WO2015156032A1 - 光輝性塗料組成物 - Google Patents
光輝性塗料組成物 Download PDFInfo
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- WO2015156032A1 WO2015156032A1 PCT/JP2015/054307 JP2015054307W WO2015156032A1 WO 2015156032 A1 WO2015156032 A1 WO 2015156032A1 JP 2015054307 W JP2015054307 W JP 2015054307W WO 2015156032 A1 WO2015156032 A1 WO 2015156032A1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/062—Copolymers with monomers not covered by C09D133/06
- C09D133/066—Copolymers with monomers not covered by C09D133/06 containing -OH groups
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/44—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications
- C09D5/4407—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications with polymers obtained by polymerisation reactions involving only carbon-to-carbon unsaturated bonds
- C09D5/4411—Homopolymers or copolymers of acrylates or methacrylates
Definitions
- 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.
- a method of applying paint by atomizing a paint is used.
- a coating method specifically, for example, Examples include spray coating and rotary atomization coating.
- 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.
- 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.
- a coating film excellent in glitter 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.
- 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.
- 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).
- 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.
- 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.
- 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.
- 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.
- 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.
- 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.
- 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.
- 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.
- 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.
- 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 following solid content ratio (A), (B) and (C), the total solid content of the resin 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.
- a non-aqueous dispersion resin (C) 1 to 20% by mass of a basic pigment (D), and 1 to 30% by mass of a bright pigment (E), and the non-aqueous dispersion resin (C )
- 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 brilliant coating 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.
- the core portion of the non-aqueous dispersion resin (C) has an acid group-containing polymerizable unsaturated monomer of 0.1 to 10% based on the total amount of the polymerizable unsaturated monomer components constituting the non-aqueous dispersion resin (C).
- the glittering paint composition according to Item 1 or 2 which contains 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.
- Item 4. The glittering paint composition according to any one of Items 1 to 3, which has 4 or more hydrocarbon groups.
- Item 5. The glittering paint composition according to any one of Items 1 to 4, 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.
- a method for forming a multilayer coating film comprising a step of heating a coating film to simultaneously cure two layers. Item 10.
- 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.
- 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.
- NV paint solid content
- 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.
- a multilayer coating film having properties can be formed.
- 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% by mass, and the hydroxyl group-containing resin (A) is 10 to 90% by mass and 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.
- 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.
- 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 further preferably 3 to 180 mgKOH / g.
- 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 usually 10 to 90% by mass, preferably 15 in terms of the solids content with the total resin solids of components (A), (B) and (C) as 100% by mass. It is in the range of ⁇ 80% by mass, more preferably 20 to 70% by 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.
- 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 products of (meth) acrylic acid such as (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, etc.
- (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”.
- 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.
- 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: for
- (Vi) Polymerizable unsaturated monomer having an alkoxysilyl group: vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, ⁇ - (meth) acryloyloxypropyltrimethoxysilane, ⁇ - (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 compounds: 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.
- Nitrogen-containing polymerizable unsaturated monomers (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.
- Epoxy group-containing polymerizable unsaturated monomer glycidyl (meth) acrylate, ⁇ -methylglycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 3,4-epoxycyclohexylethyl (meth) acrylate 3,4-epoxycyclohexylpropyl (meth) acrylate, allyl glycidyl ether and the like.
- 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.
- 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, formylstyrene, vinyl alkyl ketone having 4 to 7 carbon atoms (for example, vinyl methyl ketone) , Vinyl ethyl ketone, vinyl butyl ketone) and the like.
- the hydroxyl group-containing acrylic resin (A1) is prepared by known polymerization methods such as the solution polymerization method, bulk polymerization method, suspension polymerization method, emulsion polymerization method, etc., from the polymerizable unsaturated monomers (i) to (xix). It can be produced by copolymerization.
- 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.
- organic solvent examples include aromatic solvents such as toluene, xylene, and “Swazole 1000” (trade name, manufactured by Cosmo Oil Co., Ltd., high boiling 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.
- polymerization initiator examples 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).
- radical polymerization initiators known per se such as' -azobis (2-methylbutyronitrile).
- chain transfer agents such as 2-mercaptoethanol, n-octyl mercaptan, and ⁇ -methyl styrene dimer can be used.
- 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.
- the hydroxyl group-containing acrylic resin (A1) has a weight average molecular weight (Mw) of preferably 1,000 to 200,000, more preferably 2,000 to 100,000, and still more preferably 3,000 to 60,000. Within range.
- 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” (both 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.
- the said hydroxyl-containing polyester resin (A2) can be normally manufactured by esterification reaction or transesterification with an acid component and an alcohol component.
- the acid component compounds usually used as an acid component in the production of a polyester resin can be used.
- 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 acids anhydrides of the aliphatic polyvalent carboxylic acids; and esterified products of lower alkyl having about 1 to 4 carbon atoms of the aliphatic polyvalent carboxylic acids.
- 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 4-6 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- Alicyclic polycarboxylic acids 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, naphthalene dicarboxylic 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.
- acid components other than the above aliphatic polybasic acids, alicyclic polybasic acids and aromatic polybasic acids can 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 Acid, monocarboxylic acids such as 10-phenyloctadecanoic acid; and hydroxycarboxylic acids such as lactic
- a polyhydric alcohol having two or more hydroxyl groups in one molecule can be preferably used.
- 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,
- alcohol components other than the above polyhydric alcohols can 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.
- the method for producing the hydroxyl group-containing polyester resin (A2) is not particularly limited, and can be performed according to a known method.
- the acid component and the alcohol component are heated in a nitrogen stream at about 150 to 250 ° C. for about 5 to 15 hours to perform 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.
- the acid component and the alcohol component 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.
- 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.
- fatty acid examples 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
- oil fatty acids and safflower oil fatty acids examples include oil fatty acids and safflower oil fatty acids.
- Cardura E10 (trade name, manufactured by HEXION SpecialtyS Chemicals, glycidyl ester of synthetic highly branched saturated fatty acid) can be suitably used.
- polyisocyanate compound examples 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 triisocyanate and higher polyisocyanates such as triisocyanate Adducts of these organic polyisocyanates with polyhydric alcohols, low mole
- 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.
- 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 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.
- amino resin a partially methylolated amino resin or a completely methylolated amino resin obtained by a reaction between an amino component and an aldehyde component
- amino component examples include melamine, urea, benzoguanamine, acetoguanamine, steroguanamine, spiroguanamine, dicyandiamide and the like.
- aldehyde component examples include formaldehyde, paraformaldehyde, acetaldehyde, and benzaldehyde.
- etherification examples include methyl alcohol, ethyl alcohol, n-propyl alcohol, i-propyl alcohol, n-butyl alcohol, i-butyl alcohol, 2-ethyl-1-butanol, 2-ethyl-1 -Hexanol and the like.
- a melamine resin is preferable.
- 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 fully 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.
- 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 chemical theoretical amount.
- 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 polyphenylisocyanate], bis (isocyanatemethyl) cyclohexane, tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, isophorone diisocyanate, etc.
- 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.
- the blocking agent used in the blocked polyisocyanate compound known ones can be used without particular limitation, and examples thereof include oxime compounds such as methyl ethyl ketoxime and cyclohexanone oxime; phenol, para-t-butylphenol, and cresol.
