TW201531515A - Flexible epoxy resin composition - Google Patents

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

Soft epoxy resin composition

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

Epoxy resin is used in a wide range of applications such as coatings, electrical and electronic insulating materials, and adhesives because of its excellent mechanical properties, electrical properties, thermal properties, chemical resistance, and adhesion strength. In recent years, in addition to curing and hardening an epoxy resin and a hardener at the time of use, that is, a two-component epoxy resin composition, it has been developed to pre-mix an epoxy resin and a hardener and harden it by heat or the like. One-component epoxy resin composition. In particular, in the field of electronic circuits in recent years, research on flexibility and thinning has been actively carried out, and in order to achieve protection of semiconductor elements, increase in density of circuits, and improvement in reliability of connection, one liquid for low-temperature hardenability is improved. Type epoxy resin composition requirements.

For example, a low-temperature hardening one-liquid type using a thiol hardener is known. Epoxy resin composition (Patent Document 1). However, if the low-temperature hardening property is excessively pursued, there is a case where the peel strength is poor. Further, the curing agent contained in the conventional one-liquid epoxy resin composition having low-temperature curability generally has a problem of low moisture resistance and a problem of lowering the adhesive strength in a high-humidity environment.

[Previous Technical Literature]

[Patent Literature]

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

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

As a result of intensive studies to solve the above problems, the present inventors have found that a one-component thermosetting resin composition containing ginseng (3-mercaptopropyl)isocyanurate and a specific epoxy resin is preferably used. The above-mentioned problem can be solved by the liquid-type thermosetting resin composition having a modulus of elasticity at 25° C. of a cured product of the one-pack type thermosetting resin composition of from 10 to 2,500 MPa.

That is, the present invention is as follows.

[1] A one-component thermosetting resin composition comprising gins(3-mercaptopropyl)isocyanurate and an epoxy resin represented by the formula (1) or the formula (2) Oxygen compounds or such polymers,

(In the formulae (1) and (2), X, X ₁ and X ₂ may be the same or different from each other and contain 2 or more -(CH ₂ )-divalent non-aromatic hydrocarbon groups in the main skeleton (but X is In the case of -O-CH ₂ -CH(-OH)-CH ₂ -, the Ar, Ar ₁ and Ar ₂ groups may be the same or different from each other and contain a divalent aromatic group in the main skeleton. The hydrocarbon group, n and m are each independently an integer from 1 to 20).

[2] The resin composition according to the above [1], wherein the divalent non-aromatic hydrocarbon group containing 2 or more -(CH ₂ )- in the main skeleton is selected from those which may or may not have a substituent. An alkylene group having 2 to 20 carbon atoms and an alkyleneoxy group having 2 to 20 carbon atoms which may or may not have a substituent.

The resin composition according to any one of the above-mentioned [1], wherein the divalent non-aromatic hydrocarbon group containing 2 or more -(CH ₂ )- in the main skeleton is selected from the group consisting of (b1)-O-CH(-CH ₃ )-(O-(CH ₂ )p)qO-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)-

(However, p, q, r, s, t, u, v, w, y, and z are independent integers from 1 to 20, respectively).

[4] The resin composition according to any one of the above [1], wherein the divalent aromatic hydrocarbon group containing a divalent aromatic group in the main skeleton is independently selected from the group consisting of

and

[5] The resin composition according to any one of the above [1] to [4] further comprising a solid dispersion type latent curing accelerator.

[6] The resin composition according to any one of [1] to [5] further comprising a boric acid ester compound, a titanate compound, an aluminate compound, a zirconate compound, and an isocyanate compound. One or more of a carboxylic acid, an acid anhydride, and a mercapto organic acid.

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

[8] The resin composition according to any one of the above [1], wherein the cured product of the one-component thermosetting resin composition is placed at 120 ° C and 85% RH. After 24 hours, the peel strength B (N/25 mm) measured in accordance with JIS-K-6854-3 was 9 or more.

[9] The resin composition according to any one of the above [1] to [8], wherein the cured product of the one-liquid type thermosetting resin composition is peeled off in accordance with JIS-K-6854-3 The peeling strength measured according to JIS-K-6854-3 after the strength A (N/25 mm) and the cured product of the one-component thermosetting resin composition were allowed to stand at 120 ° C and 85% RH for 24 hours. B (N/25 mm), the strength retention ratio (B/A) of the cured product of the one-pack type thermosetting resin composition thus calculated was 0.67 or more.

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

[11] A material for sealing, which comprises the resin composition according to any one of [1] to [9] above.

[12] A cured epoxy resin obtained by heating the resin composition according to any one of the above [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 resin composition according to the above [13], wherein the mass ratio of the epoxy compound or the polymer to the bisphenol A type epoxy resin is [epoxy compound or the polymer] : [Bisphenol A type epoxy resin] = 10:1~1:10.

The liquid thermosetting resin composition of the present invention is an epoxy resin composition excellent in low-temperature curability, peel strength, and moisture resistance. In particular, it is excellent in peel strength and moisture resistance, and is excellent in, for example, an elastic modulus of, for example, about 10 to 2,500 MPa. Therefore, it can be used for an adhesive or a sealing material, and can be used for a die attachment material and underfill. Uses such as materials and sealing materials for COB. Here, the "one-liquid type" thermosetting resin composition means a composition in which a composition of a curing agent and an epoxy resin is mixed in advance, and the composition has a property of curing by heating the composition.

[Best Mode for Carrying Out the Invention]

[Ref. (3-Mercaptopropyl) Isocyanurate (TMPIC)]

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

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

When the total epoxy resin contained in the liquid thermosetting resin composition of the present invention is 100 parts by mass, the content of gin(3-mercaptopropyl)isocyanurate is, for example, 10 to 100. The mass part is preferably 20 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 liquid thermosetting resin composition of the present invention is, for example, preferably 200 to 1,000, and more preferably 300 to 600. When the epoxy equivalent of the epoxy resin is 200 or more, the volatility is small and does not become low viscosity, and it is suitable because it becomes an easy-to-operate viscosity. Further, when the epoxy equivalent of the epoxy resin is 1000 or less, it is suitable to operate the surface without becoming a high viscosity. Here, the epoxy equivalent means the mass of the epoxy resin containing 1 equivalent of an epoxy group, and can be measured, for example, according to JIS K7236 (2009).

