WO2015060439A1

WO2015060439A1 - Flexible epoxy resin composition

Info

Publication number: WO2015060439A1
Application number: PCT/JP2014/078388
Authority: WO
Inventors: 清敬古田; 硬介服部; 啓志荻野; 学増山
Original assignee: 味の素株式会社
Priority date: 2013-10-25
Filing date: 2014-10-24
Publication date: 2015-04-30
Also published as: TWI650370B; TW201531515A; JP6579381B2; CN105473634A; CN105473634B; JPWO2015060439A1; KR102217397B1; KR20160077132A

Abstract

Provided is a one-component thermosetting composition in which low-temperature curability and maintenance of adhesive strength are both obtained at the same time, and low-temperature curability and moisture resistance are both obtained at the same time. Specifically, a one-component-type thermosetting resin composition is provided containing tris(3-mercaptopropyl)isocyanurate and an epoxy resin containing an epoxy compound represented by formula (1) or formula (2) or a polymer thereof. (In formula (1) and formula (2), X, X₁, and X₂ may be mutually the same or different and are divalent non-aromatic hydrocarbon groups including two or more –(CH₂)- units in a main backbone thereof (except when X is –O-CH₂-CH(-OH)-CH₂-); Ar, Ar₁, and Ar₂ may be mutually the same or different and are divalent aromatic-containing hydrocarbon groups including divalent aromatic groups in a main backbone thereof; and n and m are each independently an integer of 1-20.)

Description

Flexible epoxy resin composition

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

Epoxy resins have excellent performance in terms of mechanical properties, electrical properties, thermal properties, chemical resistance, and adhesive strength, and are therefore used in a wide range of applications such as paints, electrical and electronic insulating materials, and adhesives. I came. In recent years, in addition to the so-called two-component epoxy resin composition in which an epoxy resin and a curing agent are mixed and cured at the time of use, the epoxy resin and the curing agent are mixed in advance and cured by heat or the like. Things have been developed. In particular, in the field of electronic circuits in recent years, studies on flexibility and thinning have been actively conducted, and low-temperature curable one-component epoxy is used to protect semiconductor elements, increase circuit density, and improve connection reliability. There is an increasing demand for resin compositions.
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 pursued, the peel strength may be inferior. Moreover, the curing agent contained in the conventional one-component epoxy resin composition having low temperature curability generally has a problem that the moisture resistance is low and the adhesive strength is lowered in a high humidity environment.

JP-A-6-211969

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

As a result of intensive studies to solve the above-mentioned problems, the present inventors preferably achieved a one-component thermosetting resin composition containing tris (3-mercaptopropyl) isocyanurate and a specific epoxy resin. The above-mentioned problems have been solved by a one-component thermosetting resin composition in which the cured product of the one-component thermosetting resin composition has an elastic modulus at 25 ° C. of 10 to 2500 MPa.
That is, the present invention is as follows.
[1] Tris (3-mercaptopropyl) isocyanurate and an epoxy resin are represented by the formula (1) or the formula (2):

(In the formulas (1) and (2), X, X ₁ and X ₂ may be the same or different from each other, and may be divalent non-valent containing two or more — (CH ₂ ) — in the main skeleton. An aromatic hydrocarbon group (except when X is —O—CH ₂ —CH (—OH) —CH ₂ —), and Ar, Ar ₁ and Ar ₂ may be the same as each other An epoxy which may be different and is a divalent aromatic-containing hydrocarbon group containing a divalent aromatic group in the main skeleton, and n and m are each independently an integer of 1 to 20) A one-component thermosetting resin composition containing a compound or a polymer thereof.
[2] The divalent non-aromatic hydrocarbon group containing two or more — (CH ₂ ) — in the main skeleton may have or not have a substituent and has 2 to 20 carbon atoms. The resin composition according to the above [1], which is selected from an alkylene group and an alkyleneoxy group having 2 to 20 carbon atoms which may or may not have a substituent.
[3] A divalent non-aromatic hydrocarbon group containing two or more — (CH ₂ ) — in the main skeleton,
(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), any one of [1] or [2] above 2. The resin composition according to item 1.
[4] The divalent aromatic-containing hydrocarbon group containing the divalent aromatic group in the main skeleton is independently

The resin composition according to any one of [1] to [3], selected from the group consisting of:
[5] The resin composition according to any one of [1] to [4], further comprising a solid dispersion type latent curing accelerator.
[6] The above-mentioned [1] to [5], further comprising one or more selected from 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 resin composition according to any one of the above.
[7] The resin composition as described in any one of [1] to [6] above, wherein the cured product of the one-component thermosetting resin composition has an elastic modulus at 25 ° C. of 10 to 2500 MPa.
[8] After leaving the cured product of the one-component thermosetting resin composition at 120 ° C. and 85% RH for 24 hours,
The resin composition according to any one of [1] to [7], wherein a peel strength B (N / 25 mm) measured according to JIS-K-6854-3 is 9 or more.
[9] A cured product of the one-component thermosetting resin composition is measured by a peel strength A (N / 25 mm) measured according to JIS-K-6854-3, and the one-component thermosetting resin composition is cured. The one-component thermosetting resin composition calculated from the peel strength B (N / 25 mm) measured according to JIS-K-6854-3 after leaving the product to stand at 120 ° C. and 85% RH for 24 hours The resin composition according to any one of [1] to [8], wherein the strength retention (B / A) of the cured product is 0.67 or more.
[10] An adhesive containing the resin composition according to any one of [1] to [9].
[11] A sealing material containing the resin composition according to any one of [1] to [9].
[12] A cured epoxy resin obtained by heating the resin composition according to any one of [1] to [9].
[13] The resin composition according to any one of [1] to [9], further comprising a bisphenol A type epoxy resin.
[14] The mass ratio of the epoxy compound or polymer thereof to the bisphenol A epoxy resin is [epoxy compound or polymer thereof]: [bisphenol A epoxy resin] = 10: 1 to 1:10. The resin composition according to [13].

