl) butane, 1,1,2,2-tetra (4-hydroxyphenyl) ethane, thiobisphenol Polyglycidyl ether compounds of polynuclear polyhydric phenol compounds such as alcohol, sulfobisphenol, oxybisphenol, phenol novolak, orthocresol novolak, ethylphenol novolak, butylphenol novolak, octylphenol novolak, resorcin novolak, terpene phenol; ethylene glycol, propylene glycol , Butylene glycol, hexanediol, polyglycol, thiodiglycol, glycerin, trimethylolpropane, pentaerythritol, sorbitol, polyglycidyl ethers of polyhydric alcohols such as bisphenol A-ethylene oxide adduct; maleic acid, fumaric acid, itaconic acid , Succinic acid, glutaric acid, suberic acid, adipic acid, azelaic acid, sebacic acid, da Aliphatic, aromatic or cycloaliphatic such as mercuric acid, trimer acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, pyromellitic acid, tetrahydrophthalic acid, hexahydrophthalic acid, endomethylenetetrahydrophthalic acid Homopolymers or copolymers of glycidyl esters of aromatic polybasic acids and glycidyl methacrylate; N, N-diglycidylaniline, bis (4- (N-methyl-N-glycidylamino) phenyl) methane, diglycidyl orthotoluidine Epoxy compounds having a glycidylamino group such as vinylcyclohexene diepoxide, dicyclopentanediene diepoxide, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-6-methylcyclohexyl Epoxidized products of cyclic olefin compounds such as rumethyl-6-methylcyclohexanecarboxylate and bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate; epoxidized conjugates such as epoxidized polybutadiene and epoxidized styrene-butadiene copolymer Examples thereof include heterocyclic compounds such as diene polymers and triglycidyl isocyanurate.

  These epoxy resins may be those internally crosslinked by a terminal isocyanate prepolymer or those having a high molecular weight with a polyvalent active hydrogen compound (polyhydric phenol, polyamine, carbonyl group-containing compound, polyphosphate ester, etc.). . In the present invention, a naphthalene type epoxy resin is particularly preferable because it has a high glass transition temperature and low thermal expansibility.

The core-shell type low elastic filler which is the component (B) used in the present invention is composed of a core layer mainly composed of an elastomer or rubbery polymer and a shell layer composed of a crosslinked polymer component which does not exhibit rubber elasticity. Polymer particles. The particle size of the particles is not particularly limited, but is preferably about 0.01 to 50 μm. If the particle size is large, the insulating property may be lowered. If the particle size is too small, the viscosity of the resin composition is increased, and the resin composition may be easily aggregated.
Examples of the core shell type low elastic filler that can be used in the present invention include KMP-605 (trade name) manufactured by Shin-Etsu Silicone Co., Ltd., Staphyloid AC-4030 (trade name) manufactured by Gantz Kasei Co., Ltd., and Asahi Kasei Wacker. Examples include GENIOPERL P52 (trade name) manufactured by Silicone Co., Ltd.

  Examples of the polyamide resin as the component (C) used in the present invention include general-purpose polyamide resins. In the present invention, the repeating unit has a phenolic hydroxyl group, and has the following general formula (I): Alternatively, it is preferable to use a polyamide resin represented by (II) because the cured product becomes tough when reacted with an epoxy resin.

但し（Ｉ）式中の環Ａは、炭素原子数６〜１８のアリーレン基又は炭素原子数１３〜２５のアルキリデンジアリーレン基を表し、これらはハロゲン原子、水酸基、及び/又は炭素原子数１〜４のアルキル基で置換されていても良い。（Ｉ）式中のＲは炭素原子数２〜１０のアルキレン基、炭素原子数６〜１８のシクロアルキレン基又はアリーレン基若しくは炭素原子数１３〜２５のアルキリデンジアリーレン基を表し、これらはハロゲン原子、水酸基及び/又は炭素原子数１〜４のアルキル基で置換されていてもよい。

However, the ring A in the formula (I) represents an arylene group having 6 to 18 carbon atoms or an alkylidene diarylene group having 13 to 25 carbon atoms, which are a halogen atom, a hydroxyl group, and / or 1 to 1 carbon atom. 4 alkyl groups may be substituted. R in formula (I) represents an alkylene group having 2 to 10 carbon atoms, a cycloalkylene group having 6 to 18 carbon atoms, an arylene group or an alkylidene diarylene group having 13 to 25 carbon atoms, and these are halogen atoms , A hydroxyl group and / or an alkyl group having 1 to 4 carbon atoms may be substituted.

