JPH10265732A - Coating material providing crepe-like pattern - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject coating material capable of uniformly maintaining the appearance of a coated membrane formed into a crepe-like pattern and further capable of forming the coating membrane improved in thereby phenomenon and excellent in design by formulating a specific amino resin. SOLUTION: This coating material comprises (A) 50-97 pts.wt. at least one kind of a hydroxide-containing polyester resin of an acrylic resin, (B) 3-50 pts.wt. amino resin having two or more triazine rings of the formula [X is H, CH2 OH, CH2 OR (R is a 1-8C linear or branched alkyl), CH2 or CH2 OCH2 , with the proviso that at least one of CH2 and CH2 OCH2 is included therein], (C) 0.1-15 pts.wt. (in terms of sulfonic acid) surfonic acid blocked by a secondary or tertiary amine having 50-250 deg.C boiling point, and (D) 0.01-5 pts.wt. surface modifier (with the proviso that the formulating amounts of the components C and D are based on the total 100 pts.wt. of the components A and B). The coating material is suitable for coating a substrate of a steel plate, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a paint which is excellent in design and is capable of forming a bent pattern, and provides a paint suitable for coating a substrate such as a steel plate.

[0002]

2. Description of the Related Art A substrate coated with a paint for forming a fine pattern exhibits an aesthetic appearance excellent in design due to the surface structure of the coating film on which the fine pattern is formed. As a paint for forming such a fine pattern, for example, Japanese Patent Publication No. Hei 3-10671 and Japanese Patent Publication No. Hei 6-11879 disclose a fine paint for pre-coated metal.

[0003] However, in the wrinkle paints described in these patent publications, the formed wrinkle pattern is fine and poor in three-dimensional appearance. Further, in order to keep the appearance of the coating film on which the fine pattern is formed uniform, it is necessary to carefully control the thickness of the coating. On the other hand, if crosslinked organic fine particles or inorganic fine particles are added, a so-called streaking phenomenon may occur when coating with a bar coater or a roll coater. If the number is relatively large, streaking becomes remarkable. Since the coating film at the striped portion has a low film thickness, the formation of the fine pattern may be insufficient, and further, the fine pattern may not be formed. As described above, in the case of the shrink paint, unlike a general paint, if any streaking phenomenon occurs, the inconvenience tends to be conspicuous.

[0004]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to maintain a uniform appearance of a coating film on which a fine pattern is formed,
Another object of the present invention is to provide a fine pattern forming paint capable of forming a coating film having a three-dimensional appearance and an excellent design property with an improved streaking phenomenon.

[0005]

Means for Solving the Problems The present inventor, by blending a specific amino resin with a wrinkle pattern forming paint on a base material such as a steel sheet, has a uniform coating film appearance and excellent design properties. Was found to be obtained.

That is, the present invention relates to (1) at least 50 to 97 parts by weight of at least one of a hydroxyl group-containing polyester resin and an acrylic resin;

[0007]

Embedded image (X is a hydrogen atom, a group —CH ₂ OH, a group —CH ₂ OR, a group —CH ₂ — or a group —CH ₂ OCH ₂ —, which may be the same or different, and at least Group -CH
₂ - and a group -CH ₂ OCH ₂ - wherein any one kind of,
R represents a linear or branched alkyl group having 1 to 8 carbon atoms) 3 to 50 parts by weight of an amino resin having two or more triazine rings, and (3) a secondary having a boiling point of 50 to 250 ° C. Alternatively, 0.1 to 15 parts by weight (in terms of sulfonic acid) of a sulfonic acid compound blocked with a tertiary amine and 0.01 to 5 parts by weight of (4) a surface conditioner [however, the blending amounts of the components (3) to (4)] Is based on 100 parts by weight of the total of the components (1) and (2)]. If (5) 0.01 to 5 parts by weight of wax is added as required, a fine pattern is more easily formed. And, the fine pattern forming paint of the present invention is a bar coater, a roll coater,
Painted using a roll curtain coater, curtain flow coater, die coater, spray gun, etc.
If further embossing is applied after coating, it can be adapted to a desired use.

The hydroxyl group-containing polyester resin and acrylic resin (1) used in the present invention are a hydroxyl group-containing polyester resin and an acrylic resin capable of reacting with an amino resin. Not limited. Examples of such a polyester resin include a polymer polyester, an oil-modified polyester, an oil-free polyester, and a silicone-modified polyester resin, and commercially available polyester resins may be used. Further, as the acrylic resin having a hydroxyl group, a fluorine-based acrylic resin modified with fluorine can also be used.

