JPH083286A - Thermosetting composition and method for curing the same - Google Patents

Abstract

PURPOSE:To obtain a composition which has excellent storage stability and can cure at a low temp. to give a cured composition free from discoloration. CONSTITUTION:This composition comprises a resin ingredient (A) and an organotin compound. The ingredient (A) is either a resin containing epoxy groups (i), reactive silicon groups (ii), and hydroxyl and/or carboxyl groups (iii) as essential functional groups in each molecule or a mixture of two or more resins each of which contains at least one of the groups (i), (ii), and (iii) and which contain all of the groups (i), (ii), and (iii) as a whole. A solution or dispersion of the composition in an organic solvent is applied to a substrate, and the coating is heated and cured.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel curable composition and a curing method using the curable composition.

[0002]

2. Description of the Related Art Conventionally, Lewis acids (eg, aluminum chloride, tin chloride, boron fluoride, boron fluoride ether complex, etc.), metal alcoholates (eg, Al trialkoxide, Ti tetraalkoxide, etc.) have been used as a curing catalyst for epoxy resins. , Metal chelate (trisacetylacetonate A
1), a complex of a metal chelate and an active hydrogen compound (a reaction product of trisacetylacetonatoaluminum and a silanol compound), and the like.

However, in these catalysts, the curing composition containing the above-mentioned Lewis acid or metal alcoholate has remarkably poor storage stability at room temperature, and
Each of the cured compositions containing the metal chelate or the composite thereof has the drawbacks of poor storage stability at room temperature and yellowing of the cured product.

[0004]

SUMMARY OF THE INVENTION The present invention has been made for the purpose of providing a curable composition which is excellent in storage stability and can be cured at a low temperature and can form a cured product without discoloration. is there.

[0005]

The present inventor has conducted extensive studies in order to solve the above-mentioned problems, and as a result, as a reaction catalyst for an epoxy group, in particular, a reactive silicon group and an organotin were used. It has been found that a curable composition using a composite catalyst used in combination has excellent storage stability, low temperature curability, discoloration resistance and the like, and has completed the present invention.

That is, the present invention provides (A) (i) an epoxy group, (ii) a reactive silicon group, and (iii)
Resin (A-1) containing a hydroxyl group and / or a carboxyl group in the same molecule as an essential functional group component, or
A mixture of two or more resins, each resin containing at least one of the functional group components (i) to (iii), wherein the functional group components (i) to (iii) above are contained in the mixture. A thermosetting composition characterized by containing a mixed resin (A-2) which is all present and (B) an organotin compound, and a thermosetting composition which is dissolved or dispersed in an organic solvent. The present invention relates to a curing method, which comprises applying an organic solution to a substrate and then heating and curing it.

In the present invention, the reactive silicon group means a silanol group which is a group in which a hydroxyl group is directly bonded to a silicon atom, or a group in which a hydrolyzable group is directly bonded to a silicon atom (a group which produces a silanol group by hydrolysis). ) Means.

In the present invention, examples of the hydrolyzable group directly bonded to a silicon atom include an alkoxyl group represented by the general formula —OR ⁴ , an acyloxy group represented by the general formula —OCOR ⁵ , and a general formula —ON = A ketoxime group represented by C (R ⁶ ) ₂ and the like are included. In the above general formula, R ⁴ represents an alkyl group having 1 to 5 carbon atoms, preferably 1 to 3 carbon atoms, such as methyl, ethyl, propyl and butyl, R ⁵ represents an alkyl group having 1 to 3 carbon atoms, R ⁶ represents an alkyl group having 1 to 5 carbon atoms.

Preferred specific examples of the above general formula include, for example, alkoxyl groups such as methoxy group, ethoxy group and propoxy group; acyloxy groups such as acetoxy group and propionyloxy group; ketoxime groups such as acetoxime group and propionyloxy group. Etc. Among these hydrolyzable groups, an alkoxyl group having 1 to 3 carbon atoms, which has excellent effects on storage stability and low temperature curability, is particularly preferable.

In the present invention, the epoxy group is an aliphatic type epoxy group in which an ether group is bonded between the carbon atoms of a linear hydrocarbon group, or an alicyclic hydrocarbon group in which an ether group is bonded between the carbon atoms of an alicyclic hydrocarbon group. Any type of cyclic type epoxy group may be used, but the alicyclic type epoxy group can easily and rapidly undergo cationic polymerization reaction or cationic addition reaction by other components (reactive silicon group and organic tin). It occurs and is excellent in low temperature curability.

The curable composition of the present invention comprises (A) (i) an epoxy group, (ii) a reactive silicon group, and (iii)
Resin (A-1) containing a hydroxyl group and / or a carboxyl group as essential functional group components in the same molecule, or
A mixture of two or more resins, each resin containing at least one of the functional group components (i) to (iii), wherein the functional group components (i) to (iii) above are contained in the mixture. All of the mixed resin (A-2) and the organic tin compound (B) are present.

In the present invention, the hydroxyl group has the effect of improving the low-temperature curability because the reaction with the epoxy group and the reactive silicon group is promoted in the presence of the organotin catalyst.

Further, the carboxyl group is recognized to promote the reaction between the hydroxyl group and the reactive silicon group, and the reaction between the reactive silicon groups, whereby the effect of improving the low temperature curability is obtained. And, the carboxyl group reacts with the epoxy group to form a cured film having excellent performance such as acid resistance, the carboxyl group is consumed by the reaction with the epoxy group, and the carboxyl group does not remain in the coating film, or Since only a small amount remains, it is effective in improving the water resistance, acid resistance, weather resistance and the like of the coating film.

The respective components to be incorporated in the composition of the present invention will be described in more detail below.

(I) an epoxy group, (ii) a reactive silicon group, and
(iii) a hydroxyl group and / or a carboxyl group as an essential functional group
In the resin (A-1) resin (A-1) contained in the same molecule as a component, the number of epoxy groups in the molecule is preferably about 1 or more on average, preferably about 2 to 100 on average. If the number of epoxy groups is less than about 1 on average in one molecule, low-temperature curability is deteriorated, which is not preferable.