但し（ＩＩ）式中の環Bは、炭素原子数６〜１８のアリーレン基又は炭素原子数１３〜２５のアルキリデンジアリール基を表し、これらはハロゲン原子、水酸基及び/又は炭素原子数１〜４のアルキル基で置換されていてもよい。

However, ring B in the formula (II) represents an arylene group having 6 to 18 carbon atoms or an alkylidene diaryl group having 13 to 25 carbon atoms, and these are a halogen atom, a hydroxyl group and / or a carbon atom having 1 to 4 carbon atoms. It may be substituted with an alkyl group.

  Examples of the arylene group having 6 to 18 carbon atoms represented by the ring A in the general formula (I) or the ring B in the general formula (II) include a 1,2-phenylene group, a 1,3-phenylene group, , 4-phenylene group, 1,5-naphthylene group, 2,5-naphthylene group, anthracene-diyl, 4,4′-biphenylene group, 4,4′-p-terphenylene group, 4,4′-m- A terphenylene group, a 2-fluoro-1,4-phenylene group, a 2,5-dimethyl-1,4-phenylene group, and the like can be given.

  Examples of the alkylidene diarylene group having 13 to 25 carbon atoms represented by the ring A in the general formula (I) or the ring B in the general formula (II) include a methylidene diphenylene group, an ethylidene diphenylene group, and propylidene diene. Examples thereof include a phenylene group, an isopropylidene diphenylene group, a hexafluoroisopropylidene diphenylene group, a propylidene-3,3 ′, 5,5′-tetrafluorodiphenylene group, and a fluorene-9-ylidene diphenylene group.

  Examples of the alkylene group having 2 to 10 carbon atoms represented by R in the general formula (I) include ethylene, propylene, trimethylene, tetramethylene, 2,2-dimethyltrimethylene, hexamethylene, octamethylene and decamethylene. Can be mentioned.

  Examples of the cycloalkylene group having 6 to 18 carbon atoms represented by R in the general formula (I) include divalent groups related to cyclohexane, cycloheptane, cyclooctane, bicyclohexane, dicyclohexane and the like.

  Examples of the arylene group represented by R in the general formula (I) include the same groups as in ring A.

  Examples of the alkylidene diaryl group represented by R in the general formula (I) include the same groups as in ring A.

  The structure of the polyamide compound of the general formula (I) used in the present invention includes the structure of the following general formula (VI) in which a dehydrating ring is closed with a phenolic hydroxyl group and an amide group adjacent to the phenolic hydroxyl group. .

但し、（ＶＩ）式中の環Ａ及びＲは、前記一般式（Ｉ）における環Ａ及びＲと同じである。

However, the rings A and R in the formula (VI) are the same as the rings A and R in the general formula (I).

  As the polyamide compound (C) used in the present invention, from the viewpoint of the physical properties (high glass transition temperature, low linear expansion coefficient, tensile strength, elongation, flexibility) of the cured product, the above general formula is used. What has the structure of the following general formula (III) or (IV) including the thing of only the structure of (I) or (II) is preferable.