The one-component thermosetting resin composition of the present invention is an epoxy resin composition excellent in low-temperature curability, peel strength, and moisture resistance. In particular, since it has excellent peel strength and moisture resistance and an elastic modulus of, for example, about 10-2500 MPa, it can be used as an adhesive and a sealing material. Further, a die attach material, an underfill material, It can be used for COB sealing material. Here, the “one-pack type” thermosetting resin composition is a composition in which a curing agent and an epoxy resin are mixed in advance, and a composition having a property of being cured by applying heat to the composition. means.

[Tris (3-mercaptopropyl) isocyanurate (TMPIC)]
Tris (3-mercaptopropyl) isocyanurate contained in the one-component thermosetting resin composition of the present invention is a thiol compound that can be represented by the following structural formula.

Tris (3-mercaptopropyl) isocyanurate acts as a curing agent for epoxy resins.
The content of tris (3-mercaptopropyl) isocyanurate is, for example, 10 to 100 parts by mass, preferably 100 to 100 parts by mass, when the total epoxy resin contained in the one-component thermosetting resin composition of the present invention is 100 parts by mass, It is 20 to 90 parts by mass, more preferably 30 to 80 parts by mass, and still more preferably 40 to 70 parts by mass.

[Epoxy resin]
The epoxy equivalent of the epoxy resin contained in the one-component thermosetting resin composition of the present invention is, for example, preferably 200 to 1000, and more preferably 300 to 600. If the epoxy equivalent of the epoxy resin is 200 or more, the volatility is low, the viscosity is not low, and the viscosity is easy to handle. Moreover, if the epoxy equivalent of an epoxy resin is 1000 or less, it does not become high viscosity and is suitable in terms of handling. Here, the epoxy equivalent is the mass of an epoxy resin containing one equivalent of an epoxy group, and can be measured according to, for example, JIS K 7236 (2009).

The epoxy resin of the present invention comprises (a) 2 or more epoxy groups, (b) a divalent non-aromatic hydrocarbon group containing 2 or more — (CH ₂ ) — in the main skeleton, and (c) a divalent It is preferable to contain an epoxy compound containing a divalent aromatic-containing hydrocarbon group containing an aromatic group in the main skeleton 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, wherein “main skeleton” has two or more epoxy groups in (a) at both ends The skeleton with the longest chain among the skeletons.
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 6 to 20.
The two or more — (CH ₂ ) — may be directly bonded, ether bond, ester bond, amide bond, two carbons bonded by a double bond, or two carbons bonded by a triple bond. And may be bonded via a thioether bond.

Examples of the “divalent non-aromatic hydrocarbon group containing two or more — (CH ₂ ) —” in the main skeleton include an alkylene group and an alkyleneoxy group, and these have a substituent. May not be included.
Here, 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 carboxy group, a cyano group, a nitro group, Examples thereof include a group selected from a hydroxy group, a mercapto group, and an oxo group.
As a halogen atom used as a substituent, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned, for example.

The alkyl group used as a substituent may be either linear or branched. The number of carbon atoms of the alkyl group is preferably 1-20, more preferably 1-14, still more preferably 1-12, still more preferably 1-6, and particularly preferably 1-3. 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 a nonyl group. And decyl group. As will be described later, the alkyl group used as a substituent may further have a substituent (“secondary substituent”). Examples of such an alkyl group having a secondary substituent include an alkyl group substituted with a halogen atom, specifically, a trifluoromethyl group, a trichloromethyl group, a tetrafluoroethyl group, a tetrachloroethyl group, and the like. Is mentioned.

The number of carbon atoms of the cycloalkyl group used as a substituent is preferably 3 to 20, more preferably 3 to 12, and 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 a substituent may be either linear or branched. The number of carbon atoms of the alkoxy group is preferably 1-20, preferably 1-12, more preferably 1-6. Examples of the alkoxy group include methoxy group, ethoxy group, propyloxy group, isopropyloxy group, butoxy group, sec-butoxy group, isobutoxy group, tert-butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, Examples include octyloxy group, nonyloxy group, and 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, and 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 linear or branched aliphatic or aromatic. The number of carbon atoms of the amino group is preferably 1-20, preferably 1-12, more preferably 1-6. Examples of the amino group include aminomethyl group, aminoethyl group, aminopropyl group, isopropylamino group, aminobutoxy group, sec-butylamino group, isobutylamino group, tert-butylamino group, aminopentyl group, aminohexyl. Group, aminoheptyl group, aminooctyl group, aminononyl group, aminodecyl group, aminophenyl group and the like.

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

The acyl group used as a substituent refers to a group represented by the formula: —C (═O) —R1 (wherein R1 is an alkyl group). The alkyl group represented by R1 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, and further 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 refers to a group represented by the formula: —O—C (═O) —R2 (wherein R2 is an alkyl group). The alkyl group represented by R2 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, and further 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 the main skeleton” includes, in addition to two or more — (CH ₂ ) —, a cycloalkylene group, a cycloalkenylene group, a cycloalkyl group. It may contain a non-aromatic divalent group other than a methylene group such as a nylene group, an alkapolyenylene group, an alkadiinylene group, an alkatriinylene group.

Examples of the “divalent non-aromatic hydrocarbon group containing two or more — (CH ₂ ) — in the main skeleton” include, for example, a carbon number of 2 to 20 which may or may not have a substituent. Or an alkyleneoxy group having 2 to 20 carbon atoms which may or may not have a substituent. Here, the carbon number is a number excluding the carbon number of the substituent when it includes a substituent.

The alkyleneoxy group may have, for example, one or more structures represented by the following formulae.
(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 more preferably 1 to 3. Here, q, s, t, v, y and z are integers of 1 to 20, more preferably 1 to 10, more preferably 1 to 6, and more preferably 1 to 3.

(C) 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 is: For example, it may be a phenylene group, a naphthalene group, an anthracene group, or a biphenyl group. The phenylene group can be an ortho, meta, or para phenylene group. Two or more of the aromatic groups may be contained in the divalent aromatic-containing hydrocarbon group. When two or more aromatic groups are included, the aromatic group may be directly bonded, or bonded by an alkylene group, an ether bond, an ester bond, an amide bond, two carbons bonded by a double bond, or a triple bond. It may be bonded via two carbons formed.
As a particularly preferred divalent aromatic-containing hydrocarbon group,

Can be mentioned.

