JPH1036761A - Coating material composition and its coated product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an inexpensive coating material having excellent resistance to flaw far superior to former coated composition and a specific feeling. SOLUTION: This coating material composition is composed of a binder resin for a coating material and at least one kind of extender pigment component. In this case, the extender pigment component comprises at least one kind of resin particle and the resin particle is obtained by subjecting a mixture of a radically polymerizable unsaturated monomer with a polymer compound to a suspension polymerization in the presence of a radical polymerization initiator. The polymer compound is a compound reducing miscibility according to polymerizing of the unsaturated monomer and gradually forming a phase- separated state from the polymer generated from the unsaturated monomer in the resin particle.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a coating composition containing specific resin particles and a coated article thereof.

[0002]

2. Description of the Related Art A coating composition is mainly composed of a binder resin as a component for forming a coating film and, if necessary, a color pigment,
It is generally composed of an extender and a leveling agent, an antifoaming agent, a crosslinking agent, a light stabilizer, an ultraviolet absorber, a rheology control agent, a slip agent, a solvent, and the like.

[0003] Among the components constituting these coating compositions, components included in the category of extenders include resin particles.

For example, when acrylic resin particles, urethane resin particles, nylon resin particles, silicone resin particles, polyethylene resin particles, etc. are added to one of the coating components, a unique pattern or texture is imparted to the coating material, It is generally known that there is an effect of improving abrasion resistance, scratch resistance, discoloration resistance, and the like.

The use of porous or irregular shaped particles in the coating composition for the surface structure of the polymer particles changes the rheological properties of the coating composition or causes the applied coating composition to form. This is one of the effective means for improving the scratch resistance of the film, imparting a unique tactile sensation and pattern, and imparting a sustained release effect of chemicals and the like.

[0006]

However, in such a conventional technique, the shape of the resin particles used is generally irregular, elliptical, or spherical, but the shape of the surface of the resin particles is not so large. In order to obtain resin particles having delicate control and a complicated internal structure, a complicated process is required, and thus it is not suitable for use as a material for a coating composition which is generally and widely used in terms of cost.

[0007] This means that the use of porous resin particles or irregularly shaped resin particles improves the rheological properties of the paint applied, and improves the scratch resistance of the coating film formed by the applied paint after application. Paints with high durability, special texture when touching the paint film, sweat absorption effect, moisture retention effect, heat retention effect, sustained release effect of chemicals, etc. are limited to use in fields that are not limited by cost etc. There was a problem.

[0008] An object of the present invention is to provide a suspension composition comprising a mixture of a radical polymerizable unsaturated monomer and a selected polymer compound as resin particles contained in a coating composition in the presence of a radical polymerization initiator. By using resin particles having a complicated internal structure and surface structure, or resin particles having an irregular surface shape, which cannot be obtained by ordinary suspension polymerization of unsaturated monomers capable of radical polymerization, conventional techniques can be used. Unique as a paint that is expressed by the fact that the shape of the resin particles used is porous, irregular, and has a complicated internal structure, while being equivalent in cost to the coating composition using the resin particles obtained in It is possible to obtain a special effect.

[0009]

Means for Solving the Problems In order to solve such a problem, in the present invention, in a coating composition comprising a paint binder resin and one or more extender pigment components, at least one or more extender pigment components are used. These resin particles are obtained by subjecting a mixture of a radical polymerizable unsaturated monomer and a polymer compound to suspension polymerization in the presence of a radical polymerization initiator, and wherein the polymer compound is Compatibility decreases as the unsaturated monomer is polymerized during polymerization, and is a compound that gradually forms a phase-separated state in the polymer and the resin particles formed from the unsaturated monomer. To provide a coating composition.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION In an embodiment of the present invention, an unsaturated monomer capable of undergoing radical polymerization is compatible with the unsaturated monomer, but the polymerization of the unsaturated monomer proceeds to polymerize the unsaturated monomer. A polymer compound that gradually deteriorates the compatibility to form a phase-separated structure according to the above, a radical polymerization initiator, and, if necessary, a mixture of an organic solvent, by dissolving a water-soluble resin such as water-soluble cellulose in water. In addition to the obtained dispersion, suspension polymerization is performed by raising the temperature while stirring, and the resin particles having a phase separation into the resin particle composition with the progress of the suspension polymerization reaction, or the resin particles with a partial phase separation, are extended pigment components. This is the coating composition used in the above.

