TWI264452B - Matte anionic electrodeposition coating composition - Google Patents

Abstract

The invention provides an anionic matted electro-deposition paint having 60 DEG gloss of less than 10, as well as having excellent performance in lower temperature curing capability, hardness of coating film and coverage of dies mark. An anionic matted electro-deposition paint comprising an emulsion formed by dispersing a resin (A) having a blocked isocyanate group and a hydroxyl group both presented simultaneously in a molecule, which is obtained by reacting a part of a free isocyanate group of a vinyl copolymer (a1) having 2 or more free isocyanate groups in one molecule with a part of hydroxyl group of a vinyl copolymer (a2) having hydroxyl group, carboxyl group and alkoxysilyl group, subsequently reacting all of the residual free isocyanate group with a blocking agent, and wherein the difference of solubility parameter (SP value) between the vinyl copolymer (a1) and vinyl copolymer (a2) is 0.4 to 1.0; and then further adding and dispersing a curing catalyst (B); which is characterized in comprising 0.1 to 10 weight parts of curing catalyst (B) with respect to 100 weight parts of total amount of resin (A).

Description

1264452 IX. Description of the Invention: [Technical Field] The present invention relates to a matte anionic plating coating which is excellent in low-temperature hardenability and coating film hardness, and has excellent masking concealability. [Prior Art]

Aluminum has a so-called light weight, easy processability, and excellent corrosion resistance. It can be used for most materials, particularly building materials related materials, by utilizing these properties of aluminum. The method for extruding the heat between the aluminum is usually a method of heating and melting a cylindrical aluminum ingot, and then putting the molten material into an extruder and pressing it on a mold having a hole having a predetermined sectional shape. A method of sequentially forming a profile is obtained by sequentially passing the holes. Further, since the aluminum itself is generally inferior in corrosion resistance, abrasion resistance, and chemical resistance, it is generally coated with a matte coating film by anodizing the aluminum after anodizing the aluminum. However, in the case where the above-mentioned matte anion plating coating is applied to the aluminum profile after the anodic oxidation treatment by electro-mineral plating, the stamping of the aluminum profile of the material is easily manifested so that there is a problem that the commercial price is deteriorated. In order to make such a stamp imprinting difficult to be apparent, there has been an invention of an anionic electromineral coating which is incompatible with two kinds of acrylic resins having different solubility parameters and their acrylic resins. The melamine resin is formed by water dispersion. [Patent Document 1]. Further, the invention is a matte coating film comprising a water-dispersible resin and a melamine resin and having a difference in S P 树脂 of the resin. [Patent Document 2]. 1264452 In the invention, since the firing of 1 70 t: or more is required, not only the anodic oxide film is liable to cause cracks, the finish property and the coating film performance are lowered, but the energy consumption is increased, so that it is economically problematic.

In other cases, when a coating material containing a hydroxyl group and a carboxyl group-containing resin or a blocked polyisocyanate compound is used, it is possible to obtain a curability of a gel fraction of 90% or more at a temperature of 140 ° C, and The coating film hardness (the pencil hardness is 4H or more) is high, but the low gloss (60° gloss is 10 or less) and the masking concealability are insufficient (Patent Document 3). In addition, a part of the free isocyanate group of the ethylene-based copolymer having two or more free isocyanate groups in one molecule, and the hydroxyl group in the acrylic resin having two or more hydroxyl groups in one molecule An invention in which a part of the reaction is carried out, and a resin having a blocked isocyanate group and a hydroxyl group having a ruthenium in one molecule is obtained by reacting all of the remaining free isocyanate groups with a blocking agent (Patent Document 4). In the case of using only the matte anionic plating coating, the matte coating film which is excellent in low-temperature curability, coating hardness, and mold hiding property is not obtained. Moreover, the mold masking property of the matte coating film is excellent. [Patent Document 1] Japanese Laid-Open Patent Publication No. JP-A No. Hei. No. Hei. 】 】 】 】 】 】 】 】 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 Anionic plating coating. [Means to solve the problem]

The present inventors have deliberately repeated the above-mentioned problems in order to solve the above-mentioned problems, and as a result, it has been found that a vinyl-based copolymer (a 1 ) having two or more free isocyanate groups in one molecule is used. A part of the free isocyanate group is reacted with a part of the hydroxyl group of the ethylene-based copolymer (a 2 ) having a hydroxyl group, a carboxyl group or an alkoxyalkyl group, and then all the remaining free isocyanate groups are blocked. The matting anion plating coating formed by the resin (A) and the hardening catalyst (B) having a blocked block isocyanate group and a hydroxyl group in the ruthenium molecule can be obtained, and thus the present invention is completed. . That is, the present invention is: 1 - a matting anionic plating coating characterized by using the free isocyanate group of the ethylene-based copolymer (a 1 ) having two or more free isocyanate groups in one molecule. a part of the reaction with a part of the hydroxyl group of the ethylene-based copolymer (a2) having a hydroxyl group, a carboxyl group and an alkoxyalkyl group, and then reacting all the remaining free isocyanate groups with the blocking agent The resin having a blocked block isocyanate group and a hydroxyl group in one molecule, and the difference in solubility parameter (SP値) between the ethylene-based copolymer (a 1 ) and the ethylene-based copolymer (a 2) is 0. 4~1 · The resin (A) is water-dispersed, and further comprises an emulsion formed by dispersing a curing catalyst (B), and contains 100% of the total amount of the resin (A). The parts by weight are 〇. 1 to 10 parts by weight of the hardening catalyst (B). 2. The matte anionic plating coating according to Item 1, wherein the hardening catalyst (B) is at least one selected from the group consisting of an organotin compound and an amine compound. 3. The matte anionic plating coating according to item 1 or 2, wherein the ethylene-based copolymer (a 1 ) is a copolymer of a vinyl monomer containing an isocyanate group and another vinyl monomer. A matte coated article, wherein the 60° gloss of the coating film formed by coating the matte anionic plating coating according to any one of items 1 to 3 on the anodized aluminum substrate is 10 or less.