The epoxy compound of the present invention is preferably a compound having an epoxy group in which the main skeleton is not cyclic but linear. If the entire epoxy compound is linear, the main skeleton may partially contain a divalent cyclic group such as a divalent aromatic group. Further, the group constituting the main skeleton may have a substituent as described above. The “epoxy compound polymer” refers to a polymer obtained by polymerizing the epoxy compound into, for example, a polymer having a molecular weight of about 500 to 1,500.

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

In the formulas (1) and (2), X, X ₁ and X ₂ are divalent non-aromatic hydrocarbon groups containing at least two — (CH ₂ ) — in the main skeleton (where X is —O —CH ₂ —CH (—OH) —CH ₂ —). Here, the definition of “a divalent non-aromatic hydrocarbon group containing two or more — (CH ₂ ) —” in the main skeleton is as described above. The n Xs in the formula (1) may be the same as or different from each other. X _1, m-number of X ₂ m pieces of the formula (2) may being the same or different. X, X ₁ and X ₂ may be a group selected from the above (b1) to (b6).

In the formulas (1) and (2), Ar, Ar ₁ and Ar ₂ may be the same or different from each other, and may or may not have a substituent. This is a divalent aromatic-containing hydrocarbon group containing an aromatic group in the main skeleton. The definition of “a divalent aromatic-containing hydrocarbon group containing a divalent aromatic group in the 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.
Furthermore, the epoxy resin of the formula (2) may have a structure represented by the following formula (2) ′.

Definition of X _{3 ~ 6} and Ar 3 _{~ 4} in the formula (2) 'are the same as defined in the above-mentioned X and Ar. X ₃ , X ₄ , m ′ X ₅ , and m ′ X ₆ in formula (2) ′ may be the same as or different from each other. X and X _{3 to 6} may be groups selected from the above (b1) to (b6). m ′ is an integer of 1 to 20, preferably 1 to 10.

Specific epoxy compounds or polymers thereof that can be used in the present invention include, for example, resins having the following structure (k is an integer of 1 to 20, preferably 1 to 5).

Further, for example, a resin having the following structure (h is an integer of 0 to 20, preferably 0 to 5, and i and j are each an integer of 1 to 20, preferably an integer of 1 to 5, I + j = 2 to an integer of 2 to 10.

as well as

Further, for example, EXA-4850-150 (corresponding to formula (1)), EXA-4816 (corresponding to formula (1)), and EXA-4822 (corresponding to formula (1)) manufactured by DIC Corporation; EP manufactured by ADEKA -4000S (corresponding to equation (2)), EP-4000SS (corresponding to equation (2)), EP-4003S (corresponding to equation (2)), EP-4010S (corresponding to equation (2)), and EP- 4011S (corresponding to the formula (2)); BEO-60E and BPO-20E manufactured by Shin Nippon Rika Co., Ltd .; YL7175-500, YL7175-1000, and YL7410 manufactured by Mitsubishi Chemical Corporation.

As long as the elastic modulus at 25 ° C. of the cured product of the resin composition is within a desired range, the one-component thermosetting resin composition of the present application is in addition to or in place of the epoxy compound or the polymer thereof. Epoxy resins can be used. For example, polyglycidyl ether obtained by reacting a polyhydric phenol such as bisphenol A, bisphenol F, bisphenol AD, bisphenol E, catechol, resorcinol, or a polyhydric alcohol such as glycerin or polyethylene glycol with epichlorohydrin; p- Polyglycidyl ether ester obtained by reaction of hydroxy acid such as hydroxybenzoic acid and β-hydroxynaphthoic acid with epichlorohydrin; reaction of polycarboxylic acid such as phthalic acid and terephthalic acid with epichlorohydrin Polyglycidyl ester obtained by further treatment; epoxidized phenol novolak resin, epoxidized cresol novolak resin, epoxidized polyolefin, cycloaliphatic epoxy resin, and other urethane-modified epoxy resins; It is, but not limited thereto.

Bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, biphenyl aralkyl type epoxy resin, phenol aralkyl type epoxy resin, aromatic glycidyl amine type epoxy from the viewpoint of maintaining high heat resistance and low moisture permeability Resins and epoxy resins having a dicyclopentadiene structure are preferred, bisphenol A type epoxy resins and bisphenol F type epoxy resins are more preferred, and bisphenol A type epoxy resins are more preferred.

These resins may be liquid or solid. Further, a mixture of a liquid resin and a solid resin may be used. Here, “liquid” and “solid” refer to the state of the epoxy resin at room temperature (25 ° C.). From the viewpoint of coatability, workability, and adhesiveness, it is preferable that at least 10% by mass or more of the entire epoxy resin to be used is a liquid epoxy resin.
Specific examples of such resins include bisphenol A type (hereinafter sometimes abbreviated as BPA type) epoxy resins (“JER828EL”, “JER827”, “JER1001” manufactured by Mitsubishi Chemical Corporation), and bisphenol F type epoxy resins (manufactured by Mitsubishi Chemical Corporation). “JER807”), liquid bisphenol AF type epoxy resin (“ZX1059” manufactured by Toto Kasei Co., Ltd.), hydrogenated structure epoxy resin (“JERYX8000” manufactured by Mitsubishi Chemical Corporation), dicyclopentadiene type polyfunctional epoxy resin (DIC) "HP7200"), epoxy resin having a butadiene structure ("PB-3600" manufactured by Daicel Chemical Industries, Ltd.), epoxy resin having a biphenyl structure ("NC3000H", "NC3000L" manufactured by Nippon Kayaku Co., Ltd., Mitsubishi Chemical Corporation) “YX4000”) and the like. Among them, it is preferable to use a BPA type epoxy resin having high heat resistance and low viscosity. “JER828EL”, “JER827”, “JER1001” and “JER807” manufactured by Mitsubishi Chemical Corporation are preferable, and “JER828EL” is more preferable. .