但し、（ＩＩＩ）式中の環Ａは炭素原子数６〜１８のアリーレン基又は炭素原子数１３〜２５のアルキリデンジアリーレン基を表し、これらはハロゲン原子、水酸基及び／又は炭素原子数１〜４のアルキル基で置換されていても良い。Ｒは炭素原子数２〜１０のアルキレン基、炭素原子数６〜１８のシクロアルキレン基又はアリーレン基、若しくは炭素原子数１３〜２５のアルキリデンジアリーレン基を表し、これらはハロゲン原子、水酸基及び／又は炭素原子数１〜４のアルキル基で置換されていてもよい。ｎは正数である。

However, the ring A in the formula (III) represents an arylene group having 6 to 18 carbon atoms or an alkylidene diarylene group having 13 to 25 carbon atoms, and these are a halogen atom, a hydroxyl group and / or 1 to 4 carbon atoms. The alkyl group may be substituted. R represents an alkylene group having 2 to 10 carbon atoms, a cycloalkylene group having 6 to 18 carbon atoms or an arylene group, or an alkylidene diarylene group having 13 to 25 carbon atoms, which are a halogen atom, a hydroxyl group and / or It may be substituted with an alkyl group having 1 to 4 carbon atoms. n is a positive number.

但し、（ＩＶ）式中の環Bは炭素原子数６〜１８のアリーレン基又は炭素原子数１３〜２５のアルキリデンジアリーレン基を表し、これらはハロゲン原子、水酸基及び／又は炭素原子数１〜４のアルキル基で置換されていてもよい。ｍは正数である。

However, ring B in the formula (IV) represents an arylene group having 6 to 18 carbon atoms or an alkylidene diarylene group having 13 to 25 carbon atoms, and these are a halogen atom, a hydroxyl group and / or 1 to 4 carbon atoms. The alkyl group may be substituted. m is a positive number.

  Examples of the arylene group represented by the ring A in the general formula (III) include the same groups as those in the general formula (I).

  Examples of the alkylidene diarylene group represented by the ring A in the general formula (III) include the same groups as those in the general formula (I).

  Examples of the alkylene group having 2 to 10 carbon atoms represented by R in the general formula (III) include the same groups as those in the general formula (I).

  Examples of the cycloalkylene group having 6 to 18 carbon atoms represented by R in the general formula (III) include the same groups as those in the general formula (I).

  Examples of the arylene group represented by R in the general formula (III) include the same groups as those in the general formula (I).

  Examples of the alkylidene diaryl group represented by R in the general formula (III) include the same groups as those in the general formula (I).

  Examples of the arylene group represented by the ring B in the general formula (IV) include the same groups as those in the general formula (II).

  Examples of the alkylidene diarylene group represented by ring B in the general formula (IV) include the same groups as those in the general formula (II).

  As a more specific structure of the polyamide compound used in the present invention, for example, the following No. The structure of 1-13 is mentioned. However, the present invention is not limited by the following examples.

  The polyamide compound used in the present invention can be obtained from a phenolic hydroxyl group-containing aromatic diamine having a phenolic hydroxyl group at a position adjacent to the amino group. That is, this polyamide compound is composed of a phenolic hydroxyl group-containing aromatic diamine having a phenolic hydroxyl group adjacent to the amino group and dicarboxylic acids (various aromatic dicarboxylic acids, aliphatic dicarboxylic acids, etc.) as raw materials. It is a polyamide compound. The number of phenolic hydroxyl groups attached to the position adjacent to the amino group is not particularly limited, and is, for example, 1 to 4 for one aromatic diamine molecule.

  Of course, this polyamide compound may contain a diamine compound (various aromatic diamines, aliphatic diamines, etc.) other than the diamine having a phenolic hydroxyl group at a position adjacent to the amino group, and further contains a phenolic hydroxyl group. A dicarboxylic acid may be further used.

