JPS6155160A - Paint resin composition - Google Patents

Abstract

PURPOSE:To provide the titled compsn. which does not cause sagging during the formation of a coating film and has greatly improved gasoline resistance, consisting of a hydroxyl group-contg. polymer, an aminoplast and a fine polymer powder. CONSTITUTION:0.1-100pts.wt. fine polymer particle obtd. by non-aqueous dispersion-polymerization of an epoxy group-contg. vinyl monomer in the presence of a dispersion stabilizer in an org. solvent which does not dissolve the polymer of said vinyl monomer and crosslinking dispersed particles by using a compd. contg. at least two carboxyl groups (e.g. polyester or alkyd resin) and/or a polycarboxylic acid anhydride (e.g. 3-methyltetrahydrophthalic anhydride), is blended with 100pts.wt. of the combined quantity of 90-30pts.wt. hydroxyl group-contg. polymer and 10-70pts.wt. aminoplast.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to a new and useful resin composition for coatings,
More specifically, it uses a hydroxyl group-containing polymer, an aminoplast, and a specific particulate polymer as essential components, and in particular, when it is formed into a coating film, it has "no coating defects such as sagging, and is resistant to gasoline." The present invention relates to a resin composition with significantly improved properties.

[Prior art]

Recent trends in the paint industry, especially 2 used for automatic T
One-coat/one-bake (two-coat/one-bake) Trends in metallic resin systems include a shift toward high solid content paints from the perspective of lower pollution, and an increase in the thickness of top clear paints to give a luxurious look to automobiles. There are many demands for film formation.

By the way, when trying to finish a thick top clear film, there is a problem that so-called paint film defects such as "sagging" of the paint film are likely to occur, and when using a high solid content type paint. However, there are problems such as gasoline resistance.

These problems should be resolved or improved (,
Although a technique has been reported in which a gelled fine particle polymer is added to a paint to give it pseudoplastic viscosity behavior and prevent coating defects, as far as conventional technology is concerned, it has not been possible to achieve sufficient gasoline resistance. The actual situation is that a fine particle polymer that can provide the desired results has not been obtained.

[Problem that the invention seeks to solve]

However, in view of the above-mentioned circumstances, the present inventors
By adding it to high solids content type paints, y
As a result of intensive research aimed at imparting plasticity to a coating film and improving the gasoline resistance of the coating film, the present invention was completed.

That is, the present inventors have developed a coating resin composition comprising a hydroxyl group-containing polymer, an aminoblast, and a fine particle polymer. In addition to non-aqueous dispersion polymerization of vinyl monomers having vinyl monomers as essential monomers, at least two carboxyl groups per molecule are added to the thus obtained fine particle polymer (non-aqueous dispersion polymer). By using a compound containing a group (hereinafter abbreviated as a polycarboxylic acid compound) and/or a polycarboxylic acid anhydride,
A high solid content paint is cleaved by adding a fine particle polymer having interparticle crosslinks to such non-aqueous dispersion polymer particles,
It has been found that the objectives as stated above are achieved.

[Means for solving problems]

In other words, the present invention deals with the treatment of hydroxyl group-containing polymer (A), aminoplus (B), and vinyl monomer in an organic solvent that does not dissolve the resulting polymer in the presence of a dispersion stabilizer. A vinyl monomer containing an epoxy group-containing vinyl monomer is non-aqueous dispersion polymerized, and at the same time, a polycarboxylic acid compound and/or a polycarboxylic acid anhydride is used to polymerize the inside of the dispersed particles. The particulate polymer (C) obtained by crosslinking is an essential component, and the hydroxyl group-containing polymer (A) is used in a range of 90 to 30 parts by weight, and the Amino Plus) (B) 10~7Of
fi parts, and the fine particle polymer (C) is used in an amount of 0.1 to 100 parts per $8 parts by weight of the hydroxyl group-containing polymer (A) and the aminoplast (B).
When used within the range of parts by weight, it is possible to impart pseudoplastic viscosity behavior to high-solids paints, and at the same time, it is possible to improve the caprin resistance of the coating film. The object of the present invention is to provide a resin composition for coating material that is useful for various purposes.

Here, first, the hydroxyl group-containing polymer (A) constituting the composition of the present invention is a (condensation) polymer containing at least 1, preferably at least 2 ([Iil) hydroxyl groups per molecule, Moreover, it refers to a compound having a necessary and sufficient molecular weight range to make the composition of the present invention highly solidified.Therefore, it can be used without exception as long as it meets these conditions, but preferably the following An appropriate one is one that satisfies the conditions.

■ A vinyl polymer with a number average molecular weight (Mn) of 500 to 8,000 and a hydroxyl value (OHV) of 40 to 250; or ■ a gl of 200 to 3"00 and an OHV of 40 to 6.
At least 1N (condensation) polymer selected from alkyd resins, oil-free alkyd resins and urethane resins within the range of 00; or (1) a mixture of the above-mentioned polymers (2) and (2).

Among these, in order to obtain a vinyl polymer that satisfies the above condition (1), a hydroxyl group-containing monomer and another monomer that can be copolymerized with it are copolymerized according to a conventional method. Representative examples of such hydroxyl group-containing monomers include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, and 2-hydroxypropyl (meth)acrylate.
(Meth) such as hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 3-chloro-2-hydroxypropyl (meth)acrylate, polyethylene glycol mono (meth)acrylate Hydroxyalkyl esters of acrylic acid; unsaturated bond-containing hydroxyalkyl ester monocarboxylic acids such as addition products of acid anhydride group-containing monomers such as maleic anhydride and itaconic anhydride and glycols such as ethylene glycol;
Examples thereof include unsaturated bond-containing polyhydroxyalkyl esters such as dihydroxyalkyl esters of unsaturated polycarboxylic acids such as maleic acid and fumaric acid; and hydroxyalkyl vinyl ethers such as hydroxyvinyl ether.