The epoxy resin of the present invention preferably contains an epoxy compound containing (a) an epoxy group of 2 or more, and (b) containing 2 or more in the main skeleton, or an epoxy compound. a divalent non-aromatic hydrocarbon group of -(CH ₂ )-, and (c) a divalent aromatic-containing hydrocarbon group containing a divalent aromatic group in the main skeleton.

(a) The epoxy group of "2 or more epoxy groups" is a monovalent group represented by the following formula.

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

Here, the "main skeleton" means a skeleton having the longest chain among the skeletons having two or more epoxy groups of (a) at both ends.

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, and particularly preferably 5 to 30. More preferably 6~20.

The two or more -(CH ₂ )- may be directly bonded, or may be bonded by an ether bond, an ester bond, a guanamine bond, two carbons bonded by a double bond, and a triple bond. The two carbon and thioether bonds are bonded to each other.

Examples of the "divalent non-aromatic hydrocarbon group containing 2 or more -(CH ₂ )- in the main skeleton" include an alkylene group and an alkylene oxide group, and these may or may not have a substituent.

Here, examples of the substituent include a hydroxyl group, a halogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an amine group, a decyl group, a decyl group, a decyloxy group, a carboxyl group, and a cyano group. a group of a nitro group, a hydroxyl group, a thiol group and an oxo group.

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

The number of carbon atoms of the cycloalkyl group to be used as a substituent is preferably from 3 to 20, more preferably from 3 to 12, still more preferably from 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 alkoxy group preferably has 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, still more preferably 1 to 6 carbon atoms. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a sec-butoxy group, an isobutoxy group, a tert-butoxy group, and a pentyloxy group. Base, hexyloxy, heptyloxy, octyloxy, decyloxy, and decyloxy.

The number of carbon atoms of the cycloalkoxy group to be used as a substituent is preferably from 3 to 20, more preferably from 3 to 12, still more preferably from 3 to 6. Examples of the cycloalkoxy group include a cyclopropoxy group, a cyclobutoxy group, a cyclopentyloxy group, and a cyclohexyloxy group.

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

The fluorenyl group which is used as a substituent may be either linear or branched. The alkyl group has preferably 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, still more preferably 1 to 6 carbon atoms. Examples of the decylalkyl group include a methyl decyl group, an ethyl decyl group, a propyl decyl group, an isopropyl decyl group, and a butyl group. Oxidylalkyl, sec-butylalkyl, isobutylalkyl, tert-butylalkyl, pentylalkyl, hexylalkyl, heptylalkyl, octylalkyl, decylalkyl, and Mercaptoalkyl.

The fluorenyl group used as a substituent is 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 sulfhydryl group preferably has 2 to 20 carbon atoms, more preferably 2 to 13 carbon atoms, still more preferably 2 to 7 carbon atoms. Examples of the fluorenyl group include an ethyl group, a propyl group, a butyl group, an isobutyl group, and a trimethyl ethane group.

The oxime group to be used as a substituent is 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 decyloxy group is preferably from 2 to 20, more preferably from 2 to 13, more preferably from 2 to 7. Examples of the decyloxy group include an ethoxycarbonyl group, a propenyloxy group, a butoxy group, an isobutyloxy group, and a trimethylacetoxy group.

In addition to 2 or more -(CH ₂ )-, the "divalent non-aromatic hydrocarbon group containing 2 or more -(CH ₂ )- in the main skeleton" may further contain a cycloalkyl group, a cycloalkenyl group, and a ring. A non-aromatic divalent group other than a methyl group, such as an alkynyl group, a polyalkylene group, an alkylenedi-alkynyl group or an alkylenetriynyl group.

The "divalent non-aromatic hydrocarbon group containing 2 or more -(CH ₂ )- in the main skeleton" is preferably, for example, an alkylene group having 2 to 20 carbon atoms which may or may not have a substituent, or may have Or a 2 to 20 carbon alkylene group having no substituent. Here, when a substituent is contained, the carbon number is a number other than the carbon number of the substituent.

The alkoxy group may have a structure represented by, for example, the following formula More than one type is made.

(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, preferably 1 to 10, more preferably 1 to 6, more preferably 1 to 3. Here, q, s, t, v, y, and z are integers of 1 to 20, preferably 1 to 10, more preferably 1 to 6, more 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 phenyl group, a naphthyl group, an anthracenyl group or a biphenyl group. The phenylene group may be an ortho, meta or para phenyl group. In the "divalent aromatic-containing hydrocarbon group", two or more of the aromatic groups may be contained. When two or more aromatic groups are contained, the aromatic group may be directly bonded, or may be bonded by an alkyl group, an ether bond, an ester bond, a guanamine bond, or a double bond. One carbon, two carbons bonded by three bonds, etc. are bonded.

As a particularly preferred "divalent aromatic hydrocarbon-containing hydrocarbon group", for example,

and

The epoxy compound of the present invention is preferably a compound having an epoxy group and a linear skeleton and having an epoxy group. As long as the epoxy compound is generally linear, a part of a divalent cyclic group such as a divalent aromatic group may be contained in the main skeleton. Further, the group constituting the main skeleton may have a substituent as described above. The "polymer of an epoxy compound" means a polymer having a molecular weight of, for example, about 500 to 1,500 after polymerization of the epoxy compound.

In the liquid thermosetting resin composition of the present invention, the epoxy resin preferably contains an epoxy compound or a polymer represented by the structure represented by the following formula (1) or formula (2).

