554016 A7 _____ B7 五、發明說明（1 ) 發明所屬之枝術領域 (請先閱讀背面之注意事項再填寫本頁) 本發明係關於形成依序塗裝有機溶劑型親水性著色塗料 、·水性著色塗料及透明塗料之多層塗膜的方法。 習知技術及其課顆 形成依序塗裝有機溶劑型親水性著色塗料、水性著色 塗料及透明塗料之多層塗膜的方法係爲習知。有機溶劑 型親水性著色塗料之未硬化塗膜具有強的吸水性，於該 塗面塗裝水性著色塗料，由於吸收該塗膜中的水分而使 黏度急劇上升，而有所謂不會產生於低溼度氛圍氣體下 塗裝該水性著色塗料之表面粗糙等缺陷的效果。又，使 用水性金屬塗料作爲該水性著色塗料，不會受塗裝時之溼 度影響，沒有金屬斑點，而有所謂可形成光澤鮮豔性優異 之塗膜的效果。另一方面，有機溶劑型親水性著色塗料爲 了維持多層塗膜之耐候性及美觀性等，而有光透過率低的 優異隱蔽性，且盡可能以薄膜爲佳，因此，從來一直含有 多量的著色顏料。該結果爲雖然可確保塗膜之隱蔽性，相 反地，有所謂塗膜之物理性能容易降低的缺點。 解決課題之手段 經濟部智慧財產局員工消費合作社印製 此處，本發明者等專心硏究關於爲了消除形成塗裝有機 溶劑親水性著色塗料、水性著色塗料及透明塗料之多層塗 膜的方法中如上述之缺點，親水性著色塗料之著色顏料含 有率少且亦爲薄膜，並形成隱蔽性優異之塗膜，而且塗膜 之物理性能不會降低的親水性著色塗料。其結果爲此次在 親水性著色塗料中，和著色顏料一起，由於含有特定量之 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 554016 A7 _______ B7 五、發明說明（3) 作爲爲了依照本發明之塗裝方法而形成多層塗膜的被塗 物者，舉例有金屬製品及或塑膠製品等，較具體而言， (請先閱讀背面之注意事項再填寫本頁) 舉例有使用金屬製品及或塑膠所形成之客車、卡車、機 車、公共汽車等之汽車車體。該等被塗物以適當之方法來 預先進行表面處理（例如，脫脂、磷酸鋅處理等）爲佳。 有機溶劑型親水性著色塗料（A)雖可直接塗裝於該等之 被塗物上，但是以塗裝親水性著色塗料於塗裝陽離子電極 沉積塗料等之底塗層塗料，更於必要時塗裝中塗層塗料， 並硬化個別之塗膜而得之被塗物上爲佳。作爲該等之底塗 層'塗料及中塗層塗料者，可使用該本身之既知者。 塗裝於如依照本發明之上述的被塗物的有機溶劑型親水 佺著色塗料（Α)係含有酸價爲5〜100之範圍內的含有羧基 之樹脂中和物、硬化劑、平均粒徑20/zm以下之鋁粉末及 著色顏料，然後該鋁粉末之含有率爲樹脂固體部份每100 重量份有0 . 1〜10重量份上之範圍內的有機溶劑型塗料。 經濟部智慧財產局員工消費合作社印製 作爲於親水性著色塗料（A)中所使用的含有羧基之樹脂 者，若分子中含有至少1個羧基且酸價爲5〜100之範圍內 的用於塗料之樹脂，並無特別之限制，可使用該本身既 知之各種用於塗料之樹脂。可舉出以下之樹脂作爲該代表 範例。 (i)共聚合下述（a)群之含有羧基之聚合性單體中至少1 種及可與其共聚合之（c)群之聚合性單體中至少1種，更 於必要時（b )群之含有羥基之聚合性單體中至少1種而 得，數目平均分子量爲約3000〜約40000、較佳爲約5000 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 554016 經濟部智慧財.產局員工消費合作社印製 A7 B7 五、發明說明（4) 〜約25000之範圍內的丙烯酸樹脂或乙烯基樹脂。 (a) 群：丙烯酸、甲基丙烯酸、馬來酸、馬來酸酐、衣 康酸、巴豆酸等之α，/3 -乙烯性不飽和羧酸。 (b) 群：（甲基）丙烯酸羥基乙酯、（甲基）丙烯酸羥基 丙酯等之（甲基）丙烯酸之碳原子數爲1〜8個的羥基烷基 酯。 (c) 群：（甲基）丙烯酸甲酯、（甲基）丙烯酸乙酯、（甲 基）丙烯酸正丙酯、（甲基）丙烯酸異丙酯、（甲基）丙烯酸 正丁酯、（甲基）丙烯酸異丁酯、（甲基）丙烯酸三級丁酯 、，（甲基）丙烯酸環己酯、（甲基）丙烯酸-2-乙基己酯酯、 (甲基）丙烯酸月桂酯、（甲基）丙烯酸硬脂酸酯、丙烯酸 癸酯等之（甲基）丙烯酸之碳原子數爲1〜24個之鏈烷基或 環烷基酯；（甲基）丙烯醯胺、N-甲基（甲基）丙烯醯胺、 Ν=·乙基（甲基）丙烯醯胺、雙丙酮丙烯醯胺、N-羥甲基（甲 基）丙烯醯胺、Ν-丁氧基甲基丙烯醯胺等之（甲基）丙烯 醯胺；（甲基）丙烯酸環氧丙酯、環氧丙基（甲基）丙烯醯 胺、烯丙基環氧丙基醚等之含有環氧丙基之乙烯基單體 ;苯乙烯、乙烯基甲苯、α-甲基苯乙烯等之乙烯基芳香 族化合物；丙酸乙烯酯、醋酸乙烯酯、（甲基）丙烯腈、 丙酸乙烯酯、三甲基醋酸乙烯酯、PEOVER單體（Shell化 學製品）等之其他乙烯基單體。 •(ii)由乙二醇、二甘醇、丙二醇、丁二醇、戊二醇、 2，2_二甲基丙二醇、丙三醇、三甲氧基丙烷、季戊四醇 等之多元醇、及於必要時倂用的單元醇或於分子中具有 -6- 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） —U---------裝--------訂--------- (請先閱讀背面之注意事項再填寫本頁) 554016 A7 B7 五、發明說明（5) (請先閱讀背面之注意事項再填寫本頁) 1個環氧丙烯之單環氧化合物，例如CARDULER E(商品名 /Shell化學（株）製品）等所構成之醇成分，與由酞酸酐、 異酞酸、四羥基酞酸酐、六羥基酞酸酐、馬來酸酐、琥 珀酸酐、己二酸、癸二酸、偏苯三酸酐、均苯四甲酸等 之多鹼基酸、及於必要時所倂用之安息香酸或三級丁基 安息香酸燈之單一鹼基酸所構成之酸成分縮合反應而得 之數量平均分子量爲500〜10000，特別是1000〜7000之 範圍內的無油醇酸樹脂；或者與於上述醇成分及酸成分 中所加入之篦麻油、桐油、紅花油、大豆油、亞麻仁油 、妥爾油、椰子油及由該等油脂而來之脂肪酸中至少1 種反應而得，數量平均分子量爲500〜10000，特別是 1000〜7000之酮圍內之油變性醇酸樹脂。 (iii)丙烯酸樹脂或乙烯基樹脂爲接枝於酸醇樹脂、數 量平均分子量在約5000〜約40000、特別在約8000〜約 20000之範圍內的接枝共聚合物。