Typical other monomers that can be copolymerized with these are methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and cyclohexyl (meth)acrylate.
(meth)acrylic acid esters such as meth)acrylate and benzyl(meth)acrylate; diesters of unsaturated dicarboxylic acids and monohydric alcohols such as maleic acid, fumaric acid, and itaconic acid; vinyl acetate, vinyl benzoate, Various vinyl esters such as "Beoba" (vinyl ester manufactured by Shell in the Netherlands); "Viscoat 8F,
8FM, 3F or 3FMJ (Osaka Organic Chemistry H, MJ
fluorine-containing (meth)acrylic monomer], or perfluorocyclohexyl (meth)acrylate, di-perfluorocyclohexyl fumarate or N-1so
- Vinyl esters containing a (per)fluoroalkyl group such as propyl perfluorooctane sulfonamide ethyl (meth)acrylate; vinyl halides (vinylidene) such as vinyl chloride, vinylidene chloride, vinyl butylene, vinylidene butylide; ethylene α-olefins such as , propylene, chlorotrifluoroethylene; aromatic vinyls such as styrene, α-methylstyrene, p-tert-butylstyrene, O-methylstyrene, p-methylstyrene; (meth)acrylic acid, crotonic acid , carboxyl group-containing monomers such as maleic acid, fumaric acid, itaconic acid, and citraconic acid; acid anhydride group-containing monomers such as those listed above; (meth)acrylamide, diacetone acrylamide, N.

N-dimethyl(meth)acrylamide, N-alkoxymethylated (meth)acrylamide, N-methylolated (
Carboxylic acid amide group-containing monomers such as meth)acrylamide; p-styrenesulfonamide, N-methyl-p
- sulfonic acid amide group-containing monomers such as styrenesulfonamide, N,N-dimethyl-p-styrenesulfonamide, and N such as N,N-dimethylaminoethyl (meth)acrylate.

N-dialkylaminoalkyl (meth)acrylate a
, or an addition product of an acid anhydride group-containing monomer as listed above and a compound having both an active hydrogen group and a tertiary amino group that can react with an acid anhydride group, such as N,N-dimethylaminopropylamine. Tertiary amino group-containing monomers such as;
Cyano group-containing monomers such as (meth)acrylonitrile; hydroxyalkyl esters of α,β-ethylenically unsaturated carboxylic acids such as the above-mentioned (meth)acrylic acid hydroxyalkyl esters; and phosphoric acid or phosphoric acid esters. phosphoric acid ester bond-containing monomers such as the condensation product of 2-acrylamido-2-methyl-propanesulfonic acid; or sulfonic acid group-containing monomers such as 2-acrylamido-2-methyl-propanesulfonic acid, or organic amine salts thereof.

The amount of each of the above-mentioned hydroxyl group-containing monomers to be copolymerized varies depending on the molecular weight of the hydroxyl group-containing polymer (A) to be obtained, but is approximately 10% of the total comonomers (total copolymerization components).
It is desirable that it accounts for ~50ffiffi%, and therefore the remaining 90~50% by weight can be appropriately selected from other monomers copolymerizable with this hydroxyl group-containing monomer.

At this time, other monomers that can be copolymerized should be determined by taking into consideration other factors such as the physical properties of the cured coating film finally obtained and pigment dispersibility, but in particular, Various acidic group-containing monomers such as carboxyl group-containing monomers and sulfonic acid group-containing monomers act as latent catalysts for the crosslinking reaction between the hydroxyl group-containing polymer (A) and the aminoplast (B). It is desirable to use the monomers as comonomers (copolymerization components).

To prepare the hydroxyl group-containing polymer (A), any known and commonly used polymerization method such as solution polymerization method or solution pressure polymerization method can be used, but among them, solution radical polymerization method is the simplest. .

Typical solvents used in this case include various hydrocarbons such as toluene, xylene, cyclohexane, n-hexane, and octane; methanol, ethanol, 1so-propanol, n-butanol, 1so-butanol, and 5ec. - Various alcohols such as butanol and ethylene glycol monomethyl ether; various esters such as methyl acetate, ethyl acetate, and butyl acetate; acetone, methyl ethyl ketone, methyl isobutyl ketone,
Examples include various ketone solvents such as methyl amyl ketone and cyclohexanone; various amide solvents such as dimethylformamide and dimethylacetamide; and mixtures thereof.

Polymerization may be carried out by a conventional method using such a solvent and various polymerization initiators such as an azo type or a peroxide type polymerization initiator.

Further, during this polymerization, various chain transfer agents such as lauryl mercaptan, octyl mercaptan, 2-mercaptoethanol or α-methylstyrene dimer can be used as molecular weight regulators.

In particular, when using 2-mercaptoethanol, which is a chain transfer agent having a hydroxyl group, hydroxyl groups can be efficiently introduced into the fraction of the obtained polymer whose molecular weight is below the average molecular weight. It also has the disadvantage that it is inferior to that of other materials, so it should be used for limited purposes.

In addition to the solution radical polymerization method, there is also an ionic polymerization method as a method for preparing the tsitt polymer (A), and the polymer obtained by this ionic polymerization method can also be used without any particular problem.

According to this ionic polymerization method, polymerization is carried out using an ionic polymerization initiator whose functional groups (polar groups) have been blocked in advance, and then the blocking agent at the end of the obtained polymer is separated, so that the molecular weight distribution is extremely controlled. A polymer is obtained which is narrow and always has one or more functional groups (polar groups) in the polymer molecule.

A typical example of such an ionic polymerization method is the method described in JP-A-58-13608.

The glass transition point of the hydroxyl group-containing polymer (A) thus obtained is suitably within the range of -20°C to +50°C.

Next, in order to obtain an alkyd resin, oil-free alkyd resin, or urethane resin that satisfies the above-mentioned condition (2), known and commonly used synthesis conditions such as esterification methods can be applied as they are.

