JP2005066440A - Method for forming crepe pattern coating and coated article - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for forming a crepe pattern coating good in adhesiveness to a polyolefin substrate and excellent in designing properties, and to provide a crepe pattern coating-coated article. <P>SOLUTION: The coating composition comprises (A) 60-95 pts.mass of a polyester resin or an acrylic resin having a hydroxy group, (B) 5-40 pts.mass of a methylated melamine resin, (C) 0.2-3 pts.mass of sulfonic acid blocked with a secondary and/or tertiary amine having a boiling point of 50-130°C, in terms of sulfonic acid, based on 100 pts.mass of the total resins of the component (A) and the component (B), and (D) 2-20 pts.mass of a chlorinated polyolefin resin based on 100 pts.mass of the total resins of the component (A) and the component (B), on the polyolefin substrate. The method for forming the crepe pattern coating by applying the coating composition is also provided. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a coating film forming method and a coated article for finishing a crease pattern on a polyolefin substrate.

As a paint that forms a stagnation pattern, a paint that uses a polyester resin having a hydroxyl group and a methylated melamine and an acid catalyst blocked with a tertiary amine is known (Patent Document 1). However, this paint has good adhesion to materials such as iron, galvanized steel, stainless steel, and aluminum, but has a defect that it has no adhesion to polyolefin substrates.
In addition, a polypropylene wax containing polypropylene as a component is added to a polyester resin or acrylic resin having a hydroxyl group, a melamine resin or a urea resin, and a sulfonic acid amine blocked with a secondary or tertiary amine having a boiling point of 50 to 250 ° C. A paint is also known (Patent Document 2). However, this paint also has no adhesion to the polyolefin substrate.

  On the other hand, as a coating composition having excellent adhesion to a polyolefin base material in an automobile interior material or the like, a modified chlorinated polyolefin and a chlorinated polyolefin obtained by copolymerizing a chlorinated polyolefin with an acrylic monomer and styrene, Modification by graft polymerization of unsaturated carboxylic acid and / or acid anhydride thereof to a coating composition comprising acrylic beads (Patent Document 3) and a propylene copolymer having a propylene content of 50% to 98% A polyolefin composition (Patent Document 4) is known. Also known is a coating composition in which an active hydrogen-containing polymerization monomer is reacted with a maleic anhydride-modified polyolefin and then an acrylic resin obtained by polymerizing an acrylic monomer and an acrylic resin are mixed (patent document). 5). However, the method of Patent Document 3, Patent Document 4 and Patent Document 5 cannot form a crease pattern.

Japanese Patent Publication No. 6-11879 JP-A-10-195346 JP 2001-348524 A JP 2002-187922 A JP 2002-188042 A

  The problem to be solved by the present invention is to obtain a method for forming a stagnation-patterned coating film having good adhesion to a polyolefin substrate and excellent design, and to obtain a coated article thereof.

  As a result of intensive studies to solve the above problems, the present inventor has (A) a polyester resin or acrylic resin having a hydroxyl group, (B) a methylated melamine resin, and (C) on a polyolefin substrate. A coating composition containing a sulfonic acid blocked with a secondary and / or tertiary amine having a boiling point of 50 to 130 ° C. and (D) a chlorinated polyolefin resin, the sum of (A) component and (B) component By coating a coating composition in which component (C) is 0.2 to 3 parts by mass in terms of sulfonic acid and component (D) is 2 to 20 parts by mass with respect to 100 parts by mass, a polyolefin base material As a result, it has been found that a stagnation-patterned coating film having excellent adhesion can be formed, and the present invention has been completed.

  That is, the present invention comprises (A) a polyester resin or acrylic resin having a hydroxyl group of 60 to 95 parts by mass on a polyolefin substrate, (B) 5 to 40 parts by mass of a methylated melamine resin, and (C) a boiling point of 50 to 130 ° C. The sulfonic acid blocked with a secondary and / or tertiary amine is 0.2 to 3 parts by mass with respect to 100 parts by mass of the resin of the component (A) and the component (B) in terms of sulfonic acid, and ( D) A paint film coating characterized by coating a chlorinated polyolefin resin with a coating composition containing 2 to 20 parts by mass with respect to 100 parts by mass of the resin of component (A) and component (B). Is the method.

