JPH0364374A - Matte coating composition - Google Patents

Abstract

PURPOSE:To obtain the title compsn. providing a matte coating film with excellent decorativeness and weather resistance by compounding a thermosetting or thermoplastic resin, a specified pigment composite particle and a solvent each in a specified amt. CONSTITUTION:100 pts.wt. thermosetting or thermoplastic resin (e.g. a chlorinated polyethylene resin), 1-100 pts.wt. pigment composite particle on the surface of which a pigment is carried [e.g. a composite particle obtd. by heat- polymerizing a paste obtd. by dispersing a carbon black in a varnish of an amphoteric ionic copolymer obtd. by heating and stirring styrene, methyl methacrylate, n-butyl acrylate and ethylhexyl methacrylate in a solvent (a mixture of xylene and butyl acetate) in the presence of a peroxide and then adding a stearylamine and dimethylethanolamine and styrene, methyl methacrylate, n-butyl acrylate and ethylene glycol dimethacrylate in the presence of an initiator] and 10-1,000 pts.wt. solvent (e.g. toluene/xylene/ethyl acetate/butyl acetate) are compound.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a matte coating composition, and particularly to a matte coating composition that provides a matte coating film with excellent design properties and weather resistance.

[Conventional technology]

Conventionally, in order to meet the demands of consumers, it has been done to create so-called matte paint films for the exterior of automobiles, etc. by blending silicon-based fine particles at high concentrations on the paint film surface to diffusely reflect light. do.

JP-A-64-16812 describes the use of polymer beads made of methyl methacrylate, acrylonitrile, and other monomers as a matting agent. JP-A-63-199776 discloses a suede-like design by drying nylon powder and a coloring agent, or colored nylon powder and a specific film-forming resin with a high elongation rate at a temperature lower than the melting point of nylon. The paints that can be obtained are listed. JP-A-63-170466 describes an aqueous coating composition that forms a matte coating film by adding anionic gel particles to an anionic electrodeposition coating. JP-A-1-167378 discloses that organic solvent-based paint contains organic gel particles that are hardly soluble in the paint as a matting agent, and baking is sometimes caused by water vapor caused by evaporation of water inside the water-based organic gel. Coating compositions are described that agitate surfaces and form matte coatings. JP-A-1-139656 describes a coating composition containing porous spherical particles and having a matting effect. However, in these matte paints, the matting agent weakens the coloring power of the coloring pigment, causing a white blurring phenomenon.
There have been problems in that it is not possible to obtain a coating film that provides reflection that is optically different from that of conventional methods, or a coating film that has sufficient weather resistance due to the occurrence of a chalking phenomenon.

[Problem to be solved by the invention]

Therefore, an object of the present invention is to solve the above-mentioned problems of conventional general matte paints and to develop a matte paint composition that provides a coating film with excellent design and weather resistance.

[Means for Solving the Problems] According to the present invention, (a) 100 parts by weight of a thermosetting or thermoplastic resin, (g)
There is provided a matte coating composition comprising:) 1 to 100 parts by weight of pigment composite particles carrying a pigment on the surface layer; and (c) 10 to 1000 parts by weight of a solvent.

As the vehicle component of the matte coating of the present invention, thermosetting or thermoplastic resins that are commonly used as vehicles for conventional coatings can be used.

Examples of thermosetting resins used as vehicles in the present invention include film-forming resins such as acrylic resins, polyester resins, alkyd resins, and isocyanate-curing acrylic resins. Used together with crosslinking agents such as resins and blocked isocyanates.

Among these thermosetting resins, acrylic resins can be polymerized, for example, from the following polymers by a conventional method.

(1) Ethylene monomers having a hydroxyl group such as hydroxylmethyl (meth)acrylate, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, N-methylolacrylamine, (2) Ethylene monomers having a carboxyl group such as (meth)acrylic acid, crotonic acid, itaconic acid, fumaric acid, maleic acid, (3
) (meth)methyl acrylate, (meth)ethyl acrylate, (meth)propyl acrylate, butyl acrylate,
(N-propyl acrylate, n-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, n-dodecyl acrylate, etc.)
The above monomers such as meth)acrylic acid alkyl esters (
Ethylenic monomers copolymerizable with 1) and (2), as well as (meth)acrylonitrile, styrene, and the like are used.

