KR20160077132A - Flexible epoxy resin composition - Google Patents

Abstract

[화학식 2]

(화학식 1 및 화학식 2 중,
X, X₁ 및 X₂는 서로 동일해도 상이해도 좋고, 2 이상의 -(CH₂)-를 주골격에 포함하는 2가의 비방향족 탄화수소기이고(단, X가 -O-CH₂-CH(-OH)-CH₂-인 경우를 제외한다),
Ar, Ar₁ 및 Ar₂는 서로 동일해도 상이해도 좋고, 2가의 방향족기를 주골격에 포함하는 2가의 방향족 함유 탄화수소기이고,
n 및 m은 각각 독립적으로, 1 내지 20의 정수이다)
로 표시되는 에폭시 화합물 또는 이들의 중합체를 함유하는, 일액형 열경화성 수지 조성물을 제공한다.A one-component thermosetting composition capable of achieving low-temperature curability and securing adhesive strength, and having both low-temperature curability and moisture resistance. Concretely, the tris (3-mercaptopropyl) isocyanurate and the epoxy resin are represented by the general formula (1) or (2)
[Chemical Formula 1]

(2)

(In the formulas (1) and (2)
X, X ₁ and X ₂ may be the same or different and each is a divalent non-aromatic hydrocarbon group containing two or more - (CH ₂ ) - in the main skeleton, provided that X is -O-CH ₂ -CH (- OH) -CH ₂ -),
Ar, Ar ₁ and Ar ₂ may be the same or different and are a divalent aromatic containing hydrocarbon group containing a divalent aromatic group in its main skeleton,
n and m are each independently an integer of 1 to 20)
, Or an epoxy compound represented by the following formula (1) or a polymer thereof.

Description

[0001] FLEXIBLE EPOXY RESIN COMPOSITION [0002]

The present invention relates to a one-part thermosetting resin composition containing tris (3-mercaptopropyl) isocyanurate and a specific epoxy resin. The present invention also relates to an adhesive and a sealing material comprising the one-part thermosetting resin composition, and a flexible epoxy resin cured product obtained by heating the curing resin composition.

Epoxy resins have been used in a wide range of applications such as dyes, electrical and electronic insulating materials and adhesives because they have excellent properties in terms of mechanical properties, electrical properties, thermal properties, chemical resistance and adhesive strength. In recent years, a one-component epoxy resin composition has been developed in which, in use, an epoxy resin and a curing agent are mixed in advance in addition to a so-called two-component epoxy resin composition in which an epoxy resin and a curing agent are mixed and cured. Particularly, in the field of electronic circuits in recent years, examination of flexible and thin has actively been carried out, and there is an increasing demand for a low-temperature curable one-pack type epoxy resin composition for protection of semiconductor elements, higher density of circuits and improved reliability of connection .

For example, a low temperature curable one-component epoxy resin composition using a thiol curing agent is known (Patent Document 1). However, if too low temperature curability is sought, the peel strength may be lowered. In addition, the curing agent contained in the conventional one-component epoxy resin composition having low-temperature curability generally has a low humidity resistance and a problem that the adhesive strength is lowered in a high-humidity environment.

Japanese Patent Application Laid-Open No. 6-211969

SUMMARY OF THE INVENTION [

An object of the present invention is to provide a one-part thermosetting composition having both low-temperature curability, peel strength and moisture resistance.

[MEANS FOR SOLVING PROBLEMS]

DISCLOSURE OF THE INVENTION As a result of intensive studies to solve the above problems, the present inventors have found that a single-component type thermosetting resin composition containing tris (3-mercaptopropyl) isocyanurate and a specific epoxy resin, The above problems are solved by a one-part type thermosetting resin composition having a cured product of a resin composition having an elastic modulus at 25 캜 of 10 to 2500 MPa.

That is, the present invention is as follows.

[1] A process for producing a tris (3-mercaptopropyl) isocyanurate comprising reacting tris (3-mercaptopropyl) isocyanurate with an epoxy resin,

[Chemical Formula 1]

(2)

(In the formulas (1) and (2)

X, X ₁ and X ₂ may be the same or different and each is a divalent non-aromatic hydrocarbon group containing two or more - (CH ₂ ) - in the main skeleton, provided that X is -O-CH ₂ -CH (- OH) -CH ₂ -),

Ar, Ar ₁ and Ar ₂ may be the same or different and are a divalent aromatic containing hydrocarbon group containing a divalent aromatic group in its main skeleton,

n and m are each independently an integer of 1 to 20)

Wherein the thermosetting resin composition is a thermosetting resin composition.

[2] The organic electroluminescent device described in [1] above, wherein the divalent non-aromatic hydrocarbon group containing two or more - (CH ₂ ) - in the main skeleton is an alkylene group having 2 to 20 carbon atoms which may or may not have a substituent, An alkyleneoxy group having 2 to 20 carbon atoms which may or may not be present.

[3] The method according to the above [1] or [2], wherein the divalent non-aromatic hydrocarbon group containing two or more - (CH ₂ )

(b1) -O-CH (-CH 3) - (O- (CH 2) p) q -O-CH (-CH 3) -,

(b2) - (O- (CH 2) r) s -,

(b3) - (O-CH 2 -CH (-CH 3)) t -,

_{(b4) -O-CH 2 -CH} (-OH) -CH 2 - (O- (CH 2) u) v -O-CH 2 -CH (-OH) -CH 2 -,

(b5) - (O- (CH ₂ ) _w ) _y -O-CH ₂ -CH (-OH) -, and

(b6) - (O-CH 2 -CH (-CH 3)) z -O-CH 2 -CH (-OH) -

(Wherein p, q, r, s, t, u, v, w, y and z are each independently an integer of 1 to 20)

≪ / RTI >

[4] The method according to any one of the above items [1] to [3], wherein the bivalent aromatic-containing hydrocarbon group containing the bivalent aromatic group in the main skeleton is,

및

And

≪ / RTI >

[5] The resin composition according to any one of [1] to [4], further comprising a solid dispersed latent curing accelerator.

[6] The organic electroluminescent device according to any one of the above items [1] to [5], which is selected from the group consisting of a borate compound, titanate compound, aluminate compound, zirconate compound, isocyanate compound, carboxylic acid, acid anhydride and mercapto organic acid 1 < / RTI >

[7] The resin composition according to any one of [1] to [6], wherein the cured product of the one-part thermosetting resin composition has an elastic modulus at 25 ° C of 10 to 2500 MPa.

[8] The cured product of the above-mentioned one-component type thermosetting resin composition according to any one of [1] to [7], which is left under the conditions of 120 ° C and 85% RH for 24 hours, And a peel strength B (N / 25 mm) measured according to the following formula is 9 or more.

[9] A method for producing a one-component thermosetting resin composition according to any one of [1] to [8], wherein the cured product of the one-component thermosetting resin composition is a mixture of the peel strength A (N / 25 mm) measured in accordance with JIS-K- The cured product of the one-part thermosetting resin composition was allowed to stand for 24 hours under the conditions of 120 ° C and 85% RH, and then the one-part type thermosetting resin (1) obtained from the peeling strength B (N / 25 mm) measured in accordance with JIS K- Wherein the strength retention ratio (B / A) of the cured product of the composition is 0.67 or more.

