TWI332038B - Matte anionic electrodeposition coating film-forming method - Google Patents

Description

[Technical Field] The present invention relates to a method for forming a de-photovoltaic film which is excellent in processability, plasticity, and film-coating performance. [Prior Art] In the past, aluminum was more easily formed by hot-pressing than other metals such as steel, and various aluminum alloys were obtained by mixing various metals in the aluminum. The aluminum alloy utilizes the excellent properties of light weight and easy processability or corrosion-resistant aluminum, in particular, the hot-squeeze method of the aluminum alloy, which is mostly used in building materials, usually by heating and melting, and then adding the melt to the extrusion. In the machine, in the mold of the fixed-section shape hole, the method of molding the shape of the hole through the hole in the form of a dish. Further, since the aluminum alloy itself is not easily corroded on the surface, such as seawater or the like, it is usually corroded by an anodizing treatment of the aluminum alloy, and the coating film of the ion-electroplating coating is usually removed after the anodizing treatment of the aluminum alloy. . The conventional invention has a method of applying a basic anion electrodeposition coating material to an aqueous solution in which a pH of 1 to 7 is added to a higher alkylarylsulfonic acid without unceasing, and then performing water washing and photoelectrodeposition coating method (refer to the patent). Document 1). However, by the electrodeposition coating method, the pH 膜 film traces are excellent in ion-electrodeposition coating workability and can be used as a mold material. In the original material with excellent sex. The cylindrical aluminum ingot is pressed against the obtained kinetic film having a shape, so that in the case of an alkaline substance, the high-grade -6- of the alkaline compound is bake-hardened by de-photo-coating and washing with water. 1332038 Alkyl sulfonic acid aqueous solution will have a catalyst effect obtained by removing the film only on the surface of the coating film, due to uneven hardening, resulting in a decrease in coating film performance, insufficient low-temperature hardenability, and creative degree of light removal. The indicator L値 is difficult to produce and satisfy problems such as 値. In the above invention, when the pH 値 is more than 7, the effect of improving the processability, the coating film property, and the low-temperature curability is insufficient. The anion electrodeposition coating tube has, for example, an invention in which a solubility parameter of a resin is adjusted, and a de-photo anionic electrodeposition coating material (see Patent Document 2) obtained by dispersing an emulsion by water dispersion is used. However, in the above-mentioned photo-anion electrodeposition coating, since the coating is fixed and fixed, the related creativeness is certain, and the degree of light removal is not easily changed. Therefore, a method for forming a photo-anionic electrodeposition coating film which is excellent in processability, mold mark concealing property, film coating property, low-temperature hardenability, and creativity can be easily changed. [Patent Document 1] JP-A-59-229494 (Patent Document 2) JP-A-2001-131494 SUMMARY OF THE INVENTION The present invention provides a processability, mold mark concealment, film properties, and low temperature hardening. It is an object of the method for forming an anion-based electrodeposition coating film which is excellent in properties and can be easily changed in creativity. The inventors of the present invention have found that the coating film obtained by electrodeposition coating of an anion electrodeposition paint having a resin solubility parameter difference of 0.5 to 1.5 is immersed in a higher alkane under uncured conditions in order to solve the above problems. The method of forming a coating film by adding an alkali compound having a ratio of 1 equivalent or more to the aryl sulfonic acid to adjust the pH 为 to an aqueous solution of 7.1 -7 to 1332038 to 14 and then washing, baking and drying the mixture, and completing the present invention . In other words, the present invention relates to a method for forming a de-photo anion electrodeposition coating film, which is characterized by the following steps: Step 1: mixing and dispersing (A) an ethylene-based copolymer resin and (B) a crosslinking agent The anion electrodeposition coating (I) of the resulting emulsion is electrodeposited on the surface of the aluminum alloy material to form an uncured electrodeposition coating film step, wherein the (A) ethylene copolymer resin and (B) crosslinking agent The difference in solubility parameter is 0.5 to 1.5. Step 2: The aluminum alloy material coated with the uncured electrodeposition coating film is immersed in a basic compound having a ratio of 1 equivalent or more to the higher alkylarylsulfonic acid, and water is dissolved. The resulting pH 7.1 1 to 14 aqueous solution (II) is subjected to a step of energizing under certain conditions, a step 3: a water washing step, and a step 4: bake hardening to form a photoelectrodeposition coating film. 2. The method for forming a photo-anion electrodeposition coating film according to item 1, wherein the energization condition is a two-stage energization of applying a voltage of 150 to 30 0 V in the second stage after applying a voltage of 1 0 to 150 V in the first stage. method. 3. The method for forming a photo-anion electrodeposition coating film according to Item 1 or 2, wherein (A) the ethylene-based copolymer resin is (a) a hydroxyl group-containing unsaturated monomer, and (b) a carboxyl group-containing unsaturated monomer. And (c) a radical polymerization of other radically polymerizable unsaturated monomers. 4. The method for forming a photo-anion electrodeposition coating film according to any one of items 1 to 3, wherein the (B) crosslinking agent is an amine resin hardener and/or a block polyisocyanate 1332038 acid ester compound. 5. The method for forming a de-photo anion electrodeposition coating film according to any one of items 1 to 4 wherein the higher alkylarylsulfonic acid is dinonylnaphthalenesulfonic acid and/or dimercapto-dioxasulfonic acid. 6. The method of forming a photo-anion electrodeposition coating film according to any one of items 1 to 5, wherein the dephotoelectrodeposition coating film has an L? of 10 to 25. 7. A coated article, which is obtained by the method according to any one of items 1 to 6. [Effect of the Invention] By coating the anionic electrodeposition coating (I) by electrodeposition on the surface of the aluminum alloy material, the obtained uncured electrodeposition coating film-coated aluminum alloy material is immersed in the higher alkyl aryl sulfonic acid to add 1 equivalent. The above-mentioned basic compound and water are dissolved in an aqueous solution (II) of p Η 7.1 to 1 4, energized, washed with water, and baked and dried to obtain processability, mold mark concealability, coating film performance, A coating of a dephotoelectrodeposition coating film excellent in low-temperature hardenability. Although the reason why the effect of the present invention can be obtained cannot be determined, the solubility parameter difference between the vinyl copolymer resin of the matrix resin and the melamine resin or the blocked polyisocyanate compound resin of the crosslinking agent is 0.5 to 1.5, which is presumed to be due to It is affected by the aqueous solution (II) having a pH of 7.1 to 14 to obtain a photo-coated film. [Embodiment] The present invention will be described in detail below. The anion electrodeposition coating resin, for example, an ethylene-based copolymer resin, a polyester resin, a fluorine-based resin, a rubber-based resin, and the like, is a resin such as _ 9 - 1332038 in terms of weather resistance. A vinyl copolymer resin is preferred. The ethylene-based copolymer resin (A) of the present invention is obtained by copolymerizing (a) a hydroxyl group-containing unsaturated monomer, (b) a carboxyl group-containing unsaturated monomer, and (c) another unsaturated monomer. A water-dispersible ethylene-based copolymer resin. (a) a hydroxyl group-containing unsaturated monomer such as hydroxyethyl (meth) acrylate, propyl propyl (meth) acrylate, hydroxybutyl (meth) acrylate, (poly) ethylene glycol mono ( Methyl)acrylate, (poly)propylene glycol mono(meth)acrylic acid vinegar, hydroxybutyl vinyl ether, (meth)propenyl alcohol, and the above hydroxyl group-containing unsaturated monomer and β_propiolactone, two Lactones such as methyl propiolactone, butyrolactone, γ-valerolactone, γ-caprolactone, γ-heptanolactone γ-laurolactone, ε-caprolactone, δ_caprolactone Reactions, etc., such as the name of the valley of the valley, the Swiss version of the FM1 (researched by Lai Xilu (transliteration) chemical company, the trade name, vinegar modified (methyl) acrylic acid vinegar), Bra Guxi Lu FM2 (same