JP2000296362A - Coated material and coating method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a coated material imparted in texture and designing property, which are never presented until now, by imparting soft feeling on the surface of ABS or modified PP without deteriorating the soiling sticking property and further imparting anti-dazzle characteristic and scratch resistance and the coating method. SOLUTION: The coated material capable of exhibiting texture and designing property, which are never presented until now, by applying an under coating material on the base plate of a resin made automobile member and next, a bead like polyurethane coating material on a part or the whole of the surface thereof and fixing at 0-110 deg.C to impart the soft feeling, the anti-dazzle characteristic, the scratch resistance or the like without increasing the cost and deteriorating the soiling sticking property and the coating device are provided.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a coated article and a coating method for an automobile member.

[0002]

2. Description of the Related Art Conventionally, an interior member or a bumper material made of a resin made of ABS or modified PP (polypropylene) is used.
It is known that a PP foam pad material laminated with a decorated polyvinyl chloride sheet is attached. However, such a member has a problem that once the surface layer is scratched, the lower layer PP foam has low strength, so that the damage spreads, and the vinyl chloride sheet of the surface layer eventually comes off. Attempts have also been made to apply paint directly on ABS or modified PP. However, with general paints such as lacquer, the film thickness is so thin that a soft feeling cannot be obtained, and since the paint is a liquid and has a uniform color, the design is inferior,
In addition, there is a drawback that when anti-glare properties are imparted, dirt tends to adhere.

[0003]

DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned problems, and provides a coated material which gives a soft feeling to the surface of ABS or modified PP without deteriorating the adhesion of dirt; Painted material that imparts scratch resistance; Painted material that imparts unprecedented texture and design;
In addition, it is an object of the invention to provide a method for coating them.

[0004]

Means for Solving the Problems The inventors of the present invention have made intensive studies to achieve the above object, and have reached the present invention. That is, the present invention provides an automobile member substrate layer, an undercoat paint (A) layer formed thereon, and at least a portion of the (A) layer a bead-like color different from the undercoat paint or a substrate visible through the undercoat paint. An automotive component coating having a layer of resin coating (B), and an undercoat (A) applied to an automobile component, and then at least a portion of the coated surface is an undercoat or a bead having a different color from a substrate visible through the undercoat. This is a method for coating the above-mentioned automotive member coating material in which the resin coating material (B) is applied and then fixed at 0 to 110 ° C.

[0005]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS A painted article for automobile parts according to the present invention is shown in FIG.
As shown in (1), an undercoat (A) layer (2) is provided on an automobile member substrate (1), and at least a part of the layer has an undercoat or a bead having a different color from the substrate visible through the undercoat. It has a structure having a layer (3) of a resin paint (B). Further, as shown in FIG. 2, if necessary, it has a structure having a layer (4) of a coating agent (C) on the layer (3).

In (A), the composition is not particularly limited as long as it is a material having an adhesive force to both the automobile member and the layer of the overcoated bead-shaped resin coating material (B). This is a composition comprising a combination of a material (a1) having good adhesion and a material (a2) having good adhesion between the material (a1) and (B). Here, the term “automobile member” refers to a resin for a molded product generally used for automobiles, and includes a thermoplastic resin and a thermosetting resin. P as thermoplastic resin
E (polyethylene, weight average molecular weight Mw 2,000-
1,000,000), PP (polypropylene, Mw
1,000 to 1,000,000), polystyrene (M
w 10,000-400,000), ABS [Mw4
0.000 or more, acrylonitrile / butadiene / styrene weight ratio (10-30) / (5-50) / (30-7)
0)] and the like, and examples of the thermosetting resin include a urea resin, a melamine resin, an unsaturated polyester resin, an epoxy resin, and a phenol resin. Good adhesion means that 90 or more squares in 100 squares and preferably 100 squares in 100 squares remain in a cross-cut cellophane tape peel test (JISK5400).

[0007] Assuming that (a1) is an example of an automobile member being the most typical PP, PP, PE, ethylene-propylene non-conjugated diene terpolymer (EPDM), ethylene-propylene copolymer (EPR) ) And non-polar polymer resins such as chlorinated (chlorination rate 5 to 30)
% By weight), maleic anhydride modification (copolymerization ratio 1 to 10% by weight), and the like. Preferred is a modified product of PP having high adhesion, and particularly preferred is maleic anhydride-modified chlorinated PP (maleic anhydride-modified 5% by weight, chlorination rate 20% by weight). Examples of (a2) include polyisocyanates and polyurethanes. Polyurethane is preferred from the viewpoint of adhesion to (B).

The polyisocyanate (a2) includes:
Those conventionally used for polyurethane production can be used. Such polyisocyanates include bifunctional to
The polyisocyanate includes a trifunctional or higher functional polyisocyanate, and the polyisocyanate includes an aromatic polyisocyanate having 6 to 20 carbon atoms (excluding the carbon in the NCO group; the same applies hereinafter);
18 aliphatic polyisocyanates, alicyclic polyisocyanates having 6 to 15 carbon atoms, araliphatic polyisocyanates having 8 to 15 carbon atoms, and modified products of these polyisocyanates (urethane groups, carbodiimide groups, allophanate groups, burettes) Group, uretdione group, uretimine group, isocyanurate group, oxazolidone group-containing modified product) and a mixture of two or more of these.

Specific examples of the aromatic polyisocyanate include, for example, 1,3- and / or 1,4-phenylene diisocyanate, 2,4- and / or 2,6
-Tolylene diisocyanate (TDI), crude TDI,
2,4'- and / or 4,4'-diphenylmethane diisocyanate (MDI), 4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-diisocyanatobiphenyl, 3,3 '-Dimethyl-4,4'-
Diisocyanatodiphenylmethane, crude MDI [crude diaminodiphenylmethane [condensation product of formaldehyde and aromatic amine (aniline) or a mixture thereof;
Mixture of diaminodiphenylmethane with a small amount (for example, 5 to 20% by weight) of a trifunctional or higher polyamine]] polyaryl polyisocyanate (PAP
I)], 1,5-naphthylene diisocyanate, 4,
4 ', 4 "-triphenylmethane triisocyanate,
m- and p-isocyanatophenylsulfonyl isocyanate.

Specific examples of the above aliphatic polyisocyanate include, for example, ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate,
6,11-undecane triisocyanate, 2,2,4
-Trimethylhexamethylene diisocyanate, lysine diisocyanate, 2,6-diisocyanatomethylcaproate, bis (2-isocyanatoethyl) fumarate, bis (2-isocyanatoethyl) carbonate,
-Isocyanatoethyl-2,6-diisocyanatohexanoate.

Specific examples of the alicyclic polyisocyanate include, for example, isophorone diisocyanate (IPD
I), dicyclohexylmethane-4,4'-diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate (hydrogenated TDI), bis (2-isocyanatoethyl) -4-cyclohexene-1,2-diene Carboxylate, 2,5- and / or 2,6-norbornane diisocyanate.

Specific examples of the above araliphatic polyisocyanate include, for example, m- and / or p-xylylene diisocyanate (XDI), α, α, α ′, α′-tetramethylxylylene diisocyanate (TMXDI)
Is mentioned.

