• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
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    • 专利摘要:
    The present invention uses an aqueous coloring coating composition comprising a neutralized acrylic copolymer containing an alkoxysilyl group and a carboxyl group and a coloring pigment and coated with a spray apparatus having a micro-aperture nozzle and a spray apparatus having a micro-aperture nozzle A step of coating a substrate with an aqueous coloring coating composition to obtain a coating film, and a step of coating the coating film with a clear coating composition.
    公开号:KR19980032711A
    申请号:KR1019970051910
    申请日:1997-10-10
    公开日:1998-07-25
    发明作者:오노게이타；하야시유끼코；호리베쿄이치；기야타히로아키；나카하타아끼마사；후쿠다미쓰히로；구와노가즈유키；스기우라마모루
    申请人:와타나베다다시；간사이페인토(주)；
    IPC主号:
    专利说明:

    Aqueous colored coating composition and method of using the same (Aqueous colored coating compound and method)
    The present invention relates to a novel aqueous coloring coating composition and a novel coating method using the composition.
    The demand for color and design has been diversified every year. There is an increasing demand for color, design and unique design, especially for young people. Also, in order to promote a company or a corporation, there is an increasing demand for differentiation by the shape stamp of a trademark or a product image. In order to cope with this tendency, it is important to improve the design effect by the shape painting.
    Generally, the pattern coating is carried out by spraying the coloring coating composition with a spraying means having a micro-aperture nozzle to obtain a thin coating film, usually about 1 mu m thick. A preferred coloring coating composition is an aqueous coloring coating composition free from air pollution problems by evaporation of an organic solvent. Color coating compositions for pattern coating are required to provide a thin film having tinting power, but high concentrations of pigment compositions have been used but have been problematic. This aqueous coloring coating composition provides a coating film that is unsatisfactory in water resistance and adhesion and can not be safely ejected from the micro-aperture nozzles of the spray means due to its large viscosity.
    It is an object of the present invention to provide a novel coating composition which comprises a step of coating an object with an aqueous colored coating composition so as to form a shape film using a spray device having a micro-aperture nozzle, and a step of coating the shape coat with a clear coating composition And to provide a method of coating a shape. Here, the aqueous coating composition is suitably applied to spray coating, and provides a coating film excellent in appearance and excellent in film properties such as adhesion, water resistance and light resistance.
    It is still another object of the present invention to provide a novel aqueous colored coating composition suitable for use in the coating method.
    Objects of the present invention will become clear from the following description.
    According to the present invention, there is provided an aqueous colored coating composition which is applied by using a spray apparatus having a micro-aperture nozzle, which comprises a neutralization product of an acrylic copolymer (A) containing an alkoxysilyl group and a carboxyl group, (C). In accordance with the present invention there is also provided a method of coating a substrate, comprising the steps of coating the substrate with the aqueous colored coating composition to form a patterned coating using a spray apparatus having a micro-aperture nozzle, and coating the patterned coating with a clear coating composition And provides a shape painting method.
    The present inventors have extensively studied to develop a shape painting method using a spray apparatus having a micro-aperture nozzle. Here, the colored coating composition is adapted to a spray coating and provides a coating film excellent in appearance and excellent in properties of a film such as adhesion, water resistance and light resistance. The inventors have anticipated that the aim is to paint the aqueous colored coating composition containing a specific acrylic copolymer as a resin component using a spray device having a micro-aperture nozzle, followed by a coating of the clear paint composition And can be accomplished by a shape-painting method. This name was completed based on this new discovery.
    The aqueous colored coating compositions used to form the coats in the process of the present invention are described below.
    The aqueous colored coating composition comprises a neutralized product of the acrylic copolymer (A) and a colored pigment (C) as its main components. This composition contains, as a resin component, a neutralized product of the acrylic copolymer (B) in addition to the neutralized product of the acrylic copolymer (A). These components are described below.
    The acrylic copolymer (A)
    The acrylic copolymer (A) (hereinafter abbreviated as copolymer (A)) contains an alkoxysilyl group and a carboxyl group. The alkoxysilyl group acts as a functional group capable of forming a crosslinking in the copolymer to improve the film properties such as adhesion to the substrate, interlayer adhesion, water resistance and the like.
    The copolymer (A) is a polymerizable unsaturated monomer containing an alkoxysilyl group (hereinafter referred to as a silane monomer), a polymerizable unsaturated monomer containing a carboxyl group (hereinafter referred to as a carboxylic acid monomer), and others capable of copolymerizing with these monomers (Hereinafter referred to as other monomers).
    The silane monomer contains, for example, a polymerizable unsaturated monomer containing an alkoxysilyl group represented by Chemical Formula (1).
    Wherein R 1 is an alkyl group having 1 to 10 carbon atoms, R 2 and R 3 are the same or different and each is a phenyl group, an alkyl group having 1 to 6 carbon atoms, or an alkoxyl group having 1 to 10 carbon atoms, n is 1 And when n is at least 2, the R 2 groups may be the same or different and the R 3 groups may be the same or different.
    In formula (1), R2And R3Examples of the alkyl group having 1 to 6 carbon atoms represented by the formula (I) include methyl, ethyl, n-propyl, isopropyl, n-butyl, i- butyl, sec- , n-hexyl, isohexyl, 1-methylpentyl, and the like. ROneExamples of the alkyl group having from 1 to 10 carbon atoms represented by R2And R3N-heptyl, 2-ethylhexyl, n-octyl, n-nonyl, n-decyl and the like, in addition to those exemplified as the alkyl group of 1 to 6 carbon atoms. R2And R3Examples of alkoxyl groups having from 1 to 10 carbon atoms represented by the general formula (I) include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, i-butoxy, sec-butoxy, n-hexyloxy, n-pentoxy, isopentoxy, n-hexyloxy, isohexyloxy, n-octyloxy and the like.
    Typical examples of silane monomers include compounds represented by formula (2).
    Where A isorAnd R4Is a hydrogen atom or a methyl group, R5Is a bivalent aliphatic saturated hydrocarbon group of 1 to 6 carbon atoms, ROne, R2, R3And n are as defined above.
    In Formula 2, R5Examples of the divalent aliphatic saturated hydrocarbon group of 1 to 6 carbon atoms represented by the formula (I) include methylene, ethylene, propylene, 1,2-butylene, 1,3-butylene, And linear or branched alkylene groups such as ethylene, pentamethylene, hexamethylene, and the like. ROne, R2And R3The specific examples of groups represented by the following are the same as given above.
    Compounds of formula 2, wherein A is ) Are as follows.
    - (meth) acryloyloxyethyltrimethoxysilane, - (meth) acryloyloxypropyltrimethoxysilane, - (meth) acryloyloxypropyltriethoxysilane, - (meth) (Meth) acryloxypropylmethyldimethoxysilane, γ- (meth) acryloyloxypropylmethyldiethoxysilane, γ- (meth) acryloyloxypropylmethyldipropoxysilane, γ- (meth) acryloyloxybutylphenyldimethoxysilane, - (meth) acryloyloxybutylphenyldiethoxysilane, - (meth) acryloyloxybutylphenyldipropoxysilane, - (Meth) acryloyloxypropyldimethylethoxysilane, - (meth) acryloyloxypropylphenylmethylmethoxysilane, - (meth) acryloyloxypropylphenylmethylethoxysilane ,
    .
    The expression (meth) acrylic oil used throughout the specification refers to acrylic oil or methacrylic oil.
    Compounds of formula 2, wherein A is ) Are as follows.
    Examples of the silane monomer other than the compound of the formula (2) include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltripropoxysilane and the like.
    Preferred examples of the silane monomers are γ- (meth) acryloyloxypropyltrimethoxysilane, γ- (meth) acryloyloxypropyltriethoxysilane, γ- (meth) acryloyloxypropyltripropoxysilane, γ- (Meth) acryloyloxypropyltri-n-butoxysilane, - (meth) acryloyloxypropylmethyldimethoxysilane, - (meth) acryloylpropylmethyl di-n-butoxysilane, and the like.
    These silane monomers may be used alone or in combination.
    The carboxylic acid monomer used in the production of the copolymer (A) may be selected from those capable of polymerizing with an unsaturated monomer having a carboxyl group and copolymerizing with the silane monomer without any particular limitation. Specific examples of carboxylic acid monomers are acrylic acid, methacrylic acid, itaconic acid, itaconic anhydride, crotonic acid, maleic acid, maleic anhydride, fumaric acid, citraconic acid and the like. The carboxylic acid monomers may be used alone or in combination.
    The other monomers to be used in the production of the copolymer (A) are not particularly limited as long as they are unsaturated monomers copolymerizable with the silane monomers and the carboxylic acid monomers.
    Specific examples of the aforementioned other monomers are methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, acrylate, cyclohexyl (meth) acrylic acid or methacrylic acid of the C 1-24 alkyl or cycloalkyl esters such as acrylate and the like; C 1-12 alkoxyalkyl esters of acrylic acid or methacrylic acid such as methoxyethyl (meth) acrylate, methoxybutyl (meth) acrylate, ethoxybutyl (meth) acrylate and the like; Esters of (meth) acrylic acid and aromatic alcohols such as benzyl (meth) acrylate and the like; C 1-12 hydroxyalkyl esters of acrylic acid and methacrylic acid such as 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate and the like; Adducts of monocarboxylic acid compounds such as capric acid, lauric acid, linoleic acid, oleic acid and the like and hydroxyalkyl esters of glycidyl (meth) acrylate or (meth) acrylic acid; (Trade name of a (meth) acrylate having fluorine on the side chain), perfluorocyclohexyl (meth) acrylate, perfluoro (meth) acrylate, Fluorine-containing compounds such as hexylethylene and the like; Vinyl aromatic compounds such as styrene, -Methylstyrene, vinyltoluene, p-chlorostyrene, p-tert-butylstyrene and the like; Unsaturated carboxylic acids such as itaconic acid, itaconic anhydride, crotonic acid, maleic acid, maleic anhydride, fumaric acid, citraconic acid and the like other than (meth) acrylic acid with an alcohol selected from the group consisting of butyl alcohol, pentyl alcohol, heptyl alcohol, octyl alcohol, Monoester or diester with aryl alcohol or monohydric alcohol of 4 to 18 carbon atoms; vinyl ethers such as n-butyl vinyl ether, ethyl vinyl ether and methyl vinyl ether; Glycidyl (meth) acrylate or glycidyl-containing monomers such as these are used in substantially the same molar ratio as monobutylphosphoric acid, monoctylphosphoric acid, monophenylphosphoric acid or a phosphoric acid compound such as (2 (2-methacryloyloxypropyl) acid phosphate, (2-methacryloyloxypropyl) acid phosphate or a phosphate group, and (2-methacryloyloxypropyl) acid phosphate and A reaction product obtained by reaction; (Meth) acrylonitrile; and the like.
