TW425419B - A novel resin-coated metallic pigment and a metallic coating material using the same - Google Patents

Abstract

A resin-coated metallic pigment having a resin layer formed on surface of a metallic pigment by polymerization carried out by using (A) at least one member selected from the group consisting of radical-polymerizable unsaturated carboxylic acids, and/or, phosphoric mono-or diesters having one or two radical-polymerizable double bonds, and/or, coupling agents having a radical-polymerizable double bond, (B) at least one monomer having three or more radical-polymerizable double bonds, and (C) a polymerization initiator, adding (A) at first to treat a metallic pigment, followed by continuous and supplementary addition, little by little, of at least one of (B) and (C), which resin-coated metallic pigment gives a metallic coating film excellent in weather resistance, chemical resistance, and gloss, and is excellent in storage stability in an aqueous coating material; and a metallic coating material obtained by using said resin-coated metallic pigment.

Description

4254 1 9 Λ * _____ Η · ______ __ 5. Description of the Invention (1) Technical Field The present invention relates to a novel resin-coated metal pigment. More particularly, it relates to a resin-coated metal pigment, which is used as a paint pigment. When you get gold coating film with excellent chemical resistance, gloss and weather resistance, and the stability stored in the water-based coating material is very good. Besides this, * This invention is about novel metal coating materials. It includes the above-mentioned resin-coated metal pigments, coating resins, and diluents. More specifically, the present invention relates to coating materials. Metal coating films with excellent chemical resistance, gloss, and weather resistance are obtained and stored in water. Excellent stability in coating materials * Technical background Metal pigments have been used • For example, on Jinye ’s coating materials and printing inks or as pigments incorporated in plastics • When the appearance of metal is considered important In order to obtain the decorative effect, however, the coating film and resin mold material obtained from traditional metal pigments * have the disadvantages of chemical resistance and water resistance. Insufficient and weather resistance is poor. That is, the surface of the paint will discolor or lose its luster over time. Therefore, it provides excellent chemical resistance and weather resistance. It is also a metal coating film with storage stability. Desirable demand · In order to solve this problem, it has been proposed to coat the resin with gold tincture pigments. * It is generally known that resin-coated aluminum pastes, which are extremely chemically resistant, can be dispersed by organic pastes. The G-scale scale of the solvent for ethylenically unsaturated monomers of the agent is applicable to the Chinese national standard (CNS > A4) (2 丨 0X297 · Gongchu} (谙 Please read the precautions for bamboo surface first, and then use this page for convenience) Printed by the Bureau of Standards and Consumers of the Ministry of Industry, printed by the Consumers' Cooperative of the Central Bureau of Probability of the Ministry of Economic Affairs ^-4 25 4 1 9 Λ ______ Β " _______ V. Description of the Invention (2) Liquid A It is obtained by heating in the presence of a reaction initiator (Japanese Patent Unexamined Publication No. 51-11 818). However, the resin-coated aluminum paste manufactured by this method is insufficient in chemical resistance and does not have Practical applicationsA method has been devised * which involves dispersing an aluminum paste in an organic solvent * first absorbing the radically polymerizable unsaturated carboxylic acid or the like on the dispersed particles of the aluminum paste * and then using A polymer produced by three or more monomers capable of radically polymerizing double bonds coats the surface of dispersed particles (Japanese Patent Examination Publication No. 1-49746). The disadvantage of this method is that it is slow to charge. The addition of the anti-corrosive monomer to the coating will reduce the gloss and produce an absolutely different appearance of the golden tincture. Japanese Patent Unexamined Publication No. 7-3 1 8 5 discloses a gold-touch pigment, which includes Silane coatings and the three-dimensional space covalently combined with silicone coatings have been combined to form resin coatings. However, * 赅 赅 靥 is not sufficient in terms of chemical resistance. Also, when used in aqueous media, The above-mentioned resin-coated aluminum paste and non-resin-coated aluminum paste will react with water to generate hydrogen gas * causing the gloss of the metal to be greatly reduced. When some pastes are used in water-based paint materials *, for example Get rid of In order to improve the uniformity and smoothness of the coating resin film, a method has been proposed which involves coating S using a copolymer of a radically polymerizable monomer and an oligomer (Japanese Patent Unexamined Publication No. 64 — No. 40566) · The coated product of this method is also very poor in terms of instrument stability. * When used as a water-based coating material * it will generate large amounts of hydrogen as described above. Therefore, the gold paper size applies the Chinese National Standard (CNS ) A4AJL · Grid (210X297mm) {Please read the precautions on the back before writing the original English) i .. wood. Order A7 • 425 B7 5 .. Invention description (3) · The gloss of the metal will be greatly reduced. { (Please read the notes on the back before filling this page) Description of the invention In order to solve such problems in traditional metal pigments, the present inventors have carefully studied and found that the purpose can be achieved by coating the surface of the metal pigment with a resin The resin is obtained by continuously and supplementally adding at least one or both of a monomer having three or more radical polymerizable double bonds and a polymerization reaction initiator in the molecule to one or more of them. Species selected from a group consisting of a radically polymerizable unsaturated carboxylic acid having one or two radically polymerizable double bonds, a mono- or diester of a phosphonic acid, and a coupling agent having a wide number of radically polymerizable double bonds Copolymers The present invention is thus completed. The detailed description of the present invention includes the following. (1) A resin-coated metal pigment. Its use. (A) At least one selected from the group consisting of one or two free radicals. Polymerizable double bond radically polymerizable unsaturated carboxylic acid * and / or phosphonic acid monoester or diester * and / or, a coupling agent having one free radical polymerizable double bond, (B) having three or central economic ministry Standard Bureau employee cooperatives print more free-radically polymerizable double bond monomers * and (C) polymerization initiators • First add (A) to process metal pigments, then continuously and supplementarily, one by one Add at least one of (B) and (C) to form a resin layer on the surface of the gold tint pigment in a polymerization manner. (2) The resin-coated gold as described in the first part Smell Pigments · There are three single radical polymerizable double bonds Monomers with four or more free-radically polymerizable double bonds with monomers As monomers (B) with three or more free-radically polymerizable double bonds and four or more free-radically polymerizable double bonds The paper size of the keypad is applicable to China Gujiazheng Standard (CNS) A4 (210X297mm) Printed by the Consumer Cooperatives of the Central Procurement Bureau of the Ministry of Economic Affairs * '-------,, " V. Invention Note that the proportion of the monomers in (4) is the total reset of the three or more free-radically polymerizable double bonds from 10% by weight to 60% reset. (3) As in the first or second part The resin-coated metal pigment, wherein the process of adding at least one of the above components (B) and (C) is completed within a period of 20% of the total polymerization time. (4) as Resin-coated metal pigments as described in any one of the three sections • Among them, there are four or more free-radically polymerizable double bonds in which each functional group has a molecular weight of not more than 200 and not less than 3 0 · (5) The resin-coated metal pigment as described in any one of the first to fourth parts, wherein the alkali resistance is 2.0 or less "(6) A golden paint material containing a resin-coated gold tincture pigment as described in any one of the first to fifth parts. (7) A method for manufacturing a resin-coated gold pigment, which (A) at least one selected from the group consisting of a radically polymerizable unsaturated carboxylic acid having one or two radically polymerizable double bonds and / or phosphonic acid-or diesters, and / or having one Coupling agent for radically polymerizable double bonds, (B) a military body with three or more radically polymerizable double bonds, and (C) a polymerization initiator, first add (A) to treat the metal pigment, then Add at least one of (B) and (C) successively and supplementally, little by little • Forming a resin layer on the surface of a metal pigment in a manner of conducting a polymerization reaction The resin-coated metal pigment of the invention has a better chemical quality than before. The paper size applies to the Chinese National Standard (CNS) A4 specification (210X297 mm > —-. ^^ 1 — ^ 1 _- m 1 ^ 1 l . ml ^^^ 1-V, ", τ < Note for reading the back of the book and continuing on this page), ^ 4 254 19 Λ Ⅴ ~. 