left), Bragu Valley Xilu FM3 (same left), Bragu Valley Xilu FA1 (same left), Bragu Valley Xilu FA2 (same left), Bragu Valley Xilu FA3 (same left), etc. The carboxyl group-containing unsaturated monomer (b) is, for example, (meth)acrylic acid, maleic acid, or glabrizil (trans) FM1A (in the following, Lai Silu Chemical Co., Ltd., caprolactone modified carboxyl group) (Meth)acrylic monomer, trade name), Bragu Siro FM4A (ibid.), Bragu Siro FM10A (ibid.), etc. Other radically polymerizable unsaturated monomers (C) such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, (meth)acrylic acid C, hexyl or cycloalkyl esters of hexyl ester, octyl (meth) acrylate, lauryl (meth) acrylate, cyclohexyl (meth) acrylate, etc., styrene And other aromatic vinyl monomers, -10- 1332038 (meth)acrylic acid decylamine, n-butoxymethyl (meth) acrylamide decyl-n-hydroxymethyl (meth) acrylamide, etc. Base) acrylamide and its derivatives, (meth)acrylonitrile compounds, and the like. Others such as polyethylene glycol monoacrylate 'polyethylene glycol monomethacrylate, polypropylene glycol monoacrylate, polypropylene glycol monomethacrylate, polyethylene glycol monomethyl ether monoacrylate, polyethylene glycol single A polyether-modified acrylic unsaturated monomer such as methyl ether monomethacrylate. The mixing ratio of these monomers is in terms of the sum total of the solid components of (a) the hydroxyl group-containing unsaturated monomer, (b) the carboxyl group-containing unsaturated monomer, and (c) the other radical polymerizable unsaturated monomer. (a) the hydroxyl group-containing unsaturated monomer is 3 to 50% by weight, preferably 5 to 40% by weight, and (b) the carboxyl group-containing unsaturated monomer is 2 to 40% by weight, preferably 4 ～30% by weight, (the other radically polymerizable unsaturated monomer is 10 to 90% by weight, preferably 20 to 70% by weight. (A) The method for producing the ethylene-based copolymer resin can be a known method, for example, It can be carried out by a solution polymerization method, a suspension polymerization method, an emulsion polymerization method, or the like, and is preferably a solution polymerization method as described below. Further, an organic solvent used in the radical copolymerization such as n-propanol, isopropanol, n-butanol, or the third Alcohols such as butanol and isobutanol, cellosolve, methyl cellosolve, butyl cellosolve, methyl carbitol, 2-methoxyethanol, 2-ethoxyethanol, 2-isopropyloxy Ethanol, 2-butoxyethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, b Ethers such as oxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol monomethyl ether, etc. Further, 'other than the aryl-11- such as xylene or toluene, which may be used as needed, 1332038 Ketones such as aroma, acetone, methyl ethyl ketone, 2-heptanone, 2-hexanone, methyl isobutyl ketone, isophorone' cyclohexanone, etc. 'methyl acetate, ethyl acetate, acetic acid Propyl ester, butyl acetate, isobutyl acetate, amyl acetate, 3-methoxybutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methyl propionate An ester of ethyl propionate, etc. Further, a radical polymerization initiator used in radical copolymerization such as benzammonium peroxide, di-tert-butyl hydroperoxide, and tert-butyl hydroperoxide , cumyl peroxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, tert-butyl peroxybenzoate, lauryl peroxide, acetyl peroxide, Peroxide such as tributylperoxy-2-ethylhexanoate, α,α'-azobisisobutyronitrile, azobisdimethylvaleronitrile, azobiscyclohexanecarbonitrile, etc. Azoylation The solution polymerization reaction can be carried out by using (a) a hydroxyl group-containing unsaturated monomer, (b) a carboxyl group-containing unsaturated monomer, (c) another radical polymerizable unsaturated monomer, etc. in the organic solvent. The monomer, the mixture of the radical polymerization initiators, for example, is reacted at a temperature of about 50 to 200 ° C, preferably about 60 to 180 ° C for about 1 to 24 hours, preferably about 2 to 1 The ethylene polymer resin obtained herein has a hydroxyl group content of 30 to 200 mgKOH/g, preferably 50 to 180 mgKOH/g, and an acid value of 15 to 150 mgKOH/g, preferably 20 to 130 nmigKOH. The range of /g, the number average molecular weight is from 10,000 to 1,00,000, preferably from 20,000 to 60,000. If the number average molecular weight is less than 10,000, the coating performance is insufficient, and if the number average molecular weight is more than 100,000, the aqueous resin is highly viscous, and when the