JPH01131203A - Cold-setting composition - Google Patents

Abstract

PURPOSE:To obtain a composition having excellent cold-setting property, by using a specific polysiloxane-based macro-monomer and an oxirane group- containing vinyl monomer as essential monomer components. CONSTITUTION:A dispersion stabilizer resin is produced by using (A) a polysiloxane-based macro-monomer containing >=2 free functional groups per one molecule, having a number-average molecular weight of 400-50,000 and produced by reacting 70-99.999mol% of a compound of formula I (R1 is aliphatic hydrocarbon group or phenyl; R2, R3 and R4 are alkoxy or OH) with 30-0.001mol% of a compound of formula II (R5 is H or CH3; R6-R8 are OH, alkoxy or aliphatic hydrocarbon group; n is 1-6) and (B) a vinyl monomer containing oxirane group as essential monomer components and copolymerizing the monomers with another polymerizable monomer copolymerizable with the monomers. A radically polymerizable unsaturated monomer is polymerized in an organic solvent in the presence of the above dispersion stabilizer resin to obtain a non-aqueous dispersion of polymer particles insoluble in said organic solvent. The objective composition can be produced by compounding a chelate compound to the non-aqueous dispersion.

Description

[Detailed description of the invention] Rini LILIIL minutes! The present invention relates to novel low temperature curable compositions.

'・ Pavi 1. Conventionally, as a composition that can be crosslinked and cured at a relatively low temperature of room temperature to 100"C, a composition prepared by adding an acid, a l!! group, an organometallic catalyst, etc. to an alkoxysilane-containing vinyl polymer is known. For example, , JP-A-60-67553 discloses a composition in which an aluminum chelate compound is blended with a vinyl polymer containing an alkoxysilane such as methacryloxypropyltrimethoxysilane.

However, in the above-mentioned conventional composition, since the silanol group produced by hydrolysis of alkoxysilane is the only crosslinking functional group, polyacid water is required for curing, and therefore by-products such as alcohol are produced during this hydrolysis. The physical properties of the cured product deteriorate because of the large amount produced, and when curing with only moisture in the air, only the surface that comes into contact with the air is cured, and the inside is hardly cured, resulting in the difference in hardening between the surface and the inside. There were drawbacks such as the tendency for stiffness to occur in the cured product.

The present inventor has conducted extensive research in order to solve the problems of the prior art as described above. As a result, a vinyl copolymer containing a specific polysiloxane macromonomer having two or more 'M# functional groups such as a hydroxyl group or an alkoxyl group and an oxirane group-containing vinyl monomer as monomer components is In the presence of a chelate compound such as an aluminum chelate compound and/or an organic zirconium chelate compound, the silanol group present in the polysiloxane macromonomer that is the monomer component of the vinyl copolymer or the alkoxyl group in the macromonomer The silanol groups generated by the hydrolysis of the oxirane group and the oxirane group in the oxirane group-containing vinyl monomer become crosslinking functional groups, and the curing reaction proceeds simultaneously on the surface and inside even at low temperatures of 100°C or less. It was discovered that there is little difference in the degree of curing between the inside and the inside, and sagging is less likely to occur.Furthermore, the present invention was completed by discovering that by making the system a non-aqueous dispersion system, the finished appearance and curing properties of the paint were improved.

That is, the present invention provides (a) 1) - formula % formula % (1) (wherein, R represents an aliphatic hydrocarbon group having 1 to 8 carbon atoms or a phenyl group, and R2, R3 and R4 represent an aliphatic hydrocarbon group having 1 to 8 carbon atoms; 70 to 99.999 mol% of the compound (A) represented by the general formula % (in which R5 represents a hydrogen atom or a methyl group, R6, R
, and R6 represent a hydroxyl group, an alkoxyl group having 1 to 4 carbon atoms, or an aliphatic hydrocarbon group having 1 to 8 carbon atoms, provided that
Not all of R6, Rt and R6 are aliphatic hydrocarbon groups having 1 to 8 carbon atoms. n represents an integer of 1 to 6.

) is reacted with 30 to o,oot mol% of the compound (B) represented by (B), has two or more 'M# functional groups selected from hydroxyl groups and alkoxyl groups per molecule, and has a number average molecular weight 400 to 50,000, and 11) an oxirane group-containing vinyl monomer as essential monomer components, and further copolymerized with other polymerizable monomers that can be copolymerized with these. A non-aqueous dispersion of polymer particles insoluble in the organic solvent obtained by polymerizing a radically polymerizable unsaturated monomer in an organic solvent in the presence of the resin using the copolymer obtained as a dispersion stabilizer resin. The present invention relates to a low-temperature curable composition characterized in that it contains a chelate compound.

The polysiloxane macromonomer used as a monomer component of the dispersion stabilizer for the non-aqueous dispersion of the present invention has a main skeleton composed of siloxane bonds, and St of this main skeleton has an aliphatic hydrocarbon group, a phenyl group, or a hydroxyl group. , an alkoxyl group, a polymerizable unsaturated bond, etc. are bonded directly or indirectly, and - formula % formula % () (wherein R1, R2, R, and R4 are the same as above) It is obtained by reacting the compound (A) represented by the formula % with the compound (B) represented by the general formula % (wherein R3, R, , R, , R, and n are the same as above). It will be done.

In the above compound (A), R1 represents an aliphatic hydrocarbon group having at to 8 carbon atoms or a phenyl group, and R2, R3 and R4 represent an alkoxyl group or a hydroxyl group having 1 to 4 carbon atoms R2, R3 and R4 teeth.

It doesn't matter if they are all the same or partially or completely different.

In compound (A), examples of the alkoxyl group having 1 to 4 carbon atoms include linear or branched ones such as methoxy, ethoxy, propoxy, and butoxy groups; Examples of the aliphatic hydrocarbon group 8 include straight chain or branched aliphatic hydrocarbon groups such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, and octyl group.

In the above compound (A), R1 is particularly preferably a methyl group or a phenyl group, and R2, R3 and R4 are particularly preferably a methoxy group, a nidoxy group, a propoxy group, a butoxy group, or a hydroxyl group. Preferred specific examples include methyltrimethoxysilane, phenyltrimethoxysilane, butyltrimethoxysilane, methyltriethoxysilane, methyltributoxysilane, phenyltrisilanol, and methyltrisilanol. Among these, methyltrimethoxysilane, phenyltrimethoxysilane, phenyltrisilanol and the like are particularly preferably used. Compound (A) can be used alone or in combination.

In the above compound (B), R% represents a hydrogen atom or a methyl group, R,, R, and R6 represent a hydroxyl group, and have a carbon number of 1 to 4.
represents an alkoxyl group or an aliphatic hydrocarbon group having 1 to 8 carbon atoms, n represents an integer of 1 to 6, R,, R, and R1
1 may be all the same or partially or completely different, but
They must not all be aliphatic hydrocarbon groups having 1 to 8 carbon atoms.

The aliphatic hydrocarbon group having 1 to 8 carbon atoms and the alkoxyl group having 1 to 4 carbon atoms in compound (B) include the compound (
The same things as in A) can be mentioned.