The resin particles used in the present invention are resin particles obtained by ordinary suspension polymerization because a plurality of resins are phase-separated or partially phase-separated in the process of suspension polymerization to synthesize particles. It is characterized by having a complicated shape, being porous, and having an uneven surface as compared with.

The resin particles used in the present invention are washed after the suspension polymerization reaction is completed, dried, pulverized, and classified if necessary.

[0013] The resin particles used in the present invention have a complicated shape that has not been seen conventionally by applying the physical phenomenon of polymer phase separation to the resin particles synthesized by suspension polymerization. And porous resin particles whose porous state is regularly and finely controlled to the inside of the particles.

Examples of the radically polymerizable unsaturated monomer that can be used in the resin particles used in the present invention include acrylic acid or methacrylic acid esters such as methyl acrylate, ethyl acrylate, propyl acrylate, and acrylic acid. Isopropyl, butyl acrylate, hexyl acrylate, octyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, hexyl methacrylate, octyl methacrylate, lauryl methacrylate, etc. Acrylic acid or alkyl ester of methacrylic acid having 1 to 18 carbon atoms, methoxybutyl acrylate, methoxybutyl methacrylate, methoxyethyl acrylate, methoxyethyl methacrylate, ethoxy acrylate Acrylic acid such as xybutyl, ethoxybutyl methacrylate, or alkoxyalkyl ester having 2 to 18 carbon atoms of methacrylic acid, allyl acrylate, acrylic acid such as allyl methacrylate, or alkenyl ester having 2 to 8 carbon atoms of methacrylic acid,
Acrylic acid such as hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, or methacrylic acid having 2 to 8 carbon atoms, allyloxyethyl acrylate, allyloxyethyl Examples thereof include alkenyloxyalkyl esters of acrylic acid such as methacrylate or methacrylic acid having 3 to 18 carbon atoms.

Further, vinyl aromatic compounds such as styrene, α-methylstyrene, vinyltoluene, and p-chlorostyrene can also be exemplified.

Further, acrylonitrile, methacrylonitrile, methyl isopropenyl ketone, vinyl acetate,
Vinyl propionate, vinyl pivalate, acrylamide, N-methylol acrylamide, N-methylol methacrylamide, N-methylol acrylamide butyl ether, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, allyl alcohol, Maleic acid and the like can be exemplified.

Examples of the polyfunctional unsaturated monomer include divinylbenzene, 1,6-hexanediol diacrylate, trimethylolpropane triacrylate, dipentaerythritol hexaacrylate, 1,6-hexanediol dimethacrylate, and trimethylolpropane trimethacrylate. , Dipentaerythritol hexamethacrylate, ethylene glycol dimethacrylate,
Examples include ethylene glycol diacrylate, 1,3 butylene glycol dimethacrylate, and 1,3 butylene glycol diacrylate.

As the resin particles used in the present invention, a bifunctional unsaturated monomer as exemplified above, or a polyfunctional unsaturated monomer having 4 or more functionalities can be used alone or in combination. Preferably, 10 to 100 parts by weight of a polyfunctional unsaturated monomer having 4 or more functional groups is used per 100 parts by weight of the bifunctional unsaturated monomer.

The polymer compound that forms a phase separation state that can be used for the resin particles used in the present invention includes:
Polyester resin, fluorine resin, silicon resin,
High molecular compounds such as acrylic resins, polyethylene resins, polyolefin resins, and polyurethane resins are exemplified.

Preferably, polyolefin resins and acrylic resins are used. Examples of the polyolefin resins include polybutadiene, polyisoprene, polypropylene, acid-modified polyolefin resins, and chlorinated polyolefin resins.

The polyolefin resin is more preferably a chlorinated polyolefin resin, which is controlled in compatibility with the radically polymerizable unsaturated monomer to be used, and is an acryl-modified chlorinated polyolefin resin or an acid-modified chlorinated polyolefin resin. Chlorinated polyolefin resins and chlorinated polyolefin resins having radically polymerizable carbon double bonds can also be exemplified.

Specific examples of the chlorinated polyolefin resin include Supercron 773H, Supercron 822, Supercron 892L, Supercron 832L, Supercron 803L, Supercron L, Supercron 803MW, Supercron manufactured by Nippon Paper Industries Co., Ltd. E, Supercron 803M, Supercron 813
A, Supercron 803H, Supercron 804
M, Supercron C, Supercron 814H, Supercron L-206, Supercron A, Supercron B, Supercron BX, and Toyo Kasei Kogyo Co., Ltd.
Hardlen B-13, Hardlen B-2038, Hardlen B-2000, Hardlen B-4000, Hardlen B-4040, Hardlen B-4041, Hardlen 13-MLJ, Hardlen 13-MLJ-T, Hardlen 13-MLJ-TL , Hardlen B-13-ML
J, CY-9020A, Hardlen 13-MLJ, and the like.

