JPH03215504A - Crosslinked polymer particle - Google Patents

Abstract

PURPOSE:To prepare crosslinked polymer particles excellent in the compatibility and useful as a flowability-controlling agent of a coating material by reacting a crosslinkable alpha,beta-ethylenically unsatd. monomer, another alpha,beta-ethylenically unsatd. monomer, and a crosslinker in a specified wt. ratio in a specific way. CONSTITUTION:3-80wt.% crosslinkable alpha,beta-ethylenically unsatd. monomer (A) (e.g. acetoacetoxyethyl methacrylate), 30-95wt.% other alpha,beta-ethylenically unsatd. monomer (B), and 2-50wt.% crosslinker (C) reactive with component A (e.g. isophorone diisocyanate) are prepd. First, component A and component B are copolymerized by emulsion, suspension, or nonaq. dispersion polymn. to give polymer particles. Then, component C is incorporated into the particles and reacted with a polymerizable group of component A in the particles to crosslink, thus giving crosslinked polymer particles.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to crosslinked polymer fine particles useful as a fluidity modifier for paints with excellent compatibility.

(Conventional technology) In recent years, the durability of paint films has made great progress and it has become possible to obtain advanced performance. There is a strong demand for quality.

In order to improve the appearance quality of the casing film, it is necessary to make the film thicker in order to hide the irregularities on the surface of the object to be coated and to improve the smoothness of the coating film itself. At this time, in order to achieve a thick film on all parts of the object to be coated, whether vertical or horizontal, a fluidity regulator is often used in the paint.

For such purposes, polymer fine particles (hereinafter sometimes simply referred to as particles) have been attracting attention and being applied for a long time because they can impart structural viscosity through interparticle interaction in paints. At this time, if the inside of the polymer fine particles is three-dimensionally cross-linked, it is possible to maintain a stable particle morphology without dissolving even in non-aqueous paints, and as a result, it is possible to stably exhibit a high level of flow control effect. It has many advantages and is used to prevent paint from sagging and as an alignment agent for metal pigments.

For example, Japanese Unexamined Patent Publication No. 53-133233 and Japanese Unexamined Patent Publication No. 53-133-
133234 discloses that α,β-ethylenically unsaturated monomers are subjected to non-aqueous dispersion polymerization using a comb-shaped copolymer having a 5-mole condensate structure of I2-hydroxystearic acid in the side chain as a dispersion stabilizer. Examples have been disclosed in which the polymer fine particles obtained by this method are used as anti-sagging agents for paints and alignment adjusting agents for metal pigments. The interior of the polymer fine 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. It is being

Also, US Patent Nos. 4,290,932 and 4,377,661
No. 4414357, No. 4477536, and No. 4598111, after emulsion polymerization of α,β-ethylenically unsaturated monomers was carried out to obtain fine polymer particles having ionic groups on the surface of the particles, the particles were Examples have been disclosed in which it is converted into an aqueous system and similarly used as an anti-sagging agent for paints and an alignment control agent for metal pigments. The interior of the polymer fine particles obtained here is three-dimensionally crosslinked by copolymerizing a polyfunctional α,β-ethylenically unsaturated monomer.

Also, U.S. Patent Nos. 4,540,740 and 46,110
No. 26 also discloses an example in which fine polymer particles are obtained by emulsion polymerization, and then used as an anti-sagging agent for paints or an orientation adjuster for metal pigments after spray drying or non-aqueous conversion treatment. The interior of the particles obtained here is three-dimensionally crosslinked through an esterification reaction between an epoxy group-containing α,β-ethylenically unsaturated monomer and a sulfonic acid group-containing α,β-ethylenically unsaturated monomer. It is being

(Invention or problem to be solved) However, US Patent Nos. 4,290,932 and 437
In the methods of No. 7661, No. 4414357, No. 4477536, and No. 4598111, polyfunctional α. Not all of the double bonds of the β-ethylenically unsaturated monomer are copolymerized, and a considerable portion remains unreacted and oriented on the particle surface. Since such particles have α,β-ethylenically unsaturated groups on their surfaces, when used in paints, they have insufficient compatibility with binders, and are especially compatible with acrylic resins such as polyester resins. In difficult paint systems, particles may aggregate to form lumps.

Also, JP-A-53-133233, JP-A No. 53-1332
No. 34, U.S. Pat. No. 4,540,740 and U.S. Pat. No. 4,540,740
In the method of No. 11026, a combination of α,β-ethylenically unsaturated monomers having functional groups that can react with each other is used to form particles through radical polymerization and three-dimensional crosslinking within the particles through an esterification reaction. Is going.

Even with this method, if the esterification reaction proceeds faster than the radical polymerization, α,β-ethylenically unsaturated groups may remain on the particle surface, resulting in insufficient compatibility with the paint binder. It often happened.

(Means for Solving the Problems) As a result of intensive research into methods for solving these problems, the present inventors found that after forming polymer fine particles by radical polymerization, impregnating the inside of the fine particles with a crosslinking agent, By three-dimensional crosslinking, almost all α. We discovered that it is possible to produce fine polymer particles that do not contain β-ethylenically unsaturated groups and that are highly three-dimensionally crosslinked inside the particles, and that these particles exhibit excellent compatibility with a wide range of paint binders. The invention was completed.

That is, the present invention provides fine polymer particles produced by a polymerization method selected from emulsion polymerization, suspension polymerization, or non-aqueous dispersion polymerization of α,β-ethylenically unsaturated monomers, in which the interior of the particles is as follows: These are crosslinked polymer fine particles characterized by being crosslinked by the reaction of That is, the following components: (a) 3-80% by weight of α,β-ethylenically unsaturated monomer having a crosslinkable functional group (30-95% by weight of other α,β-ethylenically unsaturated monomers) (c) (a
) 2-50% by weight of the crosslinking agent having a group capable of reacting with the component, component (a) and component (b) are first polymerized by a polymerization method selected from emulsion polymerization, suspension polymerization, or non-aqueous dispersion polymerization. After obtaining fine particles by polymerization, component (c) is subsequently incorporated into the fine particles (reacts with the crosslinkable functional group in the Al component).

The crosslinked polymer fine particles of the present invention have 0. It has an average particle size in the range of 1 to 50 μm, and can be easily synthesized by known polymerization methods such as emulsion polymerization, suspension polymerization, or non-aqueous dispersion polymerization.

For example, in the emulsion polymerization method, even in soap-free emulsion polymerization,
In addition, anionic surfactants, cationic surfactants,
Polymerization using nonionic surfactants or zwitterionic surfactants is also possible and under normal conditions, i.e. 1
Polymerization can be carried out at a nonvolatile concentration of 0 to 50% by weight, a temperature of 40 to 95°C, and a reaction time of 3 to 10 hours. Here, if the nonvolatile content concentration is less than 10% by weight, the production efficiency of the particles is poor, and if it exceeds 50% by weight, the particles will aggregate during polymerization, which is not preferable. Polymerization temperature is 4
If the temperature is less than 0°C, particle formation will be insufficient;
If it exceeds this, the particles will aggregate in the gas phase, which is undesirable.

If the reaction time is less than 3 hours, particle formation will be 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, i.e., a nonvolatile concentration of lO to 50% by weight, a temperature of 40 to 95°C, Polymerization can be carried out in a reaction time of 1 to 10 hours. Here, if the nonvolatile content concentration is less than 10% by weight, the production efficiency of the particles is poor, and if it exceeds 50% by weight, the average particle size of the particles is 50 μm.
When added to a paint in excess of this amount, the appearance of the paint film may actually deteriorate, which is undesirable. Polymerization temperature: 40°C
If it is less than 95°C, particle formation will be insufficient, and if it exceeds 95°C, the particles will aggregate in the gas phase, which is not preferable. If the reaction time is less than 1 hour, particle formation will be insufficient;
If the reaction time exceeds 1O time, this is not preferable since it will only result in a meaningless waste of energy after the reaction is completed.

