JP5996977B2 - Polythiourethane compound, epoxy resin curing agent containing the compound, and one-part curable epoxy resin composition comprising the epoxy resin curing agent - Google Patents

Description

  The present invention relates to a polythiourethane compound, and more particularly to a polythiourethane compound that can provide a curable epoxy resin composition excellent in storage stability and curability by being combined with a polyepoxy compound.

  Epoxy resins have excellent adhesion to various substrates, and their cured products are relatively excellent in heat resistance, chemical resistance, electrical properties, mechanical properties, etc., so paints, adhesives, and various moldings Wide range of uses such as materials.

  Conventionally, epoxy resin compositions have been mainly two-component systems in which a curing agent or a curing accelerator is added immediately before use. The two-component system has the advantage that it can be cured at room temperature or low temperature, but it must be weighed and mixed immediately before use, and since it can be used for a short time, it is difficult to apply it to an automatic machine. There is a problem that usage conditions are limited.

  In order to solve such problems, a one-pack type curable epoxy resin composition is desired, but in order to obtain a one-pack type curable epoxy resin composition, the curing reaction is not started at room temperature. There is a need for a latent curing agent that has the property of initiating a curing reaction.

As the latent curing agent, for example, dicyandiamide, dibasic acid dihydrazide, boron trifluoride amine complex salt, guanamines, melamine, imidazoles and the like have been proposed.
However, a one-part curable epoxy resin composition combining an epoxy resin with dicyandiamide, melamine, guanamines, etc. is excellent in storage stability, but does not cure unless a high temperature of 150 ° C. or higher is applied for a long time. Has drawbacks. In addition, a method of shortening the curing time by using these and a curing accelerator in combination is widely used, but in this case, there is a problem that storage stability is remarkably impaired.

On the other hand, when dibasic acid dihydrazide or imidazole is used as a latent curing agent, it cures at a relatively low temperature but has poor storage stability. In addition, the one-part curable epoxy resin composition containing boron trifluoride amine complex salt as a latent curing agent has the advantages of excellent storage stability and a short curing time, while being inferior in water resistance and metal. It has disadvantages such as being corrosive to
Furthermore, as a thermosetting resin composition in which a decrease in physical properties of the cured product is suppressed, for example, a thermosetting resin composition containing a polythiourethane bond-containing compound has been proposed (Patent Document 1). No satisfactory performance has been obtained yet.

JP-A-8-20622

Accordingly, a first object of the present invention is to provide a novel compound suitable as a curing agent for a one-component curable epoxy resin.
The second object of the present invention is to provide a curing agent for an epoxy resin that can provide a one-component curable epoxy resin composition excellent in storage stability and curability.
Furthermore, the third object of the present invention is to provide a one-component curable epoxy resin composition excellent in storage stability and curability.

  As a result of intensive investigations to achieve the above-mentioned objects, the present inventors have combined a specific polythiourethane compound with an epoxy compound to produce a one-part curable epoxy resin excellent in storage stability and curability. The inventors have found that a composition can be obtained and have reached the present invention.

