JPH1121352A - Curable composition - Google Patents

Abstract

(57) Abstract: The present invention relates to a curable composition which is cured by a reaction in which a mercapto group is added to a carbon-carbon double bond,
The catalyst has (1) a structure not containing hydrogen directly bonded to a nitrogen atom, and (2) 1,8-diazabicyclo [5.
4.0] Undecene-7 and a structure other than the acid salt thereof, wherein the curing is as good as when 1,8-diazabicyclo [5.4.0] undecene-7 and the acid salt are used as a catalyst. It is an object to provide a curable composition having a speed. (A) a compound having two or more mercapto groups in one molecule; and (B) two or more carbon-carbon double bonds in one molecule.
And (C) a tertiary amine compound having an amidine structure, which is a compound other than 1,8-diazabicyclo [5.4.0] undecene-7.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a curable composition useful as a paint, an adhesive, a sealing agent, and the like.

[0002]

2. Description of the Related Art Curable compositions of the type which are cured by a reaction in which a mercapto group is added to a carbon-carbon double bond have been known. Examples of such a curable composition include JP-A-8-100123 and US Pat. No. 5,41.
No. 1,766 can be mentioned.

[0003]

The curable composition of this type has a disadvantage that the curing speed is generally low even when a usual tertiary amine catalyst is used. Examples of the catalyst that can be cured with guanidine are a guanidine compound (described in US Pat. No. 5,411,766), 1,8-diazabicyclo [5.4.0] undecene-7 (hereinafter referred to as DBU) and its acid salt (particularly, US Pat. Kaihei 8-
No. 100123) is only known.

However, conventionally known guanidine compounds are compounds having a hydrogen directly bonded to a nitrogen atom, and can themselves cause a reaction to be added to a carbon-carbon double bond, so that the original curing It was a catalyst that might hinder the reaction. The reaction in which a guanidine-based compound having hydrogen directly bonded to a nitrogen atom adds to a carbon-carbon double bond is described, for example, in J. Org. Chem., 33, 3354 (1968), Heterocycles, 20, 9 No. 1
769 (1983), Aust. J. Chem., 31
Volume, p. 179 (1978), Synthesis, No. 9,
786 (1986).

[0005] Therefore, there is no choice but to select DBU and its acid salt as a catalyst which does not have the possibility of inhibiting the curing.

The present invention provides a curable composition which is cured by a reaction in which a mercapto group is added to a carbon-carbon double bond, wherein the catalyst has (1) a structure not containing hydrogen directly bonded to a nitrogen atom, and (2) An object of the present invention is to provide a curable composition having a structure other than DBU and an acid salt thereof, and having a curing rate almost as good as that when DBU and an acid salt thereof are used as a catalyst.

[0007]

Means for Solving the Problems In order to achieve the above object, the catalyst for thiourethane reaction and the curable composition of the present invention have the following constitutions.

"(A) a compound having two or more mercapto groups in one molecule, (B) a compound having two or more carbon-carbon double bonds in one molecule, and (C) a tertiary amine compound having an amidine structure And a curable composition comprising a compound other than 1,8-diazabicyclo [5.4.0] undecene-7. "

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION Component (A) used in the present invention,
That is, examples of compounds having two or more mercapto groups in one molecule are described below.

Diethylene glycol dimercaptan, triethylene glycol dimercaptan, 1,2-ethanedithiol, 1,3-propanedithiol, 1,4-butanedithiol, 1,6-hexanedithiol, 1,1
2-dodecanedithiol, mercaptomethyl sulfide, 2-mercaptoethyl sulfide, 3-mercaptopropyl sulfide, 4-mercaptobutyl sulfide, 6-mercaptohexyl sulfide, 1,2-bis-2-mercaptoethylthioethane, 1,2- Screw-3
-Mercaptopropylthioethane, 1,3-bis-2-
Mercaptoethylthiopropane, 1,4-bis-2-mercaptoethylthiobutane, 1,6-bis-2-mercaptoethylthiohexane, bis-2- (2-mercaptoethylthio) ethylsulfide, 2-mercaptoethylether , 3-mercaptopropyl ether, 4-mercaptobutyl ether, 6-mercaptohexyl ether, 1,4-cyclohexanedithiol, bis-2-mercaptoethoxymethane, 1,2-bis-2-mercaptoethoxyethane, bis-2- ( 2-mercaptoethoxy) ethyl ether, 2,2-bis (2-hydroxy-
3-mercaptopropoxyphenyl) propane, 1,4
-Benzenedithiol, 1,3-benzenedithiol,
1,2-benzenedithiol, 4-t-butyl-1,2
-Benzenedithiol, 1,2-bis (mercaptomethylene) benzene, 1,3-bis (mercaptomethylene)
Benzene, 1,4-bis (mercaptomethylene) benzene, 1,2-bis (mercaptoethylene) benzene,
1,3-bis (mercaptoethylene) benzene, 1,4
-Bis (mercaptoethylene) benzene, 1,2-bis (mercaptomethylenethio) benzene, 1,3-bis (mercaptomethylenethio) benzene, 1,4-bis (mercaptomethylenethio) benzene, 1,2-bis ( 2-mercaptoethylenethio) benzene, 1,3-bis (2-mercaptoethylenethio) benzene, 1,4-
Bis (2-mercaptoethylenethio) benzene, 1,2
-Bis (2-mercaptoethylenethiomethylene) benzene, 1,3-bis (2-mercaptoethylenethiomethylene) benzene, 1,4-bis (2-mercaptoethylenethiomethylene) benzene, 1,2-bis (mercaptomethylene) Oxy) benzene, 1,3-bis (mercaptomethyleneoxy) benzene, 1,4-bis (mercaptomethyleneoxy) benzene, 1,2-bis (2-mercaptoethyleneoxy) benzene, 1,3-bis (2- Mercaptoethyleneoxy) benzene, 1,4-bis (2-
Mercaptoethyleneoxy) benzene, 4,4'-thiobisbenzenethiol, 4,4'-oxybisbenzenethiol, 4,4'-biphenyldithiol, 1,3
5-trimercaptobenzene, trimercaptoethyl isocyanurate, the following formulas (α) and (β)