[10] An adhesive comprising the resin composition according to any one of [1] to [9].

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

[12] An epoxy resin cured product obtained by heating the resin composition according to any one of [1] to [9] above.

[13] A resin composition according to any one of [1] to [9], further comprising a bisphenol A type epoxy resin.

[14] The epoxy resin composition as described in [13], wherein the mass ratio of the epoxy compound or the polymer thereof to the bisphenol A epoxy resin is 10: 1 to 1: 1 [epoxy compound or polymer thereof]: [bisphenol A type epoxy resin] 10.

 The one-component type thermosetting resin composition of the present invention is an epoxy resin composition excellent in low temperature curability, peel strength and moisture resistance. Particularly, it is excellent in peel strength and moisture resistance and excellent in elasticity, for example, in the range of 10 to 2500 MPa. Therefore, it can be used for adhesives and sealing materials, and can be used for diabetic materials, underfill materials, It can be used as a material. Here, the " one-part type " thermosetting resin composition is a composition prepared by previously mixing a curing agent and an epoxy resin, and means a composition having properties of curing by applying heat to the composition.

[Tris (3-mercaptopropyl) isocyanurate (TMPIC)]

The tris (3-mercaptopropyl) isocyanurate contained in the one-part thermosetting resin composition of the present invention is a thiol compound represented by the following structural formula.

Tris (3-mercaptopropyl) isocyanurate functions as a curing agent for an epoxy resin.

The content of tris (3-mercaptopropyl) isocyanurate is, for example, 10 to 100 parts by mass, preferably 20 to 20 parts by mass, when the total epoxy resin contained in the one-part thermosetting resin composition of the present invention is 100 parts by mass To 90 parts by mass, more preferably 30 to 80 parts by mass, still more preferably 40 to 70 parts by mass.

[Epoxy resin]

The epoxy equivalent of the epoxy resin contained in the one-part thermosetting resin composition of the present invention is, for example, preferably 200 to 1000, more preferably 300 to 600. [ When the epoxy equivalent of the epoxy resin is 200 or more, volatility is low, the viscosity is not low, and the viscosity becomes easy to handle. When the epoxy equivalent of the epoxy resin is 1000 or less, a high viscosity is not obtained and it is suitable for handling. Here, the epoxy equivalent is a mass of an epoxy resin containing one equivalent of an epoxy group, and can be measured in accordance with, for example, JIS K 7236 (2009).

The epoxy resin of the present invention comprises (a) at least two epoxy groups, (b) a divalent non-aromatic hydrocarbon group containing at least 2 - (CH ₂ ) - in the main skeleton, and (c) a bivalent aromatic group in the main skeleton Containing aromatic group-containing hydrocarbon group, or a polymer thereof.

(a) the epoxy group referred to as " two or more epoxy groups " is a monovalent group represented by the following formula:

(b) a divalent non-aromatic hydrocarbon group containing two or more - (CH ₂ ) - in the main skeleton

Here, the "main skeleton" refers to a skeleton having the longest chain in the skeleton having two or more epoxy groups at both ends of (a).

In the divalent non-aromatic hydrocarbon group, the number of - (CH ₂ ) - contained in the main skeleton is preferably 2 or more, more preferably 3 or more, still more preferably 4 or more, particularly preferably 5 to 30, Particularly preferably from 6 to 20.

The above-mentioned two or more - (CH ₂ ) - may be bonded directly or may be bonded through two carbon atoms bonded by an ether bond, an ester bond, an amide bond and a double bond, two carbons bonded by a triple bond, It may be.

The "divalent non-aromatic hydrocarbon group containing two or more - (CH ₂ ) - in the main skeleton" includes, for example, an alkylene group and an alkyleneoxy group, which may or may not have a substituent.

Examples of the substituent include a hydroxyl group, a halogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkyloxy group, an amino group, a silyl group, an acyl group, an acyloxy group, a carboxyl group, a cyano group, A mercapto group and an oxo group.

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

The alkyl group used as a substituent may be either linear or branched. The number of carbon atoms of the alkyl group is preferably 1 to 20, more preferably 1 to 14, still 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, A decyl group, and a decyl group. As described later, the alkyl group used as the substituent may further have a substituent ("secondary substituent"). Examples of the alkyl group having such a secondary substituent include 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 a substituent is preferably 3 to 20, more preferably 3 to 12, still 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 the substituent may be either linear or branched. The number of carbon atoms of the alkoxy group is preferably 1 to 20, preferably 1 to 12, more preferably 1 to 6. Examples of the alkoxy group include methoxy, ethoxy, propyloxy, isopropyloxy, butoxy, sec-butoxy, isobutoxy, tert- , A heptyloxy group, an octyloxy group, a nonyloxy group, and a decyloxy group.

The number of carbon atoms of the cycloalkyloxy group used as a substituent is preferably 3 to 20, more preferably 3 to 12, still more preferably 3 to 6. Examples of the cycloalkyloxy group include a cyclopropyloxy group, a cyclobutyloxy group, a cyclopentyloxy group, and a cyclohexyloxy group.

The amino group used as a substituent may be either linear or branched aliphatic or aromatic. The number of carbon atoms of the amino group is preferably 1 to 20, preferably 1 to 12, more preferably 1 to 6. Examples of the amino group include an amino group such as an aminomethyl group, an aminoethyl group, an aminopropyl group, an isopropylamino group, an aminobutoxy group, a sec-butylamino group, an isobutylamino group, a tert-butylamino group, an aminopentyl group, An aminoethyl group, an aminonyl group, an aminodecyl group, and an aminophenyl group.

The silyl group used as a substituent may be either linear or branched. The number of carbon atoms of the silyl group is preferably 1 to 20, preferably 1 to 12, more preferably 1 to 6. Examples of the silyl group include a methylsilyl group, an ethylsilyl group, a propylsilyl group, an isopropylsilyl group, a butoxysilyl group, a sec-butylsilyl group, an isobutylsilyl group, a tert- A silyl group, a hexylsilyl group, a heptylsilyl group, an octylsilyl group, a nonylsilyl group, and a decylsilyl group.

The acyl group used as a substituent means a group represented by the formula: -C (= O) -R1 (wherein R1 is an alkyl group). The alkyl group represented by R < 1 > may be either linear or branched. The number of carbon atoms of the acyl group is preferably 2 to 20, more preferably 2 to 13, still more preferably 2 to 7. Examples of the acyl group include an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, and a pivaloyl group.

The acyloxy group used as a substituent means a group represented by the formula: -O-C (= O) -R2 (wherein R2 is an alkyl group). The alkyl group represented by R < 2 > may be either linear or branched. The number of carbon atoms of the acyloxy group is preferably 2 to 20, more preferably 2 to 13, still more preferably 2 to 7. Examples of the acyloxy group include an acetoxy group, a propionyloxy group, a butyryloxy group, an isobutyryloxy group, and a pivaloyloxy group.

