JP2017002192A - Latent curing agent and wet curable resin composition using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a latent curing agent providing excellent curability and storage stability to a wet curable resin composition and providing excellent mechanical physical property and raw material adhesion to a cured article.SOLUTION: A latent curing agent contains a compound having at least 4 ketoimino groups and at least 2 of total of a hydrogen group and an urea group. The compound has a structure by reacting polyamine having at least a secondary amino group and at least 2 primary amino groups, a compound having at least 2 functional groups selected from the group consisting of an epoxy group, an oxetane group and an isocyanate group, and ketone having 3 to 13 carbon atoms. A wet curable resin composition contains the latent curing agent, and a main agent having at least 2 functional groups reactive with the amino group. A cured article is obtained by reacting the wet curable resin composition.SELECTED DRAWING: None

Description

   The present invention relates to a latent curing agent, a moisture curable resin composition using the latent curing agent, and a cured product.

Epoxy resins have excellent electrical insulation, moisture resistance, heat resistance, solder resistance, chemical resistance, durability, adhesion, mechanical strength, etc. In various fields such as architecture, it is widely used as a sealing material, paint, adhesive and the like.
A curing agent is used when the epoxy resin is cured, and a curing accelerator may be used in combination. The curing accelerator has the role of increasing the curing speed to increase the productivity and increase the mechanical properties such as the hardness and strength of the resin.

  On the other hand, in order to simplify handling, various studies on one-pack type epoxy resin compositions have been made. For example, Patent Document 1 proposes a curing agent having ketimine and oxazoline in the molecule, and Patent Document 2 discloses a polyamine having a ketone having a substituent at the α-position and a primary amino group bonded to a secondary carbon atom. There has been proposed a curing agent which is a ketimine obtained by reacting.

JP 2001-261661 JP 2000-178343 A

  However, even in the techniques of Patent Documents 1 and 2, there are insufficient points regarding the storage stability, curability, and mechanical properties of the cured product of the one-pack type epoxy resin composition, and improvement has been desired. .

  An object of the present invention is to provide a latent curing agent that imparts excellent curability and storage stability to a moisture curable resin composition, and imparts excellent mechanical properties and substrate adhesion to a cured product. .

  The inventors of the present invention have arrived at the present invention as a result of intensive studies to solve the above problems. That is, the present invention contains at least four ketoimino groups and a compound (C) having a total of at least two hydroxyl groups and urea groups, and the (C) comprises at least one secondary amino group. A polyamine (A0) having a group and at least two primary amino groups, a compound (B) having at least two functional groups selected from the group consisting of an epoxy group, an oxetane group and an isocyanate group; A latent curing agent (Y) having a structure obtained by reacting 13 ketones (K); the latent curing agent (Y); and a main agent (D) having at least two functional groups capable of reacting with an amino group; A moisture curable resin composition comprising: a cured product obtained by reacting a moisture curable resin composition.

The latent curing agent of the present invention has the following effects.
(1) It imparts excellent storage stability and curability to the moisture curable resin composition.
(2) Giving excellent mechanical properties to the cured product of the moisture curable resin composition.
(3) Giving excellent substrate adhesion to the cured product of the moisture curable resin composition.

[Polyamine (A0)]
Examples of (A0) in the present invention include polyamines having at least one secondary amino group and at least two primary amino groups.
Among the (A0), polyamines (A01) to (A06) selected from the group represented by the following general formulas (1) to (6) are preferable. The (A0) may be used alone or in combination of two or more.
Wherein (1) ~ (6), R 1 is an alkyl group having 1 to 6 carbon atoms, n, m, p, q , r are each independently 1-6 integer. ]

Polyamine (A01) represented by the general formula (1):
(A01) includes diethylenetriamine, 3,3′-diaminodipropylamine, bis (tetramethylene) triamine, bis (pentamethylene) triamine, bis (hexamethylene) triamine, N- (2-aminoethyl) propane-1 , 3-diamine, N- (2-aminoethyl) butane-1,4-diamine, spermidine, N- (3-aminopropyl) pentane-1,5-diamine, N- (4-aminobutyl) pentane-1 , 5-diamine, N- (2-aminoethyl) hexane-1,6-diamine, N- (3-aminopropyl) hexane-1,6-diamine, N- (4-aminobutyl) hexane-1,6 -Diamine, N- (5-aminopentyl) hexane-1,6-diamine and the like.

Polyamine (A02) represented by the general formula (2):
Examples of (A02) include triethylenetetramine, N, N′-bis (2-aminoethyl) -1,3-propanediamine, N, N′-bis (3-aminopropyl) ethylenediamine, and spermine.

Polyamine (A03) represented by general formula (3):
As (A03), 2,2′-diaminodiphenylamine, 2,3′-diaminodiphenylamine, 2,4′-diaminodiphenylamine, 3,3′-diaminodiphenylamine, 3,4′-diaminodiphenylamine, 4,4 ′ -Diamino diphenylamine etc. are mentioned.

Polyamine (A04) represented by general formula (4):
(A04) includes 1,2-diaminocarbazole, 1,3-diaminocarbazole, 1,4-diaminocarbazole, 1,5-diaminocarbazole, 1,6-diaminocarbazole, 1,7-diaminocarbazole, 1, 8-diaminocarbazole, 2,3-diaminocarbazole, 2,4-diaminocarbazole, 2,5-diaminocarbazole, 2,6-diaminocarbazole, 2,7-diaminocarbazole, 3,4-diaminocarbazole, 3,5 -Diaminocarbazole, 3,6-diaminocarbazole, 4,5-diaminocarbazole and the like.

Polyamine (A05) represented by the general formula (5):
Examples of (A05) include 1,9-diaminoacridan, 2,8-diaminoacridan, 3,7-diaminoacridan, 4,6-diaminoacridan, and the like.

Polyamine (A06) represented by general formula (6):
(A06) includes 2,4-diamino-6-methylamino-1,3,5-triazine, 2,4-diamino-6-ethylamino-1,3,5-triazine, 2,4-diamino- 6-propylamino-1,3,5-triazine, cyromazine, 2,4-diamino-6-butylamino-1,3,5-triazine, 2,4-diamino-6-pentylamino-1,3,5 -Triazine, 2,4-diamino-6-hexylamino-1,3,5-triazine and the like.