As R, R, and R, methoxy group, nidoxy group, and hydroxyl group are particularly preferable, and n is particularly preferably in the range of 2 to 4. As a preferable specific example of compound (B), γ-methacryloxypropyltritri Examples include methoxysilane, γ-methacryloxypropyltriethoxysilane, γ-7cryloxypropyltrimethoxysilane, γ-methacryloxybutyltriethoxysilane, γ-acryloxypropyltrisilanol, and the like. Among these, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-acryloxypropyltrisilanol, etc. are particularly preferred;
) can be used alone or in appropriate combination.

In the present invention, the polysiloxane macromotip is
The mixing ratio of the two compounds obtained by mixing and reacting the above compound (A) and compound (B) is based on the total amount of the two compounds, and the compound (A) is 70 to 9
9.999% mol%, preferably 90-99.9 mol%,
More preferably 95299 mol%, compound (B) is 30
~0.001%, preferably 10-0.1%,
More preferably, it is within the range of 5 to 1 mol%. Compound(
If A) is less than 70 mol %, gelation tends to occur in the copolymerization reaction, whereas if it is more than 99.999 mol %, the amount of polysiloxane that is not copolymerized increases, which is not preferable, since cloudiness occurs in the resin liquid.

The reaction between compound (A) and compound (B) is carried out by dehydration condensation of the hydroxyl groups of both compounds or the hydroxyl groups produced by hydrolysis of alkoxyl groups. At this time, depending on the reaction conditions, not only dehydration condensation but also partial dealcoholization condensation occurs.

Although this reaction can be carried out without a solvent, it is preferably carried out using an organic solvent capable of dissolving compound (A) and compound (B), or water as a solvent. Such organic solvents are preferably hydrocarbon solvents such as heptane, toluene, xylene, octane, and mineral spirits;
Ester solvents such as ethyl acetate, n-butyl acetate, isobutyl acetate, methyl cellosolve acetate, butyl carpitol acetate, ketone solvents such as methyl acetate, methyl isobutyl ketone, diisobutyl ketone, ethanol, isopropanol, n- Butanol, 5
Alcohol solvents such as ec-butanol and inbutanol, ether solvents such as n-butyl ether, dioxane, ethylene glycol monomethyl ether, and ethylene glycol monomethyl ether can be used. These solvents can be used alone or in appropriate combinations.

It is appropriate that the concentration of compound (A) and compound (B) when released in a solution state is about 5% by weight or more as a total amount.

In the reaction between compound (A) and compound (B) in the present invention, the reaction temperature is usually about 20 to 180°C, preferably about 50 to 120°C. Moreover, it is appropriate that one reaction time is usually about 1 to 40 hours.

In addition, in this reaction, a polymerization inhibitor may be added as necessary.A polymerization inhibitor prevents unsaturated bonds contained in compound (B) from polymerizing during the reaction with compound (A). It is effective to prevent this, and specifically, for example, hydroquinone, hydroquinone monomethyl ether, etc. can be used.

In addition, in the production of this polysiloxane-based macromonomer, there is no problem in further adding tetraalkoxysilane, dialkyldialkoxysilane, etc. to the reaction system of the above compound (A) and compound (B), and both of the compounds 2
It can be added in an amount of about 0 mol% or less.

In the reaction between compound (A) and compound (B), R2,
When R3, R4, R6, R7 and R8 are all hydroxyl groups, dehydration condensation is preferably carried out in an organic solvent under heating and stirring.

Further, the compound (A) and/or the compound (B) may be Si
When it has an alkoxyl group bonded to, it is preferable to hydrolyze it prior to condensation, and the hydrolysis reaction and condensation reaction can be carried out continuously by heating and stirring, usually in the presence of water and a catalyst. The amount of water used in this case is not particularly limited, but it is preferably about 0.1 mole or more per mole of alkoxyl group. If the amount is less than about 1 mol of O, the reaction of both compounds may be reduced. The most preferred method is to use water as a solvent in large excess. Further, in this reaction, if water and a water-soluble organic solvent are used together, the reaction system can be made homogeneous when an alcohol that is sparingly soluble in water is produced by condensation.

As the water-soluble organic solvent, the above-mentioned alcohol-based, ester-based, ether-based, ketone-based solvents, and the like can be preferably used. As a catalyst for this hydrolysis reaction, an acid catalyst or an alkali catalyst can be used. Specifically, as an acid catalyst, hydrochloric acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, propionic acid, acrylic acid, methacrylic acid, etc. can be used. As the alkali catalyst, sodium hydroxide, triethylamine, ammonia, etc. can be used. The amount of the catalyst added is suitably within the range of about 0.0001 to 5% by weight, preferably about 0.01 to 0.1% by weight, based on the total amount of the compound (A) and compound (B). .

In the present invention, the polysiloxane macromonomer used has a number average molecular weight of about 400 to 50,000, preferably about 1,000 to 20,000. If the number average molecular weight is less than about 400, gelation tends to occur during copolymerization, and if it exceeds about 100,000, compatibility tends to decrease, which is not preferred.

In the present invention, the main skeleton of the polysiloxane macromonomer obtained by the reaction of compound (A) and compound (B) is constituted by siloxane bonds, and the structure of the main skeleton is, as one type, long chain (linear), Ladder (1a
dder) or a mixture of these. Among these, it is preferable to use one having a ladder-like structure or a mixed system having many ladder-like parts from the viewpoint of water resistance, heat resistance, light resistance, etc. These structures can be arbitrarily selected depending on the mixing ratio of compound (A) and compound CB), the amount of water and acid catalyst, etc. Then, the polysiloxane-based macromonomer connects R1 of the formulas CI) and (TI) to the Si of this siloxane bond.
, R2-R4, CH2=CCoo (CH2
) n , Re to R8, etc., and has a structure in which any of Si-bonded hydroxyl groups and/or free functional groups such as alkoxyl groups having 1 to 4 carbon atoms (i.e., silanol groups and/or or alkoxysilane group) per molecule.

Further, the polysiloxane macromonomer preferably has an average of 0.2 to 1.9 polymerizable unsaturated bonds per molecule, more preferably 0.6 to 1.4, If the number of zero-polymerizable unsaturated bonds, which is most preferably 0.9 to 1.2, is too small, the copolymerization reaction product of the macromonomer and the vinyl monomer tends to become cloudy.

On the other hand, if there are too many polymerizable unsaturated bonds, there is a risk of gelation during the copolymerization reaction, which is not preferable.

Here, the number of unsaturated bonds in the macromonomer can be determined by the following method.

(2) Various polysiloxane macromonomers are obtained by reacting under the same conditions while changing the proportions of compound (A) and compound (B) as appropriate.

(2) For each macromonomer obtained, various vinyl copolymers are synthesized by changing the proportion of non-functional vinyl monomer used.

(2) Determine the molecular weight distribution of the vinyl copolymer obtained by gel permeation chromatography (G, P, C,).