Embedded image A compound of ethylene glycol bisthioglycolate,
Ethylene glycol bismercaptopropionate, diethylene glycol bisthioglycolate, diethylene glycol bis-3-mercaptopropionate, 1,
4-butanediol bisthioglycolate, 1,4-butanediol bis-3-mercaptopropionate,
1,4-butanedithiolbis-3-mercaptopropionate, 1,4-butanedithiolbisthioglycolate, pentaerythritol tetrakisthioglycolate, pentaerythritol tristhioglycolate, pentaerythritol bisthioglycolate, pentaerythritol mono Thioglycolate, pentaerythritol tetrakis-3-mercaptopropionate, pentaerythritol tris-3-mercaptopropionate, pentaerythritol bis-3-mercaptopropionate, pentaerythritol mono-3-mercaptopropionate, trimethylol Propane tristhioglycolate, trimethylolpropane bisthioglycolate, trimethylolpropane monothioglycolate,
Trimethylolpropane tris-3-mercaptopropionate, trimethylolpropanebis-3-mercaptopropionate, trimethylolpropanemono-3-
Mercapto propionate, dipentaerythrit hexakisthioglycolate, dipentaerythrit pentakisthioglycolate, dipentaerythrit tetrakisthioglycolate, dipentaerythrit tristhioglycolate, dipentaerythrit bisthioglycolate , Dipentaerythrit monothioglycolate, dipentaerythrit hexakis-3-mercaptopropionate, dipentaerythrit pentakis-3-mercaptopropionate, dipentaerythrittetrakis-3-mercaptopropionate Dipentaerythritol tris-3-mercaptopropionate, dipentaerythritol bis-3-mercaptopropionate, dipentaerythritol mono-3-mercaptopropionate, mercaptope Pills isocyanurate, polysulfide polymers, polysulfide polyether polymer, a thiol group-containing polyethers, poly (oxyalkylene) - Polyester - poly (monosulfide) - polythiols, and the like butadiene mercaptan polymer, mercaptan-containing polymers and mercapto organopolysiloxane.

The polysulfide polymer is represented by the following general formula (I).

HS—R ² —S _x (R ¹ S _x ) _n —R ² —SH (I) (wherein R ¹ and R ² are divalent or trivalent having 2 to 20 carbon atoms)
A valent aliphatic group and / or an aliphatic ether group,
x is an integer of 1 to 5, the average of which is about 2, and n is an integer of 1 to 50. In the formula (I), specific examples of R ¹ and R ² include-
_{CH 2 CH 2 -, - CH} 2 CH 2 O -, - CH 2 CH (C
_{H 3) O -, - C} 2 H 4 OC 2 H 4 -, - C 2 H 4 OCH 2 OC
_{2 H 4 -, - C 2} H 4 OC 2 H 4 OC 2 H 4 -, - C 4 H 8 OC 4
H _8- and the like. This polysulfide polymer can be produced, for example, by the method described in US Pat. No. 2,466,953.

The above-mentioned polysulfide polyether polymer is (i)-(RO) _m-in the main chain (where R represents an alkylene group having 2 to 4 carbon atoms, and m represents an integer of 6 to 200). And (ii) -C _{2
H 4 OCH 2 OC 2 H 4} -S x - and -CH ₂ CH (O
H) CH ₂ -S _x - (where, x is an integer of 1 to 5).
And (iii)-at the terminal
_{C 2 H 4 OCH 2 OC 2} H 4 -SH and / or -C
It has a structural unit represented by H ₂ CH (OH) CH ₂ —SH.

In the polysulfide polyether polymer, the polyether portion of (i) and the structural unit represented by (ii) may be bonded in an arbitrary sequence. The proportion is as follows:-(RO) _m -component is 2 to 95% by weight, and -CH ₂ CH (OH) CH ₂ -S _x -component is 3 to 70% by weight.
The _{weight%, -CH 2 CH (OH)} CH 2 -S x - component preferably from 1 to 50% by weight. The content of the polysulfide-bonded _Sx is preferably 1 to 60% by weight. The number average molecular weight of the polysulfide polyether polymer is usually from 600 to 200,000, preferably from 800 to 50,000. This polysulfide polyether polymer is disclosed in, for example,
-363325 and JP-A-4-366121.

The thiol group-containing polyether includes, for example, a polyoxyalkylene polyol having a structure represented by the following general formula (II), a polymercaptan having a structure represented by the general formula (III), and at least one of a skeleton. And a mercaptan-terminated liquid polymer having a urethane bond or a thiourethane bond in the moiety, for example, the following general formula (I
Mercaptan-terminated liquid polymers having a urethane group-containing structure represented by V), and mercaptan-terminated liquid polythioethers having a structure represented by the general formula (V) are mentioned.

[0016]

Embedded image (In the formula, p, q, r, s, and t are integers of 2 to 100, and R ³ is hydrogen or a methyl group.) A compound having at least one mercapto group in the molecule may be used alone. Or two or more of them may be used simultaneously.

