JP2016011395A - Anion type glossy electrodeposition coating composition with self recovery function to flaw - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an anion type glossy electrodeposition coating composition which is applied to an aluminum raw material and has good coating film appearance and coating film performance, and a self recovery function to flaw in some case by being heated a little depending on degree of the flaw.SOLUTION: The anion type glossy electrodeposition coating composition is composed of (A) a vinyl copolymer which has an acid value of 10 to 150 mgKOH/g solid content, a hydroxyl group value of 20 to 200 mgKOH/g solid content and a weight average molecular weight of 3,000 to 50,000 and which is obtained by copolymerizing (a) α,β-ethylenic unsaturated carboxylic acid monomer, (b) hydroxyl group-containing α,β-ethylenic unsaturated monomer and (c) other α,β-ethylenic unsaturated monomer, (B) a crosslinking agent and (C) polycaprolactone polyol.

Description

The present invention relates to an anionic glossy electrodeposition coating composition. More specifically, it is characterized in that it can provide a coating film having a self-healing function against scratches, and is applied to electrodeposition coating of aluminum material.

Conventionally, aluminum materials coated after anodizing treatment are widely used in building materials such as window frames, doors, and exteriors of buildings and houses because they are lightweight, strong, and excellent in corrosion resistance. In recent years, such aluminum materials have been used in a wide range of electronic devices such as digital cameras and mobile phones, and the needs for aluminum materials have been diversified. Under such circumstances, as one of the problems to be solved, there is a problem of measures against scratches on the coating film.

For improving the scratch resistance, there is a technique of mixing and using a silicate material having a relatively high hardness from the viewpoint of increasing the hardness of the coating film. In Patent Document 1, a water-dispersible vinyl copolymer is produced in the presence of a tetrafunctional silicate compound to obtain a resin for coating. Although effective for improvement, it is ineffective against deep scratches, such as scratches on aluminum materials due to contact between aluminum sashes, or scratches on the paint film due to rail operation, and weather resistance and paint stability It is insufficient. Patent Document 2 is a technique for improving the scratch resistance by reacting colloidal silica and a carboxyl group-containing acrylic resin, but as in Patent Document 1, it is less effective against deep scratches. Patent Document 3 is a technique in which polysiloxane dispersed in a molecular state in an ionic resin is used in combination, and weather resistance and acid rain resistance have some performance, but scratch resistance is insufficient.

Apart from these techniques, a technique using resin particles has been devised. In Patent Document 4, it is a method of using fluororesin particles, which is effective not only for improving the scratch resistance of the coating film surface but also for deep scratches to some extent. However, the fluororesin particles are expensive, and there is a problem in adhesion with the auxiliary material. Patent Document 5 is a method of using hard resin particles, which is effective for improving the scratch resistance of the coating film surface, but has no effect on deep scratches.
Thus, in the prior art, the improvement of the scratch resistance problem is insufficient, and improvement in performance is required.

On the other hand, there is Patent Literature 6 regarding patent literature in which wax is used in combination with an electrodeposition paint. However, in Patent Document 6, it is effective to improve the scratch resistance of the surface of the coating film by using a wax together, but it is less effective against deep scratches, and the gloss value of the coating film is reduced. There arises a problem with the adhesion.

JP-A-11-315254 JP 11-172165 A JP-A-11-209694 JP 2001-329209 A JP 2001-342425 A JP 2008-260844 A

As described above, the conventional scratch resistance improvement technology is based on the idea that the coating film is hardly damaged, and an element that self-repairs the scratch once it has been scratched. Is not a technology that incorporates Therefore, for example, when packing an aluminum sash with a packing material such as corrugated cardboard or when transporting a packed coating, the problem that the coating film and the packing material are rubbed and scratches the coating film surface is solved to some extent. However, it was not an effective means especially for deep wounds. In addition, the above is a big problem especially for glossy paints. The present invention has been made to sufficiently solve such problems.