Furthermore, in the non-aqueous dispersion polymerization method, under normal conditions in a non-polar medium in the presence of a dispersion stabilizer such as a highly butyl etherified melamine resin, Nagaura Naga alkyd resin, or a comb copolymer having a low polar graft group, That is, polymerization can be carried out at a nonvolatile content concentration of 10 to 70% by weight, a temperature of 40 to 140°C, and a reaction time of 2 to 10 hours. Here, if the nonvolatile content concentration is less than 10% by weight, the production efficiency of particles is poor;
Moreover, if it exceeds 70% by weight, the particles will aggregate during polymerization, which is not preferable. If the polymerization temperature is less than 40°C, particle formation will be insufficient, and if it exceeds 140°C, the particles will tend to fuse during polymerization, which is not preferred. If the reaction time is less than 2 hours, particle formation will be insufficient, and if it exceeds 10 hours, it will simply be a meaningless waste of energy after the reaction is completed, 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 of the 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,
α-methylstyrene, p-vinyltoluene, (meth)acrylonitrile, tetracyclo(4.4, 0,
l2゜6. 1 7. 10) Dodecyl-3-(meth)acrylate, (ii) Hydroxyl group-containing α,β-ethylenically unsaturated monomer 2-hydroxyethyl (meth)acrylate, 2-hydroxybubutyr (meth)acrylate, 3-hydroxy Buchibiru (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)
ε of acrylate, 4-hydroxybutyl (meth)acrylate, diventaerythritol hexa(meth)acrylate, 2-hydroxyethyl (meth)acrylate
monocabrolactone (1-10Ji form) adduct, ε-cabrolactone (1-1041 form) adduct of 2-hydroxybrobyl(meth)acrylate l, (ii) epoxy group-containing α,β-ethylenically unsaturated monomer mer glycidyl (meth)acrylate, methylglycidyl (
meth)acrylate, vinyl glycidyl ether (iv) amide group-containing α,β-ethylenically unsaturated monomer acrylamide, methacrylamide (V) aminomethylol group-containing α,β-ethylenically unsaturated monomer N-methylol ( meth)acrylamide (vi) Alkylated aminomethyl ether group-containing αβ-ethylenically unsaturated monomer N-methoxymethyl (meth)acrylamide, N-butoxymethyl (meth)acrylamide, methylacrylamide glycolate methyl ether (vi) Isocyanate group-containing α,β-ethylenically unsaturated monomer isocyanate ethyl (meth)acrylate, m-inoprobenyl α. α-dimethylbenzyl isocyanate, a half block of isophorone diisocyanate with 2-hydroxyethyl (meth)acrylate or 2-hydroxybutyl (meth)acrylate, I,6-
Half-block of hexamethylene diisocyanate with 2-hydroxyethyl (meth)acrylate or 2-hydroxybutyl (meth)acrylate, tolylene diisocyanate and 2-hydroxyethyl (meth)acrylate, or 2-hydroxybutyr Half block product with (meth)acrylate (vi) Cyclocarbonate group-containing α,β-ethylenically unsaturated monomer 4-(meth)acryloyloxymethyl-123dioxolane-2-one, 4-(meth)acryloyloxyethyl -1. 3-dioxolan-2-one (ix) acetoacetoxy group-containing α,β-ethylenically unsaturated monomer 2-acetoacetoxyethyl (meth)acrylate, 2
-acetoacetoxibacetyl (meth)acrylate, (X) amino group-containing α,β-ethylenically unsaturated monomer Nt-butylaminoethyl methacrylate (xi) carboxyl group-containing α,β-ethylenically unsaturated monomer Monomers (meth)acrylic acid, maleic acid, maleic anhydride, itaconic acid, crotonic acid, fumaric acid The composition ratio of the above α,β-ethylenically unsaturated monomers is determined according to the refractive index required for the desired application. The monomer can be selected arbitrarily depending on the ratio, hardness, strength, toughness, glass transition temperature, functional group concentration, acid resistance, alkali resistance, etc., but during emulsion polymerization and suspension polymerization, low polar monomers are It is possible to form more stable particles by blending a high polar monomer as the main component, and by taking care to blend the high polar monomer as the main component with a low polar monomer during non-aqueous dispersion polymerization. Become.

Examples of the polymerization initiator for the α,β-ethylenically unsaturated monomer include penzoylperoxide, 2,4-dichlorobenzoylperoxide, and t-butylberoxy-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), inorganic peroxides such as potassium persulfate, sodium persulfate, ammonium persulfate, etc. These compounds can be used singly or as a mixture of two or more. Of course, in this case, it is also possible to use a redox system in which ferrous salt, acidic sodium sulfite, N,N-dimethylaniline, etc. are used in combination. The content ratio of the above-mentioned polymerization initiator varies depending on the polymerization method, polymerization conditions, type of copolymerization components, etc., but is preferably 0.00 parts by weight based on 100 parts by weight of all α,β-ethylenically unsaturated monomers. It is desirable to use it in a range of 1 to 10 parts by weight. Here, the polymerization initiator is 0
．． If the amount is less than 1 part by weight, particle formation will be insufficient and IO
If it exceeds the polymerization part, the particles tend to aggregate during polymerization, which is not preferable. Although the above polymerization initiator can be selected arbitrarily, it is more preferable to select a water-soluble polymerization initiator for emulsion polymerization, and an oil-soluble polymerization initiator for suspension polymerization and non-aqueous dispersion polymerization to ensure stability. Particles can be formed.

The three-dimensional crosslinking inside the crosslinked polymer fine particles of the present invention is
This 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 1000 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 other α,β-ethylenically unsaturated monomers (i) to (xi) are added as necessary. Fine polymer particles are formed by emulsion polymerization, suspension polymerization, or non-aqueous dispersion polymerization using a composition in which saturated monomers are mixed. Thereafter, an amino resin having a weight average molecular weight of 1000 or less is added to perform a condensation reaction with the acetoacetoxy groups in the particles. Here, the blending amounts of the acetoacetoxy group-containing α,β-ethylenically unsaturated monomer and the amino resin are not particularly limited, but preferably the former is 3-80% by weight, the latter 2-50%
It is desirable to use within a range of % by weight. When the acetoacetoxy group-containing α,β-ethylenically unsaturated monomer is less than 3% by weight or the amino resin is less than 2% by weight,
Three-dimensional crosslinking within the particles becomes insufficient, making it difficult to exert the desired flow regulating effect. On the other hand, if the former exceeds 80% by weight but the latter exceeds 50% by weight, aggregation due to interparticle crosslinking is likely to occur. To become. What is important here is that the weight average molecular weight of the amino resin must be selected to be 1000 or less. If the weight average molecular weight of the amino resin exceeds 1000, the amino resin will be incorporated into the polymer particles and become stiff, resulting in insufficient three-dimensional crosslinking within the particles. Examples of such amino resins include commercially available products such as Cymel 300, Cymel 30l1, Cymel 303, Cymel 327, Cymel 350, Cymel 1116, Cymel 1130 (manufactured by Mitsui Cyanamid ■, trade name), Nicarac MW-30,
MW-22A, MX-40, MX-45 (
Manufactured by Sanwa Chemical ■, product name), Resimin 730, Resimin 73
1, 735, 745, 746, 747, 75
Examples include alkyl etherified melamine resins such as 3, 755, and 764 (manufactured by Monsando ■, trade name).

The condensation reaction between an acetoacetoxy group and an amino resin is usually 6
Preferably, the reaction is carried out at a temperature of 0 to 140°C. If the reaction temperature is less than 60°C, intraparticle crosslinking will be insufficient, and if the reaction temperature exceeds 140°C, the fine polymer particles will settle on the sea, which is not preferable.

In addition, at this time, aromatic sulfonic acids such as p-toluenesulfonic acid, dodecylbenzenesulfonic acid, dinonylnaphthalenesulfonic acid, dinonylnaphthalene disulfonic acid,
It is also possible to promote the condensation reaction by adding an aliphatic sulfonic acid obtained by desodiumization or depotassiumation of an aliphatic sulfonic acid surfactant, or a phosphoric acid 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 1000 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 other α,β-ethylenically unsaturated monomers (i) to (xi) are added as necessary. Fine polymer particles are formed by emulsion polymerization, suspension polymerization, or non-aqueous dispersion polymerization using a composition in which saturated monomers are mixed. Thereafter, a polyisocyanate compound having a weight average molecular weight of 1000 or less is added to carry out an addition reaction with the acetoacetoxy groups in the particles. Here, acetoacetoxy group-containing α
, β-ethylenically unsaturated monomer and poly. The blending amount of the isocyanate compound is not particularly limited, but preferably the former is 3 to 80% by weight and the latter is 2% by weight in the total amount of the constituent materials of the crosslinked polymer fine particles for the same reason as (al).
It is desirable to use it within the range of 50% by weight. Further, the weight average molecular weight of the polyisocyanate compound needs to be selected to be 1000 or less for the same reason as in (a) above.

Such polyisocyanate compounds include tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, 4,4
゛-Methylenebis(cyclohexyl isocyanate),
Methylcyclohexane2. 4 (2.6) Cyisocyanate, 1,3-(isocyanatomethyl)cyclohexane, isophorone diisocyanate, trimethylhexamethylene diisocyanate, and pureed trimer thereof, isocyanurate type 3'I# form, trimethylolpropane , glycerin, trimethylolethane, pentaerythritot, and other adducts with low-molecular polyhydric alcohols.

The addition reaction between the acetoacetoxy group and the polyisocyanate compound is usually preferably carried out at a temperature of room temperature to 140°C. If the reaction temperature exceeds 140°C, it is not preferable because the polymer particles will fuse together. Further, at this time, it is also possible to accelerate the addition reaction by adding a tertiary amine such as dimethyllaurylamine or dimethylbenzylamine, or a metal ester such as dibutyltin dilaurate or tetrabutyl titanate.

(c) Condensation reaction between an 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 by the same method as in fa) above. Thereafter, formaldehyde is added to perform a condensation reaction with the acetoacetoxy groups in the particles. Here, the blending amount of the acetoacetoxy group-containing α,β-ethylenically unsaturated monomer and formaldehyde is not particularly limited, but preferably for the same reason as in (a) above, The former accounts for 3 to 80% by weight of the total amount of constituent materials;
The latter is preferably used in an amount of 2 to 50% by weight.