Examples of the modified polyisocyanate include modified MDI (urethane-modified MDI, carbodiimide-modified MDI, trihydrocarbyl phosphate-modified MDI), urethane-modified TDI, and buret-modified HD.
I, isocyanurate-modified HDI, polyisocyanate-modified products such as isocyanurate-modified IPDI, and mixtures of two or more of these [for example, a combination of modified MDI and urethane-modified TDI (isocyanate group-containing prepolymer)].

Of these, preferred are aromatic polyisocyanates having good reactivity with hydroxyl groups and the like.
DI and aliphatic and cycloaliphatic polyisocyanates with good lightfastness, especially HDI, IPDI.

As the polyurethane (a2), an NCO terminal or a hydroxyl terminal prepared by a known method using a polyol having a hydroxyl group at a molecular terminal and / or a side chain and an excess or an insufficient amount of a polyfunctional isocyanate is used. Of polyurethane. Examples of the polyol include a high molecular polyol and a low molecular polyol. Examples of the polymer polyol include an acrylic polyol, a polybutadiene polyol, a polyester polyol, and a polyether polyol. Among the polymer polyols, the acrylic polyol is a copolymer of a vinyl monomer having a hydroxyl group (for example, hydroxyethyl methacrylate) and another vinyl monomer (for example, methyl methacrylate, styrene, butyl acrylate), and has 2 to 2 functional groups. 3, those having a hydroxyl value of 10 to 150. Examples of the polybutadiene polyol include a copolymer of butadiene having a hydroxyl group at a terminal and another vinyl monomer (for example, methyl methacrylate, styrene, and acrylonitrile) having 2 to 3 functional groups and a hydroxyl value of 0.5 to 1. Can be
Examples of the polyester polyol include a condensation-based polyester polyol, a lactone-based polyester polyol, and a polycarbonate diol. As the condensation-based polyester polyol, dicarboxylic acid (for example,
Adipic acid) and a diol (e.g., ethylene glycol, diethylene glycol, 1,6-hexane glycol, neopentyl glycol) obtained by a dehydration-condensation reaction, having a number of functional groups of 2 to 3 and a hydroxyl value of 20 to 500. Can be Examples of the lactone-based polyester polyol include an addition-polymerized polyester obtained by ring-opening polymerization of ε-caprolactam, which has 2 to 3 functional groups and a hydroxyl value of 15 to 600. The polycarbonate diol is a polyester obtained by addition polymerization of a diol (for example, 1,6-hexane glycol) and ethylene carbonate, and has two functional groups and a hydroxyl value of 50 to 2.
50. Examples of the polyether polyol include an initiator [eg, water, low molecular weight polyol (diol, triol, etc.)] and an alkylene oxide (eg, ethylene oxide, propylene oxide, TH).
Which is obtained by addition polymerization of F) and has 2 to 2 functional groups.
3, those having a hydroxyl value of 10 to 600. Examples of the low molecular polyol include dihydric alcohols having 2 to 20 carbon atoms [ethylene glycol, propylene glycol, 1,3
-Butylene glycol, 1,4-butanediol, 1,
6-hexanediol, 3-methylpentanediol,
Diethylene glycol, neopentyl glycol, 1,
4-bis (hydroxymethyl) cyclohexane, 1,4
-Bis (hydroxyethyl) benzene, 2,2-bis (4,4'-hydroxycyclohexyl) propane, etc.]; a trihydric alcohol having 3 to 20 carbon atoms (glycerin,
Trimethylolpropane). Among the polymer polyols, as a method for producing an acrylic polyol, for example, a vinyl monomer having a hydroxyl group (for example, hydroxyethyl methacrylate) and another vinyl monomer (for example,
Methyl methacrylate, styrene, butyl acrylate). As a method for producing a polyester polyol, for example, in a reaction between a diol (eg, ethylene glycol, 1,4-butanediol) and a dicarboxylic acid (eg, adipic acid, isophthalic acid), the molar ratio of diol / dicarboxylic acid exceeds 1.0. Examples of the method include a method in which both ends are converted to hydroxyl groups, and a method in which a diol is added to a high-molecular-weight polyester and heated to depolymerize. Examples of the method for producing the polyether polyol include a method in which water or a low molecular weight polyol (eg, ethylene glycol, propylene glycol, glycerin) is used as an initiator to carry out ring-opening polymerization of an alkylene oxide (2 to 4 carbon atoms). Examples of the polyfunctional isocyanate include those exemplified in the section of the polyisocyanate in (a2). Of the above polyurethanes, preferred is a reaction product of a polyester polyol and diisocyanate from the viewpoint of solvent solubility and water resistance, and more preferred is a 1,4-butanediol / adipate system from the viewpoint of abrasion resistance of a coating film. It is a reaction product of polyester polyol and MDI.

The polyurethane of (a2) may have a urea bond if necessary, and is produced by a known method using the NCO-terminated polyurethane and amine obtained by the method exemplified in the section of the polyurethane of (a2). Are included. Amines include polyamines and amino alcohols.

Examples of the polyamine include: (1) an aliphatic polyamine (2 to 18 carbon atoms) alkylene (2 to 6 carbon atoms) diamine (ethylenediamine, propylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, etc.);
Polyalkylene (C2-6) polyamine [diethylenetriamine, iminobispropylamine, bis (hexamethylene) triamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, etc.]; these alkyls (C1-4) Or hydroxyalkyl (C2-4) substituted [dialkyl (C1-3) aminopropylamine, trimethylhexamethylenediamine, aminoethylethanolamine, methyliminobispropylamine, etc.]; alicyclic or heterocyclic-containing fat Group polyamine (C4-20) [3,9-
Bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro [5,5] undecane]; aromatic ring-containing aliphatic amine (8 to 15 carbon atoms) [xylylenediamine, tetrachloro-p- (2) alicyclic polyamine (4 to 15 carbon atoms) 1,3-diaminocyclohexane, isophoronediamine, menthanediamine, 4,4′-methylenedicyclohexanediamine (hydrogenated methylenedianiline), etc. 3) Heterocyclic polyamine (having 4 to 15 carbon atoms) piperazine, N-aminoethylpiperazine, 1,4-diaminoethylpiperazine, etc.