Of the above (A0), (A01), (A03) and (A04) are more preferable from the viewpoint of the curability of the moisture curable resin composition described later and the compatibility with the main agent (D) described later. Is (A01).
Of the above (A0), from the viewpoint of curability and compatibility with the main agent (D) described later, the number of primary amino groups of (A0) is preferably 2 to 6, more preferably 2 to 4. The number of secondary amino groups of (A0) is preferably 1 to 2, more preferably 1.

[Compound (B) having at least two functional groups selected from the group consisting of epoxy group, oxetane group and isocyanate group]
Examples of (B) in the present invention include a compound (B1) having at least two epoxy groups, a compound (B2) having at least two oxetane groups, and a compound (B3) having at least two isocyanate groups.

Compound (B1) having at least two epoxy groups:
(B1) includes a compound having two epoxy groups (B11) and a compound having three or more epoxy groups (B12).

Compound having two epoxy groups (B11):
(B11) includes ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, glycerin diglycidyl ether, diethylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, 1, 9-nonanediol diglycidyl ether, 1,10-decanediol diglycidyl ether, neopentyl glycol diglycidyl ether, cyclohexanediol diglycidyl ether, catechol diglycidyl ether, hydroquinone diglycidyl ether, 4,4'-dihydroxydiphenyl ether diglycidyl Ether, cyclohexanedimethanol diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, bisphenol Enol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, bisphenol F diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, hydrogenated bisphenol A 1 to 30 moles of alkylene oxide having 1 to 30 carbon atoms Diglycidyl ether of bisphenol A, diglycidyl ether of 1 to 30 moles of adduct of alkylene oxide of 2 to 4 carbon atoms of bisphenol A, diglycidyl of adduct of 1 to 30 moles of alkylene oxide of 2 to 4 carbon atoms of hydrogenated bisphenol F Examples thereof include diglycidyl ethers of ethers and 1 to 30 mol adducts of alkylene oxides having 2 to 4 carbon atoms of bisphenol F.

Compound (B12) having 3 or more epoxy groups:
(B12) includes trimethylolpropane triglycidyl ether, pentaerythritol triglycidyl ether, glycerol triglycidyl ether, triglycidyl ether of 1,1,1-tris (4-hydroxyphenyl) ethane, α, α, α'- Triglycidyl ether of tris (4-hydroxyphenyl) -1-ethyl-4-isopropylbenzene, triglycidyl ether of 1 to 30 mol adduct of alkylene oxide having 2 to 4 carbon atoms of glycerin, carbon number of 2 to 3 of trimethylolpropane Triglycidyl ether of 1 to 30 mol adduct of 4 alkylene oxides, tetraglycidyl ether of 1 to 30 mol adduct of alkylene oxide of 2 to 4 carbon atoms of ditrimethylolpropane tetraglycidyl ether and ditrimethylolpropane Ter, pentaerythritol tetraglycidyl ether, tetraglycidyl ether of 1 to 30 moles of adducts of 2 to 30 carbon atoms of pentaerythritol, sorbitol pentaglycidyl ether, dipentaerythritol pentaglycidyl ether, sorbitol hexaglycidyl ether, dipentaerythritol Examples include hexaglycidyl ether.

Compound (B2) having at least two oxetane groups:
(B2) includes 3,3 ′-(oxybismethylene) bis (3-ethyloxetane), 1,4-bis [(3-ethyloxetane-3-yl) methoxymethyl] benzene, tris phosphite ( 3-ethyloxetane-3-yl) and the like.

Compound (B3) having at least two isocyanate groups:
(B3) includes a compound (B31) having two isocyanate groups and a compound (B32) having three isocyanate groups.

Compound having two isocyanate groups (B31):
Examples of (B31) include hexamethylene diisocyanate (HDI), toluene diisocyanate (TDI), xylylene diisocyanate (XDI), hydrogenated XDI, isophorone diisocyanate (IPDI), diphenylmethane diisocyanate (MDI), and hydrogenated MDI. .

Compound having three isocyanate groups (B32):
(B32) includes lysine triisocyanate, methylsilanetriyl trisisocyanate, and the like.

Of the above (B), from the viewpoint of curability and compatibility with the main ingredient (D) described later, (B1) and (B2) are preferable, and (B11) and (B2) are particularly preferable. Is (B2).
In addition, the functional group of (B) is preferably 2 to 6, more preferably 2 to 3, and particularly preferably 2. In addition, this (B) may be used individually by 1 type, or may use 2 or more types together.

The ketone (K) in the present invention is a ketone having 3 to 13 carbon atoms. If the carbon number exceeds 14, the curability tends to be insufficient.
Examples of (K) include acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), dimethyl ketone (DMK), diethyl ketone (DEK), dipropyl ketone, dibutyl ketone, diisobutyl ketone, methyl isopropyl ketone, and ethyl butyl ketone. , Heptanone, dioctyl ketone, cyclohexanone, methyl cyclohexyl ketone, methoxymethyl butyl ketone, methyl cyclohexynyl ketone, acetophenone, dicyclohexyl ketone and the like.

Among the above (K), those having 3 to 13 carbon atoms are preferable from the viewpoint of moisture curing and industrial viewpoint, more preferably MEK, MIBK, and DEK, and particularly preferably MEK and MIBK.
In addition, ketone (K) may be used individually by 1 type, or may use 2 or more types together.

[Compound (C) having at least 4 ketoimino groups and at least 2 hydroxyl groups or urea groups]
The compound (C) in the present invention is a compound having at least four ketoimino groups and a total of at least two hydroxyl groups and urea groups. The polyamine (A0), the compound (B), and the ketone It has a structure obtained by reacting (K).
Preferred as (C) is a product obtained by reacting a secondary amino group of the compound (A) described later with the functional group of the compound (B). Examples of the compound (C) include a compound (C1) having at least 4 imino groups and at least 2 hydroxyl groups, and a compound (C2) having at least 4 imino groups and at least 2 urea groups. It is done.
Further, the ketoimino group in the present invention is a functional group represented by [> C═N—] and having a structure obtained by ketiminating a primary amino group and a ketone.

  The number of imino groups possessed by (C) is preferably 4-12, more preferably 4-6, and particularly preferably 4. The total of hydroxyl groups and urea groups is preferably 2-6, The number is preferably 2 to 4, particularly preferably 2.

