CN103965731A - Paint composition and method for forming multi-layer coating - Google Patents

Abstract

The invention provides a method for forming a transparent coating composition and a multi-layer coating film by using the transparent coating composition that includes coating a first water based color coating, a second water based color coating and a transparent coating in sequence on a to-be-coated object and curing at the same time to form the multi-layer coating film and can obtain the multi-layer coating film which is hard to be affected by the influence of surface roughness of a substrate (excellent concealment property of the surface state (unevenness) of the substrate) and has excellent smooth property and image distinctness. The invention provides a coating composition including a hydroxyl-containing acrylic resin (A), a polyisocyanate compound (B), and polyol (C) having specified number average molecular weight within 300-1500, and a method for forming the multi-layer coating film which takes use of the coating composition as a transparent coating, and coating the first water based color coating, the second water based color coating and the transparent coating in sequence on the to-be-coated object and at the same time, heating and curing to form the multi-layer coating film.

Description

Coating composition and method of forming layered coating film

Technical field

The present invention relates to coating composition and use the method for forming layered coating film of this coating composition.

Background technology

In the past, as the coating film-forming methods in car body, extensively carry out following method,, coated article is implemented after electrophoretic painting is heating and curing it, carry out intermediate layer paint paint spraying → be heating and curing → bottom coating application → preheat (preparation heating) → Clear paint application → be heating and curing such three be coated with two baking modes; And carry out the two such methods that are coated with two baking modes and form multilayer film of intermediate layer paint paint spraying → be heating and curing → finish paint paint spraying → be heating and curing.

Generally, above-mentioned three to be coated with two baking modes be that the bottom coating that contains bright pigment in use forms so-called metallic color film and carries out, and above-mentioned two to be coated with two baking modes be that the finish paint coating that contains tinting pigment in use forms the so-called plain color film of white, black etc. and carries out.

In recent years, from saving the viewpoint of the energy, study the operation that is heating and curing after the application of omitting intermediate layer paint coating, carried out successively three of the application of intermediate layer paint coating → preheat (preparation heating) → bottom coating application → preheat (preparation heating) → Clear paint application → be heating and curing and be coated with baking modes and carry out successively two of the application of intermediate layer paint coating → preheat (preparation heating) → finish paint paint spraying → be heating and curing and be coated with baking modes.

Wherein, from suppressing the viewpoint of the environmental pollution that the volatilization of organic solvent causes, special requirement have adopted water-borne coatings as above-mentioned intermediate layer paint coating, bottom coating and finish paint coating use above-mentioned three is coated with baking modes and two and is coated with baking modes.

But, three be coated with baking modes and used two of water-based intermediate layer paint coating and aqueous finish paint coating to be coated with in baking modes what used above-mentioned water-based intermediate layer paint coating and aqueous basecoat coating, the interlayer of interlayer, aqueous basecoat coating and Clear paint or the interlayer of water-based intermediate layer paint coating and aqueous finish paint coating at water-based intermediate layer paint coating and aqueous basecoat coating produce because interlaminar action causes forming the smoothness of film and the situation that clarity declines, and become problem.

In addition, omitted the above-mentioned operation that is heating and curing, three be coated with baking modes and two and be coated with one and dry in the coating process of modes, due to the operation that is heating and curing of having cut down after intermediate layer paint paint spraying, operation is therefore once heating and curing.From the hidden angle of condition of surface (convex-concave) of ground, above-mentioned three painting one baking modes and two are coated with baking modes and compare to coating process in the past, its operation is more insufficient, condition is more harsh, particularly ought become in the situation of severe situation of the large grade of surfaceness of the grounds such as electrophoretic painting face, the impact of the ground when being subject to more sensitively intermediate layer paint paint spraying, easily produce so exist the smoothness and the clarity downward trend that form film, thereby also become problem.

For example, in patent documentation 1, disclose in the multilayer film coating process that is utilizing three of water-based intermediate layer paint coating, aqueous basecoat coating and Clear paint to be coated with a baking mode, the specific aqueous basecoat coating of application on the intermediate layer paint film that is adjusted into specific solid component content, be adjusted into after specific solid component content, the Clear paint that application contains carboxylic compound and polyoxide, and then under specific heating condition, the method for forming layered coating film that intermediate layer paint film, primary coat film and transparent coating are solidified simultaneously.But, exist smoothness and the clarity of the multilayer film obtaining by this coating film-forming methods to become inadequate situation.

Realize as the interlaminar action suppressing between multilayer film the example that finished appearance improves, following method of forming layered coating film is for example disclosed in patent documentation 2, , application the 1st water-based pigmented coating successively on coated article, the 2nd water-based pigmented coating and Clear paint, the three painting one baking modes that the multilayer film of 3 layers obtaining is heating and curing simultaneously, it is characterized in that, the 1st water-based pigmented coating (X) contains acrylic resin (A), solidifying agent (B) and ester-polyurethane resin emulsion (C), the 1st painted film being formed by the 1st water-based pigmented coating (X) had the organic solvent swelling ratio below the water swelling ratio and 300% below 100% before application the 2nd undercoat.But, even if there is smoothness and the also inadequate situation of clarity of utilizing the multilayer film that this coating film-forming methods obtains.

And then, the water-based paint compositions that contains acrylic resin (A), solidifying agent (B) and polyaminoester emulsion (C) is for example disclosed in patent documentation 3, this polyaminoester emulsion (C) is obtained by the constituent that contains polymeric polyisocyanate composition and polycarbonate diol composition, polymeric polyisocyanate composition contains alicyclic diisocyanate, polycarbonate diol composition is obtained by the diol component that contains alicyclic diol, and alicyclic diol contains the more than 6 ring alkylidene group of carbonatoms.

In addition, record three paintings one and dried the method for forming layered coating film of mode,, using above-mentioned water-based paint compositions as the 1st water-based pigmented coating, application the 1st water-based pigmented coating, the 2nd water-based pigmented coating and Clear paint successively on coated article are heating and curing the multilayer film of 3 layers obtaining simultaneously.And, as the optimal way of the 1st water-based pigmented coating, the coating composition that contains specific oligopolymer is further also disclosed.But even if sometimes exist and utilize this coating film-forming methods, the finished appearance of smoothness and clarity etc. improves also inadequate situation of effect.

As the interlaminar action preventing between multilayer film, and then the internal stress of control film, thereby the method that the outward appearance that realizes multilayer film improves, in patent documentation 4, method of forming layered coating film is disclosed for example, , comprise and toast intermediate layer paint film simultaneously, primary coat film and transparent coating make three of its curing operation be coated with a drying method, it is characterized in that, the water-based intermediate layer paint coating using while forming intermediate layer paint film contains specific Emulsion acrylic resin, alkyl etherify melamine resin and carbodiimide compound completely, the aqueous basecoat coating using while forming primary coat film contains specific Emulsion acrylic resin and specific polyether glycol.But, by controlling the internal stress of this intermediate layer paint film, prevent that the outward appearance that intermediate layer paint film and primary coat are coated with the multilayer film that the coating film-forming methods of intermembranous interlaminar action obtains from also becoming inadequate situation even if exist to utilize to realize.

Patent documentation 1: TOHKEMY 2009-028576 communique

Patent documentation 2:WO2010/082607 communique

Patent documentation 3: TOHKEMY 2010-215885 communique

Patent documentation 4: TOHKEMY 2009-262002 communique

Summary of the invention

The problem that invention wish solves

The object of the invention is to, when on coated article, application the 1st water-based pigmented coating, the 2nd water-based pigmented coating and Clear paint also together solidify to form multilayer film successively, can obtain being difficult for being subject to the clear coating composition of multilayer film surface roughness affect (the disguise excellence of the condition of surface (convex-concave) of ground), smoothness and clarity and weathering resistance excellence of ground, and use the method for forming layered coating film of this clear coating composition.

The means of dealing with problems

The inventor concentrates on studies to achieve these goals repeatedly, found that utilizing three paintings one to dry in the coating process of multilayer film of mode, in order to improve the disguise of condition of surface of ground, in Clear paint, contain specific polyvalent alcohol and have positively effect, if the coating composition of the acrylic resin that contains hydroxyl (A), polyisocyanate compounds (B) and specific polyvalent alcohol (C) is as Clear paint, can realize above-mentioned purpose, thereby complete the present invention.

That is, the invention provides coating composition, it is characterized in that, in the method for forming layered coating film that coated article is carried out successively to following operation (1)～(4), be used as Clear paint (Z),

Operation (1): application the 1st water-based pigmented coating (X) is to form the operation of the 1st painted film;

Operation (2): application the 2nd water-based pigmented coating (Y) is to form the operation of the 2nd painted film on the 1st painted film forming through described operation (1);

Operation (3): transparent paint coating (Z) is to form the operation of transparent coating on the 2nd painted film forming through described operation (2); And

Operation (4): the operation that the 1st painted film, the 2nd painted film and the transparent coating that will form through described operation (1)～(3) is together heating and curing,

The polyvalent alcohol (C) of acrylic resin (A), polyisocyanate compounds (B) and the number-average molecular weight that described coating composition contains hydroxyl in 300～1500 scopes,

Described polyvalent alcohol (C) is at least one containing in polyvalent alcohol (C1) and the polycarbonate polyol (C2) of polyoxyalkylene.

And then, the invention provides method of forming layered coating film, it is characterized in that, coated article is carried out to following operation (1)～(4) successively:

Operation (1): application the 1st water-based pigmented coating (X) is to form the operation of the 1st painted film;

Operation (2): application the 2nd water-based pigmented coating (Y) is to form the operation of the 2nd painted film on the 1st painted film forming through described operation (1);

Operation (3): on the 2nd painted film forming through described operation (2) application as the aforementioned coating composition of Clear paint (Z) to form the operation of transparent coating; And

Operation (4): the operation that the 1st painted film, the 2nd painted film and the transparent coating that will form through described operation (1)～(3) is together heating and curing.

In addition, the invention provides the article that utilize above-mentioned method of forming layered coating film application and obtain.

Invention effect

Think polyvalent alcohol in coating composition of the present invention, owing to being lower molecular weight, therefore can improve the thermal fluidity in the solidification process of multilayer film, the hidden power of ground improves, the impact of the surface shape (convex-concave) of the ground that becomes finished appearance reduction reason can be effectively alleviated, thereby the multilayer film of three painting one baking modes of the finished appearance excellence of smoothness and clarity etc. can be obtained.

This effect can be by making this polyvalent alcohol be present in the very significant effect of acquisition in transparent coating.

In addition, this polyvalent alcohol is the hydroxyl with bridging property functional group, no matter be from reactive excellent angle, or is all applicable to from the angle of the film performance of weathering resistance etc.

Above, according to coating composition of the present invention, dry in the coating film-forming methods of mode in three paintings one, due to the disguise excellence of the condition of surface (convex-concave) of ground, therefore can form the multilayer film of smoothness and clarity excellence and then weathering resistance excellence.

Embodiment

Under regard to coating composition of the present invention and coating film-forming methods, be further elaborated.

Coating composition of the present invention (below sometimes referred to as " this coating "), it is characterized in that, in the method for forming layered coating film that coated article is carried out successively to following operation (1)～(4), be used as Clear paint (Z)

Operation (1): application the 1st water-based pigmented coating (X) is to form the operation of the 1st painted film;

Operation (2): application the 2nd water-based pigmented coating (Y) is to form the operation of the 2nd painted film on the 1st painted film forming through described operation (1);

Operation (3): transparent paint coating (Z) is to form the operation of transparent coating on the 2nd painted film forming through described operation (2); And

Operation (4): the operation that the 1st painted film, the 2nd painted film and the transparent coating that will form through described operation (1)～(3) is together heating and curing.

The polyvalent alcohol (C) of acrylic resin (A), polyisocyanate compounds (B) and the number-average molecular weight that this coating composition contains hydroxyl in 300～1500 scopes,

Polyvalent alcohol (C) is at least one containing in polyvalent alcohol (C1) and the polycarbonate polyol (C2) of polyoxyalkylene.

coating composition of the present invention

the acrylic resin (A) of hydroxyl

The acrylic resin (A) of the hydroxyl of coating composition of the present invention can be manufactured by the unsaturated monomer of common method copolymerization hydroxyl and other saturated mono bodies.

The unsaturated monomer of hydroxyl is the compound respectively in a molecule with a hydroxyl and unsaturated link(age), and this hydroxyl is mainly as the functional group of reacting with linking agent polyisocyanate compounds (B).As this monomer, specifically, can enumerate hydroxyalkyl (methyl) acrylate of (methyl) vinylformic acid-2-hydroxyl ethyl ester, (methyl) 2-hydroxypropyl acrylate, (methyl) vinylformic acid-3-hydroxypropyl acrylate, (methyl) vinylformic acid-3-hydroxy butyl ester, (methacrylic acid)-4-hydroxy butyl ester etc., this hydroxyalkyl (methyl) acrylate is the monoesters compound of the dibasic alcohol of acrylic or methacrylic acid and carbonatoms 2～10; The monoesters that the polyether glycol of polyoxyethylene glycol, polypropylene glycol, polytetramethylene glycol etc. becomes with the unsaturated carboxylic acid of (methyl) vinylformic acid etc.; The monoether that the polyether glycol of polyoxyethylene glycol, polypropylene glycol, polytetramethylene glycol etc. becomes with (methyl) acrylic acid hydroxy alkyl ester of 2-hydroxyethyl (methyl) acrylate etc.; Such as unsaturated compound and the ethylene glycol, 1 containing acid anhydrides of maleic anhydride, itaconic anhydride, monoesters compound or two carboxylates that the alcohols of 6-hexylene glycol, neopentyl glycol etc. becomes; Such as the hydroxyalkyl vinyl ethers of hydroxyethyl vinyl ether; Propenyl alcohol etc.; α, beta-unsaturated carboxylic acid with such as " カ-ヅ ユ ラ E10P " (trade(brand)name, HEXION Specialty Chemicals company system, the glycidyl esters of synthetic high chain saturated fatty acid), the adducts that becomes of the monocycle oxycompound of alpha-olefin epoxide; Glycidyl (methyl) acrylate and the adducts becoming such as the monoprotic acid of acetic acid, propionic acid, p-tert-butyl benzoic acid, fatty acid; The adducts that the unsaturated monomer of above-mentioned hydroxyl such as, becomes with lactone (6-caprolactone, γ-valerolactone) etc.

The unsaturated monomer of above-mentioned hydroxyl and lactone (for example 6-caprolactone, γ-valerolactone) adducts, for example can enumerate " Plaxel FA-1 ", " Plaxel FA-2 ", " PlaxelFA-3 ", " Plaxel FA-4 ", " Plaxel FA-5 ", " Plaxel FM-1 ", " PlaxelFM-2 ", " Plaxel FM-3 ", " Plaxel FM-4 ", " Plaxel FM-5 " (be above Daicel chemistry (strain) system, trade(brand)name) etc. the ring-opening polymerization adducts that becomes with the lactone of 6-caprolactone etc. of above-mentioned hydroxyalkyl (methyl) acrylate etc.

