JPH09132637A - Curable composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable epoxy resin composition which can be moisture- cured at room temperature. SOLUTION: This curable composition essentially comprises an epoxy resin having one or more epoxy groups in the molecule, a protected-amino-containing compound which can be easily hydrolyzed in the presence of water into a free- amino-containing compound, and a silane-modified compound obtained by reacting a polyether polyepoxy obtained by epoxidizing the terminals of a polyetherpolyol and an aminosilane compound and/or a mercaptosilane compound each of which has hydrolyzable alkoxyl groups at the terminals in an equivalent ratio (epoxy groups/(amino groups and/or the mercapto groups)=1/1.0 to 1/1.5.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an epoxy resin curing composition that can be moisture-cured at room temperature, and more specifically, it is a one-component curing agent that has excellent storage stability and can be easily cured by moisture in the atmosphere. The present invention relates to an epoxy-silicone-based polyether polyepoxy curable composition.

[0002]

2. Description of the Related Art
As a moisture-curable one-component curable composition, silicone and urethane are generally known.
Although it has excellent weather resistance, it has poor adhesion to the underlying surface, insufficient mechanical strength, and is problematic in terms of cost. On the other hand, in the case of the urethane type, although the elasticity is excellent, the mechanical strength is inferior and the adhesiveness to the substrate is insufficient. Therefore, both are widely used as joint materials and sealing materials, but they are unsuitable as structural resins in terms of mechanical strength. However, an epoxy resin is generally known as such a structural resin and has been put to practical use, but when it is cured at room temperature, it has a problem in workability due to its two-component property. Attempts have been made to make it a component, but the balance between storage stability and curability is extremely difficult, and it has not been put to practical use.

[0003]

As a result of intensive studies to solve the above problems, the present inventors have found that they have excellent storage stability and curability, and have mechanical strength, elasticity and flexibility as a structural resin. Then, a novel one-component epoxy-silicone polyether polyether epoxy curable composition having excellent adhesion to glass, ceramics, etc. was found, and the present invention was completed.

That is, according to the present invention, an epoxy resin having at least one epoxy group in the molecule as an essential component and a protection which can be easily hydrolyzed in the presence of water to be converted into a free amino group. Amino group-containing compound, polyetherpolyepoxy (-a) obtained by epoxidizing the end of polyetherpolyol, and aminosilane compound (-having a hydrolyzable alkoxy group at the end)
b) and / or mercaptosilane compound (-c),
(Epoxy group) / (Amino group and / or mercapto group)
The present invention provides a curable composition containing a silane-modified epoxy compound obtained by reacting in the range of 1 / 1.0 to 1 / 1.5 (equivalent ratio).

Preferred as at least one epoxy resin in the molecule used in the present invention are:
The following general formula:

[0006]

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An epoxy resin (I-1) having an average of more than one substituted or unsubstituted glycidyl ether group represented by the formula (wherein Z represents a hydrogen atom, a methyl group or an ethyl group) in the molecule, The general formula for:

[0008]

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An epoxy resin (I-2) having an average of more than one substituted or unsubstituted glycidyl ester group represented by the formula (wherein Z represents a hydrogen atom, a methyl group or an ethyl group) in the molecule, The general formula for:

[0010]

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(Wherein Z represents a hydrogen atom, a methyl group or an ethyl group), which is N-substituted or unsubstituted 1,2-
An epoxy resin (I-3) having an average of more than one epoxypropyl group in the molecule is included. Further, particularly preferable epoxy resin (I) has an epoxy equivalent of 180 to
It is 500 epoxy resin.

An epoxy resin (I-) having more than one substituted or unsubstituted glycidyl ether group in the molecule.
1) includes an epoxy resin obtained by converting a phenolic hydroxyl group into a glycidyl ether and an epoxy resin obtained by converting an alcoholic hydroxyl group into a glycidyl ether, and a preferable example of the epoxy resin (I-1) is 1 or Polyglycidyl ethers of polyhydric phenols having two or more aromatic nuclei (I-1-1) and 1
A polyglycidyl ether (I-1-2) of an alcoholic polyhydroxyl compound derived from an addition reaction of a polyhydric phenol having 1 or 2 or more aromatic nuclei with an alkylene oxide having 2 to 4 carbon atoms, and the like. Can be mentioned.

The polyglycidyl ether (I-1-1) is, for example, a polyhydric phenol (A) having at least one aromatic nucleus and an epihalohydrin (b), which is a basic catalyst or basic such as sodium hydroxide. An epoxy resin containing as a main reaction product a polyglycidyl ether as obtained by reacting in a conventional manner in the presence of a reaction amount of a compound,
Polyhalohydrin ether obtained by reacting a polyhydric phenol (A) having at least one aromatic nucleus with epihalohydrin (b) in the presence of an acidic catalyst such as boron trifluoride in a conventional manner. Or a basic compound such as sodium hydroxide, an epoxy resin, or a polyhydric phenol (A) having at least one aromatic nucleus and epihalohydrin (b) as a catalyst of a basic catalyst such as triethylamine. A polyhalohydrin ether obtained by reacting in the presence of an amount in a conventional manner,
An epoxy resin obtained by reacting with a basic compound such as sodium hydroxide.