The compound (C) in the present invention can be produced by various methods, but the following methods (i) to (ii) are preferable from an industrial viewpoint.
(I) First, a compound having at least one secondary amino group and at least two ketoimino groups by subjecting the polyamine (A0) and the ketone (K) to a ketimination reaction by a known method ( A) is obtained.
(Ii) Next, the presence of an organic solvent [for example, acetone, methyl ethyl ketone (MEK), diethyl ketone (DEK), methyl isobutyl ketone (MIBK)], if necessary, with the compound (A) and the compound (B). Under the reaction, a compound (C) having at least four ketoimino groups and a total of at least two hydroxyl groups and urea groups is obtained.

From the viewpoint of curability and mechanical properties of the cured product, the compound (C) has a number average molecular weight of (C) of preferably 500 to 5,000, more preferably 600 to 3,000.
The latent active hydrogen equivalent of (C) is preferably 50 to 500 g / eq (hereinafter, only numerical values may be shown below), more preferably from the viewpoint of curability and mechanical properties of the cured product. 60-300.

[Compound (A) having at least one secondary amino group and at least two ketoimino groups]
The compound (A) in the present invention is a compound having at least one secondary amino group and at least two ketoimino groups.
Preferable examples of (A) include so-called ketiminates having a structure in which a primary amino group of the polyamine (A0) is reacted with a ketone (K).
Further, the ketiminization rate of the ketimine product is preferably 90 to 100%, more preferably 95 to 100%, and particularly preferably 98 to 100%.

[Latent curing agent (Y)]
The latent curing agent (Y) of the present invention contains the compound (C). The latent curing agent (Y) is used as a latent curing agent for the main agent (D) described later, and is particularly useful as a latent curing agent for the compound (D1) having two or more epoxy groups. In addition, this (C) may be used individually by 1 type, or may use 2 or more types together.
Further, (Y) may be in the form of a solution containing a solvent if necessary. In this case, the content of the compound (C) in the (Y) is preferably 30 to 90% by weight, more preferably 40 to 80% by weight. Of these solvents, the ketone (K) is preferred.

[Main agent (D) having at least one functional group capable of reacting with an amino group]
Examples of the functional group capable of reacting with the amino group of the main agent (D) in the present invention include an epoxy group, an oxetane group, and an isocyanate group. Examples of the main agent (D) include a compound (D1) having two or more epoxy groups, a compound (D2) having two or more oxetane groups, and a compound (D3) having two or more isocyanate groups.

Compound (D1) having two or more epoxy groups:
(D1) includes ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, glycerin diglycidyl ether, diethylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, 1, 9-nonanediol diglycidyl ether, 1,10-decanediol diglycidyl ether, neopentyl glycol diglycidyl ether, cyclohexanediol diglycidyl ether, catechol diglycidyl ether, hydroquinone diglycidyl ether, 4,4'-dihydroxydiphenyl ether diglycidyl Ether, cyclohexanedimethanol diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, bisphenol Addition of 1 to 30 moles of alkylene oxide having 2 to 4 carbon atoms of diol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, bisphenol F diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, hydrogenated bisphenol A Diglycidyl ether of bisphenol A, diglycidyl ether of 1 to 30 moles of adduct of alkylene oxide of 2 to 4 carbon atoms of bisphenol A, diglycidyl of adduct of 1 to 30 moles of alkylene oxide of 2 to 4 carbon atoms of hydrogenated bisphenol F Ether, diglycidyl ether of 1 to 30 moles of adduct of bisphenol F having 2 to 4 carbon atoms, 1,2: 5,6-diepoxyhydrindane, 3 ′, 4′-epoxycyclohexylmethyl-3 4-epoxycyclohexanecarboxylate, ε-caprolactone modified 3 ′, 4′-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate, trimethylolpropane triglycidyl ether, pentaerythritol triglycidyl ether, glycerol triglycidyl ether, 1,1 , 1-tris (4-hydroxyphenyl) ethane triglycidyl ether, α, α, α'-tris (4-hydroxyphenyl) -1-ethyl-4-isopropylbenzene triglycidyl ether, glycerin having 2 to 2 carbon atoms Triglycidyl ether of 1 to 30 mol adduct of 4 alkylene oxides, triglycidyl ether of 1 to 30 mol adduct of alkylene oxide of 2 to 4 carbon atoms of trimethylolpropane, ditrimethylol Addition of 1 to 30 moles of adduct of alkylene oxide of 2 to 4 carbon atoms of lopantetraglycidyl ether and ditrimethylolpropane with addition of 1 to 30 moles of alkylene oxide of 2 to 4 carbon atoms of tetraglycidyl ether, pentaerythritol tetraglycidyl ether and pentaerythritol Tetraglycidyl ether, sorbitol pentaglycidyl ether, dipentaerythritol pentaglycidyl ether, sorbitol hexaglycidyl ether, dipentaerythritol hexaglycidyl ether and the like.

Compound (D2) having two or more oxetane groups:
(D2) includes 3,3 ′-(oxybismethylene) bis (3-ethyloxetane), 1,4-bis [(3-ethyloxetane-3-yl) methoxymethyl] benzene, tris phosphite ( 3-ethyloxetane-3-yl) and the like.

Compound (D3) having two or more isocyanate groups:
(D3) includes hexamethylene diisocyanate (HDI), toluene diisocyanate (TDI), xylylene diisocyanate (XDI), hydrogenated XDI, isophorone diisocyanate (IPDI), diphenylmethane diisocyanate (MDI), hydrogenated MDI, polyether diol And / or polyester diol, and if necessary, a both-terminal NCO prepolymer obtained by reaction of a chain extender with an excess of diisocyanate, lysine triisocyanate, methylsilanetriyl trisisocyanate, and the like.

  Of the above (D), (D1) and (D3) are preferred from the viewpoint of curability and mechanical properties of the cured product, and (D1) is more preferred. Moreover, the functional group which (D) has is preferably 2 to 6, more preferably 2 to 4, from the viewpoints of curability and mechanical properties of the cured product.

[Moisture curable resin composition]
The moisture curable resin composition of the present invention contains the latent curing agent (Y) and the main agent (D).
The equivalent ratio [(D) / (Y)] of (D) and (Y) is preferably 0.5 to 2.0 from the viewpoints of curability, mechanical properties of the cured product, and substrate adhesion. More preferably, it is 0.7 to 1.5, and particularly preferably 0.8 to 1.2.
The equivalent ratio [(D) / (Y)] can be calculated from the functional group equivalent of the (D) and the latent active hydrogen equivalent and the apparent active hydrogen equivalent of (Y).