That is, the present invention provides at least one selected from the group consisting of a polythiourethane compound represented by the following general formula (I- 1), (I-2) or (I-3 ) and the polythiourethane compound. An epoxy resin curing agent containing a seed compound and a one-component curable epoxy resin composition comprising the epoxy resin curing agent.
However, R ′ in the formulas (I-1) to (I-3 ) consists of a hydrogen atom, an unsubstituted alkyl group , or an unsubstituted or substituted phenyl group, naphthyl group, anthryl group or phenanthryl group. An unsubstituted or substituted aryl group selected from the group , wherein R ″ is an unsubstituted alkyl group , or a phenyl group, a 4-methylphenyl group, a 3-methylphenyl group, a 2-methylphenyl group, 2,6-dimethylphenyl group, 3,5-dimethylphenyl group, 4-ethylphenyl group, 2,6-diisopropylphenyl group, 4-butylphenyl group, 4-methoxyphenyl group, 3-methoxyphenyl group, 2- Methoxyphenyl group, 4-ethoxyphenyl group, 4-bromophenyl group, 3-bromophenyl group, 2-bromophenyl group, 4-chlorophenyl group, 3-chlorophenyl group, 2-chlorophenyl group, 2,3-dichlorophenyl group, 2,4-di Chlorophenyl group, 2,5-dichlorophenyl group, 2,6-dichlorophenyl group, 3,4-dichlorophenyl group, 3,5-dichlorophenyl group, 2,4,6-trichlorophenyl group, 4-chloro-3-nitrophenyl group 3-chloro-4-methylphenyl group, 4-fluorophenyl group, 3-fluorophenyl group, 2-fluorophenyl group, 2,4-difluorophenyl group, 2,5-difluorophenyl group, 3,4-difluoro Phenyl group, 4-trifluoromethylphenyl group, 3-trifluoromethylphenyl group, 2-trifluoromethylphenyl group, 3,5-bis (trifluoro) phenyl group, 4-trifluoromethoxyphenyl group, 4-nitro phenyl group, 3-nitrophenyl group, 2-nitrophenyl group, 3,5-dinitrophenyl group, a naphthyl group, unsubstituted or substituted aryl group is selected from the group consisting of anthryl and phenanthryl groups (I-2) R ′ ″ in the formula is a hydrogen atom, an unsubstituted alkyl group, or a non-selected group selected from the group consisting of an unsubstituted or substituted phenyl group, a naphthyl group, an anthryl group, and a phenanthryl group. A substituted or substituted aryl group .

  According to the present invention, a one-component curable epoxy resin composition having excellent curing characteristics and storage stability can be obtained. In particular, since the one-component curable epoxy resin composition of the present invention does not contain a solid component at room temperature, it has excellent workability and is also suitable for adhesion in narrow spaces and impregnation adhesion.

1 is a ¹ H NMR spectrum of NR-1-PhTU (NR-1-phenylthiourethane) which is a compound of the present invention. However, NR-1 is Karenz MT NR-1 (trade name manufactured by Showa Denko KK). For the structure, see formula (A) below. The same applies below. 1 is a ¹ H NMR spectrum of NR-1-CyTU (NR-1-cyclohexylthiourethane) which is a compound of the present invention. ^{1 is} a ¹ H NMR spectrum of TMTP-PhTU (trimethylolpropane tris (3-mercaptopropionate-phenylthiourethane)) which is a compound of the present invention.

Polythiourethane compounds of the present invention has the following formula (I-1), a compound represented by (I-2) or (I-3).

R ′ in the general formulas (I-1), (I-2) and (I-3) is a hydrogen atom, an unsubstituted alkyl group, an unsubstituted or substituted phenyl group, a naphthyl group, an anthryl. An unsubstituted or substituted aryl group selected from the group consisting of a group or phenanthryl.
Examples of the alkyl group, for example, linear from 1 to 12 carbon atoms, branched or alicyclic alkyl group and the like, and specific examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, isobutyl group, Ru and the like tertiary butyl group.