Similarly, polyglycidyl ether (I-1-
2) means, for example, a polyhydroxyl compound (B) and an epihalohydrin (b) derived by an addition reaction of a polyhydric phenol having at least one aromatic nucleus and an alkylene oxide having 2 to 4 carbon atoms. A polyhalohydrin ether obtained by reacting by a conventional method in the presence of a catalytic amount of an acidic catalyst such as boron trifluoride and a polyglycidyl ether such as obtained by reacting a basic compound such as sodium hydroxide. It is an epoxy resin containing as a main reaction product.

The polyhydric phenol (A) having at least one aromatic nucleus includes a mononuclear polyhydric phenol (A-1) having one aromatic nucleus and a polynuclear compound having two or more aromatic nuclei. There is a polyhydric phenol (A-2).

Examples of such mononuclear polyphenols (A-1) include resorcinol, hydroquinone, pyrocatechol, phloroglucinol, 1,5-dihydroxynaphthalene, 2,7-dihydroxynaphthane,
2,6-dihydroxynaphthalene and the like can be mentioned.

Further, examples of the polynuclear polyhydric phenol (A-2) include the following general formula (1):

[0018]

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[In the formula, Ar is an aromatic divalent hydrocarbon such as a naphthylene group and a phenylene group, and a phenylene group is preferred for the purpose of the present invention. Y ′ and Y ₁ may be the same or different, and are methyl group, n-propyl group, n-butyl group, n-
Alkyl group such as hexyl group and n-octyl group, preferably alkyl group having up to 4 carbon atoms, or halogen atom, that is, chlorine atom, bromine atom, iodine atom or fluorine atom, methoxy group, methoxymethyl group, ethoxy group. An alkoxy group such as a group, an ethoxyethyl group, an n-butoxy group and an amyloxy group is preferably an alkoxy group having a maximum of 4 carbon atoms. When a substituent other than a hydroxyl group is present in either or both of the aromatic divalent hydrocarbon groups, these substituents may be the same or different. m
And z are integers having a value from 0 (zero) corresponding to the number of hydrogen atoms of the aromatic ring (Ar) that can be substituted by a substituent to a maximum value, and can be the same or different. R ₁ is, for example,

[0020]

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Or an alkylene group such as methylene group, ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, 2-ethylhexamethylene group, octamethylene group, nonamethylene group, decamethylene group, or alkylidene group such as ethylidene group. Group, propylidene group, isopropylidene group, isobutylidene group,
Amylidene group, isoamylidene group, 1-phenylethylidene group, cycloaliphatic group such as 1,4-cyclohexylene group, 1,3-cyclohexylene group, cyclohexylidene group, or halogenated alkylene group or halogenated group Alkylidene groups or halogenated cycloaliphatic groups or alkoxy- and aryloxy-substituted alkylidene groups or alkoxy- and aryloxy-substituted alkylene groups or alkoxy- and aryloxy-substituted cycloaliphatic groups such as Methoxymethylene group, ethoxymethylene group, ethoxyethylene group, 2-ethoxytrimethylene group, 3-ethoxypentamethylene group, 1,4- (2-methoxycyclohexane)
Group, phenoxyethylene group, 2-phenoxytrimethylene group, 1,3- (2-phenoxycyclohexane) group, or aryl-substituted alkylene group such as phenylethylene group, 2-phenyltrimethylene group, 1-phenylpentamethylene group , 2-phenyl decamethylene group, or aromatic group such as phenylene group, naphthylene group, or halogenated aromatic group such as 1,4- (2-chlorophenylene) group, 1,4- (2-bromophenylene) Base,
1,4- (2-Fluorophenylene) group, or alkoxy- and aryloxy-substituted aromatic groups such as 1,4-
(2-methoxyphenylene) group, 1,4- (2-ethoxyphenylene) group, 1,4- (2-n-propoxyphenylene) group, 1,4- (2-phenoxyphenylene) group, or alkyl-substituted Aromatic groups such as 1,4- (2-methylphenylene) group, 1,4- (2-ethylphenylene)
Group, 1,4- (2-n-propylphenylene) group, 1,4-
A divalent group such as a divalent hydrocarbon group such as a (2-n-butylphenylene) group or a 1,4- (2-n-dodecylphenylene) group, or R ₁ is, for example, a compound represented by the formula:

[0022]

[Chemical 6]

It may be a ring fused to one Ar group as in the case of the compound represented by, or R ₁ is a polyethoxy group, a polypropoxy group, a polythioethoxy group, a polybutoxy group or a polybutoxy group. It can also be a polyalkoxy group such as a phenylethoxy group, or R ₁ can be a group containing a silicon atom such as a polydimethylsiloxy group, a polydiphenylsiloxy group, a polymethylphenylsiloxy group, or R ₁ can be two or more alkylene or alkylidene groups separated by an aromatic ring, a tertiary amino group ether linkage, a carbonyl group or a sulfur or sulfur containing linkage such as a sulfoxide]. There are polynuclear dihydric phenols.