  The moisture curable resin composition of the present invention includes a leveling agent (E1), an antioxidant (E2), an ultraviolet absorber (E3), and a filler (E4) as necessary, as long as the effects of the present invention are not impaired. You may contain the at least 1 sort (s) of additive (E) chosen from the group which consists of.

  Examples of the leveling agent (E1) include polydimethylsiloxane, a copolymer thereof, an acrylic polymer having a polydimethylsiloxane skeleton, and a urethane polymer having a polydimethylsiloxane skeleton.

  As the antioxidant (E2), di-t-butylhydroxytoluene (BHT), 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino)- 1,3,5-triazine, pentaerythrityl tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,2-thio-diethylenebis [3- (3,5 -Di-t-butyl-4-hydroxyphenyl) propionate], triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) ) Propionate, N, N′-hexamethylenebis (3,5-di-tert-butyl-4-hydroxy-hydrocinnamamide), 1,3,5-trimethyl-2,4,6-tris (3 , 5-di-tert-butyl-4-hydroxybenzyl) benzene, tris- (3,5-di-tert-butyl-4-hydroxybenzyl) -isocyanurate, octylated diphenylamine, 2,4, -bis [( Octylthio) methyl] -O-cresol, isooctyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, dibutylhydroxytoluene and the like.

As the ultraviolet absorber (E3), 2- (2-hydroxy-5-methyl) benzotriazole, 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole 2- (2′-hydroxy-5′-t-butylphenyl) benzotriazole, 2- (2′-hydroxy-3′-t-butyl-5′-methylphenyl) benzotriazole, 2- (2′- Hydroxy-3 ′, 5′-t-butylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-t-butylphenyl) -5-chlorobenzotriazole, 2- (2H-benzotriazole- 2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol, 2- (2′-hydroxy-3 ′, 5′-t-pentylbenzotriazole, 2- [2′-hydride) Roxy-5 ′-(1,1,3,3, -tetramethylbutyl)] benzotriazole, 2- (2′-hydroxy-3′-s-butyl-5′-t-butylbenzotriazole, 2- ( 2'-hydroxy-3-dodecyl-5'-methylbenzotriazole, 2- (2'-hydroxy-3'-t-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'- Hydroxy-5'-methylphenyl) benzotriazole, 2,2-methylenebis [4- (1,1,3,3-tetramethylbutyl)]-6- (2H-benzotriazol-2-yl) phenol], 3 -[3- (2H-benzotriazol-2-yl) -5-t-butyl-4-hydroxyphenyl] propionate, polyethylene glycol and the like.
Examples of the filler (E4) include silica, zirconia, and alumina.

  These additives (E) can be used alone or in combination of two or more. The amount of additive (E) added is preferably 30% by weight or less, more preferably 0.1 to 10% by weight, based on the weight {(Y) + (D)} of (Y) and (D). Particularly preferred is 0.2 to 5% by weight.

The number average molecular weight in the present invention is measured under the following conditions.
Apparatus: Gel permeation chromatography Solvent: Tetrahydrofuran Reference substance: Polystyrene Sample concentration: 3 mg / ml
Column stationary phase: PLgel MIXED-B
Column temperature: 40 ° C

  In the present invention, the apparent active hydrogen equivalent is a molecular weight per equivalent of active hydrogen directly bonded to the nitrogen atom of the amino group in the latent curing agent (Y), and is determined according to JIS K2501. The latent active hydrogen equivalent is an active hydrogen equivalent derived from an amino group produced by hydrolyzing all ketoimino groups in the latent curing agent (Y).

  In the present invention, the epoxy equivalent is a molecular weight per equivalent of an epoxy group in a compound used as a main agent, and is obtained according to JISK7236: 2001 (corresponding to ISO3001: 1999).

  In the present invention, the oxetane equivalent is a molecular weight per equivalent of an oxetane group in a compound used as a main agent, and is obtained in accordance with JISK7236: 2001 (corresponding to ISO3001: 1999).

  In the present invention, the isocyanate equivalent is a molecular weight per equivalent of an isocyanate group in a compound used as a main agent, and is determined according to JIS K 7301.

[Cured product]
The cured product of the present invention is obtained by reacting the moisture curable resin composition. The curing conditions are preferably a humidity of 40 to 90% and a curing temperature of 20 to 70 ° C. By adjusting the humidity and the curing temperature, the curability can be appropriately adjusted. Moreover, sclerosis | hardenability can be improved further by adding water to a moisture curable resin composition as needed.
The latent curing agent of the present invention can impart excellent storage stability and curability to the moisture curable resin composition. Moreover, the moisture-curable resin composition of the present invention can impart excellent mechanical properties and substrate adhesion to a cured product.
For this reason, this composition can be applied to various uses (sealant, paint, adhesive, etc.), and is particularly useful for paint.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these. In the following examples, “part” means “part by weight” and “%” means “% by weight”.

<Production Example 1>
A glass reaction vessel equipped with a Dean-Stark device, a stirrer, and a thermometer was charged with 206 parts of diethylenetriamine [manufactured by Tokyo Chemical Industry Co., Ltd.] (A01-1) and 2004 parts of MIBK (methyl isobutyl ketone). Reflux was performed at 110 ° C. to remove the generated water. After confirming that a theoretical amount of water was generated, the mixture was cooled to room temperature, and 50 parts of molecular sieve 3A [manufactured by Union Showa Co., Ltd.] were added and allowed to stand overnight. Next, molecular sieve 3A was removed by filtration, and excess MIBK was removed under reduced pressure heating to obtain 534 parts of diethylenetriamine MIBK ketiminate (A-1). (A-1) had one secondary amino group and two ketoimino groups.

<Production Example 2>
A glass reaction vessel equipped with a Dean-Stark device, a stirrer, and a thermometer was charged with 262 parts of 3,3′-diaminodipropylamine [manufactured by Tokyo Chemical Industry Co., Ltd.] (A01-2) and 2004 parts of MIBK. The product was refluxed at 80 to 110 ° C. to remove the generated water. After confirming that a theoretical amount of water was generated, the mixture was cooled to room temperature, and 50 parts of molecular sieve 3A [manufactured by Union Showa Co., Ltd.] were added and allowed to stand overnight. Next, molecular sieve 3A was removed by filtration, and excess MIBK was removed under heating under reduced pressure to obtain 592 parts of MIBK ketimine product (A-2) of 3,3′-diaminodipropylamine. (A-2) had one secondary amino group and two ketoimino groups.