water 1332038 is dispersed, it is difficult to form a uniform emulsion. As the amine-based resin used as the crosslinking agent (B), a conventional amine-based resin can be used. Amino-based resin such as melamine, urea, benzoguanamine, acetaminophen, guanamine, helixamine, dicyanoguanamine, etc. by reacting an amine component with an aldehyde Hydroxymethylated amine based resin. The aldehyde has formaldehyde, paraformaldehyde, acetaldehyde, benzaldehyde and the like. Further, an alcohol which is used for esterification of a methylolated amine-based resin by a suitable alcohol, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, 2 may be used. -ethylbutanol, 2-ethylhexanol, and the like. As the block polyisocyanate compound used as the (B) crosslinking agent, those of the conventional polyisocyanate compound may be blocked with a blocker. a polyisocyanate compound such as an aliphatic diisocyanate of hexamethylene diisocyanate or trimethyl hexamethylene diisocyanate; a cyclic aliphatic diisocyanate of hydrogenated xylylene diisocyanate or isophorone diisocyanate; The organic diisocyanate of the aromatic diisocyanate of tolylene diisocyanate or 4,4'-diphenylmethane diisocyanate itself, or the addition of these organic diisocyanates and polyols, low molecular weight polyester resins or water, etc. a product, or a cyclized polymer such as each of the above organic diisocyanates, and an isocyanate/biuret product, etc., such typical commercial products such as "Baroque D-750, -800 'D positive 950, - 970, or 1 5 - 4 5 5" "The above is the Japanese ink chemical industry product j, "Di Shi Mo Ji Lu (transliteration) L, N, HL, IL or N3390" "West Bayer (transliteration) Company-made"" "Takken Knightn (transliteration) D-102, -202, -110 or 123N" "Takeda Pharmaceutical Industry Products" 1332038, "Troneton (transliteration) L, HL, EH or 203" "Japan Polyurethane industry Product "or" Di Lanai Dayton (transliteration) 24A-90CX "" Asahi Kasei products "and so on. Among them, aliphatic diisocyanates or cyclic aliphatic diisocyanates are preferred. The block agent is, for example, a phenol type, an internal amide type, an active methyl group, an alcohol type, a thiol type, an acid amide type, a quinone type, an amine type, an imidazole type, a urea type, or an urethane type. A blocker such as an imide or a sulfite. In the present invention, the blending ratio of the (A) ethylene-based copolymer resin and the (B) crosslinking agent is (A) the ethylene-based copolymer resin is 30 to 90% by weight, and the (B) crosslinking agent is 70 to 10% by weight. Preferably, the (A) ethylene-based copolymer resin is 35 to 80% by weight, and the (B) crosslinking agent is 65 to 20% by weight. When the crosslinking agent (B) is less than 1% by weight, the film properties such as weather resistance, scratch resistance, and coating film processability are not good, and when it is more than 70% by weight, coating film such as weather resistance and coating film processability Poor performance. Further, it is understood that the difference in solubility parameter between (A) the ethylene-based copolymer resin and the (B) crosslinking agent is 0.5 to 1.5, and after the electrodeposition coating, the alkalinity is added to the higher alkylarylsulfonic acid. In the aqueous solution (II) prepared by the compound, after being electrified and washed with water, it is baked and dried to obtain a matte coating film excellent in processability, mold mark concealing property, coating film property, and low-temperature curability. Further, a solubility parameter (hereinafter referred to as SP値) indicates a molecular interaction scale of liquid molecules. The SP値 of the resin can be determined by turbidity titration, specifically, the following K.W. SUH.J.M. CORBETT (1) (Journal of Applied

Polymer Science, 12, 2359, 1968) was obtained on the basis of the benchmark. 1332038 [1] ν' ~ (1) (wherein, VH indicates the volume fraction of n-hexane, VD indicates the volume fraction of deionized water, δΗ indicates SP値 of n-hexane, and 5D indicates SP of deionized water.値) The cloud point titration is to dissolve 乙烯.5g (solid content) of the dried vinyl resin in 10ml of acetone, slowly add n-hexane, read the boiling point of the amount of H (ml), and read the same in acetone. The titer D (ml) of the cloud point of the deionized water is used to obtain VH, VD, δ Η, δ 使用 for the following formula.