Of these polynuclear dihydric phenols, particularly preferred are the following general formulas (1-1)

[0025]

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(In the formula, Y'and Y ₁ have the same meanings as described above, m and z are values of 0 to 4, and R ₁ is preferably 1 to
Alkylene or alkylidene groups or formulas having 3 carbon atoms

[0027]

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A polynuclear dihydric phenol represented by a saturated group represented by

Among the examples of such dihydric phenols are 2,2-bis (4-hydroxyphenyl) propane, 2,4'-dihydroxydiphenylmethane, bis (2-hydroxyphenyl) methane, commonly referred to as bisphenol A, Bis (4-hydroxyphenyl) methane, bis (4-hydroxy-2,6-dimethyl-3-methoxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane,
1,2-bis (4-hydroxyphenyl) ethane, 1,1-
Bis (4-hydroxy-2-chlorophenyl) ethane,
1,1-bis (3,5-dimethyl-4-hydroxyphenyl) ethane, 1,3-bis (3-methyl-4-hydroxyphenyl) propane, 2,2-bis (3,5-dichloro-4-)
Hydroxyphenyl) propane, 2,2-bis (3-phenyl-4-hydroxyphenyl) propane, 2,2-bis (3-isopropyl-4-hydroxyphenyl) propane, 2,2-bis (2-isopropyl-4) -Hydroxyphenyl) propane, 2,2-bis (4-hydroxynaphthyl) propane, 2,2-bis (4-hydroxyphenyl)
Pentane, 3,3-bis (4-hydroxyphenyl) pentane, 2,2-bis (4-hydroxyphenyl) heptane, bis (4-hydroxyphenyl) methane, bis (4
-Hydroxyphenyl) cyclohexylmethane, 1,2-
Bis (4-hydroxyphenyl) -1,2-bis (phenyl) propane, 2,2-bis (4-hydroxyphenyl)
Bis (hydroxyphenyl) alkane such as -1-phenylpropane or 4,4'-dihydroxybiphenyl, 2,
Dihydroxybiphenyl such as 2'-dihydroxybiphenyl, 2,4'-dihydroxybiphenyl or bis (4-
Hydroxyphenyl) sulfone, 2,4'-dihydroxydiphenylsulfone, chloro-2,4-dihydroxyphenylsulfone, 5-chloro-4,4'-dihydroxydiphenylsulfone, 3'-chloro-4,4'-dihydroxydiphenylsulfone Such as di (hydroxyphenyl) sulfone or bis (4-hydroxyphenyl) ether, 4,3'-
(Or 4,2'- or 2,2'-dihydroxydiphenyl) ether, 4,4'-dihydroxy-2,6-dimethyldiphenyl ether, bis (4-hydroxy-3-isobutylphenyl) ether, bis (4-hydroxy) -3-isopropylphenyl) ether, bis (4-hydroxy-3-)
Chlorphenyl) ether, bis (4-hydroxy-3)
-Fluorphenyl) ether, bis (4-hydroxy-3-bromophenyl) ether, bis (4-hydroxynaphthyl) ether, bis (4-hydroxy-3-chloronaphthyl) ether, bis (2-hydroxybiphenyl) ether , 4,4'-dihydroxy-2,6-dimethoxy-phenyl ether, 4,4'-dihydroxy-2,5-diethoxydiphenyl ether, such as di (hydroxyphenyl) ether, and 1,1-bis (4-Hydroxyphenyl) -2-phenylethane, 1,3,3-trimethyl-1- (4-hydroxyphenyl) -6-hydroxyindane, 2,4-bis (p-hydroxyphenyl)-
4-Methylpentane is also suitable.

Further, another preferred group of such polynuclear dihydric phenols is represented by the following general formula (1-2).

[0031]

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(Wherein R ₃ is a methyl or ethyl group, R ₂ is an alkylidene group having 1 to 9 carbon atoms or another alkylene group, and p is 0 to 4), for example, 1, Four
-Bis (4-hydroxybenzyl) benzene, 1,4-bis (4-hydroxybenzyl) tetramethylbenzene,
1,4-bis (4-hydroxybenzyl) tetraethylbenzene, 1,4-bis (p-hydroxycumyl) benzene, 1,3-bis (p-hydroxycumyl) benzene and the like can be mentioned.

Other polynuclear polyhydric phenols (A-2) include, for example, initial condensation products of phenols and carbonyl compounds (eg, phenol resin initial condensation products, condensation reaction formation of phenol and acrolein). Stuff,
Condensation reaction product of phenol and glyoxal, condensation reaction product of phenol and pentanediallyl, condensation reaction product of resorcinol and acetone, xylene-phenol-formaldehyde initial condensation product), condensation of phenols and polychloromethylated aromatic compounds Reaction products (eg:
A condensation reaction product of phenol and bischloromethylxylene) and the like can be mentioned.

The polyhydroxyl compound (B) means the polyhydric compound (A) having at least one aromatic nucleus and the alkylene oxide in the presence of a catalyst for promoting the reaction between the OH group and the epoxy group. Is bonded to the phenol residue by an ether bond obtained by reacting with -ROH (in the formula, R represents an alkylene group derived from alkylene oxide) or (and)-(RO) _n H (in the formula, R is an alkylene group derived from alkylene oxide, and one polyoxyalkylene chain may contain different alkylene groups, and n represents 2 or an integer of 2 or more indicating the polymerization number of the oxyalkylene group). It is a compound that has. In this case, the ratio of the polyhydric phenol (A) and the alkylene oxide is 1: 1 (mol: mol).
However, the polyhydric phenol (A) is preferable.
The ratio of alkylene oxide to OH group is 1: 1 to
It is 10, preferably 1: 1 to 3 (equivalent: equivalent).

