CN103965731B - Coating composition and method of forming layered coating film - Google Patents

Abstract

The present invention provides the aqueous pigmented finiss of application the 1st, the 2nd aqueous pigmented finiss and clear dope successively on coated article, in the case that it is solidified to form into multilayer film simultaneously, it can obtain being not easily susceptible to (surface state (convex-concave) of ground disguised excellent), the clear coating composition of flatness and the excellent multilayer film of clarity and the method for forming layered coating film for having used the clear coating composition of the surface roughness affect of ground.The acrylic resin (A) for containing hydroxyl, the coating composition of polyisocyanate compounds (B) and specific polyalcohol (C) of the number-average molecular weight in the range of 300~1500 are provided and coating composition is used as clear dope, the aqueous pigmented finiss of application the 1st, the 2nd aqueous pigmented finiss and clear dope successively on coated article, it is heating and curing to form the method for forming layered coating film of multilayer film simultaneously.

Description

Coating composition and method of forming layered coating film

Technical field

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

Background technology

In the past, as the coating film-forming methods in car body, following method has been carried out extensively, i.e. real to coated article Applying electrophoretic painting makes after it is heating and curing, and carries out intermediate layer paint paint spraying → be heating and curing → bottom coating application → preheating (preparation heating) → clear dope application →, which is heating and curing, such three applies two baking modes；And progress intermediate layer paint paint spraying → add Heat cure → topcoat paint application → is heating and curing such two two baking modes of painting method for forming multilayer film.

Generally, two baking modes of above-mentioned three painting are to form so-called gold using the bottom coating containing bright pigment Carried out in the case of category color film, two baking modes of above-mentioned two painting are to form white using the topcoat paint containing coloring pigment Carried out in the case of the so-called plain color film of color, black etc..

In recent years, from saving from the viewpoint of the energy, it have studied the work that is heating and curing after the application for omitting intermediate layer paint coating Sequence, application → preheating (preparation heating) → bottom coating application → preheating that intermediate layer paint coating is carried out successively is (prepared to add Heat) → clear dope application → be heating and curing three apply a baking modes and successively carry out intermediate layer paint coating application → preheating The two one baking modes of painting that (preparation heating) → topcoat paint application → is heating and curing.

Wherein, from the viewpoint of environmental pollution caused by the volatilization for suppressing organic solvent, special requirement are employed water Property coating as above-mentioned intermediate layer paint coating, bottom coating and topcoat paint use it is above-mentioned three apply a baking mode and two apply a bakings Mode.

However, applying a baking mode using the three of above-mentioned aqueous intermediate layer paint coating and aqueous basecoat coating and using The two of aqueous intermediate layer paint coating and aqueous finish paint coating are applied in a baking modes, are applied in aqueous intermediate layer paint coating and water-borne base coat The layer of the interlayer of material, the interlayer of aqueous basecoat coating and clear dope or aqueous intermediate layer paint coating and aqueous finish paint coating Between produce because interlaminar action result in film flatness and clarity decline situation, as problem.

In addition, eliminate the above-mentioned process that is heating and curing, three apply a baking modes and two apply one dry mode coating process In, due to reducing the process that is heating and curing after intermediate layer paint paint spraying, therefore the process that is once heating and curing.From ground From the perspective of surface state (convex-concave) is hidden, above-mentioned three, which apply one, dries mode and the baking mode of two painting one compared to conventional application side For method, its process is more insufficient, and condition is more harsh, ought particularly become the surface roughness of the grounds such as electrophoretic painting face In the case of the harsh conditions waited greatly, due to more sensitively being influenceed by ground during intermediate layer paint paint spraying, so depositing The flatness and clarity downward trend of film are formed in easy generation, thus also turns into problem.

For example, Patent Document 1 discloses utilizing aqueous intermediate layer paint coating, aqueous basecoat coating and clear dope Three apply one dry mode multilayer film coating process in, on the intermediate layer paint film for be adjusted to specific solid component content apply Fill specific aqueous basecoat coating, after specific solid component content is adjusted to, application contain carboxylic compound and The clear dope of polyoxide, and then under specific heating condition, by intermediate layer paint film, primary coat film and transparent coating simultaneously The method of forming layered coating film of solidification.However, there is the flatness of multilayer film obtained by the coating film-forming methods and fresh Reflecting property becomes insufficient situation.

The example that finished appearance is improved is realized as the interlaminar action suppressed between multilayer film, such as in patent document 2 In disclose following method of forming layered coating film, i.e. the aqueous pigmented finiss of application the 1st, the 2nd aqueous coloring successively on coated article Coating and clear dope, by obtain 3 layers of multilayer film while be heating and curing three apply a baking mode, it is characterised in that the 1st Aqueous pigmented finiss (X) contains acrylic resin (A), curing agent (B) and ester-polyurethane resin emulsion (C), is applied by the 1st aqueous coloring 1st coloring film of material (X) formation has less than 100% water-swellable rate before the priming coat of application the 2nd and less than 300% had Machine solvent swell rate.However, in the presence of the flatness and clarity of the multilayer film obtained even with the coating film-forming methods Insufficient situation.

And then, for example Patent Document 3 discloses contain acrylic resin (A), curing agent (B) and polyaminoester emulsion (C) water-based paint compositions, the polyaminoester emulsion (C) is by the structure containing polisocyanate component and PCDL composition Obtained into composition, polisocyanate component contains alicyclic diisocyanate, and PCDL composition is by containing alicyclic two The diol component of alcohol is obtained, also, alicyclic diol contains the ring alkylidene of carbon number more than 6.

In addition, describing the method for forming layered coating film that mode is dried in three paintings one, i.e. make by above-mentioned water-based paint compositions For the 1st aqueous pigmented finiss, the aqueous pigmented finiss of application the 1st, the 2nd aqueous pigmented finiss and the transparent painting successively on coated article Material, by obtain 3 layers of multilayer film while being heating and curing.Also, as the preferred embodiment of the 1st aqueous pigmented finiss, enter one Step also discloses the coating composition containing specific oligomer.However, occasionally there are even with the coating film-forming methods, smoothly Property and the finished appearance of clarity etc. improve effect also insufficient situation.

As the interlaminar action and then the internal stress of control film prevented between multilayer film, so as to realize multilayer film Outward appearance improve method, for example Patent Document 4 discloses method of forming layered coating film, i.e. including simultaneously toast middle level Paint film, primary coat film and transparent coating make the three of its process solidified to apply a drying method, it is characterised in that form intermediate layer paint film When the aqueous intermediate layer paint coating that uses contain specific emulsion acrylic resin, complete alkyl etherified melamine resin and carbon two Group with imine moiety, forms the aqueous basecoat coating used during primary coat film and contains specific emulsion acrylic resin and specific PPG.However, the internal stress by controlling the intermediate layer paint film, exist prevents intermediate layer paint film even with realization The outward appearance for the multilayer film that the coating film-forming methods for applying intermembranous interlaminar action with primary coat are obtained also becomes insufficient situation.

Patent document 1：Japanese Unexamined Patent Publication 2009-028576 publications

Patent document 2：WO2010/082607 publications

Patent document 3：Japanese Unexamined Patent Publication 2010-215885 publications

Patent document 4：Japanese Unexamined Patent Publication 2009-262002 publications

The content of the invention

The problem of invention is to be solved

It is an object of the invention on coated article successively the aqueous pigmented finiss of application the 1st, the 2nd aqueous pigmented finiss and Clear dope and when together solidifying to form multilayer film, can obtain being difficult the surface roughness affect (table of ground by ground Surface state (convex-concave) it is disguised excellent), the transparent painting of flatness and clarity and the excellent multilayer film of against weather Feed composition, and use the method for forming layered coating film of the clear coating composition.

The means solved the problems, such as

The present inventor concentrates on studies repeatedly to achieve these goals, as a result sends out and applies a multilayer for drying mode now with three In the coating process of film, for the disguise of the surface state that improves ground, specific polyalcohol is contained in clear dope There is good effect, if acrylic resin (A), polyisocyanate compounds (B) containing hydroxyl and specific polynary The coating composition of alcohol (C) can then realize above-mentioned purpose as clear dope, so as to complete the present invention.

That is, the present invention provides coating composition, it is characterised in that carrying out following processes (1)~(4) successively to coated article Method of forming layered coating film in be used as clear dope (Z),

Process (1)：Process of the aqueous pigmented finiss (X) of application the 1st to form the 1st coloring film；

Process (2)：The aqueous pigmented finiss (Y) of application the 2nd is with shape on the 1st coloring film formed through the process (1) Into the process of the 2nd coloring film；

Process (3)：Transparent paint coating (Z) is to form transparent painting on the 2nd coloring film formed through the process (2) The process of film；And

Process (4)：The 1st coloring film, the 2nd coloring film and the transparent coating one that will be formed through the process (1)~(3) With the process being heating and curing,

The coating composition contains the acrylic resin (A), polyisocyanate compounds (B) and the equal molecule of number of hydroxyl The polyalcohol (C) in the range of 300~1500 is measured,

The polyalcohol (C) be in polyalcohol (C1) and polycarbonate polyol (C2) containing polyoxyalkylene at least It is a kind of.

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

Process (1)：Process of the aqueous pigmented finiss (X) of application the 1st to form the 1st coloring film；

Process (2)：The aqueous pigmented finiss (Y) of application the 2nd is with shape on the 1st coloring film formed through the process (1) Into the process of the 2nd coloring film；

Process (3)：Formed through the process (2) the 2nd coloring film on application as clear dope (Z) above-mentioned painting Process of the feed composition to form transparent coating；And

Process (4)：The 1st coloring film, the 2nd coloring film and the transparent coating one that will be formed through the process (1)~(3) With the process being heating and curing.

In addition, the present invention provides the article obtained from above-mentioned method of forming layered coating film application.

Invention effect

Think the polyalcohol in the coating composition of the present invention, due to being low molecule amount, therefore multilayer film can be improved Solidification process in thermal fluidity, the hidden power of ground improves, and can effectively mitigate reduces reason as finished appearance Ground surface configuration (convex-concave) influence, thus can obtain the finished appearance of flatness and clarity etc. it is excellent three Apply a multilayer film for drying mode.

The effect can obtain extremely significant effect by making the polyalcohol be present in transparent coating.

In addition, the polyalcohol is the hydroxyl with cross-linking functional group, whether from the excellent angle of reactivity, also It from the angle of the film performance of against weather etc. is all suitable to be.

Above, according to the coating composition of the present invention, in three coating film-forming methods for applying a baking mode, due to ground Surface state (convex-concave) it is disguised excellent, therefore flatness can be formed and clarity is excellent and then against weather is excellent Multilayer film.

Embodiment

Below for the coating composition and coating film-forming methods of the present invention, further it is described in detail.

The coating composition (hereinafter sometimes referred to simply as " this coating ") of the present invention, it is characterised in that to coated article successively It is used as clear dope (Z) in the method for forming layered coating film for carrying out following processes (1)~(4),

Process (1)：Process of the aqueous pigmented finiss (X) of application the 1st to form the 1st coloring film；

Process (2)：The aqueous pigmented finiss (Y) of application the 2nd is with shape on the 1st coloring film formed through the process (1) Into the process of the 2nd coloring film；

Process (3)：Transparent paint coating (Z) is to form transparent painting on the 2nd coloring film formed through the process (2) The process of film；And

Process (4)：The 1st coloring film, the 2nd coloring film and the transparent coating one that will be formed through the process (1)~(3) With the process being heating and curing.

The coating composition contains the acrylic resin (A), polyisocyanate compounds (B) and number-average molecular weight of hydroxyl Polyalcohol (C) in the range of 300~1500,

Polyalcohol (C) is at least one in polyalcohol (C1) and polycarbonate polyol (C2) containing polyoxyalkylene Kind.

The coating composition of the present invention

The acrylic resin (A) of hydroxyl

The acrylic resin (A) of the hydroxyl of the coating composition of the present invention can pass through common method copolymerization hydroxyl Unsaturated monomer and other saturation monomers are manufactured.

The unsaturated monomer of hydroxyl is the compound respectively in a molecule with a hydroxyl and unsaturated bond, should Hydroxyl is mainly used as the functional group reacted with crosslinking agent polyisocyanate compounds (B)., specifically, can be with as the monomer Enumerate (methyl) acrylic acid -2- hydroxyl ethyl esters, (methyl) 2-hydroxypropyl acrylate, (methyl) acrylic acid -3- hydroxypropyl acrylates, (methyl) Hydroxyalkyl (methyl) acrylate of acrylic acid -3- hydroxy butyl esters, (methacrylic acid) -4- hydroxy butyl esters etc., the hydroxyalkyl (methyl) Acrylate is the monoesters compound of acrylic or methacrylic acid and the dihydric alcohol of carbon number 2~10；Polyethylene glycol, poly- the third two The PPG of alcohol, polytetramethylene glycol etc. and monoesters formed by the unsaturated carboxylic acid of (methyl) acrylic acid etc.；Polyethylene glycol, poly- third (methyl) acrylic acid hydroxy alkyl ester institute of the PPG and 2- ethoxys (methyl) acrylate of glycol, polytetramethylene glycol etc. etc. Into monoether；The unsaturated compound and ethylene glycol, 1,6- hexylene glycols, new penta containing acid anhydrides of such as maleic anhydride, itaconic anhydride Monoesters compound formed by the alcohols of glycol etc. or diester compound；The hydroxyalkyl vinylether class of such as hydroxyethyl vinylethers；Third Alkenyl alcohol etc.；α, beta-unsaturated carboxylic acid and such as " カ-ヅ ユ ラ E10P " (trade name, HEXION Specialty Chemicals company systems, synthesize the glycidyl esters of high branch chain saturated fatty acid), the monocyclic epoxide of alpha-olefin epoxides Adduct formed by compound；Glycidyl (methyl) acrylate and such as acetic acid, propionic acid, p-tert-butyl benzoic acid, fat Adduct formed by the monoacid of fat acids；The unsaturated monomer of above-mentioned hydroxyl and lactone (such as 6-caprolactone, γ-penta Lactone) formed by adduct etc..

The unsaturated monomer of above-mentioned hydroxyl and the adduct of lactone (such as 6-caprolactone, gamma-valerolactone), for example may be used With enumerate " Plaxel FA-1 ", " Plaxel FA-2 ", " Plaxel FA-3 ", " Plaxel FA-4 ", " Plaxel FA-5 ", " Plaxel FM-1 ", " Plaxel FM-2 ", " Plaxel FM-3 ", " Plaxel FM-4 ", " Plaxel FM-5 " (are above Daicel chemistry (strain) system, trade name) etc. above-mentioned hydroxyalkyl (methyl) acrylate and 6-caprolactone etc. lactone institute into Ring-opening polymerisation adduct etc..

It should be noted that in this manual, (methyl) acrylate is the total of acrylate and methacrylate Claim, (methyl) acrylic acid is the general name of acrylic acid and methacrylic acid.