The number of reactive silicon groups is preferably about 1 or more on average in one molecule, preferably about 1 to 300 on average. If the number of reactive silicon groups is less than about 1 on average in one molecule, low-temperature curability is deteriorated, which is not preferable.

The number of hydroxyl groups and / or carboxyl groups is
When the hydroxyl group is alone, the hydroxyl value is about 10 to 300, preferably in the range of about 20 to 200. When the carboxyl group is alone, the acid value is about 10 to 300, preferably about 20 to 200.
When the hydroxyl group and the carboxyl group are combined, the hydroxyl value is about 1 to 300, preferably about 2 to 200, and the acid value is about 1 to 300, preferably about 2 to 200. It is suitable.

When the number of hydroxyl groups and / or carboxyl groups is less than the above range, the low temperature curability is deteriorated, while when it exceeds the above range, the storage stability of the composition, the durability of the cured film and the like are deteriorated. Absent.

The resin (A-1) has an average molecular weight of about 200-
The range is 100,000, preferably about 500 to 50,000. If the average molecular weight is less than about 200, the durability of the cured product will decrease, while if it exceeds about 100,000, the storage stability, the appearance of the cured product, etc. will deteriorate.

The resin (A-1) is conventionally known as long as it satisfies the above conditions, for example, a polymer of an ethylenically unsaturated monomer, a polyester resin,
A silicon-modified polyester resin, an epoxy-modified polyester resin, a silicon-modified epoxy resin, a fluororesin or the like can be appropriately selected and used, but a polymer of the following ethylenically unsaturated monomer is particularly preferable.

The polymers of ethylenically unsaturated monomers include the following epoxy group-containing ethylenically unsaturated monomers (a), reactive silicon group-containing ethylenically unsaturated monomers (b), and hydroxyl group-containing ethylenically unsaturated monomers. Monomers (c)
And / or carboxyl group-containing ethylenically unsaturated monomers (d) and, if necessary, those obtained by radical copolymerization reaction of other ethylenically unsaturated monomers (e). Epoxy group-containing ethylenically unsaturated monomers (a): glycidyl (meth) acrylate, methylglycidyl (meth) acrylate, allyl glycidyl ether, 3,4-epoxycyclohexylmethyl (meth) acrylate, etc. Reactive silicon group-containing ethylenic Unsaturated monomers (b):
Vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, γ
-(Meth) acryloyloxypropyltrimethoxysilane, γ- (meth) acryloyloxypropyltriethoxysilane, γ- (meth) acryloyloxypropylmethyldimethoxysilane, β- (meth) acryloyloxyethylpropyltrimethoxysilane, and these , A trifunctional silane compound, a tetrafunctional silane compound, and low-condensates of these silane compounds (for example, Colcoat ES
40, Colcoat MS40 and the like (all are trade names, manufactured by Colcoat, about 2 to 20 mer), etc., a reaction product of the following hydroxyl group-containing ethylenically unsaturated monomer (c) and the above low condensation product. Etc. Hydroxyl group-containing ethylenically unsaturated monomers (c): hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, (poly) ethylene glycol mono (meth) acrylate, (poly) propylene glycol mono (meth) acrylate, And adducts of these with caprolactone (ε-caprolactone etc.), the following hydroxyl group-containing ethylenically unsaturated monomer (c) and acid anhydrides (for example, succinic anhydride, hexahydrophthalic anhydride,
(Anhydrous trimellitic anhydride) adduct, etc., (anhydrous) carboxyl group-containing ethylenically unsaturated monomers (d): (meth) acrylic acid, (anhydrous) maleic acid, etc. Other ethylenically unsaturated monomers (e) : Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate C _{1-24 of} etc.
Alkyl (meth) acrylate or cycloalkyl (meth) acrylates, perfluorobutylethyl (meth) acrylate, hydroxyethyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, perfluoroisononylethyl (meth) acrylate, Perfluoroalkyl group- or perfluoroalkenyl group-containing ethylenically unsaturated monomers such as perfluorodecylethyl (meth) acrylate, aromatic vinyl monomers such as styrene and vinyltoluene, nitrile monomers such as (meth) acrylonitrile, ( Amide monomers such as (meth) acrylamide and N-methylol (meth) acrylamide.

(I) epoxy group, (ii) reactive silicon group,
And (iii) at least a hydroxyl group and / or a carboxyl group
A mixture of two or more resins, one of which is contained in each resin
Wherein the functional groups of (i) to (iii) above are contained in the mixture.
Mixed resin (A-2) in which all components are present As the above - mentioned mixed resin (A-2), for example, the following ones can be mentioned.

(I) A mixed resin of an epoxy group-containing resin and a reactive silicon group-containing resin, and at least one of the epoxy group-containing resin and the reactive silicon group-containing resin,
A mixture of two kinds of resins having a hydroxyl group and / or a carboxyl group.

(II) A mixture of three kinds of resins including an epoxy group-containing resin, a reactive silicon group-containing resin, and a hydroxyl group- and / or carboxyl group-containing resin.

(III) A mixture of an epoxy group-containing resin, a reactive silicon group-containing resin, and a hydroxyl group- and / or carboxyl group-containing resin, and at least one resin selected from the epoxy group-containing resin and the reactive silicon group-containing resin. , A mixture of three types of resins having a hydroxyl group and / or a carboxyl group.

(IV) A mixture of two kinds of resins containing an epoxy group- and reactive silicon group-containing resin and a hydroxyl group- and / or carboxyl group-containing resin.

These mixed resins (I) to (IV) will be described in detail below.

(I) A mixed resin of an epoxy group-containing resin and a reactive silicon group-containing resin, and at least one of the epoxy group-containing resin and the reactive silicon group-containing resin,
Mixture of two types of resins having a hydroxyl group and / or a carboxyl group: Examples of the mixed resin (I) include the following.