- Phenolic compounds such as n-butanol, 2-ethylhexanol, phenyl carbinol, methylphenyl carbinol, alcohol compounds such as ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, ethylene glycol, propylene glycol; ⁇ -caprolactam, ⁇ -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 blending amount of the curing agent (B) is usually 5 to 50% by mass, preferably 10 to 10% by solid content ratio with the total resin solid content of the components (A), (B) and (C) as 100% by mass. It is in the range of 45% by mass, more preferably 15-40% by 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.
- the SP value is also called a solubility parameter, and is a scale indicating the degree of hydrophilicity (high polarity) or hydrophobicity (low polarity) of the resin.
- solubility parameter value 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 ...
- SP 1 , SP 2 ,... SP n represents the SP value of the homopolymer of each monomer
- 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 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).
- V H is the volume fraction of n-hexane
- V D is the volume fraction of deionized water
- ⁇ H is the SP value of n-hexane
- ⁇ D is the SP value of deionized water.
- V H H / (10 + H)
- V D D / (10 + D)
- ⁇ H 9.52 ⁇ 10 / (10 + H) + 7.24 ⁇ H / (10 + H)
- ⁇ 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.
- the polymer dispersion stabilizer (S1) becomes a shell portion having a low SP value
- the acrylic resin obtained by polymerizing the polymerizable unsaturated monomer becomes a core portion having a high SP value.
- 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 an optional other polymerizable unsaturated monomer (s-3) 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 polymerizable unsaturated monomer (s-1) include the following.
- 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 esters 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
- sulfonic acid group-containing polymerizable unsaturated monomer (s-2) examples 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.
- the sulfonic acid group-containing polymerizable unsaturated monomer (s-2) at least one polymerizable unsaturated group and at least one sulfone are preferred 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.
- a sulfonic acid group-containing polymerizable unsaturated monomer (s-2) represented by the following formula (I): -1) is preferred.
- the hydrocarbon group (R 1 ) of the sulfonic acid group-containing polymerizable unsaturated monomer (s-2-1) preferably has a carbon number in the range of 6 to 30, and has a carbon number of 8 to 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.
- the content of the sulfonic acid group-containing polymerizable unsaturated monomer (s-2) is, in the shell part, 0. 0 based on the total amount of the polymerizable unsaturated monomer components constituting the non-aqueous dispersion resin (C).
- 05 to 5% by mass is preferable, 0.1 to 4% by mass is more preferable, and 0.2 to 3% by mass is particularly preferable.
- the amount is less than the above range, a suitable flip-flop property may not be obtained.
- the finish property may be deteriorated.
- the other polymerizable unsaturated monomer (s-3) is not particularly limited.
- the carbon number of (meth) acrylic acid such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and the like.
- alkyl esters 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 ⁇ , ⁇ -unsaturated carboxylic acids other than (meth) acrylic acid such as fumaric acid and citraconic acid and monoalcohols 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 thereof include vinyl ether compounds such as ethyl vinyl ether and methyl vinyl ether; ⁇ -olefin compounds such as ethylene, propylene, vinyl chloride and vinylidene chloride.
- polymerizable unsaturated monomers such as 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, etc. Also included are those in which a polymerizable unsaturated monomer is substituted with a hydroxyl group or the like.
- the amount is preferably 0.1 to 80 masses with respect to the long-chain polymerizable unsaturated monomer (s-1) based on the total amount of 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.
- 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).
- the total amount of the polymerizable unsaturated monomer component is preferably 50 to 100% by mass of the non-aqueous dispersion resin (C), more preferably 75 to 95% by mass.
- Polymerization for producing the polymer dispersion stabilizer (S1) can usually be performed using a radical polymerization initiator.
- radical polymerization initiators 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.
- 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.
- 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.
- dispersion stabilizer 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).
- 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.
- a comb polymer obtained by copolymerizing the polyester macromonomer (1), methyl methacrylate and / or other (meth) acrylic acid ester, and vinyl monomer.
- 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. .
- the dispersion stabilizer of (3) can be preferably used. It can be used suitably.
- the hydroxy acid dimethylolbutanoic acid, dimethylolpropionic acid, 12-hydroxystearic acid, and the like can be used. Of these, 12-hydroxystearic acid is preferably used from the viewpoint of dispersion stability. be able to.
- the content in the case of containing a hydroxy acid is preferably 0 to 15.0% by mass with respect to the component of the hydroxy acid, based on the total amount of the polymerizable unsaturated monomer components constituting the shell portion. 0 to 13.0% by 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 to 20/80 is preferable, and the range of 80/20 to 40/60 is more preferable.
- non-aqueous dispersion resin (C) 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.
- a copolymer that becomes the core part is prepared by copolymerizing the polymerizable unsaturated monomer (c-1), and a non-aqueous dispersion of polymer particles insoluble in the organic solvent is prepared.
- 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.
- 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.
- 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 portion 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 Alkyl or cycloalkyl ester having 1 to 18 carbon atoms; alkoxyalkyl ester of (meth) acrylic acid such as methoxybutyl (meth) acrylate, methoxyethyl (meth) acrylate and e
- self-reactive polymerizable unsaturated monomers such as N-alkoxymethylated acrylamide and ⁇ -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.
- These polymerizable unsaturated monomers can be used alone or in combination of two or more.
- 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).
- 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.
- 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 monomer components, it is preferably 0.1 to 10.0% by mass, more preferably 0.5 to 8.0% by mass, and particularly preferably 1.0 to 5.0% by mass.
- the polymerization of the polymerizable unsaturated monomer (c-1) is usually performed using a radical polymerization initiator.
- Usable radical polymerization initiators include, for example, azo initiators such as 2,2′-azobisisobutyronitrile and 2,2′-azobis (2,4-dimethylvaleronitrile); benzoyl peroxide, lauryl And peroxide initiators such as peroxide, t-butyl peroctoate, and t-butyl peroxy-2-ethylhexanoate.
- azo initiators such as 2,2′-azobisisobutyronitrile and 2,2′-azobis (2,4-dimethylvaleronitrile
- benzoyl peroxide lauryl And peroxide initiators such as peroxide, t-butyl peroctoate, and t-butyl peroxy-2-ethylhexanoate.
- These polymerization initiators are generally 100 parts by mass of monomers
- the ratio of the polymer dispersion stabilizer (S1) and the polymerizable unsaturated monomer (c-1) used in 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.
- 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.
- the liquid phase is obtained by dissolving the polymer dispersion stabilizer (S1) in an organic solvent, and the solid phase is 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 ⁇ m. 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 size of the non-aqueous dispersion resin (C) was measured by “COULTERTEN4 type submicron particle analyzer” (trade name, manufactured by Beckman Coulter, Inc.).
- 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 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.
- 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.
- 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.
- 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, citraconic acid, and the like.
- Saturated carboxylic acids include 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, N, N-dimethyl-p-styrenesulfonamide Compound;
- a polymerizable unsaturated monomer is polymerized in the presence of the polymer dispersion stabilizer (S1) having a polymerizable unsaturated group. Can be done.
- a polymerizable unsaturated group is 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, and glycidyl is added to the acid group.
- the reaction can be carried out by reacting a glycidyl group-containing polymerizable unsaturated monomer such as (meth) acrylate or allyl glycidyl ether.
- 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.
- 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.
- 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.
- a non-aqueous dispersion containing a hydroxyl group in the polymer particles 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 compound having two or more isocyanate groups in the molecule may be used.
- 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.
- 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
- 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.
- 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 preferably 70/30 to 40/60. More preferred.
- 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 To a solid content ratio with the total resin solid content of components (A), (B) and (C) being 100 mass%, usually 1 to 40 mass%, preferably 3 to 28 mass%, more preferably 6 to 6 mass%. It is in the range of 20% by mass.
