JP2884653B2 - Crosslinked polymer fine particles and coating composition containing the same - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to crosslinked polymer fine particles having excellent compatibility and useful as a fluidity regulator for coatings, and to a coating composition containing the same.

(Prior art) In recent years, the durability of coating films has advanced remarkably, and high performance has been obtained. There is a strong demand for quality.

In order to improve the appearance quality of the coating film, it is necessary to increase the thickness of the coating film in order to conceal the irregularities on the surface of the coating object and to increase the smoothness of the coating film itself. At this time, a flow control agent is often used in the coating material in order to achieve a thick film at any part of the object to be coated regardless of the vertical part and the horizontal part.

For such purposes, polymer fine particles (hereinafter sometimes abbreviated simply as particles) have been attracting attention for a long time because they can impart structural viscosity by interaction between particles in paint.
Applied. At this time, if the inside of the polymer fine particles is three-dimensionally crosslinked, it does not dissolve even in the non-aqueous paint,
There is an advantage that a stable particle form can be maintained, and as a result, a high flow control action can be stably exhibited, and it has been applied as a coating anti-sagging agent and a metal pigment orientation adjusting agent.

For example, JP-A-53-133233 and JP-A-53-133234 disclose a comb-type copolymer having a 5-mol condensate structure of 12-hydroxystearic acid in a side chain as a dispersion stabilizer.
An example is disclosed in which polymer fine particles obtained by performing non-aqueous dispersion polymerization of an α, β-ethylenically unsaturated monomer are used as a sagging agent for paint and an alignment regulator for metal pigments. The inside of the polymer particles obtained here is three-dimensionally crosslinked by an esterification reaction between an epoxy group-containing α, β-ethylenically unsaturated monomer and a carboxyl group-containing α, β-ethylenically unsaturated monomer. Have been.

Also, U.S. Pat.Nos. 4,209,092, 4,377,61 and 4,414,357
Nos. 4,775,736 and 4,598,111 disclose emulsion polymerization of an α, β-ethylenically unsaturated monomer to obtain polymer fine particles having an ionic group on the particle surface, and then convert the particles to a non-aqueous system. Similarly, there is disclosed an example in which the composition is used as an anti-sagging agent for a paint or an alignment adjuster for a metal pigment. The inside of the polymer particles obtained here is three-dimensionally crosslinked by copolymerizing a polyfunctional α, β-ethylenically unsaturated monomer.

Also, in U.S. Pat.Nos. 4,540,740 and 4,610,026,
An example is disclosed in which after polymer fine particles are obtained by emulsion polymerization, after spray drying or non-aqueous conversion treatment, they are used as an anti-sagging agent for paints or an alignment regulator for metal pigments. The inside of the particles obtained here is three-dimensionally crosslinked by an esterification reaction between an α, β-ethylenically unsaturated monomer containing an epoxy group and an α, β-ethylenically unsaturated monomer containing a sulfonic acid group. Have been.

(Problems to be solved by the invention) However, U.S. Pat. Nos. 4,209,932 and 4,377,661,
In the methods of JP-A-4414357, JP-A-4477536 and JP-A-4598111, the polyfunctional α, β used for three-dimensional crosslinking inside the particles is used.
-In the ethylenically unsaturated monomer, not all of the double bonds are copolymerized and a considerable part is oriented unreacted on the particle surface. Such particles have α, β
-Since it has an ethylenically unsaturated group, when used in a paint, the compatibility with the binder becomes insufficient, and particularly in a paint system that is hardly compatible with an acrylic resin such as a polyester resin, particles are aggregated and dust is formed. May form.

Also, in the methods of JP-A-53-133233, JP-A-53-133234, U.S. Pat. Nos. 4,540,740 and 46,110,26, an α, β-ethylenically unsaturated monomer having a functional group capable of reacting with each other is used. The combination is used to form particles by radical polymerization and to perform three-dimensional cross-linking in the particles by an esterification reaction. Also in this method, when the esterification reaction proceeds faster than the radical polymerization, α, β-
There is a possibility that the ethylenically unsaturated group may remain, and the compatibility with the binder for coating materials is often insufficient.

(Means for Solving the Problems) The present inventors have conducted intensive studies on a method for solving such problems, and as a result, after forming polymer fine particles by radical polymerization, impregnating the inside of the fine particles with a crosslinking agent, By three-dimensionally cross-linking, polymer particles having almost no α, β-ethylenically unsaturated group on the particle surface and highly three-dimensionally cross-linked inside the particle can be produced. Have been found to exhibit excellent compatibility with the present invention, and have completed the present invention.

That is, the present invention relates to polymer fine particles produced by a polymerization method selected from emulsion polymerization, suspension polymerization and non-aqueous dispersion polymerization of an α, β-ethylenically unsaturated monomer, wherein the inside of the particles is as follows. And a coating composition containing the crosslinked polymer particles as an essential component. That is, the fine particles of the present invention include the following components: (a) the following groups: acetoacetoxy group, alkylated aminomethyl ether group, cyclocarbonate group, hydroxyl group, isocyanate group, epoxy group, amino group, carboxyl group and a plurality thereof. Α-β-ethylenically unsaturated monomer having a crosslinkable functional group selected from the group consisting of the following groups: 3-80% by weight (b) Other α, β-ethylenically unsaturated monomer 30-95 (C) formaldehyde or an amino resin having a weight average molecular weight of 1000 or less, a polyisocyanate compound, a polyfunctional α,
Among 2-50% by weight of a crosslinking agent having a group capable of reacting with the component (a), which is selected from the group consisting of a β-unsaturated carbonyl compound, a polyepoxy compound, a polyol, a polycarboxylic acid compound and a mixture thereof, , (A) and (b) are polymerized by a polymerization method selected from emulsion polymerization, suspension polymerization and non-aqueous dispersion polymerization to obtain fine particles, and then (c) is added to the fine particles. )
Component (a) is internally crosslinked by reacting with a crosslinkable functional group in component (a). Further, the coating composition of the present invention comprises the crosslinked polymer fine particles.

The crosslinked polymer fine particles of the present invention have an average particle size in the range of 0.01 to 50 μm, and can be easily synthesized by a known polymerization method such as an emulsion polymerization method, a suspension polymerization method or a non-aqueous dispersion polymerization method. .

For example, in the emulsion polymerization method, soap-free emulsion polymerization can be used, and polymerization using an anionic surfactant, a cationic surfactant, a nonionic surfactant, or a zwitterionic surfactant is also possible. I.e., a non-volatile content of 10 to 50% by weight, a temperature of 40 to 95C,
Polymerization can be performed in a reaction time of 10 hours. Here, when the non-volatile content is less than 10% by weight, the production efficiency of the particles is poor, and when it exceeds 50% by weight, the particles are undesirably aggregated during the polymerization. When the polymerization temperature is lower than 40 ° C., the formation of particles becomes insufficient. When the polymerization temperature is higher than 95 ° C., the particles aggregate in a gas phase, which is not preferable. If the reaction time is less than 3 hours, particle formation becomes insufficient, and if it exceeds 10 hours, the particles may aggregate due to salting out, which is not preferable.

In addition, in the suspension polymerization method, in the presence of a stabilizer such as gelatin, starch, methylcellulose, or polyvinyl alcohol, under normal conditions, that is, a non-volatile concentration of 10 to 50% by weight, a temperature of 40 to 95 ° C., The polymerization can be carried out in a reaction time of up to 10 hours. If the nonvolatile content is less than 10% by weight, the production efficiency of the particles is poor. If it exceeds 50% by weight, the average particle size of the particles exceeds 50 μm. It is not preferable because the appearance may decrease. When the polymerization temperature is lower than 40 ° C., the formation of particles becomes insufficient. When the polymerization temperature is higher than 95 ° C., the particles aggregate in a gas phase, which is not preferable. If the reaction time is less than 1 hour,
If the particle formation is insufficient, and if the time exceeds 10 hours, the waste of energy only after the completion of the reaction is undesirably caused.

Further, in the non-aqueous dispersion polymerization method, in the presence of a dispersion stabilizer such as a high butyl etherified melamine resin, a long oil-length alkyd resin, a comb copolymer having a low-polarity graft group, in a non-polar medium, under ordinary conditions. The polymerization can be carried out under a non-volatile content of 10 to 70% by weight, a temperature of 40 to 140 ° C. and a reaction time of 2 to 10 hours. Here, the nonvolatile content concentration is 10% by weight.
If it is less than 70% by weight due to poor particle production efficiency
If it exceeds, the particles are undesirably aggregated during the polymerization. If the polymerization temperature is lower than 40 ° C., the formation of particles becomes insufficient, and if it is higher than 140 ° C., the particles tend to segregate during polymerization, which is not preferable. When the reaction time is less than 2 hours, the particle formation becomes insufficient, and when the reaction time exceeds 10 hours, energy is wasted only after the completion of the reaction, which is not preferable.