  Examples of the phenolic hydroxyl group-containing aromatic diamine having a phenolic hydroxyl group adjacent to the amino group include m-phenylenediamine, p-phenylenediamine, m-tolylenediamine, 4,4′-diaminodiphenyl ether, 3 , 3′-dimethyl-4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl thioether, 3,3′-dimethyl-4,4′-diaminodiphenyl thioether, 3,3 '-Diethoxy-4,4'-diaminodiphenylthioether, 3,3'-diaminodiphenylthioether, 4,4'-diaminobenzophenone, 3,3'-dimethyl-4,4'-diaminobenzophenone, 3,3'- Diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,4'-di Aminodiphenylmethane, 3,3′-dimethoxy-4,4′-diaminodiphenylthioether, 2,2′-bis (3-aminophenyl) propane, 2,2′-bis (4-aminophenyl) propane, 4,4 '-Diaminodiphenyl sulfoxide, 4,4'-diaminodiphenylsulfone, benzidine, 3,3'-dimethylbenzidine, 3,3'-dimethoxybenzidine, 3,3'-diaminobiphenyl, p-xylylene diene Amine, m-xylylenediamine, o-xylylenediamine, 2,2′-bis (3-aminophenoxyphenyl) propane, 2,2′-bis (4-aminophenoxyphenyl) propane, 1,3-bis ( 4-aminophenoxyphenyl) benzene, 1,3′-bis (3-aminophenoxyphenyl) propane, bis (4-amino- -Methylphenyl) methane, bis (4-amino-3,5-dimethylphenyl) methane, bis (4-amino-3-ethylphenyl) methane, bis (4-amino-3,5-diethylphenyl) methane, bis (4-amino-3-propylphenyl) methane, bis (4-amino-3,5-dipropylphenyl) methane, 2,2′-bis (3-aminophenyl) hexafluoropropane, 2,2′-bis Examples include (4-aminophenyl) hexafluoropropane having 1 to 4 hydroxyl groups bonded to the position adjacent to the amino group of the aromatic diamine. However, the present invention is not limited to these. These may be used alone or in combination of two or more, or may be used in combination with an aromatic diamine to which no hydroxyl group is bonded. Examples of the aromatic diamine to which no hydroxyl group is bonded include those described above.

  Examples of dicarboxylic acids that have a phenolic hydroxyl group at a position adjacent to an amino group and react with a phenolic hydroxyl group-containing aromatic diamine to form a polyamide compound used in the present invention include phthalic acid, isophthalic acid, Terephthalic acid, 4,4′-oxydibenzoic acid, 4,4′-biphenyldicarboxylic acid, 3,3′-methylenedibenzoic acid, 4,4′-methylenedibenzoic acid, 4,4′-thiodibenzoic acid Acid, 3,3′-carbonyldibenzoic acid, 4,4′-carbonyldibenzoic acid, 4,4′-sulfonyldibenzoic acid, 1,5-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 2, 6-naphthalenedicarboxylic acid, 1,2-naphthalenedicarboxylic acid, 5-hydroxyisophthalic acid, 4-hydroxyisophthalic acid, 2-hydroxyisophthalic acid, -Hydroxyisophthalic acid, 2-hydroxyterephthalic acid, 2,2'-bis (3-carboxyphenyl) hexafluoropropane, 2,2'-bis (4-carboxyphenyl) hexafluoropropane, and the like. Is not limited to these. Moreover, you may use these 1 type or in mixture of 2 or more types.

The epoxy resin composition of the present invention is an epoxy resin composition obtained by containing (A) an epoxy resin, (B) a core-shell type low elastic filler and (C) a polyamide resin. Here, content of a polyamide resin is 50-150 mass parts with respect to 100 mass parts of epoxy resins, and it is preferable that it is 60-100 mass parts. If it is less than 50 parts by mass, the elastic modulus and the coefficient of thermal expansion increase, so that the thermal stress cannot be sufficiently relaxed after curing. On the other hand, if it exceeds 150 parts by mass, the adhesion to a silicon wafer after PCT (pressure cooker test) is lowered, which is not preferable.
Moreover, the compounding quantity of a core-shell type low elastic filler is 20-50 mass% in all the compounds, and it is preferable that it is 30-40 mass%. If it is less than 20% by mass, the elastic modulus may increase or the adhesiveness may decrease, and if it is used more than 50% by mass, the coefficient of thermal expansion increases, which is not preferable.

  Furthermore, the epoxy resin composition of this invention can use the hardening | curing agent used for an epoxy resin. Examples of the curing agent include latent curing agents, acid anhydrides, polyamine compounds, polyphenol compounds, and cationic photoinitiators.

  Examples of the latent curing agent include dicyandiamide, hydrazide, imidazole compound, amine adduct, sulfonium salt, onium salt, ketimine, acid anhydride, and tertiary amine. When these latent hardeners are used, the composition of the present invention is preferable because it can be a one-component curable composition that is easy to handle.

