JP2003119417A - Brilliant material coating composition, method for forming coating film and coated product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a brilliant coating material composition capable of giving a coating film having brilliant feeling but inconspicuous in particle feeling due to a brilliant pigment when viewed from a highlight position, with no whitish dim feeling in the case of being viewed from a shade position, and seen black when viewed from a position shifted toward a bit shade side part from the highlight position, to provide a method for forming such a coating film, and to provide a coated product coated with the composition. SOLUTION: The brilliant coating material composition comprises (A) the brilliant pigment selected from (A1) a metal oxide-coated alumina flake pigment and (A2) a metal oxide-coated mica pigment, (B) a carbon black pigment, (C) a cellulosic resin and (D) a resin other than the cellulosic resin, and meets the following requirements: I. weight ratio A/B = (20:80) to (80:20) II. weight ratio C/D = (20:80) to (80:20), and III. weight ratio [(A+B)/(C+D)] = (20:100) to (100:100). The method for forming the brilliant coating film comprises coating an object with the above composition.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a glitter coating composition, a method for forming a coating film and an article coated by this method.

[0002]

2. Description of the Related Art Currently, automobiles, automobiles, personal computers,
Highly designable properties are required for coated articles such as mobile phones. In such a coated material, the glittering pigment is required to have glitter when viewed from the highlight position, while the glittering feel from the highlighting position is such that the particle feeling due to the glittering pigment is not conspicuous. It is required to be. Furthermore, there is a need for a design that does not have a feeling of white blur when viewed from the shade position, and that at the same time, can produce a color feeling in which the color changes to black when viewed from a position slightly shifted to the shade side from the highlight. There is.

Conventionally, a glitter coating composition containing an interference mica pigment and an ordinary mica pigment as a glitter pigment in order to eliminate the white blurring feeling when viewed from the shade position, It is shown in JP 2001-164197 A.

[0004] Further, since a particle feeling due to the glittering pigment develops a glittering feeling which is inconspicuous when viewed from the highlight position, a glittering coating composition characterized by containing a fine metal foil is disclosed in Japanese Patent Laid-Open Publication No. 11-111. -290770.

[0005]

However, a glitter coating composition containing an interference mica pigment and a mica pigment as the glitter pigment loses the white blur feeling when viewed from the shade position, When viewed from the light part, the glitter pigment glitters, and the particles of the glitter material are visually observable. In addition, the glittering coating composition containing a fine metal foil (aluminum produced by the vapor deposition method) has a very thin fine foil (thickness of 0.08 μm or less), and therefore, when viewed from the highlight position, The graininess expresses an inconspicuous glittering feeling, but there is a white blurring feeling when seen from the shade position peculiar to the aluminum-containing metallic paint, and further it is seen from a position slightly shifted to the shade side from the highlight. In the present situation, it has a drawback that the color does not change to black.

The object of the present invention is to solve the above-mentioned conventional problems, by applying a specific glitter coating composition, the graininess of the glitter pigment is conspicuous when viewed from the highlight position. It has a brilliant feeling, has no white blur when viewed from the shade position, and is stable even when it is seen from a position slightly shifted to the shade side from the highlight. It is intended to obtain a glitter coating composition, a coating film forming method and a coated article which can be formed.

[0007]

That is, the present invention is the following glitter coating composition, coating film forming method and coated article. (1) Metal oxide-coated alumina flake pigment (A1)
Alternatively, a bright pigment (A) selected from metal oxide-coated mica pigments (A2), carbon black pigment (B), fibrous resin (C), and resin (D) other than fibrous resin.
A coating composition containing (I) (A) / (B) = 20/80 to 80/20 (weight ratio) (II) (C) / (D) = 20/80 to 80/20 (Weight ratio) (III) {(A) + (B)} / {(C) + (D)} = 2
A glitter coating composition satisfying the condition of 0/100 to 100/100 (weight ratio). (2) A coating film forming method for forming a coating film on a substrate using the glitter coating composition according to (1) above. (3) A coating for forming a base coat layer on a substrate using the glitter coating composition described in (1) above, and then forming a top coat layer using a clear coating or a candy coating. Film forming method. (4) A coating film forming method in which after coating a primer layer on a substrate, a coating film is formed using the glitter coating composition described in (1) above. (5) After coating a primer layer on a substrate, forming a base coat layer using the glitter coating composition described in (1) above, and then using a clear coating or a candy coating. A coating film forming method for forming a topcoat layer. (6) A coated article coated by the method for forming a coating film according to any one of (2) to (5) above.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described in detail below.