When using BPA type epoxy resin in addition to “epoxy compound or polymer thereof”, the mass ratio of “epoxy compound or polymer thereof” to BPA type epoxy resin is, for example, “epoxy compound or polymer thereof” ": BPA type epoxy resin = 10: 1 to 1:10, preferably 10: 1 to 1: 5, more preferably 9: 1 to 1: 2, and even more preferably 8: 1 to 1: 1. is there.

[Other additives]
The curable resin composition of the present invention is optionally 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, Various additives such as a coupling agent, an antioxidant, a thixotropic agent, and a dispersant can be added.

Examples of curing agents for epoxy resins other than TMPIC include imidazole curing agents and amine curing agents. Furthermore, thiol compounds other than TMPIC, such as trimethylolpropane tris (3-mercaptopropionate) (TMTP), trimethylolpropane tris (thioglycolate), pentaerythritol tetrakis (thioglycolate), ethylene glycol dithioglycolate , Trimethylolpropane tris (β-thiopropionate), pentaerythritol tetrakis (β-thiopropionate), dipentaerythritol poly (β-thiopropionate) and the like by an esterification reaction of a mercapto organic acid The resulting thiol compound can also be used as a curing agent for epoxy resins.

Examples of the curing accelerator that can be used in the present invention include a solid dispersion type latent curing accelerator. The solid dispersion type latent curing accelerator is a compound that is insoluble in the above-mentioned epoxy resin at room temperature (25 ° C.), solubilized by heating, and functions as a curing accelerator for the epoxy resin. Examples include, but are not limited to, solid imidazole compounds and solid-dispersed amine adduct-based latent curing accelerators. Examples of solid dispersion type amine adduct-based latent curing accelerators include reaction products of amine compounds and epoxy compounds (amine-epoxy adduct systems), reaction products of amine compounds and isocyanate compounds or urea compounds (urea type) Adduct system). Among these, a solid dispersion type amine adduct-based latent curing accelerator is preferable.

Examples of the imidazole compound that is solid at room temperature include 2-heptadecylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-undecylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl-4-benzyl-5-hydroxymethylimidazole, 2,4-diamino-6- (2-methylimidazolyl- (1))-ethyl-S-triazine, 2,4-diamino-6- (2 ′ -Methylimidazolyl- (1) ')-ethyl-S-triazine isocyanuric acid adduct, 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole-trimellite 1-cyanoethyl-2-phenylimidazole-trimellitate, N- (2-methylimidazolyl-1-ethyl) -urea, N, N ′-(2-methylimidazolyl- (1) -ethyl) -aziboyldiamide, etc. Although it is mentioned, it is not limited to these.

Examples of the epoxy compound used as one of the raw materials for producing the solid dispersion type amine adduct-based latent curing accelerator (amine-epoxy adduct system) include polyhydric phenols such as bisphenol A, bisphenol F, catechol, and resorcinol, A polyglycidyl ether obtained by reacting a polyhydric alcohol such as glycerin or polyethylene glycol with epichlorohydrin; reacting a hydroxy acid such as p-hydroxybenzoic acid or β-hydroxynaphthoic acid with epichlorohydrin A glycidyl ether ester obtained by reacting a polycarboxylic acid such as phthalic acid or terephthalic acid with epichlorohydrin; and an epithelial with 4,4′-diaminodiphenylmethane or m-aminophenol Glycidylamine compounds obtained by reacting with lorohydrin; moreover, polyfunctional epoxy compounds such as epoxidized phenol novolak resin, epoxidized cresol novolak resin, epoxidized polyolefin, and simple substances such as butyl glycidyl ether, phenyl glycidyl ether, and glycidyl methacrylate. Functional epoxy compounds; and the like, but are not limited thereto.

The amine compound used as a raw material for producing the solid dispersion type amine adduct-based latent curing accelerator has at least one active hydrogen capable of addition reaction with an epoxy group in the molecule, and has a primary amino group and a secondary amino group. And at least one functional group selected from tertiary amino groups in the molecule. Examples of such amine compounds include aliphatic amines such as diethylenetriamine, triethylenetetramine, n-propylamine, 2-hydroxyethylaminopropylamine, cyclohexylamine, and 4,4'-diamino-dicyclohexylmethane; Aromatic amine compounds such as 4,4'-diaminodiphenylmethane and 2-methylaniline; nitrogen such as 2-ethyl-4-methylimidazole, 2-ethyl-4-methylimidazoline, 2,4-dimethylimidazoline, piperidine and piperazine Examples thereof include, but are not limited to, heterocyclic compounds containing atoms.

Among them, a compound having a tertiary amino group in the molecule is a raw material that provides a latent curing accelerator having excellent curing acceleration ability. Examples of such a compound include dimethylaminopropyl. Amine compounds such as amine, diethylaminopropylamine, di-n-propylaminopropylamine, dibutylaminopropylamine, dimethylaminoethylamine, diethylaminoethylamine, N-methylpiperazine, 2-methylimidazole, 2-ethylimidazole, 2- Primary or secondary amines having a tertiary amino group in the molecule, such as imidazole compounds such as ethyl-4-methylimidazole and 2-phenylimidazole; 2-dimethylaminoethanol, 1-methyl-2-dimethylamino Ethanol, 1-phenoxymethyl -2-dimethylaminoethanol, 2-diethylaminoethanol, 1-butoxymethyl-2-dimethylaminoethanol, 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- Methylimidazole, 1- (2-hydroxy-3-phenoxypropyl) -2-phenylimidazoline, 1- (2-hydroxy-3-butoxypropyl) -2-methylimidazoline, 2- (dimethylaminomethyl) phenol, 2, 4,6-Tris (dimethylaminomethyl) phenol, N-β- Hydroxyethylmorpholine, 2-dimethylaminoethanethiol, 2-mercaptopyridine, 2-benzimidazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 4-mercaptopyridine, N, N-dimethylaminobenzoic acid, N, N -Tertiary amino acids in the molecule such as dimethylglycine, nicotinic acid, isonicotinic acid, picolinic acid, N, N-dimethylglycine hydrazide, N, N-dimethylpropionic hydrazide, nicotinic acid hydrazide, isonicotinic acid hydrazide, etc. And alcohols having a group, phenols, thiols, carboxylic acids and hydrazides;

When the latent curing accelerator is produced by addition reaction of the epoxy compound and the amine compound, an active hydrogen compound having two or more active hydrogens in the molecule can be added. Examples of such active hydrogen compounds include polyhydric phenols such as bisphenol A, bisphenol F, bisphenol S, hydroquinone, catechol, resorcinol, pyrogallol, phenol novolac resin, polyhydric alcohols such as trimethylolpropane, and adipic acid. And polyvalent carboxylic acids such as phthalic acid, 1,2-dimercaptoethane, 2-mercaptoethanol, 1-mercapto-3-phenoxy-2-propanol, mercaptoacetic acid, anthranilic acid, lactic acid and the like. It is not limited.