As the unsaturated monomer of hydroxyl, due to the polyisocyanate compounds (B) as crosslinking agent and acrylic acid tree The reactivity of fat (A) is relaxed, and can improve the finished appearance of obtained film, it is therefore preferable that contain unsaturated monomer, Wherein, the unsaturated monomer has secondary hydroxyl.

As the unsaturated monomer with secondary hydroxyl, for example, it can enumerate (methyl) 2-hydroxypropyl acrylate, (methyl) third The unsaturated monomer with secondary hydroxyl of olefin(e) acid 2- hydroxy butyl esters, (methyl) acrylic acid 3- hydroxy butyl esters etc., wherein, it is described unsaturated single The carbon number of the alkyl of the ester part of body is 2~8, preferably 2~4, and then preferably 2~3.Especially, it can be suitably used (methyl) 2-hydroxypropyl acrylate.If the carbon number of the alkyl is more than 5, the finished appearance of film declines, separately Outside, the thermal life that there is a situation where coating composition declines.These may be used singly or two or more in combination.

The acrylic resin (A) of hydroxyl, is regarding the unsaturated monomer with secondary hydroxyl as the feelings for constituting monomer component Under condition, the content ratio of the unsaturated monomer with secondary hydroxyl, the total amount relative to monomer component is preferably the matter of 10 mass %~50 Measure the mass % of %, particularly preferably the mass % of 15 mass %~45 and then particularly preferably 15 mass %~40.

As other unsaturated monomers, for example, it can enumerate carboxylic unsaturated monomer, (methyl) esters of acrylic acid, second Alkene ether or propenyl ether, alkenes compounds and diolefin compound, the unsaturated monomer containing hydrocarbon ring, nitrogenous unsaturation list Body, the unsaturated monomer containing epoxy radicals, acrylic monomer containing water-disintegrable alkoxysilyl etc..

Carboxylic unsaturated monomer, is the chemical combination of the carboxyl and 1 unsaturated bond in 1 molecule with more than 1 Thing, for example, can enumerate (methyl) acrylic acid, crotonic acid, itaconic acid, maleic acid, maleic anhydride, fumaric acid, 2- carboxy ethyls (methyl) acrylate, 3- carboxypropyls (methyl) acrylate, 5- carboxy pentyls (methyl) acrylate etc..

As the example of (methyl) esters of acrylic acid, can enumerate methyl acrylate, ethyl acrylate, propyl acrylate, Isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, Hexyl 2-propenoate, acrylic acid-2-ethyl Own ester, n-octyl, decyl acrylate, lauryl acrylate, stearyl acrylate acid esters, cyclohexyl acrylate, methyl-prop E pioic acid methyl ester, EMA, n propyl methacrylate, isopropyl methacrylate, n-BMA, first Base isobutyl acrylate, Tert-butyl Methacrylate, hexyl methacrylate, methacrylic acid -2- Octyl Nitrites, metering system Misery ester, decyl-octyl methacrylate, lauryl methacrylate, stearyl methacrylate, cyclohexyl methacrylate etc. Acrylic or methacrylic acid carbon number 1~24 Arrcostab or cycloalkyl ester；Methoxyethyl butyl ester, methyl-prop Olefin(e) acid methoxybutyl, methoxyethyl acrylate, methoxyethyl methacrylate, ethioxy butyl ester, methyl-prop Alkoxy alkyl of carbon number 2~18 of acrylic or methacrylic acid of olefin(e) acid Ethoxybutyl etc. etc..

As vinyl ethers or propenyl ether, for example, ethyl vinyl ether, n-propyl vinyl ether, isopropyl can be enumerated Base vinyl ethers, butyl vinyl ether, tert-Butyl vinyl ether, amyl group vinyl ethers, hexyl vinyl ethers, octyl vinyl ether Deng chain-like alkyl vinyl ethers；The cycloalkyl vinyl ethers class of cyclopentylethylene base ether, cyclohexyl vinyl ether etc.；Phenyl The aryl vinyl ethers such as vinyl ethers, trivinyl benzylic ether；The aralkyl of benzyl vinyl ether, phenethyl vinyl ethers etc. Vinyl ethers；Acrylic ethers of propenyl ethyl ether etc. etc..

As alkene based compound and diolefin compound, for example, it can enumerate ethene, propylene, butylene, ethlyene dichloride, fourth two Alkene, isoprene, chlorobutadiene etc..

As the unsaturated monomer containing hydrocarbon ring, for example, it can enumerate styrene, α-methylstyrene, phenyl (methyl) propylene Acid esters, phenylethyl (methyl) acrylate, phenyl propyl (methyl) acrylate, benzyl (methyl) acrylate, phenoxy group Ethyl (methyl) acrylate, cyclohexyl (methyl) acrylate, 2- acryloyl group epoxide ethyls diphenate, 2- third Enoyl- epoxide propyl group diphenate, 2- acryloyl group epoxide propyl group hexahydrophthalic acids hydrogen ester, 2- acryloyl groups Epoxide propyl group tetrahydrophthalic acid hydrogen ester, the carboxylate to t-butyl-benzoic acid and formed by (methyl) hydroxy-ethyl acrylate, Dicyclopentadienyl (methyl) acrylate etc..

As nitrogenous unsaturated monomer, for example, it can enumerate N, N- dimethyl aminoethyls (methyl) acrylate, N, N- (methyl) containing azanyl of diethylamino ethyl (methyl) acrylate, N- t-butylamino ethyls (methyl) acrylate etc. Acrylate；Acrylamide, Methacrylamide, N- methyl (methyl) acrylamide, N- ethyls (methyl) acrylamide, N, N- Dimethyl (methyl) acrylamide, N, N- DimethylAminopropyls (methyl) acrylamide, N, N- dimethyl aminoethyls (methyl) third The polymerizable amide class of acrylamide etc.；The fragrance of 2- vinylpyridines, l-vinyl-2-pyrrolidone, 4-vinylpridine etc. Race's nitrogen containing monomer；The polymerism nitrile such as acrylonitrile, methacrylonitrile；Acrylic amine etc..

As the unsaturated monomer containing epoxy radicals, for example, it can enumerate glycidyl (methyl) acrylate, acrylic Unsaturated monomer of the aliphatic of glycidyl ether etc. containing epoxy radicals, 3,4- epoxycyclohexylmethyls (methyl) acrylate Deng unsaturated monomer of the ester ring type containing epoxy radicals.

As the acrylic monomer containing water-disintegrable alkoxysilyl, for example, it can enumerate γ-(methyl) acryloyl Base epoxide propyl trimethoxy silicane, γ-(methyl) acryloyl group epoxide hydroxypropyl methyl dimethoxysilane, β-(methyl) propylene Acyloxy ethyl trimethoxy silane, γ-(methyl) acryloyl group epoxide propyl-triethoxysilicane, γ-(methyl) propylene Acyloxy hydroxypropyl methyl diethoxy silane etc..

In addition, can also for example use vinylacetate, propionate, ethlyene dichloride, neodecanoic acid vinyl esters Veova9, Veova10 (Japanese epoxy company system) etc. vinyl compound.

The synthesis of the acrylic resin (A) of hydroxyl, can use the polymerization of common unsaturated monomer to carry out, but examine Consider versatility, cost etc., be the most suitable by solution-type radical polymerization in organic solvent.For example can be with Pass through the aromatic solvent in dimethylbenzene, toluene etc.；The ketones solvent of methyl ethyl ketone, methyl iso-butyl ketone (MIBK) etc.；Ethyl acetate, The esters solvents such as butyl acetate, isobutyl acetate, 3- methoxybutyl acetic acid esters；The alcohols solvent of n-butanol, isopropyl alcohol etc. Deng solvent in, in the presence of the polymerization initiator of azo series catalysts, peroxide catalyst etc., about 60~about 150 Copolyreaction is carried out at a temperature of DEG C, it is possible thereby to be readily derived.

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

The hydroxyl value of the acrylic resin (A) of hydroxyl, from the finished appearance and against weather of flatness and clarity etc. Deng film performance from the viewpoint of, the scope preferably in 80~200mgKOH/g, particularly preferably 90~170mgKOH/g's Scope, and then particularly preferably in the range of 100~140mgKOH/g.

The weight average molecular weight of the acrylic resin (A) of hydroxyl, from the finished appearance of flatness and clarity etc. and resistance to From the viewpoint of the film performance of climacteric grade, in the range of preferably 4000~20000, particularly preferably 6000~16000 In the range of, and then particularly preferably in the range of 8000~12000.

It should be noted that in this manual, number-average molecular weight and weight average molecular weight are to use gel permeation chromatography (GPC) retention time (reserve capacity) determined, the guarantor of polystyrene standard known to the molecular weight determined under identical conditions Stay the value that the time (reserve capacity) is converted into the molecular weight of polystyrene and tried to achieve.Specifically, filled as gel permeation chromatography Put, use " HLC8120GPC " (trade name, eastern Cao's company system), as chromatographic column use 4 " TSKgelG-4000HXL ", " TSKgelG-3000HXL ", " TSKgelG-2500HXL " and " TSKgelG-2000HXL " (trade name is Dong Cao companies System), use differential refractometer, mobile phase as detector：Tetrahydrofuran, temperature of the measurement：40 DEG C, flow velocity：1mL/min condition Under be measured.

In the case that the acrylic resin (A) of hydroxyl has carboxyl, finishing of the acid number from flatness and clarity etc. From the viewpoint of the film performance of work outward appearance and against weather etc., preferably in the range of 1~40mgKOH/g, particularly preferably 3 In the range of~30mgKOH/g, and then preferably in the range of 5~20mgKOH/g.

Polyisocyanate compounds (B)

The polyisocyanate compounds (B) of the coating composition of the present invention, are with the trip of more than 2 in 1 molecule The compound of free isocyanate groups, can use and manufacture the compound used during polyurethane always in the past.For example, can enumerate Aliphatic polymeric isocyanate, alicyclic polymeric isocyanate, aromatic-aliphatic PIC, aromatic poly-isocyanate and these Derivative of PIC etc..

As aliphatic polymeric isocyanate, can for example enumerate trimethylene diisocyanate, tetramethylene isocyanates, Hexa-methylene isocyanates, pentamethylene isocyanates, 1,2- acryloyl isocyanates, 1,2- butylene isocyanates, 2,3- butylene Isocyanates, 1,3- butylene isocyanates, 2,4,4- or 2,2,4- tri-methyl hexamethylenes isocyanates, the isocyanos of 2,6- bis- Close the aliphatic isocyanates of methylhexanoic acid ester etc., such as lysine ester triisocyanate, Isosorbide-5-Nitrae, the isocyanato- octanes of 8- tri- Ester, the isocyanato- hendecane esters of 1,6,11- tri-, the isocyanato- -4- isocyanatomethyl octanes esters of 1,8- bis-, 1,3,6- The fat of three isocyanato- hexane esters, the isocyanato- -5- isocyanatomethyl octane esters of 2,5,7- trimethyls -1,8- two etc. Fat race triisocyanate etc..

As alicyclic polymeric isocyanate, for example, it can enumerate 1,3- cyclopentene isocyanates, Isosorbide-5-Nitrae-hexamethylene isocyanic acid Ester, 1,3- cyclohexyl isocyanates, 3- isocyanatomethyl -3,5,5- trimethylcyclohexylisocyanate (common first names：Different Buddhist Your ketone isocyanates), 4,4 '-di-2-ethylhexylphosphine oxide (cyclohexyl isocyanate), methyl -2,4- cyclohexyl isocyanates, methyl -2,6- Double (isocyanatomethyl) hexamethylene (common first names of cyclohexyl isocyanate, 1,3- or 1,4-：Hydrogenate xylylene isocyanic acid Ester) or its mixture, aminonorbornane isocyanate etc. alicyclic isocyanate, the isocyanatocyclohexanes of such as 1,3,5- three Ester, 1,3,5- trimethyl isocyanatocyclohexanes ester, 2- (3- isocyanatopropyls) (isocyanato- first of -2,5- two Base)-two rings (2.2.1) heptane ester, the rings (2.2.1) of 2- (3- isocyanatopropyls) -2,6- two (isocyanatomethyl)-two Heptane ester, ring (2.2.1) the heptane esters of 3- (3- isocyanatopropyls) -2,5- two (isocyanatomethyl)-two, (2- is different by 5- Cyanate radical closes ethyl) -2- isocyanatomethyls -3- (3- isocyanatopropyls)-two rings (2.2.1) heptane ester, (2- is different by 6- Cyanate radical closes ethyl) -2- isocyanatomethyls -3- (3- isocyanatopropyls)-two rings (2.2.1) heptane ester, (2- is different by 5- Cyanate radical close ethyl) -2- isocyanatomethyls -2- (3- isocyanatopropyls)-two rings (2.2.1)-heptane ester, 6- (2- Isocyanatoethyl) -2- isocyanatomethyls -2- (3- isocyanatopropyls)-two rings (2.2.1) heptane ester etc. fat Ring race triisocyanate etc..

As aromatic-aliphatic PIC, can for example enumerate 1,3- or Isosorbide-5-Nitrae-xylylene isocyanates or its Mixture, ω, the isocyanato- -1,4- of ω '-two diethylbenzenes, 1,3- or 1,4- are double (1- isocyanato- -1- Methylethyls) Phenyl ester (common first names：Tetramethyl xylylen isocyanates) or its mixture etc. aromatic-aliphatic isocyanates, such as 1, Aromatic-aliphatic triisocyanate of the isocyanatomethylbenzenes of 3,5- tri- etc. etc..

As aromatic poly-isocyanate, for example, it can enumerate metaphenylene isocyanates, to phenylene isocyanate, 4, 4 '-diphenylisocyanate, 1,5- naphthyl isocyanates, 2,4 '-or 4,4 '-phenylmethane isocyanates or its mixture, 2, 4- or 2,6- toluene diisocyanates or its mixture, 4,4 '-toluidine isocyanate, 4,4 '-diphenyl ether isocyanates etc. Aromatic isocyanate, such as triphenyl methane -4,4 ', 4 "-triisocyanate, the isocyanato- benzene of 1,3,5- tri-, 2,4,6- The aromatic tri-isocyanates of three isocyanato- toluene etc., such as 4,4 '-diphenyl methane -2,2 ', 5,5 '-tetraisocyanate Deng aromatic series tetraisocyanate etc..

In addition, as the derivative of PIC, can for example enumerate above-mentioned polyisocyanate compounds dimer, Tripolymer, allophanamide, allophanate, carbodiimide, urea diketone, uretonimine, isocyanuric acid ester, oxadiazines triketone, poly- Asia Methyl polyphenyl polyisocyanate (Crude MDI, Polymeric MDI), Crude TDI etc..