  Examples of the acid anhydride include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, maleic anhydride, succinic anhydride, 2 , 2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride and the like.

  Examples of the polyamine compound include aliphatic polyamines such as ethylenediamine, diethylenetriamine, and triethylenetetramine, mensendiamine, isophoronediamine, bis (4-amino-3-methylcyclohexyl) methane, bis (aminomethyl) cyclohexane, 3,9. -Aliphatic polyamines such as bis (3-aminopropyl) 2,4,8,10-tetraoxaspiro [5,5] undecane, aliphatic amines having an aromatic ring such as m-xylenediamine, m-phenylenediamine 2,2-bis (4-aminophenyl) propane, diaminodiphenylmethane, diaminodiphenylsulfone, α, α-bis (4-aminophenyl) -p-diisopropylbenzene, 2,2-bis (4-aminophenyl)- 1,1,1,3,3,3-hexaph Aromatic polyamines such as uropropane can be mentioned.

  Examples of the polyphenol compound include phenol novolak, o-cresol novolak, t-butylphenol novolak, dicyclopentadiene cresol, terpene diphenol, terpene dicatechol, 1,1,3-tris (3-tert-butyl-4- Hydroxy-6-methylphenyl) butane, butylidenebis (3-tert-butyl-4-hydroxy-6-methylphenyl), 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3,3 -Hexafluoropropane and the like. Among these, particularly when phenol novolac is used, it is preferable because the electrical properties and mechanical strength of the resulting epoxy resin are suitable for the laminate.

  Examples of the imidazole compound include 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, and 1-benzyl. 2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole, 2,4-diamino-6 (2′-methylimidazole (1 ′ )) Ethyl-s-triazine, 2,4-diamino-6 (2′-undecylimidazole (1 ′)) ethyl-s-triazine, 2,4-diamino-6 (2′-ethyl, 4-methylimidazole) (1 ′)) Ethyl-s-triazine, 2,4-diamino 6 (2′-methylimidazole (1 ′)) ethyl-s-triazine isocyanuric acid adduct, 2-methylimidazole isocyanuric acid 2: 3 adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-3 , 5-dihydroxymethylimidazole, 2-phenyl-4-hydroxymethyl-5-methylimidazole, 1-cyanoethyl-2-phenyl-3,5-dicyanoethoxymethylimidazole imidazoles; and the imidazoles and phthalic acid And salts with polyvalent carboxylic acids such as isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, naphthalenedicarboxylic acid, maleic acid and oxalic acid.

If necessary, other additives can be added to the epoxy resin composition of the present invention. Examples of such additives include plasticizers such as natural waxes, synthetic waxes and metal salts of long-chain aliphatic acids; mold release agents such as acid amides, esters and paraffins; nitrile rubber, butadiene rubber Inorganic flame retardants such as antimony trioxide, antimony pentoxide, tin oxide, tin hydroxide, molybdenum oxide, zinc borate, barium metaborate, red phosphorus, aluminum hydroxide, magnesium hydroxide, calcium aluminate Bromine-based flame retardants such as tetrabromobisphenol A, tetrabromophthalic anhydride, hexabromobenzene, brominated phenol novolak; phosphorus-based flame retardants other than those described above; silane-based coupling agents, titanate-based coupling agents, aluminum-based cups Coupling agents such as ring agents; Colorants such as dyes and pigments; Oxidation stabilizers, Mitsuan Agent, moisture resistance improver, thixotropy imparting agent, diluent, defoaming agent, other various resins, tackifier, antistatic agent, lubricant, ultraviolet absorber, alcohols, ethers, acetals, Organic solvents such as ketones, esters, alcohol esters, ketone alcohols, ether alcohols, ketone ethers, ketone esters and ester ethers, and aromatic solvents can also be blended.
Hereinafter, the epoxy resin composition of the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples.