Next, the raw materials for polyester resin are polyhydric alcohols such as ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, neopentyl glycol, and 1,21.8-12.3-1.4-butanediol. , 1,5-bentanediol, l,6-hexanediol, hydrogenated bisphenol A1, hydroxyalkylated bisphenol A, l,4-cyclohexane dimetatool, 2,2-dimethyl-3-hydroxypropyl-2, 2-dimethyl-3-hydroxypropione)
(BASHPN), N,N-bis-(2-hydroxyethyl)dimethylhydantoin, polytetramethylene ether glycol, polycaprolactone polyol, glycerin, sorbitol, annitol, trimethylrolethane, trimethylolpropane, trimethylolbutane, hexanetriol, pentaerythritol,
One or more polyhydric alcohols such as dipentaerythritol and tris-(hydroxyethyl)isocyanate can also be used in combination.

Examples of polybasic acids include phthalic acid, phthalic anhydride, tetrahydrophthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic acid, hexahydrophthalic anhydride, methyltetrahydrophthalic acid, methyltetrahydrophthalic anhydride, himic anhydride, and trimeritic acid. Acid, trimellitic anhydride, pyromellitic acid, pyromellitic anhydride, isophthalic acid, terephthalic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, adipic acid, azelaic acid, sebacic acid, succinic acid, succinic anhydride , lactic acid, dodecenyl succinic acid, dodecenyl succinic anhydride, cyclohexane-1
, 4-dicarboxylic acid, endoacid anhydride, or a combination of one or more polybasic acids can also be used.

The resin contains 30% by weight of oil or fatty acid as necessary.
It can also be used as an alkyd resin with added flexibility to a certain degree.

The crosslinking of the resin can be achieved by, for example, n-butylated melamine resin,
Examples include alkylmethylmelamine resins and benzoguanamine resins in which the alkoxy groups of tributylated melamine resins include methoxy, ethoxy, n-butoxy, and ]-butoxy groups.

These resins are usually obtained by adding or condensing an amino compound such as melamine or penduguanamine with an aldehyde such as formaldehyde or paraformaldehyde, and then adding a monohydric alcohol having 1 to 4 carbon atoms. Obtained by reaction and etherification. As the crosslinking agent component of the acrylic resin, amino resins, particularly melamine resins, blocked isocyanates, etc. can be used. As blocking agents, phenol, P-nitrophenol,
m-cresol, acetylacetone, acetone ethyl acetate, ε-caprolactam, etc. are used. The ratio (weight ratio) of acrylic resin or polyester resin/melamine resin = 9/1 to 515, which is a thermosetting resin, is 9/1.
If it exceeds 5/5, the coating film hardness will be insufficient, and if it is less than 5/5, cracks will occur. Preferably it is 85/15 to 6/4. When using an isocyanate compound as a crosslinking agent, the molar ratio of isocyanate groups to hydroxyl groups in the thermosetting resin component is 0.3/1 to 1.5/1. 0.3
If it is less than 1.5/1, curing will be poor, and if it exceeds 1.5/1, water resistance will be poor.

It is preferable to use 3 to 10 parts by weight of an epoxy resin in combination with 100 parts by weight of the above-mentioned resin within an acceptable range of compatibility, since this improves adhesion.

The isocyanate-curable acrylic resin is a paint containing a polyisocyanate such as isocyanate (particularly preferably a ring polyisocyanate) and an acrylic polyol as a vehicle.

In addition, in the case of a cold-curable coating material using non-blocking polyvalent isocyanates, the curing agent components are prepared separately to form a two-component coating material. In this case, by adjusting the type and amount of isocyanate and catalyst added, copolymer concentration, content of units based on hydroxyalkyl vinyl ether in the copolymer, etc., it has a pot life of about 1 to 10 hours. A coating that cures at room temperature in several hours to several days and provides a coating film with good physical properties can be obtained.

On the other hand, thermoplastic resins that can be used as vehicles in the present invention include chlorinated olefin resins such as chlorinated polyethylene and chlorinated polypropylene, vinyl chloride resins, vinyl acetate, and vinyl chloride, which are commonly used in the paint field. Suden and vinyl resins copolymerized with these,
Examples include cellulose resins, acetal resins, alkyd resins, chlorinated rubber resins, etc. Even when such thermoplastic resins are used, coating compositions with high design quality can be obtained.