該接枝共聚合物可由 例如如前述（I)所說明之聚合性單體反應成具有聚合性 不飽和基之酸醇樹脂而得。 經濟部智慧財產局員工消費合作社印製 該等之含有羧基之樹脂具有5〜100、以10〜50爲佳、 以30〜50更佳之範圍內之酸價。該樹脂之酸價比5小， 則與塗裝於包含該樹脂之有機溶劑型親水性著色塗料（A) 之塗面上的水性著色塗料（B)之親密性變差，同時由於 包含於該塗膜之水分吸收性降低，產生水性著色塗料（B) 之流動斑痕、滴流等之缺陷，塗膜之美觀性有劣化之傾 向。又，相反地該樹脂之酸價比1 00大，則發現有親水性 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 554016 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明（6) 著色塗料（A)之塗膜本身的耐水性等降低之傾向。 在該含有羧基之樹脂中，由於例如共聚合記載於前述 (b)群之含有羥基聚合性單體等，羥基可一起與羧基倂存 。倂存如此之兩官能基則有助於斯形成之塗膜的硬度、 耐水性、耐候性等之提昇。含有羧基及羥基兩者之樹脂 的羥基値，一般以約10〜約200、特別是15〜100、更特 別爲25〜70之範圍內爲佳。 .作爲爲了中和含有羧基之樹脂的中和劑者，例如可使 用如氨；甲胺、乙胺、等之一級醯胺；二甲基胺、二乙 基胺、二乙醇胺等之二級醯胺；三甲基胺、三乙基胺、 三甲基乙醇胺、三乙醇胺等之三級醯胺。中和劑之使用 量' 相對於樹脂中之羧基，一般以約0 . 1〜約2當量、特 別:以約0.3〜約1 . 2當量之範圍爲佳。 於有機溶劑型親水性著色塗料（A)中所使用的硬化劑， 係有助於交聯硬化上述樹脂，例如可舉出氨基樹脂或嵌 段聚異氰酸酯等。554016 A7 _____ B7 V. Description of the invention (1) The field of branching the invention belongs to (please read the precautions on the back before filling this page) This invention is about the formation of sequential coating of organic solvent-based hydrophilic coloring paints, and water coloring Method for multi-layer coating film of paint and transparent paint. Conventional techniques and lessons It is known to form a multi-layer coating film that sequentially coats organic solvent-based hydrophilic colored paints, water-based colored paints, and clear paints. The uncured coating film of the organic solvent-based hydrophilic coloring paint has strong water absorption. When the water-based coloring paint is coated on the coating surface, the viscosity rises sharply due to the absorption of the water in the coating film. The effect of coating the water-based coloring coating with defects such as rough surface under a humidity atmosphere. Further, the use of an aqueous metallic paint as the water-based coloring paint is not affected by the humidity at the time of painting, has no metal spots, and has the effect of forming a coating film excellent in gloss and vividness. On the other hand, in order to maintain the weather resistance and aesthetics of multilayer coating films, organic solvent-based hydrophilic coloring coatings have excellent concealment with low light transmittance and are preferred to be as thin as possible. Therefore, they have always contained a large amount of Color pigments. As a result, although the concealability of the coating film can be ensured, on the contrary, there is a disadvantage that the physical properties of the coating film are liable to decrease. Solution to Problem Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. The present inventors