- 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.
- 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 by measuring the moving speed of particles by electrophoresis.
- 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 the mixture with an ultrasonic vibrator for 1 hour.
- 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 ⁇ m, 0.05 Is preferably 0.5 to 0.5 ⁇ m, and more preferably 0.09 to 0.25 ⁇ m.
- 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.
- 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 as measured 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 differ greatly from 0 to 10.0, the determination of whether it is an acidic pigment, a neutral pigment or a basic pigment is actually made by measuring the pH.
- 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.
- At least one basic extender pigment (D1) 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 any 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.
- 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 usually a solid content ratio in which the total resin solid content of the components (A), (B) and (C) in the glittering paint is 100% by mass, and usually 1 to 20 It is in the range of mass%, preferably 3 to 18 mass%, more preferably 5 to 15 mass%.
- 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). .
- the basic pigment (D) 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.
- 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.
- the flake-like glitter pigment those having a longitudinal dimension of usually 1 to 100 ⁇ m, particularly 5 to 40 ⁇ m, and a thickness of usually 0.001 to 5 ⁇ m, particularly 0.01 to 2 ⁇ m, 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, usually 1 to 30. It is in the range of mass%, preferably 2 to 25 mass%, more preferably 3 to 20 mass%.
- 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 mass%, curing agent (B) 5 to 50 mass%, non-aqueous dispersion resin (C) 1 to 40 mass%, basic pigment (D) 1 to 20 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.
- the hydroxyl group-containing resin (A) is a hydroxyl group-containing acrylic resin, a hydroxyl group-containing polyester resin, or a combination thereof
- the curing agent (B) is an amino resin, a polyisocyanate compound, or a blocked poly
- the core portion has a copolymer of at least one polymerizable unsaturated monomer (c-1), and the shell portion has a long-chain polymerizable unsaturated monomer (s -1), a sulfonic acid group-containing polymerizable unsaturated monomer (s-2), and another polymerized unsaturated monomer (s-3) that is optionally used;
- the molecular dispersion stabilizer (S1) and the shell part of the non-aqueous dispersion resin (C) are sulfones based on the total amount of polymerizable unsaturated monomer components constituting the non-aqueous dispersion resin (C).
- the acid group-containing polymerizable unsaturated monomer (s-2) is contained in an amount of 0.05 to 5.0% by mass.
- 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.
- 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).
- 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.
- Method 1 2 coat 1 bake method (2C1B process) 1-1.
- 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 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.
- an electrodeposition-cured coating film formed on an automobile body subjected to chemical conversion treatment can be used.
- 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 coating of the intermediate coating, the glitter base coating and the clear coating can be performed by a normal coating method, for example, electrostatic atomization coating or non-electrostatic atomization coating.
- a rotary atomization method or an air atomization method can be used as the atomization method.
- 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 ⁇ m. When the intermediate coating is applied, it is allowed to stand at room temperature for several minutes or pre-dried at about 50-80 ° C. for several minutes.
- the glittering base coat paint which is the glittering paint composition of the present invention, is applied onto the object to be coated or the intermediate coating film.
- the film thickness after curing of the glittering base coat film is usually in the range of 5 to 30 ⁇ m, preferably 7 to 25 ⁇ m, more preferably 10 to 20 ⁇ m.
- 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.
- any 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 preferable.
- the thickness of the clear coat film after curing is usually in the range of 15 to 60 ⁇ m, preferably 10 to 50 ⁇ m, more preferably 15 to 45 ⁇ m.
- the heating for curing the multilayer coating film is usually performed at about 120 to 180 ° C. for about 20 to 90 minutes.
- 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.
- AIBN 2′-azobisisobutyronitrile
- 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 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.
- 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.
- Nonaqueous Dispersion Resin (C) Solution In a four-necked flask equipped with a stirrer, thermometer, condenser and 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, followed by aging 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 ⁇ m, 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.
- 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.
- the obtained polymerizable unsaturated group-containing macromonomer had about 1 polymerizable unsaturated group based on the number average molecular weight per molecule.
- 174 parts of butyl acetate was placed in the flask and heated to reflux.
- 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.
- 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.
- the core monomer composition was dropped into the flask without blending the polymer dispersion stabilizer and other dispersion stabilizers.
- the compounding quantity in following Table 1 is the value of solid content or an active ingredient.
- the zeta potential and the particle diameter were not measured because of the occurrence of bumps (aggregates).
- KBM-503 Trade name, manufactured by Shin-Etsu Chemical Co., Ltd., 3-methacrylooxypropyltrimethoxysilane
- 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 a hydroxyl group-containing acrylic resin (A1-1) solution obtained in Production Example 1 (9 parts of resin solids), 12.9 parts of a hydroxyl group-containing polyester resin (A2-1) solution obtained in Production Example 2 (resin solids) 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 are 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.
- A1-1 hydroxyl group-containing acrylic resin
- A2-1 hydroxyl group-containing polyester resin
- “Varifine BF-20” trade name, manufactured by Sakai Chemical Industry Co., Ltd., fine particle barium sulfate, zeta potential 6 mV
- Examples 2 to 16 and Comparative Examples 1 to 10 According to the formulation shown in Table 2 below, Ford Cup No.
- the solutions of glittering paints (X-2) to (X-26) having a viscosity according to 4 of 12 seconds were obtained.
- the compounding quantity of following Table 2 is the value of solid content or an active ingredient.
- the paint state is caused by 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.
- Siritin Z86 trade name, manufactured by Hoffman Minerals, basic hydrous aluminum silicate, zeta potential 1 mV, pH: 8, basic pigment.
- a thermosetting epoxy resin cationic electrodeposition coating composition (trade name “Electron GT-10” manufactured by Kansai Paint Co., Ltd.)
- thermosetting epoxy resin cationic electrodeposition coating composition (trade name “Electron GT-10” manufactured by Kansai Paint Co., Ltd.) to a thickness of 20 ⁇ m. It was electrodeposited and cured by heating at 170 ° C. for 30 minutes.
- 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 so as to have a film thickness of 35 ⁇ m. And cured by heating at 140 ° C. for 30 minutes.
- TP-65-3 manufactured by Kansai Paint Co., Ltd., polyester resin / amino resin organic solvent type coating composition
- 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 ⁇ m, 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 to the uncured coating surface using a rotary atomizing bell-type coating machine so that the film thickness of the cured coating film becomes 15 ⁇ m. After painting and setting for 2 minutes, preheating was performed at 80 ° C. for 5 minutes.
- TP-65-3 manufactured by Kansai Paint Co., Ltd., polyester resin / amino resin organic solvent type
- an acrylic resin organic solvent type clear coat coating composition (trade name “Magicron Kino-1210”, manufactured by Kansai Paint Co., Ltd.) was applied on the uncured coating surface so that the film thickness of the cured coating film was 40 ⁇ m.
- 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.
- the glitter paint composition (X-1) obtained in Example 1 was used as a glitter base coat paint in the three-coat one-bake method (3C1B process), and the intermediate coat film and glitter on the electrodeposition paint 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.
- Example 18 to 32 and Comparative Examples 11 to 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 coating composition H-2 obtained in Production Example 22 is coated with the glitter coating composition (X-1) using a rotary atomizing bell type coating machine so that the film thickness of the cured coating film becomes 15 ⁇ m. 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 onto the uncured coating surface so that the film thickness of the cured coating film is 40 ⁇ m. 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.