In the general formulas (I-1), (I-2) and (I-3), R ″ represents an unsubstituted alkyl group, a phenyl group, a 4-methylphenyl group, or 3-methylphenyl. Group, 2-methylphenyl group, 2,6-dimethylphenyl group, 3,5-dimethylphenyl group, 4-ethylphenyl group, 2,6-diisopropylphenyl group, 4-butylphenyl group, 4-methoxyphenyl group, 3-methoxyphenyl group, 2-methoxyphenyl group, 4-ethoxyphenyl group, 4-bromophenyl group, 3-bromophenyl group, 2-bromophenyl group, 4-chlorophenyl group, 3-chlorophenyl group, 2-chlorophenyl group 2,3-dichlorophenyl group, 2,4-dichlorophenyl group, 2,5-dichlorophenyl group, 2,6-dichlorophenyl group, 3,4-dichlorophenyl group, 3,5-dichlorophenyl group, 2,4,6-tri Chlorophenyl, 4-chloro-3-nitrophenyl, 3-chloro Ro-4-methylphenyl group, 4-fluorophenyl group, 3-fluorophenyl group, 2-fluorophenyl group, 2,4-difluorophenyl group, 2,5-difluorophenyl group, 3,4-difluorophenyl group, 4-trifluoromethylphenyl group, 3-trifluoromethylphenyl group, 2-trifluoromethylphenyl group, 3,5-bis (trifluoro) phenyl group, 4-trifluoromethoxyphenyl group, 4-nitrophenyl group, An unsubstituted or substituted aryl group selected from the group consisting of 3-nitrophenyl group, 2-nitrophenyl group, 3,5-dinitrophenyl group, naphthyl group, anthryl group and phenanthryl group.
Examples of the alkyl group, for example, linear from 1 to 12 carbon atoms, include alkyl groups of the branched or alicyclic, and specific examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group , Isobutyl group, tertiary butyl group, amyl group, isoamyl group, tertiary amyl group, hexyl group, cyclohexyl group, heptyl group, octyl group, tertiary octyl group, nonyl group, decyl group, undecyl group, dodecyl group, etc. the recited Ru.

R ′ ″ in general formula (I-2) is selected from the group consisting of a hydrogen atom, an unsubstituted alkyl group, or an unsubstituted or substituted phenyl group, naphthyl group, anthryl group, and phenanthryl group. An unsubstituted or substituted aryl group.
Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, an amyl group, an isoamyl group, a tert-amyl group, a hexyl group, a cyclohexyl group, and a heptyl group. , octyl, tert-octyl group, nonyl group, decyl group, undecyl group, dodecyl group and the Ru mentioned.

The polythiourethane compound of this invention is obtained by making a polythiol compound and an isocyanate compound react as shown by a following formula.
The amount of the thiol compound and isocyanate compound used in the above reaction is preferably 0.5 to 1, and most preferably 1, as the ratio of isocyanate group to mercapto group ([NCO] / [SH] ratio).
However, the general formula (I) in the above reaction formula is a chemical formula obtained by superposing the general formulas (I-1) to (I-3).

  Examples of the catalyst used in the reaction include tin compounds such as dibutyltin laurate and di (2-ethylhexanoic acid) tin; titanium compounds such as tetraalkyl titanate; triphenylphosphine, tributylphosphine, and tricyclohexylphosphine. Phosphines; tertiary amines such as triethylamine, tributylamine, diazabicycloundecene, diazabicyclononene, 1,4-diazabicyclo [2.2.2] octane; pyridines such as pyridine and N, N-dimethylaminopyridine And imidazoles such as 1-methylimidazole.

  Examples of the solvent used in the reaction include ketones such as methyl ethyl ketone, methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl ketone, propylene glycol monomethyl ether acetate, and cyclohexanone; tetrahydrofuran, 1,2-dimethoxyethane, Ethers such as 1,2-diethoxyethane; esters such as ethyl acetate and n-butyl acetate; amides such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone, iso- or Alcohols such as n-butanol, iso- or n-propanol and amyl alcohol; aromatic hydrocarbons such as benzene, toluene and xylene; Terpene hydrocarbon oils such as turpentine oil, D-limonene and pinene; mineral spirits and swazoles # 310 (Cosmo Matsuyama Oil Co., Ltd.), Solbec Paraffinic solvents such as # 100 (Exxon Chemical Co., Ltd.); Halogenated aliphatic hydrocarbons such as carbon tetrachloride, chloroform, trichloroethylene and methylene chloride; Halogenated aromatic hydrocarbons such as chlorobenzene; Aniline, triethylamine, pyridine, Dioxane, acetic acid, acetonitrile, carbon disulfide, dimethyl sulfoxide, N, N′-dimethylimidazolidinone and the like can be mentioned.