5. Description of the invention (5) Resistant and retain the gloss of metallic pigments • And have excellent storage stability. The metallic pigments used in the present invention include aluminum, copper, zinc, iridium, nickel and / or A good example of an alloy / metal pigment is aluminum. The shape of the gold pigment is a flake-like, spherical grain * like a needle-like or similar shape. The preferred metal pigment particle size depends on the application. The average particle size of metallic pigments * is preferably about 1-1 0 0 # on coating materials or printing inks, and is preferably about 1-200 # when incorporated into plastics. However, the average particle size of gold pigments is not It is particularly limited to the above range.... The radically polymerizable unsaturated carboxylic acid used in the present invention includes acrylic acid, methacrylic acid, methine succinic acid, trans-butenedioic acid, and the like. 01 到 Can be used alone or as a mixture • Although the use of free-radically polymerizable unsaturated carboxylic acid depends on the type and characteristics of the metal pigment, especially its surface, but it is usually 毎 part gold tincture pigment weight 0.01 to 10 parts by weight, preferably 0.1 to 5.0 resets • When the usage is less than 0.01 01 printed by the Consumers ’Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 1 ^ 1 nn ^^^ 1 ^ f. I-(rtlMi * f ¾ sheets of this page) When resetting • The effects of the invention obtained are unsatisfactory * ie * Satisfactory chemical resistance cannot be obtained (for example • Alkali and acid resistance) • Also, when those with When three or more free-radically polymerizable monomers are polymerized on the surface of the metal pigment, the polymerization system may become gelatinous in some cases and cannot be stirred. • When used in excess of 10 parts by weight · It is impossible to improve the effect like chemical resistance. · As for the phosphonic acid single or diester having one or two radical polymerizable double bonds used in the present invention, phosphonic acid monoester and phosphonic acid diphosphonium can be used. This paper size applies the Chinese National Standard (CNS) A4 Regulations (210X297 Gong). Yin Chang, an employee consumer cooperative of the Central Procurement Bureau of the Ministry of Economic Affairs-J 4 254 ^ 9 _____ Η '______ 5. Description of the invention (6) The examples of special effects are 2-Methacrylmethylethoxylate Phosphate Tris 2-methylpropenyl ethoxylate, 2-propenyl ethoxylate phosphate, di-2-propenyl ethoxylate phosphate, tri-2-propenyl ethoxylate phosphate, diphosphate Phenyl-2-propenyl ethoxylate, dibutyl-di-2-methylpropenyl ethoxylate, dioctyl phosphate-2-propenyl ethoxylate, 2-methacrylic acid phosphate Propoxylate, bis (2-chloroethyl) vinyl phosphonate and diallyldibutyl phosphonos' uccinate etc. can be used alone or as a mixture. '', * In the following *% heterogeneous mill (ph 〇sph 〇ricester (s) ^ is used to include phosphonates for simplicity. · Phosphate esters with one or two free-radically polymerizable double bonds. Best Those phosphorus-based monoesters * are speculated for the following reasons: Because the phosphate group has two 0 fluorenyl groups, the phosphorus-based monoester is more strongly fixed on the surface of the aluminum particles. An example of a preferable phosphorus-based monoester is methyl. Monoesters of propenylethoxy or propenylethoxy, for example, 2-methacryl phosphate Ethyl ethoxylate, 2-propenyl ethoxylate, etc. · Although phosphorus-based esters with one or two free-radically polymerizable double bonds are used, depending on the type and characteristics of the gold tincture pigment, especially its surface area. 01 * but usually resets 0.01 to 30 parts by weight of the metallic pigments, preferably 0.1 to 20 parts by weight. When the use is less than 0.01 parts by weight, the effect of the present invention obtained is not impressive. Satisfactory * ie • Ca n’t achieve satisfactory chemical resistance like alkali resistance • When using more than 20 parts by weight * Unpredictable This paper size applies Chinese National Standard (CNS) Α4 specification (210X297 mm)- -------- A ------ ΐτ ------ Xiang '< Please read the notes on the back and fill out this 筲) -9-Central Standards Bureau of the Ministry of Economic Affairs Printed by Consumer Cooperatives-4 25. B 'V. The description of the invention (7) period can improve the effect. · Coupling agents with free-radically polymerizable double bonds used in the present invention * such as silane coupling 剤 * titanate type coupling agents and containing Couplings for aluminum · Those silane coupling agents include 7-methacrylfluorenylpropoxytrimethylolsilane, vinyltrifluorosilane, vinyl triethoxy Silane, vinyltrimethylolsilane, vinyl • tris (s-hydroxymethylethylethyl) silane, etc. · Titanate type couplings include isopropylisodecadecanyl dipropylene titanate, etc. · Those containing Ming's coupling agent includes acetoxy aluminum diisopropoxide (acet 〇a 1 kοXy a I um i num4 ii s0P r 0Py 1 ate) 'Ming acid strict (zir co a 1 uminate) etc. The use of free-radical polymerized double-bond coupling agents depends on the type and characteristics of the metal pigments, particularly their surface area, but is usually reset from 0.01 to 20 parts per metal pigment reset, preferably 0. 1 to 10 parts by weight • When using less than 0.01 parts reset, the effect of the present invention obtained is not satisfactory, that is, "satisfactory chemical resistance like alkali resistance cannot be obtained. When the amount exceeds 2 At 0 parts by weight • The effect cannot be improved. Generally • The gold tincture pigment is treated * It is best to be performed in an emotive solvent * To prevent the metal pigment itself from reacting with water · Because it has one or two free radical polymerization Double-bonded phosphonic acid single or diesters are usually very high in emotive solvents Solubility • So it can be dispersed relatively easily uniformly • Therefore, it is almost difficult to destroy its chemical resistance and storage stability in water-based coating materials • Therefore it is more popular • Three or more free radical polymerization pairs used in the present invention The K of the key, this paper size applies to the Chinese national standard (see 0) six 4 specifications (2 丨 0 > < 297 mm > tl ^ i ^^^ 1 In ^^^ 1 ^ i · ^ — ^ ^^ 1 Ί4 (fftilw read the meanings on the back of this page and then Λκ page) -10-4 25 41 9 λ7 _________ Η " ________ 5. Explanation of the invention (8) Example 酊 Trimethylolpropane triacrylate, trimethylol Propane trimethacrylate, tetramethylolmethane tetraacrylate, tetramethylolpropane tetraacrylate, ditrimethylolpropane tetraacrylate, ditrimethylolpropane hexaacrylate, pentaerythritol tetraacrylate Esters, dipentaerythritol hexaacrylate, etc. · They can be used alone or as a mixture · Among the compounds listed above * monomers with four or more radical polymerizable double bonds * which are preferred Example is ditrimethylolpropane tetraacrylate * pentaerythrium tetraacrylate Fermented esters, dipentaerythritol hexaacrylate, etc.The total use of the military with three or more free-radically polymerizable double bonds in the present invention resets 2 to 50 parts by weight for each part of the metal pigment. Best. 3 To 40 parts by weight • When the total amount is less than 20 children, the effect of the present invention will be reduced, that is, chemical resistance. When the total amount is reset by more than 50 parts, it can not be expected to improve the effect. The basic properties (such as gloss and color) of metal coating materials can be broken. • Therefore • It is difficult to apply the metal coating materials produced in practice. • Printed by the Beige Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs--- l.