[Reference Example] Synthesis of the following polyamide resin
160.1 g (0.5 mol) of 2,2′-bistrifluoromethylbiphenyl-4,4′-diamine and 98.5 g (0.5 mol) of 2,4-diaminophenol dihydrochloride were added to N-methyl-2-pyrrolidone NMP) and dissolved in a mixed solvent of 1550 g and 275.3 g (3.5 mol) of pyridine.
Separately, 192.9 g (0.95 mol) of isophthaloyl chloride was dissolved in 770 g of NMP, and reacted dropwise at −20 to −10 ° C. in the above solution. After the entire amount was dropped, the mixture was further aged at room temperature for 1 hour. The precipitate was purified using about 15 liters of ion-exchanged water, filtered, and washed successively with ion-exchanged water and methanol. It was dried under reduced pressure at 150 ° C. for 3 hours to obtain 311 g (yield 90%) of a deep purple powder.
Formation of an amide bond was confirmed from the infrared absorption spectrum of the obtained compound, and it was confirmed from gel permeation chromatography that the polymer had a weight average molecular weight of 16,300.
The viscosity was 285 cps (25 ° C., 30 wt% NMP solution), and the OH equivalent was 704 g / eq.

[Examples 1-8 and Comparative Examples 1-4]
A resin composition having the composition shown in Tables 1 and 2 below was diluted with propylene glycol monomethyl ether, and applied to a PET film subjected to a release treatment so that the thickness of the resin after drying was 30 to 40 μm. The solvent was dried at 10 ° C. for 10 minutes. Thereafter, a cured product was produced at 180 ° C. over 1 hour, and various physical properties were measured.

(Glass transition temperature [Tg])
The cured product is molded into a size of 5 x 50 mm, and the dynamic viscoelasticity is measured with a thermal analyzer (DMS-6100; manufactured by SII Nanotechnology Co., Ltd.), and the temperature at which the maximum value of tanδ is obtained. The glass transition point.

(Elastic modulus [E '])
The initial elastic modulus obtained by a tensile test (tensile speed: 5 mm / min) using a dumbbell-type test piece described in JIS K7162 5A was described.

(Coefficient of thermal expansion [CTE])
The cured product produced above was molded into a size of 3 × 50 mm, and the thermal expansion curve was measured using a thermal analyzer (TMA / SS6100; manufactured by SII Nanotechnology Co., Ltd.). The thermal expansion coefficient was calculated from the elongation in the range of 30 to 125 ° C.

(Adhesiveness)
For the adhesion test, a resin composition having the composition shown in Tables 1 and 2 below was diluted with propylene glycol monomethyl ether and applied on a silicon wafer so that the thickness of the resin after drying was 30 to 40 μm. The solvent was dried at 100 ° C. for 10 minutes, and then the resin was cured at 180 ° C. for 1 hour to obtain a test piece. Using the obtained test piece, a peel test was performed using a cellophane adhesive tape in accordance with the cross cut test method of JIS D0202, and the remainder was shown in each table. Furthermore, after performing a pressure cooker test under the conditions of 121 ° C./2.1 atm / 100% RH for 96 hours, an adhesion test similar to that after curing was performed, and the remainders are shown in each table.

Epoxy resin 1: Adeka Resin EP-4100E (bisphenol A type epoxy resin manufactured by ADEKA Co., Ltd.)
Epoxy resin 2: EPICLON
HP-4032 (Naphthalene type manufactured by Dainippon Ink & Chemicals, Inc.)
Epoxy resin)
Low elastic filler 1: KMP-605 (silicone composite powder made by Shin-Etsu silicone)
Average particle size 2μm
Low elastic filler 2: X-52-7030 (silicone composite powder made by Shin-Etsu silicone)
Average particle size 0.8μm
Low elastic filler 3: Staphyloid AC-4030 (core shell rubber manufactured by Ganz Kasei Co., Ltd.)
Average particle size 0.5μm
Low elasticity filler 4: GENIOPERL P52 (Asahi Kasei Wacker Silicone Co., Ltd. core-shell type)
Silicone powder) Average particle size 0.1-0.2μm
Polyamide resin: Polyamide resin curing agent 1 of the above reference example: 2-phenyl-4,5-dihydroxymethylimidazole curing agent 2: Dicyandiamide silane coupling agent: KBM-403 (3-glycidoxy manufactured by Shin-Etsu Silicone Co., Ltd.) Propyltriethoxysilane)

  As is clear from the results in Tables 1 and 2, it was confirmed that the resin of the present invention has much better adhesion than the comparative example.