(1) A mixed resin of an epoxy group- and hydroxyl group-containing resin and a reactive silicon group-containing resin.

(2) Epoxy group-containing resin and mixed resin of reactive silicon group- and hydroxyl group-containing resin.

(3) Epoxy group- and hydroxyl group-containing resin, and mixed resin of reactive silicon group- and hydroxyl group-containing resin.

(4) Epoxy group-containing resin and mixed resin of reactive silicon group- and carboxyl group-containing resin.

(5) Epoxy group-containing resin and mixed resin of reactive silicon group, hydroxyl group and carboxyl group-containing resin.

(6) A mixed resin of an epoxy group- and hydroxyl group-containing resin and a reactive silicon group- and carboxyl group-containing resin.

(7) Epoxy group- and hydroxyl group-containing resin, and mixed resin of reactive silicon group-, hydroxyl group- and carboxyl group-containing resin.

The epoxy group-containing resin described in (2), (4) and (5) above has an average number of epoxy groups of 1 or more, preferably about 2 to 100, in one molecule. Thus, those having an average molecular weight of about 130 to 100,000, preferably about 200 to 80,000 are suitable.

As the epoxy group-containing resin, for example,
Polymers of the above-mentioned epoxy group-containing ethylenically unsaturated monomers (a) and, if necessary, other ethylenically unsaturated monomers (e); bis (3,4-epoxycyclohexylmethyl) adipate, bis (3 , 4-epoxy-6-methylcyclohexylmethyl) adipate,
3,4-epoxy-6-methylcyclohexylmethyl-
Alicyclic epoxy compounds such as 3,4-epoxy-6-methylcyclohexanecarboxylate, 3,4-epoxycyclohexenecarboxylic acid ethylene glycol diester, and 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate; Aliphatic epoxy compounds such as poly) ethylene glycol diglycidyl ether, (poly) propylene glycol diglycidyl ether, trimethylolpropane triglycidyl ether, epoxidized polybutadiene, triglycidyl isocyanurate; bisphenol A type epoxy resin, bisphenol F type epoxy resin , Bisphenol B type epoxy resin, hydrogenated bisphenol type epoxy resin, phenol novolac type epoxy resin and the like, and these and epichloro Glycidyl ether type epoxy resin obtained by reacting a polyhedrin the like.

Polymers of the above-mentioned epoxy group-containing ethylenically unsaturated monomers (a) and, if necessary, other ethylenically unsaturated monomers (e), particularly have an average molecular weight of about 5,000 to 100,000. Is preferred.

The epoxy group- and hydroxyl group-containing resins described in (1), (3), (6) and (7) above have an average number of epoxy groups of 1 or more per molecule, preferably about 1 of average. 2 to 100, a hydroxyl value of about 10 to 300, preferably about 20 to 200, and an average molecular weight of about 1,000 to 100,000, preferably about 5,000.
Those in the range of to 80,000 are preferable.

As the epoxy group- and hydroxyl group-containing resin,
For example, an epoxy group-containing ethylenically unsaturated monomer (a), a hydroxyl group-containing ethylenically unsaturated monomer (c),
Further, if desired, a radical copolymer of other ethylenically unsaturated monomers (e) can be mentioned as a preferable one.

The reactive silicon group-containing resin described in (1) above has an average number of reactive silicon groups of 1 or more, preferably 1 to 300, in one molecule. Average molecular weight about 76-100,000, preferably about 100
Those in the range of up to 50,000 are preferred.

As the above-mentioned reactive silicon group-containing resin,
For example, methoxytrimethylsilane, ethoxytriethylsilane, propoxytripropylsilane, butoxytributylsilane, methoxytrioctylsilane, methoxytriphenylsilane, methoxytribenzylsilane,
Monofunctional silane compounds such as triphenylhydroxysilane; dimethoxydimethylsilane, dimethoxydiethylsilane, diethoxydiphtylsilane, dipropoxydipropylsilane, dimethoxydilaurylsilane, dimethoxydiphenylsilane, dimethoxydibenzylsilane, methoxybenzyloxydipropyl Bifunctional silane compounds such as silane, methoxy 2-ethylhexyloxydipropylsilane, diphenylsilanediol; trimethoxymethylsilane, triethoxyethylsilane, tripropoxypropylsilane, trimethoxystearylsilane, trimethoxyphenylsilane, trimethoxybenzylsilane. , Methoxydibenzyloxypropylsilane, methyltrihydroxysilane, phenyltrihydroxysilane, etc. A tetrafunctional silane compound such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, trimethoxybenzyloxysilane, dimethoxy2-ethylhexylsilane, tetrahydroxysilane; the above-mentioned trifunctional silane compound and / or tetrafunctional silane compound Low condensate of silane compound (for example, Colcoat ES40, Colcoat MS40, etc.); reactive silicon group-containing ethylenically unsaturated monomer (b) and, if necessary, radical weight of other ethylenically unsaturated monomers (e) Coalescence and the like are preferred.

In the reactive silicon group- and hydroxyl group-containing resin described in (2) and (3) above, the number of reactive silicon groups is on average about 1 or more in one molecule, preferably about 1 to 300. Range, the hydroxyl value is about 10 to 300, preferably about 20.
200, with an average molecular weight of about 1,000 to 10
Those in the range of 50,000, preferably in the range of about 5,000 to 80,000 are suitable.

Examples of the resin containing a reactive silicon group and a hydroxyl group include, for example, a reactive silicon group-containing ethylenically unsaturated monomer (b), a hydroxyl group-containing ethylenically unsaturated monomer (c) and, if necessary, other ethylenic Radical copolymers of unsaturated monomers (e) and the like are preferred.

In the reactive silicon group- and carboxyl group-containing resin described in (4) and (6) above, the number of reactive silicon groups is on average about 1 or more in one molecule, preferably about 1 to about 1.
A range of 300, an acid value of about 10 to 300, preferably about 20 to 200, and an average molecular weight of about 1,000 to 100,000, preferably about 5,000.
Those in the range of to 80,000 are preferable.