It should be noted that, in this manual, (methyl) acrylate is the general name of acrylate and methacrylic ester, and (methyl) vinylformic acid is the general name of vinylformic acid and methacrylic acid.

As the unsaturated monomer of hydroxyl, because the reactivity of the polyisocyanate compounds as linking agent (B) and acrylic resin (A) is relaxed, can improve the finished appearance of the film obtaining, therefore, preferably contain unsaturated monomer, wherein, this unsaturated monomer has secondary hydroxyl.

As the unsaturated monomer with secondary hydroxyl, for example can enumerate the unsaturated monomer with secondary hydroxyl of (methyl) 2-hydroxypropyl acrylate, (methyl) vinylformic acid 2-hydroxy butyl ester, (methyl) vinylformic acid 3-hydroxy butyl ester etc., wherein, the carbonatoms of the alkyl of the ester part of described unsaturated monomer is 2～8, preferably 2～4, and then preferably 2～3.Especially, can suitably use (methyl) 2-hydroxypropyl acrylate.If the carbonatoms of this alkyl is more than 5, the finished appearance of film declines, and in addition, has the situation of the heat life decline of coating composition.These may be used singly or two or more in combination.

The acrylic resin (A) of hydroxyl, in the case of using the unsaturated monomer with secondary hydroxyl as forming monomer component, have secondary hydroxyl unsaturated monomer containing proportional, be preferably 10 quality %～50 quality %, be particularly preferably 15 quality %～45 quality % and then be particularly preferably 15 quality %～40 quality % with respect to the total amount of monomer component.

As other unsaturated monomers, for example, can enumerate the unsaturated monomer of carboxylic unsaturated monomer, (methyl) esters of acrylic acid, vinyl ether or propenyl ether, alkenes compounds and diolefin, hydrocarbonaceous ring, nitrogenous unsaturated monomer, containing the unsaturated monomer of epoxy group(ing), containing the acrylic monomer of water-disintegrable alkoxysilyl etc.

Carboxylic unsaturated monomer, be in 1 molecule, to there is more than 1 carboxyl and the compound of 1 unsaturated link(age), for example, can enumerate (methyl) vinylformic acid, β-crotonic acid, methylene-succinic acid, toxilic acid, maleic anhydride, fumaric acid, 2-carboxy ethyl (methyl) acrylate, 3-carboxyl propyl group (methyl) acrylate, 5-carboxy pentyl (methyl) acrylate etc.

As the example of (methyl) esters of acrylic acid, can enumerate methyl acrylate, ethyl propenoate, propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, Ethyl acrylate, ethyl acrylate, vinylformic acid n-octyl, decyl acrylate, lauryl acrylate, stearyl acrylate acid esters, cyclohexyl acrylate, methyl methacrylate, β-dimethyl-aminoethylmethacrylate, n propyl methacrylate, isopropyl methacrylate, n-BMA, Propenoic acid, 2-methyl, isobutyl ester, Tert-butyl Methacrylate, N-Hexyl methacrylate, methacrylic acid-2-ethylhexyl, Octyl methacrylate, decyl-octyl methacrylate, lauryl methacrylate(LMA), methacrylic acid stearate, alkyl ester or the cycloalkyl ester of the carbonatoms 1～24 of the acrylic or methacrylic acid of cyclohexyl methacrylate etc., the alkoxy alkyl of the carbonatoms 2～18 of the acrylic or methacrylic acid of vinylformic acid methoxyl group butyl ester, methacrylic acid methoxy base butyl ester, vinylformic acid methoxyl group ethyl ester, methoxyethyl methacrylate, vinylformic acid oxyethyl group butyl ester, methacrylic acid oxyethyl group butyl ester etc. etc.

As vinyl ether or propenyl ether, for example, can enumerate the chain-like alkyl vinyl ethers of ethyl vinyl ether, n-propyl vinyl ether, isopropyl-ethylene base ether, butyl vinyl ether, tert-Butyl vinyl ether, amyl group vinyl ether, hexyl vinyl ether, octyl group vinyl ether etc.; The cycloalkyl vinyl ethers of cyclopentyl vinyl ether, cyclohexyl vinyl ether etc.; The aryl vinyl ethers such as Vinyl phenyl ether, trivinyl benzylic ether; The aralkyl vinyl ethers of benzyl vinyl ether, styroyl vinyl ether etc.; The propenyl ethers of propenyl ethyl ether etc. etc.

As ethylene series compound and diolefin, for example, can enumerate ethene, propylene, butylene, ethylene chloride, divinyl, isoprene, chloroprene etc.

As the unsaturated monomer of hydrocarbonaceous ring, for example can enumerate vinylbenzene, alpha-methyl styrene, phenyl (methyl) acrylate, phenylethyl (methyl) acrylate, phenyl propyl (methyl) acrylate, benzyl (methyl) acrylate, phenoxy group ethyl (methyl) acrylate, cyclohexyl (methyl) acrylate, 2-acryl oxygen base ethyl diphenate, 2-acryl oxygen base propyl group diphenate, 2-acryl oxygen base propyl group hexahydrophthalic acid hydrogen ester, 2-acryl oxygen base propyl group tetrahydrophthalic acid hydrogen ester, the tertiary butyl-phenylformic acid is become with (methyl) Hydroxyethyl acrylate carboxylate, dicyclopentadienyl (methyl) acrylate etc.

As nitrogenous unsaturated monomer, for example can enumerate N, N-dimethyl aminoethyl (methyl) acrylate, N, N-diethylamino ethyl (methyl) acrylate, N-tertiary butyl amino-ethyl (methyl) acrylate etc. containing azanyl (methyl) acrylate; Acrylamide, Methacrylamide, N-methyl (methyl) acrylamide, N-ethyl (methyl) acrylamide, N, N-dimethyl (methyl) acrylamide, N, N-dimethyl amine propyl group (methyl) acrylamide, N, the polymerizable amide class of N-dimethyl aminoethyl (methyl) acrylamide etc.; The aromatic series nitrogen containing monomer of 2-vinyl pyridine, l-vinyl-2-pyrrolidone, 4-vinylpridine etc.; The polymerizability such as vinyl cyanide, methacrylonitrile nitrile; Propenyl amine etc.

As the unsaturated monomer containing epoxy group(ing), for example can enumerate the aliphatics of glycidyl (methyl) acrylate, propenyl glycidyl ether etc. containing the unsaturated monomer, 3 of epoxy group(ing), the ester ring type of 4-epoxy group(ing) cyclohexyl methyl (methyl) acrylate etc. is containing the unsaturated monomer of epoxy group(ing).

As the acrylic monomer containing water-disintegrable alkoxysilyl, for example, can enumerate γ-(methyl) acryl oxygen base propyl trimethoxy silicane, γ-(methyl) acryl oxygen base propyl group methyl dimethoxysilane, β-(methyl) acryl oxygen base ethyl trimethoxy silane, γ-(methyl) acryl oxygen base propyl-triethoxysilicane, γ-(methyl) acryl oxygen base propyl group methyldiethoxysilane etc.

In addition, for example also can use the vinyl compound of Veova9, the Veova10 (Japanese epoxy company system) etc. of vinyl acetate, propionate, ethylene chloride, neodecanoic acid vinyl ester.

Synthesizing of the acrylic resin (A) of hydroxyl, can be used the polymerization of common unsaturated monomer to carry out, but considers versatility, cost etc., is applicable to the most by the solution-type radical polymerization in organic solvent.For example can be by the aromatic solvent at dimethylbenzene, toluene etc.; The ketones solvent of methyl ethyl ketone, methyl iso-butyl ketone (MIBK) etc.; The esters solvents such as vinyl acetic monomer, N-BUTYL ACETATE, isobutyl acetate, 3-methoxyl group butylacetic acid ester; In the solvent of the alcoholic solvent of propyl carbinol, isopropyl alcohol etc. etc., under the existence of the polymerization starter of azo series catalysts, peroxide catalyst etc., at the temperature of approximately 60～approximately 150 DEG C, carry out copolyreaction, can easily obtain thus.

The acrylic resin (A) of hydroxyl can use one kind or two or more being used in combination.

The hydroxyl value of the acrylic resin (A) of hydroxyl, from the viewpoint of the film performance of finished appearance and the weathering resistance etc. of smoothness and clarity etc., preferably in the scope of 80～200mgKOH/g, particularly preferably in the scope of 90～170mgKOH/g, and then in scope particularly preferably in 100～140mgKOH/g.

The weight-average molecular weight of the acrylic resin (A) of hydroxyl, from the viewpoint of the film performance of finished appearance and the weathering resistance etc. of smoothness and clarity etc., preferably in 4000～20000 scope, in 6000～16000 scope, and then particularly preferably in 8000～12000 scope.

It should be noted that, in this manual, number-average molecular weight and weight-average molecular weight are the retention time (retention volume) that uses gel permeation chromatography (GPC) to measure, and the retention time (retention volume) of the polystyrene standard that the molecular weight measured under identical conditions is known is converted into the molecular weight of polystyrene and the value of trying to achieve.Specifically, as gel permeation chromatography device, use " HLC8120GPC " (trade(brand)name, Dong Cao company system), use 4 " TSKgelG-4000HXL ", " TSKgelG-3000HXL ", " TSKgelG-2500HXL " and " TSKgelG-2000HXL " (trade(brand)name as chromatographic column, be Dong Cao company system), use differential refractometer as detector, moving phase: tetrahydrofuran (THF), measure temperature: under 40 DEG C, the condition of flow velocity: 1mL/min, measure.

When the acrylic resin (A) of hydroxyl has in the situation of carboxyl, acid number is from the viewpoint of the film performance of finished appearance and the weathering resistance etc. of smoothness and clarity etc., preferably in the scope of 1～40mgKOH/g, in scope particularly preferably in 3～30mgKOH/g, and then preferably in the scope of 5～20mgKOH/g.

polyisocyanate compounds (B)

The polyisocyanate compounds (B) of coating composition of the present invention, is the compound in 1 molecule with more than 2 free isocyanate groups, can use the compound using while in the past always manufacturing urethane.For example, can enumerate the derivative etc. of aliphatic polymeric isocyanate, alicyclic polymeric isocyanate, aromatic-aliphatic polymeric polyisocyanate, aromatic poly-isocyanate and these polymeric polyisocyanates.

As aliphatic polymeric isocyanate, for example can enumerate trimethylene diisocyanate, tetramethylene isocyanic ester, hexa-methylene isocyanic ester, pentamethylene isocyanic ester, 1, 2-acryloyl isocyanate, 1, 2-butylene isocyanic ester, 2, 3-butylene isocyanic ester, 1, 3-butylene isocyanic ester, 2, 4, 4-or 2, 2, 4-tri-methyl hexamethylene isocyanic ester, 2, the aliphatic isocyanates of 6-bis-isocyanato-methylhexanoic acid esters etc., for example Methionin ester triisocyanate, 1, 4, 8-tri-isocyanato-octane esters, 1, 6, 11-tri-isocyanato-undecane esters, 1, 8-bis-isocyanato-s-4-isocyanato-methyloctane ester, 1, 3, 6-tri-isocyanato-hexane esters, 2, 5, 7-trimethylammonium-1, the aliphatics triisocyanate of 8-bis-isocyanato-s-5-isocyanato-methyloctane ester etc. etc.

As alicyclic polymeric isocyanate, for example can enumerate 1, 3-cyclopentenes isocyanic ester, 1, 4-hexanaphthene isocyanic ester, 1, 3-hexanaphthene isocyanic ester, 3-isocyanato-methyl-3, 5, 5-3-methyl cyclohexanol based isocyanate (common name: isophorone diisocyanate), 4, 4 '-methylene-bis (cyclohexyl isocyanate), methyl-2, 4-hexanaphthene isocyanic ester, methyl-2, 6-hexanaphthene isocyanic ester, 1, 3-or 1, two (isocyanato-methyl) hexanaphthenes (common name: hydrogenation xylylene isocyanic ester) of 4-or its mixture, the alicyclic isocyanate of norbornane isocyanic ester etc., for example 1, 3, 5-tri-isocyanato-hexanaphthene esters, 1, 3, 5-trimethylammonium isocyanato-hexanaphthene ester, 2-(3-isocyanato-propyl group)-2, 5-bis-(isocyanato-methyl)-bis-ring (2.2.1) heptane esters, 2-(3-isocyanato-propyl group)-2, 6-bis-(isocyanato-methyl)-bis-ring (2.2.1) heptane esters, 3-(3-isocyanato-propyl group)-2, 5-bis-(isocyanato-methyl)-bis-ring (2.2.1) heptane esters, 5-(2-isocyanatoethyl)-2-isocyanato-methyl-3-(3-isocyanato-propyl group)-bis-ring (2.2.1) heptane esters, 6-(2-isocyanatoethyl)-2-isocyanato-methyl-3-(3-isocyanato-propyl group)-bis-ring (2.2.1) heptane esters, 5-(2-isocyanatoethyl)-2-isocyanato-methyl-2-(3-isocyanato-propyl group)-bis-ring (2.2.1)-heptane esters, the alicyclic triisocyanate of 6-(2-isocyanatoethyl)-2-isocyanato-methyl-2-(3-isocyanato-propyl group)-bis-ring (2.2.1) heptane esters etc. etc.

As aromatic-aliphatic polymeric polyisocyanate, for example can enumerate 1,3-or 1,4-xylylene isocyanic ester or its mixture, ω, ω '-bis-isocyanato--Isosorbide-5-Nitrae-diethylbenzene, 1,3-or 1, the aromatic-aliphatic isocyanic ester of two (1-isocyanato--1-methylethyl) phenyl esters (common name: tetramethyl-xylylene isocyanic ester) of 4-or its mixture etc., for example 1,3, the aromatic-aliphatic triisocyanate of 5-tri-isocyanato-methylbenzene etc. etc.

As aromatic poly-isocyanate, for example can enumerate metaphenylene isocyanic ester, to phenylene isocyanic ester, 4, 4 '-phenylbenzene isocyanic ester, 1, 5-naphthyl isocyanic ester, 2, 4 '-or 4, 4 '-phenylmethane isocyanic ester or its mixture, 2, 4-or 2, 6-toluene diisocyanate or its mixture, 4, 4 '-Tolylamine isocyanic ester, 4, the aromatic isocyanate of 4 '-diphenyl ether isocyanic ester etc., for example triphenyl methane-4, 4 ', 4 "-triisocyanate, 1, 3, 5-tri-isocyanato-benzene, 2, 4, the aromatic series triisocyanate of 6-tri-isocyanato-toluene etc., for example 4, 4 '-ditan-2, 2 ', 5, the aromatic series tetraisocyanate of 5 '-tetraisocyanate etc. etc.

In addition, as the derivative of polymeric polyisocyanate, for example, can enumerate dimer, tripolymer, allophanamide, allophanate, carbodiimide, urea diketone, uretonimine, isocyanuric acid ester, oxadiazine triketone, polymethylene polyphenyl base polymeric polyisocyanate (Crude MDI, Polymeric MDI), Crude TDI of above-mentioned polyisocyanate compounds etc.