Further, the present invention is the above-described crease pattern coating film forming method, wherein the polyester resin having a hydroxyl group is selected from the group consisting of an oil-modified polyester resin, an oil-free polyester resin, and a silicon-modified polyester resin. is there.
The present invention is also the above-described crease pattern coating film forming method, wherein the acrylic resin having a hydroxyl group is selected from the group consisting of an unmodified acryl resin and a fluorine-modified acryl resin.

  Moreover, this invention is a crease pattern coating-film formation method in which the methylated melamine resin contains three or more methoxy groups in the crease-pattern coating film formation method.

  Further, the present invention relates to the above-described glazing pattern coating film forming method, wherein the sulfonic acid is paratoluenesulfonic acid, dodecylbenzene sulfonic acid, dinonylnaphthalenedisulfonic acid, methanesulfonic acid or dinonylnaphthalenesulfonic acid. It is a forming method.

  Further, the present invention provides the above-described crease pattern coating film forming method, wherein the secondary and / or tertiary amine having a boiling point of 50 to 130 ° C is diethylamine, triethylamine, morpholine, piperidine, pyridine, N-methylpiperidine, diisopropylamine, diisopropylamine. It is a glazing pattern coating film forming method which is (n-propyl) amine.

  Further, the present invention provides the above crease pattern coating film forming method, wherein the chlorinated polyolefin resin has a chlorination rate of 18 to 25% by mass when the entire chlorinated polyolefin is 100% by mass, and the weight average molecular weight is It is a crease pattern coating film formation method which is 30,000-120,000.

  Furthermore, this invention is the articles | goods coated using the said itch pattern coating-film formation method.

  When the coating composition according to the present invention is applied to a polyolefin base material such as an automotive interior part, it is possible to form a coating film with good adhesion, excellent design and a stagnation pattern, A coated article having a crease pattern on a polyolefin substrate is provided.

The polyester resin having a hydroxyl group as the component (A) used in the present invention is a polyester resin having a hydroxyl group as a functional group that reacts with the methoxy group of the methylated melamine resin as the component (B), and is generally used for paints. Polyester resin can be used. Examples of such polyester resins include oil-modified polyester resins, oil-free polyester resins, silicon-modified polyester resins, and the like, and commercially available products can be used for all.
Examples of the oil-modified polyester resin include “Beckolite M-6601-60-S” (trade name) manufactured by Dainippon Ink and Chemicals, Inc. Examples of the oil-free polyester resin include “Beckolite-M6602-60-S” and “46-118” manufactured by Dainippon Ink Chemical Co., Ltd., “Almatex P-646” manufactured by Mitsui Chemicals, Inc. All of them are trade names). Examples of the silicone-modified polyester resin include “Alloplats 1710” (trade name) manufactured by Nichichi Arrow Chemical Co., Ltd. These polyester resins can be used alone or in combination of two or more.

The acrylic resin having a hydroxyl group, which is another component (A) used in the present invention, may be unmodified or modified, and is a functional group that reacts with the methoxy group of the methylated melamine resin of component (B). As long as it is an acrylic resin having a hydroxyl group, any resin that is usually used in paints can be used without limitation, and a commercially available product can be used. Such an acrylic resin includes a fluorine-based acrylic resin modified with fluorine.
Examples of such acrylic resins include “Almatex 749-17” and “112” manufactured by Mitsui Chemicals, Inc., “Acridic A-405” and “A- 801 "(both are trade names). Moreover, if a fluorine-type acrylic resin is resin normally used for the coating material, it can be used without a restriction | limiting, and all can use a commercial item. As the fluorine-based acrylic resin, for example, “Lumiflon” (trade name) manufactured by Asahi Glass Co., Ltd., “Cefral Coat” (trade name) manufactured by Central Glass Co., Ltd. can be used.
The blending amount of these components (A) is 60 to 95 parts by weight, preferably 60 to 90 parts by weight, based on the resin content (solid content).

The methylated melamine resin of the component (B) used in the present invention is a melamine resin having a methoxy group by methylation, and preferably contains 3 or more methoxy groups, particularly hexamethoxymethylol melamine, which is generally commercially available. The methylated melamine resin can be used. Usually, a commercially available butylated melamine resin has a slow reaction with a polyester resin having a hydroxyl group, and does not give a crease pattern. Examples of such a methylated melamine resin include “Cymel 300”, “Cymel 303”, “Cymel 1130-266J” manufactured by Mitsui Cytec Co., Ltd., and “Nicarac MW-30” manufactured by Sanwa Chemical Co., Ltd. "Nicarac MX-40", "Sumimar M-100C" manufactured by Sumitomo Chemical Co., Ltd., "Sumimar M-40S" (both are trade names), and the like. These methylated melamine resins can be used alone or in combination of two or more.
(B) The compounding quantity of the methylated melamine resin which is a component is 5-40 mass parts as a resin part (solid content), Preferably it is 10-30 weight part.

