TWI657113B - Heat resistant epoxy resin composition - Google Patents

Abstract

The present invention provides a curable composition in which both the thermosetting property and the subsequent strength are secured, and the low-temperature curability and the moisture resistance are both established. Specifically, the present invention provides a one-liquid type curable resin composition containing quinone (3-mercaptopropyl) isocyanurate and a naphthalene type epoxy resin represented by the formula (1). (In the formula (1), R may be the same or different from each other as a divalent hydrocarbon group having 1 to 30 carbon atoms which may or may not have a substituent, and G may be the same or different from each other as a hydrogen atom or the following formula (2) : The epoxy group is represented, and at least two of G in the formula (1) are an epoxy group represented by the above formula (2), and n is an integer of 0 to 10).

Description

Heat resistant epoxy resin composition

The present invention relates to a liquid-type thermosetting resin composition containing ginseng (3-mercaptopropyl) isocyanurate and a specific epoxy resin. Further, the present invention relates to an adhesive and a sealing material comprising the one-component thermosetting resin composition, and a cured resin obtained by heating the curable resin composition.

Epoxy resin has excellent performance in terms of mechanical properties, electrical properties, thermal properties, chemical resistance, and adhesion strength, and can be used in a wide range of applications such as coatings, electrical and electronic insulating materials, and adhesives. So far, it has been developed to use a mixture of an epoxy resin and a hardener to harden it, that is, in addition to the two-component epoxy resin composition, an epoxy resin and a hardener are preliminarily mixed, and one of them is hardened by heat or the like. Type epoxy resin composition. In recent years, in order to improve the protection of electronic components in the field of sealing of semiconductor components and the like, and to increase the density of circuits or the reliability of connection, a one-component epoxy resin composition plays an important role. In particular, in recent years, there has been a demand for hardening at a low temperature for a short period of time for the purpose of improving productivity and workability.

For example, a low-temperature curable one-liquid epoxy resin composition using a thiol curing agent is known (Patent Document 1). However, when the low-temperature hardening property is excessively pursued, there is a case where the strength is deteriorated, and it is difficult to ensure both the low-temperature curability and the subsequent strength.

Further, the curing agent contained in the conventional one-liquid epoxy resin composition having low-temperature curability generally has low moisture resistance (migration resistance), and tends to change the shearing force during long-term storage. On the other hand, in order to improve the moisture resistance, problems such as lowering the glass transition temperature (Tg) at the time of blending have been examined.

[Previous Technical Literature] [Patent Document]

[Patent Document 1] Japanese Patent Laid-Open No. Hei 6-211969

An object of the present invention is to provide a liquid-type thermosetting composition which ensures both low-temperature curability and adhesion strength.

Another object of the present invention is to provide a liquid-type thermosetting resin composition which is both low-temperature curability and moisture resistance.

As a result of intensive studies to solve the above problems, the inventors of the present invention have a one-component thermosetting resin composition containing a curable resin of ginseng (3-mercaptopropyl)isocyanurate and an epoxy resin. The glass transition temperature of the cured product of the curable resin composition is 40~ 200 ° C, and solve the above problems.

That is, the present invention is as follows.

[1] A one-component thermosetting resin composition comprising ginseng (3-mercaptopropyl) isocyanurate and a naphthalene type epoxy resin represented by formula (1); (In the formula (1), R may be the same or different from each other as a divalent hydrocarbon group having 1 to 30 carbon atoms which may or may not have a substituent, and G may be the same or different hydrogen atom or the following formula (2) ): The epoxy group is represented, and at least two of G in the formula (1) are an epoxy group represented by the above formula (2), and n is an integer of 0 to 10).

[2] The resin composition according to the above [1], wherein, in the above formula (1), R may be the same or different from each other as a dialkylphenyl group having 8 to 14 carbon atoms which may or may not have a substituent or Alkyl groups having a carbon number of 1 to 10.

[3] The resin composition according to the above [1] or [2], which further comprises a solid dispersion type latent curing accelerator.

[4] The resin composition according to any one of [1] to [3] further comprising a boric acid ester compound, a titanate compound, an aluminate compound, a zirconate compound, an isocyanate compound, One or more of a carboxylic acid, an acid anhydride, and a mercapto organic acid.

[5] The resin composition according to any one of the above [1] to [4] wherein the cured product of the one-liquid type thermosetting resin composition is subjected to glass transfer measured in accordance with JIS-K-7244-4 The temperature is 40~200 °C.

[6] The resin composition according to any one of the above [1] to [5] wherein the cured product of the one-component thermosetting resin composition is allowed to stand at 120 ° C and 85% RH for 24 hours. Thereafter, the tensile shear strength measured by JIS-K-6850 was 8 or more in strength B (N/mm ² ).

[7] The resin composition according to any one of the above [1] to [6] wherein the cured product of the one-liquid type thermosetting resin composition has a strength retention ratio (B/A) of more than 0.4. The retention ratio (B/A) is a tensile strength A (N/mm ² ) measured by JIS-K-6850 of the cured product of the one-component thermosetting resin composition, and the above-mentioned one liquid type. The cured product of the thermosetting resin composition was allowed to stand under the conditions of 120 ° C and 85% RH for 24 hours, and then calculated according to the tensile shear strength measured by JIS-K-6850 and the strength B (N/mm ² ).

[8] An adhesive comprising the resin composition according to any one of the above [1] to [7].

[9] A material for sealing comprising the resin composition according to any one of the above [1] to [7].

[10] A cured product obtained by heating the resin composition according to any one of the above [1] to [7].

[11] The resin composition according to any one of [1] to [7] further comprising a bisphenol A type epoxy resin.

[12] The resin composition according to [11], wherein the naphthalene type epoxy The mass ratio of the resin to the bisphenol A type epoxy resin is [naphthalene type epoxy resin]: [bisphenol A type epoxy resin] = 10:1 to 1:10.

One of the liquid type thermosetting resin compositions of the present invention ensures Epoxy resin composition with low temperature hardenability and high adhesion strength. The curable resin composition of the present invention is a curable resin composition which is both low-temperature curable and moisture-resistant. The epoxy resin composition of the present invention is excellent in low-temperature curability and moisture resistance, and has a glass transition temperature of, for example, about 40 to 200 ° C. Therefore, it can be used as an adhesive or a sealing material, and can be used as a material for bonding a die. , the use of materials for underfill, and the like. Here, the "one-liquid type" thermosetting resin composition means a composition in which a composition of a curing agent and an epoxy resin is mixed in advance, and the composition has a property of being hardened by application of heat.

[参(3-Mercaptopropyl)isocyanurate (TMPIC)]

The ginseng (3-mercaptopropyl) isocyanurate contained in the liquid thermosetting resin composition of the present invention may be a thiol compound represented by the following structural formula.

