JPH0749549B2 - Curable composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to a novel curable liquid composition.

Conventional Technology and Its Problems Conventionally, as a composition capable of being crosslinked and cured at a relatively low temperature from room temperature to 100 ° C., a composition in which an aluminum chelate compound is mixed with an acrylic resin containing an alkoxysilane group is known (special feature (Kaisho 60-67553).

However, the above-mentioned conventional compositions have a drawback in that they have excellent low-temperature curability, chemical resistance of the coating film, and water resistance, but the mechanical properties of the coating film and the storage stability of the coating material are not always sufficient. That is, when high mechanical properties such as impact resistance and flex resistance are required, there is a limit only by adjusting the kind and amount of the aluminum chelate compound, the content of the alkoxysilane group, the molecular weight of the acrylic resin and the like. However, there are drawbacks such as limited applications and insufficient paint storage stability, coating surface condition, weather resistance and the like.

Means for Solving the Problems The present inventor has conducted extensive studies to solve the above-mentioned drawbacks, and as a result, a non-aqueous dispersion liquid of specific polymer particles using a specific copolymer as a dispersion stabilizer resin, By incorporating a chelate compound, which is a curing agent for cross-linking reaction, the coating film has excellent low-temperature curability, chemical resistance of the coating film, and water resistance, and the coating film has high mechanical properties. It was found that a curable composition having sufficient surface condition and weather resistance can be obtained, and the present invention has been completed.

That is, the present invention has the general formula [In the formula, A is Indicates.

R ₁ is a hydrogen atom or a methyl group, R ₂ is a divalent aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms, R ₃ and R ₄ are the same or different and are a phenyl group, an alkyl group having 1 to 6 carbon atoms. Group or carbon number 1
~ 10 alkoxy group, R ₅ represents an alkyl group having 1 to 10 carbon atoms, respectively. n shows the integer of 1-100. ] Using a copolymer obtained as an essential monomer component an alkoxysilane group-containing vinyl monomer and a hydroxyl group-containing unsaturated monomer, which are compounds represented by, as a dispersion stabilizer resin,
Compounding a non-aqueous dispersion of polymer particles insoluble in the organic liquid obtained by polymerizing a radically polymerizable unsaturated monomer in the organic liquid in the presence of the resin, a chelate compound as a crosslinking reaction curing agent. The present invention relates to a curable composition.

In the present invention, the above specific copolymer is used as the dispersion stabilizer resin. In the compound of the general formula (I) which is an essential monomer of the copolymer, n is preferably 1-10.

In the general formula (I), the number of carbon atoms represented by R ₂ is 1 to
Examples of the divalent aliphatic saturated hydrocarbon group of 6 include linear or branched alkylene groups such as methylene, ethylene, propylene, 1,2-butylene, 1,3-butylene, 2,3-butylene and tetramethylene. , Ethylethylene, pentamethylene, hexamethylene groups and the like. R ₃ and
As the alkyl group having 1 to 6 carbon atoms represented by R ₄ , a linear or branched alkyl group such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec
- butyl, tert- butyl, n- pentyl, isopentyl, neopentyl, n- hexyl, there may be mentioned Isohekisuru group, the alkyl group having 1 to 10 carbon atoms represented by R ₅ further addition of n- Heptyl, 1-methylpentyl, 2-methylhexyl, n-octyl, n-
Nonyl, n-decyl and the like can be mentioned. R ₃ and R ₄
As the alkoxy group having 1 to 10 carbon atoms, a linear or branched alkoxy group such as methoxy, ethoxy,
Examples thereof include n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentoxy, isopentoxy, n-hexyloxy, isohexyloxy and n-octyloxy. Further, in the general formula (I), when n is 2 or more, R _{3 s} and R _{4 s} may be the same or different.

Of the compounds of general formula (I) in the present invention, A is Are, for example, γ- (meth) acryloxyethyltrimethoxysilane, γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth) acryloxypropyltriethoxysilane, γ- (meth) acryloxy. Propyltripropoxysilane, γ- (meth) acryloxypropylmethyldimethoxysilane, γ- (meth) acryloxypropylmethyldiethoxysilane, γ
-(Meth) acryloxypropylmethyldipropoxysilane, γ- (meth) acryloxybutylphenyldimethoxysilane, γ- (meth) acryloxybutylphenyldiethoxysilane, γ- (meth) acryloxybutylphenyldisilane Propoxysilane, γ- (meth) acryloxypropyldimethylmethoxysilane, γ- (meth) acryloxypropyldimethylethoxysilane, γ- (meth)
Acryloxypropylphenylmethylmethoxysilane,
γ- (meth) acryloxypropylphenylmethylethoxysilane, Can be mentioned.

Further, among the compounds of general formula (I), A is Is, for example, Etc. can be mentioned.

Among these compounds of general formula (I), especially acryloxypropyltrimethoxysilane, methacryloxypropyltriethoxysilane, methacryloxypropyltri-
N-butoxysilane, acryloxypropylmethyldimethoxysilane, methacryloxypropylmethyldimethoxysilane, methacryloxypropylmethyldi-n-butoxysilane and the like are preferable.

The hydroxyl group-containing unsaturated monomer, which is another essential monomer of the specific copolymer used as the dispersion stabilizer resin in the present invention, enhances the hydrophilicity of the copolymer and has the general formula (I).
It promotes the hydrolysis of the alkoxysilane group derived from the compound (1) and acts as a functional group that reacts with the chelate compound as the crosslinking reaction curing agent.

