JP6416883B2 - Bright paint composition - Google Patents

Description

(Cross-reference of related fields)
This application claims the benefit of priority of Japanese Patent Application No. 2014-81250 filed on Apr. 10, 2014, the entirety of which is incorporated herein by reference.
(Technical field)
The present invention relates to a glittering coating composition that can provide a multi-layer coating film that has high flip-flop properties, little metallic unevenness, and excellent glitter.

  In recent years, in the painting of automobile bodies and the like, a finished appearance such as sharpness and smoothness has been improved, and a design with a high-class feeling has been demanded, and bright pigments such as metallic paints and interference color paints have been used. Many bright paints are used.

  As the above-mentioned coating, from the viewpoint of the appearance and production efficiency of the coating film to be formed, generally, a method of applying paint by atomizing a paint is used. As such a coating method, specifically, for example, Examples include spray coating and rotary atomization coating.

  In the case of coating by atomizing the paint, the paint used is generally low in viscosity when atomized, such as during spraying or rotary atomization, and smaller paint particles are formed. This is preferable because a coated film is formed. On the other hand, the coating viscosity is relatively high after the coating is applied to the object to be coated, so that it is difficult for the upper layer and / or the lower layer coating to mix with each other, and the coating has excellent sharpness and smoothness. It is preferable because a film is formed and the coating film is less likely to sag on the vertical surface of the object. In the case of a paint containing a bright pigment such as an aluminum pigment, if the paint viscosity is high after the paint is applied to an object, the bright pigment in the paint is difficult to flow and orientation is not easily disturbed. Therefore, it is possible to form a coating film excellent in glitter. Note that a coating film with excellent glitter generally has a remarkable change in brightness due to the observation angle when the coating film is observed at different angles, and the glitter pigment is relatively contained in the coating film. A coating film that exists uniformly and has almost no metallic unevenness. In addition, as described above, the fact that the change in the brightness depending on the observation angle is remarkable is generally said to have a high flip-flop property (FF property).

  On the other hand, as a method for forming a coating film on an automobile body or the like, an electrodeposition coating film is formed on an object to be coated, followed by intermediate coating coating → baking curing → base coating coating coating → clear coating coating coating → baking curing 3 Coat 2 bake system (3C2B process), intermediate coat paint application, base coat paint application, clear coat paint application, bake cure 3 baking 1 bake process (3C1B process) ), 2-coat 1-bake method without intermediate coating (2C1B process) in which no intermediate coating is applied on the electrodeposition coating, but base coat coating and intermediate coating and / or base coat coating and clear coating There was a problem that a mixed layer with the film occurred and the smoothness and sharpness of the resulting coating film were lowered. Further, when a paint containing a glitter pigment is used as the base coat paint, there is a problem that the mixed layer tends to cause deterioration of flip-flop properties and metallic unevenness, and it is difficult to obtain a sufficient glitter feeling.

  For example, in Patent Document 1, as an intermediate coating material and / or a metallic base coat coating material, a coating material to which crosslinkable polymer fine particles (microgel) are added is applied, and the intermediate coating material is applied and wet-on-wet method is used. A method is described in which a top coat, that is, a metallic base coat paint and a clear coat paint are applied, and an intermediate coat and a top coat are baked and cured simultaneously. The crosslinkable polymer fine particles (microgel) give a coating film appearance with relatively high clarity and gloss by suppressing the mixing of each layer. In the production of the crosslinkable polymer fine particles (microgel), First, an emulsion is produced, and the emulsion is spray-dried to obtain a microgel. Therefore, special production equipment and a complicated production process are required, which is disadvantageous from an economical viewpoint. Further, the finished appearance of the formed coating film may be insufficient.

  Patent Document 2 discloses a three coat 1 in which an intermediate paint is applied, a base coat paint and a clear coat paint are applied by a wet-on-wet method, and the intermediate coat, base coat paint and clear coat paint are simultaneously baked and cured. In the baking method, it is described that the base coat coating composition contains a hydroxyl group-containing resin, a curing agent capable of reacting with a hydroxyl group, a non-aqueous dispersion resin, and a pigment. However, there are cases where the expression of the viscosity is insufficient, and the sharpness and flip-flop properties of the formed coating film may be reduced, or metallic unevenness may occur.

Japanese Patent Laid-Open No. 10-5680 JP 2002-38096 A

  Therefore, the present invention is particularly excellent in finished appearance such as smoothness and sharpness, high flip-flop properties, little metallic unevenness, and excellent glitter, especially when coated in the 3C2B, 3C1B or 2C1B process. It is an object of the present invention to provide a glittering paint composition from which a multilayer coating film is obtained, a multilayer coating film forming method, and a glittering article coated by the method.

  As a result of intensive studies to solve the above-mentioned problems, the inventors of the present invention have obtained a glittering paint having a hydroxyl group-containing resin, a curing agent, a sulfonic acid group-containing non-aqueous dispersion resin, a basic pigment, and a glitter pigment. Depending on the composition and the glitter paint composition as the glitter base coat paint, the glitter base coat paint and the clear coat paint, or the intermediate coat paint, the glitter base coat paint and the clear coat paint are applied by wet-on-wet, The inventors have found that the above object can be achieved by a multilayer coating film forming method in which two or three layers are simultaneously heat-cured, and the present invention has been completed.

That is, the present invention provides the following glittering paint composition, multilayer coating film forming method and glittering article having the multilayer coating film.
Item 1. In the solid content ratio in which the total resin solid content of the following (A), (B) and (C) is 100 mass%, the hydroxyl group-containing resin (A) is 10 to 90 mass%, and the curing agent (B) is 5 to 50 mass%. Non-aqueous dispersion resin (C) 1 to 40% by mass, basic pigment (D) 1 to 20% by mass, and bright pigment (E) 1 to 30% by mass, the non-aqueous dispersion resin (C ) Has a structure having a core part and a shell part, and the shell part of the non-aqueous dispersion resin (C) is the total amount of the polymerizable unsaturated monomer components constituting the non-aqueous dispersion resin (C) A glittering paint composition containing 0.05 to 5.0% by mass of a sulfonic acid group-containing polymerizable unsaturated monomer based on
Item 2. Item 2. The glittering paint composition according to Item 1, wherein the core of the non-aqueous dispersion resin (C) is crosslinked.
Item 3. The core portion of the non-aqueous dispersion resin (C) is based on the total amount of polymerizable unsaturated monomer components constituting the non-aqueous dispersion resin (C), and the acid group-containing polymerizable unsaturated monomer 0.1 to 10. Item 3. The glittering paint composition according to Item 1 or 2, which contains 0% by mass.
Item 4. The sulfonic acid group-containing polymerizable unsaturated monomer constituting the shell portion of the non-aqueous dispersion resin (C) has at least one polymerizable unsaturated group, at least one sulfonic acid group, and at least one carbon number. Item 4. The glittering paint composition according to any one of Items 1 to 3, which has 4 or more hydrocarbon groups.
Item 5. Item 5. The glitter paint composition according to any one of Items 1 to 4, wherein a difference in SP value between the core portion and the shell portion of the non-aqueous dispersion resin (C) is 0.6 or more.
Item 6. Item 6. The glitter according to any one of Items 1 to 5, wherein a difference in SP value between the core portion of the non-aqueous dispersion resin (C) and the hydroxyl group-containing resin (A) is 1.0 or less. Paint composition.
Item 7. Any one of Items 1 to 6, wherein the non-aqueous dispersion resin (C) has a zeta potential of -20 mV or less, and the basic pigment (D) has a zeta potential of +1 mV or more. The glittering paint composition as described.
Item 8. A coated article coated with the glittering paint composition according to any one of Items 1 to 7.
Item 9. (1) A process of forming a base coat film by applying the glitter paint composition according to any one of Items 1 to 7 to an object to be coated;
(2) a step of applying a clear coat coating composition on the uncured base coat film to form a clear coat film; and (3) the uncured base coat film and the uncured clear coat. A method for forming a multilayer coating film comprising a step of heating a coating film to simultaneously cure two layers.
Item 10. (1) A process of forming an intermediate coating film by applying an intermediate coating composition to an object to be coated;
(2) A step of coating the glitter coating composition according to any one of Items 1 to 7 on the uncured intermediate coating film to form a base coat film,
(3) a step of applying a clear coat coating composition on the uncured base coat film to form a clear coat film; and (4) the uncured intermediate coat film and the uncured base coat. A method for forming a multilayer coating film comprising a step of heating a coating film and an uncured clear coat coating film to simultaneously cure three layers.
Item 11. Item having a multilayer coating film formed by the multilayer coating film forming method according to Item 9 or 10.
Item 12. Item having a multilayer coating film formed by the multilayer coating film forming method according to Item 10.

  The glittering paint composition of the present invention has a viscosity characteristic in which the viscosity is strongly expressed as the NV (paint solid content) increases. In addition, according to the glittering paint composition of the present invention, a glittering base coat paint and a clear coat paint, or an intermediate coat paint, a glitter base coat paint and a clear coat paint are applied on the substrate by wet-on-wet. Superb brightness with excellent smoothness and sharpness, high flip-flop properties, and reduced metallic unevenness, even when it is a multi-layer coating method that heats and cures two or three layers simultaneously. A multilayer coating film having properties can be formed.

  Hereinafter, the glittering paint composition and the multilayer coating film forming method of the present invention will be described in detail.

  In this specification, the singular forms (a, an, the) include the singular and the plural unless specifically stated otherwise herein or otherwise clearly contradicted by context.

Glittering paint composition The glittering paint composition of the present invention contains a hydroxyl group-containing resin (A), a curing agent (B), and a non-aqueous dispersion resin (C) as resins, and a basic pigment ( D) and a luster pigment (E) are contained. Further, the glittering coating composition has a solid content ratio in which the total resin solid content of the components (A), (B) and (C) is 100 mass%, and the hydroxyl group-containing resin (A) is 10 to 90 mass%, cured. Agent (B) 5-50% by mass, non-aqueous dispersion resin (C) 1-40% by mass, basic pigment (D) 1-20% by mass, and glitter pigment (E) 1-30% by mass It is contained within.

Hydroxyl-containing resin (A)
The hydroxyl group-containing resin (A) that can be used in the glittering paint composition of the present invention is not particularly limited as long as it is a hydroxyl group-containing resin existing in a dissolved state in the paint composition of the present invention. The hydroxyl group-containing resin known per se can be used. As a kind of resin, an acrylic resin, a polyester resin, an alkyd resin, a polyurethane resin etc. are mentioned, for example, 1 type can be used individually or in combination of 2 or more types. The hydroxyl group-containing resin (A) has a hydroxyl group as a crosslinkable functional group, and can have a functional group such as a carboxyl group, an amino group, a sulfonic acid group, a phosphoric acid group, and an epoxy group in addition to the hydroxyl group.

  As the hydroxyl group-containing resin (A) used in the glittering paint composition of the present invention, it is preferable to use a hydroxyl group-containing acrylic resin (A1) and / or a hydroxyl group-containing polyester resin (A2).

  The hydroxyl group-containing resin (A) preferably has a hydroxyl value of 1 to 300 mgKOH / g, more preferably 2 to 250 mgKOH / g, and still more preferably 3 to 180 mgKOH / g. When the hydroxyl group-containing resin (A) has an acid group such as a carboxyl group, the acid value is preferably 1 to 200 mgKOH / g, more preferably 2 to 150 mgKOH / g, and 3 to 100 mgKOH / g. Is more preferable.

  The compounding amount of the hydroxyl group-containing resin (A) is a solid content ratio with the total resin solid content of the components (A), (B) and (C) being 100% by mass, usually 10 to 90% by mass, preferably 15%. It is -80 mass%, More preferably, it exists in the range of 20-70 mass%.