As a result of intensive studies to solve the above problems, the present inventors have found that the degree of scratches can be increased by blending polycaprolactone polyol with an anionic glossy electrodeposition paint based on a specific vinyl copolymer. In some cases, by applying a little heat, the inventors succeeded in establishing a technology for an anionic glossy electrodeposition coating composition having a sufficient self-healing function against scratches and completed the present invention.

That is, the present invention
(1) (A) (a) α, β-ethylenically unsaturated carboxylic acid monomer, (b) hydroxyl group-containing α, β-ethylenically unsaturated monomer, and (c) other α, β- A vinyl copolymer having an acid value of 10 to 150 mg KOH / g solid content, a hydroxyl value of 20 to 200 mg KOH / g solid content and a weight average molecular weight of 3,000 to 50,000, copolymerized with an ethylenically unsaturated monomer, (B) A crosslinking agent, and (C) polycaprolactone polyol as an essential component, and (C) polycaprolactone polyol is 1 to 30 parts by weight based on 100 parts by weight of the total of (A) vinyl copolymer and (B) crosslinking agent. An anionic glossy electrodeposition coating composition, characterized in that
(2) An anionic glossy electrodeposition coating composition characterized in that the crosslinking agent (B) is 30 to 100 parts by weight with respect to 100 parts by weight of the (A) vinyl copolymer,
(3) Anionic glossy electrodeposition characterized in that (C) polycaprolactone polyol is 3 to 25 parts by weight with respect to 100 parts by weight in total of (A) vinyl copolymer and (B) cross-linking agent Paint composition,
(4) The anionic luster as described in (8), wherein (C) polycaprolactone polyol is 8 to 25 parts by weight with respect to 100 parts by weight as a total of (A) vinyl copolymer and (B) crosslinking agent Electrodeposition coating composition,
(5) An anionic glossy electrodeposition coating composition, wherein the weight average molecular weight of (C) polycaprolactone polyol is 300 to 5,000.

In the present invention, since the resulting coating film has a self-repairing function against scratches, it is particularly effective for repairing not only shallow scratches on the coating surface but also deep scratches, and other properties (solvent resistance, Chemical resistance, weather resistance, mechanical properties, painting workability, paint stability, etc.) are the same as conventional paints.

Next, the electrodeposition coating composition of the present invention and the electrodeposition coating method thereof will be described in detail.
[(A) Vinyl copolymer]
The vinyl polymer (A) used in the present invention comprises (a) an α, β-ethylenically unsaturated carboxylic acid monomer, (b) a hydroxyl group-containing α, β-ethylenically unsaturated monomer, and (c) ) Copolymerized with other α, β-ethylenically unsaturated monomers, having an acid value of 10 to 150 mg KOH / g solid, a hydroxyl value of 20 to 200 mg KOH / g solid, and a weight average molecular weight of 3,000 to 50,000. Vinyl copolymer.

  The α, β-ethylenically unsaturated carboxylic acid monomer (a) imparts water dispersibility and electrophoretic properties to the vinyl copolymer (A). Illustrative examples include acrylic acid, methacrylic acid, crotonic acid, vinyl acetic acid, itaconic acid, maleic acid, maleic anhydride, fumaric acid, citraconic acid and the like. These 1 type (s) or 2 or more types can be mixed and used.

  The α, β-ethylenically unsaturated carboxylic acid monomer (a) has a vinyl copolymer (A) acid value of 10 to 150 KOHmg / g (solid content), preferably 20 to 100 KOHmg / g (solid content). It is used in such a range. If the acid value of the vinyl copolymer (A) is less than 10 KOHmg / g (solid content), sufficient water dispersion stability is difficult to obtain, and if it exceeds 150 KOHmg / g (solid content), electrophoretic properties and coating film deposition properties are obtained. In addition, the water resistance and chemical resistance of the coating film are reduced.

  Further, the hydroxyl group-containing α, β-ethylenically unsaturated monomer (b) reacts with the crosslinking agent (B) to impart curability when the coating film is baked. Illustrative examples include hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate and the like, and lactone modified products thereof. Species or a mixture of two or more can be used.