Preferred examples of the hydroxyl group-containing unsaturated monomer include 2-hydroxyethyl (meth) acrylate and 2
A hydroxyalkyl ester of (meth) acrylic acid having 2 to 8 carbon atoms such as hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate; polyethylene glycol, polypropylene glycol, polybutylene glycol Etc. and a monoester of a unsaturated carboxylic acid such as (meth) acrylic acid; a monoether of a C2-8 hydroxyalkyl ester of the above (meth) acrylic acid and the above polyether polyol; Addition products of hydroxyalkyl esters of (meth) acrylic acid having 2 to 8 carbon atoms with lactones such as ε-caprolactone and γ-valerolactone; α, β-unsaturated carboacids such as (meth) acrylic acid and “cardiura” E10 "
(Ciel Petrochemical Co., Ltd., trade name, composition of glycidyl ester of versatiic acid) and α of ethylene oxide, propylene oxide, butylene oxide, etc.
-Adducts with monoepoxy compounds such as olefin epoxide; glycidyl (meth) acrylate with acetic acid, propionic acid, p-tert-butylbenzoic acid, lauric acid,
Adducts with stearic acid and other monobasic acids such as fatty acids; unsaturated compounds containing acid anhydride groups such as maleic anhydride and itaconic anhydride and ethylene glycol, 1,6-hexanediol, neopentyl glycol, etc. Examples thereof include monoesters or diesters with glycols; hydroxyalkyl vinyl ethers such as hydroxyethyl vinyl ether; and chlorine-containing ones such as 3-chloro-2-hydroxypropyl (meth) acrylate.

In the present invention, the copolymer used as the dispersion stabilizer resin contains at least one kind of the alkoxysilane group-containing vinyl monomer represented by the general formula (I) and at least one kind of the hydroxyl group-containing unsaturated monomer as an essential monomer. It is a copolymer obtained as a body component. The proportion of these essential monomers used can be selected from a wide range, but usually the monomer of the general formula (I) is about 1 to 99% by weight, preferably 5 to 30% by weight in the monomers used.
The amount of the hydroxyl group-containing unsaturated monomer is about 1 to 99% by weight, preferably about 3 to 30% by weight, of the monomers used. When the ratio of the former is less than 1% by weight (the ratio of the latter exceeds 99% by weight) or the ratio of the former exceeds 99% by weight (the ratio of the latter is less than 1% by weight), the curability is It tends to decrease and the chemical and mechanical properties of the coating film tend to decrease, such being undesirable.

Moreover, in the said copolymer, you can use another polymerizable monomer further as needed. The monomer can be appropriately selected according to the performance required for the coating film, but a long-chain vinyl-based monomer is preferable from the viewpoint of copolymerizability, solubility in an organic liquid and the like. Other polymerizable monomers that can be preferably used include, for example, n-butyl (meth).
Acrylate, isobutyl (meth) acrylate, tert
-Butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, n-octyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) ) C4-C18 alkyl or cycloalkyl ester of (meth) acrylic acid such as acrylate; of (meth) acrylic acid such as methoxybutyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxybutyl (meth) acrylate Alkoxyalkyl ester; ester of aromatic alcohol such as benzyl (meth) acrylate with (meth) acrylic acid; hydroxyalkyl ester of glycidyl (meth) acrylate or (meth) acrylic acid Phosphoric acid, lauric acid, linoleic acid, an adduct of a monocarboxylic acid compound such as oleic acid;
Addition product of (meth) acrylic acid and a monoepoxy compound such as "Cardura E10"; styrene, α-methylstyrene, vinyltoluene, p-chlorostyrene, p-tere-
Vinyl aromatic compounds such as butyl styrene; itaconic acid,
Α, β-unsaturated carboxylic acids other than (meth) acrylic acid such as itaconic anhydride, crotonic acid, maleic acid, maleic anhydride, fumaric acid and citraconic acid, and butyl alcohol,
Mono- or diesters with C 4-18 monoalcohols such as pentyl alcohol, heptyl alcohol, octyl alcohol, stearyl alcohol;
8F "," Viscoat 8FM "," Viscoat 3F "," Viscoat 3FM "(all manufactured by Osaka Organic Chemical Co., Ltd., trade name,
(Meth) acrylates having a fluorine atom in the side chain,
Examples thereof include fluorine atom-containing compounds such as perfluorocyclohexyl (meth) acrylate and perfluorohexyl ethylene.

Copolymerization for producing the dispersion stabilizer resin used in the present invention is usually carried out using a radical polymerization initiator. Examples of the radical polymerization initiator that can be used include 2,
Azo initiators such as 2'-azobisisobutyronitrile and 2,2'-azobis (2,4-dimethylvaleronitrile);
Benzoyl peroxide, lauryl peroxide,
Peroxide-based initiators such as tert-butyl peroctoate and tert-butyl peroxy-2-ethylhexanoate are listed, and these polymerization initiators are generally used per 100 parts by weight of the monomer to be polymerized. 0.2 to 10 parts by weight, preferably 0.
It can be used within the range of 5 to 5 parts by weight. It is appropriate to use a temperature in the range of about 60 to 160 ° C. during the polymerization, and the reaction is usually completed in about 1 to 15 hours.

The molecular weight of the copolymer used as the dispersion stabilizer resin in the present invention is usually about 5000 to 100,000 in terms of weight average molecular weight (about 1000 to 60,000 in terms of number average molecular weight), preferably about 5
It is preferable to set it within the range of about 000 to 50,000. When the molecular weight is less than about 5,000, the dispersion particles are insufficiently stabilized and tend to aggregate and settle, while the molecular weight is about 10
When it exceeds 0000, the viscosity becomes extremely high and handling becomes difficult, which is not preferable.

The dispersion stabilizer resin used in the present invention may be used alone or in combination of two or more having different copolymerization compositions and molecular weights. Further, if necessary, other dispersion stabilizers such as butyl etherification may be used. It is also possible to use together with a small amount of a melamine-formaldehyde resin, an alkyd resin, a general acrylic resin containing no compound of the general formula (I) as a copolymer component, or the like.

In the present invention, a radically polymerizable unsaturated monomer is polymerized in an organic liquid in the presence of the above dispersion stabilizer resin to prepare a non-aqueous dispersion liquid of polymer particles insoluble in the organic liquid.