<Production Example 3>
In a glass reaction vessel equipped with a Dean-Stark apparatus, a stirring apparatus, and a thermometer, 430 parts of bis (hexamethylene) triamine [manufactured by Tokyo Chemical Industry Co., Ltd.] (A01-3), diethyl ketone (DEK) 1,723 The portion was charged and refluxed at 80 to 110 ° C. to remove the generated water. After confirming that a theoretical amount of water was generated, the mixture was cooled to room temperature, and 50 parts of molecular sieve 3A [manufactured by Union Showa Co., Ltd.] were added and allowed to stand overnight. Next, molecular sieve 3A was removed by filtration, and excess DEK was removed by heating under reduced pressure to obtain 704 parts of a DEK ketimine product (A-3) of bis (hexamethylene) triamine. (A-3) had two secondary amino groups and two ketoimino groups.

<Production Example 4>
A glass reaction vessel equipped with a Dean-Stark apparatus, a stirrer, and a thermometer was charged with 292 parts of triethylenetetraamine [manufactured by Tokyo Chemical Industry Co., Ltd.] (A02-1) and 2004 parts of MIBK at 80 to 110 ° C. Refluxed to remove the generated water. After confirming that a theoretical amount of water was generated, the mixture was cooled to room temperature, and 50 parts of molecular sieve 3A [manufactured by Union Showa Co., Ltd.] were added and allowed to stand overnight. Next, molecular sieve 3A was removed by filtration, and excess MIBK was removed under heating under reduced pressure to obtain 933 parts of a triethylenetetraamine MIBK ketiminate (A-4). (A-4) had 2 secondary amino groups and 6 ketoimino groups.

<Production Example 5>
In a glass reaction vessel equipped with a Dean-Stark device, a stirrer, and a thermometer, 398 parts of 4,4′-diaminodiphenolamine [manufactured by Tokyo Chemical Industry Co., Ltd.] (A03-1) and MIBK 2004 parts were charged, The product was refluxed at 80 to 110 ° C. to remove the generated water. After confirming that a theoretical amount of water was generated, the mixture was cooled to room temperature, and 50 parts of molecular sieve 3A [manufactured by Union Showa Co., Ltd.] were added and allowed to stand overnight. Next, molecular sieve 3A was removed by filtration, and excess MIBK was removed under heating under reduced pressure to obtain 728 parts of MIBK ketiminate (A-5) of 4,4′-diaminodiphenolamine. (A-5) had one secondary amino group and two ketoimino groups.

<Production Example 6>
A glass reaction vessel equipped with a Dean-Stark apparatus, a stirrer, and a thermometer was charged with 394 parts of 3,6-diaminocarbazole [manufactured by Tokyo Chemical Industry Co., Ltd.] (A04-1) and 2004 parts of MIBK, 80-110 The product was refluxed at 0 ° C. to remove the generated water. After confirming that a theoretical amount of water was generated, the mixture was cooled to room temperature, and 50 parts of molecular sieve 3A [manufactured by Union Showa Co., Ltd.] were added and allowed to stand overnight. Next, molecular sieve 3A was removed by filtration, and excess MIBK was removed under heating under reduced pressure to obtain 724 parts of MIBK ketimine product (A-6) of 3,6-diaminocarbazole. (A-6) had one secondary amino group and two ketoimino groups.

<Production Example 7>
Moisture generated by charging 422 parts of 3,7-diaminoacridan (A05-1) and 2004 parts of MIBK in a glass reaction vessel equipped with a Dean-Stark device, a stirrer, and a thermometer, and refluxing at 80 to 110 ° C. Was removed. After confirming that a theoretical amount of water was generated, the mixture was cooled to room temperature, and 50 parts of molecular sieve 3A [manufactured by Union Showa Co., Ltd.] were added and allowed to stand overnight. Next, molecular sieve 3A was removed by filtration, and excess MIBK was removed under reduced pressure heating to obtain 752 parts of MIBK ketimine product (A-7) of 3,7-diaminoacridan. (A-7) had one secondary amino group and two ketoimino groups.

<Production Example 8>
A glass reaction vessel equipped with a Dean-Stark device, a stirrer, and a thermometer was charged with 322 parts of cyromazine [manufactured by Tokyo Chemical Industry Co., Ltd.] (A06-1) and 2004 parts of MIBK, and refluxed at 80 to 110 ° C. The generated water was removed. After confirming that a theoretical amount of water was generated, the mixture was cooled to room temperature, and 50 parts of molecular sieve 3A [manufactured by Union Showa Co., Ltd.] were added and allowed to stand overnight. Next, molecular sieve 3A was removed by filtration, and excess MIBK was removed under reduced pressure heating to obtain 660 parts of cyromazine MIBK ketiminate (A-8). (A-8) had one secondary amino group and two ketoimino groups.

<Production Example 9>
In a glass reaction vessel equipped with a stirrer and a thermometer, 1,200 parts of polyethylene glycol [trade name “PEG-400”, manufactured by Sanyo Chemical Industries Ltd.] and 2 parts of dibutyltin dilaurate (BTL) are uniformly mixed. Then, 870 parts of tolylene diisocyanate (TDI) [trade name “Cosmonate T-80”, manufactured by Mitsui Chemicals, Inc.] (D3-1) was added, and the mixture was stirred at about 80 ° C. for 3 hours. 2,072 parts of prepolymer (D3-2) were obtained. In addition, (D3-2) was a number average molecular weight 2,070 and an isocyanate equivalent of 1035 g / eq.

<Production Example 10>
In a glass reaction vessel equipped with a stirrer and a thermometer, 2,000 parts of polycarbonate diol [trade name “Placcel CD220”, manufactured by Daicel Corporation] and 3 parts of dibutyltin dilaurate (BTL) were uniformly mixed. 445 parts of isophorone diisocyanate (IPDI) [trade name “IPDI”, manufactured by Active Materials Chemicals Co., Ltd.] (D3-3) was charged and stirred at about 80 ° C. for 3 hours, and both terminal NCO prepolymer (D3-4) 2,448 parts were obtained. In addition, (D3-2) was number average molecular weight 2,445 and isocyanate equivalent 1,223 g / eq.