  When the mass ratio of the polyester resin or acrylic resin to the methylated melamine resin is larger than 95/5, a sufficient cured coating film cannot be obtained, and the adhesion and moisture resistance are inferior. The flexibility and moisture resistance of the film are inferior, and a uniform crease pattern cannot be formed.

The sulfonic acid blocked with a secondary and / or tertiary amine having a boiling point of 50 to 130 ° C. of the component (C) used in the present invention is obtained by converting the sulfonic acid into a salt of the secondary and / or tertiary amine. This temporarily blocks the action of the acid as a catalyst. In other words, the sulfonic acid is a reaction catalyst for the component (A) and the component (B), shortens the reaction time, increases the difference between the surface curing and the internal curing of the coating film, and improves the itch pattern. However, by catalyzing secondary and / or tertiary amine salts, this catalysis is temporarily blocked.
Examples of the sulfonic acid include p-toluenesulfonic acid, dodecylbenzenesulfonic acid, dinonylnaphthalenedisulfonic acid, methanesulfonic acid, dinonylnaphthalenesulfonic acid, and the like. These may be used alone or in combination of two or more. Is possible.

Examples of secondary and / or tertiary amines having a boiling point of 50 to 130 ° C. include diethylamine (boiling point 55 ° C.), triethylamine (90 ° C.), morpholine (128 ° C.), piperidine (106 ° C.), pyridine (same as above). 115 ° C.), N-methylpiperidine (106 ° C.), diisopropylamine (85 ° C.), di (n-propyl) amine (109 ° C.) and the like. These may be used alone or in combination of two or more. Is possible.
A sulfonic acid blocked with a secondary and / or tertiary amine having a boiling point of 50 to 130 ° C. is produced, for example, as follows. That is, a secondary and / or tertiary amine having a boiling point of 50 to 130 ° C. with respect to sulfonic acid and a sulfonic acid are charged into a container after measurement, and stirred at 20 to 30 ° C. for 10 to 20 minutes to unreacted sulfonic acid group Completely into salt form.

  A sulfonic acid blocked with a secondary and / or tertiary amine in the form of a salt is mixed with the components (A) and (B). When the boiling point of the amine is less than 50 ° C., the volatilization is significant in the stirring step when forming the salt with the sulfonic acid and the stirring step when mixing with the components (A) and (B), and the amount of the sulfonate is too small. Insufficient and stable film formation with a stagnation pattern is not possible. In case of high temperature baking such as coil coating, there is no problem, but in the case of a polyolefin substrate used in the present invention in which the baking temperature is limited from the heat resistance point of the substrate, the boiling point exceeds 120 ° C. In this case, the dissociation temperature of the amine is too high, the amine does not dissociate, the coating film is not sufficiently cured, and the curing on the surface layer does not proceed, so that no itch pattern is formed.

  The sulfonic acid blocked with the secondary and / or tertiary amine of the component (C) is necessary for the formation of a itch pattern, and is converted to sulfonic acid with respect to 100 parts by mass of the total resin of the components (A) and (B). 0.2 to 3 parts by mass, preferably 0.2 to 2.5 parts by mass. When the amount of the sulfonic acid blocked with the secondary and / or tertiary amine is less than 0.2 parts by mass in terms of sulfonic acid with respect to 100 parts by mass of the total resin of the components (A) and (B), the coating film is cured. Insufficient adhesion and moisture resistance are obtained, and a good crease pattern cannot be obtained. When the amount exceeds 3 parts by mass, sufficient moisture resistance and chemical resistance cannot be obtained.

Although the chlorinated polyolefin resin of (D) component can use the chlorinated polyolefin resin generally used for coating materials, a preferable chlorination rate is 18-25 mass% when the whole chlorinated polyolefin is 100 mass%. More preferably, it is 20-25 mass%, A preferable weight average molecular weight is 30,000-120,000, More preferably, it is 30,000-100,000, More preferably, it is 40,000-90,000. Examples of such commercially available chlorinated polyolefins include “Super Clone 822” and “842LM” manufactured by Nippon Paper Industries Co., Ltd., “Hardlen CY9122” manufactured by Toyo Kasei Co., Ltd. (all are trade names), and the like. It is done.
(D) As for the compounding quantity of a component, 2-20 mass parts is desirable with respect to a total of 100 mass parts of solid content (resin content) of (A) component and (B) component. The amount is more preferably 3 to 15 parts by mass, and particularly preferably 3 to 12 parts by mass. If the blending amount is less than 2 parts by mass, the adhesion to the polyolefin substrate is not sufficient, and if it exceeds 20 parts by mass, a uniform crease pattern cannot be obtained.