[Effect of the Invention] The matte anion plating coating of the present invention can be obtained by drying at a low temperature of 14 CTC for 20 minutes to obtain a coating film hardness (pencil hardness of 4H or more) and excellent 60° gloss of masking concealability. A matte film having a degree of 10 or less. Since the composition of the present invention has low-temperature curability of an anionic plating coating which cannot be achieved by using a melamine resin as a curing component, it is possible to remove the crack of the anodic oxide film which is fired at 170 ° C and apply it. A problem such as a decrease in film properties and an increase in energy consumption can be obtained. Further, a matte coating film which cannot be achieved by using a conventional block-type polyisocyanate compound as an anionic plating coating for a hardening component can be obtained. [Embodiment] [Best Mode for Carrying Out the Invention] The matte anionic plating coating of the present invention is an emulsion containing a resin (A) and a curing catalyst (B) and dispersed in water, and has good low-temperature curability. A matting anionic plating coating. The details are described below. Resin (A): Resin (A) is a part of the free isocyanate group of the ethylene-based copolymer (a 1 ) having two or more of 1,466,452 isocyanate groups in one molecule, and having hydrogen and oxygen on the side chain. a vinyl group-based copolymer (a 2 ) having a group, a carboxyl group and an alkoxyalkyl group (hereinafter, simply referred to as a part of a hydroxyl group of the water-dispersed ethylene-based copolymer (a 2 ), and then all remaining free isocyanate groups A resin composed of a blocked isocyanate group and a hydroxyl group having a enthalpy in one molecule, which is formed by reacting with a blocking agent. The ethylene-based copolymer (a 1 ) is a vinyl monomer containing an isocyanate group. ^ (hereinafter, simply referred to as "the monomer containing NCO group") as a necessary component, and the copolymer formed by using other vinyl monomers is mainly at the end of the linear copolymer and/or The isocyanate group is present on the side chain. The single system containing the NCO group is a compound having at least one unblocked free isocyanate group and a radical polymerizable double bond in the fluorene molecule, for example, may be used from m- P-isopropene -α,α-dimethylbenzyl isocyanate, 2-isocyanate ethyl methacrylate, hydroxyl group-containing vinyl monomer and diisocyanate compound 1: 1 (mole ratio) adduct, etc. One or two or more selected.

The hydroxyl group-containing vinyl monomer used for preparing the NCO group-containing monomer is a compound having one or more hydroxyl groups and a radical polymerizable double bond in one molecule: for example For example, it may be 2-ethyl (meth) acrylate, 2- propyl (meth) acrylate, butyl propionate, 2, 3-dihydroxypropyl acrylate, 2 - Hydroxy_3_phenoxyethyl acrylate, 2-hydroxy-3-ethoxyethyl acrylate, and the like. Further, for example, it may be a molar additive such as acrylic acid or methacrylic acid and a diol (having a carbon number of 2 to 2 Å). 1264452 The above diisocyanate compound used in the preparation of a monomer containing an NCO group is a compound having 2 isocyanate groups in one molecule, for example, it may be a tolyl diisocyanate, 4, 4'- Diphenylmethane diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, 4,4'. methylene bis(cyclohexyl isocyanate), methylcyclohexane-2,4 An aliphatic, aromatic or alicyclic diisocyanate compound such as (2,6)-diisocyanate, isophorone diisocyanate or trimethylhexane diisocyanate.

The preferred one of the above-mentioned NCO group-containing monomers is preferably m-isolated with a third-order isocyanate group from the viewpoint of preventing gelation in the reaction between the ethylene-based copolymers (a2) to be described later. Propylene, α-dimethylbenzyl isocyanate. Further, the other vinyl monomer is preferably a compound having a radical polymerizable double bond in one molecule and having no active hydrogen reactive with an isocyanate group; specifically, for example, it may be An aromatic vinyl monomer such as styrene, α-methylstyrene or vinyltoluene; methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2 -ethylhexyl (meth) acrylate, lauryl (meth) acrylate, tridecyl _ (meth) acrylate, stearic acid (meth) acrylate, cyclohexyl (meth) acrylate (Meth) acrylates such as benzyl (meth) acrylate; biscot 3 F (manufactured by Osaka Organic Chemical Co., Ltd., trade name, the following meanings), the same as 3MF, the same as 8F, the same as 8MF , perfluorocyclohexyl (meth) acrylate, N-2-propyl perfluorooctane sulfonate decyl ethyl (meth) acrylate vinegar, fluorinated ethylene, vinyl fluoride, etc. -11- *1264452 N,N'-diethylaminoethyl (methyl) Acrylate, ν, Ν, - diethylaminoethyl (meth) acrylate, hydrazine, Ν'-diethylaminoethyl (meth) acrylate, hydrazine, Ν'-diethyl ( a nitrogen-containing vinyl monomer such as methyl acrylamide; a vinyl ether monomer such as vinyl ethyl ether or vinyl butyl ether;

Glycidyl (meth)acrylate, 3,4-cycloethoxycyclohexylmethyl (meth) acrylate, acryl glycidyl ether, alkyl etherate of methylol acrylamide, (meth) propylene Hydrazine, (meth)acrylic acid chloride, vinyl chloride, vinylidene chloride, (meth)acrylonitrile, aroxyalkyltrimethoxypropane, etc.; one or a mixture of these may be used. 2 or more types.