and others have devoted themselves to a method for eliminating the formation of multilayer coatings of organic solvent-based hydrophilic coatings, water-based coatings, and clear coatings. As mentioned above, the hydrophilic pigmented paint has a small pigment content and is also a thin film, and forms a coating film with excellent concealability, and the physical properties of the coated film will not be reduced. As a result, in the case of hydrophilic coloring paints, together with the coloring pigments, the Chinese National Standard (CNS) A4 specification (210 X 297 mm) is applicable because it contains a certain amount of the paper size. 554016 A7 _______ B7 V. Description of the invention ( 3) Examples of objects to be coated in order to form a multi-layer coating film in accordance with the coating method of the present invention include metal products and / or plastic products. More specifically, (please read the precautions on the back before filling in this page) Examples include automobile bodies of passenger cars, trucks, locomotives, buses, etc. formed using metal products and / or plastics. It is preferable that the surface to be coated is previously subjected to surface treatment (for example, degreasing, zinc phosphate treatment, etc.) by an appropriate method. The organic solvent-based hydrophilic coloring paint (A) can be directly applied to such coatings, but it is more necessary to coat the hydrophilic coloring paint with a base coat paint such as a cationic electrode deposition paint. It is better to apply the middle coating paint and harden the individual coating film to the object to be coated. As such a base coat coating and a middle coat coating, those known per se can be used. The organic solvent-based hydrophilic fluorene coloring paint (A) applied to the object to be coated according to the present invention is a carboxyl-containing resin neutralizer, a hardener, and an average particle diameter containing an acid value in the range of 5 to 100. 20 / zm or less of aluminum powder and color pigment, and then the content of the aluminum powder is 100% by weight of the resin solid part of the organic solvent-based coating in the range of 0.1 to 10 parts by weight. Printed by employees of the Intellectual Property Bureau of the Ministry of Economic Affairs and Consumer Cooperatives as resins containing carboxyl groups used in hydrophilic pigmented coatings (A), if the molecule contains at least one carboxyl group and the acid value is in the range of 5 to 100 The resin of the coating is not particularly limited, and various