JP2013124365A - Photoluminescent coating composition, and article coated with the same - Google Patents

Abstract

An object of the present invention is to provide a glittering paint composition capable of obtaining a coating film having a high glossiness (glossiness) with a single coat and having a high glittering appearance, and an article coated with the composition.
SOLUTION: Acrylic resin (A) having a hydroxyl value in the range of 20 to 160 mgKOH / g, 100 parts by mass, Cellulose acetate butyrate (B) having a hydroxyl value in the range of 20 to 100 mgKOH / g, 2 to 45 parts by mass, And a glittering paint composition obtained by mixing a polyisocyanate compound (D) as a curing agent with a main agent containing a glittering material (C), in a monomer that is a raw material of the acrylic resin (A) The amount of the aromatic vinyl monomer is 40% by mass or less, and the amount of the glittering material (C) is 100 parts by mass in total of the acrylic resin (A) and the cellulose acetate butyrate (B). In addition, a glittering paint composition characterized by being 2 to 20 parts by mass is used.
[Selection figure] None

Description

  The present invention relates to a glittering paint composition capable of obtaining a coating film having a glossy (glossy) appearance with a single coat and having a high glittering appearance, and an article coated with the composition.

  Many plastic parts and metal parts are used in automobile interiors and home appliances. There are various types of paints to paint them, such as matte type, glossy type, solid type, metallic type, etc. in terms of the finished appearance. In addition, there are a one-component acrylic lacquer coating that can be applied as it is when coating a paint, and a two-component acrylic urethane coating that is used after mixing two liquids of a main agent and a curing agent before coating. Further, the coating method includes a one-coat finish that can be finished by one-time coating, a two-coat finish in which a colored paint is applied and then a clear paint is applied.

  Here, in glitter paints containing glitter materials such as aluminum flakes and pearl mica, once applied, the glitter material floats on the surface of the coating, creating irregularities, and light is diffusely reflected. In general, there has been a problem of coating with a clear coating on the surface to give gloss (glossiness) to the appearance and improve the glitter. However, in recent years, for the purpose of obtaining a high-quality appearance while reducing the cost of the paint itself and the coating cost, an appearance having high glossiness (glossiness) and high glossiness can be obtained with one coat. There is a strong demand for glittering paints.

  Therefore, in order to obtain a coating film that has a high glossiness (glossiness) with a single coat and a high gloss appearance, a vinyl resin and a cellulose acetate butyrate are grafted to the vinyl resin as the resin. A colored coating composition using a cellulose acetate butyrate-modified vinyl resin modified with a polyisocyanate compound has been proposed (for example, see Patent Document 1). However, it is difficult to graft cellulose acetate butyrate onto a vinyl resin, and the compatibility of the remaining cellulose acetate butyrate that cannot be grafted with the vinyl resin is poor. A glossy (glossy) coating film with glossiness could not be obtained.

JP 2003-13000 A

  The problem to be solved by the present invention is a glittering paint composition capable of obtaining a coating film having a high glossiness (glossiness) in one coat and having an appearance having a high glitteriness, and has been coated with the composition. It is to provide an article.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have been manufactured using styrene at a specific ratio in the raw material, and have an acrylic resin having a specific hydroxyl value and a specific hydroxyl value. By using a glittering coating composition obtained by mixing a polyisocyanate compound as a curing agent with a main component containing cellulose acetate butyrate and a glittering material in a specific ratio, high gloss (glossy) with one coat. The present invention was completed by finding that a coating film having a high brilliant appearance and a high glossy appearance can be obtained.

  That is, in the present invention, the acrylic resin (A) has a hydroxyl value in the range of 20 to 160 mgKOH / g, 100 parts by mass, and the cellulose acetate butyrate (B) in the range of 20 to 100 mgKOH / g has a hydroxyl value of 2 to 45 mass. A glitter coating composition obtained by mixing a polyisocyanate compound (D) as a curing agent with a main component containing a part and a glitter material (C), which is a raw material for the acrylic resin (A) The proportion of the aromatic vinyl monomer in the body is 40% by mass or less, and the blending amount of the glittering material (C) is a total of 100 parts by mass of the acrylic resin (A) and the cellulose acetate butyrate (B). The present invention relates to a glittering paint composition characterized by being 2 to 20 parts by mass and an article coated with the composition.