Examples of the reactive silicon group- and carboxyl group-containing resin include, for example, the reactive silicon group-containing ethylenically unsaturated monomer (b), the carboxyl group-containing ethylenically unsaturated monomer (d) and, if necessary, other Radical copolymers of ethylenically unsaturated monomers (e) and the like are preferred.

The reactive silicon group-, hydroxyl group- and carboxyl group-containing resins described in (5) and (7) above have an average of about 1 or more, preferably about 1 on average, reactive silicon groups per molecule. To 300, a hydroxyl value and an acid value of about 10 to 300, preferably about 20 to 200, and an average molecular weight of about 1,000 to 100,000, preferably about 5,000 to 80, Those in the range of 000 are preferable.

Examples of the resin containing a reactive silicon group, a hydroxyl group and a carboxyl group include a reactive silicon group-containing ethylenically unsaturated monomer (b), a hydroxyl group-containing ethylenically unsaturated monomer (c) and a carboxyl group-containing ethylenic unsaturated monomer. Preferred examples include a saturated monomer (d) and, if necessary, a radical copolymer of other ethylenically unsaturated monomers (e).

In the above-mentioned mixed resin (I), the mixing ratio of the epoxy group-containing resin and the reactive silicon group-containing resin is
Based on the total weight of the epoxy group-containing resin and the reactive silicon group-containing resin, the epoxy group-containing resin is in the range of about 5 to 95% by weight, preferably about 20 to 80% by weight, and the reactive silicon group-containing resin is about 5%. ~ 95% by weight, preferably about 20-8
It is preferable to set it in the range of 0% by weight. If the mixing ratio is out of this range, low-temperature curability, acid resistance, scratch resistance and the like are deteriorated, which is not preferable.

(II) Mixture of three kinds of resins consisting of epoxy group-containing resin, reactive silicon group-containing resin, and hydroxyl group and / or carboxyl group-containing resin: Examples of the epoxy group-containing resin include the above-mentioned mixed resins ( The same epoxy group-containing resin as described in (2) in I) can be used.

As the reactive silicon group-containing resin, for example, the same resin as the reactive silicon group-containing resin described in (1) of the above mixed resin (I) can be used.

The number of hydroxyl groups and / or carboxyl groups in the resin containing hydroxyl groups and / or carboxyl groups is about 10 to 30 when the hydroxyl group is contained alone.
0, preferably in the range of about 20 to 200, when the carboxyl group is contained alone, the acid value is about 10 to 300, preferably in the range of about 20 to 200, when both the hydroxyl group and the carboxyl group are contained, A hydroxyl value of about 1 to 300, preferably about 2 to 200, and an acid value of about 1 to 300, preferably about 2 to 200 are suitable.

The average molecular weight of the hydroxyl group- and / or carboxyl group-containing resin is suitably in the range of about 1,000 to 100,000, preferably 5,000 to 80,000.

As the hydroxyl group-containing resin, for example, conventionally known resins such as (co) polymers of ethylenically unsaturated monomers, polyester resins, alkyd resins and polyether resins can be used. Radical (co) polymers of unsaturated monomers (c), and optionally other ethylenically unsaturated monomers (e) are suitable.

As the carboxyl group-containing resin, for example, conventionally known resins such as (co) polymers of ethylenically unsaturated monomers, polyester resins and alkyd resins can be used. Particularly, carboxyl group-containing ethylenically unsaturated resins are usable. Radical (co) polymers of the monomer (d) and, if necessary, other ethylenically unsaturated monomers (e) are preferable.

As the hydroxyl group- and carboxyl group-containing resin, conventionally known ones such as copolymers of ethylenically unsaturated monomers, polyester resins, alkyd resins and the like can be used. Particularly, hydroxyl group-containing ethylenically unsaturated monomers are usable. Radical (co) polymers of (c), the carboxyl group-containing ethylenically unsaturated monomer (d), and optionally other ethylenically unsaturated monomers (e) are preferable.

In the above mixed resin (II), the mixing ratio of the epoxy group-containing resin, the reactive silicon group-containing resin, and the hydroxyl group and / or carboxyl group-containing resin is 3% or more.
Epoxy group-containing resin is about 5 to 95% by weight, preferably about 20 to 80% by weight, based on the total weight of the various types of resins.
Range of about 5 to 95% by weight of the reactive silicon group-containing resin, preferably about 20 to 80% by weight, and about 10 to 70% by weight of the hydroxyl group and / or carboxyl group-containing resin, preferably about 20 to 60% by weight. It is preferable to set it in the range of% by weight. If the mixing ratio is out of this range, low-temperature curability, acid resistance, scratch resistance and the like are deteriorated, which is not preferable.

(III) A mixture of an epoxy group-containing resin, a reactive silicon group-containing resin, and a hydroxyl group- and / or carboxyl group-containing resin, and at least one resin selected from the epoxy group-containing resin and the reactive silicon group-containing resin. , A mixture of three kinds of resins having a hydroxyl group and / or a carboxyl group: Examples of the epoxy group-containing resin and the reactive silicon group-containing resin include the epoxy group-containing resin and the reactive silicon group in the mixed resin (I) described above. The same as the contained resin can be used.

As the hydroxyl group- and / or carboxyl group-containing resin, for example, those similar to the hydroxyl group- and / or carboxyl group-containing resin in the above mixed resin (II) can be used.

As the mixed resin (III), for example, a resin containing an epoxy group, a hydroxyl group and a reactive silicon group, a resin containing a reactive silicon group, and a mixed resin containing a resin containing a hydroxyl group and a carboxyl group can be used.

Examples of the epoxy group-, hydroxyl group- and reactive silicon group-containing resin include epoxy group-containing ethylenically unsaturated monomer (a), hydroxyl group-containing ethylenically unsaturated monomer (c) and reactive silicon group-containing ethylenic resin. A radical copolymer of the unsaturated monomer (b) and optionally other ethylenically unsaturated monomers (e) is included.