■ Even when the proportion of macromonomer and non-functional vinyl monomer used is changed, the peak molecular weight (molecular weight with the highest content) of the obtained copolymer is almost the same, and the distribution curve becomes a monopeak, resulting in a low molecular weight components (macromonomers that do not have unsaturated bond components) and high molecular weight components (
If no distribution of copolymers of macromonomers having two or more unsaturated bonds is observed, it can be said that the macromonomers used have an average of one polymerizable unsaturated bond per molecule.

■For other macromonomers, compound (A)
The number of moles used for compound (B) is [A], and the number of moles used for compound (B) is [
B], the number of moles of compound (A) used to obtain a macromonomer having an average of - number of polymerizable unsaturated bonds is [A+], and the number of moles of compound (B) is [Bs ], [B] / [A] [81] / [At] The average number of polymerizable unsaturated bonds in the macromonomer can be determined.

For example, if compound (B)/compound (A) = 1/20 (mole ratio), a macromonomer with a polymerizable unsaturated bond number of 1 (1) can be obtained, then compound (B)/compound (A) = 0
．． In the case of 9720, a macromonomer having an average of 0.9 polymerizable unsaturated bonds is obtained.

Examples of the oxirane group-containing vinyl monomer which is the other monomer component of the dispersion stabilizer for the non-aqueous dispersion of the present invention include those represented by the following general formulas (III) to (X■). be able to.

R,0 1■ R900 R900 R30 R,O R,0 α [In each general formula, R9 is a hydrogen atom or methyl, (, R
Io is a divalent aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms,
Ru represents a divalent hydrocarbon group having 1 to 10 carbon atoms.] Examples of the hexamer of (X) include glycidyl (meth)acrylate and methylglycidyl (meth)acrylate.

Among these oxirane group-containing vinyl monomers, it is particularly preferable to use alicyclic oxirane group-containing vinyl monomers represented by general formulas (m) to (xvn) from the viewpoint of curability.

However, even when the monomers X (2) are used, the curability can be improved by separately adding a compound containing an alicyclic oxirane group. Glycidyl methacrylate, which is a typical example of (X), has the advantage of being inexpensive and easily available.

In the above, examples of the divalent aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms include methylene, ethyl L/7, furopylene, tetramethylene, ethylethylene, pentamethylene, and hexamethylene groups. Examples of the divalent hydrocarbon group having 1 to 1O carbon atoms include methylene, ethylene, propylene, and tetramethylene.

Ethyl ethylene, pentamethylene, hexamethylene.

The dispersion stabilizer for the non-aqueous dispersion used in the present invention is synthesized by copolymerizing the polysiloxane macromonomer and the oxirane group-containing vinyl monomer, but other vinyl monomers can be copolymerized if necessary. Monomers that can be used include (a) esters of acrylic acid or methacrylic acid, such as methyl acrylate, methyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, hexyl acrylate, octyl acrylate, acrylic lauryl, C1-18 alkyl esters of acrylic acid or methacrylic acid such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, hexyl methacrylate, octyl methacrylate, lauryl methacrylate; acrylic acid C2-18 flukoxyalkyl esters of acrylic acid or methacrylic acid such as methoxybutyl, methoxybutyl methacrylate, methoxyethyl acrylate, methoxyethyl methacrylate, ethoxybutyl acrylate, and ethoxybutyl methacrylate; allyl acrylate, allyl Flukenyl esters of acrylic acid or methacrylic acid having 2 to 8 carbon atoms such as methacrylate: hydroxyalkyl esters of acrylic acid or methacrylic acid having 2 to 8 carbon atoms such as hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, etc. Ester: C3-18 alkenyloxyalkyl ester of acrylic acid or methacrylic acid such as allyloxyethyl acrylate and allyloxymethacrylate.

(b) Vinyl aromatic compounds: for example, styrene, α
-Methylstyrene, vinyltoluene, p-chlorostyrene.

(C) Polyolefin compounds: for example, butadiene, isoprene, chloroprene.

(d) Others: 7 Acrylonitrile, methacrylaterile, methyl isopropenyl ketone, vinyl acetate, beoba monomer (Shell Chemicals), vinyl propionate, vinyl pivalate, acrylamide, methacrylamide, N-methylol acrylamide, N-methylol methacrylamide , N-methylol acrylamide butyl ether, dimethylamine ethyl methacrylate, diethylaminoethyl methacrylate, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, allyl alcohol, maleic acid, phthalic acid, and the like.

Among these, acidic monomers such as acrylic acid and methacrylic acid, basic monomers such as dimethylaminoethyl methacrylate and acrylamide are likely to gel during the polymerization reaction of the copolymer if they are copolymerized in large quantities, so their usage should be at a minimum. should be kept to a minimum.

In order to enhance the ability of the copolymer as a dispersion stabilizer, a monomer consisting of methacrylic acid or an esterified product of 04 to CII monoalcohol of acrylic acid is preferably at least 20% of the total monomers. preferably contains 40% or more.

In the vinyl copolymer used as a dispersion stabilizer, the amount of each monomer used is 0.01 of the former in the case of a vinyl copolymer consisting of two components, a polysiloxane macromonomer and an oxirane group-containing vinyl monomer. ~98% by weight and 99% of the latter
．． 99-2% by weight, preferably 0.1-80% by weight of the former
and the latter 99.9 to 20% by weight. If the amount of the polysiloxane macromonomer used is less than this range, curability tends to decrease, and if it exceeds this range, the physical properties of the cured product tend to decrease and sagging tends to occur, which is not preferable.

In addition to the above two types of monomers, when other polymerizable vinyl monomers are used as a monomer component, the polysiloxane macromonomer is 0.01 to 80% by weight, preferably 0.1% by weight. ~60% by weight, 1 to 90% by weight of oxirane group-containing vinyl monomer, preferably 3 to 60% by weight, and 0 to 98.99% by weight of other polymerizable vinyl monomers, preferably 10 to 96.9% by weight. . It is not preferable to use the polysiloxane macromonomer and the oxirane group-containing vinyl monomer in amounts outside this range for the same reasons as above.

The above-mentioned copolymer can be obtained by the same method and under the same conditions as those for general synthesis reactions of acrylic resins, vinyl resins, and the like. As an example of such a synthesis reaction, each car shows a method in which body components are dissolved or dispersed in an organic solvent and heated with stirring at a temperature of about 60 to 180°C in the presence of a radical polymerization initiator. Can be done. The reaction time is usually 1 to 10
It may be about an hour. In addition, as the organic solvent, the same alcohol solvents, ether solvents,
Ester solvents, hydrocarbon solvents, etc. can be used. When using a hydrocarbon solvent, it is preferable to use other solvents in view of solubility. In addition, as the radical initiator (polymerization initiator), any commonly used radical initiator can be used, and examples thereof include benzoyl peroxide, t-butyl peroxy-2-ethyl hexa/ate,
and azo compounds such as azoisobutylnitrile and azobisdimethylvaleronitrile.

The copolymer preferably has a number average molecular weight of about 2,000 to 50,000.

It is possible to introduce a polymerizable double bond into the vinyl copolymer for use as a dispersion stabilizer so that the dispersion stabilizer and the particle polymer are grafted together during subsequent dispersion polymerization.