Examples of the above-mentioned alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, etc., and those which generate a side chain when they react with the polyhydric phenol (A) to form an ether bond are particularly preferable. As such, there are propylene oxide, 1,2-butylene oxide and 2,3-butylene oxide, and propylene oxide is particularly preferable.

Such a polyhydroxyl compound,
A particularly preferred group is the following general formula

[0037]

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(In the formula, Y ', Y ₁ , m, z and R ₁ are the same as those in the above-mentioned general formula (1-1), and R is a carbon number of 2-4.
Alkylene groups, n ₁ and n ₂ have a value of 1 to 3).

Still another preferred group of such polyhydroxyl compounds is the following general formula

[0040]

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(In the formula, R ₂ , R ₃ and p are represented by the general formula (1-
The same as that of 2), R is an alkylene group having 2 to 4 carbon atoms, and n ₁ and n ₂ have a value of 1 to 3).

The epihalohydrin (b) is the following general formula (2):

[0043]

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(Wherein Z is a hydrogen atom, a methyl group, an ethyl group, and X'is a halogen atom). Examples of such epihalohydrin (b) include, for example, epichlorohydrin and epihalohydrin. Bromohydrin, 1,2-epoxy-2-methyl-3-chloropropane, 1,2-epoxy-2-ethyl-3-chloropropane and the like can be mentioned.

Acidic catalysts that promote the reaction of the epihalohydrin (b) with the polyhydric phenol (A) or the polyhydroxy compound (B) include boron trifluoride, stannic chloride, zinc chloride and ferric chloride. Lewis acids such as, and derivatives showing these activities (eg, boron trifluoride-ether complex compound)
Alternatively, a mixture of these can be used.

Similarly, as the basic catalyst for promoting the reaction between the epihalohydrin (b) and the polyhydric phenol (A), an alkali metal hydroxide (eg sodium hydroxide), an alkali metal alcoholate (eg sodium) is used. Ethylate), tertiary amine compounds (eg triethylamine, triethanolamine), quaternary ammonium compounds (eg tetramethylammonium bromide), or mixtures thereof can be used, however glycidyl is present at the same time as the reaction. Alkali metal hydroxides (eg sodium hydroxide) and alumina are basic compounds that form ethers or halohydrin ethers formed as a result of the reaction by cyclization by dehydrohalogenation reaction to form glycidyl ethers. Acid alkali metal salts (eg aluminic acid) Thorium), and the like can be used conveniently.

It is needless to say that these catalysts or basic compounds can be used as they are or as a suitable inorganic or / and organic solvent solution.

The epoxy resin (I-2) having an average of more than one substituted or unsubstituted glycidyl ester group in the molecule includes polyglycidyl ester of aliphatic polycarboxylic acid or aromatic polycarboxylic acid. For example, the epihalohydrin (b) represented by the general formula (2) above
It also includes an epoxy resin obtained by polymerizing glycidyl methacrylate synthesized from methacrylic acid and methacrylic acid.

Further, examples of the epoxy resin (I-3) having an average of more than one N-substituted or unsubstituted 1,2-epoxypropyl group in the molecule include aromatic amines (for example, aniline or nuclei). Aniline having an alkyl substituent)
And an epihalohydrin (b) represented by the above general formula (2)
And an epoxy resin obtained from an initial condensation product of an aromatic amine and an aldehyde (for example, aniline-formaldehyde initial condensation product, aniline-phenol-formaldehyde initial condensation product) and epihalohydrin (b). .

In addition, conventionally known adjacent epoxy group-containing epoxy resins such as various epoxy resins described in "Production and Application of Epoxy Resins" (edited by Hiroshi Kakiuchi) are used.

The protected amino group-containing compound used in the present invention, which can be easily hydrolyzed in the presence of water and converted into a free amino group, can be represented by the following general formula (II)

[0052]

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(In the formula, R ₁ represents a hydrogen atom or a monovalent hydrocarbon group such as an alkyl group or a cycloalkyl group, and R ₂ represents a monovalent hydrocarbon group such as an alkyl group or a cycloalkyl group) Examples thereof include ketimine compounds and aldimine compounds having at least one group represented by Although not essential, enamine compounds having a secondary amino group protected with a ketone or aldehyde may be contained in the same molecule.