The ginseng (3-mercaptopropyl) isocyanurate acts as a hardener for the epoxy resin.

When the total epoxy resin contained in the liquid thermosetting resin composition of the present invention is 100 parts by mass, for example, 10 to 100 parts by mass, the content of the ginseng (3-mercaptopropyl) isocyanurate is, for example, 10 to 100 parts by mass. Preferably, it is 20 to 90 parts by mass, more preferably 30 to 80 parts by mass, and even more preferably 40 to 75 parts by mass.

[epoxy resin]

The epoxy equivalent of the epoxy resin contained in the liquid thermosetting resin composition of the present invention is, for example, preferably from 150 to 1,000, more preferably from 200 to 800, still more preferably from 300 to 600. When the epoxy equivalent of the epoxy resin is 200 or more, since it has little volatility and is not low in viscosity, it is suitable for easy handling. Further, when the epoxy resin has an epoxy equivalent of 1,000 or less, it is not a high viscosity and is suitable for an operation surface. Here, the epoxy equivalent is a mass of an epoxy resin containing 1 equivalent of an epoxy group, and can be measured, for example, in accordance with JIS K 7236 (2009).

The epoxy resin of the present invention preferably contains a naphthalene type epoxy tree. fat. More specifically, it is preferably an epoxy resin containing (1) 2 or more epoxy groups and (2) 1 or more naphthalene rings.

(1) The epoxy group of "2 or more epoxy groups" is a group having a valence of the following formula.

The epoxy group is contained in the epoxy resin and contains at least two, preferably 2 ~22, more preferably 2~12. Although the epoxy group may be bonded to any part of the epoxy resin, it is preferred that the ring of the naphthalene ring is directly bonded to or through the substituent on the naphthalene ring.

(2) 1 or more naphthalene ring

The naphthalene ring is contained in the epoxy resin in at least one, preferably from 1 to 11, more preferably from 1 to 6.

When a plurality of naphthalene rings are present, each naphthalene ring may be bonded to a single bond or a divalent hydrocarbon group. Here, examples of the divalent hydrocarbon group include a carbon number of 1 to 30 excluding a substituent, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, a cycloalkenyl group, and a poly Alkapolyynylene, Alkadiynylene, Alkatriynylene, divalent aryl, dialkylaryl, etc., preferably alkyl, cycloalkyl, alkylene Alkyl, alkynyl, dialkylphenyl. Examples of the alkylene group include a methylene group, an ethylidene group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, a decyl group, a fluorene group, a fluorenyl group, and an eleventh group. Alkenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecyl, hexadecenyl, heptadecenyl, octadecyl, pentadecenyl and the like. Preferred examples of the divalent hydrocarbon group include a dialkylphenyl group having a carbon number of 8 to 14 or an alkylene group having a carbon number of 1 to 10. As a more preferred divalent hydrocarbon group, a methylene group, an ethyl group, and a stretching group are mentioned. Propyl, phenyl, dimethylphenyl, diethylphenyl, dimethylphenyl.

The above naphthalene ring and divalent hydrocarbon group may have a substituent.

Examples of the substituent include a hydroxyl group, a halogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, an aryloxy group, and an aralkyl group. a group of a aryl group, an aralkyloxy group, a monovalent heterocyclic group, an amine group, a decyl group, a decyl group, a decyloxy group, a carboxyl group, a cyano group, a nitro group, a hydroxyl group, a fluorenyl group and a pendant oxy group.

Examples of the halogen atom used as the substituent include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

The alkyl group used as a substituent may be linear or branched Any of the shapes. The alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 14, more preferably 1 to 12, still more preferably 1 to 6, and particularly preferably 1 to 3. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, and an anthracene group. Base, and base. As described later, the alkyl group used as the substituent may further have a substituent ("secondary substituent"). The alkyl group having the secondary substituent may, for example, be an alkyl group substituted with a halogen atom, and specific examples thereof include a trifluoromethyl group, a trichloromethyl group, a tetrafluoroethyl group, and a tetrachloroethyl group.

The number of carbon atoms of the cycloalkyl group used as the substituent is preferably It is 3 to 20, more preferably 3 to 12, and even more preferably 3 to 6. Examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group.

The alkoxy group used as a substituent may be linear or branched The alkoxy group has a carbon number of from 1 to 20, preferably from 1 to 12, more preferably from 1 to 6. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a sec-butoxy group, an isobutoxy group, a tert-butoxy group, and a pentyloxy group. , hexyloxy, heptyloxy, octyloxy, decyloxy, and decyloxy.

The number of carbon atoms of the cycloalkoxy group used as a substituent Good for 3~20, better for 3~12, and even better for 3~6. Examples of the cycloalkoxy group include a cyclopropoxy group, a cyclobutoxy group, a cyclopentyloxy group, and a cyclohexyloxy group.

The aryl group used as a substituent is removed from an aromatic hydrocarbon 1 The base of a hydrogen atom on an aromatic ring. The number of carbon atoms of the aryl group used as the substituent is preferably 6 to 24, more preferably 6 to 18, still more preferably 6 to 12. Examples of the aryl group include a phenyl group, a naphthyl group, and an anthracenyl group.

The number of carbon atoms of the aryloxy group used as the substituent is preferably It is 6~24, more preferably 6~18, and even more preferably 6~12. Examples of the aryloxy group used as the substituent include a phenoxy group, a 1-naphthyloxy group, and a 2-naphthyloxy group.

The number of carbon atoms of the aralkyl group used as the substituent is preferably It is 7 to 25, more preferably 7 to 19, and even more preferably 7 to 13. Examples of the aralkyl group include a phenyl-C1 to C12 alkyl group, a naphthyl-C1 to C12 alkyl group, and a fluorenyl-C1 to C12 alkyl group.

The number of carbon atoms of the aralkoxy group used as a substituent Good for 7~25, better for 7~19, and even better for 7~13. Examples of the aralkyloxy group include a phenyl-C1 to C12 alkoxy group and a naphthyl-C1 to C12 alkoxy group.

The monovalent heterocyclic group used as a substituent means The group of the hydrogen atom on one heterocyclic ring is removed from the heterocyclic compound. The number of carbon atoms of the monovalent heterocyclic group is preferably from 3 to 21, more preferably from 3 to 15, still more preferably from 3 to 9. The monovalent heterocyclic group also contains a monovalent aromatic heterocyclic group (heteroaryl). As the monovalent heterocyclic ring, for example, thiophene Base, pyrrolyl, furyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, pyrrolidinyl, piperidinyl, quinolyl, and isoquinolinyl.