(4) Aromatic polyamines (C6 to C2)
0) unsubstituted aromatic polyamines [1,2-, 1,3- and 1,4-phenylenediamine, 2,4'- and 4,
4'-diphenylmethanediamine, crude diphenylmethanediamine [polyphenylpolymethylenepolyamine], diaminodiphenylsulfone, benzidine, thiodianiline, bis (3,4-diaminophenyl) sulfone, 2,6-diaminopyridine, m-aminobenzylamine, triamine Phenylmethane-4,4 ', 4 "-triamine, naphthylenediamine, etc.]; having a nucleus-substituted alkyl group (having 1 to 4 carbon atoms, such as methyl, ethyl, n- and i-propyl, and butyl). Aromatic polyamines [2,4- and 2,6-tolylenediamine, crude tolylenediamine, diethyltolylenediamine, 4,
4'-diamino-3,3'-dimethyldiphenylmethane, 4,4'-bis (o-toluidine), dianisidine, diaminoditolyl sulfone, 1,3-dimethyl-
2,4-diaminobenzene, 1,3-diethyl-2,4
-Diaminobenzene, 1,3-dimethyl-2,6-diaminobenzene, 1,4-diethyl-2,5-diaminobenzene, 1,4-diisopropyl-2,5-diaminobenzene, 1,4-dibutyl-2 , 5-Diaminobenzene, 2,4-diaminomesitylene, 1,3,5-triethyl-2,4-diaminobenzene, 1,3,5-triisopropyl-2,4-diaminobenzene, 1-methyl-
3,5-diethyl-2,4-diaminobenzene, 1-methyl-3,5-diethyl-2,6-diaminobenzene,
2,3-dimethyl-1,4-diaminonaphthalene, 2,
6-dimethyl-1,5-diaminonaphthalene, 2,6-
Diisopropyl-1,5-diaminonaphthalene, 2,6
Dibutyl-1,5-diaminonaphthalene, 3,3 ′,
5,5′-tetramethylbenzidine, 3,3 ′, 5
5'-tetraisopropylbenzidine, 3,3 ', 5
5'-tetramethyl-4,4'-diaminodiphenylmethane, 3,3 ', 5,5'-tetraethyl-4,4'-
Diaminodiphenylmethane, 3,3 ', 5,5'-tetraisopropyl-4,4'-diaminodiphenylmethane, 3,3', 5,5'-tetrabutyl-4,4'-diaminodiphenylmethane, 3,5-diethyl- 3'-methyl-2 ', 4-diaminodiphenylmethane, 3,5-
Diisopropyl-3'-methyl-2 ', 4-diaminodiphenylmethane, 3,3'-diethyl-2,2'-diaminodiphenylmethane, 4,4'-diamino-3,3'
-Dimethyldiphenylmethane, 3,3 ', 5,5'-tetraethyl-4,4'-diaminobenzophenone, 3,
3 ′, 5,5′-tetraisopropyl-4,4′-diaminobenzophenone, 3,3 ′, 5,5′-tetraethyl-4,4′-diaminodiphenyl ether, 3,
3 ′, 5,5′-tetraisopropyl-4,4′-diaminodiphenylsulfone, and mixtures of these isomers in various proportions];
aromatic polyamines having halogens such as l, Br, I and F; alkoxy groups such as methoxy and ethoxy; nitro groups) [methylenebis-o-chloroaniline, 4-chloro-o-phenylenediamine, 2-chloro-1 , 4-
Phenylenediamine, 3-amino-4-chloroaniline, 4-bromo-1,3-phenylenediamine, 2,5
-Dichloro-1,4-phenylenediamine, 5-nitro-1,3-phenylenediamine, 3-dimethoxy-4-
Aminoaniline; 4,4'-diamino-3,3'-dimethyl-5,5'-dibromodiphenylmethane, 3,3 '
-Dichlorobenzidine, 3,3'-dimethoxybenzidine, bis (4-amino-3-chlorophenyl) oxide, bis (4-amino-2-chlorophenyl) propane, bis (4-amino-2-chlorophenyl) sulfone, bis ( 4-amino-3-methoxyphenyl) decane, bis (4-aminophenyl) sulfide, bis (4
-Aminophenyl) telluride, bis (4-aminophenyl) selenide, bis (4-amino-3-methoxyphenyl) disulphide, 4,4'-methylenebis (2-iodoaniline), 4,4'-methylenebis (2- Bromoaniline), 4,4′-methylenebis (2-fluoroaniline), 4-aminophenyl-2-chloroaniline, etc .; aromatic polyamines having a secondary amino group [part of —NH ₂ of the above aromatic polyamines] Or all of -NH-
R ′ (R ′ is an alkyl group such as a lower alkyl group such as methyl and ethyl)] [4,4′-di (methylamino) diphenylmethane, 1-methyl-2-
Methylamino-4-aminobenzene, etc.)

(5) Polyamide polyamine [dicarboxylic acid (such as dimer acid) and excess (more than 2 equivalents per equivalent of carboxyl group) polyamine [the above-mentioned alkylene (C2-6) diamine, polyalkylene (C2-C2) 6)
Low molecular weight polyamide polyamine obtained by condensation with polyamine] [6] Polyether polyamine [polyether polyol (polyalkylene (C2 to C3) glycol, etc.))
(7) cyanoethylated polyamine [acrylonitrile and polyamine [the above alkylene (C2-6) diamine, polyalkylene (C2-6) polyamine, etc.]]
(8) Other polyamines Hydrazine compounds (hydrazine, monoalkyl (C1-12) hydrazine, etc.), dihydrazide compounds (dihydrazide succinate, adipic acid) Dihydrazide, isophthalic dihydrazide, terephthalic dihydrazide, etc.), guanidine compounds (butylguanidine, 1-cyanoguanidine, etc.), dicyandiamide,
And mixtures of two or more of the above polyamines. Among these polyamines, preferred are aliphatic polyamines and alicyclic polyamines from the viewpoint of coloring the coating over time, and more preferred are isophorone diamines from the viewpoint of solvent solubility of the obtained polyurethane.

Examples of the amino alcohol include alkanolamines having 2 to 12 carbon atoms, for example, mono- and di-.
Examples thereof include alkanolamines (monoethanolamine, monoisopropanolamine, monobutanolamine, diethanolamine, dipropanolamine, and the like), and quaternized products of nitrogen atoms thereof with a quaternizing agent such as dimethyl sulfate or benzyl chloride. Of these, dialkanolamine is preferred from the viewpoint of the stability over time of the obtained polyurethane urea, and monoethanolamine is more preferred from the viewpoint of solvent solubility of the obtained urea bond-containing polyurethane.

When the polyurethane is produced using the above-mentioned isocyanate-terminated polyurethane and the above-mentioned amine, a secondary monoamine (having 2 to 20 carbon atoms, for example, dimethylamine or dibutylamine) may be added for the purpose of adjusting the molecular weight. The ratio of the isocyanate group equivalent of the polyurethane to the total equivalent of the amino group and the hydroxyl group of the amine is usually (1:
0.3) to (1: 1.1), preferably (1:
0.5) to (1: 1.0).

Of the above (a2), preferred is (B)
Depends on That is, in order to obtain an adhesive force with (B), those having similar compositions are preferable, and those having similar solubility parameters (a difference in solubility parameter is 0 to 1.
5) is preferred. The solubility parameter referred to here is represented by the square root of the ratio between the cohesive energy density and the molecular volume, and their values are referred to as “Polymer Engineering”.
and Science, Vol. 14, No. 2, p
147 to 154 (1974) ".

The number average molecular weight of (a1) is preferably from 800 to 5 from the viewpoint of adhesion to automobile members and strength.
2,000, more preferably 2,000 to 2,000.
It is 0000.

The number average molecular weight of (a2) is preferably from 100 to 5 from the viewpoint of compatibility between coating workability and (a1).
2,000, more preferably 2,000 to 2,000.
It is 0000.

The ratio of (a1) to (a2) is a weight ratio per solid content, and preferably from (1: 9) to (9: 1) from the viewpoint of the adhesion between the automobile member and the layer of (B). Yes, and more preferably (5: 5) to (8: 2).