These polyisocyanate compounds can use separately, or also can two or more be used in combination.In addition, in these polyisocyanate compounds, from the viewpoint of smoothness and clarity and the weathering resistance etc. of the film that obtains, can suitably use the derivative of aliphatic isocyanates and aliphatic isocyanates.

As polyisocyanate compounds (B), in the case of using the derivative of aliphatic isocyanates, conventionally, the derivative of aliphatic isocyanates is the mixture with molecular weight distribution that multicomponent forms, from the viewpoint of finished appearance, preferably: the component content of tripolymer above (not comprising isocyanurate trimer) is less, also contains low-molecular-weight urea diketone as constituent.

As the derivative of above-mentioned aliphatic isocyanates, particularly, can list the derivative of the aliphatic isocyanates in following ranges as preference, that is: taking the total amount of polyisocyanate compounds as benchmark, the content of isocyanurate trimer is 30～70 quality %, preferably 40～70 quality %, more preferably 50～70 quality %, the dimeric content of urea diketone is 3～30 quality %, preferably 5～25 quality %, more preferably 8～20 quality %, other polymeric content more than tripolymer are 0～67 quality %, preferably 5～55 quality %, more preferably 10～42 quality %.

In addition, as polyisocyanate compounds (B), also can use following dead front type polyisocyanate compounds, it is by obtaining by the above-mentioned isocyanate group in 1 molecule with more than 2 polyisocyanate compounds of free isocyanate groups of encapsulant sealing.

Encapsulant, is the reagent of the free isocyanate group of sealing, for example by be heated to 100 DEG C above, be preferably heated to more than 130 DEG C, isocyanate group deblocking thus, can be easily and hydroxyl reaction.As this encapsulant, for example, can enumerate the oxybenzene compound of phenol, cresols, xylenol, nitrophenols, ethylphenol, hydroxy diphenyl, butylphenol, isopropyl-phenol, nonylphenol, octyl phenol, hydroxy-benzoic acid methyl etc.; The lactone compound of 6-caprolactone, δ-valerolactone, gamma-butyrolactone, beta-propiolactone etc.; The fatty alcohol of methyl alcohol, ethanol, propyl group alcohol, butanols, amyl group alcohol, lauryl alcohol etc.; The ether compound of ethylene glycol monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, TC, propylene glycol monomethyl ether, methoxyl group methyl alcohol etc.; Benzyl alcohol; Oxyacetic acid; The ethyl glycolate of methyl glycolate, ethyl glycollate, butyl glycolate etc.; The lactate of lactic acid, methyl lactate, ethyl lactate, n-Butyl lactate etc.; The alcohol based compound of methylolurea, melamine methylol, Pyranton, 2-hydroxy ethyl methacrylate, HEMA etc.; The oxime compound of formyl amidoxime, acetyl amidoxime, acetoxime, Diacetylmonoxime, biacetyl monoxime, diphenylketoxime, hexanaphthene oxime etc.; The activity methene compound of dimethyl malonate, diethyl malonate, methyl aceto acetate, methyl acetoacetate, methyl ethyl diketone etc.; The mercaptan compound of butanethiol, tert-butyl mercaptan, hexyl mercaptans, uncle-lauryl mercaptan, 2-mercaptobenzothiazole, thiophenol, methylbenzene phenyl-sulfhydrate, ethyl thiophenol etc.; The imide compound of Acetanilide, ethanoyl anisidine, acetyl toluidine, acrylamide, Methacrylamide, ethanamide, stearylamide, benzamide etc.; The imide compound of succinimide, phthalic imidine, maleimide etc.; The amine compound of pentanoic, phenyl naphthyl amines, xylidene(s), N-phenyl xylidene(s), carbazole, aniline, naphthylamines, butylamine, dibutylamine, butyl phenyl amine etc.; The imidazolium compounds of imidazoles, 2-ethyl imidazol(e) etc.; The pyrazole compound of 3，5-dimethylpyrazole etc.; The carbamide compounds of urea, thiocarbamide, ethylidene-urea, ethylene thiourea, sym-diphenylurea etc.; The carbamate compounds of N-phenylcarbamic acid phenyl ester etc.; The group with imine moiety of ethyleneimine, propyleneimine etc.; The sulfites encapsulant of sodium bisulfite, Potassium hydrogen sulfite etc., etc.

While carrying out dead front type (making encapsulant reaction), can add as required solvent.The solvent that dead front type when reaction is used, only otherwise isocyanate group is had reactive, for example, can enumerate esters solvent, N-Methyl pyrrolidone (NMP) equal solvent of ketones solvent, the ethyl acetate etc. of acetone, methyl ethyl ketone etc.

Polyisocyanate compounds (B) can use separately, or can two or more couplings.

In coating composition of the present invention, from the viewpoint of solidified nature, the scuff resistance etc. of gained film, the equivalence ratio (NCO/OH) of the hydroxyl of the acrylic resin (A) of hydroxyl and the isocyanate group of polyisocyanate compounds (B) is preferably in 0.5～2.0 scope, more preferably in 0.8～1.5 scope.

About the solid component content ratio of acrylic resin (A) and the polyisocyanate compounds (B) of hydroxyl in coating composition of the present invention, with respect to (A) composition and (B) the solids component total amount of composition, the acrylic resin (A) of hydroxyl is in the scope of 40～85 quality %, preferably in the scope of 45～80 quality %, polyisocyanate compounds (B) is in the scope of 15～60 quality %, preferably in the scope of 20～55 quality %.

polyvalent alcohol (C)

Polyvalent alcohol (C) is at least one containing in polyvalent alcohol (C1) and the polycarbonate polyol (C2) of polyoxyalkylene.

The number-average molecular weight of polyvalent alcohol (C), from the viewpoint of the film performance excellence of finished appearance and the weathering resistance etc. of smoothness and clarity, in 300～1500 scope, preferably in 350～1000 scope, more preferably in 400～800 scope.

In addition, the hydroxyl value of polyvalent alcohol (C), from the viewpoint of the film performance excellence of finished appearance and the weathering resistance etc. of smoothness and clarity, preferably in the scope of 60～400mgKOH/g, more preferably in the scope of 100～350mgKOH/g, and then in scope particularly preferably in 150～300mgKOH/g.

As containing the polyvalent alcohol (C1) of polyoxyalkylene, can be set forth in polyvalent alcohol, polyphenol, polycarboxylic acid class etc. containing addition oxirane compound on the compound of active hydrogen compound etc.As the compound containing active hydrogen atom, for example, can enumerate water, polyalcohols (ethylene glycol, Diethylene Glycol, trimethylene, propylene glycol, BDO, 1,6-hexylene glycol, neopentyl glycol, Isosorbide-5-Nitrae-dihydroxyl methylcyclohexane, the dibasic alcohol of cyclohexanediol etc., glycerine, three oxygen base Trimethylmethanes, 1,2,3-trihydroxybutane, 1,2,3-, penta triol, 2-methyl isophthalic acid, 2,3-glycerol, 2-methyl-2,3,4-trihydroxybutane, 2-ethyl-1,2,3-trihydroxybutane, 2,3,4-, penta triol, 2,3,4-hexanetriol, 4-propyl group-3,4,5-triol in heptan, 2,4-dimethyl-2,3,4-, penta triol, pentamethyl-glycerine, five glycerine, BT, 1,2,4-, penta triol, trimethylolethane, the trivalent alcohol of TriMethylolPropane(TMP) etc., tetramethylolmethane, 1,2,3,4-, penta tetrol, the own tetrol of 2,3,4,5-, 1,2,4,5-, penta tetrol, the own tetrol of 1,3,4,5-, two glycerine, the tetravalent alcohols such as Sorbitol Powder, ribitol, arabitol, Xylitol, the pentavalent alcohol of triglycerin etc., Dipentaerythritol, Sorbitol Powder, N.F,USP MANNITOL, iditol, inositol, melampyrum, talose, the hexavalent alcohol of allose etc., eight yuan of alcohol of sucrose etc., poly-glycerine etc.), polyatomic phenol [polyphenol (pyrogallol, Resorcinol, Phloroglucinol etc.), bisphenols (dihydroxyphenyl propane, sulfonation bis-phenol (PVC ス Off エ ノ-Le ス Le Off オ Application) etc.)], poly carboxylic acid [aliphatic polycarboxylic acid's (succsinic acid, hexanodioic acid etc.), aromatic series poly carboxylic acid (phthalic acid, terephthalic acid, trimellitic acid etc.)] etc.

In above-mentioned, as containing the compound of active hydrogen, from reactive viewpoint, preferred polyol class, particularly preferably has the polyvalent alcohol of more than 3 alkylidene group of carbonatoms, wherein preferably has the polyvalent alcohol of the alkylidene group of carbonatoms 3～4.

And then, in polyalcohols, from the smoothness of gained multilayer film and the viewpoint of clarity, particularly preferably dibasic alcohol.

Especially in above-mentioned polyvalent alcohol, preferably ethylene glycol, Diethylene Glycol, trimethylene, propylene glycol, BDO, particularly preferably trimethylene, propylene glycol, BDO.

The above-mentioned polyvalent alcohol that contains polyoxyalkylene (C1), be common under the existence of basic catalyst, utilize common method at normal pressure or add to depress the temperature of 60～160 DEG C and carry out the addition reaction of the above-mentioned compound addition oxirane compound containing active hydrogen to obtain.As above-mentioned oxirane compound, can enumerate the oxirane compound of oxyethane, propylene oxide, butylene oxide ring etc., wherein preferably use propylene oxide, butylene oxide ring, propylene oxide particularly preferably.These compounds can use one or can two or more couplings.The addition form of the situation of two or more couplings can be sealing or random in any one.

As the polyvalent alcohol that contains polyoxyalkylene (C1), can preferably use polyoxy aklylene glycol.

As polyoxy alkylene alcohol, can use commercially available product, for example can enumerate as polypropylene glycol, can enumerate Ha イ プ ロ Star Network ス MP-600 (large Japanese ink chemical industry (strain) system), プ ラ イ system Port-Le PX-1000, Sunnix SP-750, Sunnix PP-400, Sunnix PP-600, SunnixPP-1000 (changing into (strain) system by Sanyo above), Diol-400, Diol-700, Diol-1000 (above by Mitsui Chemicals (strain) system); As polytetramethylene glycol, can enumerate PTMG-650, PTMG-850, PTMG-1000 (above by Mitsubishi Chemical's (strain) system) etc.

As polycarbonate polyol (C2), for example, can have with 1 for normally used, 6-hexylene glycol, as the polycarbonate polyol of basic framework, in addition, can also use the polycarbonate polyol of manufacturing by known method.For example, can enumerate that the carbonic ether composition of alkylene carbonate, diaryl carbonate, dialkyl carbonate etc. or carbonyl chloride react with following illustrative aliphatic polyol composition and the polycarbonate polyol that obtains.As aliphatic polyol composition, can enumerate the straight chain shape di-alcohols of 1,3-PD, BDO or 1,6-hexylene glycol etc. herein; 1,2-PD, neopentyl glycol, 3-methyl isophthalic acid, the branched diol of 5-pentanediol, ethyl butyl propanediol etc.; The ethers glycol of Diethylene Glycol, triethylene glycol etc. is as the example of aliphatic polyol composition.

Polycarbonate polyol (C2), the viewpoint of the thermal fluidity when being heating and curing does not preferably have the ring structure of aromatic nucleus, aliphatics ring etc. in molecular structure.

Polycarbonate polyol can use commercially available product, can enumerate ETERNACOLLUH-50, ETERNACOLLUH-100, ETERNACOLLUM-90 (1/3) (above by the emerging product of space portion (strain) system); C-1100, C-XP-2716 (above by Bayer society system) etc.

With respect to the solids component total amount of acrylic resin (A) and the polyisocyanate compounds (B) of above-mentioned hydroxyl, polyvalent alcohol (C) preferably uses 1～20 quality %, particularly preferably use 2～10 quality %, and then particularly preferably use 3～7 quality %.

By using the amount of this scope, thermal fluidity in the solidification process of multilayer film improves, the surface shape of hidden ground (concavo-convex) fully, the impact of the surface shape of ground is inhibited, and therefore can obtain the also multilayer film of excellence of film performance of finished appearance excellence and the weathering resistance etc. of smoothness and clarity.

non-aqueous dispersion type acrylic resin (D)

Non-aqueous dispersion type acrylic resin (D), in paint field, compared with the polymer particles that is called as microgel using usually used as rheology control agent, the impact that the finished appearance of film is declined reduces, and therefore can be suitable as the rheology control agent of coating composition of the present invention.

Non-aqueous dispersion type acrylic resin (D), is under the existence of macromolecular dispersion stabilizer and organic solvent, makes at least one unsaturated monomer dispersion polymerization and the acrylic resin that obtains.

The macromolecular dispersion stabilizer using in the manufacture of non-aqueous dispersion type acrylic resin (D), the polymkeric substance that normally makes long-chain unsaturated monomer obtain with other unsaturated monomer copolymerization as required.

The long-chain unsaturated monomer using in this polymkeric substance, can suitably select according to the desired performance of film, but from viewpoints such as copolymerization, solvabilities to organic solvent, can illustrate material below as the long-chain unsaturated monomer that preferably can use.

For example, can enumerate the alkyl or cycloalkyl ester of (methyl) acrylic acid carbonatoms 4～18 of (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) ethyl acrylate, (methyl) cyclohexyl acrylate, (methyl) vinylformic acid n-octyl, (methyl) lauryl acrylate, (methyl) vinylformic acid tridecane ester, (methyl) stearyl acrylate acid esters etc.; (methyl) acrylic acid alkoxy alkyl of methoxyl group (methyl) butyl acrylate, methoxyl group (methyl) ethyl propenoate, oxyethyl group (methyl) butyl acrylate etc.; The ester that (methyl) vinylformic acid of the aromatic alcohols of (methyl) benzyl acrylate etc. becomes; The affixture that (methyl) glycidyl acrylate or (methyl) acrylic acid hydroxy alkyl ester become with the monocarboxylic acid compound of capric acid, lauric acid, linolic acid, oleic acid etc.; The affixture that (methyl) vinylformic acid becomes with the monocycle oxycompound of " カ-ジ ユ ラ E10 " etc.; The vinyl aromatic compounds of vinylbenzene, alpha-methyl styrene, Vinyl toluene, p-chloro-styrene, p-t-butyl styrene etc.; α beyond (methyl) vinylformic acid of methylene-succinic acid, itaconic anhydride, β-crotonic acid, toxilic acid, maleic anhydride, fumaric acid, citraconic acid etc., list or diester compound that beta-unsaturated carboxylic acid becomes with the single methanol of the carbonatoms 4～18 of butyl alcohol, amyl group alcohol, enanthol, octyl group alcohol, stearyl alcohol etc.; " Biscoat8F ", " Biscoat8FM ", " Biscoat3F ", " Biscoat3FM " (make by Osaka organic chemistry (strain), trade(brand)name, has (methyl) acrylic compound of fluorine atom at side chain) compound of the contain fluorine atoms of perfluor cyclohexyl (methyl) acrylate, perfluoro hexyl ethene etc. etc.