    Other monomers may be appropriately selected depending on the desired properties, and may be used alone or in combination.
    The term (meth) acrylate used throughout the specification refers to acrylate or methacrylate.
    The copolymerization of the monomers for preparing the copolymer (A) is carried out by heating in an organic solvent at a temperature of about 60 to about 160 캜 for about 1 to 15 hours using an azo or peroxide radical polymerization initiator.
    The amount of the alkoxysilyl group represented by the formula (1) in the copolymer (A) depends on the reactivity during curing, the adhesion of the obtained film, the viscosity of the coating composition, and the storage stability of the copolymer (A) Preferably from about 0.03 to about 2.0 equivalents, more preferably from about 0.03 to about 0.8 equivalents, per kg of copolymer (A), calculated as solids from the viewpoint of solubility.
    The amount of the carboxyl group in the copolymer (A) is preferably an acid value of about 20 to about 150 mg KOH / g in view of the stability of the aqueous coating composition obtained from the copolymer (A) and the water resistance of the obtained film, Is in the range of about 30 to about 120 mg KOH / g of acid value.
    The copolymer (A) does not necessarily contain a hydroxyl group. However, since the hydroxyl group reacts with the alkoxysilyl group during curing while contributing to the curing reaction, the hydroxyl value of the copolymer (A) is preferably in the range of about 10 to about 150 mg KOH / g, more preferably about 20 to 100 mg KOH / g.
    The weight average molecular weight of the copolymer (A) is preferably about 3,000 to about 200,000 (or number average molecular weight is 1,000 to 60,000), more preferably about 10,000 to about 100,000.
    Useful classes of copolymers (A) can be used alone or in combination.
    Copolymer (B)
    The acrylic copolymer (B) (hereinafter abbreviated as copolymer (B)) contains a carboxyl group.
    The copolymer (B) can be produced by copolymerizing a carboxylic acid monomer and other monomers, which have been respectively used in the production of the copolymer (A). This copolymerization reaction can be carried out in the same manner as in the production of the copolymer (A).
    The amount of the carboxylic acid in the copolymer (B) is preferably an acid value of about 20 to about 150 mg KOH / g in view of the stability of the aqueous coating composition obtained from the copolymer (B) and the water resistance of the obtained film, Is in the range having an acid value of from about 30 to about 120 mg KOH / g.
    The copolymer (B) does not necessarily contain a hydroxyl group. However, since the hydroxyl group reacts with the alkoxysilyl group in the copolymer (A) during curing while contributing to the curing reaction, the amount of hydroxyl groups in the copolymer (B) is preferably such that the hydroxyl value of the copolymer (B) 150 mg KOH / g, more preferably about 20-100 mg KOH / g.
    The weight average molecular weight of the copolymer (B) is preferably about 3000 to about 200000 (or number average molecular weight is 1000 to 60000), more preferably about 10000 to about 100000. Useful classes of copolymers (B) may be used alone or in combination.
    The copolymer (B) is used as a resin component in dispersing the pigment, whereby a coating composition excellent in pigment dispersion and storage stability can be obtained.
    The colored pigment (C)
    Various coloring pigments of the paint composition or ink composition may be used as the coloring pigment (C). Useful color pigments include bright pigments. For example, if a patterned coating is formed on a white coating, the pigments of the principal primary colors of cyan, magenta, yellow and black are preferably incorporated into the coating composition to yield a wide range of colors using a limited number of colored coating compositions do.
    An example of a cyan pigment is cyan. children. Pigment Blue 15 (C. I. Pigment Blue 15), Po. children. Pigment Blue 15: 1 (C. I. Pigment Blue 15: 1), Po. children. Pigment Blue 15: 2 (C. I. Pigment Blue 15: 2), Po. children. Pigment Blue 15: 3 (C.I. Pigment Blue 15: 3), Po. children. Such as CI Pigment Blue 15: 4 (CI Pigment Blue 15: 4), Metal-Free Cyan Blue, Indanthrene Blue, Prussian Blue, Navy Blue, Cobalt Blue.
    Among these poems. Pigment Blue 15: 3, Poetry. children. Pigment Blue 15: 4 is preferable because of its color tone and light fastness.
    Examples of magenta pigments include, but are not limited to, Lake Red 4R, Carmine FB, Dinitroaniline Orange, Pyrazolone Orange, Pyrazolone Red, Purinon Orange, Permanent Red 2B, (BON Maroon Light), Bordeaux 10B, BON Maroon Medium, Tio Indigo Bordeaux, BON Maroon L, Perillian Vermillion, Perylene scarlet, perylene maroon, benzimidazolone orange, chromium vermillion / molybdenum red, toluidine red, and quinacridone red. Of these, quinacridone red, especially dimethylquinacridone and dichloroquinacridone, are preferred when considering the color tone and light fastness.
    Examples of the yellow pigments include Fast yellow G, Fast yellow 10G, Simulair Yellow 4119, Permanent Yellow FGL, benzimidazolone, and mono-azo Pigments; Disazo Yellow AAMX, Disazo Yellow AAOT, Disazo Yellow AAOA, Permanent Yellow HR, Rionol Yellow F Lionol Yellow FFR and disazo pigments like these; Cromophthal Yellow 3G; Cromophthal Yellow 6G, Cromophthal Yellow GR, and condensed azo pigments such as these; Irgazine Yellow 3RLTN, Irgazine Yellow 2RLT, Irgazine Yellow 2GLT, Fastogen Super Yellow, and the like. GROH, Fastogen Super Yellow GRO, Sandorin Yellow 6GL and the like isoindolinone pigments; Anthrapyrimidine yellow, flavanthrone yellow, acylamino yellow and the like; Green Gold, Pallitol Yellow 1070, Pallitol Yellow 1770, Irish Yellow 5GT, and metal complex pigments such as; Such as Pallitol Yellow EL 1820 (product of BASF), Pallitol Yellow L214OHD (product of BASF), Panchen Fast Yellow Y5700 (product of Bayer AG), Panchen Fast Yellow Y5705 (product of Bayer AG), and isoindoline yellow Pigments; Quinophthalone yellow pigment, chrome yellow, titanium yellow, and the like. Of these, benzimidazolone, isoindolinone pigment, isoindoline yellow pigment and quinophthalone yellow are preferable in terms of color tone and light fastness.
    Examples of the black pigment include carbon black, vegetable black, graphite, iron black and the like. Of these, carbon black is preferable.
    Examples of light bright pigments useful as color pigments are aluminum powder, copper powder, stainless steel powder, nickel powder, titanium oxide-coated mica particles, iron oxide-coated mica particles, brilliant graphite and the like.
    Other useful color pigments other than the hue include, for example, chrome green, cobalt green, chromium oxide, cyan green, brominated green, cobalt / chrome green, titanium / nickel / cobalt / zinc green and such green pigments; Cobalt violet, manganese violet, dioxazine violet, -Form quinacridone violet and the like; And titanium white, antimony white, zinc white, monobasic zinc sulfate and the like white pigments.
    The aqueous colored coating composition to be used in the method according to the present invention comprises a neutralized acrylic copolymer (A) and a colored pigment (C) as main components. This composition contains the acrylic copolymer (B) neutralized in addition to the acrylic copolymer (A) neutralized as the resin component.
    The neutralized product of the term copolymer (A) or the neutralized product of the copolymer (B) refers to the neutralized copolymer (A) or the neutralized copolymer (B). The copolymer (A) or (B) can be neutralized by neutralizing the carboxyl group of each copolymer with a basic substance such as amine, ammonia, or alkali metal hydroxide as a neutralizing agent. Copolymers (A) and (B) are dissolved or dispersed in an aqueous medium by neutralization. There is no particular limitation on the equivalence of the carboxyl group to be neutralized with the base material as long as the copolymers (A) and (B) can be stably dissolved or dispersed in the aqueous medium. Usually 0.1 to 1.5 equivalents, preferably 0.5 to 1.2 equivalents.
    The aqueous medium useful in the present invention may be water or a mixture of water-based organic solvents. The organic solvent useful in the present invention is a solvent having affinity for water.
    The aqueous colored coating composition to be used in the method of the present invention does not have, for example, a neutralized acrylic copolymer (B) as a resin component to be produced by the method described in the following (1) and (2).
    (1) mixing an organic solvent solution which is a part of the copolymer (A) with a coloring pigment (C) so that the coloring pigment (C) is dispersed in a solution, a pigment dispersion Adding water and a neutralizing agent to the water, and mixing the resulting aqueous dispersion with the remaining aqueous dispersion of the pre-neutralized copolymer (A).
    (2) adding water and a neutralizing agent to neutralize the copolymer (A) in an organic solvent solution which is a part of the copolymer (A) and to render it water-soluble, adding the copolymer (A) Mixing the obtained aqueous dispersion of (A) with a colored pigment (C) and mixing the resulting aqueous pigment dispersion with a pre-neutralized aqueous dispersion of the copolymer (A).
    In the methods of (1) and (2), the amount of the copolymer (A) to be used for dispersing the coloring pigment (C) is not particularly limited as long as the coloring pigment (C) can be well dispersed. The amount of the copolymer (A) is usually 20 to 200 parts by weight, preferably 30 to 150 parts by weight, per 100 parts by weight of the coloring pigment (C), calculated as a solid.
    In the process of (1) and (2), the resin to be used as a part of the copolymer (A) in the pigment dispersion may be used as the remainder of the copolymer (A) in the aqueous dispersion to be mixed with the aqueous pigment dispersion The resin and its composition will be the same or different.
    The aqueous colored coating composition used in the process of the present invention comprising the neutralized acrylic copolymer (B) as an additional resin component can be produced, for example, by the following methods (3) and (4).
    (3) An aqueous solution of the neutralized copolymer (B) prepared by adding water to the organic solvent solution of the neutralized copolymer (B) or the organic solvent solution is mixed with a coloring pigment (C) (C), optionally adding water and / or a neutralizing agent, mixing the organic solvent solution portion of the copolymer (A) with the pigment dispersion to neutralize the copolymer (A) and render it water- And mixing the resulting aqueous pigment dispersion with an aqueous dispersion of the remainder of the pre-neutralized copolymer (A).