As the organic liquid used in the polymerization, the dispersion polymer particles produced by the polymerization are not substantially dissolved, but they are good solvents for the stabilizer resin and the radically polymerizable unsaturated monomer. Organic liquids are included. Specific examples of such organic liquids include aliphatic hydrocarbons such as hexane, heptane, and octane; aromatic hydrocarbons such as benzene, toluene, and xylene; methyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol,
Alcohols such as octyl alcohol; ethers such as cellosolve, butyl cellosolve, and diethylene glycol monobutyl ether; ketones such as methyl isobutyl ketone, diisobutyl ketone, methyl ethyl ketone, methylhexyl ketone, ethyl butyl ketone; ethyl acetate,
Examples thereof include esters such as isobutyl acetate, amyl acetate, and 2-ethylhexyl acetate. These organic liquids may be used alone or in admixture of two or more, but generally they are mainly aliphatic hydrocarbons, and aromatic hydrocarbons, alcohols and ethers are appropriately added. A combination of compounds, ketones or esters is preferably used.

As the radically polymerizable unsaturated monomer used for the above polymerization, one having a smaller number of carbon atoms than that of the monomer used as the monomer component of the dispersion stabilizer resin having excellent polymerizability is used. It is preferable that it is easily formed as dispersed polymer particles. Examples of such radically polymerizable unsaturated monomers include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert- Butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate,
C1-C1 of (meth) acrylic acid such as cyclohexyl (meth) acrylate, n-octyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate and stearyl (meth) acrylate
18 alkyl or cycloalkyl ester; alkoxyalkyl ester of (meth) acrylic acid such as methoxybutyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxybutyl (meth) acrylate; aromatic alcohol such as benzyl (meth) acrylate Ester of (meth) acrylic acid; glycidyl (meth)
Acrylate and acetic acid, propionic acid, oleic acid, p-
Addition product of tertiary-butylbenzoic acid and other monocarboxylic acid compounds having 2 to 18 carbon atoms; addition product of (meth) acrylic acid and monoepoxy compound such as "CARDILLA E10"; styrene, α-methylstyrene, vinyl Vinyl aromatic compounds such as toluene, p-chlorostyrene and p-tert-butylstyrene: Other than (meth) acrylic acid such as itaconic acid, itaconic anhydride, crotonic acid, maleic acid, maleic anhydride, fumaric acid and citraconic acid Mono- or diesters of α, β-unsaturated carboxylic acids with monoalcohols having 1 to 18 carbon atoms such as methyl alcohol, butyl alcohol, hexyl alcohol and stearyl alcohol;
F ”,“ Viscoat 8FM ”,“ Viscoat 3F ”,“ Viscoat 3FM ”(all manufactured by Osaka Organic Chemical Co., Ltd., trade name, (meth) acrylates having a fluorine atom in the side chain), perfluorocyclohexyl (meta ) Fluorine atom-containing compounds such as acrylate and perfluorohexyl ethylene;
Cyano group-containing unsaturated compounds such as (meth) acrylonitrile; vinyl acetate, vinyl benzoate, "VEOV
A) ”(Ciel Co., Ltd.) vinyl ester; n
-Vinyl ethers such as butyl vinyl ether, ethyl vinyl ether and methyl vinyl ether; polyvinyl compounds such as di (meth) acrylate of 1,6-hexanediol, tri (meth) acrylate of trimethylolpropane and divinylbenzene; ethylene, propylene, vinyl chloride , Α-olefin compounds such as vinylidene chloride and the like. As described above, the monomer component forming the polymer particles is to stably form the particle component by combining those having a carbon number smaller than that of the monomer component of the dispersion stabilizer resin. However, particularly preferable from this viewpoint are (meth) acrylic acid esters having 8 or less and preferably 4 or less carbon atoms, vinyl aromatic compounds,
(Meth) acrylonitrile and the like.

These radically polymerizable unsaturated monomers can be used alone or in combination of two or more kinds as appropriate.

The radical-polymerizable unsaturated monomer is usually polymerized using a radical polymerization initiator. Examples of usable radical polymerization initiators include azo initiators such as 2,2′-azobisisobutyronitrile and 2,2′-azobis (2,4-dimethylvaleronitrile); benzoyl peroxide, Examples include peroxide initiators such as lauryl peroxide, tert-butyl peroctoate, and tert-butyl peroxy-2-ethylhexanoate, and these polymerization initiators are generally monomers used for polymerization. 0.2 per 100 parts by weight
It can be used in an amount of about 10 to 10 parts by weight, preferably 0.5 to 5 parts by weight. The proportion of the dispersion stabilizer resin used during the polymerization can be selected from a wide range depending on the type of the resin, etc., but in general, the radical polymerizable unsaturated monomer per 100 parts by weight of the dispersion stabilizer resin. The amount of the body is about 3 to 240 parts by weight, preferably 5 to 82 parts by weight. Further, the total concentration of the dispersion stabilizer resin and the radically polymerizable unsaturated monomer in the organic liquid is generally about 30 to 70% by weight, preferably 30 to 60% by weight.

The polymerization can be carried out by a method known per se, and it is suitable that the reaction temperature during the polymerization is usually in the range of about 60 to 160 ° C., and the reaction is usually completed in about 1 to 15 hours.

Thus, a stable non-moisture acid solution can be obtained in which the liquid phase is a dispersion stabilizer resin dissolved in an organic liquid and the solid phase is polymer particles in which a radically polymerizable unsaturated monomer is polymerized. The particle size of the polymer particles is usually in the range of about 0.1 to 1.0 μm.
If the particle size is smaller than this range, the viscosity of the varnish will be high, while if it is larger than this range, the particles will swell or aggregate during storage, which is not preferable.

In the present invention, the storage stability and mechanical properties can be further improved by binding the dispersion stabilizer resin in the non-aqueous dispersion liquid and the polymer particles. There is almost no change in the dispersed state of the appearance even when combined,
The particle size of the polymer particles is also within the above range.