In the present invention, pigment composite particles carrying pigment mainly on the surface layer are used as a pigment component at a ratio of 1 to 100 parts by weight, preferably 10 to 70 parts by weight, based on 100 parts by weight of the resin. The supported pigment composite particles contain at least one of anionic, cationic, amphoteric, or nonionic ionic groups, for example, in an amount of 0.2 mmol.
It can be obtained by heating a pigment paste dispersed with a dispersion resin containing 1/g or more, at least one α,β-unsaturated compound, and an initiator. Furthermore, it can be obtained by adding a dispersion and suspension step in water, if necessary, at least one compound having a plurality of α,β-unsaturated groups and, if necessary, a neutralizer for the ionic groups of the dispersion resin. . These pigment composite particles have the pigment dispersed in the crotch of the particle and are mainly supported on the particle surface layer, and have a particle diameter of 2 to 50 μm and a pigment composite ratio of 0.2 to 20% by weight (pigment/particle constituent polymer weight ratio). belongs to. If the particle size is smaller than 2 μm, there will be no matting effect, and if it exceeds 50 μm, spots will appear. Further, if the pigment composite ratio is less than 0.2% by weight, white blurring tends to occur, and if it exceeds 20% by weight, it becomes difficult to support the pigment mainly on the surface layer of the particles.

The above-mentioned dispersion resin includes α and β that form composite particles.
- Any resin can be used as long as it can be dissolved or copolymerized with an unsaturated compound, such as acrylic resin, polyester resin, etc., and preferably a dispersed resin made of the following ethylenically unsaturated monomers.

Ethylenically unsaturated monomers that can be used include:
Alkyl esters of acrylic acid or methacrylic acid such as methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate; Other monomers having ethylenically unsaturated bonds that can be copolymerized with this, such as ebastyrene, α-methylstyrene, vinyltoluene, t-7'tylstyrene, ethylene, propylene, vinyl acetate, vinyl propionate, (meth) Examples include acrylonitrile and dimethylaminoethyl (meth)acrylate. Two or more types of these monomers can be used, and the α,β-unsaturated compounds include, for example,
A monomer having two or more radically polymerizable ethylenically unsaturated groups in the molecule, including polymerizable unsaturated monocarboxylic acid esters of polyhydric alcohols, polymerizable unsaturated alcohol esters of polybasic acids, and 2 There are aromatic compounds substituted with one or more vinyl groups, examples of which include the following compounds.

Ethylene glycol di(meth)acrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, trimethylolpropane tri(meth)acrylate 1,14-butanediol diacrylate, neopentyl glycol diacrylate Acrylate, 1.6
-hexanediol diacrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, glycerol diC meth)acrylate, glycerol allyloxy dimethacrylate,
1.1.1-Trishydroxymethylethanedi(meth)
Acrylate, 1,1゜1-trishydroxymethylethane tri(meth)acrylate, 1.1.1-trishydroxymethylpropane di(meth)acrylate, 1,
1゜1-trishydroxymethylpropane tri(meth)
Acrylates, triallyl cyanurate, triallyl isocyanurate, triallyl trimellitate, diallyl terephthalate, diallyl phthalate and divinylbenzene.

