JPH0195116A - Curable composition - Google Patents

Abstract

PURPOSE:To offer a curable compsn. having excellent low temp. curing characteristics, water resistance and impact resistance of a coated film prepd. therefrom, by compounding a curing catalyst such as an acidic compd. in a non-aq. dispersion of polymer particles prepd. by using a specified dispersion- stabilizing resin. CONSTITUTION:A polymer comprising an alkoxysilane group-contg. vinyl monomer of formula I (wherein A is formula II or III; R1 is H or methyl; R2 is 1-6C divalent aliph. satd. hydrocarbon group; R3 and R4 are each phenyl, 1-6C alkyl or 1-10C alkoxy; R5 is 1-10C alkyl; n is 1-100) as an essential component (e.g., formula IV) is prepd. A non-aq. dispersion of polymer particles being insoluble in an org. liq. is prepd. by polymerizing a radical-polymerizable unsatd. monomer (e.g., methyl methacrylate) in said org. liq. by using this polymer as a dispersion-stabilizing resin. Then, a curing catalyst selected from acidic compd., basic compd. and tin compd. (e.g., phosphoric acid) is compoundED in this dispersion.

Description

[Detailed description of the invention] Industrial applications The present invention relates to novel curable compositions.

BACKGROUND TECHNOLOGY AND THEIR PROBLEMS Conventionally, compositions in which a curing catalyst such as a gold-tin compound is blended with an acrylic resin containing an alkoxysilane group are known as compositions that can be crosslinked and cured at relatively low temperatures of room temperature to 100°C. (Japanese Patent Application Laid-Open No. 136606/1983).

However, although the above-mentioned conventional compositions have excellent low-temperature curability, chemical resistance, and water resistance of the coating film, they have the disadvantage that the mechanical properties of the coating film, the storage stability, etc. of the coating film are not necessarily sufficient. That is, when high mechanical properties such as impact resistance and bending resistance are required, there are limits to simply adjusting the type and amount of the curing catalyst, the content of alkoxysilane groups, the molecular weight of the acrylic resin, etc. As a result, there are drawbacks such as limited usage and insufficient paint storage stability, coated surface condition, weather resistance, etc.

Means for Solving the Problems As a result of extensive research in order to eliminate the above-mentioned drawbacks, the inventor of the present invention has developed a non-aqueous dispersion of specific polymer particles using a specific polymer as a dispersion stabilizer resin. By blending catalysts such as acidic compounds and gold-tin compounds, the coating film has excellent low-temperature curing properties, chemical resistance, and water resistance, as well as high mechanical properties and paint storage stability. The present inventors have discovered that a curable composition can be obtained with sufficient coating surface condition, weather resistance, etc., and have completed the present invention.

That is, in the present invention, the general formula R1 is a hydrogen atom or a methyl group, R2 is a divalent aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms, and R3 and R4 are the same or different and are a phenyl group or a carbon number 1 -6 alkyl group or alkoxy group having 1 to 10 carbon atoms, R5 is 1 to 1 carbon atoms
0 alkyl groups are shown respectively. n represents an integer of 1 to 100. ] A polymer containing an alkoxysilane group-containing vinyl monomer, which is a compound represented by the following, as an essential monomer component is used as a dispersion stabilizer resin, and a radically polymerizable unsaturated monomer is mixed in an organic liquid in the presence of the resin. To the non-aqueous dispersion of polymer particles insoluble in the organic liquid obtained by polymerizing the organic liquid, an acidic compound, a basic compound, or a gold-tin compound alone or a combination of a gold-tin compound and an acidic compound or a basic compound is added as a curing catalyst. The present invention relates to a curable composition comprising a mixture.

In the present invention, the above-mentioned specific polymer is used as a dispersion stabilizer resin. The general formula (
In the compound 1), n is preferably 1-10.

In general formula (I), the number of carbon atoms represented by R2 is 1
-6 divalent aliphatic saturated hydrocarbon groups include linear or branched alkylene groups such as methylene, ethylene, propylene, 1,2-butylene, 1,3-butylene, 2,3
-butylene, tetramethylene, ethylethylene, pentamethylene, hexamethylene groups and the like.

Examples of the alkyl group having 1 to 6 carbon atoms represented by R3 and R4 include straight chain or branched alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, 5ec-butyl, tert- Examples include butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, isohexyl, etc. In addition to these, examples of the alkyl group having 1 to 10 carbon atoms represented by R5 include n-
heptyl, 1-methylpentyl, 2-methylhexyl,
Examples include n-octyl, n-nonyl, n-decyl, and the like. Examples of the alkoxy group having 1 to 10 carbon atoms represented by R3 and R4 include linear or branched alkoxy groups such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, 5ec-butoxy, tert- Butoxy, n-pentoxy, isopentoxy, n-hexyloxy, isohexyloxy, n-octyloxy and the like can be mentioned. Also, the general formula (
In I), when n is 2 or more, R3 and R4 may be the same or different.