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

(d) Acetoacetoxy group-containing α. β-ethylenically unsaturated monomer and polyfunctional α with a weight average molecular weight of 1000 or less
, Michael addition reaction with a β-unsaturated carbonyl compound 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-mentioned saliva). Thereafter, a polyfunctional α,β monounsaturated carbonyl compound having a weight average molecular weight of 1000 or less is added, and in the presence of a catalyst such as sodium methoxide, sodium ethoxide, sodium butoxide, etc. A Michael addition reaction is carried out with the acetoacetoxy groups in the particles at a temperature of °C.Here, the blending amount of the acetoacetoxy group-containing α,β-ethylenically unsaturated monomer and the polyfunctional α,β monounsaturated carbonyl compound is Although not particularly limited, the former preferably accounts for 3 in the total amount of constituent materials of the crosslinked polymer fine particles for the same reason as (a) above.
-80% by weight, and the latter is preferably used in a range of 2-50% by weight. Further, it is necessary to select a weight average molecular weight of the polyfunctional α,β monounsaturated carbonyl compound of 1000 or less for the same reason as in (a) above.

Examples of such polyfunctional α,β monounsaturated polyponyl compounds include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, 1.4
-butanediol di(meth)acrylate, l,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, tetrabrobylene glycol di(meth)acrylate, Examples include tribrobylene glycol di(meth)acrylate, trimethylolbroban tri(meth)acrylate, pentaerythritol tri(meth)acrylate, and dipentaerythritol(meth)acrylate.

(e) Acetoacetoxy group-containing α. Addition reaction between a β-ethylenically unsaturated monomer and a polyepoxy compound having a weight average molecular weight of 1000 or less The reaction here can be carried out by the following operation.

That is, first, polymer fine particles are formed by the same method as in (a) above. Thereafter, a polyepoxy compound having a weight average molecular weight of 1000 or less is added to carry out an addition reaction with the acetoacetoxy groups in the particles. Here, the blending amount of the acetoacetoxy group-containing α,β-ethylenically unsaturated monomer and the polyepoxy compound is not particularly limited, but preferably for the same reason as (a) above, the crosslinked polymer fine particles Of the total amount of constituent materials, the former accounts for 3 to 80% by weight, and the latter accounts for 2 to 80% by weight.
It is desirable to use it within the range of 50% by weight. In addition, the weight average molecular weight of the polyepoxy compound is as described in (a) above.
For the same reason, it is necessary to choose one with a value of 1000 or less.

Such polyepoxy compounds include bisphenol A
type epoxide, novolak epoxide, alkylphenol diglycidyl ether, tetraglycidoxytetraphenylethane, phenolphthalein epoxide, resorcinol epoxide, polychlorodiphenyl ether, polybrominated diphenyl ether, polyglycol epoxide, glycerin triglycidyl , diglycidyl adibate, diglycidyl sebatate, diglycidyl phthalate, dimer acid diglycidyl ester, tetraglycidyl amino diphenylmethane, triglycidyl melamine, triglycidyl cyanurate and the like.

The addition reaction between the acetoacetoxy group and the polyepoxy compound is preferably carried out at a temperature of usually 60 to 140°C for the same reason as in (a) above.

Further, at this time, it is also possible to add a catalyst such as dimethyllaurylamine, dimethylbenzylamine, tetramethylammonium chloride, tetraethylammonium chloride, etc. to promote the addition reaction.

(f) Alkylated aminomethyl ether group-containing α,β-
Self-condensation reaction of ethylenically unsaturated monomer The reaction here can be carried out by the following operation. That is, first, the above-mentioned (vi) alkylated aminomethyl ether group-containing α,β-ethylenically unsaturated monomer is used as an essential component, and if necessary, the above-mentioned other α. Fine polymer particles are formed by emulsion polymerization, suspension polymerization, or non-aqueous dispersion polymerization using a composition in which a β-ethylenically unsaturated monomer is mixed. After that, as a self-condensation catalyst, aromatic sulfonic acids such as p-toluenesulfonic acid, dodecylbenzenesulfonic acid, dinonylnaphthalenesulfonic acid, dinonylnaphthalene disulfonic acid, and aliphatic sulfonic acid surfactants are used to desodiumize, Or by adding aliphatic sulfonic acid obtained by depotassium or a phosphoric acid compound, usually 60~
The reaction is carried out at a temperature of 140°C to carry out a self-condensation reaction of the alkylated aminomethyl ether groups in the particles. Here, if the reaction temperature is less than 60°C, intraparticle crosslinking will be insufficient,
If the reaction temperature exceeds 140°C, the polymer particles will fuse together, which is not preferable. The amount of the alkylated aminomethyl ether group-containing α,β-ethylenically unsaturated monomer is not particularly limited, but is preferably 3 to 80% of the total amount of the constituent materials of the crosslinked polymer fine particles. weight%
It is desirable to use it within the range of . Because triple i
If it is less than jk%, three-dimensional crosslinking within the particles will be insufficient, and if it exceeds 80% by weight, aggregation due to interparticle crosslinking will easily occur.

(g) Alkylated aminomethyl ether group-containing α,β-
Condensation reaction between an ethylenically unsaturated monomer and a polyol having a weight average molecular weight of 1000 or less The reaction here can be carried out by the following operation. That is, first, polymer fine particles are formed by the same method as in (f) above. 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 blending amounts of the alkylated aminomethyl ether group-containing α,β-ethylenically unsaturated monomer and the polyol are not particularly limited, but preferably for the same reason as (f) above, the former is 3
The latter is preferably used in a range of 2 to 50% by weight. Further, the weight average molecular weight of the polyol needs to be selected to be 1000 or less in order to facilitate stable incorporation of the polyol into the particles.

Examples of such polyols include ethylene glycol, propylene glycol, 1,3-butylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, glycerin, polyethylene glycol 200, polyethylene glycol 300, polyethylene glycol 400, polyethylene glycol 600, and Uniole D.
Polyethers such as 400, 70 (trade name, polyethylene glycol and polypropylene glycol manufactured by Nippon Oil & Fats Corporation), Blaxel 205, 208, 303, 305, 308 (trade name, polycarbonate manufactured by Daicel Chemical Industries, Ltd.) brolactone), ester polyols such as K-Flex 188 (trade name, ester diol manufactured by King Company), and ester polyols such as Flexolets UD-320 (trade name, urethane diol manufactured by King Company), urethane diol LIP
Urethane diols such as -14-4 (trade name, urethane diol manufactured by Auto Kagaku Kogyo ■) can be mentioned.

(5) Addition reaction between a cyclocarbonate group-containing α,β-ethylenically unsaturated monomer and a polyamino compound having a weight average molecular weight of 1000 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 (vi) is used as an essential component, and if necessary, the other α, β-ethylenically unsaturated monomers (i) to (xi) are added as necessary. Fine polymer particles are formed by emulsion polymerization, suspension polymerization, or non-aqueous dispersion polymerization using a composition in which a β-ethylenically unsaturated monomer is mixed. Thereafter, a polyamino compound having a weight average molecular weight of 1000 or less is added to carry out an addition reaction with the cyclocarbonate-1 group in the particles. Here, cyclocarbonate group-containing α
, β-ethylenically unsaturated monomer and polyamino compound are not particularly limited, but preferably,
The former is preferably used in an amount of 3 to 80% by weight, and the latter is preferably used in an amount of 2 to 50% by weight in the total amount of constituent materials of the crosslinked polymer fine particles. This is because α, β containing cyclocarbonate groups
- If the amount of the ethylenically unsaturated monomer is less than 3% by weight or the polyamino compound is less than 2% by weight, the three-dimensional crosslinking within the particles will be insufficient, making it difficult to exert the desired flow regulating effect, while the former 80 weight exceeds 1k%, but the latter is 50
This is because if it exceeds % by weight, aggregation due to interparticle crosslinking is likely to occur. Further, the weight average molecular weight of the polyamino compound needs to be selected to be 1000 or less in order to make it easy to stably incorporate the polyamino compound into the particles.

Such polyamino compounds include ethylenediamine,
Diethylenetriamine, triethylenethe1-lamin, de1-laethylenepentamine, m-hexamethylenetriamine, epomate, l,3-aminomethylcyclohexane, l,6-hexamethylenediamine, m-phenylenediamine, diaminodiphenylmethane, Diaminodiphenylsulfone, 4, 7. Examples include 10-1-lisoxatofudecane-1-13-diamine, bis(3-aminobrobyl) polydetrahydride furan, and the like.

The addition reaction between a cyclocarbonate group and a polyamino compound is usually preferably carried out at a temperature of room temperature to 140°C. If the reaction temperature exceeds 140°C, the polymer particles will fuse together, which is not preferable.