In the resin particles used in the present invention, the polymer compound used for forming these phase separations can be used alone or in combination of two or more.

The ratio between the radically polymerizable unsaturated monomer, the polymer formed by polymerization of the unsaturated monomer, and the polymer compound that forms phase separation is as follows:
Generally, the amount is preferably 1 to 300 parts by weight based on 100 parts by weight of the radical polymerizable unsaturated monomer. More preferably, it is 5 to 100 parts by weight.

This ratio varies depending on the type of the radically polymerizable unsaturated monomer used and the type of the polymer compound that forms phase separation.

According to this ratio, the target particle shape becomes uneven or porous, and if it is porous, the pore size also changes.

The radical polymerization initiator that can be used in the resin particles used in the present invention is an azo compound or a peroxide generally used for radical polymerization.

More specifically, examples of the azo initiator include 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile) and 2,2′-azobis (2-cyclopropylpropionitrile) ), 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2-methylpropionitrile), 2,2'-azobis (2-methylbutyronitrile) 1,1 '-Azobis (cyclihexane-1-carbonitrile), dimethyl 2,2'-azobis (2-methylpropionate) and the like can be exemplified.

As the peroxide-based initiator, methyl ethyl ketone peroxide, methyl isobutyl peroxide, methylcyclixanone peroxide, diisopropylbenzene hydroperoxide,
Cumene hydroperoxide, tertiary butyl peroxide, isobutyryl peroxide, bis-
3,5,5-trimethylhexanoyl peroxide,
Lauroyl peroxide, benzoyl peroxide, dicumyl peroxide, ditertiary mil peroxide, ditertiary butyl peroxide,
Tertiary butyl peroxy-2-ethylhexanoate, tertiary butyl peroxyisobutyrate,
Examples thereof include di-3-methoxybutyl peroxydicarbonate, tertiary butyl peroxypivalate, and tertiary butyl peroxy neodecanoate.

These radical polymerization initiators can be used alone or in combination of two or more. Also,
The usage ratio of the radical polymerization initiator is preferably 0.1 to 10 parts by weight based on 100 parts by weight of the radical polymerizable unsaturated monomer.

The resin particles used in the present invention comprise the above-mentioned radically polymerizable unsaturated monomer, a polymer compound which forms a phase separation with a polymer produced by polymerization of the unsaturated monomer, and a radical polymerization initiator. The mixture can be obtained by suspension polymerization of a mixture of the mixture with an organic solvent, if necessary.

As an effect in this case, particles having a small particle diameter can be effectively obtained by lowering the viscosity of the mixture.

When an organic solvent is used, a place where a phase separation reaction occurs in the process of suspension polymerization is effectively obtained,
As a result, the structure inside the particle can be made a uniform stitch structure or a structure like an ant nest.

As the organic solvent, for example, toluene,
Hydrocarbon solvents such as xylene, methyl ethyl ketone,
Examples include ketone solvents such as methyl isobutyl ketone, ester solvents such as ethyl acetate and butyl acetate, and ether solvents such as dioxane and ethylene glycol diethyl ether. These solvents can be used alone or as a mixture.

The amount of the organic solvent used is a mixture of the unsaturated monomer capable of undergoing radical polymerization, a polymer compound capable of forming phase separation, and a radical polymerization initiator.
1 to 50 parts by weight per 0 parts by weight is preferred. More preferably, it is 5 to 20 parts by weight.

The resin particles used in the present invention can be synthesized in water in the presence of a dispersion stabilizer by a usual suspension polymerization method. As the water to be used, it is preferable to use ion exchange water or pure water.

Examples of the dispersant include water-soluble polymers such as polyvinyl alcohol, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, and polyvinylpyrrolidone.

More specifically, examples of polyvinyl alcohol include POVAL PVA-105 and PVAR manufactured by Kuraray Co., Ltd.
VA-107, PVA-110, PVA-115, PV
Fully saponified PVA such as A-117, PVA-120,
PVA-124, PVA-203, PVA-204, P
VA-205, PVA-210, PVA-215, PV
A-217, PVA-220, PVA-224, and partially saponified PVA thereof.