  Such a hydroxyl group-containing α, β-ethylenically unsaturated monomer (b) has a hydroxyl value in the vinyl copolymer (A) of 20 to 200 KOHmg / g (solid content), preferably 40 to 160 KOHmg / g (solid content). Solid content). When the hydroxyl value is less than 20 KOHmg / g (solid content), sufficient curability with the crosslinking agent (B) component is not secured, and when it exceeds 200 KOHmg / g (solid content), the cured coating becomes brittle and water resistant. It is difficult to obtain sufficient performance due to a decrease in the temperature.

  Furthermore, for the other α, β-ethylenically unsaturated monomer (c), alkyl esters of acrylic acid or methacrylic acid, or other vinyl monomers and amide monomers can be used. Specific examples of the compound include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, n-butyl acrylate, n-butyl methacrylate, isobutyl acrylate, isobutyl. Methacrylate, t-butyl acrylate, t-butyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, heptyl acrylate, alkyl esters of methacrylic acid such as heptyl methacrylate, styrene, α-methylstyrene , Vinyl toluene, vinyl acetate, acrylonitrile, Vinyl monomers such as tacrylonitrile, amide monomers such as acrylamide, methacrylamide, methylol acrylamide, methylol methacrylamide, methoxymethyl acrylamide, n-butoxymethyl acrylamide, diacetone acrylamide, diacetone methacrylamide, ethylene glycol Examples include diacrylate, ethylene glycol dimetallate, trimethylolpropane triacrylate, and trimethylolpropane trimethacrylate. These may be used alone or in combination of two or more.

The weight average molecular weight of the vinyl copolymer (A) is 3,000 to 50,000, more preferably 5,000 to 40,000, still more preferably 5,000 to 30,000. When the weight average molecular weight is 3,000 or less, it is difficult to sufficiently obtain the durability of the coating film. When the weight average molecular weight is 50,000 or more, the water dispersibility is lowered, and the handleability of the paint tends to be poor. In addition, it becomes difficult to develop a self-repair function for wounds. In addition, the weight average molecular weight said here is the value of polystyrene conversion by the measurement by GPC.

  The vinyl copolymer (A) as described above can be obtained by polymerizing each monomer by a known method such as solution polymerization, non-aqueous dispersion polymerization, bulk polymerization, emulsion polymerization, suspension polymerization, etc. Solution polymerization is preferred, and the reaction temperature is usually 40 to 170 ° C.

  Reaction solvents include n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, sec-butyl alcohol, t-butyl alcohol, propyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono It is preferable to use a hydrophilic solvent such as butyl ether. Moreover, as a polymerization initiator, well-known things, such as an organic peroxide, an azo compound, ammonium persulfate, potassium persulfate, can be used.

[(B) Crosslinking agent]
Examples of the crosslinking agent (B) used in the present invention include conventionally known blocked polyisocyanates and amino resins. Of these, blocked polyisocyanates are preferable from the viewpoint of the expression of a self-repair function for scratches.

Of the crosslinking agent (B) used in the present invention, the blocked polyisocyanate is a reaction product of a compound having two or more isocyanate groups in one molecule and a compound having active hydrogen capable of reacting with the isocyanate group, Or it is a compound which has 1 or more uretdione group in 1 molecule. This blocked polyisocyanate may be used alone or in combination of two or more.

  Such compounds having two or more isocyanate groups in one molecule are tolylene diisocyanate, diphenylmethane diisocyanate, xylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, trimethylhexamethylene diisocyanate, dimer acid diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated. Diphenylmethane diisocyanate, hydrogenated xylene diisocyanate, etc., and these isocyanurate type trimers, burette type trimers, or triazine tricarbamic acid trialkyl esters, trimethylolpropane, glycerin and other polyols and the above diisocyanates. Examples of the reactants include compounds generally called adducts.

  Among them, more preferable compounds when the weather resistance is emphasized include isophorone diisocyanate, hexamethylene diisocyanate, dimer acid diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylene diisocyanate, and their isocyanurates. Type trimer, burette type trimer, triazine tricarbamic acid trialkyl ester, trimethylolpropane or a reaction product of one molecule of glycerin and the above three molecules of diisocyanate.