  The reaction is usually carried out at a temperature of −80 to 200 ° C. for 0.5 to 72 hours. The reaction temperature is preferably room temperature to 80 ° C., and the reaction time is 1 to 8 hours. It is preferable that

  The polythiourethane compound of the present invention functions alone as the curing agent for epoxy resins of the present invention, but other epoxy resin curing agents may be used in combination as necessary. In the present specification, these are collectively referred to as the epoxy resin curing agent of the present invention.

  Examples of the epoxy resin curing agent that can be used in combination include imidazoles such as 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, and 1- (2-methylimidazol-1-ylmethyl) naphthalen-2-ol. Polyalkylpolyamines such as diethylenetriamine, triethylenetriamine and tetraethylenepentamine; alicyclic polyamines such as 1,2-diaminocyclohexane, 1,4-diamino-3,6-diethylcyclohexane and isophoronediamine; m -Aromatic polyamines such as xylylenediamine, diaminodiphenylmethane, and diaminodiphenylsulfone.

In addition, the polyamines and phenyl glycidyl ether, butyl glycidyl ether, bisphenol A-diglycidyl ether, glycidyl ethers such as bisphenol F-diglycidyl ether, or various epoxy resins such as glycidyl esters of carboxylic acids, A polyepoxy addition-modified product produced by reacting by the above; an amidation-modified product produced by reacting the organic polyamines with carboxylic acids such as phthalic acid, isophthalic acid, and dimer acid; or The polyamines and aldehydes such as formaldehyde, and phenols having at least one aldehyde-reactive site in the nucleus, such as phenol, cresol, xylenol, tert-butylphenol, resorcin, etc. It is also possible to use a Mannich modified product produced by reacting with the above.
Furthermore, latent curing agents such as dicyandiamide, acid anhydrides, and imidazoles may be used in combination.

The one-component curable epoxy resin composition of the present invention contains a polyepoxy compound and the curing agent for epoxy resin of the present invention.
Examples of the polyepoxy compound used in the one-component curable epoxy resin composition of the present invention include polyglycidyl ether compounds of mononuclear polyhydric phenol compounds such as hydroquinone, resorcin, pyrocatechol, and phloroglucinol; dihydroxynaphthalene , Biphenol, methylene bisphenol (bisphenol F), methylene bis (orthocresol), ethylidene bisphenol, isopropylidene bisphenol (bisphenol A), isopropylidene bis (orthocresol), tetrabromobisphenol A, 1,3-bis (4-hydroxyc Milbenzene), 1,4-bis (4-hydroxycumylbenzene), 1,1,3-tris (4-hydroxyphenyl) butane, 1,1,2,2-tetra (4-hydroxyphenyl) ethane, Thiobisphenol, sulfonylbisphenol, oxybi Polyglycidyl ether compounds of polynuclear polyhydric phenol compounds such as sphenol, phenol novolak, orthocresol novolak, ethylphenol novolak, butylphenol novolak, octylphenol novolak, resorcin novolak, terpene phenol; ethylene glycol, propylene glycol, butylene glycol, hexanediol , Polyglycidyl ethers of polyhydric alcohols such as polyglycol, thiodiglycol, glycerin, trimethylolpropane, pentaerythritol, sorbitol, bisphenol A-ethylene oxide adduct; maleic acid, fumaric acid, itaconic acid, succinic acid, glutaric acid , Suberic acid, adipic acid, azelaic acid, sebacic acid, dimer acid, trimer acid, phthalic acid, isophthalic acid Glycidyl esters of aliphatic, aromatic or alicyclic polybasic acids such as acids, terephthalic acid, trimellitic acid, trimesic acid, pyromellitic acid, tetrahydrophthalic acid, hexahydrophthalic acid, endomethylenetetrahydrophthalic acid; and Glycidyl methacrylate homopolymer or copolymer; N, N-diglycidylaniline, bis (4- (N-methyl-N-glycidylamino) phenyl) methane, epoxy compounds having a glycidylamino group such as diglycidyl orthotoluidine Vinylcyclohexene diepoxide, dicyclopentanediene diepoxide, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-6-methylcyclohexylmethyl-6-methylcyclohexanecarboxylate, bis (3,4-epoxy-6-methylcyclohexyl Examples thereof include epoxidized products of cyclic olefin compounds such as methyl) adipate; epoxidized conjugated diene polymers such as epoxidized polybutadiene and epoxidized styrene-butadiene copolymer, and heterocyclic compounds such as triglycidyl isocyanurate.
In addition, these polyepoxy compounds are highly crosslinked by polyhydric active hydrogen compounds such as those internally cross-linked by a prepolymer having an isocyanate at the terminal, or polyhydric phenols, polyamines, carbonyl group-containing compounds, polyphosphate esters and the like. The molecular weight may be used.