These polyisocyanate compounds can be used alone, or can also two or more be applied in combination.In addition, at these , can be with from the viewpoint of flatness and clarity and against weather of obtained film etc. in polyisocyanate compounds The derivative of aliphatic isocyanates and aliphatic isocyanates is suitably used.

As polyisocyanate compounds (B), in the case of using the derivative of aliphatic isocyanates, generally, fat The derivative of fat race isocyanates is the mixture with molecular weight distribution that multicomponent is constituted, and is gone out from the viewpoint of finished appearance Hair, preferably：It is more than tripolymer（Do not include isocyanurate trimer）Component content it is less, as constituent also Urea diketone containing low molecule amount.

As the derivative of above-mentioned aliphatic isocyanates, specifically, the aliphatic in following ranges can be included The derivative of isocyanates is as preference, i.e.,：On the basis of the total amount of polyisocyanate compounds, isocyanurate trimer Content be 30~70 mass %, preferably 40~70 mass %, more preferably 50~70 mass %, the content of urea diketone dimer for 3~ The content of polymers more than 30 mass %, preferably 5~25 mass %, more preferably 8~20 mass %, other tripolymers is 0~67 matter Measure %, more preferably preferably 5~55 mass %, 10~42 mass %.

In addition, as polyisocyanate compounds (B), following enclosed type polyisocyanate compounds can also be used, its It is by using the above-mentioned polyisocyanate compounds with more than 2 free isocyanate groups in 1 molecule of blocking agent NCO obtained from.

Sealer, is the reagent of the free NCO of closing, such as by being heated to more than 100 DEG C, preferably heating To more than 130 DEG C, thus NCO deblocking, can easily with hydroxyl reaction.As the sealer, for example, it can arrange Lift phenol, cresols, xylenols, nitrophenol, ethyl -phenol, hydroxy diphenyl, butylphenol, isopropyl-phenol, nonyl benzene The oxybenzene compound of phenol, octyl phenol, hydroxybenzoic acid methyl etc.；6-caprolactone, δ-valerolactone, gamma-butyrolacton, beta-propiolactone Deng lactone compound；The aliphatic alcohol of methanol, ethanol, propyl group alcohol, butanol, amyl group alcohol, lauryl alcohol etc.；Ethylene glycol monomethyl Ether, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, TC, propane diols list first The ether compound of base ether, methoxyl group methanol etc.；Benzyl alcohol；Glycolic；Methyl glycollate, ethyl glycolate, butyl glycolate etc. Ethyl glycolate；The lactate of lactic acid, methyl lactate, ethyl lactate, butyl lactate etc.；Methylolurea, melamine methylol, The alcohol based compound of diacetone alcohol, 2- hydroxy ethyl methacrylates, HEMA etc.；Formyl amidoxime, acetamide The oxime compound of oxime, acetoxime, diacetylmonoxime, diacetyl monoxime, diphenyl-ketoxime, hexamethylene oxime etc.；Dimethyl malenate, the third two The activity methene compound of diethyl phthalate, ethyl acetoacetate, methyl acetoacetate, acetylacetone,2,4-pentanedione etc.；Butanethiol, tertiary fourth Base mercaptan, hexyl mercaptans, tert- lauryl mercaptan, 2-mercaptobenzothiazole, benzenethiol, methylbenzene phenyl-sulfhydrate, ethyl thiophenol etc. Mercaptan compound；Antifebrin, acetyl group aminoanisole, acetyl toluidine, acrylamide, Methacrylamide, acetyl The imide compound of amine, stearmide, benzamide etc.；Succinimide, phthalimide, maleimide etc. Imide compound；Diphenylamines, phenyl naphthyl amines, dimethylaniline, N- phenyl dimethylaniline, carbazole, aniline, naphthylamines, butylamine, two The amines of butylamine, butyl phenyl amine etc.；The imidazolium compounds of imidazoles, 2- ethyl imidazol(e)s etc.；3,5- dimethyl pyrazoles etc. Pyrazole compound；The carbamide compounds of urea, thiocarbamide, ethylidene-urea, ethylene thiourea, acardite etc.；N- phenylcarbamic acid benzene The carbamate compounds of ester etc.；The group with imine moiety of aziridine, propyleneimine etc.；Sodium hydrogensulfite, potassium bisulfite Deng sulfites sealer, etc..

When carrying out enclosed type (reacting sealer), solvent can be added as needed on.It is molten that enclosed type is used when reacting Agent, as long as not having reactivity to NCO, ketones solvent such as can enumerate acetone, methyl ethyl ketone, The esters solvent of ethyl acetate etc., 1-METHYLPYRROLIDONE (NMP) equal solvent.

Polyisocyanate compounds (B) can be used alone, or can be with two or more combinations.

In the coating composition of the present invention, from the viewpoint of curability, marresistance from gained film etc., hydroxyl The hydroxyl of acrylic resin (A) and the equivalent proportion (NCO/OH) of NCO of polyisocyanate compounds (B) preferably exist In the range of 0.5~2.0, more preferably in the range of 0.8~1.5.

Acrylic resin (A) and polyisocyanate compounds (B) on hydroxyl in the coating composition of the present invention Solid component content ratio, relative to the solid constituent total amount of (A) composition and (B) composition, the acrylic resin (A) of hydroxyl is In the range of 40~85 mass %, preferably in the range of 45~80 mass %, polyisocyanate compounds (B) are in 15~60 matter In the range of amount %, preferably in the range of 20~55 mass %.

Polyalcohol (C)

Polyalcohol (C) is at least one in polyalcohol (C1) and polycarbonate polyol (C2) containing polyoxyalkylene Kind.

The number-average molecular weight of polyalcohol (C), from the film of flatness and the finished appearance and against weather of clarity etc. From the viewpoint of excellent performance, in the range of 300~1500, preferably in the range of 350~1000, more preferably 400~ In the range of 800.

In addition, the hydroxyl value of polyalcohol (C), from the film of flatness and the finished appearance and against weather of clarity etc. From the viewpoint of energy is excellent, preferably in the range of 60~400mgKOH/g, the scope more preferably in 100~350mgKOH/g It is interior, and then particularly preferably in the range of 150~300mgKOH/g.

As the polyalcohol (C1) containing polyoxyalkylene, polyalcohol, polyhydric phenols, polybasic carboxylic acid class etc. can be set forth in and contained Compound etc. obtained by addition epoxy alkide in the compound of reactive hydrogen.As the compound containing active hydrogen atom, for example may be used With enumerate water, polyalcohols (ethylene glycol, diethylene glycol, trimethylene, propane diols, 1,4- butanediols, 1,6-HD, The dihydric alcohol of neopentyl glycol, 1,4- bishydroxymethyls hexamethylene, cyclohexanediol etc., glycerine, three epoxide iso-butanes, 1,2,3- fourths three Alcohol, the triols of 1,2,3- penta, 2- methyl isophthalic acids, 2,3- glycerine, 2- methyl -2,3,4- butantriols, 2- ethyl -1,2,3- butantriols, The triols of 2,3,4- penta, 2,3,4- hexanetriols, 4- propyl group -3,4,5- triols in heptan, the triols of 2,4- dimethyl -2,3,4- penta, pentamethyl The trihydroxylic alcohol of glycerine, five glycerine, 1,2,4- butantriols, the triols of 1,2,4- penta, trimethylolethane, trimethylolpropane etc., season Penta tetrol, the tetrols of 1,2,3,4- penta, the own tetrols of 2,3,4,5-, the tetrols of 1,2,4,5- penta, the own tetrols of 1,3,4,5-, two glycerine, mountain The pentabasis alcohol of the tetrahydroxylic alcohols such as pears sugar alcohol, ribitol, arabite, xylitol, triglycerin etc., dipentaerythritol, D-sorbite, Eight yuan of alcohol, poly-glycerines of hexahydroxylic alcohols, the sucrose of mannitol, iditol, inositol, galactitol, talose, allose etc. etc. Deng)；Polyatomic phenol [polyhydric phenols (pyrogallol, hydroquinones, phloroglucin etc.), bisphenols (bisphenol-A, sulfonated bis phenol（ビス フエノ-ルスルフオン）Deng)]；[aliphatic polycarboxylic acid's (butanedioic acid, adipic acid etc.), aromatic series polycarboxylic acids are (adjacent for polycarboxylic acids Phthalic acid, terephthalic acid (TPA), trimellitic acid etc.)] etc..

In above-mentioned, as the compound containing reactive hydrogen, from the viewpoint of reactivity, preferred polyol class is especially excellent The polyalcohol of alkylidene of the choosing with carbon number more than 3, wherein it is preferred that the polyalcohol of the alkylidene with carbon number 3~4.

And then, in polyalcohols, from the viewpoint of the flatness and clarity of gained multilayer film, particularly preferred two First alcohol.

Especially in above-mentioned polyalcohol, preferably ethylene glycol, diethylene glycol, trimethylene, propane diols, Isosorbide-5-Nitrae-fourth two Alcohol, particularly preferred trimethylene, propane diols, BDO.

The above-mentioned polyalcohol (C1) containing polyoxyalkylene, is that typically in the presence of base catalyst, using conventional Method is carried out to the above-mentioned compound addition epoxy alkide containing reactive hydrogen under normal pressure or pressurization in 60~160 DEG C of temperature Obtained from addition reaction.As above-mentioned epoxy alkide, the ring of oxirane, expoxy propane, epoxy butane etc. can be enumerated Oxygen alkide, wherein preferably using expoxy propane, epoxy butane, particularly preferred expoxy propane.These compounds can use one Kind can be with two or more combinations.The addition form of situation associated with two or more can be any in closing or being random Person.

As the polyalcohol (C1) containing polyoxyalkylene, polyoxyalkylene glycol can be preferably used.

As polyoxyalkylene alcohol, commercially available product can be used, for example, can be enumerated as polypropylene glycol, Ha can be enumerated イ プ ロ Star Network ス MP-600 (big Japanese ink chemical industry (strain) system), プ ラ イ system Port-Le PX-1000, Sunnix SP- 750th, Sunnix PP-400, Sunnix PP-600, Sunnix PP-1000 ((strain) system is melted into by Sanyo above), Diol- 400th, Diol-700, Diol-1000 (being made above by Mitsui Chemicals (strain))；As polytetramethylene glycol, can enumerate PTMG-650, PTMG-850, PTMG-1000 (being made above by Mitsubishi Chemical's (strain)) etc..

As polycarbonate polyol (C2), for example, can have for usually used with 1,6- hexylene glycols as basic The polycarbonate polyol of skeleton, in addition to this it is possible to use the polycarbonate polyol manufactured by known method.Example Such as, can enumerate the carbonate component or phosgene of alkylene carbonate, diaryl carbonate, dialkyl carbonate etc. with Polycarbonate polyol obtained from the aliphatic polyol composition reaction of lower illustration.Herein, as aliphatic polyol composition, The straight-chain di-alcohols of 1,3- propane diols, 1,4- butanediols or 1,6-HD etc. can be enumerated；1,2- propane diols, new penta 2 Alcohol, 3- methyl isophthalic acids, the branched diol of 5- pentanediols, ethyl butyl propanediol etc.；The ethers glycol of diethylene glycol, triethylene glycol etc. It is used as the example of aliphatic polyol composition.

Polycarbonate polyol (C2), from the viewpoint of thermal fluidity when being heating and curing, preferably in the molecular structure Ring structure without aromatic rings, aliphatic ring etc..

Polycarbonate polyol can use commercially available product, can enumerate ETERNACOLLUH-50, ETERNACOLLUH- 100th, ETERNACOLLUM-90 (1/3) (above by emerging production (strain) system in space portion)；C-1100, C-XP-2716 are (above by Bayer societies System) etc..

It is many relative to the acrylic resin (A) and the solid constituent total amount of polyisocyanate compounds (B) of above-mentioned hydroxyl First alcohol (C) preferably uses 1~20 mass %, particularly preferably using 2~10 mass %, and then particularly preferably uses 3~7 mass %.

By using the amount of the scope, the thermal fluidity in the solidification process of multilayer film is improved, can be fully hidden The surface configuration (bumps) of ground, the influence of the surface configuration of ground is inhibited, therefore can obtain flatness and clarity Finished appearance is excellent and the film performance of weatherability etc. also excellent multilayer film.

Non-aqueous dispersion type acrylic resin (D)

Non-aqueous dispersion type acrylic resin (D), it is micro- with being referred to as of being used usually as rheology control agent in paint field The polymer particles of gel are compared, and the influence that the finished appearance to film declines reduces, therefore can be suitable as the present invention Coating composition rheology control agent.

Non-aqueous dispersion type acrylic resin (D), is in the presence of macromolecular dispersion stabilizer and organic solvent, to make at least Acrylic resin obtained from a kind of unsaturated monomer dispersin polymerization.

The macromolecular dispersion stabilizer used in the manufacture of non-aqueous dispersion type acrylic resin (D), is typically to make long-chain not Saturation monomer as needed with polymer obtained from other unsaturated monomer copolymerization.

The long-chain unsaturated monomer used in the polymer, performance that can be according to required by film is properly selected, But from combined polymerization, to viewpoints such as the dissolubilities of organic solvent, the long-chain unsaturated monomer that can preferably use Following material can be illustrated.

For example, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, the tertiary fourth of (methyl) acrylic acid can be enumerated Ester, (methyl) acrylic acid-2-ethyl caproite, (methyl) cyclohexyl acrylate, (methyl) n-octyl, (methyl) acrylic acid The carbon number 4 of (methyl) acrylic acid of lauryl, (methyl) acrylic acid tridecane ester, (methyl) stearyl acrylate acid esters etc.~ 18 alkyl or cycloalkyl ester；Methoxyl group (methyl) butyl acrylate, methoxyl group (methyl) ethyl acrylate, ethyoxyl (methyl) The alkoxy alkyl of (methyl) acrylic acid of butyl acrylate etc.；(methyl) of the aromatic alcohols of (methyl) benzyl acrylate etc. Ester formed by acrylic acid；The hydroxy alkyl ester of (methyl) glycidyl acrylate or (methyl) acrylic acid and capric acid, laurate, Asia Addition product formed by the monocarboxylic acid compound of oleic acid, oleic acid etc.；(methyl) acrylic acid and " カ-ジ ユ ラ E10 " etc. monocyclic oxygen Addition product formed by based compound；Styrene, α-methylstyrene, vinyltoluene, p- chlorostyrene, p- tert-butyl benzene second The vinyl aromatic compounds of alkene etc.；Itaconic acid, itaconic anhydride, crotonic acid, maleic acid, maleic anhydride, fumaric acid, citraconic acid Deng (methyl) acrylic acid beyond alpha, beta-unsaturated carboxylic acid and butyl alcohol, amyl group alcohol, enanthol, octyl group alcohol, stearyl alcohol etc. carbon List or diester compound formed by the single methanol of atomicity 4~18；“Biscoat8F”、”Biscoat8FM”、“Biscoat3F”、 " Biscoat3FM " (makes, trade name has (methyl) acroleic acid esterification of fluorine atom in side chain by Osaka organic chemistry (strain) Compound) perfluorocyclohexyl (methyl) acrylate, perfluorohexyl ethylene etc. the compound containing fluorine atom etc..