In the above mixed resin (III), the mixing ratio of the epoxy group-containing resin, the reactive silicon group-containing resin, and the hydroxyl group- and / or carboxyl group-containing resin is based on the total measurement of these three kinds of resins. The epoxy group-containing resin is in the range of about 5 to 95% by weight, preferably about 20 to 80% by weight, the reactive silicon group-containing resin is in the range of about 5 to 95% by weight,
It is preferable that the range is about 20 to 80% by weight, and the range is about 10 to 70% by weight, and preferably about 20 to 60% by weight, in the hydroxyl group- and / or carboxyl group-containing resin. If the mixing ratio is out of this range, low-temperature curability, acid resistance, scratch resistance and the like are deteriorated, which is not preferable.

(IV) Epoxy group- and reactive silicon group-containing resin, and mixture of two kinds of resins consisting of hydroxyl group- and / or carboxyl group-containing resin: The epoxy group- and reactive silicon group-containing resin is the number of epoxy groups. Is an average of about 1 or more in one molecule, preferably about 2 to 100 on average,
The number of reactive silicon groups is in the range of about 1 or more on average in one molecule, preferably about 1 to 300, and the average molecular weight is about 1,000 to 100,000, preferably about 5,000.
Those in the range of to 80,000 are preferable.

As the epoxy group- and reactive silicon group-containing resin, for example, an epoxy group-containing ethylenically unsaturated monomer (a), a reactive silicon group-containing ethylenically unsaturated monomer (b) and, if necessary, other Radical copolymers of ethylenically unsaturated monomers (e) can be used.

Examples of the hydroxyl group- and / or carboxyl group-containing resin include those similar to the hydroxyl group- and / or carboxyl group-containing resin in the mixed resin (II) described above.

In the mixed resin (IV) described above, the mixing ratio of the epoxy group- and reactive silicon group-containing resin and the hydroxyl group- and / or carboxyl group-containing resin is based on the total weight of the two. The group-containing resin is in the range of about 30 to 90% by weight, preferably about 40 to 80% by weight, and the hydroxyl group and / or carboxyl group-containing resin is about 1%.
A range of 0 to 70% by weight, preferably about 20 to 60% by weight is suitable. If the mixing ratio is out of this range, low-temperature curability, acid resistance, scratch resistance and the like are deteriorated, which is not preferable.

In the above mixed resin (A-2), if the number of epoxy groups and reactive silicon groups deviates from the above range, low temperature curing property, acid resistance, scratch resistance and the like are deteriorated, which is not preferable. On the other hand, if the average molecular weight is less than the above range, the durability of the coating film decreases, while if it exceeds the above range, the storage stability, the appearance of the coating film, etc. are deteriorated.

In the present invention, the radical polymerization reaction carried out to obtain each of the above resin components can be carried out by a conventionally known method, for example, a radical polymerization initiator (eg, azoisobutyronitrile, azobisdimethyl). In the presence of valeronitrile, di-tert-butyl hydroperoxide, benzoyl peroxide, etc.) in an organic solvent (eg, ketone type, ester type, alcohol type, ether type, hydrocarbon type, etc.), for example, about 60 ~ 200 ° C
Then, the ethylenically unsaturated monomer may be polymerized for about 1 to 10 hours.

Organotin Compound (B) The organotin compound (B) that can be used in the present invention is 2
It is a compound in which an organic group is bonded to a valent or tetravalent tin atom, and is a liquid or solid compound having a boiling point of 150 ° C. or higher at room temperature (20 ° C.). Examples of the organic group bonded to the tin atom include a monovalent hydrocarbon group having 1 to 20 carbon atoms, a group containing an ether bond and / or an ester bond together with this hydrocarbon group, and the like. Further, the organotin compounds include compounds having two or more tin molecules in one molecule.

In the present invention, among the above-mentioned organotin compounds (B), an organic group represented by the following general formula (I) or (II) containing a hydrocarbon group as an organic group and an ether bond and / or an ester bond. A curable composition using a tin-based compound has the advantage of further improved storage stability, low temperature curability, yellowing resistance and the like, and the compound of the general formula (I) is particularly preferable.

(R ¹ ) _n Sn (OR ² ) _4-n (I) (R ¹ ) _p Sn (OR ² ) _2-p (II) (wherein R ¹ is the same or different and It represents a monovalent hydrocarbon group of 1 to 20. R ^{2 s} are the same or different,
A monovalent hydrocarbon group having 1 to 20 carbon atoms,

[0072]

Embedded image

Is shown. R ³ represents a monovalent hydrocarbon group having 1 to 20 carbon atoms. Moreover, n shows the integer of 0 or 1-3, p shows the integer of 0 or 1, and m shows the integer of 1-20. ) The organotin compounds may be used alone or in combination of two or more.

The above-mentioned organic group and the general formula (I) or (I
1) having 1 to 20 carbon atoms of the organotin compound represented by I)
The valent hydrocarbon group may be any type of an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group and a combination of these groups. The aliphatic hydrocarbon group may be linear or branched, and may contain an unsaturated bond, for example, methyl, ethyl, n-.
Propyl, iso-propyl, n-butyl, iso-butyl, tert-butyl, n-pentyl, iso-pentyl, tert-pentyl, neo-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n
-Decyl, dodecyl, tridecyl, tetradecyl groups and the like.

Examples of the alicyclic hydrocarbon group include a cyclohexyl group and the like. Examples of the aromatic hydrocarbon group include phenyl, methylphenyl, dimethylphenyl, toluyl and xylyl groups. In addition, examples of the group in which the aliphatic hydrocarbon group and the aromatic hydrocarbon group are combined include a benzyl group and a phenethyl group.
Among these hydrocarbon groups, an alkyl group having 1 to 20 carbon atoms and a phenyl group are preferable.