The metal oxide-coated alumina flake pigment (A1) used as the bright pigment (A) in the present invention.
Is flaky aluminum oxide (Al ₂ O ₃ ), preferably flaky aluminum oxide containing titanium oxide coated with a metal oxide having a high refractive index such as titanium dioxide or iron oxide. The titanium oxide contained can be 0.1 to 4% by weight, preferably 0.5 to 3% by weight. Such a metal oxide-coated alumina flake pigment (A1) is disclosed in JP-A-9-77.
The scale-like aluminum oxide pigment described in Japanese Patent No. 512 is suitable.

The particle size of the metal oxide-coated alumina flake pigment (A1) used in the present invention has an average particle size of 5 μm to 1 μm.
00 μm, preferably 5 μm to 60 μm, average thickness 1 μm
It is preferably m or less, preferably 0.1 μm to 1 μm, and an aspect ratio (particle diameter / thickness) of 20 or more.

As the above-mentioned metal oxide-coated alumina flake pigment (A1), a commercially available product can be used, and examples thereof include "Chiraric (trade name)" of Merck & Co., Inc.

In the present invention, the metal oxide-coated mica pigment (A2) used as the bright pigment (A) is obtained by forming a metal oxide coating on the surface of flaky mica particles. Black iron oxide (Fe
Interference mica pigment coated with ₃ O ₄ ), an interference mica pigment coated with a titanium compound containing a low order titanium oxide and then coated with titanium dioxide, a titanium dioxide film obtained by sputtering titanium metal after coating the surface with a titanium dioxide layer. Interference mica pigments in which low-order titanium oxide parts obtained by reducing a part of the above are scattered. Such a metal oxide-coated mica pigment (A
As 2), the interference mica pigment described in JP 2001-164197 A is preferable.

The particle size of the metal oxide-coated mica pigment (A2) used in the present invention has an average particle size of 1 μm to 100 μm,
An average thickness of 0.1 μm to 1.0 μm is preferable.

The above metal oxide-coated mica pigment (A2)
A commercially available product can be used as, for example, Engelhard Co., Ltd. “Exterior Lumina (trade name)” and the like.

The metal oxide-coated alumina flake pigment (A1) and the metal oxide-coated mica pigment (A2) used in the present invention may be used alone in the glitter coating composition. Further, metal oxide-coated alumina flake pigment (A
1) and the metal oxide-coated mica pigment (A2) may be used in combination.

As the carbon black pigment (B) used in the present invention, those generally used as pigments can be used without limitation, and either of the channel type and furnace type production methods may be used.

Commercially available products can be used as the above carbon black pigment (B). For example, "FW1" from Degussa Co.
(Brand name) "," FW200 (brand name) "," Black Pearl 1300 (brand name) "manufactured by Cabot Corporation, and the like.

The content of the metal oxide-coated alumina flake pigment (A) or the metal oxide-coated mica pigment (A) used in the present invention in the glitter coating composition is based on the carbon black pigment (B). And (A) / (B) = 20 /
80-80 / 20 (weight ratio), preferably 30/70
˜70 / 30 (weight ratio). (A) / (B) = 20
When the content is less than 80% (weight ratio), the glittering property is lowered, and when the content is more than (A) / (B) = 80/20 (weight ratio), the L value is increased and slightly lower than the highlight. It does not appear black when viewed from the position moved to the shade side.

The fibrin resin (C) used in the present invention
Is a resin containing a cellulose derivative such as a cellulose ester, and those conventionally used for paints can be used. Examples of such a fibrous resin include cellulose acetate butyrate (CAB), cellulose acetate propionate (CAP), and nitrocellulose (NC).

As the above-mentioned fibrous resin (C), commercially available products can be used. For example, "CAB" produced by Eastman Kodak Company.
"318-05 (trade name)", "CAB531-1 (trade name)", and "HIG1 / 2 (trade name)" manufactured by Asahi Kasei Corporation.