In the formulae (1) and (2), X, X ₁ and X ₂ are a divalent non-aromatic hydrocarbon group containing 2 or more -(CH ₂ )- in the main skeleton (but X is -O-CH ₂ -CH) Except for (-OH)-CH ₂ -). Here, the definition of "a divalent non-aromatic hydrocarbon group containing 2 or more -(CH ₂ )- in the main skeleton" is as described above. The n of the formula (1) may be the same or different from each other. The m X ₁ and m X ₂ in the formula (2) may be the same or different from each other. X, X ₁ and X ₂ may be a group selected from the above (b1) to (b6).

In the formulae (1) and (2), Ar, Ar ₁ and Ar ₂ may be the same or different, may or may not have a substituent, and contain a divalent 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 formulae (1) and (2), the n and m systems are each independently from 1 to 20, preferably from 1 to 10.

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

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

Specific examples of the epoxy compound or the polymer which can be used in the present invention include a resin having the following structure (k is an integer of from 1 to 20, preferably an integer of from 1 to 5).

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

and

Further, for example, 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; ADEKA company EP-4000S (equivalent to formula (2)), EP-4000SS (equivalent to formula (2)), EP-4003S equivalent (2)), EP-4010S (equivalent to formula (2)), and EP-4011S (equivalent to formula (2)); BEO-60E and BPO-20E manufactured by Nippon Chemical and Chemical Co., Ltd.; and YL7175- manufactured by Mitsubishi Chemical Corporation 500, YL7175-1000, and YL7410.

In addition to the above epoxy compound or the polymer instead of the above, the one-component thermosetting resin composition of the present invention can be used in various types as long as the modulus of elasticity of the cured product of the resin composition is 25 ° C. Oxygen resin. For example, a polyphenol such as bisphenol A, bisphenol F, bisphenol AD, bisphenol E, catechol or resorcin, or a polyol such as glycerin or polyethylene glycol may be reacted with epichlorohydrin. Polyglycidyl ether obtained after the reaction; polyglycidyl ether ester obtained by reacting a hydroxy acid such as p-hydroxybenzoic acid or β-hydroxynaphthoic acid with epichlorohydrin; and phthalic acid and terephthalic acid a polyglycidyl ester obtained by reacting a polycarboxylic acid with epichlorohydrin; an epoxidized phenol phenolic resin, an epoxidized cresol novolac resin, an epoxidized polyolefin, a cyclic aliphatic epoxy resin, or the like The amine ester-modified epoxy resin or the like is not limited thereto.

From the viewpoint of maintaining high heat resistance and low moisture permeability, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a phenol novolac type epoxy resin, a biphenyl aralkyl type ring is preferable. Oxygen resin, phenol aralkyl type epoxy resin, aromatic glycidylamine type epoxy resin, epoxy resin having a dicyclopentadiene structure, preferably bisphenol A type epoxy resin and bisphenol F type The epoxy resin is preferably a bisphenol A type epoxy resin.

These resins may be in a liquid or solid shape. It is also possible to use a mixture of a liquid resin and a solid resin. Here, the term "liquid" and "solid shape" mean the state of the epoxy resin at normal temperature (25 ° C). on From the viewpoint of coatability, workability, and adhesion, it is preferred that at least 10% by mass or more of the total epoxy resin used is a liquid epoxy resin.

Specific examples of the related resin include bisphenol A type (hereinafter sometimes referred to as BPA type) epoxy resin ("JER828EL", "JER827", "JER1001" manufactured by Mitsubishi Chemical Corporation), and bisphenol F type epoxy. Resin ("JER807" manufactured by Mitsubishi Chemical Corporation), liquid bisphenol AF epoxy resin ("ZX1059" manufactured by Tohto Kasei Co., Ltd.), epoxy resin of hydrogenated structure ("JERYX8000" manufactured by Mitsubishi Chemical Corporation), and dicyclopentane Ethylene-type polyfunctional epoxy resin ("HP7200" manufactured by DIC Corporation), epoxy resin having a butadiene structure ("PB-3600" manufactured by Daicel Chemical Industry Co., Ltd.), epoxy resin having a biphenyl structure (Japan) "NC3000H", "NC3000L" manufactured by Chemicals Co., Ltd., "YX4000" manufactured by Mitsubishi Chemical Corporation). Among them, it is preferable to use a BPA-type epoxy resin having high heat resistance and low viscosity, preferably "JER828EL", "JER827", "JER1001", and "JER807" manufactured by Mitsubishi Chemical Corporation, and preferably "JER828EL". .

In addition to "epoxy compounds or such polymers", when a BPA type epoxy resin is used, the mass ratio of "epoxy compound or these polymers" to BPA type epoxy resin, such as "epoxy compound" Or such polymers": BPA type epoxy resin = 10:1 to 1:10, preferably 10:1 to 1:5, more preferably 9:1 to 1:2, more preferably 8: 1~1:1.

[Other additives]

The curable resin composition of the present invention can be used in addition to TMPIC A curing agent for a epoxy resin, a hardening accelerator, a flame retardant, a storage stability enhancer, a filler, a diluent, a solvent, a pigment, a flexibility imparting agent, a coupling agent, an antioxidant, a thixotropic imparting agent, Various additives such as dispersants.

Examples of the curing agent for the epoxy resin other than the TMPIC include an imidazole curing agent or an amine curing agent. Further, a thiol compound other than TMPIC is, for example, trimethylolpropane ginseng (3-mercaptopropionate) (TMTP), trimethylolpropane ginsyl (mercaptoacetate), neopentyl pentoxide (mercaptoacetate), ethylene glycol dimercaptoacetate, trimethylolpropane ginseng (β-thiopropionate), neopentyl quinone oxime (β-thiopropionate), dipentaerythritol A thiol compound obtained by esterification reaction of a polyalcohol such as poly(β-thiopropionate) with a mercapto organic acid can also be used as a curing agent for an epoxy resin.