  Furthermore, in the present invention, if necessary, the coating composition includes inorganic pigments such as titanium dioxide, carbon black, iron oxide, and chrome lead, organic pigments such as cyanine green and cyanine blue, metals such as aluminum powder and copper powder. Additives and solvents such as powders, extender pigments such as barium sulfate, talc and mica, pigment dispersants, leveling agents, anti-settling agents and foam breakers can be added.

  In the wrinkle pattern coating film forming method of the present invention, when the wrinkle coating composition is used as a clear or color clear coating, it is preferable to use a polyolefin such as polypropylene as a base material. Specific examples include automobile interior parts such as polyolefin instrument panels, center consoles, and door rims, and weak electrical parts such as radio cassette tape recorders and computer cases.

In the glazing pattern coating film forming method of the present invention, when the coating composition is applied to the substrate, the coating composition is diluted to a coating viscosity with a solvent such as xylol if necessary. Moreover, although it can coat directly on a base material, it can be heat-hardened and it can be set as a coating film, it does not specifically limit as a coating method, Spray coating, a flow coater coating, etc. can be used.
In the glazing pattern coating film forming method of the present invention, a coating material in which a polyester resin or acrylic resin having a hydroxyl group and a methylated melamine resin and an amine-blocked sulfonic acid are mixed is prepared in the container A, and a chlorinated polyolefin resin is prepared. It is particularly desirable to use a method in which each solution is prepared in a separate container B, sucked from each container to the tip nozzle of the coating gun with a hose, and mixed at the tip of the coating gun at the moment of painting. In this case, if there is no problem in the performance as a coating film, it is not necessary to consider the storage stability when the coating composition mixed in the container A and the chlorinated polyolefin resin in the container B are mixed. There is an advantage that the selection range of the combination is expanded. As such a multi-liquid metered and mixed coating apparatus, there is a value mix manufactured by Graco.

  Moreover, it is preferable that a dry film thickness shall be 10-50 micrometers, More preferably, it is 15-35 micrometers. The baking conditions for heat curing are preferably 100 to 160 ° C. for 10 to 60 minutes, and particularly preferably 120 to 140 ° C. for 20 to 30 minutes.

  The glazing paint of the present invention is contained in the paint in a state where the sulfonic acid serving as a catalyst is blocked with a secondary and / or tertiary amine having a boiling point of 50 to 130 ° C., so that the action as a catalyst is temporarily suppressed, and storage stability Good sex. And after baking, when the baking is performed, the secondary and / or tertiary amines blocked from the coating film close to the surface are liberated and volatilized. At the same time, the released sulfonic acid recovers the catalytic action, and only the surface layer is accelerated. A curing reaction is caused, and as a result, a coating film having a stagnation pattern is obtained. The resulting coating film has fine irregularities in a two-dimensional pattern in an unspecified direction, and the size and shape of the irregularities vary depending on the composition of the paint, painting conditions, baking conditions, etc. By adjusting, a coating film having an arbitrary itch pattern can be obtained.