Examples of the method for binding the dispersion stabilizer resin and the polymer particles include, for example, a hydroxyl group, an acid group, an acid anhydride group, an epoxy group, a methylol group, an isocyanate group, an amide group, and an amino group in the step of producing the dispersion stabilizer resin in advance. A monomer component having a functional group such as a group has been partially copolymerized, and further a hydroxyl group, an acid group, an acid anhydride group, an epoxy group, which reacts the functional group as a monomer component for forming polymer particles, It can be carried out by using a monomer having a functional group such as a methylol group, an isocyanate group, an amide group or an amino group. Examples of these combinations include isocyanate groups and hydroxyl groups, isocyanate groups and methylol groups, epoxy groups and acid (anhydrous) groups, epoxy groups and amino groups, isocyanate groups and amide groups, acid (anhydrous) groups and hydroxyl groups. .

As the monomer having such a functional group, for example,
Α, β-ethylenically unsaturated carboxylic acids such as (meth) acrylic acid, crotonic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, fumaric acid and citraconic acid;
Glycidyl group-containing compounds such as glycidyl (meth) acrylate, vinyl glycidyl ether, and allyl glycidyl ether; (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N-alkoxymethylated (meth) acrylamide, diacetone acrylamide, N −
Carboxylic acid amide compounds such as methylol (meth) acrylamide; p-styrenesulfonamide, N-methyl-
Sulfonamide group-containing compounds such as p-styrenesulfonamide and N, N-dimethyl-p-styrenesulfonamide; amino group-containing compounds such as (meth) acrylic acid-tert-butylaminoethyl; 2-hydroxyethyl (meth ) A condensate of acrylate and phosphoric acid or phosphoric acid ester,
A phosphoric acid group-containing compound such as a compound having a glycidyl group such as glycidyl (meth) acrylate to which a phosphoric acid or phosphoric acid ester is added to a glycidyl group; a sulfone such as 2-acrylamido-2-methyl-propanesulfonic acid Acid group-containing compound; m-isopropenyl-α, α-dimethylbenzoyl isocyanate, equimolar adduct of isophorone diisocyanate or tolylene diisocyanate and hydroxy (meth) acrylate, isocyanate group-containing compound such as isocyanoethyl methacrylate, etc. You can

Further, as another method for binding the dispersion stabilizer resin and the polymer particles, it is carried out by polymerizing a radically polymerizable unsaturated monomer in the presence of the dispersion stabilizer resin having a polymerizable double bond. be able to. The introduction of the polymerizable double bond into the dispersion stabilizer resin is carried out, for example, by using an acid group-containing monomer such as carboxylic acid, phosphoric acid or sulfonic acid as a copolymerization component of the resin, and adding glycidyl (meta ) Acrylate,
The reaction can be carried out by reacting a glycidyl group-containing unsaturated monomer such as allyl glycidyl ether, but of course, conversely, the glycidyl group is contained in the resin and the acid group-containing unsaturated monomer is added to the resin. Can also be performed by reacting. These reactions can follow conventionally known conditions.

Further, as still another method of binding the dispersion stabilizer resin and the polymer particles, after producing a non-aqueous dispersion liquid in which functional groups that do not react with each other are introduced into the dispersion stabilizer resin and the polymer particles, It can also be carried out by blending a binder that binds both. Specifically, for example, by polymerizing a hydroxyl group-containing unsaturated monomer alone or a mixture with another unsaturated monomer in the presence of a hydroxyl group-containing dispersion stabilizer resin and an organic liquid, both groups contain a hydroxyl group. It can be carried out by producing a non-moisture acid solution, and then adding a polyisocyanate compound or the like and reacting them at room temperature for several days and at 60 to 100 ° C. for about 1 to 5 hours. As the polyisocyanate compound, any one having at least one isocyanate group in the molecule can be used, and examples thereof include aromatic diisocyanates such as tolylene diisocyanate, xylylene diisocyanate, 4,4′-diphenylmethane diisocyanate and the like. Examples thereof include hydrides thereof; aliphatic diisocyanates such as hexamethylene diisocyanate, lysine diisocyanate, and dimer acid (a dimer of tall oil fatty acid) diisocyanate; alicyclic diisocyanates such as isophorone diisocyanate. In addition to the above combination of combinations, a dispersion stabilizer resin containing an acid group and a combination of polymer particles and a polyepoxide, a dispersion stabilizer resin containing an epoxy group and a combination of a polymer particle and a polycarboxylic acid. , A dispersion stabilizer resin containing an epoxy group or an isocyanate group and a polymer particle in combination with a polysulfide compound. Examples of the polyepoxide include bisphenol A type epoxy resin, bisphenol F type epoxy resin,
Novolac type epoxy resin, epoxy group-containing acrylic resin, etc .; as the polycarboxylic acid, for example, adipic acid,
Sebacic acid, azelaic acid, isophthalic acid and the like; examples of the polysulfide include pentamethylene disulfide, hexamethylene disulfide, poly (ethylene disulfide) and the like.

As described above, the dispersion stabilizer resin and the polymer particles can be chemically bonded, but at this time, various functional groups and polymerizable double bonds are introduced into the dispersion stabilizer resin and / or the polymerizable particles. The amount to be added is sufficient to be at least 0.1 on average in one molecule of the resin and / or particles.

The amount of the hydroxyl group-containing unsaturated monomer in the dispersion stabilizer resin used in the present invention is, as described above, 1 to 99 in the monomers used.
It is about wt%, but when the hydroxyl group is reacted with the polymer particles, the amount used is adjusted so that the hydroxyl group-containing unsaturated monomer component in the resin after the reaction is in the range of 1 to 99% by weight. Just do it.

The non-aqueous dispersion thus obtained has excellent storage stability because the dispersion stabilizer resin and the polymer particles are chemically bonded, and the formed coating film is chemically and mechanically Shows excellent properties.

The curable composition of the present invention is a composition in which a chelate compound as a crosslinking reaction curing agent is added to the above non-aqueous dispersion. The chelate compound imparts excellent low temperature curability to the composition. That is, the alkoxy group derived from the monomer of the general formula (I) in the dispersion stabilizer resin is hydrolyzed in the presence of water using the chelate compound as a catalyst to generate a silanol group, and then the silanol group is dehydrated. It is a compound which is cross-linked by condensation or binding through a chelate compound to be cured at a low temperature.