Examples of commercially available polyester resins or acrylic resins having a hydroxyl group include Beccolite M-6003-60 (manufactured by Dainippon Ink) and Beccolite M-6601-60-S (manufactured by Dainippon Ink). , Byron GK-13CS (Toyobo Co., Ltd.), Alloplats 1
711 (manufactured by Nisshin Arrow Chemical Co., Ltd.), Alloset 5534-
SB60 (manufactured by Nippon Shokubai Co., Ltd.) and the like. These hydroxyl-containing polyester resins and acrylic resins can be used alone or in combination of two or more. The amount of these resins is
It is 50 to 97 parts by weight, preferably 60 to 90 parts by weight, based on the resin solids. If the blending amount of the polyester resin or the acrylic resin is less than 50 parts by weight, the processability is lowered, and if it is more than 97 parts by weight, poor curing is caused and the formation of shrinkage pattern is reduced.

The general formula used in the present invention

[0011]

Embedded image (X is a hydrogen atom, a group —CH ₂ OH, a group —CH ₂ OR, a group —CH ₂ — or a group —CH ₂ OCH ₂ —, which may be the same or different, and at least Group -CH
₂ - and a group -CH ₂ OCH ₂ - wherein any one kind of,
R represents a linear or branched alkyl group having 1 to 8 carbon atoms), and the amino resin (2) having two or more triazine rings exhibits a bead-like unevenness excellent in design. It is an essential component of the paint of the present invention, and its structure can be confirmed by organic trace element analysis, proton nuclear magnetic resonance absorption analysis, and gel permeation chromatography analysis.

As the amino resin having two or more triazine rings, for example, Super Beckamine J-820-60
(Butylated melamine resin, triazine ring number: 3.0)
[Manufactured by Dainippon Ink and Chemicals, Inc.], Cymel 1128 (butylated benzoguanamine resin, triazine ring number: 3.
0) [Mitsui Cytec Co., Ltd.], ISO. MF (isobutylated melamine resin, triazine ring number: 3.7) [Nippon Paint Co., Ltd.], Uban 20SE-60 (butylated melamine resin, triazine ring number: 2.9) [Mitsui Toatsu Co., Ltd.], etc. Is mentioned. The compounding amount of the amino resin is 3 to 50 parts by weight, preferably 8 to 45 parts by weight, based on the solid content of the resin. If the compounding amount is less than 3 parts by weight, poor curing or poor formation of a fine pattern occurs, and if it exceeds 50 parts by weight, processability is reduced. In addition, in addition to the amino resin having two or more triazine rings of the present invention as a resin component, a melamine resin having less than two triazine rings can be used in combination.

The sulfonic acid compound (3) blocked with a secondary or tertiary amine used in the present invention is a curing catalyst for a paint for forming a fine pattern and has a boiling point of 50 to 50%.
Blocked with a secondary or tertiary amine at 250 ° C. By forming a sulfonic acid salt blocked with a secondary or tertiary amine, the curing speed is inclined between the surface and the inside during curing of the coating film, and as a result, an unevenness (dense pattern) is formed on the coating film surface. There is.

Examples of the sulfonic acid include paratoluenesulfonic acid, dodecylbenzenesulfonic acid, methanesulfonic acid, dinonylnaphthalenesulfonic acid, dinonylnaphthalenedisulfonic acid, and the like, and two or more of them may be used in combination. it can.

The secondary or tertiary amine having a boiling point of 50 to 250 ° C. is not particularly restricted but includes, for example, diethylamine, di-n-propylamine, diisopropylamine, diisobutylamine, di-n-butylamine, diamylamine, diallylamine, di-sec-butylamine, N-butylamine. Ethyl-1,2-dimethylpropylamine, N
-Methylhexylamine, di-octylamine, piperidine, 2-pipecholine, 3-pipecholine, 4-pipecholine, 2,4-lupetidine, 2,6-lupetidine,
3,5-lupetidine, 3-piperidinemethanol, triethylamine, tributylamine, triallylamine,
N, N-dimethylethanolamine, N-methyldiallylamine, pyridine, N, N-dimethylallylamine,
N-methylpiperidine, 4-ethylpyridine, N-methylpiperazine, N-methylmorpholine and the like,
Two or more kinds can be used in combination. More preferably, a secondary or tertiary amine having a boiling point of 70 to 220 ° C is used.

The sulfonic acid compound blocked with a secondary or tertiary amine can be easily obtained as a sulfonic acid salt by, for example, stirring a secondary or tertiary amine and sulfonic acid at 20 to 30 ° C. for 10 to 20 minutes.

