JPH09249727A - Moisture-curable composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a moisture-curable compsn. which can rapidly cure and evolves no carbon dioxide by combining a silylamine compd. with an isocyanate compd. SOLUTION: This compsn. comprises a silylamine compd. and an isocyanate compd. The silylamine compd. is pref. a compd. contg. two or more silylamine structures in its molecule. The isocyanate compd. is pref. a compd. having two or more isocyanate groups in its molecule. This silylamine structure is still pref. one represented by the formula (wherein R<1> represents a hydrogen atom, a 1-15 C alkyl group, a halogen-substd. alkyl group, a 6-20 C aryl group, a halogensubstd. aryl group, a 7-20 C aralkyl group, or a halogensubstd. aralkyl group; and R<2> , R<3> , and R<4> represent each a 1-10C alkyl group, a 6-10 C aryl group, or a vinyl group.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a moisture-curable composition containing a silylamine compound and an isocyanate compound. More specifically, it cures in a short time due to moisture in the air and has excellent physical properties.
The present invention relates to a moisture-curable composition that is preferably used as a coating material, an adhesive, or the like.

[0002]

2. Description of the Related Art As a moisture curable composition, a composition containing a compound having an isocyanate group is generally used, and curing proceeds by the reaction shown below.

[0003]

Embedded image However, the above composition has a problem that the curing is slow because the reaction between the isocyanate group and water is slow. further,
Since carbon dioxide gas is generated by the reaction between isocyanate and water, there is a problem that foaming occurs and the performance as a coating material, a coating material, an adhesive agent, etc. is deteriorated.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a moisture-curable composition which cures quickly and does not generate carbon dioxide gas.

[0005]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventor has found that a combination of a silylamine compound and an isocyanate compound causes rapid curing and generation of carbon dioxide gas. It was found that a moisture-curable composition that does not exist was obtained, and the present invention was reached.

That is, the present invention is a moisture-curable composition containing a silylamine compound and an isocyanate compound.

[0007]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.

The silylamine compound of the present invention is an organic substance in which a nitrogen atom and a silicon atom are directly bonded, and is preferably a compound having two or more silylamine structures in the molecule. The silylamine structure of the silylamine compound of the present invention preferably has the following general formula:

Embedded image (In the formula, R ¹ Is a hydrogen atom, an alkyl group having 1 to 15 carbon atoms, a halogen-substituted alkyl group, an aryl group having 6 to 20 carbon atoms.
Group, halogen-substituted aryl group, or C7-2
The aralkyl group of 0 and the halogen-substituted aralkyl group are shown.
R ² , R ³ , R ⁴ Represents an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or a vinyl group, and preferably R ² , R ³ and R ⁴ Represents a methyl group, an ethyl group, or a vinyl group. ), Or preferably the following general formula

Embedded image (In the formula, R ⁵ , R ⁶ , R ⁷ Represents an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or a vinyl group, and preferably R ⁵ , R ⁶ , R ⁷ Represents a methyl group, an ethyl group, or a vinyl group. ).

The silylamine structure of the silylamine compound of the present invention has a corresponding amino group shown below.

[Chemical 6] (In the formula, R ¹ Is a hydrogen atom, an alkyl group having 1 to 15 carbon atoms, a halogen-substituted alkyl group, an aryl group having 6 to 20 carbon atoms.
Group, halogen-substituted aryl group, or C7-2
The aralkyl group of 0 and the halogen-substituted aralkyl group are shown. ) Containing compound and the following general formula

Embedded image (In the formula, X represents a halogen atom such as Cl, Br or I, or an acetoxy group, and R ² , R ³ , R ⁴ Is 1 carbon
An alkyl group having 10 to 10, an aryl group having 6 to 10 carbon atoms, or a vinyl group, preferably R ² , R ³ , R ⁴
Is a methyl group, an ethyl group, or a vinyl group) and is obtained by a reaction with a silane compound or hexaalkyldisilazane.