  The presence in the paint composition in a dissolved state means that the resin has good solubility when mixed with the organic solvent component in the paint composition, and the resin is uniformly spread and transparent. . Therefore, it is clearly distinguished from the non-aqueous dispersion resin (C) that exists in a non-transparent state.

Hydroxyl group-containing acrylic resin (A1)
The hydroxyl group-containing acrylic resin (A1) is usually a hydroxyl group-containing polymerizable unsaturated monomer and another polymerizable unsaturated monomer copolymerizable with the hydroxyl group-containing polymerizable unsaturated monomer, in a manner known per se, for example, It can be produced by copolymerization by a method such as solution polymerization in an organic solvent.

  The hydroxyl group-containing polymerizable unsaturated monomer is a compound having at least one hydroxyl group and one polymerizable unsaturated bond in one molecule, such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl ( Monoesterified product of (meth) acrylic acid such as (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate and a dihydric alcohol having 2 to 8 carbon atoms; the (meth) acrylic acid Ε-caprolactone modified product of monoesterified product of C 2 and C 8 dihydric alcohol; N-hydroxymethyl (meth) acrylamide; allyl alcohol, and further having a polyoxyethylene chain whose molecular terminal is a hydroxyl group (meta ) Acrylate and the like.

  In the present specification, “(meth) acrylate” means “acrylate or methacrylate”. “(Meth) acrylic acid” means “acrylic acid or methacrylic acid”. “(Meth) acryloyl” means “acryloyl or methacryloyl”. “(Meth) acrylamide” means “acrylamide or methacrylamide”.

Moreover, the other polymerizable unsaturated monomer copolymerizable with the said hydroxyl-containing polymerizable unsaturated monomer can be suitably selected and used according to the characteristic desired for a hydroxyl-containing acrylic resin (A1). Specific examples of the monomer are listed in (i) to (xix). These can be used alone or in combination of two or more.
(I) alkyl or cycloalkyl (meth) acrylate: for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, tert-butyl (meth) acrylate, n-hexyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, tridecyl (meth) Acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) a Relate, cyclododecyl (meth) acrylate, tricyclodecanyl (meth) acrylate.
(Ii) Polymerizable unsaturated monomer having an isobornyl group: isobornyl (meth) acrylate and the like.
(Iii) Polymerizable unsaturated monomer having an adamantyl group: adamantyl (meth) acrylate and the like.
(Iv) Polymerizable unsaturated monomer having a tricyclodecenyl group: tricyclodecenyl (meth) acrylate and the like.
(V) Aromatic ring-containing polymerizable unsaturated monomers: benzyl (meth) acrylate, styrene, α-methylstyrene, vinyltoluene and the like.
(Vi) Polymerizable unsaturated monomer having an alkoxysilyl group: vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, γ- (meth) acryloyloxypropyltrimethoxysilane, γ- (meth) Such as acryloyloxypropyltriethoxysilane.
(Vii) Polymerizable unsaturated monomer having a fluorinated alkyl group: perfluoroalkyl (meth) acrylate such as perfluorobutylethyl (meth) acrylate and perfluorooctylethyl (meth) acrylate; fluoroolefin and the like.
(Viii) A polymerizable unsaturated monomer having a photopolymerizable functional group such as a maleimide group.
(Ix) Vinyl compound: N-vinyl pyrrolidone, ethylene, butadiene, chloroprene, vinyl propionate, vinyl acetate and the like.
(X) Phosphoric acid group-containing polymerizable unsaturated monomer: 2-acryloyloxyethyl acid phosphate, 2-methacryloyloxyethyl acid phosphate, 2-acryloyloxypropyl acid phosphate, 2-methacryloyloxypropyl acid phosphate and the like.
(Xi) Carboxy group-containing polymerizable unsaturated monomer: (meth) acrylic acid, maleic acid, crotonic acid, β-carboxyethyl acrylate and the like.
(Xii) Nitrogen-containing polymerizable unsaturated monomer: (meth) acrylonitrile, (meth) acrylamide, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylamino Propyl (meth) acrylamide, methylene bis (meth) acrylamide, ethylene bis (meth) acrylamide, 2- (methacryloyloxy) ethyltrimethylammonium chloride, adducts of glycidyl (meth) acrylate and amines.
(Xiii) Polymerizable unsaturated monomers having two or more polymerizable unsaturated groups in one molecule: allyl (meth) acrylate, 1,6-hexanediol di (meth) acrylate, and the like.
(Xiv) Epoxy group-containing polymerizable unsaturated monomer: glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 3,4-epoxycyclohexylethyl (meth) acrylate 3,4-epoxycyclohexylpropyl (meth) acrylate, allyl glycidyl ether and the like.
(Xv) (meth) acrylate having a polyoxyethylene chain whose molecular end is an alkoxy group.
(Xvi) polymerizable unsaturated monomer having a sulfonic acid group: 2-acrylamido-2-methylpropanesulfonic acid, 2-sulfoethyl (meth) acrylate, allylsulfonic acid, 4-styrenesulfonic acid, etc .; sodium salt of these sulfonic acids And ammonium salts.
(Xvii) polymerizable unsaturated monomer having an ultraviolet-absorbing functional group: 2-hydroxy-4- (3-methacryloyloxy-2-hydroxypropoxy) benzophenone, 2-hydroxy-4- (3-acryloyloxy-2-hydroxy) Propoxy) benzophenone, 2,2′-dihydroxy-4- (3-methacryloyloxy-2-hydroxypropoxy) benzophenone, 2,2′-dihydroxy-4- (3-acryloyloxy-2-hydroxypropoxy) benzophenone, 2- (2′-hydroxy-5′-methacryloyloxyethylphenyl) -2H-benzotriazole and the like.
(Xviii) UV-stable polymerizable unsaturated monomer: 4- (meth) acryloyloxy-1,2,2,6,6-pentamethylpiperidine, 4- (meth) acryloyloxy-2,2,6,6- Tetramethylpiperidine, 4-cyano-4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine, 1- (meth) acryloyl-4- (meth) acryloylamino-2,2,6,6 -Tetramethylpiperidine, 1- (meth) acryloyl-4-cyano-4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine, 4-crotonoyloxy-2,2,6,6- Tetramethylpiperidine, 4-crotonoylamino-2,2,6,6-tetramethylpiperidine, 1-crotonoyl-4-crotonoyloxy-2,2, , Such as 6-tetramethylpiperidine.
(Xix) polymerizable unsaturated monomer having a carbonyl group: acrolein, diacetone acrylamide, diacetone methacrylamide, acetoacetoxyethyl methacrylate, formylstyrol, vinyl alkyl ketone having 4 to 7 carbon atoms (for example, vinyl methyl ketone) , Vinyl ethyl ketone, vinyl butyl ketone) and the like.

  In the present invention, the hydroxyl group-containing acrylic resin (A1) is obtained by subjecting the polymerizable unsaturated monomers (i) to (xix) to known polymerization methods such as solution polymerization, bulk polymerization, suspension polymerization, and emulsion polymerization. It can be produced by copolymerization. For example, when the hydroxyl group-containing acrylic resin (A1) is produced by a solution polymerization method, the monomer is copolymerized in the presence of an organic solvent and a polymerization initiator.

  Examples of the organic solvent include aromatic solvents such as toluene, xylene, and “Swazole 1000” (trade name, manufactured by Cosmo Oil Co., Ltd., high boiling point petroleum solvent); ethyl acetate, 3-methoxybutyl acetate, ethylene glycol ethyl Ester solvents such as ether acetate and propylene glycol methyl ether acetate; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone and methyl amyl ketone; propyl propionate, butyl propionate and ethoxy ethyl propionate Water or various alcohols may be contained. These organic solvents can be used alone or in combination of two or more.

  Examples of the polymerization initiator include 2,2′-azobisisobutyronitrile, benzoyl peroxide, di-t-butyl peroxide, di-t-amyl peroxide, t-butyl peroctoate, 2,2 Mention may be made of radical polymerization initiators known per se, such as' -azobis (2-methylbutyronitrile). Optionally, a chain transfer agent such as 2-mercaptoethanol, n-octyl mercaptan, α-methyl styrene dimer can be used.

  As the hydroxyl group-containing acrylic resin (A1), as a part thereof, a so-called urethane-modified acrylic resin in which a polyisocyanate compound is extended to a high molecular weight by a urethanization reaction on a part of the hydroxyl groups in the resin may be used in combination. Good.

  As a weight average molecular weight (Mw) of the said hydroxyl-containing acrylic resin (A1), Preferably it is 1,000-200,000, More preferably, it is 2,000-100,000, More preferably, it is 3,000-60,000. Within range.

  In addition, the number average molecular weight (Mn) and the weight average molecular weight (Mw) of the resin in this specification are the number average molecular weight or the weight average molecular weight measured with a gel permeation chromatograph (manufactured by Tosoh Corporation, “HLC8120GPC”). It is the value converted on the basis of the molecular weight of standard polystyrene. In this measurement, four columns of “TSKgel G-4000HXL”, “TSKgel G-3000HXL”, “TSKgel G-2500HXL”, and “TSKgel G-2000HXL” (all trade names, manufactured by Tosoh Corporation) were used as the columns. The measurement conditions of phase tetrahydrofuran, measurement temperature 40 ° C., flow rate 1 mL / min, detector RI were used.

Hydroxyl-containing polyester resin (A2)
The said hydroxyl-containing polyester resin (A2) can be normally manufactured by esterification reaction or transesterification with an acid component and an alcohol component.

  As said acid component, the compound normally used as an acid component can be used at the time of manufacture of a polyester resin. Examples of the acid component include an aliphatic polybasic acid, an alicyclic polybasic acid, an aromatic polybasic acid, and the like.

  The aliphatic polybasic acid is generally an aliphatic compound having two or more carboxyl groups in one molecule, an acid anhydride of the aliphatic compound, and an esterified product of the aliphatic compound. Examples of the aliphatic polybasic acid include succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, brassic acid, octadecanedioic acid, and citric acid. Aliphatic polyvalent carboxylic acid; anhydride of the aliphatic polyvalent carboxylic acid; esterified product of lower alkyl having about 1 to 4 carbon atoms of the aliphatic polyvalent carboxylic acid. The above aliphatic polybasic acids can be used alone or in combination of two or more.

  The alicyclic polybasic acid is generally a compound having one or more alicyclic structures and two or more carboxyl groups in one molecule, an acid anhydride of the compound, and an esterified product of the compound. The alicyclic structure is mainly a 4- to 6-membered ring structure. Examples of the alicyclic polybasic acid include 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 4-cyclohexene-1,2-dicarboxylic acid, 3-methyl- An alicyclic polycarboxylic acid such as 1,2-cyclohexanedicarboxylic acid, 4-methyl-1,2-cyclohexanedicarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, 1,3,5-cyclohexanetricarboxylic acid; An anhydride of an alicyclic polyvalent carboxylic acid; an esterified product of a lower alkyl having about 1 to 4 carbon atoms of the alicyclic polyvalent carboxylic acid. The said alicyclic polybasic acid can be used individually or in combination of 2 or more types.

  The aromatic polybasic acid is generally an aromatic compound having two or more carboxyl groups in one molecule, an acid anhydride of the aromatic compound, and an esterified product of the aromatic compound, for example, phthalic acid , Isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, 4,4′-biphenyldicarboxylic acid, trimellitic acid, pyromellitic acid, and other aromatic polycarboxylic acids; anhydrides of the aromatic polyvalent carboxylic acids; aromatics Examples include esterified products of lower alkyl having about 1 to 4 carbon atoms of polyvalent carboxylic acids. The aromatic polybasic acids can be used alone or in combination of two or more.