Next, the component (B) used in the present invention, that is, a compound having two or more carbon-carbon double bonds in one molecule will be described.

The component (B) may be a compound having two or more carbon-carbon double bonds in one molecule, and the carbon-carbon double bond may be located at any position in the molecule.

From the viewpoint of ease of production and high reactivity, preferred types of carbon-carbon double bonds include double bonds of a (meth) acryloyl group and 2-ethoxycarbonylallyloxy group. Double bond of alkoxycarbonyl allyloxy group, double bond of maleic acid derivative such as maleimide group, double bond of fumaric acid derivative, double bond of oleic acid derivative, double bond of cinnamic acid derivative, double bond of styrene derivative Double bond, double bond of α-methylstyrene derivative, double bond of vinyl group, double bond of allyl group, double bond of methallyl group, and the like. Among them, double bond of (meth) acryloyl group Heavy bonds are most preferred.

When a compound having a large molecular weight is used as the component (B), the fact that the carbon-carbon double bond is located at the terminal or side chain of the molecule means that the production is easy and the reactivity is high. It is preferred in that respect.

One of the methods for producing the component (B), that is, a compound having two or more carbon-carbon double bonds in one molecule, includes (a) a compound having two or more active hydrogen-containing groups in one molecule. With (b) a compound having a group capable of reacting with an active hydrogen-containing group having a carbon-carbon double bond.

Examples of the (b) compounds having a carbon-carbon double bond and having a group capable of reacting with an active hydrogen-containing group include (meth) acrylic acid halides and (meth) acrylic anhydrides. Products, (meth) acrylates,
(Meth) acrylic acid, 2-methacryloyloxyethyl isocyanate, methacryloyl isocyanate, m-
Isopropenyl-α, α-dimethylbenzyl isocyanate, p-isopropenyl-α, α-dimethylbenzyl isocyanate, glycidyl (meth) acrylate, vinylbenzoic acid halide, vinylbenzoic anhydride, vinylbenzoic acid ester, vinylbenzoic acid , Maleic halide, maleic anhydride, maleic ester,
Maleic acid, fumaric acid halide, fumaric anhydride,
Fumaric acid ester, fumaric acid, oleic acid halide, oleic anhydride, oleic acid ester, oleic acid, cinnamic acid halide, cinnamic anhydride, cinnamic acid ester, cinnamic acid, chloromethylstyrene, allyl Examples thereof include halide, methallyl halide, and a silicon compound having a carbon-carbon double bond-containing group.

Examples of the compound (a) having two or more active hydrogen-containing groups in one molecule used in the production of the component (B) include (a1) a compound having two or more hydroxyl groups in one molecule, and (a2) Compounds having two or more amino groups in one molecule and (a3) compounds having two or more mercapto groups in one molecule are preferred.

(A1) The compound having two or more hydroxyl groups in one molecule is not particularly limited, but may be glycerin, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, butanediol, hexanediol, or the like. Low molecular weight polyols such as cyclohexanedimethanol, trimethylolpropane, pentaerythritol, dipentaerythritol, bisphenol A, an alkylene oxide adduct of bisphenol A, bisphenol F, an alkylene oxide adduct of bisphenol F, polyether polyol, polyester polyol, polycarbonate Polyol, polybutadiene polyol, acrylic polyol, polyurethane polyol, polyvinyl alcohol, Examples include high molecular weight polyols such as phenolic resins, cellulose resins and derivatives thereof. More specific examples of polyether polyols, polyester polyols, polycarbonate polyols, polybutadiene polyols, acrylic polyols and the like include “functional polyurethane” (published year: 1989).
(Published by CMC Co., Ltd.).

(A2) The compound having two or more amino groups in one molecule may be any compound having two or more primary amino groups and / or secondary amino groups in one molecule. There is no particular limitation. For example, "New development of epoxy resin curing agent" (issued in 1994;
Compounds described on pages 41 to 93 satisfying the above conditions can be exemplified.

(A3) The compound having two or more mercapto groups in one molecule is not particularly limited, but the compounds already mentioned as examples of (a) can also be mentioned as examples of (a3). .

As another method for producing the component (B),
A method in which (c) a compound having two or more groups capable of reacting with an active hydrogen-containing group in one molecule is reacted with (d) a compound having an active hydrogen-containing group having a carbon-carbon double bond.

(C) one group capable of reacting with an active hydrogen-containing group
Examples of the compound having two or more isocyanate groups in the molecule include (c1) a compound having two or more isocyanato groups in one molecule, and (c1)
2) a compound having two or more epoxy groups in one molecule,
(C3) Compounds having two or more carboxyl groups and / or groups derived from carboxyl groups in one molecule.

(C1) Compounds having two or more isocyanato groups in one molecule include "Network Polymers", Vol. 17, No. 2, pp. 19-26 (1996).
Compounds having two or more isocyanate groups in one molecule described in "Yakusetsu", "Functional polyurethane" (published by CMC Corporation, published year: 1989), isocyanate groups described on pages 3 to 24 And a compound having the following formula (12) in one molecule. Among them, the compounds of the following formulas (1) to (19) are more preferable, and the compounds of the formulas (1) to (12) are more preferable.

[0030]

Embedded image

Embedded image

Embedded image Further, isocyanurate modified products of these compounds, uretidinedione modified products of these compounds, biuret modified products of these compounds, and these compounds (excess amount)
A urethane prepolymer obtained by adding the compound to a compound having two or more active hydrogen-containing groups in one molecule is also suitable.