(i) Condensation reaction between a hydroxyl group-containing α,β-ethylenically unsaturated monomer and an amino resin having a weight average molecular weight of ffilOOOO or less The reaction here 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 if necessary, other α,β-ethylenically unsaturated monomers of the above (i) to (xi) are added. Polymer fine particles are formed by emulsion polymerization, suspension polymerization, or non-aqueous dispersion polymerization using a composition in which polymers are mixed. after that,
Adding an amino resin with a weight average molecular weight of 000 or less,
Performs a condensation reaction with the hydroxyl groups in the particles.

Here, the blending amount of the hydroxyl group-containing α,β-ethylenically unsaturated monomer and the amino resin is not particularly limited, but preferably, for the same reason as in (a) above, the amount of the crosslinked polymer fine particles is It is desirable that the former be used in an amount of 3 to 80% by weight, and the latter in an amount of 2 to 50% by weight, based on the total amount of the constituent materials. Further, the type of amino resin and the reaction conditions with the hydroxyl group can be exactly the same as in (a) above.

(j) Addition reaction between a hydroxyl group-containing α,β-ethylenically unsaturated monomer and a polyisocyanate compound having a weight average molecular weight of 1000 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 (i) above. Then, the weight average molecule ffi1000
The following polyisocyanate compound is added to carry out an addition reaction with the hydroxyl groups in the particles. Here, hydroxyl group-containing α, β-
The blending amounts of the ethylenically unsaturated monomer and the polyisocyanate compound are not particularly limited, but for the same reason as (a) above, the former is preferably 3% of the total amount of constituent materials of the crosslinked polymer fine particles. -80% by weight, and the latter is preferably used in a range of 2-50% by weight. Further, the type of polyisocyanate compound and the reaction conditions with the hydroxyl group can be exactly the same as in (b) above.

(k) Addition reaction between an isocyanate group-containing α,β-ethylenically unsaturated monomer and a polyol having a weight average molecular weight of 1000 or less The reaction here can be carried out by the following procedure.

That is, first, the isocyanate group-containing α of the above (vj)
, β-ethylenically unsaturated monomer is an essential component, and if necessary, other α,β-ethylenically unsaturated monomers of the above (i) to (xi) are mixed. Fine polymer particles are formed by turbidity polymerization or non-aqueous dispersion polymerization.

Thereafter, a polyol having a weight average molecular weight of 1000 or less as described above is added and an addition reaction is carried out with the isocyanate groups in the particles.
- The blending amount of the ethylenically unsaturated monomer and polyol is not particularly limited, but preferably the above (a)
For the same reason as above, in the total amount of constituent materials of crosslinked polymer fine particles,
The former is preferably used in an amount of 3 to 80% by weight, and the latter is preferably used in an amount of 2 to 50% by weight.

The addition reaction between the isocyanate group and the polyester is usually preferably carried out at a temperature of room temperature to 140°C. If the reaction temperature exceeds 140°C, the polymer particles will fuse together, which is not preferable. Further, at this time, it is also possible to accelerate the addition reaction by adding a tertiary amine such as dimethyllaurylamine or dimethylbenzylamine, or a metal ester such as dibutyltin dilaurate or tetrabutyl titanate.

(1) Addition reaction between an isocyanate group-containing α,β-ethylenically unsaturated monomer and a polymercapto compound having a weight average molecular weight of iooo or less The reaction here can be carried out by the following operation.

That is, first, polymer fine particles are formed by the same method as in (k) above. Thereafter, a polymercapto compound having a weight average molecular weight of 1000 or less is added to carry out an addition reaction with the isocyanate groups in the particles. Here, the blending amount of the isocyanate group-containing α,β-ethylenically unsaturated monomer and the borimerkabuto compound is not particularly limited, but preferably crosslinked polymer fine particles are used for the same reason as in (a) above. Of the total amount of constituent materials, the former accounts for 3 to 80% by weight, and the latter accounts for 2% by weight.
It is desirable to use it within the range of 50% by weight. In addition, the weight average molecular weight of the polymercapto compound is as described above (
For the same reason as a), it is necessary to select a value of 1000 or less.

Examples of such polymercapto compounds include ethanedil, 1. 3- Brobanjichi Saiichiru, 1,4-
Butanediol, ethylene glycol dithioglycolate, l,4-butanediol dithioprobionate, trimethylolpropane tris(thioglycolate)
, trimethylolpropane tris (β-thiobrobionate), pentaerythritol tetrakis (thioglycolate), pentaerythritol tetrakis (β-thiobrobionate), and the like.

The addition reaction between an isocyanate group and a polymercapto group is preferably carried out at a temperature of usually room temperature to 140°C for the same reason as the former (kl).

(e) Addition reaction between an isocyanate group-containing α,β-ethylenically unsaturated monomer and a polyamino compound having a weight average molecular weight of 1000 or less The reaction here can be carried out by the following operation.

That is, first, polymer fine particles are formed by the same method as in (k) above. Thereafter, a polyamino compound having a weight average molecular weight of 1000 or less as described in (hl) is added, and an addition reaction is carried out with the isocyanate groups in the particles. The compounding amount of the compound is not particularly limited, but preferably, for the same reason as (a) above, the former is 3 to 80% by weight based on the total amount of the constituent materials of the crosslinked polymer fine particles.
The latter is preferably used in an amount of 2 to 50% by weight.

The addition reaction between an isocyanate group and a polyamino compound can usually be carried out easily at room temperature.

(nl Addition reaction between an epoxy group-containing α,β-ethylenically unsaturated monomer and a polyamino compound having a weight average molecular weight of 1000 or less) The reaction here can be carried out by the following operation.

That is, first, the epoxy group-containing α,β-
Emulsion polymerization, suspension polymerization or Fine polymer particles are formed by non-aqueous dispersion polymerization.

Thereafter, a polyamino compound having a weight average molecular weight of 1000 or less as described in the above-mentioned company is added to carry out an addition reaction with the epoxy groups in the particles. Here, the blending amounts of the epoxy group-containing α,β-ethylenically unsaturated monomer and the polyamino compound are:
Although not particularly limited, the former is preferably used in an amount of 3 to 80% by weight, and the latter is used in an amount of 2 to 50% by weight based on the same theory as the above-mentioned En. It is desirable that

The addition reaction between an epoxy group and a polyamino compound is described in (h) above.
For the same reason, it is usually preferable to react at a temperature of room temperature to 140°C.

(0) Addition reaction of an epoxy group-containing α,β to ethylenically unsaturated monomer and a polycarboxylic acid compound having a weight average molecular weight of 1000 or less The reaction here can be carried out by the following operation.

That is, first, polymer fine particles are formed by the same method as in (n) above. Thereafter, a polycarboxylic acid compound having a weight average molecular weight of 1000 or less is added to carry out an addition reaction with the epoxy groups in the particles. Here, epoxy group-containing α, β-
The blending amount of the ethylenically unsaturated monomer and the polycarboxylic acid compound is not particularly limited, but preferably the former is 3 to 80% by weight and the latter is 2% by weight based on the total amount of the constituent materials of the crosslinked polymer fine particles. It is desirable to use it within the range of 50% by weight. This is because 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, the three-dimensional crosslinking within the particles will be insufficient, resulting in the desired flow control. This is because if the former exceeds 80% by weight, but the latter exceeds 50% by weight, aggregation due to interparticle crosslinking becomes more likely to occur. Further, the weight average molecular weight of the polycarboxylic acid compound needs to be selected to be 1000 or less in order to facilitate the stable incorporation of the polycarboxylic acid compound into the particles.

Ru.

Examples of such polycarboxylic acid compounds include phthalic acid, phthalic anhydride, terephthalic acid, isophthalic acid, hexahydrophthalic anhydride, trimellitic anhydride, trimellitic acid, pyromellitic acid, 3,6-endomethylenetetrahydride anhydride, etc. Phthalic acid, 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 acid esters derived from these polybasic acids and polyhydric alcohols.

The addition reaction between an epoxy group and a polycarboxylic acid compound is usually preferably carried out at a temperature of 60 to 140°C. If the reaction temperature is less than 60°C, intraparticle crosslinking will be insufficient,
If the reaction temperature exceeds 140°C, the polymer fine particles will fuse together, which is not preferable. In addition, at this time, the tel
It is also possible to accelerate the addition reaction by adding the catalyst described in .

(p) Addition reaction between an epoxy group-containing α,β-ethylenically unsaturated monomer and a polymercapto compound having a weight average molecular weight of 1000 or less The reaction here can be carried out by the following operation.

That is, first, polymer fine particles are formed by the same method as in (n) above. Then, adding the polymercapto compound having a weight average molecular weight of 1000 or less as described in (11),
Performs an addition reaction with the epoxy groups in the particles. Here, the blending amount of the epoxy group-containing α,β-ethylenically unsaturated monomer and the borimerkabuto compound is not particularly limited, but preferably, for the same reason as (0) above, a crosslinked polymer is used. The former accounts for 3 to 80% by weight of the total amount of constituent materials of the fine particles;
The latter is preferably used in an amount of 2 to 50% by weight.

The addition reaction between an epoxy group and a polymercapto compound is preferably carried out at a temperature of usually room temperature to 140°C. If the reaction temperature exceeds 140°C, the polymer particles will fuse together, which is not preferable.