resins for coatings known per se can be used. The following resins can be cited as representative examples. (i) Copolymerize at least one of the carboxyl group-containing polymerizable monomers of the following group (a) and at least one of the polymerizable monomers of the (c) group that can be copolymerized therewith, and (b) if necessary It is obtained from at least one of the polymerizable monomers containing hydroxyl groups, and the number average molecular weight is about 3,000 to about 40,000, preferably about 5,000. This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm). 554016 Printed by A7 B7, Consumer Cooperatives of the Ministry of Economic Affairs, Intellectual Property, Production Bureau. 5. Description of the invention (4) Acrylic resin or vinyl resin in the range of about 25,000. (a) Group: α, / 3-ethylenically unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, and crotonic acid. Group (b): hydroxyalkyl esters having 1 to 8 carbon atoms in (meth) acrylic acid such as hydroxyethyl (meth) acrylate and hydroxypropyl (meth) acrylate. (c) Group: methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, (formyl) Base) isobutyl acrylate, tertiary butyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, ( (Meth) acrylic acid stearate, decyl acrylate, etc. (meth) acrylic acid alkyl chains or cycloalkyl esters having 1 to 24 carbon atoms; (meth) acrylamidonium, N-methyl (Meth) acrylamide, N = · ethyl (meth) acrylamide, diacetone acrylamide, N-methylol (meth) acrylamide, N-butoxymethacrylamide (Meth) acrylamide; glycidyl (meth) acrylate, glycidyl (meth) acrylamine, allyl glycidyl ether, etc. Monomers; vinyl aromatic compounds such as styrene, vinyl toluene, α-methylstyrene; vinyl propionate, vinyl acetate, (meth) propylene , Vinyl propionate, vinyl trimethyl acetate, PEOVER monomers (Shell Chemical products), the other vinyl monomers. • (ii) Polyols such as ethylene glycol, diethylene glycol, propylene glycol, butanediol, pentanediol, 2,2-dimethylpropylene glycol, glycerol, trimethoxypropane, pentaerythritol, etc., and where necessary The unit alcohol used in the time may have -6 in the molecule. This paper size applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) —U --------- pack ----- --- Order --------- (Please read the notes on the back before filling this page) 554016 A7 B7 V. Description of the invention (5) (Please read the notes on the back before filling this page) 1 A single epoxy compound of propylene oxide, such as an alcohol component composed of CARDULER E (trade name / Shell Chemical Co., Ltd.), and phthalic