  Since the glittering paint composition of the present invention has a high glossiness (glossiness) in one coat and a coating film having a high glittering appearance, the composition can be applied to various articles. Thus, an article having a high design property can be obtained at a low cost. Therefore, the glittering paint composition of the present invention includes a housing for home appliances such as a television, a refrigerator, a washing machine, and an air conditioner; a housing for an electronic device such as a personal computer, a smartphone, a mobile phone, a digital camera, and a game machine; Interior materials for various vehicles such as railway vehicles; Various building materials such as decorative panels; Woodwork materials such as furniture; Artificial / synthetic leather; Can do.

  The glittering paint composition of the present invention comprises 100 parts by mass of an acrylic resin (A) having a hydroxyl value in the range of 20 to 160 mgKOH / g, and cellulose acetate butyrate (B) having a hydroxyl value in the range of 20 to 100 mgKOH / g. A glittering paint composition obtained by mixing a polyisocyanate compound (D) as a curing agent with a main agent containing 2 to 45 parts by mass and a glittering material (C), and is a raw material for the acrylic resin (A) The ratio of the aromatic vinyl monomer in the monomer is 40% by mass or less, and the blending amount of the glitter material (C) is that of the acrylic resin (A) and the cellulose acetate butyrate (B). It is 2-20 mass parts with respect to a total of 100 mass parts.

  First, the acrylic resin (A) will be described. The hydroxyl value of the acrylic resin (A) is in the range of 20 to 160 mgKOH / g because the glossiness (glossiness) and glossiness of the coating film surface of the glittering coating composition are high, but 50 to 150 mgKOH. / G is preferable, and a range of 60 to 140 mgKOH / g is more preferable. In addition, in order to make the hydroxyl value of the said acrylic resin (A) into this range, it can be used by using the acrylic monomer (a1) which has a hydroxyl group as a raw material, and adjusting the usage-amount.

  Examples of the acrylic monomer (a1) having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxy-n-butyl (meth) acrylate, and 2-hydroxypropyl. (Meth) acrylate, 2-hydroxy-n-butyl (meth) acrylate, 3-hydroxy-n-butyl (meth) acrylate, 1,4-cyclohexanedimethanol mono (meth) acrylate, N- (2-hydroxyethyl) (Meth) acrylamide, glycerin mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2- (meth) acryloyloxy Ethyl-2-hydroxyethyl phthalate, lactone-modified (meth) acrylate having a hydroxyl group at the terminal. In addition, the acrylic monomer (a1) having these hydroxyl groups can be used alone or in combination of two or more.

  In the present invention, “(meth) acrylic acid” refers to one or both of methacrylic acid and acrylic acid, “(meth) acrylate” refers to one or both of methacrylate and acrylate, and “(meta) “) Acryloyl” refers to one or both of methacryloyl and acryloyl.

  Examples of the other acrylic monomer (a2) that can be used as a raw material other than the acrylic monomer having a hydroxyl group of the acrylic resin (A) include (meth) acrylic acid, methyl (meth) acrylate, Ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, n-heptyl (meth) Acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, acrylamide, N, - dimethyl (meth) acrylamide, (meth) acrylonitrile, 3- (meth) acryloyl trimethoxysilane, 2-dimethylaminoethyl (meth) acrylate, glycidyl (meth) acrylate. These can be used alone or in combination of two or more.

  Furthermore, as a raw material of the acrylic resin (A), an unsaturated monomer (a3) other than the acrylic monomer may be used. For example, styrene, α-methylstyrene, p-methylstyrene, p- Examples thereof include aromatic vinyl monomers such as methoxystyrene. In addition, when using an aromatic vinyl monomer as a raw material of the said acrylic resin (A), the ratio of the aromatic vinyl monomer in a monomer composition is 40 mass% or less, but 1-30 mass% Is preferable, the range of 3 to 20% by mass is more preferable, and the range of 5 to 15% by mass is further preferable.

  As a method for producing the acrylic resin (A), the acrylic monomer (a1), the acrylic monomer (a2), and the unsaturated monomer (a3) are used in an organic solvent using a polymerization initiator. The method of making it copolymerize is mentioned. The organic solvent used here is preferably a ketone compound, an ester compound, an amide compound, a sulfoxide compound, an ether compound or a hydrocarbon compound. Specifically, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, butyl acetate, Examples include propylene glycol monomethyl ether acetate, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, toluene, xylene and the like. These can be appropriately selected in consideration of boiling point, compatibility, and polymerizability.