-i -I— ^^ 1 I ί— ^^ 1 L ^ I -1 11 HI {Please read the precautions on the back and talk about this page first) When there are three monomers that can polymerize double bonds by radicals When used with four or more free-radically polymerizable double bond monomers as three or more free-radically polymerizable double bond monomers in the present invention *, the effect of the present invention will be improved. • Four or more The proportion of single hips with free radical polymerizable double bonds is the total reset of monomers with three free radical polymerizable double bonds from 10 to 60% by weight. Good 20 to 50% by weight. When using a monomer having four or more radical polymerizable double bonds. Excellent chemical resistance including alkali resistance and acid resistance. When having four or more When each functional group of a radically polymerizable double bond has a molecular weight of not more than 2000 and at least 30, it is very necessary to improve this effect. · This paper is applicable to China ’s national building rate {CNS) A4 specification (210X297 (Mm) -11-Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs t 4 254 彳 9 λ, __ Β- — ----.-—-— ——V. Description of the Invention (9). Although the effect is enhanced The reason is not obvious. But it can be speculated that the degree of cross-linking in the third space is very high. Military hips with one or two free-radically polymerizable double bonds in the molecule can be used, as long as they do not reduce the effect of the present invention. Those military bodies can Examples are styrene, α_methylstyrene * acrylic esters (e.g. methyl acrylate), methacrylic vinegars (e.g. methyl methacrylate), acryl, methacrylonitrile, acetic acid Vinyl Ester • Vinyl Propionate, Di Ethylene glycol methacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, neopentyl glycol diacrylate 1 , 6 —Hexanediol, and divinylbenzene • It can be used alone or as a mixture • The monomer is used at 0.1 to 10 parts by weight per 100 parts of metal pigments • When the amount used exceeds 10 The effect of the present invention is reduced when the weight is parts by weight, that is, the characteristics of the metal coating film formed by using the resin-coated metal pigment are broken, and the thermal stability of the gold tincture is also broken. Resin-coated metal pigments cannot be used in practice. The resin-coated metal pigments of the present invention can be obtained by the following methods: First, disperse the untreated metal pigments in an organic solvent, and by heating and stirring. (A) at least one selected from the group consisting of a radically polymerizable unsaturated carboxylic acid having one or two radically polymerizable double bonds and / or a phosphonic acid single or diester, and / or having a radically polymerizable Coupling agent for polymerized double bonds When the surface is treated by the method of adding • Then • At least one of (B) a single hip with three or more free-radically polymerizable double bonds and (C) a polymerization initiator is slowly and continuously added * Complete the polymerization reaction to apply the national standard (CNS) A4 ^ grid (210X297 male dragon) to this paper standard {note the item in the back of You reading and read the smart book I)

-12-Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 4 2 ^ 41 9 ^ II · I Round Five. Description of the invention (10) A resin layer is formed on the surface of the metal pigment * First, the untreated metal material is dispersed in In the organic solvent, and then add (A) to the processing portion with stirring while heating. Although the concentration of the metal pigment in the organic solvent is not particularly limited, it is preferably 1 to 30 weight ft%. · When the degree is less than 1% * a uniform dispersion can be obtained, but the amount of solvent to be processed becomes too large. So, it takes a lot of labor to remove the solvent afterwards but does not want to increase the labor. When the concentration exceeds 30% * The dispersion of metallic pigments tends to be undesired but becomes non-uniform. • It is best to process at a temperature of 40-150 ° C for about 5 minutes to about 10 hours, hours. When the processing temperature is lower than 4 0 eC · It takes a lot of time to raise the temperature to the polymerization temperature of (B) · When the processing temperature is higher than 1 5 0eC * Be very careful to avoid steam such as organic solvents Ignition • So • Such a processing temperature is not desirable When the processing time is less than 5 minutes shovel * (A) tends to have insufficient spreading effect. • When the processing time exceeds 10 hours. • Not only wasted time but no enhancement effect. • Therefore, the number of processing times of the sample is not desirable. Important · After the treatment, at least one of (B) a monomer having three or more free-radically polymerizable double bonds and (C) a polymerization reaction initiator is added successively little by little * Polymerization is performed to form a resin layer on the surface of the metallic pigment. In the present invention, it is important to add at least one of (B) and (C) one by one. In other words, any one of the following methods can be used: (B) and (C) are added in succession and supplementary, one by one: one after another in succession and supplementary; * will be added (C) Join first and then add (B) separately: The paper scale is applicable to the Chinese National Standard (CNS) A4 specifications (2) 0X297 mm. Note on the back of the page? Please fill in this page to refill this page) Order-13-i- d 25 4 1 9 Λ7 B 'V. Description of the invention (11) (B) is added first, and then (C) is added separately. It can be inferred that in the present invention, the polymerization completed when at least one of (B) and (C) is added one by one Reaction • Three-degree spatially connected resin layer will be formed on the metal surface. Although not particularly limited, the polymerization temperature is preferably 60 to 150 ° C. • To increase the efficiency of the polymerization reaction, it is best to Under an inert gas such as nitrogen or helium • To add at least one of (B) and (C) • Dilute (B) and / or (C) preferably with an organic solvent or the like and borrow at a constant rate Feeding by metering pump or the like * The feeding time is preferably 20% or longer during the polymerization reaction • Although, not particularly limited * The polymerization reaction time is about 2-10 hours • Here · 'Polymerization reaction time #' means the time required when (B) and (C) have the unprocessed sheet "(B) becomes less than 1% after the reaction system appears at the same time. Print {Please read the notes on the back first and save the smart book 筲) Feeding time (also When the addition time is less than 20% of the polymerization reaction time, the effect of continuous addition does not want to be reduced but is reduced. To reduce the reaction time * the feeding time is preferably 90% or more of the polymerization reaction time. Less • In order to further reduce the reaction time to increase productivity. The feeding time is preferably 70% or less of the polymerization reaction time. The metallic pigment of the present invention is characterized by how much compared with the untreated metallic pigment. There is an increase in surface ratio | But the added system is much smaller than the resin-coated gold tincture pigment obtained by the traditional method *. Therefore, the resin-coated metal pigment of the present invention has a relatively small oil absorption. The reason is speculated as follows: The resin layer on the metal surface is a very uniform and three-dimensionally cross-linked resin layer. • Because of the above characteristics, the paper size of this paper is applicable to China National Standard (CNS) A4 grid (210 × 2ί > 7). Public money) Printed by the Consumers ’Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs " '4 25 4 1 9 A7 ____B7________ V. Description of the invention (12) The metal surface coated with resin The formed coating film is excellent in characteristics such as chemical resistance, gloss, weather resistance, etc. The organic solvents used in the polymerization of the present invention include, for example, aliphatic diameters such as hexane, heptane, and octane * Olein, etc .; for example, aromatic hydrocarbons * such as benzene, toluene, xylene, solvent oils, etc .; for example, ethers, such as tetrahydrofuran, diethyl ether, etc .; and, for example, esters, hydrazone is ethyl acetate, butyl acetate, etc. Deer, etc. · The polymerization initiators used in the present invention are generally known as free-radical initiators and include peroxides, such as dibenzoyl peroxide, lauryl peroxide, and peroxydicarbonate. Cyclohexyl esters, etc .; and azo compounds, such as 2, 2 > -Azobis-isoisobutyl, 2, Azobis-2,4-Dimethylpentane, etc. • Although the polymerization initiator The amount used is not particularly limited in the present invention, but is approximately 份 100 parts of a monomer having three or more radical polymerizable double bonds. Reset. 