(Q) Addition reaction between amino group-containing α,β-ethylenically unsaturated monomer and polyisocyanate compound having a weight average molecular weight of 1000 or less The reaction here can be carried out by the following operation.

That is, first, the amino group-containing α,β-ethylenically unsaturated monomer (X) is used as an essential component, and if necessary, the α,β-ethylenically unsaturated monomers (i) to (xi) are added as necessary. Fine polymer particles are formed by emulsion polymerization, suspension polymerization, or non-aqueous dispersion polymerization using a mixed composition of the polymers. Then, the above (
The polyisocyanate compound described in b) having a weight average molecular weight of 1000 or less is added to carry out an addition reaction with the amino groups 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
For the same reason, it is desirable that the former be used in an amount of 3 to 80% by weight, and the latter be used in an amount of 2 to 50% by weight in the total amount of constituent materials of the crosslinked polymer fine particles.

The addition reaction between an amino group and a polyisocyanate compound can usually be carried out easily 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 less than itoo 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 (Q+). Thereafter, a polyepoxy compound having a weight average molecular weight of 1000 or less as described in curve (e) is added to cause an addition reaction with the amino groups in the particles. The amount of the amino group-containing α,β ethylenically unsaturated monomer and the polyepoxy compound is not particularly limited, but preferably for the same reason as (a) above, crosslinking is carried out. The former accounts for 3 to 80% by weight, and the latter accounts for 2 to 80% by weight of the total amount of constituent materials of the polymer fine particles.
It is desirable to use it within the range of 50% by weight.

The addition reaction between an amino group and a polyepoxy compound is carried out using the above (I
For the same reason as 1), it is usually preferable to react at a temperature of room temperature to 140°C.

(S) Addition reaction between a carpogycyl group-containing α,β-ethylenically unsaturated monomer and a polyepoxy compound having a weight average molecular star of 1000 or less The reaction here can be carried out by the following operation.

That is, first, the carpoxy group-containing α, β of (xi)
- Emulsion polymerization or suspension polymerization with a composition in which an ethylenically unsaturated monomer is an essential component, and other α,β-ethylenically unsaturated monomers as described in (i) to (x) are mixed as necessary. Alternatively, fine polymer particles are formed by non-aqueous dispersion polymerization. Thereafter, the polyepoxy compound having a weight average molecular weight of 1000 or less as described in (e) above is added to carry out an addition reaction with the carboxyl groups in the particles. Here, 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 (a) above, the former is It is desirable to use the latter in an amount of 3 to 80% by weight, and the latter in an amount of 2 to 50% by weight.

The addition reaction between a carboxyl group and a polyepoxy compound is
For the same reason as (a) above, it is usually preferable to carry out the reaction at a temperature of 60 to 140°C. In addition, at this time, the above (e
It is also possible to accelerate the addition reaction by adding the catalyst described in ).

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 polymerization can be added to water-based paints as they are, but in order to be applied to non-aqueous casings, it is necessary to remove water. There are two methods for this: spray drying and conversion to a non-aqueous dispersion system.

However, the spray drying method is not preferable because the crosslinked polymer fine particles tend to aggregate during drying, making it difficult to exhibit 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 is less likely to occur.

In this method, an organic solvent with a solubility in water at 20°C or less than 5% by weight is added to the aqueous dispersion, and then an organic acid amine salt is added and left to stand, thereby creating a system with two layers: an organic layer and an aqueous layer. Separate into layers.

The organic solvent used here whose solubility in water at 20°C is 5% by weight or less can be either a single solvent or a mixed solvent, but when used in a single solvent system, an alcohol-based solvent can be used. Alternatively, it is preferable to use a ketone solvent; if other solvents, for example non-polar solvents such as aliphatic solvents or aromatic solvents, are used alone, the crosslinked polymer fine particles may aggregate, so this is preferable. do not have. Examples of alcohol-based solvents having water solubility of 5% by weight or less at 20°C that can be used as a single solvent system include, for example, 21-ethyl-l-butylalfur, 3-hebutyl alcohol, 11-butyl alcohol, 2-octyl alcohol, 2-ethylhexyl alcohol, monononyl alcohol, 3,5.5-}limethyl-1-hexyl alcohol, l-decyl alcohol, l-undecyl alcohol,
Examples of ketone solvents include 1-dodecyl alcohol, methyl n-propyl ketone, methyl iso
-propyl ketone, diethyl ketone, methyl n-butyl ketone, methyl iso-butyl ketone, methyl n-pentyl ketone, di-n-propyl ketone, diiso-butyl ketone, ethyl n-butyl ketone, etc., and the present invention applies to these. The solvents are not limited, and these solvents may be used not only alone but as a mixture of two or more in any proportion.

When using a mixture of two or more solvents, the solvent composition should be adjusted so that it contains at least one of alcohol-based solvents or ketone-based solvents, and the solubility of water at 20°C is 5% by weight or less. In addition to the above-mentioned alcoholic solvents, examples of alcoholic solvents that can be used at this time include n-butyl alcohol, n-pentyl alcohol, n-hexyl alcohol,
sec butyl alcohol, iso-butyl alcohol,
2-bentyl alcohol, 3-pentyl alcohol, 2
-Methyl-1-butyl alcohol, 4-methyl-2-pentanol, etc., and examples of ketone solvents include methyl ethyl ketone in addition to the above-mentioned ketone solvents. As organic solvents other than alcohol solvents and ketone solvents, aliphatic solvents, aromatic solvents, and ester solvents can be used. Examples of aliphatic solvents include n-pentane, n-hexane, Examples include n-hebutane, cyclohexane, methylcyclohexane, and ethylcyclohexane.

Examples of aromatic solvents include benzene, toluene, and xylene. Examples of ester solvents include ethyl acetate, n-propyl acetate, isopropyl acetate, and n-propyl acetate.
-butyl, iso-butyl acetate, sec-butyl acetate, etc., but the present invention is not limited thereto.

The organic acids used in the organic acid amine salt to be added include:
These include organic carboxylic acids, organic sulfonic acids, and organic phosphoric acids. As examples of such organic carboxylic acids,
Examples of organic sulfonic acids are methanesulfonic acid, ethanesulfonic acid, etc.; organic phosphoric acids include monomethyl phosphoric acid, monoethyl phosphoric acid, dimethyl phosphoric acid, diethyl phosphoric acid, etc. There is.

On the other hand, amines include primary amines, secondary amines, tertiary amines,
Any of the class amines can be used, such examples include
Primary amines include monoethylamine, iso-probylamine, n-butylamine, etc., secondary amines include dimethylamine, diethylamine, diethanolamine, etc., and tertiary amines include triethylamine, l-liprobyl, etc. Examples include amine, dimethylethanolamine, and pyridine, but the present invention is not limited thereto.

An organic acid amine salt consisting of the above combination of an organic acid and an amine can be easily produced by mixing a predetermined amount of an organic acid and an amine at room temperature.

According to the above method of converting to a non-aqueous dispersion system, the added organic acid amine salt inhibits the electrical stabilization of the crosslinked polymer particles in water due to the formation of an electric double layer of the surfactant present on the particle surface. and dispersed in the organic layer. After removing the separated water, residual water present in the organic solvent layer is removed by adding orthocarboxylic acid esters such as methyl orthoformate, ethyl orthoformate, methyl orthoacetate, and ethyl orthoacetate to the organic solvent layer. It is then decomposed by heating, but azeotropic distillation is carried out under normal pressure, or 760 mmt {g
It can be completely removed by dehydration under reduced pressure in a temperature range of 50 to 100°C.

Here, when converting the crosslinked polymer fine particles into a non-aqueous dispersion system,
It is also possible to hydrolyze the surfactant and polymerization initiator fragments fixed on the particle surface under a basic or acidic catalyst and remove them from the particle surface. With such particles, since the particle surface can be non-ionized, a high-quality coating film can be obtained without any adverse effects on coating performance, such as a decrease in water resistance.

When using the crosslinked polymer fine particles of the present invention in a paint, for example, acrylic resin, polyester resin, alkyd resin, epoxy resin, epoxy ester resin, silicone resin, fluororesin, polyurethane resin, melamine resin, urea resin, penzoguanamine resin. , phenolic resin, xylene resin, toluene resin, vinyl chloride resin, phenoxy resin,
Cellulose resins and the like can be arbitrarily selected and mixed while considering compatibility. At this time, the crosslinked polymer fine particles can be added in small amounts to the paint and used as a fluidity controlling additive for preventing flow during vertical coating, improving the orientation of metal pigments, etc., and can also be used as the main component of the paint. In addition, in the production of paint, the resins to be mixed are mixed using equipment used in normal paint production, such as a ball mill, paint shaker sand mill, roll mill, kneader, etc., using a normal addition method. Can be manufactured.

At this time, add pigments, dyes, glass flakes,
In addition to colorants such as aluminum paste, additives commonly used in paints, such as pigment dispersants, viscosity modifiers, leveling agents, curing catalysts, anti-gelling agents, ultraviolet absorbers, and radical scavengers, can also be added. .