In the polymerization of macromolecular dispersion stabilizer, use as required, as the unsaturated monomer beyond long-chain unsaturated monomer, as long as enumerating the unsaturated monomer beyond such long-chain unsaturated monomer in above-mentioned, be not particularly limited, can enumerate the alkyl ester of (methyl) acrylic acid carbonatoms 1～3 of (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) propyl acrylate etc.; The affixture that glycidyl (methyl) acrylate becomes with the monocarboxylic acid compound of the carbonatoms such as acetic acid, propionic acid 2～3; α beyond (methyl) vinylformic acid of methylene-succinic acid, itaconic anhydride, β-crotonic acid, toxilic acid, maleic anhydride, fumaric acid, citraconic acid etc., list or diester compound that beta-unsaturated carboxylic acid becomes with the single methanol of the carbonatoms 1～3 of methyl alcohol, propyl alcohol etc.; The unsaturated compound of the cyano-containing of (methyl) vinyl cyanide etc.; The vinyl ester compound of vinyl-acetic ester; The vinyl ether compound of ethyl vinyl ether, methylvinylether etc.; The alpha-olefines compound of ethene, propylene, ethylene chloride, vinylidene chloride etc. etc.Unsaturated monomer beyond long-chain unsaturated monomer, as 2-hydroxyethyl (methyl) acrylate etc., also comprises the monomer that unsaturated monomer hydroxyl etc. is replaced of enumerating in above-mentioned.

In order to manufacture the polymerization of above-mentioned macromolecular dispersion stabilizer, conventionally can use radical polymerization initiator to carry out.As radical polymerization initiator, for example, can enumerate 2,2 '-Diisopropyl azodicarboxylate, 2, the azo-initiator of 2 '-azo two (2,4-methyl pentane nitrile) etc.; The catalyzer peroxide initiator of benzoyl peroxide, lauroyl peroxide, the peroxidation tert-butyl ester, tert-butyl peroxide-2-ethylhexanoate etc. etc., in the scope of the normally every 100 parts of monomers for polymerization of these polymerization starters with 0.2～10 mass parts left and right, use, preferably in the scope with 0.5～5 mass parts, use.Temperature of reaction when polymerization is 60～160 DEG C of left and right normally, and reaction times when polymerization can be made as about 1～15 hour conventionally.

The molecular weight of the multipolymer using as above-mentioned dispersion stabilizer, weight-average molecular weight is in the scope of 5000～100000 left and right, preferably in the scope of 5000～50000 left and right conventionally.By the multipolymer with above-mentioned scope molecular weight is used as dispersion stabilizer, can make dispersed particle stabilization, cohesion and sedimentation and the viscosity of can being inhibited thus can be not too high and easy to handle coating.

Macromolecular dispersion stabilizer can use separately or two kinds with in coupling.And then, also can share as required other dispersion stabilizer, such as butyl etherificate melamine formaldehyde resin, Synolac etc.

Manufacturing non-aqueous dispersion type acrylic resin when (E), under the existence of above-mentioned macromolecular dispersion stabilizer in organic solvent at least one unsaturated monomer of polymerization, in this organic solvent, prepare the non-aqueous dispersion of insoluble polymer particle.

As the organic solvent using when the above-mentioned polymerization, comprise that the polymer particle generating through this polymerization does not dissolve substantially, but the organic solvent of the good solvent that is to above-mentioned macromolecular dispersion stabilizer and this unsaturated monomer.As the concrete example of this organic solvent, can enumerate the fat hydrocarbon solvent of hexane, heptane, octane etc.; The aromatic hydrocarbon of benzene,toluene,xylene etc.; The alcoholic solvent of methyl alcohol, Virahol, normal-butyl alcohol, isobutyl alcohol, octyl group alcohol etc.; The ether solvent of cellosolve, ethylene glycol butyl ether, Diethylene Glycol single-butyl ether etc.; The ketones solvent of methyl iso-butyl ketone (MIBK), diisobutyl ketone, methyl ethyl ketone, methyl ethyl ketone, ethyl butyl ketone etc.; The esters solvent of ethyl acetate, isobutyl acetate, pentyl acetate, 2-ethylhexyl acetic ester etc. etc.These organic solvents can use separately or can share two or more.

As above-mentioned organic solvent, especially taking aliphatic hydrocarbon as main body, combine therein suitable aromatic hydrocarbon, alcoholic solvent, ether solvent, ketones solvent, esters solvent etc. and the solvent that obtains.

As the unsaturated monomer for above-mentioned polymerization, the less unsaturated monomer of carbonatoms that uses carbonatoms to have than monomer polymerizability excellence and that use as the monomer component of macromolecular dispersion stabilizer, is applicable to from the aspect easily forming as dispersed polymeres particle.

As such unsaturated monomer, for example can enumerate (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) propyl acrylate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, 2-ethyl (methyl) Ethyl acrylate, (methyl) cyclohexyl acrylate, (methyl) vinylformic acid n-octyl, (methyl) lauryl acrylate, (methyl) tridecyl acrylate, the alkyl or cycloalkyl ester of (methyl) acrylic acid carbonatoms 1～18 of (methyl) vinylformic acid stearyl etc., (methyl) acrylic acid alkoxy alkyls such as methoxyl group (methyl) butyl acrylate, methoxyl group (methyl) ethyl propenoate, oxyethyl group butyl (methyl) acrylate, the acrylic acid ester of aromatic alcohols (methyl) of benzyl (methyl) acrylate etc., the adducts that glycidyl (methyl) acrylate becomes with the monocarboxylic acid compound of the carbonatomss 2～18 such as acetic acid, propionic acid, oleic acid, p-p t butylbenzoic acid, the adducts that (methyl) vinylformic acid becomes with monocycle oxycompounds such as " カ-ヅ ユ ラ E10 ", the vinyl aromatic compounds of vinylbenzene, alpha-methyl styrene, Vinyl toluene, p-chloro-styrene, p-t-butyl styrene etc., α beyond (methyl) vinylformic acid of methylene-succinic acid, itaconic anhydride, β-crotonic acid, toxilic acid, maleic anhydride, fumaric acid, citraconic acid etc., list or diester compound that the single methanol of the carbonatomss 1～18 such as beta-unsaturated carboxylic acid and methylol, butyl alcohol, hexyl alcohol, stearyl alcohol becomes, " Biscoat8F ", " Biscoat8FM ", " Biscoat3F ", " Biscoat3FM " (make by Osaka organic chemistry (strain), trade(brand)name, has (methyl) acrylic compound of fluorine atom at side chain), the compound of the contain fluorine atoms of perfluor cyclohexyl (methyl) acrylate, perfluoro hexyl ethene etc., the unsaturated compound of the cyano-containing of (methyl) vinyl cyanide etc., the vinyl ester compound of vinyl-acetic ester, phenylformic acid vinyl ester, " Veova (VEOVA) " (SHELL (strain) system) etc., the vinyl ether compound of n-butyl vinyl ether, ethyl vinyl ether, methylvinylether etc., the polyvinyl compound of two (methyl) acrylate of 1,6-hexylene glycol, three (methyl) acrylate, the Vinylstyrene etc. of TriMethylolPropane(TMP), the alpha-olefines compound of ethene, propylene, ethylene chloride, vinylidene chloride etc. etc.

Form the monomer component of polymer particle, as mentioned above, by using carbonatoms than the carbonatoms of the monomer component of macromolecular dispersion stabilizer composition still less, can stably form particle composition, but from this viewpoint, can suitably use carbonatoms below 8, preferably (methyl) acrylic compound below 4, vinyl aromatic compounds, (methyl) vinyl cyanide etc.These unsaturated monomers can use separately or can two or more couplings.

The polymerization of above-mentioned unsaturated monomer can be carried out with common radical polymerization initiator.As operable radical polymerization initiator, for example, can enumerate 2,2 '-Diisopropyl azodicarboxylate, 2, the azo-initiator of 2 '-azo two (2,4-methyl pentane nitrile) etc.; The catalyzer peroxide initiator of benzoyl peroxide, lauroyl peroxide, the peroxidation tert-butyl ester, tert-butyl peroxide-2-ethylhexanoate etc. etc., these polymerization starters are with respect to the monomer total amount that is generally used for polymerization, can in the scope of 0.2～10 mass parts left and right, use, preferably can in the scope of 0.5～5 mass parts, use.

The macromolecular dispersion stabilizer existing in the time of above-mentioned polymerization and the usage ratio of unsaturated monomer, unsaturated monomer is 3～240 mass parts left and right with respect to macromolecular dispersion stabilizer 100 mass parts conventionally, preferably 5～82 mass parts left and right.And then the total concentration of the macromolecular dispersion stabilizer in organic solvent and unsaturated monomer is 30～70 quality % left and right normally, preferably 30～60 quality % left and right.

Polymerization can be undertaken by itself known method, and temperature of reaction when polymerization is 60～160 DEG C of left and right normally, and reaction times when polymerization is normally about 1～15 hour.

Carry out as described above polyreaction, can obtain liquid phase and be dissolving macromolecular dispersion stabilizer, solid phase and be the stable non-aqueous dispersion of the non-aqueous dispersion type acrylic resin of the polymer particle that polymerization of unsaturated monomers obtains in organic solvent.The median size of polymer particle is conventionally about the scope of 0.1～1.0 μ m.By the median size of polymer particle is located to above-mentioned scope, the viscosity of non-aqueous dispersion can be not too high, and can suppress expansion or the cohesion of the polymer particle of coating in storage, therefore preferred.

In the time manufacturing non-aqueous dispersion type acrylic resin (D), by the macromolecular dispersion stabilizer in non-aqueous dispersion is combined with polymer particle, can improve thus package stability and the mechanical characteristics of non-aqueous dispersion.It should be noted that, even the in the situation that of combination, outward appearance, dispersion state does not also almost change, and the median size of polymer particle does not also almost change.

As the method that macromolecular dispersion stabilizer is combined with polymer particle, for example, in the stage of manufacturing in advance macromolecular dispersion stabilizer, first make to have the partly copolymerization of monomer component of the functional groups such as hydroxyl, acidic group, anhydride group, epoxy group(ing), methylol, isocyanate group, amide group, amino, then carry out as the monomer component of formation polymer particle with the monomer having with the functional group such as the hydroxyl of above-mentioned functional group reactions, acidic group, anhydride group, epoxy group(ing), methylol, isocyanate group, amide group, amino.As their combination, for example, can enumerate isocyanate group and hydroxyl, isocyanate group and methylol, epoxy group(ing) and acid (acid anhydride) base, epoxy group(ing) and amino, isocyanate group and amide group, acid (acid anhydride) base and hydroxyl etc.

As the monomer with such functional group, for example, can enumerate the α of (methyl) vinylformic acid, β-crotonic acid, toxilic acid, maleic anhydride, methylene-succinic acid, itaconic anhydride, fumaric acid, citraconic acid etc., β-ethylenically unsaturated carboxylic acids; The compound containing glycidyl of (methyl) glycidyl acrylate, vinyl glycidyl ether, propenyl glycidyl ether etc.; (methyl) acrylamide, N, the carboxylic acid amide compounds of N-dimethyl (methyl) acrylamide, N-alkoxy methyl (methyl) acrylamide, diacetone acrylamide, N-methylol (methyl) acrylamide etc.; P-vinylbenzene sulphonamide, N-methyl-p-vinylbenzene sulphonamide, N, the compound that N-dimethyl-p-vinylbenzene sulphonamide etc. contains sulfonic acid amides base; (methyl) vinylformic acid-tertiary butyl amino-ethyl etc. contain amino compound; Condenses that 2-hydroxyethyl (methyl) acrylate becomes with phosphoric acid or phosphate compound, there is addition phosphoric acid on the glycidyl of compound of glycidyl or phosphate compound at glycidyl (methyl) acrylate etc. and the compound of the phosphorous acidic group of compound of obtaining etc.; 2-acrylamide-2-methyl-propane sulfonic acid etc. contain sulfonic compound; M-pseudoallyl-alpha, alpha-dimethylbenzyl isocyanic ester, isophorone diisocyanate or inferior cresyl vulcabond become with hydroxyl (methyl) acrylate etc. the compound that contains isocyanate group etc. of mole affixture, isocyano-ethyl-methyl acrylate etc.

In addition, as the additive method that macromolecular dispersion stabilizer is combined with polymer particle, can under the macromolecular dispersion stabilizer with the two keys of polymerizability exists, polymerization of unsaturated monomers be carried out.

Macromolecular dispersion stabilizer is imported to the two keys of polymerizability, for example can, by using the monomer that contains acidic group of carboxylic acid, phosphoric acid, sulfonic acid etc. as the copolymerization composition of this resin, make this acidic group react to carry out with the unsaturated monomer that glycidyl (methyl) acrylate, propenyl glycidyl ether etc. contain glycidyl.In addition, on the contrary, make in advance to contain glycidyl in macromolecular dispersion stabilizer, make it react to carry out with the unsaturated monomer that contains acidic group.These reactions can be carried out according to known condition.

In addition, as the other additive method that macromolecular dispersion stabilizer is combined with polymer particle, can mutually after the non-aqueous dispersion of mutual nonreactive functional group, make it and can react to carry out in conjunction with both bonding agents by having imported in manufacture with macromolecular dispersion stabilizer and polymer particle.

Specifically, for example can be under the existence of the macromolecular dispersion stabilizer that contains hydroxyl and organic solvent, by the unsaturated monomer of hydroxyl individually polymerization or with the polymerization of mixtures of other unsaturated monomers, in both, manufacture after the non-aqueous dispersion that contains hydroxyl, coordinate the stoichiometric number hour at normal temperatures～a couple of days such as polyisocyanate compounds or within about 1～5 hour, carry out about 60～100 DEG C reactions.

As polyisocyanate compounds, as long as there is more than 2 isocyanate group in molecule, for example can enumerate inferior cresyl vulcabond, eylylene diisocyanate, 4, the aromatic diisocyanate of 4 '-diphenylmethanediisocyanate etc. or their hydride; The aliphatic diisocyanate of hexamethylene diisocyanate, lysinediisocyanate, dimeracid (dimer of ready denier oil acid) vulcabond etc.; The ester ring type vulcabond of isophorone diisocyanate etc. etc.

In addition, outside above-mentioned, can carry out with the combination of the combination of the combination of the macromolecular dispersion stabilizer that contains acidic group and polymer particle and polyoxide, the macromolecular dispersion stabilizer that contains epoxy group(ing) and polymer particle and poly carboxylic acid, the macromolecular dispersion stabilizer that contains epoxy group(ing) or isocyanate group and polymer particle and polysulfide compound etc.

As above-mentioned polyoxide, acrylic resin that for example can enumerate bisphenol type epoxy base resin, Bisphenol F type epoxy, phenolic varnish type epoxy, contains epoxy group(ing) etc.; For example can enumerate hexanodioic acid, sebacic acid, nonane diacid, different m-phthalic acid etc. as poly carboxylic acid; Can enumerate sulfuration pentamethylene, sulfuration hexanaphthene, poly-(ethene disulphide) etc. as polysulfide.