Furthermore, in place of the monomer having two or more radically polymerizable ethylenically unsaturated groups in the molecule as a monomer for crosslinking purposes, or optionally together with them, each carries a group capable of reacting with each other. It is also possible to use monomers with some ethylenically unsaturated groups. For example, glycidyl group-containing ethylenically unsaturated monomers such as glycidyl (meth)acrylate, and cyboxyl group-containing ethylenically unsaturated monomers such as (meth)acrylic acid and crotonic acid; 2-
Hydroxyl group-containing ethylenically unsaturated monomers such as hydroxyethyl acrylate, hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxybutyl (meth)acrylate, (meth)allyl alcohol, vinyl isocyanate, isopropenyl Examples include ethylenically unsaturated monomers having an isocyanate group such as isocyanate. However, in addition to these, any combination of two ethylenically unsaturated monomers each carrying a group capable of reacting with each other can be used, and as the initiator, for example, benzoyl peroxide, t- Organic peroxides such as butyl peroxide, cumene hydroperoxide, azobiscyanovaleric acid, azobisisobutyronitrile, azobis-(2,4-dimethyl)valeronitrile, azobis-(2-amidinopropane) hydrochloride, etc. Inorganic water-soluble radical initiators such as azo compounds, potassium persulfate, ammonium persulfate, sodium persulfate, and hydrogen peroxide; Examples include leto- and cous-based initiators obtained in combination, and one or a mixture of two or more of these can be used. Further, the compound having a plurality of α,β-unsaturated groups used as necessary for preparing the pigment composite particles may include a monomer having a functional group capable of reacting with a crosslinking agent. Examples include carboxyl group-containing monomers, such as (meth)acrylic acid, crotonic acid, (anhydrous) itaconic acid, (anhydrous) maleic acid, fumaric acid, etc., and hydroxyl group-containing monomers, such as 2-hydroxyethyl (meth) ) acrylate, bitroxypropyl (meth)acrylate, hydroxybutyl (
Meth)acrylate, allyl alcohol, methacrylic alcohol, and nitrogen-containing compounds such as acrylic acid amide and methacrylic acid amide can be used, and as neutralizing agents, for example, monomethylamine, dimethylamine, trimethylamine, monoethylamine, triethylamine, monoethylamine, etc. can be used. Isopropylamine, diisopropylamine, diethylenetriamine, triethylenetetramine, monoethanolamine, jetanolamine, triethanolamine, tripropylamine, monoisopropylamine, diisopropylamine, NN-diethyldiaminepropane, dimethylethanol Amine, stearylamine, morpholine, methylmorpholine, piperazine, ammonia, sodium hydroxide, potassium hydroxide, lithium hydroxide, etc. Preferably, a tertiary amine or an alkali metal ion can be used.

Pigments incorporated into the pigment composite particles used in the present invention include, for example, titanium dioxide, phthalosyanine flu, phthalosyanine green, quinacridone, indanthrone, isoindolinone, perylene, anthrapyrimidine, carbon black, benzyl imidacylon,
Colored pigments such as graphite, yellow iron oxide, red iron oxide,
Depending on the case, one or more extender pigments such as barium sulfate and aluminum silicate may be used.

If the amount of pigment composite particles blended into the coating composition of the present invention is too high, the smoothness of the coating film may be impaired.
On the other hand, if the amount is too small, a sufficient matting effect may not be obtained.

In the matte coating composition of the present invention, 10 to 1000 parts by weight per 100 parts by weight of the thermosetting or thermoplastic resin composition.
Part by weight, preferably 50 to 500 parts by weight As the solvent, any solvent or solvent mixture conventionally used in paints can be used. Examples of such solvents include aromatic hydrocarbons such as toluene or xylene, aliphatic hydrocarbons such as n-hexane and heptane, and various solvents consisting primarily of aliphatic hydrocarbons and containing some aromatic hydrocarbons. esters such as butyl acetate, ethylene glycol diacetate, 2-ethoxyethyl acetate, acetate and ketones such as methyl isobutyl ketone and alcohols such as butyl alcohol, and water. However, when a polyisocyanate compound is blended as a crosslinking agent, a solvent having an active hydrogen group that reacts with the polyisocyanate compound cannot be used.

If the amount of solvent added to the coating composition of the present invention is too small, it will be difficult to manufacture the coating material, and if it is too large, the viscosity will become too low, which may cause sag during coating film formation.

In addition to the above-mentioned essential components, the matte coating composition of the present invention may contain optional components commonly used in conventional coating compositions, such as pigments and various additives.

The pigments mentioned above include titanium dioxide, phthaloshanine blue, phthaloshanine green, quinacridone, indanthrone, isoindolinone, perylene, anthrapyrimidine, carbon black, benzimidacylon, graphite, yellow iron oxide, red iron oxide. In some cases, one or more selected from among coloring pigments such as, and extender pigments such as barium sulfate and aluminum silicate may be used. In addition, as glittering pigments, metals such as mica pigment, aluminum foil, bronze foil, tin foil, gold foil, silver foil, titanium metal foil, stainless steel foil, metal 7δ coated with alloys such as nickel-coated plastic, and metals such as foil-shaped phthalocyanine blue. Foil pigments can also be used.

The pigment blended into the coating composition of the present invention is a thermosetting or thermoplastic resin 100i! It is preferably used in an amount of 50 parts by weight or less based on i parts by weight. If the amount of pigment added is too large, the smoothness of the coating film may be impaired, which is not preferable.