The paints obtained as described above are, for example, 1 coat solid color, 1 coat metallic color, 2 coats l bake solid color, 2 coats 1 bake metallic color, 3 coats 2 bake solid color, 3 coats 2 bake metallic color, etc. in the form of conventional coating methods such as air spray coating, airless spray coating, electrostatic coating,
Dip coating is used to coat ordinary objects, such as metals and other inorganic materials, plastics and other organic materials, and the temperature is 0.5 to 200 degrees Celsius under normal baking conditions of 60 to 200 degrees Celsius.
A 60 minute bake drying time produces an excellent coating.

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

(Example) Next, the present invention will be explained in more detail with reference to manufacturing examples and comparative examples. In the examples, parts are parts by weight, and % is weight %.

(Emulsion polymerization example) Production example A Surfactant aqueous solution Deionized water 380. 0 parts Ravisol B90 (described later) 5.5 parts Polymerization initiator aqueous solution -1 Deionized water 10.0 parts Ammonium persulfate 0.3 parts α,β-ethylenically unsaturated monomer mixture acetoacetoxyethyl methacrylate (described later) 22 ．． 5 parts n-butyl methacrylate 66.4 parts Polymerization initiator aqueous solution -2 Deionized water 10.0 parts Ammonium persulfate 0.3 parts Crosslinking agent isophorone diisocyanate 11.1 parts Catalyst dibutyltin dilaurate 0.5 parts Stirrer, reflux cooling A surfactant aqueous solution was charged into a flask equipped with a dropping funnel (two), a nitrogen introduction tube, and a thermometer, and the temperature was raised to 80°C under a nitrogen stream to form a polymerization initiator aqueous solution-1.
added. After raising the temperature to 80°C again, the α,β-ethylenically unsaturated monomer mixture was added dropwise over 3 hours while keeping the mixture in the flask at 80±2°C. During the dropwise addition of the monomer mixture, the polymerization initiator aqueous solution was added 1 hour after the start of the dropwise addition.
2 was added dropwise over 2 hours. After the completion of dropping α,β-ethylenically unsaturated monomer and polymerization initiator aqueous solution-2,
After polymerization at .degree. C. for 2 hours, a crosslinking agent and catalyst were added, and the reaction temperature was raised to 95.degree. Thereafter, stirring was continued at 95° C. for 4 hours to obtain an aqueous dispersion of crosslinked polymer fine particles with a heating residue of 20%.

Next, 2 methyl pentyl ketone was added to 500 parts of this aqueous dispersion.
00 parts and 22.7 parts of a 3N aqueous sodium hydroxide solution were charged, and a hydrolysis reaction was carried out at 85±2°C for 3 hours. Next, the temperature was lowered to 80°C, and after neutralization by adding 22.7 parts of a 3N formic acid aqueous solution, 166 parts of a solution of acrylic resin A (described below) was added as a particle dispersion stabilizing resin. After adding 7 parts and stirring for 10 minutes, 2 parts of triethylamine acetate was added.
Immediately after adding 25 parts of a 0% aqueous solution (described later), stirring was stopped and the mixture was allowed to stand. An organic layer in which crosslinked polymer fine particles were dispersed was separated into an upper layer and an aqueous layer below, so the lower aqueous layer was removed.

Add 20% deionized water to the remaining organic layer containing dispersed polymer particles.
0 parts was added, the temperature was raised to 70°C with stirring, and when the temperature reached 70°C, 12% of a 20% aqueous solution of triethylamine acetate was added.
．． 5 parts were added, stirring was immediately stopped, and the mixture was allowed to stand still. Once again, two layers were separated: an organic layer in which cross-linked polymer fine particles were dispersed, and an aqueous layer in the lower layer, so the lower aqueous layer was removed. The remaining organic layer contained 3.5% by weight as measured by a Karl Fischer moisture meter.
of water remained.

Next, the temperature of the organic layer was cooled to 50°C, and 94.2 parts of methyl nitrate was added dropwise from the dropping funnel over 30 minutes, and the reaction was continued at 50°C for 2 hours to decompose the remaining water. .

After that, 130 parts of xylene was added, a new Dean-Stark trap was installed between the reflux condenser and the flask, the upper part of the reflux condenser was connected to the aspirator, and the pressure inside the flask was reduced to 300 ± 100 mmHg, 8
A non-aqueous polymer dispersion A having the properties shown in Table 1 was obtained by removing the solvent under conditions of 0±io''C until the heating residue became 50±1.5%.

Production Examples B~■ Using the same equipment as Production Example A, emulsion polymerization and non-aqueous conversion treatment were carried out in exactly the same manner as Production Example A, based on the formulations shown in Table 1 B~■, respectively. A non-aqueous polymer dispersion B-1 having the characteristics described in 1 was obtained.

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

(Suspension polymerization example) Production example J Stabilizer aqueous solution Deionized water 400. 0 parts Denkabovar Kl7E (described below) 5.5 parts α,β-ethylenically unsaturated monomer mixture t-butylaminoethyl methacrylate 37.0 parts n-
Butyl methacrylate 51.9 parts Perbutyl O
(described later) 2.0 parts crosslinking agent isophorone diisocyanate 11.1 parts stirring device,
The aqueous stabilizer solution was placed in a flask equipped with a reflux condenser, dropping funnel, nitrogen inlet tube, and thermometer, and heated for 80 minutes under a nitrogen stream.
After raising the temperature to 80±2°C, the α,β-ethylenically unsaturated monomer mixture was added dropwise over 3 hours.

After the dropwise addition was completed, polymerization was further carried out at 80°C for 2 hours, then a crosslinking agent was added and the crosslinking reaction was continued at 80°C for 2 hours.
An aqueous dispersion of crosslinked polymer fine particles with a heating residue of 20% was obtained. Next, this aqueous dispersion was treated in exactly the same manner as in Production Example A to obtain a non-aqueous polymer dispersion J having the properties listed in Table 1.

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

Table 1 Footnotes (Note 1) Surfactant (a) Ravisol B90 (manufactured by NOF ■, trade name of sodium di-2-ethylhexyl sulfosuccinate, active ingredient 90%) (manufactured by ■, trade name of octadecyldimethylbenzylammonium chloride, active ingredient 100%) (c) Syntrex LIOO (manufactured by NOF ■, trade name of sodium lauryl sulfate, active ingredient 100%) (d) POESMS: Abbreviation, polyoxy Ethylene sorbitol monostearate (Note 2) Stabilizer K17E (manufactured by Denki Kagaku Kogyo ■, fully saponified polyvinyl alcohol, active ingredient 94%) (Note 3) Polymerization initiator (a) (NH.) 2320t: Ammonium persulfate (bl Na2S20*: Sodium persulfate (
c) AAP-HCI: Abbreviation, 2.2-1-azobis(2-amidinopropane) dihydrochloride (d) K2S20$: Potassium persulfate (e) Perbutyl 0 (manufactured by NOF ■, t-butylberoxy 2- Trade name of ethylhexanoate, active ingredient 100%) (Note 4) Crosslinkable α,β-ethylenically unsaturated monomer AAE
M: Acetoacetoxyethyl methacrylate (manufactured by Eastman Kodak Company, active ingredient 95%) MPC: 4-methacrylate oxymethyl-1,3
-Dioxolan-2-one (cyclocarbonate group-containing monomer obtained by adding carbon dioxide to glycidyl methacrylate, active ingredient 95%) HPMA: 2-Hydroxybrobyl methacrylate IE
MA: 2-isocyanatoethyl methacrylate GMA: glycidyl methacrylate TBAEMA
: t-Butylaminoethyl methacrylate (Note 5) and other α,β-ethylenically unsaturated monomers BMA:
n-butyl methacrylate BA: n-butyl acrylate E}fMA: 2-ethylhexyl methacrylate (Note 6) crosslinking agent IPDI: Isophorone diisocyanate (weight average molecular weight 222) HCHO: 37% of formalin (polymerization average molecular weight 30)
Aqueous solution TMPTA: Trimethylolpropane triacrylate (polymerization average molecular weight 2%) GTG: Glycerin liglycidyl (weight average molecular weight 260) TET: Triethylenetetramine (weight average molecular weight 146) PETG: Pentaerythritol tetrakis (thioglycolate) ( Yodo Chemical (made by Kiki, mercapto equivalent 118
) (Note 7) Catalyst DBTDL: Dibutyltin dilaurate BDMA:
Dimethylbenzylamine DBU: Manufactured by San Abbott, 1,8-acerbicyclo(5.4.0) undecene-7 (Note 8) dispersion stabilized resin solution (a) Acrylic A Stirrer, thermometer, reflux condenser , 42 parts of xylene was charged into a reactor equipped with a nitrogen gas introduction pipe and a dropping funnel,
The mixture was heated and stirred while introducing nitrogen gas, and when the temperature reached 140°C, a mixture of monomer components and a polymerization initiator shown below was added dropwise from the dropping funnel at a constant temperature of 140°C.