0.1-50 parts by weight. Coating film formed from coatings obtained by applying metallic pigments * Often good. The reason for guessing is as follows: a resin layer crosslinked with a three-dimensional height is coated on the surface of the metal pigment so that even if the alkali penetrates the coating film, it is difficult to obtain the surface of the gold tincture pigment. The anti-sagging property is described as 0.01 to 2. 0. The metal coating material of the present invention can be used as a solvent-based material, a water-based coating material or the like * and is mainly composed of three basic ingredients *, that is (a ) Coating resin · (b) Resin-coated gold tincture pigment and (c) thinner · This paper size applies to Chinese national standards (CNS > A4 specification (2 丨 0X297 mm) {Please read the precautions on the back first Refill this page) Order-15-Printed by the Central Standards Bureau of the Ministry of Economic Affairs and Consumer Cooperatives. V. Description of Invention (13) When coating resin is used as a solvent-based coating material Coating resins • Coating resins include acrylic resins, alkyd resins, oil-free alkyd resins, gas resins, urethane resins, * ntelamine resins, no And polyester resins, urinary resins, vinyl resins, epoxy resins, fluororesins, etc. • These resins can be used alone or as a mixture. • The proportion of resin-coated metal pigments used in solvent-based coating materials. It is best to use 0.1 to 100 parts by weight per 100 parts by weight of the coating resin. Even more preferably 1 to £ | 0 parts reset. When the resin coated JI metal pigment ratio is less than 0.1 parts reset. The coating material is insufficient in the gloss properties of the metal coating material required for the metal coating material. When the proportion exceeds 100 parts by weight, the amount of the metal pigment in the coating material becomes too large, so not only the coating efficiency but also the film properties will be deteriorated. · Therefore · Such ratios are not practical · Diluents used in solvent-based coating materials include, for example, aromatic compounds such as toluene, xylene, etc .; aliphatic compounds * such as hexane, heptane, octane, etc .; Alcohols • Ester such as ethanol and butanol, such as ethyl acetate, butyl acetate, etc .: For example, ketones, such as methyl ethyl ketone, etc .; Gas compounds, three gas ethylene, etc .: and solvent Agents such as ethylene glycol monoethyl ether, etc. These diluents can be used alone or as a mixture. The combination can be measured from the viewpoints of coating resin solubility, film-forming properties, and coating efficiency. Solvent type coating materials can be used with additives Merging together, for example, the paper size of this paper applies the Chinese standard (CNS) Α4 size (210X297 mm) (please «read the precautions on the back before filling this page) > ^ It— 4 -16-: 425419 at _____B7___________ V. Description of the invention (14), dyes, wetting agents, dispersants, segregation-preventing agents, leveling agents, slip agents, anti-skinnig agents, anti-reverse adhesives Coagulants, defoamers, etc. · It is generally used in the field of coatings · The coating material of the present invention can be used as a water-based coating material by using a resin of a water-based coating material • The resin of a water-based coating material includes a water-soluble resin and a water dispersion Resin • These can be used alone or as a mixture. • The resin type of the water-based coating material is not particularly limited and can be infinitely changed depending on the purpose. • In general, resins for water-based coating materials include, for example, water-based coating materials. Materials such as propylene-based types, propylene-based dimelamine types, poly-ester types, or polyurethane types. Among these * water-based coating materials 1 to 100 parts by weight, and more preferably 1 to 50 parts per 100 parts of coating resin Parts reset • When the proportion of Jinyang pigment coated with resin is less than 0.1 part by weight • The coating materials produced are printed by Jinye Coating Materials for printing by the Consumers ’Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the back first) Please pay attention to this page and fill in this page again.) The glossiness of the golden tincture is insufficient. * When the ratio exceeds 100 parts by weight * The number S of the metal pigment in the coating material becomes too large, so not only the coating efficiency but also the film properties will be deteriorated. • Therefore * such a ratio is not practical. • Various additives can be added * such as dispersant * thickener * reagent to avoid uneven surface film * antifungal agent * bactericide, ultraviolet absorber · film formation aid Surfactants * Other organic solvents • Water etc. * are added to water-based coating materials, as long as they are commonly used in technology, and the type and number of paper sizes are applicable to Chinese national standards (CNS > A4 specifications (210X297 mm)- 17-'-4 25 419 A7 ____ · ___ B7 _ V. Description of the invention (15) · The amount does not reduce the effect of the invention · The metal coating material of the invention can be used as a commonly used coating * Except for solvent type coating materials and water-based coatings In addition to materials • Commonly used coating materials include coating material powder. [Examples] The implementation examples of the present invention are as follows * but they should not be interpreted as a restricted group of inventions • Beyond this • test methods and The method used in the set-up example is described in detail as follows: (1) Method for preparing evaluation-coated boards-using resin-coated aluminum paste for evaluation of alkali resistance, metallic coating materials | Prepared according to the coating formula shown in Table 1. (谙 Read the precautions on the back before filling out this page) Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Tao. Table 1: Coating Details (parts by weight) Number) Resin-coated aluminum paste (in terms of non-volatile matter) 9 Thinner * 1 40 Acrylic resin * 2 100 Nitrifying resin solution * 3 50 This paper is applicable to China National Standards (CNS) A4 (210X297 mm) 18 4254 19 A7 B7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (16) * 1: Butyl acetate (30 parts by weight *), toluene (45 parts by weight), isopropyl alcohol (20 parts by weight) and ethyl solvents (5 parts by weight). * 2: ACRYDIC A-166 (non-volatile content: 4 5%) (room temperature one-curing acrylic resin. Dainippon Ink and Chemicals Co., Ltd. Manufacturing * 3: Made from LIG 1/2 (non-volatile content: 70%) (industrial nitrification, manufactured by ASAH I Chemical Industry Co., Ltd.) and thinner * 1. Adjust the indene to 16% non-volatile content _The solution obtained · The viscosity of the coating material was adjusted to 13 seconds with the thinner in Table 1 above (FC # 4 · 2 0 eC), and then the coating material was sprayed on an ABS resin dish to a thickness of 1 0 #. • Drying on a 50eCHABS resin dish for 30 minutes · Production of coated boards for evaluation · (2) Measurement of alkali resistance above The lower half of the coated board is immersed in a 2.5N N a 0H aqueous solution and placed at 20eC 2 for 4 hours. • The coated dish after treatment is washed with water and dried. And the unimmersed part were measured for color under the conditions d (8-d method) specified in Japanese Industrial Standard No. Z8722 (1982) · and measured in accordance with Japanese Industrial Standard No. Z-8730 (1980) (color difference) ^ E. · (3) Gloss retention (please read the notes on the back before filling in this page) Ϊ The size of this paper applies the Chinese National Standard (CNS) Α4 specification (210X297 mm) ) -19 — Printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs — 425419 a? _____B7_____ V. Description of the invention (17). For the above coated dishes, 6 0 · gloss (incident angle and reflection angle: 60 · The ft and gloss retention R measured by the gloss measuring pin are calculated according to the following formulas:

R = (G ^ / G) x 100 where G is the 60 ° gloss of untreated aluminum paste and G > is the 60 ° beta gloss of resin-coated aluminum paste. (4 > oil absorption is placed in 1 0 5 ° C. The resin-coated wrought paste of the tincture sample was hot-spotted for 3 hours. * Using dibutyl phthalate according to Japanese Industrial Standard K 6 2 2 1 1 9 8 2 (Knife-kneading method) Determine its oil absorption. (5) Surface ratio. Remove the solvent contained in the aluminum paste. • Replace it with acetone, and measure the surface of the powder sample thus obtained using the BET military spot type surface ratio. Meter (Shimadzu FL0VS0RB 2300) Measurement Example 1 In a four-necked flask with a capacity of 1 liter, put 7 5 g of aluminum paste (MG-1 51, manufactured by ASAHI Chemical Industry Co., Ltd .: metal containing 6 7 %) And 300 grams of osmium olein • and stirred while introducing nitrogen, and the temperature in the system was raised to 80 eC • Then, 0.375 grams of acrylic acid was added and stirred at 80 * C for 30 minutes • Next • The trimethylolpropane trimethacrylate 2-5 wide, ditrimethylolpropane tetrarule paper standard applicable to the Chinese national standard (CNS > A4 specifications ( 210X297mm) (#Please read the notes on the back before filling this page) Order -20-4 2 5 4] b A7 ___B7___ V. Description of the invention (18) acrylate 1.0 g (fluorene functional group molecule Set: 116. 5) and 2. 2 > —Nitrazine bis 2 · 4 —Dimethylpentamethylene 0.3 5 g was dissolved in 19 g of holm oil • The resulting solution was added to the mixture obtained above , Using a metering pump at a speed of about 0.13 g / min. For more than 3 hours * afterwards * when the temperature in the system is maintained at 80 eC • polymerization in all substances for 6 hours • at the same time • using the gas phase Chromatographic analysis measured the unreacted trimethylolpropane trimethacrylate in the filtrate, and found that 99.5% or more of the added trimethylolpropane trimethacrylate had reacted. After completion * The obtained slurry was filtered to obtain a resin-coated aluminum paste. The non-volatile content of the paste (according to the Japanese Industrial Specification K-5910) was 65. 0% by weight. Set to 毎 100 parts metal aluminum weight 8.3 parts weight • From these results it seems * presumably 毎 a acrylic acid * Methylmethylpropane trimethacrylate • Ditrimethylolpropane tetraacrylate and 2 * 2 > -Azobis-2 * 4-Dimethylpentane has 9 8% or more sticking to aluminum On the surface * Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs {Please read the precautions on the back before filling this page) Example 2 The same method as in Example 1 was used to prepare the resin-coated aluminum paste. Different It is a combination of 3.5 g of trimethylolpropane trimethacrylate instead of trimethylolpropane trimethacrylate and ditrimethylolpropane tetraacrylate. Example 3 This paper is applicable to China Standard (CNS M4 specification (210X297 mm) -21-Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 4254 1 9 at _ B7 V. Description of the invention (19) In a 1-liter four-necked flask, place 75 grams of aluminum paste (MG-51, manufactured by ASAHI Chemical Industry Co., Ltd .: metal content of 6 7%) and 300 grams of mineral spirits * and stirred while introducing nitrogen, and the temperature in the system was raised to 6 0X · Then, add 0.35 grams of acrylic acid and stir for 30 minutes at 60 • Next, 6.4 g of trimethylolpropane triacrylate and 1.6 g of dipentaerythritol hexaacrylate (fluorene functional group molecule: 96.3) were dispersed in the system. Then 2,2 azobis 0.8 g of 2 · 4-dimethylvaleronitrile was dissolved in 19 g of sulphur olein · and the resulting solution was added with a meter ft pump at a rate of about 0 8 g / min. For more than 4 hours. System __ System • Later, when the temperature in the system is maintained at 6 OeC * Polymerization is performed in all substances for 7 hours • After the completion of the polymerization reaction • The obtained slurry is filtered to obtain a resin-coated Aluminum paste • The non-volatile content of the paste (according to the Japanese industrial specification K-5910) is 60. 0% reset. • The resin coating is used for 100% metal aluminum reset 18.2 parts by weight. * From these results * It is generally speculated that each acrylic acid * trimethylolpropane triacrylate, dipentaerythritol hexaacrylate and 2 * 2 > — azobisone 2 * 4 — dimethylpentane has 9 9% or more adhered to aluminum surface. Example 4 In a 1-liter four-necked flask, put 75 g of aluminum paste (MG-51, ASAHI Chemical). Manufactured by Industrial Co., Ltd .: metal content 6 7%) and 300 grams of osmium olein • and stirred when nitrogen is introduced, the paper size is in accordance with China National Standard (CNS) A4 specification (210X297 mm) (cuff first K Read the notes on the back and fill in this page again.) Book-22-Printed bags for consumer cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 42R4 1 9 at ______B7____ V. Description of the invention (20) and raise the temperature in the system to 70 eC · Then, 0.4 g of acrylic acid was added and stirred at 80 eC for 30 minutes. Next, 0.5 g of diacrylic acid hexamethylene diester, 3.0 g of trimethylolpropane trimethacrylic acid · 1 · 5 grams of pentaerythritol tetraacrylate (molecular weight of each functional group: 8 8) and 0.5 grams of «bisisobutyl eye dissolve in 38 grams of osmium olein * and the resulting solution with a meter pump at about 0.24 Addition to the above mixture at a rate of g / min over 3 hours. After that, when the temperature in the system is maintained at 80 ° C, polymerization is carried out in all substances for 6 hours. After the completion of the polymerization reaction * The obtained slurry was filtered to obtain a resin-coated aluminum paste. The non-volatile content (according to Japanese Industrial Specification K-59 10) is 62.0% reset. The amount of resin coating is reset by 11.6 parts by weight per 100 parts of metal aluminum. * From these results, * —Generally speculated that 毎 monoacrylic acid, trimethylolpropane trimethacrylate *, pentaerythritol tetraacrylate_, and 2,2 ^ -nitrodiazepine have 9 8% or more stick on aluminum surface · Example 5 A resin-coated aluminum paste was prepared by the same method as in Example 1 except that the amounts of trimethylolpropane trimethacrylate and ditrimethylolpropane tetraacrylate deer were changed respectively. 1.0 g and 2.5 g. Non-volatile content of the paste (according to Japanese industrial specifications-K-5 9 1 0) is 60.0% by weight. Example 6 This paper size applies Chinese national standards (CNS ) Α4 size (210 × 297 mm) .HI .....— -I i. ^ Ϋ ^^ 1 ^^ 1 ^^ 1 {Please read the precautions on the back before filling this page) -23--·- 4 2 5 4 1 9 a? ___; ____B7____ V. Description of the invention (21) · 'The resin coated aluminum paste was prepared by the same method as in Example 1 except that the trimethylol 2.5 克。 