[0039] Specific examples of the water-soluble cellulose include Metroose 60SH50 and 65S manufactured by Shin-Etsu Chemical Co., Ltd.
H50, 60SH4000, 65SH4000, 90S
H4000 or the like, or HEC Daicel SP200, SP250, SP400, manufactured by Daicel Chemical Industries, Ltd.
SP500, SP550, SP600, SP750, S
P800, SP850, SP900 or the like, or CMC Daicel NO. 1105, N
O. 1107, NO. 1110, N30, NO. 114
0, NO. 1150, NO. 1160, NO. 117
0, NO. 1180, NO. 1190 and the like.

The concentration of the dispersant varies depending on the dispersant to be used, but is 0.1 to 100 parts by weight of water.
-30 parts by weight are preferred.

Further, an anionic surfactant, a nonionic surfactant, and a cationic surfactant can be used in combination as a dispersing aid. The addition amount varies depending on the surfactant used, but is preferably 0.001 to 20 parts by weight based on 100 parts by weight of water.

In order to form a particularly complicated porous state, it is preferable to use a mixture of water-soluble cellulose and a small amount of a surfactant such as sodium dodecylbenzenesulfonate dissolved in water to obtain a dispersion stabilizer. .

In the synthesis of the resin particles used in the present invention, components that are not directly related to the synthesis of particles such as a pigment component, a fragrance component, a pharmaceutical component, a pesticide, a lubricating oil, etc., are contained in an unsaturated monomer component or a dispersion system. By adding to the above, a carrier having an effect expressed by each component can be obtained.

For example, in the case of synthesis by adding a coloring pigment, colored porous particles and irregular shaped particles are obtained.

The resin particles used in the present invention can be obtained by subjecting a mixture having the above composition to ordinary suspension polymerization, and the resin particles obtained after the suspension polymerization reaction are washed with water to remove the dispersant from the resin particles. Then, by drying, dried resin particles are obtained.

The dried particles are pulverized and classified as needed.

The average particle size of the resin particles of the present invention is 0.1
The thickness is preferably from 200 to 200 μm, but it differs slightly depending on the purpose of the pattern paint, matte paint, finger touch paint, etc., and more preferably 1 in the case of a grain-pattern paint.
5 to 100 μm. 5 to 2 for matte paint
0 μm. In the case of a touch-sensitive paint such as a suede-like paint, the thickness is 10 to 50 μm.

If the average particle size is 200 μm or more, the appearance of the coating composition of the present invention after drying after application is not preferable. On the other hand, when the average particle size is 0.1 μm or less, the reaction product is in an emulsified state, and it becomes difficult to perform a washing step such as washing with water after the suspension polymerization reaction, which is not preferable.

The present invention is a coating composition using the above resin particles. As the binder resin which can be used in the present invention, all kinds of resins generally used for coating can be used.

For example, acrylic resins, polyester resins, urethane resins, epoxy resins, polyolefin resins, silicone resins, fluorine resins, which are generally soluble in organic solvents,
Examples include nitrocellulose resins.

In addition, water-soluble, suspension, and emulsion acrylic resins, polyester resins, urethane resins, epoxy resins, polyolefin resins, silicone resins, fluorine resins, and nitrocellulose resins can also be exemplified.

These binder resins can be used alone or
More than one kind can be blended and used.

The crosslinking resin such as an isocyanate-based resin, an amino-based resin, an epoxy-based resin, and a silicone-based resin used for crosslinking and curing the coating resin is also crosslinked after the coating film is formed, and the coating film component Therefore, it can be considered as a component of the binder resin.

The resin particles used in the coating composition of the present invention is preferably 0.1 to 150 parts by weight based on 100 parts by weight of the dry weight of the binder resin.
It may be slightly different depending on the purpose of matte paint, finger touch paint, etc., more preferably 5 to 50 parts by weight in the case of a textured paint, and in the case of a matte paint, it is used in combination. It is 10 to 120 parts by weight, depending on the extender pigment, and 10 to 110 parts by weight in the case of a finger tactile coating such as a suede pattern paint, depending on the extender used together.

When the resin particles are used in an amount of 150 parts by weight or more with respect to 100 parts by weight of the dry weight of the binder resin, it is not preferable because appearance defects such as cracks in the dried coating film occur.

The dry weight of the binder resin is 100
When the resin particles are used in an amount of 0.1 part by weight or less with respect to parts by weight, the rheological properties of the coating composition expressed by the resin particles and the good scratch resistance in the applied dried coating film It is not preferable because textures such as properties, chemical resistance and tactile sensation cannot be obtained.