Examples of the compound having two or more active hydrogen-containing groups in one molecule include those described above as examples (a1) to (a3).

(C2) As the compound having two or more epoxy groups in one molecule, a compound commercially available as a so-called epoxy resin can be used.

(C3) Compounds having two or more carboxyl groups and / or groups derived from carboxyl groups in one molecule include phthalic acid, terephthalic acid, isophthalic acid, oxalic acid, malonic acid, succinic acid and glutaric acid. acid,
Adipic acid, pimelic acid, suberic acid, azelaic acid,
Examples include various carboxylic acids such as sebacic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, camphoric acid, naphthalenedicarboxylic acid, trimellitic acid, and acid halide derivatives and ester derivatives thereof.

(D) Examples of the compound having an active hydrogen-containing group having a carbon-carbon double bond include ethyl α- (hydroxymethyl) acrylate, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate,
Hydroxypropyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxybutyl methacrylate, 2-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, cyclohexane dimethanol monomethacrylate, cyclohexane dimethanol monoacrylate,
2-methacryloyloxyethyl-2-hydroxypropyl phthalate, 2-acryloyloxyethyl-2-hydroxypropyl phthalate, 3-chloro-2-hydroxypropyl methacrylate, 3-chloro-2-hydroxypropyl acrylate, 2-hydroxy- 3-phenoxypropyl methacrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-
Acryloyloxypropyl methacrylate, N- (2-
Examples thereof include (aminoethyl) methacrylamide, N- (2-aminoethyl) acrylamide, N- (6-aminohexyl) methacrylamide, and N- (6-aminohexyl) acrylamide.

Further, as still another method for producing the component (B), a compound having two or more active hydrogen-containing groups (a) in any one of the optional (B) and any kind may be used. Another type of component (B) can be obtained by reacting at a ratio of carbon-carbon double bonds in excess of the group (ie, adding an active hydrogen-containing group to the carbon-carbon double bond).

As the component (B), a corresponding commercial product may be used. As an example of such a commercially available product, those having two or more (meth) acryloyl groups in one molecule include two (meth) acryloyl groups in one molecule in the Aronix series of Toa Gosei Chemical Industry Co., Ltd. Of the "NK Ester" series of Shin-Nakamura Chemical Co., Ltd., those having two or more (meth) acryloyl groups in one molecule, and of the "Light Ester" and "Light Acrylate" series of Kyoeisha Chemical Co., Ltd. Among them, those having two or more (meth) acryloyl groups in one molecule, "AH-600", "AT-600",
“UA-306H”, “AI-600”, “UA-10”
1T "," UA-101I "," UA-306T ",
“UA-306I”, “UF-8001”, “UF-8”
003 ", etc. Examples of the compound having two or more maleimide groups in one molecule include" BMI "and" BM "manufactured by K.I.
And bismaleimides such as "I-70", "BMI-80", etc. Examples of the compound having two or more allyl groups in one molecule include "Dap" and "Isodap" series of Daiso, Asahi Denka Kogyo Co., Ltd. Of the "ADEKANOL SDX-236" and "ADEKA CARPOL MRA" series, compounds having two or more allyl groups in one molecule are examples of compounds having two or more methallyl groups in one molecule. Compounds having two or more methallyl groups in one molecule from the "ADEKA CARPOL MRM" series of Denka Kogyo Co., Ltd. Also, Idemitsu Petrochemical Co., Ltd., Nippon Soda Co., Ltd., Nippon Petrochemical Co., Ltd. Polybutadiene and its derivatives can also be used. It can be said that commercially available products other than those exemplified here can also be used. But no.

In the curable composition of the present invention, as the component (B), a single compound may be used, or two or more compounds may be used simultaneously.

Next, the component (C) used in the present invention, that is, a compound other than DBU, which is a tertiary amine compound having an amidine structure, will be described.

In the present invention, a tertiary amine compound having an amidine structure is represented by the following formula (VI)

Embedded image A tertiary amine compound having a structure represented by In the present invention, a tertiary amine compound means an amine compound having no hydrogen directly bonded to a nitrogen atom.

Examples of the compounds used for the component (C) include N ¹ , N ¹ , N ² -trimethylformamidine, N ^2-
Methyl-N ¹ , N ¹ -dipropylformamidine, N ^2-
Methyl-N ¹ , N ¹ -dioctylformamidine, N ¹ ,
N ¹ , N ² -trimethylacetamidine, N ² -methyl-
N ¹ , N ¹ -dipropylacetamidine, N ² -methyl-
N ^1, N ¹ - dioctyl ^{acetamidine, N 1, N 1, N} 2
- trimethyl benzamidine, N ² - methyl -N ^1, N ¹
- dipropyl benzamidine, N ² - methyl -N ^1, N ¹
Compounds having an acyclic amidine structure, such as dioctylbenzamidine, N-methyl- (1-pyrrolidinyl) azomethine, N-methylpiperidinoazomethine, N-methylmorpholinoazomethine, imidazoline compounds, imidazole compounds, pyrimidine compounds Compound, dihydropyrimidine compound, tetrahydropyrimidine compound, purine compound, quinazoline compound, pteridine compound, perimidine compound, triazabicycloalkene compound, diazabicycloalkene compound (DB
And a compound having a cyclic amidine structure such as a compound in which these compounds are further fused to another ring.

Among these compounds, compounds having a cyclic amidine structure are preferable from the viewpoint of catalytic activity, and imidazoline compounds, tetrahydropyrimidine compounds, triazabicycloalkene compounds and diazabicycloalkene compounds are preferred. Compounds selected from (but not including DBU) are more preferred.