  Examples of the polymerization initiator include ketone peroxide compounds such as cyclohexanone peroxide, 3,3,5-trimethylcyclohexanone peroxide, and methylcyclohexanone peroxide; 1,1-bis (tert-butylperoxy) -3, 3,5-trimethylcyclohexane, 1,1-bis (tert-butylperoxy) cyclohexane, n-butyl-4,4-bis (tert-butylperoxy) valerate, 2,2-bis (4,4-di tert-butylperoxycyclohexyl) propane, 2,2-bis (4,4-ditert-amylperoxycyclohexyl) propane, 2,2-bis (4,4-ditert-hexylperoxycyclohexyl) propane, 2 , 2-bis (4,4-ditert-octylpa Peroxyketal compounds such as oxycyclohexyl) propane and 2,2-bis (4,4-dicumylperoxycyclohexyl) propane; cumene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, etc. Hydroperoxides: 1,3-bis (tert-butylperoxy-m-isopropyl) benzene, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, diisopropylbenzene peroxide, tert Dialkyl peroxide compounds such as butyl cumyl peroxide; diacyl peroxide compounds such as decanoyl peroxide, lauroyl peroxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide; bis (tert-butyl) Peroxycarbonate compounds such as (cyclohexyl) peroxydicarbonate; organic peroxides such as peroxyester compounds such as tert-butylperoxybenzoate and 2,5-dimethyl-2,5-di (benzoylperoxy) hexane; Azo compounds such as 2,2′-azobisisobutyronitrile and 1,1′-azobis (cyclohexane-1-carbonitrile).

  Further, when the acrylic resin (A) is produced, a chain transfer agent such as lauryl mercaptan, 2-mercaptoethanol, thioglycerol, ethylthioglycolic acid, octylthioglycolic acid or the like is used as necessary. May be used.

  The cellulose acetate butyrate (B) will be described. The cellulose acetate butyrate (B) is obtained by acetylating and butyrylating a hydroxyl group of cellulose obtained from cotton linter, wood pulp, kenaf and the like. Further, in the present invention, the cellulose acetate butyrate (B) is a cellulose having a free hydroxyl group that is not acetylated or butylated with a part of the hydroxyl group of the raw material cellulose. The compatibility with the acrylic resin (A) is good, and the glossiness (glossiness) and glossiness of the coating film surface of the glittering paint composition are high, so the range is from 20 to 100 mgKOH / g. The range of 30-90 mgKOH / g is preferable, and the range of 40-80 mgKOH / g is more preferable.

  Further, the blending amount of the cellulose acetate butyrate (B) in the glittering paint composition of the present invention is in the range of 2 to 45 parts by mass with respect to 100 parts by mass of the acrylic resin (A). The range of 5 to 40 parts by mass is preferred since the gloss (glossiness) and glossiness of the coating film surface of the conductive coating composition become higher.

  The glitter material (C) will be described. Examples of the bright material (C) include flake pigments such as aluminum flakes, colored aluminum flakes, nickel flakes, titanium flakes, copper flakes, plate-like iron oxide, and glass flakes; mica pigments such as pearl mica and colored pearl mica; Polarizing pigments such as silica flakes and alumina flakes; glass flake pigments coated with metal or titanium dioxide; colored aluminum flake pigments or metal oxide-coated alumina flake pigments; metal oxide-coated silica flake pigments or fine-particle titanium oxide pigments Can be mentioned. Among these glittering materials (C), aluminum pigments such as leafing type aluminum flakes, non-leafing type aluminum flakes, and aluminum powder are preferred, and among them, non-leafing type aluminum flakes are preferred. These aluminum pigments can also be colored.

  Further, the amount of the glitter material (C) added to the glitter paint composition of the present invention increases the gloss (glossiness) and glitter of the coating film surface of the glitter paint composition. Although it is the range of 2-20 mass parts with respect to a total of 100 mass parts of resin (A) and the said cellulose acetate butyrate (B), the range of 5-15 mass parts is preferable.