Various additives that can be incorporated into the matte coating composition of the present invention include curing catalysts such as dodecylbenzenesulfonic acid, ultraviolet absorbers such as benzophenol, antioxidants such as phenol and sulfide, and silicone. Additives such as surface conditioners, organic polymers, anti-sagging agents, thickeners, etc. can be added to the paint in an amount of 5 parts by weight or less to improve paint performance and film performance. It can be improved. However, if these amounts are too large, repellency may occur during coating film formation or glabella adhesion may deteriorate, which is not preferable.

The matte coating composition of the present invention is not limited to metals such as iron, aluminum, copper, or alloys thereof, but also inorganic materials such as glass, cement, and concrete, FRP, polyethylene, polypropylene, and ethylene-vinyl acetate copolymer. , polyamide, polyacrylic, polyester, ethylene-polyvinyl alcohol copolymer, vinyl chloride resin,
It can be applied to various base materials such as plastics such as vinylidene chloride resin, polycarbonate, and polyurethane, wood, and fibers. Note that it is optional to apply an appropriate undercoat or precoat to these base materials before painting.

[For production]

According to the present invention, since pigment composite particles carrying a pigment on the surface layer are blended into the coating composition, white blurring on the surface of the coating film is prevented due to the coloring effect and matting effect of the colored pigment on the surface layer.
Further, the organic particles prevent chalking, and the desired matting effect can be obtained due to the optical effect of the particle shape of the pigment composite particles.

[Examples] Hereinafter, the present invention will be described in more detail based on Examples, but it goes without saying that the technical scope of the present invention is not limited to these Examples. In the following examples, unless otherwise specified, "parts" and "%" indicate parts by weight and % by weight, respectively.

7. Injection of Color Paste A 3 parts of component (1) and 60 parts (2) of the following composition were premixed in a disper, dispersed in a sand grind mill, and dispersed in a grind gauge until the particle size became 10 μm or less. .

■Carbon blank 3 parts ■Acrylic resin face (ACR-420) “” i3
5.8 parts ■solvent''
212.7 parts Then, 288.5 parts of the remaining component (■) were added and mixed for 20 minutes using a disper to obtain primary color base) A.

2. II+1 method of Paste B-D Primary color pastes B, C and D were prepared by the same method as primary color paste A) from those having the following compositions.

Rooftop Koya≦1-dan■Phthaloshanine Blue 10 parts■Acrylic resin festival (ACR-420> 126
Part ■ Solvent 152.3
Buri negative two nim Jodan Mabiko Ero LL-XLO” 20
■Acrylic resin varnish (ACR-420)
112 parts■Solvent
113.7 parts Shinko ≧≦ (E and ■ Paliogen Red 391014 10 parts ■ Acrylic resin varnish (ACR-420) 1
26 parts Solvent 1
52.3 Part 1, Pour of Pastes E-H Primary color pastes E, F, G and H were prepared by the same method as primary color paste A from the components having the following compositions.