The hardening accelerator which can be used in the present invention may, for example, be a solid dispersion type latent curing accelerator. The solid dispersion type latent curing accelerator refers to a solid which is insoluble in the above epoxy resin at room temperature (25 ° C), which is solubilized by heating and functions as a curing accelerator for the epoxy resin. The functional compound may, for example, be an imidazole compound which is solid at normal temperature and a latent amine-additive latent curing accelerator, but is not limited thereto. As an example of the solid dispersion type amine addition type latent curing accelerator, a reaction product of an amine compound with an epoxy compound (amine-epoxy adduct system), an amine compound and an isocyanate compound or a urea compound can be exemplified. Product (urea type adduct system) and the like. Among these, a solid dispersion type amine adduct is a latent curing accelerator.

As the aforementioned imidazole compound which is solid at normal temperature, For example, 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 ‧ isocyanate adduct, 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole-p-triphenylcarboxylate, 1-cyanoethyl-2-benzene Imidazole-p-benzoic acid ester, N-(2-methylimidazolyl-1-ethyl)-urea, N,N'-(2-methylimidazolyl-(1)-ethyl)-hexane Mercaptodiamine or the like is not limited thereto.

The epoxy compound which is one of the raw materials for the production of the solid dispersion-type amine-additive-based latent curing accelerator (amine-epoxy adduct) is exemplified by bisphenol A and bisphenol F. a polyphenol such as catechol or resorcin, or a polyglycidyl ether obtained by reacting a polyhydric alcohol such as glycerin or polyethylene glycol with epichlorohydrin; and p-hydroxybenzoic acid, β-hydroxynaphthalene a glycidyl ether ester obtained by reacting a hydroxy acid such as formic acid with epichlorohydrin; a polyglycidyl ester obtained by reacting a polycarboxylic acid such as phthalic acid or terephthalic acid with epichlorohydrin; a glycidylamine compound obtained by reacting 4,4'-diaminodiphenylmethane or m-aminophenol with epichlorohydrin; further an epoxidized phenol phenolic resin, an epoxidized cresol novolac resin, a ring A monofunctional epoxy compound such as a polyfunctional epoxy compound such as oxidized polyolefin or butyl glycidyl ether, phenyl glycidyl ether or glycidyl methacrylate; however, it is not limited thereto.

The amine compound to be used as a raw material for producing the latent solid amine-based amine-based latent curing accelerator is an active hydrogen having one or more reactive groups capable of reacting with an epoxy group in the molecule, and having at least a molecule in the molecule. One or more functional groups selected from the group consisting of a primary amine group, a secondary amine group, and a tertiary amine group may be used. Examples of such an amine compound include diethylenetriamine, triethylenetetramine, n-propylamine, 2-hydroxyethylaminopropylamine, cyclohexylamine, and 4,4'-diamino group. - an aliphatic amine such as dicyclohexylmethane; an aromatic amine compound such as 4,4'-diaminodiphenylmethane or 2-methylaniline; 2-ethyl-4-methylimidazole, 2- Ethyl-4-methylimidazolium, 2,4-dimethylimidazolium, piperidine, piperidine The heterocyclic compound containing a nitrogen atom or the like is not limited thereto.

In addition, in particular, a compound having a tertiary amino group in the molecule is a raw material which imparts a hardening accelerator having excellent curing acceleration energy. Examples of such a compound include dimethyl group. Aminopropylamine, diethylaminopropylamine, di-n-propylaminopropylamine, dibutylaminopropylamine, dimethylaminoethylamine, diethylamino Ethylamine, N-methylpiperidone An amine compound, or an imidazole compound such as 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole or 2-phenylimidazole, or the like having a tertiary amino group in the molecule Grade or 2 amines; 2-dimethylaminoethanol, 1-methyl-2-dimethylaminoethanol, 1-phenoxymethyl-2-dimethylaminoethanol, 2-two Ethylaminoethanol, 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-hydroxyl 3-butoxypropyl)-2-ethyl-4-methylimidazole, 1-(2-hydroxy-3-phenoxypropyl)-2-phenylimidazolium, 1-(2-hydroxyl -3-butoxypropyl)-2-methylimidazolium, 2-(dimethylaminomethyl)phenol, 2,4,6-gin(dimethylaminomethyl)phenol, N- Β-hydroxyethyl orfolin, 2-dimethylaminoethanethiol, 2-mercaptopyridine, 2-benzimidazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 4-mercaptopyridine, N,N-dimethylamino benzoic acid, N,N-dimethylglycine, nicotinic acid, isonicotinic acid, picolinic acid, N,N-dimethyl Alcohols, phenols, thiols having a grade 3 amine group in the molecule, such as bismuth glycinate, bismuth N,N-dimethylpropionate, bismuth nicotinate or guanidine nicotinic acid Classes, carboxylic acids and terpenoids.

When the above-mentioned epoxy compound and the amine compound are subjected to an addition reaction to produce a latent curing accelerator, an active hydrogen compound having two or more active hydrogens in the molecule may be added. Examples of such an active hydrogen compound include polyphenols such as bisphenol A, bisphenol F, bisphenol S, hydroquinone, catechol, resorcin, gallic phenol, and phenol novolac resin; a polyhydric alcohol such as methyl propane; a polycarboxylic acid such as adipic acid or phthalic acid; 1,2-dimercaptoethane, 2-mercaptoethanol, 1-mercapto-3-phenoxy-2-propene The alcohol, thioglycolic acid, ortho-amino acid, lactic acid, and the like are not limited thereto.

As the isocyanate compound to be used as a raw material for producing the solid dispersion type amine addition-based latent curing accelerator, for example, n-butyl isocyanate, isopropyl isocyanate, phenyl isocyanate, benzyl isocyanate or the like can be used. Monofunctional isocyanate compound; hexamethylene diisocyanate, toluene diisocyanate (eg: 2,4-toluene diisocyanate, 2,6-toluene diisocyanate), 1,5-naphthalene diisocyanate, diphenylmethane-4,4 '-Diisocyanate, isophorone diisocyanate, xylene diisocyanate, pair a polyfunctional isocyanate compound such as phenyl diisocyanate, 1,3,6-hexamethylene triisocyanate or bicycloheptane triisocyanate; and further obtained by reacting a polyfunctional isocyanate compound with an active hydrogen compound A compound containing a terminal isocyanate group or the like. As an example of such a terminal isocyanate group-containing compound, an addition compound having a terminal isocyanate group obtained by reacting toluene diisocyanate with trimethylolpropane, by toluene diisocyanate and neopentyl alcohol can be exemplified. The addition compound having a terminal isocyanate group obtained after the reaction is not limited thereto.