In the organotin compound of the above general formula (I) or (II), R ² is

[0077]

[Chemical 4]

The one having an ester bond is excellent in storage stability and low temperature curability. Further, in the general formula (I) or (II), it is preferable that R ³ is an alkyl group having 1 to 20 carbon atoms or a phenyl group.

Further, among the organotin compounds of the above general formula (I), particularly those in which n is 0 or 1, the storage stability,
Excellent low temperature curability.

Examples of the organotin compound of the above general formula (I) containing an ester bond include, for example, tin tetraacetate, tin tetraoctate, tin tetralaurate, butyltin triacetate, butyltin tributyrate, and butyltin trihexane. Xylate, butyltin trioctate, butyltin trilaurate, butyltin trimethylmalate, octyltin triacetate,
Octyltin tributyrate, octyltin trihexylate, octyltin trioctate, octyltin trilaurate, octyltin trimethylmalate, phenyltin tributyrate, phenyltin trilaurate, dibutyltin diacetate, dibutyltin dibutyrate, Dibutyltin dihexylate, dibutyltin dioctate, dibutyltin dilaurate, dibutyltin diethylmalate, dioctyltin diacetate, dioctyltin dibutyrate, dioctyltin dihexylate, dioctyltin dioctate, dioctyltin dilaurate, dioctyltin diethylmalate, Tributyltin acetate, tributyltin butyrate, tributyltin hexylate, tributyltin octate, tributyltin laureth , Tributyltin methyl maleate, tri-octyl tin acetate, tri-octyl tin butyrate, trioctyltin f carboxylate, trioctyl tin octoate, trioctyltin laurate, include trioctyltin methyl maleate and the like. In addition, examples containing an ether bond include butyltin trimethoxy, butyltin tributoxy, octyltin trimethoxy, phenyltin trimethoxy, dibutyltin dimethoxy, dioctyltin dimethoxy, dioctyltin dibutoxy, tributyltin butoxy, and the like.

Among the above, tin tetraacetate, butyltin triacetate, butyltin tributyrate, butyltin trioctate, butyltin trilaurate, octyltin triacetate, octyltin tributyrate and the like are particularly preferable.

Examples of the organotin compound represented by the general formula (II) include tin diacetate, tin dibutyrate, tin dioctate and tin dilaurate.

In the thermosetting composition of the present invention, the resin component (A) consisting of the resin (A-1) or the mixed resin (A-2) and the organic tin compound (B) are mixed in proportions of resin components. (A) Organotin compound (B) per 100 parts by weight
Is about 0.001 to 20 parts by weight, preferably about 0.01 to
A range of 15 parts by weight is preferred.

When the organotin compound (B) is less than the above range, the low temperature curability is deteriorated, while when it exceeds the above range, further low temperature curability is not obtained, and the finished appearance and durability of the cured product are not obtained. Also decreases, which is not preferable.

The thermosetting composition of the present invention comprises, in addition to the resin component (A) and the organotin compound (B) components described above, if necessary, a colorant, a filler, an organic solvent, an ultraviolet stabilizer,
An ultraviolet absorber, a fluidity modifier and other additives can be added.

The thermosetting composition of the present invention can be cured at a temperature of 60 ° C. or higher, and its application is not particularly limited and can be selected from a wide range of fields and applied. Particularly preferably, it can be applied to the field of paints, for example.

Next, the curing method of the present invention will be described.

The curing method of the present invention is carried out by applying an organic solution or dispersion prepared by dissolving or dispersing the above-mentioned thermosetting composition in an organic solvent onto a substrate and then heating to cure it. be able to. At this time, the solid content concentration is
It is preferably about 20 to 99% by weight.

The organic solvent that dissolves or disperses the thermosetting composition may be appropriately selected depending on the type of the thermosetting composition, but is usually an ester type, a ketone type, an ether type, an alcohol type, or a hydrocarbon type. A solvent such as can be used.

The base material is not particularly limited as long as it is soluble in an organic solvent and does not melt or deteriorate by heating at about 60 ° C., and a conventionally used material is selected and used. be able to. Specific examples thereof include treated or untreated metals, plastics, papers, fibers, and coated products of these.

As a method for applying to the base material, for example, usual coating means such as spray coating, brush coating, roller coating and dip coating can be used. Thereby, the coating is applied so that the dry film thickness is in the range of about 1 to 100 μm.

The heat curing is usually carried out at a temperature of about 60 ° C. or higher, preferably about 100 to 300 ° C. Also, the heating time varies greatly depending on the temperature,
For example, it is usually about 10 seconds at about 250 ° C, or about 6 seconds.
At 0 ° C., it takes about 3 hours.

[0093]

The thermosetting composition of the present invention does not react at room temperature (about 20 ° C.), but the reaction rapidly occurs when a temperature of about 60 ° C. is applied, so that the composition is stable during storage. It has excellent properties, excellent low temperature curability, and excellent discoloration resistance of the cured product. The reason for this is not clear, but the heat causes the organotin compound and the reactive silicon-containing compound to bond with each other to form a complex of tin and silicon, which is then subjected to a cationic polymerization reaction of the epoxy group or a cationic reaction. It is presumed that it acts as a curing catalyst that accelerates the addition reaction.

[0094]

EXAMPLES Hereinafter, production examples, examples and comparative examples will be described.
The present invention will be described more specifically.

Production Example of Acrylic Resin (1) Methacryloxypropyltrimethoxysilane 150 g, 3,4-using a reaction vessel equipped with a reflux device and a stirrer
Epoxy cyclohexyl methyl methacrylate 220
g, 232 g of hydroxyethyl acrylate, 200 g of cyclohexylmethyl acrylate, 198 g of butyl methacrylate and 10 g of azoisobutyronitrile were added dropwise to 1,000 g of xylene at 110 ° C., and the mixture was reacted for 5 hours to give a number average molecular weight of 10,000. Acrylic resin (about 11 epoxy groups in one molecule, hydroxyl value = 112
And containing about 19 alkoxysilyl groups).