The ratio between the monomer having an NC 0 group and another vinyl monomer may be in the range of two or more free isocyanate groups in one molecule of the ethylene copolymer (a 1 ). It is not particularly limited, but a suitable range based on the monomer containing NCO^ group/other vinyl monomer (weight ratio) is 100/0 to 1/99, preferably 65/35 to 30/ 70 range. Further, the polymerization reaction between the monomer containing only the NCO group or the other ethylene monomer other than the above is usually carried out in an inert organic solvent which does not have active hydrogen which can react with the isocyanate group. As such an inert organic solvent, for example, a single or mixed solvent of an aliphatic hydrocarbon such as hexane, heptane or octane, such as an ester system or a ketone system, can be used. Specifically, for example, a mixed solvent of methoxypropyl acetate and butylbutyl-peroxyisopropyl carbonate can be used. Since these solvents are water-containing substances, it is preferred to carry out dehydration in advance as occasion demands. The polymerization of this % is carried out by using a radical polymerization initiator at a temperature of 50 to 180 ° C. The molecular weight of the ethylene copolymer (a1) can be 1,264,452 by the reaction concentration, starting. The dose is adjusted to adjust. The reaction concentration is carried out in the range of 20 to 80% by weight of the polymer. In particular, in order to increase the polymerization rate, it is preferred to use a peroxide-based or carbonate-based initiator at a reaction temperature of 1 Torr or higher. More preferably, when it is used in combination with an acrylate monomer, a polymer having a high polymerization rate can be easily obtained. The concentration of the polymerization initiator may be in the range of 0.01 to 15% by weight based on the total monomers, and is preferably 0.1 to 10 by weight. /. Within the scope.

The weight average molecular weight (Note 1) of the ethylene-based copolymer (a 1 ) is preferably from 500 to 50,000, particularly preferably from 1,500 to 30,000. Also, a suitable isocyanate valence is 30 to 200 mg NC 0/10 g. Further, the ethylene-based copolymer (a1) has two or more free isocyanate groups in one molecule, but it is preferred that there is no active hydrogen which can react with the isocyanate group. _ (Note 1) Weight average molecular weight: based on JIS K01 24-83, and the separation column is TSK GEL 4000 HXL + G 3000 HXL + G 2500 HXL + G 2000 HXL (manufactured by Toyo Soda Co., Ltd.) It was obtained by using GPC using tetrahydrofuran as a dissolving solution at 40 ° C and a flow rate of 1.0 ml/min, and measuring the color column and polystyrene by a R1 refractometer. Ethylene-based copolymer (a 2 ): The ethylene-based copolymer (a2) is suitably used as (1) an alkoxyalkyl group-containing unsaturated monomer, (2) a hydroxyl group-containing unsaturated monomer, and (3) The unsaturated monomer containing a carboxyl group is used as an essential component and, if necessary, copolymerized with (4) other unsaturated monomers. The monomer components of these may, for example, be as described below. (1) an alkoxyalkylalkyl group-containing unsaturated monomer: for example, 1,268,452 thereof may be r-(meth)acryloyloxypropyltrimethoxy decane, r-(meth) propylene decyl oxypropylene Methyl dimethoxy decane, r-(methyl) propylene decyl oxypropyl triethoxy decane, vinyl trimethoxy decane, and the like.

(2) a hydroxyl group-containing unsaturated monomer: for example, it may be hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and the like, FM1 (made by Daisy Chemicals, trade name, _ amine modified (meth) hydroxy acrylate), pracusill F Μ 2 (same left), pracusill FM3 (same left), Hydroxyl-containing unsaturated monomers such as pracusill FA1 (same as left), pracusill FA2 (same as left), and pracusill FA3 (same as left). (3) A carboxyl group-containing unsaturated monomer: for example, it may be (meth)acrylic acid, maleic acid or the like. (4) Other unsaturated monomers: for example, it may be methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, a C 1 ～C 18 alkyl ester of (meth)acrylic acid such as hexyl (meth) acrylate, octyl (meth) acrylate, lauryl (meth) acrylate or cyclohexyl (meth) acrylate or Aromatic vinyl monomers such as cycloalkyl esters and styrene, (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N-hydroxymethyl (decyl) propylene oxime (Meth) acrylamide and its derivatives, (meth) acrylonitrile compounds, etc., such as amines. The weight average molecular weight of the ethylene-based copolymer (a2) is preferably from 500 to 50,000, particularly preferably from 2,000 to 35,000, and particularly preferably a hydroxyl group, in the range of from 20 to 200 mg KOH / gram based on the valence of the hydroxyl group. In the production of the resin (A), the reaction between the ethylene-based copolymer (ai) and the ethylene-based copolymer 1264452 (a 2 ) is an aminoesteration reaction between an isocyanate group and a hydroxyl group, specifically In general, the ethylene-based copolymer (a 2) may be blended in an organic solution of the ethylene-based copolymer (a1), usually at a temperature of from 20 to 100 ° C, preferably from 25 to 60 t. Acidification reaction. The reaction is controlled by the reduced amount of isocyanate groups, i.e., the isocyanate valence. Further, in such a reaction, it is preferred to use a curing catalyst such as an organic tin compound in order to obtain low-temperature curability and coating film * hardness. The blending amount of the ethylene-based copolymer (a2) may be at least an average of 〇·1 urethane in the ethylene-based copolymer (a1) having a weight average S molecular weight of 500 to 50,000 per molecule. The blending amount of the bond may be, however, it is preferably an ethylene-based copolymer having a weight average molecular weight of from 500 to 30,000 per molecule > (a 1 ) at least an average of 5 to 1 · 5 amine groups may be introduced. The formate bond is preferably one in which one urethane bond can be introduced into the vinyl copolymer (a 1 ) per molecule. Next, the urethane bond is introduced by reacting the ethylene-based copolymer (a 2 ) as described above and the ethyl sulphate of the water-dispersible ethylene-based copolymer (a 2 ) is added. The remaining free isocyanuric acid contained in the copolymer (a 1 ) and the following block agent are reacted at a temperature of usually 20 to 100 ° C to carry out a reaction, whereby a resin (A) can be obtained. The block agent may, for example, be phenol, indophenol, xylenol, p-ethylphenol, guanidine-propofol, P_tert-butanol, P-tert-octylphenol, thymol, p-naphthalene Phenols such as phenol, p-nitrophenol, and P-chlorophenol; methanol, ethanol, propanol, butanol, ethylene glycol, methyl cellosolve, ethyl cellosolve, methyl carbitol, benzyl Alcohols such as benzyl alcohol, phenyl cellosolve, mercapto alcohol, cyclohexanol 1268452 alcohol; active methylene groups such as dimethyl malonate and acetamidine acetate; butanol, thiophenol, a thiol group such as te rt-dodecyl thiol; an amide amine such as acetanilide, acetamidine anilide, decylamine or benzoguanamine; guanyl succinate or bismuth maleate An imine or the like of an imine;