This improves the stability of the non-aqueous dispersion and makes it easier to form a transparent and smooth coating during film formation. A method for introducing polymerizable double bonds into a dispersion stabilizer is to add α,β-ethylenically unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, and itaconic acid to some of the oxirane groups in the copolymer. There are a method of adding an isocyanate group-containing monomer such as isocyanoethyl methacrylate to a hydroxyl group that has been included in the copolymer in advance, and the like. In the presence of the above-mentioned dispersion stabilizer, one or more monomers and a polymerization initiator are mixed with an organic solvent or an organic solvent in which the monomer is dissolved but the polymer obtained from the monomer is not dissolved. A non-aqueous dispersion can be produced by adding it to an organic solvent mixture (hereinafter simply referred to as organic solvent) and causing a polymerization reaction. As for the types of monomers that can be used to form the polymer serving as the particle component of the non-aqueous dispersion, all the monomers described above as being usable in the production of the dispersion stabilizer can be used.

Since the polymer serving as the particle component must not be dissolved in the organic solvent used, it is preferably a copolymer containing a large amount of highly polar monomer. Namely, methyl (meth)acrylate, ethyl (meth)acrylate, (meth)acrylonitrile, 2-hydroxy (meth)acrylate, hydroxypropyl (meth)acrylate, (meth)
Acrylamide, acrylic acid, methacrylic acid, itaconic acid, styrene, vinyltoluene, α-methylstyrene,
It is preferable that a large amount of monomer such as N-methylol (meth)acrylamide is contained. The non-aqueous dispersion particles can be crosslinked if desired. The inside of the particles can be crosslinked by copolymerizing polyfunctional heptamers such as divinylbenzene or ethylene glycol methacrylate, or by using one or more monomers having functional groups that react with each other or react alone. It can be produced by copolymerizing the polymers and crosslinking the particles during or after producing the nonaqueous dispersion. As the intraparticle crosslinking reaction that can be used, various reactions such as those described in JP-A-53-133236 can be used.

The organic solvent used for the non-aqueous dispersion includes one that does not substantially dissolve the dispersed polymer particles produced by the polymerization, but is a good solvent for the dispersion stabilizer and radically polymerizable monomer. be done. Examples of organic liquids that can be used include aliphatic hydrocarbons such as pentane, hexane, heptane, octane, mineral spirits, and naphtha; benzene;
Aromatic hydrocarbons such as toluene and xylene; alcohol, ether, ester and ketone solvents such as isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, octyl alcohol, cellosolve, butyl cellosolve, diethylene glycol monobutyl ether, methyl isobutyl ketone, diisobutyl ketone,
Examples include ethyl acyl ketone, methylhexyl ketone, ethyl butyl ketone, ethyl acetate, isobutyl acetate, acyl acetate, 2-ethylhexyl acetate, etc. Each of these may be used alone, or two or more types may be used in combination. However, in general, aliphatic hydrocarbons are preferably used in combination with aromatic hydrocarbons and alcohol-based, ether-based, ester-based, or ketone-based solvents such as those mentioned above. Furthermore, trichlorotrioleoethane, meta-xylene hexafluoride, tetrachlorohexafluorobutane, etc. can also be used if necessary.

Polymerization of the above monomers is carried out using a radical polymerization initiator. Usable radical polymerization initiators include, for example, azo initiators such as 2.2-7zoisobutyronitrile and 2.2'-azobis(2,4-dimethylvaleronitrile); benzoyl peroxide, lauryl peroxide, etc. Examples include peroxide-based initiators such as oxide and tert-butyl peroctoate, and these polymerization initiators are generally used within a range of 0.2 to 10 parts by weight per 100 parts by weight of monomers to be subjected to polymerization. can do. The formulation of the dispersion stabilizer resin to be present during the above polymerization can be selected from a wide range depending on the type of resin, but - in general, a radically polymerizable unsaturated monomer is added to 100 parts by weight of the resin. It is appropriate that the amount is about 3 to 240 parts by weight, preferably 5 to 82 parts by weight.

As the chelate compound used in the present invention, chelate compounds of various transition metals can be used, and among them, hexa-coordinated organoaluminum chelate compounds and 8-coordinated organozirconium chelate compounds are preferred.

The hexa-coordinated organoaluminum chelate compound is preferably obtained by treating organoaluminium with a chelating agent, and the organoaluminum has the following formula -No%%() [wherein RL2, At least one of R13 and R14
One is a flukoxy group having 1 to 13 carbon atoms (e.g. methoxy,
ethoxy, n-propoxy, impropoxy, n-butoxy, imbutoxy, 5ec-butoxy, tert-butoxy, n-pentoxy, isoamyloxy, n-hexyloxy, n-hebutyloxy, n-octyloxy, etc.) or carbon number 3 to 10 alkoxyalkoxy groups (e.g., methoxymethoxy, methoxyethoxy, ethoxybutoxy, butoxypentoxy groups, etc.), and the remainder is an alkyl group having 1 to 6 carbon atoms (e.g., methyl, ethyl, n-propyl, isopropyl) , n-butyl, isobutyl, 5
ec-butyl, tert-butyl, amyl group, etc.), aryl group (especially buenyl, tolyl group), alkenyl group (
(e.g. vinyl, allyl group, etc.) or an alkyl group having 1 to 6 carbon atoms substituted with a methcapto group or an amino group (e.g.
[gamma]-mercaptopropyl, aminoethyl, aminopropyl, aminobutyl group, etc.] Compounds represented by these are preferred, and specifically, for example, aluminum isopropylate, aluminum 5eC-
Examples include butyrate, aluminum tert-butyrate, and the like.

Examples of the chelating agent that can be reacted with the organoaluminum include lower alkanolamines (e.g., nitriethanolamine, jetanolamine, dimethylaminoethanol, etc.), acetoacetate (e.g., methyl acetoacetate, ethyl acetoacetate, etc.) , diketone alcohols (e.g. diacetone alcohol, etc.), diketones (e.g. niacetylacetone, etc.), glycols (e.g. ethylene glycol, octylene glycol, etc.), oxycarboxylic acids (e.g. lactic acid, tartaric acid, etc.), dicarboxylic acids or Examples include esters thereof (eg, maleic acid, ethyl malonate, etc.), salicylic acid, catechol, pyrogallol, etc. Among them, lower alkanolamines, oxycarboxylic acids, and diketones are preferred.

The organoaluminum chelate compound advantageously used in the present invention is a compound that does not have a hydroxyl group or an alkoxyl group directly bonded to an aluminum atom. If the aluminum chelate compound has a hydroxyl group or alkoxyl group directly bonded to the aluminum atom, the storage stability of the resin composition will deteriorate when it is blended into the resin composition, and the flatness of the coating film after curing will deteriorate. This is not preferable because it reduces lubricity.