Vh = H/ (1 Ο+Η) Vd = D/ (1 O+D), δΗ=9· 7 5X10/ (10+H) +7. 2 4XH/ (10+Η) , δΌ = 9. 75X10 / (10 + D) + 2 3. 4 3 XD/ (lO^D) Further, the SP値 of each solvent was acetone: 9.75, n-hexane: 7.24, and deionized water: 23.43. In addition, the adjustment of SP値 can be easily carried out by the composition or ratio of the monomers. The basic compound used in the neutralization of the (A) ethylene-based copolymer resin is ethylamine, propylamine, butylamine, benzylamine, monoethanolamine, a primary monoamine such as octanolamine, 2-aminopropanol or 3-aminopropanol; diethylamine diethanolamine, di- or di-isopropanolamine, n-methylethanolamine, n-ethylethanolamine, etc. a secondary monoamine; a tertiary monoamine such as dimethylethanolamine, trimethylamine, triethylamine, triisopropylamine, methyldiethanolamine 'dimethylaminoethanol; diethyltriamine, hydroxy-15- 1332038 Polyaminotriethylamine such as ethylaminoethylamine, ethylaminoethylamine or methylaminopropylamine. The compounding ratio of the above basic compound in the anion electrodeposition coating material (I) is preferably from 0.1 to 1.0 in terms of equivalents, and is basic in terms of total solid content of (A) ethylene-based copolymer resin and (B) crosslinking agent. The compound is 0.01 to 10% by weight, preferably 0.05 to 5% by weight. If the basic compound is less than 〇.〇1% by weight, the water-dispersibility of the aqueous emulsion is not good, and if it is more than 10% by weight, the coating film performance is deteriorated due to an increase in hydrophilicity. An ultraviolet absorber and a photosensitizer may be added to the above anionic electrodeposition paint (I). The ultraviolet absorber is, for example, a salicylic acid derivative such as phenyl salicylate, p-octylphenyl salicylate or 4th butylphenylsalicylate; 2,4-dihydroxydiphenyl Methyl ketone '2-hydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-2,-carboxyl Benzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2-hydroxy-4 - Octyloxybenzophenone, 2-hydroxy-4-octadecanyloxybenzophenone, sodium-2,2'-dihydroxy-4,4'-dimethoxy-5-sulfoyl Benzene, 2,2',4,4'-tetrahydroxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 5-chloro-2-hydroxybenzophenone, Hydroquinone monobenzoate, 2,4-dibenylhydrazino-resorcinol, 4,6-diphenylmercaptoresorcinol, hydroxydodecylbenzophenone, 2,2 '-Dihydroxy-4(3-methylpropenyloxy-2-transpropoxy)diphenyl- benzophenone; 2-(2,-hydroxy-5'-methyl Benzotriazoles such as phenyl)benzotriazole and others (aniline oxalate, cyanoacrylate Or a compound, etc., -16-1332038 A light stabilizer used in the mixing system, such as a hindered amine derivative, specifically, for example, bis(2,2',6,6'-tetramethyl-4-piperidyl) phthalate 4-benzylideneoxy-2,2',6,6'-tetramethylpiperidine or the like, and these may be appropriately selected alone or in combination of two or more. The emulsion of the anionic electrodeposition coating material (I) may be prepared by adding a basic compound or deionized water to the (A) ethylene-based copolymer resin or the (B) crosslinking agent, and stirring with a disperser or the like. The anion electric enthalpy product (I) can be adjusted according to the required addition of pigments, dyes, hardening catalysts and flow regulators, and deionized water can be added to obtain an anion of 5 to 20% by weight of solid components. Deposition paint. The anion electrodeposited coating (I) is preferably coated with a colored or non-colored anodized aluminum alloy. When the coating film is formed by using the anion electrodeposition paint, the obtained anion electrodeposition paint is used as a bath, and the aluminum alloy material is treated in a bath at a bath temperature of 10 to 30 ° C, preferably 15 to 25 ° (:: bath) After the collapse, the anion electrodeposition coating of about 5 to 30 μm is carried out after drying the film. About the aqueous solution (I Π After washing with the coating film obtained by anionic electrodeposition coating, the aluminum alloy coated with the uncured electrodeposition coating film is applied. The material is immersed in an aqueous solution (II) in which a basic compound having a ratio of 1 equivalent or more or more is added to a higher alkylarylsulfonic acid, and is energized at a voltage of 50 to 350 V for 10 to 240 seconds. After the water washing, it is baked and dried at 140 to 200 ° C for 10 to 120 minutes to obtain a matte coating film. The quaternary acid is obtained by the following formula (2) to (6). 1332038 These compounds may be used alone or in combination of two or more. [Chemical Formula 1] General Formula (2)

(R series is not the base of C3~C18) [Chemical 2] General formula (3).