Dipropane trimethacrylate 2.5 grams • Ditrimethylolpropane tetraacrylate 1.0 grams and 2, 2 # —Azobis-2,4-dimethylvaleronitrile 0.35g dissolved In 19 grams of mineral oil, knead the solution with a metering pump at a rate of about 0.32 g / min over a period of more than 1.2 hours. The non-volatile content of the paste (according to the Japanese Industrial Specification 1 K—5910) is 65.0% reset (please read the precautions on the back before filling out this page) Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs Example 7 Placed in a 2-liter four-necked flask * Put 150 grams of aluminum paste (MG — 51, manufactured by ASAHI Chemical Industry Co., Ltd .: gold tin content 6 7%) and 600 grams of mineral spirits, and stir when nitrogen is introduced *. The temperature rose to 7 0 * t. Then, 7 grams of vinyltrimethoxysilane and 7 grams of deionized water were added and stirred for another 5 hours. The resulting slurry was filtered and the remainder was washed with olein. In a 1 liter capacity. Into a four-necked flask, put 75 g of the obtained aluminum paste and 300 g of olein * and stir it while introducing nitrogen. Raise to 8 0eC • Next, trimethylolpropane trimethacrylate 2.5 g "di-trimethylolpropane tetraacrylate 1.0 g and 2 · 2 '—Azobis-1 2, 4 — 0.35 g of dimethyl pentylene was dissolved in 19 g of olein, and the resulting solution was added to the above-obtained mixture, using a metered pump at a speed of about 0.13 g / min for more than 3 hours • Thereafter • When the temperature in the system is maintained at 80 eC • Polymerization in all substances-* · This paper size applies to China National Standard (CNS) A4 specification (210X297 mm) -24 _ Central Bureau of Standards, Ministry of Economic Affairs W Industry and Consumer Cooperation Du Yinshang f 4254 1 9 at _______B7_ 5. Description of the Invention (22) Action for 6 hours • After the polymerization reaction is completed, the aluminum paste thus obtained is filtered to obtain a resin-coated aluminum paste. Non-volatile paste containing ft (according to Japanese industrial specifications K-5 9 1 〇) is 6 5 0 reset% • S system for resin coating is 8.3 parts reset per 100 parts of metal aluminum weight * From these results, it is generally speculated that each vinyltrimethoxysilane · trimethylolpropanetrimethyl Ethyl ester · Ditrimethylolpropane tetraacrylate and 2,2-—Azobis-2,4—Dimethylvaleronitrile adhered to the aluminum surface at 98% or more. Example 8 '· · · Resin-coated aluminum paste was prepared in the same manner as in Example 1 except that 2-methacrylfluorenyl ethoxy acid phosphate (MR — 2 0 0 DAIHACH manufactured by Chemical) was used. The non-volatile content (according to the Japanese Industrial Standard K5 591 1 0) of substituted acrylic acid paste is 65.0% by weight. • From these results, it is generally estimated that each 2-methacrylfluorenylethoxy Acid phosphate, trimethylolpropane trimethacrylate, ditrimethylolpropane tetraacrylate and 2,2 # —azobis-2,4-dimethylvaleronitrile have 9 8% or More adhesion on the aluminum surface. Comparative Example 1 A resin-coated aluminum paste was prepared in the same manner as in Example 1. The difference was that the monomer (B) and the polymerization initiator were added at one time. The pump is added one by one successively and supplementally. This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X29). 7 mm) 111 ^^ 1 *-«II-II ^^ 1 1 ^ 1 I ^^ 1 _ I— 1 ^ 1 ^^ 1. Fang i {Please read the precautions on the back before filling this page ) -25-Printed by Shellfish Consumer Cooperative, Central Bureau of Standards, Ministry of Economic Affairs ^-4 254 19 A7 ____B7___ V. Description of Invention (23) * Comparative Example 2 A resin-coated aluminum was prepared in the same manner as in Example 2. Paste * The difference is that the general hip (B) and the polymerization reaction initiator are added at one time. • Instead of using a pump to add a little sticky, supplementary addition. Comparative Example 3 Prepared by the same method as in Example 1 0 克 和 2, 2 # — 氢。 The resin-coated aluminum paste, the difference is that trimethylolpropane trimethacrylate 2.5 grams • ditrimethylolpropane tetraacrylate 1.0 grams and 2, 2 # —azo 0.5g of bis-2,4-dimethylpenta crumb was dissolved in 19 wide olein. The resulting solution was pumped with a pedometer at a speed of about 0.76 g / min for more than 0.5 hours. • The non-volatile content of the paste added (according to the Japanese Industrial Standard K-5910) is 60. 0 reset%. Comparative Example 4 The warp tree was prepared in the same manner as in Example 1. Coated aluminum paste * The difference is that 0.88 g of vinyltrimethoxysilane * will be used. 0. 06 g of phosphoric acid, 0.06 g of water and 1. 00 g of 2-butanol in place of acrylic acid, and trihydroxy The combination of methylpropane trimethacrylate 3.5 g of substituted trimethylolpropane trimethacrylate and ditrimethylolpropane tetraacrylate, 19 g of trimethylolpropane in mineral spirits垸 The solution of trimethacrylate is added at a rate of about 0.88 g / min over a period of 0.5 hours with a meter pump. • Paste non-volatile containing children (according to Japanese industrial specifications -K- 5910) is 60. 0% by weight. This paper size is applicable to the Chinese National Standards (CNS) A4 Zhuge (210 × 297 mm) (Please read the precautions on the back before filling out this page) Order-26--· 425419 V. Description of the Invention (24) «Comparative Example 5 A resin-coated aluminum paste was prepared in the same manner as in Example 4, except that a solution of 19 g of trimethylolpropane trimethacrylate in olein was prepared. One-time addition • Instead of using pumps to add successively, supplementally • Non-volatile content of paste (According to Japanese Industrial Standard-K-5910) is 60. 0% reset. Table 2 shows the performance characteristics (performan, ce) of the pastes of Examples 1 to 8 and Comparative Examples 1 to 5. Table 2 shows * 'Polyfunctional monomer inclusion means the percentage of monomers with four or more radical polymerizable double bonds contained in all monomers with three or more radical polymerizable double bonds (reset% ) · ---------— f • Pan (please read the notes on the back before filling this page) Like the Central Bureau of Standards of the Ministry of Economic Affairs, another industry, consumer cooperation, printed on paper, the standard of Chinese painting is applicable (CNS) Α4 Specification (2 丨 0 × 2μm) -27-Printed by the staff of the Central Standards Bureau of the Ministry of Economic Affairs and printed by the cooperative 4 25 419 a? B7 V. Description of the invention (25) Table 2: The characteristics of the paddle paste are multifunctional Ji Cui's "* 1 containing (X) supplementary added time * 2 (X) oil absorption (g / g) stability in water-based materials * 3 cabin resistance △ E (8-d method) light Retention (X) Example 1 29 50 1.42 〇0.7 gi Yin Example 2 0 50 1.61 〇1 · 7 90 Example 3 20 57 1 · 56 〇2 · 90 90 Example 4 33 50 L45 〇.0.3 90 Implementation Example 5 71 50 1.70 〇2.0 89 Example 6 29 20 1.60 〇1.0 90 Example 7 29 50 1.31 〇2, 92 92 Example 8 29 50 1-41 〇0.6 90 Comparative Example 1 29 0 1.82 X 2.5 88 Comparative Example 2 0 0 Κ90 X 3.0 85 Comparative Example 3 29 8 1.84 X 2.3 88 Comparative Example 4 0 7 1.44 〇15.0 88 Comparative Example 5 0 0 1.44 〇17.0 88 * 1: 4 or more radical polymerizable double Tt * 2: W (% of polymerization time) when feeding ingredients (B) and / ¾ (C) * 3: «Storage stability in water-based coatings 0: Gas generated * Set to 10 (cc) / g) The following X: The generated gas β is set to 10 (cc / g) or more. This paper size applies the Chinese National Standard (CNS) A4 specification (2 丨 〇 X 297 cm)

If — —I— I--I -ii ^ m ^^ 1 I 1 ^ 1 1_ (Please read the notes on the back before filling this page) -28-4 25419 a? ________B7___ V. Description of the invention (26) Implementation Example 9 Using the resin-coated aluminum paste obtained in Example 1 • Comparative resin-coated aluminum paste obtained in Example 2 and resin-free aluminum paste (MG — 51, (Manufactured by ASAHI Chemical Industry Co., Ltd.) and cyano resin to prepare coating materials based on the materials shown in Table 3. • Apply a coating material to the giant board (1 X70x 150 mm), spray the resin to the 3 Ο ί thickness • Then, dry the aluminum plate at 10 OeC for 30 minutes | to form a metal coating film mainly composed of fluororesin. Table 3: Material of the coating (reset number) {Please read the back (Note the $ items and then fill in this page) LUHIFURON LF200 11 100 Aluminum Paste (based on 100X non-volatile) printed by the Central Standards Bureau of the Ministry of Economic Affairs and Consumer Cooperatives 10.2 DURANATE TPA-100 12 7. 8 Thinner 13 150 Total 268. 