The polyamine compound used for producing the above-mentioned protected amino group-containing compound may be any of an aliphatic type, an aromatic type and an alicyclic type. The polyamine compound needs to have at least one primary amino group that undergoes a curing reaction with the epoxy resin, but the primary amino group equivalent is preferably in the range of about 30 to 1000. The polyamine compound has a number average molecular weight of 4000
Below, it is preferable to be in the range of 3000 or less. As a polyamine compound that can be suitably used, ethylenediamine, propylenediamine, butylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexamethylenediamine, trimethylhexamethylenediamine, N-aminoethylpiperazine, 1, 2-
Aliphatic polyamines such as diaminopropane, iminobispropylamine, methyliminobispropylamine,
aromatic polyamines such as m, p-xylylenediamine,
Isophorone diamine, 1,3-bisaminomethylcyclohexane, 1,4-bisaminopropylpiperazine, 1,3-
Bisaminocyclohexane, di (aminodicyclohexyl) methane, 3,3′-dimethyldi (aminocyclohexyl) methane, 1-cyclohexylamino-3-aminopropane, 1,4-diaminocyclohexane, 1,3-diaminocyclopentane, di ( Aminocyclohexyl) methane, di (aminocyclohexyl) sulfone, 1,3-di (aminocyclohexyl) propane, 4-isopropyl-1,2-diaminocyclohexane, 2,4-diaminocyclohexane, N, N'-diethyl-1, Aliphatic polyamines such as 4-diaminocyclohexane, 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane, 3-aminomethyl-3,3,5-trimethylcyclohexylamine, and polyoxypropylenediamine and other polyamines Examples include ether diamines.

The second polyamine compound has a second intramolecular compound.
When a secondary amino group is contained, the secondary amino group is enamined with a ketone compound or an aldehyde compound, or an adduct obtained by reacting with an epoxy group-containing compound, an isocyanate group-containing compound, a vinyl group-containing compound or the like is used. Is desirable.

Ketiminization of the above polyamine compound,
Examples of the ketone compound that can be used for aldimination and enamine conversion include any commonly used ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclohexanone, cyclopentanone, acetophenone, and trimethylcyclohexanone. . Examples of aldehyde compounds include acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde, diethylacetaldehyde, benzaldehyde and the like.

The reaction of the polyamine compound with these ketones or aldehydes can be carried out by a known method, in which substantially all the primary amino groups present react with the ketones or aldehydes. It is desirable to use quantitative proportions and reaction conditions, which can be prepared, for example, by continuously removing water from the reaction mixture by condensation by azeotropic distillation.

In the silane-modified epoxy compound used in the present invention, the preferred polyether polyepoxy (-a) in which the end of the polyether polyol is epoxidized is that the polyether polyol and epihalohydrin are acidic such as boron trifluoride. Epoxy equivalent obtained by reacting a polyhalohydrin ether obtained by reacting by a conventional method in the presence of a catalytic amount of a catalyst with a basic compound such as sodium hydroxide 500 to 5000, number average molecular weight of 1000 to 10000 belongs to.

Preferred examples of the above polyether polyols include, for example, the following general formula: R [(OR ₁ ) _n OH] _p (wherein R is a polyhydric alcohol residue; (OR ₁ ) _n is a carbon number 2).
~ A polyoxyalkylene chain consisting of an oxyalkylene group having 4 alkylene groups; n is a number indicating the degree of polymerization of the oxyalkylene group and has a molecular weight of 900 to 9900; p is preferably 2 to 6 Is a number).

Preferred examples of the polyhydric alcohol corresponding to the polyhydric alcohol residue in the above general formula include, for example, aliphatic dihydric alcohols (eg ethylene glycol, propylene glycol, 1,4-butylene glycol, neopentane glycol). ), Trihydric alcohol (eg, glycerin, trioxyisobutane, 1,2,3-butanetriol, 1,
2,3-Pentanetriol, 2-methyl-1,2,3-propanetriol, 2-methyl-2,3,4-butanetriol, 2-ethyl-1,2,3-butanetriol, 2,3, 4-
Pentanetriol, 2,3,4-hexanetriol, 4
-Propyl-3,4,5-heptanetriol, 2,4-dimethyl-2,3,4-pentanetriol, pentamethylglycerin, pentaglycerin, 1,2,4-butanetriol, 1,2,4-pentane Triol, trimethylolpropane, etc., tetrahydric alcohol (eg erythritol, pentaerythritol, 1,2,3,4-pentanetetrol, 2,3,
4,5-Hexanetetrol, 1,2,3,5-Pentanetetrol, 1,3,4,5-Hexanetetrol, etc.), pentahydric alcohols (eg Adnit, arabite, xylit, etc.),
Hexahydric alcohols (eg, sorbit, mannitol, idite, etc.) and the like can be mentioned.

The polyhydric alcohol is preferably a dihydric to tetrahydric alcohol, particularly propylene glycol and glycerin.

Further, the polyether polyol represented by the above general formula is produced by adding an alkylene oxide having 2 to 4 carbon atoms to the polyhydric alcohol by a conventional method so that the alkylene oxide has a desired molecular weight. You can

Examples of the alkylene oxide having 2 to 4 carbon atoms include ethylene oxide, propylene oxide and butylene oxide, and propylene oxide is particularly preferably used.

Further, polytetramethylene glycol obtained by ring-opening polymerization of tetrahydrofuran, hydroxyl group-terminated liquid polybutadiene, hydroxyl group-containing glyceride such as castor oil, and the like can be mentioned.

The epihalohydrin has the following general formula:

[0066]

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(Wherein Z is a hydrogen atom, a methyl group or an ethyl group, and X'is a halogen atom) are preferable, and examples of such epihalohydrin include
For example epichlorohydrin, epibromohydrin, 1,2
-Epoxy-2-methyl-3-chloropropane, 1,2-
Epoxy-2-ethyl-3-chloropropane and the like can be mentioned.