  Moreover, acid components other than the said aliphatic polybasic acid, alicyclic polybasic acid, and aromatic polybasic acid can also be used. Such acid component is not particularly limited, for example, coconut oil fatty acid, cottonseed oil fatty acid, hemp seed oil fatty acid, rice bran oil fatty acid, fish oil fatty acid, tall oil fatty acid, soybean oil fatty acid, linseed oil fatty acid, tung oil fatty acid, rapeseed oil fatty acid, Fatty acids such as castor oil fatty acid, dehydrated castor oil fatty acid, safflower oil fatty acid; lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, benzoic acid, p-tert-butylbenzoic acid, cyclohexane Examples thereof include monocarboxylic acids such as acid and 10-phenyloctadecanoic acid; hydroxycarboxylic acids such as lactic acid, 3-hydroxybutanoic acid, and 3-hydroxy-4-ethoxybenzoic acid. These acid components can be used alone or in combination of two or more.

  As said alcohol component, the polyhydric alcohol which has a 2 or more hydroxyl group in 1 molecule can be used conveniently. Examples of the polyhydric alcohol include ethylene glycol, propylene glycol, diethylene glycol, trimethylene glycol, tetraethylene glycol, triethylene glycol, dipropylene glycol, 1,4-butanediol, 1,3-butanediol, 2,3 -Butanediol, 1,2-butanediol, 3-methyl-1,2-butanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,2-pentanediol, 1,5-pentanediol 1,4-pentanediol, 2,4-pentanediol, 2,3-dimethyltrimethylene glycol, tetramethylene glycol, 3-methyl-4,3-pentanediol, 3-methyl-1,5-pentanediol, 2,2,4-trimethyl-1,3-pentane 1,6-hexanediol, 1,5-hexanediol, 1,4-hexanediol, 2,5-hexanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, tricyclodecane dimethanol, water Dihydric alcohols such as hydrogenated bisphenol A and hydrogenated bisphenol F; polylactone diols obtained by adding lactones such as ε-caprolactone to these dihydric alcohols; ester diols such as bis (hydroxyethyl) terephthalate; alkylenes of bisphenol A Oxide adducts, polyether diols such as polyethylene glycol, polypropylene glycol, polybutylene glycol; glycerin, trimethylolethane, trimethylolpropane, diglycerin, triglycerin, 1,2,6- Trivalent or higher alcohols such as hexanetriol, pentaerythritol, dipentaerythritol, tris (2-hydroxyethyl) isocyanuric acid, sorbitol, mannitol; lactones such as ε-caprolactone are added to these trivalent or higher alcohols And polylactone polyols.

  Moreover, alcohol components other than the said polyhydric alcohol can also be used. The alcohol component is not particularly limited, and examples thereof include monoalcohols such as methanol, ethanol, propyl alcohol, butyl alcohol, stearyl alcohol, and 2-phenoxyethanol; propylene oxide, butylene oxide, “Cardura E10” (trade name, HEXION Specialty Chemicals Examples thereof include alcohol compounds obtained by reacting monoepoxy compounds such as glycidyl esters of synthetic hyperbranched saturated fatty acids) and acids.

  It does not specifically limit as a manufacturing method of a hydroxyl-containing polyester resin (A2), According to a well-known method, it can carry out. For example, by heating the acid component and the alcohol component in a nitrogen stream at about 150 to 250 ° C. for about 5 to 15 hours, and performing an esterification reaction and / or a transesterification reaction of the acid component and the alcohol component. A hydroxyl group-containing polyester resin can be produced.

  When the acid component and the alcohol component are esterified and / or transesterified, they may be added to the reaction vessel at one time, or one or both may be added in several portions. Also good. Moreover, after synthesizing a hydroxyl group-containing polyester resin, the resulting hydroxyl group-containing polyester resin may be reacted with an acid anhydride and half-esterified to obtain a carboxyl group- and hydroxyl group-containing polyester resin. First, after synthesizing a carboxyl group-containing polyester resin, the alcohol component may be added to obtain a hydroxyl group-containing polyester resin.

  In the esterification or transesterification reaction, as a catalyst for promoting the reaction, dibutyltin oxide, antimony trioxide, zinc acetate, manganese acetate, cobalt acetate, calcium acetate, lead acetate, tetrabutyl titanate, tetraisopropyl Known catalysts such as titanates can be used.

  The hydroxyl group-containing polyester resin (A2) can be modified with a fatty acid, a monoepoxy compound, a polyisocyanate compound or the like during or after the preparation of the resin.

  Examples of the fatty acid include coconut oil fatty acid, cottonseed oil fatty acid, hemp seed oil fatty acid, rice bran oil fatty acid, fish oil fatty acid, tall oil fatty acid, soybean oil fatty acid, linseed oil fatty acid, tung oil fatty acid, rapeseed oil fatty acid, castor oil fatty acid, dehydrated castor Examples include oil fatty acids and safflower oil fatty acids.

  As the monoepoxy compound, for example, “Cardura E10” (trade name, manufactured by HEXION Specialty Chemicals, glycidyl ester of synthetic highly branched saturated fatty acid) can be suitably used.

  Examples of the polyisocyanate compound include aliphatic diisocyanates such as lysine diisocyanate, hexamethylene diisocyanate, and trimethylhexane diisocyanate; hydrogenated xylylene diisocyanate, isophorone diisocyanate, methylcyclohexane-2,4-diisocyanate, methylcyclohexane-2,6. Alicyclic diisocyanates such as diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate), 1,3- (isocyanatomethyl) cyclohexane; aromatic diisocyanates such as tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate; lysine Organic polyisocyanates such as triisocyanates and higher polyisocyanates such as triisocyanates Itself; adducts of these organic polyisocyanates with polyhydric alcohols, low molecular weight polyester resins, water, etc .; cyclized polymers of these organic polyisocyanates (for example, isocyanurates), biuret type adducts, etc. Can be mentioned. These polyisocyanate compounds can be used alone or in combination of two or more.

  The hydroxyl group-containing polyester resin (A2) has a number average molecular weight (Mn) of preferably 500 to 50,000, more preferably 1,000 to 30,000, and still more preferably 1,200 to 10,000. is there.

Curing agent (B)
The curing agent (B) used in the glittering paint composition of the present invention reacts with a crosslinkable functional group such as a hydroxyl group, a carboxyl group, and an epoxy group in the hydroxyl group-containing resin (A) to cure the coating composition. The resulting compound. Examples of the curing agent (B) include amino resins, polyisocyanate compounds, blocked polyisocyanate compounds, epoxy group-containing compounds, carboxyl group-containing compounds, carbodiimide group-containing compounds, and the like. Alternatively, two or more kinds can be used in combination. Of these, amino resins, polyisocyanate compounds and / or blocked polyisocyanate compounds capable of reacting with hydroxyl groups are preferred, amino resins and / or blocked polyisocyanate compounds are more preferred, and amino resins are particularly preferred.

  As said amino resin, the partial methylolation amino resin obtained by reaction of an amino component and an aldehyde component, or a complete methylolation amino resin can be used. Examples of the amino component include melamine, urea, benzoguanamine, acetoguanamine, steroguanamine, spiroguanamine, dicyandiamide and the like. Examples of the aldehyde component include formaldehyde, paraformaldehyde, acetaldehyde, and benzaldehyde.

  Moreover, what methylated the methylol group of the said methylolated amino resin partially or completely with suitable alcohol can also be used. Examples of the alcohol used for etherification include methyl alcohol, ethyl alcohol, n-propyl alcohol, i-propyl alcohol, n-butyl alcohol, i-butyl alcohol, 2-ethyl-1-butanol, and 2-ethyl-1. -Hexanol and the like.

  As said amino resin, a melamine resin is preferable. In particular, methyl ether melamine resins in which methylol groups of partially or fully methylolated melamine resins are partially or completely etherified with methyl alcohol, methylol groups of partially or fully methylolated melamine resins are partially or completely with butyl alcohol. Preferred is a methyl-butyl mixed etherified melamine resin in which the methylol group of a partially or completely methylolated melamine resin is partially or completely etherified with methyl alcohol and butyl alcohol. Etherified melamine resins are more preferred.

  The melamine resin preferably has a weight average molecular weight of 400 to 6,000, more preferably 500 to 4,000, and still more preferably 600 to 3,000.

  A commercially available product can be used as the melamine resin. Examples of commercially available product names include “Cymel 202”, “Cymel 203”, “Cymel 204”, “Cymel 211”, “Cymel 238”, “Cymel 251”, “Cymel 303”, “Cymel 323”, “Cymel 324”, “Cymel 325”, “Cymel 327”, “Cymel 350”, “Cymel 385”, “Cymel 1156”, “Cymel 1158”, “Cymel 1116”, “Cymel 1130” , "Uban 120", "Uban 20HS", "Uban 20SE60", "Uban 2021", "Uban 2028", "Uban 28-60" (above, Mitsui Chemicals).

  When a melamine resin is used as the curing agent (B), sulfonic acids such as paratoluenesulfonic acid, dodecylbenzenesulfonic acid, dinonylnaphthalenesulfonic acid, alkyl phosphate esters; these acidic compounds and basic compounds And the like can be used as catalysts.

  The blocked polyisocyanate compound is an addition reaction product of a polyisocyanate compound and an isocyanate blocking agent in a substantially theoretical amount. As the polyisocyanate compound used in the blocked polyisocyanate compound, known compounds can be used without particular limitation, and examples thereof include tolylene diisocyanate, xylylene diisocyanate, phenylene diisocyanate, diphenylmethane-2,2′-diisocyanate, Diphenylmethane-2,4′-diisocyanate, diphenylmethane-4,4′-diisocyanate, crude MDI [polymethylene polyphenyl isocyanate], bis (isocyanate methyl) cyclohexane, tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, isophorone diisocyanate, etc. Aromatic, aliphatic or alicyclic polyisocyanate compounds; cyclization weight of these polyisocyanate compounds Body or biuret thereof; or a combination thereof can be mentioned.

  On the other hand, the isocyanate blocking agent is added and blocked to the isocyanate group of the polyisocyanate compound, and the blocked polyisocyanate compound produced by the addition is stable at room temperature, but the baking temperature of the coating film (usually about When heated to 100 to about 200 ° C., it is desirable that the blocking agent dissociates to regenerate free isocyanate groups. As the blocking agent used in the above-mentioned blocked polyisocyanate compound, known ones can be used without particular limitation. For example, oxime compounds such as methyl ethyl ketoxime and cyclohexanone oxime; phenol, para-t-butylphenol, cresol Phenolic compounds such as n-butanol, 2-ethylhexanol, phenyl carbinol, methyl phenyl carbinol, alcohol compounds such as ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, ethylene glycol, propylene glycol; ε-caprolactam, γ -Lactam compounds such as butyrolactam; active compounds such as dimethyl malonate, diethyl malonate, ethyl acetoacetate, methyl acetoacetate, acetylacetone Examples include a tylene-based compound (preferably an alcohol-based compound), and these can be used alone or in combination of two or more.

  The compounding quantity of the said hardening | curing agent (B) is a solid content ratio which makes the resin solid content total amount of component (A), (B) and (C) 100 mass%, and is 5-50 mass% normally, Preferably it is 10-10. It is 45 mass%, More preferably, it exists in the range of 15-40 mass%.

Non-aqueous dispersion resin (C)
The glittering coating composition of the present invention contains a non-aqueous dispersion resin (C) that exists in an insoluble state (opaque state) in the coating composition.

  The non-aqueous dispersion resin (C) has a core and shell structure, that is, a structure having a core part and a shell part, and usually comprises a core part having a high SP value and a shell part having a low SP value. Since the core portion has a high SP value (high polarity), it is insoluble in the organic solvent in the paint, and the swelling rate by the solvent can be reduced. Furthermore, the mixed layer with the intermediate coating or the clear coating can prevent the appearance of the coating film from being deteriorated and the flip-flop property from being deteriorated and / or the occurrence of metallic unevenness due to the disorder in the orientation of the glitter pigment. The shell portion having a low SP value (low polarity) serves as a dispersion stabilizer.