0 -29-1 1: Manufactured by Asahi Glass Co., Ltd. This paper is suitable for China Standard (CNS) A4 specification (2 丨 0X297 mm) Printed by the Consumers 'Cooperative of the Central Bureau of Economics " 4 254 1 9 at _B7 _ V. Description of the invention (27) · * 2': ASAHI Chemical Industry Co., Ltd. Manufactured by the company * 3: Toluene / xylene / ethyl acetate / butyl acetate ratio = 30/20/20/30 · Coating film using metal * Chemical resistance spot test at 20 ° C 10 days * Estimated after Degree of discoloration • In addition, the same coating film was used for exposure test by sunshine weatherometer (SW0M) for 3 · 0 0 0 hours. · In the chemical resistance test experiment, each 10% argon aqueous solution of acid, 10% N a 0 tritium hydroxide solution and 1 Q% sulfuric acid aqueous solution were used as chemical devices. The results obtained are shown in Table 4. {Please read the precautions on the back before filling this page ) This paper size applies to China National Standard (CNS) A4 specification (210 × 297 mm) -30-Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs-4 25 4 1 9 at ___B7 V. Description of Invention (28) Table 4 : Judging the degree of discoloration of coating film Aluminum paste 100XBC1 Stain test 10KN & OH staining test mHsScu staining test »light weather meter spray test Example 1 resin-coated aluminum paste 〇00〇 Comparative Example 2 resin-coated aluminum paste △ Δ 〇Δ MG-51 (Aluminum paste without resin coating) XXX Δ 〇: No discoloration △: How much discoloration X: Significantly discoloration 1 ^ 1 n-1--^^^ 1 —4 · --ei. (Please read first Note on the back page, please fill in this page again) This paper size is applicable to Chinese National Standard (CNS) A4 specification (210X297mm) -31-425419 A7 B7 V. Description of the invention (29) The coating film formed by the coated aluminum paste has not changed in the chemical resistance test. However, in the test performed by the sunshine weather meter *, it was formed by using the resin-coated aluminum paste of Example 1 of the present invention. It is difficult to change the appearance of the coating film, that is, it has excellent weather resistance. Example 10 According to the materials shown in Table 5, a vinylidene fluoride type fluororesin is used as a resin component to prepare a coating material. • Apply each coating material on an aluminum plate • The rod coater was used to coat the resin with a thickness of M3 0 #. Then, the aluminum plate was dried at 240 ° C for 5 minutes to form a coating film. The chemical resistance test was performed in the same manner as in Example 9. • The coating film formed by using the resin-coated aluminum paste of Example 1 is very good in terms of chemical resistance. * As in Example 9 (Please read the notes on the back before filling this page) Order the Ministry of Economic Affairs Printed by the Central Bureau of Standards Consumer Cooperatives The paper size applies to Chinese National Standard (CNS) A4 specifications (210X297 mm) -32-• 4254 1 9 at ___B7 V. Description of the invention (30) Table 5: Coating materials (parts by weight) number)

Paraloid B-44 * 1 15.2 Aluminum paste (based on 100X non-volatile) 9.2 Thinner * 2 120.0 NE0FL0N VDF VP-850 * 3 45. 6 v Total 199.0 0 I-: --.----- ^ ------ # < Please read the notes on the back before filling out this page) Printed by the Consumers ’Cooperative of the Central Bureau of Standards, Ministry of Economic Affairs * 1: Made by Rohm & Haas * 2: Isophorone / Dimethyl phthalate / toluene / isobutyl acetate / ethyl acetate ratio = 45/24/15/8/8 · * 3: manufactured by DYKIN Industry Co., Ltd. Example 1 1 Example 1 Resin-coated aluminum paste and Comparative Example 2 Resin-coated aluminum paste. Acrylic-based coating materials were prepared according to the coating materials shown in Table 6. • A coating material was applied to an ABS resin board by air spraying. Sprayed to a thickness of 30 A • Dry the AB S resin board in a room for 24 hours, and measure the 60 · gloss of the resulting coating film. • Use this paper standard to comply with China Garden Standard (CNS) A4 specifications (2 丨 0X297). (Mm) -33--4 2541 9 a7 ___B7____ V. Description of the invention (31) Example 1 The coating film formed by the resin-coated aluminum paste has a high gloss of 65% However, the coating film formed by using the resin-coated aluminum paste of Comparative Example 2 had only 53% gloss. Table 6: Material of coating (parts by weight) ACRYDIC Α-801 * 1 100 aluminum paste (with 100 × Non-volatile meter) 5 V. ·. DURANATE ΤΑ-100 16.2 Diluent * 2 120 Catalyst (dibutyl dilaurate) 1. 0 Total 242.2-: --_------- ----- ΐτ (Please read the notes on the back before filling out this page) Printed by the Central Bureau of Standards of the Ministry of Economic Affairs—Industrial and Consumer Cooperatives * 1: Made by Dainippon Lishui and Chemicals Co., Ltd. (30 parts reset), toluene (45 parts reset) * Mixture of isopropanol (20 parts reset) and ethyl androgen (5 parts by weight) * 2: Butyl acetate / butyl acetate / toluene / xylene / methoxyacetic acid Propyl ratio = 20/30/30/15/5 This paper size is applicable to Chinese National Standard (CNS) Α4 Zhuge (210X297 mm) -34 _ " 4 25419 a? One B7 V. Description of Invention (32) Implementation Example 1 2 For the resin-coated pastes of Examples 1 to 8 and Comparative Examples 1 to 5 • Use the materials shown in Table 7 to prepare coating materials • Test to store them in water-based coatings Stability in the material • In a 200 liter conical flask * 100 grams of each coating material is placed, and a straw with a rubber stopper is placed in the conical flask. Table 2 above shows that Erlenmeyer flask is set at 50 ° (: 24 hours after measurement). In addition, the water-based paint material is based on the aluminum paste coated with resin in Example 1 according to Table 7. The material is prepared by applying it on an aluminum plate by air spraying to a thickness of 30 *. Then it is dried at 1 70 eC for 20 minutes to form a material film. The coating film is very good in terms of metal appearance. Table 7 : Coating material (parts by weight) (Please read the precautions on the back before filling out this page) The Ministry of Economic Affairs, Standard Bureau Bei Gong Xiaoxian Cooperative Co., Ltd. Ink Resin Coating Metallic Pigment Metal Component 2821 Water-soluble acrylic resin (heating Residue = 5 0X) 370 Water-soluble melamine resin (heating residue = 50? 〇 * 2 100 pure water 491 total 3782) This paper size is applicable to China's national sample rate (0) 8 gauge / div (2 丨 0 > < 297 mm) -35-4 2 5 4 1 a? B7 V. Description of the invention (33) · 1 Resin (made by Mitsui Toatsu Chemical Co., Ltd.) prepared by adding dimethylacetamide to ALKATEX 1A-911, and then adjusted the acid test value to 9 (2: CYMEL 350 OCITSBI CYTEC) · Example 1 3 Measurement Example 1 Surface coating ratio of resin-coated Ming paste 'Comparative Example 2 and resin-coated aluminum paste (MG_51, manufactured by ASAHI Chemical Industry Co., Ltd.) • Results obtained Shown in Table 8, · Chapter Example 1 is a resin-coated tantalum paste, Comparative Example 2 is a resin-coated aluminum paste, the surface ratio is aluminum paste without resin coating 1. 9 And 3.0 times • From the facts, it can be speculated that the resin-coated aluminum paste of Example 1 has a three-dimensionally highly cross-linked resin coating. --------- X- -(Please read the poem first, and then fill in this i) Order the paper printed by the Central Bureau of Standards, Ministry of Economic Affairs, Du Yin ¾ This paper size applies to Chinese national standards (CMS > A4 dead grid (210X297 mm)- 36 " Shellfish Consumption Cooperation by the Central Bureau of Standards of the Ministry of Economic Affairs, Printing 4254 1 9 A7 ________B7 V. Description of the Invention (3 4) Table 8: Surface-to-surface ratio to surface-to-surface ratio (S) (cm²) Surface area of resin-coated U uncoated surface A1 Example 1 10. 5 1. 9 Comparative Example 2 16.3 '. 3. 0 MG-51 5. 5-Example 1 4 Resin-coated aluminum paste was prepared by the same method as in Example 1, except that MH-8801 (manufactured by ASAHI Chemical Industry Co., Ltd., gold嬲 Contains 6 5%) instead of the aluminum paste used in Example 1. The resistance of the resin-coated aluminum paste was tested, and its color difference was found Δ E = 0.3. Therefore, the resin-coated aluminum paste The paste has excellent alkali resistance * Comparative Example 6 This paper size is applicable to the Central and South China National Standards (CNS) A4 (210X297 mm) ---- ^ ----- 1-^ ----- -、 Order ------ bundle- {Please read the precautions on the back before filling this page) -37-4254 A7 B7 V. Description of the invention (35) * First, use the same method as in Comparative Example 2 to prepare the warp Resin-coated aluminum paste * The difference is * Use MH-8 8 0 1 (made by ASAHI Chemical Industry Co., Ltd .: metal containing 6 5¾) instead of the aluminum paste used in Comparative Example 2 The resistance of the coated aluminum paste was found to have a color difference of ΔE = 0.31. Example 1 5 The resin-coated aluminum paste of Example 14 was measured separately. Comparative Example 6 The resin-coated aluminum paste was measured. Surface ratio of aluminum paste without resin coating (MΗ-8801, manufactured by AS, AHI Chemical Industry Co., Ltd .: metal containing 6 596) · The results obtained are shown in Table 9 · Example 14 The surface ratios of the coated aluminum paste and the resin coated aluminum paste of Comparative Example 6 were 1.5 times and 3.0 times the aluminum paste without resin coating, respectively. From this fact, It can be inferred that tree Example 13 The resin-coated aluminum paste has a three-dimensionally highly cross-linked resin coating (please read the precautions on the back before filling this page) Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs This paper size applies the Chinese Standard (CNS) A4 Zhuge (210X297 mm) -38 · 5 2 4