Here, urethane resins include isocyanate-modified acrylic resins, isocyanate-modified alkyd resins, isocyanate-modified oil-free alkyd resins, etc.
Although it is possible to use an isocyanate-modified alkyd resin or an isocyanate-modified oil-free alkyd resin from the viewpoint of ease of synthesis or low risk of gelation, it is possible to use a resin having at least one urethane bond in the molecule. Use is preferred.

First, a suitable method for preparing such a urethane resin is to extend the molecular chain of an alkyd oligomer or oil-free alkyd oligomer having at least one hydroxyl group in the molecule with a polyisocyanate compound.

Typical such polyisocyanate compounds include aliphatic diisocyanates such as hexamethylene diisocyanate and trimethylhexamethylene diisocyanate; cycloaliphatic diisocyanates such as xylylene diisocyanate and isophorone diisocyanate; or tolylene diisocyanate, 4.4 There are aromatic diisocyanates such as '-diphenylmethane diisocyanate, but it goes without saying that these may also be used in combination. From the viewpoint of yellowing resistance of the coating film, it is desirable to use an aliphatic diisocyanate film.

The alkyd resin, oil-free alkyd resin and/or
Typical polybasic acid components used in synthesizing the polyester component of urethane resin include terephthalic acid, isophthalic acid, orthophthalic acid, 2,6
- Naphthalenedicarboxylic acid, 4,4'-diphenyldicarboxylic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, hexahydrophthalic acid, hexahydroterephthalic acid, methylhexahydrophthalic acid, endomethylenetetrahydrophthalic acid, methylendomethylenetetrahydro Phthalic acid, maleic acid, fumaric acid, itaconic acid, succinic acid, glutaric acid, adipic acid, azelaic acid, pimelic acid, speric acid, sebacic acid or dimeric fatty acids,
Alternatively, there are reactive derivatives such as cyclopentanetetracarboxylic acid, trimellitic acid, pyromellitic acid, trimesic acid, or their alkyl esters and anhydrides.

Among these, in particular, one or more of hexahydrophthalic acid, methylhexahydrophthalic acid, hexahydroterephthalic acid, or various reactive derivatives thereof accounts for 50 mol% or more of the total polybasic acid component. When used, these polybasic acids are desirable because they provide compositions with excellent curability and weather resistance, as well as solubility and low viscosity. should be selected accordingly.

On the other hand, typical alcohol components used in synthesizing the polyester component include ethylene glycol, propylene glycol, trimethylene glycol, 1.4-butanediol, 1.3-butanediol, and 1.5-butanediol. Aliphatic glycols such as bentanediol, 1,6-hexanediol, neopentyl glycol; cycloaliphatic glycols such as 1゜4-cyclohexane dimetatool; bishydroxyethyl terephthalate, hydrogenated hisphenol A or bisphenol A Examples include aromatic glycols such as alkylene oxide adducts, and monoepoxy compounds can also be used as the glycol component.

Furthermore, typical polyols with a valence of 3 or higher include glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, dipentaerythritol, or mannitol, and 6-caprolactone is added to the various alcohol components listed above. It is also possible to use polyester compounds with added .

Among these, it is particularly desirable to use neopentyl glycol in an amount of 30 mol % or more based on the total alcohol component, as it gives favorable results in terms of weather resistance. It should be selected appropriately depending on the required performance of the membrane.

Further, typical fatty acids used to obtain the alkyd resin include octyl acid, stearic acid, persatic acid, oleic acid, lyluic acid, coconut oil fatty acid, hydrogenated coconut oil fatty acid, etc. , tall oil fatty acids, castor oil fatty acids, dehydrated castor oil fatty acids, rice bran oil fatty acids, linseed oil fatty acids, soybean oil fatty acids, safflower oil fatty acids, etc. It should be selected in consideration of solubility and economic efficiency.

In this way, a polyester resin is obtained, but in addition to these, polyester-forming components are added in an amount of 40 to 90% based on the total amount of all acid components and all alcohol components.
When a polyester resin with mol % of ε-caprolactone added thereto is used, a composition with excellent flexibility of the cured coating film can be obtained.

An alkyd resin, an oil-free alkyd resin or a urethane resin can be obtained using the various raw material components listed above, and these can be used alone or as a mixture of two or more.

As for the usage in the above-mentioned form (■), it is used in the form of a mixture of the above-mentioned vinyl polymer (■) and (condensation) polymer (■), but in this case, if weather resistance is desired, For this purpose, a large amount of vinyl polymer (2) is used, and on the other hand, when flexibility is desired, a large amount of cleavage polymer (2) is used to create a coating composition with the desired coating performance. can be designed.

The hydroxyl group-containing polymer (A) detailed above is suitably used in the composition of the present invention in an amount of 30 to 90% by weight.

Next, the above-mentioned aminoplast (B) functions as a curing agent in the present invention.

Representative aminoplasts (B) include:
A condensate obtained by reacting an amine group-containing compound such as melamine, benzoguanamine, acetoguanamine, steroguanamine, spiroguanamine or urea with an aldehyde compound such as formaldehyde, paraformaldehyde, acetaldehyde or glyoxal by a known and commonly used method. , or those obtained by etherifying each of these condensates with alcohol, but any of those commonly used for paints can be used.

Among these, those partially or completely etherified with 01 to C4 alcohols are particularly desirable, and typical examples of such aminoplasts include methyl etherified melamine, n-butyl etherified melamine, and 1so- Examples include butyl etherified melamine and condensates thereof, and methyl etherified melamine is particularly desirable from the viewpoint of high volatile content.

The aminoplast (B) detailed above is suitably used in the composition of the present invention in an amount of 10 to 70% by weight.

Next, the above-mentioned fine particle polymer (C) is used to impart pseudoplastic viscosity behavior to the mixture of the above-mentioned hydroxyl group-containing polymer (A) and aminoplast (B), and the fine particle polymer (C) is Typical examples of coalescence (C) include inorganic types such as finely powdered silica, and organic types such as low-molecular polyolefin polymers or non-aqueous dispersion polymers. be.