Examples of the isocyanate compound used as a raw material for producing the solid dispersion type amine adduct-based latent curing accelerator include monofunctional isocyanate compounds such as n-butyl isocyanate, isopropyl isocyanate, phenyl isocyanate, and benzyl isocyanate; hexamethylene diisocyanate, Range isocyanate (eg, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate), 1,5-naphthalene diisocyanate, diphenylmethane-4,4'-diisocyanate, isophorone diisocyanate, xylylene diisocyanate, paraphenylene diisocyanate, 1 , 3,6-hexamethylene triisocyanate, bicycloheptane triisocyanate and other polyfunctional isocyanate compounds; , Obtained by reaction of these polyfunctional isocyanate compound and active hydrogen compound, terminal isocyanate group-containing compounds; and the like 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 diisocyanate and trimethylolpropane, and a terminal isocyanate group obtained by the reaction of tolylene diisocyanate and pentaerythritol. However, the present invention is not limited thereto.

Further, examples of the urea compound used as a raw material for producing the solid dispersion type amine adduct-based latent curing accelerator include urea and thiourea, but are not limited thereto.

The solid dispersion type latent curing accelerator may be prepared by, for example, appropriately mixing the above-mentioned production raw materials and reacting at room temperature to 200 ° C. and then cooling and solidifying, or pulverizing, or methyl ethyl ketone, dioxane, tetrahydrofuran It can be easily obtained by pulverizing the solid content after the reaction in a solvent such as

Typical examples of commercially available solid dispersion type latent curing accelerators include, for example, amine-epoxy adduct systems (amine adduct systems) such as “Amicure PN-23” and “Amicure” manufactured by Ajinomoto Fine Techno Co., Ltd. PN-H ”, manufactured by ARC,“ Hardner X-3661S ”,“ Hardner X-3670S ”,“ Novacure HX-3742 ”,“ Novacure HX-3721 ”manufactured by Asahi Kasei Co., Ltd. Examples of the urea type adduct system include “FXE-1000”, “FXR-1030”, “FXR-1081” manufactured by T & K TOKA, but are 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, and 5 to 30 parts by mass. Part is more preferred.

The storage stability improver that can be used in the present invention may be added to realize the excellent storage stability of the curable resin composition of the present invention. Examples of the storage stability improver include borate compounds, titanate compounds, aluminate compounds, zirconate compounds, isocyanate compounds, carboxylic acids, acid anhydrides, and mercapto organic acids.

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, and tricyclohexyl borate. , Trioctyl borate, trinonyl borate, tridecyl borate, tridodecyl borate, trihexadecyl borate, trioctadecyl borate, tris (2-ethylhexyloxy) borane, bis (1,4,7,10-tetraoxaundecyl ) (1,4,7,10,13-pentaoxatetradecyl) (1,4,7-trioxaundecyl) borane, tribenzyl borate, triphenyl borate, tri-o-tolyl borate, tri-m- Thrill Rate, triethanolamine borate and the like.

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

Examples of the aluminate compound include triethyl aluminate, tripropyl aluminate, triisopropyl aluminate, tributyl aluminate, trioctyl aluminate and the like.

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

Examples of the isocyanate compound include n-butyl isocyanate, isopropyl isocyanate, 2-chloroethyl isocyanate, phenyl isocyanate, p-chlorophenyl isocyanate, benzyl isocyanate, hexamethylene diisocyanate, 2-ethylphenyl isocyanate, and 2,6-dimethylphenyl isocyanate. , Tolylene diisocyanate (eg, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate), 1,5-naphthalene diisocyanate, diphenylmethane-4,4′-diisocyanate, tolidine diisocyanate, isophorone diisocyanate, xylylene diisocyanate, Examples include paraphenylene diisocyanate and bicycloheptane triisocyanate.

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, and monochloro. Halogenated fatty acids such as acetic acid and dichloroacetic acid, monobasic oxyacids such as glycolic acid and lactic acid, aliphatic aldehyde acids such as glyoxalic acid and glucose, ketonic acid, oxalic acid, malonic acid, succinic acid, maleic acid, etc. Examples include aliphatic polybasic acids, benzoic acids, halogenated benzoic acids, toluic acid, aromatic monobasic acids such as 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 polysuccinic anhydrides such as succinic anhydride, dodecynyl succinic anhydride, maleic anhydride, an adduct of methylcyclopentadiene and maleic anhydride, hexahydrophthalic anhydride, and methyltetrahydrophthalic anhydride. Examples include basic acid anhydrides, aromatic polybasic acid anhydrides such as phthalic anhydride, trimellitic anhydride, and pyromellitic anhydride. A typical example of a commercially available acid anhydride is HN-2200 (molecular weight = 166) manufactured by Hitachi Chemical Co., Ltd., which is methyltetrahydrophthalic anhydride that can also be used as a curing agent for epoxy resins. However, the present invention is not limited to this.

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

Among these, as the storage stability improver, borate compounds are preferred from the viewpoint of high versatility and safety, and improvement in storage stability. Triethyl borate, tri-n-propyl borate, triisopropyl borate, tri- n-Butyl borate is more preferable, and triethyl borate is more preferable. The content of the storage stability improver is not particularly limited as long as the storage stability of the epoxy resin is increased, but when the total content of the epoxy resin is 100 parts by mass, the content of the storage stability improver is The amount is preferably 0.001 to 50 parts by mass, more preferably 0.05 to 30 parts by mass, and still more preferably 0.1 to 10 parts by mass.