As the chelate compound used in the present invention, an aluminum chelate compound, a titanium chelate compound,
Zirconium chelate compounds are preferred. Further, among these chelate compounds, a chelate compound containing a compound capable of forming a keto / enol tautomer as a ligand forming a stable chelate ring is preferable.

Examples of the compound capable of forming the keto / enol tautomer include β-diketones (acetylacetone, etc.), acetoacetic acid esters (methyl acetoacetate, etc.), malonic acid esters (ethyl malonate, etc.), and β-position. A ketone having a hydroxyl group (diacetone alcohol, etc.), an aldehyde having a hydroxyl group at the β-position (salicylaldehyde, etc.), an ester having a hydroxyl group at the β-position (methyl salicylate), etc. can be used. In particular, acetoacetic acid esters,
Good results are obtained with β-diketones.

Aluminum chelate compounds are, for example, of the general formula [In the formula, R ₆ represents an alkyl group or an alkenyl group having 1 to 20 carbon atoms. ] The compound capable of forming the keto / enol tautomer is usually mixed at a molar ratio of about 3 mol or less with 1 mol of an aluminum alcoholate represented by be able to.

As the alkyl group having 1 to 20 carbon atoms, the alkyl group having 1 to 10 carbon atoms
In addition to the above alkyl group, undecyl, dodecyl, tridecyl, tetradecyl, octadecyl group, and the like, and the alkenyl group can include vinyl, allyl group, and the like.

Examples of the aluminum alcoholates represented by the general formula (II) include aluminum trimethoxide, aluminum triethoxide, aluminum tri-n-propoxide, aluminum triisopropoxide, aluminum tri-n-butoxide, aluminum triisobutoxide, There are aluminum tri-sec-butoxide, aluminum tri-tert-butoxide and the like, and it is particularly preferable to use aluminum triisopropoxide, aluminum tri-sec-butoxide, aluminum tri-n-butoxide and the like.

Titanium chelate compounds are represented by the general formula [In the formula, n represents an integer of 0 to 10 and R ₇ represents an alkyl group or an alkenyl group having 1 to 20 carbon atoms. ] It is preferably prepared by mixing 1 mole of Ti in the titanates represented by the above with the compound capable of forming the keto-enol tautomer in a molar ratio of usually about 4 moles or less, and heating if necessary. can do. The alkyl group and alkenyl group having 1 to 20 carbon atoms are the same as above.

Examples of the titanates represented by the general formula (III) include n
1 is tetramethyl titanate, tetraethyl titanate, tetra-n-propyl titanate, tetraisopropyl titanate, tetra-n-butyl titanate, tetraisobutyl titanate, tetra-tert-butyl titanate, tetra-n-pentyl titanate, tetra -N-hexyl titanate, tetraisooctyl titanate, tetra-n-lauryl titanate, etc.,
Especially tetraisopropyl titanate, tetra-n-butyl titanate, tetraisobutyl titanate, tetra-
Suitable results are obtained with tert-butyl titanate and the like. In addition, when n is 1 or more, tetraisopropyl titanate, tetra-n-butyl titanate, tetraisobutyl titanate, tetra-tert-butyl titanate dimers to 11-mers (n in the general formula (III):
Those of 1-10) give good results.

The zirconium chelate compound has, for example, a general formula [In the formula, n represents an integer of 0 to 10 and R ₈ represents an alkyl group or an alkenyl group having 1 to 20 carbon atoms. ] A compound capable of constituting the above keto-enol tautomer is usually added to 1 mol of Zr in the zirconate represented by
It can be suitably prepared by mixing at a molar ratio of about less than or equal to mol and heating if necessary. 1 to 20 carbon atoms
The alkyl group and alkenyl group of are the same as above.

Examples of the zirconates represented by the general formula (IV) include tetraethyl zirconate, tetra-n-propyl zirconate, tetraisopropyl zirconate and tetra-n.
-Butyl zirconate, tetra-sec-butyl zirconate, tetra-tert-butyl zirconate, tetra-n
-Pentyl zirconate, tetra-tert-pentyl zirconate, tetra-tert-hexyl zirconate, tetra-n-heptyl zirconate, tetra-n-octyl zirconate, tetra-n-stearyl zirconate, etc. Isopropyl zirconate, tetra-n-propyl zirconate, tetraisobutyl zirconate, tetra-n-butyl zirconate, tetra-se
Suitable results are obtained using c-butyl zirconate, tetra-tert-butyl zirconate and the like. Also, n is 1
For the above, tetraisopropyl zirconate, tetra-n-peropyrupirconate, tetra-n-
Butylconate, tetraisobutyl zirconate, tetra-sec-butyl zirconate, tetra-tert-butyl zirconate dimers to 11-mers (n = 1 to 10 in the general formula (IV)) give favorable results. give. Further, it may contain a constituent unit in which these zirconates are associated with each other.

Thus, particularly preferred chelate compounds in the present invention include diisopropylate ethylacetoacetate aluminum, tris (ethylacetoacetate) aluminum, tris (n-propylacetoacetate) aluminum, tris (isopropylacetoacetate) aluminum, tris ( n-Butylacetoacetate) aluminum, isopropoxybisethylacetoacetate aluminum, diisopropoxyethylacetoacetate aluminum, tris (acetylacetonate) aluminum, tris (ethylacetonate) aluminum, diisopropylate ethylacetonate aluminum, monoacetyl Acetonate, bis (ethylacetonate) aluminum, monoethylacetoacetate bis (acetylacetoate Aluminum, tris (isopropylate) aluminum, tris (sec-butyrate) aluminum, diisopropylate mono-sec-butoxyaluminum, tris (acetylacetone) aluminum and other aluminum chelate compounds; diisopropoxy bis (ethylacetoacetate). ) Titanate,
Titanium chelate compounds such as diisopropoxy, bis (acetylacetate) titanate and diisopropoxy bis (acetylacetone) titanate; tetrakis (acetylacetone) zirconium, tetrakis (n-)
Examples thereof include zirconium chelate compounds such as propyl acetoacetate) zirconium, tetrakis (acetylacetonato) zirconium, and tetrakis (ethylacetoacetate) zirconium.