- an acrylic resin-based organic solvent-type clear coat coating composition (trade name “Magicron Kino-1210”, manufactured by Kansai Paint Co., Ltd.) is applied onto the uncured coating surface so that the film thickness of the cured coating film is 40 ⁇ m.
- the film was allowed to stand for 7 minutes and then heated at 140 ° C. for 30
- 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 process), and the glittering basecoat coating was applied on 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 the following Table 3 as the glitter base coat paint in the 2-coat 1-bake method (2C1B process), the same paint as in Example 33 was applied in the same steps and conditions, and Comparative Examples 19 to 21 test plates were obtained.
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Abstract
Description
本願は、2014年4月10日に出願した特願2014-81250号明細書(その全体が参照により本明細書中に援用される)の優先権の利益を主張するものである。
(技術分野)
本発明は、フリップフロップ性が高くメタリックムラが少ない、光輝性に優れた複層塗膜が得られる光輝性塗料組成物に関する。
項1.下記(A)、(B)及び(C)の樹脂固形分総量を100質量%とする固形分比で、水酸基含有樹脂(A)10~90質量%、硬化剤(B)5~50質量%、非水ディスパージョン樹脂(C)1~40質量%、塩基性顔料(D)1~20質量%、及び光輝性顔料(E)1~30質量%を含有し、該非水ディスパージョン樹脂(C)が、コア部及びシェル部を備えた構造を有し、かつ、該非水ディスパージョン樹脂(C)のシェル部が、該非水ディスパージョン樹脂(C)を構成する重合性不飽和モノマー成分の総量を基準として、スルホン酸基含有重合性不飽和モノマー0.05~5.0質量%を含有することを特徴とする光輝性塗料組成物。
項2.非水ディスパージョン樹脂(C)のコア部が、架橋されていることを特徴とする前記項1に記載の光輝性塗料組成物。
項3.非水ディスパージョン樹脂(C)のコア部が、該非水ディスパージョン樹脂(C)を構成する重合性不飽和モノマー成分の総量を基準として、酸基含有重合性不飽和モノマー0.1~10.0質量%を含有することを特徴とする前記項1又は2に記載の光輝性塗料組成物。
項4.非水ディスパージョン樹脂(C)のシェル部を構成するスルホン酸基含有重合性不飽和モノマーが、少なくとも1個の重合性不飽和基、少なくとも1個のスルホン酸基、及び少なくとも1個の炭素数4以上の炭化水素基を有することを特徴とする前記項1~3のいずれか1項に記載の光輝性塗料組成物。
項5.非水ディスパージョン樹脂(C)のコア部とシェル部のSP値の差が0.6以上であることを特徴とする前記項1~4のいずれか1項に記載の光輝性塗料組成物。
項6.非水ディスパージョン樹脂(C)のコア部と水酸基含有樹脂(A)のSP値の差が1.0以下であることを特徴とする前記項1~5のいずれか1項に記載の光輝性塗料組成物。
項7.非水ディスパージョン樹脂(C)のゼータ電位が-20mV以下であり、かつ、塩基性顔料(D)のゼータ電位が+1mV以上であることを特徴とする前記項1~6のいずれか1項に記載の光輝性塗料組成物。
項8.前記項1~7のいずれか1項に記載の光輝性塗料組成物が塗装された塗装物品。
項9.(1)被塗物に、前記項1~7のいずれか1項に記載の光輝性塗料組成物を塗装してベースコート塗膜を形成する工程、
(2)上記の未硬化のベースコート塗膜上に、クリヤーコート塗料組成物を塗装してクリヤーコート塗膜を形成する工程、並びに
(3)上記の未硬化のベースコート塗膜及び未硬化のクリヤーコート塗膜を、加熱して2層を同時に硬化させる工程
を含む複層塗膜形成方法。
項10.(1)被塗物に、中塗り塗料組成物を塗装して中塗り塗膜を形成する工程、
(2)上記の未硬化の中塗り塗膜上に、前記項1~7のいずれか1項に記載の光輝性塗料組成物を塗装してベースコート塗膜を形成する工程、
(3)上記の未硬化のベースコート塗膜上に、クリヤーコート塗料組成物を塗装してクリヤーコート塗膜を形成する工程、並びに
(4)上記の未硬化の中塗り塗膜、未硬化のベースコート塗膜及び未硬化のクリヤーコート塗膜を、加熱して3層を同時に硬化させる工程
を含む複層塗膜形成方法。
項11.前記項9又は10に記載の複層塗膜形成方法により形成された複層塗膜を有する物品。
項12.前記項10に記載の複層塗膜形成方法により形成された複層塗膜を有する物品。
本発明の光輝性塗料組成物は、樹脂として、水酸基含有樹脂(A)、硬化剤(B)及び非水ディスパージョン樹脂(C)を含有し、顔料として、塩基性顔料(D)及び光輝性顔料(E)を含有することを特徴とする。また、光輝性塗料組成物は、成分(A)、(B)及び(C)の樹脂固形分総量を100質量%とする固形分比で、水酸基含有樹脂(A)10~90質量%、硬化剤(B)5~50質量%、非水ディスパージョン樹脂(C)1~40質量%、塩基性顔料(D)1~20質量%、及び光輝性顔料(E)1~30質量%の範囲内で含有することを特徴とする。
本発明の光輝性塗料組成物で用いることができる水酸基含有樹脂(A)としては、本発明の塗料組成物中に溶解状態で存在する水酸基含有樹脂であれば特に制限はなく、従来から塗料に使用されているそれ自体既知の水酸基含有樹脂を使用することができる。樹脂の種類としては、例えば、アクリル樹脂、ポリエステル樹脂、アルキド樹脂、ポリウレタン樹脂などが挙げられ、1種を単独で又は2種以上を組み合わせて使用できる。また、水酸基含有樹脂(A)は、架橋性官能基として水酸基を有し、水酸基以外にカルボキシル基、アミノ基、スルホン酸基、リン酸基、エポキシ基などの官能基を有することができる。
上記水酸基含有アクリル樹脂(A1)は、通常、水酸基含有重合性不飽和モノマー及び該水酸基含有重合性不飽和モノマーと共重合可能な他の重合性不飽和モノマーを、それ自体既知の方法、例えば、有機溶媒中での溶液重合法などの方法により、共重合せしめることによって製造することができる。