    (4) An aqueous solution of the neutralized copolymer (B) prepared by adding water to be dispersed in the organic solvent solution of the neutralized copolymer (B) or the organic solvent solution and the coloring pigment (C) are mixed in a solution Dispersing the colored pigment (C), optionally hydrating the pigment dispersion, and mixing the resulting aqueous pigment dispersion with an aqueous dispersion of the remainder of the neutralized copolymer (A) ≪ / RTI >
    (3) and (4), the amount of the organic solvent solution of the neutralized copolymer (B) or the amount of the neutralized copolymer (C) produced by adding water to the organic solvent solution used for dispersing the colored pigment The amount of the coalescent (B) is not particularly limited as long as it is within a range in which the coloring pigment (C) can be well dispersed. The amount of the solution is usually 20 to 200 parts by weight, preferably 30 to 150 parts by weight, per 100 parts by weight of the coloring pigment (C), calculated as solids.
    Among the methods (1) to (4), the method (3) is preferable because an aqueous colored coating composition excellent in pigment dispersibility and stability can be easily produced without agglomeration of the pigment.
    The method of producing the aqueous colored coating composition of the present invention is one of the methods capable of producing an aqueous colored coating composition excellent in pigment dispersibility and stability.
    The proportion of the resin component (that is, the amount of the colorant pigment (C) relative to the copolymer (A) or the copolymers (A) and (B)) is particularly limited so long as the resultant coating film is sufficiently strong and the colored coating composition is in a range of exhibiting a desired tinting strength Usually, these components are used in a weight ratio of the coloring pigment (C) / resin component of 5: 100 to 200: 100. If the coloring pigment is organic, a suitable weight ratio of the coloring pigment to the resin component is from 15: 100 to 150: 100 to 200: 100, preferably 80: 100 to 160: 100. When the coloring pigment is an inorganic substance other than carbon black, a suitable weight ratio is 50: 100 to 200: 100, In the case of black, a suitable weight ratio is from 5: 100 to 50: 100, preferably from 10: 100 to 30: 100. When the bright pigment is used as a coloring pigment, a suitable weight ratio is from 5: 100 to 200: 100, 15: 100 to 1 50: 100.
    When the aqueous colored coating composition contains the neutralized copolymer (B), the solid weight ratio of the copolymer (A) / the copolymer (B) is from 10:90 to 90:10.
    If the colored coating composition of the present invention contains a transparent iron oxide pigment and / or particulate zinc white as a pigment component in addition to the colored pigment (C), the resulting coating film has improved weatherability.
    Examples of the transparent iron oxide pigments include Transoxid Yellow (product of Hilton Davis Co.), Sikotrans Yellow L1916 (product of BASF), and fine particle transparent iron oxide yellow pigment such as Transoxid Red (product of Hilton Davis Co.) TRANSRED 2817 (a product of BASF), and a particulate transparent iron oxide red pigment and the like.
    The particulate zinc white used in the present invention is one of the zinc white pigment particles whose average diameter of the injector is not larger than 0.1 mu m. Of these, the surface of which is preferably treated with at least one of silica, alumina and zirconia. Examples of commercially available suitable zinc white particles are Pinex 50A (Finex 50A) and Finex 25A (trademarked product of Sakai Chemical Industry Co., Ltd., zinc white particles surface-treated with silica and alumina).
    The transparent iron oxide pigments and the particulate zinc white as described above may be used alone or in combination. The amount of these pigments to be used in the present invention is 100 parts by weight or less per 100 parts by weight of the colored pigment (C). Even when the pigment is used in an amount exceeding 100 parts by weight, corresponding effects are scarcely produced, and the color of the coating composition is discolored, viscosity is increased, coating suitability is lowered, and film strength is decreased.
    The coating composition of the present invention comprises a neutralized copolymer (A), a neutralized copolymer (B), a coloring pigment (C), water, a neutralizing agent and optionally a transparent iron oxide pigment and particulate zinc white, Because of reasons or viscosity control.
    Optionally, the coating composition of the present invention contains an appropriate amount of a crosslinking agent, a pigment dispersant, a surface modifier, a surface active agent, a defoaming agent, a flow regulator, a UV absorber, a light stabilizer, a curing catalyst and the like. Useful crosslinking agents are, for example, butyl-etherified melamine resins, methyl-etherified melamine resins, methyl / butyl-etherified melamine resins, urea resins and amino resins, blocked polyisocyanate compounds and the like.
    The coating composition to be used in the present invention is applied using a spray device having a micro-aperture nozzle, and as a result preferably has a low viscosity, i.e., a viscosity of from about 1 to about 20 mPa.s. The composition having a high viscosity is not stably ejected through the micro-aperture nozzle, and the coating suitability is low. A composition with a high viscosity is therefore undesirable.
    A method of shape painting according to the present invention using the above-mentioned paint composition will be described below.
    According to the method of the present invention, the aqueous colored coating composition is formed by coating a substrate with a spray device having a micro-aperture nozzle, followed by applying a clear coating composition to the coating film.
    One or more water-based tinting paint compositions are used according to the desired DIC.
    First, a method of applying a shape to an automobile body or an automobile part as a substrate will be described below.
    The automobile body to be painted and the automobile parts can be used as long as they can be used as such after painting.
    Typical examples of automotive bodies and parts to be painted are those made of metal such as copper plates, aluminum plates, zinc-plated steel plates and iron-zinc alloy plated steel plates; Said metal plate having a surface treated by chemical conversion, such as a chromate-treated, zinc phosphate-treated or iron phosphate-treated surface; Made of plastic such as FRP or SMC; And a plurality of films such as a single film or two films (undercoat and topcoat) or three films (undercoat, intercoat and topcoat).
    Next, a substrate according to the present invention will be described.
    For example, (1) a metal substrate such as a steel sheet coated with three films (undercoat, intercoat and topcoat by electrodeposition) or two films (undercoat and topcoat by electrodeposition), and (2) Plastic coatings painted with two layers (undercoat and topcoat) are described below.
    In producing the substrate 1, the undercoat composition will be applied to a metal surface such as an electrically conductive metal surface treated by chemical conversion, i. E. Zinc phosphate-treated metal surface. In this case, the undercoat composition can be applied by conventional methods such as spray coating, roll coating, dip coating, electrodeposition coating and the like. The undercoat is suitably formed by electrodeposition coating from a composition capable of electrodeposition.
    A suitable dry thickness of the undercoat is from about 3 to about 40 microns, preferably from about 15 to about 30 microns.
    The undercoat formed by the electrodeposition coating is optionally washed with water, air-dried or cured by baking. The topcoat composition is then coated after coating the intercoat composition or without coating the intercoat composition.
    The intercoat composition to be used for this purpose will be one of an aqueous coating composition, an organic solvent coating composition and a powder coating composition. Useful intercoat compositions contain various resin components, such as alkyd resins, polyester resins, acrylic resins, polyurethane resins or vinyl resins. Of these, polyester resin intercoat compositions are preferred.
    The pigment will be incorporated into the intercoat composition to cover the substrate. Thus, the painted intercoat composition is cured by a non-limiting method, but is usually cured by baking. The intercoat has the chipping property. When the intercoat composition is applied to an uncured undercoat, the intercoat composition is cured by burning together with the undercoat. The dry thickness of the intercoat is from about 15 to about 50 microns, preferably from about 20 to about 40 microns.
    The topcoat composition to be applied to an undercoat or intercoat can form a topcoat that is superior in appearance, paint strength and durability. Topcoat compositions of useful automobiles can be used without any particular limitation. Useful topcoat compositions contain the same resins and the same resins as the intercoat compositions described above.
    The color of the topcoat composition is not critical. When the shape coat is formed on the topcoat, the shape formed on the topcoat can be easily seen, so that pale or preferably white is suitably selected as the color of the topcoat. If the topcoat formed on the deep color topcoat exhibits the expected design effect, a deep topcoat composition can be used.
    The topcoat will be formed from the colored topcoat composition or will be a two-membrane topcoat obtained by coating the clearcoat composition on the film of the colored topcoat composition.
    The film of the colored topcoat composition has a dry thickness of from about 10 to about 40 microns, preferably from about 15 to about 30 microns. The film of the clear paint composition formed on the film of the topcoat composition colored in the two-membrane topcoat has a dry thickness of from about 10 to about 50 microns, preferably from about 15 to about 40 microns.
    When the coating is formed on a plastic substrate that produces the substrate 2, the undercoat composition, which can increase the adhesion of the topcoat when applied to plastic substrates, is generally used because the plastic is less adherent to the coating . Useful undercoat compositions include conventional primers for plastics. The undercoat composition is applied by conventional coating methods such as spray coating, roll coating, dip coating, and the like. A suitable dry thickness of the undercoat is from about 3 to 40 microns, preferably from about 15 to about 30 microns.
    In producing the substrate 2, the topcoat composition to be applied to the primer coat is the same type of topcoat composition to be used to prepare the substrate 1 and is of the same resin type. Suitable topcoat compositions include conventional compositions for plastic substrates to be used in automotive coatings. The topcoat formed with respect to the substrate 2 has the same color and the same thickness as the topcoat for the substrate 1. The topcoat for the substrate 2 has a film structure such as a topcoat for the substrate 1.
    Next, a shape painting method of the present invention for an automobile body and an object other than the parts will be described below.
    These objects are other than the body and parts of the vehicle, and a shape film can be formed. Examples of such objects are walls and roofs of buildings, warehouses, fences and other outdoor structures; External surfaces of household electrical devices such as refrigerators, freezers, electric washing machines, electric ovens, personal computers and word processors; And a desk, a stool, an office cupboard, a backpack, shoes, a signboard, a bridge, a steel tower, a ship, and an accessory.
    For example, when forming a coating film on a wall or roof of an outdoor structure, a clear coating composition can be applied after forming a direct coating film on the wall or roof of the outdoor structure.
    Signboards to be painted include metal plates such as steel plates, aluminum plates, zinc-plated steel plates and iron-zinc alloy-plated steel plates; A metal substrate treated by chemical conversion, such as chromate-treated, zinc phosphate-treated or iron phosphate-treated metal substrate; Plastic plates such as FRP plates, acrylic plastic, polycarbonate plastic, vinyl chloride resin and polyethylene plastic; Glass plates; And a film coated with a plurality of films such as a single film or two films (undercoat and topcoat).
    Other objects other than automobile bodies and parts for a shape paint such as a steel plate or a metal plate painted with a single film (topcoat) or two films (undercoat and topcoat) are described below.
    When the coating is formed on a metal substrate treated by chemical conversion, that is, a zinc phosphate-treated metal substrate, the coating composition is applied by a conventional method such as spray coating, roll coating, dip coating, electrodeposition coating and the like. In the case of mass production, a suitable coating method is roll coating by coil coating or sheet coating.