(Ri, R2 are not the base of C3~C18) [Chemical 3]

General formula (4)

(R series is not the base of C3~C12) [Chemical 4] -18- 1332038

(R1' L system represents an alkyl group of C3 to C12) [Chemical 5] General formula (6)

(R!, R2 represents an alkyl group of c3 to c12) Specific examples of higher alkylarylsulfonic acids such as n-butylbenzenesulfonic acid, n-aminobenzenesulfonic acid, n-dodecylbenzenesulfonate n-dodecylbenzenesulfonate Acid, n-octadecylbenzenesulfonic acid, n-dibutylbenzenesulfonic acid, isopropylnaphthalenesulfonic acid, dodecylnaphthalenesulfonic acid, dinonylnaphthalenesulfonic acid, dinonylnaphthalene disulfonic acid and the like. The concentration of the higher alkylarylsulfonic acid is 0.1 to 20% by weight, preferably 0.3 to 10% by weight, more preferably 0.5 to 8% by weight. Among them, dinonylnaphthalenesulfonic acid and dinonylnaphthalene disulfonic acid are preferred. Basic compounds added to such higher alkylaryl sulfonic acids such as ethylamine 'propylamine' butylamine, benzylamine, monoethanolamine, neopentylamine, 2-aminopropanol, 3-aminopropanol, etc. a primary monoamine; a secondary monoamine such as diethylamine diethanolamine, di- or di-isopropanolamine, n-methylethanolamine or n-ethylethanolamine; dimethylethanolamine, trimethylamine, triethylamine, three a tertiary monoamine such as isopropylamine, methyldiethanolamine or dimethylaminoethanol; diethyltriamine, hydroxyethylaminoethylamine-19-1332038, ethylaminoethylamine, methylamino Polyamine triethylamine such as propylamine. When the photo-deposition electrodeposition coating film forming method of the present invention is used, 'the coating film evaluation item can easily obtain the creative value of L値 in the range of 10 to 25' and can be changed by the following coating conditions to make the degree of light removal. change. In addition, the energization condition of the aqueous solution (II) can be in the range of 10 to 35 ° C water temperature, voltage 10 to 350 V, preferably 100 to 250 V, by energization for 1 to 300 seconds, in the unhardened coating film. A higher alkylaryl sulfonic acid is precipitated. Further, in the energization method, when a two-stage energization method of applying a voltage of 10 to 150 V in the first stage and applying a voltage of 150 to 300 V in the second stage is applied, the higher alkylarylsulfonic acid is impregnated to the first at a low voltage. By deepening the deep portion of the coating film, the higher alkyl aryl sulfonic acid is easily precipitated on the coating film having the film resistance at a high voltage, and the effect of improving the performance of the coating film can be improved by moving to the coating film. When the method of the present invention is illustrated in Fig. 1, the electrodeposition coating of the above step 1 is carried out in the electrodeposition tank 1, and after washing in the water washing tank (1), the step 2 is carried out in the aqueous solution (II) immersion tank 3. Immersion and energization, and then the water washing of the above step 3 is carried out in the water washing tank (2) 4. In the figure, an arrow 9 indicates that the process proceeds to step 2 by the above step 1. [Embodiment] [Embodiment] Hereinafter, the present invention will be more specifically described by way of examples. However, the invention is not limited by this. Moreover, "parts" and "%" mean "parts by weight" and "% by weight j. Manufacturing Example 1 -20- 1332038 Add 280 g of isopropyl alcohol to the reaction vessel, keep at 80 ° C, and drip in 3 hours. 40 g of styrene, 96 g of methyl methacrylate, 40 g of n-butyl acrylate, 120 g of ethyl acrylate, 48 g of 2-hydroxyethyl acrylate, 28 g of acrylic acid, and 8 g of azobisdimethylammonium The mixture was then added with 4 g of azobisdimethylvaleronitrile and kept at 80*>C for 1 hour to obtain a vinyl copolymer resin No. 1 « This vinyl copolymer resin No. 1 system was obtained. The weight average molecular weight is about 25,000, the acid value is 55 mgKOH/g, and the hydroxyl value is 58 mgKOH/g. Production Example 2 Emulsion No. 1 Production Example 1 to 70 parts (solid content) Production Example 1 Ethylene-based copolymer resin No The carboxyl group of .1 is mixed with 0.4 equivalent of triethylamine, and then mixed and dispersed. Then, 30 parts of Nicara MX430 (Note 1) are mixed and dispersed, then stirred and slowly dripped into deionized water, and three are added. The ethylamine has a pH of 7.5, and a solid content of 10% of the emulsion No. 1 is obtained. The difference in the solubility parameter between the polymer resin No. 1 and the Nikalaq MX4 30 was 0.7. Production Example 3 Emulsion No. 2 Production Example For the ethylene-based copolymer resin No. 170 (solid content) Production Example 1 The carboxyl group of .1 is mixed with 0.4 equivalent of triethylamine, and then mixed and dispersed, then 20 parts of Nikalaq MX430 (Note 1), 12.5 parts of Girardine 24:80-90% (Note 2) After mixing and dispersing 10 parts of the solid component, the mixture was stirred and slowly dripped with deionized water, and triethylamine was further added thereto to adjust the pH to 7.5 to obtain an emulsion No. 1 of a solid content of 10%. 