An amine system such as diphenylamine, phenylnaphthylamine, aniline or carbazole; an imidazole system such as imidazole or 2-ethylimidazole; a urea system such as urea, sulfur urea, and ethyl urea; N-phenyl Amino acid salt of phenyl carbamate, 2-oxazolinone, etc.; imine of ethyl imine; formaldehyde oxime, acetald oxime, acetone oxime, methyl ethyl ketone oxime, methyl isobutyl ketone肟, cyclohexanone oxime, etc.; sulfite system such as sulfite soda, potassium hydrogen sulfite, ε-caprolactam, (5-valeroguanamine, r-valerolactone, propiolactone And lactones; 3,5-dimethylpyrazole, 3-methylpyrazole, 4-nitro-3,5-dimethylpyrazole, and 4-bromo-3,5-dimethylpyrazole Pyrazole or the like of azole or the like. Resin (A) is an ethylene-based copolymer (a1) and an ethylene-based copolymer by reacting a urethane between isocyanate-based hydroxyl groups and passing through a urethane bond. (a2) bonded together. The resin (A) obtained in this way has an average of at least one block isocyanate group and at least one hydroxyl group in the molecule, and has a weight average molecular weight of about 1000 to 120,000. It is about 5,000 to 50,000, and the suitable value of the hydroxyl group (mg KOH / gram) is in the range of 25 to 250. In particular, in order to obtain a matte coating film having a low gloss (60° gloss of 1 Å or less), ethylene copolymerization The difference between the solubility parameter (SP値(Note 2)) between the substance (a1) and the ethylene-based copolymer (a2) is preferably in the range of 0.4 to 1.0, more preferably 1,644,452 〇·5 〇. 8 〇 (Note 2) Solubility parameter: S Ρ値 is S ο I ubi丨ity Ρ arameter's abbreviation 'is the scale of the intermolecular interaction of liquid molecules. For this SP値, the ethylene copolymer (a 1 And the water-dispersible ethylene-based copolymer (a2) composition theory. When the SP-based system of the monomer is known, the following formula (1) can be used to determine the SP 値 of the copolymer monomer, and thus the SP 値To use SP as a copolymer, use 0

The SP of the monomer has been collated in the Journal of Paint Technology, Vol. 42, p. 176 (1 970). SP = SP1xfw1+SP2xfW2+...S Pnxfwn Equation (1) (SPi, SP2... f W 1 ' f W 2 ........ wn weight fraction.) • The spn system represents the SP値 of each monomer and represents the total amount of each monomer relative to the monomer.

In addition, when the SP of the monomer is unknown, it can be determined by cloud point titration to determine 'specifically' according to the following formula (2), ie, κ_W_SUH, J_M_CORBETT (Application of Polymer Science Journal) , Vol. 12, p. 2359 '1968' is calculated as a benchmark. Formula (2)

Vv η * δ·Η ^ Vv ρ ^ δη 7vh (wherein VH represents the volume fraction of n-hexane, vD represents the volume fraction of deionized water -17-1264452 Z, (5η represents η-hexane z SP値” δ, which represents s P値 of deionized water.) The cloud point titration is used as a sample of resin Ο „ 5 g (solid matter) dissolved in 1 毫升 ml of acetone, slowly added η - Hexane, the amount of Η (ml) when the cloud point is read, and the same amount of D (ml) when the deionized water is added to the cloud point in the acetone solution is used to calculate VH, VD, 5h, using the following formula. 5D. In addition, SP値 of each solvent, acetone: 9.75, N-hexane: 7.24, deionized water: 23.43 °