anhydride, isophthalic acid, tetrahydroxyphthalic anhydride, hexahydroxyphthalic anhydride, Polybasic acids such as maleic anhydride, succinic anhydride, adipic acid, sebacic acid, trimellitic anhydride, pyromellitic acid, etc., and a single base of benzoic acid or tertiary butyl benzoic acid lamp, if necessary An oil-free alkyd tree having a number average molecular weight of 500 to 10,000, especially 1,000 to 7,000, obtained by the condensation reaction of an acid component composed of an acid Or at least one of ramie oil, tung oil, safflower oil, soybean oil, linseed oil, tall oil, coconut oil, and fatty acids derived from these oils and fats added to the alcohol and acid components mentioned above Thus, the oil-denatured alkyd resin having a number-average molecular weight of 500 to 10,000, especially 1,000 to 7000, is contained in the ketone. (iii) An acrylic resin or a vinyl resin is a graft copolymer which is grafted onto an acid-alcohol resin and has a number average molecular weight of about 5,000 to about 40,000, particularly in a range of about 8000 to about 20,000. The graft copolymer can be obtained, for example, by reacting a polymerizable monomer as described in (I) above to an acid-alcohol resin having a polymerizable unsaturated group. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. These carboxyl-containing resins have an acid value in the range of 5 to 100, preferably 10 to 50, and more preferably 30 to 50. If the acid value of the resin is less than 5, the affinity with the water-based coloring paint (B) coated on the coating surface of the organic solvent-type hydrophilic coloring paint (A) containing the resin is deteriorated. The moisture absorption of the coating film is reduced, causing defects such as flow marks and drips of the water-based colored paint (B), and the appearance of the coating film tends to deteriorate. On the contrary, if the acid value of the resin is greater than 100, it is found that the paper is hydrophilic. The paper size applies to the Chinese National Standard (CNS) A4 (210 X 297 mm). 554016 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. A7 B7 5. Description of the invention (6) The water resistance of the coating film of the colored paint (A) tends to decrease. In this carboxyl group-containing resin, for example, a hydroxyl group-containing polymerizable monomer described in the above-mentioned (b) group is copolymerized, so that the hydroxyl group may coexist with the carboxyl group. The existence of such two functional groups can help improve the hardness, water resistance, and