The amine group used as a substituent may be linear or branched Any of a variety of aliphatic or aromatic. The number of carbon atoms of the amine group is preferably from 1 to 20, preferably from 1 to 12, still more preferably from 1 to 6. Examples of the amine group include an aminomethyl group, an aminoethyl group, an aminopropyl group, an isopropylamino group, an aminobutoxy group, a sec-butylamino group, an isobutylamino group, and a tert-. Butylamino, aminopentyl, aminohexyl, aminoheptyl, aminooctyl, amine sulfhydryl, and amine fluorenyl, aminophenyl, and the like.

The alkylene group used as a substituent may be linear or divided Any of the branches. The alkyl group has preferably 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms. Examples of the decyl group include a methyl decyl group, an ethyl decyl group, a propyl sulfonyl group, an isopropyl decyl group, a butoxy decyl group, a sec-butyl decyl group, an isobutyl decyl group, and a tert-. Butylalkyl, pentylalkyl, hexylalkyl, heptylalkyl, octylalkyl, fluorenylalkyl, and fluorenylalkyl.

The thiol group used as a substituent is a formula: -C(=O)-R1 The base of the formula (wherein R1 is an alkyl group or an aryl group). The alkyl group represented by R1 may be either linear or branched. Examples of the aryl group represented by R1 include a phenyl group, a naphthyl group, and an anthracenyl group. The sulfhydryl group preferably has 2 to 20 carbon atoms, more preferably 2 to 13 carbon atoms, still more preferably 2 to 7 carbon atoms. Examples of the fluorenyl group include an ethyl group, a propyl group, a butyl group, an isobutyl group, a neopentyl group, and a benzamidine group.

The methoxy group used as a substituent is a formula: -O- C(=O)-R2 represents a group (wherein R2 is an alkyl group or an aryl group). The alkyl group represented by R2 may be either linear or branched. Examples of the aryl group represented by R2 include a phenyl group, a naphthyl group, and an anthracenyl group. The number of carbon atoms of the decyloxy group is preferably from 2 to 20, more preferably from 2 to 13, more preferably from 2 to 7. Examples of the decyloxy group include an ethoxycarbonyl group, a propenyloxy group, a butoxy group, an isobutyloxy group, a neopentyloxy group, and a benzamidine group.

A liquid type thermosetting resin composition of the present invention, as The epoxy resin is preferably a naphthalene type epoxy resin represented by the following formula (1).

In the formula (1), R may be the same or different from each other as a divalent hydrocarbon group having 1 to 30 carbon atoms which may or may not have a substituent, and the carbon number herein means the carbon number of the carbon excluding the substituent portion. R is preferably a divalent hydrocarbon group having 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms. When R does not contain an aromatic group, the number of carbon atoms excluding the substituent is suitably from 1 to 15, preferably from 1 to 10, more preferably from 1 to 5.

Here, as the "divalent hydrocarbon group", those exemplified as the divalent hydrocarbon group of the above naphthalene ring can be used. R is preferably a dialkylphenyl group having a carbon number of 8 to 14 or an alkylene group having a carbon number of 1 to 10, more preferably a methylene group, an ethyl group, a propyl group, a phenyl group or a dimethyl group. The base is phenyl, diethylphenyl, dimethylphenyl, and particularly preferably methylene or dimethylphenyl.

Examples of R include the following structures.

When there are plural R in formula (1), R may be the same as each other Or different. R may or may not have a substituent. Here, as the substituent, those exemplified as the above-mentioned naphthalene ring and a hydrocarbon group can be used. The substituent of R is preferably a halogen atom, a methyl group, an ethyl group, a propyl group or a hydroxyl group.

In the formula (1), G may be the same or different from each other as a hydrogen atom or the following formula (2): The epoxy group represented by the formula (1) is at least two of the epoxy groups represented by the above formula (2).

In the formula (1), n is from 0 to 10, preferably from 0 to 7, more preferably from 1 to 5.

A particularly good naphthalene type epoxy resin, which is in the above formula (1), G All are epoxy groups represented by the formula (2), R is a methylene group or a dimethylphenyl group, and n is an epoxy resin of 0 to 10.

Specific examples of the specific naphthalene type epoxy resin which can be used in the present invention include HP-4032D manufactured by DIC Corporation, EXA-4710 manufactured by DIC Corporation, and ESN-475V manufactured by Nippon Steel & Sumitomo Metal Co., Ltd.

One of the liquid thermosetting resin compositions of the present invention, added or In place of the above naphthalene type epoxy resin, various epoxy resins can be used in the glass transition temperature of the resin composition of the resin composition within a desired range. For example, polyphenols such as bisphenol A, bisphenol F, bisphenol AD, catechol, resorcin, or polyhydric alcohol such as glycerin or polyethylene glycol may be reacted with epichlorohydrin. Glycidyl ether; such as p-hydroxybenzoic acid, β-hydroxyl a polyglycidyl ether ester obtained by reacting a hydroxy acid of a naphthoic acid with epichlorohydrin; a polyglycidyl ester obtained by reacting a polycarboxylic acid such as phthalic acid or terephthalic acid with epichlorohydrin; The epoxidized phenol novolak resin, the epoxidized cresol novolac resin, the epoxidized polyolefin, the cyclic aliphatic epoxy resin, and other urethane modified epoxy resins are not limited thereto.

From the standpoint of maintaining high heat resistance and low moisture permeability, Preferred are bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol E type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, biphenyl aralkyl type Epoxy resin, phenol aralkyl type epoxy resin, aromatic glycidylamine type epoxy resin, epoxy resin having a structure of dicyclopentadiene, more preferably bisphenol A type epoxy resin and bisphenol F type ring The oxygen resin is more preferably a bisphenol A type epoxy resin.

These resins may be in the form of a liquid and may be in a solid shape. Can make A mixture of a liquid resin and a solid resin is used. Here, the term "liquid" and "solid shape" refer to the state of the epoxy resin at normal temperature (25 ° C). From the viewpoint of coatability, workability, and adhesion, it is preferred that at least 10% by mass or more of the entire epoxy resin used is a liquid epoxy resin.

Specific examples of the resin include bisphenol A type (hereinafter sometimes abbreviated as BPA type) epoxy resin ("JER828EL" manufactured by Mitsubishi Chemical Corporation, "JER827", "JER1001"), and bisphenol F type epoxy resin. ("JER807" manufactured by Mitsubishi Chemical Corporation), bisphenol AF epoxy resin ("ZX1059" manufactured by Tohto Kasei Co., Ltd.), cresol novolac epoxy resin (manufactured by DIC Corporation, N-695), hydrogenated structure epoxy Resin (Mitsubishi Chemical "YX8000" manufactured by the company, a dicyclopentadiene type polyfunctional epoxy resin ("HP7200" manufactured by DIC Corporation), an epoxy resin having a butadiene structure ("PB-3600" manufactured by Daicel Chemical Industry Co., Ltd.), and Epoxy resin of biphenyl structure ("NC3000H", "NC3000L" manufactured by Nippon Kayaku Co., Ltd., "YX4000" manufactured by Mitsubishi Chemical Corporation). Among them, it is preferable to use a BPA-type epoxy resin having high heat resistance and low viscosity, and it is preferable to use "JER828EL", "JER827", "JER1001", and "JER807" manufactured by Mitsubishi Chemical Corporation, and it is preferable to use "JER828EL".