(i)アルキル又はシクロアルキル(メタ)アクリレート:例えば、メチル(メタ)アクリレート、エチル(メタ)アクリレート、n-プロピル(メタ)アクリレート、i-プロピル(メタ)アクリレート、n-ブチル(メタ)アクリレート、i-ブチル(メタ)アクリレート、tert-ブチル(メタ)アクリレート、n-ヘキシル(メタ)アクリレート、n-オクチル(メタ)アクリレート、2-エチルヘキシル(メタ)アクリレート、ノニル(メタ)アクリレート、トリデシル(メタ)アクリレート、ラウリル(メタ)アクリレート、ステアリル(メタ)アクリレート、イソステアリル(メタ)アクリレート、シクロヘキシル(メタ)アクリレート、メチルシクロヘキシル(メタ)アクリレート、t-ブチルシクロヘキシル(メタ)アクリレート、シクロドデシル(メタ)アクリレート、トリシクロデカニル(メタ)アクリレートなど。
(ii)イソボルニル基を有する重合性不飽和モノマー:イソボルニル(メタ)アクリレートなど。
(iii)アダマンチル基を有する重合性不飽和モノマー:アダマンチル(メタ)アクリレートなど。
(iv)トリシクロデセニル基を有する重合性不飽和モノマー:トリシクロデセニル(メタ)アクリレートなど。
(v)芳香環含有重合性不飽和モノマー:ベンジル(メタ)アクリレート、スチレン、α-メチルスチレン、ビニルトルエンなど。
(vi)アルコキシシリル基を有する重合性不飽和モノマー:ビニルトリメトキシシラン、ビニルトリエトキシシラン、ビニルトリス(2-メトキシエトキシ)シラン、γ-(メタ)アクリロイルオキシプロピルトリメトキシシラン、γ-(メタ)アクリロイルオキシプロピルトリエトキシシランなど。
(vii)フッ素化アルキル基を有する重合性不飽和モノマー:パーフルオロブチルエチル(メタ)アクリレート、パーフルオロオクチルエチル(メタ)アクリレートなどのパーフルオロアルキル(メタ)アクリレート;フルオロオレフィンなど。
(viii)マレイミド基などの光重合性官能基を有する重合性不飽和モノマー。
(ix)ビニル化合物:N-ビニルピロリドン、エチレン、ブタジエン、クロロプレン、プロピオン酸ビニル、酢酸ビニルなど。
(x)リン酸基含有重合性不飽和モノマー:2-アクリロイルオキシエチルアシッドホスフェート、2-メタクリロイルオキシエチルアシッドホスフェート、2-アクリロイルオキシプロピルアシッドホスフェート、2-メタクリロイルオキシプロピルアシッドホスフェートなど。
(xi)カルボキシル基含有重合性不飽和モノマー:(メタ)アクリル酸、マレイン酸、クロトン酸、β-カルボキシエチルアクリレートなど。
(xii)含窒素重合性不飽和モノマー:(メタ)アクリロニトリル、(メタ)アクリルアミド、N,N-ジメチルアミノエチル(メタ)アクリレート、N,N-ジエチルアミノエチル(メタ)アクリレート、N,N-ジメチルアミノプロピル(メタ)アクリルアミド、メチレンビス(メタ)アクリルアミド、エチレンビス(メタ)アクリルアミド、2-(メタクリロイルオキシ)エチルトリメチルアンモニウムクロライド、グリシジル(メタ)アクリレートとアミン類との付加物など。
(xiii)重合性不飽和基を1分子中に2個以上有する重合性不飽和モノマー:アリル(メタ)アクリレート、1,6-ヘキサンジオールジ(メタ)アクリレートなど。
(xiv)エポキシ基含有重合性不飽和モノマー:グリシジル(メタ)アクリレート、β-メチルグリシジル(メタ)アクリレート、3,4-エポキシシクロヘキシルメチル(メタ)アクリレート、3,4-エポキシシクロヘキシルエチル(メタ)アクリレート、3,4-エポキシシクロヘキシルプロピル(メタ)アクリレート、アリルグリシジルエーテルなど。
(xv)分子末端がアルコキシ基であるポリオキシエチレン鎖を有する(メタ)アクリレート。
(xvi)スルホン酸基を有する重合性不飽和モノマー:2-アクリルアミド-2-メチルプロパンスルホン酸、2-スルホエチル(メタ)アクリレート、アリルスルホン酸、4-スチレンスルホン酸など;これらスルホン酸のナトリウム塩及びアンモニウム塩など。
(xvii)紫外線吸収性官能基を有する重合性不飽和モノマー:2-ヒドロキシ-4-(3-メタクリロイルオキシ-2-ヒドロキシプロポキシ)ベンゾフェノン、2-ヒドロキシ-4-(3-アクリロイルオキシ-2-ヒドロキシプロポキシ)ベンゾフェノン、2,2' -ジヒドロキシ-4-(3-メタクリロイルオキシ-2-ヒドロキシプロポキシ)ベンゾフェノン、2,2' -ジヒドロキシ-4-(3-アクリロイルオキシ-2-ヒドロキシプロポキシ)ベンゾフェノン、2-(2' -ヒドロキシ-5' -メタクリロイルオキシエチルフェニル)-2H-ベンゾトリアゾールなど。
(xviii)紫外線安定性重合性不飽和モノマー:4-(メタ)アクリロイルオキシ-1,2,2,6,6-ペンタメチルピペリジン、4-(メタ)アクリロイルオキシ-2,2,6,6-テトラメチルピペリジン、4-シアノ-4-(メタ)アクリロイルアミノ-2,2,6,6-テトラメチルピペリジン、1-(メタ)アクリロイル-4-(メタ)アクリロイルアミノ-2,2,6,6-テトラメチルピペリジン、1-(メタ)アクリロイル-4-シアノ-4-(メタ)アクリロイルアミノ-2,2,6,6-テトラメチルピペリジン、4-クロトノイルオキシ-2,2,6,6-テトラメチルピペリジン、4-クロトノイルアミノ-2,2,6,6-テトラメチルピペリジン、1-クロトノイル-4-クロトノイルオキシ-2,2,6,6-テトラメチルピペリジンなど。
(xix)カルボニル基を有する重合性不飽和モノマー:アクロレイン、ダイアセトンアクリルアミド、ダイアセトンメタクリルアミド、アセトアセトキシエチルメタクリレート、ホルミルスチロール、4~7個の炭素原子を有するビニルアルキルケトン(例えば、ビニルメチルケトン、ビニルエチルケトン、ビニルブチルケトン)など。
上記水酸基含有ポリエステル樹脂(A2)は、通常、酸成分とアルコール成分とのエステル化反応又はエステル交換反応によって製造することができる。
本発明の光輝性塗料組成物で用いる硬化剤(B)は、水酸基含有樹脂(A)中の水酸基、カルボキシル基、エポキシ基などの架橋性官能基と反応して、該塗料組成物を硬化し得る化合物である。上記硬化剤(B)としては、例えば、アミノ樹脂、ポリイソシアネート化合物、ブロック化ポリイソシアネート化合物、エポキシ基含有化合物、カルボキシル基含有化合物、カルボジイミド基含有化合物などが挙げられ、これらは1種を単独で又は2種以上を組み合わせて用いることができる。これらのうち、水酸基と反応し得るアミノ樹脂、ポリイソシアネート化合物及び/又はブロック化ポリイソシアネート化合物が好ましく、アミノ樹脂及び/又はブロック化ポリイソシアネート化合物がより好ましく、アミノ樹脂が特に好ましい。
本発明の光輝性塗料組成物は、塗料組成物中において不溶状態(不透明状態)で存在する非水ディスパージョン樹脂(C)を含有する。
具体的には、下記式(2)、K.W.SUH、J.M.CORBETTの式(Journalof Applied Polymer Science,12,2359,1968)に準じてSP値を算出することができる。