The main component of the crosslinked polymer fine particles of the present invention can be formed, for example, by copolymerizing one or more kinds of α, β-ethylenically unsaturated monomers shown below. That is, (i) non-functional α, β-ethylenically unsaturated monomer methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) Acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, stearyl (meth) acrylate, styrene, alpha-methyl styrene, p- vinyl toluene, (meth) acrylonitrile, tetracyclo [4,4,0,1 ^2,5, 1
^7,10 ] dodecyl-3- (meth) acrylate, (ii) hydroxyl group-containing α, β-ethylenically unsaturated monomer 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxy Propyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth)
Acrylate, 4-hydroxybutyl (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ε of 2-hydroxyethyl (meth) acrylate
-Caprolactone (1 to 10-mer) adduct, ε-caprolactone (1 to 10-mer) adduct of 2-hydroxypropyl (meth) acrylate, (iii) epoxy group-containing α, β-ethylenically unsaturated monomer Glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, vinyl glycidyl ether (iv) amide group-containing α, β-ethylenically unsaturated monomer acrylamide, methacrylamide (v) aminomethylol group-containing α, β-ethylene Unsaturated monomer N-methylol (meth) acrylamide (vi) alkylated aminomethyl ether group-containing α, β-
Ethylenically unsaturated monomer N-methoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, methylacrylamide glycolate methyl ether (vii) isocyanate group-containing α, β-ethylenically unsaturated monomer isocyanate ethyl (Meth) acrylate, m-isopropenyl-α, α-dimethylbenzyl isocyanate, a half-block of isophorone diisocyanate with 2-hydroxyethyl (meth) acrylate or 2-hydroxypropyl (meth) acrylate, 1,6-hexamethylene Half-block of diisocyanate with 2-hydroxyethyl (meth) acrylate or 2-hydroxypropyl (meth) acrylate, tolylene diisocyanate and 2-hydroxyethyl (meth) acrylate, Half-block with 2-hydroxypropyl (meth) acrylate (viii) α, β-ethylenically unsaturated monomer containing cyclocarbonate group 4- (meth) acryloyloxymethyl-1,3 dioxolan-2-one, -(Meth) acryloyloxyethyl-1,3-dioxolan-2-one (ix) α, β-ethylenically unsaturated monomer containing acetoacetoxy group 2-acetoacetoxyethyl (meth) acrylate, 2
-Acetoacetoxypropyl (meth) acrylate (x) amino group-containing α, β-ethylenically unsaturated monomer Nt-butylaminoethyl methacrylate (xi) carboxyl group-containing α, β-ethylenically unsaturated monomer (Meth) acrylic acid, maleic acid, maleic anhydride, itaconic acid, crotonic acid, fumaric acid The composition ratio of the above α, β-ethylenically unsaturated monomer is as follows:
The refractive index, hardness, strength, toughness, glass transition temperature, functional group concentration, acid resistance, alkali resistance, etc. required for the desired application can be arbitrarily selected, but in the case of emulsion polymerization and suspension polymerization, In the case of non-aqueous dispersion polymerization, consider blending a low-polar monomer with a high-polar monomer as the main component. More stable particle formation becomes possible.

Examples of the polymerization initiator for the α, β-ethylenically unsaturated monomer include, for example, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, t-butylperoxy-2-
Organic peroxides such as ethylhexanoate, t-butylperoxybenzoate, dicumyl peroxide, azobisisobutyronitrile, azobis-2,4-dimethylvaleronitrile, dimethyl-2,2'-azobisisobutyrate, Azo compounds such as 2,2'-azobis (2-amidinopropane) dihydrochloride and 4,4'-azobis (4-cyanovaleric acid), and inorganic peroxides such as potassium persulfate, sodium persulfate and ammonium persulfate Are preferred compounds,
One or a mixture of two or more can be used. Of course, at this time, a redox system using a ferrous salt, sodium acid sulfite, N, N-dimethylaniline or the like in combination is also possible. The content of the above-mentioned polymerization initiator varies depending on the polymerization method, polymerization conditions, types of copolymerization components, and the like, but is preferably 0.1 to 100 parts by weight based on 100 parts by weight of all α, β-ethylenically unsaturated monomers. It is desirable to use in the range of 10 parts by weight. Here, when the amount of the polymerization initiator is less than 0.1 part by weight, the formation of particles becomes insufficient, and when the amount exceeds 10 parts by polymerization, the particles are apt to aggregate during polymerization, which is not preferable.
The selection of the polymerization initiator is optional, but more preferably a water-soluble polymerization initiator at the time of emulsion polymerization and an oil-soluble polymerization initiator at the time of suspension polymerization and non-aqueous dispersion polymerization are easily stable. Particles can be formed.

The three-dimensional crosslinking inside the particles of the crosslinked polymer fine particles of the present invention can be achieved by the following reactions (a) to (s).

(A) Condensation reaction between an acetoacetoxy group-containing α, β-ethylenically unsaturated monomer and an amino resin having a weight average molecular weight of 1,000 or less The reaction here can be performed by the following operation. That is, first, the acetoacetoxy group-containing α, β-ethylenically unsaturated monomer (ix) is used as an essential component, and the other α, β-ethylenically unsaturated monomers (i) to (xi) are used as necessary. Polymer fine particles are formed by emulsion polymerization, suspension polymerization or non-aqueous dispersion polymerization with a composition in which a saturated monomer is mixed. Thereafter, an amino resin having a weight average molecular weight of 1,000 or less is added, and a condensation reaction is performed with acetoacetoxy groups in the particles. Here, the blending amount of the acetoacetoxy group-containing α, β-ethylenically unsaturated monomer and the amino resin is not particularly limited, but preferably, the former is the total amount of the constituent materials of the crosslinked polymer fine particles. It is desirable to use 3 to 80% by weight, and the latter to be used in the range of 2 to 50% by weight. 3% by weight of acetoacetoxy group-containing α, β-ethylenically unsaturated monomer
When the amount is less than 2% by weight or the amino resin is less than 2% by weight, the three-dimensional cross-linking in the particles becomes insufficient, and it becomes difficult to exert a desired flow control effect. On the other hand, the former exceeds 80% by weight or the latter exceeds 50% by weight. %, The aggregation due to cross-linking between particles is likely to occur. What is important here is that the amino resin must have a weight average molecular weight of 1,000 or less. Weight average molecular weight of amino resin is 1000
If it exceeds 3, the amino resin becomes difficult to be taken into the polymer particles, and the three-dimensional crosslinking in the particles becomes insufficient. As such an amino resin, for example, as a commercial product,
Cymel 300, 301, 303, 327, 350, 1116,
1130 (Mitsui Cyanamid Co., Ltd., trade name), Nicaraq MW-30, MW-22A, MX-40, MX-45 (Miwa Chemical Co., Ltd., trade name), Regimin 730, 731, same
Alkyl etherified melamine resins such as 735, 745, 746, 747, 753, 755, and 764 (manufactured by Monsanto Co., Ltd.).

The condensation reaction between an acetoacetoxy group and an amino resin is usually carried out.
The reaction is preferably carried out at a temperature of from 60 to 140 ° C. Reaction temperature 6
If the temperature is lower than 0 ° C., the intra-particle crosslinking becomes insufficient and the reaction temperature becomes 1
If the temperature exceeds 40 ° C., the polymer fine particles are undesirably fused. Also, at this time, sodium elimination or desorption of aromatic sulfonic acid such as p-toluenesulfonic acid, dodecylbenzenesulfonic acid, dinonylnaphthalenesulfonic acid, dinonylnaphthalenedisulfonic acid, and aliphatic sulfonic acid-based surfactant is performed. The condensation reaction can be promoted by adding an aliphatic sulfonic acid obtained by potassiumation or a phosphoric acid-based catalyst.

(B) Addition reaction between an acetoacetoxy group-containing α, β-ethylenically unsaturated monomer and a polyisocyanate compound having a weight average molecular weight of 1,000 or less The reaction here can be carried out by the following operation. That is, first, the acetoacetoxy group-containing α, β-ethylenically unsaturated monomer (ix) is used as an essential component, and the other α, β-ethylenically unsaturated monomers (i) to (xi) are used as necessary. Polymer fine particles are formed by emulsion polymerization, suspension polymerization or non-aqueous dispersion polymerization with a composition in which a saturated monomer is mixed. Thereafter, a polyisocyanate compound having a weight average molecular weight of 1,000 or less is added, and an addition reaction is performed with an acetoacetoxy group in the particles. Here, the acetoacetoxy group-containing α,
The blending amounts of the β-ethylenically unsaturated monomer and the polyisocyanate compound are not particularly limited, but are preferably the same as the former in the total amount of the constituent materials of the crosslinked polymer fine particles for the same reason as in the above (a). Is preferably used in the range of 3 to 80% by weight, and the latter is preferably used in the range of 2 to 50% by weight. In addition, the weight average molecular weight of the polyisocyanate compound is as described in the above (a).
For the same reason as above, you need to choose something less than 1000.

Such polyisocyanate compounds include tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, and 4,4 '
Methylene bis (cyclohexyl isocyanate), methylcyclohexane 2,4 (2.6) diisocyanate, 1,3
-(Isocyanatomethyl) cyclohexane, isophorone diisocyanate, trimethylhexamethylene diisocyanate, and their bewrate trimers,
Isocyanurate-type trimer, trimethylolpropane,
Adducts with low molecular weight polyhydric alcohols such as glycerin, trimethylolethane and pentaerythritol can be mentioned.

It is preferable that the addition reaction between the acetoacetoxy group and the polyisocyanate compound is usually performed at a temperature of room temperature to 140 ° C. If the reaction temperature exceeds 140 ° C., the polymer fine particles are undesirably fused. At this time, a tertiary amine such as dimethyllaurylamine and dimethylbenzylamine, and a metal ester such as dibutyltin dilaurate and tetrabutyltitanate can be added to accelerate the addition reaction.

(C) Condensation reaction between acetoacetoxy group-containing α, β-ethylenically unsaturated monomer and formaldehyde The reaction here can be carried out by the following operation. That is, first, polymer fine particles are formed in the same manner as in the above (a). Thereafter, formaldehyde is added, and a condensation reaction is performed with acetoacetoxy groups in the particles.
Here, the compounding amounts of the acetoacetoxy group-containing α, β-ethylenically unsaturated monomer and formaldehyde are not particularly limited, but are preferably those of the crosslinked polymer fine particles for the same reason as in the above (a). Of the total constituent materials, the former is 3 ~
80% by weight, the latter being desirably used in the range of 2 to 50% by weight.