    In forming the two-coatcoat (undercoat and topcoat) on the metal substrate, the undercoat is dried to a dry thickness of from about 2 to about 30 microns and from about 2 to about 10 microns when formed by roll coating .
    The undercoat composition to be used may form an anticorrosive coating and comprises a resin component such as an epoxy resin, a polyester resin and an acrylic resin. The undercoat composition to be used comprises an anticorrosive pigment in terms of corrosion resistance. Useful anticorrosive pigments are zinc chromate, strontium chromate, calcium chromate, lid cyanamide, calcium plumate and zinc phosphate.
    The topcoat composition to be used for forming a single film coating or a two-coating film on a substrate is one which is capable of forming a coating film excellent in appearance, paint strength and durability, and is capable of forming any one of a water-base coating composition, an organic solvent coating composition and a powder coating composition Lt; / RTI > The topcoat composition contains a resin component, for example, an alkyd resin, a polyester resin, a silicone-polyester resin, an acrylic resin, a polyurethane resin or a vinyl resin. Among them, a polyester resin coating composition is generally used. The topcoat has a dry thickness of from about 8 to about 40 microns, preferably from about 10 to about 30 microns.
    The color of the topcoat composition is not critical. When the shaped coating is formed on the topcoat, pale or preferably white is suitable because it makes the shape formed on the topcoat easier to see. A topcoat composition of such a dark color may be used if the topcoat formed on the dark colored topcoat exhibits the expected design effect. Optionally, the topcoat composition may contain an anti-corrosive pigment.
    Shapes are applied on the car body or part or other substrate by the method of the present invention.
    No particular limitation is imposed on the hue of the aqueous colored coating composition for forming the shape coat by the method of the present invention. Shape coatings having a wide range of colors can form paint compositions of various colors such as cyan, magenta, yellow and black, and as a result, the painted compositions overlap each other to exhibit the desired color. Alternatively, a paint composition of lustrous hue may be used.
    The coating composition of the present invention is painted using spray means having a micro-aperture nozzle (hereinafter referred to as micro-aperture spray means). The micro-aperture spraying means to be used in the present invention are classified into two types: air spray type having micro-two-fluid nozzles for preventing spray diffusion and airless spray type having single-hole nozzles. These shapes are used according to the sophistication of the design or the area of the portion of the article to which the composition is to be sprayed. When a borderline should be drawn clearly or a delicate design should be drawn, a mono-nozzle shape is used, and a micro-2-oil nozzle shape is used to change the color stepwise or to paint a large area. The coating composition can be dispensed at a particular point on the substrate using either of two types of spray means having an on / off mechanism and an on-demand system.
    The micro-aperture spray means may comprise a nozzle having a diameter of 20 to 0.8 탆, preferably 30 to 70 탆 (in the case of a single-hole nozzle), or preferably 0.2 to 0.5 mm (in the case of a micro- I have.
    The coating head of the sprayer in the form of a micro-aperture spray means is preferably provided separately for three or four primary colors (referred to as basic primary colors), i.e. for each of the cyan, magenta, yellow and optionally black coating compositions It has a nozzle to be used. The colored coating composition to be used comprises a colored coating composition of a light-bright hue, a coloring coating composition of another color such as white, green, purple, etc., and a mixture of at least two coloring coating compositions other than the basic primary colors. When using such a coating composition, it is appropriate to provide a spray device having a nozzle to be used individually for each coating composition. A wide range of colors can be produced by applying paint compositions of three or four primary primary colors in such a way that the painted paint compositions are superimposed on each other. Thus, if only the basic primary colors are used, three or four nozzles to be used individually are required.
    If the spray means has not only the nozzle for the paint composition of the basic primary color but also the paint composition of the main color other than the basic primary color, the paint composition of the mixed color and the nozzle for the paint composition of the broad color, It is possible to make a special color tone that can not be produced by using only the color tone, and the expected degree of the design effect will be remarkably increased.
    The painting head having the nozzle moves in association with the automatic spray painting machine. The sprayer moves according to position data of the three-dimensional space at a specific short distance away from the substrate. The coating head at a specific position can discharge the coating composition from the nozzle. Optionally, the coating composition can be continuously applied to the overcoat (suitably arranged in advance according to the order) by the coating head to obtain the expected coating film. The time to paint using a micro-caliber spraying device will vary depending on the type and area of the coating to be coated. The coating composition can be continuously applied because it is linked with the automatic coating machine (automatic coating robot) while leading to increased productivity.
    The micro-aperture spraying means has the advantage of achieving a coating efficiency of about 100% since the object to be coated is sprayed onto the solid coating at a short distance. Because of this, it is possible to significantly reduce the size of the air supply and air discharge systems to be installed and significantly reduce the operating costs for the supply and exhaust systems.
    The thickness of the shape coat to be formed according to the method of the present invention is not particularly limited as long as it is such a thickness as to produce the expected color. Coating particles discharged from the nozzle move through the air only at a short distance. The solvent containing the particles can not significantly volatilize while moving over a short distance. Therefore, the sprayed composition can not significantly increase viscosity in motion, and as a result, the wetcoat of the composition is susceptible to sagging. It is therefore difficult to obtain a thick coat. The dry thickness of the formed coating is from about 0.1 to about 10 microns, preferably from about 0.5 to about 5 microns.
    According to the method of the present invention, a clear coating composition is coated on the shaped coating film formed as described above. The shape coat is optionally heated to dry or cure the paint surface prior to application of the clear paint composition. Suitable heating conditions are heating at about 40 to about 180 DEG C for about 1 to about 40 minutes.
    Since the coating film is a thin film, the coating composition is generally required to contain a large amount of pigment in order to obtain tinting strength in a thin film. When not treated, the shape coat will exhibit a low gloss and coarse appearance and will have low chemical resistance. These problems can be overcome by coating the clear paint composition on the shaped coating.
    The clear coating composition to be used is suitably selected according to the desired performance and other factors. The form of the clear paint composition is not particularly limited and includes, for example, an organic solvent paint composition, a water-based paint composition, a powder paint composition and the like. The clear paint composition contains various resin components such as an acrylic resin, a polyester resin, an alkyd resin, a silicone resin, a fluorine-containing resin and the like. The clear paint composition is one that can be cured by heat or can be cured by exposure to an actinic ray such as ultraviolet ray or electron ray. The kind of the clear coating composition can be appropriately selected depending on the purpose. For example, it is desirable to use a clear topcoat composition that has been used in automobiles to date, if it is applied to automotive bodies. Of these, a clear thermosetting resin coating composition is more preferable. Useful clear coating compositions contain UV absorbers and light stabilizers to improve light fastness. The clear paint composition is applied only to the portion of the shape coat, preferably to the front surface of the object including the shape coat.
    The thickness of the clear coating film is appropriately determined according to the type of the clear coating film, and is not particularly limited. The dry thickness of the clear coat is usually about 10 to about 50 mu m.
    The clear coating composition is applied after curing the shape coat. Preferably, however, the clear thermosetting coating composition is applied over the air-dried but not yet cured shaped coating to improve the interlayer adhesion between the shaped coating and the clear coating and to reduce the amount of energy consumed during heating, The coating film and the clear coating film are heated for baking. The firing conditions after application of the clear paint composition are baking at about 60 to about 180 DEG C for about 5 to about 40 minutes.
    In this method, a multilayer coating film composed of a shape coat and a clear coat film is formed on the automobile body, automobile parts and other objects.
    The present invention will be described in detail with reference to the following Preparation Examples, Examples and Comparative Examples. Where both parts and percentages are by weight.
    Production Example 1 Preparation of acrylic copolymer (A)
    100 parts of isopropyl alcohol was placed in a four-necked flask equipped with a thermometer, a stirrer, a condenser and a dropping funnel, and heated to 83 DEG C while flowing nitrogen. 10 parts of γ-methacryloyloxypropyltrimethoxysilane, 20 parts of 2-hydroxyethyl acrylate, 10 parts of acrylic acid, 25 parts of n-butyl methacrylate, 25 parts of methyl methacrylate, 10 parts of styrene, And 2 parts of 2,2'-azobis (2-methylbutylonitrile) was added at reflux over a period of 3 hours. After the addition, the resulting mixture was aged under reflux for 2 hours and cooled to obtain a solution of the acrylic copolymer (A) -1. The resulting solution was clear and had a solids content of 50% and a viscosity of 0 (determined by Gardner Foam Viscometer at 25 ° C, then the same). The copolymer solids had an acid value of 78 mg KOH / g, a hydroxyl value of 97 mg KOH / g, 0.41 equivalents / kg of methoxysilyl groups and a weight average molecular weight of about 25000.
    Production Example 2 Production of acrylic copolymer (A)
    100 parts of isopropyl alcohol was placed in a four-necked flask equipped with a thermometer, a stirrer, a condenser and a dropping funnel, and heated to 83 DEG C while flowing nitrogen. 15 parts of γ-methacryloyloxypropyltrimethoxysilane, 25 parts of 2-hydroxyethyl methacrylate, 5 parts of acrylic acid, 25 parts of n-butyl methacrylate, 30 parts of styrene, and 2, 2'-azo And 2 parts of bis (2-methylbutyronitrile) was added under reflux over a period of 3 hours. After the addition was complete, the resulting mixture was aged under reflux for 2 hours and cooled to obtain a solution of the acrylic copolymer (A) -2. The resulting solution was clear and had a solids content of 50% and a viscosity R. [ The copolymer solids had an acid value of 39 mg KOH / g, a hydroxyl value of 108 mg KOH / g, 0.62 equivalents / kg of methoxysilyl groups and a weight average molecular weight of about 25000.
    Production Example 3 Production of aqueous dispersion of acrylic copolymer (A)
    288 parts of water was added to 200 parts of the solution of the acrylic copolymer (A) -1 obtained in Production Example 1 with 50% of the solid component. 11.2 parts of triethylamine was neutralized with 0.8 equivalents of a carboxyl group and added to the mixture with stirring over a period of 10 minutes to make an aqueous mixture. Isopropyl alcohol was then removed by distillation under reduced pressure and a water-based product of the acrylic copolymer (A) -1E was obtained. The resulting aqueous dispersion had a solids content of 25% and a viscosity A.