  Moreover, you may mix | blend a normal coloring pigment with the glittering paint composition of this invention other than the said glittering material (C). As the coloring pigment, any pigment or dye can be used as long as it can be colored. The pigment can be either an organic pigment or an inorganic pigment. As the organic pigment, pigments of various hues such as a red pigment, a green pigment, a blue pigment, a yellow pigment, a purple pigment, an orange pigment, and a brown pigment can be used. Examples of the chemical structure of the organic pigment include azo, phthalocyanine, quinacridone, benzimidazolone, isoindolinone, dioxazine, indanthrene, and perylene. Examples of the inorganic pigment include white pigments such as titanium dioxide, zinc white, and barium sulfate; red pigments such as petals; yellow pigments such as zinc yellow; blue pigments such as ultramarine and bitumen; carbon black, iron black, and titanium. Examples thereof include black pigments such as black.

  The above-mentioned color pigments can be used alone or in combination of two or more to adjust to any color. Moreover, the compounding quantity of the said color pigment to the glittering paint composition of this invention can be suitably set with the quantity in which the desired hue is obtained.

  Further, it is preferable to disperse the above organic pigment with cellulose acetate butyrate because it can be stably dispersed in the glittering paint composition of the present invention and aggregation of the organic pigment can be suppressed.

  In the glittering paint composition of the present invention, the acrylic resin (A), cellulose acetate butyrate (B), and glittering material (C), and, if necessary, a coloring pigment are mixed, However, in order to facilitate this mixing, the acrylic resin (A) and the cellulose acetate butyrate (B) are preferably used as a solution dissolved in an organic solvent or a dispersed dispersion (dispersion paste). About (C) and a coloring pigment, it is preferable to use as a dispersion liquid (dispersion paste) disperse | distributed to the organic solvent.

  Examples of the polyisocyanate compound (D) used as the curing agent of the glittering paint composition of the present invention include aromatics such as tolylene diisocyanate, diphenylmethane diisocyanate, m-xylylene diisocyanate, m-phenylenebis (dimethylmethylene) diisocyanate. Diisocyanate compounds; hexamethylene diisocyanate, lysine diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, 2-methyl-1,3-diisocyanatocyclohexane, 2-methyl-1,5-diisocyanatocyclohexane, isophorone diisocyanate And aliphatic or alicyclic diisocyanate compounds.

  Further, as the polyisocyanate compound (D), a prepolymer having an isocyanate group obtained by addition reaction of the diisocyanate compound with a polyhydric alcohol; an isocyanurate ring obtained by cyclization and trimerization of the diisocyanate compound. A compound having urea bond or burette bond obtained by reacting the above diisocyanate compound with water; 2-isocyanatoethyl (meth) acrylate, 3-isopropenyl-α, α-dimethylbenzyl isocyanate, ( A homopolymer of an acrylic monomer having an isocyanate group such as (meth) acryloyl isocyanate; the acrylic monomer having an isocyanate group and other acrylic monomers, a vinyl ester compound, a vinyl ether compound, an aromatic vinyl A copolymer having an isocyanate group obtained by copolymerization with a monomer such as an nyl monomer or fluoroolefin can also be used.

  Said polyisocyanate compound (D) can be used individually or can be used together 2 or more types.

  The polyisocyanate for the main component of the glittering paint composition of the present invention obtained by mixing the acrylic resin (A), cellulose acetate butyrate (B), glittering material (C), and, if necessary, a coloring pigment. As a compounding quantity of a compound (D), the equivalent of the isocyanate group which a polyisocyanate compound (D) has, and the hydroxyl group (Acrylic resin (A) and cellulose acetate butyrate (B) which exist in the said main ingredient) exist in the said main ingredient. The ratio (isocyanate group / hydroxyl group) is preferably in the range of 0.5 to 2.0, more preferably in the range of 0.7 to 1.3.

  In addition, the glittering paint composition of the present invention includes an antistatic agent, an antifoaming agent, a viscosity modifier, a light-resistant stabilizer, a weather-resistant stabilizer, a heat-resistant stabilizer, an ultraviolet absorber, an antioxidant, if necessary. Additives such as leveling agents and pigment dispersants can be used.

  Since the glittering paint composition of the present invention has a high glossiness (glossiness) in one coat and a coating film having a high glittering appearance, the composition can be applied to various articles. Thus, an article having a high design property can be obtained at a low cost. Articles that can be coated with the glittering paint composition of the present invention include housings for home appliances such as televisions, refrigerators, washing machines, and air conditioners; electronic devices such as personal computers, smartphones, mobile phones, digital cameras, and game machines. Housing materials for various vehicles such as automobiles and railway vehicles; various building materials such as decorative panels; woodwork materials such as furniture; artificial and synthetic leather; FRP bathtubs and the like.