As the acidic catalyst for promoting the reaction between the epihalohydrin and the polyether polyol, there are Lewis acids such as boron trifluoride, stannic chloride, zinc chloride and ferric chloride, and their active derivatives (eg, : Boron trifluoride first ether complex compound) or a mixture thereof.

Alkali metal hydroxides (eg, sodium hydroxide, potassium hydroxide, etc.) can be used as basic compounds for cyclizing the halohydrin ether produced as a result of the reaction by dehydrohalogenation to produce glycidyl ether. , Alkali metal aluminate (eg, sodium aluminate) and the like are preferably used.

Further, these catalysts and basic compounds are
Of course, it can be used as it is or as a solution of an appropriate inorganic and / or organic solvent.

Preferred polyether polyepoxys are ACR epoxy R-1760 and ACR epoxy R-1761.
, ACR epoxy R-1762 (manufactured by AC R Co., Ltd.) and the like.

Aminosilane compound (-b) having a hydrolyzable alkoxy group at the terminal which reacts with the polyether polyepoxy having an epoxy group at the terminal (-a)
And preferred as the mercaptosilane compound (-c) are, for example, the following general formula:

[0073]

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(In the formula, A is a methoxy group, an ethoxy group, β
An alkoxy group having 1 to 6 carbon atoms represented by a methoxyethoxy group, B is an alkyl group having 1 to 12 carbon atoms represented by a methyl group, an ethyl group, a propyl group, a butyl group, etc., m is 0,
An integer of 1 or 2, R is a methylene group, an ethylene group, a propylene group, a butylene group or another alkylene group having 1 to 12 carbon atoms, and X is NH ₂ or SH).

In the present invention, the reaction between the polyether polyepoxy and the aminosilane compound and / or mercaptosilane compound is carried out by a known reaction method. The reaction temperature is
The temperature is 50 to 150 ° C, preferably 70 to 130 ° C. The reaction time is preferably about 1 to 7 hours. The equivalent ratio is (epoxy group) / (amino group and / or mercapto group) = 1 / 1.0 to 1 / 1.5, preferably 1 / 1.0-1.
It is /1.2. The aminosilane compound and / or the mercaptosilane compound can be added to the polyether polyepoxy at any stage of the above reaction and reacted, and in order to accelerate the reaction, a tertiary amine as a catalyst (eg triethanolamine etc.) Alternatively, an alkylphosphine (eg, triphenylphosphine, etc.) can be used, and a hydrolyzable alkoxy group-containing aminosilane and / or a hydrolyzable alkoxy group-containing mercaptosilane / polyether polyepoxy-modified compound can be obtained.

The above compound is a reaction of polyether polyepoxy with aminosilane containing a hydrolyzable alkoxy group,
Any reaction of a reaction between a polyether polyepoxy and a hydrolyzable alkoxy group-containing mercaptosilane, a reaction between a polyether polyepoxy and a hydrolyzable alkoxy group-containing aminosilane and a hydrolyzable alkoxy group-containing mercaptosilane, and an addition method May be at any stage of the above reaction.

When exposed to the atmosphere, the composition of the present invention forms a three-dimensional network structure by the action of moisture in the atmosphere and hardens. The curing speed needs to consider the atmospheric temperature, the relative temperature, and the types and amounts of the hydrolyzable groups (protected amines and alkoxysilanes). Among the silane-modified epoxy compounds, the alkoxy group is preferably a methoxy group or an ethoxy group.

Further, the composition of the present invention must be stored under anhydrous condition so as not to come into contact with water until it is actually used. A dehydrating agent may be added to make the storage stability during storage more stable. As such a dehydrating agent, vinyl silanes, methyl orthoformate and ethyl orthoformate are used in combination. Furthermore, the composition of the present invention has a purpose of improving the adhesiveness to a substrate, particularly the adhesiveness to an organic surface, aminoalkoxysilanes, epoxyalkoxysilanes,
It may contain mercaptoalkoxysilanes or alkoxysilane derivatives which are copolymers thereof.

The composition of the present invention preferably contains a silanol condensation catalyst in order to accelerate the silanol condensation of the silicon-terminated compound. As a silanol condensation catalyst, alkyl titanates, organosilicon titanates, tin octylates, dibutyltin laurate, dibutyltin maleate, metal salts of carboxylic acids such as dibutyltin phthalate, tin compounds such as dibutyltin oxide, and dibutylamine- An amine salt such as 2-ethylhexoate is used. The content of silanol condensation catalyst is silane-modified epoxy compound 1
0.1-10 parts by weight, preferably 0.3-5, relative to 00 parts by weight
Parts by weight are good.

The proportion of each component in the composition of the present invention is not particularly limited, but 5 to 80 parts by weight, preferably 10 to 50 parts by weight, of the protected amino group-containing compound relative to 100 parts by weight of the epoxy resin, silane. Modified epoxy compound 10-200
Parts by weight, preferably 30 to 150 parts by weight.

Although not essential, the blending amount of vinyl silanes, formic acid esters, and silicate esters used as a dehydrating agent is 1 to 150 parts by weight with respect to 100 parts by weight of the epoxy resin. The amount of the silane coupling agent used as the adhesion improver is 0.5 to 30 parts by weight, preferably 1 to 15 parts by weight.