Such a silylamine compound is easily hydrolyzed by moisture in the air to regenerate the starting compound containing an amino group and react with the isocyanate compound to give a cured product.

As such a silylamine compound,
For example, N, N'-bis (trimethylsilyl) ethylenediamine, N, N'-bis (trimethylsilyl) trimethylenediamine, N, N'-bis (trimethylsilyl)
Tetramethylenediamine, N, N'-bis (trimethylsilyl) hexamethylenediamine, N, N'-bis (trimethylsilyl) octamethylenediamine, N, N'-
Bis (trimethylsilyl) decamethylenediamine, N,
N'-bis (trimethylsilyl) 1,2-diaminopropane, N, N'-bis (trimethylsilyl) di- (3-
Aminopropyl) ether, N, N'-bis (trimethylsilyl) α, ω-di- (3-aminopropyl) -polyethylene glycol, N, N'-bis (trimethylsilyl) 1,2-diaminocyclohexane, N, N'-bis (trimethylsilyl) 1,3-diaminocyclohexane, N, N'-bis (trimethylsilyl) 1,4-diaminocyclohexane, N, N'-bis (trimethylsilyl) isophoronediamine, N, N'- Bis (trimethylsilyl) o-phenylenediamine, N, N'-bis (trimethylsilyl) m-phenylenediamine, N, N
′ -Bis (trimethylsilyl) p-phenylenediamine, N, N′-bis (trimethylsilyl) -4,4′-
Diaminobiphenyl, N, N'-bis (trimethylsilyl) -4,4'-diaminodiphenylmethane, N, N '
-Bis (trimethylsilyl) -4,4'-diaminodiphenyl ether, N, N'-bis (trimethylsilyl)
m-xylylenediamine, N, N'-bis (triethylsilyl) ethylenediamine, N, N'-bis (triethylsilyl) trimethylenediamine, N, N'-bis (triethylsilyl) tetramethylenediamine, N, N ' −
Bis (triethylsilyl) hexamethylenediamine,
N, N'-bis (triethylsilyl) octamethylenediamine, N, N'-bis (triethylsilyl) decamethylenediamine, N, N'-bis (triethylsilyl)
1,2-diaminopropane, N, N'-bis (triethylsilyl) di- (3-aminopropyl) ether, N,
N′-bis (triethylsilyl) α, ω-di- (3-aminopropyl) -polyethylene glycol, N, N′-
Bis (triethylsilyl) 1,2-diaminocyclohexane, N, N′-bis (triethylsilyl) 1,3-diaminocyclohexane, N, N′-bis (triethylsilyl) 1,4-diaminocyclohexane, N, N ′ -Bis (triethylsilyl) isophoronediamine, N, N
'-Bis (triethylsilyl) o-phenylenediamine, N, N'-bis (triethylsilyl) m-phenylenediamine, N, N'-bis (triethylsilyl) p-
Phenylenediamine, N, N'-bis (triethylsilyl) -4,4'-diaminobiphenyl, N, N'-bis (triethylsilyl) -4,4'diaminodiphenylmethane, N, N'-bis (triethylsilyl) -4,
4'-diaminodiphenyl ether, N, N'-bis (dimethylvinylsilyl) ethylenediamine, N, N '
-Bis (dimethylvinylsilyl) trimethylenediamine, N, N'-bis (dimethylvinylsilyl) tetramethylenediamine, N, N'-bis (dimethylvinylsilyl) hexamethylenediamine, N, N'-bis (dimethylvinyl) Silyl) o-phenylenediamine, N, N'-
Bis (dimethylvinylsilyl) m-phenylenediamine, N, N'-bis (dimethylvinylsilyl) p-phenylenediamine, N, N, N ', N'-tetrakis (trimethylsilyl) ethylenediamine, N, N, N', N
′ -Tetrakis (trimethylsilyl) trimethylenediamine, N, N, N ′, N′-tetrakis (trimethylsilyl) tetramethylenediamine, N, N, N ′, N′-
Tetrakis (trimethylsilyl) hexamethylenediamine, N, N, N ', N'-Tetrakis (trimethylsilyl) octamethylenediamine, N ,, N, N', N'-
Tetrakis (trimethylsilyl) decamethylenediamine, N, N, N ', N'-tetrakis (trimethylsilyl) 1,2-diaminopropane, N, N, N', N'-
Tetrakis (trimethylsilyl) di- (3-aminopropyl) ether, N, N, N ', N'-tetrakis (trimethylsilyl) α, ω-di- (3-aminopropyl)