濁点滴定では、サンプルとして樹脂0.5g(固形分)をテトラヒドロフラン10mlに溶解した中にn-ヘキサンを徐々に加え、濁点での滴定量H(ml)を読み、同様に樹脂0.5g(固形分)をテトラヒドロフラン10mlに溶解した中に脱イオン水を加えての濁点における滴定量D(ml)を読んで、これらを下記式(3)に適用し、VH、VD、δH、δDを算出する。なお、各溶剤のSP値はテトラヒドロフラン:9.52、n-ヘキサン:7.24、脱イオン水:23.43である。
また、上記スルホン酸基含有重合性不飽和モノマー(s-2-1)の炭化水素基(R1)としては、炭素数が6~30の範囲であることがより好ましく、炭素数が8~25の範囲であることが特に好ましい。
(1)ヒドロキシ酸などの水酸基を含有する脂肪酸の自己縮合ポリエステルとアクリル酸グリシジル又はメタクリル酸グリシジルを付加して分子中に約1.0個の重合性不飽和基を導入したポリエステルマクロモノマー。
(2)上記(1)のポリエステルマクロモノマーとメチルメタクリレート及び/又はその他の(メタ)アクリル酸エステル、ビニルモノマーを共重合した櫛型ポリマー。
(3)上記(2)に少量のグリシジル(メタ)アクリレートを共重合させておき、そのグリシジル基に後から(メタ)アクリル酸を付加して不飽和基を導入したもの。
(4)炭素数4以上のモノアルコールの(メタ)アクリル酸エステルを少なくとも20%共重合してなる水酸基含有アクリル共重合体。
(5)上記(4)に数平均分子量基準で1分子当たり0.3以上の不飽和基を導入したもの。導入する方法としては、例えば、もとのアクリル共重合体中に少量の(メタ)アクリル酸グリシジルを共重合しておき、後からそのグリシジル基に(メタ)アクリル酸を付加する方法が挙げられる。
(6)ミネラルスピリット許容率の高いアルキルメラミン樹脂。
(7)脂肪酸含有量15%以上のアルキド樹脂及び/又はそれに重合性不飽和基を導入したもの。重合性不飽和基を導入する方法としては、例えばアルキド樹脂中のカルボキシル基に(メタ)アクリル酸グリシジルを付加する方法が挙げられる。
(8)ミネラルスピリット許容率の高いオイルフリーポリエステル樹脂、脂肪酸含有量15%以上のアルキド樹脂及び/又はそれに重合性不飽和基を導入したもの。
(9)重合性不飽和基を導入したセルロースアセテートブチレート。重合性不飽和基を導入する方法としては、例えばセルロースアセテートブチレートにイソシアネートエチルメタクリレートを付加する方法が挙げられる。
〔η:粘度(ポイズ)、V:移動速度(cm/sec)、ε:誘電率、E:電場(V/cm)〕
本発明の光輝性塗料組成物で用いる塩基性顔料(D)は、顔料を蒸留水中に縣濁させた液の水素イオン濃度を測定して、pHが7.0~13.0の範囲のものである。塩基性顔料のpHは、顔料自体の表面状態や、溶解性、製造条件、表面処理剤などによって支配されるため、例えば、同じ白顔料の二酸化チタンであっても、そのpHが、例えば4.0~10.0と大きく異なることがあるので、酸性顔料か中性顔料か塩基性顔料かの判断は実際にはpHを測定することによって判別される。
本発明の光輝性塗料組成物で用いる光輝性顔料(E)は、塗膜にキラキラとした光輝性や光干渉性模様を付与する顔料であり、上記塩基性顔料(D)とは区別される。具体的には、例えば、アルミニウム(蒸着アルミニウムも含む)、銅、亜鉛、真ちゅう、ニッケル、酸化アルミニウム、雲母、酸化チタンや酸化鉄で被覆された雲母、酸化チタンや酸化鉄で被覆された酸化アルミニウムなどを挙げることができる。なかでも、アルミニウム、雲母、酸化チタンや酸化鉄で被覆された雲母、酸化チタンや酸化鉄で被覆された酸化アルミニウムが好ましく、アルミニウムがさらに好ましい。これらの顔料はそれぞれ単独で又は2種以上組み合わせて使用することができる。
本発明の光輝性塗料組成物は、水酸基含有樹脂(A)、硬化剤(B)、非水ディスパージョン樹脂(C)、塩基性顔料(D)、及び光輝性顔料(E)を必須成分とする塗料組成物であって、通常、有機溶剤を含有し、さらに任意選択で、上記水酸基含有樹脂(A)及び硬化剤(B)以外の樹脂、上記非水ディスパージョン樹脂(C)以外のレオロジーコントロール剤成分、塩基性顔料(D)及び光輝性顔料(E)以外の顔料、硬化触媒、顔料分散剤、レベリング剤、紫外線吸収剤、光安定剤、可塑剤など、通常、塗料の分野で用いられる塗料用添加剤を任意選択で含有することができる。
(方式1)2コート1ベーク方式(2C1B工程)
1-1.被塗物に、本発明の光輝性塗料組成物を塗装してベースコート塗膜を形成する工程、
1-2.上記の未硬化のベースコート塗膜上に、クリヤーコート塗料組成物を塗装してクリヤーコート塗膜を形成する工程、並びに
1-3.上記の未硬化のベースコート塗膜及び未硬化のクリヤーコート塗膜を、加熱して2層を同時に硬化させる工程
を含む複層塗膜形成方法。
(方式2)3コート1ベーク方式(3C1B工程)
2-1.被塗物に、中塗り塗料組成物を塗装して中塗り塗膜を形成する工程、
2-2.上記の未硬化の中塗り塗膜上に、本発明の光輝性塗料組成物を塗装してベースコート塗膜を形成する工程、
2-3.上記の未硬化のベースコート塗膜上に、クリヤーコート塗料組成物を塗装してクリヤーコート塗膜を形成する工程、並びに
2-4.上記の未硬化の中塗り塗膜、未硬化のベースコート塗膜及び未硬化のクリヤーコート塗膜を、加熱して3層を同時に硬化させる工程
を含む複層塗膜形成方法。
製造例1
温度計、サーモスタット、撹拌装置、還流冷却器、窒素導入管及び滴下装置を備えた反応容器に、「スワゾール1000」(商品名、丸善石油化学社製、石油系芳香族炭化水素系溶剤)30部を仕込み、窒素を吹き込みながら110℃に昇温後、同温度にて、スチレン10部、メチルメタクリレート50部、n-ブチルアクリレート28部、下記リン酸基含有重合性モノマー溶液4部、及び2,2’-アゾビスイソブチロニトリル(AIBN)1.5部からなるモノマー混合物を4時間かけて滴下した。滴下終了後1時間熟成し、その後さらに酢酸ブチル15部及び2,2´-アゾビスイソブチロニトリル1.0部の混合物を1時間かけて反応容器に滴下した。滴下終了後1時間熟成させたのち、メチルエチルケトンで希釈し、固形分50%の水酸基含有アクリル樹脂(A1-1)溶液を得た。得られた水酸基含有アクリル樹脂(A1-1)は、酸価6mgKOH/g、水酸基価48mgKOH/g、重量平均分子量20,000であった。
製造例2
温度計、サーモスタット、攪拌装置、還流冷却器及び水分離器を備えた反応容器に、1,2-シクロヘキサンジカルボン酸無水物69部、1,4-シクロヘキサンジカルボン酸86部、1,6-ヘキサンジオール59部、エチレングリコール25部及びトリメチロールプロパン13部を仕込み、160℃から230℃まで3時間かけて昇温させた後、縮合水を水分離器により留去させながら230℃で保持し、酸価が6mgKOH/gとなるまで反応させた。次いで、キシレン/「スワゾール1000」(商品名、丸善石油化学社製、石油系芳香族炭化水素系溶剤)=50/50(質量比)の混合溶剤で固形分濃度70%となるように希釈し、水酸基含有ポリエステル樹脂(A2-1)溶液を得た。得られた水酸基含有ポリエステル樹脂(A2-1)は、酸価6mgKOH/g、水酸基価56mgKOH/g、数平均分子量3,000であった。