It is being used as needed in the polymerization of macromolecular dispersion stabilizer, be used as the insatiable hunger beyond long-chain unsaturated monomer And monomer, as long as enumerating the unsaturated monomer beyond such long-chain unsaturated monomer in above-mentioned, it is not particularly limited, can With the carbon of (methyl) acrylic acid for enumerating (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) propyl acrylate etc. The Arrcostab of atomicity 1~3；The monocarboxylic acid of the carbon number 2~3 such as glycidyl (methyl) acrylate and acetic acid, propionic acid Addition product formed by compound；Itaconic acid, itaconic anhydride, crotonic acid, maleic acid, maleic anhydride, fumaric acid, citraconic acid etc. Alpha, beta-unsaturated carboxylic acid beyond (methyl) acrylic acid and list or two formed by the single methanol of the carbon number 1~3 of methanol, propyl alcohol etc. Ester compounds；The unsaturated compound of the cyano-containing of (methyl) acrylonitrile etc.；The vinyl ester compound of vinyl-acetic ester；Second The vinyl ether compound of base vinyl ethers, methyl vinyl ether etc.；The α of ethene, propylene, ethlyene dichloride, vinylidene chloride etc.- Alkenes compounds etc..Unsaturated monomer beyond long-chain unsaturated monomer, such as 2- ethoxys (methyl) acrylate, are also wrapped Include it is above-mentioned in the monomer that unsaturated monomer hydroxyl etc. is substituted enumerated.

In order to manufacture the polymerization of above-mentioned macromolecular dispersion stabilizer, radical polymerization initiator can be generally used to carry out. As radical polymerization initiator, for example, it can enumerate 2,2 '-azodiisobutyronitrile, 2, (2, the 4- dimethyl-pentens of 2 '-azo two Nitrile) etc. azo-initiator；Benzoyl peroxide, lauroyl peroxide, t-butylperbenzoate, tert-butyl peroxide -2- second Catalyst peroxide type initiators of base capronate etc. etc., these polymerization initiators are typically the every 100 parts lists for being used to polymerize Body in the range of 0.2~10 mass parts or so to use, preferably to be used in the range of 0.5~5 mass parts.Reaction during polymerization Temperature is typically 60~160 DEG C or so, and reaction time during polymerization can generally be set to 1~15 hour or so.

The molecular weight of the copolymer used as above-mentioned dispersion stabilizer, usual weight average molecular weight is left 5000~100000 Right scope, preferably in the range of 5000~50000 or so.By using the copolymer with above range molecular weight as point Dispersion stabilizer is used, and can stabilize dispersed particle, it is hereby achieved that suppress cohesion and sedimentation and viscosity will not it is too high and The coating being easily processed.

Macromolecular dispersion stabilizer can be used alone or two kinds with combination.And then, it can also share as needed Other dispersion stabilizers, such as butyl it is etherified melamine formaldehyde resin, alkyd resin.

When manufacturing non-aqueous dispersion type acrylic resin (E), organic in the presence of above-mentioned macromolecular dispersion stabilizer It polymerize at least one unsaturated monomer in solvent, the non-aqueous dispersion of insoluble polymer particle is prepared in the organic solvent.

As the organic solvent used in above-mentioned polymerization, including the polymer particle generated through the polymerization is essentially insoluble Solution, but the organic solvent for the good solvent for being to above-mentioned macromolecular dispersion stabilizer and the unsaturated monomer.It is organic molten as this The concrete example of agent, can enumerate the fat hydrocarbon solvent of hexane, heptane, octane etc.；The aromatic hydrocarbon of benzene,toluene,xylene etc.；First The alcohols solvent of alcohol, isopropanol, normal-butyl alcohol, isobutyl alcohol, octyl group alcohol etc.；Cellosolve, butyl cellosolve, diethylene glycol mono butyl The ether solvent of base ether etc.；Methyl iso-butyl ketone (MIBK), DIBK, methyl ethyl ketone, methyl ethyl ketone, ethyl butyl ketone etc. Ketones solvent；Esters solvent of ethyl acetate, isobutyl acetate, pentyl acetate, 2- ethylhexyl acetates etc. etc..These are organic Solvent can be used alone or can share two or more.

As above-mentioned organic solvent, especially based on aliphatic hydrocarbon, appropriate aromatic hydrocarbon, alcohols are combined wherein molten Solvent obtained from agent, ether solvent, ketones solvent, esters solvent etc..

It is more excellent than polymerism and be used as macromolecule point using carbon number as the unsaturated monomer for above-mentioned polymerization The smaller unsaturated monomer of carbon number that the monomer that the monomer component of dispersion stabilizer is used has, from being used as dispersed polymeres The aspect that particle is easily formed is suitable.

As such unsaturated monomer, can for example enumerate (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, 2- Ethyl (methyl) Hexyl 2-propenoate, (methyl) cyclohexyl acrylate, (methyl) n-octyl, (methyl) lauryl The carbon number 1 of (methyl) acrylic acid of ester, (methyl) tridecyl acrylate, (methyl) octadecyl acrylate etc.~ 18 alkyl or cycloalkyl ester；Methoxyl group (methyl) butyl acrylate, methoxyl group (methyl) ethyl acrylate, ethoxybutyl The alkoxy alkyl of (methyl) acrylate etc. (methyl) acrylic acid；Aromatic alcohols (the first of benzyl (methyl) acrylate etc. Base) acrylic acid ester；The carbon such as glycidyl (methyl) acrylate and acetic acid, propionic acid, oleic acid, p- p t butylbenzoic acid is former Adduct formed by the monocarboxylic acid compound of subnumber 2~18；(methyl) acrylic acid and the " mono-epoxy such as カ-ヅ ユ ラ E10 " Adduct formed by compound；Styrene, α-methylstyrene, vinyltoluene, p- chlorostyrene, p- t-butyl styrene etc. Vinyl aromatic compounds；Itaconic acid, itaconic anhydride, crotonic acid, maleic acid, maleic anhydride, fumaric acid, citraconic acid etc. The carbon numbers 1~18 such as alpha, beta-unsaturated carboxylic acid and methylol, butyl alcohol, hexyl alcohol, stearyl alcohol beyond (methyl) acrylic acid Single methanol formed by list or diester compound；“Biscoat8F”、“Biscoat8FM”、“Biscoat3F”、“Biscoat3FM” (being made by Osaka organic chemistry (strain), trade name has (methyl) acrylate compounds of fluorine atom in side chain), perfluor ring The compound containing fluorine atom of hexyl (methyl) acrylate, perfluorohexyl ethylene etc.；The cyano-containing of (methyl) acrylonitrile etc. Unsaturated compound；The ethene of vinyl-acetic ester, vinyl benzoate, " Veova (VEOVA) " (SHELL (strain) systems) etc. Base ester compound；The vinyl ether compound of n-butyl vinyl ether, ethyl vinyl ether, methyl vinyl ether etc.；1,6- oneself The polyvinyl of two (methyl) acrylate of glycol, three (methyl) acrylate, the divinylbenzene of trimethylolpropane etc. Compound；Alpha-olefines compound of ethene, propylene, ethlyene dichloride, vinylidene chloride etc. etc..

The monomer component of polymer particle is formed, as described above, comparing macromolecular dispersion stabilizer by using carbon number Monomer component the less composition of carbon number, particle components can be stably formed, but from this viewpoint, can be appropriate Ground uses carbon number below 8, preferably less than 4 (methyl) acrylate compounds, vinyl aromatic compounds, (methyl) Acrylonitrile etc..These unsaturated monomers can be used alone or can be with two or more combinations.

The polymerization of above-mentioned unsaturated monomer can use common radical polymerization initiator to carry out.As can use Radical polymerization initiator, can for example enumerate 2,2 '-azodiisobutyronitrile, 2,2 '-azo two (2,4- methyl pentane nitrile) Deng azo-initiator；Benzoyl peroxide, lauroyl peroxide, t-butylperbenzoate, tert-butyl peroxide -2- ethyl hexyls Catalyst peroxide type initiators of acid esters etc. etc., these polymerization initiators relative to be generally used for polymerization monomer total amount, It can use, can preferably be used in the range of 0.5~5 mass parts in the range of 0.2~10 mass parts or so.

The macromolecular dispersion stabilizer and the use ratio of unsaturated monomer existed in above-mentioned polymerization, it is generally unsaturated single Body phase is 3~240 mass parts or so, preferably 5~82 mass parts or so for the mass parts of macromolecular dispersion stabilizer 100.And then, The total concentration of macromolecular dispersion stabilizer and unsaturated monomer in organic solvent is typically 30~70 mass % or so, preferably It is 30~60 mass % or so.

Polymerization can be carried out with itself known method, and reaction temperature during polymerization is typically 60~160 DEG C or so, is gathered Reaction time during conjunction is typically 1~15 hour or so.

Polymerisation is carried out as described above, and it is scattered steady to have dissolved macromolecule in organic solvent to obtain liquid phase Determine the non-moisture of the stabilization for the non-aqueous dispersion type acrylic resin that agent, solid phase are the polymer particles that polymerization of unsaturated monomers is obtained Dispersion liquid.The average grain diameter of polymer particle is normally about in 0.1~1.0 μm of scope.By by the average grain diameter of polymer particle Above range is located at, the viscosity of non-aqueous dispersion will not be too high, and the swollen of polymer particle of the coating in storage can be suppressed Swollen or cohesion, therefore preferably.

When manufacturing non-aqueous dispersion type acrylic resin (D), by making the macromolecular dispersion stabilizer in non-aqueous dispersion Combined with polymer particle, it is possible thereby to improve the bin stability and mechanical property of non-aqueous dispersion.It should be noted that i.e. Make in the case of combination, dispersity also has almost no change from the point of view of in appearance, and the average grain diameter of polymer particle is also several Do not change.

It is as the method for making macromolecular dispersion stabilizer be combined with polymer particle, such as scattered in previously fabricated macromolecule In the stage of stabilizer, first make with hydroxyl, acidic group, anhydride group, epoxy radicals, methylol, NCO, amide groups, amino etc. The partly combined polymerization of the monomer component of functional group, then using have with the hydroxyl of above-mentioned functional group reactionses, acidic group, anhydride group, The monomer of the functional groups such as epoxy radicals, methylol, NCO, amide groups, amino as formed polymer particle monomer into Divide to carry out.As combinations thereof, for example, it can enumerate NCO and hydroxyl, NCO and methylol, epoxy Base and sour (acid anhydride) base, epoxy radicals and amino, NCO and amide groups, acid (acid anhydride) base and hydroxyl etc..

As the monomer with such functional group, for example, it can enumerate (methyl) acrylic acid, crotonic acid, maleic acid, horse Come the α of acid anhydrides, itaconic acid, itaconic anhydride, fumaric acid, citraconic acid etc., β-ethylenically unsaturated carboxylic acids；(methyl) acrylic acid shrinks sweet The compound containing glycidyl of grease, vinyl glycidyl ether, acrylic glycidyl ether etc.；(methyl) propylene Acid amides, N, N- dimethyl (methyl) acrylamide, N- alkoxy methyls (methyl) acrylamide, diacetone acrylamide, N- hydroxyls The carboxylic acid amide compounds of methyl (methyl) acrylamide etc.；P- styrene sulfonamide, N- methyl-p- styrene sulfonamide, The compounds containing sulfonic acid amides base such as N, N- dimethyl-p- styrene sulfonamide；(methyl) acrylic acid-tert-butylamino second The compound containing amino of base etc.；2- ethoxys (methyl) acrylate and phosphoric acid or the formed condensation of phosphate compound Thing, glycidyl (methyl) acrylate etc. have glycidyl compound glycidyl on addition phosphoric acid or The compound of the phosphorous acidic group of compound obtained from phosphate compound etc.；2- acrylamide -2- methyl-propanesulfonic acids etc. Contain sulfonic compound；M- isopropenyl-bis (alpha, alpha-dimethylbenzyl) based isocyanate, IPDI or Asia Toluenediisocyanate and equimolar addition product, isocyano group ethylmethyl acrylate formed by hydroxyl (methyl) acrylate Deng the compound containing NCO etc..

In addition, can be with poly- as the other method for making macromolecular dispersion stabilizer be combined with polymer particle Make polymerization of unsaturated monomers in the presence of the macromolecular dispersion stabilizer of conjunction property double bond and carry out.

Polymerism double bond is imported to macromolecular dispersion stabilizer, such as can be by using containing carboxylic acid, phosphoric acid, sulfonic acid There is the monomer of acidic group as the combined polymerization composition of the resin, make the acidic group and glycidyl (methyl) acrylate, acrylic The unsaturated monomer containing glycidyl such as glycidyl ether reacts to carry out.In addition, on the contrary, making macromolecule point in advance Contain glycidyl in dispersion stabilizer, make it react to carry out with the unsaturated monomer containing acidic group.These reactions can be by Carried out according to known condition.

In addition, as the other other method for making macromolecular dispersion stabilizer be combined with polymer particle, can pass through After manufacture has imported the non-aqueous dispersion with the mutual mutual nonreactive functional group of macromolecular dispersion stabilizer and polymer particle, Make it with both bonding agent reactions can be combined to carry out.

Specifically, it be able to will such as contain in the presence of the macromolecular dispersion stabilizer and organic solvent containing hydroxyl The unsaturated monomer of hydroxyl individually polymerize or polymerize with the mixture of other unsaturated monomers, and manufacture contains hydroxyl in both After the non-aqueous dispersion of base, polyisocyanate compounds etc. are coordinated to react a few hours~a couple of days at normal temperatures or 60~100 DEG C or so reaction carry out within 1~5 hour or so.

As polyisocyanate compounds, as long as having more than 2 NCOs in the molecule, for example, it can arrange Lift the aromatic series of inferior cresyl vulcabond, eylylene diisocyanate, 4,4 '-methyl diphenylene diisocyanate etc. Diisocyanate or their hydride；Hexamethylene diisocyanate, lysine diisocyanate, dimeric dibasic acid (tall oil fat The dimer of fat acid) diisocyanate etc. aliphatic diisocyanate；The ester ring type two of IPDI etc. is different Cyanate etc..

In addition, outside above-mentioned, macromolecular dispersion stabilizer and polymer particle and polyoxide containing acidic group can be used Combination, the combination of the macromolecular dispersion stabilizer containing epoxy radicals and polymer particle and polycarboxylic acids, contain epoxy radicals or different Combination of macromolecular dispersion stabilizer and polymer particle and polysulfide compounds of cyanic acid ester group etc. is carried out.