In (A) and (B), the adhesion is improved by making the solubility parameters of (a2) and (B) close to each other, but they are reactive with each other under the condition of 0 to 110 ° C. The group having the group (1) further improves the adhesion. In the combination, a cross-linking agent functional group (for example, a hydroxyl group and an isocyanate group) and a resin functional group (for example, a hydroxyl group and an isocyanate group) used in a usual two-part thermosetting paint can be used as they are. Further, among (A), those having a functional group may be only (a1) or only (a2), and (a1)
(A2) Both may be used. Examples of preferred combinations of the functional group (A) / the functional group (B) include those having a carboxyl group / epoxy group, an isocyanate group / hydroxyl group, an isocyanate group / amino group, a hydroxyl group / epoxy group, and the reverse combination thereof. And the like. Of these, more preferred are isocyanate groups / hydroxyl groups, isocyanate groups / amino groups, and vice versa. In these combinations, the reactivity between (A) and (B) is high, so that extremely high adhesion can be obtained.

The number-average molecular weight per reactive group in (a1) is preferably from 1,000 in view of the strength of the layer (A) and the adhesion between the layer (A) and the layer (B). 9,000,
More preferably, it is 1,500 to 4,000.

The number average molecular weight per reactive group in (a2) is preferably from 100 to 5, from the viewpoint of the strength of the layer (A) and the adhesion between the layer (A) and the layer (B). 000, more preferably 200 to 4,000.

In (A), a diluting solvent is used in an amount of 0 to 90% (% by weight, the same applies hereinafter), preferably 30 to 80%, more preferably 50%, based on the total weight of (a1) and (a2).
To 70%, and as a diluting solvent, those equivalent to ordinary solvent-based paints can be used. For example, aromatic hydrocarbons (toluene, xylene, ethylbenzene,
Aliphatic or alicyclic hydrocarbon solvents (n-hexane, n-heptane, mineral spirit,
Halogen-based solvents (methyl chloride,
Methyl bromide, methyl iodide, methylene dichloride, carbon tetrachloride, trichloroethylene, perchloroethylene, etc .; ester or ester ether solvents (ethyl acetate, butyl acetate, methoxybutyl acetate, methyl cellosolve acetate, ethyl cellosolve acetate, etc.) Ether solvents (diethyl ether, tetrahydrofuran, dioxane, ethyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether, etc.); ketone solvents (acetone, methyl ethyl ketone,
Methyl isobutyl ketone, di-n-butyl ketone, cyclohexanone, etc.); alcoholic solvents (methanol,
Ethanol, n-propanol, isopropanol, n
-Butanol, isobutanol, t-butanol, 2-
Amide solvents (dimethylformamide, dimethylacetamide, etc.); sulfoxide solvents (dimethylsulfoxide, etc.); heterocyclic compound solvents (N-methylpyrrolidone, etc.); and two or more of these solvents A mixed solvent is mentioned. Preferred are toluene and toluene / methyl ethyl ketone (2/1 by weight) from the viewpoint of drying speed and solubility after coating.

In (A), 0 to 3%, preferably 0 to 3% of a reaction accelerator is added to the total weight of (a1) and (a2).
1%, more preferably 0-0.5%, and the reaction accelerator that can be used is not particularly limited, but (A) / (B) is preferably an isocyanate group / hydroxyl group or an amino group or the reverse thereof. In the case of a combination, a tin-based catalyst (tin octylate, dibutyltin dilaurate,
Stannous octoate, etc.), lead catalyst (such as lead naphthenate), tertiary amine (triethylenediamine, 1,8-
Diazabicyclo [5.4.0. ] Undec-7-ene,
Triethylamine, dimethylbenzylamine, dibutyldodecylamine, etc.). Of these, tin catalysts, particularly dibutyltin dilaurate, are preferred from the viewpoint of the reaction promoting effect. (A) / (B) is an epoxy group / carboxyl group or a hydroxyl group or a combination thereof in the case where the reaction is promoted as an alkaline earth metal catalyst (magnesium oxide, magnesium hydroxide, calcium oxide, etc.); Examples include tertiary amines (as exemplified above), phosphorus-based catalysts (such as triphenylphosphine), and onium salts (such as benzyltrimethylammonium chloride and dibutyldimethylphosphonium chloride). Of these, preferred are phosphorus-based catalysts, particularly triphenylphosphine, from the viewpoint of the reaction promoting effect.

In (A), a coloring agent is added in an amount of 0 to 10%, preferably 0 to 7%, based on the total weight of (a1) and (a2).
%, More preferably 0 to 5%,
The colorant that can be used is not particularly limited, and examples thereof include inorganic pigments, organic pigments, and dyes. Examples of inorganic pigments include white pigments (titanium oxide, lithopone, lead white,
Zinc compounds); cobalt compounds (aureolin, cobalt green, cerulean blue, cobalt blue, cobalt violet, etc.); iron compounds (iron oxide, navy blue, etc.); chromium compounds (chromium oxide, lead chromate, barium chromate, etc.); Sulfides (cadmium sulfide, cadmium yellow, ultramarine, etc.). As organic pigments, azo lake type, mono azo type, disazo type,
Azo pigments such as chelate azo, benzimidazolone,
Phthalocyanine, quinacridone, dioxazine,
Examples include polycyclic pigments such as isoindolinone-based, thioindigo-based, perylene-based, quinophthalone-based, and anthraquinone-based pigments. Dyes include azo, anthraquinone, indigoid, sulfide, triphenylmethane, pyrazolone, stilbene, diphenylmethane, xanthene, alizarin, acridine, quinone imine, thiazole, methine, nitro, Nitroso type, aniline type and the like can be mentioned.

(A) contains a pigment dispersant in an amount of 0 to 10%, preferably 0.1 to 7%, more preferably 0.5 to 5%, based on the total weight of (a1) and (a2). The pigment dispersant that can be used is not particularly limited, but surfactants such as anionic surfactants, cationic surfactants, and nonionic surfactants (for example, those described in US Pat. No. 4,331,447) ). The pigment dispersant may be bound to a resin. Among these pigment dispersants, a nonionic surfactant is preferable from the viewpoint of compatibility with a solvent, and an ethylene oxide adduct of laurylamine (10 to 30 mol) is preferable from the viewpoint of pigment dispersibility.
More preferred.

In (A), a reinforcing agent is added in an amount of 0 to 3%, preferably 0 to 1%, based on the total weight of (a1) and (a2).
%, More preferably 0 to 0.5%. The reinforcing agent that can be used is not particularly limited, but inorganic (glass fiber, carbon fiber, etc.), organic (terephthalic acid / p-phenylenediamine) Polyamide).

In (A), a matting agent is used in an amount of 0 to 30%, preferably 0 to 30%, based on the total weight of (a1) and (a2).
The matting agent can be contained at 15%, more preferably 0 to 10%, and the matting agent that can be used is not particularly limited. For example, inorganic matting agents (such as talc and sila powder),
Organics (such as protein powder) can be mentioned.

In the present invention, (B) is not particularly limited as long as it has good adhesion to (A) or (a2) in (A). (B) has a color different from that of the undercoat paint or the substrate seen through the undercoat paint, and is composed of one or more bead-like resins (b). Here, the different color means a color difference meter (for example, SPECTROPHOTOMETET manufactured by Minolta).
L obtained by measurement according to ER CM-3600d)
^{In the *} a ^* b ^* color system, the color difference ΔE ^* ab indicates a value of 0.6 or more, preferably 1 to 90, more preferably 2
~ 80. By making the color of (B) different from the undercoat paint or the substrate visible through the undercoat paint,
A plurality of colors can be obtained depending on the viewing angle, and an effect of obtaining an unprecedented excellent design property can be obtained.