In the present invention, any one of the above chelate compounds may be used as the crosslinking reaction curing agent, or two or more thereof may be appropriately used in combination. The chelate compound is homogeneously compatible with the non-aqueous dispersion in a fairly wide range of proportions, and its compounding ratio is 0.1 to 10 relative to 100 parts by weight of the non-aqueous dispersion based on the solid content ratio.
It is suitable that the amount is about 0 parts by weight. If it is less than this range, the curability of the cross-linking reaction tends to decrease, and if it is more than this range, the coating film tends to become brittle, which is not preferable. The preferable blending amount is about 0.1 to 20 parts by weight.

The curable composition of the present invention, if necessary, extender pigment,
Color pigments, dyes, plasticizers and the like can be added. Examples of the plasticizer include known ones, for example, low molecular weight plasticizers such as dimethyl phthalate and dioctyl phthalate, high molecular weight plasticizers such as vinyl polymer plasticizers and polyester plasticizers, and these are added to the non-hydric acid solution. It is also possible to mix it in advance or to dissolve it in a radically polymerizable unsaturated monomer at the time of producing the dispersion liquid and to distribute it in the dispersion polymer particles of the resulting dispersion liquid. Further, if necessary, amino resins, epoxy resins, polyisocyanates and the like which are generally used as a curing agent may be used in combination. Furthermore,
Other acrylic resins, alkyd resins, polyester resins, epoxy resins, etc. may be blended and used.

The curable composition of the present invention can be suitably used, for example, in paints, adhesives, inks, etc., and as impregnating agents for fibers and papers, surface treatment agents, etc.

The curable composition of the present invention can be easily crosslinked and cured in the presence of water at a low temperature of 100 ° C or lower. That is, the composition can be sufficiently cured in about 8 hours to 7 days without any heating by simply adding water to the composition and then coating the composition or exposing the composition to the air after coating. Also,
A small amount of moisture, such as the humidity in the air, is sufficient for curing. When water is added before coating, an addition amount of about 0.1 to 1% by weight is usually sufficient.

EFFECTS OF THE INVENTION According to the curable composition of the present invention, low temperature curability, chemical resistance of a coating film, and water resistance are excellent, and the coating film has high mechanical properties such as impact resistance and flex resistance. In addition, the effect is obtained that the storage stability of the coating, the state of the coated surface, the weather resistance, etc. are sufficient.

That is, the curable composition of the present invention is a non-aqueous dispersion of a solid phase which is polymer particles obtained by polymerizing a radically polymerizable unsaturated monomer in a liquid phase in which a dispersion stabilizer resin is dissolved in an organic liquid. A dispersion liquid contains a chelate compound which is a crosslinking reaction curing agent. A coating film formed from such a composition,
The continuous phase of the coating film is a light and chemically stable coating film having a siloxane bond, and the polymer particle component in the coating film is stabilized by the continuous phase and the coating film is reinforced by the particle portion. Mechanical properties such as impact resistance and bending resistance,
Excellent weather resistance. It is considered that the improvement of the mechanical properties is due to a stress relaxation action such as absorption of external energy due to large plastic deformation of polymer particles and absorption of impact energy by crazes generated from the particles.

In addition, the composition of the present invention causes repulsion between the dispersion stabilizer resin component present on the surface of the polymer particles and the dispersion stabilizer resin component present on the surface of another polymer particle even after long-term storage. The reaction of these comrades hardly occurs, and there is almost no fear of gelation. Further, the composition of the present invention, as described above, can be easily crosslinked and cured at a low temperature of 100 ° C. or lower in the presence of a small amount of water such as moisture in the air. Since there are few reaction products such as alcohol at the time, it is less likely to cause streaking, shrinkage, etc., and is excellent in coated surface state and mechanical properties.

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples. In each example, parts and% are, as a rule, on a weight basis.

Example 1 Synthesis of Dispersion Stabilizer Resin (A) Isobutyl acetate 40 parts Toluene 40 parts was heated to reflux, the following monomers and polymerization initiators were added dropwise over 3 hours, and the mixture was aged for 2 hours.

Methacryloxypropyltrimethoxysilane 5 parts Styrene 10 parts Isobutyl methacrylate 49 parts 2-Ethylhexyl methacrylate 25 parts 2-Hydroxyethyl methacrylate 11 parts 2,2'-Azobisisobutyronitrile 2 parts The resulting acrylic resin varnish is non-volatile. The content was 55%, viscosity (Gardner, 25 ° C., the same below) G, and weight average molecular weight 16,000.

Preparation of Non-Aqueous Dispersion Heptane 93 parts 55% Dispersion stabilizer Resin (A) varnish 98 parts was charged into a flask and heated to reflux, and the following monomers and polymerization initiators were added dropwise over 3 hours, followed by aging for 2 hours. did.

Styrene 15 parts Methyl methacrylate 40 parts Acrylonitrile 30 parts 2-Hydroxyethyl methacrylate 15 parts tert-Butylperoxy-2-ethylhexanoate 1.
5 parts The obtained non-aqueous dispersion liquid has a nonvolatile content of 53%, a viscosity B, a particle size of polymer particles (measured by an electron microscope, the same applies hereinafter) 0.2 to
It was a milky white stable low-viscosity polymer particle dispersion of 0.3 μm. No precipitation or coarse particles were observed even after standing still for 3 months at room temperature.

1 part of monoethyl acetoacetate bis (acetylacetonato) aluminum was mixed with 100 parts of the solid content of this non-aqueous dispersion and uniformly mixed to obtain a curable composition of the present invention.

Example 2 Synthesis of Dispersion Stabilizer Resin (B) Isobutyl acetate (40 parts) Toluene (40 parts) was heated to reflux, the following monomer and polymerization initiator were added dropwise over 3 hours, and the mixture was aged for 2 hours.

Methacryloxypropylmethyldimethoxysilane 30 parts Styrene 15 parts Isobutyl methacrylate 37 parts Lauryl methacrylate 15 parts 2-Hydroxyethyl methacrylate 3 parts 2,2'-Azobisisobutyronitrile 1.8 parts The acrylic resin varnish obtained has a nonvolatile content of 55 %, Viscosity M, and weight average molecular weight 18,000.