Specific examples of such compounds are shown below.

Examples of the imidazoline compounds include 1-methylimidazoline, 1,2-dimethylimidazoline, 1-methyl-2-ethylimidazoline, 1-methyl-2-octylimidazoline and the like.

Examples of the tetrahydropyrimidine compounds include 1-methyl-1,4,5,6-tetrahydropyrimidine, 1,2-dimethyl-1,4,5,6-tetrahydropyrimidine and 1-methyl-2-ethyl-1. , 4,5,6
-Tetrahydropyrimidine, 1-methyl-2-butyl-
Examples thereof include 1,4,5,6-tetrahydropyrimidine and 1-ethyl-2-octyl-1,4,5,6-tetrahydropyrimidine.

As the triazabicycloalkene-based compound, 7-methyl-1,5,7-triazabicyclo [4.
4.0] decene-5,7-ethyl-1,5,7-triazabicyclo [4.4.0] decene-5.

Examples of the diazabicycloalkene compound include 1,5-diazabicyclo [4.2.0] octene-5,
1,8-diazabicyclo [7.2.0] undecene-
8,1,4-diazabicyclo [3.3.0] octene-
4,3-Methyl-1,4-diazabicyclo [3.3.
0] octene-4,3,6,7,7-tetramethyl-
1,4-diazabicyclo [3.3.0] octene-4,
7,8,8-Trimethyl-1,5-diazabicyclo [4.3.0] nonene-5,1,8-diazabicyclo [7.3.0] dodecene-8,1,7-diazabicyclo [4.3. 0] nonene-6,8-phenyl-1,7-diazabicyclo [4.3.0] nonene-6,1,5-diazabicyclo [4.3.0] nonene-5,1,5-diazabicyclo [4. 4.0] decene-5,4-phenyl-
1,5-diazabicyclo [4.4.0] decene-5,
1,8-diazabicyclo [5.3.0] decene-7,
1,8-diazabicyclo [7.4.0] tridecene-
8,6-Methylbutylamino-1,8-diazabicyclo [5.4.0] undecene-7,6-methyloctylamino-1,8-diazabicyclo [5.4.0] undecene-7,6-dibutylamino -1,8-diazabicyclo [5.4.0] undecene-7,6-butylbenzylamino-1,8-diazabicyclo [5.4.0] undecene-7,6-dihexylamino-1,8-diazabicyclo [ 54.0] undecene-7,9-methyl-1,8
-Diazabicyclo [5.4.0] undecene-7,9-
Methyl-1,8-diazabicyclo [5.3.0] decene-7,1,6-diazabicyclo [5.5.0] dodecene-6,1,7-diazabicyclo [6.5.0] tridecene-7, 1,8-diazabicyclo [7.5.0] tetradecene-8,1,10-diazabicyclo [7.3.0]
Dodecene-9,1,10-diazabicyclo [7.4.
0] tridecene-9,1,14-diazabicyclo [1
1.3.0] hexadecene-13, 1,14-diazabicyclo [11.4.0] heptadecene-13 and the like.

Among them, 1,2-dimethyl-1,4,5,6-tetrahydropyrimidine and 7-methyl-1,5,7-triazabicyclo [4. 4.0] decene-5,1,5-diazabicyclo [4.3.0] nonene-5 and 6-dibutylamino-1,8-diazabicyclo [5.4.0] undecene-7 are most preferred.

These compounds are all conventionally known compounds and can be produced by a conventionally known method.

In the present invention, the component (C) may be used in the form of an acid salt. As the acid, organic acids and inorganic acids such as phenols, carboxylic acids, sulfonic acids and imides can be used. Examples of acid compound names include phenol, cresol, catechol, resorcin, hydroquinone, phenols such as hydroxynaphthalene, formic acid, propionic acid acetate, butanoic acid, hexanoic acid,
Octylic acid, decanoic acid, lauric acid, stearic acid, behenic acid, oleic acid, oxalic acid, succinic acid, adipic acid, phthalic acid, isophthalic acid, terephthalic acid, maleic acid, fumaric acid, cinnamic acid, itaconic acid, etc. Organic acids such as carboxylic acids, sulfonic acids such as benzenesulfonic acid, p-toluenesulfonic acid, and trifluoromethanesulfonic acid; imides such as phthalimide, maleimide, and saccharin; and hydrochloric acid, hydrobromic acid, sulfuric acid, sulfurous acid, nitric acid, and nitrous acid. Inorganic acids such as nitric acid, carbonic acid, boric acid, phosphoric acid, phosphorous acid, and silicic acid. Needless to say, acids other than these can also be used. By using the component (C) as an acid salt, the activity of the catalyst can be adjusted, and there is an advantage that the vapor pressure is reduced and the toxicity is reduced.

In the present invention, the component (C) may be used alone or in combination of two or more.

The compounding amount of the component (C) is 100 parts of the component (A).
0.0001 to 10 parts by weight of the component (C) is preferable, and 0.001 to 3 parts by weight is more preferable.
If the amount of the component (C) is less than 0.0001 part by weight, the curing speed becomes too slow.

Next, (A) in the curable composition of the present invention
The mixing ratio of the component and the component (B) will be described. (A)
The blending ratio of the component (B) is, (B) the number of moles of carbon-carbon double bonds in the component (a N _B) and (A) the number of moles of the mercapto groups in component (a N _A) the ratio of the (N _B /
N _A ) is from 0.4 to 1.5, preferably from 0.5 to 1.3. N _B / N _A curability becomes poor is less than 0.4,
If it exceeds 1.5, the component (B) tends to separate and the curing reaction tends to be slow.