As above, can make macromolecular dispersion stabilizer and polymer particle chemical bonding, but now by the amount of various functional groups and/or the two keys importing macromolecular dispersion stabilizers of polymerizability and/or polymerizability particle, in a part of this dispersion stabilizer and/or particle, on average has 0.1 at least, 0.1～1.0 of average out to, be particularly preferably 0.1～0.5, and then the scope amount of 0.1～0.3 particularly preferably.

The non-aqueous dispersion so obtaining like this, is chemically bonding of macromolecular dispersion stabilizer and polymer particle, therefore package stability excellence, and the film forming can show excellent chemistry, mechanical properties.

In coating composition of the present invention, in the situation that using non-aqueous dispersion type acrylic resin (D), its amount is from the viewpoint of the finished appearance of the painting face smoothness of the painting operation (sag resistance) of coating composition of the present invention and the film that obtains etc., with respect to the solids component total amount of acrylic resin (A) and the melamine resin (B) of hydroxyl, as solids component 15 quality % be below applicable to, preferably in the scope of 2～10 quality %, and then preferably in the scope of 3～8 quality %.

In addition, resin in addition of the acrylic resin (A) that further can contain as required hydroxyl in this coating, the tinting pigment that does not hinder transparent degree, bright pigment, dyestuff etc., and then can also suitably contain pigment extender, UV light absorber, photostabilizer, defoamer, viscosifying agent, rust-preventive agent, surface conditioner, organic solvent etc.

As above-mentioned catalyzer, for example, can enumerate organo-metallic catalyst, the tertiary amine etc. of stannous octoate, two (2 ethyl hexanoic acid) dibutyl tin, two (2 ethyl hexanoic acid) dioctyl tin, oxalic acid dioctyl tin, dibutyl tin laurate, dibutyl tin oxide, dioctyltin oxide, 2-ethyl hexane lead plumbate etc.

Can use separately or can two or more couplings as above-mentioned these compounds of catalyzer.The amount of catalyzer is according to its kind and difference, with respect to (A) composition and (B) the solids component total amount of composition, conventionally can be made as 0～5 quality %, is preferably made as 0.1～4 quality % left and right.

As above-mentioned UV light absorber, can use in the past known UV light absorber always, for example can enumerate the UV light absorber of benzotriazole category absorption agent, triazines absorption agent, salicylic acid absorption agent, benzophenone absorption agent etc.

The content of UV light absorber in coating composition, from the angle of weathering resistance, yellowing resistance, conventionally with respect to resin solid composition total amount preferably in the scope of 0～10 quality %, particularly preferably in the scope of 0.2～5 quality %, and then in scope particularly preferably in 0.3～2 quality %.

As photostabilizer, can use in the past known photostabilizer always, for example can enumerate hindered amine light stabilizer.

Content as photostabilizer in coating composition, from the angle of weathering resistance, yellowing resistance, conventionally with respect to resin solid composition total amount preferably in the scope of 0～10 quality %, particularly preferably 0.2～5 quality %, and then in scope particularly preferably in 0.3～2 quality %.

In the time that the isocyanate group of the polyisocyanate compounds of conduct (B) composition of coating composition of the present invention is not closed type, from the viewpoint of storage stability, be preferably: make into 2 liquid type coating,, the acrylic resin (A) that contains hydroxyl and the composition of polyvalent alcohol (C) are isolated from each other with the composition that contains polyisocyanate compounds (B), in use above-mentioned binary are mixed to use.

The solid component concentration of this coating preferred 35～70 quality % conventionally, more preferably 40～70 quality %, and then preferred 45～65 quality %.

This coating can utilize itself known method, and additional static is carried out in the applications such as such as Airless spraying, aerial spraying, rotary-atomizing coating machine in the time of application.Application thickness can be made as in the scope of 10～60 μ m conventionally to solidify film thickness gauge, is preferably made as in the scope of 25～50 μ m.

method of forming layered coating film

coated article

According to the present invention, as the coated article that is suitable for the 1st water-based pigmented coating (X) and obtains, be not particularly limited, for example can enumerate the outer board of the car bodies such as passenger vehicle, truck, power truck, motorbus; Trolley part; The outer board of the household electrical appliance goods of mobile phone, audio-frequency apparatus etc. etc., wherein, preferably outer board and the automotive department of car body.

In addition, as the starting material of above-mentioned coated article, be not particularly limited, for example, can enumerate the metallic substance of iron, aluminium, brass, copper, tinplate, stainless steel, galvanized steel, alloy plating zinc (Zn-Al, Zn-Ni, Zn-Fe etc.) steel etc.; The plastic material of resene, the various FRP etc. of polyvinyl resin, acrylic resin, acrylonitrile-butadiene-styrene (ABS) (ABS), polyamide resin, acrylic resin, vinylidene resin, polycarbonate resin, urethane resin, epoxy resin etc.; The inorganic materials of glass, cement, concrete etc.; Timber; Filamentary materials (paper, cloth etc.) etc., wherein metallic substance and plastic material are applicable to.

Above-mentioned coated article can be to above-mentioned metallic substance, be imposed the surface treatment of phosphatizing, chromic salt processing, composite oxides processing etc. by the metallic surface of car body of its moulding etc.And then this coated article can be to form various electricity the primer coating film of coating etc. and obtain on above-mentioned metal base, car body etc., wherein particularly preferably utilize cation electrodeposition material to have formed the car body of primer coating film.

operation (1)

In this operation, on coated article, application the 1st water-based pigmented coating (X) forms the 1st painted film.

the 1st water-based pigmented coating (X)

As the 1st water-based pigmented coating (X) to above-mentioned coated article application, contain heat-curing resin composition and water, and then as required, can collaboration organic solvent, the water-based liquid coating that obtains such as tinting pigment, pigment extender, bright pigment, surface conditioner, sedimentation preventing agent.It should be noted that, in this specification sheets, so-called water-borne coatings is the coating that the principal constituent of solvent is water.

As above-mentioned heat-curing resin composition, can use the hydrophilic functional group's of bridging property functional group and the carboxyl etc. with hydroxyl etc. matrix resin (I) and linking agent (II) forms itself known coating resin composition, described matrix resin (I) is vibrin, acrylic resin, Vinylite, Synolac, urethane resin etc., polyisocyanate compounds that described linking agent (II) is melamine resin, can seal etc.

Wherein, as matrix resin (I), use the acrylic resin (I-1) of hydroxyl and/or the vibrin (I-2) of hydroxyl, as linking agent (II), be applicable to using aminoresin (II-1) and/or dead front type polyisocyanate compounds (II-2).

The acrylic resin (I-1) of hydroxyl, for example can by under usual conditions by the unsaturated monomer that contains hydroxyl with comprise as required and can manufacture with at least one unsaturated monomer (being total to) polymerization of other unsaturated monomers of this monomer copolymerizable.

The unsaturated monomer that contains hydroxyl, in 1 molecule, at least there is respectively the compound of 1 hydroxyl and polymerizability unsaturated link(age), for example, can enumerate the monoesters compound of (methyl) vinylformic acid of (methyl) vinylformic acid-2-hydroxyl ethyl ester, (methyl) 2-hydroxypropyl acrylate, (methyl) vinylformic acid-3-hydroxypropyl acrylate, (methyl) vinylformic acid-4-hydroxy butyl ester etc. and the dibasic alcohol of carbonatoms 2～8; The 6-caprolactone modification body of the monoesters compound that (methyl) vinylformic acid becomes with the dibasic alcohol of carbonatoms 2～8; Propenyl alcohol; Molecular end has (methyl) acrylate of the polyethylene oxide chain that belongs to hydroxyl etc.

As can with other unsaturated monomer of the above-mentioned unsaturated monomer copolymerization that contains hydroxyl, for example can enumerate (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) vinylformic acid n-propyl, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, the just own ester of (methyl) vinylformic acid, (methyl) Octyl acrylate, (methyl) ethyl acrylate, (methyl) vinylformic acid ester in the ninth of the ten Heavenly Stems, (methyl) lauryl acrylate, (methyl) tridecyl acrylate, (methyl) vinylformic acid stearyl, " IsostearylAcrylate " (trade(brand)name, Osaka organic chemistry industrial system), (methyl) cyclohexyl acrylate, (methyl) acrylic methyl cyclohexyl, (methyl) vinylformic acid tertiary butyl cyclohexyl, alkyl or cycloalkyl (methyl) acrylate of (methyl) vinylformic acid cyclododecane ester etc., the unsaturated monomer with isobornyl of isobornyl (methyl) acrylate etc., adamantyl (methyl) acrylate etc. has the unsaturated monomer of adamantyl, the unsaturated monomer containing aromatic nucleus of vinylbenzene, alpha-methyl styrene, Vinyl toluene, phenyl (methyl) acrylate etc., the unsaturated monomer with alkoxysilyl of vinyltrimethoxy silane, vinyltriethoxysilane, vinyl three (2-methoxy ethoxy) silane, γ-(methyl) acryloxy propyl trimethoxy silicane, γ-(methyl) acryloxy propyl-triethoxysilicane etc., perfluoroalkyl (methyl) acrylate of perfluoro butyl ethyl (methyl) acrylate, perfluoro capryl ethyl (methyl) acrylate etc., the unsaturated monomer with fluorinated alkyl of fluoroolefin etc., there is the unsaturated monomer of the optical polymerism functional groups such as dimaleoyl imino, the vinyl compound of NVP, ethene, divinyl, chloroprene, vinyl propionate base, jealous woman acid vinyl etc., the carboxylic unsaturated monomer of (methyl) vinylformic acid, toxilic acid, β-crotonic acid, β-propyloic acrylic ester etc., the nitrogenous unsaturated monomer of the affixture that (methyl) vinyl cyanide, (methyl) acrylamide, dimethylaminopropyl (methyl) acrylamide, dimethylamino (methyl) ethyl propenoate, glycidyl (methyl) acrylate become with amine etc., glycidyl (methyl) acrylate, glycidyl (methyl) acrylate, Beta-methyl glycidyl (methyl) acrylate, 3,4-epoxy group(ing) cyclohexyl (methyl) methyl acrylate, 3,4-epoxy group(ing) cyclohexyl ethyl (methyl) acrylate, 3, the unsaturated monomer containing epoxy group(ing) of 4-epoxy group(ing) cyclohexyl propyl group (methyl) acrylate, propenyl glycidyl ether etc., molecular end has (methyl) acrylate as the polyoxy ethylene chain of alkoxyl group, 2-acrylamide-2-methyl propane sulfonic acid, propenyl sulfonic acid, styrene sulfonic acid sodium salt, sulfoethyl methacrylic ester and sodium salt, ammonium salt etc. have sulfonic unsaturated monomer, the unsaturated monomer with phosphate of 2-acryl oxygen base ethylhexyldithiophosphoric acid phosphoric acid ester, 2-methacryloxyethyl acid phosphoric acid ester, 2-acryl oxygen base acid propyl phosphoric acid ester, 2-methacryloxypropyl acid phosphoric acid ester etc., 2-hydroxyl-4-(3-methacryloxy-2-hydroxyl propoxy-) benzophenone, 2-hydroxyl-4-(3-acryl oxygen base-2-hydroxyl propoxy-) benzophenone, 2,2 '-dihydroxyl-4-(3-methacryloxy-2-hydroxyl propoxy-) benzophenone, 2,2 '-dihydroxyl-4-(3-acryl oxygen base-2-hydroxyl propoxy-) benzophenone, 2-(2 '-hydroxyl-5 '-methacryloxyethyl phenyl)-2H-benzotriazole etc. have the unsaturated monomer of ultraviolet-absorbing group, 4-(methyl) acryl Oxy-1, 2, 2, 6, 6-pentamethyl-piperidines, 4-(methyl) acryl oxygen base-2, 2, 6, 6-tetramethyl piperidine, 4-cyano group-4-(methyl) acryl amino-2, 2, 6, 6-tetramethyl piperidine, 1-(methyl) acryl-4-(methyl) acryl amino-2, 2, 6, 6-tetramethyl piperidine, 1-(methyl) acryl-4-cyano group-4-(methyl) acryl amino-2, 2, 6, 6-tetramethyl piperidine, 4-crotonyl oxygen base-2, 2, 6, 6-tetramethyl piperidine, 4-crotonyl amino-2, 2, 6, 6-tetramethyl piperidine, 1-crotonyl-4-crotonyl oxygen base-2, 2, 6, 6-tetramethyl piperidine etc. has the unsaturated monomer of ultraviolet stabilization performance, propenal, diacetone acrylamide, two acetone Methacrylamides, acetoacetoxy groups ethyl-methyl acrylate, formyl radical vinylbenzene, have the unsaturated monomer compound with carbonyl etc. of the vinyl alkyl ketone (such as ethenyl methyl ketone, vinyl ethyl ketone, vinyl butyl ketone) etc. of 4～7 carbon atoms, these can be distinguished and use separately or can two or more couplings.

The acrylic resin (I-1) of hydroxyl, from package stability, obtain the viewpoint of water tolerance of film etc., conventionally can there is the hydroxyl value within the scope of 1～200mgKOH/g, the preferably hydroxyl value within the scope of 2～100mgKOH/g, and then preferably there is the hydroxyl value within the scope of 3～60mgKOH/g, and conventionally there is the acid number within the scope of 1～200mgKOH/g, preferably there is the acid number within the scope of 2～150mgKOH/g, and then preferably there is the acid number within the scope of 5～100mgKOH/g.In addition, the acrylic resin of hydroxyl (A1) has the weight-average molecular weight in 1,000～5,000,000 scope conventionally, preferably there is the weight-average molecular weight in 2,000～3,000,000 scope, and then preferably there is the weight-average molecular weight in 3,000～1,000,000 scope.

The use level of the acrylic resin (I-1) of hydroxyl, taking the solids component total amount of the matrix resin (I) in the 1st water-based pigmented coating (X) and linking agent (II) (hereinafter referred to as resinous principle) as benchmark, conventionally can be made as in the scope of 0～90 quality %, preferably be made as in the scope of 5～60 quality %, and then be preferably made as in the scope of 10～40 quality %.

The vibrin (I-2) of hydroxyl, for example can manufacture by the esterification of polyprotonic acid composition and polyhydroxy reactant or transesterification reaction, specifically for example can, by the equivalence ratio of the hydroxyl in the carboxyl in polyprotonic acid composition and polyhydroxy reactant (COOH/OH) is made as below 1, under the hydroxyl state more than carboxyl, carry out esterification and manufacture.

Above-mentioned polyprotonic acid composition is the compound at least in 1 molecule with 2 carboxyls, for example, can enumerate the polyprotonic acid of phthalic acid, isophthalic acid, terephthalic acid, succsinic acid, pentanedioic acid, hexanodioic acid, nonane diacid, sebacic acid, tetrahydrochysene phthalic acid, hexahydrobenzene dioctyl phthalate, toxilic acid, fumaric acid, methylene-succinic acid, trimellitic acid, pyromellitic acid etc.; The acid anhydrides of these polyprotonic acids; The low alkyl group carboxylates of these polyprotonic acids etc., these compounds can use respectively or also can two or more couplings.