As above-mentioned polyoxide, for example, it can enumerate bisphenol type epoxy base resin, bisphenol F type epoxy base resin, phenolic aldehyde Type epoxy base resin, acrylic resin containing epoxy radicals etc.；Adipic acid, the last of the ten Heavenly stems two can be for example enumerated as polycarboxylic acids Acid, azelaic acid, different isophthalic acid etc.；Vulcanization pentamethylene, vulcanization hexamethylene, the poly- (sulphur of ethene two can be enumerated as polysulfide Compound) etc..

As above, macromolecular dispersion stabilizer can be made to be chemically bonded with polymer particle, but now will be various Functional group and/or polymerism double bond import the amount of macromolecular dispersion stabilizer and/or polymerism particle, the dispersion stabilizer and/ Or it is average at least 0.1 in a molecule of particle, average out to 0.1~1.0, enters by particularly preferably 0.1~0.5 And the scope amount of particularly preferred 0.1~0.3.

The non-aqueous dispersion so so obtained, is that macromolecular dispersion stabilizer is chemically bonded with polymer particle, because This bin stability is excellent, and the film formed can show excellent chemistry, engineering properties.

In the coating composition of the present invention, in the case where using non-aqueous dispersion type acrylic resin (D), its amount is from originally The finished appearance for applying face flatness etc. of the painting operation (sag resistance) of the coating composition of invention and obtained film From the viewpoint of, relative to the acrylic resin (A) and the solid constituent total amount of melmac (B) of hydroxyl, as solid In the range of the mass % of body composition 15 is the following is suitable, preferably 2~10 mass %, and then in the range of preferably 3~8 mass %.

In addition, resin beyond acrylic resin (A) that further as needed can be containing hydroxyl in this coating, Coloring pigment, bright pigment, dyestuff of transparent degree etc. are not hindered, and then can also suitably contain extender pigment, purple Ultraviolet absorbers, light stabilizer, defoamer, thickening agent, antirust agent, surface conditioner, organic solvent etc..

As above-mentioned catalyst, for example, it can enumerate tin octoate, two (2 ethyl hexanoic acid) dibutyl tins, two (2- ethyl hexyls Acid) dioctyl tin, dioctyl tin diacetate, dibutyl tin laurate, dibutyl tin oxide, dioctyltin oxide, 2- Organo-metallic catalyst, tertiary amine of ethyl hexane lead plumbate etc. etc..

It can be used alone as these above-mentioned compounds of catalyst or can be with two or more combinations.The amount of catalyst It is different according to its species, relative to the solid constituent total amount of (A) composition and (B) composition, 0~5 mass % can be generally set to, It is preferably set to 0.1~4 mass % or so.

As above-mentioned ultra-violet absorber, conventional ultra-violet absorber known always can be used, for example, can be enumerated The ultraviolet radiation absorption of benzotriazole absorbent, triazines absorbent, salicylic acid absorbent, benzophenone absorbent etc. Agent.

The content of ultra-violet absorber in the coating composition, from against weather, the angle of yellowing resistance, usual phase In the range of resin solid content total amount preferably 0~10 mass %, in the range of particularly preferred 0.2~5 mass %, Jin Erte Not preferably in the range of 0.3~2 mass %.

As light stabilizer, conventional light stabilizer known always can be used, for example, can enumerate hindered amines light steady Determine agent.

As the content of light stabilizer in the coating composition, from against weather, the angle of yellowing resistance, usual phase For resin solid content total amount preferably in the range of 0~10 mass %, particularly preferred 0.2~5 mass %, and then particularly preferably In the range of 0.3~2 mass %.

When the NCO of the polyisocyanate compounds as (B) composition of the coating composition of the present invention is not sealed During closed form, from the viewpoint of storage-stable, it is preferably：2 liquid type coating are made into, i.e. the acrylic acid tree containing hydroxyl The composition of fat (A) and polyalcohol (C) is isolated from each other with the composition containing polyisocyanate compounds (B), when in use will be above-mentioned Binary, which is mixed, to be used.

Solid component concentration generally preferable 35~70 mass %, more preferably 40~70 mass %, and then preferably 45 of this coating ~65 mass %.

This coating can be using itself known method, such as airless spraying, aerial spraying, rotary-atomizing coating machine Application, additional electrostatic is carried out in application.Application thickness can be generally set in the range of 10~60 μm with solidifying film thickness gauge, excellent Choosing is set in the range of 25~50 μm.

Method of forming layered coating film

Coated article

According to the present invention, as the coated article that the 1st aqueous pigmented finiss (X) obtains is applicable, it is not particularly limited, for example may be used To enumerate the outer plate portion of the car bodies such as passenger vehicle, truck, electric motor car, bus；Automobile component；Mobile phone, audio frequency apparatus etc. The outer plate portion of household electrical appliance product etc., wherein, the preferred outer plate portion and automotive department of car body.

In addition, as the raw material of above-mentioned coated article, being not particularly limited, for example, it can enumerate iron, aluminium, brass, copper, horse The metal material of mouth iron, stainless steel, galvanized steel, alloy plating zinc (Zn-Al, Zn-Ni, Zn-Fe etc.) steel etc.；Polyvinyl resin, It is acrylic resin, acrylonitrile-butadiene-styrene (ABS) (ABS), polyamide, acrylic resin, vinylidene resin, poly- The resinae of carbonate resin, polyurethane resin, epoxy resin etc., various FRP etc. plastic material；Glass, cement, concrete Deng inorganic material；Timber；Fibrous material (paper, cloth etc.) etc., wherein metal material and plastic material are suitable.

Above-mentioned coated article can impose phosphate to above-mentioned metal material, by the metal surface of the car body of its shaping etc. The surface treatment of reason, the processing of chromic acid salt treatment, composite oxides etc..And then, the coated article can be in above-mentioned metal base, car Formed on body etc. various electricity the primer coating film of coating etc. obtain, formd wherein particularly preferably material using cation electrodeposition The car body of primer coating film.

Process (1)

In this process, the aqueous pigmented finiss (X) of application the 1st forms the 1st and colours film on coated article.

1st aqueous pigmented finiss (X)

As the 1st aqueous pigmented finiss (X) to above-mentioned coated article application, containing heat-curing resin composition and water, enter And it is as needed, cooperation organic solvent, coloring pigment, extender pigment, bright pigment, surface conditioner, sedimentation can be used The aqueous liquid coating that preventing agent etc. is obtained.It should be noted that in this specification, so-called water paint is the principal component of solvent For the coating of water.

As above-mentioned heat-curing resin composition, the parent of cross-linking functional group and carboxyl with hydroxyl etc. etc. can be used Itself known coating resin composition, the base that the matrix resin (I) and crosslinking agent (II) of aqueous functional group are constituted Body resin (I) is polyester resin, acrylic resin, vinylite, alkyd resin, polyurethane resin etc., the crosslinking agent (II) it is melmac, the polyisocyanate compounds that can be closed etc..

Wherein, as matrix resin (I), the acrylic resin (I-1) and/or the polyester resin of hydroxyl of hydroxyl are used (I-2), as crosslinking agent (II), it is adapted to using amino resins (II-1) and/or enclosed type polyisocyanate compounds (II-2).

The acrylic resin (I-1) of hydroxyl, for example can be by single by the unsaturation containing hydroxyl at typical condition Body and as needed comprising can with least one unsaturated monomers of other unsaturated monomers of the monomer copolymerizable is (common) gathers Close and manufacture.

Unsaturated monomer containing hydroxyl, at least has 1 hydroxyl and polymerism unsaturated bond respectively in 1 molecule Compound, can for example enumerate (methyl) acrylic acid -2- hydroxyl ethyl esters, (methyl) 2-hydroxypropyl acrylate, (methyl) acrylic acid - The mono-esterification of (methyl) acrylic acid of 3- hydroxypropyl acrylates, (methyl) acrylic acid -4- hydroxy butyl esters etc. and the dihydric alcohol of carbon number 2~8 Thing；(methyl) acrylic acid and the 6-caprolactone modified body of monoesters compound formed by the dihydric alcohol of carbon number 2~8；Acrylic alcohol； Molecular end, which has, belongs to (methyl) acrylate of polyethylene oxide chain of hydroxyl etc..

As other unsaturated monomers that can be with the above-mentioned unsaturated monomer copolymerization containing hydroxyl, for example, it can enumerate (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) n-propyl, (methyl) isopropyl acrylate, (first Base) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) the just own ester of acrylic acid, (first Base) 2-ethyl hexyl acrylate, (methyl) acrylic acid-2-ethyl caproite, (methyl) acrylic acid nonyl ester, (methyl) lauryl acrylate, (first Base) tridecyl acrylate, (methyl) octadecyl acrylate, " Isostearyl Acrylate " (trade name, Osaka Organic Chemical Industry company system), (methyl) cyclohexyl acrylate, (methyl) acrylic methyl cyclohexyl, (methyl) acrylic acid uncle Alkyl or cycloalkyl (methyl) acrylate of butylcyclohexyl ester, (methyl) acrylic acid cyclododecane ester etc.；Isobornyl (first Base) acrylate etc. the unsaturated monomer with isobornyl；Adamantyl (methyl) acrylate etc. has adamantyl Unsaturated monomer；Styrene, α-methylstyrene, vinyltoluene, phenyl (methyl) acrylate etc. containing aromatic rings Unsaturated monomer；Vinyltrimethoxy silane, VTES, vinyl three (2- methoxy ethoxies) silicon Alkane, γ-(methyl) acryloxypropyl trimethoxy silane, γ-(methyl) acryloxypropyl triethoxysilane etc. The unsaturated monomer with alkoxysilyl；Perfluoro butyl ethyl (methyl) acrylate, perfluorooctylethyl group (first Base) acrylate etc. perfluoroalkyl (methyl) acrylate；The unsaturated monomer with fluorinated alkyl of fluoroolefins etc.；Have The unsaturated monomer of the optical polymerism such as dimaleoyl imino functional group；NVP, ethene, butadiene, neoprene two The vinyl compound of the sour vinyl of alkene, vinyl propionate base, jealous woman etc.；(methyl) acrylic acid, maleic acid, crotonic acid, β-carboxyethyl The carboxylic unsaturated monomer of acrylate etc.；(methyl) acrylonitrile, (methyl) acrylamide, dimethylaminopropyl (first Base) acrylamide, dimethylamino (methyl) ethyl acrylate, glycidyl (methyl) acrylate and amine it is formed plus Into the nitrogenous unsaturated monomer of thing etc.；Glycidyl (methyl) acrylate；Glycidyl (methyl) acrylate, β-first Base glycidyl (methyl) acrylate, 3,4- expoxycyclohexyls (methyl) methyl acrylate, 3,4- expoxycyclohexyls Ethyl (methyl) acrylate, 3,4- expoxycyclohexyls propyl group (methyl) acrylate, acrylic glycidyl ether etc. Unsaturated monomer containing epoxy radicals；Molecular end has (methyl) acrylate of the polyoxy ethylene chain as alkoxy；2- Acrylamide -2- methyl propane sulfonic acids, acrylic sulfonic acid, styrene sulfonic acid sodium salt, sulfoethyl methacrylate and its sodium salt, Ammonium salt etc. has sulfonic unsaturated monomer；2- acryloyl group epoxide ethylhexyldithiophosphoric acids phosphate, 2- methacryloxyethyls Acid phosphoric acid ester, 2- acryloyl group epoxide acid propyls phosphate, 2- methacryloxypropyl acid phosphoric acid esters etc. have phosphoric acid The unsaturated monomer of base；2- hydroxyls -4- (3- methacryloxy -2- hydroxy propyloxy groups) benzophenone, 2- hydroxyl -4- (3- Acryloyl group epoxide -2- hydroxy propyloxy groups) benzophenone, 2,2 '-dihydroxy -4- (3- methacryloxy -2- the third oxygen of hydroxyl Base) benzophenone, 2,2 '-dihydroxy -4- (3- acryloyl group epoxide -2- hydroxy propyloxy groups) benzophenone, 2- (2 '-hydroxyl - 5 '-methaciylyloxyethylphenyl) -2H- BTAs etc. have the unsaturated monomer of ultraviolet-absorbing group；4- (methyl) acryloyl group Oxy-1,2,2,6,6- pentamethvls, 4- (methyl) acryloyl group epoxide -2,2,6,6- tetramethyl piperazines Pyridine, 4- cyano group -4- (methyl) Acryloyl amino -2,2,6,6- tetramethyl piperidines, 1- (methyl) acryloyl group -4- (methyl) third Enoylamino -2,2,6,6- tetramethyl piperidines, 1- (methyl) acryloyl group -4- cyano group -4- (methyl) Acryloyl amino -2, 2,6,6- tetramethyl piperidines, 4- crotonyl epoxide -2,2,6,6- tetramethyl piperidines, 4- crotonyl amino -2,2,6,6- four Methyl piperidine, 1- crotonyl -4- crotonyl epoxide -2,2,6,6- tetramethyl piperidines etc. have ultraviolet stabilization performance Unsaturated monomer；Methacrylaldehyde, diacetone acrylamide, two acetone Methacrylamides, acetoacetoxyethyl metering system Acid esters, formoxyl styrene, vinyl alkyl ketone (such as ethenyl methyl ketone, vinyl ethyl with 4~7 carbon atoms Ketone, vinyl butyl ketone) etc. the unsaturated monomer compound with carbonyl etc., these can individually use or can be with Two or more combinations.

The acrylic resin (I-1) of hydroxyl, from the viewpoint of bin stability, the water resistance for obtaining film etc., leads to Can often have the hydroxyl value in the range of the hydroxyl value in the range of 1~200mgKOH/g, preferably 2~100mgKOH/g, and then preferred tool There is a hydroxyl value in the range of 3~60mgKOH/g, and generally there is the acid number in the range of 1~200mgKOH/g, preferably with 2~ Acid number in the range of 150mgKOH/g, and then preferably there is the acid number in the range of 5~100mgKOH/g.In addition, the third of hydroxyl Olefin(e) acid resin (A1) generally has the weight average molecular weight in the range of 1,000~5,000,000, preferably with 2,000~3,000, Weight average molecular weight in the range of 000, and then preferably there is the weight average molecular weight in the range of 3,000~1,000,000.

The use level of the acrylic resin (I-1) of hydroxyl, with the matrix resin (I) in the 1st aqueous pigmented finiss (X) and On the basis of the solid constituent total amount of crosslinking agent (II) (hereinafter referred to as resinous principle), 0~90 mass % scope can be generally set to It is interior, it is preferably set in the range of 5~60 mass %, and then be preferably set in the range of 10~40 mass %.

The polyester resin (I-2) of hydroxyl, for example can by the esterification of polyacid constituent and polyol component or Ester exchange reaction is manufactured, specifically for example can be by by hydroxyl in the carboxyl and polyol component in polyacid constituent Equivalent proportion (COOH/OH) be set to less than 1, esterification is carried out in the state of hydroxyl is more than carboxyl and is manufactured.