(B) is not particularly limited, and commercially available organic and / or inorganic beads can be used. For example, styrene (PB-200H manufactured by Kao), phenol (Bellpearl R-900 manufactured by Kanebo), silicone (Trefill E-850 manufactured by Toray), polyethylene (Flow beads LE manufactured by Sumitomo Seika) -1080 etc.),
Acrylic (such as Techpolymer MB manufactured by Sekisui Plastics Co., Ltd.), polyurethane (such as Burnock CFB300B manufactured by Dainippon Ink and Chemicals, Inc.), and nylon (S by Toray Industries, Inc.)
Organic beads such as P-500) and melamine (Honen Microsphere MB-903 manufactured by Honen Corporation), and inorganic beads such as glass and shirasu. Of these, polyurethane-based organic beads are preferred in that the softness and scratch resistance of the coating film are good.

The method for producing (b) is not particularly limited. Examples thereof include a method of suspending a solvent solution of the above resin in water and distilling off the solvent under heating, and a method of spray drying the solvent solution. The polyurethane beads (b1), which are particularly preferred resins, will be described in detail. For example, in order to introduce a urethane bond, the polyol and the polyisocyanate are converted into a hydroxyl group / isocyanate group ratio (1/1.
2) to (1/5) to react in a water-insoluble solvent to obtain a prepolymer solution, and furthermore a reaction terminator (for example, a dialkylamine having 4 to 24 carbon atoms, a dialkanolamine having 4 to 24 carbon atoms) Is reacted in a solvent to form a urea bond, the solvent is distilled off under reduced pressure after dispersing the solution in water containing a dispersant, dehydration, a method of drying, and dispersing in water containing a dispersant. Isocyanate group-terminated urethane prepolymer (b2) and ketimine compound (b3)
Are reacted, dehydrated, and dried. Preferably, a method using the above ketimine compound, which has a spherical particle shape and is excellent in smoothness of a coating film, is used.

The dispersant is not particularly limited, and includes a low molecular dispersant and a high molecular dispersant. As the low molecular dispersant, U.S. Pat. No. 4 exemplified as the pigment dispersant of (A) above
Surfactants described in 331447. Examples of the polymer dispersant include a water-insoluble dispersant and a water-soluble dispersant. The water-insoluble dispersant is composed of a portion having affinity for (b2) and a portion having hydrophilicity in the molecule, and the portion having affinity and the portion having hydrophilicity are ester-bonded or urethane-containing. Those bonded by a bond (preferably a urethane bond),
A preferred specific example is polycaprolactone diol (number average molecular weight 1,000 to 4,000) / IPDI /
Polyethylene glycol (number average molecular weight 1,000 ~
3,000) propylene oxide (hereinafter abbreviated as PO)
And ethylene oxide (hereinafter abbreviated as EO) (the ratio of EO excluding PO and polyethylene glycol is 20% by weight.
/ 80) random co-adduct (number average molecular weight 2,000-
6,000) [1/1/1 mol] Reactant, polyethylene adipate diol (number average molecular weight 1,000 to 3.0
00) / IPDI / polyethylene glycol (number average molecular weight: 1,000 to 3,000) [1/1/1 mol]. Examples of the water-soluble dispersant include cellulose-based water-soluble resins (methylcellulose, hydroxyethylcellulose, hydroxypropylmethylcellulose, carboxymethylcellulose, etc.), polyvinyl alcohol,
Examples thereof include polyacrylates (such as alkali metal salts), polyethylene glycol, polyvinylpyrrolidone, and polyacrylamide. Of these, polyvinyl alcohol is preferred.

As the (b2), the NCO-terminated polyurethane exemplified in the section of the polyurethane of the above (a2) can also be mentioned.

(B3) is obtained by reacting a polyamine with a ketone compound by a known method such as heat dehydration, and the polyamine is an alicyclic diamine having 4 to 15 carbon atoms [4,4'-diamino-3]. , 3'-dimethyldicyclohexylmethane, diaminocyclohexane, isophoronediamine and the like]; aliphatic diamine having 2 to 12 carbon atoms [1,
2-ethylenediamine, 1,6-hexanediamine and the like]; aromatic ring-containing diamine [xylylenediamine, α,
α, α ′, α′-tetramethylxylylenediamine, etc.] and a combination of two or more of these. Examples of the ketone compound include an aliphatic or alicyclic ketone compound having 3 to 9 carbon atoms (such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone). Of these, preferred combinations are isophoronediamine / acetone and 1,6-hexylenediamine / methylethylketone.

In the synthesis of (b1), a reaction terminator can be used together if necessary for the purpose of adjusting the molecular weight. As the reaction terminator, a monohydric alcohol (having 1 carbon atom)
-6, for example, methyl alcohol, ethyl alcohol, cellosolve) and monoamines [alkylamines having 4 to 12 carbon atoms (diethylamine, mono-n-butylamine,
Di-n-butylamine and the like), alkanolamines having 4 to 12 carbon atoms (such as monoethanolamine and diethanolamine), and combinations of two or more of these. Of these, preferred are alkanolamines, and particularly preferred is diethanolamine. By using diethanolamine as a reaction terminator, the molecular terminal of (b1) becomes a hydroxyl group, and as described in detail in (A), (A) and (B) have reactivity and thus have extremely high adhesion. I can do it.

In the synthesis of (b1), the equivalent ratio of the isocyanate group to the functional group such as a hydroxyl group and an amino group that reacts with the isocyanate group is usually (1: 1) from the viewpoint of the appearance stability and the water resistance of the coating film. 0.8) to (1: 2), preferably (1: 0.9) to (1: 1.8). The ratio of the functional group is such that the hydroxyl group / amino group (equivalent ratio) is usually 0.2 to 10, preferably 0.7 to 3, from the viewpoint of the appearance and weather resistance of the coating film.
It is.

The number average molecular weight of the constituent resin (b1) is preferably from 1,000 in view of powder storage stability and coating film appearance.
0 to 40,000, and more preferably 3,000.
~ 20,000.

In (b1), a hardener is added to the resin in an amount of 0 to 6;
0%, preferably 1 to 40%, more preferably 3 to 2
The curing agent that can be contained in an amount of 5% can be used, for example, an isocyanate compound and / or a blocked product thereof [the above-mentioned (a2) and modified products thereof, for example, isocyanurate, buret, carbodiimide and the like] Modified isomers, oximes, lactams, blocked polyisocyanates such as basic nitrogen-containing compounds, etc.].

In (b1), a pigment dispersant is added to the resin in an amount of 0%.
To 30%, preferably 0.1 to 20%, more preferably 0.5 to 10%. The pigment dispersant that can be used is not particularly limited, and those exemplified in the section (A) can be used. Similarly mentioned.

In (b1), a reaction accelerator is added to the resin in an amount of 0%.
To 3%, preferably 0.05 to 1%, more preferably 0.1 to 0.5%. The reaction accelerator that can be used is not particularly limited, and is exemplified in (A). Things are mentioned as well.