As the resin (D) other than the fibrin-based resin used in the present invention, a resin usually used as a coating film forming resin for paints can be used without limitation. For example, an acrylic resin, a polyester resin, an alkyd resin, a polyolefin resin, a chlorinated polyolefin resin, a fluororesin, a silicone resin or the like may be used alone or in combination to form a non-crosslinked lacquer type. For example, an amino resin or (block) polyisocyanate It is also possible to use a cross-linking-curable resin by combining with a cross-linking resin such as an epoxy compound or an epoxy compound.

The content of the fibrous resin (C) used in the present invention in the glitter coating composition is (C) / (D) = 20 / based on the resin (D) other than the fibrous resin. 80 ~
80/20 (weight ratio), preferably 30/70 to 70
/ 30 (weight ratio). When the content is more than 80/20 (weight ratio), the coating film performance is deteriorated, and when the content is less than 20/80 (weight ratio), the orientation of the glittering flake pigment is decreased and the glittering effect is decreased. Feeling deteriorates.

Metal oxide-coated alumina flake pigment or metal oxide-coated mica pigment (A) used in the present invention
+ The content of the carbon black pigment (B) in the glitter coating composition is {(A) + (B) based on the resin (D) other than the fibrous resin (C) + the fibrous resin. } / {(C)
+ (D)} = 20/100 to 100/100 (weight ratio), preferably 40/60 to 60/40 (weight ratio)
Is. When the content is more than 100/100 (weight ratio), the coating film performance is deteriorated, and when the content is less than 20/100 (weight ratio), the brilliant flake pigment is contained in a small amount, resulting in a brilliance. Feeling deteriorates.

The bright coating composition of the present invention may contain other color pigments and various additives as required. As the coloring pigment, those conventionally used for paints are used.For example, as an organic pigment, an azolake pigment, a phthalocyanine pigment, an indigo pigment, a perinone pigment, a perylene pigment, a quinophthalone pigment, a dioxazine pigment. Examples thereof include pigments and quinacridone pigments, and examples of the inorganic pigments include yellow lead, yellow iron oxide, red iron oxide, titanium dioxide and the like. The addition amount of the color pigment can be arbitrarily set as long as it does not prevent the effect of suppressing white blur when viewed from the shade portion. As an additive, benzotriazole, an ultraviolet absorber such as anilide oxalate, an antioxidant such as benzophenol, a leveling agent such as silicone, a wax, a viscosity control agent such as organic bentonite,
A curing catalyst and the like can be mentioned.

The glitter coating composition of the present invention can be used by dissolving it in an organic solvent. As the organic solvent, aromatic hydrocarbon solvents, ester solvents, ketone solvents, alcohol solvents, ether solvents and the like can be used.

In the coating film forming method of the present invention, a coating film is formed using the glitter coating composition described above. In this case, a coating film may be formed by one coat using the above glitter coating composition, or a base coat may be formed using the above glitter coating composition and then a top coat may be formed by a clear paint or a candy paint. May be formed. Here, the clear paint contains a film-forming resin and is a transparent paint containing no colorant, and the candy paint contains a film-forming resin,
It is a colored transparent paint containing a dye as a colorant. As these, known ones can be used. Further, in the present invention, the primer layer can be formed prior to the above-mentioned coating film formation, and the coating film can be formed on the primer layer by the above-mentioned 1 coat or a combination of the base coat and the top coat. .

The coating of the coating composition used in the present invention is
It can be carried out by a conventionally known coating method such as brush coating, coating with a roll coater, an air spray method using an atomizing type coating machine, and an electrostatic method. Drying, baking, etc. may be performed for each layer of the coating film, or a plurality of layers may be collectively performed.

As the article to which the present invention is applied, iron,
Metals including aluminum, magnesium or alloys thereof, glass, inorganic materials such as concrete, polyethylene, polypropylene, ethylene-vinyl acetate copolymer, polyamide, polyacryl, polyester, vinyl chloride resin, vinylidene chloride resin, polycarbonate -Bonette, polyurethane, resin molded products such as acrylonitrile-butadiene-styrene copolymer, and plastic materials such as various FRPs, wood, paper and the like. It should be noted that it is optional to previously subject these substrates to be coated to appropriate primer or precoat treatment.