The "divalent non-aromatic hydrocarbon group containing two or more - (CH ₂ ) - in its main skeleton" means a divalent non-aromatic hydrocarbon group containing two or more - (CH ₂ ) - in addition to two or more - (CH ₂ ) A nonaromatic divalent group other than a methylene group such as an alkylene group, an alkylene group, an alkylene group, an alkylene group,

The "divalent non-aromatic hydrocarbon group containing two or more - (CH ₂ ) - in the main skeleton" includes, for example, an alkylene group having 2 to 20 carbon atoms which may or may not have a substituent, An alkyleneoxy group having 2 to 20 carbon atoms which may not be present is preferable. Here, the number of the carbon atoms is the number excluding the carbon number of the substituent when it contains a substituent.

The alkyleneoxy group may have at least one of the structures represented by the following formulas, for example.

(b1) -O-CH (-CH 3) - (O- (CH 2) p) q -O-CH (-CH 3) -,

(b2) - (O- (CH 2) r) s -,

(b3) - (O-CH 2 -CH (-CH 3)) t -,

_{(b4) -O-CH 2 -CH} (-OH) -CH 2 - (O- (CH 2) u) v -O-CH 2 -CH (-OH) -CH 2 -,

(b5) - (O- (CH ₂ ) _w ) _y -O-CH ₂ -CH (-OH) -, and

(b6) - (O-CH 2 -CH (-CH 3)) z -O-CH 2 -CH (-OH) -

Here, p, r, u and w are integers of 1 to 20, more preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 to 3. Here, q, s, t, v, y and z are integers of 1 to 20, more preferably 1 to 10, further preferably 1 to 6, and further preferably 1 to 3.

(c) a divalent aromatic containing hydrocarbon group containing a divalent aromatic group in the main skeleton

In the divalent aromatic-containing hydrocarbon group containing a divalent aromatic group in the main skeleton, the aromatic group may be, for example, a phenylene group, a naphthalene group, an anthracene group, or a biphenyl group. The phenylene group may be an ortho, meta or para phenylene group. The aromatic divalent hydrocarbon group may contain two or more of the aromatic groups. When the aromatic group contains two or more aromatic groups, the aromatic group may be bonded directly or may be bonded through two carbon atoms bonded through an alkylene group, an ether bond, an ester bond, an amide bond, a double bond, It may be.

Particularly, as the preferable divalent aromatic-containing hydrocarbon group,

및

And

.

The epoxy compound of the present invention is preferably a compound having an epoxy group whose main skeleton is linear rather than cyclic. As long as the epoxy compound as a whole is linear, a bivalent cyclic group such as a divalent aromatic group may be partially included in the main skeleton. The group constituting the main skeleton may have a substituent as described above. The term "polymer of an epoxy compound" means that the epoxy compound is polymerized to form a polymer having a molecular weight of, for example, 500 to 1,500.

The one-part thermosetting resin composition of the present invention preferably contains an epoxy compound represented by the following formula (1) or (2) or a polymer thereof as an epoxy resin.

[Chemical Formula 1]

(2)

X, X ₁ and X ₂ in the general formulas (1) and ( ₂ ) are divalent non-aromatic hydrocarbon groups containing two or more - (CH ₂ ) - in the main skeleton, provided that X is -O-CH ₂ -CH -CH ₂ -). Here, the definition of the "divalent non-aromatic hydrocarbon group containing two or more - (CH ₂ ) - in the main skeleton" is as described above. The n number of X in the formula (1) may be the same or different. Formula (2) of the m pieces of X _1, X ₂ is the m may be the same or different from each other. X, X ₁ and X ₂ may be a group selected from the above-mentioned (b1) to (b6).

In the general formulas (1) and (2), Ar, Ar ₁ and Ar ₂ may be the same or different and are divalent aromatic hydrocarbon groups containing a divalent aromatic group in the main skeleton, which may or may not have a substituent. The definition of a bivalent aromatic hydrocarbon-containing hydrocarbon group containing a bivalent aromatic group in its main skeleton is as described above.

In the formulas (1) and (2), n and m are each independently an integer of 1 to 20, preferably 1 to 10.

The epoxy resin of formula (2) may have a structure represented by the following formula (2 ').

[Formula 2 ']

The definitions of X _3-6 and Ar _3-4 in formula (2 ') are the same as those of X and Ar defined above. X ₃ , X ₄ , m 'X ₅ and m' X ₆ in formula (2 ') may be the same or different. X and X _3-6 may be a group selected from the above-mentioned (b1) to (b6). m 'is an integer of 1 to 20, preferably 1 to 10.

Specific examples of epoxy compounds or polymers thereof usable in the present invention include resins having the following structures (k is an integer of 1 to 20, preferably an integer of 1 to 5).

For example, the resin of the following structure (h is an integer of 0 to 20, preferably 0 to 5, and each of i and j is an integer of 1 to 20, preferably an integer of 1 to 5 And preferably, i + j = 2 to 10).

및

And

EXA-4850-150 (corresponding to the formula 1), EXA-4816 (corresponding to the formula 1) and EXA-4822 (corresponding to the formula 1) manufactured by DIC Corporation; (Corresponding to formula 2), EP-4000S (corresponding to formula 2), EP-4000SS (corresponding to formula 2), EP-4003S ); BEO-60E and BPO-20E manufactured by Shin-Etsu Chemical Co., Ltd.; And YL7175-500, YL7175-1000, and YL7410 manufactured by Mitsubishi Kagaku Co., Ltd., and the like.

The one-part thermosetting resin composition of the present invention may contain various epoxy resins as long as the cured product of the resin composition has a modulus of elasticity at 25 DEG C in a desired range in addition to or in place of the epoxy compound or the polymer thereof. For example, polyglycidyl ethers obtained by reacting polyhydric phenols such as bisphenol A, bisphenol F, bisphenol AD, bisphenol E, catechol and resorcinol, polyhydric alcohols such as glycerin and polyethylene glycol with epichlorohydrin; polyglycidyl ether esters obtained by reacting epichlorohydrin with a hydroxy acid such as p-hydroxybenzoic acid and? -hydroxynaphthoic acid; Polyglycidyl esters obtained by reacting polycarboxylic acids such as phthalic acid and terephthalic acid with epichlorohydrin; Epoxylated phenol novolac resins, epoxylated cresol novolak resins, epoxylated polyolefins, cyclic aliphatic epoxy resins, and other urethane-modified epoxy resins; , But are not limited to these.

A phenol novolak type epoxy resin, a biphenyl aralkyl type epoxy resin, a phenol aralkyl type epoxy resin, an aromatic glycidyl amine, a phenol novolak type epoxy resin, a phenol novolac type epoxy resin, Type epoxy resin and an epoxy resin having a dicyclopentadiene structure are preferable, and a bisphenol A type epoxy resin and a bisphenol F type epoxy resin are more preferable, and a bisphenol A type epoxy resin is more preferable.