In addition, above-mentioned polyhydroxy reactant is the compound at least in 1 molecule with 2 hydroxyls, for example can enumerate ethylene glycol, 1,2-propylene glycol, 1,2-butyleneglycol, 2,3-butanediol, 1,2-hexylene glycol, 1,2-dihydroxyl hexanaphthene, 3-epoxy group(ing) propane-1,2-glycol, 3-phenoxypropane-1, the salmefamol of 2-glycol etc., neopentyl glycol, 2-methyl isophthalic acid, ammediol, 2-methyl-2,4-pentanediol, 3-methyl isophthalic acid, 3-butyleneglycol, 2-ethyl-1,3-hexylene glycol, 2,2-diethyl-1,3-PD, 2,2,4-trimethylammonium-1,3-pentanediol, 2-butyl-2-ethyl-1,3-PD, 2-phenoxypropane-1,3-glycol, 2-methyl-2-phenyl-propane-1,3-glycol, 1,3-PD, 1,3 butylene glycol, 2-ethyl-1,3-ethohexadiol, 1,3-dihydroxyl hexanaphthene, BDO, Isosorbide-5-Nitrae-dihydroxyl hexanaphthene, 1,5-PD, 1,6-hexylene glycol, 2,5-hexylene glycol, 3-methyl isophthalic acid, 5-pentanediol, Isosorbide-5-Nitrae-hydroxymethyl-cyclohexane, tristane dimethanol, 2,2-dimethyl-3-hydroxypropyl-2,2-dimethyl-3-hydroxy propionate (this is the carboxylate that hydroxy new pentane acid becomes with neopentyl glycol), dihydroxyphenyl propane, Bisphenol F, two (4-hydroxyethyls)-2,2-propane, two (4-hydroxyethyl) methane, two (1, the 1-dimethyl-2-hydroxyethyls)-2,4,8 of 3,9-, 10-tetra-oxygen volution [5,5] undecanes, Diethylene Glycol, triethylene glycol, glycerine, two glycerine, triglycerin, tetramethylolmethane, Dipentaerythritol, Sorbitol Powder, N.F,USP MANNITOL, trimethylolethane, TriMethylolPropane(TMP), two (trishydroxymethyl) propane, three (2-hydroxyethyl) chlorinated isocyanurates etc., these can distinguish use or two or more coupling separately.

The esterification of above-mentioned polyprotonic acid composition and polyhydroxy reactant or transesterification reaction can be undertaken by itself known method, for example can be by the polycondensation at approximately 180～approximately 250 DEG C of temperature of above-mentioned polyprotonic acid composition and polyhydroxy reactant is carried out.

In addition, the vibrin of hydroxyl (I-2), in this vibrin process for preparation or after esterification, can use the modifications such as lipid acid, monocycle oxycompound as required.As above-mentioned lipid acid, for example can enumerate coco-nut oil fatty acid, continuous seed oil fatty acid, hemp seed oil lipid acid, Rice pollard oil lipid acid, fish oil fatty acid, ready denier oil acid, soya fatty acid, linseed oil fatty acid, tung oil lipid acid, rapeseed oil fatty acid, Castor Oil Fatty Acid, dehydrated castor oil fatty acid, Thistle oil lipid acid etc., for example can enumerate " カ-ジ ユ ラ E10P " (trade(brand)name as above-mentioned monocycle oxycompound, HEXION Specialty Chemicals company system, the glycidyl esters of a synthetic high chain saturated fatty acid) etc.

The vibrin (I-2) of hydroxyl can have the hydroxyl value within the scope of 10～300mgKOH/g conventionally, the preferably hydroxyl value within the scope of 25～250mgKOH/g, and then preferably there is the hydroxyl value within the scope of 50～200mgKOH/g, and conventionally there is the acid number within the scope of 1～200mgKOH/g, preferably there is the acid number within the scope of 5～100mgKOH/g, and then preferably there is the acid number within the scope of 10～60mgKOH/g.In addition, the vibrin of hydroxyl (I-2) has the weight-average molecular weight in 500～50,000 scope conventionally, preferably has the weight-average molecular weight in 1,000～40,000 scope, and then preferably has the weight-average molecular weight in 1,500～30,000 scope.

The use level of the vibrin (I-2) of hydroxyl, taking the resinous principle solids component total amount in the 1st water-based pigmented coating (X) as benchmark, conventionally can be made as in the scope of 0～90 quality %, preferably be made as in the scope of 10～60 quality %, and then be preferably made as in the scope of 15～50 quality %.

In addition, the vibrin (I-2) of the acrylic resin of hydroxyl (I-1) and hydroxyl, in order easily to carry out water-solubleization or water-dispersion, preferably will be contained in partly or entirely neutralizing with basic cpd of carboxyl in them.As basic cpd, for example, can enumerate the basic metal of sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide, hydrated barta etc. or the oxyhydroxide of alkaline-earth metal; Ammonia; Uncle's monoamine of ethylamine, propyl group amine, butylamine, benzyl amine, monoethanolamine, neopentyl alcohol amine, 2-aminopropanol, 2-amino-2-methyl-1-propanol, 3-aminopropanol etc.; The secondary monoamine of diethylamide, diethanolamine, two n-propyl alcohol amine, diisopropanolamine (DIPA), N-Mono Methyl Ethanol Amine, N-ehtylethanolamine etc.; The tertiary monoamine of dimethylethanolamine, Trimethylamine, triethylamine, triisopropylamine, methyldiethanolamine, 2-(dimethylamino) ethanol etc.; The polyamine of diethylenetriamine, hydroxyethylamino ethylamine, ethylamino ethylamine, methylamino propyl group amine etc.As the usage quantity of basic cpd, conventionally can be made as in the scope of 0.1～1.5 equivalent with respect to the acidic group of matrix resin (I), be preferably made as in the scope of 0.2～1.2 equivalent.

As above-mentioned urethane, except conventional urethane, the part that can also enumerate the hydroxyl in the acrylic resin (I-1) of above-mentioned hydroxyl and the vibrin (I-2) of hydroxyl and polyisocyanate compounds carry out that urethane reacts and the urethane that it extends, polymer quantizes that obtains etc.

On the other hand, as aminoresin (II-1), for example, can enumerate the part or all of methylolation aminoresin that the amino component of trimeric cyanamide, urea, benzoguanamine, methyl guanamines, steroid guanamines (ス テ ロ グ ア Na ミ Application), spiral shell guanamines (ス ピ ロ グ ア Na ミ Application), dicyan diamide etc. obtains with reacting of aldehyde.As aldehyde, for example, can enumerate formaldehyde, paraformaldehyde, acetaldehyde, benzaldehyde etc.In addition, its part or all of methylolation aminoresin can be carried out to the material that part or all of etherificate obtains with alcohol, the example of the alcohol using during as etherificate, can enumerate methyl alcohol, ethyl alcohol, n-propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, 2-ethyl butanol, 2-Ethylhexyl Alcohol etc.

As aminoresin (II-1), preferably melamine resin, wherein by the methylol of part or all of methylolation melamine resin with methyl alcohol carry out the methyl etherified melamine resin that part or all of etherificate obtains, the butyl etherify melamine resin obtaining by the part or all of etherificate of butanols, the alkyl etherify melamine resin of methyl-butyl complex etherified melamine resin of obtaining by methyl alcohol and the part or all of etherificate of butanols etc.

In addition, melamine resin preferably has the weight-average molecular weight in 500～5,000 scope conventionally, particularly preferably has the weight-average molecular weight in 600～4,000 scope, and then particularly preferably has the weight-average molecular weight in 700～3,000 scope.

In addition, when (II) uses using melamine resin as linking agent, can use the sulfonic acid, these salt of becoming with amine of acid of tosic acid, Witco 1298 Soft Acid, dinonylnaphthalene sulfonic acid etc. as catalyzer.

As dead front type polyisocyanate compounds (II-2), can use the encapsulant of oxime, phenol, alcohol, activity methene compound, lactan, mercaptan etc. for isocyanate group of the polyisocyanate compounds at least in 1 molecule with 2 isocyanate group is sealed to the material obtaining.

The ratio of matrix resin (I) and linking agent (II), the two the solids component total amount based on them, the former is adapted in the scope of 40～90 quality % conventionally, be particularly suitable in the scope of 50～80 quality %, the latter is adapted in the scope of 60～10 quality % conventionally, in the scope particularly preferably in 50～20 quality %.

As above-mentioned tinting pigment, for example can enumerate titanium oxide, zinc oxide, carbon black, lead sulfate, calcium plumbite, zinc phosphate, aluminum phosphate, zinc molybdate, calcium molybdate, dark purple, ultramarine, cobalt blue, copper phthalocyanine blue, anthraquinone blue, chrome yellow, synthesizing yellow ferric oxide, transparent Indian red (Huang), pucherite, titan yellow, zinc yellow, monoazo yellow, isoindolone Huang, metallic complex salt azophosphine, quinophthalone Huang, benzimidazolone yellow, Indian red, tri-lead tetroxide, monoazo is red, quinacridone is red, azo lake (Mn salt), quinacridone magenta, anthracene is formed anthrone orange, dianthraquinone red (ヅ ア Application ス ラ キ ノ ニ Le レ ッ De), perylene bright red (ペ リ レ Application マ Le-Application), quinacridone magenta, perylene is red, diketopyrrolo-pyrrole molybdenum red, chlorination phthalocyanine green, bromination phthalocyanine green, pyrazolone orange, benzimidazolone orange, dioxazine violet, perylene purple etc., wherein can be applicable to using titanium oxide, carbon black.

In the time that the 1st water-based pigmented coating (X) contains above-mentioned tinting pigment, the use level of this tinting pigment, taking the resinous principle solids component total amount in the 1st water-based pigmented coating (X) as benchmark, conventionally can be made as in the scope of 1～120 quality %, preferably be made as in the scope of 10～100 quality %, and then be preferably made as in the scope of 15～90 quality %.

In addition, as above-mentioned pigment extender, such as clay, kaolin, barium sulfate, barium carbonate, calcium carbonate, talcum, silicon-dioxide, white lake etc. be can enumerate, barium sulfate and/or talcum wherein preferably used.

In the time that the 1st water-based pigmented coating (X) contains above-mentioned pigment extender, the use level of this pigment extender, taking the resinous principle solids component total amount in the 1st water-based pigmented coating (X) as benchmark, conventionally can be made as in the scope of 1～100 quality %, preferably be made as in the scope of 5～60 quality %, and then be preferably made as in the scope of 8～40 quality %.

In addition, as above-mentioned bright pigment, for example, can enumerate the aluminum oxide that non-floating type or floated are covered by aluminium (also comprising AM aluminum metallization), copper, zinc, brass, nickel, aluminum oxide, mica, titanium oxide, ferric oxide; Mica that oxidized titanium, ferric oxide cover, sheet glass, holography (ホ ロ グ ラ system) pigment etc., these can use separately, or can two or more couplings.

In the time that the 1st water-based pigmented coating (X) contains above-mentioned bright pigment, the use level of this bright pigment is taking the resinous principle solids component total amount in the 1st water-based pigmented coating (X) as benchmark, conventionally can be made as in the scope of 1～50 quality %, preferably be made as in the scope of 2～30 quality %, and then be preferably made as in the scope of 3～20 quality %.

The 1st water-based pigmented coating (X), can utilize itself known method, and the applications on coated article such as such as aerial spraying, Airless spraying, rotary-atomizing coating machine, in the time of application, also can carry out additional static.Application thickness is made as conventionally to solidify film thickness gauge in the scope of 10～100 μ m, is preferably made as in the scope of 10～50 μ m, is more preferably made as in the scope of 15～35 μ m.

It should be noted that, at application the 2nd water-based pigmented coating (Y) before, the 1st painted film that utilizes the 1st water-based pigmented coating (X) to form in operation (1), preferably be adjusted in the scope that solid component content reaches 70～100 quality %, particularly preferably be adjusted in the scope of 75～99 quality %, and then be particularly preferably adjusted in the scope of 80～98 quality %.

The adjustment of above-mentioned solid component content, can heat by preparation the methods such as (preheating), air spray and carry out.Pre-warmed temperature can be made as in room temperature～approximately 100 DEG C, is preferably made as approximately 40～approximately 90 DEG C, and then is preferably made as approximately 60～approximately 80 DEG C, and the pre-warmed time can be made as 30 seconds～and 15 points, be preferably made as 1～10 point, and then be preferably made as 3～5 points of left and right.

operation (2)

On the 1st painted film that utilizes the 1st water-based pigmented coating to form, follow application the 2nd water-based pigmented coating (Y) in operation (1).

the 2nd water-based pigmented coating (Y)

In the 2nd water-based pigmented coating (Y) using in the present invention, contain heat-curing resin composition and water, and then collaboration organic solvent, tinting pigment, pigment extender, bright pigment, surface conditioner, anti-settling agent etc. and the aqueous coating of water-based that obtains as required.

As heat-curing resin composition, itself known coating resin composition that the linking agent (II) of the polyisocyanate compounds that can use matrix resin (I) hydrophilic functional group, vibrin, acrylic resin, Vinylite, Synolac, urethane etc. that the 1st water-based pigmented coating (X) was carried out to bridging property functional group and carboxyl etc. explanation, that have hydroxyl etc. and, melamine resin, can seal etc. forms.

Wherein, as matrix resin (I), use the acrylic resin (I-1) of aforesaid hydroxyl and/or the vibrin (I-2) of hydroxyl, use aminoresin (II-1) and/or dead front type polyisocyanate compounds (II-2) to be applicable to as linking agent (II).

In addition, the 2nd water-based pigmented coating (Y), and then can contain separately respectively or combine as required two or more curing catalysts, UV light absorber, photostabilizer, defoamer, fluidizer etc. the common additive for coatings etc. that contain.

Wherein, in the 2nd water-based pigmented coating (Y), if use bright pigment as at least one of pigment composition, can form and have the metal sense of fine and close sense or the film of pearl sense, this is applicable to.

The 2nd water-based pigmented coating (Y), can utilize itself known method, such as aerial spraying, Airless spraying, rotary-atomizing coating machine etc. to carry out application, carries out additional static in the time of application.Application thickness is made as conventionally to solidify film thickness gauge in the scope of 5～40 μ m, is preferably made as in the scope of 10～30 μ m.

It should be noted that, in transparent paint coating (Z) before, the 2nd painted film that utilizes the 2nd water-based pigmented coating (Y) to form in operation (2), its solid component content is preferably made as the scope of 70～100 quality %, particularly preferably be made as the scope of 75～99 quality %, and then be particularly preferably made as in the scope of 80～98 quality %.

operation (3)

In operation (2), utilize on the 2nd painted film of the 2nd water-based pigmented coating formation then transparent paint coating (Z).As Clear paint (Z), the coating composition (this coating) of application the invention described above.