Since the curable composition of the present invention contains a compound having two or more carbon-carbon double bonds in one molecule as the component (B), radicals may be generated under closed storage conditions or high temperatures. There is a possibility that the generated carbon-carbon double bond may react. Such a reaction is not preferable because storage stability is significantly reduced. In order to prevent this, it is effective to add a radical polymerization inhibitor and / or a radical polymerization inhibitor to the component (B).

As the radical polymerization inhibitor and / or the radical polymerization inhibitor to be used, those generally used can be used. For example, phenols such as phenols, hydroquinones, catechols and resorcinols can be used. Phenothiazines, N-nitrosophenylhydroxylamine salts and the like. Among these, when compounds particularly suitable for the curable composition of the present invention are exemplified, 4-methoxyphenol, 4-t-butylcatechol, 2,6-di- T-butyl-p-cresol, N-nitrosophenylhydroxylamine aluminum salt and the like, among which N-nitrosophenylhydroxylamine aluminum salt is the most excellent in terms of polymerization inhibiting effect. These are used alone or as a mixture, and are used in an amount of up to about 5 parts by weight based on 100 parts by weight of the component (B).

The curable composition of the present invention may contain a curing agent that induces a curing reaction other than the addition reaction of a mercapto group to a carbon-carbon double bond. Examples of such a curing agent include metal oxides such as lead peroxide, zinc peroxide, calcium peroxide, lithium peroxide, and barium peroxide.
Examples thereof include metal compounds of carboxylic acids or β-diketones described on page 3 of JP-A-38852, and rubber vulcanizing agents or vulcanization accelerators described on page 4 of JP-A-57-38852.

The curable composition of the present invention may further contain calcium carbonate, magnesium carbonate, talc, mica, graphite, kaolin, clay, silica, alumina, titania, magnesia, zeolite, aluminum hydroxide, depending on the purpose of use. Magnesium hydroxide, zinc oxide, diatomaceous earth, terra alba, wood flour, walnut husk flour, rice husk flour, pulp, cotton chips, resin particles, resin paste, glass beads, aluminum powder, zinc powder, glass balloon, resin balloon, asbestos, sepiolite , Glass fiber, carbon fiber, resin fiber, gypsum fiber and other fillers; benzoic acid, phthalic acid, trimellitic acid, pyromellitic acid, adipic acid,
Derivatives such as sebacic acid, fumaric acid, maleic acid, itaconic acid, and citric acid; plasticizers such as chlorinated hydrocarbons, polyesters, polyethers, and epoxy resins; aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents, and esters Solvents such as system solvents, ether solvents, ketone solvents, carbonate solvents and aprotic polar solvents; coloring agents such as various pigments and dyes; adhesion of various silane coupling agents, various isocyanate compounds and various epoxy compounds Property imparting agent;
Various UV absorbers, various UV reflectors, various antioxidants, various light stabilizers and other deterioration inhibitors, calcium chloride,
Inorganic dehydrating agents represented by lithium chloride, barium oxide, calcium oxide, potassium fluoride, potassium thiocyanate, sodium thiocyanate, ammonium thiocyanate, sodium sulfate, magnesium sulfate, various zeolites, various oxazolidine compounds, various ketimine compounds Can contain an organic dehydrating agent such as various acid anhydrides, various acid halides, various silane compounds, and the like, but the curable composition of the present invention is not limited to these. .

The curable composition of the present invention is usually used as a so-called two-pack type curable composition. Therefore, at the time of storage, each of them contains at least one of the components (A), (B) and (C).
Liquids and stored in three or more liquid states. At the time of use, the components (A), (B) and (C)
The components are mixed and curing proceeds.

The curable composition of the present invention is suitably used for resin applications requiring curability, but is particularly suitable for applications selected from paints, adhesives and sealing agents.

[0059]

EXAMPLES The present invention will now be described specifically with reference to examples, but the present invention is not limited thereto.

Example 1 (1) NK ester A-400 (manufactured by Shin-Nakamura Chemical Co., Ltd., polyethylene glycol # 400 diacrylate; 15.2 parts by weight), light acrylate TMP-6
EO-3A (manufactured by Kyoeisha Chemical Co., Ltd., ethylene oxide modified trimethylolpropane triacrylate; 1.2
Parts by weight), N-nitrosophenylhydroxylamine aluminum salt (manufactured by Wako Pure Chemical Industries, Ltd .; 0.1 part by weight) and 1,5-diazabicyclo [4.3.0] nonene-5 (manufactured by San Apro; 1 part by weight) 0.0 parts by weight).

(2) To the mixture obtained in the above (1), thiocol LP-56 (manufactured by Toray Thiokol Co., Ltd., polysulfide polymer, mercapto group content: 2.2% by weight;
(100 parts by weight), and the mixture was left to stand for 5 hours. As a result, the resin was completely cured, and the resin did not adhere to the finger even when touched with the finger.

Example 2 (1) 1,5-diazabicyclo [4.3.0] nonene-
An octylic acid salt of 1,5-diazabicyclo [4.3.0] nonene-5 was prepared by adding an octylic acid in an equimolar amount to 5 little by little with stirring.

(2) 1,5-diazabicyclo [4.3.
Except that the octylate of 1,5-diazabicyclo [4.3.0] nonene-5 was used instead of [0] nonene-5, the procedure was performed in exactly the same manner as in Example 1- (2). When left for 5 hours, the resin was completely cured and the resin did not adhere to the finger even when touched with the finger.