These resins may be liquid or solid. Further, a mixture of a liquid resin and a solid resin may be used. Here, the terms "liquid phase" and "solid phase" refer to the state of the epoxy resin at room temperature (25 ° C.). From the viewpoints of coatability, workability and adhesiveness, it is preferable that at least 10 mass% or more of the entire epoxy resin used is a liquid epoxy resin.

Specific examples of such a resin include bisphenol A type epoxy resin (hereinafter sometimes abbreviated as BPA type) epoxy resin (JER828EL, JER827, JER1001 manufactured by Mitsubishi Kagaku), bisphenol F type epoxy resin (Mitsubishi Kagaku Co., (JERYX8000 manufactured by Mitsubishi Kagaku Co., Ltd.), dicyclopentadiene type polyfunctional epoxy resin (DIC (manufactured by Mitsubishi Kagaku Kogyo KK)), bisphenol AF type epoxy resin ("ZX1059" Epoxy resin having a butadiene structure ("PB-3600" manufactured by Daicel Chemical Industries Ltd.), epoxy resin having a biphenyl structure ("NC3000H" manufactured by Nippon Kayaku Co., Ltd., "NC3000L" Quot; YX4000 " manufactured by Kusa Co., Ltd.). Of these, BPA type epoxy resins having high heat resistance and low viscosity are preferably used, and "JER828EL", "JER827", "JER1001" and "JER807" manufactured by Mitsubishi Kagaku are preferred, and "JER828EL" Do.

When the BPA type epoxy resin is used in addition to the " epoxy compound or polymer thereof ", the mass ratio of the " epoxy compound or polymer thereof " and the BPA type epoxy resin is, for example, " Epoxy resin is 10: 1 to 1:10, preferably 10: 1 to 1: 5, more preferably 9: 1 to 1: 2, and still more preferably 8: 1 to 1:

[Other additives]

The curable resin composition of the present invention may optionally contain a curing agent for epoxy resins other than TMPIC, a curing accelerator, a flame retardant, a storage stability improver, a filler, a diluent, a solvent, a pigment, a flexibility imparting agent, a coupling agent, an antioxidant, , And a dispersant may be added.

Examples of the curing agent for epoxy resins other than TMPIC include imidazole-based curing agents and amine-based curing agents. Further, a thiol compound other than TMPIC such as trimethylolpropane tris (3-mercaptopropionate) (TMTP), trimethylolpropane tris (thioglycolate), pentaerythritol tetrakis (thioglycolate) Polyols such as glycol dithiol glycolate, trimethylolpropane tris (? -Thiopropionate), pentaerythritol tetrakis (? -Thiopropionate), and dipentaerythritol poly (? -Thiopropionate) The thiol compound obtained by the esterification reaction of an organic acid can also be used as a curing agent for an epoxy resin.

Examples of the curing accelerator that can be used in the present invention include a solid dispersed latent curing accelerator. The solid dispersed latent curing accelerator is a compound insoluble in the above-mentioned epoxy resin at room temperature (25 캜), which is solubilized by heating to function as a curing accelerator for epoxy resin, and is an imidazole compound which is solid at room temperature, Dispersant amine adduct latent curing accelerators, and the like. Examples of the solid dispersed amine adduct latent curing accelerator include reaction products of amine compounds and epoxy compounds (amine-epoxy adduct system), reaction products of amine compounds and isocyanate compounds or urea compounds (urea type adduct system), etc. . Of these, a solid dispersed amine adduct latent curing accelerator is preferable.

Examples of the imidazole compound which is solid at room temperature include 2-heptadecylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-undecylimidazole, 4-benzyl-5-hydroxymethylimidazole, 2,4-diamino-6- (2-methylimidazolyl- ) -Ethyl-S-triazine, isocyanuric acid adduct, 2,4-diamino-6- (2'-methylimidazolyl- (1) Imidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl- (2-methylimidazolyl-1-ethyl) -urea, N, N '- (2-methylimidazolyl- 1) -ethyl) -adipoyldiamide, and the like, but are not limited thereto.

Examples of the epoxy compound used as one of raw materials for producing the solid dispersed amine adduct latent curing accelerator (amine-epoxy adduct system) include bisphenol A, bisphenol F, catechol, resorcinol, Polyglycidyl ethers obtained by reacting phenol or a polyhydric alcohol such as glycerin or polyethylene glycol with epichlorohydrin; glycidyl ether esters obtained by reacting epichlorohydrin with a hydroxy acid such as p-hydroxybenzoic acid and? -hydroxynaphthoic acid; Polyglycidyl esters obtained by reacting polycarboxylic acids such as phthalic acid and terephthalic acid with epichlorohydrin; A glycidylamine compound obtained by reacting 4,4'-diaminodiphenylmethane, m-aminophenol or the like with epichlorohydrin; Polyfunctional epoxy compounds such as epoxidized phenol novolak resins, epoxidized cresol novolak resins, and epoxidized polyolefins; monofunctional epoxy compounds such as butyl glycidyl ether, phenyl glycidyl ether, and glycidyl methacrylate; compound; , But the present invention is not limited to these.

The amine compound used as a raw material for the production of the solid dispersed amine adduct latent curing accelerator is a compound having at least one active hydrogen capable of addition reaction with an epoxy group and having at least one primary amino group, Amino group and at least one functional group selected from among amino groups. Such amine compounds include, for example, diethylenetriamine, triethylenetetramine, n-propylamine, 2-hydroxyethylaminopropylamine, cyclohexylamine, 4,4'-diamino-dicyclohexylmethane Aliphatic amines; Aromatic amine compounds such as 4,4'-diaminodiphenylmethane and 2-methylaniline; Heterocyclic compounds containing a nitrogen atom such as 2-ethyl-4-methylimidazole, 2-ethyl-4-methylimidazoline, 2,4-dimethylimidazoline, piperidine and piperazine; And the like, but are not limited thereto.

Among them, in particular, compounds having a tertiary amino group in the molecule are raw materials which give a latent curing accelerator having an excellent curing promoting ability, and examples of such compounds include dimethylaminopropylamine, diethylaminopropylamine, di an amine compound such as -n-propylaminopropylamine, dibutylaminopropylamine, dimethylaminoethylamine, diethylaminoethylamine or N-methylpiperazine, or an amine compound such as 2-methylimidazole, Primary or secondary amines having a tertiary amino group in the molecule such as imidazole compounds such as 2-ethyl-4-methylimidazole and 2-phenylimidazole; 2-dimethylaminoethanol, 1-butoxymethyl-2-dimethylaminoethanol, 1- (2-dimethylaminoethanol, (2-hydroxy-3-phenoxypropyl) -2-ethyl-4-methylimidazole, 1- (2- Hydroxy-3-butoxypropyl) -2-methylimidazole, 1- (2-hydroxy-3- 2-methylimidazoline, 2- (dimethylaminomethyl) phenol, 2,4,6-trimethylphenoxyphenyl) -2-phenylimidazoline, (Dimethylaminomethyl) phenol, N -? - hydroxyethylmorpholine, 2-dimethylaminoethanethiol, 2-mercaptopyridine, 2-benzoimidazole, 2-mercaptobenzoimidazole, 2- Mercaptobenzothiazole, 4-mercaptopyridine, N, N-dimethylaminobenzoic acid, N, N-dimethylglycine, nicotinic acid, isonicotinic acid, picoline , Alcohols having a tertiary amino group in the molecule such as N, N-dimethylglycine hydrazide, N, N-dimethylpropionic acid hydrazide, nicotinic acid hydrazide, isonicotinic acid hydrazide, Complex acids and hydrazides; And the like.