Preparation of Non-Aqueous Dispersion Heptane 82 parts 55% Dispersion stabilizing resin (B) 121 parts varnish was charged into a flask and heated to reflux, and the following monomers and polymerization initiators were added dropwise over 3 hours, followed by aging for 2 hours. .

Methacryloxypropyltrimethoxysilane 7 parts Styrene 8 parts Methyl methacrylate 30 parts Acrylonitrile 40 parts 2-Hydroxyethyl methacrylate 15 parts 2,2'-azobisisobutyronitrile 2 parts The resulting non-aqueous dispersion has a nonvolatile content of 55 %, Viscosity E, and a particle size of polymer particles of 0.45 to 0.50 μm, which was a milky white stable low viscosity polymer particle dispersion liquid. No precipitation or coarse particles were observed even after standing still for 3 months at room temperature.

10 parts of diisopropoxy bis (acetylacetate) titanate was added to 100 parts of the solid content of this non-aqueous dispersion and uniformly mixed to obtain a curable composition of the present invention.

Example 3 Synthesis of Dispersion Stabilizer Resin (C) Toluene (80 parts) was heated and kept at 110 ° C., the following monomers and polymerization initiators were added dropwise over 3 hours, and the mixture was aged for 2 hours.

Methacryloxypropyltriethoxysilane 25 parts "Placcel FM-3 monomer" (manufactured by Daicel Chemical Industries, Ltd., ε-caprolactone modified acrylic hydroxyl group-containing monomer) 20 parts Lauryl methacrylate 30 parts n-Butyl acrylate 25 Parts 2,2'-azobisisobutyronitrile 2 parts The resulting acrylic resin varnish had a nonvolatile content of 55%, a viscosity C, and a polymerization average molecular weight of 16000.

Preparation of Non-Aqueous Dispersion Cyclohexane 20 parts Mineral Spirits 62 parts 55% Dispersion stabilizer Resin (C) 121 parts varnish was charged into a flask and heated to 95 ° C, and the following monomers and polymerization initiator were added for 3 hours. It dripped over, and aged for further 2 hours.

Styrene 15 parts Methyl methacrylate 42 parts Acrylonitrile 20 parts Glycidyl methacrylate 5 parts Acrylic acid 3 parts 2-Hydroxyethyl methacrylate 15 parts 2,2'-azobisisobutyronitrile 2 parts The resulting non-aqueous dispersion has a nonvolatile content of 55 %, Viscosity D, and a particle size of polymer particles of 0.50 to 0.55 μm, which was a milky white stable low viscosity polymer particle dispersion liquid. The inside of the polymer particles was crosslinked by the reaction between the epoxy group of glycidyl methacrylate and the carboxyl group of acrylic acid. No precipitate or coarse particles were observed in this dispersion even after standing at room temperature for 3 months.

20 parts of tetrakis (acetylacetonato) zirconium was added to 100 parts of the solid content of this non-aqueous dispersion,
The mixture was uniformly mixed to obtain a curable composition of the present invention.

Example 4 Synthesis of dispersion stabilizer resin (D) Isobutyl acetate (50 parts) Toluene (30 parts) was heated to reflux, the following monomers and polymerization initiators were added dropwise over 3 hours, and the mixture was aged for 3 hours.

Methacryloxypropylmethyldiethoxysilane 22 parts Styrene 20 parts Isobutyl methacrylate 10 parts 2-Ethylhexyl methacrylate 38 parts 2-Hydroxyethyl methacrylate 9 parts Glycidyl methacrylate 1 part tert-Butylperoxy-2-ethylhexanoate 3
The obtained acrylic resin varnish had a nonvolatile content of 55%, a viscosity H, and a weight average molecular weight of 16,000.

Next, 0.8 part of methacrylic acid, 0.02 part of 4-tert-butylpyrocatechol, and 0.1 part of dimethylaminoethanol were added to the whole amount of the above varnish, and the reflux reaction was carried out for 5 hours to form a copolymerizable double bond in the dispersion stabilizer resin molecular chain. Introduced. The number of introduced double bonds is about 0.6 per one molecular chain as measured by the resin acid value.
It was individual.

Preparation of Non-Aqueous Dispersion Heptane 93 parts 55% Dispersion stabilizer Resin (D) Varnish 98 parts was charged into a flask and heated to reflux, and the following monomers and polymerization initiators were added dropwise over 3 hours, followed by aging for 2 hours. did.

Styrene 10 parts Methyl methacrylate 45 parts Acrylonitrile 25 parts 2-Perfluorooctylethyl methacrylate 5 parts 2-Hydroxyethyl methacrylate 15 parts tert-Butylperoxy-2-ethylhexanoate 1.
5 parts The obtained non-aqueous dispersion was a milky white stable low-viscosity polymer particle dispersion having a nonvolatile content of 54%, a viscosity H, and a particle size of polymer particles of 0.2 to 0.3 μm. No precipitate or coarse particles were observed in this dispersion even after standing at room temperature for 3 months. However, the viscosity had increased to L.

15 parts of tris (acetylacetonato) aluminum was mixed with 100 parts of the solid content of this non-aqueous dispersion and uniformly mixed to obtain a curable composition of the present invention.

Example 5 Synthesis of Dispersion Stabilizer Resin (E) In the synthesis of the dispersion stabilizer resin (A) of Example 1, instead of methacryloxypropyltrimethoxysilane, In the same manner except that the same amount was used, the dispersion stabilizer resin (E)
Was synthesized. The obtained acrylic resin varnish has a nonvolatile content.
It had a viscosity of 55%, a viscosity H, and a weight average molecular weight of 15,000.

Preparation of non-aqueous dispersion: 93 parts of heptane, 98 parts of 55% dispersion stabilizer resin (E) varnish were charged into a flask and heated to reflux, and the following monomers and polymerization initiator were added dropwise over 3 hours, followed by aging for 2 hours. did.