Clear paint (Z) can utilize the applications such as itself known method, such as Airless spraying, aerial spraying, rotary-atomizing coating machine, carries out additional static in the time of application.Application thickness can be made as in the scope of 10～60 μ m conventionally to solidify film thickness gauge, is preferably made as in the scope of 25～50 μ m.

operation (4)

The multilayer film being formed by the film of 3 layers of the 1st painted film forming as described above, the 2nd painted film and transparent coating, utilize the method that is heating and curing of common film, for example utilize Hot-blast Heating, infrared heating, ratio-frequency heating etc., can be conventionally approximately 80～approximately 170 DEG C, preferably heat about approximately 20～approximately 40 minutes the temperature of approximately 120～approximately 160 DEG C, together make it solidify.

Embodiment

Below enumerate embodiment and comparative example, the present invention is further specifically described.Wherein, the present invention is not only limited to these embodiment.It should be noted that, " part " and " % " is and obtains according to quality criteria.

the manufacture of the acrylic resin (I-1) of hydroxyl

Production Example 1

Possessing in the reaction vessel of thermometer, thermostatted, whipping appts, reflux exchanger and dropper, add 70.7 of deionized waters and " ア Network ア ロ Application KH-10 " (trade(brand)name, the first industrial drugmaker system, emulsifying agent, effective constituent 97%) 0.52 part, in nitrogen gas stream, be uniformly mixed, be warmed up to 80 DEG C.Then, inherent 5 parts of importing reaction vessels of 1% amount of the total amount in following monomer emulsification and 6% ammonium persulfate aqueous solution 80 DEG C are kept 15 minutes.Then, with 3 hours, remaining monomer emulsification is added drop-wise in the reaction vessel that remains uniform temp, drip and finish post curing 1 hour, then 40 parts of 5% 2-(dimethylamino) aqueous ethanolic solutions are added to reaction vessel lentamente, be cooled to 30 DEG C simultaneously, with 100 object nylon cloths filtrations, discharge simultaneously, obtain the Emulsion acrylic resin (I-1-1) of the hydroxyl of solid component concentration 45%.The acid number of the acrylic resin of the hydroxyl obtaining is 12mgKOH/g, and hydroxyl value is 43mgKOH/g.

Monomer emulsification: 0.03 part of 50 parts of mix and blend deionized waters, 10 parts of vinylbenzene, 40 parts of methyl methacrylates, 35 parts of ethyl propenoates, 3.5 parts of normal-butyl methacrylic esters, 10 parts of HEMAs, 1.5 parts, vinylformic acid, ア Network ア ロ Application KH-101.0 part and ammonium persulphate, obtain monomer emulsification.

Production Example 2

Possessing in the reaction vessel of thermometer, thermostatted, whipping appts, reflux exchanger and dropper, add 130 parts of deionized waters and " ア Network ア ロ Application KH-10 " 0.52 part, in nitrogen gas stream, be uniformly mixed, be warmed up to 80 DEG C.Then, inherent 5.3 parts of importing reaction vessels of 1% amount of the total amount in following monomer emulsification (1) and 6% ammonium persulfate aqueous solution 80 DEG C are kept 15 minutes.Then,, be then added drop-wise in the reaction vessel that remains uniform temp remaining monomer emulsification (1) with 3 hours, drip and finish post curing 1 hour.Then with 1 hour following monomer emulsification (2) of dropping, after slaking 1 hour, add lentamente reaction vessel to be cooled to 30 DEG C 40 parts of 5% dimethyl ethanol amine aqueous solutions simultaneously, filter with 100 object nylon cloths, discharge simultaneously, obtain median size 100nm (Submicron particle size distribution device " COULTER N4 type " (trade(brand)name, Beckman Coulter company system), be diluted in 20 DEG C with deionized water and measure), the Emulsion acrylic resin (I-1-2) of the hydroxyl of solid component concentration 30%.The acid number of the acrylic resin of the hydroxyl obtaining is 33mgKOH/g, and hydroxyl value is 25mgKOH/g.

Monomer emulsification (1): 21 parts of 42 parts, 0.72 part ア Network ア ロ Application KH-10 of mix and blend deionized water, 2.1 parts of methylene-bisacrylamides, 2.8 parts of vinylbenzene, 16.1 parts of methyl methacrylates, 28 parts of ethyl propenoates and n-butyl acrylates, obtain monomer emulsification (1).

Monomer emulsification (2): 9 parts of 18 parts, 0.31 part ア Network ア ロ Application KH-10 of mix and blend deionized water, 0.03 part of ammonium persulphate, 5.1 parts of methacrylic acids, 5.1 parts of 2-hydroxy ethyl methacrylates, 3 parts of vinylbenzene, 6 parts of methyl methacrylates, 1.8 parts of ethyl propenoates and n-butyl acrylates, obtain monomer emulsification (2).

the manufacture of the vibrin (I-2) of hydroxyl

Production Example 3

Possessing in the reaction vessel of thermometer, thermostatted, whipping appts, reflux exchanger and water separator, add 109 parts of 174 parts of TriMethylolPropane(TMP)s, 327 parts of neopentyl glycol, 352 parts of hexanodioic acids, isophthalic acid and 1,101 parts, 2-cyclohexane dicarboxylic acid acid anhydrides, be warmed up to after 230 DEG C from 160 DEG C with 3 hours, the utilization of condensed water water separator distillation of generation is removed, remain on 230 DEG C simultaneously, react until acid number reaches below 3mgKOH/g.In this reaction product, add 59 parts of trimellitic acid 1,2-anhydrides, carry out 30 points of addition reactions at 170 DEG C, then be cooled to below 50 DEG C, 2-(dimethylamino) ethanol that adds acidic group equivalent neutralizes, then add lentamente deionized water, obtain thus the polyester resin solution (I-2-1) of the hydroxyl of solid component concentration 45%, pH7.2.The acid number of the vibrin of the hydroxyl obtaining is that 35mgKOH/g, hydroxyl value are that 128mgKOH/g, weight-average molecular weight are 13,000.

Production Example 4

Possessing in the reaction vessel of thermometer, thermostatted, whipping appts, reflux exchanger and water separator, add 109 parts of TriMethylolPropane(TMP)s, 1,141 parts of 6-hexylene glycols, 126 parts of hexahydrophthalic acid anhydrides and 120 parts of hexanodioic acids heating, be warmed up to after 230 DEG C from 160 DEG C with 3 hours, carry out condensation reaction in 4 hours at 230 DEG C.Then, for the condensation reaction products addition carboxyl to obtaining, further add 38.3 parts of trimellitic acid 1,2-anhydrides, 170 DEG C of reactions 30 minutes, then use 1-octanol (boiling point is the alcoholic solvent of 195 DEG C) dilution, obtain the polyester resin solution (I-2-2) of the hydroxyl of solid component concentration 70%.The acid number of the vibrin of the hydroxyl obtaining is 46mgKOH/g, and hydroxyl value is 150mgKOH/g, and weight-average molecular weight is 6,400.

the manufacture of the 1st water-based pigmented coating (X)

Production Example 5

Mix 56 parts of the polyester resin solutions (I-2-1) (25 parts of resin solid compositions) of the hydroxyl obtaining in Production Example 3, JR-806 (Tayca company system, trade(brand)name, rutile titanium dioxide) 60 parts, Carbon MA-100 (Mitsubishi Chemical Ind's system, trade(brand)name, carbon black) 1 part, BARYACEB-35 trade(brand)name, Sakai chemical industrial company system, barium sulfate powder, m) 15 parts of average primary particle diameter 0.5 μ, MICRO ACES-3 (trade(brand)name, talcum company of Japan system, talcum powder, m) 5 parts of 3 parts and deionized waters of average primary particle diameter 4.8 μ, be adjusted into after pH8.0 with 2-(dimethylamino) ethanol, disperse within 30 minutes, to obtain colo(u)rant dispersion thickener with PAINT SHAKER.

Then, 140 parts of the colo(u)rant dispersion thickeners being mixed to get equably, in Production Example 1, obtain 33 parts of the Emulsion acrylic resins (I-1-1) of hydroxyl, 33 parts of the polyester resin solutions (I-2-1) of the hydroxyl obtaining in Production Example 3, CYMEL325 (trade(brand)name, Cytec Industries company of Japan system, melamine resin, solids component 80%) 37.5 parts, バ イ ヒ ヅ ユ-Le VPLS2310 (trade(brand)name, Sumika Bayer Urethane company system, dead front type polyisocyanate compounds, solids component 38%) 26 parts and ユ-コ-ト UX-8100 (trade(brand)name, Sanyo changes into industrial's system, polyaminoester emulsion, solids component 35%) 43 parts.

Then, in the mixture obtaining, add UH-752 (trade(brand)name, ADEKA company system, viscosifying agent), 2-(dimethylamino) ethanol and deionized water, obtain viscosity that pH8.0, coating solids component 48%, Ford Cup No.4 at 20 DEG C obtain and be the 1st water-based pigmented coating (X-1) of 30 seconds.

Production Example 6

In Production Example 5,43 parts of ユ-コ-ト UX-8100 are replaced to 5 parts of 28.6 parts of ユ-コ-ト UX-8100 and Sunnix PP-1000 (trade(brand)name, Sanyo change into company's system, polyoxypropylene glycol, number-average molecular weight 1000, effective constituent 100%), with Production Example 5 similarly, obtain the 1st water-based pigmented coating (X-2).

the Production Example of the dense liquid of bright pigment

Production Example 7

Being uniformly mixed in container, aluminum mixture pigment thickener GX-180A (trade(brand)name equably, the メ タ of Asahi Chemical Industry Le ズ company system, metal amount 74%) 0.2 part of 19 parts, 35 parts of 1-octanols (alcoholic solvents that boiling point is 195 DEG C), 8 parts of resin solutions (※ 1) that contain phosphate and 2-(dimethylamino) ethanol, obtain the dense liquid of bright pigment (P-1).

The resin solution that (※ 1) contains phosphate: possessing thermometer, thermostatted, agitator, in the reaction vessel of reflux exchanger and dropper, add the mixed solvent of 27.5 parts of 27.5 parts of methoxypropanol and isopropylcarbinols, be heated to 110 DEG C, added in above-mentioned mixed solvent with 4 hours by 25 parts of vinylbenzene, 27.5 parts of normal-butyl methacrylic esters, " Isostearyl Acrylate " (trade(brand)name, Osaka organic chemistry industrial system, side chain senior alkyl acrylate) 20 parts, 7.5 parts of 4-hydroxyl butylacrylic acid esters, 15 parts of the polymerizable monomers (※ 2) that contains phosphate, 12.5 parts of 2-methacryloxyethyl acid phosphoric acid esters, 121.5 parts, the mixture of 10 parts of isopropylcarbinols and 4 parts of formations of tert-butyl peroxide octanoate, then dripped by 0.5 part of tert-butyl peroxide octanoate and 20 parts of mixtures that form of Virahol with 1 hour.Then, stirring slaking obtains the resin solution that contains phosphate of solid component concentration 50% for 1 hour.The acid number being obtained by the phosphate of this resin is that 83mgKOH/g, hydroxyl value are that 29mgKOH/g, weight-average molecular weight are 10,000.

The polymerizable monomer that (※ 2) contains phosphate: possessing in the reaction vessel of thermometer, thermostatted, agitator, reflux exchanger and dropper, add 41 parts of 57.5 parts of monobutyl phosphoric acid and isopropylcarbinols, be warmed up to after 90 DEG C, drip after 42.5 parts of glycidyl methacrylates with 2 hours, then stir slaking 1 hour.Afterwards, add 59 parts of Virahols, obtain the polymerizable monomer solution that contains phosphate of solid component concentration 50%.The acid number being obtained by the phosphate of the monomer obtaining is 285mgKOH/g.

the manufacture of the 2nd water-based pigmented coating (Y)

Production Example 8

Be blended in equably 100 parts of the Emulsion acrylic resins (I-1-2) of the hydroxyl obtaining in Production Example 2, 57 parts of the polyester resin solutions (I-2-2) of the hydroxyl of manufacturing in Production Example 4, 62 parts of the dense liquid of bright pigment (P-1) and the CYMEL325 (trade(brand)name that in Production Example 7, obtain, Cytec Industries company of Japan system, melamine resin, solids component 80%) 37.5 parts, then add PRIMAL ASE-60 (trade(brand)name, Rohm and Haas company system, viscosifying agent), 2-(dimethylamino) ethanol and deionized water, obtain pH8.0, coating solids component 25%, the viscosity that Ford Cup No.4 at 20 DEG C obtains is the 2nd water-based pigmented coating (Y-1) of 40 seconds.

the manufacture of the acrylic resin (A) of hydroxyl

Production Example 9

In the four neck flasks with whipping appts, thermometer, cooling tube, nitrogen inlet, add 31 parts of ethoxyl ethyl propionates, under logical nitrogen, be warmed up to 155 DEG C.Reaching after 155 DEG C, stop the ventilation of nitrogen, the monomer mixture with dropping in 4 hours by the component proportion of 30 parts of vinylbenzene, 37.5 parts of n-butyl acrylates, 30 parts of 2-hydroxypropyl acrylates, 2.5 parts, vinylformic acid and 4 parts of formations of two t-amyl peroxy things (polymerization starter).After 30 minutes, drip 2 with 1 hour, 0.5 part of 2 '-azo two (2,4-methyl pentane nitrile) (polymerization starter) is dissolved in the polymerization starter solution obtaining in 3 parts of SWASOL1000 (varsol).Then, pass into nitrogen slaking simultaneously at 155 DEG C and after 2 hours, be cooled to 100 DEG C, with 29 parts of dilutions of butylacetate, obtain the acrylic resin (A1) of the hydroxyl of solids component 60%.

The hydroxyl value of the acrylic resin (A1) of the hydroxyl obtaining is 129mgKOH/g, acid number 19mgKOH/g, weight average molecular weight approximately 12000.

Production Example 10

Except the monomer mixture of the component proportion by 30 parts of vinylbenzene, 37.5 parts of n-butyl acrylates, 30 parts of 2-hydroxypropyl acrylates, 2.5 parts, vinylformic acid and 4 parts of formations of two t-amyl peroxy things (polymerization starter) in Production Example 9 is become

Outside monomer mixture by the component proportion of 30 parts of vinylbenzene, 40.5 parts of n-butyl acrylates, 27 parts of 2-hydroxy ethyl methacrylates, 2.5 parts, vinylformic acid and 4 parts of formations of two t-amyl peroxy things (polymerization starter), all the other and Production Example 9 are similarly manufactured, and obtain the acrylic resin (A2) of the hydroxyl of solids component 60%.