The addition reaction between the acetoacetoxy group and formaldehyde is preferably performed at a temperature of usually 60 to 140 ° C. for the same reason as in the above (a). At this time, it is also possible to add a basic catalyst such as sodium hydroxide, potassium hydroxide or dimethylbenzylamine to promote the condensation reaction.

(D) Michael addition reaction of an acetoacetoxy group-containing α, β-ethylenically unsaturated monomer with a polyfunctional α, β-unsaturated carbonyl compound having a weight average molecular weight of 1,000 or less The reaction here is performed by the following operation Can do it. That is, first, polymer fine particles are formed in the same manner as in the above (a). Thereafter, a polyfunctional α, β-unsaturated carbonyl compound having a weight-average molecular weight of 1,000 or less is added, and in the presence of a catalyst such as sodium methoxide, sodium ethoxide, sodium butoxide, and the like. A Michael addition reaction with acetoacetoxy groups in the particles is performed at a temperature of 140 ° C. Here, an acetoacetoxy group-containing α, β-ethylenically unsaturated monomer and a polyfunctional α, β
The blending amount of the β-unsaturated carbonyl compound is not particularly limited, but preferably the former is 3 to 80 in the total amount of the constituent materials of the crosslinked polymer fine particles for the same reason as the above (a).
% By weight, and the latter is preferably used in the range of 2 to 50% by weight. The weight average molecular weight of the polyfunctional α, β-unsaturated carbonyl compound is 10% for the same reason as in the above (a).
You need to choose something less than 00.

Such polyfunctional α, β-unsaturated carbonyl compounds include, for example, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, 1,4-
Butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, tetrapropylene glycol di (meth) acrylate, tripropylene glycol Examples thereof include di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, and dipentaerythritol (meth) acrylate.

(E) Addition reaction between an acetoacetoxy group-containing α, β-ethylenically unsaturated monomer and a polyepoxy compound having a weight average molecular weight of 1,000 or less The reaction here can be performed by the following operation. That is, first, polymer fine particles are formed in the same manner as in the above (a). Thereafter, a polyepoxy compound having a weight average molecular weight of 1000 or less is added, and an addition reaction is performed with acetoacetoxy groups in the particles. Here, the blending amounts of the acetoacetoxy group-containing α, β-ethylenically unsaturated monomer and the polyepoxy compound are not particularly limited, but preferably, for the same reason as in the above (a), the crosslinked polymer In the total amount of the constituent materials of the fine particles, the former is 3-80% by weight and the latter is 2-50% by weight.
It is desirable to use within the range of weight%. The weight average molecular weight of the polyepoxy compound must be 1000 or less for the same reason as in the above (a).

Examples of such polyepoxy compounds include bisphenol A type epoxide, novolak epoxide, alkylphenol diglycidyl ether, tetraglycidoxytetraphenylethane, phenolphthalein epoxide, resorcin epoxide, polychlorodiphenyl ether, polybromodiphenyl ether, polyglycol epoxide, Glycerin triglycidin, diglycidyl adipate, diglycidyl sebate, diglycidyl phthalate, diglycidyl dimer acid, tetraglycidylaminodiphenylmethane, triglycidyl melamine, triglycidyl cyanurate and the like can be mentioned.

The addition reaction between the acetoacetoxy group and the polyepoxy compound is usually preferably performed at a temperature of 60 to 140 ° C. for the same reason as in the above (a). At this time, a catalyst such as dimethyllaurylamine, dimethylbenzylamine, tetramethylammonium chloride, or tetraethylammonium chloride can be added to accelerate the addition reaction.

(F) alkylated aminomethyl ether group-containing α, β-
Self-condensation reaction of ethylenically unsaturated monomer The reaction here can be performed by the following operation. That is, first, the alkylated aminomethyl ether group-containing α, β-ethylenically unsaturated monomer (vi) is used as an essential component, and the other α, β- (α)-(xi) The ethylenically unsaturated monomers are mixed to form polymer fine particles by emulsion polymerization, suspension polymerization or non-aqueous dispersion polymerization. Then, as a self-condensing catalyst, p-
Aromatic sulfonic acids such as toluenesulfonic acid, dodecylbenzenesulfonic acid, dinonylnaphthalenesulfonic acid, dinonylnaphthalenedisulfonic acid, and aliphatic sulfonic acid surfactants obtained by desodiumation or depotassiumation of aliphatic surfactants A sulfonic acid or a phosphoric acid compound is added, and the reaction is carried out usually at a temperature of 60 to 140 ° C. to perform a self-condensation reaction of the alkylated aminomethyl ether group in the particles.
Here, if the reaction temperature is lower than 60 ° C., the intra-particle crosslinking becomes insufficient, and if the reaction temperature exceeds 140 ° C., the polymer fine particles are undesirably fused. The amount of the α, β-ethylenically unsaturated monomer containing an alkylated aminomethyl ether group is not particularly limited, but preferably ranges from 3 to 80 in the total amount of the constituent materials of the crosslinked polymer fine particles. weight%
It is desirable to use within the range. If the amount is less than 3% by weight, three-dimensional crosslinking in the particles becomes insufficient,
If it exceeds 80% by weight, aggregation due to cross-linking between particles is likely to occur.

(G) α, β-containing alkylated aminomethyl ether group
Condensation reaction between ethylenically unsaturated monomer and polyol having a weight average molecular weight of 1,000 or less The reaction here can be performed by the following operation. That is, first, polymer fine particles are formed in the same manner as in the above (f). Thereafter, a polyol having a weight average molecular weight of 1000 or less is added, and a condensation reaction (ether exchange reaction) with the alkylated aminomethyl ether group in the particles is performed under the same catalyst and under the same conditions as in (f) above. . Here, the compounding amounts of the alkylated aminomethyl ether group-containing α, β-ethylenically unsaturated monomer and the polyol are not particularly limited, but preferably the former is used for the same reason as the above (f). It is desirable to use 3 to 80% by weight, and the latter to be used in a range of 2 to 50% by weight. In addition, it is necessary to select a polyol having a weight average molecular weight of 1,000 or less so that the polyol can be stably incorporated into particles.

Such polyols include ethylene glycol, propylene glycol, 1,3-butylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, glycerin, polyethylene glycol
Polyethers such as 200, 300, 400, 600, Uniol D400, 70 (trade names, Nippon Oil & Fats Co., Ltd. polyethylene glycol and polypropylene glycol), Praxel 205, 208, 303, 305, 308 (trade name, polycaprolactone manufactured by Daicel Chemical Industries, Ltd.), K-flex 188 (trade name, ester diol manufactured by King Co., Ltd.)
Such as ester polyols, and Flexoletz UD-
320 (trade name, urethane diol manufactured by King Corporation), urethane diol UP-14-4 (trade name, Auto Chemical Industry Co., Ltd.)
Urethane diols).

(H) Addition reaction of cyclocarbonate group-containing α, β-ethylenically unsaturated monomer with a polyamino compound having a weight average molecular weight of 1,000 or less The reaction here can be carried out by the following operation. That is, first, the cyclocarbonate group-containing α, β-ethylenically unsaturated monomer of (viii) is used as an essential component, and the other α, β-ethylenically unsaturated monomers of (i) to (xi) are used as necessary. Polymer fine particles are formed by emulsion polymerization, suspension polymerization or non-aqueous dispersion polymerization with a composition in which a saturated monomer is mixed. Thereafter, a polyamino compound having a weight average molecular weight of 1,000 or less is added, and an addition reaction is performed with the cyclocarbonate group in the particles. Here, cyclocarbonate group-containing α,
The blending amounts of the β-ethylenically unsaturated monomer and the polyamino compound are not particularly limited, but preferably, the former is 3 to 80% by weight and the latter is 2 to 80% by weight in the total amount of the constituent materials of the crosslinked polymer fine particles. It is desirable to use within the range of 5050% by weight. This is because cyclocarbonate group-containing α, β-
When the amount of the ethylenically unsaturated monomer is less than 3% by weight or the amount of the polyamino compound is less than 2% by weight, three-dimensional crosslinking in the particles becomes insufficient, and it becomes difficult to exert a desired flow control effect. If the content exceeds 50% by weight or the content of the latter exceeds 50% by weight, agglomeration due to inter-particle crosslinking is likely to occur. The weight average molecular weight of the polyamino compound must be 1,000 or less so that the polyamino compound can be stably incorporated into the particles.

Such polyamino compounds include ethylenediamine, diethylenetriamine, triethylenetetramine,
Tetraethylenepentamine, m-hexamethylenetriamine, epomate, 1,3-aminomethylcyclohexane, 1,6-hexamethylenediamine, m-phenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, 4,7,10-trisoxatri Decane-1-13
-Diamine, bis (3-aminopropyl) polytetrahydrofuran and the like.

It is preferable that the addition reaction between the cyclocarbonate group and the polyamino compound is usually performed at a temperature of room temperature to 140 ° C.
When the reaction temperature exceeds 140 ° C., the polymer fine particles are undesirably fused.

(I) Condensation reaction between a hydroxyl group-containing α, β-ethylenically unsaturated monomer and an amino resin having a weight average molecular weight of 1,000 or less This reaction can be carried out by the following operation. That is, first, the hydroxyl group-containing α, β-ethylenically unsaturated monomer of (ii) is used as an essential component, and the other α, β-ethylenically unsaturated monomers of (i) to (xi) are used as necessary. Polymer fine particles are formed by emulsion polymerization, suspension polymerization or non-aqueous dispersion polymerization with a composition obtained by mixing the monomers. afterwards,
An amino resin having a weight average molecular weight of 1,000 or less is added, and a condensation reaction with a hydroxyl group in the particles is performed. Here, the hydroxyl group-containing α,
The compounding amount of the β-ethylenically unsaturated monomer and the amino resin is
Although not particularly limited, preferably, for the same reason as in the above (a), the former is in the range of 3 to 80% by weight, and the latter is in the range of 2 to 50% by weight in the total amount of the constituent materials of the crosslinked polymer fine particles. Preferably, it is used. The type of amino resin and the reaction conditions with hydroxyl groups can be exactly the same as those in the above (a).