In addition, examples of the urea compound to be used as a raw material for the production of the solid dispersion-type amine-additive-based latent curing accelerator include urea, sulfur urea, and the like, but are not limited thereto.

The solid dispersion type latent curing accelerator is prepared by, for example, appropriately mixing the above-mentioned raw materials, and reacting it at a temperature of from room temperature to 200 ° C, followed by cooling and solidifying, and then pulverizing; or in methyl ethyl ketone or dioxane The reaction is carried out in a solvent such as an alkane or tetrahydrofuran, and the solid fraction is pulverized after solvent removal, and is easily obtained.

A commercially available representative example of the solid dispersion type latent curing accelerator is, for example, "Ajicure PN-23" manufactured by Ajinomoto Fine-Techno Co., Ltd., which is an amine-epoxy adduct system (amine addition system). "Ajicure PN-H", "Hardener X-3661S" by ACR, "Hardener X-3670S", "Novacure HX-3742" by Asahi Kasei Co., Ltd., "Novacure HX-3721", etc. Further, as a urea type addition system, T&K TOKA can be exemplified. Company system "FXE-1000", "FXR- 1030", "FXR-1081", etc., but not limited to these.

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 storage stability improving agent used in the present invention can be added in order to achieve excellent storage stability of the curable resin composition of the present invention. Examples of the storage stability improving agent include a boric acid ester 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 boric acid ester compound include trimethyl borate, triethyl borate (TEB), tri-n-propyl borate, triisopropyl borate, and tri-n-. Butyl borate, triamyl borate, triallyl borate, trihexyl borate, tricyclohexyl borate, trioctyl borate, tridecyl borate, triterpene Boronate, tri-dodecyl borate, trihexadecyl borate, tri-octadecyl borate, ginseng (2-ethylhexyloxy)borane, bis (1) ,4,7,10-tetraoxaundecyl)(1,4,7,10,13-pentaoxatetradecyl)(1,4,7-trioxadecyl)boron Alkane, tribenzyl borate, triphenyl borate, 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, and tetraoctyl titanate.

Examples of the above aluminate compound include triethyl aluminate, tripropyl aluminate, triisopropyl aluminate, tributyl aluminate, and aluminum aluminate. Octyl ester 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, and 2 -ethylphenylisocyanate, 2,6-dimethylphenylisocyanate, toluene diisocyanate (eg 2,4-toluene diisocyanate, 2,6-toluene diisocyanate), 1,5-naphthalene diisocyanate, two Benzene-4,4'-diisocyanate, di-toluidine diisocyanate, isophorone diisocyanate, xylene diisocyanate, p-phenylene 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; a halogenated fatty acid such as acetic acid or dichloroacetic acid, glycolic acid, lactic acid, or the like; an aliphatic aldehyde acid such as glyoxylic acid or racemic tartaric acid, and keto acid, oxalic acid, malonic acid, succinic acid, and horse An aliphatic polybasic acid such as benzoic acid, halogenated benzoic acid, toluic acid, phenylacetic acid, cinnamic acid or mandelic acid; aromatic polybasic acid such as phthalic acid or trimesic acid; Wait.

Examples of the acid anhydride include succinic anhydride, dodecyl succinic anhydride, maleic anhydride, an adduct of methyl dicyclopentadiene and maleic anhydride, hexahydrophthalic anhydride, and methyl tetrahydrogen Phthalic anhydride, etc. An aromatic polybasic acid anhydride such as an aliphatic or aliphatic polybasic acid anhydride such as phthalic anhydride, trimellitic anhydride or pyromellitic dianhydride. As a typical example of the commercially available acid anhydride, for example, methyltetrahydrophthalic anhydride which is a curing agent for an epoxy resin can be used, and HN-2200 (molecular weight = 166) manufactured by Hitachi Chemical Co., Ltd. can be used, but is not limited thereto. This one.

Examples of the mercapto organic acid include mercapto aliphatic monocarboxylic acids such as mercaptoacetic acid, mercaptopropionic acid, mercaptobutyric acid, mercaptosuccinic acid, and dimercaptosuccinic acid, and esterification of a hydroxy organic acid with a mercapto organic acid. The mercapto aromatic monocarboxylic acid obtained by the reaction, the mercapto aromatic monocarboxylic acid such as mercaptobenzoic acid, and the like.

Among these, among the viewpoints of high versatility, safety, and improvement in storage stability, a storage stability enhancer is preferably a borate compound, and preferably a triethyl borate or a tri-n. -propyl borate, triisopropyl borate, tri-n-butyl borate, more preferably triethyl borate. The content of the storage stability enhancer is not particularly limited as long as it can improve the storage stability of the epoxy resin. However, if the total content of the epoxy resin is 100 parts by mass, it is preferable to contain the storage stability enhancer. The amount is 0.001 to 50 parts by mass, 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 produced by using the above-mentioned ginseng (3-mercaptopropyl) isocyanurate, an epoxy resin, and various additives of any component as raw materials. The preparation of the curable resin composition is not particularly difficult, and can be carried out according to a conventionally known method. For example, by mixing a component with a mixer such as a three-roller or a planetary mixer, it is possible to prepare A liquid type thermosetting epoxy resin composition of the present invention.

Further, the curing of the obtained one-liquid type thermosetting resin composition is not particularly difficult, and it can also be carried out according to a conventionally known method. For example, the one-liquid type thermosetting resin composition obtained by heating can be cured. The heating is suitably carried out, for example, at a temperature of 50 to 150 ° C, preferably 60 to 120 ° C, and more preferably 70 to 100 ° C, for example, 1 to 60 minutes, preferably 3 to 30 minutes, and more preferably 5 ~15 minutes to carry out. In particular, when it is heated at 80 ° C or 100 ° C for 10 minutes or less, it can be judged to have moderate low-temperature-speed hardenability.