weather resistance of the coating film formed by Stanley. The hydroxyl hydrazone of a resin containing both a carboxyl group and a hydroxyl group is preferably in the range of about 10 to about 200, particularly 15 to 100, and more particularly 25 to 70. As a neutralizer for neutralizing a resin containing a carboxyl group, for example, secondary fluorene such as ammonia; methylamine, ethylamine, and the like; secondary fluorene such as dimethylamine, diethylamine, and diethanolamine can be used. Amine; tertiary ammonium amines such as trimethylamine, triethylamine, trimethylethanolamine, and triethanolamine. The amount of the neutralizer used is generally about 0.1 to about 2 equivalents relative to the carboxyl group in the resin, and particularly: about 0.3 to about 1.2 equivalents. The hardening agent used in the organic solvent-based hydrophilic coloring paint (A) is used to crosslink and harden the resin, and examples thereof include amino resins and block polyisocyanates.
I 作爲醯胺樹脂者，例如可舉出三聚氰胺、苯并鳥糞胺、 三嗪系化合物、尿素、二氰基肼等之氨基化合物與甲醛 之縮合或共縮合物，特別以三聚氰胺甲醛樹脂爲佳。適 於使用碳數爲.1-8個之單元醇反應成該等之縮合物的烷基 醚化氨基樹脂。 嵌段聚異氰酸酯化合物係以封端劑來切斷聚異氰酸酯 化合物之異氰酸酯基的化合物，於封端劑之解離溫度（例 如約100〜約170°C)加熱，則封端劑解離，游離異氰酸酯 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -----------裝--------訂--------- (請先閱讀背面之注音？事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 554016 Α7 Β7 五、發明說明（7) 基再生，可與交聯性官能基反應。 聚異氰酸酯化合物係於1分子中具有2個以上之異氰酸 酯基的化合物，例如可舉出甲苯撐二異氰酸酯、二苯基 甲烷二異氰酸酯、苯二甲基二異氰酸酯、萘二異氰酸酯 等之芳香族二異氰酸酯；四甲撐二異氰酸酯、六甲撐二 異氰酸酯、二聚物酸二異氰酸酯、賴氨酸二異氰酸酯等 之脂肪族二異氰酸酯；甲撐雙（環己基異氰酸酯）、異佛 爾酮二異氰酸酯、甲基環己烷基二異氰酸酯、環己烷基 二異氰酸酯、環戊烷基二異氰酸酯等之環狀脂肪族二異 氰酸酯；該等之聚異氰酸酯化合物之縮二脲型、三聚異 氰酸環型、含有與聚醇類反應之游離異氰酸酯基之預聚 物等。又，作爲封端劑者，舉例有酚類、肟類、內醯胺 類、活性甲撐系、醇類、酸醯胺系、醯亞胺系、胺系、 咪唑系、尿素類、氨基甲醯酸系、亞胺系、硫醇類等。 嵌段聚異氰酸酯化合物之分子量約爲200〜約10000，特 別以約500〜約5000之範圍內爲佳。 親水性著色塗料（A)中之含有羧基之樹脂與硬化劑之配 合比例係以兩者之合計固體部份重量爲基準，一般而言 ，含有羧基之樹脂爲約50〜約90%，以約60〜約85%爲 佳，然後硬化劑爲約10〜約50%，以約15〜約40%佳之 範圍內爲適。 有機溶劑型親水性著色塗料（A)係添加於上述之含有羧 基之樹脂的中和劑及硬化劑中，再者，係含有平均粒徑 2〇μιη以下之鋁粉末及著色顏料。 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） ---------I I IAW ^ I-----—訂- ----- (請先閱讀背面之注意事項再填寫本頁) 554016 A7 一 B7 五、發明說明（1G) (請先閱讀背面之注意事項再填寫本頁) 醇、二丙二醇及其單醚、丙酮、雙丙酮醇等之親水性有 機溶劑爲佳。該等有機溶劑一般在20°C，爲每100重量 份的水具有50重量份以上、特別以70重量份以上之水溶 解性爲佳。相對於全部之有機溶劑之親水性有機溶劑之 比例，以包含於塗裝時之親水性著色塗料（A )之有機溶劑 的總合重量爲基準，係在20重量％以上，特別在40〜100 童量％之範圍內爲適。 含有上述各成分之親水性著色塗料（A)，以硬化塗膜爲 基準，可具有l〇//m以下、特別在8〜5em之範圍內之塗 底隱蔽性。此處，塗底隱蔽性係塗裝該親水性著色塗料 (A )於黑白之方格花紋的表面上，而不能目視透過該塗膜 之模樣之最薄塗膜之膜厚。 經濟部智慧財產局員工消費合作社印製 親水性著色塗料（A)雖可直接塗裝於被塗物上，但是在 塗裝電極沉積塗料（陰離子型、陽離子型）等之底塗層塗 料以及更進一步的情況來塗裝中塗層塗料，則以於硬化 後塗裝該等塗膜爲佳。塗裝係以霧化型式來進行爲佳， 例如，可使用空氣噴霧器、無氣噴霧器、空氣霧化型式 或迴轉式靜電塗裝機等來進行。