Among these, particularly preferred are non-aqueous dispersible polymers.

Such a non-aqueous dispersion type polymer refers to the presence of a dispersion stabilizer in an organic solvent in which the vinyl monomer itself is dissolved but the resulting polymer of the vinyl monomer is not dissolved. However, it is obtained by non-aqueous dispersion polymerization of the vinyl monomer, and as is known, it consists of a segment that is soluble in an aliphatic or alicyclic hydrocarbon solvent and a segment that is insoluble in the solvent. In the presence of a dispersion stabilizer that also has a segment that can be formed or swelled, the polymer itself is insoluble, but the monomer is soluble (hereinafter abbreviated as a moldable polymer). ) is chemically or physically bonded to a dispersion stabilizer as described above, and it refers to a polymer that has the shape of particles (dispersed particles) that can be stably dispersed in the solvent. In the present invention, it is particularly important to use an epoxy group-containing vinyl monomer, an IX-mer having a specific functional group (polar group), as an essential vinyl monomer.

A specific method for preparing such a non-aqueous dispersion type polymer is as follows.

First, the solvent used is a non-polar one or has a relatively low dissolving power, and although it does not dissolve the polymer produced from the above-mentioned cutting die polymer (hereinafter abbreviated as stacking polymer), it does not dissolve the above-mentioned dispersion. Any solvent can be used as long as it can dissolve or swell the stabilizer. Typical examples of such solvents include aliphatic hydrocarbons such as hexane, heptane, and octane; petroleum benzine, ligroin,
Hydrocarbon mixtures having a boiling point of 30 to 300°C, such as mineral spirit, petroleum naphtha, and kerosene; or alicyclic hydrocarbons, such as cyclohexane, methylcyclohexane, and ethylcyclohexane; or mixtures thereof.

In some cases, in addition to these nN aliphatic hydrocarbons, hydrocarbon mixtures, and/or alicyclic hydrocarbons, aromatic hydrocarbons, esters, and ethers may be added up to about 70% by weight of the total solvent. Solvents including polar solvents such as alcohol-based solvents, alcohol-based solvents, and ketone-based solvents may also be used.

The appropriate amount of the solvent used is within a range such that the resulting dispersion of the non-aqueous dispersion type polymer has a solid content of 30 to 70% by weight, preferably 40 to 60% by weight.

Next, typical dispersion stabilizers mentioned above include:
A graft copolymer obtained by copolymerizing an unsaturated bond-containing polymer such as polybutadiene or polyisoprene with a stacking body as described below, or a graft copolymer obtained by copolymerizing a stacking body and (meth)acrylic with the unsaturated bond-containing polymer. After copolymerizing with acid,
An unsaturated bond-containing graft copolymer obtained by adding an epoxy group-containing vinyl monomer such as glycidyl (meth)acrylate to the carboxyl group of the copolymer;
■ Alkyd resin; ■ An alkyl etherified melamine resin condensate etherified with an alkyl alcohol of C~C/λ, and soluble in the above-mentioned solvent;
■Polyester resin containing terminal unsaturated bonds obtained by adding an epoxy base such as glycidyl (meth)acrylate to the terminal carboxyl group of a self-condensed polyester resin of saturated fatty acid having a hydroxyl group such as 12-hydroxystearic acid and a vinyl monomer. , or a graft copolymer obtained by copolymerizing the resin with a laminate as shown below, or a graft copolymer obtained by copolymerizing the unsaturated bond-containing polyester resin with a laminate as shown below and (meth)acrylic acid. Later,
An unsaturated bond-containing graft copolymer obtained by adding an epoxy group-containing vinyl monomer such as glycidyl (meth)acrylate to the carboxyl group of the copolymer; or On-butyl (meth)acrylate, iso-
The main component is alkyl esters of (meth)acrylic acid esterified with alkyl alcohols of 04 or higher, such as butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, and stearyl (meth)acrylate. , obtained by (co)polymerizing other vinyl monomers as necessary.
The main component is a polymer or an alkyl ester of (meth)acrylic acid esterified with an alkyl alcohol of 04 or higher listed above, and (meth)acrylic acid is added to this, as necessary, with other vinyl monomers. Copolymers containing unsaturated bonds obtained by adding a vinyl monomer to an epoxy base such as glycidyl (meth)acrylate to the carboxyl group of a copolymer obtained by copolymerizing a copolymer with A graft copolymer obtained by copolymerizing a saturated bond-containing copolymer and a seed polymer, and a graft copolymer obtained by copolymerizing a stack polymer and (meth)acrylic acid to the unsaturated bond-containing copolymer. Glycidyl (meth) in the carboxyl group of the graft copolymer
Examples include unsaturated bond-containing graft copolymers obtained by addition-reacting epoxy group-containing vinyl monomers such as acrylates.

Among these, when using each of the above-mentioned dispersion stabilizers of group ① and 0, in the above-mentioned dispersion stabilizers of group 0, terminal unsaturated bond Kiniku polyester resin is used as a dispersion stabilizer. In the case of dispersion stabilizers of the above-mentioned group 0, a copolymer whose main component is an alkyl ester of (meth)acrylic acid esterified with an alkyl alcohol of 04 or more, or a copolymer thereof When copolymers having unsaturated bonds derived from When preparing a non-aqueous dispersion type polymer using a dispersion stabilizer, the above-mentioned solvent-insoluble segments are formed during the initial polymerization of the core i-mer, and the desired non-aqueous dispersion type polymer is formed. A polymer is obtained.

Here, representative examples of the stack are those esterified with alkyl alcohols up to C3 such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, and 1so-propyl (meth)acrylate. Examples include alkyl esters of (meth)acrylic acid, cyano group-containing monomers such as (meth)acrylonitrile, and other monomers that can be copolymerized with such a stack. is butyl (meth)acrylate, 2-ethylhexyl (meth)
Alkyl esters of (meth)acrylic acid esterified with 04 or higher alkyl alcohols such as acrylate and cyclohexyl (meth)acrylate, as well as vinyl polymers of group 0 of the hydroxyl group-containing polymers (A) detailed above. The hydroxyl group-containing monomer and other monomers copolymerizable with the hydroxyl group-containing monomer used in producing tlIa can be used as they are.