  In addition, in the isocyanate group blocking reaction, compounds having active hydrogen capable of reacting with isocyanate groups include alcohols having 1 to 4 carbon atoms, ε-caprolactam, methyl ethyl ketoxime, alkyl acetoacetate, dialkyl malonate, furfuryl. Alcohol, phenol, butyl cellosolve, etc. are mentioned.

  The reaction product of the compound having two or more isocyanate groups in one molecule and the compound having active hydrogen capable of reacting with the isocyanate group has an equivalent ratio of isocyanate group to active hydrogen group of about 1/1. Usually, it is obtained by reacting at 50 to 150 ° C. If necessary, an organic solvent or a reaction catalyst (mainly an organic tin compound) may be used. Moreover, the compound which has a uretdione group is a compound obtained by the uretdione reaction of the isocyanate groups of the said isocyanate compound.

Among the cross-linking agents (B) used in the present invention, one of the other amino resins includes conventionally known melamine resins, benzoguanamine resins, urea resins, etc., among which methylol is preferred. An alkyl etherified methylol melamine resin in which at least a part of the group is alkoxylated with a lower alcohol. As the lower alcohol, one or more of methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol and the like can be used. This amino resin can be used alone or in combination of two or more.

  Examples of alkyl etherified methylol melamine resins include Cymel 266, 232, 235, 238, 236, My Coat 506, 508, 548, M-66B, etc., manufactured by Ornex Japan, but are not limited thereto. It is not something.

A preferable range of the amount of the crosslinking agent (B) used in the present invention is 30 to 100 parts by weight with respect to 100 parts by weight of the (A) vinyl copolymer in terms of solid content ratio. If the amount is less than this range, mechanical properties, water resistance, boiling water resistance, solvent resistance, chemical resistance, etc. will decrease due to insufficient crosslinking of the coating film. Insufficient water stability causes problems such as poor water dispersion stability, uneven dispersion particle size, poor water washability after electrodeposition, water repellency, uneven gloss of coating film, yellowing of coating film, etc. . Further, a blocked polyisocyanate and an amino resin can be used in combination as a crosslinking agent.

[(C) Polycaprolactone polyol]
The polycaprolactone polyol (C) used in the present invention is generally a compound having a plurality of caprolactone bonds and a plurality of hydroxyl groups in the molecule. The caprolactone bond represents a bond represented by the following general formula (1) and is hereinafter referred to as a caprolactone bond in the present invention. More specifically, the structure is exemplified by compounds represented by the following general formula (2), general formula (3), or general formula (4), but is not limited thereto.

[Wherein, R ¹ represents a linking group having 1 to 6 carbon atoms. a shows the integer of 1-20. b shows the integer of 1-20. ]

[Wherein R ² represents a linking group having 1 to 6 carbon atoms. c shows the integer of 1-20. d shows the integer of 1-20. e shows the integer of 1-20. ]

[Wherein R ³ represents a linking group having 1 to 6 carbon atoms. f shows the integer of 1-20. g shows the integer of 1-20. h represents an integer of 1 to 20. i represents an integer of 1 to 20. ]

  The polycaprolactone polyol (C) has a weight average molecular weight of 300 to 5,000, preferably 800 to 2,500. In addition, the weight average molecular weight said here is the value of polystyrene conversion by the measurement by GPC.

  As the commercially available polycaprolactone polyol (C), Plaxel 205, Plaxel 208, Plaxel 210, Plaxel 212, Plaxel 220, Plaxel 305, Plaxel 308, Plaxel 312, Plaxel 410 (Daicel Chemical) or Capa2100, Capa2200, Capa3091 , Capa3201, Capa4101 (Perstorp), and the like, but are not limited thereto.

The preferred range of the amount of polycaprolactone polyol (C) used in the present invention is 1 to 30 parts by weight with respect to 100 parts by weight of the total of (A) vinyl copolymer and (B) cross-linking agent. If the amount is less than this range, the self-repairing property is not sufficiently developed. If the amount is too large, the affinity with the vinyl copolymer is insufficient, the stability of the aqueous dispersion is poor, and the dispersed particle size is not uniform. , Problems such as poor washability after electrodeposition and water repellency occur. In addition, the hardness, water resistance, chemical resistance, etc. of the coating film are greatly reduced. The more preferable range of the usage-amount of polycaprolactone polyol (C) is 3-25 weight part, and a more preferable range is 8-25 weight part.