製造例3
撹拌装置、温度計、冷却管及び窒素ガス導入口を備えた四ツ口フラスコにヘプタン60部、キシレン60部、下記高分子分散安定剤(S1-1)溶液(注1)75部、及び下記その他の分散安定剤(S2-1)溶液(注3)10部を仕込んで窒素を吹き込みながら100℃まで昇温させた。次いで、下記コアモノマー組成物(注4)51部を3時間かけて滴下し、更に2時間熟成することにより、非水ディスパージョン樹脂(C-1)溶液を得た。得られた非水ディスパージョン樹脂(C-1)は、固形分40%、平均粒子径146μm、ゼータ電位-55mVであった。また、コア/シェル比は50/50であり、シェル部のSP値は9.0、コア部のSP値は9.9であった。
(注1)高分子分散安定剤(S1-1)溶液
撹拌装置、温度計、水分離器、窒素ガス導入口を備えた四ツ口フラスコに、オレイル2-ヒドロキシ-(3-アリルオキシ)-プロピルスルホサクシネートアンモニウム塩2.05部、キシレン30部を仕込み、水を水分離器により留去させながら130℃まで昇温させた。次いで、メチルメタクリレート16.3部、メチルアクリレート3.3部、n-ブチルアクリレート10.4部、2-エチルヘキシルアクリレート5.3部、2-ヒドロキシエチルアクリレート5.5部及びt-ブチルパーオキシ-2-エチルヘキサノエート2.5部の混合物を3時間かけて滴下し、さらに1時間熟成させた。その後、マクロモノマー(IPDI-HEA)(注2)2.15部を加え、さらに4時間熟成を行なうことにより固形分60%の高分子分散安定剤(S1-1)溶液を得た。
(注2)マクロモノマー(IPDI-HEA)
温度計、サーモスタット、撹拌機、還流冷却器及び空気吹込装置を備え付けた反応容器に、イソホロンジイソシアネート888部(4モル)、2-ヒドロキシエチルアクリレート464部(4モル)及びハイドロキノンモノメチルエーテル0.7部を仕込み、反応容器内に空気を吹き込みながら、80℃に昇温してその温度に5時間保ち、加えた2-ヒドロキシエチルアクリレートが実質的に全て反応したのを確認して、イソホロンジイソシアネートと2-ヒドロキシエチルアクリレートの付加物であるマクロモノマー(IPDI-HEA)を得た。
(注3)その他の分散安定剤(S2-1)溶液
撹拌装置、温度計、冷却管、窒素ガス導入口を備えた四ツ口フラスコに、トルエン還流下、メタンスルホン酸を触媒として12-ヒドロキシステアリン酸を脱水縮合して、樹脂酸価30まで縮合を行なった。得られた数平均分子量約1,800の自己縮合ポリエステルの末端カルボキシル基に、ジメチルアミノエタノールを触媒としてグリシジルメタクリレートを付加して重合性不飽和基を導入し、固形分70%の重合性不飽和基含有マクロモノマー溶液を得た。得られた重合性不飽和基含有マクロモノマーは1分子当り数平均分子量に基づき約1個の重合性不飽和基を有していた。次いで、フラスコ中に酢酸ブチル174部を入れて加熱還流させ、この中に、上記70%重合性不飽和基含有マクロモノマー溶液297部、メチルメタクリレート195.9部、グリシジルメタクリレート18.5部、キシレン163部、2,2’-アゾビスイソブチロニトリル9.6部の混合物を3時間かけて均一速度で滴下し、さらに2時間熟成した。ついでp-t-ブチルカテコール0.05部、メタクリル酸3.8部、ジメチルアミノエタノール0.5部の混合物をフラスコ中に加えて樹脂酸価が0.5になるまで140℃で約5時間反応を続け、固形分50%のその他の分散安定剤(S2-1)溶液を得た。得られたその他の分散安定剤(S2-1)は、12-ヒドロキシステアリン酸によるセグメントと、メチルメタクリレートとグリシジルメタクリレートの共重合体によるセグメントとを有するグラフトポリマーであって、1分子中平均約4個の重合性不飽和基を有している。
(注4)コアモノマー組成物
スチレン12.5部、メチルメタクリレート12.44部、メチルアクリレート5部、アクリロニトリル5部、2-ヒドロキシエチルアクリレート12.5部、グリシジルメタクリレート0.5部、メタクリル酸2.06部及び2,2´-アゾビスイソブチロニトリル1.0部の混合物。
下記表1に示す配合に従って、製造例3と同様の方法により、固形分40%の非水ディスパージョン樹脂(C-2)~(C-18)溶液を得た。非水ディスパージョン樹脂(C-14)に関しては、フラスコに高分子分散安定剤及びその他の分散安定剤を配合せずにコアモノマー組成物を滴下した。
尚、下記表1中の配合量は、固形分又は有効成分の値である。また、非水ディスパージョン樹脂(C-14)及び(C-18)については、ブツ(凝集物)が発生したため、ゼータ電位と粒子径の測定は行わなかった。
(注6)ライトエステルP-1M:商品名、共栄社化学社製、アシッドホスホキシエチルメタクリレート。
実施例1
製造例1で得た水酸基含有アクリル樹脂(A1-1)溶液18部(樹脂固形分9部)、製造例2で得た水酸基含有ポリエステル樹脂(A2-1)溶液12.9部(樹脂固形分9部)、「バリファインBF-20」(商品名、堺化学工業社製、微粒子硫酸バリウム、ゼータ電位6mV、pH9、塩基性顔料)10部及びキシレン20部を広口ガラスビン中に入れ、ガラスビーズを加えて密封し、ペイントシェーカーで60分間分散した後、ガラスビーズを除去して、顔料分散ペーストを得た。
次いで、得られた顔料分散ペースト60.9部、製造例1で得た水酸基含有アクリル樹脂(A1-1)溶液32部、製造例2で得た水酸基含有ポリエステル樹脂(A2-1)溶液30部、「ユーバン28-60」(商品名、ブチルエーテル化メラミン樹脂、三井化学社製、固形分60%、硬化剤)50部、非水ディスパージョン樹脂(C-1)溶液37.5部、「GX-180A」(商品名、旭化成メタルズ社製、アルミニウム顔料ペースト、アルミニウム含有量74%、光輝性顔料)13.5部、「Nacure4167」(商品名、King Industries社製、アルキルリン酸エステルのアミン塩、有効成分25%)4部を均一に混合した。次いで、キシレン/「スワゾール1000」(商品名、丸善石油化学社製、石油系芳香族炭化水素系溶剤)=50/50(質量比)の混合溶剤を添加して、20℃におけるフォードカップNo.4の粘度が12秒になるように調整して、光輝性塗料(X-1)組成物を得た。
下記表2に示す配合に従って、実施例1と同様の方法により、20℃におけるフォードカップNo.4による粘度が12秒である光輝性塗料(X-2)~(X-26)溶液を得た。尚、下記表2中の配合量は、固形分又は有効成分の値である。また、光輝性塗料組成物(X-17)及び(X-21)については、非水ディスパージョン樹脂(C-14)及び(C-18)から持ち込まれるブツ(凝集物)により、塗料状態は「不良」と判断し、以降の塗装、塗膜評価は行わなかった。
製造例21
30cm×45cmのリン酸亜鉛処理された冷延鋼板に、熱硬化性エポキシ樹脂系カチオン電着塗料組成物(商品名「エレクロンGT-10」、関西ペイント社製)を膜厚20μmになるように電着塗装し、170℃で30分加熱して硬化させた。かくして、鋼板上に電着塗膜を形成してなる被塗物H-1を作製した。