Further, in order to put the present invention into practical use, various fillers and pigments may be added and modified. As the filler, fumed silica, precipitated silica, silicic anhydride,
Reinforcing fillers such as hydrous silicic acid and carbon black;
Calcium carbonate, magnesium carbonate, diatomaceous earth, calcined clay, clay, talc, titanium oxide, bentonite,
Fillers such as organic bentonite, ferric oxide, zinc oxide, activated zinc oxide, and shirasu balloons; fibrous fillers such as asbestos, glass fibers and filaments can be used.

In order to obtain a hardened composition having high strength with these fillers, mainly fumed silica, precipitated silica, silicic acid anhydride, carbon black, surface-treated fine calcium carbonate, calcined clay, clay, and active zinc are used. Preferable results can be obtained by using a filler selected from flowers and the like within the range of 1 to 100 parts by weight with respect to 100 parts by weight of the silane-modified epoxy compound. Further, when it is desired to obtain a curable composition having a low strength and a large elongation, a filler mainly selected from titanium oxide, calcium carbonate, magnesium carbonate, talc, ferric oxide, zinc oxide, and shirasu balloon. When the agent is used within the range of 5 to 200 parts by weight based on 100 parts by weight of the silane-modified epoxy compound, preferable results are obtained. Of course, these fillers may be used alone or in combination of two or more.

In the present invention, the use of a plasticizer in combination with a filler is more effective because it can increase the elongation of the cured product and can mix a large amount of filler. As the plasticizer, there are commonly used ones, for example, phthalates such as dioctyl phthalate, dibutyl phthalate and butylbenzyl phthalate; aliphatic compounds such as dioctyl adipate, isodecyl succinate and dibutyl sebacate. Dibasic acid esters; glycol esters such as diethylene glycol dibenzoate and pentaerythritol ester; aliphatic esters such as butyl oleate and methyl acetylricinoleate; tricresyl phosphate, trioctyl phosphate, octyl diphenyl phosphate, etc. Phosphoric acid esters such as these; epoxy plasticizers such as epoxidized soybean oil and epoxy benzyl stearate; plasticizers such as chlorinated paraffin can be optionally used alone or in the form of a mixture of two or more kinds. The amount of plasticizer is 100% silane-modified epoxy compound.
When used in the range of 0 to 100 parts by weight, the preferable results are obtained.

In the composition of the present invention, a filler, a plasticizer and a condensation catalyst are mainly used in addition to the above-mentioned essential components, but an adhesion-imparting agent such as phenol resin and epoxy resin, a pigment,
It is also possible to contain additives such as an antiaging agent and an ultraviolet absorber.

When exposed to the atmosphere, the composition of the present invention can be easily cured at atmospheric humidity and at room temperature. The curing mechanism is that atmospheric moisture hydrolyzes the protected amino group-containing compound to form a free amino group, which reacts with the epoxy group of the epoxy resin. At the same time, moisture in the atmosphere reacts with the alkoxy groups of the silane-modified epoxy compound to obtain a cured product having a high crosslink density.

Therefore, the composition of the present invention is superior in adhesiveness to the underlying surface and mechanical strength as compared with the one-component curing type silicone type and urethane type and one component of epoxy resin-ketimine type. It is superior in storage stability and curability compared to curing systems.

[0088]

EXAMPLES The present invention will be described in more detail with reference to production examples and examples, but the present invention is not limited thereto. In the examples, “parts” and “%” are based on weight unless otherwise specified.

Production Example 1 ACR Epoxy R-1760 (polyether polyepoxy manufactured by AC R, epoxy equivalent: 2000, number average molecular weight: 4000) 2000 parts and γ-aminopropyltriethoxysilane (molecular weight: 221) 221 parts was reacted in a 3 liter four-necked flask equipped with a stirrer, a thermometer, and a cooling tube at 70 ° C. for 3 hours to react an epoxy group and an amino group with a terminal hydrolyzable alkoxy group-containing aminosilane. A polyether polyepoxy modified compound A was obtained. The (epoxy group) / (amino group and / or mercapto group) of the compound A is 1/1.

Production Example 2 1600 parts of ACR epoxy R-1761 (polyether polyepoxy manufactured by AC R, epoxy equivalent: 1600, number average molecular weight: 4800) and γ-mercaptopropyltrimethoxysilane (molecular weight: 196) 196 parts and 1 part of triphenylphosphine are reacted in a 3-liter four-necked flask equipped with a stirrer, a thermometer, and a cooling tube at 120 ° C for 3 hours, and the epoxy group and the mercapto group react to hydrolyze the end. A mercaptosilane / polyether polyepoxy-modified compound B having a hydrophilic alkoxy group was obtained. The (epoxy group) / (amino group and / or mercapto group) of the compound B is 1/1.

Production Example 3 2100 parts of ACR epoxy R-1762 (polyether polyepoxy manufactured by AC R, epoxy equivalent: 2100, number average molecular weight: 6300) and γ-mercaptopropyltrimethoxysilane (molecular weight: 196) 196 parts and 1 part of triphenylphosphine are reacted in a 3-liter four-necked flask equipped with a stirrer, a thermometer, and a cooling tube at 120 ° C for 3 hours, and the epoxy group and the mercapto group react to hydrolyze the end. A mercaptosilane-polyether polyepoxy-modified compound C containing a hydrophilic alkoxy group was obtained. The (epoxy group) / (amino group and / or mercapto group) of the compound C is 1/1.