Above-mentioned polyacid constituent is the compound at least in 1 molecule with 2 carboxyls, for example, can enumerate benzene diformazan Acid, isophthalic acid, terephthalic acid (TPA), butanedioic acid, glutaric acid, adipic acid, azelaic acid, decanedioic acid, four hydrogen phthalates, hexahydro The polyacid of phthalic acid, maleic acid, fumaric acid, itaconic acid, trimellitic acid, pyromellitic acid etc.；The acid anhydrides of these polyacids；This Low alkyl group carboxylate of a little polyacids etc., these compounds can respectively be used or two or more can also be combined.

In addition, above-mentioned polyol component is the compound at least in 1 molecule with 2 hydroxyls, for example, it can enumerate Ethylene glycol, 1,2- propane diols, 1,2- butanediols, 2,3- butanediols, 1,2- hexylene glycols, 1,2- dihydroxies butylcyclohexane, 3- epoxy radicals The salmefamol of propane -1,2- glycol, 3- phenoxypropane -1,2- glycol etc.；Neopentyl glycol, 2- methyl-1,3-propanediols, 2- first Base -2,4-PD, 3- methyl isophthalic acids, 3- butanediols, 2- ethyl -1,3- hexylene glycols, 2,2- diethyl -1,3- propane diols, 2,2, 4- trimethyl -1,3- pentanediols, 2-butyl-2-ethyl-1,3-propanediol, 2- phenoxypropane -1,3- glycol, 2- methyl -2- Phenyl-propane -1,3- glycol, 1,3- propane diols, 1,3 butylene glycol, 2- ethyl -1,3- ethohexadiols, 1,3- dihydroxies butylcyclohexane, 1, 4- butanediols, 1,4- dihydroxies butylcyclohexane, 1,5- pentanediols, 1,6-HD, 2,5-HD, 3- methyl isophthalic acids, 5- pentanediols, 1,4- hydroxymethyl-cyclohexanes, Tricyclodecane Dimethanol, 2,2- dimethyl -3- hydroxypropyl -2,2- dimethyl -3- hydroxy propionates It is (this is carboxylate formed by hydroxy new pentane acid and neopentyl glycol), bisphenol-A, Bisphenol F, double (4- ethoxys) -2,2- propane, double (4- ethoxys) methane, 3,9- double (1,1- dimethyl -2- ethoxys) -2,4,8,10- four oxygen loop coil [5,5] hendecane, diethyls Glycol, triethylene glycol, glycerine, two glycerine, triglycerin, pentaerythrite, dipentaerythritol, D-sorbite, mannitol, trihydroxy methyl Ethane, trimethylolpropane, two (trihydroxy methyl) propane, three (2- ethoxys) chlorinated isocyanurates etc., these can be individually Using or two or more combinations.

The esterification of above-mentioned polyacid constituent and polyol component or ester exchange reaction can pass through itself known method To carry out, for example, it can be entered by making the polycondensation at a temperature of about 180~about 250 DEG C of above-mentioned polyacid constituent and polyol component OK.

In addition, the polyester resin (I-2) of hydroxyl, in the polyester resin process for preparation or after esterification, Ke Yigen It is modified with aliphatic acid, mono-epoxy compound etc. according to needing.As above-mentioned aliphatic acid, can for example enumerate coco-nut oil fatty acid, Continuous seed oil fatty acid, hemp seed oil aliphatic acid, rice bran oil fatty acid, fish oil fatty acid, ready denier oil acid, soybean oil fat Acid, linseed oil fatty acid, tung oil fatty acid, rapeseed oil fatty acid, Castor Oil Fatty Acid, dehydrated castor oil fatty acid, safflower oil Aliphatic acid etc., " カ-ジ ユ ラ E10P " (trade name, HEXION can be for example enumerated as above-mentioned mono-epoxy compound Specialty Chemicals company systems, synthesize the glycidyl esters of high branch chain saturated fatty acid) etc..

The polyester resin (I-2) of hydroxyl generally can have 10~300mgKOH/g in the range of hydroxyl value, preferably 25~ Hydroxyl value in the range of 250mgKOH/g, so preferably have 50~200mgKOH/g in the range of hydroxyl value, and generally have 1~ Acid number in the range of 200mgKOH/g, preferably with the acid number in the range of 5~100mgKOH/g, and then preferably have 10~ Acid number in the range of 60mgKOH/g.In addition, the polyester resin (I-2) of hydroxyl generally has the weight in the range of 500~50,000 Average molecular weight, preferably with the weight average molecular weight in the range of 1,000~40,000, and then preferably has 1,500~30,000 model Enclose interior weight average molecular weight.

The use level of the polyester resin (I-2) of hydroxyl, with the resinous principle solid in the 1st aqueous pigmented finiss (X) into Divide on the basis of total amount, can generally be set in the range of 0~90 mass %, be preferably set in the range of 10~60 mass %, and then It is preferably set in the range of 15~50 mass %.

In addition, the acrylic resin (I-1) and the polyester resin (I-2) of hydroxyl of hydroxyl, in order to easily enter water-filling Dissolve or moisture dispersion, will preferably be contained in the part or all of of carboxyl in them and neutralized with alkali compounds.It is used as alkaline chemical combination Thing, alkali metal or alkaline earth gold such as can enumerate NaOH, potassium hydroxide, lithium hydroxide, calcium hydroxide, barium hydroxide The hydroxide of category；Ammonia；Ethylamine, propyl group amine, butylamine, benzyl amine, MEA, neopentyl alcohol amine, 2- aminopropanols, 2- ammonia The primary monoamines of base -2- methyl isophthalic acids-propyl alcohol, 3- aminopropanols etc.；Diethylamide, diethanol amine, two normal propyl alcohol amine, diisopropanol The secondary monoamine of amine, N- methylethanolamines, N- ehtylethanolamines etc.；Dimethylethanolamine, Trimethylamine, triethylamine, three isopropyls The tertiary monoaminess of base amine, methyl diethanolamine, 2- (dimethylamino) ethanol etc.；Diethylenetriamine, hydroxyethylaminoethyl amine, second The polyamine of base amino ethyl amine, dimethylaminopropyl amine etc..As the usage amount of alkali compounds, relative to matrix resin (I) Acidic group can generally be set in the range of 0.1~1.5 equivalent, be preferably set in the range of 0.2~1.2 equivalent.

As above-mentioned polyurethane, in addition to conventional polyurethane, the acrylic resin of above-mentioned hydroxyl can also be enumerated (I-1) part for the hydroxyl and in the polyester resin (I-2) of hydroxyl carries out carbamate with polyisocyanate compounds Its extension, polyurethane of molecular weight etc. obtained from changing reaction.

On the other hand, as amino resins (II-1), for example, melamine, urea, benzoguanamine, methylguanidine can be enumerated Amine, steroid guanamines（ステログアナミン）, spiral shell guanamines（スピログアナミン）, dicyandiamide etc. amino component and aldehyde Reaction obtained from part or all of methylolation amino resins.As aldehyde, for example, it can enumerate formaldehyde, paraformaldehyde, second Aldehyde, benzaldehyde etc..Furthermore it is possible to which its part or all of methylolation amino resins is carried out into what partly or entirely etherificate was obtained with alcohol Material, the example of the alcohol used during as etherificate, can enumerate methanol, ethyl alcohol, normal propyl alcohol, isopropanol, n-butanol, isobutyl Alcohol, 2- ethyl butanols, 2-Ethylhexyl Alcohol etc..

As amino resins (II-1), preferably melmac, wherein by part or all of methylolated melamine The methylol of resin carried out partly or entirely being etherified with methanol obtain methyl etherified melamine resin, with butanol fraction or complete Butyl etherificate melmac that portion's etherificate is obtained, the methyl-butvl obtained with methanol and butanol fraction or be all etherified are mixed Close the alkyl etherified melamine resin of etherified melamine polyimide resin etc..

In addition, melmac generally preferably has the weight average molecular weight in the range of 500~5,000, particularly preferably tool There is the weight average molecular weight in the range of 600~4,000, and then particularly preferably there is the weight average molecular weight in the range of 700~3,000.

In addition, using melmac as crosslinking agent (II) in use, p-methyl benzenesulfonic acid, detergent alkylate can be used The sulfonic acid of sulfonic acid, dinonylnaphthalene sulfonic acid etc., these acid are used as catalyst with salt formed by amine.

As enclosed type polyisocyanate compounds (II-2), can use will at least have 2 isocyanates in 1 molecule NCO oxime, phenol, alcohol, activity methene compound, lactams, the mercaptan of the polyisocyanate compounds of base etc. The material that blocking agent is obtained.

The ratio of matrix resin (I) and crosslinking agent (II), based on the solid constituent total amount both them, the former generally fits Close in the range of 40~90 mass %, be particularly suitable in the range of 50~80 mass %, the latter generally is suitable in 60~10 matter In the range of amount %, particularly preferably in the range of 50~20 mass %.

As above-mentioned coloring pigment, can for example enumerate titanium oxide, zinc oxide, carbon black, lead sulfate, calcium plumbate, trbasic zinc phosphate, It is aluminum phosphate, zinc molybdate, calcium molybdate, dark purple, ultramarine, cobalt blue, copper phthalocyanine blue, anthraquinone blue, chrome yellow, synthesizing yellow iron oxide, transparent Indian red (Huang), pucherite, titan yellow, zinc yellow, monoazo yellow, isoindolone Huang, metallic complex salt azophosphine, quinophthalone Huang, benzo Imidazolone Huang, Indian red, lead orthoplumbate, monoazo are red, quinacridone is red, azo lake (Mn salt), quinacridone magenta, anthracene Form anthrone orange, dianthraquinone red（ヅアンスラキノニルレッド）, perylenes are bright red（ペリレンマル-ン）, quinacridone product Hong, perylenes are red, diketopyrrolo-pyrrole molybdate red, chlorination phthalocyanine green, green brominated phthalocyanine, pyrazolone orange, benzimidazolone orange, two Oxazine Zi, perylene purples etc., wherein can be adapted to use titanium oxide, carbon black.

When the 1st aqueous pigmented finiss (X) contains above-mentioned coloring pigment, the use level of the coloring pigment is aqueous with the 1st On the basis of resinous principle solid constituent total amount in color coating (X), it can generally be set in the range of 1~120 mass %, preferably It is set in the range of 10~100 mass %, and then is preferably set in the range of 15~90 mass %.

In addition, as above-mentioned extender pigment, such as clay, kaolin, barium sulfate, barium carbonate, calcium carbonate, cunning can be enumerated Stone, silica, alumina white etc., wherein preferably using barium sulfate and/or talcum.

When the 1st aqueous pigmented finiss (X) contains above-mentioned extender pigment, the use level of the extender pigment is aqueous with the 1st On the basis of resinous principle solid constituent total amount in color coating (X), it can generally be set in the range of 1~100 mass %, preferably It is set in the range of 5~60 mass %, and then is preferably set in the range of 8~40 mass %.

In addition, as above-mentioned bright pigment, such as non or float type can be enumerated by aluminium (also comprising evaporation Aluminium), copper, zinc, brass, nickel, aluminum oxide, mica, titanium oxide, iron oxide covering aluminum oxide；It is oxidized what titanium, iron oxide were covered Mica, sheet glass, holography (ホ ロ グ ラ system) pigment etc., these can be used alone, or can be with two or more combinations.

When the 1st aqueous pigmented finiss (X) contains above-mentioned bright pigment, the use level of the bright pigment is with the 1st water On the basis of resinous principle solid constituent total amount in property pigmented finiss (X), it can generally be set in the range of 1~50 mass %, it is excellent Choosing is set in the range of 2~30 mass %, and then is preferably set in the range of 3~20 mass %.

1st aqueous pigmented finiss (X), it is possible to use itself known method, such as aerial spraying, airless spraying, rotation Turn the application on coated article such as atomization spraying machine, in application, additional electrostatic can also be carried out.Application thickness is to solidify film thickness gauge It is typically set in the range of 10~100 μm, is preferably set in the range of 10~50 μm, is more preferably set to 15~35 μm of scope It is interior.

It should be noted that before the aqueous pigmented finiss (Y) of application the 2nd, the 1st aqueous coloring is utilized in process (1) 1st coloring film of coating (X) formation, is preferably regulated as in the range of solid component content reaches 70~100 mass %, especially It is preferably regulated as in the range of 75~99 mass %, and then is particularly preferably adjusted in the range of 80~98 mass %.

The adjustment of above-mentioned solid component content, can be carried out by methods such as preparation heating (preheating), air injections. Pre-warmed temperature can be set in room temperature~about 100 DEG C, be preferably set to about 40~about 90 DEG C, and then it is preferably set to about 60~about 80 DEG C, the pre-warmed time can be set to 30 seconds~15 points, be preferably set to 1~10 point, and then be preferably set to 3~5 points or so.

Process (2)

The then aqueous coloring of application the 2nd on the 1st coloring film of the 1st aqueous pigmented finiss formation is utilized in process (1) Coating (Y).

2nd aqueous pigmented finiss (Y)

In the 2nd aqueous pigmented finiss (Y) used in the present invention, contain heat-curing resin composition and water, Jin Ergen Obtained according to cooperation organic solvent, coloring pigment, extender pigment, bright pigment, surface conditioner, anti-settling agent etc. is needed to use Aqueous liquid coating.

As heat-curing resin composition, can use the 1st aqueous pigmented finiss (X) was carried out explanation, with hydroxyl The hydrophilic functional group of the cross-linking functional group of base etc. and carboxyl etc., polyester resin, acrylic resin, vinylite, alcohol The friendship of the matrix resin (I) of acid resin, polyurethane etc. and, melmac, the polyisocyanate compounds that can be closed etc. Join itself known coating resin composition that agent (II) is constituted.

Wherein, as matrix resin (I), the acrylic resin (I-1) of foregoing hydroxyl and/or gathering for hydroxyl are used Ester resin (I-2), amino resins (II-1) and/or enclosed type polyisocyanate compounds (II-2) are used as crosslinking agent (II) It is suitable.

In addition, the 2nd aqueous pigmented finiss (Y), and then can individually contain as needed or combine two or more Contain common additive for coatings of curing catalysts, ultra-violet absorber, light stabilizer, defoamer, plasticiser etc. etc..

Wherein, in the 2nd aqueous pigmented finiss (Y), if using bright pigment as at least one of pigment composition, The film of metal sense or pearl sense with fine and close sense can be then formed, this is suitable.

2nd aqueous pigmented finiss (Y), it is possible to use itself known method, such as aerial spraying, airless spraying, rotation Turn atomization spraying machine etc. and carry out application, additional electrostatic is carried out in application.Application thickness is typically set to 5~40 to solidify film thickness gauge In the range of μm, it is preferably set in the range of 10~30 μm.