In (b1), a colorant is added to the resin in an amount of 0 to 6;
0%, preferably 0.5-40%, more preferably 1%
The coloring agent that can be contained is not particularly limited, and examples thereof include those exemplified in the section (A).

In (b1), a reinforcing agent is added in an amount of 0 to 3 to the resin.
%, Preferably 0 to 1%, more preferably 0 to 0.5%
%, And there is no particular limitation on the reinforcing agent that can be used, and those exemplified in the section (A) can be mentioned as well.

In (b1), a matting agent is added to the resin in an amount of 0 to 10.
30%, preferably 0 to 15%, more preferably 0 to
The matting agent which can be contained at 10% and which can be used is not particularly limited, and those exemplified in the section (A) can be similarly mentioned.

As the method of adding the above-mentioned various additives, there are a method of adding before the high molecular weight when preparing (b), a method of adding the high molecular weight and then adding it under melting,
A method in which (b) is once dissolved in a solvent, a method in which an additive is mixed in a homogeneous state and then the solvent is distilled off, and a method in which (b) is prepared and then added and impregnated, are preferred. (B) This is a method in which components are less likely to drop off after preparation and are added before increasing the molecular weight.

The particle shape of the bead-like resin (b) may be irregular or spherical, but the spherical shape is preferred in terms of smoothness and uniformity of the coating film. Here, the term “spherical” refers to particles having a particle volume average of 70% or more and a ratio of the shortest diameter / longest diameter of the particles in the range of 0.7 to 1.0. Within this range, the appearance of the coating film becomes extremely good. The method for making the particles spherical is not particularly limited, and a known method can be used. For example, a mixture of the obtained resin and an additive such as a pigment is once pulverized, the temperature is adjusted to such an extent that the individual pulverized particles do not coalesce, a method of flowing and spheroidizing, and the obtained resin is melted. Examples thereof include a method of spraying in a low-temperature atmosphere to form a spherical solid, a method of dispersing the obtained resin in an organic solvent in water and distilling off the solvent under reduced pressure, and a method of obtaining a spherical resin by dispersion polymerization.

The number average particle diameter of the beads (b) in the present invention is preferably from 10 to 500 μm, more preferably from 30 to 350 μm from the viewpoint of design. The secondary particle content of the beads is preferably 10% or less, more preferably 5% or less. As used herein, the term "secondary particles" refers to particles in which spherical primary particles obtained during the production are bonded to each other to form an irregular aggregate. In addition, the number average particle diameter mentioned here is a Coulter counter (COULTE
COULTE manufactured by R ELECTRONICS INC
R COUNTER MODEL TAII).

Of (b) constituting (B), at least one kind of heat softening point is preferably from 120 to 200 ° C., more preferably from 140 to 200 ° C., from the viewpoint of design and antiglare property.
80 ° C. However, when (B) is composed of two or more kinds of (b), a resin having a lower thermal softening point than the above can be used in combination, and in this case, a resin having a lower thermal softening point (less than 120 ° C.) ) The resin and the high (120 ° C. or higher) resin constitute an islands-in-the-sea state, and the color depth and depth are further emphasized, and a coating film having excellent design properties can be obtained. The mixing ratio (weight ratio) is preferably high heat softening point resin / low heat softening point resin = (60-100) / (40-
0).

(B) may contain, in addition to (b), a diluting solvent, a colorant, a pigment dispersant, a curing agent, a reaction accelerator, a reinforcing agent, and a matting agent. There are no particular restrictions on each of them, and the types and preferred amounts of addition are the same as those exemplified in (A) and (b). If necessary, a binder resin can be added. The binder resin is not particularly limited as long as it is used in a usual coating agent, and examples thereof include an acrylic resin (eg, methyl methacrylate / butyl acrylate / styrene three-component random copolymer), a urethane-based fat (polycaprolactone polyol / MDI). Polyadduct). In this case, a urethane resin is preferable from the viewpoint of a soft feeling on the surface of the coated body, which is one of the effects of the present invention.

The coated product of the present invention is obtained by coating (B) on the layer (A).
Is coated, but if necessary, a layer of the coating agent (C) may be further provided on the layer of (B). By coating (C), not only the strength and stability of the coating film can be increased, but also special effects such as a sense of depth and a sense of depth can be given to the design.

There is no particular limitation on (C) in the present invention, and commercially available paints (for example, nitrocellulose, urethane and acrylic) can be used. Preferably, it is a one- or two-pack urethane coating having good abrasion resistance on the surface of the obtained coating film, and more preferably a two-pack urethane coating which can be easily cured at a relatively low temperature. In addition, (C) may optionally contain a diluting solvent (for example, a resin concentration of 15 to 40% by weight), a curing agent, a coloring agent, a pigment dispersant, a reaction accelerator, a reinforcing agent, a matting agent, and the like. Each of them is not particularly limited, and the kind and the preferable addition amount are the same as those exemplified in the section (A) and (B). However, (C) is preferably clear from the viewpoint of design.

The coating method of (A) and (C) in the present invention is not particularly limited, but includes a general liquid coating method such as brushing, spraying and electrostatic spraying. Preferably, an electrostatic spray method capable of uniform coating is used.

The coating method of (B) in the present invention is not particularly limited, but is the same as a general method of coating a powdery coating material.
For example, in addition to an electrostatic coating method such as a fluid immersion method, a corona charging method, and a friction charging method, when (A) is sticky, simple air spraying may be used. The optimal coating method differs depending on the desired design.However, if you want to express a uniform surface, use the electrostatic coating method.If you want to express a three-dimensional effect, or if you want to paint only a narrow area, use the air spray method that can easily attach a slope etc. preferable.

The coating method of the present invention is a method in which (A) is coated on a substrate, (B) is coated, and (C) is further coated and fixed if necessary. It is preferably performed at 0 to 110 ° C, more preferably 60 to 90 ° C, in view of the appearance of the member and the fixing efficiency.

The thickness of the coating (A) in the present invention is not particularly limited, but is preferably from 1 to 100 μm, more preferably from 2 to 50 μm, from the viewpoint of appearance and adhesion.

The coating thickness of (B) in the present invention is not particularly limited, but is preferably 10 to 1000 μm, more preferably 15 to 2 from the viewpoint of three-dimensional design.
00 μm.

The thickness of the coating of (C) in the present invention is not particularly limited, but is preferably 6 to 200 μm, more preferably 15 to 70 μm from the viewpoint of three-dimensional design.
It is.

The automotive parts to be coated according to the present invention include instrument panels, meter clusters, consoles, steering wheels, door trims, armrests, assist grips, bumpers, bumper moldings, side moldings, door protectors, rear garnishes, wheel caps, and the like. Can be

[0064]

The present invention will be further described with reference to the following examples, but the present invention is not limited to these examples. Hereinafter, "part" indicates "part by weight".