  Here, the SP value (solubility parameter) is also called a solubility parameter, and is a scale indicating the degree of hydrophilicity (high polarity) or hydrophobicity (low polarity) of the resin. In addition, it is an important measure for judging compatibility between resins, and resins with similar solubility parameter values (small absolute values of solubility parameter differences) are generally compatible with each other. It becomes good. The solubility parameter value (SP value) of the acrylic resin obtained by copolymerization of at least two kinds of monomers can be calculated by the following formula (1).

SP value = SP ₁ × f _W1 + SP ₂ × f _W2 +... + SP _n × f _Wn ... Formula (1)

In the above formula (1), SP ₁ , SP ₂ ,... SP _n represents the SP value of the homopolymer of each monomer, and f _W1 , f _{W2 ,.} Represents a rate. The SP value of the homopolymer of the monomer is J. Paint Technology, vol. 42, 176 (1970).

The SP value of a resin other than an acrylic resin (for example, a polyester resin) can be numerically quantified based on a turbidity measurement method known to those skilled in the art as described below.
Specifically, the following formula (2), K.I. W. SUH, J. et al. M.M. The SP value can be calculated according to the CORBETT equation (Journalof Applied Polymer Science, 12, 2359, 1968).

(In the formula, V _H represents the volume fraction of n-hexane, V _D represents the volume fraction of deionized water, δ _H represents the SP value of n-hexane, and δ _D represents the SP value of deionized water.)
In the cloud point titration, 0.5 g of resin (solid content) as a sample was dissolved in 10 ml of tetrahydrofuran, n-hexane was gradually added, and the titration amount H (ml) at the cloud point was read. Min) was dissolved in 10 ml of tetrahydrofuran, and the titration amount D (ml) at the turbidity point by adding deionized water was read and applied to the following formula (3) to obtain V _H , V _D , δ _H , δ _D is calculated. In addition, SP value of each solvent is tetrahydrofuran: 9.52, n-hexane: 7.24, deionized water: 23.43.

[V _H = H / (10 + H), V _D = D / (10 + D), δ _H = 9.52 × 10 / (10 + H) + 7.24 × H / (10 + H), δ _D = 9.52 × 10 / (10 + D) + 23.43 × D / (10 + D)] Equation (3)

  The non-aqueous dispersion resin (C) used in the glittering paint composition of the present invention is obtained by dispersing and polymerizing at least one polymerizable unsaturated monomer in the presence of the polymer dispersion stabilizer (S1) and an organic solvent. An acrylic resin is preferable. Here, the polymer dispersion stabilizer (S1) becomes a shell portion having a low SP value, and the acrylic resin obtained by polymerizing the polymerizable unsaturated monomer becomes a core portion having a high SP value.

  In the production of the resin (C), as the polymer dispersion stabilizer (S1) serving as the shell portion, a long-chain polymerizable unsaturated monomer (s-1) and a sulfonic acid group-containing polymerizable unsaturated monomer (s- A polymer obtained by copolymerizing 2) with another polymerizable unsaturated monomer (s-3) optionally used can be used.

  The long-chain polymerizable unsaturated monomer (s-1) can be appropriately selected according to the performance required for the coating film, but can be preferably used from the viewpoints of copolymerizability and solubility in organic solvents. Examples of the unsaturated monomer (s-1) include the following.

  For example, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, n-octyl (meth) acrylate, lauryl (meth) C4-C18 alkyl or cycloalkyl ester of (meth) acrylic acid such as acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate; methoxybutyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxybutyl ( Alkoxyalkyl esters of (meth) acrylic acid such as meth) acrylate; esters of aromatic alcohol such as benzyl (meth) acrylate with (meth) acrylic acid; glycidyl (meth) acrylate or (meth) ) Adducts of hydroxyalkyl esters of acrylic acid with monocarboxylic acid compounds such as capric acid, lauric acid, linoleic acid, and oleic acid; Adducts of (meth) acrylic acid with monoepoxy compounds such as “Cardiula E10”; Polyester macromonomer in which about 1.0 polymerizable unsaturated group is introduced into the molecule by adding a self-condensing polyester of a fatty acid containing a hydroxyl group such as 12-hydroxystearic acid and glycidyl acrylate or glycidyl methacrylate; , Α-methylstyrene, vinyltoluene, p-chlorostyrene, pt-butylstyrene, etc. vinyl aromatic compounds; itaconic acid, itaconic anhydride, crotonic acid, maleic acid, maleic anhydride, fumaric acid, citraconic acid, etc. Α, β-unsaturated carboxylic acids other than (meth) acrylic acid Mono- or diester compounds of C 4-18 monoalcohols such as butyl alcohol, pentyl alcohol, heptyl alcohol, octyl alcohol, stearyl alcohol; “Biscoat 8F”, “Biscoat 8FM”, “Biscoat 3F”, “Biscoat 3FM” (All of them are manufactured by Osaka Organic Chemical Co., Ltd., trade names, (meth) acrylate compounds having a fluorine atom in the side chain), fluorine atom-containing compounds such as perfluorocyclohexyl (meth) acrylate, perfluorohexylethylene, etc. be able to.

  Examples of the sulfonic acid group-containing polymerizable unsaturated monomer (s-2) include vinyl sulfonic acid, sulfoethyl (meth) acrylate, 2-acrylamido-2-methylpropane sulfonic acid, allyl sulfonic acid, styrene sulfonic acid, and these Examples thereof include sulfonic acid group-containing polymerizable unsaturated monomers having at least one polymerizable unsaturated group and at least one sulfonic acid group, such as alkali metal salts and ammonium salts.

  Among them, as the sulfonic acid group-containing polymerizable unsaturated monomer (s-2), at least one polymerizable unsaturated group and at least one sulfone are preferable from the viewpoints of resin production suitability, storage stability, and flip-flop properties. Those having an acid group and at least one hydrocarbon group having 4 or more carbon atoms, preferably 6 or more carbon atoms are preferred. For example, a sulfonic acid group-containing polymerizable unsaturated monomer (s-2) represented by the following formula (I): -1) is preferred.

(Wherein R ₁ has a hydrocarbon group having 4 or more carbon atoms)
The hydrocarbon group (R ₁ ) of the sulfonic acid group-containing polymerizable unsaturated monomer (s-2-1) is more preferably in the range of 6 to 30 carbon atoms, and 8 to 8 carbon atoms. A range of 25 is particularly preferred.

Examples of the sulfonic acid group-containing polymerizable unsaturated monomer (s-2-1) include oleyl 2-hydroxy- [3-allyloxy] -propylsulfosuccinate ammonium salt [wherein R ₁ carbon number in the above formula (I) is About 18]. These sulfonic acid group-containing polymerizable unsaturated monomers (s-2) can be used alone or in combination of two or more.

  As content of the said sulfonic-acid-group-containing polymerizable unsaturated monomer (s-2), in a shell part on the basis of the total amount of the polymerizable unsaturated monomer component which comprises non-aqueous dispersion resin (C), it is set to 0. 05-5 mass% is preferable, 0.1-4 mass% is more preferable, 0.2-3 mass% is especially preferable. When the amount is less than the above range, a suitable flip-flop property may not be obtained. When the amount is more than the above range, the finish may be deteriorated.

  Although it does not specifically limit as said other polymerizable unsaturated monomer (s-3), For example, carbon number of (meth) acrylic acid, such as methyl (meth) acrylate, ethyl (meth) acrylate, and propyl (meth) acrylate 1 to 3 alkyl esters; adducts of glycidyl (meth) acrylate and monocarboxylic acid compounds having 2 to 3 carbon atoms such as acetic acid and propionic acid; itaconic acid, itaconic anhydride, crotonic acid, maleic acid, maleic anhydride Mono- or diester compounds of α, β-unsaturated carboxylic acids other than (meth) acrylic acid such as fumaric acid and citraconic acid, and mono-alcohols having 1 to 3 carbon atoms such as methyl alcohol and propyl alcohol; (meth) acrylonitrile Cyano group-containing unsaturated compounds such as vinyl ester compounds such as vinyl acetate; Examples include vinyl ether compounds such as til vinyl ether and methyl vinyl ether; α-olefin compounds such as ethylene, propylene, vinyl chloride, and vinylidene chloride. Other polymerizable unsaturated monomers (s-3) are listed above, such as 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and the like. Also included are those in which a polymerizable unsaturated monomer is substituted with a hydroxyl group or the like.

  Blending of the above long-chain polymerizable unsaturated monomer (s-1), sulfonic acid group-containing polymerizable unsaturated monomer (s-2), and other polymerizable unsaturated monomer (s-3) optionally used The amount is preferably 0.1 to 80 mass with respect to the long-chain polymerizable unsaturated monomer (s-1) based on the total amount of the polymerizable unsaturated monomer components constituting the non-aqueous dispersion resin (C). %, More preferably 0.5 to 65% by mass, particularly preferably 1.0 to 50% by mass. The sulfonic acid group-containing polymerizable unsaturated monomer (s-2) is preferably 0.05 to 5% by mass, more preferably 0.1 to 4% by mass, and particularly preferably 0.2 to 3% by mass. . The other polymerizable unsaturated monomer (s-3) is preferably 0 to 80% by mass, more preferably 0.5 to 65% by mass, and particularly preferably 1.0 to 50% by mass.

  Blending of the above long-chain polymerizable unsaturated monomer (s-1), sulfonic acid group-containing polymerizable unsaturated monomer (s-2), and other polymerizable unsaturated monomer (s-3) optionally used The total amount is preferably 10 to 90% by mass, more preferably 20 to 70% by mass, based on the total amount of the polymerizable unsaturated monomer components constituting the non-aqueous dispersion resin (C).

  In addition, the total amount of the polymerizable unsaturated monomer component is preferably 50 to 100% by mass, more preferably 75 to 95% by mass in the non-aqueous dispersion resin (C).

  The polymerization for producing the polymer dispersion stabilizer (S1) can usually be carried out using a radical polymerization initiator. Examples of the radical polymerization initiator include azo initiators such as 2,2′-azobisisobutyronitrile and 2,2′-azobis (2,4-dimethylvaleronitrile); benzoyl peroxide, lauryl peroxide, and peroxide initiators such as t-butyl peroctoate and t-butyl peroxy-2-ethylhexanoate. These polymerization initiators are generally 0 per 100 parts by mass of the monomer used for polymerization. .About 2 to 10 parts by mass, preferably 0.5 to 5 parts by mass. The reaction temperature during the polymerization is usually about 60 to 160 ° C., and the reaction time during the polymerization is usually about 1 to 15 hours.

  The copolymer used as the polymer dispersion stabilizer (S1) usually has a weight average molecular weight of about 5,000 to 100,000, preferably about 5,000 to 50,000. Use of a copolymer having a molecular weight in the above range as a dispersion stabilizer is preferable because stabilization of the dispersed particles can suppress aggregation and sedimentation and can provide a paint that is easy to handle without being too high in viscosity.

  Further, as the shell part of the non-aqueous dispersion resin (C) used in the glittering paint composition of the present invention, in addition to the polymer dispersion stabilizer (S1), a sulfonic acid group-containing polymerizable unsaturated monomer is used as a constituent component. It is preferable to use other dispersion stabilizer (S2) in combination.