  In addition, the method for applying the glitter paint composition of the present invention varies depending on the application, for example, gravure coater, roll coater, comma coater, knife coater, air knife coater, curtain coater, kiss coater, shower coater, wheeler coater, spin Examples thereof include a coater, dipping, screen printing, spraying, applicator, and bar coater. Among these coating methods, a method by spraying is preferable because a coating film having higher glossiness (glossiness) and glitter and high design properties can be obtained.

  Hereinafter, the present invention will be described in more detail with reference to specific examples. In addition, the hydroxyl value of an acrylic resin and cellulose acetate butyrate is measured based on JIS test method K0070-1992.

(Production Example 1)
A reaction vessel equipped with a thermometer, a reflux condenser, a stirrer, a dropping funnel and a nitrogen gas introduction tube was charged with 667 parts by mass of n-butyl acetate and heated to 120 ° C. under a nitrogen gas stream. Next, at the same temperature, 625 parts by weight of methyl methacrylate, 133 parts by weight of n-butyl acrylate, 232 parts by weight of 2-hydroxyethyl methacrylate, 10 parts by weight of methacrylic acid, 70 parts by weight of tert-butyl peroxy-2-ethylhexanoate Was added dropwise over 4 hours. Even after completion of dropping, the reaction was continued for 5 hours at the same temperature to obtain a 60% by mass solution of acrylic resin (A-1). The hydroxyl value of this acrylic resin (A-1) was 100 mgKOH / g.

(Production Example 2)
A reaction vessel equipped with a thermometer, a reflux condenser, a stirrer, a dropping funnel and a nitrogen gas introduction tube was charged with 667 parts by mass of n-butyl acetate and heated to 120 ° C. under a nitrogen gas stream. Next, at the same temperature, 100 parts by mass of styrene, 525 parts by mass of methyl methacrylate, 133 parts by mass of n-butyl acrylate, 232 parts by mass of 2-hydroxyethyl methacrylate, 10 parts by mass of methacrylic acid, tert-butylperoxy-2-ethylhexa A mixture of 70 parts by weight of Noate was added dropwise over 4 hours. Even after completion of the dropping, the reaction was continued for 5 hours at the same temperature to obtain a 60% by mass solution of the acrylic resin (A-2). The hydroxyl value of this acrylic resin (A-2) was 100 mgKOH / g.

(Production Examples 3 to 6)
60 mass% of acrylic resins (A-3) to (A-6) were similarly operated except that the raw materials such as acrylic monomers used in Production Example 2 were changed to the amounts shown in Table 1. A solution was obtained.

  Table 1 shows the charged amounts of monomers as raw materials for the acrylic resins (A-1) to (A-6) produced above.

Example 1
[Preparation of main ingredient of glitter coating composition]
100 parts by mass of a 60% by mass solution of acrylic resin (A-1) obtained above (60 parts by mass as acrylic resin (A-1)), cellulose acetate butyrate (“CAB551-0.2 manufactured by Eastman Chemical Co., Ltd.) ”, A hydroxyl value of 59 mg KOH / g; hereinafter abbreviated as“ CAB (B-1) ”.) 33.2 parts by mass of a 20% by mass solution with methyl isobutyl ketone (6.64 as CAB (B-1)). 9.7 parts by mass (6.77 parts by mass as an aluminum pigment) and aluminum pigment paste ("Alpaste 5660NS" manufactured by Toyo Aluminum Co., Ltd., non-leafing type, aluminum content 70% by mass) with a disper The main component of the glittering paint composition (1) was prepared.

[Preparation of glitter paint composition]
With respect to the main component of the glittering paint composition (1) obtained above, a polyisocyanate compound (“Bernock DN-980” manufactured by DIC Corporation, non-volatile content: 75% by mass, isocyanate group content: 15. 5 mass%) was blended so that isocyanate group / hydroxyl group = 1/1 (equivalent ratio). Next, Ford Cup No. 4 is diluted with diluted thinner (toluene / methyl isobutyl ketone / ethoxyethyl propionate mixed at a mass ratio of 30/40/30) until 13 seconds (25 ° C.) to give the glittering paint composition (1). Prepared.