In addition, typical examples of the epoxy group-containing vinyl monomer used together with these stacks and subjected to particulate crosslinking of the non-aqueous dispersion type polymer include glycidyl (meth)acrylate or β. -methylglycidyl (meth)acrylate, etc., and as mentioned above, such epoxy group-containing vinyl monomers are essential vinyl monomers in the present invention.

In addition, in the present invention, the above-mentioned polycarboxylic acid compound and/or polycarboxylic acid anhydride, which is the other compound used for particulate crosslinking of the dispersed particles, can also be used in the present invention.
It is an essential crosslinking agent.

Among them, polycarboxylic acid anhydrides are - compounds having at least one acid anhydride group in the molecule and soluble in aliphatic and/or alicyclic hydrocarbon solvents as mentioned above. Something like this is preferable.

Any compound that meets these conditions can be used, but representative examples include phthalic anhydride, 3-methyl phthalic anhydride, tetrahydrophthalic anhydride, 3-methyltetrahydrophthalic anhydride, Examples include hexahydrophthalic anhydride, 3-methylhexahydrophthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, and methylcyclohexenetricarboxylic anhydride.

Among these, 3-methyltetrahydrophthalic anhydride or 3-methylhexahydrophthalic anhydride is particularly preferred from the viewpoint of solubility in the above-mentioned solvents.

When such a polycarboxylic acid anhydride is used as a crosslinking agent, a hydroxyl group-containing monomer must also be included in the above-mentioned cutting mold polymer.

On the other hand, the above-mentioned polycarboxylic acid compound can be used without any particular limitation as long as it has at least two carboxyl groups in one molecule, but the solubility in the various solvents mentioned above and such compounds Polyester resins and alkyd resins are particularly desirable because of their ease of preparation.

Such polyester resins and alkyd resins may be manufactured according to known and commonly used synthesis methods, and typical polybasic acid components used in this process include isophthalic acid, terephthalic acid, orthophthalic acid, and 2,6-naphthalene dicarboxylic acid. acid, 4,4'-diphenyldicarboxylic acid, tetrahydrocarboxylic acid, methyltetrahydrophthalic acid,
Hexahydrophthalic acid, hexahydroterephthalic acid, methylhexahydrophthalic acid, endomethylenetetrahydrophthalic acid, methylendomethylenetetrahydrophthalic acid, maleic acid, fumaric acid, itaconic acid, succinic acid, glutaric acid, adipic acid, azelaic acid , pimelic acid, superric acid, sebacic acid or dimeric fatty acids, cyclopenkune tetracarboxylic acid, trimellitic acid, pyromellitic acid or trimesic acid, or various reactive derivatives thereof such as their alkyl esters or anhydrides. .

On the other hand, typical alcohol components used in synthesizing such polyester resins and alkyd resins include ethylene glycol, propylene glycol,
trimethylene glycol, 1,4-butanediol, 1
．． 3-butanediol, 1,5-bentanediol, 1
．． Aliphatic glycols such as 6-hexanediol and neopentyl glycol; cycloaliphatic glycols such as 1,4-cyclohexane dimetatool and hydrogenated bisphenol A; or bishydroxyphenyl terephthalate and alkylene oxide adducts of bisphenol A. Examples of the glycol component include aromatic glycols, and if necessary, a monoepoxy compound can also be used in combination as the glycol component.

Further, typical polyols having a valence of 3 or higher include hydroxide, trimethylolethane, trimethylolpropane, pentaerythritol, dipentaerythritol, mannitol, etc., and various alcohols listed above. Polyester compounds obtained by adding ε-caprolactone to the components are also
It can be used as such a trivalent or higher polyol.

Furthermore, typical fatty acids used in synthesizing the alkyd resin include octylic acid, palmitic acid, stearic acid, persatic acid, oleic acid, linoleic acid, liluic acid, and coconut oil fatty acid. ,
Hydrogenated coconut oil fatty acids, tall oil fatty acids, castor oil fatty acids,
Dehydrated castor oil fatty acids, rice bran oil fatty acids, linseed oil fatty acids,
0, such as soybean oil fatty acids or safflower oil fatty acids, etc.
There are long chain monobasic acids of 8 or more.

In this way, polyester resins and alkyd resins are obtained, but in addition to these, polyester compounds such as 12-hydroxystearic acid or its self-condensates can also be used as polyester-forming components.

The polycarboxylic acid compounds listed above have a gl of 2 in terms of solubility and crosslinking efficiency in the various solvents listed above.
00 to 3,000 and preferably has an acid value of 40 to 600.

It goes without saying that a polycarboxylic acid compound and a polycarboxylic anhydride may be used in combination.

Furthermore, it is desirable to introduce hydroxyl groups into both the above-mentioned dispersion stabilizer and the cutting mold polymer.

This is the fine particle polymer (C) used in the present invention.
When the dispersed particles of a non-aqueous dispersible polymer are blended into a melamine curable paint to form a cured coating, both the dispersion stabilizing agent part and the core part of the non-aqueous dispersible polymer react with the curing agent. This is because a uniform and highly transparent coating film can be obtained.

To prepare the fine particle polymer (C), an epoxy group-containing vinyl monomer is contained in the presence of the various solvents, dispersion stabilizers, and polycarboxylic acid compounds and/or polycarboxylic anhydrides listed above. The cutting mold polymer is polymerized in a non-aqueous dispersion, or in the presence of the above-mentioned solvent, a dispersion stabilizer and
After non-aqueous dispersion polymerization of the molding material containing the epoxy group-containing vinyl monomer, a polycarboxylic acid compound and/or G-iζ-ricarponic acid anhydride is added to the reaction system for reaction (crosslinking). Intragranular crosslinked fine particle polymers can often be obtained by such a method.