-Polyethylene glycol, N, N, N ', N'-tetrakis (trimethylsilyl) 1,2-diaminocyclohexane, N, N, N', N'-tetrakis (trimethylsilyl) 1,3-diaminocyclohexane, N, N, N
′, N′-Tetrakis (trimethylsilyl) 1,4-diaminocyclohexane, N, N, N, N ′, N′-tetrakis (trimethylsilyl) isophoronediamine,
N, N, N ', N'-tetrakis (trimethylsilyl)
o-phenylenediamine, N, N, N ', N'-tetrakis (trimethylsilyl) m-phenylenediamine,
N, N, N ', N'-tetrakis (trimethylsilyl)
p-phenylenediamine, N, N, N ', N'-tetrakis (trimethylsilyl) -4,4'-diaminobiphenyl, N, N, N', N'-tetrakis (trimethylsilyl) -4,4'-diaminodiphenylmethane , N,
N, N ', N'-tetrakis (trimethylsilyl)-
4,4'-diaminodiphenyl ether, N, N, N
′, N′-Tetrakis (trimethylsilyl) m-xylylenediamine, N, N ,, N ′, N′-tetrakis (triethylsilyl) ethylenediamine, N ,, N, N ′,
N'-tetrakis (triethylsilyl) trimethylenediamine, N, N ,, N ', N'-tetrakis (triethylsilyl) tetramethylenediamine, N, N, N', N
'-Tetrakis (triethylsilyl) hexamethylenediamine, N, N, N', N'-Tetrakis (triethylsilyl) octamethylenediamine, N, N, N ', N'
-Tetrakis (triethylsilyl) decamethylenediamine, N, N, N ', N'-Tetrakis (triethylsilyl) 1,2-diaminopropane, N, N, N', N'-
Tetrakis (triethylsilyl) di- (3-aminopropyl) ether, N, N, N ', N'-tetrakis (triethylsilyl) α, ω-di- (3-aminopropyl)
-Polyethylene glycol, N, N, N ', N'-tetrakis (triethylsilyl) 1,2-diaminocyclohexane, N, N, N', N'-tetrakis (triethylsilyl) 1,3-diaminocyclohexane, N, N, N
′, N′-Tetrakis (triethylsilyl) 1,4-diaminocyclohexane, N, N, N ′, N′-tetrakis (triethylsilyl) isophoronediamine, N,
N, N ', N'-tetrakis (triethylsilyl) o-
Phenylenediamine, N, N, N ', N'-tetrakis (triethylsilyl) m-phenylenediamine, N,
N, N ', N'-tetrakis (triethylsilyl) p-
Phenylenediamine, N, N, N ', N'-tetrakis (triethylsilyl) -4,4'-diaminobiphenyl, N, N, N', N'-tetrakis (triethylsilyl) -4,4'diaminodiphenylmethane, N, N, N
′, N′-Tetrakis (triethylsilyl) -4,4 ′
-Diaminodiphenyl ether, N, N, N ', N'-
Tetrakis (dimethylvinylsilyl) ethylenediamine, N, N, N ', N'-Tetrakis (dimethylvinylsilyl) trimethylenediamine, N, N, N', N'-
Tetrakis (dimethylvinylsilyl) tetramethylenediamine, N, N, N ', N'-tetrakis (dimethylvinylsilyl) hexamethylenediamine, N, N, N',
N'-tetrakis (dimethylvinylsilyl) o-phenylenediamine, N, N, N ', N'-tetrakis (dimethylvinylsilyl) m-phenylenediamine, N, N,
N ', N'-tetrakis (dimethylvinylsilyl) p-
Phenylenediamine, 1,2-bis [1- (2,5-di-dimethylsila) pyrrolidinyl] ethane, 1,3-bis [1- (2,5-di-dimethylsila) pyrrolidinyl] propane, 1,4-bis [1- (2,5-Di-dimethylsila) pyrrolidinyl] butane, 1,6-bis [1-
(2,5-Di-dimethylsila) pyrrolidinyl] hexane, 1,2-bis [1- (2,5-di-dimethylsila) pyrrolidinyl] cyclohexane, 1,3-bis [1
-(2,5-Di-dimethylsila) pyrrolidinyl] cyclohexane, 1,4-bis [1- (2,5-di-dimethylsila) pyrrolidinyl] cyclohexane, 1,2-bis [1- (2,5-di- Dimethylsila) pyrrolidinyl] benzene, 1,3-bis [1- (2,5-di-dimethylsila) pyrrolidinyl] benzene, 1,4-bis [1-
(2,5-Di-dimethylsila) pyrrolidinyl] benzene, 4,4'-bis [1- (2,5-di-dimethylsila) pyrrolidinyl] diphenyl, 4,4'-bis [1-