(J) Addition reaction between a hydroxyl group-containing α, β-ethylenically unsaturated monomer and a polyisocyanate compound having a weight average molecular weight of 1,000 or less This reaction can be carried out by the following operation. That is, first, polymer fine particles are formed in the same manner as in the above (i). Thereafter, a polyisocyanate compound having a weight average molecular weight of 1000 or less is added, and an addition reaction is performed with a hydroxyl group in the particles. Here, the blending amounts of the hydroxyl group-containing α, β-ethylenically unsaturated monomer and the polyisocyanate compound are not particularly limited, but preferably, the crosslinked polymer fine particles are the same as in (a) above. It is preferable that the former is used in the range of 3 to 80% by weight and the latter is used in the range of 2 to 50% by weight. The type of the polyisocyanate compound and the reaction conditions with the hydroxyl group can be exactly the same as those in the above (b).

(K) Addition reaction between an isocyanate group-containing α, β-ethylenically unsaturated monomer and a polyol having a weight average molecular weight of 1,000 or less This reaction can be carried out by the following operation. That is, first, the isocyanate group-containing α, β-ethylenically unsaturated monomer (vii) is used as an essential component, and the other α, β-ethylenically unsaturated monomers (i) to (xi) are used as necessary. Polymer fine particles are formed by emulsion polymerization, suspension polymerization or non-aqueous dispersion polymerization with a composition in which monomers are mixed. Thereafter, the polyol having a weight average molecular weight of 1,000 or less described in (g) is added, and an addition reaction is performed with an isocyanate group in the particles. Here, isocyanate group-containing α,
The blending amount of the β-ethylenically unsaturated monomer and the polyol is
Although not particularly limited, preferably, for the same reason as in the above (a), the former is in the range of 3 to 80% by weight, and the latter is in the range of 2 to 50% by weight in the total amount of constituent materials of the crosslinked polymer fine particles. Preferably, it is used.

The addition reaction between the isocyanate group and the polyol is preferably performed at a temperature of usually from room temperature to 140 ° C. If the reaction temperature exceeds 140 ° C., the polymer fine particles are undesirably fused. In this case, dimethyl lauryl amine,
A tertiary amine such as dimethylbenzylamine, or a metal ester such as dibutyltin dilaurate or tetrabutyl titanate can be added to accelerate the addition reaction.

(L) Addition reaction between an isocyanate group-containing α, β-ethylenically unsaturated monomer and a polymercapto compound having a weight average molecular weight of 1,000 or less The reaction here can be carried out by the following operation. That is, first, polymer fine particles are formed in the same manner as in the above (k). Thereafter, a polymercapto compound having a weight average molecular weight of 1000 or less is added, and an addition reaction is performed with an isocyanate group in the particles. Here, the compounding amounts of the isocyanate group-containing α, β-ethylenically unsaturated monomer and the polymercapto compound are not particularly limited, but preferably, the crosslinked polymer is used for the same reason as in the above (a). In the total amount of the constituent materials of the fine particles, the former is 3-80% by weight, and the latter is 2-80% by weight.
Preferably, it is used within the range of 50% by weight. Also,
The weight average molecular weight of the polymercapto compound is as defined in (a) above.
For the same reason as above, you need to choose something less than 1000.

Such polymercapto compounds include, for example, ethanediol, 1,3-propanedithiol, 1,4-butanediol, ethylene glycol dithioglycolate, 1,4
-Butanediol dithiopropionate, trimethylolpropane tris (thioglucolate), trimethylolpropane tris (β-thiopropionate), pentaerythritol tetrakis (thioglycolate), pentaerythritol tetrakis (β-thiopropionate) ) Etc. can be given.

The addition reaction between the isocyanate group and the polymercapto group is
For the same reason as the former (k), it is preferable that the reaction is usually performed at a temperature of room temperature to 140 ° C.

(M) Addition reaction between an isocyanate group-containing α, β-ethylenically unsaturated monomer and a polyamino compound having a weight average molecular weight of 1,000 or less This reaction can be carried out by the following operation. That is, first, polymer fine particles are formed in the same manner as in the above (k). Thereafter, the polyamino compound having a weight average molecular weight of 1,000 or less described in (h) is added, and an addition reaction is performed with an isocyanate group in the particles. Here, the compounding amounts of the isocyanate group-containing α, β-ethylenically unsaturated monomer and the polyamino compound are not particularly limited, but are preferably crosslinked polymer fine particles for the same reason as in the above (a). Of the constituent materials, the former is 3-80% by weight,
The latter is desirably used in the range of 2 to 50% by weight.

The addition reaction between the isocyanate group and the polyamino compound is
Usually, it can easily react at room temperature.

(N) Addition reaction between an epoxy group-containing α, β-ethylenically unsaturated monomer and a polyamino compound having a weight average molecular weight of 1,000 or less The reaction here can be performed by the following operation. That is, first, the epoxy group-containing α,
Emulsion polymerization and suspension with a composition comprising a β-ethylenically unsaturated monomer as an essential component and, if necessary, other α, β-ethylenically unsaturated monomers described in (i) to (xi) above. Polymer fine particles are formed by polymerization or non-aqueous dispersion polymerization. Thereafter, the polyamino compound having a weight average molecular weight of 1000 or less described in (h) is added, and an addition reaction is performed with an epoxy group in the particles. Here, the blending amounts of the epoxy group-containing α, β-ethylenically unsaturated monomer and the polyamino compound are not particularly limited, but preferably, the crosslinked polymer fine particles are used for the same reason as in the above (h). It is preferable that the former is used in the range of 3 to 80% by weight and the latter is used in the range of 2 to 50% by weight.

For the same reason as in the above (h), the addition reaction between the epoxy group and the polyamino compound is preferably performed at a temperature of usually room temperature to 140 ° C.

(O) Addition reaction between an epoxy group-containing α, β-ethylenically unsaturated monomer and a polycarboxylic acid compound having a weight average molecular weight of 1,000 or less The reaction here can be carried out by the following operation. That is, first, polymer fine particles are formed in the same manner as in the above (n). Thereafter, a polycarboxylic acid compound having a weight average molecular weight of 1000 or less is added, and an addition reaction is performed with an epoxy group in the particles. Here, the epoxy group-containing α, β-
The blending amounts of the ethylenically unsaturated monomer and the polycarboxylic acid compound are not particularly limited, but preferably, the former is 3 to 80% by weight, and the latter is 2 to 80% by weight of the total constituent materials of the crosslinked polymer fine particles. It is desirable to use within the range of 5050% by weight. If the epoxy group-containing α, β-ethylenically unsaturated monomer is less than 3% by weight or the polycarboxylic acid compound is less than 2% by weight, three-dimensional cross-linking in the particles becomes insufficient and the desired flow control is obtained. This is because when the former is more than 80% by weight or the latter is more than 50% by weight, agglomeration due to cross-linking between particles easily occurs. In addition, it is necessary to select a polycarboxylic acid compound having a weight average molecular weight of 1,000 or less in order to easily incorporate the polycarboxylic acid compound into particles stably.

Such polycarboxylic acid compounds include, for example, phthalic acid, phthalic anhydride, terephthalic acid, isophthalic acid, hexahydrophthalic anhydride, trimellitic anhydride, trimellitic acid, pyromellitic acid, 3,6-endomethylenetetrahydrophthalic anhydride , Diphenolic acid, sebacic acid, dimer acid, tetrahydrophthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic acid, adipic acid, maleic acid, fumaric acid, succinic acid, azelaic acid, sebacic acid,
Examples include polybasic acids such as maleic anhydride and polycarboxylic esters derived from these polybasic acids and polyhydric alcohols.

The addition reaction between the epoxy group and the polycarboxylic acid compound is preferably performed at a temperature of usually 60 to 140 ° C. If the reaction temperature is lower than 60 ° C., intraparticle crosslinking becomes insufficient, and if the reaction temperature is higher than 140 ° C., polymer fine particles are undesirably fused. At this time, it is also possible to promote the addition reaction by adding the catalyst described in (e) above.

(P) Addition reaction of α, β-ethylenically unsaturated monomer containing a xypoxy group with a polymercapto compound having a weight average molecular weight of 1,000 or less This reaction can be carried out by the following operation. That is, first, polymer fine particles are formed in the same manner as in the above (n). Thereafter, a polymercapto compound having a weight average molecular weight of 1,000 or less described in the above (1) was added,
An addition reaction is performed with an epoxy group in the particles. Here, the blending amount of the epoxy group-containing α, β-ethylenically unsaturated monomer and the polymercapto compound is not particularly limited, but preferably, the crosslinking weight is the same as the above (o). It is desirable that the former is used in a range of 3 to 80% by weight and the latter is used in a range of 2 to 50% by weight in the total amount of the constituent materials of the coalesced fine particles.

The addition reaction of the epoxy group with the polymercapto compound is preferably performed at a temperature of usually room temperature to 140 ° C. If the reaction temperature exceeds 140 ° C., the polymer fine particles are undesirably fused.