Robeyl methacrylate 36.4 parts 2-
Ethylhexyl methacrylate 11.7 parts 2-hydroxylethyl methacrylate 11.1 parts acrylic acid
After dropping 3.0 parts of 0.8 parts t-butylperoxybenzoe-1-1, 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) Acrydik A-413-7OS (Dainippon Ink Chemical Industry vFJ, trade name of acrylic resin solution, heating residue 70%) (c) John Kryl 500 (manufactured by Johnson Wax Co., Ltd.)
(trade name of acrylic resin solution, heating residue 80%) (d) Alobratz 1713-R60 (manufactured by Nissaku Arrow Co., Ltd., trade name of silicone polyester resin solution, heating residue 60%,
Hydroxyl value l40) (e) Betsu-1 Light M-6602-6OS (manufactured by Dainippon Ink & Chemicals, trade name of alkyd resin solution, heating residue 60%) (Note 9) (a) heating residue: JIS K 5400, 8.2
+. :evening.

(b) Viscosity: Measured using a Brookfield viscometer.

60 rpm, 20°C (cl average particle size: measured with “Naicomp, Model 370” (trade name) manufactured by Pacific Scientific.

(Note 10) 20% aqueous solution of triethylamine acetate salt, deionized water 8
It was prepared by dissolving 7.5 parts of acetic acid in 0 parts of acetic acid and adding 12.5 parts of triethylamine thereto over 30 minutes while 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, and a mixture of the following composition was added and heated while stirring. It was heated to 140°C.

Benzoic acid 122. O Part Cardular E10 (Yuka Ciel Evo 250.0 Part Kishi ■, trade name of Versatic Acid Glycidyl Ester) Phthalic Anhydride 148. 0 part N
, N-dimethylbenzylamine 2.0 parts xylene 327. The mixture was stirred for 2 hours at a temperature of 0 parts and 140° C. without introducing nitrogen gas, and the non-volatile acid value was adjusted to 108 to obtain a solution of a reaction intermediate having a carboxyl group at the end of the molecule. Then, the above reaction intermediate solution was mixed with Cardura-EIO/phthalic anhydride=
250. The reaction was carried out twice under the above reaction conditions with a mixture of 0 parts/148.0 parts, and the reaction was terminated when the final non-volatile acid value reached 43.The heating residue was 80% polyester with carboxyl group at the end of the molecule. A compound solution was obtained. Using this polyester compound solution, a mixture of the following composition was prepared for 14 hours.
The mixture was stirred at a temperature of 0°C for 4 hours, and the reaction was terminated when the nonvolatile acid value became less than 1 month. A solution of α,β-ethylenically unsaturated monomer containing a polyester chain group with a heating residue of 80% was obtained. Ta.

Above polyester compound solution 1645.0 parts Glycidyl methacrylate 142. 0 parts hydroquinone 2.0 parts xylene
35.0 parts Next, a dispersion stabilizer was produced using the above monomer solution in the following manner.

Four flasks were equipped with a stirrer, a reflux condenser, a thermometer, and a dropping funnel, and 85.5 parts of xylene was added thereto, and the temperature was raised to 95°C while stirring. Next, a mixture having the following composition was added at a constant addition rate over 2 hours at a temperature of 95°C, and the temperature was maintained at 95°C for an additional 2 hours to obtain a solution of acrylic B with a heating residue of 50%.

Production example of the above polyester chain group-containing α,β-ethylenically unsaturated monomer solution n-butyl methacrylate t-butylberoxy 2-ethylhexanoate Initial charging solvent n-butyl acetate Mineral spirit Dispersion stabilizer Acrylic B (Previous) α,β-ethylenically unsaturated monomer mixture acetoacetoxyethyl methacrylate methyl methacrylate acrylonitrile perbutyl 0 62.5 parts 50.0 parts 2.0 parts 84.7 parts 84.7 parts 85.7 parts 40.2 parts 14.8 parts 15.0 parts 1.5 parts Crosslinking agent Cymel 303 (described later) 30.
0 parts Catalyst Dodecylbenzenesulfonic acid 1.5 parts 4 Attach a stirrer, reflux condenser, thermometer and dropping funnel to a flask, charge the initial charging solvent and dispersion stabilizer, and raise the temperature to 95°C while stirring. Heated. Then,
The α,β-ethylenically unsaturated monomer mixture was added at a constant addition rate over a period of 2 hours at a temperature of 95°C, and the temperature was maintained at 95°C for an additional 2 hours.

After that, a crosslinking agent and a catalyst were added, and the temperature was raised while stirring.
By carrying out the crosslinking reaction at a temperature of 0°C for 2 hours, a non-aqueous polymer dispersion L having the properties listed in Table 2 was obtained.

Production Example M-S Using the same equipment as in Production Example, non-aqueous dispersion polymerization was carried out based on the formulations in Table 2 M-S.
A non-aqueous polymer dispersion M-S having the properties listed in the table was obtained.

Comparative Production Example T (a) Production of α,β-ethylenically unsaturated monomer Stirrer,
Put 1500 parts of 12-hydroxystearic acid into a fourth flask equipped with a thermometer, a Dean-Stark trap equipped with a reflux condenser, and a nitrogen gas inlet tube, and raise the temperature while blowing nitrogen gas until the temperature reached 200°C. Stir until the acid value is 3.
The reaction was terminated when the temperature reached 9, and after cooling, 159 parts of xylene was added to obtain a 5 molar 12-hydroxystearic acid condensate solution with a heating residue of 90%. In addition, 72 parts of water was eliminated in this reaction. Next, using this 12-hydroxystearic acid 5 molar condensate solution, a mixture having the following composition was heated at a temperature of 120°C in a fourth flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen gas inlet tube. The mixture was stirred at a temperature of 100.degree. C., and an esterification reaction was carried out until the acid value of the heated residue became 1.0 or less, to obtain an α,β-ethylenically unsaturated monomer solution with a heated residue of 80%.

l2-Hydroxystearic acid 5 molar condensate solution 158
6. 67 parts glycidyl methacrylate 142. 00 parts N,N-dimethylbenzylamine 3.93 parts Hydroquinone 1. % parts xylene 227. 94 parts (b) Preparation of amphiphilic dispersion stabilizer Next, 405. 0 parts of ethyl acetate and 203. 4 parts of loubutyl acetate was added and the mixture was refluxed with stirring. Next, a mixture having the following composition was added at a constant addition rate over 3 hours under reflux, and the mixture was further refluxed for 2 hours to obtain an amphiphilic dispersion stabilizer solution with a heating residue of 33%.

α,β-ethylenically unsaturated monomer solution 27 of (a) above
5. 0 parts methyl methacrylate 104. 5 parts acrylic acid 5.5 parts abdiisobutylene nitrile 6.6 parts (c) Preparation of non-aqueous polymer dispersion Four-loop flask equipped with stirrer, reflux condenser, and device for adding liquid feed to recirculated condensate A mixture having the following composition was charged into the tank.

Mineral Spirit 1588. 0 parts hexane 389. 0 parts hebutane 2080. Bipartite methyl methacrylate 236. 4 parts Azodiisobutyronitrile 18.7 parts Amphiphilic dispersion stabilizer solution of (b) above 88.1 parts
The temperature was raised to 00°C and maintained under reflux for 1 hour. Next, the following components were premixed and added to the hydrocarbons 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 (b) above 945. 3 parts except that an additional 3.3 parts of triethylenediamine were mixed into the above addition mixture during the last hour of addition. After the addition was complete, the reaction mixture was held under reflux for 3 hours to obtain a non-aqueous polymer dispersion with a heating residue of 52% containing 48.2% polymer particles with an average particle size of 200 nm.

(d) Modification of particles with auxiliary polymer A fourth flask equipped with the apparatus of step (c) above was charged with the following ingredients and heated to reflux temperature (115°C).

Polymer non-aqueous dispersion of (c) above 4747. 1
Part ethylcyclohexane 1638. 2 parts The following components were then premixed and added to the hydrocarbons returned from the condenser at a constant addition rate over a period of 3 hours.