When the latent curing accelerator is produced by subjecting the epoxy compound and the amine compound to an addition reaction, an active hydrogen compound having two or more active hydrogens in the molecule may be further added. Examples of such active hydrogen compounds include polyhydric phenols such as bisphenol A, bisphenol F, bisphenol S, hydroquinone, catechol, resorcinol, pyrogallol and phenol novolak resin, polyhydric alcohols such as trimethylolpropane, Dimercaptoethane, 2-mercaptoethanol, 1-mercapto-3-phenoxy-2-propanol, mercaptoacetic acid, anthranilic acid, lactic acid, and the like, But are not limited to these.

Examples of the isocyanate compound used as a raw material for preparing the solid dispersed amine adduct type latent curing accelerator include monofunctional isocyanate compounds such as n-butyl isocyanate, isopropyl isocyanate, phenyl isocyanate and benzyl isocyanate; Hexamethylene diisocyanate, tolylene diisocyanate (e.g., 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate), 1,5-naphthalene diisocyanate, diphenylmethane-4,4'-diisocyanate , Polyfunctional isocyanate compounds such as isophorone diisocyanate, xylene diisocyanate, paraphenylene diisocyanate, 1,3,6-hexamethylene triisocyanate, and bicycloheptane triisocyanate; Further, a terminal isocyanate group-containing compound obtained by reacting these polyfunctional isocyanate compound with an active hydrogen compound; Can also be used. Examples of such a terminal isocyanate group-containing compound include an addition compound having a terminal isocyanate group obtained by the reaction of tolylene isocyanate and trimethylolpropane, an addition compound having a terminal isocyanate group obtained by the reaction of tolylene diisocyanate and pentaerythritol, and the like However, it is not limited to these.

Examples of the urea compound used as a raw material for producing the solid dispersed amine adduct latent curing accelerator include urea and thiourea, but are not limited thereto.

The solid dispersed latent curing accelerator may be prepared by, for example, appropriately mixing the above-mentioned raw materials for production, reacting the mixture at a temperature from room temperature to 200 ° C, cooling and solidifying the mixture and then pulverizing the mixture, or adding methyl ethyl ketone, dioxane, tetra The reaction is carried out in a solvent such as tetrahydrofuran or the like, and after the desolvation, the solid content is pulverized.

Examples of commercially available solid dispersion type latent curing accelerators include, for example, "Amicure PN-23", "Amicure PN-H" manufactured by Ajinomoto Fine Techno Co., , "Hardener X-3661S", "Hardener X-3670S", "Nova Cure HX-3742" manufactured by Asahi Kasei Corporation, and "Nova Cure HX-3721" FXA-1000 "," FXR-1030 ", and" FXR-1081 "manufactured by T & K TOKA, and the like, but the present invention is not limited thereto.

When the total content of the epoxy resin is 100 parts by mass, the content of the curing accelerator is preferably 0.1 to 100 parts by mass, more preferably 1 to 60 parts by mass, still more preferably 5 to 30 parts by mass.

The preservation stability improver usable in the present invention may be added in order to realize excellent storage stability of the curable resin composition of the present invention. Examples of the preservation stability improver 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.

Examples of the borate compound include trimethyl borate, triethyl borate (TEB), tri-n-propyl borate, triisopropyl borate, tri-n-butyl borate, tripentyl borate, triallyl borate, trihexyl borate, Tricyclohexyl borate, trioctyl borate, trinonyl borate, tridecyl borate, tridodecyl borate, trihexadecyl borate, trioctadecyl borate, tris (2-ethylhexyloxy) (1,4,7,10,13-pentaoxatetradecyl) (1,4,7-trioxandecyl) borane, tribenzylborate, triphenylborate, tri-o- Tolyl borate, tri-m-tolyl borate, triethanolamine borate and the like.

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

Examples of the aluminate compound include triethylaluminate, tripropylaluminate, triisopropylaluminate, tributylaluminate, trioctylaluminate, and the like.

As the above-mentioned zirconate compound, for example, tetraethyl zirconate, tetrapropyl zirconate, tetraisopropyl zirconate, tetrabutyl zirconate and the like can be given.

Examples of the isocyanate compound include n-butyl isocyanate, isopropyl isocyanate, 2-chloroethyl isocyanate, phenyl isocyanate, p-chlorophenyl isocyanate, benzyl isocyanate, hexamethylene diisocyanate, -Dimethylphenyl isocyanate, tolylene diisocyanate (e.g., 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate), 1,5-naphthalene diisocyanate, diphenylmethane-4,4'-diisocyanate , Tolidine diisocyanate, isophorone diisocyanate, xylene diisocyanate, paraphenylene diisocyanate, bicycloheptane triisocyanate, and the like.

Examples of the carboxylic acid include saturated aliphatic monobasic acids such as formic acid, acetic acid, propionic acid, butyric acid, caproic acid and caprylic acid, unsaturated aliphatic monobasic acids such as acrylic acid, methacrylic acid and crotonic acid, Halogenated fatty acids such as acetic acid and dichloroacetic acid, aliphatic aldehyde acids such as monobasic oxyacids such as glycolic acid and lactic acid, aliphatic aldehyde acids such as glyoxalic acid and vinic acid, and ketonic acids, aliphatic polybasic acids such as oxalic acid, malonic acid, succinic acid and maleic acid, Aromatic monobasic acids such as benzoic acid halide, toluic acid, phenylacetic acid, cinnamic acid and mandelic acid, and aromatic polybasic acids such as phthalic acid and trimesic acid.

Examples of the acid anhydride include aliphatic or aliphatic polybasic acids such as succinic anhydride, dodecenylsuccinic anhydride, maleic anhydride, adducts of methylcyclopentadiene and maleic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride and the like Anhydrides, aromatic phthalic anhydrides such as phthalic anhydride, trimellitic anhydride and pyromellitic anhydride, and the like. Representative examples of commercially available acid anhydrides include, for example, HN-2200 (molecular weight = 166) manufactured by Hitachi Chemical Co., Ltd., which is methyltetrahydrophthalic anhydride, which can also be used as a curing agent for epoxy resins. no.

Examples of the mercapto organic acids include esters of mercapto aliphatic monocarboxylic acids such as mercaptoacetic acid, mercaptopropionic acid, mercaptobutyric acid, mercaptosuccinic acid and dimercaptosuccinic acid, esterification of hydroxy organic acids with mercapto organic acids And mercapto-aromatic monocarboxylic acids such as mercapto-aliphatic monocarboxylic acids and mercaptobenzoic acids.