    Production Example 4 Production of aqueous dispersion of acrylic copolymer (A)
    290 parts of water were added to 200 parts of the solution of the acrylic copolymer (A) -2 obtained in Production Example 2 with 50% of the solid component. 7.0 parts of triethylamine was neutralized with 1.0 equivalent of the carboxyl group and added to the mixture with stirring over a period of 10 minutes to make an aqueous mixture. Isopropyl alcohol was then removed by distillation under reduced pressure and a water-based product of the acrylic copolymer (A) -2E was obtained. The resulting aqueous dispersion had a solids content of 25% and a viscosity B. [
    Production Example 5 Production of acrylic copolymer (B)
    60 parts of ethylene glycol monobutyl ether and 15 parts of isobutyl alcohol were placed in a four-necked flask equipped with a thermometer, a stirrer, a condenser and a dropping funnel, and heated to 115 DEG C while flowing nitrogen. While maintaining the system at 115 占 폚, 27 parts of n-butyl acrylate, 47 parts of methyl methacrylate, 10 parts of styrene, 10 parts of 2-hydroxymethacrylate, 6 parts of acrylic acid and 1 part of azobisisobutyronitrile The mixture was placed in the reactor over a period of 3 hours. After the addition was complete, the resulting mixture was aged at < RTI ID = 0.0 > 115 C < / RTI > A mixture of 1 part of azobisisobutyronitrile and 115 parts of ethylene glycol monobutyl ether was added over a period of 1 hour and aged for 30 minutes or more to obtain a solution of acrylic copolymer (B) -1. The resulting solution had a solids content of 55% and a viscosity Z 4 . The copolymer solids had an acid value of 48 mg KOH / g, a hydroxyl value of 43 mg KOH / g, and a weight average molecular weight of about 30000.
    Production Example 6 Production of acrylic copolymer (B)
    60 parts of ethylene glycol monobutyl ether and 15 parts of isobutyl alcohol were placed in a four-necked flask equipped with a thermometer, a stirrer, a condenser and a dropping funnel, and heated to 115 DEG C while flowing nitrogen. While maintaining the system at 115 占 폚, a mixture of 47 parts of n-butyl methacrylate, 30 parts of methyl methacrylate, 15 parts of 2-hydroxyethyl acrylate, 8 parts of acrylic acid, and 1 part of azobisisobutyronitrile was mixed with 3 parts of 3 Over a period of time. After the addition was complete, the resulting mixture was aged at < RTI ID = 0.0 > 115 C < / RTI > A mixture of 1 part of azobisisobutyronitrile and 115 parts of ethylene glycol monobutyl ether was added over a period of 1 hour and aged for 30 minutes or more to obtain a solution of the acrylic copolymer (B) -2. The resulting solution had a 55% solids content and viscosity of Z 2. The copolymer solids had an acid value of 64 mg KOH / g, a hydroxyl value of 73 mg KOH / g, and a weight average molecular weight of about 30000.
    Preparation Example 7 Preparation of aqueous solution of acrylic copolymer (B)
    A solution of the acrylic copolymer (B) -1 obtained in Production Example 5 having a solid content of 55% was equivalently neutralized with diethanolamine. Deionized water was added to the neutralized solution to obtain an aqueous solution of acrylic copolymer (B) -1 W having 50% solids content.
    Preparation Example 8 Preparation of aqueous solution of acrylic copolymer (B)
    A solution of the acrylic copolymer (B) -2 obtained in Production Example 6 having a solid content of 55% was equivalently neutralized with diethanolamine. Deionized water was added to the neutralized solution to obtain an aqueous solution of acrylic copolymer (B) -2W having 50% solids content.
    Preparation Example 9 Preparation of comparative acrylic resin emulsion
    The reactor was filled with 140 parts of deionized water, 2.5 parts of 30% Niucol 707 SF (product of Nikon Corporation), and 80 parts of the following monomer mixture (1). The resulting mixture was stirred while flowing nitrogen, heated to 60 캜, and 3% aqueous ammonium persulfate solution was added. The mixture was then heated to 80 < 0 > C. While maintaining the system at 80 占 폚, a monomer emulsion containing the remaining 79 parts of 80 parts of the following monomer mixture (1), 2.5 parts of 30% Niucol 707 SF, 4 parts of a 3% aqueous solution of ammonium persulfate and 42 parts of deionized water A metering pump was used to feed the reactor over a period of 4 hours. After the addition is complete, the resulting mixture is aged for 1 hour.
    While maintaining the system at 80 占 폚, the following monomer mixture (2) was added to the reactor over a period of 1.5 hours and aged for 1 hour. The resulting mixture was filtered through a 200-mesh nylon cloth at 30 ° C. Deionized water was added to the filtrate and the mixture was adjusted to pH 7.5 with diethanolamine to give an emulsion of acrylic resin (C) -1E with 20% solids content.
    The monomer mixture (1) was composed of 55 parts of methyl methacrylate, 10 parts of styrene, 9 parts of n-butyl acrylate, 5 parts of 2-hydroxyethyl acrylate and 1 part of methacrylic acid.
    5 parts of methylmethacrylate, 7 parts of n-butyl acrylate, 5 parts of 2-ethylhexyl acrylate, 3 parts of methacrylic acid, 0.5 part of 30% Niucol 707SF, a 3% aqueous solution of ammonium persulfate 4 parts of deionized water and 30 parts of deionized water.
    The solid of the obtained emulsion had an acid value of 26 mg KOH / g and a hydroxyl value of 24 mg KOH / g.
    Preparation of aqueous coloring paint composition
    Example 1
    Hosuta Furum Pink EB 10 pieces
    (A product of Hoechst, a magenta dimethylquinacridone pigment)
    Acrylic copolymer (A) -1E having a solid component of 25%
    Of an aqueous dispersion of 40 parts
    Ethylene glycol monobutyl ether 5 parts
    Deionized water 20 parts
    75 parts in total
    A mixture of the above ingredients was shaken in a paint shaker to disperse the pigment for 2 hours. To the resulting pigment dispersion was added an aqueous dispersion 40 of the acrylic copolymer (A) -1E obtained in Production Example 3 and 35 parts of deionized water with 25% of a solid component. The resulting mixture was stirred to obtain an aqueous magenta paint composition of the present invention having a solid weight ratio of 20% of solid component to a color pigment / resin of 10:20.
    Example 2
    Hosuta Furum Pink EB 10 pieces
    10 parts of an acrylic copolymer (A) -1 solution having a solid component of 50%
    Ethylene glycol monobutyl ether 55 parts
    75 parts in total
    A mixture of the above ingredients was shaken in a paint shaker to disperse the pigment for 2 hours. To the resulting pigment dispersion were added 14 parts of deionized water and 1 part of diethanolamine. The resulting mixture was stirred to become a homogeneous neutralization product. To the product was added 60 parts of an aqueous dispersion of the acrylic copolymer (A) -1E obtained in Production Example 3 with 25% of a solid component. The mixture was stirred to obtain an aqueous magenta coating composition of the present invention having a solid weight ratio of solid component of 20% to a color pigment / resin of 10:20.
    Example 3
    The aqueous cyan coating composition of the present invention is a cyan coating composition of the present invention, which is a cyan pigment such as Cyan Blue G-314 (a product of Sanyo Color Factory, cyanic peroxycarbocyanine blue pigment) used as a pigment and an aqueous dispersion of acrylic copolymer (A) Was prepared in the same manner as in Example 1 except that an aqueous dispersion of an acrylic copolymer (A) -2E having a solid component content of 25% was used.
    Example 4
    The aqueous yellow paint composition of the present invention was prepared in the same manner as in Example 2 except for the following pigment dispersion.
    Pallitol Yellow L1820 10 parts
    (Product of BASF, isoindoline yellow pigment)
    10 parts of an acrylic copolymer (A) -2 solution having a solid component of 50%
    Ethylene glycol monobutyl ether 55 parts
    75 parts in total
    Example 5
    Mitsubishi carbon black MA-100 10 parts
    (Product of Mitsubishi Chemical Co., Ltd., carbon black pigment)
    20 parts of an acrylic copolymer (A) -1 solution having a solid component of 50%
    Ethylene glycol monobutyl ether 45 parts
    75 parts in total
    A mixture of the above ingredients was shaken in a paint shaker to disperse the pigment for 2 hours. To the obtained pigment dispersion, 34 parts of deionized water and 1 part of diethanolamine were added. The resulting mixture was stirred to become a homogeneous neutralization product. 120 parts of the aqueous dispersion of the acrylic copolymer (A) -1E obtained in Preparation Example 3 and 20 parts of deionized water were added to the product with a solid component content of 25%. The mixture was stirred to obtain an aqueous black coating composition of the present invention having a solids content of 20% and a color pigment / resin solid weight ratio of 10:40.
    Example 6
    Hosuta Furum Pink EB 10 pieces
    Acrylic copolymer (B) having a solid component of 50% - 1 W aqueous solution 10 parts
    Ethylene glycol monobutyl ether 5 parts
    Deionized water 50 parts
    75 parts in total
    A mixture of the above ingredients was shaken in a paint shaker to disperse the pigment for 2 hours. To the obtained pigment dispersion was added 60 parts of the aqueous dispersion of the acrylic copolymer (A) -1E obtained in Production Example 3 and 15 parts of deionized water with a solid component of 25%. The resultant mixture was stirred to obtain an aqueous magenta coating composition of the present invention having a solid weight ratio of 20% and a color pigment / resin of 10:20.
    Example 7
    Hosuta Furum Pink EB 10 pieces
    Solution of acrylic copolymer (B) -1 having solid component 55% 9.1 parts
    Ethylene glycol monobutyl ether 55.45 parts
    Diethanolamine 0.45 part
    75 parts in total
    A mixture of the above ingredients was shaken in a paint shaker to disperse the pigment for 2 hours. 10 parts of the solution of the acrylic copolymer (A) -1 obtained in Production Example 1, 24 parts of deionized water, and 1 part of triethylamine were added to the resulting pigment dispersion with a solid content of 50%. The resulting mixture was stirred to neutralize and hydrate. 40 parts of the aqueous dispersion of the acrylic copolymer (A) -1E obtained in Production Example 3, having a solid component of 25%, was mixed with 20% of the solid component and 10% of the aqueous pigment / Was added with stirring to obtain a magenta coating composition.
    Examples 8 and 9
    The aqueous colored coating composition of the present invention was prepared in the same manner as in Example 6 except that the pigment and resin shown in Table 1 were used in the amounts shown in Table 1 and the amount of deionized water was adjusted. In Examples 8 and 9, a solution of acrylic copolymer (B) -2W was used as a resin solution for pigment dispersion.