Preparation Example of Resin (a1) 300 parts of polypropylene having a number average molecular weight of 10,000,
30 parts of maleic anhydride and 700 parts of xylene are charged into a flask equipped with a reflux tube, and the temperature is raised to 150 ° C. after replacement with nitrogen. After uniformly dissolving, 16.5 parts of dicumyl peroxide was added over 3 hours, and the reaction was further continued for 4 hours.
After distilling off xylene and unreacted maleic anhydride under reduced pressure, the mixture was cooled to obtain a maleic anhydride-added propylene polymer. Next, 200 parts of the present polymer and 800 parts of carbon tetrachloride were charged into a device equipped with a reflux tube, heated to 65 to 70 ° C. and uniformly dissolved, and then chlorine gas was introduced at a rate of 35 parts / hour for 4 hours. The remaining chlorine and carbon tetrachloride are distilled off at 160 ° C. under reduced pressure,
A colorless and transparent resin (a1-1) was obtained.

Preparation Example 1 of Resin (a2) Ethylene glycol 200 parts, adipic acid 44
The reaction was allowed to proceed for 3 hours while adding 0 parts and heating to 230 ° C. to distill off the generated water. Thereafter, 0.2 parts of dibutyltin oxide was added, and the reaction was continued until the acid value became 0.5 or less. After cooling to 100 ° C, 1,000 parts of toluene was added, and the mixture was further cooled to 40 ° C. Here, 90 parts of isophorone diisocyanate (IPDI)
Was added, and the mixture was reacted at 120 ° C. for 5 hours under reflux of toluene. After cooling to room temperature, the solid content was adjusted to 25% with toluene to obtain a colorless and transparent resin (a2-1).

Preparation Example 2 of Resin (a2) Ethylene glycol 200 parts, adipic acid 44
The reaction was allowed to proceed for 3 hours while adding 0 parts and heating to 230 ° C. to distill off the generated water. Thereafter, 0.2 parts of dibutyltin oxide was added, and the reaction was continued until the acid value became 0.5 or less. After cooling to 100 ° C, 1,000 parts of toluene was added, and the mixture was further cooled to 40 ° C. Here, 30 parts of IPDI was added, and 12 parts of
After performing the reaction at 0 ° C. for 5 hours, the mixture was cooled to room temperature, adjusted to a solid content of 25% with toluene, and was then converted to a colorless and transparent resin (a2-2)
I got

Preparation Example 3 of Resin (a2) 100 parts of Resin a2-1 was mixed with a red pigment [SANYO
Pigment Red manufactured by COLOR WORKS
GF-608 (azo pigment)] 2 parts were stirred and uniformized for 20 minutes with a paint conditioner, and a red transparent resin (a
2-3) was obtained.

Preparation Example of Urethane Prepolymer (b2) Neopentyl adipate having a hydroxyl value of 56 (“San Ester 5620”, manufactured by Sanyo Chemical Industries) 65 in a reactor
Four parts and 146 parts of IPDI were charged and reacted at 110 ° C. for 10 hours. After cooling, add 80 parts of ethyl acetate,
It mixed at 40 degreeC until it became uniform, and obtained the isocyanate group terminal urethane prepolymer (b2-1).

Example of Preparation of Ketimine Compound (b3) After 50 parts of isophoronediamine and 50 parts of methyl ethyl ketone were reacted in a reactor at 50 ° C. for 5 hours, 5 parts of diethanolamine was added thereto, and the mixture was homogenized to obtain a ketimine compound (b3). -1) was obtained.

Preparation Example 1 of Bead-shaped Resin Paint (B) 200 parts of neopentyl glycol, 93 parts of ethylene glycol and 355 parts of terephthalic acid were charged into a reactor.
The reaction was allowed to proceed for 3 hours while heating to 0 ° C. and distilling off generated water. Thereafter, 0.2 parts of dibutyltin oxide was added, and the reaction was continued until the acid value became 0.5 or less. 100
After cooling to ℃, 1,000 parts of toluene was added,
It was further cooled to 40 ° C. Here, 60 copies of IPDI
After reacting at 120 ° C. under reflux of toluene for 5 hours, the mixture was cooled to room temperature, 27 parts of diethanolamine was added, and the reaction was carried out at 60 ° C. for 5 hours. Then, toluene was distilled off under reduced pressure. Thus, a polyester resin having a hydroxyl group at both ends and having a urethane and urea bond was obtained. 400 parts of the obtained resin and 442 parts of ethyl acetate were mixed, and a 0.5% aqueous solution of polyvinyl alcohol 0.5% prepared in advance was prepared.
Dispersed while dropping in 0 parts. Thereafter, ethyl acetate was distilled off at 40 ° C., and the obtained spherical resin was taken out of water by filter paper filtration, and dried with a circulating drier at 40 ° C. This spherical body is classified by an acoustic classifier, and the number average particle diameter is 100 to
A colorless and transparent polyurethane-based bead-like coating material (B-1) having a heat-softening point of 155 ° C. and 300 μm was obtained.

Preparation Example 2 of Bead-shaped Resin Paint (B) 200 parts of ethylene glycol and 44 adipic acid were placed in a reactor.
The reaction was allowed to proceed for 3 hours while adding 0 parts and heating to 230 ° C. to distill off the generated water. Thereafter, 0.2 parts of dibutyltin oxide was added, and the reaction was continued until the acid value became 0.5 or less. After cooling to 100 ° C, 1,000 parts of toluene was added, and the mixture was further cooled to 40 ° C. To this, 142 parts of IPDI were added, and 1 part was refluxed under toluene.
After performing the reaction at 20 ° C. for 5 hours, it is cooled to room temperature, and
After adding part of diethanolamine and performing a reaction at 60 ° C. for 5 hours, toluene was distilled off under reduced pressure to obtain a polyester resin having hydroxyl groups at both ends and having urethane and urea bonds. 400 parts of the obtained resin, 12 parts of benzidine yellow, and 442 parts of ethyl acetate were mixed, and a 0.5% aqueous solution of polyvinyl alcohol 0.5% prepared in advance was prepared.
The mixture was dispersed while dripping into the part. Thereafter, ethyl acetate was distilled off at 40 ° C., and the obtained resin was taken out of water by filter paper filtration and dried with a 40 ° C. normal air dryer. This spherical body is classified by a sound classifier, and the number average particle diameter is 100 to 300.
A yellow transparent polyurethane bead-like paint (B-2) having a μm of 165 ° C. and a thermal softening point of 165 ° C. was obtained.

Preparation Example 3 of Bead-shaped Resin Paint (B) 248 parts of polycaprolactone diol (number average molecular weight 2,000) and polyether diol (number average molecular weight 4,000, EO content 90% by weight, PO content 496 parts, 10% by weight random copolymer), IPDI5
5.3 parts and 0.06 part of dibutyltin dilaurate were charged and reacted at 80 ° C. for 5 hours to obtain a dispersant. In another reactor, 280 parts of the urethane prepolymer b and 30 parts of the ketimine compound b3 were mixed, and 250 parts of an aqueous solution of the above-mentioned dispersant, which had been previously diluted to 1% with water, was added, and an ultra disperser [Yamato Kagaku Co., Ltd.] 9000r using
Mix for 1 minute at pm. Thereafter, the reaction was carried out at 50 ° C. for 6 hours while stirring with a stirring rod to obtain a dispersion. Next, this dispersion was separated by filtration and dried at 50 ° C. for 1 hour. 17 parts of a mixture of benzidine yellow and diisodecyl phthalate (weight ratio 2:15) was added to 100 parts of the dried product, and the mixture was mixed with a Henschel mixer [Mitsui Mining Co., Ltd.].
The mixture was mixed at 5 ° C. and 300 rpm for 10 minutes, and the number average particle diameter was 1
A yellow and transparent polyurethane bead coating (B-3) having a heat softening point of 160 ° C and a temperature of 00 to 300 µm was obtained.