(2,5-Di-dimethylsila) pyrrolidinyl] diphenylether, 4,4'-bis [1- (2,5-di-dimethylsila) pyrrolidinyl] diphenylmethane, 1,2-
Bis [1- (2,6-di-dimethylsila) piperidinyl] ethane, 1,3-bis [1- (2,6-di-dimethylsila) piperidinyl] propane, 1,4-bis [1-
(2,6-di-dimethylsila) piperidinyl] butane,
1,6-bis [1- (2,6-di-dimethylsila) piperidinyl] hexane, 1,2-bis [1- (2,6-di-dimethylsila) piperidinyl] cyclohexane, 1,
3-bis [1- (2,6-di-dimethylsila) piperidinyl] cyclohexane, 1,4-bis [1- (2,6-
Di-dimethylsila) piperidinyl] cyclohexane,
1,2-bis [1- (2,6-di-dimethylsila) piperidinyl] benzene, 1,3-bis [1- (2,6-di-dimethylsila) piperidinyl] benzene, 1,4-bis [1- (2,6-Di-dimethylsila) piperidinyl]
Benzene, 4,4'-bis [1- (2,6-di-dimethylsila) piperidinyl] diphenyl, 4,4'-bis [1- (2,6-di-dimethylsila) piperidinyl] diphenylether, 4 4'-bis [1- (2,6-di-dimethylsila) piperidinyl] diphenylmethane,
N, N'-dimethyl-N, N'-bis (trimethylsilyl) ethylenediamine, N, N'-dimethyl-N, N '
-Bis (trimethylsilyl) trimethylene diamine,
N, N'-dimethyl-N, N'-bis (trimethylsilyl) tetramethylenediamine, N, N'-dimethyl-
N, N'-bis (trimethylsilyl) hexamethylenediamine, N, N'-dimethyl-N, N'-bis (trimethylsilyl) octamethylenediamine, N, N'-dimethyl-N, N'-bis (trimethylsilyl) deca Methylenediamine, N, N'-dimethyl-N, N'-bis (trimethylsilyl) 1,2-diaminopropane, N, N '
-Dimethyl-N, N'-bis (trimethylsilyl) di-
(3-aminopropyl) ether, N, N'-dimethyl-N, N'-bis (trimethylsilyl) α, ω-di-
(3-aminopropyl) -polyethylene glycol,
N, N'-dimethyl-N, N'-bis (trimethylsilyl) 1,2-diaminocyclohexane, N, N'-dimethyl-N, N'-bis (trimethylsilyl) 1,3-diaminocyclohexane, N, N ' -Dimethyl-N, N '
-Bis (trimethylsilyl) 1,4-diaminocyclohexane, N, N'-dimethyl-N, N'-bis (trimethylsilyl) isophoronediamine, N, N'-dimethyl-N, N'-bis (trimethylsilyl) o- Phenylenediamine, N, N'-dimethyl-N, N'-bis (trimethylsilyl) m-phenylenediamine, N, N'-
Dimethyl-N, N'-bis (trimethylsilyl) p-phenylenediamine, N, N'-dimethyl-N, N'-bis (trimethylsilyl) -4,4'-diaminobiphenyl, N, N'-dimethyl-N, N'-bis (trimethylsilyl) -4,4'-diaminodiphenylmethane, N,
N'-dimethyl-N, N'-bis (trimethylsilyl)
-4,4'-diaminodiphenyl ether, N, N'-
Dimethyl-N, N'-bis (trimethylsilyl) m-xylylenediamine, N-methyl-N, N ', N'-tris (trimethylsilyl) ethylenediamine, N-methyl-N, N', N'-tris (trimethylsilyl) ) Trimethylenediamine, N, N'-dimethyl-N, N'-bis (trimethylsilyl) tetramethylenediamine, N-methyl-N, N ', N'-tris (trimethylsilyl) hexamethylenediamine, N-methyl-N , N ', N'-
Tris (trimethylsilyl) octamethylenediamine,
N-methyl-N, N ', N'-tris (trimethylsilyl) decamethylenediamine, N-methyl-N, N', N
′ -Tris (trimethylsilyl) 1,2-diaminopropane, N-methyl-N, N ′, N′-tris (trimethylsilyl) di- (3-aminopropyl) ether, N-
Methyl-N, N ', N'-tris (trimethylsilyl)
α, ω-di- (3-aminopropyl) -polyethylene glycol, N-methyl-N, N ′, N′-tris (trimethylsilyl) 1,2-diaminocyclohexane, N-
Methyl-N, N ', N'-tris (trimethylsilyl)
1,3-diaminocyclohexane, N-methyl-N, N
Examples thereof include, but are not limited to, ', N'-tris (trimethylsilyl) 1,4-diaminocyclohexane and N-methyl-N, N', N'-tris (trimethylsilyl) isophoronediamine.