The coated article of the present invention is a coated article obtained by the above coating, and a glitter coating film is formed by the glitter coating composition of the present invention. This glittering coating film gives an excellent glittering feeling by combining a specific glittering pigment and carbon black, combining a fibrin-based resin with another resin, and using these in specific proportions. In this case, when viewed from the highlight position, a glittering feeling is obtained, but graininess is not conspicuous, and when viewed from the shade position, there is no white blurring feeling, and a little (about 3
When viewed from a position shifted to the shade side, it has a color feeling that the color changes to black, and excellent designability can be obtained. Such a design property can be obtained even when the pliers or the top coat is not formed, but when the primer is formed, the adhesion of the coating film is improved, and when the top coat is formed,
The protective properties and design of the coating film are improved.

[0030]

As described above, according to the glitter coating composition, the coating method and the coated article of the present invention, the graininess of the glitter pigment when viewed from the highlight position has a glitter which is not conspicuous. It is possible to stably form a glittering coating film which has no white blur when viewed from the shade position and which appears black when viewed from a position slightly shifted from the highlight position to the shade side.

[0031]

EXAMPLES The present invention will be described more specifically below with reference to Examples and Comparative Examples. However, the scope of the present invention is in no way limited to these examples. In each example, parts represent parts by weight unless otherwise specified.

Example 1 Acrylic resin Acridic A-190, an acrylic resin, which was previously compounded.
Part of (* 7) and Carbon Black FW200 (* 5)
And 3.6 parts were dispersed by an attritor using glass beads as a dispersion medium until the particle size became 5 μm or less, to prepare a carbon black colored paste. Metal oxide coated alumina flake pigment Silary T60-23WNT (* 1)
8.4 parts, Acridic A-190 20 parts as a total amount with the above part, 25 parts of a 30% ethyl acetate solution of the fibrous resin cellulose acetate acetate butyrate CAB531-1 (* 6), coloring -Stroke was added sequentially and stirred. Next, polyisocyanate compound Sumidule N-75
(* 8) Add 3.3 parts, and further add 39.7 parts of a mixed solvent of xylene: isobutyl acetate 50:50 and stir,
It was prepared as a bright paint 1. The above composition is shown in Table 1.

Examples 2 to 5 and Comparative Examples 1 to 3 A glitter coating material was prepared and diluted in the same manner as in Example 1 except that the ratios of the mixtures were as shown in Table 1. The above composition is shown in Table 1.

[0034]

[Table 1]

(* 1) Syralic T60-23WNT:
Metal oxide-coated alumina flake pigment Merck Co., Ltd., average particle size 17 μm, average thickness 0.3 μm, heating residue 100%, trade name (* 2) Exterior Lumina Red-Blue: Metal oxide-coated mica pigment Engelhard Co., average particle size 17 μm, heating residue 100%, trade name (* 3) Iriodin 225 WNT: pearl pigment Merck Co., Inc., heating residue 100%, trade name (* 4) Metalure : Small metal foil AVERY
Dennis Co., average thickness 0.06 μm, heating residue 10%, trade name (* 5) FW200: carbon black, Degussa Co., Ltd.
Product name (* 6) CAB531-1: Fiber-based resin cellulose acetate butyrate, Eastman Chemicals,
Trade name (* 7) Acridic A-190: Acrylic resin manufactured by Dainippon Ink and Chemicals, Inc., 50% heating residue, Trade name (* 8) Sumidule N-75: Polyisocyanate compound, Sumitomo Bayer , Heating residue 75%, trade name

Test Example A coating test was conducted using the glitter coating compositions of Examples 1 to 4 and Comparative Examples 1 to 3. (Preparation of primer) An acrylic urethane resin-based paint "High Urethane No. 5000 Primer Black: NOF BASF Coatings" was prepared and diluted as a primer coating material.

(Preparation of Top Coat) As a clear coat for the top coat, an acrylic urethane resin-based paint "High Urethane No. 6500 Clear: NOF BASF Coatings" was prepared and diluted.