As the preservation stability improver, a borate compound is preferable from the viewpoints of high versatility and safety and improvement of storage stability, and triethyl borate, tri-n-propyl borate, triisopropyl borate, tri- More preferred is triethyl borate. The content of the preservation stability improver is not particularly limited as long as the preservation stability of the epoxy resin is enhanced. When the total content of the epoxy resin is 100 parts by mass, the content of the preservation stability improver is preferably 0.001 to 50 parts by mass, more preferably 0.05 to 30 parts by mass More preferably 0.1 to 10 parts by mass.

The curable resin composition of the present invention can be prepared from the above-described tris (3-mercaptopropyl) isocyanurate, epoxy resin, and various additives as optional ingredients as raw materials. The preparation of the curable resin composition is not particularly difficult, and can be carried out according to conventionally known methods. For example, the single-component type thermosetting epoxy resin composition of the present invention can be prepared by mixing the respective components with a mixer such as a three-roll or planetary mixer.

The curing of the obtained one-pack type thermosetting resin composition is not particularly difficult, and it can also be carried out according to conventionally known methods. For example, the obtained one-part type thermosetting resin composition can be cured by heating. The heating is carried out at a temperature of, for example, 50 to 150 ° C, preferably 60 to 120 ° C, more preferably 70 to 100 ° C, for example, for 1 to 60 minutes, preferably 3 to 30 minutes, Is suitably carried out for 5 to 15 minutes. Particularly, if it is cured by heating at 80 캜 or 100 캜 for 10 minutes or less, it can be judged that there is a proper low-temperature curability.

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

[Characteristics of one-component thermosetting resin composition]

· Modulus of elasticity

In the one-part thermosetting resin composition of the present invention, the cured product has an elastic modulus at 25 ° C of, for example, 10 to 2500 MPa. Such an elastic modulus is preferable because the adhesive strength of the resulting cured product can be improved. More preferably, the modulus of elasticity of the cured article is, for example, 20 to 2450 MPa, more preferably, the modulus of elasticity of the cured article is 30 to 2400 MPa, and particularly preferably, the modulus of elasticity of the cured article is 50 to 2300 MPa. The elastic modulus can be measured according to JIS-K-7161 by conducting a tensile test under the environment of 25 ° C and 40% RH using a Tensilon universal testing machine (RTM-500, Orientech).

Peel strength A (T-peel test)

The one-part type thermosetting resin composition of the present invention preferably has a tensile strength value (hereinafter sometimes referred to as peeling strength A) in a T-peel test according to JIS-K-6854-3 of 5 N / 25 mm or more, Is 8 to 40 N / 25 mm, and more preferably 11 to 30 N / 25 mm. Here, the tensile strength (peel strength A) by the T-peel test can be measured as follows. First, wipe a test piece of a steel plate (25 mm x 150 mm x 0.4 mm) with a rag soaked with acetone, and wipe the oil. Further, the surface of the bonding surface of the steel sheet is polished with an endless belt # 120. The resin composition is uniformly applied to the polished surface of the steel sheet with a thickness of about 20 to 30 占 퐉. In addition, one steel sheet is stacked and pushed with four clips. At this time, it is better to wipe out the resin composition that has leaked out immediately. The test specimens are uniformly aligned in an oven and cured by heating at 80 ° C for 60 minutes. The tensile strength of the obtained test piece was measured with a Tensilon universal tester (RTM-500, Orientech Co., Ltd.) (measurement environment; temperature 25 占 폚 / humidity 40%, tensile speed 50 mm / min). Based on the average peel load N, the peel strength A per 25 mm width is calculated. For measurement of the tensile strength by the T-peel test, it is appropriate to prepare three test pieces each for the same resin composition.

· Peel strength B (High humidity test)

The tensile strength (hereinafter sometimes referred to as peel strength B) when the peel strength A is repeatedly allowed to stand for a predetermined period under high humidity is 9 N / 25 mm or more, preferably 10 N / 25 mm or more , More preferably 10 to 50 N / 25 mm, and still more preferably 11 to 30 N / 25 mm. This peel strength B is carried out to evaluate the moisture resistance of the one-pack type thermosetting resin composition. Here, the tensile strength (peel strength B) under the high humidity can be measured as follows. That is, three test specimens separately prepared in the procedure of the T-peel test peel test conforming to JIS-K-6854-3 are preferably prepared. Each of the test pieces was left in a pressure cooker tester set at 120 ° C and 85% RH for 24 hours, and the obtained test pieces were measured for tensile strength with a tensile tensile tester (RTM-500, Orientech). Temperature: 25 DEG C / humidity: 40%, tensile speed: 50 mm / min). Based on the average peel load N, the peel strength B per 25 mm width can be calculated.

· Strength retention

The strength retention ratio of the one-part thermosetting resin composition of the present invention is,

[Strength retentivity] = [Peel strength B] / [Peel strength A]

For example, 0.67 or more, preferably 0.68 or more, more preferably 0.80 to 2.0, and further preferably 1.0 to 1.5. The influence of the humidity on the peel strength of the one-pack type thermosetting resin composition of the present invention can be evaluated by the strength maintenance ratio. The larger the value of the strength retention, the more resistant the specimen is to high humidity.

[Epoxy resin cured products, adhesives, sealing materials, etc.]

The present invention also includes a cured product of an epoxy resin obtained by heating the one-component thermosetting resin composition, and includes a functional product containing the cured product of the epoxy resin. Examples of the functional product include an adhesive, a casting agent, a sealing material, a sealing agent, a fiber-reinforced resin, a coating agent or a pigment.

Among them, the present invention relates to an adhesive containing the one-component thermosetting resin composition described above. Here, the adhesive is an adhesive that can be used in the field of bonding of electronic parts and diamond touch of semiconductor devices. The adhesive is preferably a single-component epoxy resin adhesive in which a curing agent and an epoxy resin composition are mixed in advance.

In addition to the one-component thermosetting resin composition of the present invention, the adhesive may optionally contain a curing agent, a curing accelerator, a flame retardant, a storage stability improver, a filler, a diluent, a solvent, a pigment, a flexibility imparting agent, a coupling agent, An antioxidant, an antioxidant, a tropic property-imparting agent, and a dispersing agent.

The present invention also relates to a sealing material containing the one-component thermosetting resin composition described above. Herein, the sealing material is not limited to the one-liquid thermosetting resin composition of the present invention, but may be a sealing material such as an underfill agent for flip chip mounting and a sealant for chip on- A stabilizer, a stabilizer, a filler, a diluent, a solvent, a pigment, a flexibility imparting agent, a coupling agent, an antioxidant, a thixotropic property-imparting agent, and a dispersing agent.

Example

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples. In the following description, " part " means " part by mass ".

[Preparation of one-component thermosetting resin composition]

Each resin composition having the composition shown in Table 1 was prepared. A predetermined amount of the material shown in Table 1 was weighed and taken in a plastic container, and the mixture was sufficiently mixed at 2000 rpm at room temperature (25 캜) using a rotary mixer and a rotary stirrer (ARE-250, , And the resulting resin composition was further defoamed for one minute.

Details of the materials used are as follows.