Among these silylamine compounds, N,
N'-bis (trimethylsilyl) diamino compound, N,
N, N ', N'-tetrakis (trimethylsilyl) diamino compounds are more preferably used.

The isocyanate compound which is the other component of the present invention is a compound having an isocyanate group in the molecule, preferably a compound having two or more isocyanate groups in the molecule. is there.

As such an isocyanate compound, both low molecular weight polyisocyanate and high molecular weight polyisocyanate can be used. Specifically, for example, hexamethylene diisocyanate and isophorone diisocyanate are used. Net, tolylene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate
, Hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, trimethylolpropane and other low molecular weight polyols, hexamethylene diisocyanate
Adduct, isophorone diisocyanate adduct, tolylene diisocyanate adduct, diphenylmethane diisocyanate adduct, xylylene diisocyanate adduct, hydrogenated diphenylmethane diisocyanate adduct , Hydrogenated xylylene diisocyanate adduct, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyester diol, polycaprolactone diol and other high molecular weight polyol hexamethylene Diisocyanate adduct, Isophorone diisocyanate adduct, Tolylene diisocyanate adduct, Diphenylmethane diisocyanate adduct, Xylylene diisocyanate adduct, Hydrogenated diphenylmethane diisocyanate Examples thereof include a net adduct and a hydrogenated xylylene diisocyanate adduct. But it is not limited thereto.

The compounding amount of the silylamine compound and the isocyanate compound is preferably 0.1 to 1.2, more preferably 0.5 to 1.1, of the silylamine structure with respect to one isocyanate group. Chosen to be. When the silylamine structure is less than 0.1 or exceeds 1.2,
Curability tends to be insufficient.