As the other dispersion stabilizer (S2), known ones conventionally used in the field of non-aqueous dispersion can be used without limitation, and examples thereof include the following (1) to (9). .
(1) A polyester macromonomer in which about 1.0 polymerizable unsaturated groups are introduced into a molecule by adding a self-condensed polyester of a fatty acid containing a hydroxyl group such as a hydroxy acid and glycidyl acrylate or glycidyl methacrylate.
(2) A comb polymer obtained by copolymerizing the polyester macromonomer (1), methyl methacrylate and / or other (meth) acrylic acid ester, and vinyl monomer.
(3) A copolymer obtained by copolymerizing a small amount of glycidyl (meth) acrylate in the above (2), and later adding (meth) acrylic acid to the glycidyl group to introduce an unsaturated group.
(4) A hydroxyl group-containing acrylic copolymer obtained by copolymerizing at least 20% of (meth) acrylic acid ester of monoalcohol having 4 or more carbon atoms.
(5) Introducing 0.3 or more unsaturated groups per molecule on the basis of number average molecular weight in (4) above. For example, a method of copolymerizing a small amount of glycidyl (meth) acrylate in the original acrylic copolymer and then adding (meth) acrylic acid to the glycidyl group can be mentioned. .
(6) Alkylmelamine resin with high mineral spirit tolerance.
(7) An alkyd resin having a fatty acid content of 15% or more and / or one having a polymerizable unsaturated group introduced thereto. Examples of a method for introducing a polymerizable unsaturated group include a method of adding glycidyl (meth) acrylate to a carboxyl group in an alkyd resin.
(8) Oil-free polyester resin having a high mineral spirit tolerance, alkyd resin having a fatty acid content of 15% or more, and / or one having a polymerizable unsaturated group introduced therein.
(9) Cellulose acetate butyrate having a polymerizable unsaturated group introduced therein. Examples of a method for introducing a polymerizable unsaturated group include a method of adding isocyanate ethyl methacrylate to cellulose acetate butyrate.

  As the other dispersion stabilizer (S2), from the viewpoint of dispersion stability and storage stability, the dispersion stabilizer of (3) can be preferably used. It can be used suitably. As the hydroxy acid, dimethylolbutanoic acid, dimethylolpropionic acid, 12-hydroxystearic acid, and the like can be used. Among them, 12-hydroxystearic acid is preferably used from the viewpoint of dispersion stability. be able to. Moreover, as content in the case of containing a hydroxy acid, it is a component of a hydroxy acid on the basis of the total amount of the polymerizable unsaturated monomer component which comprises a shell part, and 0-15.0 mass% is preferable. 0-13.0 mass% is more preferable.

  The blending ratio (S1 / S2) of the polymer dispersion stabilizer (S1) and the other dispersion stabilizer (S2) is a solid content ratio in which the total resin solid content in the shell part is 100% by mass. The range of 0-20 / 80 is preferable, and the range of 80 / 20-40 / 60 is more preferable.

  In the production of the non-aqueous dispersion resin (C), at least one polymerization is carried out in an organic solvent in the presence of the polymer dispersion stabilizer (S1) and optionally another dispersion stabilizer (S2) optionally used together. The unsaturated unsaturated monomer (c-1) is copolymerized to prepare a polymer to be a core part, and a non-aqueous dispersion of polymer particles insoluble in the organic solvent is prepared.

  As an organic solvent used for the polymerization, polymer particles produced by the polymerization are not substantially dissolved, but with respect to the polymer dispersion stabilizer (S1) and the polymerizable unsaturated monomer (c-1). Includes an organic solvent which is a good solvent. Specific examples of such organic solvents include aliphatic hydrocarbon solvents such as hexane, heptane, and octane; aromatic hydrocarbons such as benzene, toluene, and xylene; methyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, octyl Alcohol solvents such as alcohol; ether solvents such as cellosolve, butyl cellosolve, diethylene glycol monobutyl ether; ketone solvents such as methyl isobutyl ketone, diisobutyl ketone, methyl ethyl ketone, methyl hexyl ketone, ethyl butyl ketone; ethyl acetate, isobutyl acetate, amyl acetate And ester solvents such as 2-ethylhexyl acetate. These organic solvents can be used alone or in combination of two or more.

  As the organic solvent, in particular, those mainly composed of aliphatic hydrocarbons and suitably combined with aromatic hydrocarbons, alcohol solvents, ether solvents, ketone solvents, ester solvents and the like are preferably used. Can do.

  The polymerizable unsaturated monomer (c-1) that is subjected to the above polymerization and serves as a constituent component of the core part is excellent in polymerizability and has the carbon number of the monomer used as the monomer component of the polymer dispersion stabilizer (S1). It is preferable to use a polymerizable unsaturated monomer having a carbon number smaller than that in view of easy formation as dispersed polymer particles.

  Examples of such polymerizable unsaturated monomers include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, and t-butyl (meth). ) Acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, n-octyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate and the like of (meth) acrylic acid C1-C18 alkyl or cycloalkyl ester; alkoxyalkyl ester of (meth) acrylic acid such as methoxybutyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxybutyl (meth) acrylate, etc. Ester of aromatic alcohol such as benzyl (meth) acrylate with (meth) acrylic acid; glycidyl (meth) acrylate and acetic acid, propionic acid, oleic acid, pt-butylbenzoic acid and the like having 2 to 18 carbon atoms Adducts with monocarboxylic acid compounds; adducts with (meth) acrylic acid and monoepoxy compounds such as “Kardura E10”; styrene, α-methylstyrene, vinyltoluene, p-chlorostyrene, pt- Vinyl aromatic compounds such as butylstyrene; α, β-unsaturated carboxylic acids and methyl other than (meth) acrylic acid such as itaconic acid, itaconic anhydride, crotonic acid, maleic acid, maleic anhydride, fumaric acid, citraconic acid C1-C18 monoal, such as alcohol, butyl alcohol, hexyl alcohol, stearyl alcohol Mono or diester compound with Cole; “Biscoat 8F”, “Biscoat 8FM”, “Biscoat 3F”, “Biscoat 3FM” (both manufactured by Osaka Organic Chemical Co., Ltd., trade name, fluorine atom in side chain (meta ) Acrylate compounds), fluorine atom-containing compounds such as perfluorocyclohexyl (meth) acrylate, perfluorohexylethylene; cyano group-containing unsaturated compounds such as (meth) acrylonitrile; vinyl acetate, vinyl benzoate, “VEOVA” Vinyl ester compounds such as (manufactured by Shell); vinyl ether compounds such as n-butyl vinyl ether, ethyl vinyl ether and methyl vinyl ether; and α-olefin compounds such as ethylene, propylene, vinyl chloride and vinylidene chloride. it can

  Self-reactive polymerizable unsaturated monomers such as N-alkoxymethylated acrylamide and γ-methacryloxytrialkoxysilane, allyl (meth) acrylate, ethylene glycol di (meth) acrylate, and 1,6-hexanediol The inside of the particle is cross-linked by copolymerizing a monomer having two or more polymerizable unsaturated groups such as di (meth) acrylate, methylenebis (meth) acrylamide, or pentaerythritol tetra (meth) acrylate to form gelled particles. be able to. These polymerizable unsaturated monomers can be used alone or in combination of two or more.

  As described above, the monomer component that forms the polymer particles in the core is stably formed by using a monomer having a carbon number smaller than that of the monomer component used in the polymer dispersion stabilizer (S1). From this point of view, it contains a (meth) acrylic acid ester compound, a vinyl aromatic compound, (meth) acrylonitrile, an acid group-containing polymerizable unsaturated monomer having 8 or less carbon atoms, preferably 4 or less carbon atoms. Among them, it is particularly preferable to contain (meth) acrylic acid. In addition, when an acid group-containing polymerizable unsaturated monomer is contained as a constituent component of the core part, the content of the acid group-containing polymerizable unsaturated monomer is the polymerizable unsaturated monomer constituting the non-aqueous dispersion resin (C). Based on the total amount of the monomer components, 0.1 to 10.0% by mass is preferable, 0.5 to 8.0% by mass is more preferable, and 1.0 to 5.0% by mass is particularly preferable.

  The polymerization of the polymerizable unsaturated monomer (c-1) is usually performed using a radical polymerization initiator. Examples of usable radical polymerization initiators include azo initiators such as 2,2′-azobisisobutyronitrile and 2,2′-azobis (2,4-dimethylvaleronitrile); benzoyl peroxide, lauryl And peroxide initiators such as peroxide, t-butylperoctoate, t-butylperoxy-2-ethylhexanoate, and the like. These polymerization initiators are generally 100 parts by mass of monomers used for polymerization. It can be used within a range of about 0.2 to 10 parts by mass, preferably 0.5 to 5 parts by mass.

  The use ratio of the polymer dispersion stabilizer (S1) and the polymerizable unsaturated monomer (c-1) to be present during the polymerization is usually polymerizable with respect to 100 parts by mass of the polymer dispersion stabilizer (S1). The amount of the unsaturated monomer (c-1) is about 3 to 240 parts by mass, preferably about 10 to 160 parts by mass. Furthermore, the total concentration of the polymer dispersion stabilizer (S1) and the polymerizable unsaturated monomer (c-1) in the organic solvent is usually about 30 to 70% by mass, preferably about 30 to 60% by mass. . Polymerization of the polymerizable unsaturated monomer (c-1) can be carried out by a method known per se, the reaction temperature during the polymerization is usually about 60 to 160 ° C., and the reaction time during the polymerization is usually about 1 to 15 hours. It is.

  By performing the polymerization reaction as described above, the liquid phase is a solution in which the polymer dispersion stabilizer (S1) is dissolved in an organic solvent, and the solid phase is a polymerized polymer obtained by polymerizing the polymerizable unsaturated monomer (c-1). A stable non-aqueous dispersion of a non-aqueous dispersion type acrylic resin that is a coalesced particle can be obtained. The average particle size of the polymer particles is usually in the range of about 0.01 to 1.0 μm. By setting the average particle diameter of the polymer particles in the above range, it is preferable because the viscosity of the non-aqueous dispersion does not become too high and swelling or aggregation of the polymer particles during storage of the paint can be suppressed.

  The particle diameter of the non-aqueous dispersion resin (C) was measured with a “COULTER N4 type submicron particle analyzer” (trade name, manufactured by Beckman Coulter, Inc.).

  In the production of the non-aqueous dispersion resin (C), the storage stability of the non-aqueous dispersion and the polymer dispersion stabilizer (S1) in the non-aqueous dispersion are combined with the polymer particles in the core. It is preferable to improve the mechanical properties.

  Examples of a method for binding the polymer dispersion stabilizer (S1) and the polymer particles in the core include, for example, a hydroxyl group, an acid group, an acid anhydride group, an epoxy in the stage of producing the polymer dispersion stabilizer (S1) in advance. A hydroxyl group or an acid group that reacts with the above functional group as a monomer component that forms a polymer particle by partially copolymerizing a monomer component having a functional group such as a group, a methylol group, an isocyanate group, an amide group, or an amino group. , By using a monomer having a functional group such as an acid anhydride group, an epoxy group, a methylol group, an isocyanate group, an amide group, or an amino group. Examples of these combinations include an isocyanate group and a hydroxyl group, an isocyanate group and a methylol group, an epoxy group and an acid (anhydrous) group, an epoxy group and an amino group, an isocyanate group and an amide group, and an acid (anhydrous) group and a hydroxyl group. Can do.