[Vh = H/(1 O + H), Vd = D/(1 0 + D), ά Η = 9·75χ1 0/(1 0 + Η) + 7·24 χΗ/(10 + Η), ( 5 〇 = 9.75 χ 1 0 / (1 0 + D) + 23.43 x D / (10 + D)] Further, the glass transition temperature (Tg) of the ethylene copolymer (a1) and the ethylene copolymer (a2) is simultaneously When 彳〇°c or more, it is preferable in terms of improvement of coating property. Hardening catalyst (B): The anionic plating coating of the present invention is a low-temperature hardening property and an excellent hardness of a coating film, and contains a hardening touch. An essential component of the medium (B). As an organotin compound of the hardening catalyst (B), for example, tin octylate, dibutyltin diacetate, dibutyltin dioctoate, dibutyltin dilaurate, or the like may be used. Butadiene dimaleate, tetrabutyltin, dibutyltin oxide, dibutyltin dibenzoate oxygen, dioctyldibenzoate oxygen, etc.: an amine compound, for example, for example, it may be Trimethylamine, triethylamine, dimethylcyclohexylamine, N-tetramethylhexane_1, 6-diamine, N-pentamethyldiethylenetriamine, 2-methyl-1,4·2 a tertiary amine such as a nitrogen heterocyclic [2,2,2]octane. These hardening catalysts (B) are It is preferable to use it alone or in combination of two or more types to improve low-temperature hardenability and film hardness. The total amount of 8 1264452 (converted into solid matter) of the hardening catalyst varies depending on the type. From the viewpoint of catalyst capacity and paint stability, the solid content of the hardening catalyst (B) is usually 0»1~1 〇 by weight, based on 100 parts by weight of the total amount of the resin (A). It is contained in an amount of 0-5 to 8 parts by weight. The emulsion used in the anionic electromineral coating of the present invention can be obtained by adding a hardening catalyst (B) to the resin (A) and a carboxyl group relative to the resin (A). Mixing 〇1~1. 5 equivalents, preferably 0 2~1 _ 2 equivalents of neutralizer (base, compound), then mixing and dispersing, then adding deionized water to the material, ^ The solid matter is 10 to 60% by weight, more preferably 1 〇 to 40% by weight, and then the neutralizing agent is added to adjust P Η値 to 7 · 0 to 8.0. For example, it may be, for example, ethylamine, propyl: amine, butylamine, benzylamine, monoethanolamine, neopentylamine, a monoamine of a first order such as 2-aminopropanol or 3-aminopropanol; diethylamine diethanolamine, di-n- or di-iso-propanolamine, hydrazine-methylethanolamine, hydrazine-ethyl a second-stage monoamine such as ethanolamine; a third-stage monoamine such as dimethylethanolamine, trimethylamine 'triethylamine, triisopropylamine, methyldiethanolamine or dimethylamine ethanol; A polyaminotriamine such as ethyltri Upamine, hydroxyethylaminoethylamine, ethylaminoethylamine or methylaminopropylamine. In the matting anion plating coating of the present invention, a pigment, a dye, a hardening catalyst, a flow regulating agent may be added as needed, and pH 値 adjustment may be performed, and ionic water is added to obtain an ionic plating coating material having a solid content of 5 to 20% by weight. . Further, a UV absorber and a light stabilizer can be further blended to obtain a coating film having high weather resistance. The above ultraviolet absorber may, for example, be water such as phenyl water -19-1264452 salicylic acid ester or octylphenyl salicylate '4-t-butylphenyl salicylate.

Salicylic acid derivative, 254-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,2, dihydroxy-4-methoxybenzophenone, 2-hydroxy-4 -Methoxy-2, carboxybenzophenone, 2-hydroxy-4-methoxy-5-thiobenzophenone trihydrogen ester, 2,2'-dihydroxy-4,4'-dimethoxy Benzophenone, 2-hydroxy-4-octylbenzophenone, 2-hydroxy-4-octadecyloxybenzophenone, 2,2,-dihydroxy-4,4'-dimethoxy Sodium 5-thiobenzophenone sodium, 2,2',4,4'-tetrahydroxybenzophenone, 4-decyloxy-2-hydroxybenzophenone, 5-chloro-2-hydroxyl Benzophenone, resorcinol monobenzoate, 2,4-dibenylhydrazino-resorcinol, 4,6-diphenylmercaptoresorcinol, hydroxydecylbenzophenone, a benzophenone series such as 2,2'-dihydroxy-4(3-methylpropenyloxy-2-hydroxypropoxy)benzophenone; 2-(2'-hydroxy-5'-methyl a benzotriazole-based benzotriazole-based benzotriazole-based compound or other compound (anilinic acid oxalate, amino acrylate). A light stabilizer for use in combination with a UV absorber, for example, it may be a hindered amine derivative, specifically, for example, bis(2,2',6,6'-tetramethyl-4-piperidin Ordinary azelaic acid ester, 4-benzylideneoxy-2,2',6,6'-tetramethylpiperidine, etc., and one or more of these may be appropriately selected and used. . In order to form a coating film by using the matting anionic plating coating of the present invention, the anion plating coating obtained above may be made into a bath, and after the aluminum material is immersed in the bath, a colored or non-colored anodized aluminum material is used. As an object to be coated, an anion plating is applied to form a dried film having a thickness of about 5 to 30 μm, without washing with water (norwinse) or with water washing ("inse", followed by setting at room temperature, and then 60~ 150 ° C, preferably 80 ~ 140 ° C under -20 -

1264452 was fired for about 20 to 40 minutes and dried to form a coating film. The coating film hardness of the coating material obtained by coating the matte anion plating coating shows a pencil hardness of 4 Η or more (Note 3) and a high coating film of 4 or more TUKON hardness (Note 4). hardness. (Note 3) The pencil hardness is based on JIS Κ 5600-5-4, and the pencil lead is pressed against the test coating surface at an angle of about 45°, and the test coating surface is pressed against the strength of the right and left of the refill. The uniform speed moves forward by approximately 10 mm. This operation was repeated 5 times by changing the test place, and the hardest pencil hardness mark in which the film was not damaged was regarded as the pencil hardness. (Note 4) TUKON hardness: The coated plate was placed in a thermostatic chamber at 20 ° C for 4 hours, and then measured by a TUKON microhardness tester manufactured by American Chain & Cable Co., Ltd. Further, in the matte anionic plating coating, it is also possible to easily adjust the degree of extinction by using at least two types of emulsions in combination. For example, the ethylene-based copolymer (a 1)/ethylene-based copolymer (a2) may be used in an amount of 1 part by weight based on the total amount of the ethylene-based copolymer (a 1 ) and the ethylene-based copolymer (a2). = 30 to 90 parts by weight / 10 to 70 parts by weight of the blending ratio, and the ethylene-based copolymer (a1) / ethylene-based copolymer 02) composed of water dispersion = 30 to 90 parts by weight/10 to 7 Torr An anionic plating coating of the emulsion (2) in the range of parts by weight. For example, in the case of a coating line, in the case where a coated article having a varying degree of extinction is desired, the replenishment to the anion can be appropriately adjusted by changing the blending ratio of the emulsion (1) / emulsion (2). Electroplating coatings. [Embodiment] - 21 - 1264452 Hereinafter, the present invention will be described in further detail by way of examples. However, the present invention is not limited to the embodiments. Also, "parts" and "%" mean "parts by weight" and "parts by weight"