(Example 2)
It replaced with the 60 mass% solution of the acrylic resin (A-1) used in Example 1 similarly to Example 1 except having used the 60 mass% solution of the acrylic resin (A-2) obtained above. By operating, a glittering coating composition (2) was prepared.

(Example 3)
It replaced with the 60 mass% solution of the acrylic resin (A-1) used in Example 1 similarly to Example 1 except having used the 60 mass% solution of the acrylic resin (A-3) obtained above. By operating, a glittering coating composition (3) was prepared.

Example 4
Instead of the 60% by mass solution of the acrylic resin (A-1) used in Example 1, using the 60% by mass solution of the acrylic resin (A-4) obtained above, the blending amount of the aluminum pigment paste was changed. A glittering coating composition (4) was prepared in the same manner as in Example 1 except that the amount was changed from 9.7 parts by mass to 10.3 parts by mass (7.21 parts by mass as an aluminum pigment).

(Example 5)
Instead of the 60% by mass solution of the acrylic resin (A-1) used in Example 1, using the 60% by mass solution of the acrylic resin (A-2) obtained above, the CAB (B-1) The amount of the 20 mass% methyl isobutyl ketone solution was changed from 33.2 parts by mass to 105 parts by mass (21 parts by mass as CAB (B-1)), and the amount of the aluminum pigment paste was changed from 9.7 parts by mass to 11 parts by mass. A glittering coating composition (5) was prepared in the same manner as in Example 1 except that the amount was changed to 0.9 parts by mass (8.33 parts by mass as an aluminum pigment).

(Example 6)
Instead of the 60% by mass solution of the acrylic resin (A-1) used in Example 1, using the 60% by mass solution of the acrylic resin (A-2) obtained above, the CAB (B-1) The compounding amount of the 20 mass% methyl isobutyl ketone solution was changed from 33.2 parts by mass to 29.5 parts by mass (5.9 parts by mass as CAB (B-1)), and the compounding amount of the aluminum pigment paste was 9.7. The pigment was changed from 6.6 parts by mass (4.62 parts by mass as an aluminum pigment) and further dispersed in cellulose acetate butyrate ("PREDISOL CAB Violet PVA2683" manufactured by Sun Chemical Co., Ltd.), used cellulose acetate butyrate: 20% by mass obtained by diluting “CAB-531-1” manufactured by Eastman Chemical Co., Ltd., hydroxyl value 56 mgKOH / g) with methyl isobutyl ketone Liquid; hereinafter abbreviated as "CAB color pigment dispersion". ) A bright paint composition (6) was prepared in the same manner as in Example 1 except that 9.8 parts by mass (1.96 parts by mass as the total amount of cellulose acetate butyrate and color pigment) was added. .

(Comparative Example 1)
Instead of the 60% by mass solution of the acrylic resin (A-1) used in Example 1, using the 60% by mass solution of the acrylic resin (A-5) obtained above, the blending amount of the aluminum pigment paste was changed. A glittering paint composition (R1) was prepared in the same manner as in Example 1 except that 9.7 parts by mass was changed to 10.9 parts by mass (7.63 parts by mass as an aluminum pigment).

(Comparative Example 2)
It replaced with the 60 mass% solution of the acrylic resin (A-1) used in Example 1 similarly to Example 1 except having used the 60 mass% solution of the acrylic resin (A-6) obtained above. By operating, a glittering paint composition (R2) was prepared.

(Comparative Example 3)
Instead of the 60% by mass solution of the acrylic resin (A-1) used in Example 1, using the 60% by mass solution of the acrylic resin (A-2) obtained above, the CAB (B-1) Instead of the 20 mass% methyl isobutyl ketone solution, cellulose acetate butyrate (“CAB500-1” manufactured by Eastman Chemical Co., Ltd., hydroxyl value 17 mgKOH / g; hereinafter abbreviated as “CAB (B-2)”) is methylated. A glittering coating composition (R3) was prepared in the same manner as in Example 1 except that the solution was changed to a 20% by mass solution dissolved in isobutyl ketone.