Then, the intraparticle crosslinking of the non-aqueous dispersion type polymer, that is, the epoxy group derived from the epoxy group-containing vinyl monomer, and the >35
The esterification reaction between the carboxylic acid compound and/or the carboxyl group derived from the polycarboxylic acid anhydride may proceed simultaneously with the non-aqueous dispersion polymerization, or the reaction system may be terminated upon completion of the non-aqueous dispersion polymerization reaction. The esterification reaction may be allowed to proceed by increasing the temperature or by increasing the temperature.Furthermore, in order to promote the esterification reaction, known and commonly used catalysts such as basic catalysts such as 2-methylimidazole and dimethylaminoethanol may be coexisting. You may go.

In addition, in the case of non-aqueous dispersion polymerization, the polymerization can be proceeded by a conventional method using a known and commonly used polymerization initiator such as an azo type or a peroxide type. Known and conventional chain transfer agents such as mercaptan, octylmercaptan, 2-mercaptoethanol or α-methylstyrene dimer can also be used as molecular weight regulators.

In this way, a non-aqueous dispersion polymer, that is, a finely dispersed particulate polymer, is obtained in the form of a dispersion liquid. By distilling off the solvent bone from the polymer dispersion and further carrying out a pulverization step if necessary, it can be used in the form of a powdery fine particle polymer.

The amount of the fine particle polymer (C) to be used is 0.1 to 1100 parts by weight of the hydroxyl group-containing polymer (A) and aminoplast (B) in total.
A range of 100 parts by weight is suitable.

In this way, the desired composition of the present invention is obtained, but in addition to the above-mentioned components (A), (B), and (C), the composition of the present invention contains pigments and various resins commonly used for paints. First, fluidity regulators, color separation inhibitors, antioxidants,
Ultraviolet absorbers, silane coupling agents or curing catalysts may also be added.

Typical examples of pigments include inorganic pigments such as titanium oxide and carbon black, various organic pigments such as quinacridone and azo pigments, and various metal powders such as aluminum powder, copper powder, and zinc powder. can be mentioned.

Representative examples of various resins include cellulose resins such as nitrocellulose, cellulose acetate butyrate, ketone resins, and petroleum resins.

Typical silane coupling agents include γ-aminopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, vinyltrimethoxysilane,
Examples include vinyltriethoxysilane and T-mercaptopropyltrimethoxysilane.

Typical examples of faeces catalysts include para-toluenesulfonic acid,
Beckamin P-198J (Dainippon Ink & Chemicals @ product) or “Neikyu 7-155.2500X,
X-49-110, 5225 or 3525J (
(Products from King Company, USA), etc.

The composition of the present invention obtained by mixing the various components listed above in a conventional manner is coated by a known or commonly used method such as spray coating, brush coating, or roll coater.
A cured coating is obtained by baking at C for 10 to 40 minutes.

[Applications of the present invention]

The composition of the present invention has a wide range of uses as paints, but among them, it can be used particularly for general baking of home appliances, etc., or as an automobile paint. , metallic base paint or clear paint.

〔Example〕

Next, the present invention will be explained in more detail with reference to Reference Examples, Examples, and Comparative Examples. In the following, all parts and percentages are based on weight unless otherwise specified.

Reference Example 1 [Example of preparation of hydroxyl group-containing polymer (A)] 160 parts of xylene and 160 parts of n-butanol were placed in a reactor equipped with a stirring device, a thermometer, a nitrogen inlet tube, and a reflux condenser tube.
The temperature was raised to 125°C in a nitrogen atmosphere, and 120 parts of styrene and 18 parts of n-butyl acrylate were charged.
0 parts, 120 parts of n-butyl methacrylate, 108 parts of β-hydroxypropyl acrylate, 66 parts of β-hydroxypropyl methacrylate and 6 parts of acrylic acid, 80 parts of n-butanol, tart-butyl peroxyoctoate A mixture of 48 parts of di-tert-butyl peroxide, 3 parts of azobisisobutyronitrile, and 12 parts of azobisisobutyronitrile was added dropwise over 8 hours,
By continuing the reaction by maintaining the same temperature for 15 hours after the completion of the dropwise addition, the nonvolatile content (NV) is 60%, the Gardner color (G, C,) is 1 or less, and the Gardner viscosity (G, Vis, ) is E, and M″n is ao
A solution of the target polymer with a glass transition temperature (Tg) of 0 °C was obtained, but the OH per solid content of this
V was 109. Hereinafter, this will be abbreviated as a solution of polymer (A-1).

Reference Example 2 (same as above) The composition of the monomers to be used was 114 parts of styrene, n
- 110 parts of butyl acrylate, 120 parts of n-butyl methacrylate, 90 parts of β-hydroxypropyl acrylate, 60 parts of β-hydroxypropyl methacrylate, 6 parts of acrylic acid, and 90 parts of methyl methacrylate, except for reference. A solution of the desired polymer was obtained in the same manner as in Example 1. The NV of this is 60%, and G
, C, is less than or equal to 1, G.

Vis is H, M″n is 3000, and Tg
was 20°C. Also, the OH per solid content of this product
V was 94. Hereinafter, this will be abbreviated as a solution of polymer (A-2).

Reference Example 3 (same as above) 215 parts of adipic acid and 63 parts of the total polybasic acid components were placed in a reactor equipped with a stirring device, a thermometer, a nitrogen inlet tube, and a reaction product water distillation tube. 400 parts of hexahydrophthalic anhydride corresponding to 8 mol% and 400 parts of trimethylolpropane
4.6 parts of ethylene glycol, 50 parts of ethylene glycol, and 390.2 parts of neopentyl glycol, which corresponds to 76.7 mol% of the total alcohol component, were gradually raised to 23 (l) over 5 hours in a nitrogen stream. 0f (V is 111 and Mn
An oil-free alkyd resin having a value of 1010 was obtained.