  Examples of the monomer having such a functional group include (meth) acrylic acid, crotonic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, fumaric acid, and citraconic acid. Saturated carboxylic acids; glycidyl group-containing compounds such as glycidyl (meth) acrylate, vinyl glycidyl ether, allyl glycidyl ether; (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N-alkoxymethyl (meth) acrylamide, diacetone Carboxylic acid amide compounds such as acrylamide and N-methylol (meth) acrylamide; containing sulfonic acid amide groups such as p-styrenesulfonamide, N-methyl-p-styrenesulfonamide, and N, N-dimethyl-p-styrenesulfonamide Compound; (meta ) Amino group-containing compounds such as acrylic acid-t-butylaminoethyl; condensates of 2-hydroxyethyl (meth) acrylate and phosphoric acid or phosphate ester compounds, compounds having a glycidyl group such as glycidyl (meth) acrylate Phosphoric acid group-containing compounds such as those obtained by adding phosphoric acid or phosphoric acid ester compounds to glycidyl groups; sulfonic acid group-containing compounds such as 2-acrylamido-2-methyl-propanesulfonic acid; m-isopropenyl-α, α -An equimolar adduct of dimethylbenzyl isocyanate, isophorone diisocyanate or tolylene diisocyanate and hydroxy (meth) acrylate, an isocyanate group-containing compound such as isocyanoethyl methacrylate, and the like.

  As another method for bonding the polymer dispersion stabilizer (S1) and the polymer particles, a polymerizable unsaturated monomer is polymerized in the presence of the polymer dispersion stabilizer (S1) having a polymerizable unsaturated group. Can be done.

  For example, polymerizable unsaturated groups are introduced into the polymer dispersion stabilizer (S1) by using an acid group-containing monomer such as carboxylic acid, phosphoric acid or sulfonic acid as a copolymerization component of the resin, The reaction can be carried out by reacting a glycidyl group-containing polymerizable unsaturated monomer such as (meth) acrylate or allyl glycidyl ether. Conversely, it can also be carried out by allowing a polymer dispersion stabilizer (S1) to contain a glycidyl group and reacting it with an acid group-containing polymerizable unsaturated monomer. These reactions can be performed according to known conditions.

  Further, as another method for bonding the polymer dispersion stabilizer (S1) and the polymer particles in the core part, a non-reactive functional group is introduced into the polymer dispersion stabilizer (S1) and the polymer particles. It can also be carried out by preparing an aqueous dispersion and then reacting it with a binder that binds both.

  Specifically, for example, a hydroxyl group-containing polymerizable unsaturated monomer is polymerized alone or as a mixture with another polymerizable unsaturated monomer in the presence of a hydroxyl group-containing polymer dispersion stabilizer and an organic solvent, and the polymer dispersion stabilizer is obtained. And a polymer particle, a non-aqueous dispersion containing a hydroxyl group is prepared, and then mixed with a polyisocyanate compound and reacted at room temperature for several hours to several days at about 60 to 100 ° C. for about 1 to 5 hours. Can be done.

  Any polyisocyanate compound may be used as long as it has two or more isocyanate groups in the molecule. For example, aromatic diisocyanates such as tolylene diisocyanate, xylylene diisocyanate, 4,4′-diphenylmethane diisocyanate, or hydrides thereof. An aliphatic diisocyanate such as hexamethylene diisocyanate, lysine diisocyanate, dimer acid (dimer of tall oil fatty acid) diisocyanate; and an alicyclic diisocyanate such as isophorone diisocyanate.

  In addition to the above, polymer dispersion stabilizers containing acid groups and combinations of polymer particles and polyepoxides, polymer dispersion stabilizers containing epoxy groups and combinations of polymer particles and polycarboxylic acids, epoxy groups Alternatively, a polymer dispersion stabilizer containing an isocyanate group and a combination of polymer particles and a polysulfide compound can also be used.

  Examples of the polyepoxide include bisphenol A type epoxy resin, bisphenol F type epoxy resin, novolac type epoxy resin, and epoxy group-containing acrylic resin; examples of the polycarboxylic acid include adipic acid, sebacic acid, azelaic acid, and isophthalic acid; Examples of polysulfide include pentamethylene disulfide, hexamethylene disulfide, poly (ethylene disulfide), and the like.

  As described above, the polymer dispersion stabilizer (S1) and the polymer particles can be chemically bonded. At this time, various functional groups and / or polymerizable unsaturated groups are bonded to the polymer dispersion stabilizer. It is sufficient that the amount introduced into the polymerizable particles is an amount that averages at least 0.1 per molecule of the dispersion stabilizer and / or particles.

  The non-aqueous dispersion obtained in this way is excellent in storage stability and formed because the polymer dispersion stabilizer (S1) in the shell and the polymer particles in the core are chemically bonded. The coated film can exhibit excellent chemical and mechanical properties.

  The core / shell ratio of the non-aqueous dispersion resin (C) is usually 90/10 to 10/90 in mass ratio, preferably 80/20 to 30/70, and 70/30 to 40/60. More preferred.

  In addition, the blending amount of the non-aqueous dispersion resin (C) is from the viewpoint of finished appearance such as coating workability (sag resistance) of the obtained coating composition and smoothness of the coated surface of the obtained coating film, and glitter From the solid content ratio in which the total amount of resin solids of components (A), (B) and (C) is 100% by mass, usually 1 to 40% by mass, preferably 3 to 28% by mass, more preferably 6 to 6%. It is in the range of 20% by mass.

  Since the non-aqueous dispersion resin (C) used in the glittering paint composition of the present invention has a sulfonic acid group in the shell portion, the paint is particularly covered by acid-base interaction with the basic pigment (D) described later. Viscosity develops strongly when NV rises after being applied to the coating. Therefore, it is possible to obtain a multilayer coating film having excellent finished appearance such as smoothness and sharpness, excellent flip-flop property, little metallic unevenness and excellent glitter.

  Moreover, in order to strengthen the viscosity expression by acid-base interaction, the zeta potential of the non-aqueous dispersion resin (C) is usually −20 mV or less, preferably −30 mV or less, more preferably −40 mV or less. is there.

  The zeta potential is determined by the following equation (4) of Helmholtz-Smoluchowski after measuring the moving speed of particles by electrophoresis.

Zeta potential (ζ) = ηV / εE (4)
[Η: viscosity (poise), V: moving speed (cm / sec), ε: dielectric constant, E: electric field (V / cm)]

  In the present specification, the zeta potential means a value measured by a dynamic light scattering measurement method after adding 100 mL of deionized water to 5 g of particles and dispersing for 1 hour with an ultrasonic vibrator. For example, LASER ZEE MODEL501 manufactured by PemKem can be used for the measurement of the zeta potential.

  The non-aqueous dispersion resin (C) used in the coating composition of the present invention is insoluble in the resin and solvent in the coating composition, and usually has a particle size of usually 0.01 to 1.0 μm, 0.05 -0.5 micrometer is preferable and 0.09-0.25 micrometer is still more preferable.

  In addition, the glitter paint composition of the present invention has an SP value from the viewpoint of the suitability for production of the resin (C), the compatibility of the hydroxyl group-containing resin (A) and the resin (C), and the finish of the multilayer coating film. The difference in SP value between the core portion and the shell portion of the non-aqueous dispersion resin (C) is preferably 0.6 or more, and the difference in SP value between the core portion and the hydroxyl group-containing resin (A) is 1 0.0 or less is preferable.

Basic pigment (D)
The basic pigment (D) used in the glittering paint composition of the present invention has a pH in the range of 7.0 to 13.0 by measuring the hydrogen ion concentration of a liquid in which the pigment is suspended in distilled water. It is. Since the pH of the basic pigment is governed by the surface state of the pigment itself, solubility, production conditions, surface treatment agent, and the like, for example, even when the same white pigment is titanium dioxide, the pH is, for example, 4. Since it may be greatly different from 0 to 10.0, it is actually determined by measuring pH whether it is an acidic pigment, a neutral pigment or a basic pigment.

  The basic pigment (D) is a pigment other than the glitter pigment described later, and is a colored pigment (for example, a white pigment, a blue pigment, a green pigment, a red pigment, a yellow pigment, an orange pigment, a purple pigment) or a transparent pigment. Or a non-transparent extender pigment etc. are mentioned, These can be used individually by 1 type or in combination of 2 or more types.

  Among them, it is preferable to contain at least one basic extender pigment (D1), and as the basic extender pigment, it is more preferable to contain basic hydrous aluminum silicate and / or basic barium sulfate. It is further particularly preferable to contain barium.

  The basic extender pigment (D1) can be used without particular limitation. Examples of the commercially available basic hydrous aluminum silicate include Silicolloid P87 and Siritin Z86 manufactured by Hoffman Mineral Co., Ltd., and examples of commercially available basic barium sulfate include Varifine BF manufactured by Sakai Chemical Industry Co., Ltd. -10, Varifine BF-20, and the like.

  In addition, the zeta potential of the basic pigment (D) is preferably +1 mV or more, and more preferably +3 mV or more, because of the viscous expression due to the acid-base interaction with the non-aqueous dispersion resin (C). More preferably, it is +5 mV or more.

  The blending amount of the basic pigment (D) is a solid content ratio in which the total resin solid content of the components (A), (B) and (C) in the glitter paint is 100% by mass, and usually 1 to 20%. It is in the range of 5% by mass, preferably 3-18% by mass, more preferably 5-15% by mass.

Bright pigment (E)
The glitter pigment (E) used in the glitter paint composition of the present invention is a pigment that imparts glittering glitter or light interference pattern to the coating film, and is distinguished from the basic pigment (D). . Specifically, for example, aluminum (including vapor-deposited aluminum), copper, zinc, brass, nickel, aluminum oxide, mica, mica coated with titanium oxide or iron oxide, aluminum oxide coated with titanium oxide or iron oxide And so on. Among these, aluminum, mica, mica coated with titanium oxide or iron oxide, and aluminum oxide coated with titanium oxide or iron oxide are preferable, and aluminum is more preferable. These pigments can be used alone or in combination of two or more.

  The glitter pigment (E) is preferably flake shaped. As the flake-like glitter pigment, those having a longitudinal dimension of usually 1 to 100 μm, particularly 5 to 40 μm, and a thickness of usually 0.001 to 5 μm, particularly 0.01 to 2 μm, are preferably used. it can.

  The blending amount of the glitter pigment (E) is a solid content ratio in which the total resin solid content of the components (A), (B), and (C) in the glitter paint is 100% by mass, and usually 1-30. It is in the range of mass%, preferably 2 to 25 mass%, more preferably 3 to 20 mass%.

  In one preferred embodiment, the glittering coating composition of the present invention comprises a hydroxyl group-containing resin (A) in a solid content ratio in which the total resin solid content of the following (A), (B) and (C) is 100% by mass. ) 10 to 90% by mass, curing agent (B) 5 to 50% by mass, non-aqueous dispersion resin (C) 1 to 40% by mass, basic pigment (D) 1 to 20% by mass, and glitter pigment (E 1) to 30% by mass, the hydroxyl group-containing resin (A) is a hydroxyl group-containing acrylic resin, a hydroxyl group-containing polyester resin, or a combination thereof, and the curing agent (B) is an amino resin, a polyisocyanate compound, or a blocked polyisocyanate. 1 type or 2 types or more selected from a compound, an epoxy group-containing compound, a carboxyl group-containing compound, and a carbodiimide group-containing compound, and the non-aqueous dispersion resin (C) Part and a shell part, the core part has a copolymer of at least one polymerizable unsaturated monomer (c-1), and the shell part has a long-chain polymerizable unsaturated monomer (s- 1), a polymer comprising a polymer obtained by copolymerizing a sulfonic acid group-containing polymerizable unsaturated monomer (s-2) and an optional other polymerizable unsaturated monomer (s-3). The sulfonic acid has a dispersion stabilizer (S1) and the shell part of the non-aqueous dispersion resin (C) is based on the total amount of polymerizable unsaturated monomer components constituting the non-aqueous dispersion resin (C). It contains 0.05 to 5.0% by mass of the group-containing polymerizable unsaturated monomer (s-2). Preferably, the polymerizable unsaturated monomer (c-1) as a constituent component of the core part is a polymerizable unsaturated monomer having a carbon number smaller than that of the monomer used as the monomer component of the polymer dispersion stabilizer (S1). It is a saturated monomer.