Preferred specific examples of the six-coordinate organoaluminum chelate compound include aluminum tris(ethylacetoacetate), tristrifluoroacetylacetonadoaluminum, trishexafluoroacetylacetonadoaluminum, trisethylacedoacetoacetoaluminum, tris(n- Tris(1so-propylacetoacetato)aluminum, tris(n-butylacetoacetato)aluminum, trissalicylaldehydatoaluminum, tris(2-ethoxycarbonylphenolate)aluminum, tris(acetyl Acetonato)aluminum, tris(ethylacetonato)aluminum, tris(salicylaldehydato)aluminum, etc. may be partially condensed.

As the 8-coordinated organic zirconium chelate compound, one obtained by treating organic zirconium with a chelating agent is suitable, and the organic zirconium has the following formula: At least two of 3, R16, R17 and RlB are alkoxy groups having 1 to 13 carbon atoms (e.g. methoxy, nidoxy, n-propoxy, inpropoxy, n
-butoxy, isobutoxy, 5ec-butoxy, te
rt-butoxy, n-pentoxy, inamyloxy,
n-hexyloxy, n-hebutyloxy, n-octyloxy, etc.) or an alkoxyalkoxy group having 3 to 10 carbon atoms (side methoxymethoxy, methoxyethoxy, ethoxybutoxy, butoxypentoxy group, etc.), and the remainder is carbon. Number 1 to 6 alkyl groups (e.g. methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, 5ec-butyl, tert-butyl, amyl groups, etc.), aryl groups (especially phenyl, tolyl groups), An alkenyl group (e.g. vinyl, allylno, !i, etc.) or an alkyl group having 1 to 6 carbon atoms substituted with a mercapto group or an amine group (e.g. γ-mercaptopropyl, aminethyl, aminopropyl, aminobutyl group, etc.) ) is preferable, and specifically, for example, tetramethyl zirconate, tetraethyl zirconate,
Tetraisopropyl zirconate.

Examples include tetra-n-butyl zirconate, tetraisobutyl zirconate, and tetra-tert-butyl zirconate.

As the chelating agent to be reacted with the organic zirconium compound, those similar to the chelating compounds used in the case of the aluminum compound described above are preferably used.

The organic zirconium chelate compound advantageously used in the present invention is a compound that does not have a hydroxyl group or an alkoxyl group directly bonded to a zirconium atom. When a hydroxyl group or alkoxyl group directly bonded to a zirconium atom is present, it is not preferable because it causes a decrease in the storage stability of the resin composition and a decrease in the smoothness of the cured coating film, as in the case of aluminum compounds.

Preferred specific examples of the 8-coordinated organic zirconium chelate compound include tetrakis (oxalic acid) zirconium, tetrakis (acetylacetone) zirconium, tetrakis (n-propylacetoacetate) zirconium, tetrakis (ethylacetoacetate) zirconium, and tetrakis (ethylacetoacetate) zirconium. (Salicylaldehydato)zirconium, etc., and these may be partially condensed □.

The proportion of the chelate compound used is approximately 0.01 to 30 parts by weight per 100 parts by weight of the resin solid content of the curable composition.

If the amount is less than this range, crosslinking curability tends to decrease, and if it is more than this range, it tends to remain in the cured product and reduce water resistance, which is not preferable. The preferred amount is 0.1-10 parts by weight.

In addition to the above-mentioned non-aqueous dispersion and chelate compound, the composition of the present invention may contain a solution-type vinyl copolymer and a compound containing at least two alicyclic oxirane groups in one molecule.

As the solution type vinyl copolymer, the same dispersion stabilizer resin as used for the above-mentioned non-aqueous dispersion can be used. However, this copolymer does not have any restrictions as a dispersion stabilizer, such as its function as a dispersion stabilizer or the inclusion of double bonds for bonding with the polymer, so it is better than the one used as a dispersion stabilizer. Also, monomer components can be selected from a wide range. The proportion of the solution type vinyl copolymer used is 1 part by weight of the solid content of the non-aqueous dispersion. By blending the solution type vinyl copolymer, the finished appearance of the cured product can be improved.

Compounds having at least two alicyclic oxirane groups in one molecule used in the present invention include, for example, compounds represented by the following chemical formula, and adducts with anate compounds (polyisocyanate compounds that can be used include, for example, hexamethylene Aliphatic diisocyanates such as diisocyanate or trimethylhexamethylene diisocyanate; cycloaliphatic diisocyanates such as xylylene diisocyanate or isophorone diisocyanate; organic diisocyanates themselves such as aromatic diisocyanates such as nitrilene diisocyanate or 4,4'-diphenylmethane diisocyanate; , or adducts of these diisocyanates with polyhydric alcohols, low molecular weight polyester resins, water, etc.

Alternatively, polymers of organic diisocyanates as listed in 1 above, as well as incyanate biuret bodies, etc. may be mentioned. Typical commercial products thereof include "Parnock D-750, -800, 0N-950, -97
0 or 15-455J [the above, products of Dainippon Ink & Chemicals], "Desmodur L, NHL, IL or N3390J [products of Bayer AG, West Germany]
, "Takenate D-102, -202, -11ON or -123NJ [Takeda Pharmaceutical Company ■ product]", "Coronate L, HL, EH or 203" [Japan Polyurethane Industry ■ product] or "Duranate 24A-90C
XJ [Asahi Kasei Kogyo product], etc.); Esterified products having groups (for example, polyester obtained by esterifying tetrahydrophthalic anhydride, trimethylolpropane, 1,4-butanediol, etc.) with peracetic acid, etc. Examples include those obtained by oxidizing with.

By adding the above alicyclic oxirane group-containing compound, the curability of the composition can be improved even when the oxirane group contained in the dispersion stabilizer of the non-dispersed liquid is not an alicyclic oxirane group.

The number average molecular weight of the resin of the solution type vinyl copolymer is 10
A value in the range of 00 to 50,000 is preferred. Molecular weight 10
If the molecular weight is less than 0.00, it is actually difficult to synthesize by radical polymerization, which is easy to carry out industrially, and if the molecular weight exceeds 50,000, the workability during coating and the finished appearance will deteriorate.

The number average molecular weight of the alicyclic oxirane group-containing compound is preferably 1000 or less. When the molecular weight exceeds 1,000, the compatibility with stabilizers for non-aqueous dispersions and the solution-type vinyl copolymer decreases.

The amount of the alicyclic oxyoxirane group-containing compound 1^ is 0 to 200 parts by weight per 100 parts by weight of the total resin solid content of the non-aqueous dispersion and the solution type vinyl copolymer. Furthermore, the low temperature curable composition of the present invention does not contain the alicyclic oxirane group-containing compound as an essential component, but contains a fat such as glycidyl methacrylate in the resin of the non-aqueous dispersion and solution type vinyl copolymer. When containing only the oxirane group of the group oxirane group, the presence of the alicyclic oxirane group-containing compound can exhibit low-temperature curability. In general, glycidyl methacrylate is the cheapest vinyl monomer containing oxirane groups, so when glycidyl methacrylate copolymers are used in non-aqueous dispersions and solution-type vinyl copolymers, a certain amount of alicyclic It is very preferred to add compounds containing oxirane groups. Even if the non-aqueous dispersion or solution type vinyl copolymer already contains an alicyclic oxirane group, the addition of an alicyclic oxirane group-containing compound may increase the solids concentration of the composition or affect the finish of the coating. It has the effect of improving appearance. On the other hand, if the amount of the oxirane group-containing compound exceeds 200 parts by weight, the composition will contain too many low molecular weight components, resulting in poor curability.