  The epoxy resin composition of the present invention not only has a low modulus of elasticity (stress relaxation), but also has a high glass transition temperature (Tg) and a low coefficient of thermal expansion. In addition, it has sufficient adhesiveness, and also exhibits good insulation, so as an insulating adhesive for electronic parts that require thermal cycle tests and impact tests, and itself as an insulating layer Since it can be suitably used for applications such as electronic substrates, it is extremely significant in industry.

Claims (8)

(A) An epoxy resin, (B) a core-shell type low elastic filler, and (C) an epoxy resin composition obtained by containing a polyamide resin, wherein the content of the polyamide resin (C) is an epoxy resin (A) 50 to 150 parts by mass with respect to 100 parts by mass, and the content of the core-shell type low elastic filler (B) is 20 to 50% by mass in the total formulation.   The epoxy resin composition according to claim 1, wherein the epoxy resin (A) is a naphthalene type epoxy resin.   The core-shell type low elastic filler (B) is a polymer particle composed of a core layer mainly composed of an elastomer or a rubber-like polymer and a shell layer composed of a crosslinked polymer component that does not exhibit rubber elasticity. The epoxy resin composition described in 1 or 2. The polyamide resin (C) is a polyamide resin having a structure having a phenolic hydroxyl group represented by the following general formula (I) or (II) in a repeating unit. Made epoxy resin composition;

However, the ring A in the formula (I) represents an arylene group having 6 to 18 carbon atoms or an alkylidene diarylene group having 13 to 25 carbon atoms. These may be substituted with a halogen atom, a hydroxyl group and / or an alkyl group having 1 to 4 carbon atoms. R in the formula (I) represents an alkylene group having 2 to 10 carbon atoms, a cycloalkylene group having 6 to 18 carbon atoms or an arylene group, or an alkylidene diarylene group having 13 to 25 carbon atoms, It may be substituted with a halogen atom, a hydroxyl group and / or an alkyl group having 1 to 4 carbon atoms.

However, ring B in the formula (II) represents an arylene group having 6 to 18 carbon atoms or an alkylidene diaryl group having 13 to 25 carbon atoms, which are a halogen atom, a hydroxyl group, or a carbon atom having 1 to 4 carbon atoms. It may be substituted with an alkyl group. The epoxy resin composition according to claim 4, wherein the structure of the polyamide resin (C) is a structure having a phenolic hydroxyl group represented by the following general formula (III) or (IV):

However, the ring A in the formula (III) represents an arylene group having 6 to 18 carbon atoms or an alkylidene diarylene group having 13 to 25 carbon atoms, and these are a halogen atom, a hydroxyl group and / or 1 to 1 carbon atom. It may be substituted with 4 alkyl groups. (III) R in the formula represents an alkylene group having 2 to 10 carbon atoms, a cycloalkylene group having 6 to 18 carbon atoms or an arylene group, or an alkylidene diarylene group having 13 to 25 carbon atoms, It may be substituted with a halogen atom, a hydroxyl group and / or an alkyl group having 1 to 4 carbon atoms. n is a positive number.

However, ring B in the formula (IV) represents an arylene group having 6 to 18 carbon atoms or an alkylidene diarylene group having 13 to 25 carbon atoms, and these are a halogen atom, a hydroxyl group and / or 1 to 1 carbon atom. It may be substituted with 4 alkyl groups. m is a positive number. The epoxy resin composition according to claim 4 or 5, wherein the ring A is a phenylene group or a naphthylene group.
Said   The epoxy resin composition according to any one of claims 4 to 6, wherein R is a phenylene group or a naphthylene group.   An insulating adhesive comprising the epoxy resin composition according to any one of claims 1 to 7.