Moreover, the epoxy equivalent of a polyepoxy compound needs to be 70-3000, and it is especially preferable that it is 90-2000.
If the epoxy equivalent of the polyepoxy compound is less than 70, the physical properties of the cured product may be deteriorated. If it is greater than 3000, sufficient curability may not be obtained.

  Furthermore, the one-pack type curable epoxy resin composition of the present invention can be used as necessary by a curing catalyst; reactive or non-reactive dilution of monoglycidyl ethers, dioctyl phthalate, dibutyl phthalate, benzyl alcohol, coal tar, etc. Agent or plasticizer: glass fiber, carbon fiber, cellulose, silica sand, cement, kaolin, clay, aluminum hydroxide, bentonite, talc, silica, finely divided silica, titanium dioxide, carbon black, graphite, iron oxide, bitumen substance, etc. Or γ-aminopropyltriethoxysilane, N-β- (aminoethyl) -γ-aminopropyltriethoxysilane, N-β- (aminoethyl) -N′-β- (aminoethyl)- γ-aminopropyltriethoxysilane, γ-anilinopropyltriethoxysilane, γ-glycidoxypropyltriethoxysilane , Β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, vinyltriethoxysilane, N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltriethoxysilane, γ-methacryloxypropyltrimethoxy Silane coupling agents such as silane, γ-chloropropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, etc .; Lubricants such as fatty acid waxes, fatty acid esters, fatty acid ethers, aromatic esters, aromatic ethers; thickeners; thixotropic agents; antioxidants; light stabilizers; ultraviolet absorbers; Agent; may contain conventional additives such as colloidal silica and colloidal alumina Furthermore, xylene resin, may be used in combination tacky resin such as petroleum resin.

  The one-component curable epoxy resin composition of the present invention includes, for example, paints or adhesives for concrete, cement mortar, various metals, leather, glass, rubber, plastic, wood, cloth, paper, etc .; adhesive tape for packaging, adhesive Labels, frozen food labels, removable labels, POS labels, adhesive wallpaper, adhesives for adhesive flooring; art paper, lightweight coated paper, cast coated paper, coated paperboard, carbonless copier, impregnated paper and other processed paper; natural Fiber treatment agents such as fibers, synthetic fibers, glass fibers, carbon fibers, metal fibers, etc., fraying preventives, processing agents, etc .; building materials such as sealing materials, cement admixtures, waterproofing materials; sealing for electronic and electrical equipment It can be used for a wide range of applications such as a stopper.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited at all by these Examples.

[Synthesis of NR-1-PhTU (NR-1-phenylthiourethane)]
34.03 g of Karenz MT NR-1 (trade name, manufactured by Showa Denko KK) as a trifunctional thiol was charged into a 500 mL two-necked round bottom flask, dried under reduced pressure and purged with nitrogen, then anhydrous DMF (Kanto Chemical) 42 mL and 0.83 mL triethylamine were added and cooled to 0 ° C.