(Comparative Example 4)
Instead of the 60% by mass solution of the acrylic resin (A-1) used in Example 1, using the 60% by mass solution of the acrylic resin (A-2) obtained above, the CAB (B-1) Instead of the 20 mass% methyl isobutyl ketone solution, cellulose acetate butyrate (“CAB553-0.4” manufactured by Eastman Chemical Co., hydroxyl value of 158 mg KOH / g; hereinafter abbreviated as “CAB (B-3)”) The main component of the glittering paint composition was prepared in the same manner as in Example 1 except that the solution was changed to a 20% by mass solution dissolved in methyl isobutyl ketone, but acrylic resin (A-2) and cellulose acetate were prepared. Since the compatibility with butyrate (CAB (B-3) was poor and a uniform main agent could not be obtained even when mixed, the glittering paint composition (R4) was not prepared.

(Comparative Example 5)
Instead of the 60% by mass solution of the acrylic resin (A-1) used in Example 1, using the 60% by mass solution of the acrylic resin (A-2) obtained above, the CAB (B-1) The blending amount of the 20% by weight methyl isobutyl ketone solution was changed from 33.2 parts by weight to 150 parts by weight (30 parts by weight as CAB (B-1)), and the blending amount of the aluminum pigment paste was changed from 9.7 parts by weight to 13 parts by weight. A glittering paint composition (R5) was prepared in the same manner as in Example 1 except that the amount was changed to 2 parts by mass (9.24 parts by mass as an aluminum pigment).

(Comparative Example 6)
Instead of the 60% by mass solution of the acrylic resin (A-1) used in Example 1, using the 60% by mass solution of the acrylic resin (A-2) obtained above, the blending amount of the aluminum pigment paste was changed. A glittering coating composition (R6) was prepared in the same manner as in Example 1 except that the amount was changed from 9.7 parts by mass to 1 part by mass (0.7 parts by mass as an aluminum pigment).

(Comparative Example 7)
Instead of the 60% by mass solution of the acrylic resin (A-1) used in Example 1, using the 60% by mass solution of the acrylic resin (A-2) obtained above, the blending amount of the aluminum pigment paste was changed. A glittering paint composition (R7) was prepared in the same manner as in Example 1 except that 9.7 parts by mass was changed to 23.5 parts by mass (16.45 parts by mass as an aluminum pigment).

  In addition, Table 2 shows the composition of the main component of the glittering paint composition prepared above.

(Example 7)
[Preparation of sample for evaluation]
The glittering paint composition (1) obtained in Example 1 was spray-coated on an acrylonitrile-butadiene-styrene (ABS) resin plate so that the film thickness after curing was 20 μm. Next, after drying at 70 ° C. for 30 minutes, the sample for evaluation was obtained by leaving it at 25 ° C. for 3 days.

[Measurement of specular gloss]
The coating surface of the sample for evaluation obtained above was measured for specular gloss at 20 ° and 60 ° in accordance with JIS test method K 5600-4-7: 1999.

[Evaluation of gloss (feel)]
Glossiness (glossiness) was evaluated from the specular gloss measured above according to the following evaluation criteria.
A: The 20 ° specular gloss is 80 or more, and the 60 ° specular gloss is 90 or more.
Δ: 20 ° specular gloss is less than 80, or 60 ° specular gloss is less than 90.
X: The 20 ° specular gloss is less than 80 and the 60 ° specular gloss is less than 90.

[Evaluation of glitter]
The coating film surface of the evaluation sample obtained above was visually observed, and the glitter was evaluated according to the following evaluation criteria.
○: High brightness.
Δ: Slightly low brightness.
X: No glitter.

(Examples 8-12 and Comparative Examples 8-14)
Instead of the glittering paint composition (1) used in Example 7, the glittering paint compositions (2) to (6) and (R1) obtained in Examples 2 to 6 and Comparative Examples 1 to 7 were used. A sample for evaluation was prepared in the same manner as in Example 7 except that (R7) was used, and then the specular gloss was measured, the gloss (glossiness) was evaluated, and the glitter was evaluated. In Comparative Example 11, since a uniform main agent of the glittering paint composition (R4) was not obtained, no glittering paint composition (R4) was prepared, and the measurement of specular gloss and glossiness (glossiness) Evaluation of brightness and brightness were not performed.

  Table 3 shows the measurement results of the specular gloss, the evaluation results of the glossiness (glossiness), and the evaluation results of the glitter of Examples 7 to 12 and Comparative Examples 8 to 14.