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

[Characteristics of a one-component thermosetting resin composition]

‧ elastic rate

In the liquid thermosetting resin composition of the present invention, the elastic modulus of the cured product at 25 ° C is, for example, 10 to 2500 MPa. It is preferable to increase the adhesion strength of the obtained cured product as long as the elastic modulus is so. Further, the elastic modulus of the cured product is, for example, 20 to 2450 MPa, the elastic modulus of the cured product is preferably 30 to 2400 MPa, and the elastic modulus of the more preferable cured product is 50 to 2300 MPa. Here, the modulus of elasticity is measured by a tensile test using a TENSILON universal testing machine (manufactured by Orientec, RTM-500) in an environment of 25° C. and 40% RH in accordance with JIS-K-7161.

‧ peel strength A (T-stripping test)

The liquid thermosetting resin composition of the present invention has a tensile strength value (hereinafter sometimes referred to as a peeling strength A) of a T-shaped peeling test according to JIS-K-6854-3 of 5 N/25 mm or more. Preferably, it is 8~40N/25mm, and preferably 11~30N/25mm. Here, the tensile strength (peeling strength A) by the T-stripping test can be measured as follows. First, the oil was wiped off by wiping the test piece of the steel plate (25 mm × 150 mm × 0.4 mm) with a rag soaked with acetone. Further, the surface of the adhesive surface of the steel sheet was ground with an endless belt #120. A resin composition having a thickness of about 20 to 30 μm is uniformly applied to the polished surface of the steel sheet. The other piece of steel plate was overlapped and pressed with 4 clamps. At this time, it is preferred that the exuded resin composition is immediately wiped off. The test pieces were uniformly placed in an oven, and heat-hardened at 80 ° C for 60 minutes to adhere them. The obtained test piece was measured for tensile strength by a TENSILON universal testing machine (RTM-500, manufactured by Orientec Co., Ltd.) (measurement environment: temperature: 25° C./humidity: 40%, tensile speed: 50 mm/min). The peel strength A per 25 mm width was calculated based on the average peeling load (N). In the measurement of the tensile strength by the T-stripping test, it is appropriate to prepare three test pieces for the same resin composition.

‧ peel strength B (high humidity test)

When the tensile strength (hereinafter, referred to as peeling strength B) at the time of the test of the peeling strength A is repeated after standing for a certain period of time under high humidity, it is suitably, for example, 9 N/25 mm or more, preferably 10 N/25 mm or more. It is preferably 10 to 50 N/25 mm, more preferably 11 to 30 N/25 mm. Peel strength B is carried out in order to evaluate the moisture resistance of the one-component thermosetting resin composition. Here, the tensile strength (peeling strength B) at the high humidity can be measured as follows. That is, in the procedure of the T-test peeling test according to JIS-K-6854-3, it is preferable to prepare three separately prepared test pieces. Each test piece was placed in a pressure cooker under the conditions of 120 ° C and 85% RH for 24 hours, and then the obtained test piece was subjected to measurement by a TENSILON universal testing machine (RTM-500, manufactured by Orientec Co., Ltd.). Extensive strength (measurement environment: temperature 25 ° C / humidity 40%, tensile speed: 50 mm / min). The peel strength B per 25 mm width can be calculated based on the average peeling load (N).

‧ Strength retention rate

The strength retention ratio of the liquid type thermosetting resin composition of the present invention can be [Strength retention rate] = [peel strength B] / [peel strength A]

The calculation is suitably, for example, 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. By the strength retention ratio, the influence of the humidity on the peel strength of the liquid type thermosetting resin composition of the present invention can be evaluated. The larger the value of the strength retention ratio, the test piece can be resistant to high humidity.

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

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

Among these, the present invention relates to an adhesive containing the above-described one-component thermosetting resin composition. Here, the adhesive is an adhesive for use in the field of adhesion of electronic parts and adhesion of crystal grains of semiconductor elements. As the adhesive, a one-liquid epoxy resin adhesive in which a hardener and an epoxy resin composition are previously mixed is preferably used.

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

The present invention is also directed to a sealing material containing the above-described one-liquid thermosetting resin composition. Here, the sealing material is a sealing material such as an underfill for sealing a crystal and a sealing agent for direct sealing of a wafer, and may be any material other than the liquid thermosetting resin composition of the present invention. Contains hardeners for hardeners other than TMPIC, hardening accelerators, flame retardants, storage stability enhancers, fillers, thinners, solvents, pigments, flexibility-imparting agents, coupling agents, antioxidants, touch Various additives such as a denaturation-imparting agent and a dispersing agent.

[Examples]

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

[Preparation of one-component thermosetting resin composition]

Each resin composition having the composition shown in Table 1 was prepared. After measuring the amount of the material as specified in Table 1 in a plastic container, the mixture was thoroughly mixed at room temperature (25 ° C) at 2000 rpm using a rotation ‧ revolution vacuum mixer Awatori Chain Taro (ARE-250, manufactured by Thinky Co., Ltd.). Defoaming for 1 minute gave the desired resin composition.