Production Example 4 116 parts of hexamethylenediamine (molecular weight: 116), 200 parts of methyl isobutyl ketone (molecular weight: 100), and 50 parts of benzene were placed in a four-necked flask equipped with a stirrer, a thermometer, and a water divider.
120 ℃ × 10 hours dehydration reaction, then 120 ℃, 50mmHg ×
The solvent was removed under reduced pressure for 1 hour to obtain a protected amino group-containing compound D. Compound D has a number average molecular weight of 280 and a primary amino group equivalent weight of 140.

Example 1 Epoxy resin (Adeka Resin EP-4100: bisphenol A type epoxy resin manufactured by Asahi Denka Co., Ltd., epoxy equivalent: 190)
100 parts, 50 parts aminosilane / polyetherpolyepoxy modified compound A prepared in Preparation Example 1, calcium carbonate 1
00 parts and 10 parts of titanium oxide were kneaded in a vacuum kneader at 30 mmHg or less, and the protected amino group-containing compound D produced in Production Example 4 was kneaded.
20 parts, dehydrating agent vinyltrimethoxysilane (KBM-1003
: Shin-Etsu Chemical Co., Ltd.) 1 part, dibutyltin dilaurate
0.5 part was added and kneaded to obtain a one-component epoxy-silicone polyether polyepoxy composition. About the obtained composition, the physical property was evaluated by the following method. Table 1 shows the results.
Shown in

<Evaluation Method> Curing time: The curing time from the surface to a depth of 3 mm was measured at 25 ° C. and a humidity of 60%. Hardness Shore A: Hardness Sh after curing for 7 days at 25 ° C and 60% humidity
ore A was measured. Storage stability: The state of the composition after storage at 40 ° C. for 3 weeks was observed. No change: ○ Thickening: △ Gelation: × Adhesive strength: H type mortar test piece used, 25 ℃, humidity
The adhesive strength after curing at 60% for 7 days was measured.

Examples 2 to 4 Curable compositions were prepared in the same manner as in Example 1 with the formulations shown in Table 1, and further evaluated. Table 1 shows the results.

Comparative Examples 1 and 2 Curable compositions were prepared in the same manner as in Example 1 with the formulations shown in Table 1 and evaluated further. Table 1 shows the results.

Comparative Example 3 A commercially available polyurethane sealing material was evaluated.
Table 1 shows the results.

[0098]

[Table 1]

As shown in Table 1, increasing the amount of aminosilane polyetherpolyepoxy modified compound increases flexibility. On the other hand, when only the epoxy resin and the protected amino group-containing compound are used, the curing is slow and the storage stability is poor. Further, it can be seen that the adhesiveness is poor when only the aminosilane / polyether polyepoxy modified compound is used. Further, it is found that the polyurethane sealing material subjected to the comparative test is slow in curing up to a depth of 3 mm and has poor storage stability as compared with the product of the present invention.

Examples 5 to 7 Curing compositions having the formulations shown in Table 2 were produced in the same manner as in Example 1 and further evaluated in the same manner as in Table 1.
Adhesion is applied evenly on aluminum plate, glass plate, mortar plate to a thickness of 3 mm, and after curing at 25 ° C and humidity 60% for 7 days
A peeling test was performed and the following evaluations were performed. Table 2 shows the results. Cohesive failure: ◯, Semi-cohesive failure: Δ, Interfacial peeling: × Comparative Example 4 A curable composition was prepared and evaluated in the same manner as in Example 1 with the composition shown in Table 2. Table 2 shows the results.

[0101]

[Table 2]

In each of Examples 5 to 7, the adhesiveness to glass and aluminum is good, while the epoxy-ketimine composition cures slowly and the adhesiveness is poor.

 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Kazutaka Baba 8-4-1 Higashiohisa, Arakawa-ku, Tokyo Asahi Denka Kogyo Co., Ltd. (72) Inventor Kiyo Muto 8-4-1 Higashiohisa, Arakawa-ku, Tokyo Asahi Denka Kogyo Co., Ltd.

Claims (2)

[Claims] 1. An epoxy resin having at least one epoxy group in its molecule as essential components, and a protected amino group-containing compound which can be easily hydrolyzed in the presence of water to be converted into a free amino group. And a polyetherpolyepoxy (-a) obtained by epoxidizing the end of a polyetherpolyol, and an aminosilane compound having a hydrolyzable alkoxy group at the end (-
b) and / or mercaptosilane compound (-c),
(Epoxy group) / (Amino group and / or mercapto group)
= 1 / 1.0 to 1 / 1.5 (equivalent ratio), and a silane-modified epoxy compound obtained by reacting the curable composition. 2. The compounding ratio of the essential components is 5 parts by weight of the protected amino group-containing compound based on 100 parts by weight of the epoxy resin.
The curable composition according to claim 1, wherein the amount is -80 parts by weight and the silane-modified epoxy compound is 10-200 parts by weight.