(Method for preparing coated plate) Thickness 3 mm, 7 cm ×
A 12 cm ABS substrate manufactured by Japan A & L Co., Ltd. and a test piece of Clarastic MVF was used. This was degreased with isopropyl alcohol to obtain an article to be coated. The diluted bright paint was applied by an air sprayer so that the dry film thickness was 15 μm. Leave at room temperature for about 10 minutes and then at 75 ℃ for 30 minutes.
Baked for a minute. For the top coat, high urethane No. 65 is used after the diluted glitter paint is applied.
00 clear was coated with an air sprayer to a dry film thickness of 25 μm and left at room temperature for about 10 minutes, then at 75 ° C.
And baked for 30 minutes to obtain a coated plate. The primer is applied by coating Hi Urethane No. 5000 Primer Black with an air spray to a dry film thickness of 10 μm, then applying a diluted glittering paint, and leaving it at room temperature for about 10 minutes. The coated plate was obtained by baking at 75 ° C. for 30 minutes. Table 2 shows the presence or absence of a primer and the presence or absence of a top coat clear.

Using this coated plate, 10 persons who can evaluate the finished appearance of the coating film can be evaluated in the room where sunlight is shining.
Visual evaluation was performed with sunlight applied to a part of the coated plate. A little shade from bright feeling, white blurring, highlight
The black discoloration on the side was evaluated. The evaluation results are shown in Table 2.

[0040]

[Table 2]

(1) Brightness Brightness when viewed from the highlight was judged according to the following evaluation criteria. 3; The particle feeling due to the bright pigment is not conspicuous 2; The particle feeling due to the bright pigment is conspicuous. Glittering 1; 3 in which the orientation of the bright pigment was inferior was passed.

(2) White blur feeling The white blur feeling seen from the shade was judged according to the following evaluation criteria. 2; no white blur 1; white blur 2 was accepted.

From the above results, A / B, C / D, A + B
Examples 1 to 4 in which / C + D is within the range of the present invention are excellent in glittering feeling, white blurring feeling, and black discoloration feeling, but in Comparative Examples 1 to 3 outside the range, poor results are obtained.

(3) Black discoloration slightly on the shade side from the highlight The black discoloration feeling when viewed on the shade side at an angle of 30 ° from the highlight was judged according to the following evaluation criteria. 2; Black color change 1; No color change 2 was accepted.

From the above results, the samples of Examples 1 to 4 are excellent in the feeling of brightness, white blur and black discoloration, but Comparative Examples 1 to 3
The ones gave inferior results.

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 4D075 AE03 AE07 CB13 DA23 DC12                       DC18 EA05 EA43 EB07 EB13                       EB16 EB22 EB35 EB36 EB42                       EB45 EB56 EC02 EC04 EC07                       EC23 EC54                 4J038 BA041 BA042 BA081 BA082                       CB001 CB002 CB171 CB172                       CD091 CD092 CG001 CG002                       DA131 DA132 DB001 DB002                       DD001 DD002 DL001 DL002                       HA026 HA166 HA546 KA06                       KA08 KA15 KA20 NA01 PB03                       PB05 PB09 PC02 PC03 PC06                       PC08 PC10

Claims (6)

[Claims] 1. A bright pigment (A) selected from a metal oxide-coated alumina flake pigment (A1) or a metal oxide-coated mica pigment (A2), a carbon black pigment (B), and a fibrous resin ( A coating composition containing C) and a resin (D) other than the fibrin-based resin, which comprises: (A) / (B) = 20/80 to 80/20 (weight ratio) II. (C) / (D) = 20/80 to 80/20 (weight ratio) III. {(A) + (B)} / {(C) + (D)} = 20
/ 100 to 100/100 (weight ratio), the glitter coating composition. 2. A coating film forming method for forming a coating film on a substrate using the glitter coating composition according to claim 1. 3. A base coat layer is formed on a substrate by using the glitter coating composition according to claim 1, and then a top coat layer is formed by using a clear paint or a candy paint. Coating film forming method. 4. A method for forming a coating film, which comprises coating a primer layer on a substrate and then forming a coating film using the glitter coating composition according to claim 1. 5. A base material is coated with a primer layer, a base coat layer is formed using the glitter coating composition according to claim 1, and then a clear paint or a candy paint is used. Coating film forming method for forming a topcoat layer. 6. A coated article coated by the method for forming a coating film according to claim 2.