7 7 AB V. Description of the invention (36) Table 9 ': Surface area specific surface 稹 Surface area (S) (square cm) of A1 coated with resin 1 Example 14 14. 2 1.5 Comparison 28 . 5 3. 0 .. Example 6 MH-8801 9.5-(Please read the precautions on the back before filling out this page) The Central Coatings Bureau of the Ministry of Economic Affairs printed the resin-coated metal pigment of the present invention Resin coating with 髙 crosslinking density * and excellent in chemical resistance, weather resistance, and storage stability. • In addition, because the resin-coated gold pigment has a small surface area, it has a small oil absorption. The degree of gloss reduction caused by resin coating can be minimized. The resin-coated metal pigment of the present invention can be applied to metallic coating materials and printing inks or as a combination of pigment and plastic due to the above reasons. The resin-coated metal pigment of the present invention has good weather. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) -39-425419 A7 B7. 5. Description of the invention (37) Resistance and therefore suitable for use in areas where the following durability products are required: for example • automotive parts * such as car bodies, bumpers, side mirrors, etc .: components outside the building * such as bricks, roofs, box walls Etc .; and household electrical appliances · (Please try first, please take note of the back, then fill out this page) Co-operation with the staff of the Central Bureau of Standards of the Ministry of Economic Affairs, printed on this paper The size of the paper is applicable to China National Standard (CNS) A4 (210X297 mm) ) -40-

Claims (1)

4 2541 9 89. Π. Α8 Β8 C8 D8 Patent Application Brigade # Monthly Charge No. 8 5 1 〇 6 3 8 6 Attachment A of Patent Application No .: Chinese Patent Application Scope Amendment This time the Ministry of Economic Affairs Zhilong has time-sharing labor consumption Cooperative India, Republic of China, November 1989 Amendment 1 A resin-coated metal pigment consisting of (A) at least one selected from the group consisting of radically polymerizable unsaturated carboxylic acids having one or two radically polymerizable double bonds, And / or phosphonic monoester or diester, and / or, a coupling agent having one free-radically polymerizable double bond, (B) a monomer having three or more free-radically polymerizable double bonds, and (C ) Polymerization initiator, by first adding (A) to treat the metallic pigment, and then continuously and supplementally adding at least one of (B) and (C) to the polymerization reaction A resin layer is formed on the surface of a metallic pigment, in which three monomers having free radical polymerizable double bonds and a single system having four or more free radical polymerizable double bonds are treated as having three or more free radical polymerizable Monomer (B) with a double bond, and four or more of which are free The proportion of the monomers of the polymerized double bond is the total weight of the three or more free-radically polymerizable double bond monomers from 10% to 60% by weight, wherein at least one of the above components (B) and (C) is supplemented. 0 或 小。 The process of adding more than 20% of the total polymerization time, wherein the resulting resin-coated metal pigment has an alkali resistance of 2.0 or less. 2. For example, the resin-coated metal pigment of item 1 of the patent application, wherein the molecular weight of each functional group in the monomer having four or more free-radically polymerizable double bonds is not more than 2 0 and not less than 3 0. 3. —A kind of metal coating material, which contains the item 1 of the scope of patent application —...---: -------. Equipment ------ order ------ Λ. (Please Please read the notes on the back before filling this page.) This paper size is applicable to Chinese national standard (CMS > A4 size (210X297 mm)). Patent-coated resin-coated metal pigment A8 Β8 C8 D8 (Please read the back first Note: Please fill in this page again.) Stupid-Order the paper printed by the Ministry of Economic Affairs and the Smart Industrial Co., Ltd. 3 Industrial Consumer Cooperatives. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) -2-Application date 85 days, days Case No. 85106386 Farewell C 1 / l ·> '. (The above sheds are filled by the Bureau) fij ^ 7¾ A4 425419 Relying on the patent specification of the Union (revised version) The resin coated gold tincture of the Chinese new tincture contains the other Members of the metal coatings are requested to show their talents clearly -l:, r: i ::-^^ f; l Printed by the WC Industrial and Consumer Cooperatives of the Central Bureau of Economic Affairs of the Ministry of Economic Affairs «. New Name Inventions-III. Applicant English -coated metallic pigment and a mildew coating 鼸 aterial usingthe saae name nationality 、 Resident name (name) Nationality residence, residence (office) Representative name ⑴Azumi Shunsuke 0 Imamori Shinjuku ⑶ Hayami Jinji (1) Japan 0 Japan ⑴ Japan, Shizuoka Prefecture, Shizuoka Prefecture, Japan (2J Japan, Ibaraki Prefecture, Ibaraki Prefecture, Ibaraki-gun, Asahi-cho, Tomoka-cho, 506 »Three (3) Japanese painting Totsuka plaque Hirado, Yokohama-shi, Kanagawa Prefecture _ Yakojima Asahi Kasei Metal Co., Ltd. (1) Japanese version (1) Chiyoda, Tokyo, Japan, Tokyo, Yoshinoya-cho, Ichibiya, Ichiban, Takiura, Takura-fu, and the paper size are applicable to the Chinese National Standard (CNS) Α4 size (210X297 mm) Gutter 4 2541 9 89. Π Α8 Β8 C8 D8 Patent Application Travel # 月 充 No. 8 5 1 Ο 6 3 8 6 Patent Application Annex A.: Chinese Patent Application Scope Amended Amendment November 1 A resin-coated metal pigment consisting of (A) at least one selected from the group consisting of a radically polymerizable unsaturated carboxylic acid having one or two radically polymerizable double bonds, and / or a monophosphonic acid ester Or diester, and / or, a coupling agent having one free-radically polymerizable double bond, (B) a monomer having three or more free-radically polymerizable double bonds, and (C) a polymerization initiator, The resin layer is formed on the metallic pigment by first adding (A) to treat the metallic pigment, and then continuously and supplementally adding at least one of (B) and (C). On the surface, there are three monomers with free-radically polymerizable double bonds and a single system with four or more free-radically polymerizable double bonds as monomers with three or more free-radically polymerizable double bonds (B ), And the proportion of the monomers having four or more radically polymerizable double bonds is the total weight of the three or more radically polymerizable double bonds of the above 10% to 60% by weight, where 0 或 小。 The process of adding at least one of the above components (B) and (C) to account for more than 20% of the total polymerization reaction time, wherein the alkali resistance of the obtained resin-coated metal pigment is 2.0 or less. 2. For example, the resin-coated metal pigment of item 1 of the patent application, wherein the molecular weight of each functional group in the monomer having four or more free-radically polymerizable double bonds is not more than 2 0 and not less than 3 0. 3. —A kind of metal coating material, which contains the item 1 of the scope of patent application —...---: -------. Equipment ------ order ------ Λ. (Please Please read the notes on the back before filling in this page) This paper size is applicable to China National Standard (CMS > A4 size (210X297mm)