In addition to naphthalene type epoxy resin and BPA type epoxy resin When the ratio of the naphthalene type epoxy resin to the BPA type epoxy resin, for example, a naphthalene type epoxy resin: BPA type epoxy resin = 10:1 to 1:10, preferably 10:1 to 1:2, more Good for 9:1~1:1, and even better for 8:1~2:1.

[Other additives]

The curable resin composition of the present invention may optionally contain a curing agent for an epoxy resin other than TMPIC, a curing accelerator, a storage stability enhancer, a filler, a diluent, a solvent, a pigment, a flexibility imparting agent, and a coupling agent. Various additives such as an antioxidant, a thixotropic imparting agent, and a dispersing agent.

As a hardener for epoxy resins other than TMPIC, for example An imidazole hardener or an amine hardener can be mentioned. Further, a thiol compound other than TMPIC, for example, by trimethylolpropane ginseng (3-mercaptopropionate) (TMTP), trimethylolpropane ginseng (hydrogen thioacetate), pentaerythritol bismuth (hydrogen thioacetate) Acid ester), ethylene glycol dihydrothioacetate, trimethylolpropane ginseng (β-thiopropionate), pentaerythritol bismuth (β-thiopropionate), two A thiol compound obtained by esterification of a polyol such as pentaerythritol poly(β-thiopropionate) with a mercapto organic acid can also be used as a curing agent for an epoxy resin.

As a hardening accelerator which can be used in the present invention, for example, A solid dispersion type latent hardening accelerator is listed. The solid dispersion type latent curing accelerator is a hardening accelerator which is an epoxy resin, and is soluble in a solid which is insoluble in the above-mentioned epoxy resin at room temperature (25 ° C), and is a hardening accelerator function as an epoxy resin. The compound, the imidazole compound which is solid at normal temperature, and the solid dispersion type amine addition type latent curing accelerator are not limited to these. Examples of the solid dispersion type amine adduct-based latent curing accelerator include a reaction product of an amine compound and an epoxy compound (amine-epoxy adduct system), an isocyanate compound of an amine compound, or a urea compound. A product (urea type adduct system) or the like. Among these, a solid dispersion type amine adduct is preferably a latent curing accelerator.

Examples of the imidazole compound which is solid at normal temperature include, for example, 2-heptadecylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-undecylimidazole, and 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 '- methyl imidazolyl - (1')) - ethyl -S- triazine. Isocyanuric acid adduct, 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2 -methylimidazole-p-benzoic acid ester, 1-cyanoethyl-2-phenylimidazole-p-benzoic acid ester, N-(2-methylimidazolyl-1-ethyl)-urea, N,N ' -(2-Methylimidazolyl-(1)-ethyl)-hexanediyldiamine or the like, but is not limited thereto.

Examples of the epoxy compound used as one of the raw materials for producing the latent amine-based amine-based latent curing accelerator (amine-epoxy adduct) are bisphenol A, bisphenol F, and catechu. a polyphenol such as phenol or resorcin, or a polyglycidyl ether obtained by reacting a polyol such as glycerin or polyethylene glycol with epichlorohydrin; and a hydroxyl group such as p-hydroxybenzoic acid or β-hydroxynaphthoic acid a glycidyl ether ester obtained by reacting an acid with epichlorohydrin; a polyglycidyl ester obtained by reacting a polycarboxylic acid such as phthalic acid or terephthalic acid with epichlorohydrin; and a 4,4 ' -diamino group a glycidylamine compound obtained by reacting epichlorohydrin with diphenylmethane or m-aminophenol; and a polyfunctional ring of an epoxidized phenol novolak resin, an epoxidized cresol novolak resin, an epoxidized polyolefin, or the like The monofunctional epoxide such as an oxygen compound or butyl glycidyl ether, phenyl glycidyl ether or glycidyl methacrylate is not limited thereto.

An amine compound used as a raw material for producing a solid dispersion type amine addition-based latent curing accelerator is an active hydrogen having one or more reactive groups capable of reacting with an epoxy group in a molecule, and having at least a molecule One or more of the functional groups selected from the group consisting of a primary amine group, a secondary amine group, and a tertiary amine group may be used. Thus, as an amine compound, such as, for example, although two projecting include ethyl, triethylenetetramine, tetraethylenepentamine extending, N- propylamine, 2-hydroxyethyl amino propylamine, cyclohexylamine, 4,4 '- diamino - an aliphatic amine of dicyclohexylmethane; an aromatic amine compound such as 4,4 ' -diaminodiphenylmethane or 2-methylaniline; 2-ethyl-4-methylimidazole, 2-B The heterocyclic compound containing a nitrogen atom such as a 4-methylimidazoline, a 2,4-dimethylimidazoline, a piperidine or a piperazine is not limited thereto.

Also, in particular, there is a grade 3 amine group in the molecule. A compound which is a latent hardening accelerator which has an excellent hardening-promoting ability, and examples of such a compound include, for example, dimethylaminopropylamine, diethylaminopropylamine, di-n-propylaminopropylamine. An amine compound such as dibutylaminopropylamine, dimethylaminoethylamine, diethylaminoethylamine or N-methylpiperazine, or such as 2-methylimidazole or 2-ethylimidazole, 2 An imidazole compound such as ethyl-4-methylimidazole or 2-phenylimidazole, having a grade 3 amine group or a grade 2 amine in the molecule; for example, 2-dimethylaminoethanol, 1- Methyl-2-dimethylaminoethanol, 1-phenoxymethyl-2-dimethylaminoethanol, 2-diethylaminoethanol, 1-butoxymethyl-2-dimethyl Aminoethanol, 1-(2-hydroxy-3-phenoxypropyl)-2-methylimidazole, 1-(2-hydroxy-3-phenoxypropyl)-2-ethyl-4- Methylimidazole, 1-(2-hydroxy-3-butoxypropyl)-2-methylimidazole, 1-(2-hydroxy-3-butoxypropyl)-2-ethyl-4-methyl Imidazole, 1-(2-hydroxy-3-phenoxypropyl)-2-phenylimidazoline, 1-(2-hydroxy-3-butoxypropyl)-2-methylimidazoline, 2 -(dimethylaminomethyl)phenol, 2,4,6-para ( Dimethylaminomethyl)phenol, N-β-hydroxyethylmorpholine, 2-dimethylaminoethanethiol, 2-mercaptopyridine, 2-benzimidazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 4-mercaptopyridine, N,N-dimethylaminobenzoic acid, N,N-dimethylglycine, nicotinic acid, isonicotinic acid, picolinic acid, N,N-di An alcohol, a phenol, or a thiol having a tertiary amino group in the molecule, such as methyl glutamate, N,N-dimethylpropionate, strontium nicotinate or isonicotinic acid strontium , carboxylic acids and terpenoids.