Among the compounds of general formula (I) in the present invention, those in which AI is -C-0- include, for example, γ-(meth)
Acryloxyethyltrimethoxysilane, γ-(meth)
Acryloxypropyltrimethoxysilane, γ-(meth)acryloxypropyltriethoxysilane, γ-(meth)acryloxypropyltripropoxysilane, γ-
(meth)acryloxypropylmethyldimethoxysilane, γ-(meth)acryloxypropylmethyljethoxysilane, γ-(meth)acryloxypropylmethyldipropoxysilane, γ-(meth)acryloxybutylphenyldimethoxysilane, γ -(meth)acryloxybutylphenyldiethoxysilane, γ-(meth)acryloxybutylphenyldipropoxysilane, γ-(meth)acryloxypropyldimethylmethoxysilane, γ-(meth)acryloxypropyldimethylethoxysilane , γ
-(meth)acryloxypropylphenylmethylmethoxysilane, and γ-(meth)acryloxypropylphenylmethylethoxysilane.

etc. can be mentioned.

Among these compounds of formula (I), in particular, acryloxypropyltrimethoxysilane, methacryloxypropyltriethoxysilane, methacryloxypropyltri-n-butoxysilane, acryloxypropylmethyldimethoxysilane, methacryloxypropylmethyldimethoxysilane , methacryloxypropylmethyl di-n-butoxysilane, etc. are suitable.

In the present invention, the polymer used as the dispersion stabilizer resin has at least one alkoxysilane group-containing vinyl monomer represented by formula (I) as an essential monomer component, and if necessary, other monomers. It is a polymer made by copolymerizing two bodies. The proportion of the essential monomer to be used can be selected from a wide range, but is usually about 1 to 100% by weight, preferably about 5 to 30% by weight of the monomers used. If the proportion of the essential monomer used is less than 1% by weight, it is not preferable because the curability tends to decrease and the chemical and mechanical properties of the coating film tend to decrease.

Other polymerizable monomers used in the polymer can be selected as appropriate depending on the performance required for the coating film, but from the viewpoint of copolymerizability, solubility in organic liquids, etc. Long chain vinyl monomers are preferred. 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, and cyclohexyl (meth)acrylate.
Alkyl having 4 to 18 carbon atoms in (meth)acrylic acid such as meth)acrylate, n-octyl(meth)acrylate, lauryl(meth)acrylate, tridecyl(meth)acrylate, stearyl(meth)acrylate, and cyclohexyl(meth)acrylate or cycloalkyl ester; alkoxyalkyl ester of (meth)acrylic acid such as methoxybutyl (meth)acrylate, methoxyethyl (meth)acrylate, and ethoxybutyl (meth)acrylate; (meth) of aromatic alcohol such as benzyl (meth)acrylate; ) Esters with acrylic acid; adducts of glycidyl (meth)acrylate or hydroxyalkyl esters of (meth)acrylic acid with monocarboxylic acid compounds such as capric acid, lauric acid, linoleic acid, oleic acid, (meth)acrylic acid and “Cardura E10
Adducts with monoepoxy compounds such as ``Styrene, α-
Vinyl aromatic compounds such as methylstyrene, vinyltoluene, p-chlorostyrene, p-teri-butylstyrene; itaconic acid, itaconic anhydride, crotonic acid-
α,β-unsaturated carboxylic acids other than (meth)acrylic acid, such as maleic acid, maleic anhydride, fumaric acid, and citraconic acid, and carbon atoms of 4 or more, such as butyl alcohol, pentyl alcohol, heptyl alcohol, octyl alcohol, stearyl alcohol, etc. Mono- or diesters with 18 monoalcohols; "Viscoat 8F", "Viscoat 8F"
MJ, “Viscoat 3FJ,” “Viscoat 3FMJ”
Examples include fluorine atom-containing compounds such as (all manufactured by Osaka Organic Chemical ■, trade name, (meth)acrylates having a fluorine atom in the side chain), perfluorocyclohexyl (meth)acrylate, perfluorohexylethylene, etc. .

Polymerization for producing the dispersion stabilizer resin used in the present invention is usually carried out using a radical polymerization initiator.

Examples of usable radical polymerization initiators include 2,2
Azo initiators such as -azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile); benzoyl peroxide, lauryl peroxide, tert-butyl peroctoate, tert −
Examples include peroxide-based initiators such as butyl peroxy-2-ethylhexanoate, and these polymerization initiators are generally about 0.2 to 10 parts by weight per 100 parts by weight of the monomer to be subjected to polymerization. , preferably 0. It can be used in a range of 5 to 5 parts by weight. The reaction temperature during polymerization is usually in the range of 60 to 160°C, and usually 1 to 1
The reaction is completed in about 5 hours.

The molecular weight of the copolymer used as the dispersion stabilizer resin in the present invention is usually about 5,000 to 100 in terms of weight average molecular weight.
000 (number average molecular weight of about 1,000 to 60,000), preferably about 5,000 to 50,000. If the molecular weight is less than about 5,000, the stabilization of the dispersed particles is insufficient and tends to cause aggregation and sedimentation, while if the molecular weight exceeds about 100,000, the viscosity becomes extremely high and handling may become difficult. Undesirable.

The dispersion stabilizer resin used in the present invention may be used alone or in combination of two or more with different copolymerization compositions and molecular weights, and if necessary, other dispersion stabilizers such as butyl etherification may be used. It is also possible to use melamine-formaldehyde resins, alkyd resins, general acrylic resins that do not contain the compound of formula (I) as a copolymer component, and other natural teeth.