EXA4850-150: vinyl ether-modified bisphenol type epoxy resin, epoxy equivalent 450 g / eq (corresponding to formula 1)

EXA4816: an aliphatic chain-modified bisphenol A type epoxy resin, epoxy equivalent 403 g / eq (corresponding to formula 1)

EP-4010S: PO-modified bisphenol A type epoxy resin, epoxy equivalent 350 g / eq (corresponding to formula 2)

YL7410: polyether-modified epoxy resin, epoxy equivalent 420 g / eq (corresponding to formula 1), manufactured by Mitsubishi Kagaku Co.,

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

JER1001: solid bisphenol A type epoxy resin manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 1475 g / eq

(n=3)

(n = 3)

TMPIC: manufactured by Ajinomoto Fine Techno Co., tris (3-mercaptopropyl) isocyanurate, thiol group total equivalent 117 g / eq

TMTP: trimethylolpropane tris (3-mercaptopropionate), manufactured by Yodogagakusha, thiol group equivalent 133 g / eq

PN-23: manufactured by Ajinomoto Fine Techno Co., Ltd., amine adduct type latent curing accelerator

FXR-1081: a modified polyamine latent curing agent, manufactured by T & K TOKA

AEROSIL 200: manufactured by Nippon Aerosil Co., Ltd., fumed silica

TEB: triethyl borate manufactured by Tokyo Kasei Co., Ltd.

HN-2200: manufactured by Hitachi Kasei Kogyo Co., Ltd. 3 or 4-methyl-1,2,3,6-tetrahydrophthalic anhydride

(Thiol group equivalent = mass of thiol group-containing compound containing one equivalent of thiol group)

[Thiol / epoxy equivalence ratio]

The " thiol / epoxy equivalent ratio " in Table 1 was obtained from the following formula.

&Quot; Thiol / epoxy equivalent ratio " = (thiol mass / thiol group total equivalent) / (epoxy resin mass / epoxy equivalent)

[Measurement of viscosity]

A cone rotor (rotor code No. 6; 3 ° xR9.7) was mounted on a RE80 type viscometer (manufactured by Toki San) and 0.2 to 0.3 ml of the resin composition to be measured was weighed with a syringe. During the measurement, the temperature of the measuring chamber of the viscometer was maintained at 25.0 ° C in an external circulating thermostatic chamber. The number of revolutions of the rotor was set to 0.5, 1, 20 and 100 rpm, and the viscosity after 120 seconds at each revolution was measured (unit: Pa · s).

[Measurement of modulus of elasticity of cured product of one-component thermosetting resin composition]

The elastic moduli of the epoxy resin cured products of the examples and comparative examples obtained as described above were measured as follows. First, each of the obtained resin compositions was coated on a release PTFE film (Flex 50N, manufactured by Asahi Glass Co., Ltd.) using a bar coater and cured by heating at 80 占 폚 for 60 minutes. The thickness of the cured product was 50 mu m. Thereafter, the PTFE film was released. A tensile test was conducted using a tensile tensile tester (RTM-500 manufactured by Orientec Co., Ltd.) at 25 占 폚 and 40% RH at a tensile speed of 50 mm / min in accordance with JIS-K-7161.

[Measurement of glass transition point]

A test piece of 7 mm x 30 mm was prepared and subjected to a tensile test at a frequency of 1 Hz, a temperature raising rate of 2 DEG C / min, a measurement temperature range of 0 (zero) using a DMA measurement device (DMS6100, manufactured by Seiko Instruments Inc.) according to JIS- Deg.] C to 300 [deg.] C. The temperature at which the peak appeared in the obtained tan? Curve was defined as the glass transition temperature. Unit is ℃.

[Evaluation of low temperature curability]

The low temperature curability of the resin composition of the present invention was evaluated by measuring a gel time (gel time) in accordance with JIS C6521.

Specifically, the time at which the resin composition of each of the Examples and Comparative Examples was not drawn at 60 占 폚 and 80 占 폚 was measured by a hot-plate gelation tester (GT-D: manufactured by Nissin Kagaku). Specifically, a sample (resin composition) of about 0.5 g was placed on a hot-plate gelation tester, and the point of time at which the temperature became 60 캜 (gel time at 60 캜) or 80 캜 (gel time at 80 캜) The resin composition was repeatedly subjected to contact circle motion (one second for one second) with a spatula having a tip width of 5 mm so that the resin composition was within a range of 25 mm in diameter from the hot plate, The measurement was carried out assuming that the time when the shape was broken was regarded as the end point and the time from the present point of time to the end point was regarded as the time until gelation. In addition, the spatula was not lifted while the viscosity of the resin was low, and when the viscosity was elevated, it was sometimes lifted up about 30 mm vertically from the hot plate, and this vertical movement was repeated until the thread was broken. The measurement was repeated three times and the average value was used.

[Evaluation of peel strength]

T-peel test

The test piece of steel plate (25 mm x 150 mm x 0.4 mm) was wiped with a rag soaked with acetone to wipe the oil. Further, the surface of the adhesion surface of the steel sheet was polished with Endless belt # 120. The resin composition was uniformly applied to the polished surface of the steel sheet with a thickness of about 20 to 30 占 퐉. In addition, one steel sheet was superimposed and pushed with four clips. At this time, the resin composition that had leaked out was wiped off immediately. The test pieces were uniformly aligned in an oven and cured by heating at 80 DEG C for 60 minutes. Three test pieces were prepared for the same resin composition. The tensile strength of the obtained test piece was measured according to JIS-K-6854-3 with a tensile tensile tester (RTM-500, Orientech) at 25 ° C / minute). The peel strength A per 25 mm width was calculated based on the average peel load (N).

[Evaluation of moisture resistance]

In order to evaluate the moisture resistance of the test piece, the test of the peel strength A was repeated for a predetermined period of time under high humidity. Specifically, three specimens separately prepared in the procedure of the above T-peel test peeling test were prepared. Each test piece was left in a pressure cooker tester set at 120 ° C and 85% RH for 24 hours, and then the obtained test piece was subjected to a tensile tester (RTM-500, manufactured by Orientec Co., Ltd.) according to JIS-K-6854-3 Tensile strength was measured (measuring environment: temperature 25 占 폚 / humidity 40%, tensile speed 50 mm / min). Based on the average peel load N, the peel strength B per 25 mm width was calculated.

[Strength retention rate]

The strength retention was calculated to evaluate the effect of humidity on the peel strength. The strength retention ratio was calculated from the peel strength A and the peel strength B as follows.

[Strength retentivity] = [Peel strength B] / [Peel strength A]

The larger the value of the strength retention, the more resistant the specimen is to high humidity.

[Review of Evaluation Results]

The results of the above evaluations are shown in Table 1. As shown in Table 1, it was found that the one-liquid thermosetting resin compositions of Examples 1 to 9 had better low temperature curing properties and good moisture resistance than the resin compositions of the comparative examples.

Further, the present invention may be in the following aspects.

[One]

A one-part thermosetting resin composition containing tris (3-mercaptopropyl) isocyanurate and an epoxy resin, wherein the cured product of the resin composition has an elastic modulus at 25 ° C of 10 to 2500 MPa.