<Example 1>
In a glass reaction vessel equipped with a condenser, a stirrer, and a thermometer, 534 parts of diethylenetriamine MIBK ketiminate (A-1), 1,6-hexanediol diglycidyl ether [trade name “Epolite 1600”, Kyoeisha Co., Ltd. )]] (B-1) 230 parts and MIBK 764 parts were charged, stirred at 60 ° C. for 24 hours, MIBK was distilled off under reduced pressure, and a latent curing agent containing compound (C-1) ( Y-1) 764 parts were obtained.
In addition, the compound (C-1) had 4 ketoimino groups and 2 hydroxyl groups, the number average molecular weight was 764, and the latent active hydrogen equivalent was 95.5 g / eq.

<Example 2>
In a glass reaction vessel equipped with a condenser, a stirrer and a thermometer, 534 parts of diethylenetriamine MIBK ketimine compound (A-1), neopentyl glycol diglycidyl ether [manufactured by Tokyo Chemical Industry Co., Ltd.] (B-2) 216 parts and 750 parts of MIBK were charged and stirred at 60 ° C. for 24 hours, and then MIBK was distilled off under reduced pressure to obtain 750 parts of a latent curing agent (Y-2) containing the compound (C-2). It was.
The compound (C-2) had 4 ketoimino groups and 2 hydroxyl groups, the number average molecular weight was 750, and the latent active hydrogen equivalent was 93.8 g / eq.

<Example 3>
In a glass reaction vessel equipped with a condenser, a stirrer, and a thermometer, 534 parts of MIBK ketimine compound (A-1) of diethylenetriamine, bisphenol A diglycidyl ether [manufactured by Tokyo Chemical Industry Co., Ltd.] (B-3) 340 Part and MIBK874 parts were charged and stirred at 60 ° C. for 24 hours, and then MIBK was distilled off under reduced pressure to obtain 874 parts of a latent curing agent (Y-3) containing the compound (C-3). .
Compound (C-3) had 4 ketoimino groups and 2 hydroxyl groups, the number average molecular weight was 874, and the latent active hydrogen equivalent was 109.3 g / eq.

<Example 4>
In a glass reaction vessel equipped with a condenser, a stirrer, and a thermometer, 801 parts of diethylenetriamine MIBK ketimine product (A-1), trimethylolpropane triglycidyl ether [trade name “Epolite 100MF”, manufactured by Kyoeisha Co., Ltd.] (B-4) 302 parts and MIBK 1,103 parts were charged, stirred at 60 ° C. for 24 hours, MIBK was distilled off under reduced pressure, and the latent curing agent containing compound (C-4) (Y -4) 1,103 parts were obtained.
In addition, the compound (C-4) had 6 ketoimino groups and 3 hydroxyl groups, the number average molecular weight was 1,103, and the latent active hydrogen equivalent was 91.9 g / eq.

<Example 5>
In a glass reaction vessel equipped with a condenser, a stirrer, and a thermometer, 534 parts of diethylenetriamine MIBK ketiminate (A-1), 3,3 ′-(oxybismethylene) bis (3-ethyloxetane) [trade name “OXT-221”, manufactured by Toa Gosei Co., Ltd.] (B-5) 214 parts and MIBK 748 parts were charged, stirred at 60 ° C. for 24 hours, and MIBK was distilled off under reduced pressure to give compound (C-5). 748 parts of a latent curing agent (Y-5) containing
Compound (C-5) had 4 ketoimino groups and 2 hydroxyl groups, the number average molecular weight was 748, and the latent active hydrogen equivalent was 93.5 g / eq.

<Example 6>
In a glass reaction vessel equipped with a condenser, a stirrer, and a thermometer, 534 parts of MIBK ketimine compound (A-1) of diethylenetriamine, 168 parts of HDI [manufactured by Tokyo Chemical Industry Co., Ltd.] (B-6), 702 parts of MIBK After stirring at 60 ° C. for 24 hours, MIBK was distilled off under reduced pressure to obtain 702 parts of a latent curing agent (Y-6) containing compound (C-6).
Compound (C-6) had four ketoimino groups and two urea groups, a number average molecular weight of 702, and a latent active hydrogen equivalent weight of 87.8 g / eq.

<Example 7>
In a glass reaction vessel equipped with a condenser, a stirrer, and a thermometer, 534 parts of diethylenetriamine MIBK ketimine compound (A-1), TDI [trade name “Cosmonate T-80”, manufactured by Mitsui Chemicals, Inc.] B-7) A latent curing agent (Y-7) containing Compound (C-7) was charged with 174 parts and 708 parts of MIBK, stirred at 60 ° C. for 24 hours, and then distilled off MIBK under reduced pressure. 708 parts were obtained.
Compound (C-7) had four ketoimino groups and two urea groups, had a number average molecular weight of 708 and a latent active hydrogen equivalent of 88.5 g / eq.

<Example 8>
In a glass reaction vessel equipped with a condenser, a stirrer, and a thermometer, 534 parts of diethylenetriamine MIBK ketiminate (A-1), XDI [trade name “Takenate 500”, manufactured by Mitsui Chemicals, Inc.] (B-8) 188 parts and 722 parts of MIBK, and after stirring at 60 ° C. for 24 hours, MIBK was distilled off under reduced pressure to obtain 722 parts of a latent curing agent (Y-8) containing compound (C-8). Obtained.
Compound (C-8) had 4 ketoimino groups and 2 urea groups, a number average molecular weight of 722, and a latent active hydrogen equivalent of 90.3 g / eq.

<Example 9>
In a glass reaction vessel equipped with a condenser, a stirrer, and a thermometer, 534 parts of diethylenetriamine MIBK ketimine compound (A-1), IPDI [trade name “IPDI”, manufactured by Active Materials Chemicals Co., Ltd.] (B-9 ) 222 parts and 756 parts of MIBK were charged and stirred at 60 ° C. for 24 hours, and then MIBK was distilled off under reduced pressure to obtain 756 parts of a latent curing agent (Y-9) containing compound (C-9). Obtained.
The compound (C-9) had 4 ketoimino groups and 2 urea groups, a number average molecular weight of 756, and a latent active hydrogen equivalent of 94.5 g / eq.