A sulfonic acid compound blocked with a secondary or tertiary amine having a boiling point of 50 to 250 ° C. is a curing catalyst effective for forming irregularities (dense patterns) on the surface of a coating film, and has a total resin content of 100 parts by weight. 0.1 to 15 parts by weight, preferably 0.5 to 10 parts by weight, based on sulfonic acid. If the addition amount of the sulfonic acid compound is less than 0.1 parts by weight (in terms of sulfonic acid), the formation of irregularities (dense patterns) on the coating film surface becomes insufficient, and if it exceeds 15 parts by weight, the chemical resistance becomes poor. descend. For this curing catalyst, not all sulfonic acid groups need necessarily be blocked with secondary or tertiary amines, and secondary or tertiary amines should be used at least 0.5 times in equivalent ratio to sulfonic acid. preferable.

The surface conditioner (4) used in the present invention comprises:
It is a component necessary for forming a uniform fine pattern, and is an acrylic antifoaming agent, a silicone antifoaming agent, a fluorine antifoaming agent, a leveling agent, and the like. Specifically, for example, Modaflow (manufactured by Monsanto) as an acrylic polymer, silicone KP-330 (manufactured by Shin-Etsu Chemical Co., Ltd.) as a silicone oil, Paintad 7 (manufactured by Dow Corning Asia) as a fluorine-based surfactant and the like can be mentioned.

The surface conditioner is added in an amount of 0.01 to 5 parts by weight, preferably 0.03 to 4 parts by weight, based on 100 parts by weight of the total amount of the resin. If the amount of the surface conditioner is less than 0.01 part by weight, a uniform shrinkage pattern is not formed, and if it exceeds 5 parts by weight, the surface of the coating film sticks.

If necessary, a wax (5) can be blended into the crepe pattern forming paint of the present invention. If a wax is added, the pattern tends to be more easily formed. As the wax used in the present invention, polyethylene wax, microcrystalline wax, polypropylene wax, carnauba wax, paraffin,
Oxides thereof or neutralized salts thereof are exemplified.

Specifically, for example, HI-DISPER is used as a microcrystalline wax.
1229 (manufactured by Gifu Shellac Co., Ltd.) and Slip Aid SL-506 (manufactured by San Nopco) as carnauba wax. The wax is added in an amount of 5 parts by weight or less based on 100 parts by weight of the total amount of the resin. 5 wax added
When the amount is more than the weight part, the paint is easily foamed, and the workability of the coating is rather deteriorated.

Furthermore, in addition to the above components (1) to (5), pigments, metal flakes (aluminum, stainless steel, copper, etc.), pigment dispersants, antisettling agents, An ultraviolet absorber, an antioxidant, a matting agent represented by silica powder, a solvent and the like can be added. Examples of the pigments include inorganic pigments such as titanium dioxide, carbon black, iron oxide, and graphite; organic pigments such as azo, phthalocyanine, quinacridone, and perylene; nylon, melamine, acrylic, polyester, and fluorine.
Organic beads such as polyethylene, inorganic beads such as glass,
Fibers such as carbon, glass and potassium titanate, metal flakes such as aluminum, stainless steel and copper, barium sulfate, aluminum silicate, calcium carbonate, talc, silica sand, quartz, zinc flower,
Volume pigments such as mica, feldspar, strontium chromate,
Rust preventing pigments such as calcium chromate and zinc chromate are exemplified. The amount of the pigment is preferably 300 parts by weight or less based on 100 parts by weight of the coating resin.
If the amount exceeds 300 parts by weight, the workability is reduced.

The lacquer pattern forming paint of the present invention can be applied to any substrate, and examples of the substrate include a metal plate and a synthetic resin plate. Examples of the metal sheet include a cold-rolled steel sheet, a hot-dip galvanized steel sheet, an electro-galvanized steel sheet, a zinc alloy-plated steel sheet, an aluminum-plated steel sheet, a stainless steel sheet, an aluminum sheet, and the like. However, it is common to perform zinc phosphate or chromate treatment. Examples of the synthetic resin plate include an epoxy resin, a polyimide resin, a silicon resin, a polyethylene terephthalate resin, a diallyl phthalate resin, and a resin obtained by filling these resins with an inorganic substance such as glass or silica.