30cm×45cmのリン酸亜鉛処理された冷延鋼板に、熱硬化性エポキシ樹脂系カチオン電着塗料組成物(商品名「エレクロンGT-10」、関西ペイント社製)を膜厚20μmになるように電着塗装し、170℃で30分加熱して硬化させた。次いで、この電着塗膜上に中塗り塗料組成物(商品名「TP-65-3」、関西ペイント社製、ポリエステル樹脂・アミノ樹脂系有機溶剤型塗料組成物)を膜厚35μmになるように塗装し、140℃で30分間加熱して硬化させた。かくして、鋼板上に電着塗膜及び中塗り塗膜を形成してなる被塗物H-2を作製した。
実施例17
製造例21で得た被塗物H-1の電着塗膜上に、中塗り塗料組成物(商品名「TP-65-3」、関西ペイント社製、ポリエステル樹脂・アミノ樹脂系有機溶剤型塗料組成物)を硬化塗膜の膜厚として25μmになるように塗装し、5分間放置した後、80℃で5分間プレヒートを行った。7分間セッティングした後、その未硬化塗面上に光輝性塗料組成物(X-1)を、回転霧化型のベル型塗装機を用いて、硬化塗膜の膜厚として15μmになるように塗装し、2分間セッティングした後、80℃で5分間プレヒートを行った。次いで、その未硬化塗面上にアクリル樹脂系有機溶剤型クリヤーコート塗料組成物(商品名「マジクロンKINO-1210」、関西ペイント社製)を硬化塗膜の膜厚として40μmになるように塗装し、7分間放置した後、140℃で30分間加熱して、この3層の複層塗膜を同時に硬化させた。
下記表3に示した光輝性塗料組成物を3コート1ベーク方式(3C1B工程)における光輝性ベースコート塗料として用いる以外は、実施例17と同じ塗料組成物を同じ工程及び条件で塗り重ね、実施例18~32及び比較例11~18の試験板を得た。
製造例22で得た被塗物H-2に、光輝性塗料組成物(X-1)を、回転霧化型のベル型塗装機を用いて、硬化塗膜の膜厚として15μmになるように塗装し、2分間セッティングした後、80℃で5分間プレヒートを行った。次いで、その未硬化塗面上にアクリル樹脂系有機溶剤型上塗りクリヤーコート塗料組成物(商品名「マジクロンKINO-1210」、関西ペイント社製)を硬化塗膜の膜厚として40μmになるように塗装し、7分間放置した後、140℃で30分間加熱して、この2層の複層塗膜を同時に硬化させた。
下記表3に示した光輝性塗料組成物を2コート1ベーク方式(2C1B工程)における光輝性ベースコート塗料として用いる以外は、実施例33と同じ塗料を同じ工程及び条件で塗り重ね、比較例19~21の試験板を得た。
上記実施例及び比較例で得られた各試験板について、下記の試験方法により評価を行なった。評価結果を表3に示す。
角度を変えて各試験板を目視し、下記基準でフリップフロップ性を評価した。評価としては、S~Bが合格で、Cが不合格である。
S:目視の角度による明度の変化が顕著である(極めて優れたフリップフロップ性を有する)。
A:目視の角度による明度の変化が大きい(フリップフロップ性に優れる)。
B:目視の角度による明度の変化がやや小さい(フリップフロップ性がやや劣る)。
C:目視の角度による明度の変化が小さい(フリップフロップ性が劣る)。
各試験板について、「Wave Scan」(商品名、BYKGardner社製)によって測定されるShort Wave(SW)値に基づいて、鮮映性を評価した。SW値が小さいほど塗面の鮮映性が高いことを示し、評価としては、SW値20以上が不合格である。
各試験板について、「Wave Scan」(商品名、BYKGardner社製)によって測定されるLong Wave(LW)値に基づいて、下記のように平滑性を評価した。LW値が小さいほど塗面の平滑性が高いことを示し、評価としては、LW値10以上が不合格である。
Claims (12)
- 下記(A)、(B)及び(C)の樹脂固形分総量を100質量%とする固形分比で、水酸基含有樹脂(A)10~90質量%、硬化剤(B)5~50質量%、非水ディスパージョン樹脂(C)1~40質量%、塩基性顔料(D)1~20質量%、及び光輝性顔料(E)1~30質量%を含有し、該非水ディスパージョン樹脂(C)が、コア部及びシェル部を備えた構造を有し、かつ、該非水ディスパージョン樹脂(C)のシェル部が、該非水ディスパージョン樹脂(C)を構成する重合性不飽和モノマー成分の総量を基準として、スルホン酸基含有重合性不飽和モノマー0.05~5.0質量%を含有することを特徴とする光輝性塗料組成物。
- 非水ディスパージョン樹脂(C)のコア部が、架橋されていることを特徴とする請求項1に記載の光輝性塗料組成物。
- 非水ディスパージョン樹脂(C)のコア部が、該非水ディスパージョン樹脂(C)を構成する重合性不飽和モノマー成分の総量を基準として、酸基含有重合性不飽和モノマー0.1~10.0質量%を含有することを特徴とする請求項1に記載の光輝性塗料組成物。
- 非水ディスパージョン樹脂(C)のシェル部を構成するスルホン酸基含有重合性不飽和モノマーが、少なくとも1個の重合性不飽和基、少なくとも1個のスルホン酸基、及び少なくとも1個の炭素数4以上の炭化水素基を有することを特徴とする請求項1に記載の光輝性塗料組成物。
- 非水ディスパージョン樹脂(C)のコア部とシェル部のSP値の差が0.6以上であることを特徴とする請求項1に記載の光輝性塗料組成物。
- 非水ディスパージョン樹脂(C)のコア部と水酸基含有樹脂(A)のSP値の差が1.0以下であることを特徴とする請求項1に記載の光輝性塗料組成物。
- 非水ディスパージョン樹脂(C)のゼータ電位が-20mV以下であり、かつ、塩基性顔料(D)のゼータ電位が+1mV以上であることを特徴とする請求項1に記載の光輝性塗料組成物。
- 請求項1~7のいずれか1項に記載の光輝性塗料組成物が塗装された塗装物品。
- (1)被塗物に、請求項1~7のいずれか1項に記載の光輝性塗料組成物を塗装してベースコート塗膜を形成する工程、
(2)上記の未硬化のベースコート塗膜上に、クリヤーコート塗料組成物を塗装してクリヤーコート塗膜を形成する工程、並びに
(3)上記の未硬化のベースコート塗膜及び未硬化のクリヤーコート塗膜を、加熱して2層を同時に硬化させる工程
を含む複層塗膜形成方法。 - (1)被塗物に、中塗り塗料組成物を塗装して中塗り塗膜を形成する工程、
(2)上記の未硬化の中塗り塗膜上に、請求項1~7のいずれか1項に記載の光輝性塗料組成物を塗装してベースコート塗膜を形成する工程、
(3)上記の未硬化のベースコート塗膜上に、クリヤーコート塗料組成物を塗装してクリヤーコート塗膜を形成する工程、並びに
(4)上記の未硬化の中塗り塗膜、未硬化のベースコート塗膜及び未硬化のクリヤーコート塗膜を、加熱して3層を同時に硬化させる工程
を含む複層塗膜形成方法。 - 請求項9に記載の複層塗膜形成方法により形成された複層塗膜を有する物品。
- 請求項10に記載の複層塗膜形成方法により形成された複層塗膜を有する物品。
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