The coating composition of the present invention may optionally contain
Known coating surface adjusters, fluidity adjusters, ultraviolet absorbers, light stabilizers, curing catalysts, extenders, coloring pigments, metal pigments, mica powder pigments, dyes, and the like can be added.

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

The coating composition of the present invention can be applied by a general coating method such as spray coating, roll coating, brush coating and the like.

[0060]

EXAMPLES Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited thereto.

Example 1 Synthesis of Resin Particles (hereinafter referred to as Resin Particles A) As a dispersant solution, METROZE 60S manufactured by Shin-Etsu Chemical Co., Ltd.
Using an H502.5% aqueous solution, the resin particle composition was butyl methacrylate / trimethylolpropane trimethacrylate / hardlen B-4000 / TX23-C75 =
A monomer mixture consisting of 50/30/20/2 was used.

Here, Hardlen B-4000 is a chlorinated polyolefin resin manufactured by Toyo Kasei Kogyo Co., Ltd., and is a 30% solution diluted with toluene. Also, T
X23-C75 is a peroxide-based polymerization initiator manufactured by Kayaku Akzo Co., Ltd., and is 75% diluted with a saturated aliphatic hydrocarbon.
It is a diluted product. Therefore, this is an example in which an organic solvent is contained in a part of the particle forming component.

As a synthesis method, 300 g of the above dispersant solution was charged into a 500-ml glass four-necked round-bottomed flask equipped with a stirrer, a cooling pipe, and a nitrogen inlet pipe, and was stirred at room temperature (about 25 ° C.) with a stainless steel stirring blade. While stirring vigorously (about 300 RPM), 75 g of the above monomer mixture was added little by little. After stirring for 15 minutes, gradually raise the temperature to 50
C. kept constant. 63 ° C after keeping at 50 ° C for 30 minutes
And kept for 4 hours. Then, the reaction was terminated by cooling to near room temperature.

The reaction was washed with a large amount of water and dried at 80 ° C. for 2 hours using a dryer. The dried product was broken with a finger to obtain a powder.

The obtained dried resin particles were classified to obtain resin particles having an average particle diameter of 10 μm.

When the resin particles were observed with an electron microscope, they were truly spherical resin particles. Further detailed observation revealed that the porous particles had many pores of 1 micrometer or less. Further, when a cross section was formed with a microtome and observed, the inside of the particle was shaped like an ant nest.

Synthesis of Binder Resin for Paint (hereinafter referred to as Resin B) In a four-necked flask equipped with a nitrogen inlet tube, a thermometer, a cooling tube, a dropping funnel, and a stirrer, 240 parts of toluene and xylene 2
Forty parts were charged and heated to 120 ° C.

Separately prepared methyl methacrylate
6 parts, styrene 96 parts, 2-hydroxyethyl acrylate 68.6 parts, normal butyl methacrylate 121 parts,
FM-5 (Polylactone compound manufactured by Daicel Chemical Industries, Ltd.)
A mixture consisting of 96 parts of 4.8 parts of methacrylic acid and 38.4 parts of tert-butyl peroxy 2-ethylhexanoate was added to the flask over 2 hours using a dropping funnel.

After completion of the addition, tert-butyl peroxy 2-ethylhexanoate (2 parts) was added every 20 minutes for 100 minutes in total, 5 times.

Further, the temperature in the flask was maintained at 120 ° C. for 100 minutes, and then cooled to room temperature to terminate the reaction, thereby obtaining a resin B.

Adjustment of paint curing resin (hereinafter referred to as curing agent C)
50 parts of duranate E-402 90T (an isocyanate compound manufactured by Asahi Kasei Corporation), duranate 24A-10
0 (a burette-added type isocyanate compound of hexamethylene diisocyanate manufactured by Asahi Kasei Corporation) 30
And 20 parts of toluene were mixed to obtain a curing agent C.

Adjustment of paint thinner (hereinafter referred to as thinner D) Thinner D was obtained by mixing 20 parts of ethyl acetate, 30 parts of methyl isobutyl ketone, 30 parts of toluene, and 20 parts of Solvesso 150 (hydrocarbon-based mixed solvent). Was.

A binder resin was obtained by mixing a curing agent C in an amount equivalent to 1.1 equivalents of isocyanate groups with respect to 1 equivalent of hydroxyl groups contained in the resin B.