Production Example of Acrylic Resin (2) Using a reaction vessel equipped with a reflux device and a stirrer, 150 g of methacryloxypropyltrimethoxysilane, 3,4-
Epoxy cyclohexyl methyl methacrylate 220
g, 263 g of hydroxyethyl acrylate, 170 g of cyclohexylmethyl acrylate, 169 g of butyl methacrylate and 10 g of azoisobutyronitrile were added dropwise to 1,000 g of xylene at 110 ° C., and the mixture was reacted for 5 hours, and then succinic anhydride at 80 ° C. After adding 28 g and reacting for 2 hours, an acrylic resin having a number average molecular weight of 10,000 (containing about 11 epoxy groups and about 19 alkoxysilyl groups in one molecule, a hydroxyl value of 112 and an acid value of 1
5.6) was produced.

Production Example of Epoxy Group-Containing Resin (3) Using a reaction vessel equipped with a reflux device and a stirring device, 3,4-
Epoxy cyclohexyl methyl methacrylate 400
g, 600 g of butyl methacrylate and 10 g of azoisobutyronitrile were added to xylene 1.00 at 110 ° C.
It was added dropwise to 0 g and reacted for 5 hours to give a number average molecular weight of 1
10,000 acrylic resins (about 2 epoxy groups per molecule)
Containing 0).

Production Example of Epoxy Group-Containing Resin (4) Using a reaction vessel equipped with a reflux device and a stirring device, 284 g of glycidyl methacrylate and 35 of butyl methacrylate were used.
A mixture of 8 g, 358 g of cyclohexylmethyl acrylate and 10 g of azoisobutyronitrile was added dropwise to 1,000 g of xylene at 110 ° C. and reacted for 5 hours to obtain an acrylic resin having a number average molecular weight of 10,000 (epoxy group in one molecule. Containing about 20).

Production Example of Acrylic Resin (5) Using a reaction vessel equipped with a reflux device and a stirrer, 232 g of hydroxyethyl acrylate, 384 g of cyclohexylmethyl acrylate, 384 g of butyl methacrylate.
And a mixture of 10 g of azoisobutyronitrile at 110 ° C.
Was added dropwise to 1,000 g of xylene and reacted for 5 hours to produce an acrylic resin having a number average molecular weight of 10,000 (hydroxyl value = 112).

Production Example of Acrylic Resin (6) Using a reaction vessel equipped with a reflux device and a stirrer, 232 g of hydroxyethyl acrylate, 10 g of acrylic acid, 384 g of cyclohexylmethyl acrylate, 384 g of butyl methacrylate and 10 g of azoisobutyronitrile were used.
The resulting mixture was added dropwise to 1,000 g of xylene at 110 ° C. and reacted for 5 hours, and then 28 g of succinic anhydride was added at 80 ° C.
Was added and reacted for 2 hours to give a number average molecular weight of 10,000
0 acrylic resin (hydroxyl value = 112, acid value = 15.
6) was produced.

Production Example of Epoxy Group-Containing Resin (7) Using a reaction vessel equipped with a reflux device and a stirrer, 3,4-
Epoxy cyclohexyl methyl methacrylate 400
g, 232 g of hydroxyethyl acrylate, 184 g of butyl methacrylate, 184 g of cyclohexylmethyl acrylate, and 10 g of azoisobutyronitrile were added dropwise to 1,000 g of xylene at 110 ° C., and the mixture was reacted for 5 hours to give a number average molecular weight of 10,000. Acrylic resin (containing about 20 epoxy groups in one molecule, hydroxyl value =
112) was produced.

Production Example of Acrylic Resin (8) Using a reaction vessel equipped with a reflux device and a stirrer, 243 g of methacryloxypropyltrimethoxysilane, 232 g of hydroxyethyl acrylate, 263 g of cyclohexylmethyl acrylate, 262 g of butyl methacrylate.
And a mixture of 10 g of azoisobutyronitrile at 110 ° C.
Xylene of 1,000 g and reacted for 5 hours to obtain an acrylic resin having a number average molecular weight of 10,000 (containing about 30 alkoxysilyl groups in one molecule, a hydroxyl value of 1
12) was produced.

Production Example of Acrylic Resin (9) Using a reaction vessel equipped with a reflux device and a stirrer, 243 g of methacryloxypropyltrimethoxysilane, 20 g of acrylic acid, cyclohexylmethyl acrylate 368
g, 369 g of butyl methacrylate and 10 g of azoisobutyronitrile were added to xylene 1.00 at 110 ° C.
It was added dropwise to 0 g and reacted for 5 hours to give a number average molecular weight of 1
10,000 acrylic resins (containing about 30 alkoxysilyl groups in one molecule, acid value = 15.6) were produced.

Production Example of Acrylic Resin (10) Using a reaction vessel equipped with a reflux device and a stirring device, 243 g of methacryloxypropyltrimethoxysilane, 232 g of hydroxyethyl acrylate, 20 g of acrylic acid, 253 g of cyclohexylmethyl acrylate, 252 g of butyl methacrylate and Azoisobutyronitrile 10g
The mixture was added dropwise to 1,000 g of xylene at 110 ° C. and reacted for 5 hours to obtain an acrylic resin having a number average molecular weight of 10,000 (containing about 30 alkoxysilyl groups in one molecule, hydroxyl value = 112, acid Value = 15.6) was produced.

Production Example of Acrylic Resin (11) Using a reaction vessel equipped with a reflux device and a stirrer, 80 g of acrylic acid and 460 cyclohexylmethyl acrylate were used.
g, 460 g of butyl methacrylate and 10 g of azoisobutyronitrile were added to xylene 1.00 at 110 ° C.
It was added dropwise to 0 g and reacted for 5 hours to give a number average molecular weight of 1
10,000 acrylic resins (acid value = 62) were produced.