The curable resin composition of the present invention can be produced from the above-described tris (3-mercaptopropyl) isocyanurate, epoxy resin, and various additives as optional components. The preparation of the curable resin composition is not particularly difficult and can be performed according to a conventionally known method. For example, the one-component thermosetting epoxy resin composition of the present invention can be prepared by mixing each component with a mixer such as a three-roller or a planetary mixer.

Moreover, the obtained one-component thermosetting resin composition can be cured without any particular difficulty and can also be performed according to a conventionally known method. For example, the obtained one-component thermosetting resin composition can be cured by heating. The heating is, for example, at a temperature of 50 to 150 ° C., preferably 60 to 120 ° C., more preferably 70 to 100 ° C., for example 1 to 60 minutes, preferably 3 to 30 minutes, more preferably 5 to 15 It is appropriate to do this for minutes. In particular, if it is cured by heating at 80 ° C. or 100 ° C. for 10 minutes or less, it can be judged that there is an appropriate low-temperature fast curing property.
Examples of the thixotropic property-imparting agent include fine powder silica, fatty acid amide, polyolefin polymer and the like. Specifically, fine powder silica “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]
Elastic modulus The one-component thermosetting resin composition of the present invention has an elastic modulus at 25 ° C. of the cured product of, for example, 10 to 2500 MPa. Such an elastic modulus is preferable because the adhesive strength of the obtained cured product can be improved. A more preferable elastic modulus of the cured product is, for example, 20 to 2450 MPa, a further preferable elastic modulus of the cured product is 30 to 2400 MPa, and an even more preferable elastic modulus of the cured product is 50 to 2300 MPa. Here, the elastic modulus should be measured in accordance with JIS-K-7161 using a Tensilon universal testing machine (RTM-500, manufactured by Orientec Co., Ltd.) in an environment of 25 ° C. and 40% RH. Can do.
・ Peel strength A (T-shaped peel test)
The one-component thermosetting resin composition of the present invention has a tensile strength value (hereinafter sometimes referred to as “peel strength A”) of 5 N / 25 mm according to a T-shaped peel test in accordance with JIS-K-6854-3. The above is preferably 8 to 40 N / 25 mm, more preferably 11 to 30 N / 25 mm. Here, the tensile strength (peel strength A) by the T-shaped peel test can be measured as follows. First, a test piece of a steel plate (25 mm × 150 mm × 0.4 mm) is wiped with a cloth moistened with acetone to wipe off oil. Further, the surface of the bonding surface of the steel plate is polished with an endless belt # 120. The resin composition is uniformly applied to the polished surface of the steel plate with a thickness of about 20 to 30 μm. Laminate another steel plate and bond and clamp with 4 clips. At this time, it is better to wipe off the exuded resin composition immediately. The test pieces are arranged evenly in an oven, heated and cured at 80 ° C. for 60 minutes, and bonded. The tensile strength of the obtained test piece was measured with a Tensilon universal testing machine (RTM-500, manufactured by Orientec Co., Ltd.) (measuring environment: temperature 25 ° C./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 measuring the tensile strength by the T-peel test, it is appropriate to prepare three test pieces for each of the same resin composition.

・ Peel strength B (High humidity test)
The tensile strength (hereinafter sometimes referred to as “peel strength B”) when the above test of the peel strength A is repeated after being left for a certain period of time in high humidity is, for example, 9 N / 25 mm or more, preferably 10 N / 25 mm. As described above, it is more preferable that the thickness is 10 to 50 N / 25 mm, and further preferably 11 to 30 N / 25 mm. This peel strength B is performed in order 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, preferably three test pieces each prepared separately by the procedure of the T-shaped test peel test according to the above JIS-K-6854-3 are prepared. After leaving each test piece in a pressure cooker test machine set at 120 ° C. and 85% RH for 24 hours, the obtained test piece was tested with a Tensilon universal tester (Orientec Co., Ltd., RTM-500). Measure the tensile strength (measuring environment: temperature 25 ° C / humidity 40%, pulling 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 of the one-component thermosetting resin composition of the present invention is
[Strength retention] = [Peel strength B] / [Peel strength A]
For example, it is appropriate that it is 0.67 or more, preferably 0.68 or more, more preferably 0.80 to 2.0, and still more preferably 1.0 to 1.5. Based on the strength retention, the influence of humidity on the peel strength of the one-component thermosetting resin composition of the present invention can be evaluated. It can be said that the larger the strength retention value, the more resistant the test piece is to high humidity.

[Hardened epoxy resin, adhesive, sealing material, etc.]
The epoxy resin cured product obtained by heating the one-component thermosetting resin composition is also included in the present invention, and a functional product containing the epoxy resin cured product is also included. 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 paint.

Especially, this invention relates to the adhesive agent containing the one-component thermosetting resin composition mentioned above. Here, the adhesive is an adhesive that can be used in the fields of adhesion of electronic components and die attach of semiconductor elements. The adhesive is preferably a one-pack type 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 is optionally a curing agent for epoxy resins other than TMPIC, a curing accelerator, a flame retardant, a storage stability improver, a filler, a diluent, Various additives such as a solvent, a pigment, a flexibility imparting agent, a coupling agent, an antioxidant, a thixotropic property imparting agent, and a dispersant may be included.

The present invention also relates to a sealing material containing the above-described one-component thermosetting resin composition. Here, the sealing material is an optional material other than the one-component thermosetting resin composition of the present invention, such as an underfill agent during flip-chip mounting and a sealing agent for chip-on-board. Curing agents for epoxy resins other than TMPIC, curing accelerators, flame retardants, storage stability improvers, fillers, diluents, solvents, pigments, flexibility imparting agents, coupling agents, antioxidants, thixotropic properties imparting agents Various additives such as a dispersant may be included.

Hereinafter, the present invention will be described more specifically based on 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. After weighing the specified amount of material shown in Table 1 into a plastic container, use a rotating / revolving vacuum mixer Awatori Rentaro (Shinky Corp .; ARE-250) and mix thoroughly at 2000 rpm at room temperature (25 ° C). The mixture was further degassed for 1 minute to obtain the desired resin composition.
The details of the materials used are as follows.