[2]

The resin composition according to [1], wherein the epoxy equivalent of the epoxy resin is 200 to 1,000.

[3]

The epoxy resin according to any one of [1] to [2], wherein the epoxy resin comprises (a) at least two epoxy groups, (b) a divalent nonaromatic hydrocarbon group containing two or more - (CH ₂ ) c) an epoxy compound comprising a divalent aromatic containing hydrocarbon group containing a bivalent aromatic group in its main skeleton, or a polymer thereof.

[4]

The epoxy resin composition according to any one of [1] to [3], wherein the epoxy resin is represented by Formula (1) or Formula (2)

[Chemical Formula 1]

(2)

(In the formulas (1) and (2)

X, X ₁ and X ₂ may be the same or different and each is a divalent non-aromatic hydrocarbon group containing two or more - (CH ₂ ) - in the main skeleton, provided that X is -O-CH ₂ -CH (- OH) -CH ₂ -),

Ar, Ar ₁ and Ar ₂ may be the same or different and are a divalent aromatic containing hydrocarbon group containing a divalent aromatic group in its main skeleton,

n and m are each independently an integer of 1 to 20)

, Or a polymer thereof.

[5]

( ₂ ), wherein the divalent non-aromatic hydrocarbon group containing two or more - (CH ₂ ) - in the main skeleton is an alkylene group having 2 to 20 carbon atoms which may or may not have a substituent, An alkyleneoxy group having 2 to 20 carbon atoms which may or may not be present.

[6]

(B) a divalent non-aromatic hydrocarbon group containing two or more - (CH ₂ ) - in the main skeleton, in any one of [3] to [5]

(b1) -O-CH (-CH 3) - (O- (CH 2) p) q -O-CH (-CH 3) -,

(b2) - (O- (CH 2) r) s -,

(b3) - (O-CH 2 -CH (-CH 3)) t -,

_{(b4) -O-CH 2 -CH} (-OH) -CH 2 - (O- (CH 2) u) v -O-CH 2 -CH (-OH) -CH 2 -,

(b5) - (O- (CH ₂ ) _w ) _y -O-CH ₂ -CH (-OH) -, and

(b6) - (O-CH 2 -CH (-CH 3)) z -O-CH 2 -CH (-OH) -

(Wherein p, q, r, s, t, u, v, w, y and z are each independently an integer of 1 to 20)

≪ / RTI >

[7]

The aromatic hydrocarbon-containing polymer according to any one of [3] to [6], wherein the divalent aromatic-containing hydrocarbon group containing the bivalent aromatic group in the main skeleton is,

및

And

≪ / RTI >

[8]

The resin composition according to any one of [1] to [7], further comprising a solid dispersed latent curing accelerator.

[9]

The organic electroluminescent device according to any one of [1] to [8], further comprising at least one selected from a borate compound, titanate compound, aluminate compound, zirconate compound, isocyanate compound, carboxylic acid, acid anhydride and mercapto organic acid By weight.

[10]

An adhesive containing the resin composition according to any one of [1] to [9].

[11]

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

[12]

An epoxy resin cured product obtained by heating the resin composition according to any one of [1] to [9].

Claims (14)

Tris (3-mercaptopropyl) isocyanurate with an epoxy resin having the formula (1) or (2)
[Chemical Formula 1]

(2)

(In the formulas (1) and (2)
X, X ₁ and X ₂ may be the same or different and each is a divalent non-aromatic hydrocarbon group containing two or more - (CH ₂ ) - in the main skeleton, provided that X is -O-CH ₂ -CH (- OH) -CH ₂ -),
Ar, Ar ₁ and Ar ₂ may be the same or different and are a divalent aromatic containing hydrocarbon group containing a divalent aromatic group in its main skeleton,
n and m are each independently an integer of 1 to 20)
Wherein the thermosetting resin composition is a thermosetting resin composition. The compound according to claim 1, wherein the divalent non-aromatic hydrocarbon group having 2 or more - (CH ₂ ) - in the main skeleton is an alkylene group having 2 to 20 carbon atoms which may or may not have a substituent, And an alkyleneoxy group having 2 to 20 carbon atoms which may not be present. 3. The method according to claim 1 or 2, wherein the divalent non-aromatic hydrocarbon group containing two or more - (CH ₂ )
(b1) -O-CH (-CH 3) - (O- (CH 2) p) q -O-CH (-CH 3) -,
(b2) - (O- (CH 2) r) s -,
(b3) - (O-CH 2 -CH (-CH 3)) t -,
_{(b4) -O-CH 2 -CH} (-OH) -CH 2 - (O- (CH 2) u) v -O-CH 2 -CH (-OH) -CH 2 -,
(b5) - (O- (CH ₂ ) _w ) _y -O-CH ₂ -CH (-OH) -, and
(b6) - (O-CH 2 -CH (-CH 3)) z -O-CH 2 -CH (-OH) -
(Wherein p, q, r, s, t, u, v, w, y and z are each independently an integer of 1 to 20)
≪ / RTI > The method according to any one of claims 1 to 3, wherein the bivalent aromatic hydrocarbon-containing hydrocarbon group containing the bivalent aromatic group in the main skeleton is,

And

≪ / RTI > The resin composition according to any one of claims 1 to 4, further comprising a solid dispersed latent curing accelerator. The positive resist composition according to any one of claims 1 to 5, wherein at least one selected from a borate compound, titanate compound, aluminate compound, zirconate compound, isocyanate compound, carboxylic acid, acid anhydride and mercapto organic acid is added By weight. The resin composition according to any one of claims 1 to 6, wherein the cured product of the one-part thermosetting resin composition has an elastic modulus at 25 ° C of 10 to 2500 MPa. The cured product of the one-part thermosetting resin composition according to any one of claims 1 to 7, wherein the cured product of the one-part thermosetting resin composition is allowed to stand for 24 hours at 120 ° C and 85% RH, And the strength B (N / 25 mm) is 9 or more. The method for producing a one-part thermosetting resin composition according to any one of claims 1 to 8, wherein the cured product of the one-part type thermosetting resin composition has a peel strength A (N / 25 mm) measured according to JIS-K-6854-3, The cured product of the composition was allowed to stand under the conditions of 120 占 폚 and 85% RH for 24 hours, and then the cured product of the one-component thermosetting resin composition calculated from the peel strength B (N / 25 mm) measured according to JIS- And the strength retention ratio (B / A) of water is 0.67 or more. An adhesive comprising the resin composition according to any one of claims 1 to 9. A sealing material comprising the resin composition according to any one of claims 1 to 9. An epoxy resin cured product obtained by heating the resin composition according to any one of claims 1 to 9. The resin composition according to any one of claims 1 to 9, further comprising a bisphenol A type epoxy resin. 14. The epoxy resin composition according to claim 13, wherein the mass ratio of the epoxy compound or the polymer thereof to the bisphenol A epoxy resin is 10: 1 to 1:10 [epoxy compound or polymer thereof]: [bisphenol A type epoxy resin] Resin composition.