Styrene 15 parts Methyl methacrylate 40 parts Acrylonitrile 30 parts 2-Hydroxyethyl methacrylate 15 parts tert-Butyl peroxy-2-ethylhexanoate 1.
5 parts of the obtained non-aqueous dispersion liquid was a milky white stable low-viscosity polymer particle dispersion liquid having a nonvolatile content of 53%, a viscosity C and a polymer particle diameter of 0.3 to 0.4 μm. No precipitation or coarse particles were observed even after standing still for 3 months at room temperature.

To 100 parts of the solid content of this non-aqueous dispersion, 5 parts of diisopropoxyethyl acetoacetate aluminum was blended and uniformly mixed to obtain a curable composition of the present invention.

Example 6 Synthesis of Dispersion Stabilizer Resin (F) 40 parts of isobutyl acetate and 40 parts of toluene were heated to reflux, the following monomers and polymerization initiators were added dropwise over 3 hours, and the mixture was aged for 2 hours.

Methacryloxypropyltributoxysilane 80 parts 2-hydroxyethyl methacrylate 20 parts 2,2'-azobisisobutyronitrile 2 parts The resulting acrylic resin varnish has a nonvolatile content of 55%, a viscosity G, and a weight average molecular weight of 16000. Atsuta

Preparation of Non-Aqueous Dispersion Heptane 93 parts 55% Dispersion stabilizer resin (F) varnish 98 parts was charged into a flask and heated to reflux, and the following monomers and polymerization initiators were added dropwise over 3 hours, followed by aging for 2 hours. did.

Styrene 15 parts Methyl methacrylate 40 parts Acrylonitrile 30 parts 2-Hydroxyethyl methacrylate 15 parts tert-Butyl peroxy-2-ethylhexanoate 1.
5 parts of the obtained non-aqueous dispersion liquid was a milky white stable low-viscosity polymer particle dispersion liquid having a nonvolatile content of 53%, a viscosity C and a polymer particle diameter of 0.3 to 0.4 μm. No precipitation or coarse particles were observed even after standing still for 3 months at room temperature.

12 parts of tris (ethylacetoacetate) aluminum was mixed with 100 parts of the solid content of this non-aqueous dispersion and uniformly mixed to obtain a curable composition of the present invention.

Comparative Example 1 1 part of monoethylacetoacetate bis (acetylacetonato) aluminum was blended with 100 parts of the solid content of the dispersion stabilizer resin (A) and uniformly dispersed to obtain a comparative composition.

Comparative Example 2 A comparative composition was obtained in the same manner as in Example 1 except that the monoethylacetoacetate bis (acetylacetonato) aluminum was not added in the formulation of Example 1.

Comparative Example 3 In the synthesis of the dispersion stabilizer resin (A) of Example 1, the non-volatile content was 55%, the viscosity was H, and the molecular weight was 16000 in the same manner except that the same amount of isobutyl methacrylate was used instead of methacryloxypropyltrimethoxysilane. A dispersion stabilizer resin of was obtained. A nonvolatile content of 53%, a viscosity C, and a dispersion stabilizer resin (A) were used in the same manner as in Example 1 except that this resin was used.
A non-aqueous dispersion having a particle size of 0.2 to 0.3 μm was prepared, and further 1 part of monoethylacetoacetate bis (acetylacetonato) aluminum was blended to obtain a comparative composition.

Next, a performance test was conducted on each composition obtained in the examples and comparative examples. The test method is as follows.

Stability of paint storage: Time required to perform a closed storage test in a thermostatic chamber at 30 ° C until the viscosity increases to a pudding (Hr)
I checked.

Coating performance: Each composition is polished on a mild steel plate with a dry film thickness of 50μ
The following various tests were carried out on the coating film after being coated so that the temperature was 20 ° C. and the humidity was 75% for 7 days.

Gel fraction: The isolated coating film was placed in toluene held at the reflux temperature, and the residual ratio (%) of the insoluble coating film after extraction for 4 hours was examined.

Coating state ... Visual observation and evaluation according to JIS K 5400.

Water resistance: It was examined by the state of the coated surface after immersion in tap water at 40 ° C for 168 hours.

Alkali resistance: The condition of the coated surface after immersion in a 10% NaOH aqueous solution (25 ° C) for 24 hours was examined.

Acid resistance: The state of the coated surface after being immersed in a 5% HCI aqueous solution (25 ° C) for 24 hours was examined.

Weather resistance: Using a sunshine weather ometer,
The state of the coated surface was examined over time, and the time (Hr) until abnormalities such as gloss and blistering occurred was examined.

Impact resistance: Using a DuPont impact tester, a 500 g weight was dropped on the coated surface, and the maximum drop distance (cm) at which no abnormalities such as cracks or peeling were observed in the coating film was examined.

Alcohol resistance ... Lauryl alcohol was placed on a part of the coated surface, and a spot test was conducted to examine the coated surface state after standing at 20 ° C. for 24 hours.

Bending resistance: JI using a bending resistance tester (10 mm diameter core rod)
The test was carried out according to SK 5400.

The test results are shown in Table 1.

Claims (1)

[Claims] 1. A general formula [In the formula, A is Indicates. R ₁ is a hydrogen atom or a methyl group, and R ₂ has 1 to 1 carbon atoms.
6 divalent saturated aliphatic hydrocarbon group, R ₃ and R ₄ are the same or different and are phenyl group, alkyl group having 1 to 6 carbon atoms or alkoxy group having 1 to 10 carbon atoms, and R ₅ is carbon number 1 to 10 alkyl groups are shown respectively. n shows the integer of 1-100. ] Using a copolymer obtained as an essential monomer component an alkoxysilane group-containing vinyl monomer and a hydroxyl group-containing unsaturated monomer, which are compounds represented by, as a dispersion stabilizer resin,
Compounding a non-aqueous dispersion of polymer particles insoluble in the organic liquid obtained by polymerizing a radically polymerizable unsaturated monomer in the organic liquid in the presence of the resin, a chelate compound as a crosslinking reaction curing agent. Curable composition characterized by the above.