2. Vinyl copolymer resin No. 1 The difference in solubility parameter of Nicarak MX430 / Gilard Nylon 1332038 24A-90CX was 〇.6. Production Example 4 Emulsion N 〇·3 Production Example For 170 parts (solid content) Production Example 1 ethylene copolymerization The carboxyl group of the resin No. 1 was mixed and dispersed with 0.4 equivalent of triethylamine, and then 10 parts of Nikalaq MX430 (Note 1) and 25 parts of Girardington 24A-90CX (Note 2) ( After mixing and dispersing 20 parts of the solid component, stirring was carried out, and deionized water was slowly added dropwise, and triethylamine was further added to adjust the pH to 7.5 to obtain a solid. 10% of the composition of the emulsion No. 3. The solubility parameter difference between the vinyl copolymer resin No. 1 and the Nikala MX430 / Gilardon 24A-90CX is 〇. 3. (Note 1) Nikala MX430: three And Chemical Co., Ltd., trade name, butoxylated melamine resin, solid content of 00% (Note 2) Girardington 24A-90CX: manufactured by Asahi Kasei Industrial Co., Ltd., trade name, block polyisocyanate, Solid component 80% Production Example 5 An anion electrodeposition paint No. 1 was obtained by adding 3,000 parts of the above-mentioned iodine% emulsion No. 1 and triethylamine having a pH of 8.5. Production Example 6 Anion electrodeposition paint No. 2 was obtained by adding 3000 parts of the above-mentioned 1% by weight emulsion ν〇·2, and triethylamine having a pH of 8.5. Production Example 7 An anion electrodeposition paint Ν〇·3 was prepared by adding 3000 parts of the above 10% emulsion No. 3 and a pH of 8.5 to triethylamine. Production Example 8 -22- 1332038 In a solution of 90 parts of isopropyl alcohol, Taycacure AC-901 (manufactured by Decathlon Corporation, trade name, dinonylnaphthalenesulfonic acid) was placed in 1 part of the solution. 0. 28 parts of triethylamine (equivalent to 5 equivalents) was added. Further, deionized water was added to prepare 1,000 parts of an aqueous solution of 1% solid content. The pH of the aqueous solution Νο·1 was 9.0. Production Example 9 20 parts of Taycacure AC-330 (manufactured by Decathlon Corporation, trade name, dimercaptobenzenesulfonic acid) were added to 80 parts of isopropyl alcohol, and 0.34 parts of triethyl was added to 1 part of the solution. Amine (equivalent to 5 equivalents). ® Add deionized water to make 1 000 parts of a 1% solids solution. The pH of the aqueous solution Νο.2 was 8.5. Production Example 10 20 parts of Taycacure AC-430 (manufactured by Decathlon Corporation, trade name, dodecanebenzenesulfonic acid) were added to 80 parts of isopropyl alcohol, and 0.1 part of this solution was added to 0.3. 7 parts of triethylamine (equivalent to 5 equivalents). Further, deionized water was added to prepare 1000 parts of an aqueous solution of 1% solid content. The aqueous solution N. The pH of .3 is 10.0. Φ

Production Example U 20 parts of Taycacure AC-901 (manufactured by Decathlon Corporation, trade name, dinonylnaphthalenesulfonic acid) were added to 80 parts of isopropyl alcohol, and 0.25 parts of triethylamine was added to 100 parts of the solution. (equivalent to 2 equivalents). Further, deionized water was added to prepare 1000 parts of an aqueous solution of 1% solid content. The pH of the aqueous solution No. 4 was 3.5. Production Example 1 2 -23- 1332038 20 parts of butyl 37 〇 3 (: 11 "six (: _330 (made by Deca), trade name, pentadecyl sulfonic acid) in 80 parts of isopropyl alcohol, To 100 parts of this solution, 0.14 parts of triethylamine (equivalent to 0.2 equivalent) was added. Further, deionized water was added to prepare 1 000 parts of an aqueous solution of 1% solid content. The pH of the aqueous solution No. 5 was 3.0. The production of the board was carried out by performing two times of electrolytic treatment on the aluminum alloy material (#5000) (degreasing-etching-neutralizing-anodizing treatment-sealing) to obtain an anodizing test with a film thickness of about ιομπι. Plate (Siruba: size: 150 X70x〇.5mm) 〇Example 1 Two test plates were used, each immersed in the anionic electrodeposition paint Nol obtained in Production Example 1, and subjected to electrodeposition of a dried film thickness of 18 μm. Then, 'the aqueous solution No. 1 obtained in Production Example 3 was energized at a voltage of 15 〇 1 for 1 minute', and then washed with water at a temperature of 160 for 30 minutes and at 180 for 30 minutes. The experiments of Examples 2 to 4 and Comparative Examples 1 to 3 were carried out in the same manner as in Example 1. The results obtained are shown in Table 1. 