<Production Example 1> Production Example of Ethylene-Based Copolymer (a 1 ) Solution No. 1 In a reactor equipped with a stirrer, a reflux condenser, and a thermometer, 65 parts of methoxypropyl acetate was charged and heated. While maintaining at 1 3 〇〇c, 25 parts of m-isopropenyl-α, α-dimethylbenzyl isocyanate (m_TM|), 4 parts of iso-butyl methacrylate, 4 parts of η were added dropwise over 3 hours. a mixture of butyl acrylate and 31 parts of methoxyethyl acrylate. Then, a mixture of 35 parts of methoxypropyl acetate and 5 parts of butyl peroxyisopropyl carbonate was added dropwise over 1 hour, and further matured for 3 hours to obtain a solid matter of 50%. A vinyl copolymer (a) solution. The ethylene-based copolymer (a1) in the ethylene-based copolymer (a1) solution of No. 1 had a weight average molecular weight of about 5,000, an SP値 of 9.0, and a Tg of 24.1 °C. <Production Examples 2 to 5 &gt; In the same manner as in Production Example 1, the solid content was adjusted with a solvent in accordance with the blending contents of Table 1, and a vinyl-based copolymer (a) having a number of 2 to 5 was obtained. -22 - 1264452 Manufacturing Example 5 No. 5 LO CD Ο) CO LO C0 LO 5000 Inch οό 00 LO 1 Manufacturing Example 4 No. 4 L〇CD 〇 LT) 00 IT) g 5000 00 〇6 LO CD Manufacturing Example 3 No. 3 L〇CD L〇CvJ CvJ Inch CD LO C0 LT) g 5000 〇〇00 24.4 Manufacturing Example 2 No. 2 ΙΟ CD L〇CM 33.4 CO T-inch LO C0 LO s 5000 00 00 00 C0 Manufacturing Example 1 No. 1 L 〇CD ΙΟ CvJ o inch LT) C0 LO s 5000 〇σ> 24.1 Vinyl copolymer (a1) solution methoxypropyl acetate ll - am ? Ml i|l K峨 «ν WE tf iso-butyl Acrylate η-butyl acrylate methoxyethyl acrylate 2-ethylhexyl acrylate methyl methacrylate ethyl methacrylate methoxypropyl acetate butyl peroxy isopropyl carbonate solid ( %) Weight average molecular weight SP値Tg(°c) Blending characteristics

<Production Example 6> No. 6 ethylene-based copolymer (a2) solution -23 - 1264452 275 parts of methoxypropyl acetate was placed in a reactor and kept at 8 (TC, 3 hours) 7 5 parts of styrene, 155 parts of methyl methacrylate, 9.5 parts of η-butyl acrylate, 50 parts of ethyl acrylate, and 7 parts of 2-hydroxyethyl acrylate , 35 parts of acrylic acid, 15 parts of r-methacryloxypropyltrimethoxydecane, and 1 part of azide

a mixture of valeronitrile, followed by the addition of 3 parts of azide dimethyl valeronitrile, and maintaining the reaction at 80 ° C for 3 hours to obtain a water having an alkoxyalkyl group as a solid content of 65% by weight. A solution of a dispersible ethylene-based copolymer (a2). The water-dispersible ethylene-based copolymer (a2) in the solution of No. 1 had an SP値 of 9 to 54 and a Tg of 25 °C. <Production Example 7> Production of Resin (A) Solution No. 1 In a reactor equipped with a stirrer, a reflux condenser, and a thermometer, 700 parts (350 parts of solid matter) of solid matter was added as 50% of ethylene of No. 1 a copolymer (a 1 ) solution and 1 000 parts (650 parts by weight) of the water-dispersible ethylene-based copolymer (a2) solution of No. 1 obtained in Production Example 6, at room temperature (25 ° C) The mixture was stirred for 15 minutes, and the isocyanate valence was measured. The isocyanate price of the mixed varnish is 4 7 · 6. Next, heating was maintained at 40 ° C while stirring, and after about 3 hours of reaction, 300 parts of methyl ethyl ketone oxime was added at a time when the isocyanate value became 45.8, and it was aged at 60 ° C for 2 hours to obtain a solid. A resin (A) solution having a weight of 50.0% and a weight average of about 16,000. <Production Examples 8 to 1 2> A resin (A) solution of No. 2 -24 to 1264452 Z resin (A) solution to No. 6 was obtained in the same manner as in Production Example 7 in accordance with the blending contents of Table 2. In Table 2, the amount of solid matter is indicated in brackets. Table 2 Manufacturing Example 12 No. 6 700 (350) 1000 (650) 300 2000 (1000) 1.14 Manufacturing Example 11 No. 5 r 700 I (350) I 1000 (650) 300 I 2000 (1000) 1.24 Manufacturing Example 10 No. 4 600 (300) 1077 (700) 323 2000 (1000) 0.54 Manufacturing Example 9 Series 5 Tiger 3 700 (350) 1000 (650) 300 2000 (1000) 0.74 Manufacturing Example 8 No. 2 700 (350) 1000 (650) 300 2000 ( 1000) 0.74 Production Example 7 No. 1 700 (350) I 1000 (650) I 300 2000 (1000) j 0.54 : Resin (A) solution (type) No. 1 ethylene copolymer (a1) Solution No. 2 of ethylene Copolymer (a1) Solution No. 3 of ethylene-based copolymer (a1) Solution No. 4 of ethylene-based copolymer (a1) Solution No. 5 of ethylene-based copolymer (a1) solution ΦΚ Let methyl ethyl ketone oxime resin (A) solution (doped Mixing) |She I nn Q. I (7) K]Hole <Manufacturing Example 1 3> Put 5 5 parts of isopropanol in the reactor and keep at 80 °C, 3 small -25 - 1264452