A moisture-curable composition is prepared from a silylamine compound and an isocyanate compound, and if necessary, this is dissolved in a solvent, coated on a substrate or the like, and then left in the air to obtain a cured film. be able to. If necessary, a pigment, an inorganic filler, a curing catalyst such as a tin compound, and the like can be added to these compositions.

[0017]

EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited to the following examples.

Synthesis Example 1 11.6 g of hexamethylenediamine and 21.4 g of triethylamine were dissolved in benzene, and a benzene solution of 23.9 g of trimethylchlorosilane was added dropwise thereto. After the generated triethylamine hydrochloride was filtered off, benzene was distilled off to obtain N, N'-bis (trimethylsilyl) hexamethylenediamine. Synthesis Example 2 4,4′-diaminodiphenylmethane 1 in benzene
9.8 g and 68.6 g of tripropylamine were dissolved.
A benzene solution containing 44 g of trimethylsilyl iodide was added dropwise to the mixture, and the mixture was reacted at room temperature and then further reacted under reflux. After filtering off the produced tripropylamine hydrochloride,
By distilling off benzene, N, N, N ', N'-
Tetrakis (trimethylsilyl) 4,4'-diaminodiphenylmethane was obtained.

Example 1 26 g of N, N'-bis (trimethylsilyl) hexamethylenediamine and hexamethylene diisocyanate 16.
8 g was dissolved in a mixed solvent of methyl ethyl ketone / toluene to prepare a moisture curable composition. This was applied on a glass plate and left in air at room temperature for 5 minutes to obtain a cured film having a film thickness of 5 μm.

Example 2 N, N, N ', N'-tetrakis (trimethylsilyl)
A moisture-curable composition was prepared by dissolving 39.2 g of 4,4′-diaminodiphenylmethane and 25 g of diphenylmethane diisocyanate in a mixed solvent of methyl ethyl ketone / toluene. Apply this on an iron plate, and in the air at room temperature 2
After leaving for a minute, a cured film having a film thickness of 5 μm was obtained.

[0021]

According to the present invention, a moisture-curable composition excellent in curability and free from foaming can be obtained, and a coating material, a coating material,
It is preferably used as an adhesive or the like.

Claims (10)

[Claims] 1. A moisture-curable composition comprising a silylamine compound and an isocyanate compound. 2. The moisture-curable composition according to claim 1, wherein the silylamine compound is a compound having two or more silylamine structures in the molecule. 3. The moisture-curable composition according to claim 1, wherein the isocyanate compound is a compound having two or more isocyanate groups in the molecule. 4. The silylamine structure has the general formula: (In the formula, R ¹ Is a hydrogen atom, an alkyl group having 1 to 15 carbon atoms, a halogen-substituted alkyl group, an aryl group having 6 to 20 carbon atoms.
Group, halogen-substituted aryl group, or C7-2
The aralkyl group of 0 and the halogen-substituted aralkyl group are shown.
R ² , R ³ , R ⁴ Represents an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or a vinyl group. ) Is represented by this), The moisture curable composition of Claim 2 characterized by the above-mentioned. 5. The silylamine structure according to claim 4, wherein R ² , R ³ and R ^{4 are} Is a methyl group, an ethyl group, or
The moisture-curable composition according to claim 4, which is a vinyl group. 6. The silylamine structure has the general formula: (In the formula, R ⁵ , R ⁶ , R ⁷ Represents an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or a vinyl group. ) Is represented by this), The moisture curable composition of Claim 2 characterized by the above-mentioned. 7. The silylamine structure according to claim 6, wherein R ⁵ , R ⁶ and R ^{7 are} Is a methyl group, an ethyl group, or
The moisture-curable composition according to claim 6, which is a vinyl group. 8. The moisture curable composition according to claim 1, wherein the silylamine compound is an N, N′-bis (trimethylsilyl) diamino compound. 9. The silylamine compound is N, N, N ',
The moisture curable composition according to claim 1, which is an N'-tetrakis (trimethylsilyl) diamino compound. 10. The moisture-curable composition according to claim 1, which contains 0.1 to 1.2 silylamine structures per one isocyanate group.