Next, this resin was cooled to 100° C. or lower, and 250 parts of xylene was added to obtain a solution of an oil-free alkyd resin with an NV of 80%. Hereinafter, this will be abbreviated as a solution of polymer (A-3).

Reference Example 4 (same as above) In a polyester reaction apparatus similar to Reference Example 3, 83.2 parts of adipic acid, 400 parts of hexahydrophthalic anhydride corresponding to 82 mol% of the total polybasic acid components, and 61 parts of trimethylolpropane were added. 1 part and 423 parts of neopentyl glycol, which corresponds to 90 mol% of the total alcohol components, were charged, and the temperature was gradually raised to 230'C over 5 hours under a nitrogen atmosphere, and the temperature was kept at the same temperature until the acid value reached 10. The temperature was maintained to obtain an oil-free alkyd 4M fat.

Next, this resin was cooled to below 100'C, 250 parts of xylene and 0.1 part of diptyltin dilaurate were added, the temperature was raised to 65°C, and while maintaining the same temperature, 100 parts of hexamethylene diisocyanate was added. was gradually added dropwise over 2 hours while being careful not to generate heat.

After the dropwise addition was completed, the solution was kept at the same temperature for 2 hours and then at 80'C for 1 hour to obtain a partially urethanized oil-free alkyd resin solution with an NV of 80%. The OHV of this product was 118, and the Mn was 1070. Hereinafter, this will be abbreviated as a solution of polymer (A-4).

Reference Example 5 (same as above) In a polyester reaction apparatus similar to Reference Example 3, 157.4 parts of adipic acid and 64.4 mol% of the total polybasic acid components were added.
300 parts of hexahydrophthalic anhydride, 203.8 parts of trimethylolpropane and 230 parts of neopentyl glycol, representing 59 mol% of the total alcohol content.
1 part and 200 parts of coconut oil fatty acid, the temperature was gradually raised to 230°C over 5 hours in a nitrogen atmosphere, and the temperature was maintained until the acid value reached 10 to react. A resin was obtained, which was then heated to 100
Cool to below 250°C and add 250 parts of xylene to NV.
A solution of an alkyd resin having a concentration of 80% was prepared.

The OHV per solid content of this product is 125, and M″
n was 1140. Hereinafter, this will be referred to as polymer (A-5).
It is abbreviated as a solution of

Reference Example 6 (same as above) In a reactor similar to Reference Example 1, 134 parts (1 mol) of trimethylolpropane and 684 parts (1 mol) of ε-caprolactone were added.
6 mol) and 0.04 part of tetrabutyl titanate were charged, the temperature was raised to 180°C, and the temperature was maintained at loVf to obtain a lactone-added polyester resin.

This one has NV of 100%, G, Vis, and X, and O
Hv was 206 and Bi1 was 820. Hereinafter, this will be abbreviated as polymer (A-6).

Reference Example 7 (Preparation example of polycarboxylic acid compound) In a reactor equipped with a stirring device, a thermometer, a cooling tube and a nitrogen introduction tube,
1800 parts of 12-hydroxystearic acid was charged, and the temperature was raised to 220°C to perform esterification.

During this temperature rise, 12-hydroxystearic acid begins to melt when the temperature reaches 72°C, so stirring is started at the same time as this melting.

Then, water began to distill out at about 190°C, and esterification proceeded until the acid value reached about 38. After continuing the reaction for about 7 hours, it was cooled and taken out.

The self-condensed polyester of 12-hydroxystearic acid obtained here has an NV of too%, and G, Vis, and Z.
2, and G, C, were 16. Hereinafter, this will be abbreviated as intermediate (b-1).

This intermediate (
1000 parts of bi) and 1 part of hexahydrophthalic anhydride
15 parts and heated to 140°C in a nitrogen stream,
The mixture was maintained at the same temperature for 4 hours, and hexahydrophthalic anhydride was added to the intermediate (b-1) to obtain the desired polycarboxylic acid compound.

After that, the temperature was lowered to below 100°C and "Isopar E"
47 (aliphatic hydrocarbon mixture manufactured by Exxon, USA)
By adding 8 parts, a solution of a polycarboxylic acid compound having an NV of 70% and an acid value of 52.5 was obtained. Below, I will explain this in the middle.
It is abbreviated as mer (b-2).

Reference Example 8 [Example of Preparation of Fine Particle Polymer (C)] The intermediate (b-1) obtained in Reference Example 7 was placed in the same reaction apparatus as in Reference Example 1.
450 parts of n-butyl acetate, 46 parts of glycidyl methacrylate equivalent to the carboxyl group in this intermediate (b-1), 1 part of 2-methylimidazole, and 1 part of hydroquinone. 13.
Glycidyl methacrylate is added to intermediate (b-1) by raising the temperature to 0° C. and reacting at the same temperature for 6 hours, but this reaction may be carried out by monitoring the acid value.

The terminal unsaturated bond-containing polyester thus obtained is N
V is 60%, G, νis, is A1, G, C, is 16,
The solution had an acid value of 1 or less. Hereinafter, this will be abbreviated as a dispersion stabilizer (b-3).

Separately, in a reactor similar to Reference Example 1, “Isopar E
'' and heated to 100°C, and at the same temperature 168 parts of methyl methacrylate, 105 parts of ethyl acrylate, 70 parts of β-hydroxyethyl methacrylate, 3.2 parts of glycidyl methacrylate, and reference example. 12.1 parts of intermediate (b-2) of No. 7, 3.4 parts of azobisisobutyronitrile, and No. 4 of the above dispersion stabilizer (b-3).
1.1 parts, 0.7 parts of 2-methylimidazole and "
A mixture consisting of 356.3 parts of Isopar E was added dropwise over 8 hours, and the reaction was continued by maintaining the same temperature for 10 hours even after the dropwise addition was completed, resulting in the desired particulate polymer (C
) was obtained.