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

The organic liquid used in the polymerization does not substantially dissolve the dispersed polymer particles produced by the polymerization, but is a good solvent 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, methyl hexyl ketone, and ethyl butyl ketone; ethyl acetate,
Examples include esters such as isobutyl acetate, amyl acetate, and 2-ethylhexyl acetate. These organic liquids may be used alone or in a mixture of two or more, but in general, they are mainly composed of aliphatic hydrocarbons, and aromatic hydrocarbons and alcohols are added as appropriate. , ethers, ketones or esters are preferably used.

The radically polymerizable unsaturated monomer used in the above polymerization is one that has excellent polymerizability and has a smaller number of carbon atoms than the single n monomer used as the monomer component of the dispersion stabilizer resin. It is preferable to do so because it is easy to form 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, and tert- Butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, n-octyl (meth)acrylate, lauryl (meth)acrylate, tridecyl (meth)acrylate
Acrylate, stearyl (meth)acrylate, etc. (
C1-18 alkyl or cycloalkyl ester of meth)acrylic acid; alkoxyalkyl ester of (meth)acrylic acid such as methoxybutyl (meth)acrylate, methoxyethyl (meth)acrylate, ethoxybutyl (meth)acrylate; benzyl Ester of aromatic alcohol such as (meth)acrylate with (meth)acrylic acid; Glycidyl (meth)acrylate and monocarboxylic acid having 2 to 18 carbon atoms such as acetic acid, propionic acid, oleic acid, p-tert-butylbenzoic acid, etc. Adducts with acid compounds; Adducts between (meth)acrylic acid and monoepoxy compounds such as "Cardura E10"; styrene, α-methylstyrene, vinyltoluene, p-chlorostyrene, p-
Vinyl aromatic compounds such as tert-butylstyrene; itaconic acid, itaconic anhydride, crotonic acid, maleic acid,
(Meth) of maleic anhydride, fumaric acid, citraconic acid, etc.
Mono- or diesters of α, β-unsaturated carboxylic acids other than acrylic acid and monoalcohols having 1 to 18 carbon atoms such as methyl alcohol, butyl alcohol, hexyl alcohol, and stearyl alcohol; “Viscoat 8F”,
[Viscoat 8FMJ, “Viscoat 3F”, “Viscoat 3FMJ (all manufactured by Osaka Organic Chemical ■, product name,
(meth)acrylates having a fluorine atom in the side chain),
Fluorine atom-containing compounds such as perfluorocyclohexyl (meth)acrylate and perfluorohexyl ethylene; Cyano group-containing unsaturated compounds such as (meth)acrylonitrile; Vinyl acetate, vinyl benzoate,
Vinyl esters such as OVA) J (manufactured by Shell ■); vinyl ethers such as n-butyl vinyl ether, ethyl vinyl ether, methyl vinyl ether; 1,6
- Polyvinyl compounds such as di(meth)acrylate of hexanediol, tri(meth)acrylate of trimethylolpropane, and divinylbenzene; α-olefin compounds such as ethylene, propylene, vinyl chloride, vinylidene chloride, etc. can be mentioned.

As mentioned above, the monomer components forming the polymer particles can be stably formed by combining those having a carbon number smaller than that of the monomer components of the dispersion stabilizer resin. However, from this point of view, particularly preferred are (meth)acrylic acid esters, vinyl aromatic compounds, (meth)acrylonitrile, etc. having 8 or less carbon atoms, preferably 4 or less carbon atoms.

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

Polymerization of the above-mentioned radically polymerizable unsaturated monomer is usually carried out using a radical polymerization initiator. Usable radical polymerization initiators include, for example, azo initiators such as 2゜2'-azobisisobutyronitrile and 2,2'-azobis(2,4-dimethylvaleronitrile); benzoyl peroxide, and lauryl. Peroxide, tert-butyl peroctoate, tert-butyl peroxy-2
Examples include peroxide-based initiators such as -ethylhexanoate, and these polymerization initiators are generally about 0.2 to 10 parts by weight, preferably 0.5 parts by weight, per 100 parts by weight of monomers to be subjected to polymerization. It can be used in a range of 5 parts by weight.

The proportion of the dispersion stabilizer resin present during the above polymerization can be selected from a wide range depending on the type of resin, etc.
Generally, it is appropriate that the radically polymerizable unsaturated monomer be used in an amount of 3 to 240 parts by weight, or 5 to 82 parts by weight, per 100 parts by weight of the dispersion stabilizer resin. Furthermore, 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 the reaction temperature during polymerization is usually within the range of about 60 to 160°C, and the reaction is usually completed in about 1 to 15 hours.

In this way, a stable non-aqueous dispersion is obtained in which the liquid phase is a dispersion stabilizer resin dissolved in an organic liquid and the solid phase is polymer particles obtained by polymerizing a radically polymerizable unsaturated monomer. The particle size of the polymer particles is typically in the range of 0.1 to 1.0 μm. If the particle size is smaller than this range, the viscosity of the face will increase, while if the particle size is larger than this range, the particles will swell or aggregate during storage, which is not preferable.