Addition reaction of the above epoxy compound and amine compound When a latent hardening accelerator is produced, an active hydrogen compound having two or more active hydrogens may be added to the molecule. Examples of such an active hydrogen compound include polyphenols such as bisphenol A, bisphenol F, bisphenol S, hydroquinone, catechol, resorcin, pyrogallol, and phenol novolac resin. Polyols such as trimethylolpropane, polycarboxylic acids such as adipic acid and phthalic acid, 1,2-dimercaptoethane, 2-mercaptoethanol, 1-mercapto-3-phenoxy- 2-propanol, thioglycolic acid, o-amine benzoic acid, lactic acid, etc., but are not limited thereto.

As the isocyanate compound used as a raw material for producing the solid dispersion type amine addition-based latent curing accelerator, for example, a monofunctional isocyanate such as n-butyl isocyanate, isopropyl isocyanate, phenyl isocyanate or benzyl isocyanate may be used. a compound; hexamethylene diisocyanate, methylphenyl diisocyanate (eg 2,4-methylphenylene diisocyanate, 2,6-methylphenylene diisocyanate), 1,5-naphthalene diisocyanate, Phenylmethane-4,4 ' -diisocyanate, isophorone diisocyanate, diphenylphenylene diisocyanate, p-phenylene diisocyanate, 1,3,6-hexamethylene triisocyanate, bicycloheptane A polyfunctional isocyanate compound such as a triisocyanate; and a compound having an isocyanate group having a terminal end obtained by a reaction between a polyfunctional isocyanate compound and an active hydrogen compound. Examples of such a compound having an isocyanate group at the terminal end include an addition compound having an isocyanate group at the end obtained by a reaction of methylphenyl diisocyanate with trimethylolpropane, and a phenyl diisocyanate. The addition compound having an isocyanate group at the terminal obtained by the reaction with pentaerythritol is not limited thereto.

Further, as the solid dispersion type amine adduct system The urea compound to be used as a raw material for the production of the curing accelerator is, for example, urea or thiourea, but is not limited thereto.

The above solid dispersion type latent hardening accelerator, for example, suitable When the above-mentioned raw materials are mixed and reacted at a temperature of from room temperature to 200 ° C, they are solidified by cooling, pulverized, or reacted in a solvent such as methyl ethyl ketone, dioxane or tetrahydrofuran. After the solvent, it can be easily obtained by pulverizing the solid content.

Commercially available as the above-mentioned solid dispersion type latent hardening accelerator Representative examples of the amine-epoxy adduct system (amine addition system) include AMICURE PN-23, AMICUREPN-H, and A. C. "Hardener X-3661S", "Hardener X-3670S", and "Novacure HX-3742" and "Novacure HX-3721" manufactured by Asahi Kasei Co., Ltd., and T&K TOKA as a urea-based additive system. The company's "FXE-1000" and "FXR-1030" are not limited to these.

Hardening when the content of the epoxy resin is 100 parts by mass The content of the accelerator is preferably from 0.1 to 100 parts by mass, more preferably from 1 to 60 parts by mass, still more preferably from 5 to 30 parts by mass.

The preservation stability enhancer which can be used in the invention can be It is added to achieve excellent storage stability of the curable resin composition of the present invention. Examples of the storage stability enhancer include a borate compound, a titanate compound, an aluminate compound, a zirconate compound, an isocyanate compound, a carboxylic acid, an acid anhydride, and a mercapto organic acid.

As the above boric acid ester compound, for example, trimethyl group is mentioned Borate, triethyl borate (TEB), tri-n-propyl borate, triisopropyl borate, tri-n-butyl borate, triamyl borate, tri Allyl borate, trihexyl borate, tricyclohexyl borate, trioctyl borate, tridecyl borate, tridecyl borate, (c) dodecyl boric acid Ester, (tri)hexadecyl borate, (tri)octadecyl borate, ginseng (2-ethylhexyloxy)borane, bis(1,4,7,10-tetraoxa Undecyl)(1,4,7,10,13-pentaoxatetradecyl)(1,4,7-trioxadecyl)borane, tribenzyl borate, three Phenyl borate, tri-o-tolyl borate, tri-m-tolyl borate, triethanolamine borate, and the like.

As the titanate compound, for example, tetraethyl group can be mentioned. Titanate, tetrapropyl titanate, tetraisopropyl titanate, tetrabutyl titanate, tetraoctyl titanate, and the like.

As the above-mentioned aluminate compound, for example, triethyl group can be mentioned Aluminate, tripropyl aluminate, triisopropyl aluminate, tributyl aluminate, trioctyl aluminate, and the like.

As the aforementioned zirconate compound, for example, tetraethyl group can be mentioned. Zirconate, tetrapropyl zirconate, tetraisopropyl zirconate, tetrabutyl zirconate, and the like.

As the above isocyanate compound, for example, n-butyl can be mentioned Isocyanate, isopropyl isocyanate, 2-chloroethyl isocyanate, phenyl isocyanate, p-chlorophenyl isocyanate, benzyl isocyanate, hexamethylene diisocyanate, 2-ethylphenyl isocyanate, 2, 6-di Methyl phenyl isocyanate, methyl phenyl diisocyanate (Example: 2,4-methylphenyl diisocyanate) Ester, 2,6-methylphenylene diisocyanate, 1,5-naphthalene diisocyanate, diphenylmethane-4,4'-diisocyanate, tolidine diisocyanate, isophorone diisocyanate, dimethyl Phenylene diisocyanate, p-phenylene diisocyanate, bicycloheptane triisocyanate, and the like.

Examples of the carboxylic acid include formic acid, acetic acid, and C. Halogenated fatty acids such as saturated aliphatic monobasic acids such as acid, butyric acid, caproic acid and caprylic acid, unsaturated aliphatic monobasic acids such as acrylic acid, methacrylic acid and crotonic acid, monochloroacetic acid and dichloroacetic acid, and glycol Aliphatic aldehydes such as acid, lactic acid, etc., alkaline oxyacids such as glyoxylic acid and gluconic acid, and aliphatic polybasic acids such as keto acid, malonic acid, malonic acid, succinic acid and maleic acid, and benzoic acid An aromatic polybasic acid such as halogenated benzoic acid, toluic acid, phenylacetic acid, cinnamic acid or mandelic acid, an aromatic polybasic acid such as phthalic acid or trimesic acid.