1332038 Table 1 Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Anionic electrodeposition coating (1) N0.1 NO. 7 N0.1 NO. 2 N0. 1 N0.1 NO.2 NO. 3 Ethylene copolymer resin and crosslinker 0.7 0.7 0.7 0.8 0.7 0.7 0.6 0.3 Meltability parameter difference water soluble No. N0.1 NO.2 NO.3 N0.1 NO.4 NO.5 NO.4 N0.1 Liquid pH 9.0 8.5 10.0 9.0 3.5 3.0 3.5 9.0 (II) Voltage (V) 1st voltage (V) 150 200 200 50 150 200 50 200 2nd voltage (V) 200 200 Coating Surface smoothness (Note 3) 〇〇〇〇Δ Δ Δ Diaphragm mold mark visual (Note 4) 〇〇〇〇Δ Δ △ X Concealed L値 (Note 5) 21 20 20 20 3 5 6 6 Low temperature Hardening 160 °C 〇〇〇〇Δ Δ Δ △ (Note 6) 180. 〇〇〇〇〇〇〇〇 Water resistance 160 ° C 〇〇〇 ◎ Δ Δ 〇 Δ (Note 7) 180 ° C ◎ ◎ ◎ ◎ 〇〇〇〇 (Note 3) Smoothness of the coating film: The surface of the coating film (the surface of the orange peel, the unevenness, etc.) was visually evaluated. Baking is carried out using a coating at 180 °C. ◎: Jia Hao: slightly better △: slightly poor X: poor (Note 4) mold mark concealment (visual evaluation): baking is used 1 8 (coated under TC. -25- 1332038 Sexual occult faint note with a mold • . · *〇△ X: The mold mark is significantly poorly concealed (Note 5) Mold mark concealment (L値 evaluation) · · Baking is used at 180 ° C The coated plate was measured using a variable angle spectrophotometer GCMS-4 (manufactured by Murakami Color Research Laboratory Co., Ltd., trade name) at an incident angle of 90. By the method for forming a coating film of the present invention, L値 can be easily produced. The coating film is in the range of 10 to 25. (Note 6) Low-temperature hardening property: Acetone is infiltrated into the gauze and rubbed back and forth 20 times on the coated surface to etch the coated surface. 〇: No problem △: The coated surface is dissolved and White turbidity X: Significantly dissolved on the coated surface (Note 7) Water resistance: The coated plate was immersed in warm water at 40 ° C for 240 hours, and cross-cut was added to perform peeling test by tape. ◎: No peeling, no problem 〇: Although not Peeling situation, slight expansion near the cutting part △: Self-cutting part Partial peeling situation x: peeling off from the cutting part [Simplified illustration of the drawing] Fig. 1 is a schematic diagram showing steps 1 to 3 of the method of the present invention. [Component Symbol Description Table] 1 Electrodeposition tank 2 Washing tank (1) 1332038 3 Aqueous solution (II) Dip tank 4 Washing tank (2) 5 Electrodeposition electrode 6 Wash nozzle (1) 7 Electrode electrode 8 Wash nozzle (2) 9 Arrow

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Claims (1)

I322〇aS~ η Years?丨 丨 曰 曰 吏 吏 正 尽 尽 92 92 92 92 92 92 92 92 92 92 92 92 92 92 92 92 92 92 92 92 92 92 92 92 92 92 92 92 92 92 92 92 92 92 92 92 92 92 92 92 92 92 A method for forming a photo-anion electrodeposition coating film, which is characterized by the following steps: Step 1: From (a) a hydroxyl group-containing unsaturated monomer, (b) a carboxyl group-containing unsaturated monomer, (c) other freedom (A) an ethylene-based copolymer resin obtained by radical polymerization of a radically unsaturated monomer, and an anion of the emulsion formed by mixing and dispersing the crosslinking agent with an amine-based resin hardener and/or a block polyisocyanate compound (B) The electrodeposition coating (I) is electrodeposited on the surface of the aluminum alloy material to form an uncured electrodeposition coating film, wherein the solubility parameter of the (A) ethylene copolymer resin and the (B) crosslinking agent is poor. 〇.5~1.5, Step 2: The aluminum alloy material coated with the uncured electrodeposition coating film is immersed in a higher alkylaryl group of dinonylnaphthalenesulfonic acid and/or dinonylnaphthalenedisulfonic acid A pH 7.1~14 aqueous solution (II) is prepared by adding a basic compound to a sulfonic acid and dissolving with water. In the case where the energization condition is a voltage of 10 to 150 V applied in the first stage, the second stage is applied with a voltage of 150 to 30 V, and the step of energizing the two-stage energization method, step 3: water washing step, and step 4: bake hardening, A step of forming a photoelectrodeposition coating film is formed. 2. The method of forming a photo-anion electrodeposition coating film according to claim 1, wherein the de-electrodeposition coating film has an L? of 10 to 25.