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

As a method for bonding the dispersion stabilizer resin and the polymer particles, for example, in the step of manufacturing the dispersion stabilizer resin in advance, hydroxyl groups, acid groups, acid anhydride groups, epoxy groups, methylol groups, isocyanate groups, amide groups, amino A monomer component having a functional group such as a group is partially copolymerized, and further a hydroxyl group, an acid group, an acid anhydride group, an epoxy group, which reacts with the above functional group as a monomer component to form polymer particles. methylol group,
This can be carried out by using a monomer having a functional group such as 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 (anhydride) groups, epoxy groups and amino groups, isocyanate groups and amide groups, acid (anhydride) groups and hydroxyl groups, etc. .

Examples of monomers having such functional groups include (
α, β-ethylenically unsaturated carboxylic acids such as meth)acrylic acid, crotonic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, fumaric acid, citraconic acid; glycidyl (meth)acrylate, vinyl glycidyl ether, Glycidyl group-containing compounds such as allyl glycidyl ether; (meth)acrylamide, N,N-dimethyl (
Carboxylic acid amide compounds such as meth)acrylamide, N-alkoxymethylated (meth)acrylamide, diacetone acrylamide, and N-methylol(meth)acrylamide; p-styrenesulfonamide, N-methyl-
p-styrenesulfonamide, N,N-dimethyl-p-
Sulfonic acid amide group-containing compounds such as styrene sulfonamide; amino group-containing compounds such as tert-butylaminoethyl (meth)acrylate; combinations of 2-hydroxyethyl (meth)acrylate and phosphoric acid or phosphoric acid esters; Condensates, phosphoric acid group-containing compounds such as glycidyl group-containing compounds such as glycidyl (meth)acrylate with phosphoric acid or phosphoric acid esters added; 2-acrylamido-2-methyl-propanesulfonic acid Sulfonic acid group-containing compounds such as m-isopropenyl-
α.

Examples include isocyanate group-containing compounds such as equimolar adducts of α-dimethylbenzyl isocyanate, isophorone diisocyanate, or tolylene diisocyanate and hydroxy (meth)acrylate, and isocyanoethyl methacrylate.

Another method for bonding the dispersion stabilizer resin and polymer particles is to polymerize a radically polymerizable unsaturated monomer in the presence of a dispersion stabilizer resin having a polymerizable double bond. can. The introduction of a polymerizable double bond into a dispersion stabilizer resin can be achieved, 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 (meth) to this acid group. ) acrylate,
This can be done by reacting a glycidyl group-containing unsaturated monomer such as allyl glycidyl ether, but of course, it can also be done by making the resin contain a glycidyl group and then reacting it with an acid group-containing unsaturated monomer. It can also be done by forcing.

These reactions can follow conventionally known conditions.

In addition, as yet another method for bonding the dispersion stabilizer resin and polymer particles, after producing a non-aqueous dispersion in which a functional group that does not react with each other is introduced into the dispersion stabilizer resin and the polymer particles, this method can be used. This can also be done by adding a binder to bind the two. Specifically, for example, a hydroxyl group-containing unsaturated monomer alone or a mixture with other unsaturated monomers is polymerized in the presence of a hydroxyl group-containing dispersion stabilizer resin and an organic liquid. After producing an aqueous dispersion, a polyisocyanate compound and the like may be added and reacted for several days at room temperature or for about 1 to 5 hours at about 60 to 100°C. As the polyisocyanate compound, any compound having one or more isocyanate groups in the molecule can be used, such as aromatic diisocyanates such as tolylene diisocyanate, xylylene diisocyanate, 4,4'-diphenylmethane diisocyanate, etc. Hydride; aliphatic diisocyanates such as hexamethylene diisocyanate, lysine diisocyanate, dimer acid (dimerized product of tall oil fatty acid) diisocyanate; alicyclic diisocyanates such as isophorone diisocyanate; and the like. In addition to the above combinations, combinations of dispersion stabilizer resins and polymer particles containing acid groups and polyepoxides, and combinations of dispersion stabilizer resins and polymer particles containing epoxy groups and polycarboxylic acids are also available. , a combination of a dispersion stabilizer resin and polymer particles containing an epoxy group or an isocyanate group, and a polysulfide compound. Examples of polyepoxides include bisphenol A epoxy resins, bisphenol F epoxy resins, novolac epoxy resins, and epoxy group-containing acrylic resins; examples of polycarboxylic acids include adipic acid, sepacic acid, azelaic acid, isophthalic acid, etc.; Examples of polysulfides 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 attached to the dispersion stabilizer resin and/or the polymer particles. It is sufficient that the amount introduced is at least 0.1 on average per molecule of the resin and/or particles.

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

The curable composition of the present invention is a composition in which an acidic compound, a basic compound, or a gold-tin compound alone or a mixture of a gold-tin compound and an acidic compound or a basic compound is blended with the above-mentioned non-aqueous dispersion as a curing catalyst. . The curing catalyst imparts excellent low-temperature curability to the composition. That is, the alkoxy group derived from the monomer of general formula (I) in the dispersion stabilizer resin is hydrolyzed by the curing catalyst in the presence of moisture to produce a silanol group, and then the silanol groups are dehydrated and condensed with each other. It is crosslinked and cured at low temperature by bonding.