(Q) Addition reaction between an amino group-containing α, β-ethylenically unsaturated monomer and a polyisocyanate compound having a weight average molecular weight of 1,000 or less The reaction here can be carried out by the following operation. That is, first, the amino group-containing α, β-
Emulsion polymerization, suspension polymerization or non-aqueous polymerization is carried out in a composition comprising an ethylenically unsaturated monomer as an essential component and, if necessary, a mixture of the above α, β-ethylenically unsaturated monomers (i) to (xi). Polymer fine particles are formed by dispersion polymerization. Thereafter, the polyisocyanate compound having a weight average molecular weight of 1,000 or less described in (b) is added, and an addition reaction is performed with an amino group in the particles. Here, the blending amounts of the amino group-containing α, β-ethylenically unsaturated monomer and the polyisocyanate compound are not particularly limited, but are preferably the same as those described in (a) above for the reason that In the total amount of constituent materials of the coalesced fine particles,
The former is desirably used within a range of 3 to 80% by weight, and the latter is desirably used within a range of 2 to 50% by weight.

The addition reaction between the amino group and the polyisocyanate compound is
Usually, it can easily react at room temperature.

(R) Addition reaction between an amino group-containing α, β-ethylenically unsaturated monomer and a polyepoxy compound having a weight average molecular weight of 1,000 or less The reaction here can be performed by the following operation. That is, first, polymer fine particles are formed in the same manner as in the above (q). Thereafter, a polyepoxy compound having a weight average molecular weight of 1,000 or less described in (e) is added, and an addition reaction is performed with an amino group in the particles. Here, the blending amounts of the amino group-containing α, β-ethylenically unsaturated monomer and the polyepoxy compound are not particularly limited, but are preferably the same as those in the above (a), for the same reason as the crosslinking weight. In the total amount of the constituent materials of the combined fine particles, the former is 3-80% by weight, and the latter is 2-80% by weight.
Preferably, it is used within the range of 50% by weight.

The addition reaction between the amino group and the polyepoxy compound is preferably performed at a temperature of usually room temperature to 140 ° C. for the same reason as in the above (h).

(S) Addition reaction of carboxyl group-containing α, β-ethylenically unsaturated monomer with a polyepoxy compound having a weight average molecular weight of 1,000 or less The reaction here can be carried out by the following operation. That is, first, the carboxy group-containing α,
Emulsion polymerization and suspension with a composition comprising a β-ethylenically unsaturated monomer as an essential component, and if necessary, other α, β-ethylenically unsaturated monomers described in (i) to (x) above. Polymer fine particles are formed by polymerization or non-aqueous dispersion polymerization. Thereafter, the polyepoxy compound having a weight average molecular weight of 1000 or less described in (e) is added, and an addition reaction is performed with a carboxyl group in the particles. Here, the carboxyl group-containing α, β-
The blending amounts of the ethylenically unsaturated monomer and the polyepoxy compound are not particularly limited, but preferably, for the same reason as in the above (a), in the total amount of the constituent materials of the crosslinked polymer fine particles, It is desirable to use 3 to 80% by weight, and the latter to be used in the range of 2 to 50% by weight.

The addition reaction between the carboxyl group and the polyepoxy compound is usually preferably performed at a temperature of 60 to 140 ° C. for the same reason as in the above (a). At this time, the above (e)
Can be added to promote the addition reaction.

The crosslinked polymer fine particles obtained as described above are used by being added to an aqueous or non-aqueous paint. At this time, particles synthesized by emulsion polymerization or suspension polymer can be added to the water-based paint as it is, but it is necessary to remove water in order to apply to the non-aqueous paint. As this method, there are two methods, a method by spray drying and a method of converting to a non-aqueous dispersion system.

However, the spray drying method is not preferable because the crosslinked polymer fine particles are apt to aggregate during drying, and it is difficult to exert the effects of the present invention.

On the other hand, the method of converting to a non-aqueous dispersion system is a more preferable method because particle aggregation hardly occurs. In this method, an organic solvent having a water solubility of 5% by weight or less at 20 ° C. is added to an aqueous dispersion, and then an organic acid amine salt is added and allowed to stand. To separate.

Water solubility at 20 ° C used here is 5% by weight
The following organic solvents can be used either as a single solvent or a mixed solvent, but when used in a single solvent system, it is desirable to use an alcohol solvent or a ketone solvent, and other solvents, for example, When a non-polar solvent such as an aliphatic solvent or an aromatic solvent is used alone, the crosslinked polymer fine particles may aggregate, which is not preferable. 5% by weight water solubility at 20 ° C that can be used as a single solvent system
The following alcohol solvents include, for example, 2-ethyl-
1-butyl alcohol, 3-heptyl alcohol, 1-
Octyl alcohol, 2-octyl alcohol, 2-
Ethylhexyl alcohol, 1-nonyl alcohol, 3,
There are 5,5-trimethyl-1-hexyl alcohol, 1-decyl alcohol, 1-undecyl alcohol, 1-dodecyl alcohol, and the like. Examples of the ketone solvent include methyl n-propyl ketone, methyl iso-propyl ketone, and diethyl. Ketone, methyl n-butyl ketone, methyl iso-butyl ketone, methyl n-pentyl ketone,
Examples thereof include di-n-propyl ketone, di-iso-butyl ketone, and ethyl n-butyl ketone, but the present invention is not limited to these.
Species or more can be used by mixing at an arbitrary ratio.

When a mixture of two or more solvents is used, it is necessary to include at least one of an alcohol solvent and a ketone solvent and adjust the solvent composition so that the solubility of water at 20 ° C. becomes 5% by weight or less. Well, as a solvent that can be used at this time, as the alcohol-based solvent, in addition to the alcohol-based solvent described above, for example, n-butyl alcohol,
n-pentyl alcohol, n-hexyl alcohol, se
c-butyl alcohol, iso-butyl alcohol, 2-pentyl alcohol, 3-pentyl alcohol, 2-methyl-1-butyl alcohol, 4-methyl-2-pentanol, and the like. And methyl ethyl ketone. As the organic solvent other than the alcohol-based solvent and the ketone-based solvent, an aliphatic solvent, an aromatic-based solvent, and an ester-based solvent can be used. As the aliphatic solvent, for example, n-pentane, n-
Hexane, n-heptane, cyclohexane, methylcyclohexane, ethylcyclohexane and the like. Examples of the aromatic solvent include benzene, toluene, xylene and the like. Examples of the ester solvent include ethyl acetate, n-propyl acetate, iso-propyl acetate, n-butyl acetate, iso-butyl acetate, sec-butyl acetate, and the like, but the present invention is not limited thereto. .

Examples of the organic acid used for the organic acid amine salt to be added include organic carboxylic acids, organic sulfonic acids, and organic phosphoric acids. Examples of such organic carboxylic acids include formic acid, acetic acid, and propionic acid, and organic sulfonic acids include methanesulfonic acid and ethanesulfonic acid, and organic phosphoric acids include monomethyl phosphoric acid, monoethyl phosphoric acid, and the like. Examples include dimethyl phosphate and diethyl phosphate. On the other hand, any of primary amines, secondary amines and tertiary amines can be used as the amine. Examples of such amines include monoethylamine and iso-amine.
Examples of the secondary amine include dimethylamine, diethylamine, and diethanolamine. Examples of the tertiary amine include triethylamine, tripropylamine, dimethylethanolamine, and pyridine. Is not limited to these.

The organic acid amine salt comprising the combination of the organic acid and the amine is easily produced by mixing a predetermined amount of the organic acid and the amine at room temperature.

According to the above-described method of converting into a non-aqueous dispersion system, the crosslinked polymer fine particles are inhibited from being electrically stabilized in water by the formation of an electric double layer of the surfactant present on the particle surface due to the added organic acid amine salt. And dispersed in the organic layer. After removing the separated water, the residual water present in the organic solvent layer is obtained by adding an orthocarboxylic acid ester such as methyl orthoformate, ethyl orthoformate, methyl orthoacetate, ethyl orthoacetate to the organic solvent layer. It can be completely removed by decomposition by heating, by azeotropic distillation under normal pressure, or by dehydration under reduced pressure at a temperature of 50 to 100 ° C. below 760 mmHg.

Here, when converting the crosslinked polymer fine particles into a non-aqueous dispersion system, a surfactant or a polymerization initiator piece fixed on the particle surface is hydrolyzed under a basic or acidic catalyst and removed from the particle surface. It is also possible. In such particles,
Since the particle surface can be deionized, a high-quality coating film can be obtained without any adverse effect on the coating film performance, such as a decrease in water resistance.

When using the crosslinked polymer fine particles of the present invention in a coating, for example, acrylic resin, polyester resin, alkyd resin,
Epoxy resin, epoxy ester resin, silicone resin,
Fluorine resin, polyurethane resin, melamine resin, urea resin, benzoguanamine resin, phenol resin, xylene resin, toluene resin, vinyl chloride resin, phenoxy resin, cellulose resin, etc. are arbitrarily selected and mixed in consideration of compatibility. be able to. At this time, the crosslinked polymer fine particles are added to the paint in a small amount to prevent flow during vertical coating, and used as a fluidity control additive such as improving the orientation of the metal pigment.
It can be used as a main component of paint. Further, in the production of paint, using the resin to be mixed, using a device used in normal paint production, for example, using a ball mill, paint shaker, sand mill, roll mill, kneader, etc., by using a normal addition method to mix Can be manufactured. At this time, if necessary, in addition to coloring agents such as pigments, dyes, glass flakes, and aluminum paste, additives usually used in paints, such as pigment dispersants, viscosity regulators, leveling agents, curing catalysts, and gelation prevention. Agents, ultraviolet absorbers, radical scavengers and the like can also be added.

The paints obtained as described above are, for example, one coat solid color, one coat metallic color, two coats one color.
In the form of bake solid color, 2 coat 1 bake metallic color, 3 coat 2 bake solid color, 3 coat 2 bake metallic color, etc., a normal coating method such as air spray coating, airless spray coating, electrostatic coating, dip coating, etc. By coating on ordinary objects to be coated, such as metals and other inorganic materials, plastics and other organic materials, with a baking and drying time of 0.5 to 60 minutes at 60 to 200 ° C., which is the usual baking conditions, excellent coating film Is obtained.