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

EXA4850-150: Made from DIC, vinyl ether denatured bisphenol epoxy resin (epoxy equivalent 450g/eq (equivalent to formula (1))

EXA4816: Aliphatic chain-denatured bisphenol A epoxy resin manufactured by DIC Corporation (epoxy equivalent 403g/eq (equivalent to formula (1))

EP-4010S: Made from ADEKA, PO-denatured bisphenol A epoxy resin (epoxy equivalent 350g/eq (equivalent to formula (2))

YL7410: Polyether modified epoxy resin manufactured by Mitsubishi Chemical Corporation (epoxy equivalent 420g/eq (equivalent to formula (1))

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

JER1001: Solid bisphenol A epoxy resin (epoxy equivalent 1475g/eq) manufactured by Mitsubishi Chemical Corporation

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

TMTP: manufactured by Dian Chemical Co., Ltd., trimethylolpropane ginseng (3-mercaptopropionate) (total equivalent of thiol group 133g/eq)

PN-23: Ajinomoto Fine-Techno, a amine addenda potential hardening accelerator

FXR-1081: T&K TOKA, a denatured polyamine-based latent hardener

AEROSIL 200: manufactured by Aerosil, Japan, fumed silica

TEB: manufactured by Tokyo Chemical Industry Co., Ltd., triethyl borate

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

(Total equivalent of thiol group = mass of "thiol group-containing compound" containing 1 equivalent of thiol group)

[thiol/epoxy equivalent ratio]

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

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

[Measurement of viscosity]

A conical rotor (rotor number No. 6; 3° x R9.7) was attached to a RE80 type viscometer (manufactured by Toki Sangyo Co., Ltd.), and 0.2 to 0.3 ml of the resin composition to be measured was taken out from the measurement chamber via a syringe. At the time of measurement, the temperature of the measurement chamber of the viscometer was managed to 25.0 ° C via an external circulation type thermostat. The number of rotations of the rotor was set at 0.5, 1, 20, and 100 rpm, and the viscosity (unit: Pa ‧ s) after 120 seconds of the respective rotations was measured.

[Determination of the elastic modulus of the cured product of the one-component thermosetting resin composition]

The elastic modulus of the cured epoxy resin of the examples and the comparative examples obtained in the above manner was measured by the following manner. First, each of the obtained resin compositions was applied onto a release PTFE film (Aflas 50N, manufactured by Asahi Glass Co., Ltd.) using a rod, and was cured by heating at 80 ° C for 60 minutes. The thickness of the hardened body was 50 μm. Thereafter, the PTFE film was released from the mold. According to JIS-K-7161, a tensile test was carried out by 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 transfer point]

A test piece of 7 mm × 30 mm was produced, and a DMA measuring apparatus (DMS6100, manufactured by Seiko Instruments Co., Ltd.) was used in accordance with JIS-K-7244-4, and the stretching method, the number of cycles of 1 Hz, the temperature increase rate of 2 ° C/min, and the measurement temperature range of 0 ° C were used. The tan δ was measured under conditions of ~300 °C. The temperature exhibited by the peak in the obtained tan δ curve was taken as the glass transition temperature. The unit is °C.

[Evaluation of low temperature hardenability]

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

Specifically, first, the time at which the resin composition of each of the examples and the comparative examples could not be drawn at 60 ° C and 80 ° C was measured by a hot plate gelation tester (GT-D, manufactured by Nisshin Scientific Co., Ltd.). . Specifically, about 0.5 g of the sample (resin composition) was placed on a hot plate gelation tester, and the time of 60 ° C (60 ° C gel time) or 80 ° C (80 ° C gel time) was set. The starting point was such that the resin composition was controlled within a range of 25 mm in diameter on the hot plate, and the resin composition was repeatedly contacted with a spatula having a tip end width of 5 mm (circular rotation for 1 second), and the resin was composed. The object was pulled up vertically from the heating plate by 30 mm, and the time when the yarn was broken was taken as the end point, and the time from the start point to the end point was regarded as "the time until completion of gelation", and the measurement was performed. Further, the spatula does not pull up during the period when the viscosity of the resin is low, and if the viscosity gradually rises, the vertical pulling of the heating plate is about 30 mm until the filament breaks, and the vertical movement is repeated. The assay was repeated 3 times and the average was used.

[Evaluation of peel strength]

T-stripping test

The test piece of the steel plate (25 mm × 150 mm × 0.4 mm) was wiped with a rag soaked in acetone to wipe off the oil. Further, the surface of the adhesive surface of the steel sheet is ground with an endless belt #120. Uniformly coating the thickness on the polished surface of the steel sheet A resin composition of 20 to 30 μm. The other piece of steel plate was overlapped and pressed with 4 clamps. At this time, the resin composition oozing out at this time was immediately wiped off. The test pieces were uniformly placed in an oven, and heat-hardened at 80 ° C for 60 minutes to adhere them. Three test pieces were prepared for each of the same resin compositions. The obtained test piece was subjected to tensile strength according to JIS-K-6854-3 via a TENSILON universal testing machine (RTM-500, manufactured by Orientec Co., Ltd.) (measurement environment: temperature 25 ° C / humidity 40%, stretching speed: 50 mm) /min). The peel strength A per 25 mm width was calculated based on the average peeling load (N).

[Evaluation of moisture resistance]

In order to evaluate the moisture resistance of the test piece, the test of the peel strength A described above was repeated after standing for a certain period of time under high humidity. Specifically, three separately prepared test pieces were prepared by the procedure of the above-described T-test peel test. Each test piece was placed in a pressure cooker under the conditions of 120 ° C and 85% RH for 24 hours, and the obtained test piece was passed through a TENSILON universal testing machine (RTM-500, manufactured by Orientec Co., Ltd.) according to JIS. -K-6854-3 to measure tensile strength (measurement environment: temperature 25 ° C / humidity 40%, tensile speed: 50 mm / min). The peel strength B per 25 mm width was calculated based on the average peeling load (N).

[Strength retention rate]

In order to evaluate the influence of the humidity on the peel strength, the strength retention ratio was calculated. The strength retention ratio is determined by the above peel strength A and peel strength B. The value is calculated as follows.

[Strength retention rate] = [peel strength B] / [peel strength A]

The larger the value of the strength retention ratio, the more the test piece can be said to be resistant to high humidity.

[Investigation of evaluation results]

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

[Table 1]

Further, the present invention can also be as follows.

[1] A one-component thermosetting resin composition containing ginseng (3- A one-component thermosetting resin composition of 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 the above [1], wherein the epoxy resin has an epoxy equivalent of from 200 to 1,000.