Other Components The glittering paint composition of the present invention comprises a hydroxyl group-containing resin (A), a curing agent (B), a non-aqueous dispersion resin (C), a basic pigment (D), and a glittering pigment (E). A coating composition as an essential component, which usually contains an organic solvent, and optionally, a resin other than the hydroxyl group-containing resin (A) and the curing agent (B), and the non-aqueous dispersion resin (C). Other than rheology control agent components, pigments other than basic pigment (D) and glitter pigment (E), curing catalyst, pigment dispersant, leveling agent, ultraviolet absorber, light stabilizer, plasticizer, etc. Additives for paints used in the field can optionally be included.

Next, a method for forming a multilayer coating film using the glittering paint composition of the present invention is described below. As the coating film forming method of the present invention, the following two methods can be suitably used.
(Method 1) 2 coat 1 bake method (2C1B process)
1-1. A step of forming a base coat film by applying the glitter paint composition of the present invention to an object to be coated;
1-2. A step of applying a clear coat coating composition on the uncured base coat film to form a clear coat film, and 1-3. A method for forming a multilayer coating film comprising a step of heating the uncured base coat film and the uncured clear coat film to simultaneously cure two layers.
(Method 2) 3-coat 1-bake method (3C1B process)
2-1. A process of forming an intermediate coating film by applying an intermediate coating composition to an object to be coated;
2-2. A step of coating the glitter coating composition of the present invention on the uncured intermediate coating film to form a base coat film,
2-3. A step of applying a clear coat coating composition on the uncured base coat film to form a clear coat film, and 2-4. A method for forming a multilayer coating film comprising a step of heating the above-mentioned uncured intermediate coating film, uncured base coat film and uncured clear coat film to simultaneously cure three layers.

  As the object to be coated, conventionally known materials such as metal materials, plastic materials and composites thereof can be used without particular limitation, for example, an electrodeposition-cured coating film formed on an automobile body subjected to chemical conversion treatment. Can be used. In addition, as the above-mentioned (Method 1) to be coated, an electrodeposition-cured coating is coated with an intermediate coating and cured by heating. In this case, a 3-coat 2-bake method ( 3C2B process).

  The intermediate coating material, the glitter base coating material, and the clear coating material can be applied by an ordinary coating method, for example, electrostatic atomization coating or non-electrostatic atomization coating. As the atomization method, a rotary atomization method or an air atomization method can be used.

  As the intermediate coating material, a conventionally known coating material can be used without particular limitation, but a melamine-curing organic solvent-based coating material or an isocyanate-curing organic solvent-based coating material is preferable. The thickness of the intermediate coating film after curing is preferably about 5 to 30 μm. When the intermediate coating is applied, it is allowed to stand at room temperature for several minutes, or is pre-dried for several minutes at about 50 to 80 ° C.

  Next, the glittering base coat paint which is the glittering paint composition of the present invention is applied onto the article to be coated or the intermediate coating film. The film thickness after curing of the glittering base coat film is usually 5 to 30 μm, preferably 7 to 25 μm, more preferably 10 to 20 μm. After the glittering base coat paint is applied, it is allowed to stand at room temperature for several minutes or pre-dried at about 50 to 80 ° C. for several minutes, and then the clear coat paint is applied.

  As the clear coat paint, a conventionally known paint can be used without any particular limitation, but an acid / epoxy curable organic solvent type paint, an isocyanate curable organic solvent type paint or a melamine curable organic solvent type paint is preferred. The film thickness of the clear coat film after curing is usually 15 to 60 μm, preferably 10 to 50 μm, more preferably 15 to 45 μm. Moreover, the heating for hardening a multilayer coating film is normally performed at about 120-180 degreeC for about 20-90 minutes.

  Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. However, the present invention is not limited to only these examples. “Part” and “%” are based on mass.

Production and production example 1 of hydroxyl group-containing acrylic resin (A1) solution
In a reaction vessel equipped with a thermometer, thermostat, stirrer, reflux condenser, nitrogen inlet tube, and dropping device, 30 parts of “Swazol 1000” (trade name, manufactured by Maruzen Petrochemical Co., Ltd., petroleum aromatic hydrocarbon solvent) And heated to 110 ° C. while blowing nitrogen, and at the same temperature, 10 parts of styrene, 50 parts of methyl methacrylate, 28 parts of n-butyl acrylate, 4 parts of the following phosphoric acid group-containing polymerizable monomer solution, and 2, A monomer mixture consisting of 1.5 parts of 2′-azobisisobutyronitrile (AIBN) was added dropwise over 4 hours. After completion of the dropping, the mixture was aged for 1 hour, and then a mixture of 15 parts of butyl acetate and 1.0 part of 2,2′-azobisisobutyronitrile was added dropwise to the reaction vessel over 1 hour. After completion of dropping, the mixture was aged for 1 hour and diluted with methyl ethyl ketone to obtain a hydroxyl group-containing acrylic resin (A1-1) solution having a solid content of 50%. The obtained hydroxyl group-containing acrylic resin (A1-1) had an acid value of 6 mgKOH / g, a hydroxyl value of 48 mgKOH / g, and a weight average molecular weight of 20,000.

  Phosphoric acid group-containing polymerizable monomer solution: put 57.5 parts of monobutyl phosphoric acid and 41 parts of isobutanol in a reaction vessel equipped with a thermometer, thermostat, stirrer, reflux condenser, nitrogen gas inlet tube and dropping device. Then, 42.5 parts of glycidyl methacrylate was added dropwise over 2 hours, and the mixture was further aged and stirred for 1 hour. Thereafter, 59 parts of isopropanol was added to obtain a phosphate group-containing polymerizable monomer solution having a solid content concentration of 50%. The acid value of the obtained monomer was 285 mgKOH / g.

Production example 2 of hydroxyl group-containing polyester resin (A2) solution
In a reaction vessel equipped with a thermometer, thermostat, stirrer, reflux condenser and water separator, 69 parts 1,2-cyclohexanedicarboxylic anhydride, 86 parts 1,4-cyclohexanedicarboxylic acid, 1,6-hexanediol 59 parts, 25 parts of ethylene glycol and 13 parts of trimethylolpropane were charged, and the temperature was raised from 160 ° C. to 230 ° C. over 3 hours, and then the condensed water was kept at 230 ° C. while being distilled off by a water separator. The reaction was continued until the value was 6 mgKOH / g. Next, it was diluted with a mixed solvent of xylene / “Swazol 1000” (trade name, manufactured by Maruzen Petrochemical Co., Ltd., petroleum aromatic hydrocarbon solvent) = 50/50 (mass ratio) so as to have a solid content concentration of 70%. Then, a hydroxyl group-containing polyester resin (A2-1) solution was obtained. The obtained hydroxyl group-containing polyester resin (A2-1) had an acid value of 6 mgKOH / g, a hydroxyl value of 56 mgKOH / g, and a number average molecular weight of 3,000.

Production Example 3 of Nonaqueous Dispersion Resin (C) Solution
In a four-necked flask equipped with a stirrer, a thermometer, a condenser tube and a nitrogen gas inlet, 60 parts of heptane, 60 parts of xylene, 75 parts of the following polymer dispersion stabilizer (S1-1) solution (Note 1), and 10 parts of other dispersion stabilizer (S2-1) solution (Note 3) was charged, and the temperature was raised to 100 ° C. while blowing nitrogen. Next, 51 parts of the following core monomer composition (Note 4) was added dropwise over 3 hours, and further aged for 2 hours to obtain a non-aqueous dispersion resin (C-1) solution. The obtained non-aqueous dispersion resin (C-1) had a solid content of 40%, an average particle size of 146 μm, and a zeta potential of −55 mV. The core / shell ratio was 50/50, the SP value of the shell part was 9.0, and the SP value of the core part was 9.9.
(Note 1) Polymer dispersion stabilizer (S1-1) solution In a four-necked flask equipped with a stirrer, thermometer, water separator and nitrogen gas inlet, oleyl 2-hydroxy- (3-allyloxy) -propyl 2.05 parts of sulfosuccinate ammonium salt and 30 parts of xylene were charged, and the temperature was raised to 130 ° C. while water was distilled off by a water separator. Then, 16.3 parts of methyl methacrylate, 3.3 parts of methyl acrylate, 10.4 parts of n-butyl acrylate, 5.3 parts of 2-ethylhexyl acrylate, 5.5 parts of 2-hydroxyethyl acrylate, and t-butylperoxy- A mixture of 2.5 parts of 2-ethylhexanoate was added dropwise over 3 hours, and the mixture was further aged for 1 hour. Thereafter, 2.15 parts of a macromonomer (IPDI-HEA) (Note 2) was added, and further aging was performed for 4 hours to obtain a polymer dispersion stabilizer (S1-1) solution having a solid content of 60%.
(Note 2) Macromonomer (IPDI-HEA)
In a reaction vessel equipped with a thermometer, thermostat, stirrer, reflux condenser and air blowing device, 888 parts (4 moles) of isophorone diisocyanate, 464 parts (4 moles) of 2-hydroxyethyl acrylate and 0.7 parts of hydroquinone monomethyl ether While blowing air into the reaction vessel, the temperature was raised to 80 ° C. and maintained at that temperature for 5 hours. After confirming that all of the added 2-hydroxyethyl acrylate had reacted, isophorone diisocyanate and 2 -Macromonomer (IPDI-HEA) which is an adduct of hydroxyethyl acrylate was obtained.
(Note 3) Other dispersion stabilizer (S2-1) solution 12-hydroxy with a methanesulfonic acid as a catalyst in a four-necked flask equipped with a stirrer, thermometer, condenser, and nitrogen gas inlet under reflux of toluene. Stearic acid was dehydrated and condensed until the resin acid value was 30. Glycidyl methacrylate was added to the terminal carboxyl group of the resulting self-condensed polyester having a number average molecular weight of about 1,800 to add a polymerizable unsaturated group using dimethylaminoethanol as a catalyst, and polymerizable unsaturated group having a solid content of 70%. A group-containing macromonomer solution was obtained. The obtained polymerizable unsaturated group-containing macromonomer had about 1 polymerizable unsaturated group based on the number average molecular weight per molecule. Next, 174 parts of butyl acetate was placed in the flask and heated to reflux. In this, 297 parts of the above 70% polymerizable unsaturated group-containing macromonomer solution, 195.9 parts of methyl methacrylate, 18.5 parts of glycidyl methacrylate, xylene A mixture of 163 parts and 9.6 parts of 2,2′-azobisisobutyronitrile was added dropwise at a uniform rate over 3 hours, followed by further aging for 2 hours. Subsequently, a mixture of 0.05 part of pt-butylcatechol, 3.8 parts of methacrylic acid and 0.5 part of dimethylaminoethanol was added to the flask, and the resin acid value reached 0.5 at 140 ° C. for about 5 hours. The reaction was continued to obtain another dispersion stabilizer (S2-1) solution having a solid content of 50%. The obtained other dispersion stabilizer (S2-1) is a graft polymer having a segment of 12-hydroxystearic acid and a segment of a copolymer of methyl methacrylate and glycidyl methacrylate, and an average of about 4 per molecule. Having one polymerizable unsaturated group.
(Note 4) Core monomer composition Styrene 12.5 parts, methyl methacrylate 12.44 parts, methyl acrylate 5 parts, acrylonitrile 5 parts, 2-hydroxyethyl acrylate 12.5 parts, glycidyl methacrylate 0.5 parts, methacrylic acid 2 0.06 part and a mixture of 1.0 part of 2,2′-azobisisobutyronitrile.