  Such polycaprolactone polyol (C) has sufficient compatibility with the vinyl copolymer (A), has high plasticizing performance based on a plurality of caprolactone bonds, and contains a plurality of hydroxyl groups. It also has high reactivity. Therefore, polycaprolactone polyol (C) is an essential component in order to develop a self-healing function with respect to scratches generated after the coating film is formed.

[Preparation of electrodeposition paint]
The electrodeposition paint of the present invention is prepared by, for example, stirring and mixing the above-mentioned (A) vinyl copolymer, (B) crosslinking agent and (C) polycaprolactone polyol usually at 40 to 100 ° C., and then a neutralizing base. After stirring and mixing the deionized water containing the active substance at a temperature of 20 to 80 ° C., the mixture is heated as necessary, or diluted with deionized water or deionized water partially containing a hydrophilic solvent. It can prepare by setting it as an emulsified dispersion. Alternatively, (A) only a vinyl copolymer and (B) a crosslinking agent may be prepared as described above to obtain an emulsified dispersion, and then (C) a polycaprolactone polyol may be added. Further, for the preparation of the electrodeposition paint of the present invention, if necessary, a film-forming resin other than the copolymer, an organic solvent, organic resin fine particles, crosslinked resin particles, an emulsifier, an antifoaming agent, a surface conditioner, Additives used in ordinary electrodeposition paints such as ultraviolet absorbers, hindered amine light stabilizers, antioxidants, curing catalysts, and the like can also be used without any problem. Furthermore, in the preparation of the electrodeposition paint of the present invention, color pigments such as organic pigments and inorganic pigments, extender pigments and pigments such as rust preventive pigments may be used in combination.

[Electrodeposition coating method]
As for the coating method, electrodeposition is performed using the object to be coated as an anode. The coating voltage is 30 to 350 V, preferably 50 to 300 V, and the energization time is 0.5 to 7 minutes, preferably 1 to 5 minutes. is there. The higher the voltage, the shorter the energization time, and conversely, the lower the voltage, the longer the energization time. The painting voltage may be either a method of applying a set voltage simultaneously with energization or a method of gradually increasing to a set voltage. The electrodeposition-coated object is washed with water if necessary, and then heated at 120 to 200 ° C. for 15 to 60 minutes to obtain a final coating film. The coating thickness is preferably about 5 to 30 μm.

The object to which the electrodeposition coating composition of the present invention is applied is mainly aluminum or an aluminum alloy, but can be applied as long as it has electrical conductivity. Excellent appearance such as uniformity, and excellent performance such as mechanical properties, solvent resistance, chemical resistance, and weather resistance.

  EXAMPLES Next, although an Example is given and this invention is demonstrated further in detail, this invention is not limited to these. In addition, unless otherwise indicated, the compounding quantity in a table | surface represents a weight part and weight%.

[Production of vinyl copolymer (A)]
Production Examples 1 to 3 (Production of Resin Liquids A1 to A3)
A reactor having a stirring device, a thermometer, a raw material dropping device, and a reflux cooling device is prepared. In accordance with the formulation shown in Table 1, (1) and (2) were charged into a reactor, raised to reflux temperature with stirring, and (3) to (9) were mixed uniformly in advance and then added dropwise over 3 hours. . The temperature was maintained at 90 ° C. (1.5) is added 1.5 hours after the completion of the dropping, and the reaction is further continued at 90 ° C. for 1.5 hours to obtain transparent and viscous resin liquids A1 to A3 having a resin solid content of 60%. Obtained.