To 100 parts by weight of the dry weight of the binder resin, 100 parts by weight of resin particles A and 50 parts by weight of thinner D were added and sufficiently stirred. After the stirring, thinner D was further added and diluted with a Ford cup # 4 at 25 ° C. until the viscosity became 11.5 seconds.

(Coating and drying) ABS as a coating material
The coating composition was uniformly applied on a blackboard by air spray coating so that the dry film thickness became 25 μm.
After the completion of the air spray, the mixture was allowed to stand for 5 minutes, and dried in a box-type drying oven at 80 ° C. for 30 minutes. Furthermore, the drying process was completed by leaving it to stand at room temperature for one week.

After finishing the drying process, the texture of the applied paint is
The matte soft coating film had a smooth finger feel. Table 1 shows the evaluation results of the nail scratch resistance and the appearance.

Example 2 Resin particles A, resin B and paint hardener C described in Example 1
And paint thinner D, using 110 parts by weight of resin particles A with respect to 100 parts by weight of the dry weight of the binder resin.
Was obtained, and the same coating and drying as in Example 1 were performed to obtain a coating film of Example 2.

The texture of the applied paint after the drying process is
The matte soft coating film had a smooth finger feel. Table 1 shows the evaluation results of the nail scratch resistance and the appearance.

Example 3 The resin particles A, the resin B, and the paint hardener C described in Example 1
And a paint composition using 120 parts by weight of the resin particles A with respect to 100 parts by weight of the dry weight of the binder resin using the paint thinner D and a thinner D for coating dilution. The same coating and drying as in Example 1 were performed. 3 was obtained.

After the drying process, the texture of the applied paint is
The matte soft coating film had a smooth finger feel. Table 1 shows the evaluation results of the nail scratch resistance and the appearance.

Comparative Example 1 Instead of the resin particles A described in Example 1, crosslinked resin particles MBX which are spherical acrylic resin particles having a smooth surface.
-8 (resin particles manufactured by Sekisui Plastics Co., Ltd.) was used. Otherwise, the resin B obtained in Example 1, the paint hardener C and the paint thinner D were used, and the dry weight of the binder resin was 10%.
A coating composition using 100 parts by weight of MBX-8 with respect to 0 parts by weight was obtained, and the same coating and drying as in Example 1 were performed to obtain a coating film of Comparative Example 1.

The texture of the applied paint after the drying process is
The coating was hard and matte. Table 1 shows the evaluation results of the nail scratch resistance and the appearance.

Comparative Example 2 Instead of the resin particles A described in Example 1, crosslinked resin particles MBX which are spherical acrylic resin particles having a smooth surface.
-8 (resin particles manufactured by Sekisui Plastics Co., Ltd.) was used. Otherwise, the resin B obtained in Example 1, the paint hardener C and the paint thinner D were used, and the dry weight of the binder resin was 10%.
A coating composition using 110 parts by weight of MBX-8 with respect to 0 parts by weight was obtained, and the same coating and drying as in Example 1 were performed to obtain a coating film of Comparative Example 2.

The texture of the applied paint after the drying process is
The coating was hard and matte. Table 1 shows the evaluation results of the nail scratch resistance and the appearance.

Comparative Example 3 Instead of the resin particles A described in Example 1, crosslinked resin particles MBX, which are spherical acrylic resin particles having a smooth surface.
-8 (resin particles manufactured by Sekisui Plastics Co., Ltd.) was used. Otherwise, the resin B obtained in Example 1, the paint hardener C and the paint thinner D were used, and the dry weight of the binder resin was 10%.
A coating composition using 120 parts by weight of MBX-8 with respect to 0 parts by weight was obtained, and coating and drying were performed in the same manner as in Example 1 to obtain a coating film of Comparative Example 3.

[0086] The texture of the applied paint after the drying process is
The coating was hard and matte. Table 1 shows the evaluation results of the nail scratch resistance and the appearance.

Table 1 The scratch resistance evaluation is a relative evaluation of the scratched state when the coating film is scratched with a nail.

Example 4 Synthesis of Binder Resin for Paint (hereinafter referred to as Resin E) Toluene 200 was placed in a 1-liter four-necked flask equipped with a nitrogen inlet tube, a thermometer, a cooling tube, a dropping funnel, and a stirring device.
And 200 parts of n-butanol, and heated to 90 ° C.

Separately prepared methyl methacrylate 150
Part, n-butyl methacrylate 117.5 parts, tertiary butyl methacrylate 100 parts, 2-hydroxyethyl methacrylate 5 parts, styrene 25 parts, methacrylic acid 2.5 parts, tertiary butyl peroxy 2-ethylhexanoate The mixture of 2 parts was added to the flask using a dropping funnel over 2 hours.