Primary color paste E ■Carbon color rank 3 parts ■Alkyd resin varnish (R-1327)” ii
3.2 parts ■) Container 2
35. Part 3 Hara Kami 2 ≧ Goshi Hi Dan ■ Phthaloshanine Blue ■ Alkyd Resin Varnish (R-1327) ■ Solvent - 22 Prisoners ■ Mapico Yellow LL-XLO ■ Alkyd Resin Varnish (R-1327) ■ N Container 1=Gummy-,2,)-H- ■Varioan Red 3910 ■Alkyd resin varnish (R-1327) ■Solvent 10 parts 105 parts 173.3 parts 20 parts 93.3 parts 132.4 parts 10 parts 105 Part 173.3 parts ■ Carbon black ■ 'Baryta BA'' ■ Chlorinated polyethylene resin (Superflon 510)*? ■'Plasticizer (Toyoba Rank 150)''■'Stabilizer (Epicoat 828) 69 2 parts 18 parts 20 parts 4 parts 0.5 parts■'Thixotropic agent (Disbaron 6900-20X)''■
Solvent (xylene) Raw Ebisanim Asari - ■ Phthaloshanine Blue ■ Alkyd resin varnish (Phthalkyd 351-50) ``■' Dryer-It 1.5 parts ■' Anti-skinning side (Disbaron 501)'' 0.2 parts ■'Thixotropic agent (Bentone 34) 1.0 part■
Solvent 27 parts 8 parts 56 parts 2.5 parts 53 parts *1 *2 Thermosetting acrylic resin varnish (NV-50%) (manufactured by Nippon Paint) Toluene/xylene/ethyl acetate/butyl acetate-70/
15/1015 (weight ratio) Inorganic yellow pigment
(Titan Kogyo) Organic red color '#Jr
(Manufactured by BASF) Thermosetting alkyd resin varnish (N
Sea 60%) Extender pigment (barium sulfate) (manufactured by Sakai Chemical Industries) Umbrella 7 Car 8 9 *10 11 12 13 Chlorinated polyethylene resin (Desumi Kokusaku Pulp) Chlorinated paraffin (Tosoh) Epoxy resin (
Made of oil-based shell epoxy) amide wax (
(manufactured by Kusumoto Kasei) Alkyd resin varnish (Hitachi Chemical type) Dryer [Lead naphthenate / Manganese naphthenate / Cobalt naphthenate = 2/1/i (weight ratio)] M E K
Oxime (manufactured by Kusumoto Kasei) thermometer, stirrer,
150 g of xylene and 200 g of butyl acetate in a 5 liter flask equipped with two dropping funnels and a nitrogen inlet tube.
The solution was heated and maintained at 105°C. Next, 92 g of styrene, 140 g of methyl methacrylate, 20 g of n-butyl acrylate, 116 g of ethylhexyl meccrylate, and 32 g of itaconic anhydride were weighed and charged into the dropping funnel, and t-butylperoxy-2-ethylhexanatrog and 50 g of xylene was weighed out and charged into another dropping funnel.

The contents of the two dropping funnels were dropped into the flask over 3 hours while stirring while heating, and then stirring was continued for 2 hours at the same temperature.

Further, at the same temperature, 38.5 g of stearylamine and 50.8 g of dimethylethanolamine were sequentially added to the flask.
By stirring for 1 hour, a varnish of a zwitterionic copolymer with a number average molecular weight of 8.000 and a non-volatile content of 51.5% was obtained.

Carbon black 16 was added to the varnish thus obtained.
8g, butyl acetate 480g and steel beads 1000c
A pigment dispersion paste with coarse particles of 5 μm or less was prepared using Red Devil.

Using the same reaction vessel and reaction solvent as in Synthesis Example 1, resin varnishes and pigment pastes having the formulations shown in Tables 1 and 2 were synthesized.

Black pigment paste Log obtained in Synthesis Example 1 and styrene 30
g, 20 g of methyl methacrylate, 10 g of n-butyl acrylate, 40 g of ethylene glycol dimethacrylate
g and 1 g of 2.2-azobis(2-methylpropylnitrile) were weighed into a beaker and stirred to homogenize.
A suspension was prepared by adding with stirring into 900 g of deionized water in a stainless steel beaker.

This suspension was placed in a 11 reaction vessel equipped with a stirrer, a cooler, a temperature controller, and a nitrogen inlet tube, heated to 80° C. for 30 minutes while stirring, and polymerized at this temperature for 6 hours.

The non-volatile content of the resulting dispersion was 11%, and it was filtered and dried to obtain internally crosslinked particles having a particle size center of 40 JJm. These particles were composite particles in which carbon black was arranged on the surface layer.

15g of the blue pigment paste obtained in Seiji Gomata Synthesis Example 2 was added to 40g of styrene.
g, methyl methacrylate) 15 g Sn-butyl acrylate 15 g and ethylene glycol dimethacrylate 3
A solution uniformly dispersed in 0 g and 2,2-azobis(2,4
- dimethylvaleronitrile) was weighed out in a beaker, stirred to homogenize, and then added to 400 g of deionized water in a stainless steel beaker with high speed stirring to produce a suspension.

This suspension was placed in a 0.52 reaction vessel equipped with a stirrer, a cooler, a temperature control device and a nitrogen inlet tube, heated to 60°C for 30 minutes while stirring, and polymerized at this temperature for 6 hours.

The non-volatile content of the resulting dispersion was 22%, and it was filtered and dried to obtain composite particles whose particle diameters were centered at 3 μm and whose interiors were crosslinked.