<Example 10>
In a glass reaction vessel equipped with a condenser, a stirrer, and a thermometer, 534 parts of diethylenetriamine MIBK ketiminate (A-1), MDI [trade name “Millionate MT”, manufactured by Tosoh Corporation] (B-10) 250 parts and 784 parts of MIBK were charged and stirred at 60 ° C. for 24 hours, and then MIBK was distilled off under reduced pressure to obtain 784 parts of a latent curing agent (Y-10) containing the compound (C-10). It was.
Compound (C-10) had four ketoimino groups and two urea groups, had a number average molecular weight of 784 and a latent active hydrogen equivalent of 98.0 g / eq.

<Example 11>
In a glass reaction vessel equipped with a condenser, a stirrer, and a thermometer, 592 parts of MIBK ketimine product (A-2) of 3,3′-diaminodipropylamine, bisphenol A diglycidyl ether [Tokyo Chemical Industry Co., Ltd.] Product] (B-3) 340 parts and MIBK 932 parts were charged, stirred at 60 ° C. for 24 hours, MIBK was distilled off under reduced pressure, and the latent curing agent containing compound (C-11) (Y -11) 932 parts were obtained.
The compound (C-11) had 4 ketoimino groups and 2 hydroxyl groups, the number average molecular weight was 932, and the latent active hydrogen equivalent was 116.5 g / eq.

<Example 12>
In a glass reaction vessel equipped with a condenser, a stirrer, and a thermometer, 704 parts of DEK ketimine compound (A-3) of bis (hexamethylene) triamine, bisphenol A diglycidyl ether [manufactured by Tokyo Chemical Industry Co., Ltd.] B-3) 340 parts and DEK 1,044 parts were charged, and the mixture was stirred at 60 ° C. for 24 hours. Then, DEK was distilled off under reduced pressure, and the latent curing agent containing compound (C-12) (Y— 12) 1,044 parts were obtained.
The compound (C-12) had 4 ketoimino groups and 2 hydroxyl groups, a number average molecular weight of 1,044, and a latent active hydrogen equivalent of 134.0 g / eq.

<Example 13>
In a glass reaction vessel equipped with a condenser, a stirrer, and a thermometer, 933 parts of triethylenetetraamine MIBK ketimine compound (A-4), bisphenol A diglycidyl ether [manufactured by Tokyo Chemical Industry Co., Ltd.] (B- 3) 680 parts and MIBK 1,613 parts were charged, stirred at 60 ° C. for 24 hours, MIBK was distilled off under reduced pressure, and the latent curing agent (Y-13) containing compound (C-13) 1,613 parts were obtained.
Compound (C-13) had 6 ketoimino groups and 3 hydroxyl groups, a number average molecular weight of 1,613, and a latent active hydrogen equivalent weight of 115.2 g / eq.

<Example 14>
In a glass reaction vessel equipped with a condenser, a stirrer, and a thermometer, 728 parts of MIBK ketimine product (A-5) of 4,4′-diaminodiphenolamine, bisphenol A diglycidyl ether [Tokyo Chemical Industry Co., Ltd.] Product] (B-3) 340 parts and MIBK 1,068 parts were charged, stirred at 60 ° C. for 24 hours, MIBK was distilled off under reduced pressure, and the latent curing agent containing compound (C-14) (Y-14) 1,068 parts were obtained.
Compound (C-14) had 4 ketoimino groups and 2 hydroxyl groups, a number average molecular weight of 1,068, and a latent active hydrogen equivalent weight of 133.5 g / eq.

<Example 15>
In a glass reaction vessel equipped with a condenser, a stirrer, and a thermometer, 724 parts of MIBK ketimine compound (A-6) of 3,6-diaminocarbazole, bisphenol A diglycidyl ether [manufactured by Tokyo Chemical Industry Co., Ltd.] ( B-3) 340 parts and MIBK 1,064 parts were charged, stirred at 60 ° C. for 24 hours, MIBK was distilled off under reduced pressure, and the latent curing agent containing compound (C-15) (Y— 15) 1,064 parts were obtained.
Compound (C-15) had 4 ketoimino groups and 2 hydroxyl groups, the number average molecular weight was 1,064, and the latent active hydrogen equivalent was 133.0 g / eq.

<Example 16>
In a glass reaction vessel equipped with a condenser, a stirrer, and a thermometer, 752 parts of MIBK ketimine product (A-7) of 3,7-diaminoacridane, bisphenol A diglycidyl ether [manufactured by Tokyo Chemical Industry Co., Ltd.] (B-3) 340 parts and MIBK 1,092 parts were charged, stirred at 60 ° C. for 24 hours, MIBK was distilled off under reduced pressure, and the latent curing agent containing compound (C-16) (Y -16) 1,092 parts were obtained.
In addition, the compound (C-16) had 4 ketoimino groups and 2 hydroxyl groups, the number average molecular weight was 1,092, and the latent active hydrogen equivalent was 136.5 g / eq.

<Example 17>
In a glass reaction vessel equipped with a condenser, a stirrer, and a thermometer, 660 parts of MIBK ketimine compound (A-8) of cyromazine, bisphenol A diglycidyl ether [manufactured by Tokyo Chemical Industry Co., Ltd.] (B-3) 340 Parts, MIBK 1,000 parts, and stirred for 24 hours at 60 ° C., then, MIBK was distilled off under reduced pressure, and latent curing agent (Y-17) 1,000 containing compound (C-17) was obtained. Got a part.
In addition, the compound (C-17) had 4 ketoimino groups and 2 hydroxyl groups, the number average molecular weight was 1,000, and the latent active hydrogen equivalent was 125.0 g / eq.

<Example 18>
In a glass reaction vessel equipped with a condenser, a stirrer, and a thermometer, 1,602 parts of MIBK ketiminate (A-1) of diethylenetriamine, 675 parts of dipentaerythritol hexaglycidyl ether (B-11), and 2,277 parts of MIBK After stirring at 60 ° C. for 24 hours, MIBK was distilled off under reduced pressure to obtain 2,277 parts of a latent curing agent (Y-18) containing the compound (C-18).
Compound (C-17) had 12 ketoimino groups and 6 hydroxyl groups, had a number average molecular weight of 2,277 and an active hydrogen equivalent of 94.9 g / eq.