The crepe pattern forming paint of the present invention is produced by mixing the above-mentioned components, and if necessary, is diluted with a solvent such as xylol and applied preferably in a dry film thickness of 2 to 70 μm. It may be applied directly to a substrate such as a galvanized steel plate, a stainless steel plate, or an aluminum plate, or may be applied to a pre-coated steel plate. Baking after painting is 1
By performing the treatment at 80 to 300 ° C. for 10 to 200 seconds, it is possible to form irregularities (dense pattern) on the coating film surface.

Before applying the lacquer pattern forming paint of the present invention, an undercoat paint can be applied in advance, if necessary. Examples of the undercoat paint include an epoxy / melamine paint, an epoxy / urethane / melamine paint, and a polymer polyester / melamine paint.

The paint for forming a pattern of the present invention can be applied using a bar coater, a roll coater, a roll curtain coater, a curtain flow coater, a die coater, a spray gun or the like, and if necessary, can be further embossed. .

[0027]

Next, the present invention will be described with reference to Examples and Comparative Examples. The numbers in the table indicate the weight (g) of the solid content unless otherwise specified. However, the amine indicates the weight of the active ingredient.

Coating of undercoat paint A 0.5 mm thick hot-dip galvanized steel sheet is coated with an undercoat paint (Super Lac DIF P-01 primer (epoxy / urethane / melamine-based: Nippon Paint Co., Ltd.)) using a bar coater. The steel plate was baked at 210 ° C. for 40 seconds to obtain a coating having a dry coating thickness of 5 μm.

Example 1 70 parts of oil-free polyester resin, titanium dioxide 9
8 parts, 2 parts of carbon black, and 70 parts of a solvent (xylene / cyclohexane = 1/1) in the same amount as the resin component were mixed, dispersed using a glass bead as a dispersion medium for 60 minutes using a paint shaker, and then subjected to wire mesh filtration. The glass beads were removed to obtain a mixture having a particle size of 10 μm or less. Dodecylbenzenesulfonic acid 4 blocked with 30 parts of butylated melamine resin and 1.2 parts of triethylamine was added to this mixture.
And 1 part of an acrylic polymer were blended and stirred with a dissolver for 30 minutes to obtain a test paint. A solvent (xylene / cyclohexane = 1/1) was added to this test paint to add a viscosity suitable for coating [dilution viscosity: Ford Cup No. 4 in 1
20 seconds (25 ° C)].

Examples 2-6, 8-17 and Comparative Examples 1
4 By performing the same operation as in Example 1, and according to the formulations in Tables 1 to 4,
Each test paint was obtained.

Example 7 70 parts of an oil-free polyester resin, 30 parts of a butylated melamine resin, 4 parts of dodecylbenzenesulfonic acid blocked with 1.2 parts of triethylamine and 1 part of an acrylic polymer were mixed, and the mixture was stirred with a dissolver for 30 minutes. This was used as a clear test paint. A solvent (xylene / cyclohexane = 1/1) was added to this coating material to add a viscosity suitable for coating [dilution viscosity: Ford Cup No. 1]. 4 for 120 seconds (25
° C)].

Next, each of the test paints obtained in Examples 1 to 17 and Comparative Examples 1 to 4 was applied to a hot-dip galvanized steel sheet coated with the undercoat using a bar coater.
Baking was performed at 210 ° C. for 60 seconds to obtain a coating having a dry coating thickness of 25 μm. The following tests were performed on samples coated with the test paints, and the test results are shown in Tables 1 to 4.

1. Judgment of the check pattern by visual observation ：: Check pattern is formed on the coating film. ×: No dust pattern was formed on the coating film.

2. Visual confirmation test of the uniformity and clarity of the fine pattern. 均一: The uniform and clear fine pattern is formed. Δ: A fine pattern is formed, but slightly uneven or indistinct. ×: A fine pattern is formed, but remarkably uneven or indistinct.

3. Judgment of bead-like unevenness by visual inspection A: Granular projections are extremely large, and bead-like unevenness is noticeable. ：: Large granular protrusions, rich in bead-like unevenness. Δ: There are granular projections, and a bead-like unevenness can be observed. C: Almost no granular protrusions were observed, and no bead-like unevenness was observed.