The curing catalyst used in the present invention includes p-toluenesulfonic acid, trichloroacetic acid, phosphoric acid, mono-n-propyl phosphoric acid, monoisopropyl phosphoric acid, mono-n-butyl phosphoric acid, monoisobutyl phosphoric acid, mono-tert-butyl phosphoric acid, mono- Monoalkyl phosphoric acids such as octyl phosphoric acid and monodecyl phosphoric acid, di-n-propyl phosphoric acid, diisopropyl phosphoric acid,
di-n-butyl phosphoric acid, diisobutyl phosphoric acid, di-tert
- Dialkyl phosphoric acids such as butyl phosphoric acid, dioctyl phosphorous acid, didecyl phosphoric acid, phosphoric acid esters of β-hydroxyethyl (meth)acrylate, mono-n-propyl phosphorous acid, monoisopropyl phosphorous acid, mono-n-butyl phosphorous acid, monoisobutyl phosphorous acid, etc. Phosphoric acid, monoalkyl phosphorous acids such as mono-tert-butyl phosphorous acid, mono-octyl phosphorous acid, monodecyl phosphorous acid, di-n-propyl phosphorous acid, diisopropyl phosphite, di-n-butyl phosphorous acid, diisobutyl phosphorous acid, di-t
Acidic compounds such as dialkyl phosphorous acids such as ert-butyl phosphorous acid, dioctyl phosphorous acid, didecyl phosphorous acid; tetraisopropyl titanate, tetrabutyl titanate, tin octylate, dibutyl tin diacetate, dibutyl tin dioctoate, dibutyl tin dilaurate, dibutyl tin Gold-tin compounds such as simalate; basic compounds such as butylamine, tert-butylamine, dibutylamine, hexylamine, ethylenediamine, triethylamine, isophoronediamine, imidazole, lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium methylate, etc. At least one of these can be used. Among these, it is preferable to use phosphoric acid compounds and gold-tin compounds. However, it is not preferable to use an acidic compound and a basic compound at the same time.

The blending ratio of the curing catalyst in the present invention is suitably about 0.01 to 10 parts by weight based on the solid content ratio per 100 parts by weight of the non-aqueous dispersion.

If the amount is less than this range, the curability of the coating film tends to decrease, and if it is more than this range, the coating film becomes brittle and storage stability tends to decrease, which is not preferable. The preferred amount is about 0.1 to 2 parts by weight.

The curable composition of the present invention may optionally include an extender pigment,
Color pigments, dyes, plasticizers, etc. can be added. Examples of the plasticizer include known ones, such as low molecular weight plasticizers such as dimethyl phthalate and dioctyl phthalate, and high molecular weight plasticizers such as vinyl polymer plasticizers and polyester plasticizers, and these may be added to the non-aqueous dispersion. It can also be mixed in advance or dissolved in the radically polymerizable unsaturated monomer during the production of the dispersion, and then distributed in the dispersed polymer particles of the produced dispersion. Further, if necessary, amino resins, epoxy resins, polyisocyanates, etc., which are generally used as curing agents, may be used in combination. Furthermore,
It is also possible to use a blend of other acrylic resins, alkyd resins, polyester resins, epoxy resins, etc.

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

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

Effects of the Invention According to the curable composition of the present invention, the coating film has excellent mechanical properties such as high impact resistance and bending resistance in addition to being excellent in low-temperature curability, chemical resistance, and water resistance of the coating film. Moreover, the storage stability of the paint, the condition of the painted surface, the weather resistance, etc. are also sufficient.

That is, the curable composition of the present invention is a non-aqueous composition in which a solid phase, which is a polymer particle formed by polymerizing a radically polymerizable unsaturated monomer, is stably dispersed in a liquid phase in which a dispersion stabilizer resin is dissolved in an organic liquid. A dispersion containing a specific curing catalyst. The coating film formed from such a composition is a photo- and chemically stable coating film in which the continuous phase of the coating film has siloxane bonds, and the polymer particle components in the coating film are stabilized by the continuous phase. In addition, since the coating film is reinforced by the particles, it has excellent mechanical properties such as impact resistance and bending resistance, and weather resistance. This improvement in mechanical properties is thought to be due to stress relaxation effects such as absorption of external energy due to large plastic deformation of the polymer particles and absorption of impact energy by crazes generated from the particles.

In addition, even if the composition of the present invention is stored for a long period of time, the dispersion stabilizer resin component present on the surface of the polymer particle and the dispersion stabilizer resin component present on the surface of other polymer particles will repel. These comrade reactions are unlikely to occur and there is little risk of gelation. Further, as mentioned above, the composition of the present invention can be prepared at 100° C. in the presence of a small amount of moisture, for example, the moisture level in the air.
It can be easily cross-linked and cured at the following low temperatures, but since it contains polymer particles, there are few reaction products such as alcohol during curing, so it is difficult to cause stiffness, shrinkage, etc., and it does not affect the coating surface condition or mechanical properties. Are better.

EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples and Comparative Examples. In each example, parts and percentages are in principle based on weight.

Example 1 Synthesis of 0 Dispersion Stabilizer Resin (U) 100 parts of xylene was heated to 120° C., the following polymer and polymerization initiator were added dropwise over 3 hours, and the mixture was aged for 2 hours after the addition.