  Examples 7 to 12 coated with the glittering paint composition of the present invention had a glossiness of 20 (high gloss) (glossiness) because the 20 ° specular gloss was 80 or more and the 60 ° specular gloss was 90 or more. In addition, it was highly brilliant visually. This is presumably because the coating is separated into a coating layer containing a large amount of the bright material on the substrate side and a clear layer containing almost no bright material on the surface of the coating in one coat.

  On the other hand, Comparative Example 8 is an example using a glittering paint composition containing a 180 mg KOH / g acrylic resin having a hydroxyl value of more than 160 mg KOH / g, but the 20 ° specular gloss is 77 and less than 80, Since the 60 ° specular gloss was 89 and less than 90, sufficient glossiness (glossiness) could not be obtained, and the visual glossiness was insufficient.

  Comparative Example 9 is an example using a glittering paint composition containing 50% by mass of an acrylic resin in which the proportion of the aromatic vinyl monomer in the monomer that is the raw material of the acrylic resin exceeds 40% by mass. However, since the 20 ° specular gloss is less than 72 and 80, and the 60 ° specular gloss is also less than 83 and 90, sufficient glossiness (glossiness) cannot be obtained, and the visual glitter Was inferior.

  Comparative Example 10 is an example using a glittering paint composition containing a cellulose acetate butyrate having a hydroxyl value of less than 20 mgKOH / g and having a 20 ° specular gloss of 76 and less than 80. Since the 60 ° specular gloss was also less than 86 and 90, sufficient glossiness (glossiness) could not be obtained, and visual glossiness was insufficient.

  Comparative Example 11 is an example using a glittering paint composition containing 158 mg KOH / g cellulose acetate butyrate having a hydroxyl value exceeding 100 mg KOH / g, and the compatibility between the cellulose acetate butyrate and the acrylic resin is high. Unfortunately, a uniform coating composition could not be obtained.

  Comparative Example 12 is an example using a glittering paint composition in which the blending amount of cellulose acetate butyrate was 50 parts by mass exceeding 45 parts by mass with respect to 100 parts by mass of acrylic resin, but 20 ° specular gloss. The degree was less than 78 and 80, and the 60 ° specular gloss was also less than 88 and 90. Therefore, sufficient glossiness (glossiness) could not be obtained, and the visual glossiness was insufficient. there were.

  Comparative Example 13 is an example using a glittering coating composition in which the blending amount of the glittering material is 1.05 parts by mass, which is less than 2 parts by mass, with respect to 100 parts by mass in total of the acrylic resin and cellulose acetate butyrate. However, since the 20 ° specular gloss was 85 and the 60 ° specular gloss was 96, it had high glossiness (glossiness), but the visual glossiness was inferior. .

  Comparative Example 14 is an example using a glittering paint composition in which the blending amount of the glittering material was 24.7 parts by mass exceeding 20 parts by mass with respect to a total of 100 parts by mass of the acrylic resin and cellulose acetate butyrate. However, since the 20 ° specular gloss was 74 and less than 80 and the 60 ° specular gloss was also less than 82 and 90, sufficient glossiness (glossiness) could not be obtained, and the visual brightness The property was also insufficient.

Claims (5)

  100 parts by mass of an acrylic resin (A) having a hydroxyl value of 20 to 160 mgKOH / g, 2 to 45 parts by mass of a cellulose acetate butyrate (B) having a hydroxyl value of 20 to 100 mgKOH / g, and a glittering material ( A glittering coating composition obtained by mixing a polyisocyanate compound (D) as a curing agent with a main component containing C), and an aromatic vinyl in a monomer that is a raw material of the acrylic resin (A) The proportion of the monomer is 40% by mass or less, and the blending amount of the glittering material (C) is 2 to 2 parts per 100 parts by mass in total of the acrylic resin (A) and the cellulose acetate butyrate (B). A glittering paint composition characterized by being 20 parts by mass.   The glitter paint composition according to claim 1, wherein the aromatic vinyl monomer is styrene.   The glitter paint composition according to claim 1 or 2, wherein the glitter material (C) is an aluminum pigment.   The glittering paint composition according to any one of claims 1 to 3, further comprising a coloring pigment dispersed in cellulose acetate butyrate in the main agent.   An article coated with the glittering paint composition according to any one of claims 1 to 4.