捺_ π 1 5 parts of styrene, 3 · gram of methyl methacrylate '15 parts of butyl acrylate '10 parts of ethyl acrylate, 15 parts of 2 ~ hydroxyethyl acrylate A mixture of '7 parts of acrylic acid, 7 parts of hydrazine = butoxy methacryl decylamine' and 1.0 part of azide dimethyl valeronitrile was left at this temperature for 1 hour, followed by dropping 1 A portion of azide dimethyl valeronitrile and 45 parts of butyl cellosolve were further subjected to a reaction at 80 ° C for 4 hours to obtain a solid matter of 50 parts by weight. /. The weight average molecular weight is 30 〇〇〇, S P 値 is 9.6 0, and the T g is 16 _ 5 . (Production No. 7 of the resin solution. <Production Example 1 4> The emulsion of No. 1 was produced by blending the resin of No. 1 produced in Production Example 7 with respect to 200 parts (100 parts of solid matter). After the carboxyl group of the solution is 〇 4 equivalents of triethylamine, it is mixed and dispersed, and 5 parts (solid matter) of SCAT-7 (Note 5) is mixed and dispersed, and then slowly dripped while stirring. The ionized water was further added with triethylamine, and the deionized water was adjusted to make P 7.5 to obtain an emulsion having a solid content of 10% of No. 1. The same as in Production Example 1 4, according to Table 3 In the case of the mixing, the emulsion of No. 2 to No. 6 was obtained in an amount of 1% by weight. <Production Example 20> In the number of 7 of 40 parts (solid content: 70 parts), the number 7 was produced in Production Example 13. In the resin solution, 37,5 parts (30 parts of solids) of Duranet MF-B80M (Note 6), and 5 parts (0.5 parts of solid matter) of SCAT-7 (Note 5) were mixed. While stirring, slowly drip the ionized water, further add triethylamine, adjust ρ Η値 to 7.5 with -26 - 1264452 deionized water to obtain a solid content of 1 Ο % 7 The emulsion.

Manufacturing Example 20 No. 7 140 (70) 0.5 (0.5) 37.5 (30) Adjustment to 1 〇% solid matter Production Example 19 _I No. 6 | | 200 (100) | 0.5 (0.5) !___ 1 Manufacturing Example 18 j _ No. 5 200 (100) 0.5 (0.5) Manufacturing Example 17 No. 4 200 (100) 0.5 (0.5) c \T τ - ^ T - Manufacturing Example 16 No. 3 200 (100) 0.5 (0.5) 0.4 (0.4) Manufacturing Example 15 No. 2 200 (100) 0.5 (0.5) 1 Production Example 14 No. 1 200 (100) 0.5 (0.5) ^7.5 Resin No. 1 Resin (A) Solvent No. 2 Resin (A) Solution No. 3 Resin (A) Solution No. 4 Resin (A) Solution No. 5 Resin (A) Solution No. 6 Resin (A) Solution No. 7 Resin Solution SCAT-7 (Note 5) Duranet MF-80M (Note 6) U -CAT18X(Note 7) 汽内毕328(Note 8) 汽内毕292(Note 9) Triethylamine deionized water (Song Liuhua) -27 - 1264452 (Note 5) S CAT-7: Sankyo Organic Synthesis (Stock) company, trade name, dibutyltin dihydrothiocarboxylate; (Note 6) Duranet MF-B80M: Asahi Kasei Co., Ltd., trade name, hexamethylene isocyanate isocyanate type, methyl ethyl ketone Barium block The chemical agent and the solid matter are 80%; (Note 7) U-CAT18X: Sanyo Chemical Co., Ltd., trade name, amine hardening catalyst;

(Note 8) Vapor Completion 328: manufactured by Ciba Bags Co., Ltd., trade name, UV absorber; (Note 9) Vapor Bi 292: Commodity name, light stabilizer; [Example 1] In 1 000 parts (100 parts of solid matter), the emulsion of No. 1 solid matter was 1% by weight, and triethylamine was added to make P Η値 8.5, and an anion of No. 1 was obtained. Electroplating coatings.

An anionic plating coating of Nos. 2 to 5 of Examples 2 to 5 as shown in Table 4 was obtained by the same operation as in Example 1. [Comparative Examples 1 to 4] An anionic plating coating of Nos. 6 to 9 of Comparative Examples 1 to 4 as shown in Table 5 was obtained by the same operation as in Example 1. [Comparative Example 5] Aerecuron AG-300 (manufactured by Kansai Paint Co., Ltd.) propylene -28 - 1264452 acid resin/melamine hardening type anion plating coating) was used. Preparation of test plate _ The anion plating coatings obtained in the examples and the comparative examples were bathed, and the thickness of the film which had been subjected to two treatments (degreasing-etching-neutralizing-anodizing-sealing) was about 1 〇. The micron anodized bismuth material (silver: 1 5 〇^ 7 0x0.5 mm) is immersed in the bath to make the dried film thickness 1 〇 micron, washed and then 140 ° C is baked for 20 minutes.