After completion of the addition, 0.5 parts of tert-butyl peroxy 2-ethylhexanoate was added every 30 minutes for 120 minutes, for a total of 4 times. In addition, 120
The temperature inside the flask was kept at 90 ° C. for minutes, and then the temperature was raised to 110 ° C. and kept for 100 minutes. Then, 100 parts of toluene, 10 parts of n-butanol
After adding 0 parts and cooling to room temperature, the reaction was completed to obtain resin E.

Preparation of thinner for dilution (hereinafter referred to as thinner F) 20 parts of ethyl acetate, 30 parts of isobutanol, and 3 parts of toluene
0 parts and 20 parts of diacetone alcohol were mixed to obtain a thinner F.

To 100 parts by weight of the dry weight of the resin E, 3 parts by weight of the resin particles A of Example 1 and 50 parts by weight of the thinner F were added and stirred. Mizukasil P-801, a matte extender (fine powdered hydrous silicic acid manufactured by Mizusawa Chemical Industry Co., Ltd.), is used until the gloss of the dried coating film after coating is 5.0 on a 60 ° gloss meter. And add another 25
The coating composition of Example 4 was obtained by diluting with Thinner F until the viscosity at 0 ° C was 10.5 seconds with Ford Cup # 4.

(Coating and Drying) ABS as a coating material
The coating composition of Example 4 was uniformly applied on a blackboard by air spray coating so that the dry film thickness became 15 μm.

[0094] After the end of the air spray, let stand for 5 minutes.
Drying was performed in a box-type drying oven at 60 ° C. for 30 minutes.
Furthermore, the drying process was completed by leaving it to stand at room temperature for one week.

The texture of the applied paint after the drying process is
It was a hard matte shape. Table 2 shows the evaluation results of the nail scratch resistance.

Example 5 A coating composition using the resin particles A, the resin E, and the paint thinner F described in Example 4, and using 5 parts by weight of the resin particles A with respect to 100 parts by weight of the dry weight of the binder resin. The product was obtained and subjected to the same coating and drying as in Example 4 to obtain a coating film of Example 5.

The texture of the applied paint after the drying process was a hard matte. Table 2 shows the evaluation results of the nail scratch resistance.

Example 6 A coating composition using the resin particles A, the resin E, and the paint thinner F described in Example 4, and using 10 parts by weight of the resin particles A based on 100 parts by weight of the dry weight of the binder resin. The product was obtained and subjected to the same coating and drying as in Example 4 to obtain a coating film of Example 6.

The texture of the applied paint after the drying process is
It was a hard matte shape. Table 2 shows the evaluation results of the nail scratch resistance.

Example 7 A coating composition using 30 parts by weight of resin particles A with respect to 100 parts by weight of a dry weight of a binder resin, using the resin particles A, the resin E, and the thinner F for coating dilution described in Example 4. The product was obtained and subjected to the same coating and drying as in Example 4 to obtain a coating film of Example 7.

After the drying process, the texture of the applied paint is
It was a hard matte shape. Table 2 shows the evaluation results of the nail scratch resistance.

Table 2 The scratch resistance evaluation is a relative evaluation of the scratched state when the coating film is scratched with a nail.

Comparative Example 4 Instead of the resin particles A described in Example 4, crosslinked resin particles MBX which are spherical acrylic resin particles having a smooth surface.
-8 (resin particles manufactured by Sekisui Plastics Co., Ltd.) was used. Except for this, the resin E obtained in Example 4 and the paint thinner F were used.
To obtain a coating composition using 3 parts by weight of MBX-8 with respect to 100 parts by weight of the dry weight of the binder resin, and performing the same coating and drying as in Example 4 to obtain the coating film of Comparative Example 4. Was.

After the drying process, the texture of the applied paint is
The coating was hard and matte. Table 2 shows the evaluation results of the nail scratch resistance and the appearance.

Comparative Example 5 Instead of the resin particles A described in Example 4, crosslinked resin particles MBX- which are spherical acrylic resin particles having a smooth surface.
8 (resin particles manufactured by Sekisui Plastics Co., Ltd.). Except for this, using the resin E obtained in Example 4 and the thinner F for diluting the coating material, a coating composition using 5 parts by weight of MBX-8 with respect to 100 parts by weight of the dry weight of the binder resin was obtained. The same coating and drying as described above were performed to obtain a coating film of Comparative Example 5.