Preparation Example 1 of Coating Agent (C) Polyurethane (Coatron TCM-3 manufactured by Sanyo Chemical Industries, Ltd.)
10) 160 parts, 226 parts of toluene, 75 parts of methyl isobutyl ketone, and 0.06 part of dibutyltin dilaurate were mixed and homogenized, and then hexamethylene diisocyanate (HDI) trimer (Duranate TPA-100 manufactured by Takeda Birdish Co., Ltd.) 2 .2 parts were added and mixed to obtain a colorless and transparent coating agent (C-1) having a solid content of 35%.

Preparation Example 2 of Coating Agent (C) Polyurethane (Coatron TCM-3 manufactured by Sanyo Chemical Industries, Ltd.)
10) 160 parts, toluene 281 parts, methyl isobutyl ketone 93 parts, talc (5000PJ manufactured by Shiraishi Industry Co., Ltd.) 4
0 parts, 0.06 parts of dibutyltin dilaurate,
After homogenization, 2.2 parts of an HDI trimmer (Duranate TPA-100 manufactured by Takeda Birdish Co., Ltd.) was added and mixed to obtain a colorless and translucent coating agent (C-2) having a solid content concentration of 35%. .

Preparation Example 3 of Coating Agent (C) Polyurethane (Coatron TCM-3 manufactured by Sanyo Chemical Industries, Ltd.)
10) 160 parts, toluene 226 parts, methyl isobutyl ketone 75 parts, red pigment (SANYO COLOR W)
Pigments Red GF-608 manufactured by ORKS)
After 0.1 parts and 0.06 parts of dibutyltin dilaurate were mixed and homogenized, 2.2 parts of an HDI trimer (trade name: Duranate TPA-100 manufactured by Takeda Burdish Co., Ltd.) was added and mixed. % Of a slightly reddish transparent coating agent (C-3) was obtained.

Examples 1 to 7, Comparative Examples 1 to 3 Resins (a1-1) and (a2-1) to (a2)
-3) was blended in a weight ratio of 70:30 and cast on a black polypropylene plate so as to have a dry film thickness of 5 μm. After leaving at room temperature for 5 minutes, (B) in Table 1 was sprayed with an air spray. Further, (C) is sprayed by using an air spray gun, and fixed at 80 ° C. for 20 minutes.
Examples 1 to 7 and Comparative Examples 1 to 3 were obtained. Table 2 shows the coating film evaluation results.

Evaluation Method 1) Evaluation of Adhesion The coated polypropylene plate is scratched with a cutter so as to reach the substrate so that 100 squares of 2 mm × 2 mm are formed. Cellophane tape was attached to the surface, and the number of squares remaining after being rapidly removed was checked.
The larger the number of remaining squares, the better the adhesion. 2) Evaluation of design properties The test plate was observed in a sufficiently bright room, and the appearance of the painted surface was visually judged. ：: The color of the coating film is vivid, has a sense of depth, and has a sense of quality. Δ: The color of the coating film is inexpensive without any sense of depth. ×: The color of the coating film is uneven.

[0079]

[Table 1]

[0080]

[Table 2]

[0081]

According to the coating method of the present invention, coating can be performed on an olefin-based resin substrate, which has been conventionally difficult to coat,
Automotive component coating that imparts a soft feeling to the surface of ABS or modified PP without deteriorating stain adhesion; automotive component coating that imparts antiglare properties; automotive component coating that imparts abrasion resistance; There is an effect that it is possible to provide an automobile member coated material that imparts a texture and a design that is not present.

[Brief description of the drawings]

FIG. 1 is an example of an automobile member painted product of the present invention having an automobile member substrate layer, an undercoat layer (A), and a layer of bead-like resin paint (B) having a different color from the undercoat or the substrate seen through the undercoat. FIG.

FIG. 2 shows an automobile member substrate layer, an undercoating layer (A),
BRIEF DESCRIPTION OF THE DRAWINGS It is sectional drawing which shows an example of the coating material for automobile parts of this invention which has a layer of a bead-like resin paint (B) and a layer of a coating agent (C) different from the color of the substrate seen through the undercoat or the undercoat.

[Explanation of symbols]

 Reference Signs List 1 automobile member substrate layer 2 layer of undercoat paint (A) 3 layer of bead resin paint (B) 4 layer of coating agent (C)

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) // C09D 175/04 C09D 175/04 (72) Inventor Takao Nomura 1 Toyota Town, Toyota City, Aichi Prefecture Toyota Auto (72) Inventor Koji Miyamoto 1 Toyota Town, Toyota City, Aichi Prefecture Toyota Motor Corporation (72) Inventor Kazuyuki Kuwano 1 Toyota Town, Toyota City, Aichi Prefecture Toyota Motor Corporation (72) Invention Person Hiromitsu Nakayama 11 Sanyo Kasei Kogyo Co., Ltd., 11-11 Hitotsubashi Nohonmachi, Higashiyama-ku, Kyoto (72) Inventor Keiji Tanaka 1 Sanyo Kasei Kogyo Co., Ltd.

Claims (11)

[Claims] An automobile member substrate layer, an undercoat paint (A) layer formed thereon, and at least a part of the layer of (A) a bead having a different color from the undercoat or a substrate visible through the undercoat. An automotive component coating having a resin coating (B) layer. 2. A material (a1) having good adhesion to an automobile member and a material (a2) having good adhesion to (B).
The coated article according to claim 1, comprising: 3. The coated article according to claim 1, wherein (B) comprises at least one bead resin (b), and a bead resin having a heat softening point of 120 to 200 ° C. is essential. 4. The number average particle diameter of the beads of (b) is 10 to 5
The coated product according to any one of claims 1 to 3, which has a thickness of 00 µm. 5. The coated article according to claim 1, wherein (b) is a beaded polyurethane (b1). 6. An isocyanate group-terminated urethane prepolymer (b) wherein (b1) is dispersed in water containing a dispersant.
The coated article according to claim 5, which is a bead-like polyurethane formed from 2) and a ketimine compound (b3). 7. The coated article according to claim 1, wherein (A) and (B) have reactive functional groups that are reactive with each other under the condition of 0 to 110 ° C. 8. The coated article according to claim 7, wherein the reactive functional group (A) is an isocyanate group and the reactive functional group (B) is a hydroxyl group and / or an amino group. 9. The coated article according to claim 1, further comprising a layer of a coating agent (C) on the layer of (B). 10. An automobile component comprising an instrument panel, a meter cluster, a console, a steering wheel, a door trim,
10. An armrest, an assist grip, a bumper, a bumper molding, a side molding, a door protector, a rear garnish, and a wheel cap.
Any of the painted objects described. 11. An undercoat paint (A) is applied to an automobile member, and then at least a part of the coated surface is applied with an undercoat paint or a bead-like resin paint (B) having a different color from a substrate visible through the undercoat paint. The method for coating an automotive member coating according to any one of claims 1 to 10, wherein the coating is performed at 0 to 110 ° C.