(Effect of the Invention) As described above, the crosslinked polymer fine particles of the present invention have no α, β-ethylenically unsaturated group on the surface of the particles, and the inside of the particles is highly three-dimensionally crosslinked. Therefore, excellent compatibility with a wide range of paint binders can be exhibited. As a result, in the paint to which the particles are added, an excellent flow control effect can be obtained, and a thick film coating having excellent appearance quality can be obtained.

(Examples) Next, the present invention will be described in more detail with reference to Production Examples and Comparative Examples. In the examples, parts are parts by weight and% is% by weight.

(Example of emulsion polymerization) Production example A Detergent water in surfactant solution 380.0 parts Rapisol B90 (described later) 5.5 parts Aqueous initiator solution-1 deionized water 10.0 parts Ammonium persulfate 0.3 part α, β-ethylenically unsaturated monomer Mixture acetoacetoxyethyl methacrylate (described later) 22.5 parts n-butyl methacrylate 66.4 parts aqueous solution of polymerization initiator-2 deionized water 10.0 parts ammonium persulfate 0.3 part crosslinking agent isophorone diisocyanate 11.1 parts catalyst dibutyltin dilaurate 0.5 part stirrer, reflux condenser, A surfactant aqueous solution was charged into a flask equipped with two dropping funnels, a nitrogen inlet tube and a thermometer, and the temperature was raised to 80 ° C. under a nitrogen stream to obtain a polymerization initiator aqueous solution.
One was added. After the temperature was raised to 80 ° C again, the mixture of α, β-ethylenically unsaturated monomers was added dropwise over 3 hours while maintaining the mixture in the flask at 80 ± 2 ° C. During the dropping of the monomer mixture, the polymerization initiator aqueous solution-2 was dropped in 2 hours after 1 hour from the start of dropping. After the addition of the α, β-ethylenically unsaturated monomer and the polymerization initiator aqueous solution-2, the mixture was further heated at 80 ° C.
After polymerization for a period of time, a crosslinking agent and a catalyst are added, and the reaction temperature is increased to 95%.
The temperature was raised to ° C. Thereafter, stirring was continued at 95 ° C. for 4 hours to obtain an aqueous dispersion of crosslinked polymer fine particles having a heating residue of 20%.

Next, 200 parts of methylpentyl ketone was added to 500 parts of the aqueous dispersion.
And 22.7 parts of a 3N aqueous sodium hydroxide solution, and a hydrolysis reaction was carried out at 85 ± 2 ° C. for 3 hours. Then
After lowering the temperature to 80 ° C and adding 22.7 parts of 3N formic acid aqueous solution to neutralize, acrylic resin A is used as a particle dispersion stabilizing resin.
After adding 166.7 parts of the above solution (described later) and stirring for 10 minutes, 25 parts of a 20% aqueous solution of triethylamine acetate (described later) was added, stirring was immediately stopped, and the mixture was allowed to stand. Since an aqueous layer separated into an upper layer and an aqueous layer below, a lower aqueous layer was removed.

Deionized water 20 is applied to the organic layer in which the remaining polymer particles are dispersed.
0 parts were added, the temperature was raised to 70 ° C. with stirring, and when the temperature reached 70 ° C., 12.5 parts of a 20% aqueous solution of triethylamine acetate was added, and the stirring was stopped immediately and allowed to stand. Again, the organic layer in which the crosslinked polymer fine particles were dispersed was separated into an upper layer and the aqueous layer was separated into a lower layer, and the lower aqueous layer was removed. In the remaining organic layer, 3.5% by weight of water remained by a Karl Fischer moisture meter.

Next, the temperature of the organic layer was cooled to 50 ° C., and 94.2 parts of methyl orthoformate was dropped from the dropping funnel over 30 minutes.
The reaction was continued at 2 ° C. for 2 hours to decompose residual water. Thereafter, 130 parts of xylene was added, a new Dean-Stark trap was attached between the reflux condenser and the flask, the upper part of the reflux condenser was connected to the aspirator, and the flask was heated and stirred to reduce the pressure to 300 ± 100 mmHg, 80 ± Heating residue at 10 ℃
The solvent was removed to 50 ± 1.5% to obtain a polymer non-aqueous dispersion A having the properties shown in Table 1.

Production Examples B to I Using the same apparatus as in Production Example A, and performing emulsion polymerization and non-aqueous conversion treatment in exactly the same manner as in Production Example A, based on the blends in Tables B to I, Table 1 was obtained. Polymer non-aqueous dispersions B to I having the characteristics described in (1) to (3) were obtained.

However, in Production Examples E and H, the reaction after the addition of the cross-linking agent was completed in 2 hours at 80 ° C., and proceeded to the next non-aqueous conversion step.

(Suspension polymerization example) Production example J Stabilizer aqueous solution deionized water 400.0 parts Denkapavar K17E (described later) 5.5 parts α, β-ethylenically unsaturated monomer mixture t-butylaminoethyl methacrylate 37.0 parts n-butyl methacrylate 51.9 Part Perbutyl O (described later) 2.0 parts Cross-linking agent isophorone diisocyanate 11.1 part Charge the aqueous stabilizer solution into a flask equipped with a stirrer, reflux condenser, dropping funnel, nitrogen inlet tube and thermometer, and raise the temperature to 80 ° C under a nitrogen stream. Α, β while keeping at 80 ± 2 ℃
-The ethylenically unsaturated monomer mixture was added dropwise over 3 hours. After completion of the dropwise addition, the mixture was further polymerized at 80 ° C. for 2 hours, followed by adding a crosslinking agent and continuing the crosslinking reaction at 80 ° C. for 2 hours to obtain an aqueous dispersion of crosslinked polymer fine particles having a heating residue of 20%. Next, this aqueous dispersion was treated in exactly the same manner as in Production Example A to obtain a polymer non-aqueous dispersion J having the properties shown in Table 1.

Production Example K Emulsion polymerization was carried out in exactly the same manner as in Production Example J, and a non-aqueous conversion treatment was carried out in exactly the same manner as in Production Example A, using the same apparatus as in Production Example J and based on the formulation in Table K. As a result, a polymer non-aqueous dispersion K having the properties shown in Table 1 was obtained.

Table 1 Footnotes (1) surfactant (a) RAPISOL B90 (manufactured by NOF Corporation, trade name of di-2-ethylhexyl sodium sulfosuccinate, active ingredient 90%) (b) cationic S ₂ -100 (Nippon (Trade name of octadecyldimethylbenzylammonium chloride, 100% active ingredient) (c) Syntrex L100 (trade name of sodium lauryl sulfate, 100% active ingredient, manufactured by NOF Corporation) (d) POESMS : Abbreviation, polyoxyethylene sorbitan monostearate (Note 2) Stabilizer K17E (manufactured by Denki Kagaku Kogyo Co., Ltd., fully saponified polyvinyl alcohol, active ingredient 94%) (Note 3) Polymerization initiator (a) (NH ₄ ) ₂ S ₂ O ₈ : ammonium persulfate (b) Na ₂ S ₂ O ₈ : sodium persulfate (c) AAP-HCl: abbreviation, 2,2′-azobis (2-
Amidinopropane) dihydrochloride manufactured by _{(d) K 2 S 2 O} 8 Potassium persulfate (e) PERBUTYL O (NOF Corporation, trade name of t- butyl peroxy-2-ethylhexanoate, the active ingredient
(Note 4) Crosslinkable α, β-ethylenically unsaturated monomer AAEM: acetoacetoxyethyl methacrylate (manufactured by Eastman Kodak Co., Ltd., active ingredient 95%) MPC: 4-methacryloyloxymethyl-1,3- Dioxolan-2-one (cyclocarbonate group-containing monomer obtained by adding carbon dioxide to glycidyl methacrylate, active ingredient
95%) HPMA: 2-hydroxypropyl methacrylate IEMA: 2-isocyanatoethyl methacrylate GMA: glycidyl methacrylate TBAEMA: t-butylaminoethyl methacrylate (Note 5) Other α, β-ethylenically unsaturated monomers BMA: n -Butyl methacrylate BA: n-butyl acrylate EHMA: 2-ethyl exyl methacrylate (Note 6) Crosslinking agent IPDI: isophorone diisocyanate (weight average molecular weight 22
2) HCHO: 37% aqueous solution of formalin (polymerization average molecular weight 30) TMPTA: trimethylolpropane triacrylate (weight average molecular weight 296) GTG: glycerin triglycidyl (weight average molecular weight 260) TET: triethylenetetramine (weight average molecular weight 146) PETG: pentaerythritol tetrakis (thioglycolate) (manufactured by Yodo Chemical Co., Ltd., mercapto equivalent: 118) (Note 7) Catalyst DBTDL: dibutyltin dilaurate BDMA: dimethylbenzylamine DBU: 1,8-diaza, manufactured by Sun Abbot Bicyclo (5,4,
0) Undecene-7 (Note 8) Dispersion-stabilized resin solution (a) Acrylic A 42 parts of xylene was charged into a reactor equipped with a stirrer, thermometer, reflux condenser, nitrogen gas inlet tube and dropping funnel,
When the temperature reached 140 ° C. while heating and stirring while introducing nitrogen gas, a mixed solution of a monomer component and a polymerization initiator shown below was
It dripped from the dropping funnel at 140 degreeC constant.

n-Butyl methacrylate 36.4 parts 2-ethylhexyl methacrylate 11.7 parts 2-hydroxylethyl methacrylate 11.1 parts Acrylic acid 0.8 parts t-butyl peroxybenzoate 3.0 parts After dropping, the mixture was kept at 140 ° C for 2 hours, cooled, and the contents were taken out. Heating residue 60%, Gardner viscosity (25 ° C.) Y (b) Acrylic A-413-70S (manufactured by Dainippon Ink and Chemicals, Inc., trade name of acrylic resin solution, heating residue 70)
%) (C) John Krill 500 (manufactured by Johnson Wax Co., trade name of acrylic resin solution, heating residue 80%) (d) Alloplats 1713-R60 (manufactured by Nisshin Arrow Co., Ltd.
Product name of silicone polyester resin solution, heating residue 60
%, Hydroxyl value 140) (e) Beccolite M-6602-60S (trade name of alkyd resin solution, manufactured by Dainippon Ink and Chemicals, Inc., heating residue 60)
%) (Note 9) (a) Residue after heating: According to JIS K 5400,8.2.