Production Examples 4 to 20
According to the composition shown in Table 1 below, non-aqueous dispersion resins (C-2) to (C-18) having a solid content of 40% were obtained in the same manner as in Production Example 3. Regarding the non-aqueous dispersion resin (C-14), the core monomer composition was dropped into the flask without blending the polymer dispersion stabilizer and other dispersion stabilizers.
In addition, the compounding quantity in following Table 1 is the value of solid content or an active ingredient. In addition, with respect to the non-aqueous dispersion resins (C-14) and (C-18), no zeta potential and particle size were measured because lumps (aggregates) were generated.

(Note 5) KBM-503: Trade name, manufactured by Shin-Etsu Chemical Co., Ltd., 3-methacrylooxypropyltrimethoxysilane (Note 6) Light ester P-1M: Trade name, manufactured by Kyoeisha Chemical Co., Ltd., acid phosphoxyethyl methacrylate .

Production Example 1 of Glittering Paint Composition
18 parts of hydroxyl group-containing acrylic resin (A1-1) solution obtained in Production Example 1 (9 parts of resin solid content), 12.9 parts of hydroxyl group-containing polyester resin (A2-1) solution obtained in Production Example 2 (resin solid content) 9 parts), “Varifine BF-20” (trade name, manufactured by Sakai Chemical Industry Co., Ltd., fine particle barium sulfate, zeta potential 6 mV, pH 9, basic pigment) 10 parts and xylene 20 parts were placed in a wide-mouth glass bottle, and glass beads Was added and sealed, and after dispersing for 60 minutes with a paint shaker, the glass beads were removed to obtain a pigment dispersion paste.
Next, 60.9 parts of the obtained pigment dispersion paste, 32 parts of the hydroxyl group-containing acrylic resin (A1-1) solution obtained in Production Example 1, and 30 parts of the hydroxyl group-containing polyester resin (A2-1) solution obtained in Production Example 2 "Uban 28-60" (trade name, butyl etherified melamine resin, manufactured by Mitsui Chemicals, solid content 60%, curing agent), 50 parts of non-aqueous dispersion resin (C-1) solution, "GX -180A "(trade name, manufactured by Asahi Kasei Metals Corporation, aluminum pigment paste, aluminum content 74%, glitter pigment) 13.5 parts," Nacure 4167 "(trade name, manufactured by King Industries, amine salt of alkyl phosphate ester 4 parts of active ingredient 25%) was mixed uniformly. Next, a mixed solvent of xylene / “Swazole 1000” (trade name, manufactured by Maruzen Petrochemical Co., Ltd., petroleum aromatic hydrocarbon solvent) = 50/50 (mass ratio) was added, and the Ford Cup No. 20 at 20 ° C. was added. The viscosity of 4 was adjusted to 12 seconds to obtain a glittering paint (X-1) composition.

Examples 2-16 and Comparative Examples 1-10
According to the formulation shown in Table 2 below, Ford Cup No. Thus, bright paints (X-2) to (X-26) solutions having a viscosity of 4 according to 12 seconds were obtained. In addition, the compounding quantity of following Table 2 is the value of solid content or an active ingredient. In addition, for the glittering paint compositions (X-17) and (X-21), the paint state is due to the solids (aggregates) brought in from the non-aqueous dispersion resins (C-14) and (C-18). It was judged as “bad”, and subsequent coating and coating film evaluation were not performed.

(Note 7) Siritin Z86: trade name, manufactured by Hoffman Minerals, basic hydrous aluminum silicate, zeta potential 1 mV, pH: 8, basic pigment.

Preparation and production example 21 of article
A thermosetting epoxy resin-based cationic electrodeposition coating composition (trade name “Electron GT-10”, manufactured by Kansai Paint Co., Ltd.) is applied to a 30 cm × 45 cm zinc phosphate-treated cold rolled steel sheet so as to have a film thickness of 20 μm. It was electrodeposited and cured by heating at 170 ° C. for 30 minutes. Thus, an article to be coated H-1 formed by forming an electrodeposition coating film on the steel plate was produced.

Production Example 22
A thermosetting epoxy resin-based cationic electrodeposition coating composition (trade name “Electron GT-10”, manufactured by Kansai Paint Co., Ltd.) is applied to a 30 cm × 45 cm zinc phosphate-treated cold rolled steel sheet so as to have a film thickness of 20 μm. It was electrodeposited and cured by heating at 170 ° C. for 30 minutes. Next, an intermediate coating composition (trade name “TP-65-3”, manufactured by Kansai Paint Co., Ltd., polyester resin / amino resin organic solvent type coating composition) is formed on the electrodeposition coating film to a film thickness of 35 μm. And cured by heating at 140 ° C. for 30 minutes. Thus, an article to be coated H-2 formed by forming an electrodeposition coating film and an intermediate coating film on a steel plate was produced.

Test plate preparation Example 17
An intermediate coating composition (trade name “TP-65-3”, manufactured by Kansai Paint Co., Ltd., polyester resin / amino resin organic solvent type) is applied on the electrodeposition coating film of the object H-1 obtained in Production Example 21. The coating composition was applied so that the film thickness of the cured coating film was 25 μm, allowed to stand for 5 minutes, and then preheated at 80 ° C. for 5 minutes. After setting for 7 minutes, the glitter coating composition (X-1) is applied onto the uncured coating surface using a rotary atomizing bell-type coating machine so that the film thickness of the cured coating film becomes 15 μm. After painting and setting for 2 minutes, preheating was performed at 80 ° C. for 5 minutes. Next, an acrylic resin-based organic solvent-type clear coat coating composition (trade name “Magicron KINO-1210”, manufactured by Kansai Paint Co., Ltd.) is applied on the uncured coating surface so that the film thickness of the cured coating film is 40 μm. The film was allowed to stand for 7 minutes and then heated at 140 ° C. for 30 minutes to simultaneously cure the three-layer coating film.

  Thus, the glittering paint composition (X-1) obtained in Example 1 was used as a glittering basecoat paint in the 3-coat 1-bake method (3C1B process), and an intermediate coating film and glitter were applied on the electrodeposition coating film. A test plate on which a multilayer coating film composed of an adhesive base coat film and a clear coat film was formed was obtained.

Examples 18-32 and Comparative Examples 11-18
The same paint composition as in Example 17 was applied in the same process and under the same conditions except that the glitter paint composition shown in Table 3 below was used as a glitter base coat paint in the 3-coat 1-bake method (3C1B process). Test plates of 18 to 32 and Comparative Examples 11 to 18 were obtained.

Example 33
The glossy paint composition (X-1) is applied to the article H-2 obtained in Production Example 22 using a rotary atomizing bell-type coater so that the film thickness of the cured coating film becomes 15 μm. And set for 2 minutes, followed by preheating at 80 ° C. for 5 minutes. Next, an acrylic resin-based organic solvent-type clear coat coating composition (trade name “Magicron KINO-1210”, manufactured by Kansai Paint Co., Ltd.) is applied on the uncured coating surface so that the film thickness of the cured coating film is 40 μm. The film was allowed to stand for 7 minutes and then heated at 140 ° C. for 30 minutes to simultaneously cure the two-layer coating film.

  Thus, the glittering paint composition (X-1) obtained in Example 1 was used as a glittering basecoat paint in the 2-coat 1-bake method (2C1B step), and the glittering basecoat coating was applied onto the cured intermediate coating film. A test plate on which a multilayer coating film composed of a film and a clear coat coating film was formed was obtained.

Comparative Examples 19-21
Except for using the glitter paint composition shown in Table 3 below as the glitter base coat paint in the 2-coat 1-bake method (2C1B process), the same paint as Example 33 was applied in the same steps and conditions, and Comparative Examples 19 to 21 test plates were obtained.

Evaluation Test Each test plate obtained in the above Examples and Comparative Examples was evaluated by the following test method. The evaluation results are shown in Table 3.

<Flip-flop (FF)>
Each test plate was visually observed while changing the angle, and the flip-flop property was evaluated according to the following criteria. As evaluation, S-B is a pass and C is a failure.
S: The change in brightness depending on the viewing angle is remarkable (has extremely excellent flip-flop properties).
A: The change of the brightness by a visual angle is large (excellent flip-flop property).
B: The change in brightness depending on the viewing angle is slightly small (flip-flop property is slightly inferior).
C: The change of the brightness by a visual angle is small (the flip-flop property is inferior).

<Vividness>
For each test plate, the sharpness was evaluated based on the Short Wave (SW) value measured by “Wave Scan” (trade name, manufactured by BYK Gardner). The smaller the SW value, the higher the clearness of the coated surface. As an evaluation, an SW value of 20 or more is rejected.

<Smoothness>
About each test board, smoothness was evaluated as follows based on the Long Wave (LW) value measured by "Wave Scan" (trade name, manufactured by BYKGardner). It shows that the smoothness of a coating surface is so high that LW value is small, and LW value 10 or more is rejected as evaluation.

Claims (12)

In the solid content ratio in which the total resin solid content of the following (A), (B) and (C) is 100% by mass, the hydroxyl group-containing resin (A) is 10 to 90% by mass, and the curing agent (B) is 5 to 50% by mass. Non-aqueous dispersion resin (C) 1 to 40% by mass, basic pigment (D) 1 to 20% by mass, and bright pigment (E) 1 to 30% by mass, the non-aqueous dispersion resin (C ) Has a structure having a core part and a shell part, and the shell part of the non-aqueous dispersion resin (C) is the total amount of the polymerizable unsaturated monomer components constituting the non-aqueous dispersion resin (C) A glittering paint composition containing 0.05 to 5.0% by mass of a sulfonic acid group-containing polymerizable unsaturated monomer based on The glitter paint composition according to claim 1, wherein the core of the non-aqueous dispersion resin (C) is crosslinked. The core portion of the non-aqueous dispersion resin (C) is based on the total amount of polymerizable unsaturated monomer components constituting the non-aqueous dispersion resin (C), and the acid group-containing polymerizable unsaturated monomer 0.1 to 10. The glittering paint composition according to claim 1, comprising 0% by mass. The sulfonic acid group-containing polymerizable unsaturated monomer constituting the shell portion of the non-aqueous dispersion resin (C) has at least one polymerizable unsaturated group, at least one sulfonic acid group, and at least one carbon number. The glittering paint composition according to claim 1, which has 4 or more hydrocarbon groups. The glitter paint composition according to claim 1, wherein the difference in SP value between the core portion and the shell portion of the non-aqueous dispersion resin (C) is 0.6 or more. The glitter paint composition according to claim 1, wherein the difference in SP value between the core portion of the non-aqueous dispersion resin (C) and the hydroxyl group-containing resin (A) is 1.0 or less. The glitter paint composition according to claim 1, wherein the non-aqueous dispersion resin (C) has a zeta potential of -20 mV or less and the basic pigment (D) has a zeta potential of +1 mV or more. . A coated article coated with the glittering paint composition according to any one of claims 1 to 7. (1) A process of forming a base coat film by applying the glittering paint composition according to any one of claims 1 to 7 to an object to be coated;
(2) a step of applying a clear coat coating composition on the uncured base coat film to form a clear coat film; and (3) the uncured base coat film and the uncured clear coat. A method for forming a multilayer coating film comprising a step of heating a coating film to simultaneously cure two layers. (1) A process of forming an intermediate coating film by applying an intermediate coating composition to an object to be coated;
(2) A step of coating the glitter coating composition according to any one of claims 1 to 7 on the uncured intermediate coating film to form a base coat film,
(3) a step of applying a clear coat coating composition on the uncured base coat film to form a clear coat film; and (4) the uncured intermediate coat film and the uncured base coat. A method for forming a multilayer coating film comprising a step of heating a coating film and an uncured clear coat coating film to simultaneously cure three layers. An article having a multilayer coating film formed by the multilayer coating film forming method according to claim 9. An article having a multilayer coating film formed by the multilayer coating film forming method according to claim 10.