As the above acid anhydride, for example, succinic anhydride, twelve An alkenyl succinic anhydride, maleic anhydride, an adduct of methylcyclopentadiene and maleic anhydride, an aliphatic or aliphatic polybasic acid anhydride such as hexahydrophthalic anhydride or methyltetrahydrophthalic anhydride, An aromatic polybasic acid anhydride such as phthalic anhydride, trimellitic anhydride or pyromellitic anhydride. As a typical example of the commercially available acid anhydride, for example, methyltetrahydrophthalic anhydride which can be used as a curing agent for an epoxy resin, HN-2200 (manufactured by Hitachi Chemical Co., Ltd., molecular weight = 166), is not It is limited to this.

As the above mercapto organic acid, for example, mercapto B is exemplified. a mercapto aliphatic monocarboxylic acid such as an acid, a mercaptopropionic acid, a mercaptobutyric acid, a mercapto succinic acid or a dimercaptosuccinic acid, and an ester of a hydroxy organic acid and a mercapto organic acid A mercapto aromatic monocarboxylic acid such as a mercapto aliphatic monocarboxylic acid or mercaptobenzoic acid obtained by a reaction.

As a preservation stability enhancer, among these, by general Sex. From the viewpoint of high safety and improved storage stability, a borate compound is preferred, and more preferably triethyl borate, tri-n-propyl borate, triisopropyl borate, Tri-n-butyl borate, more preferably triethyl borate. The content of the stability improving agent is not particularly limited, but if the total content of the epoxy resin is 100 parts by mass, the content of the stability improving agent is preferably 0.001. ~50 parts by mass, more preferably 0.05 to 30 parts by mass, still more preferably 0.1 to 10 parts by mass.

Ginseng (3-mercaptopropyl) isocyanuric acid as described above The curable resin composition of the present invention can be produced by using various additives such as an ester, an epoxy resin, and an optional component as raw materials. The preparation of the curable resin composition is not particularly difficult, and can be carried out by a conventionally known method. For example, a liquid thermosetting epoxy resin composition of the present invention can be prepared by mixing the components with a mixer such as a Henschel mixer.

Further, one of the obtained liquid thermosetting resin compositions is hard It is not particularly difficult, and it can be carried out in a manner known in the past. For example, it can be hardened by heating the obtained curable resin composition. The heating is, for example, suitably 60 to 150 ° C, preferably 75 to 120 ° C, more preferably 80 to 100 ° C, for example, 1 to 60 minutes, preferably 3 to 30 minutes, more preferably 5 to 15 Minutes of time to come. In particular, if it is hardened by heating for 10 minutes or less at 80 ° C or 100 ° C, it can be judged. Broken moderately low temperature sclerosing.

Examples of the thixotropic imparting agent include fine powder of ceria, fatty acid decylamine, and polyolefin-based polymer. Specifically, fine powder ceria "AEROSIL 200" (manufactured by Nippon Aerosil Co., Ltd.), "AEROSIL R805" (manufactured by Nippon Aerosil Co., Ltd.), or the like can be used.

[Characteristics of one-component thermosetting resin composition] . Glass transition temperature

The cured product of the liquid thermosetting resin composition of the present invention has a glass transition temperature of, for example, 40 to 200 ° C as measured by JIS-K-7244-4. In the case of such a glass transition temperature, it is preferable to protect the electronic component or the like from temperature, humidity, and mechanical external force. The glass transition temperature of the preferred cured product is, for example, 45 to 180 ° C, more preferably 50 to 160 ° C. Here, the glass transition temperature of the cured product is the peak temperature of the tan δ curve obtained by the DMA measurement of the resin composition sample hardened under specific conditions.

. Tensile shear followed by strength A (maximum load / subsequent area)

The liquid type thermosetting resin composition of the present invention has a tensile shear strength measured by JIS-K-6850 as determined by the maximum load/adjacent area (hereinafter, sometimes referred to as stretch shear) The breaking strength A) is, for example, suitably 12 N/mm ² or more, preferably 12.5 to 50 N/mm ² , more preferably 13 to 30 N/mm ² , still more preferably 14 to 20 N/mm ² . Here, the tensile strength (stretching strength A) can be measured as follows. First, the test piece of the soft steel plate (JISG3141, SPCC) was wiped off with a rag moistened with acetone, and the surface of the back surface of the soft steel plate was ground with an endless belt #120. The resin composition was uniformly coated to a thickness of about 1 mm on the polished surface of the soft steel sheet, and the coated surface was overlapped by about 12.5 mm, and the two clips were attached and compacted. At this time, the exuded resin composition is immediately wiped off with a rag. The test pieces were evenly arranged in an oven, and heat-hardened at 80 ° C for 60 minutes and allowed to continue. The obtained test piece was subjected to tensile strength (measurement environment; temperature: 25° C./humidity: 40%, tensile speed; 5 mm/min) on a Tensilon universal testing machine (UTM-5T manufactured by TOYO BALDWIN Co., Ltd.). In the measurement of the tensile strength and the strength A, it is suitable to prepare three test pieces for each of the same resin composition.

The maximum load (N) of the damaged test piece was used as a reference, and the area (mm ² ) was measured, and the tensile shear strength A was calculated from the following formula.

Tensile shear followed by strength (N/mm ² ) = maximum load (N) / subsequent area (mm ² )

. Tensile shear followed by strength B (high humidity test)

The tensile shear strength measured by JIS-K-6850 and the strength A test are repeated for a certain period of time under high humidity, and the tensile strength is repeated (hereinafter, sometimes referred to as tensile shear strength). B) is, for example, suitably 8 N/mm ² or more, preferably 10 N/mm ² or more, more preferably 11 to 50 N/mm ² , still more preferably 12 to 30 N/mm ² . This tensile shearing was followed by the strength B in order to evaluate the moisture resistance of the one-component thermosetting resin composition. Here, the tensile strength (tensile shearing strength B) under the high humidity can be measured as follows. That is, three test pieces prepared in other manners were prepared in the same order as the evaluation of the adhesion. After being placed in a pressure cooker tester at 120 ° C and 85% RH for 24 hours, the obtained test piece was measured in a Tensilon universal testing machine (UTM-5T manufactured by TOYO BALDWIN Co., Ltd.) in the same manner as the adhesion test. Environment; temperature 25 ° C / humidity 40%, tensile speed; 5 mm / min). The maximum load (N) of the damaged test piece was used as a reference, and the area (mm ² ) was measured, and the tensile shear strength B was calculated in the same manner as the evaluation of the adhesion.