    Examples 10 to 12
    The aqueous colored coating composition of the present invention was prepared in the same manner as in Example 7 except that the pigment and resin shown in Table 1 were used in the amounts shown in Table 1 and the amount of deionized water was adjusted. In Examples 10 and 12, a solution of the acrylic copolymer (B) -1 was used as a resin solution for pigment dispersion, and diethanolamine was used in an amount of 0.9 part. In Example 11, the solution of the acrylic copolymer (B) -2 was used as a resin solution for pigment dispersion, and 0.6 part of diethanolamine was used
    Comparative Example 1
    Hosuta Furum Pink EB 10 pieces
    Acrylic copolymer (B) having a solid component of 50% - 1 W aqueous solution 10 parts
    Ethylene glycol monobutyl ether 5 parts
    Deionized water 50 parts
    75 parts in total
    A mixture of the above ingredients shaken in the paint to disperse the pigment in the shaker for 2 hours. 50 parts of the aqueous dispersion of the acrylic copolymer (C) -1E obtained in Production Example 9, 20 parts of the solid component of the obtained pigment dispersion, 50 parts of Cymel 370 (product of Mitsui Cytec Co., Ltd., methyl-ether having 88% 5.7 parts of melamine resin) and 19.3 parts of deionized water were added. The resultant mixture was stirred to obtain a comparative aqueous magenta paint composition having a solid weight ratio of 20% and a pigment / resin solids ratio of 10:20.
    Comparative Example 2
    75 parts of the same pigment dispersion as that used in Comparative Example 1 were mixed with 75 parts of the aqueous dispersion of the acrylic copolymer (C) -1E obtained in Production Example 9, with 20% of the solid component. The mixture was stirred to obtain a comparative aqueous magenta paint composition with a solid weight ratio of 20% of solid component to colored pigment / resin of 10:20.
    Comparative Examples 3 to 5
    The comparative aqueous coloring paint composition was prepared in the same manner as in Comparative Example 1, except that the pigment and resin shown in Table 1 were used in the amounts shown in Table 1 and the amount of deionized water was adjusted. In Comparative Examples 3 to 5, an aqueous solution of the acrylic copolymer (B) -1 W was used as a resin solution for pigment dispersion.
    Table 1 shows the blend of the aqueous colored coating compositions obtained in Examples and Comparative Examples and the viscosity (mPa 占 퐏) at 25 占 폚.
    Table 1Example No.One23456 Resin componentA solution of the copolymer (A) -1 5 10A solution of the copolymer (A) -2 5 The water component product of the copolymer (A) -1E2015 153015 The water component product of the copolymer (A) -2E 20 A solution of the copolymer (B) -1 A solution of the copolymer (B) -2 Copolymer (B) An aqueous solution of -1 W 5 Copolymer (B) An aqueous solution of -2W Emulsion of acrylic resin (C) -1E Cymel 370 Pigment componentHosuta Furum Pink EB1010 10 Cyanine Blue G-314 10 Pallitol Yellow L1820 10 Mitsubishi carbon black MA-10010The pigment concentration (PHR)505050502550 Solid body weight (%)202020202020 Viscosity (mPa · s)1012810810
    Table 1 ContinuedExample No.789101112 Resin componentA solution of the copolymer (A) -15 5 10 A solution of the copolymer (A) -25The water component product of the copolymer (A) -1E10 11251030 The water component product of the copolymer (A) -2E 15 A solution of the copolymer (B) -15 10 10 A solution of the copolymer (B) -25Copolymer (B) An aqueous solution of -1 W Copolymer (B) An aqueous solution of -2W 55 Emulsion of acrylic resin (C) -1E Cymel 370 Pigment componentHosuta Furum Pink EB10Cyanine Blue G-314 101010 Pallitol Yellow L182010Mitsubishi carbon black MA-100 10 The pigment concentration (PHR)505063255020 Solid body weight (%)202020202020 Viscosity (mPa · s)10151281513
    Table 1 ContinuedComparative Example No.One2345 Resin componentA solution of the copolymer (A) -1A solution of the copolymer (A) -2The water component product of the copolymer (A) -1EThe water component product of the copolymer (A) -2EA solution of the copolymer (B) -1A solution of the copolymer (B) -2Copolymer (B) An aqueous solution of -1 W555510 Copolymer (B) An aqueous solution of -2WEmulsion of acrylic resin (C) -1E1015101030 Cymel 3705 5510 Pigment componentHosuta Furum Pink EB1010 Cyanine Blue G-314 10 Pallitol Yellow L1820 10Mitsubishi carbon black MA-10010 The pigment concentration (PHR)5050505020 Solid body weight (%)2020202020 Viscosity (mPa · s)250300185150125
    In Table 1, the amounts of the resin component and the pigment component are expressed as parts by weight calculated as solids.
    How to paint shape
    Examples 13 to 62 and Comparative Examples 6 to 25
    (1), (2), (3), (4) and (5) using the aqueous colored coating compositions obtained in Examples 1 to 12 and Comparative Examples 1 to 5 . Test The painted panel was tested by the test method described later.
    Painting method (1)
    (1) Manufacture of substrate
    The cold rolled steel panel treated with zinc phosphate was painted by cation electrodeposition using Electron GT-10 (a trademark for the product of Kansai Paint Co., Ltd., cationic electrodeposition coating composition). The substrate was baked to have an undercoat thickness of 20 탆. TP-37 Gray (a trademark for the product of Kansai Petit Co., Ltd., polyester-based intercoat composition, gray) was coated on an undercoat with a dry thickness of 30 탆 and baked to obtain an intercoat. Neo-Amilac White (a trademark for the product of Kansai Petit Co., Ltd., polyester topcoat composition, white) was coated in an intercoat to a dry thickness of 30 占 퐉 and blanketed to obtain a topcoat. The obtained panel was used as a car body sample (substrate-1).
    (2) Manufacture of test paint panel
    Each of the aqueous colored coating compositions obtained in Examples 1 to 12 and Comparative Examples 1 to 5 was coated on the topcoat of Coated-1 using a micro-aperture air spraying means having a nozzle diameter of 0.3 mm at a dry thickness of about 1.5 占 퐉. The paint was dried at 80 ° C for 5 minutes to remove water and was coated with Clear PG60 Clear (trademark for the product of Kansai Paint Co., Ltd., acrylic-urethane, to-pack clear topcoat composition) to a dry thickness of 35 μm . The coatings were baked at 140 DEG C for 20 minutes to obtain test panels of each color (Examples 13 to 24 and Comparative Examples 6 to 10).
    Painting method (2)
    The topcoat of Coated-1 was continuously coated with the aqueous yellow, magenta, cyan and black coating compositions obtained in Examples 4, 1, 3 and 5, respectively, using micro-aperture air spray means with a nozzle diameter of 0.3 mm. Each film of four colors had a dry thickness of 1.5 占 퐉, and the portion where the four films were overlapped had a total dry thickness of 6 占 퐉. The membrane was dried at 80 占 폚 for 5 minutes to remove water and was coated with 35 占 퐉 dry thickness with Clear PG 60 and dried at 140 占 폚 for 20 minutes to obtain a test paint panel having a coating film of a layered film of an aqueous colored coating composition Lt; 0 > C (Example 25). When the cyan composition was applied to a superimposed film, the coating was removed to partially reveal the underlying magenta film. When the black paint composition was overlaid, the coatings were removed so that the underlying cyan and magenta films appeared on the surface.
    The procedure was repeated except that the topcoat of Coat-1 was continuously coated with the yellow, magenta, cyan and black aqueous coloring coating compositions obtained in Examples 11, 6, 8 and 12, respectively (Example 26 ).
    Painting method (3)
    (1) Manufacture of substrate
    The washed polypropylene substrate to be used as an automobile part was coated with SOPREX # 2508 primer (trademark of Kansai Paint Co., Ltd., primer for plastic) at a dry thickness of 10 μm, and the coating was baked at 120 ° C for 5 minutes. SOPREX # 1410 silver metal (a trademark of Kansai Paint Co., Ltd., a metal-based coating composition for forming a topcoat on plastic) was coated on a primer coat with a dry thickness of 15 mu m. Solex # 1611 clear (trademark of Kansai Paint Co., Ltd., clear paint composition for plastic) was applied to the uncured paint to a dry thickness of 35 占 퐉. The base coating and clear coating were baked at 120 ° C for 30 minutes, and then cured at the same time, and the resultant paint panel was used as a sample of automobile parts (coating-2).
    (2) Manufacture of test paint panel
    Each of the aqueous colored coating compositions obtained in Examples 1 to 12 and Comparative Examples 1 to 5 was applied to the Topcoat of Coating-2 at a dry thickness of about 1.5 占 퐉 using micro-aperture air spraying means having a nozzle diameter of 0.3 mm. The coatings were dried at 80 캜 for 5 minutes to remove water and dried to a dry thickness of 35 탆 using SOPLEX # 500-1 clear (trademark for the product of Kansai Paint Co., Ltd., TOP-PACK Clear topcoat composition for plastic ). The coatings were baked at 120 DEG C for 30 minutes to obtain test panels of each color (Examples 27 to 38 and Comparative Examples 11 to 15).
    Painting method (4)
    (1) Manufacture of substrate
    A hot-dipped galvanized steel panel treated with zinc phosphate was prepared according to the procedure described in KR Kra. 1700 white (trademark of Kansai Paint Co., Ltd., polyester-based topcoat composition for pre-painted metal, white). The steel panel was baked for 45 seconds under the condition of 220 DEG C to obtain a coating film having a thickness of 17 mu m. The obtained paint panel was used as a sign sample (object-3).
    (2) Manufacture of test paint panel
    Each of the aqueous colored coating compositions obtained in Examples 1 to 12 and Comparative Examples 1 to 5 was coated on the topcoat of Coat-3 at a dry thickness of about 1.5 mu m using micro-aperture air spraying means having a nozzle diameter of 0.3 mm. The coating material was dried at 80 ° C for 5 minutes to remove water and was coated with Clear PG60 Clear (trade mark, acrylic-urethane, to-pack clear topcoat composition, manufactured by Kansai Paint Co., Ltd.) Respectively. The coatings were baked at 140 DEG C for 20 minutes to obtain test panels of each color (Examples 39 to 50 and Comparative Examples 16 to 20).
    Painting method (5)
    (1) Manufacture of substrate
    The concrete plate was coated with an alkali silane (trademark of Kansai Paint Co., Ltd., vinyl chloride resin undercoat composition, transparent) to a dry thickness of about 30 탆. After drying, the exterior bean-deluxe and white (trade mark of acrylic resin emulsion paint composition, manufactured by Kansai Paint Co., Ltd.) was coated on an undercoat at a dry thickness of about 100 μm and dried at room temperature. The resultant paint panel was used as a concrete structure sample (substrate-4).