The hydroxyl value that obtains the acrylic resin (A2) of hydroxyl is 129mgKOH/g, and acid number is 19mgKOH/g, and weight average molecular weight is about 12000.

the manufacture of non-aqueous dispersion type acrylic resin (D1)

Production Example 11

In the four neck flasks with whipping appts, thermometer, cooling tube and nitrogen inlet, add 98 parts of 93 parts of heptane and following 55% macromolecular dispersion stabilizer solution (※ 1), make its reflux, with the mixture that drips following monomer and polymerization starter for 3 hours, then slaking slaking in 2 hours, obtains non-aqueous dispersion type acrylic resin (D1) thus.

(mixture of monomer and polymerization starter)

The mixture that 15 parts of vinylbenzene, 40 parts of methyl methacrylates, 30 parts of vinyl cyanide, 15 parts of HEMAs and tert-butyl peroxide-2-ethylhexanoate are 1.5 parts.

The non-aqueous dispersion type acrylic resin (D1) obtaining is the dispersion liquid of the milky stable low viscosity polymer of quality solid component concentration 53%, Gardner viscosity B, median size (mensuration of utilizing electron microscope to carry out) 0.2～0.3 μ m.

(synthesizing of macromolecular dispersion stabilizer solution (※ 1))

In the four neck flasks that possess whipping appts, thermometer, cooling tube, nitrogen inlet, add 40 parts of 40 parts of isobutyl acetates and toluene to make its reflux, with the following monomer of dropping in 3 hours and the mixture of polymerization starter, after dropping, carry out slaking in 2 hours, obtain thus macromolecular dispersion stabilizer solution.

(mixture of monomer and polymerization starter)

The mixture that 10 parts of vinylbenzene, 49 parts of isobutyl-methacrylic esters, 30 parts of 2-ethylhexyl methacrylic esters, 11 parts of HEMAs and Diisopropyl azodicarboxylate are 2 parts.

The macromolecular dispersion stabilizer solution obtaining, quality solid component concentration 55%, Gardner viscosity G, weight-average molecular weight 16000.

the manufacture of Clear paint (Z)

Production Example 12

Mix equably 110 parts of acrylic resin (A1) solution (60 parts of solids components) of the hydroxyl obtaining in Production Example 9, 40 parts of polyisocyanate compounds A (note 1), Sunnix PP-1000 (trade(brand)name, Sanyo changes into company's system, polyoxypropylene glycol, number-average molecular weight 1000, effective constituent 100%) 5 parts, BYK-300 (trade(brand)name, BYK company system, surface conditioner, effective constituent 52%) 0.2 part, TINUVIN900 (trade(brand)name, B.A.S.F. company's system, benzotriazole is UV light absorber, effective constituent 100%) 2.0 parts and TINUVIN292 (trade(brand)name, B.A.S.F. company's system, hindered amine is photostabilizer, effective constituent 100%) 1.0 parts, add SWASOL1000 (trade(brand)name, COSMO oil company system, varsol), obtain viscosity that the Ford CupNo.4 at 20 DEG C obtains and be the Clear paint (Z-1) of 25 seconds.

(note 1) the polyisocyanate compounds A:Duranate TLA-100 ケ ミ カ Le ズ of Asahi Chemical Industry (strain) company system.The polyisocyanate compounds being made up of hexamethylene diisocyanate, polymeric ratio of components is that chlorinated isocyanurates 3 aggressiveness are 63%, urea diketone dimer is 12%, other polymers more than tripolymer are 25%.Solids component 100%, NCO content 21.8%.

Production Example 13～26

With Production Example 12 similarly, with the coating formula shown in following table 1, obtain the viscosity being obtained by Ford CupNo.4 at 20 DEG C and be each Clear paint (Z-2)～(Z-15) of 25 seconds.Clear paint (Z-12)～(Z-15) is that comparative example is used.

It should be noted that, the coating formula of each Clear paint (Z-1) of table 1～(Z-15) is solids component proportioning.

(note 2)～(note 10) of table 1 is as follows respectively.

(note 2) polyisocyanate compounds B: ス ミ ヅ ユ-Le N-3300Sumika BayerUrethane company system.The polyisocyanate compounds being formed by hexamethylene diisocyanate, polymeric ratio of components is that chlorinated isocyanurates 3 aggressiveness are 53%, other polymers more than tripolymer are 47%.Solids component 100%, NCO content 21.8%.

(note 3) Sunnix PP-400; Trade(brand)name, Sanyo changes into company's system, polyoxypropylene glycol, number-average molecular weight 400, effective constituent 100%

(note 4) Sunnix PP-600; Trade(brand)name, Sanyo changes into company's system, polyoxypropylene glycol, number-average molecular weight 600, effective constituent 100%

(note 5) Sunnix PP-2000; Trade(brand)name, Sanyo changes into company's system, polyoxypropylene glycol, number-average molecular weight 2000, effective constituent 100%

(note 6) GP-600; Trade(brand)name, Sanyo changes into company's system, polyoxy propylene glyceryl ether (triol), number-average molecular weight 600, effective constituent 100%

(note 7) PTMG-850; Trade(brand)name, Mitsubishi Chemical Ind's system, polyoxybutylene glycol, number-average molecular weight 850, effective constituent 100%

(note 8) ETERNACOLL UH-50; Trade(brand)name, Yu Buxingchan company system, the polycarbonate diol (1,6-Hexylene Glycol Base Polycarbonatediol) based on 1,6-hexylene glycol, number-average molecular weight 500, effective constituent 100%

(note 9) ETERNACOLL UH-200; Trade(brand)name, Yu Buxingchan company system, based on the polycarbonate diol of 1,6-hexylene glycol, number-average molecular weight 2000, effective constituent 100%

(note 10) Polylite OD-X-240; Trade(brand)name, DIC company system, polyester polyol, number-average molecular weight 1000, effective constituent 100%

coating film-forming methods

Use the Clear paint (Z-1) that obtains in the 2nd water-based pigmented coating (Y-1) that obtains in the 1st water-based pigmented coating (X-1) that obtains in Production Example 5 and 6～(X-2), Production Example 8 and Production Example 12～26～(Z-15), make like that respectively as follows test board, carry out evaluation test.

(making of coated article for test)

Imposing on the cold-rolled steel sheet of zinc phosphate chemical conversion processing, electrophoretic painting エ レ Network ロ Application GT-10 (trade(brand)name, Northwest paint company system, cation electrophoretic coating) makes dry film thickness reach 20 μ m, within 30 minutes, make it solidify 170 DEG C of heating, obtain test coated article 1.Test is that Ra is 0.21 by the surfaceness of coated article 1.

Then use the cold-rolled steel sheet obtaining after the zinc phosphate chemical conversion processing that imposes the more coarse surfaceness using while testing with coated article 1 than making, use coated article 1 similarly with test, make than the thicker coated article 2 of test of surfaceness of test coated article 1.Test is 0.38 by the surface roughness Ra of coated article 2.

(making of test board)

Embodiment 1

Make dry film thickness reach 25 μ m in above-mentioned test with obtaining the 1st water-based pigmented coating (X-1) in the above-mentioned Production Example 5 of electrostatic atomizer electrostatic coating with rotary-atomizing type on coated article 1, place after 2 minutes, carry out preheating for 3 minutes at 80 DEG C.

Then, the 2nd water-based pigmented coating (Y-1) obtaining in electrostatic atomizer electrostatic coating Production Example 8 with rotary-atomizing type on this 1st uncured painted film makes dry film thickness reach 15 μ m, place after 2 minutes, carry out preheating for 3 minutes at 80 DEG C.

And then the Clear paint (Z-1) obtaining in electrostatic coating Production Example 12 on the 2nd painted film makes dry film thickness reach 35 μ m, place 7 minutes.Then, 140 DEG C of 20 minutes (hold-times) of heating, thereby the 1st painted film, the 2nd painted film and transparent coating are heating and curing and make test board.

Embodiment 2～12 and comparative example 1～6

In embodiment 1, by the coated article 1 or 2 for test shown in following table 1 for coated article for test, the 1st water-based pigmented coating (X-1) is made as to the 1st water-based pigmented coating (X-1) shown in following table 1 or (X-2), Clear paint (Z-1) is made as to any one in the Clear paint shown in following table 1 (Z-1)～(Z-15), in addition, make similarly to Example 1 test board.

evaluation test

For the each test board obtaining in above-described embodiment 1～12 and comparative example 1～6, utilize following test method to evaluate.Evaluation result is shown in to following table 1 in the lump.

(test method)

smoothness: use the Wc value of measuring by Wave Scan DOI (trade(brand)name, BYKGardner company system) to evaluate.Wc value is the index of the amplitude of the surfaceness of wavelength 1～3mm left and right, and measured value is less shows that the smoothness of painting face is higher.

clarity: use the Wa value of utilizing Wave Scan DOI to measure to evaluate.Wa value is the index of the amplitude of the surfaceness of wavelength 0.1～0.3mm left and right, and measured value is less shows that the clarity of painting face is higher.

promote weathering resistance: use Super xenon weather meter (trade(brand)name, promote atmospheric exposure test machine, SUGA trier company system), under the test conditions of recording, carry out the round-robin test of combination irradiation and condition of raining in JISK5600-7-7 (method 1).Having evaluated the round-robin test time added up to after 3000 hours, then in the warm water of 40 DEG C, flooded the tack of the film after 2 days.Tack is as the evaluation of getting off,, what each test board was made to 2mm × 2mm according to JIS K5600-5-6 (1990) on film draws 100 of lattice, and Continuous pressing device for stereo-pattern on this face, promptly peels off postevaluation and remain in the number of drawing lattice film on painting face.It is qualified level above that residual stroke of lattice film number is 98.

It should be noted that, use 100 of the embodiment 2 of Clear paint (Z-2) and the film numbers of 5 residual strokes of lattice of embodiment of use Clear paint (Z-5), and can't see edge defect completely, therefore more excellent than the tack of the embodiment of 100 of other residual stroke of lattice film numbers in embodiment.

Then,, for using the embodiment 1 of Clear paint (Z-1) and the embodiment 6 of use Clear paint (Z-6), as a comparison, also carried out following sag resistance (sagging limit thickness) and evaluated.

sagging limit thickness: using making size is 21 of the punchings that the part of end 3cm of the long side of the test coated article 1 of 11cm × 45cm starts to arrange with a row every 2cm diameter 5mm, at the 1st water-based pigmented coating (X-1) obtaining in using the electrostatic atomizer electrostatic coating Production Example 5 of rotary-atomizing type on coated article 1 for this test, make dry film thickness reach 25 μ m, place after 2 minutes, carry out preheating for 3 minutes at 80 DEG C.

Then, the 2nd water-based pigmented coating (Y-1) obtaining in electrostatic atomizer electrostatic coating Production Example 8 with rotary-atomizing type on this 1st uncured painted film makes dry film thickness reach 15 μ m, place after 2 minutes, carry out preheating for 3 minutes at 80 DEG C.

And then, on the 2nd painted film, use MINI BELL type rotation type atomization electrostatic atomizer with spray volume 200cc, rotating speed 40,000rpm, moulding air pressure 1kg/cm ², rifle is apart from 30cm, to obtain long side direction the chances are the mode of thickness of 30 μ m～60 μ m, with film thickness gradient in embodiment 1 transparent paint coating (Z-1), in embodiment 6 transparent paint coating (Z-6), this coated plate is almost vertically being stood, after application after 7 minutes, 140 DEG C of 20 minutes (hold-times) of heating, the 1st painted film, the 2nd painted film and transparent coating are heating and curing, make thus test board.

Study the position of the sagging of the film of the punching bottom 2mm of observable each test board, (sagging limit thickness (μ m)), carries out the evaluation of sag resistance to measure the thickness of this position.Sagging limit thickness more represents that sag resistance is better.

scuff resistance:roof is carried out after 15 carwash with car washer under the condition of 20 DEG C with the automobile of the water-fast adhesive tape sticking test board of Nichiban company system, 20 degree minute surface emittance (20 ° of gloss numbers) of determination test plate, adopt its gloss retention (%) with respect to 20 ° of gloss numbers before testing to evaluate.The higher scuff resistance of this gloss retention is better.Car washer has used the ヤ ス イ industry PO20FWRC processed of company.

[table 1]

Claims (9)

1. coating composition, is characterized in that, in the method for forming layered coating film that coated article is carried out successively to following operation (1)～(4), is used as Clear paint (Z),

Operation (1): application the 1st water-based pigmented coating (X) is to form the operation of the 1st painted film;

Operation (2): application the 2nd water-based pigmented coating (Y) is to form the operation of the 2nd painted film on the 1st painted film forming through described operation (1);

Operation (3): transparent paint coating (Z) forms the operation of transparent coating on the 2nd painted film forming through described operation (2); And

Operation (4): the operation that the 1st painted film, the 2nd painted film and the transparent coating that will form through described operation (1)～(3) is together heating and curing,

The polyvalent alcohol (C) of acrylic resin (A), polyisocyanate compounds (B) and the number-average molecular weight that described coating composition contains hydroxyl in 300～1500 scopes,

Described polyvalent alcohol (C) is at least one containing in polyvalent alcohol (C1) and the polycarbonate polyol (C2) of polyoxyalkylene.

2. coating composition according to claim 1, is characterized in that, it is more than 3 alkylidene groups that the described polyvalent alcohol (C1) containing polyoxyalkylene has carbonatoms.

3. coating composition according to claim 1 and 2, it is characterized in that, with respect to the solids component total amount of acrylic resin (A) and the described polyisocyanate compounds (B) of described hydroxyl, the amount of described polyvalent alcohol (C) is 1 quality %～20 quality %.

4. coating composition according to claim 1 and 2, is characterized in that, also contains at least one unsaturated monomer of dispersion polymerization under the existence of macromolecular dispersion stabilizer and organic solvent and the non-aqueous dispersion type acrylic resin (D) that obtains.

5. coating composition according to claim 3, is characterized in that, also contains at least one unsaturated monomer of dispersion polymerization under the existence of macromolecular dispersion stabilizer and organic solvent and the non-aqueous dispersion type acrylic resin (D) that obtains.

6. coating composition according to claim 1, it is characterized in that, taking the two solids component total amount of the acrylic resin (A) of described hydroxyl and described polyisocyanate compounds (B) as standard, the amount of the acrylic resin (A) of described hydroxyl is 40 quality %～85 quality %, and the amount of described polyisocyanate compounds (B) is 15 quality %～60 quality %.

7. method of forming layered coating film, is characterized in that, coated article is carried out to following operation (1)～(4) successively:

Operation (1): application the 1st water-based pigmented coating (X) is to form the operation of the 1st painted film;

Operation (2): application the 2nd water-based pigmented coating (Y) is to form the operation of the 2nd painted film on the 1st painted film forming through described operation (1);

Operation (3): on the 2nd painted film forming through described operation (2) application as the claim 1～5 of Clear paint (Z) in coating composition described in any one to form the operation of transparent coating; And

Operation (4): the operation that the 1st painted film, the 2nd painted film and the transparent coating that will form through described operation (1)～(3) is heating and curing simultaneously.

8. method of forming layered coating film according to claim 7, is characterized in that, described coated article is to utilize electrocoating paint to form the car body of primer film.

9. the article that obtain by the method for forming layered coating film application described in claim 7 or 8.