It should be noted that before transparent paint coating (Z), the 2nd aqueous pigmented finiss (Y) is utilized in process (2) The 2nd coloring film formed, its solid component content is preferably set to 70~100 mass % scope, is particularly preferably set to 75~99 Quality % scope, and then be particularly preferably set in the range of 80~98 mass %.

Process (3)

Coloured in process (2) using the 2nd of the 2nd aqueous pigmented finiss formation the on film, then transparent paint coating (Z).It is used as clear dope (Z), the coating composition (this coating) of application the invention described above.

Clear dope (Z) can be applied using itself known method, such as airless spraying, aerial spraying, rotary-atomizing The applications such as installation, additional electrostatic is carried out in application.Application thickness can generally be set to 10~60 μm of model to solidify film thickness gauge In enclosing, it is preferably set in the range of 25~50 μm.

Process (4)

By 3 layers of film structure of the 1st coloring film, the 2nd coloring film and the transparent coating that are formed as described above Into multilayer film, using the method that is heating and curing of common film, for example, added using Hot-blast Heating, infrared heating, high frequency Heat etc., generally can heat about 20~about 40 minutes left sides in about 80~about 170 DEG C, the temperature preferably at about 120~about 160 DEG C The right side, together solidifies it.

Embodiment

Embodiment and comparative example are exemplified below, the present invention is further specifically described.Wherein, the present invention is not only limited Due to these embodiments.It should be noted that " part " and " % " is what is obtained according to quality criteria.

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

Production Example 1

In the reaction vessel for possessing thermometer, thermostat, agitating device, reflux condenser and dropper, addition is gone Ionized water 70.7 and " ア Network ア ロ Application KH-10 " (trade name, the first industrial pharmaceutical company system, emulsifying agent, active ingredient 97%) 0.52 part, mixing is stirred in nitrogen stream, 80 DEG C are warming up to.Then, by 1% amount of the total amount in following monomer emulsions With in 6% ammonium persulfate aqueous solution, 5 parts of importing reaction vessels 80 DEG C keep 15 minutes.Then, with 3 hours by remaining monomer Emulsion, which is added drop-wise to, to be remained in mutually synthermal reaction vessel, completion of dropwise addition post curing 1 hour, then by 5% 2- (diformazans Base amino) 40 parts of ethanol water is slowly added into reaction vessel, while being cooled to 30 DEG C, filtered with the nylon cloth of 100 mesh, together When discharge, obtain the emulsion acrylic resin (I-1-1) of the hydroxyl of solid component concentration 45%.The propylene of obtained hydroxyl The acid number of acid resin is 12mgKOH/g, and hydroxyl value is 43mgKOH/g.

Monomer emulsion：Mix 50 parts of deionized water, 10 parts of styrene, 40 parts of methyl methacrylate, acrylic acid 35 parts of ethyl ester, 3.5 parts of normal-butyl methacrylate, 10 parts of HEMA, 1.5 parts of acrylic acid, ア Network ア 0.03 part of KH-101.0 parts of ロ Application and ammonium persulfate, obtain monomer emulsion.

Production Example 2

In the reaction vessel for possessing thermometer, thermostat, agitating device, reflux condenser and dropper, addition is gone 130 parts of ionized water and " 0.52 part of ア Network ア ロ Application KH-10 ", mixing is stirred in nitrogen stream, 80 DEG C are warming up to.Then, 5.3 parts of importing reaction vessels of 1% amount of the total amount in following monomer emulsions (1) and 6% ammonium persulfate aqueous solution are interior at 80 DEG C Kept for 15 minutes.Then, remaining monomer emulsion (1) is then added drop-wise to and remains mutually synthermal reaction appearance with 3 hours In device, completion of dropwise addition post curing 1 hour.Then following monomer emulsions (2) were added dropwise with 1 hour, after curing 1 hour, by 5% 40 parts of aqueous dimethylethanolamine is slowly added into reaction vessel while being cooled to 30 DEG C, is carried out with the nylon cloth of 100 mesh Filter, simultaneously discharge, obtain average grain diameter 100nm (Submicron particle size distribution devices " COULTER N4 types " (trade name, Beckman Coulter company systems), 20 DEG C are diluted in deionized water and is measured), the hydroxyl of solid component concentration 30% Emulsion acrylic resin (I-1-2).The acid number of the acrylic resin of obtained hydroxyl is 33mgKOH/g, and hydroxyl value is 25mgKOH/g。

Monomer emulsion (1)：Mix deionized water 42 parts, 0.72 part ア Network ア ロ Application KH-10, methylene bisacrylamide 21 parts of 2.1 parts of acid amides, 2.8 parts of styrene, 16.1 parts of methyl methacrylate, 28 parts of ethyl acrylate and n-butyl acrylate, Obtain monomer emulsion (1).

Monomer emulsion (2)：Mix deionized water 18 parts, 0.31 part ア Network ア ロ Application KH-10, ammonium persulfate 0.03 Part, 5.1 parts of methacrylic acid, 5.1 parts of 2- hydroxy ethyl methacrylates, 3 parts of styrene, 6 parts of methyl methacrylate, acrylic acid second 9 parts of 1.8 parts of ester and n-butyl acrylate, obtain monomer emulsion (2).

The manufacture of the polyester resin (I-2) of hydroxyl

Production Example 3

In the reaction vessel for possessing thermometer, thermostat, agitating device, reflux condenser and separator, three are added 174 parts of hydroxymethyl-propane, 327 parts of neopentyl glycol, 352 parts of adipic acid, 109 parts of isophthalic acid and 1,2- cyclohexane dicarboxylic acids acid 101 parts of acid anhydride, was warming up to after 230 DEG C with 3 hours from 160 DEG C, the utilization of condensed water separator of generation was distilled off, simultaneously 230 DEG C are maintained at, reaction reaches below 3mgKOH/g until acid number.59 parts of trimellitic anhydride is added in the reaction product, 170 DEG C of progress, 30 points of addition reactions, are then cooled to less than 50 DEG C, 2- (dimethylamino) ethanol of addition acidic group equivalent is carried out Neutralize, then slowly add deionized water, thus obtain solid component concentration 45%, pH7.2 hydroxyl polyester resin it is molten Liquid (I-2-1).The acid number of the polyester resin of obtained hydroxyl is that 35mgKOH/g, hydroxyl value are 128mgKOH/g, weight average molecular weight For 13,000.

Production Example 4

In the reaction vessel for possessing thermometer, thermostat, agitating device, reflux condenser and separator, three are added 120 parts of 109 parts of hydroxymethyl-propane, 141 parts of 1,6- hexylene glycols, 126 parts of hexahydrophthalic acid anhydride and adipic acid are simultaneously heated, small with 3 When be warming up to from 160 DEG C after 230 DEG C, 230 DEG C carry out condensation reaction in 4 hours.Then, in order to obtained condensation reaction production Thing addition carboxyl, further adds 38.3 parts of trimellitic anhydride, is reacted at 170 DEG C 30 minutes, then with 1- octanols, (boiling point is 195 DEG C of alcohols solvent) dilution, obtain the polyester resin solution (I-2-2) of the hydroxyl of solid component concentration 70%.Obtain The acid number of the polyester resin of hydroxyl is 46mgKOH/g, and hydroxyl value is 150mgKOH/g, and weight average molecular weight is 6,400.

The manufacture of 1st aqueous pigmented finiss (X)

Production Example 5

56 parts of the polyester resin solution (I-2-1) (25 parts of resin solid content) of the hydroxyl obtained in mixing Production Example 3, 60 parts of JR-806 (Tayca company systems, trade name, rutile titanium dioxide), Carbon MA-100 (Mitsubishi Chemical Ind's system, Trade name, carbon black) 1 part, BARYACEB-35 trade names, Sakai chemical industrial company system, barium sulfate powder, average primary particle diameter 0.5 μm) 15 parts, 3 parts of MICRO ACES-3 (trade name, Japanese talcum company system, talcum powder, 4.8 μm of average primary particle diameter) and go 5 parts of ionized water, is adjusted to after pH8.0 with 2- (dimethylamino) ethanol, and pigment is obtained within 30 minutes with PAINT SHAKER are scattered Scattered thickener.

Then, the acrylic acid tree of hydroxyl is obtained in 140 parts of the pigment dispersion paste material being equably mixed to get, Production Example 1 33 parts of fat liquor (I-1-1), 33 parts of the polyester resin solution (I-2-1) of the hydroxyl obtained in Production Example 3, CYMEL325 37.5 parts of (trade name, Japan's Cytec Industries company systems, melmac, solid constituent 80%), バ イ ヒ ヅ ユ-Le VPLS2310 (trade name, Sumika Bayer Urethane company systems, enclosed type polyisocyanate compounds, solid Composition 38%) 26 parts and ユ-U-ト UX-8100 (trade name, Sanyo's chemical conversion industry company system, polyaminoester emulsion, solid constituent 35%) 43 parts.

Then, UH-752 (trade name, ADEKA company systems, thickening agent), 2- (dimethyl are added in obtained mixture Amino) ethanol and deionized water, obtain pH8.0, coating solid composition 48%, the viscosity that the Ford Cup No.4 at 20 DEG C are obtained For the 1st aqueous pigmented finiss (X-1) of 30 seconds.

Production Example 6

In Production Example 5,43 parts of ユ-U-ト UX-8100 are substituted for 28.6 parts of ユ-U-ト UX-8100 and Sunnix 5 parts of PP-1000 (trade name, Sanyo's chemical conversion company system, polyoxypropylene glycol, number-average molecular weight 1000, active ingredient 100%), with Production Example 5 similarly, obtains the 1st aqueous pigmented finiss (X-2).

The Production Example of the dense liquid of bright pigment

Production Example 7

In stirring stainless steel, equably (trade name, Asahi Chemical Industry メ タ Le ズ is public by aluminum mixture pigment thickener GX-180A Department's system, metal amount 74%) 19 parts, 35 parts of 1- octanols (alcohols solvent that 195 DEG C of boiling point), the resin solution containing phosphate 8 parts of (※ 1) and 0.2 part of 2- (dimethylamino) ethanol, obtain the dense liquid of bright pigment (P-1).

The resin solution of (※ 1) containing phosphate：Possessing thermometer, thermostat, agitator, reflux condenser and dropping liquid In the reaction vessel of device, the mixed solvent of 27.5 parts of 27.5 parts of methoxypropanol and isobutanol is added, 110 DEG C are heated to, with 4 Hour added in above-mentioned mixed solvent by 25 parts of styrene, 27.5 parts of normal-butyl methacrylate, " Isostearyl 20 parts of Acrylate " (trade name, Osaka Organic Chemical Industry company system, branched one acrylate), 4- hydroxyls butyl third 7.5 parts of olefin(e) acid ester, 15 parts of the polymerizable monomer (※ 2) containing phosphate, 2- methacryloxyethyl acid phosphoric acids ester 12.5 Part, 121.5 parts of the mixture of 4 parts of compositions of 10 parts of isobutanol and tert-butyl peroxide caprylate, were then added dropwise by peroxide with 1 hour Change the mixture of 20 parts of compositions of 0.5 part of tert-butyl group caprylate and isopropanol.Then, to obtain solid constituent within 1 hour dense for stirring curing The resin solution containing phosphate of degree 50%.The acid number obtained by the phosphate of this resin is that 83mgKOH/g, hydroxyl value are 29mgKOH/g, weight average molecular weight are 10,000.

The polymerizable monomer of (※ 2) containing phosphate：Possessing thermometer, thermostat, agitator, reflux condenser and drop In the reaction vessel of liquid device, 41 parts of 57.5 parts of monobutyl phosphoric acid and isobutanol are added, is warming up to after 90 DEG C, be added dropwise with 2 hours After 42.5 parts of glycidyl methacrylate, then stirring curing 1 hour.Afterwards, 59 parts of isopropanol is added, solid is obtained The polymerizable monomer solution containing phosphate of constituent concentration 50%.The acid number obtained by the phosphate of the monomer obtained is 285mgKOH/g。

The manufacture of 2nd aqueous pigmented finiss (Y)

Production Example 8

Equably it is blended in 100 parts of emulsion acrylic resin (I-1-2), the Production Example 4 of the hydroxyl obtained in Production Example 2 The dense liquid of bright pigment (P-1) obtained in 57 parts of the polyester resin solution (I-2-2) of the hydroxyl of middle manufacture, Production Example 7 62 parts and CYMEL325 (trade name, Japanese Cytec Industries company systems, melmac, solid constituent 80%) 37.5 parts, then add PRIMAL ASE-60 (trade name, Rohm and Haas company systems, thickening agent), 2- (dimethylaminos Base) ethanol and deionized water, obtain pH8.0, coating solid composition 25%, the viscosity that the Ford Cup No.4 at 20 DEG C are obtained is The 2nd aqueous pigmented finiss (Y-1) of 40 seconds.

The manufacture of the acrylic resin (A) of hydroxyl

Production Example 9

Ethoxyl ethyl propionate is added in agitating device, thermometer, cooling tube, the four-neck flask of nitrogen inlet 31 parts, 155 DEG C are warming up under logical nitrogen.After reaching 155 DEG C, stop the ventilation of nitrogen, be added dropwise with 4 hours by styrene 30 Part, 37.5 parts of n-butyl acrylate, 30 parts of 2- hydroxypropyl acrylates, 2.5 parts of acrylic acid and the (polymerization of two t-amyl peroxy compounds Initiator) 4 parts of monomer mixtures of component proportion for constituting.After 30 minutes, it was added dropwise with 1 hour by 2,2 '-azo two (2,4- bis- Methyl valeronitrile) 0.5 part of (polymerization initiator) to be dissolved in the polymerization initiator obtained in 3 parts of SWASOL1000 (varsol) molten Liquid.Then, 100 DEG C are cooled to after being passed through nitrogen while curing 2 hours at 155 DEG C, with 29 parts of dilutions of butyl acetate, solid is obtained The acrylic resin (A1) of the hydroxyl of composition 60%.

The hydroxyl value of the acrylic resin (A1) of obtained hydroxyl is 129mgKOH/g, acid number 19mgKOH/g, weight average Molecular weight about 12000.

Production Example 10

Except by Production Example 9 by 30 parts of styrene, 37.5 parts of n-butyl acrylate, 2- hydroxypropyl acrylates 30 Part, the monomer mixture of the component proportion of 4 parts of compositions of 2.5 parts of acrylic acid and two t-amyl peroxy compounds (polymerization initiator) become

By 30 parts of styrene, 40.5 parts of n-butyl acrylate, 27 parts of 2- hydroxy ethyl methacrylates, 2.5 parts of acrylic acid and two Outside the monomer mixture of the component proportion of 4 parts of compositions of t-amyl peroxy compound (polymerization initiator), remaining is same with Production Example 9 Ground is manufactured, and obtains the acrylic resin (A2) of the hydroxyl of solid constituent 60%.