γ-Methacryloxypropyltrimethoxysilane 5 parts Styrene 10 parts n-butyl methacrylate 35 parts 2-ethylhexyl methacrylate 25 parts lauryl methacrylate
25 parts 2.2' -Azobisisobutyronitrile
The acrylic resin face obtained in 4 parts had a non-volatile content of 50%,
The viscosity (Gardner, 25° C., hereinafter the same) was B and the weight average molecular weight was 10,000.

0 Synthesis of non-aqueous dispersion of polymer particles 100 parts Heptane 83 parts of dispersion stabilizer resin (U) were charged into a flask, heated to reflux, and the following monomers and polymerization initiator were added dropwise over 3 hours, and Aged for 2 hours.

Methacryloxypropyltrimethoxysilane 20 parts Styrene 15 parts Acrylonitrile 15 parts Methyl methacrylate
50 parts 2.2' - 2 parts of azobisisobutyronitrile The obtained liquid has a non-volatile content of 50% and a viscosity of A.
1. It was a milky-white, stable, low-viscosity polymer dispersion with a particle size of polymer particles (as measured by a Coulter counter, the same applies hereinafter) of 0.30 to 0.35 μm. No precipitation or coarse particles were observed even after this was left at room temperature for 3 months.

Per 100 parts of solid content of this non-aqueous dispersion, 0.5 part of monobutyl phosphoric acid was blended and mixed uniformly to obtain a curable composition of the present invention.

Example 2 Synthesis of 0 Dispersion Stabilizer Resin (V) 100 parts of xylene was heated to 120° C., the following monomers and polymerization initiator were added dropwise over 3 hours, and the mixture was aged for 2 hours after the addition.

γ-methacryloxypropyltrimethoxysilane 30 parts Styrene 15 parts n-butyl methacrylate 20 parts 2-ethylhexyl methacrylate 15 parts lauryl methacrylate
20 parts 2.2' -Azobisisobutyronitrile
The acrylic resin face obtained in 4 parts had a non-volatile content of 50%,
The viscosity and total average molecular weight were approximately 10,000.

Synthesis of non-aqueous dispersion of O polymer particles 100 parts of heptane and 83 parts of dispersion stabilizer resin (V) were charged into a flask, heated to reflux, and the following monomers and polymerization initiator were added dropwise over 3 hours. Aged for 2 hours.

Styrene 15 parts Acrylonitrile 15 parts Methyl methacrylate 70 parts 2.2'-azobisisobutyronitrile 1 part The obtained liquid has a non-volatile content of 50%,
It was a milky-white, stable, low-viscosity polymer dispersion with a viscosity of A and a polymer particle diameter of 0.30 to 0,640 μm. No precipitation or coarse particles were observed even after this was left at room temperature for 3 months.

0 parts of monobutyl phosphoric acid in 100 parts of solid content of this non-aqueous dispersion.
．． 5 parts were blended and mixed uniformly to obtain a composition of the present invention.

Example 3 Synthesis of 0 Dispersion Stabilizer Resin (W) 80 parts of toluene was heated and kept at 110° C., and the following monomers and polymerization initiator were added dropwise over 3 hours, followed by aging for 2 hours.

Methacryloxypropyltrimethoxysilane 25 parts 2-ethylhexyl methacrylate 20 parts lauryl methacrylate 30 parts n-butyl acrylate
25 parts 2.2' -Azobisisobutyronitrile 2 parts The obtained acrylic resin face had a nonvolatile content of 55%, a viscosity E, and a weight average molecular weight of about 16,000.

0 Synthesis of non-aqueous dispersion of polymer particles Cyclohexane 20 parts Mineral spirit 62 parts Dispersion stabilizer resin (
W) 121 parts were charged into a flask and heated, maintained at 95°C, the following monomers and polymerization initiator were added dropwise over 3 hours, and further aged for 2 hours.

Styrene 15 parts Methyl methacrylate 42 parts Acrylonitrile 20 parts Glycidyl methacrylate 5 parts Acrylic acid
3 parts 2-hydroxyethyl acrylate 1
5 parts 2.2'-Azobisisobutyronitrile 2 parts The obtained liquid is a milky white stable low viscosity polymer with a nonvolatile content of 55% and a viscosity D1 polymer particle size of 0.50 to 0.55 μm. It was a dispersion liquid. Note that the inside of the particle was crosslinked due to the reaction between the epoxy group of glycidyl methacrylate and the carboxyl group of acrylic acid. No precipitation or coarse particles were observed in this dispersion even after it was allowed to stand at room temperature for 3 months.

0.5 part of monobutyl phosphoric acid was added to 100 parts of the solid content of this non-aqueous dispersion and mixed uniformly to obtain a composition of the present invention.

Example 4 Synthesis of 0 dispersion stabilizer resin (X) 50 parts of isobutyl acetate and 30 parts of toluene were heated to reflux, the following monomers and polymerization initiator were added dropwise over 3 hours, and the mixture was aged for 3 hours after the addition. .