Next, the present invention will be described in more detail with reference to examples and comparative examples. In each example, unless otherwise specified, parts are based on mass parts of solid content. However, amine is shown in parts by mass of the active ingredient. Moreover,% represents the mass%. In addition, (C1) and (C2) in the table are represented by mass parts of sulfonic acid.
Example 1
Based on the formulation shown in Table 1 (Table 1), Beckolite 46-118 (trade name, non-volatile content 60%, hydroxyl value 115, number average molecular weight) manufactured by Dainippon Ink & Chemicals, Inc. as an oil-free polyester resin. 2,500) in terms of resin solids and 70 parts of methylated melamine resin and Cymel 303 (trade name, 100% non-volatile content, hexamethoxymethylol melamine) manufactured by Mitsui Cytec Co., Ltd. in terms of resin solids As a sulfonic acid blocked with a tertiary amine having a boiling point of 50 to 130 ° C., 0.5 part of paratoluenesulfonic acid blocked with 0.32 part of triethylamine (boiling point 90 ° C.), and as a leveling agent Kyoeisha Yushi Co., Ltd. MIKI LEVELING MK CONC (non-volatile content 50%) is converted to resin solid content and mixed with 0.5 part, and dissolved. And the mixture was stirred for 30 minutes at over. Next, Super Clon 842LM (trade name, nonvolatile content 20%, chlorination rate 20%, weight average molecular weight 60,000) manufactured by Nippon Paper Industries Co., Ltd. as a chlorinated polyolefin resin is converted to resin solids and 7 parts. In addition, the mixture was stirred for 5 minutes to be uniform. The resulting clear paint was diluted with xylol at 25 ° C for 15 seconds with a # 4 Ford Cup viscometer, air-sprayed onto a polypropylene material that had been washed and degreased with isopropanol, and dried at 140 ° C for 30 minutes. Thus, a coating film having a dry film thickness of 25 μm was obtained. Evaluation was performed according to the following evaluation methods, and the results are shown in Table 1 (Table 1).

Example 2
Based on the formulation shown in Table 1 (Table 1), container B was filled with Beckolite 46-118 (trade name, nonvolatile content 60%, hydroxyl value 115) manufactured by Dainippon Ink & Chemicals, Inc. as an oil-free polyester resin. , 1700 parts of the number average molecular weight 2,500) in terms of resin solids, and Cymel 303 (trade name, 100% non-volatile content, hexamethoxymethylol melamine) manufactured by Mitsui Cytec Co., Ltd. as a methylated melamine resin As a sulfonic acid blocked with a tertiary amine having a boiling point of 50 to 130 ° C in terms of solid content, 10 parts of paratoluenesulfonic acid blocked with 6 parts of triethylamine (boiling point 90 ° C), and as a leveling agent Kyoeisha Oil & Fat Co., Ltd. Miki Leveling MK Conk (non-volatile content 50%) was converted to resin solids and 10 parts were charged. , Stirred for 30 minutes at a dissolver, then at xylol, it was diluted to 25 ° C., # 15 seconds at 4 Ford cup viscometer.
In a separate container B, Super Clon 842LM (trade name, nonvolatile content 20%, chlorination rate 20%, weight average molecular weight 60,000) manufactured by Nippon Paper Industries Co., Ltd. is converted into resin solids as chlorinated polyolefin resin. 100 parts, and while stirring, diluted with xylol to 25 seconds at 25 ° C. with a # 4 Ford cup viscometer. Suction up from containers A and B to the tip of a paint gun that can be mixed with multi-component paint with a hose, spray-paint on polypropylene material that has been washed and degreased with isopropanol as the coating object, and dry at 140 ° C for 30 minutes. A coating film having a dry film thickness of 25 μm was obtained. Evaluation was performed according to the following evaluation methods, and the results are shown in Table 1 (Table 1).

Example 3
Based on the formulation shown in Table 1 (Table 1), as an acrylic resin, “Acrydic A-801” (trade name, 50% nonvolatile content, hydroxyl value 100, number average, manufactured by Dainippon Ink & Chemicals, Inc. 65 parts in terms of molecular weight 12,000) converted to resin solids and 35 parts in terms of methylated melamine resin, Cymel 303 (trade name, 100% non-volatile content) manufactured by Mitsui Cytec Co., Ltd. converted into resin solids As a sulfonic acid blocked with a secondary amine having a boiling point of 50 to 130 ° C., 0.5 part of paratoluenesulfonic acid was blocked with 0.25 part of diethylamine (boiling point 55 ° C.), and as a leveling agent, Kyoeisha Yushi Co., Ltd. ) Miki Leveling MK Conk (non-volatile content: 50%) was mixed with 0.5 part of the resin solid content, and stirred with a dissolver for 30 minutes. Next, Super Clone 822 (trade name, nonvolatile content 20%, chlorination rate 25%, weight average molecular weight 60,000) manufactured by Nippon Paper Industries Co., Ltd. as a chlorinated polyolefin resin is converted into a resin solid content of 10 parts. In addition, the mixture was stirred for 5 minutes to be uniform. The resulting clear paint was diluted with xylol at 25 ° C for 15 seconds with a # 4 Ford Cup viscometer, air-sprayed onto a polypropylene material that had been washed and degreased with isopropanol, and dried at 140 ° C for 30 minutes. Thus, a coating film having a dry film thickness of 25 μm was obtained. Evaluation was performed according to the following evaluation methods, and the results are shown in Table 1 (Table 1).