The composition of the present invention may contain, for example, Epicoat 1, if necessary.
Epoxy group-containing resins such as 001 (manufactured by Shell Chemical Co., Ltd.); hydroxyl group-containing resins such as styrene allyl alcohol copolymers; It is also possible to add other resins such as the silane compound of No. 1 and general silicone resins having alkoxysilane groups.

Furthermore, the composition of the present invention may contain known coating surface conditioners, fluidity conditioners, ultraviolet absorbers, light stabilizers, curing catalysts, extender pigments, coloring pigments, metal powder pigments, mica powder pigments, if necessary. ,
Dyes etc. can be added.

The composition of the present invention is usually used after being diluted with an organic solvent.

Preferred organic solvents include, for example, toluene.

Hydrocarbon solvents such as xylene, ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone, ethyl acetate,
Examples include ester solvents such as butyl acetate, ether solvents such as dioxane and ethylene glycol diethyl ether, and alcohol solvents such as butanol and propatool. These solvents can be used alone or in appropriate mixtures while taking into consideration the stability of the non-aqueous dispersion, but when using alcoholic solvents, they should be used in combination with other solvents from the viewpoint of solubility of the resin. The concentration of the resin solution varies depending on the intended use, but is generally l
It may be about 0 to 70% by weight.

The composition of the present invention can be coated by common coating methods such as spray coating, roll coating, and brush coating.

The composition of the present invention can be easily crosslinked and cured at a low temperature of too'a or lower. For example, when it is cured at room temperature without any heating, it can be sufficiently cured in about 8 hours to 7 days. Furthermore, when heated to about 40-100''C, it can be sufficiently cured in about 5 minutes to 3 hours.

The curing reaction of the resin composition begins with the volatilization of the solvent,
It is thought that the process proceeds in a chain manner due to volatilization of the chelating agent from the crosslinking curing agent. It is presumed that the progress of the curing reaction by the crosslinking curing agent follows the mechanism shown below. That is, for example, when an organoaluminum chelate compound is used as a crosslinking curing agent, in the second stage reaction, after the chelating agent has volatilized, the aluminum compound is mixed into the polysiloxane macromonomer.
＼ Causes a combination. Then, as the second reaction, /
\ Teichi5i-Oe-HΦ /.

/ \ and polarizes the silanol group. This polarized silanol group reacts with the epoxy group to form an oxonium salt.Next, ionic polymerization of the epoxy group and addition reaction to the hydroxyl group occur.

It is presumed that the curing reaction in the resin composition of the present invention proceeds by various reactions such as the condensation reaction between silanol groups occurring in parallel, in addition to the crosslinking reaction caused by the catalytic action of the crosslinking curing agent described above. It is thought that the following various curing reactions occur.

(A) Condensation of silanol groups (B) Condensation of silanol groups with hydroxyl groups generated from oxolane groups (C) Addition of silanol groups to oxirane groups (D) Addition of hydroxyl groups to oxirane groups (E) Addition of oxirane groups to each other Note that in the resin composition of the present invention, when the polysiloxane macromonomer contains an alkoxyl group as a functional group (that is, when it contains an alkoxysilane group), hydrolysis is required to produce a silanol group. Although necessary, this hydrolysis reaction proceeds sufficiently in the presence of a small amount of moisture, such as that in the air.

In the composition of the present invention, a functional group such as a silanol group derived from a polysiloxane macromonomer as a monomer component is present in the dispersion stabilizer of the non-aqueous dispersion and in the solution-type vinyl copolymer added as necessary. and oxirane groups derived from oxirane group-containing vinyl monomers. Therefore, various curing reactions as shown in (A) to (E) above occur concurrently. As a result, curing proceeds simultaneously on the surface and inside of the cured product, and the degree of hardening is small on the surface and inside of the cured product, making it difficult to cause distortion.

Furthermore, the composition of the present invention is a non-aqueous dispersion in which a dispersion stabilizer resin is dissolved in an organic solvent and a solid phase, which is a polymer particle formed by polymerizing a radically polymerizable unsaturated monomer, is stably dispersed in a liquid phase. The liquid contains a chelate compound. As a result, the solid content of the composition during coating can be significantly increased, and since the viscosity after coating is increased, a film with excellent finished appearance without sagging or running can be formed. Furthermore, the formed film is a photo- and chemically stable film in which the continuous phase of the film has a siloxane bond, and the integrated particle component in the film is stabilized by the continuous phase, and the film is stabilized by the particles. Because it is reinforced with other components, it has excellent optical and chemical properties, as well as mechanical properties such as impact resistance.

The cured product obtained from the resin composition of the present invention has excellent weather resistance and water resistance, and is suitable for applications such as painting and repairing automobiles and containers, painting outdoor building materials, and PCM (precoated metal). used for.

The resin composition of the present invention has the following excellent characteristics.

(2) It has excellent low-temperature curability and can be easily crosslinked and cured at a low temperature of 100''C or lower.For example, a cured product having a gel fraction of 95% or more can be obtained by just curing at 80'O for 30 minutes.

(c) Moisture is not necessary for the curing reaction, or the curing reaction proceeds in the presence of a small amount of moisture, comparable to the humidity in the air.

・■ Since curing begins with solvent volatilization, storage stability is good even when used as a one-liquid composition.

t4+ Do not use highly toxic curing agents such as incyanate.

Since various crosslinking reactions such as the condensation reaction of silanol groups and the on-polymerization reaction of epoxy groups occur simultaneously, there is little difference in hardenability between the surface and the inside, so there is no sagging and thick coating is possible. Excellent in sex.

(3) Since there are few by-products during curing, a cured product with excellent physical properties can be obtained. In particular, the cured product has excellent weather resistance and water resistance.

(7) Almost no uncured material is present on the surface layer of the cured product, resulting in a cured product with excellent overcoatability, recoatability, adhesion, etc.

4i) Since the polymer particles are stably present in the M1 composition, a film can be formed which has excellent storage stability and has an excellent finish without running or dripping.

(1) The formed film contains polymer particles, and the continuous phase has siloxane bonds, so it has excellent physical properties, weather resistance, etc.

Sosei Haku Hereinafter, the present invention will be explained in more detail with reference to Examples.

"1 part" and "%" are based on weight, respectively.

A of a-1 The following mixture was reacted at 80°C for 5 hours to synthesize a polysiloxane macromonomer Ml.

Methyltrimethoxysilane 2720 parts (20 moles) γ-methacryloxyprobilt 256 parts Rimesoxysilane (1 mole) Deionized water
11341136% hydrochloric acid
2 //Hydroquinone
l //This macromonomer has a number average molecular weight of 20
00, and had an average of one polymerizable double bond and four hydroxyl groups per molecule.