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

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

Production Example 11

In the four-neck flask with agitating device, thermometer, cooling tube and nitrogen inlet, 93 parts of heptane is added with 55% 98 parts of macromolecular dispersion stabilizer solution (※ 1) is stated, it is heated to reflux, following monomers were added dropwise with 3 hours and polymerization triggers The mixture of agent, cures, thus obtains non-aqueous dispersion type acrylic resin (D1) for 2 hours followed by aging.

(mixture of monomer and polymerization initiator)

15 parts of styrene, 40 parts of methyl methacrylate, 30 parts of acrylonitrile, 15 parts of HEMA and mistake Aoxidize the mixture of the tert-butyl group -1.5 parts of 2 ethyl hexanoic acid ester.

Obtained non-aqueous dispersion type acrylic resin (D1), is quality solid constituent concentration 53%, Gardner viscosity B, puts down The dispersion liquid of the milky stable low viscosity polymer of equal 0.2~0.3 μm of particle diameter (measure carried out using electron microscope).

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

40 parts of isobutyl acetate is added in the four-neck flask for possessing agitating device, thermometer, cooling tube, nitrogen inlet 40 parts are heated to reflux it with toluene, and with the following monomer of dropwise addition in 3 hours and the mixture of polymerization initiator, 2 are carried out after dropwise addition Hour curing, thus obtains macromolecular dispersion stabilizer solution.

(mixture of monomer and polymerization initiator)

10 parts of styrene, 49 parts of isobutyl methacrylate, 30 parts of 2- ethylhexy methacrylates, 2- ethoxys The mixture of 2 parts of 11 parts of methacrylate and azodiisobutyronitrile.

Obtained macromolecular dispersion stabilizer solution, quality solid constituent concentration 55%, Gardner viscosity G, Weight-average molecular Amount 16000.

The manufacture of clear dope (Z)

Production Example 12

110 parts of (solid constituents 60 of acrylic resin (A1) solution of the hydroxyl equably obtained in mixing Production Example 9 Part), 40 parts of polyisocyanate compounds A (note 1), Sunnix PP-1000 (trade name, Sanyo chemical conversion company system, polyoxygenated third Glycol, number-average molecular weight 1000, active ingredient 100%) 5 parts, BYK-300 (trade name, BYK company systems, surface conditioner, effectively Composition 52%) 0.2 part, TINUVIN900 (trade name, B.A.S.F. company systems, enumerate BTA system ultra-violet absorber, effectively into Divide 100%) 2.0 parts and TINUVIN292 (trade name, B.A.S.F. company systems, amine system of being obstructed light stabilizer, active ingredient 100%) 1.0 parts, SWASOL1000 (trade name, COSMO oil companies system, varsol) is added, the Ford at 20 DEG C is obtained The viscosity that CupNo.4 is obtained is the clear dope (Z-1) of 25 seconds.

(note 1) polyisocyanate compounds A：Duranate TLA-100 Asahi Chemical Industries ケ ミ カ Le ズ (strain) company system.By six The polyisocyanate compounds that methylene diisocyanate is constituted, the ratio of components of polymer be the aggressiveness of chlorinated isocyanurates 3 be 63%, Urea diketone dimer is that polymers more than 12%, other tripolymers is 25%.Solid constituent 100%, NCO content 21.8%.

Production Example 13~26

In the same manner as Production Example 12, with the coating formula shown in table 1 below, obtain at 20 DEG C by Ford The viscosity that CupNo.4 is obtained is each clear dope (Z-2)~(Z-15) of 25 seconds.Clear dope (Z-12)~(Z-15) is to compare Example is used.

It should be noted that each clear dope (Z-1)~(Z-15) of table 1 coating formula is solid constituent proportioning.

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

(note 2) polyisocyanate compounds B：ス ミ ヅ ユ-Le N-3300Sumika Bayer Urethane company systems.By The polyisocyanate compounds that hexamethylene diisocyanate is constituted, the ratio of components of polymer is that the aggressiveness of chlorinated isocyanurates 3 is 53%, polymers more than other tripolymers is 47%.Solid constituent 100%, NCO content 21.8%.

(note 3) Sunnix PP-400；Trade name, Sanyo's chemical conversion company system, polyoxypropylene glycol, number-average molecular weight 400, Active ingredient 100%

(note 4) Sunnix PP-600；Trade name, Sanyo's chemical conversion company system, polyoxypropylene glycol, number-average molecular weight 600, Active ingredient 100%

(note 5) Sunnix PP-2000；Trade name, Sanyo's chemical conversion company system, polyoxypropylene glycol, number-average molecular weight 2000, active ingredient 100%

(note 6) GP-600；Trade name, Sanyo's chemical conversion company system, polyoxy propylene glycerin ether (triol), number-average molecular weight 600, active ingredient 100%

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

(note 8) ETERNACOLL UH-50；Trade name, the emerging production company system in space portion, the makrolon based on 1,6- hexylene glycols Glycol (1,6-Hexylene Glycol Base Polycarbonatediol), number-average molecular weight 500, active ingredient 100%

(note 9) ETERNACOLL UH-200；Trade name, the emerging production company system in space portion, the makrolon based on 1,6- hexylene glycols Glycol, number-average molecular weight 2000, active ingredient 100%

(note 10) Polylite OD-X-240；Trade name, DIC company systems, PEPA, number-average molecular weight 1000 has Imitate composition 100%

Coating film-forming methods

Use the 2nd obtained in the 1st aqueous pigmented finiss (X-1)~(X-2), Production Example 8 obtained in Production Example 5 and 6 Clear dope (Z-1)~(Z-15) obtained in aqueous pigmented finiss (Y-1) and Production Example 12~26, makes respectively as follows Plate is tested, evaluation test is carried out.

(making of experiment coated article)

On the cold-rolled steel sheet for imposing trbasic zinc phosphate chemical conversion treatment, electrophoretic painting エ レ Network ロ Application GT-10 (trade name, Northwest paint company system, cation electrophoretic coating) such that dry film thickness reaches 20 μm, solidify it within 30 minutes in 170 DEG C of heating, Obtain experiment coated article 1.Experiment is that Ra is 0.21 with the surface roughness of coated article 1.

Then using the phosphoric acid zinc impregnation imposed than making experiment with the more coarse surface roughness used during coated article 1 Obtained cold-rolled steel sheet after conversion processing is learned, with experiment of in the same manner as coated article 1, is made thicker of the surface of coated article 1 than experiment Rugosity thicker experiment coated article 2.The surface roughness Ra of experiment coated article 2 is 0.38.

(making of breadboard)

Embodiment 1

Obtained in above-mentioned experiment with the above-mentioned Production Example 5 of electrostatic atomizer electrostatic spraying on coated article 1 with rotary-atomizing type Dry film thickness is reached 25 μm to the 1st aqueous pigmented finiss (X-1), after placing 2 minutes, carry out preheating for 3 minutes at 80 DEG C.

Then, the electrostatic atomizer electrostatic spraying Production Example 8 of rotary-atomizing type is used on the 1st uncured coloring film In obtained the 2nd aqueous pigmented finiss (Y-1) dry film thickness is reached 15 μm, after placing 2 minutes, carried out at 80 DEG C 3 minutes it is pre- Heating.

And then, the clear dope (Z-1) obtained on the 2nd coloring film in electrostatic spraying Production Example 12 causes desciccator diaphragm Thickness reaches 35 μm, places 7 minutes.Then, 20 minutes (retention time) is heated at 140 DEG C, colouring film, the 2nd coloring by the 1st applies Film and transparent coating be heating and curing making breadboard.

Embodiment 2~12 and comparative example 1~6

In embodiment 1, by experiment with coated article with the experiment coated article 1 or 2 shown in table 1 below, it is aqueous by the 1st Pigmented finiss (X-1) is set to the 1st aqueous pigmented finiss (X-1) shown in table 1 below or (X-2), and clear dope (Z-1) is set For any one of clear dope (Z-1)~(Z-15) for being shown in table 1 below, in addition, make similarly to Example 1 Breadboard.

Evaluation test

For each breadboard obtained in above-described embodiment 1~12 and comparative example 1~6, following test methods is utilized Evaluated.Evaluation result is shown in table 1 below in the lump.

(test method)

Flatness：Commented using by Wave Scan DOI (trade name, BYKGardner company systems) the Wc values determined Valency.Wc values are the index of the amplitude of 1~3mm of wavelength or so surface roughness, the smaller flatness for then showing painting face of measured value It is higher.

Clarity：Evaluated using using the Wave Scan DOI Wa values determined.Wa values are 0.1~0.3mm of wavelength left The index of the amplitude of right surface roughness, the smaller clarity for then showing painting face of measured value is higher.

Promote weatherability：Using Super xenon weather meter, (trade name promotes weathering tester, SUGA Testing machine company system), irradiation and condition of raining are combined under the experimental condition described in JISK5600-7-7 (method 1) Cyclic test.Have rated the cyclic test time added up to after 3000 hours, the film after then being impregnated 2 days in 40 DEG C of warm water Tack.Tack is such as evaluation of getting off, i.e. each breadboard is made on film according to JIS K5600-5-6 (1990) That makees 2mm × 2mm draws lattice 100, and the Continuous pressing device for stereo-pattern on the face is evaluated to remain on painting face after promptly peeling off and draws lattice film Number.Residual draws lattice film number for 98 above is qualified level.

It should be noted that using the embodiment 2 of clear dope (Z-2) and residual using the embodiment 5 of clear dope (Z-5) The film number 100 for drawing lattice is stayed, and can't see edge defect completely, therefore lattice film number is drawn than other residuals in embodiment The tack of the embodiment of 100 is more excellent.

Then, for the embodiment 1 using clear dope (Z-1) and the embodiment 6 using clear dope (Z-6), as Compare, also carried out following sag resistance (sagging limit thickness) and evaluated.

Sagging limit thickness：Using in the end for the long side that the experiment coated article 1 that size is 11cm × 45cm is made 3cm part starts to set diameter 5mm punching 21 with a row every 2cm, in the experiment with using rotation mist on coated article 1 The 1st aqueous pigmented finiss (X-1) obtained in the electrostatic atomizer electrostatic spraying Production Example 5 of change type so that dry film thickness reaches 25 μm, after placing 2 minutes, carry out preheating for 3 minutes at 80 DEG C.

Then, the electrostatic atomizer electrostatic spraying Production Example 8 of rotary-atomizing type is used on the 1st uncured coloring film In obtained the 2nd aqueous pigmented finiss (Y-1) such that dry film thickness reaches 15 μm, after placing 2 minutes, carried out 3 minutes at 80 DEG C Preheating.

And then, on the 2nd coloring film, with MINI BELL type rotation type atomization electrostatic atomizers with spray volume 200cc, rotating speed 40,000rpm, shape air pressure 1kg/cm², rifle apart from 30cm, to obtain long side direction be probably 30 μm~ The mode of 60 μm of thickness, with film thickness gradient transparent paint coating (Z-1), the transparent painting of application in embodiment 6 in embodiment 1 Expect (Z-6), the coated plate is nearly vertically stood, after application after 7 minutes, 20 minutes (retention time) is heated at 140 DEG C, will 1st coloring film, the 2nd coloring film and transparent coating are heating and curing, and thus make breadboard.

The position of the sagging of the punching bottom 2mm for each breadboard that research observation is obtained film, determines the position Thickness (sagging limit thickness (μm)), carries out the evaluation of sag resistance.Sagging limit thickness is more big then to represent that sag resistance is better.

Marresistance：By roof with the automobile of the water-fast tape-stripping breadboard of Nichiban company systems under conditions of 20 DEG C Carried out with car washer after 15 carwash, 20 degree of minute surface emissivity (20 ° of gloss numbers) of determination test plate, using it relative to experiment The gloss retention (%) of 20 ° of preceding gloss numbers is evaluated.The more high then marresistance of the gloss retention is better.Car washer makes With ヤ ス イ industry companies PO20FWRC.

[table 1]

Claims (6)

1. coating composition, it is characterised in that formed in the multilayer film for carrying out following processes (1)~(4) successively to coated article It is used as clear dope (Z) in method,

Process (1)：Process of the aqueous pigmented finiss (X) of application the 1st to form the 1st coloring film；

Process (2)：The aqueous pigmented finiss (Y) of application the 2nd is to form the 2nd on the 1st coloring film formed through the process (1) The process for colouring film；

Process (3)：The work of transparent paint coating (Z) formation transparent coating on the 2nd coloring film formed through the process (2) Sequence；And

Process (4)：The 1st coloring film, the 2nd coloring film and the transparent coating that will be formed through the process (1)~(3) together add The process of heat cure,

Acrylic resin (A), polyisocyanate compounds (B) and the number-average molecular weight that the coating composition contains hydroxyl exist Polyalcohol (C) in the range of 300~1500,

The polyalcohol (C) is at least one in polyalcohol (C1) and polycarbonate polyol (C2) containing polyoxyalkylene Kind, wherein the polyalcohol (C1) containing polyoxyalkylene has the alkylidene that carbon number is more than 3,

Wherein, it is total relative to the acrylic resin (A) of the hydroxyl and the solid constituent of the polyisocyanate compounds (B) Amount, the amount of the polyalcohol (C) is the mass % of 1 mass %~20, and

With the acrylic resin (A) of the hydroxyl and the polyisocyanate compounds (B) the solid constituent total amounts of both For standard, the amount of the acrylic resin (A) of the hydroxyl is the mass % of 40 mass %~85, the polyisocyanate compounds (B) amount is the mass % of 15 mass %~60.

2. coating composition according to claim 1, it is characterised in that the polyalcohol (C1) containing polyoxyalkylene It is polyoxypropylene glycol, polyoxy propylene glycerin ether or polyoxybutylene glycol.

3. coating composition according to claim 1 or 2, it is characterised in that also containing in macromolecular dispersion stabilizer and Non-aqueous dispersion type acrylic resin (D) obtained from dispersin polymerization at least one unsaturated monomer in the presence of organic solvent.

4. method of forming layered coating film, it is characterised in that carry out following processes (1)~(4) successively to coated article：

Process (1)：Process of the aqueous pigmented finiss (X) of application the 1st to form the 1st coloring film；

Process (2)：The aqueous pigmented finiss (Y) of application the 2nd is to form the 2nd on the 1st coloring film formed through the process (1) The process for colouring film；

Process (3)：Formed through the process (2) the 2nd coloring film on application as clear dope (Z) claim 1 Process of the coating composition to form transparent coating any one of~3；And

Process (4)：The 1st coloring film, the 2nd coloring film and the transparent coating that will be formed through the process (1)~(3) add simultaneously The process of heat cure.

5. method of forming layered coating film according to claim 4, it is characterised in that the coated article is applied using electro-deposition Material forms the car body of primer film.

6. the article obtained by the method for forming layered coating film application described in claim 4 or 5.