Examples 4-7
Based on the formulation shown in Table 1 (Table 1), the mixture was stirred with a dissolver to obtain a uniform clear paint in the same manner as in Example 1, and the resulting paint was used in xylene as in Example 1. Dilute to the same paint viscosity as in Example 1. In the same manner as in Example 1, the polypropylene material washed and degreased with isopropanol was spray-coated and dried at 140 ° C. for 30 minutes to obtain a coating film having a dry film thickness of 25 μm. In the same manner as in Example 1, evaluation was performed according to the following evaluation method, and the results are shown in Table 1 (Table 1).

Comparative Examples 1-7
Based on the formulation shown in Table 2 (Table 2), the mixture was stirred with a dissolver to obtain a uniform clear paint in the same manner as in Example 1, and the resulting paint was used in xylene as in Example 1. Dilute to the same paint viscosity as in Example 1. In the same manner as in Example 1, the polypropylene material washed and degreased with isopropanol was spray-coated and dried at 140 ° C. for 30 minutes to obtain a coating film having a dry film thickness of 25 μm. In the same manner as in Example 1, evaluation was performed according to the following evaluation method, and the results are shown in Table 2 (Table 2).

Evaluation method (1) Secondary adhesion test The adhesion after the moisture resistance test is called secondary adhesion.
After performing a moisture resistance test in accordance with JIS K5600-7-2 moisture resistance (continuous condensation method) for 240 hours, in accordance with a JIS K5600-5-6 adhesion (cross-cut method) test, cuts are made at intervals of 1 mm. The adhesion test was conducted and evaluated.
○: 100/100
Δ: 99/100 to 95/100
X: 94 or less / 100
(2) Appearance:
The itch pattern was visually evaluated as follows.
○: The texture of the wrinkle pattern is clear visually, the pattern is large and uniform, and the design is good.
Δ: A stagnation pattern can be visually observed, but the pattern is small or non-uniform, and the design is poor.
X: The itch pattern is not visually recognized or the itch pattern is not generated.

The glazing pattern coating film forming method of the present invention is suitable for coating polyolefin products such as polypropylene, such as automotive interior parts such as instrumental panels, center consoles, door rims, weak electrical parts such as radio cassette tape recorders and computer housings. Used, a coated article with good adhesion, excellent design and a familiar pattern is obtained.

Claims (8)

On the polyolefin substrate,
(A) 60 to 95 parts by mass of a polyester resin or acrylic resin having a hydroxyl group,
(B) 5-40 parts by mass of methylated melamine resin,
(C) A sulfonic acid blocked with a secondary and / or tertiary amine having a boiling point of 50 to 130 ° C., in terms of sulfonic acid, is 0.2 with respect to 100 parts by mass of the resin of the component (A) and the component (B). ~ 3 parts by mass, and
(D) 2-20 parts by mass of the chlorinated polyolefin resin with respect to 100 parts by mass of the resin of the component (A) and the component (B),
A paint pattern forming method characterized by coating a paint composition containing The crease pattern coating film forming method according to claim 1, wherein the polyester resin having a hydroxyl group is selected from the group consisting of an oil-modified polyester resin, an oil-free polyester resin, and a silicon-modified polyester resin. The crease pattern coating film forming method according to claim 1, wherein the acrylic resin having a hydroxyl group is selected from the group consisting of an unmodified acrylic resin and a fluorine-modified acrylic resin. The method for forming a wrinkle pattern coating film according to any one of claims 1 to 3, wherein the methylated melamine resin contains three or more methoxy groups. 5. The crease pattern coating film forming method according to claim 1, wherein the sulfonic acid is p-toluenesulfonic acid, dodecylbenzenesulfonic acid, dinonylnaphthalenedisulfonic acid, methanesulfonic acid, or dinonylnaphthalenesulfonic acid. The secondary and / or tertiary amine having a boiling point of 50 to 130 ° C is diethylamine, triethylamine, morpholine, piperidine, pyridine, N-methylpiperidine, diisopropylamine, di (n-propyl) amine. A method for forming a stagnation-pattern coating film according to claim 1. The chlorinated polyolefin resin has a chlorination rate of 18 to 25% by mass and a weight average molecular weight of 30,000 to 120,000 when the entire chlorinated polyolefin is 100% by mass. The method for forming a stagnation-pattern coating film as described in 1. An article coated by the method for forming a patterned coating film according to any one of claims 1 to 7.