Subsequently, 19.5 mL of phenyl isocyanate (manufactured by Kanto Chemical Co., Inc.) was added with stirring, and the mixture was stirred for 30 minutes and then returned to room temperature. Further, after stirring for 3 hours, 600 mL of ethyl acetate was added. The organic phase was washed with 300 mL distilled water. After performing the above washing 4 times, the organic phase was dried over sodium sulfate, filtered and the solvent was removed under reduced pressure.
The reaction product thus obtained was dried under reduced pressure at 60 ° C. for 2 hours to obtain 56.0 g of the target compound NR-1-PhTU in the form of white crystals. NR-1-PhTU was obtained quantitatively.

[Synthesis of NR-1-CyTU (NR-1-cyclohexylthiourethane)]
As a trifunctional thiol compound, 34.03 g of Karenz MT NR-1 (trade name manufactured by Showa Denko KK) and 0.025 g of dibutyltin dilaurate (Bu ₂ SnLau ₂ ) (manufactured by Tokyo Chemical Industry Co., Ltd.) After charging in a two-necked round bottom flask, drying under reduced pressure and nitrogen substitution, 14 mL of anhydrous DMF (manufactured by Kanto Chemical Co., Inc.) was added.

Next, 7.6 mL of cyclohexyl isocyanate (manufactured by Tokyo Chemical Industry Co., Ltd.) was added with stirring, and after stirring for 23 hours at room temperature, 7.6 mL of cyclohexyl isocyanate (manufactured by Tokyo Chemical Industry Co., Ltd.) was further added. .
After stirring for 23 hours at room temperature, 0.83 mL of triethylamine was added. After 3 hours, 100 mL of distilled water was added and stirred for 1 hour. After adding 100 mL of ethyl acetate and stirring for 1 hour, 100 mL of ethyl acetate was further added. After separating the aqueous phase, the organic phase was washed with 100 mL of saturated brine. After repeating the above washing three times, the aqueous phase was separated, the organic phase was dried over sodium sulfate, filtered, and the solvent was removed under reduced pressure.
The product thus obtained was dried under reduced pressure at 60 ° C. for 2 hours to obtain 16.6 g of the target compound NR-1-CyTU in the form of white crystals.
The yield of NR-1-CyTU was 88%.

The reaction in Examples 1 and 2 is represented by the following formula (A).

[Synthesis of TMTP-PhTU (TMTP-phenylthiourethane)]
A trifunctional thiol, TMTP (trimethylolpropane tris (3-mercaptopropionate) (manufactured by Sakai Chemical Co., Ltd.) (15.94 g) was charged into a 300 mL two-necked round bottom flask and dried under reduced pressure. Anhydrous DMF (manufactured by Kanto Chemical Co., Inc.) 28 mL and triethylamine 0.55 mL were added and cooled to 0 ° C. Phenyl isocyanate (manufactured by Kanto Chemical Co., Ltd.) 13.0 mL was added with stirring, and after stirring for 30 minutes, It returned to room temperature.

After stirring for 3 hours, 200 mL of ethyl acetate was added and the organic phase was washed with 200 mL of distilled water. After repeating the above washing 4 times, the aqueous phase was separated, the organic phase was dried using sodium sulfate, filtered, and the solvent was removed under reduced pressure.
The product thus obtained was dried under reduced pressure at 60 ° C. for 2 hours to obtain 29.8 g of a colorless viscous target compound TMTP-PhTU. The yield of TMTP-PhTU was 99%.

The reaction in Example 3 is represented by the following formula (B).

[Structural analysis]
The structure of the synthesized polythiourethane was confirmed by ¹ H NMR measurement (JNM EX-400, manufactured by JEOL Ltd.).
The NMR spectrum of each compound in deuterated chloroform is as shown in FIGS. In the figure, x represents a peak of ethyl acetate.

[Production of cured product]
Adeka Resin EP-4100E (trade name, manufactured by ADEKA, bisphenol A type epoxy resin, epoxy equivalent: 190), NR-1-PhTU obtained in Example 1, Bu ₂ SnLau ₂ (dibutyltin dilaurate), PPh ₃ (Triphenylphosphine) and BnOH (benzyl alcohol) were mixed at the ratio shown in Table 1 to prepare a one-pack type curable epoxy resin composition.