Example 3 (1) 1,5-diazabicyclo [4.3.0] nonene-
Instead of 5, 7-methyl-1,5,7-triazabicyclo [4.4.0] decene-5 (manufactured by Aldrich; 1.
Except for using 0 parts by weight), the procedure was exactly the same as in Example 1- (2). When left for 5 hours, the resin was completely cured and the resin did not adhere to the finger even when touched with the finger.

Example 4 (1) 1,5-diazabicyclo [4.3.0] nonene-
Example 1 was repeated except that 6-dibutylamino-1,8-diazabicyclo [5.4.0] undecene-7 (manufactured by San Apro Corporation; 1.0 part by weight) was used instead of 5.
The procedure was performed exactly as in (2). When left for 5 hours, the resin was completely cured and the resin did not adhere to the finger even when touched with the finger.

Example 5 (1) Sannics PP-3000 (manufactured by Sanyo Chemical Co., Ltd., polypropylene glycol, 100 parts by weight), toluene (100 parts by weight), Karenz MOI (manufactured by Showa Denko KK, 2-methacryloyloxyethyl) Isocyanate; 10.6 parts by weight), N-nitrosophenylhydroxylamine aluminum salt (manufactured by Wako Pure Chemical Industries, Ltd .;
0.1 parts by weight) and dibutyltin dilaurate (manufactured by Nacalai Tesque, Inc .; 0.1 parts by weight) and mixed at 50 ° C.
For 5 hours. After the reaction, toluene was distilled off under reduced pressure using a rotary vacuum evaporator to obtain PP-3.
000 Karenz MOI variants were obtained.

(2) Modified Karenz MOI of PP-3000 (224.4 parts by weight), light acrylate TMP
-6EO-3A (manufactured by Kyoeisha Chemical Co., Ltd., ethylene oxide modified trimethylolpropane triacrylate;
2.8 parts by weight) and 1,2-dimethyl-1,4,5,
6-tetrahydropyrimidine (manufactured by Koei Chemical Industry Co., Ltd .; 1.0 part by weight) was mixed well.

(3) Thiochol LP-3 (manufactured by Toray Thiokol Co., Ltd., polysulfide polymer, mercapto group content 6.5% by weight) was added to the mixture obtained in (2) above.
(100.0 parts by weight) was added, mixed and left for 5 hours. As a result, the resin was completely cured, and the resin did not adhere to the finger even when touched with the finger.

Example 6 (1) Toluene (100 parts by weight), urethane prepolymer A (polyether polyol / hexamethylene diisocyanate system, trifunctional, isocyanato group content: 2.83)
% By weight; 100 parts by weight), 2-hydroxyethyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd., abbreviated as HEMA;
8.8 parts by weight), N-nitrosophenylhydroxylamine aluminum salt (manufactured by Wako Pure Chemical Industries, Ltd .; 0.1
Parts by weight) and dibutyltin dilaurate (manufactured by Nacalai Tesque, Inc .; 0.1 parts by weight) were mixed and reacted at 50 ° C. for 5 hours. After the reaction, toluene was distilled off under reduced pressure using a rotary vacuum evaporator to obtain a modified HEMA of urethane prepolymer A.

(2) Toluene (100 parts by weight), urethane prepolymer B (polyether polyol / hexamethylene diisocyanate system, bifunctional, isocyanato group content: 1.11% by weight; 100 parts by weight), HEMA (Tokyo Chemical Industry) 3.4 parts by weight), N-nitrosophenylhydroxylamine aluminum salt (manufactured by Wako Pure Chemical Industries, Ltd .; 0.1 parts by weight) and dibutyltin dilaurate (manufactured by Nacalai Tesque, Inc .; 0.1 parts by weight) Parts) were mixed and reacted at 50 ° C. for 5 hours. After the reaction, toluene was distilled off under reduced pressure using a rotary vacuum evaporator to obtain a modified HEMA of urethane prepolymer B.

(3) HEMA of urethane prepolymer A
Modified product (48.8 parts by weight), HEMA modified product of urethane prepolymer B (118.4 parts by weight) and 1,2-dimethyl-1,4,5,6-tetrahydropyrimidine (manufactured by Koei Chemical Industry Co., Ltd .; 1.0 parts by weight).

(4) To the mixture obtained in the above (3), thiochol LP-282 (polysulfide polyether polymer, bifunctional, mercapto group content 2.0% by weight; 100 parts by weight, manufactured by Toray Thiokol Co., Ltd.) (100.0 parts by weight), mixed and left for 5 hours. As a result, the resin was completely cured, and the resin did not adhere to the finger even when touched with the finger.

Example 7 (1) Urethane prepolymer A obtained in Example 6- (1)
HEMA modified form (48.8 parts by weight) of Example 6
HEMA-modified urethane prepolymer B obtained in (2) (118.4 parts by weight), Thiokol LP-282 (manufactured by Toray Thiokol Co., Ltd., polysulfide polyether polymer, bifunctional, mercapto group content 2.0% by weight) ;
100 parts by weight) (100.0 parts by weight), calcium carbonate (260 parts by weight) and dioctyl phthalate (manufactured by Daihachi Chemical Co., Ltd .; 90 parts by weight) were put into a planetary mixer, mixed for 30 minutes, and used for a sealing agent. A composition was obtained.