This product had a milky white color with an NV of 40% and G and Vis of A. Hereinafter, this will be abbreviated as fine particle polymer (C-1).

Reference Example 9 (same as above) In the same reaction apparatus as Reference Example 1, 2 of “Isopar E” was added.
00, and 2 parts of hexahydrophthalic anhydride were charged, and the temperature was raised to 100°C in a nitrogen atmosphere.

Thereafter, the raw material composition was 168 parts of methyl methacrylate,
105 parts of ethyl acrylate, 70 parts of β-hydroxyethyl methacrylate, 3.2 parts of glycidyl methacrylate, 6.2 parts of intermediate (b-2) of Reference Example 7, dispersion stabilizer (b- 3) 41.1 parts, 0.7 parts of 2-methylimidazole, 356 parts of "Isopar E"
．． A dispersion of the desired fine particle polymer (C) was obtained in the same manner as in Reference Example 8 except that the amount of azobisisobutyronitrile was changed to 3 parts and 3.4 parts of azobisisobutyronitrile.

This product had a milky white color with an NV of 40% and G, Vis, and As. Hereinafter, this will be abbreviated as fine particle polymer (C-2).

Reference Example 10 (same as above) In the same reaction apparatus as Reference Example 1, 2 of “Isopar E” was added.
00, 2 parts and 4.1 parts of hexahydrophthalic anhydride were charged, and the temperature was raised to 100°C in a nitrogen stream.

Thereafter, the raw material composition was 168 parts of methyl methacrylate,
105 parts of ethyl acrylate, 70 parts of β-hydroxyethyl methacrylate, 3.2 parts of glycidyl/tafrylate, dispersion stabilizer (b-3) of Reference Example 8 41.1
The same procedure as in Reference Example 1 was carried out to achieve the objective, except that the amounts were changed as follows: A dispersion liquid of fine particle pure aggregate (C) was obtained.

This thing has NV of 40%, and G, Vis, force < A
It had a milky white color. Hereinafter, this will be abbreviated as fine particle polymer (C-3).

Reference Example 11 (Same as above) Same as Reference Example 8 except that the intermediate (b-2) of Reference Example 7 was completely omitted and 7.4 parts of methacrylic acid was used instead. A fine particle polymer dispersion was obtained as a control.

This product had a milky white color with an NV of 40% and G, Vis, and As. Hereinafter, this will be abbreviated as fine particle polymer (C'-1).

Examples 1 to 9 Each fine particle polymer (C-1) obtained in Reference Examples 8 to 10
(C-3), each of the hydroxyl group-containing polymers (A-1) to (A-6) obtained in Reference Examples 1 to 6, and "Sumimar M-10'OCJ (Sumitomo Chemical @ hexamethoxymethyl melamine; NV-100%
], along with pigments if necessary, were mixed in a composition as shown in Table 1, and "Tsurpetz 100J (aromatic hydrocarbon mixture manufactured by Exxon, USA)/n-butanol = 70/30 (by volume)" was mixed. For "colored paints" using pigments, the paint is diluted to a spray viscosity using a thinner (ratio) of 0.8%.
After spray painting to a thick mild steel plate to a dry film thickness of 40 μm and setting for 30 minutes, on the other hand, for clear paints that do not contain pigments, use the following formula for metallic base paints. The paint has a dry film thickness of 12 μm.
After applying this clear paint to a dry film thickness of 40 μm and setting it for 5 minutes, after setting it for 30 minutes,
Bake at C for 30 minutes.

When the gasoline resistance of each of the cured coating films thus obtained was evaluated, the results shown in Table 2 were obtained.

The formulation of the metallic base paint is as follows.

That is, hydroxyl group-containing polymer (A-2) 80 parts fine particle polymer (C-1) 26.
Part 7 “Sumimar M-100CJ 60
Part “Alpaste 1109-MAJ 46.
2 parts [Aluminum paste manufactured by Toyo Aluminum ■, NV-65%] Diluting thinner [Toluene/xylene volume/Ethyl acetate/Cellosolve acetate-40/20/20/20 (volume ratio)] "Naicure 5225J (U.S. 0.6
Bung Co. product) Comparative Examples 1 to 4 A coating was prepared in the same manner as in Example 1 except that C'-1 was used as the fine particle polymer, a film was formed, and the gasoline resistance was evaluated.

In addition, the metallic base paint used at that time is tR.
[In doing so, the fine particle polymer (C'-1) was similarly used.

〔Effect of the invention〕

Claims (1)

[Claims] 1. As an essential component, (A) 90% of the hydroxyl group-containing polymer
~30 parts by weight, (B) 10 to 70 parts by weight of aminoplast, and (C) vinyl monomer in an organic solvent that does not dissolve the produced polymer, in the presence of a dispersion stabilizer, epoxy A compound and/or polycarboxylic acid anhydride obtained by non-aqueous dispersion polymerization of a vinyl monomer whose essential monomer is a group-containing vinyl monomer, and which also contains at least two carboxyl groups in one molecule. The fine particle polymer (C) obtained by intraparticle crosslinking of the dispersed particles using 0.1~
A resin composition for paint, characterized in that it is used within a range of 100 parts by weight. 2. The composition according to claim 1, wherein the compound containing at least two carboxyl groups in one molecule is a polyester resin. 3. The composition according to claim 1, wherein the compound containing at least two carboxyl groups in one molecule is an alkyd resin. 4. The composition according to claim 1, characterized in that a polyester resin and an alkyd resin are used together as the compound containing at least two carboxyl groups in one molecule. 5. The composition according to claim 1, wherein the polycarboxylic anhydride is 3-methyltetrahydrophthalic anhydride. 6. The composition according to claim 1, wherein the polycarboxylic anhydride is 3-methylhexahydrophthalic anhydride. 7. The composition according to claim 1, wherein 3-methyltetrahydrophthalic anhydride and 3-methylhexahydrophthalic anhydride are used together as the polycarboxylic anhydride.