[Production of cross-linking agent (B)]
Production Example 4 (Production of blocked polyisocyanate B1)
In a reactor having a stirrer, a thermometer, a raw material dropping device, and a reflux cooling device, 133 parts of isophorone, 150 parts of toluene, 333 parts of VESTANAT T-1890 / 100 (nurate of isophorone diisocyanate manufactured by Daicel-Evonik), coronate HX ( 300 parts of hexamethylene diisocyanate nurate manufactured by Nippon Polyurethane Co., Ltd. were charged and heated to 60 ° C. Next, 261 parts of methyl ethyl ketone oxime was added dropwise over 1 hour while maintaining 60 ° C., and the mixture was further kept at 60 ° C. for 2 hours. Finally, 100 parts of propylene glycol monomethyl ether was charged to obtain a blocked polyisocyanate B1 having a solid content of 70%.

Production Example 5 (Production of blocked polyisocyanate B2)
A reactor having a stirrer, a thermometer, a raw material dropping device, and a reflux cooling device was charged with 120 parts of isophorone, 136 parts of toluene, and 571 parts of coronate HX (a hexamethylene diisocyanate nurate body manufactured by Nippon Polyurethane Co., Ltd.) up to 60 ° C. The temperature rose. Next, 261 parts of methyl ethyl ketone oxime was added dropwise over 1 hour while maintaining 60 ° C., and the mixture was further kept at 60 ° C. for 2 hours. Finally, 100 parts of propylene glycol monomethyl ether was charged to obtain a blocked polyisocyanate B2 having a solid content of 70%.

[Production of dispersed resin liquid]
Examples 1 to 7 and Comparative Examples 1 to 4 (Production of Dispersed Resin Liquids C1 to C11)
A reactor having a stirrer, a thermometer, a raw material dropping device, and a reflux cooling device was prepared, and (11) to (18) were charged according to the formulations shown in Tables 2 and 3, and stirred and mixed at 60 ° C. for 1 hour. After adding (19) to this, (20) was gradually added, and then (21) was added to prepare dispersion resin liquids C1 to C11 having a solid content of 30% to obtain an electrodeposition coating material stock solution.

Cymel 235 in the table is an amino resin manufactured by Ornex Japan.
Plaxel 305 is a polycaprolactone polyol (weight average molecular weight = 1,100) manufactured by Daicel Chemical Industries, Ltd.
Plaxel 312 is a polycaprolactone polyol (weight average molecular weight = 2,300) manufactured by Daicel Chemical Industries, Ltd.
(*) The content of polycaprolactone polyol (C) in the table is expressed in parts by weight of polycaprolactone polyol (C) with respect to 100 parts by weight in total of (A) vinyl copolymer and (B) cross-linking agent.

[Adjustment of electrodeposition paint]
After adding deionized water to the above dispersion resin liquids C1 to C11 to adjust the solid content to 10%, triethylamine was added to adjust the pH to 8.0 to obtain the respective electrodeposition paints D1 to D11. .

[Electrodeposition coating]
The electrodeposition paints obtained above (Examples 1 to 7 use electrodeposition paints D1 to D7, and Comparative Examples 1 to 4 use electrodeposition paints D8 to D11) are placed in a vinyl chloride tank, and the cathode is a SUS304 steel plate. Then, the 6063S aluminum alloy plate was alumite-treated (alumite film thickness = 9 μm), further colored electrolytically to black, and then electrodeposited with an aluminum material washed with hot water by a conventional method as an anode (coating material). . The specific conditions for the electrodeposition coating were as follows: the bath temperature was 22 ° C., the electrode distance was 12 cm, and the electrode ratio (+/−) 2/1. After completion, the film was washed and subsequently baked and dried at 185 ° C. for 30 minutes to obtain a cured coating film.

[Paint properties and coating film performance evaluation]
The properties of the electrodeposition paint prepared above and the performance of the obtained electrodeposition coating film were evaluated, and the results are shown in Tables 4-5.