Production Example of Reactive Silicon Group-Containing Resin (a) "Colcoat ES40" 530 g "Colcoat company, trade name, the same as hereinafter, 1 to 10 tetramer of tetraethyl silicate, average about 5 mer" Benzyl alcohol 470 g Tris 200 g of a mixture of 0.1 g of (acetylacetonato) aluminum was removed at 160 ° C. for 6 hours to obtain a reactive silicon group-containing resin (a). This product has 6 out of 12 ethoxy groups on average in one molecule.

[0107]

Embedded image

Is replaced by.

Example 1 200 g of the above-mentioned acrylic resin (1) (resin solid content 10
0 g) was mixed with 3.0 g of butyltin triacetate.

Examples 2 to 22 The formulations of Examples 2 to 22 were prepared with the formulations shown in Table 1.

Comparative Examples 1 to 4 Compounds of Comparative Examples 1 to 4 were produced with the formulations shown in Table 1.

The storage stability results of Examples and Comparative Examples are summarized in Table 1.

The curable compositions of the above Examples and Comparative Examples were applied to degreased mild steel plates so that the dry film thickness was about 50 μm, and then heated at 130 ° C. for 30 minutes to improve the performance of the cured products. Examined. The results are summarized in Table 1.

In Table 1, * 1 to * 6 have the following meanings.

* 1 ERL-4221: Union Carbide, trade name,
Alicyclic diepoxy compound * 2 a: the above-mentioned reactive silicon group-containing resin (a) b: phenyltrimethoxysilane * 3 Metal chelate: trisacetylacetonatoaluminum * 4 Storage stability: evaluated according to the following criteria.

⊚: No thickening at 40 ° C. for 7 days or more, ◯: Slightly thickening at 40 ° C. for 7 days or more, Δ: Thickening and gelation at 40 ° C. in 1 to 6 days, ×: 40 ° C. Gels below.

* 5 Appearance: The presence or absence of abnormalities such as cracks and glossiness of the cured film were observed.

Curability: The peeled cured film was extracted with an acetone solvent at a reflux temperature for 2 hours, and the residual ratio (%) of the cured film was examined.

Yellowing resistance: The yellowing was visually observed by comparing the film before and after heating. ○: Good with no change,
X: Yellowing and bad.

* 6: Combination of 2 or 3 types.

[0121]

[Table 1]

[0122]

[Table 2]

[0123]

[Table 3]

[0124]

[Table 4]

[0125]

[Table 5]

Claims (15)

[Claims] 1. A resin (A-) containing (A) (i) an epoxy group, (ii) a reactive silicon group, and (iii) a hydroxyl group and / or a carboxyl group in the same molecule as an essential functional group component.
1) or a mixture of two or more resins, each resin containing at least one of the functional group components of (i) to (iii) above, wherein the mixture contains (i) to (iii) above. ) A mixed resin (A-2) in which all functional group components are present, and (B) an organotin-based compound, which is a thermosetting composition. 2. The mixed resin (A-2) is a mixture of an epoxy group-containing resin and a reactive silicon group-containing resin, and at least one of the epoxy group-containing resin and the reactive silicon group-containing resin has a hydroxyl group. And / or the carboxyl group is present, The thermosetting composition according to claim 1. 3. The thermosetting composition according to claim 1, wherein the mixed resin (A-2) is a mixture of an epoxy group-containing resin, a reactive silicon group-containing resin, and a hydroxyl group and / or carboxyl group-containing resin. . 4. The mixed resin (A-2) is a mixture of an epoxy group-containing resin, a reactive silicon group-containing resin, and a hydroxyl group and / or a carboxyl group-containing resin, and the epoxy group-containing resin and the reactive silicon group. The thermosetting composition according to any one of claims 1 to 3, wherein a hydroxyl group and / or a carboxyl group is present in at least one of the contained resins. 5. The thermosetting composition according to claim 1, wherein the mixed resin (A-2) is a mixture of an epoxy group- and reactive silicon group-containing resin and a hydroxyl group- and / or carboxyl group-containing resin. 6. The thermosetting resin according to claim 3, wherein the mixed resin (A-2) is a mixture of an epoxy group- and hydroxyl group-containing resin, a reactive silicon group-containing resin, and a hydroxyl group- and carboxyl group-containing resin. Composition. 7. A mixed resin (A-2) is an epoxy group-, hydroxyl group- and reactive silicon group-containing resin, a reactive silicon group-containing resin,
The thermosetting composition according to claim 3 or 4, which is a mixture of a resin containing a hydroxyl group and a carboxyl group. 8. The thermosetting composition according to claim 1, wherein the epoxy group is an alicyclic epoxy group. 9. The thermosetting composition according to claim 1, wherein the reactive silicon group is an alkoxysilyl group. 10. An organotin compound (B) has the following general formula (I) (R ¹ ) _n Sn (OR ² ) _4-n (I) (wherein R ¹ has the same or different carbon number). 1-2
A monovalent hydrocarbon group of 0 and each of R ^{2 is the} same or different and has 1 to 20 carbon atoms; R ³ represents a monovalent hydrocarbon group having 1 to 20 carbon atoms, n represents an integer of 0 or 1 to 3, and m represents an integer of 1 to 20. The thermosetting composition according to claim 1, which is a compound represented by the formula (1). 11. An organotin compound (B), wherein R ² is represented by the following formula (1): The thermosetting composition according to claim 10, which is a compound of 12. The thermosetting compound according to claim 10, wherein the organotin compound (B) is a compound represented by the general formula (1), wherein R ³ is an alkyl group having 1 to 20 carbon atoms or a phenyl group. Sex composition. 13. The organotin compound (B) is a compound in which n is 0 or 1 in the general formula (1).
The thermosetting composition according to any one of 0 to 12. 14. The organotin compound (B) according to any one of claims 10 to 13, wherein in the general formula (1), R ¹ is an alkyl group having 1 to 20 carbon atoms or a phenyl group. The thermosetting composition described in 1. 15. A method comprising applying an organic solution prepared by dissolving or dispersing the thermosetting composition according to any one of claims 1 to 14 in an organic solvent onto a substrate and then heating to cure the solution. Characterizing curing method.