[3] The resin composition according to the above [1] or [2] wherein the epoxy resin contains an epoxy compound or a polymer, and the epoxy compound contains: (a) an epoxy group of 2 or more, (b) a divalent non-aromatic hydrocarbon group containing 2 or more -(CH ₂ )- in the main skeleton, and (c) a divalent aromatic group in the main skeleton; A divalent aromatic hydrocarbon group.

[4] The resin composition according to any one of the above [1], wherein the epoxy resin is an epoxy compound represented by the formula (1) or the formula (2) or the polymerization. Object,

(In the formulae (1) and (2), X, X ₁ and X ₂ may be the same or different from each other and contain 2 or more -(CH ₂ )-divalent non-aromatic hydrocarbon groups in the main skeleton (but X is In the case of -O-CH ₂ -CH(-OH)-CH ₂ -, the Ar, Ar ₁ and Ar ₂ groups may be the same or different from each other and contain a divalent aromatic group in the main skeleton. The hydrocarbon group, n and m are each independently an integer from 1 to 20).

The resin composition according to any one of the above-mentioned [3], wherein the divalent non-aromatic hydrocarbon group containing 2 or more -(CH ₂ )- in the main skeleton is selected from the group consisting of The alkylene group having 2 to 20 carbon atoms which may or may not have a substituent, and the alkyleneoxy group having 2 to 20 carbon atoms which may or may not have a substituent.

[6] The resin composition according to any one of the above [3], wherein the (b) includes a divalent non-aromatic hydrocarbon group of -(CH ₂ )- in the main skeleton, Is selected from (b1)-O-CH(-CH ₃ )-(O-(CH ₂ ) _p ) _q -O-CH(-CH ₃ )-, (b2)-(O-(CH ₂ ) _r ) _s -, (b3)-(O-CH ₂ -CH(-CH ₃ )) _t -, (b4)-O-CH ₂ -CH(-OH)-CH ₂ -(O-(CH ₂ ) _u ) _v -O-CH ₂ -CH(-OH)-CH ₂ -, (b5)-(O-(CH ₂ ) _w ) _y -O-CH ₂ -CH(-OH)-, and (b6)-( O-CH ₂ -CH(-CH ₃ )) _z -O-CH ₂ -CH(-OH)-

(However, p, q, r, s, t, u, v, w, y, and z are independent integers from 1 to 20, respectively).

The resin composition according to any one of the above-mentioned [3], wherein the divalent aromatic hydrocarbon group containing a divalent aromatic group in the main skeleton is independently selected from the group consisting of

and

[8] The resin composition according to any one of [1] to [7] above, wherein It contains a solid dispersion type latent hardening accelerator.

[9] The resin composition according to any one of the above [1] to [8] further comprising a boric acid ester compound, a titanate compound, an aluminate compound, a zirconate compound, an isocyanate compound, One or more kinds of a carboxylic acid, an acid anhydride, and a mercapto organic acid.

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

[11] A material for sealing, which comprises the resin composition according to any one of [1] to [9] above.

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

Claims (14)

A one-component thermosetting resin composition comprising ginseng (3-mercaptopropyl)isocyanurate and an epoxy compound represented by formula (1) or formula (2) or Polymer, (In the formulae (1) and (2), X, X ₁ and X ₂ may be the same or different from each other and contain 2 or more -(CH ₂ )-divalent non-aromatic hydrocarbon groups in the main skeleton (but X is In the case of -O-CH ₂ -CH(-OH)-CH ₂ -, the Ar, Ar ₁ and Ar ₂ groups may be the same or different from each other and contain a divalent aromatic group in the main skeleton. The hydrocarbon group, n and m are each independently an integer from 1 to 20). The resin composition of claim 1, wherein the divalent non-aromatic hydrocarbon group containing 2 or more -(CH ₂ )- in the main skeleton is selected from carbon atoms 2 to 20 which may or may not have a substituent. An alkylene group, and a 2 to 20 carbon alkylene group which may or may not have a substituent. The resin composition according to any one of claims 1 to 2, wherein the divalent non-aromatic hydrocarbon group containing 2 or more -(CH ₂ )- in the main skeleton is selected from (b1)-O-CH. (-CH ₃ )-(O-(CH ₂ )p)qO-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)- (but p, q, r, s, t, u, v, w, y, and z are each independently an integer from 1 to 20). The resin composition according to any one of claims 1 to 3, wherein the divalent aromatic-containing hydrocarbon group containing a divalent aromatic group in the main skeleton is independently selected from the group consisting of and The resin composition according to any one of claims 1 to 4, further comprising a solid dispersion type latent curing accelerator. The resin composition according to any one of claims 1 to 5, further comprising a boric acid ester compound, a titanate compound, an aluminate compound, a zirconate compound, an isocyanate compound, a carboxylic acid, an acid anhydride, and a mercapto group. One or more organic acids. 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 resin composition according to any one of claims 1 to 7, wherein the cured product of the one-component thermosetting resin composition is at 120 ° C, After leaving for 24 hours under conditions of 85% RH, the peel strength B (N/25 mm) measured in accordance with JIS-K-6854-3 was 9 or more. The resin composition according to any one of claims 1 to 8, wherein the cured product of the one-component thermosetting resin composition has a peel strength A (N/25 mm) measured in accordance with JIS-K-6854-3. And the peeling strength B (N/25 mm) measured according to JIS-K-6854-3 after leaving the cured product of the one-component thermosetting resin composition under conditions of 120 ° C and 85% RH for 24 hours. The strength retention ratio (B/A) of the cured product of the one-liquid type thermosetting resin composition thus calculated was 0.67 or more. An adhesive comprising the resin composition according to any one of claims 1 to 9. A material for sealing 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, which further comprises a bisphenol A type epoxy resin. The resin composition of claim 13, wherein the mass ratio of the epoxy compound or the polymer to the bisphenol A type epoxy resin is [epoxy compound or the polymer]: [bisphenol A Type epoxy resin] = 10:1~1:10.