Methacryloxypropylmethyldimethoxysilane 22 parts Styrene 20 parts 2-ethylhexyl methacrylate 38 parts 2-hydroxyethyl methacrylate 9 parts Glycidyl methacrylate
1 part tert-butyl peroxy 2-ethylhexanoate 3 parts The obtained acrylic resin face had a nonvolatile content of 55%, a viscosity H, and a weight average molecular weight of about 16,000. Then, add 0.8 parts of 4-te methacrylic acid to the entire face.
0.02 part of rt-butylpyrocatechol and 0.1 part of dimethylaminoethanol were added, and a reflux reaction was carried out for 5 hours to introduce a copolymerizable double bond into the molecular chain of the dispersion stabilizer resin.

The number of introduced double bonds was approximately 0.6 per molecular chain as determined by resin acid value measurement.

Synthesis of non-aqueous dispersion of 0 polymer particles 98 parts of heptane 93 parts Dispersion stabilizer resin (X) was charged into a flask and heated to reflux, the following monomer and polymerization initiator were added dropwise over 3 hours, and Aged for 2 hours.

Styrene 15 parts Methyl methacrylate 50 parts Acrylonitrile 25 parts 2-perfluorooctylethyl methacrylate 10 parts tert
-Butyl peroxy 2-ethylhexanoate 1.5 parts The obtained liquid had a nonvolatile content of 55%, a viscosity of J, and a polymer particle size of 0.
It was a milky white stable low viscosity polymer dispersion of 2 to 0.3 μm. Even when this dispersion was allowed to stand at room temperature for 3 months, no precipitation or coarse particles were observed.

0.0 parts of monobutyl phosphoric acid was added to 100 parts of the solid content of this non-aqueous dispersion. 5 parts were blended and mixed uniformly to obtain a composition of the present invention.

Example 5 Synthesis of 0 Dispersion Stabilizer Resin (Y) 100 parts of xylene was heated to 120°C, the following monomers and polymerization initiator were added dropwise over 3 hours, and the mixture was aged for 2 hours after the addition.

γ-methacryloxypropyldimethoxysilane 30 parts Styrene 15 parts n-butyl methacrylate 20 parts 2-ethylhexyl methacrylate 15 parts lauryl methacrylate
20 parts 2.2' -Azobisisobutyronitrile
The acrylic resin face obtained in 4 parts had a non-volatile content of 50%,
The viscosity was C and the weight average molecular weight was 10,000.

0 Synthesis of non-aqueous dispersion of polymer particles Heptane 10000 Part 83 parts of dispersion stabilizer resin) were charged into a flask, heated to reflux, the following monomers and polymerization initiator were added dropwise over 3 hours, and further aged for 2 hours. did.

Styrene 15 parts Acrylonitrile 15 parts Methyl methacrylate 70 parts 2.2'-Azobisisobutyronitrile 1 part The obtained liquid had a non-volatile content of 50%,
It was a milky white stable low viscosity polymer dispersion with a particle size of B1 polymer particles of 0.35 to 0.40 μm. No precipitation or coarse particles were observed even after this was left at room temperature for 3 months.

0 parts of monobutyl phosphoric acid in 100 parts of solid content of this non-aqueous dispersion.
．． 5 parts were blended and mixed uniformly to obtain a composition of the present invention.

Example 6 0.1 part of monobutyl phosphoric acid was added to 100 parts of the solid content of the non-aqueous dispersion obtained in Example 1 and mixed uniformly to obtain a composition of the present invention.

Example 7 1 part of dibutyltin diacetate was added to 100 parts of the solid content of the non-aqueous dispersion obtained in Example 1 and mixed uniformly to obtain a composition of the present invention.

Example 8 Synthesis of 0 Dispersion Stabilizer Resin (Z) 100 parts of xylene was heated to 120° C., the following monomers and polymerization initiator were added dropwise over 3 hours, and the mixture was aged for 2 hours after the addition.

CH.

Styrene 25 parts n-butyl methacrylate 10 parts 2-ethylhexyl methacrylate 15 parts lauryl methacrylate
25 parts 2.2' -4 parts of azobisisobutyronitrile The obtained acrylic resin face had a nonvolatile content of 50%, a viscosity E, and a weight average molecular weight of 10,000.

○Synthesis of non-aqueous dispersion of polymer particles 100 parts of heptane and 83 parts of dispersion stabilizer resin (Z) were charged into a flask, heated to reflux, and the following polymer and polymerization initiator were added dropwise over 3 hours. Time aged.

Styrene 15 parts Acrylonitrile 15 parts Methyl methacrylate 70 parts 2.2'-azobisisobutyronitrile 1 part The obtained liquid has a non-volatile content of 50%,
It was a milky-white, stable, low-viscosity polymer dispersion with a viscosity of A and a polymer particle diameter of 0.35 to 0845 μm. No precipitation or coarse particles were observed even after this was left at room temperature for 3 months.

1 part of dibutyl phosphorous acid per 100 parts of solid content of this non-aqueous dispersion.
．． 0 parts were blended and mixed uniformly to obtain a composition of the present invention.

Comparative Example 1 100 parts of xylene was heated to 120°C, the following monomers and polymerization initiator were added dropwise over 3 hours, and the mixture was aged for 2 hours after the addition.

γ-methacryloxypropyltrimethoxysilane 12.5 parts Styrene 12.5 parts Acrylonitrile 7.5 parts n-butyl methacrylate)
17.5 parts 2-ethylhexyl methacrylate
) 12.5 parts lauryl methacrylate 12.
5 parts methyl methacrylate 25 parts 2.
3 parts of 2'-azobisisobutyronitrile The obtained acrylic resin face had a nonvolatile content of 50%, a viscosity G, and a weight n-average molecular weight of about 14,000.