The texture of the applied paint after the drying process is
The coating was hard and matte. Table 2 shows the evaluation results of the nail scratch resistance and the appearance.

Comparative Example 6 Instead of the resin particles A described in Example 4, crosslinked resin particles MBX which are spherical acrylic resin particles having a smooth surface.
-8 (resin particles manufactured by Sekisui Plastics Co., Ltd.) was used. Except for this, the resin E obtained in Example 4 and the paint thinner F were used.
To obtain a coating composition using 10 parts by weight of MBX-8 with respect to 100 parts by weight of the dry weight of the binder resin, and performing the same coating and drying as in Example 4 to obtain the coating film of Comparative Example 6. Was.

The texture of the applied paint after the drying process is
The coating was hard and matte. Table 2 shows the evaluation results of the nail scratch resistance and the appearance.

Comparative Example 7 Instead of the resin particles A described in Example 4, crosslinked resin particles MBX which are spherical acrylic resin particles having a smooth surface.
-8 (resin particles manufactured by Sekisui Plastics Co., Ltd.) was used. Except for this, the resin E obtained in Example 4 and the paint thinner F were used.
To obtain a coating composition using 30 parts by weight of MBX-8 with respect to 100 parts by weight of the dry weight of the binder resin, and performing the same coating and drying as in Example 4 to obtain the coating film of Comparative Example 7. Was.

[0110] The texture of the applied paint after the drying process is
The coating was hard and matte. Table 2 shows the evaluation results of the nail scratch resistance and the appearance.

[0111]

As described above, according to the present invention, one of the extender components in the coating composition is a radical polymerization initiator containing a mixture of a radically polymerizable unsaturated monomer and a polymer compound. In the resin particles obtained by suspension polymerization in the presence of, the compatibility decreases as the unsaturated monomer is polymerized during the suspension polymerization as the polymer compound, gradually formed from the unsaturated monomer The use of resin particles that form a phase-separated state within the particles with the polymer that has been used makes it possible to obtain paints with excellent scratch resistance and special texture not found in conventional paint compositions did.

Furthermore, since the resin particles can be synthesized at low cost in the coating composition of the present invention, the properties imparted to the coating composition and the application paint can be widely and generally provided by using porous resin particles. Enabled.

Claims (12)

[Claims] 1. A coating composition comprising a binder resin for a coating material and one or more extender pigment components, wherein the extender pigment component is at least one or more resin particles, and the resin particles are radically polymerizable unsaturated polymers. A mixture comprising a monomer and a polymer compound is obtained by suspension polymerization in the presence of a radical polymerization initiator, and the polymer compound becomes a phase as the unsaturated monomer polymerizes during the suspension polymerization. A coating composition comprising a compound having reduced solubility and gradually forming a phase-separated state in the resin particles with the polymer generated from the unsaturated monomer. 2. The coating composition according to claim 1, wherein the resin particles are porous. 3. The coating composition according to claim 1, wherein the surface of the resin particles is irregular. 4. The coating composition according to claim 1, wherein the polymer compound is at least one kind of polyolefin-based resin compound. 5. The coating composition according to claim 1, wherein the polymer compound is at least one or more chlorinated polyolefin resin compounds. 6. The polymer according to claim 1, wherein the polymer compound is modified by acid modification or acrylic graft modification for the purpose of adjusting the compatibility with a radical polymerizable unsaturated monomer in which the polymer compound coexists. A coating composition characterized in that the coating composition is improved. 7. The coating composition according to claim 1, wherein the radically polymerizable unsaturated monomer has four or more functional groups. 8. The radical-polymerizable unsaturated monomer according to claim 1, wherein the radical-polymerizable unsaturated monomer comprises a mixture of two or more kinds of monomers, and
A coating composition characterized in that at least one kind is a monomer having four or more functionalities. 9. The matte coating composition according to claim 1, wherein the resin particles are contained in an amount of 10 to 120 parts by weight based on 100 parts by weight of the dry weight of the binder resin. Stuff. 10. The pattern paint composition according to claim 1, wherein the resin particles are contained in an amount of 5 to 50 parts by weight based on 100 parts by weight of the dry weight of the binder resin. Stuff. 11. A suede-like paint according to any one of claims 1 to 8, wherein the resin particles are contained in an amount of 10 to 110 parts by weight based on 100 parts by weight of the dry weight of the binder resin. Composition. 12. A coated article according to any one of claims 1 to 11, wherein the coating composition is applied to at least a part thereof.