[Electrodeposition and coating performance evaluation]
The evaluation method is as follows.
(1) Paint filterability: The electrodeposition paint obtained above was filtered through a 320 mesh wire mesh, and the presence or absence of a filtration residue was confirmed.
○ = The liquid is filtered without any problem and there is no residue.
Δ = Liquid is somewhat difficult to filter and some residue is seen.
X = Liquid is quite difficult to filter, and a large amount of residue is seen.
(2) Paint settling: The electrodeposition paint obtained above was allowed to stand for 1 week at room temperature, and the presence or absence of precipitation was confirmed.
○ = No precipitation.
Δ = There is a small amount of precipitate.
× = There is a large amount of precipitate.
(3) Coating film appearance: The electrodeposition coating film obtained above was confirmed visually.
○ = No abnormality.
Δ = Slightly uneven.
X = There is considerable unevenness.
(4) Gloss value: 60 ° specular reflectance is measured with a gloss meter.
(5) Adhesiveness: After making 100 grids with a cutter knife on the coating film and attaching cellophane adhesive tape (CT-12S made by Nichiban Co., Ltd.) on it, quickly peel off the cellophane adhesive tape. Observe the state of adhesion. The resulting numbers mean the following:
100/100: No peeling of coating film.
0/100: All peeled off.
(6) Alkali resistance: The coated surface state was observed after immersion in a 1% aqueous sodium hydroxide solution at 20 ° C. for 48 hours.
(7) Acid resistance: The state of the coated surface was observed after immersion in a 5% sulfuric acid aqueous solution at 20 ° C. for 48 hours.
(8) Scratch resistance: A load of 200 g / cm @ 2 was applied to corrugated paper, and 50 reciprocating frictions were made with a 5 cm stroke. After the test material was kept at 50 DEG C. for 1 hour, the degree of scratches on the painted surface was visually evaluated. .
○ = Scratches are not visible.
Δ = Scratches are visible but not so white as to be planar.
× = The scar appears as a white surface.
(9) Self-healing test: Evaluation was performed using Tribogear TYPE 18 manufactured by Shinto Kagaku Co., Ltd. The measuring method is as follows. The measurement mode is constant load (20g), the tip needle is made of sapphire R processing 0.1φmm, stroke distance is 40mm, stroke speed is 10mm / sec, the number of strokes is performed once and the test material is scratched. The presence or absence of self-healing ability of the scratches attached after keeping at 50 ° C. for 1 hour was visually evaluated.
Self-healing: Yes = no scratches are visible.
Self-healing property: None = Scratches are visible.

  By applying the anionic electrodeposition coating composition of the present invention, it has excellent coating film appearance and coating film performance, and also has a self-healing function against scratches. It has become possible to provide a coating film particularly effective for restoration. In addition, the object to be coated is particularly applied to the coating of an aluminum material.

Claims (5)

(A) (a) α, β-ethylenically unsaturated carboxylic acid monomer, (b) hydroxyl-containing α, β-ethylenically unsaturated monomer, and (c) other α, β-ethylenically unsaturated monomers A vinyl copolymer having an acid value of 10 to 150 mg KOH / g solid content, a hydroxyl value of 20 to 200 mg KOH / g solid content, and a weight average molecular weight of 3,000 to 50,000, copolymerized with a saturated monomer, (B) a crosslinking agent, And (C) polycaprolactone polyol as an essential component, and (C) polycaprolactone polyol is 1 to 30 parts by weight with respect to 100 parts by weight in total of (A) vinyl copolymer and (B) cross-linking agent. An anionic glossy electrodeposition coating composition characterized by The anionic glossy electrodeposition coating composition according to claim 1, wherein the crosslinking agent (B) is 30 to 100 parts by weight with respect to 100 parts by weight of the (A) vinyl copolymer. The (C) polycaprolactone polyol is 3 to 25 parts by weight with respect to 100 parts by weight of the total of (A) vinyl copolymer and (B) cross-linking agent. An anionic glossy electrodeposition coating composition. (C) The polycaprolactone polyol is 8 to 25 parts by weight based on 100 parts by weight of the total of (A) vinyl copolymer and (B) cross-linking agent. Item 4. An anionic glossy electrodeposition coating composition according to Item 3. The weight average molecular weight of (C) polycaprolactone polyol is 300 to 5,000, and the anionic glossy electrodeposition coating composition according to claim 1, 2, 3, or 4 object.