. Strength retention rate

The strength retention rate of the liquid type thermosetting resin composition of the present invention can be

[Strength retention ratio] = [stretching shearing strength B] / [stretching shearing strength A] is, for example, suitably more than 0.4, preferably 0.5 or more, more preferably 0.6 to 2.0, and even more preferably 0.7~1.6. By the strength retention ratio, the influence of the humidity on the subsequent strength can be evaluated. It can be said that the larger the value of the strength retention ratio, the more resistant the test piece is to high humidity.

[Epoxy resin cured, adhesive, sealing material, etc.]

Further, the present invention also includes an epoxy resin cured product obtained by heating one of the above liquid thermosetting resin compositions, and also includes a functional product containing the cured epoxy resin. Examples of the functional product include an adhesive, an injection molding agent, a sealing material, a sealant, a fiber-reinforced resin, a coating agent, and a paint.

Wherein, the present invention relates to the inclusion of one of the above liquid thermal hard An adhesive for the composition of the resin. Here, the adhesive is an adhesive that can be used in the field of adhesives for electronic parts. As the adhesive, a liquid epoxy resin adhesive which is one of a hardener and an epoxy resin composition is preferably mixed in advance.

In addition to the liquid thermosetting resin composition of the present invention, the above-mentioned adhesive may optionally contain a curing agent for an epoxy resin other than TMPIC, a hardening accelerator, a flame retardant, a storage stability enhancer, and a filler. Various additives such as a diluent, a solvent, a pigment, a flexibility imparting agent, a coupling agent, an antioxidant, a thixotropic imparting agent, and a dispersing agent.

The present invention additionally relates to the inclusion of one of the above liquid thermosetting A sealing material for a resin composition. Here, the term "sealing material" refers to a sealing material such as an underfill or a wafer sealing agent for flip chip mounting.

In addition to the curable resin composition of the present invention, the sealing material may optionally contain a curing agent for an epoxy resin other than TMPIC, a hardening accelerator, a flame retardant, a storage stability enhancer, a filler, and a diluent. Various additives such as a solvent, a pigment, a flexibility-imparting agent, a coupling agent, an antioxidant, a thixotropic imparting agent, and a dispersing agent.

[Examples]

Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited to the following examples. In addition, the "parts" in the following description means "parts by mass".

[Preparation of one-component thermosetting resin composition]

Each resin composition of the blending composition shown in Table 1 was prepared. For the specific plastic container, the specific amount of material shown in Table 1 is used, and the rotation is used. The revolutionary vacuum mixer defoaming chain Taro (manufactured by Thinky Co., Ltd.; ARE-250) was thoroughly mixed at 2000 rpm at room temperature (25 ° C), and further defoamed for 1 minute to obtain a desired resin composition.

Also, the details of the materials used are as follows.

HP-4032D: DIC Corporation, naphthalene epoxy resin, epoxy equivalent 172g/eq

EXA4710: Naphthalene novolac epoxy resin, epoxide equivalent 171g/eq

ESN-475V Nippon Steel & Sumitomo Co., Ltd., naphthalene novolac epoxy resin, epoxy equivalent 190g/eq

JER828EL: bisphenol A type (BPA type) epoxy resin manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 190g/eq

N-695: cresol novolak type epoxy resin

TMPIC: Ajinomoto Fine Techno, ginseng (3-mercaptopropyl) isocyanurate, thiol group total equivalent 117g / eq

TMTP: Trimethylolpropane ginseng (3-mercaptopropionate, thiol group total equivalent 133g/eq)

PN-23: Ajinomoto Fine Techno Co., Ltd., amine epoxy addition system hardener

FXR-1081: T&K TOKA company, modified polyamine system potential hardener

AEROSIL 200: Made from Japan Aerosil Co., Ltd., particulate cerium oxide

TEB: Triethyl Borate, manufactured by Pure Chemical Industry Co., Ltd.

HN-2200: 3 or 4-methyl-1,2,3,6-tetrahydrophthalic anhydride manufactured by Hitachi Chemical Co., Ltd. (total equivalent of thiol group = thiol group containing 1 equivalent of thiol group Quality of the compound)

[thiol/epoxy equivalent ratio]

The "thiol/epoxy equivalent ratio" in Table 1 was determined by the following formula.

"thiol/epoxy equivalent ratio" = (thiol mass ÷ thiol group total equivalent) ÷ (epoxy resin mass ÷ epoxy equivalent)

[Measurement of viscosity]

A conical rotor (Rotor code No. 6, 3° x R9.7) was attached to a RE80 type viscometer (manufactured by Toki Sangyo Co., Ltd.), and 0.2 to 0.3 ml of a resin composition to be measured was measured by a syringe in a measuring chamber. At the time of measurement, the measurement chamber of the viscometer was subjected to temperature management at 25.0 ° C in an external circulation type thermostatic chamber. The number of rotations of the rotor was set to 0.5, 10, 20, and 100 rpm, and the viscosity (unit: Pa.s) after 120 seconds of various rotation numbers was measured.

[Measurement of glass transition temperature]

Each of the resin compositions obtained in the examples and the comparative examples was used to prepare a test piece of 7 mm x 30 mm, which was measured by DMA according to JIS-K-7244-4. The device (manufactured by Seiko Instruments Inc., DMS6100) was measured for tan δ by a stretching method, a frequency of 1 Hz, a temperature increase rate of 2 ° C/min, and a measurement temperature range of 0 ° C to 300 ° C. The temperature at which the obtained tan δ curve represents a peak is taken as the glass transition temperature. The unit is °C.

[Evaluation of low temperature hardenability]

The low-temperature curability of the resin composition of the present invention is evaluated by measuring the gel time (gelation time) according to JIS C6521.

Specifically, first, the time when the resin composition of each of the examples and the comparative examples could not be drawn at 60 ° C and 80 ° C was measured by a hot plate type gelation tester (GT-D: manufactured by Nisshin Scientific Co., Ltd.). Specifically, about 0.5 g of the sample (resin composition) was placed on a hot plate type gelation tester, and it became a time point of 60 ° C (60 ° C gel time) or 80 ° C (80 ° C gel time). As a starting point, the resin composition was subjected to repeated contact circular motion (1 second rotation) with a spatula having a tip end width of 5 mm in a manner of shrinking to a diameter of 25 mm on a hot plate to form a resin composition. 30 mm was lifted vertically upward from the hot plate, and the time from the start point to the end point was regarded as the end time from the start of the gelation, and the measurement was performed. Further, the spatula and the viscosity of the resin are maintained in such a manner that the viscosity is maintained in a low range, and if the viscosity is increased, the vertical movement is repeated from the hot plate by about 30 mm to the segmented filament. The measurement was repeated 3 times, and the average value thereof was used.