0.5 monobutyl phosphoric acid per 100 parts of solid content of this festival
A comparative composition was obtained by blending the components and uniformly mixing them.

Comparative Example 2 100 parts of xylene was heated to 120° C., the following monomers and polymerization initiator were added dropwise over 3 hours, and the mixture was aged for 2 hours after the addition.

γ-methacryloxypropyltrimethoxysilane 30 parts Styrene 10.0 parts Acrylonitrile 7.5 parts n-Butyl methacrylate 12.5 parts 2-ethylhexyl methacrylate 10 parts Lauryl methacrylate 1
0 parts methyl methacrylate 20 parts 2.
3 parts of 2'-azobisisobutyronitrile The obtained acrylic resin face had a nonvolatile content of 50%, a viscosity F, and a weight average molecular weight of 14,000.

0.5 monobutyl phosphoric acid per 100 parts of solid content of this festival
A comparative composition was obtained by blending the components and uniformly mixing them.

Comparative Example 3 100 parts of xylene was heated to 120°C, the following monomers and polymerization initiator were added dropwise over 3 hours, and the mixture was aged for 2 hours after the addition.

γ-methacryloxypropyltrimethoxysilane 5 parts Styrene 15 parts Acrylonitrile 7.5 parts n-butyl methacrylate 20 parts 2-ethylhexyl methacrylate 12.5 parts Lauryl methacrylate 1
0 parts Methyl methacrylate 30 parts 2.
3 parts of 2'-azobisisobutyronitrile The obtained acrylic resin face had a nonvolatile content of 50%, a viscosity H, and a weighted average molecular weight of about 14,000.

0.5 monobutyl phosphoric acid per 100 parts of solid content of this festival
A comparative composition was obtained by blending the components and uniformly mixing them.

Comparative Example 4 An acrylic resin face was synthesized in the same manner as in Example 1, except that γ-methacryloxypropyltrimethoxysilane was partially replaced with n-butyl methacrylate. The obtained acrylic resin face has a non-volatile content of 50%.
, viscosity A and weight average molecular weight of 10,000.

A non-aqueous dispersion with a non-volatile content of 50% and a particle size of 0.20 to 0.30 μm of viscosity B1 polymer particles was prepared in the same manner as in Example 1 except that this face was used in place of the dispersion stabilizer resin (U). Obtained.

0.5 parts of monobutyl phosphoric acid was added to 100 parts of the solid content of this non-aqueous dispersion and mixed uniformly to obtain a comparative composition.

Next, performance tests were conducted on each of the compositions obtained in Examples and Comparative Examples. The test method is as follows.

0 Paint storage stability: A sealed storage test was conducted in a constant temperature room at 30°C, and the number of days until the paint thickened and became pudding-like was determined.

O Paint film performance: Each composition was applied to a polished mild steel plate to a dry film thickness of 50μ, and after baking at a temperature of 80°C for 30 minutes, the following various tests were conducted on the paint film. .

0 Gel fraction: The isolated coating film was placed in an equal weight mixture of acetone/methanol kept at reflux temperature, and the residual rate (%) of the insoluble coating film was examined after extraction for 4 hours.

0 Paint surface condition: Visually observed, JIS K54
Evaluation was made according to 00.

0 Water resistance: Examined the condition of the coated surface after immersion in tap water at 40°C for 168 hours.

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

O acid resistance: The condition of the coated surface was examined after immersion in a 5% HCQ aqueous solution (25°C) for 24 hours.

0 Weather resistance: Using a Sunshine Weather-Ometer, the condition of the painted surface was examined over time, and the time (Hr) until abnormalities such as fading and blistering occurred was determined.

0 Impact resistance: 500 using a DuPont impact tester
A weight of g was dropped onto the painted surface, and the maximum falling distance (cm 2 ) at which no abnormality such as cracking or peeling of the paint film was observed was determined.

O Flexibility: A test was conducted in accordance with JIS K 5400 using a bending resistance tester (10 mm diameter core rod).

The test results are shown in Table 1.

Claims (1)

[Claims] [1] General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (I) [In the formula, A is ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲
There are mathematical formulas, chemical formulas, tables, etc. Showing ▼. R_1 is a hydrogen atom or a methyl group, R_2 is a carbon number of 1 to
6 divalent aliphatic saturated hydrocarbon groups, R_3 and R_4
are the same or different and each represents a phenyl group, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, and R_5 represents an alkyl group having 1 to 10 carbon atoms. n represents an integer of 1 to 100. ] A polymer containing an alkoxysilane group-containing vinyl monomer, which is a compound represented by the following, as an essential monomer component is used as a dispersion stabilizer resin, and a radically polymerizable unsaturated monomer is mixed in an organic liquid in the presence of the resin. An acidic compound, a basic compound, or a tin-containing compound alone or a combination of a tin-containing compound and an acidic compound or a basic compound is added to the non-aqueous dispersion of polymer particles insoluble in the organic liquid obtained by polymerizing the organic liquid. A curable composition comprising a mixture.