EXA4850-150: manufactured by DIC, vinyl ether modified bisphenol type epoxy resin) epoxy equivalent 450 g / eq (corresponding to formula (1))
EXA4816: manufactured by DIC, aliphatic chain-modified bisphenol A type epoxy resin, epoxy equivalent 403 g / eq (corresponding to formula (1))
EP-4010S: Made by Adeka, PO-modified bisphenol A type epoxy resin, epoxy equivalent 350 g / eq (corresponding to formula (2))
YL7410: manufactured by Mitsubishi Chemical Corporation, polyether-modified epoxy resin, epoxy equivalent 420 g / eq (corresponding to formula (1))
JER828EL: manufactured by Mitsubishi Chemical Corporation, bisphenol A type epoxy resin, epoxy equivalent 190 g / eq
JER1001: manufactured by Mitsubishi Chemical Corporation, solid bisphenol A type epoxy resin, epoxy equivalent of 1475 g / eq

TMPIC: manufactured by Ajinomoto Fine Techno Co., tris (3-mercaptopropyl) isocyanurate, total equivalent of thiol group 117 g / eq
TMTP: manufactured by Sakai Chemical Industry Co., Ltd., trimethylolpropane tris (3-mercaptopropionate, thiol group total equivalent 133 g / eq
PN-23: manufactured by Ajinomoto Fine Techno Co., Ltd., amine adduct-based latent curing accelerator FXR-1081: manufactured by T & K TOKA, modified polyamine-based latent curing agent AEROSIL 200: manufactured by Nippon Aerosil Co., Ltd., fumed silica TEB: Tokyo Kasei Co., Ltd. Triethylborate HN-2200 manufactured by Hitachi Chemical Co., Ltd. 3 or 4-methyl-1,2,3,6-tetrahydrophthalic anhydride (total thiol group equivalent = thiol group-containing compound containing 1 equivalent thiol group) mass)

[Thiol / epoxy equivalent ratio]
The “thiol / epoxy equivalent ratio” in Table 1 was determined from the following formula.
“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 ° x R9.7) is attached to the RE80 viscometer (manufactured by Toki Sangyo Co., Ltd.), and 0.2 to 0.3 ml of the resin composition to be measured is syringed into the measurement chamber. Weighed in. During measurement, the temperature of the viscometer measurement chamber was controlled at 25.0 ° C. in an external circulation thermostat. The rotation speed of the rotor was set to 0.5, 1, 20 and 100 rpm, and the viscosity after 120 seconds at each rotation speed was measured (unit: Pa · s).

[Measurement of elastic modulus of cured product of one-pack type thermosetting resin composition]
The elastic moduli of the cured epoxy resins of Examples and Comparative Examples obtained as described above were measured as follows. First, each obtained resin composition was applied onto a release PTFE film (Aflex 50N: manufactured by Asahi Glass Co., Ltd.) using a bar coat, and cured by heating at 80 ° C. for 60 minutes. The thickness of the cured body was 50 μm. Thereafter, the PTFE film was released. In accordance with JIS-K-7161, a tensile test was conducted using a Tensilon universal testing machine (RTM-500, manufactured by Orientec Co., Ltd.) at 25 ° C., 40% RH, and a tensile speed of 50 mm / min.

[Measurement of glass transition point]
A test piece of 7 mm × 30 mm was prepared, and using a DMA measuring device (Seiko Instruments, DMS6100) according to JIS-K-7244-4, a tensile method, a frequency of 1 Hz, a heating rate of 2 ° C./min, a measurement temperature Tan δ was measured under the conditions of 0 ° C. to 300 ° C. in the range. The temperature at which a peak appears in the obtained tan δ curve was defined as the glass transition temperature. The unit is ° C.

[Evaluation of low-temperature curability]
The low temperature curability of the resin composition of the present invention was evaluated by measuring the gel time (gelation time) according to JISC6521.
Specifically, first, the time during which the resin compositions of each Example and Comparative Example did not pull the yarn at 60 ° C. and 80 ° C. using a hot plate type gelation tester (GT-D: manufactured by Nisshin Kagaku Co., Ltd.) Was measured. Specifically, about 0.5 g of a sample (resin composition) is placed on a hot plate type gelation tester and the starting point is 60 ° C. (60 ° C. gel time) or 80 ° C. (80 ° C. gel time). In order for the resin composition to fall within the range of 25 mm in diameter on the hot plate, the contact composition is repeatedly moved with a spatula having a tip width of 5 mm (one rotation per second), and the resin composition is placed on the hot plate. The measurement was performed by taking the time from the start point to the end point as the time until gelation, with the end point being the time when the thread-like material was cut by 30 mm vertically from the end point. The spatula was not lifted while the resin viscosity was low. When the viscosity increased, the spatula was sometimes lifted about 30 mm vertically from the hot plate, and this vertical movement was repeated until the thread-like material was cut. The measurement was repeated three times and the average value was used.

[Evaluation of peel strength]
T-peeling test A test piece of steel plate (25 mm × 150 mm × 0.4 mm) was wiped with a cloth moistened with acetone to wipe off the oil. Furthermore, the surface of the bonding surface of the steel plate was polished with an endless belt # 120. The resin composition was uniformly applied to the polished surface of the steel plate with a thickness of about 20 to 30 μm. Another steel plate was overlapped and bonded with four clips and pressed. At this time, the exuded resin composition was immediately wiped off. The test pieces were evenly arranged in an oven and cured by heating at 80 ° C. for 60 minutes for adhesion. 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 using a Tensilon universal testing machine (RTM-500, manufactured by Orientec Co., Ltd.) (measuring environment; temperature 25 ° C./humidity 40%, tensile Speed; 50 mm / min). Based on the average peel load (N), the peel strength A per 25 mm width was calculated.
[Evaluation of moisture resistance]
In order to evaluate the moisture resistance of the test piece, the test of the peel strength A was repeated after being left for a certain period under high humidity. Specifically, three test pieces separately prepared by the procedure of the T-shaped test peel test were prepared. After leaving each test piece in a pressure cooker test machine set at 120 ° C. and 85% RH for 24 hours, the obtained test piece was tested with a Tensilon universal tester (Orientec Co., Ltd., RTM-500). The tensile strength was measured according to JIS-K-6854-3 (measuring environment: temperature 25 ° C./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]
In order to evaluate the effect of humidity on peel strength, strength retention was calculated. The strength retention was calculated from the values of the peel strength A and the peel strength B as follows.
[Strength retention] = [Peel strength B] / [Peel strength A]
It can be said that the larger the strength retention value, the more resistant the test piece is to high humidity.