A mixture of 200 parts of macromonomer M1 and 100 parts of styrene 2-ethylhexylmethac 400 //rylate 2-hydroxyethylac l OQ tt rylate 2.2'-7 zobisisobutylene 20/l tyronitrile in 1000 parts of xylene at 120°C. It was added dropwise and polymerized to obtain a transparent copolymer solution. The number average molecular weight of the obtained copolymer was 19,000, and the solution had a solid content concentration of 50% and a Gardner viscosity (20°C) of T. Isocyanoethyl methacrylate was added to the copolymer to introduce 0.3 polymerizable double bonds per molecule based on the number average molecular weight. Using this vinyl copolymer as a dispersion stabilizer, a non-aqueous dispersion (a-1) was synthesized as follows.

100 parts of the above vinyl copolymer solution (dispersant solution), 180 parts of ethylcyclohexane, and 20 parts of n-butanol were placed in a flask, and the following monomers and polymerization initiator were added dropwise at current temperature over a period of 4 hours. Then, 0.2 part of t-butyl peroctoate is added, and the mixture is aged for 3 hours.

Thereafter, the solvent was removed under reduced pressure to produce a well water dispersion (a-1).

Styrene 10 parts Methyl methacrylate 451/2-Hydroxyethyl acetate 10//Relate acrylonitrile 15 parts Macromonomer M 1 1 Q tr2.2'-
The solid content concentration of the azobisisobutyronitrile non-aqueous dispersion (a-1) was 55%, and the Gardner viscosity (25°C) was QR.

2;ノ)"a-28 '491 48 moles of phenyltrimethoxysilane and 2 moles of γ-methacryloxyethyltriethoxysilane were reacted in the same manner as in Example 1 to produce polysiloxane-based macromonomer M2.
I got it. Obtained polysiloxane macromonomer M2
The number average molecular weight of is about 5000, and on average per molecule,
It had one vinyl group and 5-10 methoxy groups.

A mixture of 300 parts of macromonomer M2, 200 parts of glycidyl methacrylate, 400 parts of lauryl methacrylate, 100 parts of tr2-hydroxyethyl methacrylate (t-butyl peroctoate) 3 Q // was dropped into 1000 parts of xylene at 120°C,
Polymerization was conducted to obtain a copolymer solution. The number average molecular weight of the obtained copolymerization was 15,000, and the solid content concentration of the solution was 50%.
, Gardner viscosity (25°C) was N.

120 parts of the above vinyl copolymer solution (dispersant solution), 180 parts of ethylcyclohexane, and 20 parts of n-butanol were charged into a flask, and the following monomers and polymerization initiator were added at reflux temperature for 4 hours. Dropwise, 0.2 part of t-butyl peroctoate is further added, and the mixture is aged for 3 hours. After that, the solvent was removed under reduced pressure to obtain a non-aqueous dispersion (a-2).
was manufactured.

Styrene 15 parts Methyl methacrylate) 40 tr2-Hydroxyethyl ac 1O7l rylate acrylonitrile 15 parts Glycidyl methacrylate 1Oll Macromonomer M2 10 tr2.
The solid content concentration of the 2'-azobisisobu l//tyronitrile non-aqueous dispersion (a-2) was 55%, and the Gardner viscosity (25°C) was L.

Proceed in the same manner as in the synthesis example of the non-aqueous dispersion (a-1), except that the monomer composition of the dispersion stabilizer and the monomer composition forming the particles are as follows. A non-aqueous dispersion (a-3) was synthesized.

Monomer composition of dispersion stabilizer Maktomotsuma-Ml 200 parts Styrene 100 tr2-ethylhexylmethac 400 // Rylate 2-hydroxyethyl ac 100 parts Composition of monomers forming rylate particles Styrene 10 parts Methyl methacrylate 65 // Acrylonitrile
101/Ethylene glycol dimethacrylate glycidyl methacrylate 1O7/The solid content concentration of the obtained non-aqueous dispersion (a-3) was 55%, and the Gardner viscosity (25°C) was V.

゛ Vinyl 1 b-1 xylene/n-butanol = 4/1i in a mixed solvent of 2,2
A vinyl copolymer solution (b-1) having the following monomer composition was synthesized using '-azobisisobutyronitrile as an initiator.

Polysiloxane Macromo 20 parts Styrene 20 //2-ethylhexyl methacrylate 20 tt rate 2-hydroxyethyl methacrylate Q The solid content concentration of ttcrete (b-1) is 50%, Gardner viscosity (2
5°C) was T, and the number average molecular weight of the resin component was 16,000.

A vinyl copolymer solution (b-2) having the following monomer composition was synthesized in the same manner as in the synthesis of 11vinyl 7r b-2'' (b-1).

Glycidyl methacrylate 25 parts Polysiloxane macromono 1o/mer-M2 Styrene l Q ttn-
Butyl methacrylate 351/2-ethylhexyl methacrylate 20 tt (b-2) had a solid concentration of 50%, a Gardner viscosity (25°C) of P, and a number average molecular weight of the resin component of 14,000.

A vinyl copolymer solution (b-3) having the following monomer composition was synthesized in the same manner as in the synthesis of Kubiniruni 1r-b-3-8J9 (b-1).

Polysiloxane macromono 20 trmer M
l Styrene 20 tt Methyl methacrylate 20 tt (b-3)
The solid content concentration is 50%, the Gardner viscosity (25°C) is X, and the resin content is e! Imo average molecular weight was 29,000.

・・Livinyl ITA b-4 no Hachigi (b-1)
A vinyl copolymer solution (b-4) having the following monomer composition was synthesized in the same manner as in the synthesis of .

CH2=C-COOCH2CH2CH2-S i -0
CH30CH340 parts Styrene 20 ttn-butyl methacrylate 4 Q //(b -4
) solids concentration is 50%, Gardner viscosity (25°C)
was M, and the number average molecular weight of the resin component was 13,500.

Branch autopsy” A curable composition was prepared using the following formulation.

Non-aqueous dispersion (a-1) 109 parts (solid content 55%) Vinyl copolymer solution (b'l) 80 tt (solid content 50%) Aluminum tris l tt (ethyl acetoacetate) Acetylacetone 511 The above composition was mixed with acetic acid. Isobutyl/Sufuzol 1000 (Cosmo Oil■
Aromatic solvent)=l/1 #4 with nail dipping ratio thinner
The viscosity was adjusted to 20°C for 35 seconds using a Ford Camb and used for painting.

A zinc phosphate-treated dull steel plate was coated with epoxy cationic electrodeposition paint using the electrodeposition coating method to a dry film thickness of 20 cm. Bake for 20 minutes.

Next, the painted surface was polished with #400 sandpaper, and then wiped with gauze soaked in petroleum benzene to degrease it.

After that, I applied an amine polyester automotive paint to a dry film thickness of 30cm, and it was 140cm thick! Bake for 30 minutes.

Then, the painted surface was sanded with #400 sandpaper, drained and dried, and the painted surface was wiped with petroleum benzine to make the material.