The test was carried out in accordance with the test conditions described below. The examples are shown in Table 4, and the comparative examples are shown in Table 5. Table 4 Example 1 Example 2 Example 3 Example 4 Example 5 Anion plating material No. 1 No. 2 No. 3 No. 4 No. 5 Mixed emulsion type No. 1 No. 2 No. 3 No. 4 No. 1 Blending amount 1000 1000 1000 1000 500 Kind No. 2 Blending amount 500 Triethylamine adjusted to pH=8_5 &lt;- &lt;- &lt;- &lt;- Coating film performance gel fraction (Note 10) 95 95 98 93 95 Pencil hardness (Note 11) 4H 4H 5H 4H 4H Buchhole hardness (Note 12) 4 5 6 4 4.5 60° gloss (Note 13) 4 8 5 7 6 Imprinting concealability (Note 14) 〇〇〇〇〇 Friction adhesion (Note) 15) ◎ ◎ ◎ ◎ 〇 weather resistance (Note 16) 90 94 91 96 92 -29- 1264452 Table 5 —----— ---------- ______ Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Anionic Electroplating Coating----__________________ - No.6 No.7 No.8 No.9 No.5 No.6 No.5 No.7 Mixed Emulsion Mixing 1000 1000 500 1000 Ai Lei Type No.6 Coulomb Mixing amount 500 AG-300 Triethylamine adjusted to ρΗ=8·5 &lt;- &lt;- &lt;- Gel fraction (Note 10) 9 1 93 92 90 84 Coating performance Pencil hardness (Note 11) 2Η 2Η 2Η 2Η 2Η Dielectric hardness (Note 12) 3 3 3 2 2 60° Gloss (Note 13) 23 35 27 38 5 Imprinting concealment (Note) 14) Δ Δ Δ Δ X Friction adhesion (Note 15) 〇〇〇Δ X Weather resistance (Note 16) 87 88 87 91 53 (I main 10) Gel fraction:

The coating film peeled from the tinplate coated with the tinplate is placed in a mesh container made of stainless steel of 300 mesh, and extracted with a solvent of acetone/methanol=彳/1 at reflux temperature for 6 hours. The gel fraction was calculated by the following formula. Gel fraction (%) = (weight of coating film after extraction) / (weight of coating film before extraction) χ 1 〇〇 (Note 1 1 ) Pencil hardness: Based on J IS Κ 56 0 0-5-4, Make the pencil lead at about 45. The angle of the test is applied to the surface of the test plate, and the test plate surface is pressed about the strength of the left and right sides of the refill, and the front side is moved at a uniform speed by about 10 mm. The test was repeated five times, and the hardest pencil hardness mark with no damage to the film was used as the pencil hardness. -30-

1264452 (Note 12) TUKON hardness: The coated plate was placed in a thermostatic chamber at 20 °C for 4 hours and then determined by a TUKON microhardness tester. The harder the film is. (Note 13) 60° gloss: The degree of gloss of the coating film is measured according to JIS K-5400 7 · degree specular gloss, and the incident angle and rate at 60 degrees are respectively measured, and the gloss of the reference surface of the specular gloss is made. It is represented by 1 0 0. (Note 14) Mold imprint concealability: Evaluation by visual evaluation. 〇: The stamp is well concealed. △: The impression is poorly concealed. X: The imprinting of the stamp is significantly inferior. (Note 1 5) Friction adhesion: Cut the 觅 line (to reach the aluminum surface) in the longitudinal direction of the center portion of the test plate. It is peeled off from the end face of one side by only 90 bends by 180 degrees (refer to Fig. 1). Using an automatic drawing S-D type (manufactured by Shimadzu Corporation, a universal tensile tester for a constant temperature bath), the product was stretched at a distance of 50 mm/min for about 30 mm (ambient gas temperature was 25 ° C ± 5 rpm), and peel strength. ◎: The peel strength was 39.2 N (4 kg weight) or more. 〇: Peel strength is 2 9 _ 4~3 9 · 2 N. The higher the US chain & cable, the higher the percentage of 6 (1 990) 60 reflected by the light angle to the film layer of 25 mm square meters, the trade name, the attached tensile speed and the measurement of the film 1644452 △ : Peeling strength is 20 to 29 „4N. X: Peeling strength is less than 20 N. (Note 16) Weather resistance: The gloss retention rate (%) of 2000 hours is measured by using a sunlight climatometer. Utilization possibility

By using the matte anionic plating coating of the present invention, 60 which is excellent in low-temperature hardenability, coating film hardness, and mold-blocking concealability can be obtained. Light, ze g ] 〇 The following matte coating film, and matte coated items. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic view of a frictional adhesion test. [Component Symbol Description] 1 Coating film 2 3

The aluminum plate of the object to be coated is used to fix the part of the test plate -32 -

Claims (1)

126.4452 X. Patent application scope: 1 - a matte anionic plating coating characterized by using a part of the free isocyanate group of the ethylene-based copolymer (a1) having two or more free isocyanate groups in one molecule, and having chlorine a part of the hydroxyl group of the ethylene-based copolymer (a2) of the oxy group, the mercapto group and the alkoxyalkyl group is reacted, and then all the remaining free isocyanate groups are reacted with the blocking agent to form one molecule. a resin having a blocked block isocyanate group and a hydroxyl group-containing resin, and a difference in solubility parameter (SP値) between the ethylene-based copolymer (a1) and the ethylene-based copolymer (a2) is 0.4 to 1.0% ( A) The water is dispersed, and further, an emulsion formed by dispersing a curing catalyst (Β) is further added, and is contained in an amount of 〇 10 parts by weight based on 100 parts by weight of the total amount of the resin. Hardening catalyst (Β). 2. The matte anionic plating coating according to the first aspect of the invention, wherein the hardening catalyst (Β) is at least one selected from the group consisting of an organotin compound and an amine compound. 3. The matte anionic plating coating according to claim 1 or 2, wherein the ethylene copolymer (a1) is a copolymer of a vinyl monomer containing an isocyanate group and another vinyl monomer. 4 _ A matte coated article which is coated on an anodized aluminum substrate with a coating surface formed by a matte anionic plating coating according to any one of claims 1 to 3; The gloss is 1 〇 or less. -33 -