(B) Viscosity: Measured with a Brookfield viscometer. 60
rpm, 20 ° C. (c) Average particle size: measured by “Nycomp, Model 370” (trade name) manufactured by Pacific Scientific.

(Note 10) 20% aqueous solution of triethylamine acetate, 80 deionized water
The mixture was prepared by dissolving 7.5 parts of acetic acid in 1 part, and adding 12.5 parts of triethylamine over 30 minutes with stirring at room temperature.

(Example of Non-Aqueous Dispersion Polymerization) Production of Acrylic B (Dispersion Stabilizer) A stirrer, a reflux condenser, a thermometer, and a nitrogen gas inlet tube were attached to four flasks, a mixture having the following composition was added, and the mixture was heated while stirring. Heated to 140 ° C.

Benzoic acid 122.0 parts Kajura E10 (Yukai Shell Epo 250.0 parts Glycidyl ester of versatic acid manufactured by Kishi Co., Ltd.) Phthalic anhydride 148.0 parts N, N-dimethylbenzylamine 2.0 parts Xylene 327.0 parts At a temperature of 140 ° C The mixture was stirred for 2 hours while introducing nitrogen gas to obtain a non-volatile acid value of 108 to obtain a reaction intermediate solution having a carboxyl group at the molecular end. Next, the above reaction intermediate aqueous solution was added to Kjular E10 / phthalic anhydride = 25.
The mixture was reacted twice with the mixture of 0.0 parts / 148.0 parts under the above-mentioned reaction conditions. When the final nonvolatile acid value reached 43, the reaction was terminated. I got Using this polyester compound solution, a mixture having the following composition was stirred at a temperature of 140 ° C. for 4 hours. When the nonvolatile acid value became 1 or less, the reaction was terminated. β-
An ethylenically unsaturated monomer solution was obtained.

The above polyester compound solution 1645.0 parts Glycidyl methacrylate 142.0 parts Hydroquinone 2.0 parts Xylene 35.0 parts Next, using the above monomer solution, a dispersion stabilizer was produced by the following method.

A stirrer, a reflux cooling system, a thermometer, and a dropping funnel were attached to the four flasks, and 85.5 parts of xylene was added. The mixture was heated with stirring and heated to 95 ° C. Then, a mixture having the following composition was added at a constant addition rate over 2 hours at a temperature of 95 ° C,
By keeping the temperature at 95 ° C. for another 2 hours, a solution of acrylic B having a heating residue of 50% was obtained.

62.5 parts n-butyl methacrylate 50.0 parts t-butyl peroxy 2-ethyl hexanoate 2.0 parts Preparation example L Initial charge solvent n-butyl acetate 84.7 parts Mineral spirit 84.7 parts of dispersion stabilizer acrylic B (supra) 85.7 parts alpha, beta-ethylenically unsaturated monomer mixture acetoacetoxyethyl methacrylate rate 40.2 parts of methyl methacrylate 14.8 parts of acrylonitrile 15.0 parts Perbutyl O 1.5 parts crosslinker Cymel 303 (described later) 30.0 parts Catalyst dodecylbenzenesulfonic acid 1.5 parts A stirrer, a reflux condenser, a thermometer, and a dropping funnel were attached to four flasks, an initial charging solvent and a dispersion stabilizer were charged, and the mixture was heated to 95 ° C. with stirring. Then, at a temperature of 95 ° C., the α, β-ethylenically unsaturated monomer mixture was added at a constant addition rate over 2 hours, and kept at 95 ° C. for another 2 hours. Thereafter, a crosslinking agent and a catalyst were added, and the temperature was increased while stirring, and a crosslinking reaction was performed at a temperature of 120 ° C. for 2 hours to obtain a polymer non-aqueous dispersion L having the properties shown in Table 2.

Production Examples M to S Polymer non-aqueous dispersions having the properties described in Table 2 by performing non-aqueous dispersion polymerization based on the blending of Tables 2 to 2 using the same apparatus as in Production Example L. MS were obtained.

Comparative Production Example T (a) Production of α, β-ethylenically unsaturated monomer In a four-necked flask equipped with a stirrer, a thermometer, a Dean-Stark trap equipped with a reflux condenser, and a nitrogen gas inlet tube.
1500 parts of 12-hydroxystearic acid was added, the temperature was increased while blowing nitrogen gas, and the mixture was stirred at a temperature of 200 ° C. to obtain an acid value of 39.
When the reaction reached, the reaction was terminated, and after standing to cool, 159 parts of xylene was added, and 12-hydroxystearic acid 5% having a heating residue of 90% was added.
A molar condensate solution was obtained. In this reaction, 72 parts of water were eliminated. Next, using the 12-hydroxystearic acid 5 mol condensate solution, a mixture having the following composition was heated at a temperature of 120 ° C in a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen gas inlet tube. Stir and heat residue acid value
Esterification until 1.0 or less, heating residue 80%
Of α, β-ethylenically unsaturated monomer was obtained.

12-hydroxystearic acid 5 mol condensate solution 1586.67 parts Glycidyl methacrylate 142.00 parts N, N-dimethylbenzylamine 3.93 parts Hydroquinone 1.96 parts Xylene 227.94 parts (b) Production of amphiphilic dispersion stabilizer Next, a stirrer and reflux cooling In a four-necked flask equipped with a vessel, thermometer and dropping funnel, 405.0 parts of ethyl acetate and 20
3.4 parts of n-butyl acetate was added and refluxed with stirring.
Then, a mixture having the following composition was added at a constant addition rate under reflux.
By adding over time and refluxing for another 2 hours,
An amphiphilic dispersion stabilizer solution having a heating residue of 33% was obtained.

Α, β-ethylenically unsaturated monomer solution of (a) 275.0 parts Methyl methacrylate 104.5 parts Acrylic acid 5.5 parts Azodiisobutyronitrile 6.6 parts (c) Production of polymer non-aqueous dispersion Stirrer, reflux condenser And a four-necked flask equipped with a device for adding a liquid feed to the returned condensate was charged with a mixture having the following composition.

Mineral spirit 1588.0 parts Hexane 389.0 parts Heptane 2080.2 parts Methyl methacrylate 236.4 parts Azodiisobutyronitrile 18.7 parts Amphiphilic dispersion stabilizer solution of the above (b) 88.1 parts The above contents are heated to 100 ° C and refluxed for 1 hour. Held. Next, after the following components were premixed, they were added to the hydrocarbon returned from the condenser at a constant addition rate over 6 hours.

Methyl methacrylate 4491.8 parts Methacrylic acid 45.8 parts Glycidyl methacrylate 45.8 parts Azodiisobutyronitrile 60.2 parts Amphiphilic dispersion stabilizer solution of above (b) 945.3 parts However, in the last hour of addition, 3.3 parts of triethylenediamine was added to the above mixture. During the additional mixing. After completion of the addition, the reaction mixture was kept under reflux for 3 hours to obtain a polymer non-aqueous dispersion having a heating residue of 52% containing 48.2% of polymer particles having an average particle size of 200 nm.

(D) Modification of particles with auxiliary polymer The following components were charged into a four-necked flask equipped with the device of the above step (c), and heated to a reflux temperature (115 ° C).

4747.1 parts of the polymer non-aqueous dispersion of (c) above 1638.2 parts of ethylcyclohexane Next, the following components were premixed, and then added to the hydrocarbon returned from the condenser at a constant addition rate over 3 hours.

Methyl methacrylate 334.2 parts 2-hydroxyethyl methacrylate 190.6 parts Methacrylic acid 49.6 parts Butyl methacrylate 369.1 parts 2-Ethylhexyl acrylate 381.2 parts Styrene 571.2 parts T-butylperoxybenzoate 90.6 parts Octyl mercaptan 84.7 parts Amphiphilic dispersion stabilizer of the above (b) After the completion of the addition, the reaction mixture was refluxed for 2 hours, and then the following solvent mixture was added to reduce the crosslinked polymer fine particles to 25%.
A polymer non-aqueous dispersion T having a heating residue of 45% was obtained.

n-butyl alcohol 559.0 parts xylene 372.3 parts butyl acetate 462.7 parts Comparative Production Example U Aerosol 18 (trade name of N-octadecyl-sulfosuccinic acid monoamide disodium salt manufactured by American Cyanamid) 3.00 parts Aerosol AY65 (American Cyanamid) 1.50 parts Sodium bicarbonate 0.25 parts Deionized water (first) 39.75 parts Ammonium persulfate 0.25 parts Deionized water (second) 7.25 parts Styrene 11.975 parts n-butyl methacrylate 11.050 parts 2-Ethylhexyl acrylate 9.215 parts 2-Hydroxypropyl methacrylate 11.050 parts Acrylic acid 0.95 parts Trimethylolpropane triacrylate 3.85 parts Aerosol 18, Aerosol AY65 in a five-necked flask equipped with a reflux condenser, thermometer and stirrer , Sodium bicarbonate And first deionized water. The ammonium persulfate and the second deionized water were premixed and placed in a small dropping funnel. Styrene, n-butyl methacrylate, 2-ethylhexyl acrylate, 2-hydroxypropyl methacrylate, acrylic acid, and trimethylolpropane triacrylate were premixed and placed in another dropping funnel. The mixture in the flask was heated to 87 ± 2 ° C., at which time 10% of the ammonium persulfate solution was added. α,
The β-ethylenically unsaturated monomer was continuously dropped at a constant rate into the flask in 2 hours and 30 minutes, and at the same time, the remaining ammonium persulfate solution was dropped at a constant rate in 3 hours. After the ammonium persulfate solution was added dropwise, the mixture was cooled to room temperature and the aqueous polymer dispersion was taken out. The heating residue of this dispersion was 48.2%, and the average particle size was 153 nm.