A dry film thickness of about 50 #L is made from the composition whose viscosity has been adjusted as described above.
The film was air-sprayed, left at room temperature for 10 minutes, and then baked at 80°C for 30 minutes. Evaluation of the coating is shown in Table 1.

In the following Examples and Comparative Examples, the materials and adjustments to coating viscosity are the same as in Example 1 unless otherwise specified.

A composition was prepared using the following formulation. Dispersion of titanium white was performed using vinyl copolymer (b-2).

Non-aqueous dispersion (a-2) 73 parts (solid content 55%) Vinyl copolymer solution (b-2) 80 tt (solid content 50%) Aluminum tris (ethyl acetoacetate) Titanium white J R -60260// (manufactured by Teikoku Kako Shogiku) Acetylacetone 5//Mitsu' U-Kyou] A base coat for wet-on-wet painting was prepared with the following formulation.

Non-aqueous dispersion (a-3) g □ parts (solid content 5
5%) Vinyl copolymer solution (b-3) 100 // (Solid content 50%) Aluminum tris l〃 (acetylacetone) Aluminum paste # 4919 5 // (Toyo Aluminum product) Aluminum paste # 55-519 1 Q tt (Toyo Aluminum Product) Acetylacetone 3 tt Heat this in xylene in a #4 Ford Cup for 15 seconds (20″C)
) and used for coating.

A top coat clear composition for wet-on-wet painting was prepared using the following formulation.

Non-aqueous dispersion (a-1) 1 part g (solid content 55%) Vinyl copolymer solution (b-1) 100 // (solid content 50%) Aluminum tris (71 parts cetyl acetoacetate) Acetylacetone 3 // Above The clear paint was adjusted to a viscosity of 35 seconds using a #4 Ford cup with a thinner of Swasol-1000 (aromatic solvent manufactured by Cosmo Oil Co., Ltd.) and butanol in a ratio of 80/20 ml, and then used for painting.

The base coat is applied to the coating material to a dry film thickness of 18I.
Spray air so that it becomes L, leave it at room temperature for 5 minutes, and then
The top coat was air-sprayed to a dry film thickness of about 40 tons, left at room temperature for 10 minutes, and then baked at 80° C. for 30 minutes.

Sogodou” A composition was prepared using the following formulation.

Non-aqueous dispersion (a-1) 73 parts (solid content 55%) Vinyl copolymer solution (b 1) 80 // (solid content 50%) Tetrakis (acetyl 2 // setone)
Zirconium alicyclic oxirane group-containing 20-part compound (*l) Acetylacetone 5 tt (*l)
: Adduct with 1 mol of adipic acid. Painted to a dry film thickness of 501 L and heated at 90°C for 30°C.
Bake for a minute.

``Shiran 舊'' A composition was prepared using the following formulation.

Non-aqueous dispersion (a-2) 109 parts (solid content 5
5%) Aluminum tris (wood 2-part tylacetoacetate) Alicyclic oxirane group-containing 40// compound (wood 2
) Acetylacetone 57/ethylene diisocyanate) 1 mol adduct. Painted to a dry film thickness of 50 JL and heated at 100'O.
Baked for 0 minutes.

Emperor J A composition was prepared using the following formulation.

Non-aqueous dispersion (a-2) 91 parts Vinyl copolymer solution (b 2) 100 // Aluminum tris (tt tylacetoacetate) Acetylacetone 2 // Painted so that the dry film thickness was about 50 mm. It was baked and hardened at ℃ for 30 minutes.

Le Kasa Neiyu A composition was prepared using the following formulation.

Vinyl copolymer solution (b-4) 200 parts (solid content concentration 50%) Aluminum Tris (Tylacetoacetate) Coated to a dry film thickness of 50 μm and baked at 80° C. for 30 minutes.

Comparison] Coating was carried out in exactly the same manner as in case (b-1) except that the polysiloxane macromonomer Ml in (b-i) was replaced with all-ff mira n-butyl methacrylate as the solution-type vinyl copolymer. A polymer solution (b-5) was obtained. The solid content concentration of this product is 50%, and the Gardner viscosity (25'C
) was Q, and the number average molecular weight of the resin component was 15,000.

Using this, the following composition was created.

Vinyl copolymer solution (b-5) 200 parts (solid content 5
0%) Aluminum Tris (Tylacetoacetate) Painted to give a dry explosion film thickness of approximately 50% and heated to 3% at 100'C.
Baked for 0 minutes.

Table 1 shows the curing i+ value results of Examples 1 to 6 and Comparative Examples 1 to 2.

(Note) in Table 1 (Note 1) The finished appearance was visually evaluated.

(Note 2) Resistance to gasoline wiping A gauze was moistened with silver gasoline and the coated surface was rubbed vigorously 8 times over a length of 10 cm, and then the coated surface was observed. Those with almost no scratches or glossy spots on the painted surface were considered good.

(Note 3) #Impact resistance Using a DuPont impact tester, the firing pin tip End radius 1/2 inch, falling plow weight 500 Test at g. No cracks on the painted surface The maximum height is shown in 5cm increments.

(Note 4) Water resistance Place the test piece in a constant temperature water bath at 40°C. Soak for an hour. After removing the paint film, Please select one that does not have any abnormalities such as pimples or blisters. I liked it.

(Note 5) Acid resistance 10% sulfuric acid Q, 5 cct - Spotted on the painted surface and left at 20°, 075% RH for 48 hours, washed with water, and observed the painted surface.

(Note 6) 1 Weather resistance Sunshine Weather Ometer The gloss retention rate when exposed for 800 hours ijQ is shown.

Procedural amendment (white side) January 2″″2, 1988

Claims (1)

[Claims] (1) A) i) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼・・・・・・( I
(In the formula, R_1 represents an aliphatic hydrocarbon group having 1 to 8 carbon atoms or a phenyl group, and R_2, R_3, and R_4 represent an alkoxyl group or hydroxyl group having 1 to 4 carbon atoms.) Compound (A) represented by 70 to 99.999 mol% and the general formula ▲ Numerical formulas, chemical formulas, tables, etc. ▼・・・・・・(II) (In the formula, R_5 is a hydrogen atom or a methyl group, R_6
, R_7 and R_8 represent a hydroxyl group, an alkoxyl group having 1 to 4 carbon atoms, or an aliphatic hydrocarbon group having 1 to 8 carbon atoms. However, R_6, R_7 and R_8 all have 1 carbon number.
~8 aliphatic hydrocarbon groups. n is 1 to 6
indicates an integer. ) is reacted with 30 to 0.001 mol% of the compound (B) represented by (B), has two or more free functional groups per molecule selected from hydroxyl groups and alkoxyl groups, and has a number average molecular weight of 400. ~50,000, and ii) an oxirane group-containing vinyl monomer as essential monomer components, and further copolymerized with other polymerizable monomers copolymerizable with these. A non-aqueous dispersion of polymer particles insoluble in the organic solvent obtained by polymerizing a radically polymerizable unsaturated monomer in an organic solvent in the presence of the resin using the copolymer obtained as a dispersion stabilizer resin, A low-temperature curable composition comprising a chelate compound.