The obtained resin composition was heated at 180 ° C. for 1 hour to obtain a flexible cured product.
Moreover, as a result of measuring the viscosity of the one-component curable epoxy resin composition using a viscometer (manufactured by Tokyo Keiki Co., Ltd.), the initial viscosity was 26.3 Pa · s and stored at 25 ° C. for 1 day. The later viscosity was 67.7 Pa · s.

[Comparative Example 1]
EP-4100E, NR-1 and PPh ₃ in the amounts shown in Table 1 were mixed to obtain a one-part curable epoxy resin composition.

  As a result of measuring the viscosity of the obtained resin composition in the same manner as in Example 4, the initial viscosity was 15.7 Pa · s. When stored at 25 ° C., the resin composition was cured after one day. And it became impossible to measure.

Table 1 shows the composition of the one-component curable epoxy resin composition of Example 4 and Comparative Example 1 and the evaluation results of the storage stability.
As is apparent from this result, it was confirmed that the one-pack thermosetting epoxy resin composition containing the polythiourethane compound of the present invention as a curing agent is excellent in storage stability.

  Since the polythiourethane compound of the present invention can provide a one-part curable epoxy resin composition excellent in storage stability and curability, a paint, an adhesive, an adhesive, a processed paper, a fiber treatment agent, It has a wide range of applications such as building materials and sealants for electronic and electrical equipment, and is extremely useful in industry.

Claims (3)

A polythiourethane compound represented by the following general formula (I- 1), (I-2) or (I-3 );
In the formulas (I-1) to (I-3 ) , R ′ is a hydrogen atom , an unsubstituted alkyl group , or a group consisting of an unsubstituted or substituted phenyl group, naphthyl group, anthryl group, or phenanthryl group. An unsubstituted or substituted aryl group selected from : R ″ represents an unsubstituted alkyl group , a phenyl group, a 4-methylphenyl group, a 3-methylphenyl group, a 2-methylphenyl group, 2 , 6-dimethylphenyl group, 3,5-dimethylphenyl group, 4-ethylphenyl group, 2,6-diisopropylphenyl group, 4-butylphenyl group, 4-methoxyphenyl group, 3-methoxyphenyl group, 2-methoxy Phenyl group, 4-ethoxyphenyl group, 4-bromophenyl group, 3-bromophenyl group, 2-bromophenyl group, 4-chlorophenyl group, 3-chlorophenyl group, 2-chlorophenyl group, 2,3-dichlorophenyl group, 2 , 4-di Lolophenyl group, 2,5-dichlorophenyl group, 2,6-dichlorophenyl group, 3,4-dichlorophenyl group, 3,5-dichlorophenyl group, 2,4,6-trichlorophenyl group, 4-chloro-3-nitrophenyl group 3-chloro-4-methylphenyl group, 4-fluorophenyl group, 3-fluorophenyl group, 2-fluorophenyl group, 2,4-difluorophenyl group, 2,5-difluorophenyl group, 3,4-difluoro Phenyl group, 4-trifluoromethylphenyl group, 3-trifluoromethylphenyl group, 2-trifluoromethylphenyl group, 3,5-bis (trifluoro) phenyl group, 4-trifluoromethoxyphenyl group, 4-nitro phenyl group, 3-nitrophenyl group, a 2-nitrophenyl group, 3,5-dinitrophenyl group, a naphthyl group, an unsubstituted or substituted aryl group is selected from the group consisting of anthryl and phenanthryl groups, I-2) R ″ ′ in the formula is a hydrogen atom, an unsubstituted alkyl group, or an unsubstituted or substituted phenyl group selected from the group consisting of a phenyl group, a naphthyl group, an anthryl group, and a phenanthryl group. Or it is a substituted aryl group . A curing agent for epoxy resins, comprising at least one compound selected from the group consisting of the polythiourethane compounds according to claim 1. A one-component curable epoxy resin composition comprising a polyepoxy compound and a curing agent for an epoxy resin according to claim 2 .