Next, the polymer aqueous dispersion was converted to a non-aqueous one by performing the following operations.

n-butyl alcohol 17.60 parts cellosolve acetate 17.60 parts aqueous polymer dispersion above 11.37 parts t-butyl-2-ethylhexanoate (50% solution in mineral spirits) 0.71 part premix I styrene 13.34 parts n-butyl methacrylate 11.50 parts n Dodecyl mercaptan 1.70 parts Premix II 2-ethylhexyl acrylate 10.76 parts 2-hydroxyethyl acrylate 9.25 parts Acrylic acid 0.97 parts t-butyl-2-ethylhexanoate (50% solution in mineral spirits) 4.54 parts Additional catalyst t- Butyl-2-ethylhexanoate (50% solution in mineral spirits) 0.23 parts Cellosolp acetate 0.43 parts n-butyl alcohol, acetic acid in a 5-neck flask equipped with a reflux condenser, Dean Stark trap, thermometer and stirrer Cellosolve, aqueous polymer dispersion and t-butyl Chill-2-ethylhexanoate was charged. Styrene, n-butyl methacrylate and n-dodecyl mercaptan were premixed and placed in a dropping funnel (Premix I). 2-Ethylhexyl acrylate, 2-hydroxyethyl acrylate, acrylic acid and t-butyl-2-ethylhexanoate were premixed and placed in a second dropping funnel (Premix II). The solvent, aqueous polymer dispersion and t-butyl-2-ethylhexanoate were heated to 95 ° C. and refluxed. Thereafter, premixes I and II were simultaneously dropped at a constant rate over 4 hours. α, β-
During the addition of the ethylenically unsaturated monomer, water was continuously removed from the aqueous polymer dispersion by azeotropic distillation from the Dean-Stark trap. After dripping of premixes I and II,
Immediately, a mixture of t-butyl-2-ethylhexanoate and cellosolve acetate was dropped at a constant speed over 1 hour. After refluxing until all the theoretical amount of water was removed, the mixture was cooled to obtain a polymer non-aqueous dispersion U. This polymer non-aqueous dispersion contains 11% of crosslinked polymer particles based on the total heating residue with the resin, and has the following characteristics: heating residue: 56.2%, average particle size: 0.17 μm, Gardner viscosity (25 ° C.) T, the acid value of nonvolatile components was 17.5.

APPLICATION EXAMPLES 1 to 11 Application to 2-coat 1-baked metallic paint (A) Production of base coat paint A third coat was prepared using polymer non-aqueous dispersions A to H and L to N.
A paint was manufactured with the composition shown in the table, and thinner (toluene / acetic acid n
-Butyl = 1/1 weight ratio) and paint viscosity (Ford Cup No.
4, 20 ° C for 14 seconds).

However, in Application Examples 7, 8 and 9, coronate EH was added and mixed immediately before dilution.

(B) Production of clear coating material Using polymer non-aqueous dispersions A to H and L to N,
Paints were prepared according to the compositions shown in the table, and diluted with a thinner (xylene / n-butylpropionate = 1/1 weight ratio) to a coating viscosity (Ford Cup No. 4, 25 seconds at 20 ° C.).

However, in Application Examples 7, 8 and 9, coronate EH was added and mixed immediately before dilution.

(C) Preparation of coating film Cathodic electrodeposition paint Aqua No.4 on mild steel sheet treated with zinc phosphate
200 (trade name, manufactured by Nippon Oil & Fat Co., Ltd.) is electrodeposited to a dry film thickness of 20 μm and baked at 175 ° C. for 25 minutes. ) Was applied by air spraying so as to have a dry film thickness of 40 μm, and the base coat paints 1 (A) to 11 (A) were air-sprayed on test plates baked at 140 ° C. for 30 minutes. Seconds, dry film thickness in 2 stages
Painted to 15 μm, set up vertically at 20 ° C for 3 minutes, set the above clear paints 1 (B) to 11 (B) by air spray, and kept it upright at 140 ° C for 30 minutes ( However, application examples 7, 8 and 9 were baked at 120 ° C. for 30 minutes).

As shown in Table 5, coating films excellent in aluminum orientation, sagging limit film thickness, and coating film appearance were obtained.

Application Examples 12 to 19 Application to One Coat Solid (A) Production of Paint Using the polymer non-aqueous dispersions I to K and O to S, during the compounding of Table 6, the curing agent was removed and charged into a paint shaker. The particles were dispersed until the particle size became 10 μm or less. Application Example 12 ~
In 14 and 17 to 19, a curing agent was charged and agitated to obtain a one-pack type paint, and in applied examples 15 and 16, a two-pack type paint was used as it was.

(B) Preparation of coating film A paint having the composition shown in Table 6 was thinned (xylene / n-acetic acid n-
Butyl = 9/1 weight ratio) and coating viscosity (Ford Cup No.
4, 25 seconds at 20 ° C). However, for Application Examples 15 and 16, they were added and mixed immediately before dilution.

Then, in the same manner as in Application Examples 1 to 11, the test plate on which the electrodeposition coating film and the intermediate coating film were prepared was applied by air spray coating, and was set upright. The mold paint was baked at 120 ° C. for 30 minutes while standing upright. As shown in Table 7, all of the coating films obtained were excellent in glossiness, sagging limit film thickness, and coating film appearance.

Comparative Examples 1 and 2 (A) Production of base coat paint A paint was produced with the composition shown in Table 8 using polymer non-aqueous dispersions T and U, and thinner (toluene / n-butyl acetate =
Paint viscosity (Ford Cup No.4, 1 at 20 ° C)
4 seconds).

(B) Production of clear paint A paint was produced with the composition shown in Table 8 using polymer non-aqueous dispersions T and U, and the coating viscosity was measured with thinner (xylene / n-butyl propionate = 1/1 weight ratio). (Ford Cup No.
4, 25 seconds at 20 ° C).

(C) Preparation of coating film On the test plate in which an electrodeposition coating film and an intermediate coating film were prepared in the same manner as in Application Examples 1 to 11, the above base coat paint and clear coating were applied in exactly the same manner as in Application Examples 1 to 11. Bake after painting with air spray. As a result, as shown in Table 9, in Comparative Example 1, the crosslinked polymer fine particles were crosslinked with a polyfunctional α, β-ethylenically unsaturated monomer, and in Comparative Example 2, the functional groups capable of reacting with each other were used. Since the particles are cross-linked using a combination of α, β-ethylenically unsaturated monomers having a group, in each case, the α, β-ethylenically unsaturated group remains on the particle surface and the binder and Was inferior in the appearance of the coating film as compared with Application Example 1 due to a decrease in compatibility.

Comparative Examples 3 and 4 (A) Production of Paint In Comparative Example 3, a polymer non-aqueous dispersion T was used, and in Comparative Example 4, no polymer non-aqueous dispersion was used.
Except for the hardener, put it in a paint shaker, and the particle size is 10
The dispersion was continued until the particle size became less than μm.

(B) Preparation of coating film A paint having the composition shown in Table 8 was applied to a thinner (xylene / n-acetic acid-
Butyl = 9/1 weight ratio) and coating viscosity (Ford Cup No.
4, 25 seconds at 20 ° C). Then, in the same manner as in Application Examples 1 to 11, the test plate on which the electrodeposition coating film and the intermediate coating film were formed was applied by air spray coating, and after setting vertically, 140
Bake at ℃ for 30 minutes.

As a result, in Comparative Example 3, for the same reason as Comparative Example 2, the coating film appearance was inferior to Application Example 17.

In Comparative Example 4, since the crosslinked polymer fine particles were not included, the sagging resistance of the coating film was poor, and the appearance of the coating film was poor.

Claims (2)

(57) [Claims] 1. Crosslinked polymer fine particles comprising the following components: (a) the following groups: acetoacetoxy group, alkylated aminomethyl ether group, cyclocarbonate group, hydroxyl group, isocyanate group, epoxy group, amino group, carboxyl group Α-β-ethylenically unsaturated monomer having a cross-linkable functional group selected from the group consisting of a group and a plurality of these groups 3-80% by weight (b) other α, β-ethylenically unsaturated monomer (C) formaldehyde or an amino resin having a weight average molecular weight of 1000 or less, a polyisocyanate compound, a polyfunctional α,
Among 2-50% by weight of a crosslinking agent having a group capable of reacting with the component (a), which is selected from the group consisting of a β-unsaturated carbonyl compound, a polyepoxy compound, a polyol, a polycarboxylic acid compound and a mixture thereof, , (A) and (b) are polymerized by a polymerization method selected from emulsion polymerization, suspension polymerization and non-aqueous dispersion polymerization to obtain fine particles, and then (c) is added to the fine particles. )
The crosslinked polymer fine particles are characterized in that they are internally crosslinked by incorporating a component and reacting with a crosslinkable functional group in the component (a). 2. A coating composition comprising the crosslinked polymer fine particles according to claim 1 as an essential component.