Examples 19 to 44, Comparative Example 1
According to the blending composition (parts) shown in Table 1, the moisture-curing resin compositions were obtained by batch blending and mixing.
180 ml of the obtained moisture curable resin composition is put into a 200 ml glass bottle and stored in a sealed state at 50 ° C. for 28 days. From the viscosity before and after storage, the storage stability is improved according to [Evaluation method], (1). evaluated.
Separately, the obtained moisture curable resin composition was applied to a 1 mm thick SUS304 plate that had been subjected to alkaline degreasing and then pickled to form a 50 μm thick coating film, 25 ° C., humidity 50%, 72 hours. The coating film was cured under the above conditions to obtain a cured product. The cured product was evaluated according to the following [Evaluation methods], (2) to (4). The results are shown in Table 1.

[Evaluation method]
(1) Viscosity change before and after storage (%) [Storage stability]
[Viscosity change before and after storage (%)] = (viscosity after storage) × 100 / (viscosity before storage)
The change in viscosity (%) before and after storage determined by the above formula was evaluated according to the following evaluation criteria.
◎: Less than 110% ○: 110% or more, less than 120% △: 120% or more, less than 150% ×: 150% or more

(2) Tackiness [curability]
The following evaluation criteria were evaluated by finger touch.
A: There is no tack on the surface.
○: There is a slight tack on the surface.
Δ: There is tack on the surface.
X: The surface tack is large.

(3) Nail scratch resistance [Evaluation of mechanical properties]
The surface of the cured product was scratched with a nail and visually evaluated according to the following criteria.
A: There is no scratch.
○: Scratches are slight.
Δ: Scratched
X: Scratches are evident.

(4) Substrate adhesion [adhesion]
The cured coating film on the SUS304 plate was cross-cut into 1 mm × 1 mm grids (100 pieces), cellophane tape was pasted thereon, peeled off, and visually evaluated according to the following criteria.
A: 100/100
○: 99/100 to 90/100
Δ: 89/100 to 50/100
X: 49/100 to 0/100

Abbreviations in Table 1 are as follows.
Latent curing agent (ratio Y-1)
MIBK ketiminate of hexamethylenediamine Potential active hydrogen equivalent: 70.1 g / eq
Main agent (D1-1):
Polyethylene glycol diglycidyl ether (average number of moles of added ethylene oxide 9),
[Product name "Epolite 400E", manufactured by Kyoeisha Co., Ltd.]
Epoxy equivalent 263.5 g / eq
Main agent (D1-2):
Bisphenol A diglycidyl ether [manufactured by Tokyo Chemical Industry Co., Ltd.]
Epoxy equivalent 170.0 g / eq
Main agent (D1-3):
3 ′, 4′-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate [trade name “Celoxide 2021P”, manufactured by Daicel Corporation],
Epoxy equivalent 126.0 g / eq
Main agent (D1-4):
Trimethylolpropane triglycidyl ether [trade name “Epolite 100MF”, manufactured by Kyoeisha Co., Ltd.]
Epoxy equivalent 101.0 g / eq
Main agent (D2-1):
3,3 '-(Oxybismethylene) bis (3-ethyloxetane)
[Product name “OXT-221”, manufactured by Toa Gosei Co., Ltd.]
Oxetane equivalent 107.0 g / eq

  From the results in Table 1, it can be seen that the latent curing agent (Y) of the present invention imparts excellent storage stability and curability to the moisture curable resin composition as compared with the comparative one. Further, it is apparent that the moisture curable resin composition imparts excellent mechanical properties and substrate adhesion to the cured product.

  The latent curing agent and moisture curable resin composition of the present invention are excellent in storage stability and curability when blended with the main agent, and a cured product obtained by curing the composition has mechanical properties and substrate adhesion. Since it is excellent, it can be widely used for various applications such as sealing materials, paints, adhesives and the like in various fields such as electricity, electronics, civil engineering and construction, and is extremely useful.

Claims (9)

  At least four ketoimino groups and a compound (C) having a total of at least two hydroxyl groups and urea groups, wherein (C) comprises at least one secondary amino group and at least two A polyamine (A0) having a primary amino group, a compound (B) having at least two functional groups selected from the group consisting of an epoxy group, an oxetane group and an isocyanate group, and a ketone (K) having 3 to 13 carbon atoms A latent curing agent (Y) having a structure obtained by reacting with.   (C) has at least two functional groups selected from the group consisting of a compound (A) having at least one secondary amino group and at least two ketoimino groups, and an epoxy group, an oxetane group and an isocyanate group. The latent curing agent according to claim 1, having a structure obtained by reacting the compound (B).   The latent curing agent according to claim 2, wherein the compound (A) has a structure in which a primary amino group of the polyamine (A0) and a ketone (K) having 3 to 13 carbon atoms are ketiminized.   The latent curing agent according to any one of claims 1 to 3, wherein the compound (C) has a number average molecular weight of 500 to 5,000. The latent curing agent according to any one of claims 1 to 4, wherein (A0) is at least one selected from the group represented by the following general formulas (1) to (6).
Wherein (1) ~ (6), R 1 is an alkyl group having 1 to 6 carbon atoms, n, m, p, q , r are each independently 1-6 integer. ]    A moisture curable resin composition comprising the latent curing agent (Y) according to any one of claims 1 to 5 and a main agent (D) having at least two functional groups capable of reacting with an amino group.   The moisture curable resin composition according to claim 6, wherein an equivalent ratio [(D) / (Y)] of (D) and (Y) is 0.5 to 2.0.   Hardened | cured material formed by making the moisture curable resin composition of Claim 6 or 7 react. A latent curing agent (Y) comprising the compound (C) comprising at least four imino groups and a total of at least two hydroxyl groups and urea groups, including the following steps (1) to (2): Production method.
Step (1): A polyamine (A0) having at least one secondary amino group and at least two primary amino groups and a ketone (K) having 3 to 13 carbon atoms are subjected to ketiminization reaction, so that at least 1 Step (2) for obtaining a compound (A) having two secondary amino groups and at least two imino groups: The compound (A) and a functional group selected from the group consisting of an epoxy group, an oxetane group and an isocyanate group Reacting the compound (B) having at least two groups to obtain a compound (C) having at least four imino groups, and a total of at least two hydroxyl groups and urea groups