(2) 1,5,5
-A solution consisting of diazabicyclo [4.3.0] nonene-5 (1 part by weight) and xylene (20 parts by weight) was added and mixed, and left to stand for 5 hours. The resin did not adhere to the finger.

Example 8 (1) Instead of HEMA, ethyl α- (hydroxymethyl) acrylate (abbreviated as RHM, manufactured by Nippon Shokubai Co., Ltd.)
A-E; 8.8 parts by weight), except that
The same procedure as in (1) was carried out to obtain the R of urethane prepolymer A.
An HMA-E modified product was obtained.

(2) Instead of HEMA, RHMA-E
(3.4 parts by weight), except that RHMA-E of urethane prepolymer B was used in exactly the same manner as in Example 6- (2).
A modified product was obtained.

(3) HEMA of urethane prepolymer A
RHMA- of urethane prepolymer A instead of modified product
Example 6 was repeated except that the E modified product (75.2 parts by weight) was used and the RHMA-E modified product of the urethane prepolymer B (182.3 parts by weight) was used instead of the HEMA modified product of the urethane prepolymer B. The procedure was performed exactly as in (3).

(4) To the mixture obtained in the above (3), thiochol LP-282 (polysulfide polyether polymer, bifunctional, mercapto group content: 2.0% by weight; 100 parts by weight, manufactured by Toray Thiokol Co., Ltd.) (100.0 parts by weight), mixed and left for 5 hours. As a result, the resin was completely cured, and the resin did not adhere to the finger even when touched with the finger.

Examples 9 to 15 and Comparative Examples 1 to 6 (1) Thiokol LP-56 (manufactured by Toray Thiokol Co., Ltd., polysulfide polymer, mercapto group content 2.2% by weight; 291 parts by weight) and Thiochol LP-3
(Manufactured by Toray Thiokol Co., Ltd., polysulfide polymer, mercapto group content 6.5% by weight; 100 parts by weight)
(Hereinafter, this mixture is referred to as an LP mixture).

(2) LP mixture (100 parts by weight), NK
Ester A-400 (manufactured by Shin-Nakamura Chemical Co., Ltd., polyethylene glycol # 400 diacrylate; 10.7
Parts by weight), light acrylate TMP-6EO-3A
(Ethylene oxide modified trimethylolpropane triacrylate; 1.2 parts by weight, manufactured by Kyoeisha Chemical Co., Ltd.) and the catalyst described in Table 1 (1.0 part by weight) were mixed.
When the catalyst was an acid salt, the acid salt was prepared from the corresponding amine compound and acid according to the method described in Example 2- (1) and used.

(3) The mixture obtained in (2) was allowed to stand at room temperature and touched with the back of a polyethylene dropper to measure the time until the resin did not adhere to the dropper. The results are shown in Table 1.

The curable composition of the present invention has an overwhelmingly high curing rate as compared with a usual curable composition using a tertiary amine as a catalyst, and exhibits a curability using DBU and its acid salt as a catalyst. It was found that the composition had a curing rate comparable to that of the hydrophilic composition.

[0083]

[Table 1]

[0084]

According to the present invention, there is provided a curable composition which is cured by a reaction in which a mercapto group is added to a carbon-carbon double bond, wherein the catalyst comprises (1) a structure not containing hydrogen directly bonded to a nitrogen atom. And (2) a curable composition having a structure other than DBU and its acid salt, and having a curing rate almost as good as that obtained when DBU and its acid salt are used as a catalyst.

Claims (9)

[Claims] (1) a compound having two or more mercapto groups in one molecule; and (B) a compound having two or more carbon-carbon double bonds in one molecule.
And (C) a tertiary amine compound having an amidine structure, which is a compound other than 1,8-diazabicyclo [5.4.0] undecene-7. 2. The component (B) comprises a double bond of a (meth) acryloyl group, a double bond of a 2-alkoxycarbonylallyloxy group, a double bond of a maleic acid derivative, a double bond of a fumaric acid derivative, Double bond of oleic acid derivative, double bond of cinnamic acid derivative, double bond of styrene derivative, double bond of α-methylstyrene derivative, double bond of vinyl group,
2. A compound having at least two carbon-carbon double bonds in one molecule selected from an allyl group double bond and a methallyl group double bond.
The curable composition according to the above. 3. The curable composition according to claim 1, wherein the component (B) is a compound having two or more (meth) acryloyl groups in one molecule. 4. The component (C) is a tertiary amine compound having a cyclic amidine structure and is a compound other than 1,8-diazabicyclo [5.4.0] undecene-7. Item 4. The curable composition according to any one of Items 1 to 3. 5. The component (C) is a compound selected from the group consisting of an imidazoline compound, a tetrahydropyrimidine compound, a triazabicycloalkene compound and a diazabicycloalkene compound, and is 1,8-diazabicyclo [5.4]. 0.0] The curable composition according to any one of claims 1 to 4, which is a compound other than undecene-7. 6. Component (C) is 1,2-dimethyl-1,1,
4,5,6-tetrahydropyrimidine, 7-methyl-
1,5,7-triazabicyclo [4.4.0] decene-
5,1,5-diazabicyclo [4.3.0] nonene-5
And a compound selected from 6-dibutylamino-1,8-diazabicyclo [5.4.0] undecene-7. 7. The curable composition according to claim 1, wherein the component (C) is used in the form of an acid salt. 8. The curable composition according to claim 1, wherein the component (B) contains a radical polymerization inhibitor and / or a radical polymerization inhibitor. 9. The curable composition according to claim 1, wherein the curable composition is used for an application selected from a paint, an adhesive and a sealing agent.