Methyl methacrylate 334. 2 part 2
-Hydroxyethyl methacrylate} 190.6 parts Methacrylic acid 49.6 parts Butyl methacrylate 369. 1 part 2-ethylhexyl acrylate 381.2 parts Styrene 571.2 parts t-butyl peroxybenzoate 90.6 parts Butane 84.7 parts Amphiphilic dispersion stabilizer solution of (b) above 149.5 parts After the addition was completed, the reaction mixture was refluxed for 2 hours, and then the following solvent mixture was added to obtain a non-aqueous polymer dispersion T containing 25% crosslinked polymer fine particles and a heating residue of 45%.

n-Butyl alcohol 559. 0 parts xylene 372. Tripartite butyl acetate 462. 7 parts Comparative Production Example U Aerosol 18 (manufactured by American Cyanamid, trade name of N-year-old ctadecyl sulfosuccinate monoamide disodium) 3. 00 parts Aerosol AY65 (manufactured by American Cyanamid, trade name of sodium diamyl sulfosuccinate) 1.50 parts sodium bicarbonate 0.25 parts deionized water (1') 39. 75 parts Ammonium persulfate 0.25 parts Deionized water (2nd) 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 trimethylolbroban triacrylate 3. An 85 part 5-lough flask equipped with a reflux condenser, thermometer, and stirrer was charged with Aerosol 18, Aerosol AY65, sodium bicarbonate, and the first deionized water. Ammonium persulfate and second deionized water were premixed and placed in a small addition funnel. Styrene, n-butyl methacrylate, 2-ethylhexyl acrylate, 2-hydroxybutyl methacrylate, acrylic acid, and trimethylolpropane triacrylate were premixed and placed in a separate dropping port. The flask mixture was heated to 87±2°C at which time 10% ammonium persulfate solution was added. The α,β-ethylenically unsaturated monomer was continuously added dropwise into the flask over a period of 2 hours and 30 minutes at a uniform rate, and at the same time, the remaining ammonium persulfate solution was continuously added dropwise at a constant rate over a period of 3 hours. After dropping the ammonium persulfate solution, it 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 aqueous polymer dispersion was converted to a non-aqueous dispersion by the following operation.

n-butyl alcohol 17. 60 parts cellosolve acetate 17. 60 parts aqueous dispersion of the above polymer 11.37 parts t-butyl-2-ethylhexanoate (50% solution in mineral spirits) 0.71 parts Premix I Styrene 13.34 parts n-butyl methacrylate} 11. 50 parts n-dodecylbutane 1.70 parts Premix■ 2-ethylhexyl acrylate 10. 76 parts 2-hydroxyethyl acrylate 9. 2! J 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 cellosolve acetate
A 0.43 part reflux condenser, a Dean-Stark trap, a thermometer, and a stirrer were placed in a five-bottle flask equipped with n-butyl alcohol, cellosolve acetate, aqueous polymer dispersion, and t-butyl-2-ethylhexanoate. I entered. Styrene, n-butyl methacrylate and n-dodecyl butane were premixed and placed in the dropping funnel (premixer). 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate,
Acrylic acid and t-butyl-2-ethylhexanoate were premixed and placed in the second addition funnel (premix ■). The solvent, aqueous polymer dispersion, and t-butyl-2-ethylhexanoate were heated to 95°C and refluxed. After that, premix I and
It was dropped at a uniform rate over time. During addition of the α,β-ethylenically unsaturated monomer, water is removed from the aqueous polymer dispersion by azeotropic distillation.
Continuously removed from the Dean-Stark trap. Immediately after dropping premixes ■ and ■, add t-butyl-2-
A mixture of ethylhexanoate and cellosolve acetate was added dropwise at a constant rate over 1 hour. After refluxing until all the theoretical amount of water was removed, the mixture was cooled to obtain a non-aqueous polymer dispersion U. This polymer non-aqueous dispersion is 1% of the total heating residue with the resin.
Contains 1% crosslinked polymer particles and has properties such as heating residue of 56.
2%, average particle size 0.17 μm, Gardner viscosity (25'
C) T, non-volatile content acid value was 17.5.

Application Examples 1 to 11 Application to 2-coat baked metallic paint (A) Production of base coat paint Using polymer non-aqueous dispersions A-H and L-N, paints were manufactured with the composition shown in Table 3, and thinner (Toluene/acetic acid n-
Butyl = l/1 weight ratio) and coating viscosity (Ford Cup N
α4, 14 seconds at 20°C).

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

(B) Production of clear paint A paint was manufactured using the non-aqueous polymer dispersions A-H and L-N according to the composition shown in Table 4, and thinner (xylene/n-butylpropione} = 1/1 weight) The paint was diluted to a coating viscosity (Folded Cup Nα4, 25 seconds at 20°C).

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

(c) Creation of coating film Aqua Nα4 cationic electrodeposition paint on mild steel plate treated with zinc phosphate
200 (trade name, manufactured by NOF ■) with a dry film thickness of 20 μm
Electrodeposition paint so that
Furthermore, the intermediate coating paint Epico Nal 500 cp sealer (trade name, manufactured by NOF ■) was air-sprayed to a dry film thickness of 40 μm and baked at 140°C for 30 minutes. 11(A) with air spray, interval 1 minute 30 seconds,
Painted in 2 stages to a dry film thickness of 15 μm,
After setting it vertically at 0°C for 3 minutes, apply the above clear paints 1 (B) to 11 (B) by air spray, and stand it vertically at 140°C for 30 minutes (however, application example 7,
8 and 9 were baked at 120°C for 30 minutes).

As shown in Table 5, each coating film was excellent in aluminum orientation, sag limit film thickness, and coating film appearance.

Application Examples 12 to 19 Application to l-coat solids (A) Production of paint Using the polymer non-aqueous dispersions 1-K and O-S in the formulation shown in Table 6, remove the curing agent and place in a paint shaker. Preparation,
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 is added and stirred to make a l-liquid type paint, and application example 15. No. 16 was used as a two-component paint.

(B) Preparation of paint film Paint with the composition shown in Table 6 is coated with thinner (xylene/n-butyl acetate, 9/1 weight ratio) to achieve a coating viscosity (Ford Cup Nα).
4, diluted at 20°C for 25 seconds). However, application example 1
5. No. 16 was added and mixed immediately before dilution.

Then, the test board on which the electrodeposited coating film and the intermediate coating film were prepared in the same manner as in Application Examples 1 to 1l was air-sprayed, and after being set vertically, the liquid-type paint was heated at 140°C for 30 minutes.
The two-component paint was baked at 120°C for 30 minutes while standing vertically. As shown in Table 7, all coating films were excellent in gloss, sagging limit film thickness, and film appearance.

Comparative example 1. 2 (A) Production of base coat paint A paint was manufactured using the non-aqueous polymer dispersions T and U with the composition shown in Table 8, and thinner (toluene/n-butyl acetate 1
/l! Quantity ratio) and coating viscosity (Ford Cup Nα4, 20
14 seconds at °C).

(B) Manufacture of clear paint A paint was manufactured using the non-aqueous polymer dispersions T and U with the composition shown in Table 8, and a coating viscosity (Ford Cup Nα
4, diluted at 20°C for 25 seconds).

(c) Creation of coating film Application example The above base coat paint and clear paint were applied to the test plate on which the electrodeposition coating film and intermediate coating film were created in the same manner as in Application Examples 1 to 11 in the same manner as in Application Examples 1 to 11. Baked after air spray painting. 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 crosslinked polymer particles were crosslinked with a polyfunctional α,β-ethylenically unsaturated monomer. Since particle crosslinking is performed using a combination of unsaturated monomers, α,β-ethylenically unsaturated groups remain on the particle surface in both cases, reducing compatibility with the binder. The appearance of the coating film was inferior to that of No. 1.

Comparative Examples 3 and 4 (A) Production of paint In Comparative Example 3, non-aqueous polymer dispersion T was used, and in Comparative Example 4, no non-aqueous polymer dispersion was used. Particle size is 10.
It was dispersed until it became less than μm.

(B) Preparation of coating film Paint with the composition shown in Table 8 is coated with thinner (xylene/n-butyl acetate = 9/l weight ratio) to reduce the coating viscosity (foed cup Nα).
4, diluted at 20°C for 25 seconds). And application example 1
The electrodeposited coating film and the intermediate coating film were prepared in the same manner as in 1L, and then air sprayed on the test plate, set in an upright position, and baked at 140°C for 30 minutes.

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

Moreover, in Comparative Example 4, since the crosslinked polymer fine particles were not included, the coating film had poor sagging resistance and poor coating film appearance.

Claims (1)

[Claims] 1. Among the following components: (a) 3-80% by weight of α,β-ethylenically unsaturated monomer having a crosslinkable functional group (b) Other α,β-ethylenically unsaturated monomers Saturated monomer 30-95
Weight% (c) Crosslinking agent 2-5 having a group capable of reacting with component (a)
0% by weight First, fine particles are obtained by polymerizing components (a) and (b) by a polymerization method selected from emulsion polymerization, suspension polymerization, or non-aqueous dispersion polymerization, and then the fine particles are obtained. A crosslinked polymer fine particle characterized in that it is internally crosslinked by incorporating component (c) therein and reacting with a crosslinkable functional group in component (a). 2. The crosslinkable functional group in component (a) is selected from the group consisting of an acetoacetoxy group, an alkylated aminomethyl ether group, a cyclocarbonate group, a hydroxyl group, an isocyanate group, an epoxy group, an amino group, a carboxyl group, and a mixture thereof. The crosslinked polymer fine particles according to claim 1, wherein the crosslinked polymer fine particles are selected from the group consisting of: 3. Component (c) is formaldehyde or an amino resin with a polymerization average molecular weight of 1000 or less, a polyisocyanate compound, a polyfunctional α,β-unsaturated carbonyl compound, a polyepoxy compound, a polyol, a polyamine compound, a polymercapto compound, a polycarbonate The crosslinked polymer fine particles according to claim 1, wherein the crosslinked polymer fine particles are selected from the group consisting of acid compounds and mixtures thereof.