4. Visual confirmation test of streaking phenomenon: No streaking. ×: There are streaks.

[0037]

[Table 1]

Note) * 1: Beckolite M-6003-6
0 (number average molecular weight 3000, non-volatile content 60% [manufactured by Dainippon Ink and Chemicals, Inc.] * 2: Alloset 5534-SB60 (number average molecular weight 8
* 3, Super Beckamine J-820-60 (number of triazine rings: 3.0) [manufactured by Dainippon Ink and Chemicals, Inc.] * 4: ISO. MF (number of triazine rings: 3.7) [manufactured by Nippon Paint Co., Ltd.] * 5: Cymel 300 (number of rings of triazine rings: 1.0)
[Mitsui Cytec Co., Ltd.] * 6: Modaflow [Monsanto] * 7: Silicon KP-330 [Shin-Etsu Chemical] * 8: Painted 7 [Dow Corning Asia] * 9: P Flat [Toyo Ink] * 10: High Disper 1229 (manufactured by Gifu Shellac)

[0039]

[Table 2]

[0040]

[Table 3]

[0041]

[Table 4]

Note) * 11: Olgasol ES-5 (average particle size: 50 μm) [Ann Shimmy]

[0043]

The wrinkle pattern forming paint containing the specific amino resin of the present invention is susceptible to so-called wrinkles at the time of baking and curing, and the wedges flow appropriately to produce a bead-like unevenness. Further, the components (1) to (4) of the present invention
Since the curing rate containing paint contains a gradient in the curing speed between the surface and the inside of the coating film, a fine pattern is formed with excellent design properties. And, Tables 1 to 3 (Examples 1 to 17)
As is clear from the above, the coated object coated with the crepe pattern forming paint of the present invention has a coating formed as a result of the combination of the occurrence of buzzing during baking hardening and the gradient of the curing speed on the surface and inside of the coating. The fine pattern (appearance) of the film is kept uniform, and a bead-like unevenness with excellent design is exhibited. Further, by adjusting the blending ratio of the components (1) to (4), the coating film thickness, the baking temperature, and the like, an arbitrary size,
It is possible to obtain a coating film in which a heat-like irregularity pattern having a desired texture is formed and which is rich in unevenness.

[0044]

[Brief description of the drawings]

FIG. 1 is an example of an enlarged view (100 ×) of a coating film exhibiting a fine fine pattern formed by a conventional fine paint.

FIG. 2 is an enlarged view (100 ×) of a coating film having a bead-like unevenness formed by the crepe pattern forming paint of the present invention.
This is an example.

Claims (8)

[Claims] (1) 50 to 97 parts by weight of at least one of a polyester resin and an acrylic resin having a hydroxyl group,
(2) General formula (X is a hydrogen atom, a group —CH ₂ OH, a group —CH ₂ OR, a group —CH ₂ — or a group —CH ₂ OCH ₂ —, which may be the same or different, and at least Group -CH
₂ - and a group -CH ₂ OCH ₂ - wherein any one kind of,
R represents a linear or branched alkyl group having 1 to 8 carbon atoms) 3 to 50 parts by weight of an amino resin having two or more triazine rings, and (3) a secondary having a boiling point of 50 to 250 ° C. Alternatively, 0.1 to 15 parts by weight (in terms of sulfonic acid) of a sulfonic acid compound blocked with a tertiary amine and 0.01 to 5 parts by weight of (4) a surface conditioner [however, the blending amounts of the components (3) to (4)] Is based on 100 parts by weight of the total of the components (1) and (2)]. 2. The pattern according to claim 1, wherein the polyester resin and the acrylic resin having a hydroxyl group are a high molecular polyester, an oil-modified polyester, an oil-free polyester, a silicone-modified polyester resin, an unmodified acrylic resin or a fluorine-based acrylic resin. Forming paint. 3. The crepe pattern forming paint according to claim 1, wherein the secondary or tertiary amine having a boiling point of 50 to 250 ° C. is triethylamine, N, N-dimethylethanolamine, diisopropylamine or diisobutylamine. 4. The paint for forming a fine pattern according to claim 1, wherein the surface conditioner is an acrylic defoamer, a silicon defoamer, a fluorine defoamer or a leveling agent. 5. The coating composition according to claim 1, further comprising (5) a wax in an amount of 0.01 to 5 parts by weight (provided that the component (5) is incorporated in an amount of 100% in total of the components (1) and (2)). (Based on parts by weight). 6. The wax is a polyethylene wax, a microcrystalline wax, a polypropylene wax,
6. The fine pattern forming paint according to claim 5, which is carnauba wax, an oxide thereof or a neutralized salt thereof. 7. A coated steel sheet obtained by applying the crepe pattern forming paint according to claim 1 or an embossed coated steel sheet obtained by further embossing after coating. 8. A method of applying the crepe pattern forming paint according to claim 1 to a substrate using a bar coater, a roll coater, a roll curtain coater, a curtain flow coater, a die coater or a spray gun.