[Consideration of evaluation results]
Table 1 shows the results of the above evaluations. As shown in Table 1, the one-component thermosetting resin compositions of Examples 1 to 9 have better low-temperature curability and better moisture resistance than the resin compositions of Comparative Examples. all right.

Moreover, the following aspects may be sufficient as this invention.
[1]
A one-component 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. One-component thermosetting resin composition.
[2]
The resin composition according to [1], wherein the epoxy equivalent of the epoxy resin is 200 to 1000.
[3]
The epoxy resin contains in its molecule (a) two or more epoxy groups, (b) a divalent non-aromatic hydrocarbon group containing-(CH ₂ )-in the main skeleton, and (c) two The resin composition according to [1] or [2], comprising an epoxy compound containing a divalent aromatic-containing hydrocarbon group containing a valent aromatic group in the main skeleton, or a polymer thereof.
[4]
The epoxy resin is represented by formula (1) or formula (2):

(In the formulas (1) and (2), X, X ₁ and X ₂ may be the same or different from each other, and may be divalent non-valent containing two or more — (CH ₂ ) — in the main skeleton. An aromatic hydrocarbon group (except when X is —O—CH ₂ —CH (—OH) —CH ₂ —), and Ar, Ar ₁ and Ar ₂ may be the same as each other An epoxy which may be different and is a divalent aromatic-containing hydrocarbon group containing a divalent aromatic group in the main skeleton, and n and m are each independently an integer of 1 to 20) The resin composition according to any one of [1] to [3], which comprises a compound or a polymer thereof.
[5]
The divalent non-aromatic hydrocarbon group containing two or more — (CH ₂ ) — in the main skeleton, which may or may not have a substituent, has 2 to 20 carbon atoms, And [3] or [4], wherein the resin composition is selected from alkylene groups having 2 to 20 carbon atoms which may or may not have a substituent.
[6]
(B) a divalent non-aromatic hydrocarbon group containing two or more — (CH ₂ ) — in the main skeleton,
(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) any one of [3] to [5] The resin composition according to item.
[7]
The divalent aromatic-containing hydrocarbon group containing the divalent aromatic group in the main skeleton is independently

The resin composition according to any one of [3] to [6], selected from:
[8]
The resin composition according to any one of [1] to [7], further comprising a solid dispersion type latent curing accelerator.
[9]
[1] to [8], further comprising at least one selected from 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 resin composition described in 1.
[10]
[1] An adhesive containing the resin composition according to any one of [9].
[11]
[1] A sealing material containing the resin composition according to any one of [9].
[12]
A cured epoxy resin obtained by heating the resin composition according to any one of [1] to [9].

Claims

Tris (3-mercaptopropyl) isocyanurate and an epoxy resin are represented by the formula (1) or the formula (2):

(In the formulas (1) and (2), X, X 1 and X 2 may be the same or different from each other, and may be divalent non-valent containing two or more — (CH 2 ) — in the main skeleton. An aromatic hydrocarbon group (except when X is —O—CH 2 —CH (—OH) —CH 2 —), and Ar, Ar 1 and Ar 2 may be the same as each other An epoxy which may be different and is a divalent aromatic-containing hydrocarbon group containing a divalent aromatic group in the main skeleton, and n and m are each independently an integer of 1 to 20) A one-component thermosetting resin composition containing a compound or a polymer thereof.
The divalent non-aromatic hydrocarbon group containing two or more — (CH 2 ) — in the main skeleton, which may or may not have a substituent, has 2 to 20 carbon atoms, The resin composition according to claim 1, wherein the resin composition is selected from an alkyleneoxy group having 2 to 20 carbon atoms which may or may not have a substituent.
A divalent non-aromatic hydrocarbon group containing two or more — (CH 2 ) — in the main skeleton,
(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) —
3. The method according to claim 1, wherein p, q, r, s, t, u, v, w, y, and z are each independently an integer of 1 to 20. The resin composition described in 1.
The divalent aromatic-containing hydrocarbon groups containing the divalent aromatic group in the main skeleton are each independently

The resin composition according to any one of claims 1 to 3, which is selected from the group consisting of:
The resin composition according to any one of claims 1 to 4, further comprising a solid dispersion type latent curing accelerator.
6. The composition according to claim 1, further comprising at least one selected from 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. Resin composition.
The resin composition according to any one of claims 1 to 6, wherein the cured product of the one-component thermosetting resin composition has an elastic modulus at 25 ° C of 10 to 2500 MPa.
The peel strength B (N / 25 mm) measured according to JIS-K-6854-3 is 9 or more after the cured product of the one-component thermosetting resin composition is allowed to stand for 24 hours at 120 ° C. and 85% RH. The resin composition according to any one of claims 1 to 7, wherein
A cured product of the one-pack type thermosetting resin composition is peel strength A (N / 25 mm) measured according to JIS-K-6854-3, and a cured product of the one-pack type thermosetting resin composition is 120. Curing of the one-component thermosetting resin composition calculated from the peel strength B (N / 25 mm) measured according to JIS-K-6854-3 after standing for 24 hours under the conditions of 85 ° C. and 85 ° C. The resin composition according to any one of claims 1 to 8, wherein the strength retention (B / A) of the product is 0.67 or more.
An adhesive comprising the resin composition according to any one of claims 1 to 9.
A sealing material containing 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.
The mass ratio of the epoxy compound or polymer thereof to the bisphenol A epoxy resin is [epoxy compound or polymer thereof]: [bisphenol A epoxy resin] = 10: 1 to 1:10. Item 14. The resin composition according to Item 13.