    (2) Manufacture of test paint panel
    Each of the aqueous colored coating compositions obtained in Examples 1 to 12 and Comparative Examples 1 to 5 was applied to a white topcoat of Coat-4 at a dry thickness of about 1.5 占 퐉 using a nozzle-diameter 0.3 mm micro-aperture air spraying means. The coating material was dried at room temperature to remove water, and was coated with Clear PG60 (trademark for the product of Kansai Paint Co., Ltd., acrylic-urethane, to-pack clear topcoat composition) with a dry thickness of 35 탆. The paints were dried at room temperature to obtain test painted panels of each color (Examples 51 to 62 and Comparative Examples 21 to 25).
    Painting Methods The test panels obtained from (1), (2), (3), (4) and (5) were tested according to the following test methods. In the coating method (1), the aqueous colored coating compositions obtained in Examples 1 to 12 and Comparative Examples 1 to 5 were tested for coating suitability.
    Test Methods
    Adhesion: The test panels obtained above were tested for initial adhesion after standing at room temperature (20 ° C) for 24 hours. The test panel was also tested to assess the adhesion after the water resistance test. The water resistance test method includes a step of leaving the paint panel for 24 hours at room temperature (20 占 폚), a step of immersing in water at 40 占 폚 for 10 days, a step of removing water and a step of leaving at room temperature (20 占 폚) . The adhesion test was carried out by the crosscut tape test method under JIS K 5400 8.5.2 (1990). Each test paint panel was cross cut into the substrate to form 100 squares (1 mm x 1 mm). Then, the adhesive cellophane tape was attached to the cut surface and peeled off quickly. Adhesion was assessed by degree of peeling and graded as follows.
    A: Not peeled
    B: 5 or less squares are peeled off
    C: 6 to 50 squares peeled off
    D: 51 or more squares peeled off
    Membrane Appearance: The membrane surface was visually inspected and rated A (excellent) if no blemish was found, or B (poor) when a blemish was found.
    Gloss: 60. The reflectance of the panel surface was measured according to JIS K-5400 7.6 (1990).
    Light fastness: The surface of the test paint panel was subjected to a 2000-hour accelerated four-point test using Sunshine Weather-O-Meter (trademark of Suga Test Instruments Co., Ltd., accelerated weather resistance test apparatus). Thereafter, the color difference (DELTA E * ) between the before and after coating surfaces was determined using a colorimeter. The smaller the color difference (DELTA E * ), the better the weather resistance. Also, gloss changes were visually inspected and rated as follows.
    A: Almost no reduction in gloss
    B: significant gloss reduction
    C: Significant reduction in gloss
    Coating suitability: Each coloring coating composition was visually sprayed using an automatic coater with a micro-bore nozzle (KER 420, a product of Cove Steel Company) to evaluate the spray conditions and the discharge stability of the coating composition. The conditions of the painting operation were air pressure of 2 kg / cm 2 ; Diameter 0.3 mm; The distance between the tip of the nozzle and the coating surface was 2 cm. Spray conditions and discharge stability were rated as follows.
    A: The coating composition was uniformly sprayed and stably discharged
    B: The paint composition was sprayed irregularly and unstably discharged even if it was not successfully sprayed or successfully sprayed
    The test results are shown in Tables 2 to 6. Table 2 shows the result of the paint panel obtained by the method (1), Table 3 shows the test result of the paint panel obtained by the method (2), Table 4 shows the test result of the paint panel obtained by the method (3) 5 shows the test results of the paint panel obtained by the method (4), and Table 6 shows the test results of the paint panel obtained by the method (5).
    Table 2Example 131415161718192021 Drafting methodDrafting method (1) Blood waterBlood Water - 1 An aqueous coloring coating composition (Example No.)Example One23456789 Initial-state adhesionAAAAAAAAA Adhesion after water resistance testAAAAAAAAA Membrane appearanceAAAAAAAAA Polish989898989898989898 Light resistanceThe color difference (DELTA E * )0.30.30.30.30.30.30.30.30.3 Gloss changeAAAAAAAAA StabilityAAAAAAAAA
    Table 2 ContinuedExampleComparative example 222324678910 Drafting methodDrafting method (1) Blood waterBlood Water - (1) An aqueous coloring coating composition (Example No.)ExampleComparative example 101112One2345 Initial-state adhesionAAABDBBB Adhesion after water resistance testAAADDDDD Membrane appearanceAAAAAAAA Polish98971009696969497 Light resistanceThe color difference (DELTA E * )0.30.50.11.51.82.03.01.0 Gloss changeAAABCBBB Paint suitabilityAAABBBBB
    EXAMPLES 25EXAMPLES 26 Drafting methodDrafting method (2) Blood waterBlood Water - 1 Aqueous coloring paint composition (Example No.)Example 4, 14, 1, 34, 1, 3, 511, 611, 6, 811, 6, 8, 12 The color of the top layer of the aqueous colored coating composition filmmagentadraftblackmagentadraftblack Initial-state adhesionAAAAAA Adhesion after water resistance testAAAAAA Membrane appearanceAAAAAA Polish989898989898 Light resistanceThe color difference (DELTA E * )0.20.30.10.20.30.1 Gloss changeAAAAAA
    Table 4Example 272829303132333435 Drafting methodDrafting method (3) Blood waterBlood Water - 2 Aqueous coloring paint composition (Example No.)Example One23456789 Initial-state adhesionAAAAAAAAA Adhesion after water resistance testAAAAAAAAA Membrane appearanceAAAAAAAAA Polish999999999999999999 Light resistanceThe color difference (DELTA E * )0.30.30.30.30.30.30.30.30.3 Gloss changeAAAAAAAAA
    Table 4 ContinuedExampleComparative example 3637381112131415 Drafting methodDrafting method (3) Blood waterBlood Water - 2 An aqueous coloring coating composition (Example No.)ExampleComparative example 101112One2345 Initial-state adhesionAAACDCCC Adhesion after water resistance testAAADDDDD Membrane appearanceAAAAAAAA Polish98981029696969596 Light resistanceThe color difference (DELTA E * )0.30.40.12.53.02.52.51.5 Gloss changeAAACCCCC
    Table 5Example 394041424344454647 Drafting methodDrafting method (4) Blood waterBlood Water - 3 Aqueous coloring paint composition (Example No.)Example One23456789 Initial-state adhesionAAAAAAAAA Adhesion after water resistance testAAAAAAAAA Membrane appearanceAAAAAAAAA Polish9999999810099999999 Light resistanceThe color difference (DELTA E * )0.30.30.30.50.10.30.30.30.3 Gloss changeAAAAAAAAA
    Table 5 ContinuedExampleComparative example 4849501617181920 Drafting methodDrafting method (4) Blood waterBlood Water - 3 An aqueous coloring coating composition (Example No.)ExampleComparative example 101112One2345 Initial-state adhesionAAABDBBB Adhesion after water resistance testAAADDDDD Membrane appearanceAAAAAAAA Polish99981009695969496 Light resistanceThe color difference (DELTA E * )0.30.50.11.51.82.03.01.0 Gloss changeAAACCCCC
    Table 6Example 515253545556575859 Drafting methodDrafting method (5) Blood waterBlood Water - 4 Aqueous coloring paint composition (Example No.)Example One23456789 Initial-state adhesionAAAAAAAAA Adhesion after water resistance testAAAAAAAAA Membrane appearanceAAAAAAAAA Polish969696969696969696 Light resistanceThe color difference (DELTA E * )0.30.30.30.40.10.30.30.30.3 Gloss changeAAAAAAAAA
    Table 6 ContinuedExampleComparative example 6061622122232425 Drafting methodDrafting method (5) Blood waterBlood Water - 4 An aqueous coloring coating composition (Example No.)ExampleComparative example 101112One2345 Initial-state adhesionAAACDCCC Adhesion after water resistance testAAADDDDD Membrane appearanceAAAAAAAA Polish9696969393929393 Light resistanceThe color difference (DELTA E * )0.30.40.12.53.02.52.51.5 Gloss changeAAACCCCC
    Example 63
    The expected shape was obtained by using an automatic sprayer (KER 420, a product of Kobe Steel Co., Ltd.) having heads of four micro-aperture nozzles corresponding to the four colors, the four-color aqueous system obtained in Examples 1, 3, 4 and 5 Lt; / RTI > was formed on the topcoat of the object-1 as an automobile body sample from the coloring material composition. The shape coat was dried at 80 DEG C for 5 minutes. The head of the sprayer is equipped with a micro-2-oil nozzle (micro-bore nozzle) having a nozzle diameter of 0.3 mm. The distance between the tip of the nozzle and the surface to be painted was about 2 cm. Subsequently, using a rotary electrostatic organs, a clear topcoat of about 35 탆 thick was formed by applying a clear PG 60 to the shaped coating and baking at 140 캜 for 20 minutes. Thus, a coated article containing the shape coat and the clear top coat formed on the article-1 was obtained.
    Example 64
    The coated article containing the Coated-on-Form-1 and clear topcoat was prepared in the same manner as in Example 63, except that the coating compositions obtained in Examples 2, 3, 4 and 5 were used as aqueous coloring coating compositions of four colors Were prepared in the same manner.
    Example 65
    The coated article containing the Form coat-1 and the clear top coat was prepared in the same manner as in Example 63 except that the coating composition obtained in Examples 6, 8, 11 and 12 was used as a four-color aqueous coloring coating composition Were prepared in the same manner.
    Example 66
    The coated article containing the Formcoat-1 on top of Formcoat-1 and the clear topcoat was obtained in Example 63, except that the coating composition obtained in Examples 7, 9, 11 and 12 was used as an aqueous coloring coating composition of four colors Were prepared in the same manner.
    Example 67
    The coated product containing the shape coat on the substrate-1 and the clear top coat was prepared in the same manner as in Example 63 except that the aqueous coloring coating composition obtained in Example 3 was used instead of the aqueous coloring coating composition obtained in Example 10 .
    Comparative Example 26
    The coated article containing the Coated-on-Coat-1 shaped top coat and clear topcoat was obtained in Example 63, except that the coating composition obtained in Comparative Examples 1, 3, 4 and 5 was used as an aqueous colored coating composition of four colors Were prepared in the same manner.
    Comparative Example 27
    The coated article containing the coating film on the substrate-1 was prepared in the same manner as in Example 63, except that the coating film was not coated with the clear coating composition.
    Comparative Example 28
    The coated article containing the shape coat on the coated article-1 was prepared in the same manner as in Example 65, except that the coated film was not coated with the clear coating composition.
    Example 68
    The coated article containing the coating film on the substrate 2 and the clear top coat film was coated with the substrate 2 instead of the substrate 1 as a sample of an automobile part and SOPREX # 1611 clear in place of the clear CG60 as a clear top coat composition, Was prepared in the same manner as in Example 63, except that the water was baked at 120 DEG C for 20 minutes to form a clear topcoat having a thickness of about 35 mu m.