Add 10g of the yellow pigment base obtained in Synthesis Example 3 to 50g of styrene.
g1 A solution uniformly dispersed in 30 g of methyl methacrylate and 20 g of n-butyl acrylate and 1 g of t-butylperoxy-2-ethylhexanate were weighed out in a beaker, stirred to homogenize, and then desorbed in a stainless steel beaker. A suspension was prepared by adding it to 900 g of ionized water with stirring.

This suspension was placed in a 1°C reaction vessel equipped with a stirrer, a cooler, a temperature control device, and a nitrogen inlet tube, heated to 80°C for 30 minutes while stirring, and polymerized at this temperature for 6 hours.

The nonvolatile content of the resulting dispersion was 11%, and it was filtered and dried to obtain composite particles whose particle diameters were centered at 20 μm and whose interiors were crosslinked.

Next day, add 15 g of the red pigment paste obtained in Soil Synthesis Example 4 to 30 g of styrene.
g, 0.5 g of 2,2-azobis-isobutylnitrile in a solution in which 30 g of methyl methacrylate, 10 g of n-butyl acrylate, and 30 g of divinylbenzene were uniformly dispersed.
Weighed and added to a beaker, stirred to homogenize,
A suspension was prepared by adding to 400 g of deionized water in a stainless steel beaker with high speed stirring.

This was placed in a 0.51 reaction vessel equipped with a stirrer, a cooler, a temperature control device, and a nitrogen introduction tube, and the mixture was heated for 30 minutes under stirring.
It was heated to 0°C and polymerized at this temperature for 6 hours.

The non-volatile content of the resulting dispersion was 19%, and it was filtered and dried to obtain composite particles whose particle diameters were centered at 3 μm and whose interiors were crosslinked.

Table 1-ov MMA-methyl methacrylate, ST: styrene, nBA: n-butyl acrylate 6IA anhydrous itacone aEIIMA: 2-ethylhexyl methacrylate.

HEMA + 2-hydroxyethyl,
1. MA nilauryl methacrylate 8M methacrylate) 14 isobutyl and 1llA
: i-F'thyl acrylate AA: Ac ° J) La
MAN: M water maleic acid SτA: stearylamine.

DMEA dimethylethanolamine,
TPA: ) Libroviramine DEDAP:
N, N-diethyldiamine propane, TEA = triethylamine MAA A paint was prepared by mixing each component with a disper in the composition shown in Table 3.

11 Made by Kosara Co., Ltd. A dull steel plate chemically treated with 0.8 ms thick zinc phosphate (Surfdyne 16NC-4 made by Nippon Paint ■) is further coated with a cationic electrodeposition coating (Power Top PU made by Nippon Paint ■).
-50) On the substrate (polyester, melanin resin) coated with a 40 μm intermediate coating film (13 paints prepared by Luga 0P-2 Gray) of 25 μm, Tsurubenz 100 (Exxon): Xylene: Tsurubenz 150 (Exxon) Using a solvent mixed in a ratio of 5:3:2, air spray a matte paint with a viscosity adjusted to 15 to 20 seconds (20°C) using a #4 Ford cup to a film thickness of 40 μm. Painted. After setting this at room temperature for 7 minutes, it was baked at 140"C for 30 minutes to prepare a test piece.

111 After greasy wiping (Evaluation method) (1) i''it weatherability test A 1000-hour weather-o-meter (WOM) test was conducted to evaluate the chalking properties of the coating film.

(2) Paint film appearance The appearance of the coating surface was visually evaluated for skin and white blurring.

(3) The 60 degree specular gloss of the 60" gloss coating surface was measured using a specular gloss meter (digital variable angle gloss meter [IGV-3D/Suga Test Instruments).

<Evaluation criteria> (1) Weather resistance test O: No chalking Δ: Slight chalking O: No white blur ×: White pockets [Effects of the invention] As explained above, by using pigment composite particles carrying pigment on the surface, the surface of the paint film does not become white due to the pigment on the surface layer. A matte coating film with a high design quality can be obtained, and since it is an organic particle (having a strong affinity with the paint), a matte coating film with a high design quality that does not blur the coating surface can be obtained.

Claims (1)

[Claims] 1. (a) 100 parts by weight of a thermosetting or thermoplastic resin, (
A matte coating composition containing b) 1 to 100 parts by weight of pigment composite particles carrying a pigment on the surface layer, and (c) 10 to 1000 parts by weight of a solvent.