[Evaluation of strength] Tensile shear test

The test piece of the soft steel plate (JISG3141, SPCC) was wiped off with a rag moistened with acetone. Further, the surface of the back surface of the soft steel sheet was ground with an endless belt #120. The resin composition was uniformly coated to a thickness of about 1 mm on the polished surface of the soft steel sheet, and the coated surface was overlapped by about 12 mm, and the two clips were attached and compacted. At this time, the exuded resin composition was immediately wiped off with a rag. The test pieces were evenly arranged in an oven, and heat-hardened at 80 ° C for 60 minutes and allowed to continue. For the same resin composition, three test pieces were prepared for each. The obtained test piece was subjected to tensile shearing strength according to JIS-K-6850 in a Tensilon universal testing machine (UTM-5T manufactured by TOYO BALDWIN Co., Ltd.) (measurement environment; temperature 25 ° C / humidity 40%, stretching speed; 5mm/min).

The maximum load (N) of the damaged test piece was used as a reference, and the subsequent area (mm ² ) was measured, and the tensile shearing strength A was calculated from the following formula.

Tensile shear followed by strength (N/mm ² ) = maximum load (N) / subsequent area (mm ² )

[Evaluation of moisture resistance]

Three test pieces each prepared in the other manner were prepared in the same order as the evaluation of the adhesion. After being placed in a pressure cooker tester at 120 ° C and 85% RH for 24 hours, the obtained test piece was placed in a Tensilon universal test machine (UTM-5T manufactured by TOYO BALDWIN Co., Ltd.) in the same manner as the adhesion test according to JIS-K-6850. The tensile shearing was followed by the strength (measurement environment; temperature 25 ° C / humidity 40%, stretching speed; 5 mm / min). The maximum load (N) of the damaged test piece was used as a reference, and the subsequent area (mm ² ) was measured, and the tensile shear strength B was calculated in the same manner as the evaluation of the adhesion.

[strength retention rate]

In order to evaluate the effect of the humidity on the adhesion strength, the strength retention ratio was calculated. The strength retention ratio was calculated from the values of the above-described tensile shearing strength A and the tensile shearing strength B, as follows.

[Strength retention ratio] = [stretching shearing strength B] / [stretching shearing strength A] It can be said that the larger the value of the strength retention ratio, the more resistant the test piece is to high humidity.

[Investigation of evaluation results]

The results of the above evaluations are shown in Table 1. As shown in Table 1, it was found that one of the liquid thermosetting resin compositions of Examples 1 to 9 had good low-temperature curability and good moisture resistance as compared with the resin composition of the comparative example.

The present invention can also be as follows.

〔1〕

A one-component thermosetting resin composition comprising ginseng (3-mercaptopropyl)isocyanurate and a liquid-type thermosetting resin composition of an epoxy resin, characterized in that the resin composition The glass transition temperature is 40~200 °C.

〔2〕

The resin composition according to [1], wherein the epoxy resin has an epoxy equivalent of from 150 to 1,000.

[3]

The resin composition according to [1] or [2] wherein the epoxy resin contains a naphthalene type epoxy resin.

[4]

The resin composition according to any one of the above aspects, wherein the epoxy resin contains a naphthalene type epoxy resin represented by the formula (1). (In the formula (1), R may be the same or different from each other as a divalent hydrocarbon group having 1 to 30 carbon atoms which may or may not have a substituent, and G may be the same or different from each other as a hydrogen atom or the following formula (2) : The epoxy group is represented, and at least two of G in the formula (1) are an epoxy group represented by the above formula (2), and n is an integer of 0 to 10).

[5]

The resin composition according to [4], wherein, in the above formula (1), R may be the same or different from each other, and may have or may have a substituent of a dialkylphenyl group having a carbon number of 8 to 14 or a carbon number of 1. ~10 alkylene.

[6]

The resin composition according to any one of [1] to [5] further comprising a solid dispersion type latent curing accelerator.

[7]

The resin composition according to any one of [1] to [6] further comprising a boric acid ester compound, a titanate compound, an aluminate compound, a zirconate compound, an isocyanate compound, or a carboxylic acid. 1 or more of an acid anhydride and a mercapto organic acid.

〔8〕

An adhesive composition according to any one of [1] to [7].

〔9〕

A resin composition according to any one of [1] to [7].

[10]

A cured product obtained by heating the resin composition according to any one of [1] to [7].

Claims (12)

A one-component thermosetting resin composition comprising ginseng (3-mercaptopropyl)isocyanurate and a naphthalene type epoxy resin represented by formula (1); (In the formula (1), R may be the same or different from each other as a divalent hydrocarbon group having 1 to 30 carbon atoms which may or may not have a substituent, and G may be the same or different from each other as a hydrogen atom or the following formula (2) : The epoxy group is represented, and at least two of G in the formula (1) are an epoxy group represented by the above formula (2), and n is an integer of from 1 to 10). The resin composition of claim 1, wherein, in the above formula (1), R may be the same or different from each other, and may be a dialkylphenyl group having a carbon number of 8 to 14 or a carbon number 1 which may or may not have a substituent. ~10 alkylene. The resin composition of claim 1 or 2, which further comprises a solid dispersion type latent hardening accelerator. The resin composition of claim 1 or 2, which further comprises a compound selected from the group consisting of a borate compound, a titanate compound, an aluminate compound, a zirconate compound, an isocyanate compound, a carboxylic acid, an acid anhydride, and a mercapto organic acid. the above. The resin composition of claim 1 or 2, wherein the cured product of the one-liquid type thermosetting resin composition has a glass transition temperature of 40 to 200 ° C as measured according to JIS-K-7244-4. The resin composition of claim 1 or 2, wherein the cured product of the one-component thermosetting resin composition is allowed to stand at 120 ° C and 85% RH for 24 hours, and then measured according to JIS-K-6850 The tensile shearing is then followed by an intensity B (N/mm ² ) of 8 or more. The resin composition of claim 1 or 2, wherein the cured product of the one-liquid type thermosetting resin composition has a strength retention ratio (B/A) of more than 0.4, and the strength retention ratio (B/A) is determined by The cured product of the one-component thermosetting resin composition has a tensile strength A (N/mm ² ) measured by JIS-K-6850 and a cured product of the one-component thermosetting resin composition. After standing for 24 hours under conditions of 120 ° C and 85% RH, the tensile shear measured by JIS-K-6850 was used to calculate the strength B (N/mm ² ). An adhesive comprising the resin composition according to any one of claims 1 to 7. A material for sealing comprising the resin composition according to any one of claims 1 to 7. A cured product obtained by heating the resin composition according to any one of claims 1 to 7. The resin composition of claim 1 or 2, which further comprises a bisphenol A type epoxy resin. The resin composition of claim 11, wherein the naphthalene ring The mass ratio of the oxygen resin to the bisphenol A type epoxy resin is [naphthalene type epoxy resin]: [bisphenol A type epoxy resin] = 10:1 to 1:10.