    Example 69
    The coated article containing the coating film on the substrate 2 and the clear top coat film was coated with the substrate 2 instead of the substrate 1 as a sample of an automobile part and SOPREX # 1611 clear in place of the clear CG60 as a clear top coat composition, Was prepared in the same manner as in Example 65, except that the water was baked at 120 DEG C for 20 minutes to form a clear topcoat having a thickness of about 35 mu m.
    Comparative Example 29
    The coated article containing the form coat on the substrate-2 and the clear top coat film was prepared in the same manner as in Example 68, except that the coating composition obtained in Comparative Examples 1, 3, 4 and 5 was used as a four-color aqueous coloring coating composition Were prepared in the same manner.
    Example 70
    The coated article containing the form coat on the coated article-3 and the clear top coat film was prepared in the same manner as in Example 63 except that the article-3 was used instead of the coated article-1 as a sign board sample.
    Example 71
    The coated article containing the form coat on the coated article-3 and the clear top coat film was prepared in the same manner as in Example 70, except that the coating composition obtained in Examples 2, 3, 4 and 5 was used as a four-color aqueous colored coating composition Were prepared in the same manner.
    Example 72
    The coated article containing the form coat of Form 3 and the clear top coat film was prepared in the same manner as in Example 70, except that the coating composition obtained in Examples 6, 8, 11 and 12 was used as a four-color aqueous coloring coating composition Were prepared in the same manner.
    Example 73
    The coated articles containing the shape coat and clear top coat film on the object-3 phase were the same as in Example 70 except that the paint compositions obtained in Examples 7, 9, 11 and 12 were used as four-color aqueous coloring paint compositions. Were prepared in the same manner.
    Example 74
    The coated article containing the form coat on the coated article-3 and the clear top coat film was prepared in the same manner as in Example 70 except that the article obtained in Example 10 was used in place of the aqueous colored coating composition obtained in Example 3 .
    Comparative Example 30
    The coated article containing the form coat on the coated article-3 and the clear top coat film was prepared in the same manner as in Example 70, except that the coating composition obtained in Comparative Examples 1, 3, 4 and 5 was used as a four-color aqueous colored coating composition Were prepared in the same manner.
    Example 75
    The coated product containing the shape coat and the clear top coat film on the support-4 phase is a sample of the concrete structure, except that the support-4 is formed instead of the support-1, and the shape coat and the clear top coat film are formed, Was prepared in the same manner as in Example 63.
    Example 76
    The coated article containing the form coat on the coated article-4 and the clear top coat film was prepared in the same manner as in Example 75, except that the coating composition obtained in Examples 6, 8, 11 and 12 was used as a four-color aqueous colored coating composition Were prepared in the same manner.
    Comparative Example 31
    The coated article containing the form coat on the coated article-4 and the clear top coat film was prepared in the same manner as in Example 75, except that the coating composition obtained in Comparative Examples 1, 3, 4 and 5 was used as a four-color aqueous colored coating composition Were prepared in the same manner.
    Coatings of the articles obtained in Examples 63 to 76 and Comparative Examples 26 to 31 were tested by the above test method. Evaluation was done on the same part of the shape.
    The degree of discoloration in the light resistance test was visually inspected and evaluated according to the following criteria, not according to the color difference ( E * ).
    A: Some discoloration
    B: Large discoloration
    C: Significant discoloration
    The test results are shown in Table 7.
    Table 7 Yes NoExampleComparative exampleExampleComparative Example 6364656667262728686929 Blood waterBlood Water - 1Substrate - 2 Initial-state adhesionAAAAABAAAAC Adhesion after water resistance testAAAAADAAAAD Membrane appearanceAAAAAAAAAAA Polish989898989896555510010096 Light resistanceDegree of discolorationAAAAABBBAAC Gloss changeAAAAABCCAAB
    Table 7 Continued Yes NoExampleComparative ExampleExampleComparative Example 707172737430757631 Blood waterBlood Water - 3Blood Water - 4 Initial-state adhesionAAAAABAAC Adhesion after water resistance testAAAAADAAD Membrane appearanceAAAAAAAAA Polish989898989898969896 Light resistanceDegree of discolorationAAAAABAAC Gloss changeAAAAABAAB
    As shown in Tables 2 to 7, the multilayer film according to the present invention comprising the film of the aqueous colored coating composition formed on the substrate and the clear coating film is excellent in adhesion, gloss and light fastness before and after the water resistance test. In addition, the aqueous colored coating composition of the present invention shows excellent paintability when forming a shape film.
    The shape coat formed according to the present invention using the micro-aperture spraying means is excellent in adhesion to the substrate and interlayer adhesion even when the pigment concentration is somewhat high. Good adhesion is probably obtained for the following reasons. The copolymer (A) in the aqueous coloring coating composition has an alkoxysilyl group which is converted to a silanol group when the composition is formed into a film. The silanol groups contributed to increasing the adhesion to the substrate. In addition, the interlayer adhesion is improved by the condensation reaction between the silanol groups or between the silanol groups and the hydroxyl groups. Also, the formed coating film formed according to the present invention has a high water resistance because the aqueous colored coating composition causes cross-linking reaction. In the aqueous coloring coating composition to be used in the method of the present invention, the alkoxysilyl group-containing copolymer (A) reduces the viscosity of the composition while allowing the composition to be easily coated with a micro-aperture spraying means.
    According to the present invention, a multilayer film formed of a shape coat film and a clear coat film formed on a substrate is excellent in appearance, gloss, light resistance and the like. In addition, excellent chemical resistance or scratch resistance or other favorable properties can be imposed on the film by appropriate selection of the clear coating composition to be applied to the coating film.
    权利要求:
    Claims (18)
    [1" claim-type="Currently amended] (C) containing an alkoxysilyl group and a carboxyl group-containing acrylic copolymer (A) to be painted by using a spray device having a micro-aperture nozzle, and a coloring pigment (C).
    [2" claim-type="Currently amended] The coating composition according to claim 1, wherein the amount of the alkoxysilyl group in the copolymer (A) is about 0.03 to about 2.0 equivalents per kg of the copolymer (A), calculated as a solid.
    [3" claim-type="Currently amended] The coating composition according to claim 1, wherein the copolymer (A) has an acid value of about 20 to about 150 mg KOH / g.
    [4" claim-type="Currently amended] The coating composition according to claim 1, wherein the copolymer (A) contains a hydroxyl group and the hydroxyl value of the copolymer (A) is about 10 to about 150 mg KOH / g.
    [5" claim-type="Currently amended] The coating composition according to claim 1, wherein the copolymer (A) has a weight average molecular weight of from about 3,000 to about 200,000.
    [6" claim-type="Currently amended] Mixing a portion of the organic solvent solution of the copolymer (A) with a coloring pigment (C) to disperse the coloring pigment (C) in the solution, a step of mixing the pigment dispersion (A) obtained to neutralize and hydrolyze the copolymer And a step of mixing the obtained aqueous dispersion with the remaining aqueous dispersion of the pre-neutralized copolymer (A). The coating composition according to Claim 1,
    [7" claim-type="Currently amended] The coating composition according to claim 1, wherein the weight ratio of the coloring pigment (C) / resin component is from 5: 100 to 200: 100.
    [8" claim-type="Currently amended] The coating composition according to claim 1, which comprises a neutralized product of an acrylic copolymer (B) containing a carboxyl group as a resin component in addition to the neutralized acrylic copolymer (A).
    [9" claim-type="Currently amended] The coating composition according to claim 8, wherein the copolymer (B) has an acid value of about 20 to about 150 mg KOH / g.
    [10" claim-type="Currently amended] The coating composition according to claim 8, wherein the copolymer (B) contains a hydroxyl group and the hydroxyl value of the copolymer (B) is about 10 to about 150 mg KOH / g.
    [11" claim-type="Currently amended] The coating composition according to claim 8, wherein the copolymer (B) has a weight average molecular weight of about 3000 to 200000.
    [12" claim-type="Currently amended] An aqueous solution of the neutralized copolymer (B) prepared by adding water to the organic solvent solution of the neutralized copolymer (B) or the organic solvent solution and the coloring pigment (C) are mixed to prepare a colored pigment (C) And mixing the resulting aqueous dispersion of the neutralized copolymer (A) with the resultant pigment dispersion. The coating composition according to claim 8, which is prepared by a process comprising the steps of:
    [13" claim-type="Currently amended] An aqueous solution of the neutralized copolymer (B) prepared by adding water to the organic solvent solution of the neutralized copolymer (B) or the organic solvent solution and the coloring pigment (C) are mixed to prepare a colored pigment (C) (A), and mixing the remaining aqueous dispersion of the pre-neutralized copolymer (A) with water. The coating composition according to claim 8, wherein the coating composition is prepared by a method comprising the steps of:
    [14" claim-type="Currently amended] The coating composition according to claim 8, wherein the weight ratio of the coloring pigment (C) / resin component is from 5: 100 to 200: 100.
    [15" claim-type="Currently amended] Coating a coated film with the aqueous colored coating composition of claim 1 using a spray device having a micro-aperture nozzle to obtain a coated film, and coating the shaped film with a clear coating composition.
    [16" claim-type="Currently amended] 16. The method of claim 15, wherein the aqueous colored coating composition is at least one composition having a color selected from the group consisting of cyan, magenta, yellow, and black.
    [17" claim-type="Currently amended] The shape painting method according to claim 15, wherein the object is an automobile body or an automobile part.
    [18" claim-type="Currently amended] The shape painting method according to claim 16, wherein the object is other than an automobile body or an automobile part.
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    同族专利:
    公开号 | 公开日
    EP0835913A2|1998-04-15|
    DE69712008T2|2002-11-28|
    EP0835913B1|2002-04-17|
    CA2217847C|2002-04-09|
    CA2217847A1|1998-04-11|
    EP0835913A3|1998-07-08|
    DE69712008D1|2002-05-23|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    法律状态:
    1996-10-11|Priority to JP26952496A
    1996-10-11|Priority to JP269524/1996
    1996-10-11|Priority to JP26956096A
    1996-10-11|Priority to JP269560/1996
    1997-10-10|Application filed by 와타나베다다시, 간사이페인토(주)
    1998-07-25|Publication of KR19980032711A
    优先权:
    申请号 | 申请日 | 专利标题
    JP26952496A|JPH10114883A|1996-10-11|1996-10-11|Water-based color coating composition|
    JP269524/1996|1996-10-11|
    JP26956096A|JP3275070B2|1996-10-11|1996-10-11|Pattern painting method|
    JP269560/1996|1996-10-11|
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