塗裝時之親水性著色塗 料（A)的黏度以調整至於福特杯（Ford cup)#4中約15〜 60秒、特別在15〜約35秒（20°C)之範圍內爲佳，塗裝膜 厚係硬化塗膜中均爲較厚於塗底隱蔽膜厚，例如以約5〜 約25vm、特別在約8〜約20//m之範圍內爲適。 於本發明中，塗裝親水性著色塗料（A)於被塗物上， 該·塗膜尙未硬化，以從必要時在室溫下放置1〜10分鐘 -12- 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 554016 A7 B7 ^___ 經濟部智慧財產局員工消費合作社印製 發明說明（n) 的時間範圍內，塗裝水性著色塗料（B)於該未硬化塗面 上爲佳。 (請先閱讀背面之注意事項再填寫本頁) 水性著色塗料（B)係以水爲主要溶劑或分散劑之水性 塗料，具體而言，係使用含有水性乙烯基樹脂及/或水 性聚酯樹脂、硬化劑及著色顏料之水性著色塗料爲適。 作爲水性著色塗料（B)中的水性乙烯基樹脂者，可使 用其本身既知者。例如，可舉出共聚合含有羧基聚合性 單體、含有羥基聚合性單體及其他聚合性單體而得，數 量平均分子量爲約3000〜約40000、而以約5000〜約 20000爲佳，酸價爲約20〜約100、而以約30〜約80爲佳 ，羥基爲約20〜約200、而以約30〜150爲佳之水性乙烯 基.樹脂。 作爲含有羧基聚合性單體者，舉例有（甲基）丙烯酸、 馬來酸、衣康酸等之單乙烯基性不飽和羧酸類；又，作 爲含有羥基聚合性單體者，舉例有（甲基）丙烯酸-2-羥基 乙酯、（甲基）丙烯酸-2-羥基丙酯等之單乙烯基性不飽和 羧酸之羥基烷基酯類等。作爲其他聚合性單體者，例如 可舉出（甲基）丙烯酸甲酯、（甲基）丙烯酸乙酯、（甲基） 丙烯酸正丁酯、（甲基）丙烯酸異丁酯、（甲基）丙烯酸-2-乙基己酯、（甲基）丙烯酸月桂基酯、（甲基）丙烯酸癸酯 等之單乙烯基性不飽和羧酸類之烷基酯類；（甲基）丙烯 醯胺、N-羥甲基（甲基）丙烯醯胺、二丙酮丙烯醯胺等之 丙烯醯胺衍生體；（甲基）丙烯酸縮水甘油酯等之單乙烯 基性不飽和羧酸之縮水甘油酯類；醋酸乙烯酯、丙酸乙 -13- 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 經濟部智慧財產局員工消費合作社印製 554016 Α7 Β7 五、發明說明（12) 烯酯等之飽和羧酸之乙烯基酯類；苯乙烯、α-甲基苯 乙烯、乙烯基甲苯等之芳香族不飽和單體。 因此所得之乙烯基樹脂可爲以氨或三甲基胺、單乙醇 胺、二乙醇胺、三乙醇胺、二甲胺基乙醇等之胺類，或 氫氧化鈉等之鹼金屬之氫氧化物等之鹼性物質來中和之 非’水溶性之水分散性。 又，於使用或不使用含有羧基聚合性單體中，亦可使 用分散共聚合含有羥基聚合性單體及其他聚合性單體而 得之共聚合體於水中所形成之水分散體作爲水性乙烯基 樹脂。 作爲水性聚酯樹脂者，關於作爲於前述親水性著色塗 料（Α)中之含有羧基樹脂的酸醇樹脂所舉例之醇成分及酸 成分，使其縮合反應而得之聚酯樹脂之中，可使用酸價 在15〜100、特別是20〜80，然後羥基價在20〜200、特 別是30〜150之範圍內爲適。 作爲水性著色塗料（Β)中之硬化劑者，舉例有三聚氰胺 、苯并鳥糞胺、三嗪系化合物、尿素、二氰基肼等與甲 醛之縮合或共縮合物，更進一步以碳數1〜8之單醇類變 性者或含有羧基之胺基樹脂。其中特別以醇類酯化所得 之三聚氰胺樹脂爲佳。該等之硬化劑亦可無妨使用親水 性及疏水性者。 水性著色塗料（Β)中，水性乙烯基樹脂及/或水性聚酯 樹脂與硬化劑之配合比例，一般係以兩者總合之固體部 份重量爲基準，樹脂成分爲約50〜約90重量％、而以約 -14- 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -----------裝---I----訂-------- (請先閱讀背面之注意事項再填寫本頁) 554016 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明（汐 60〜約85重量％爲佳，然後硬化劑成分爲約1〇〜約50重 量％、而以約1 5〜約40重量％之範圍內爲佳。 水性著色塗料（B)係形成著色成實體色調、金屬色調 、光干涉色調等之塗膜者，該著色之範圍可任意爲透過 該塗膜見到鄰接於下層之親水性著色塗料（A)之塗膜的色 調之透明，或爲不可見該色調之不透明，任何一種亦無 妨。 形成實體色調之塗膜的塗料，係以如前述關於親水型 著色塗料（A)所示範之著色顏料來配合而得。形成金屬色 調之塗膜的塗料，係以配合鋁片等之已知的金屬顏料來 調製；又，形成光干涉色調之塗膜的塗料，係以配合氧 化鈦等之金屬氧化物將表面覆蓋之鱗片狀雲母粉末等之 干涉色顏料來調製。 水性著色塗料（B)可與前述親水性著色塗料（A )相同地 來塗裝，塗裝時之黏度通常爲以福特杯#4約10〜50秒鐘 (20°C)，特別可爲約5〜約30秒鐘（20°C)，又，塗裝厚度 以加熱硬化塗膜爲基準，以在約5〜約3〇em、特別在約10 〜約2〇vm之範圍內爲佳。 以本發明之方法，如上述來塗裝有機溶劑型親水性著 色塗料（A)及水性著色塗料（B)，由於在室溫下放置1〜 10分鐘範圍，或由於在約50〜約100°C、而最好在約60 〜約80t下1〜20分鐘範圍之預加熱，而以塗裝透明塗 料（C)爲佳。 透明塗料（C)係爲形成透明塗膜於必要時經預加熱之未硬 -15- 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） •--^----r I--------11--訂--- (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 554016 A7 B7 五、發明說明（14) 化水性著色塗料（B)之塗面的塗料，可更上一層來提昇多 層塗膜之美觀性、潤飾的外觀、耐候性、耐藥品性、耐 水性、耐濕性等。具體而言，舉例有由丙烯酸樹脂（基 材樹脂）及胺基樹脂（交聯）所形成之熱硬化性樹脂組成物 爲調漆料之有機溶劑型或非水分散液型之塗料，更可適 r地配合紫外線吸收劑、著色劑等。 透明塗料（c)係由公害防止、節省資源的觀點，以高固 體部份型爲佳，具體而言，例如希望調整塗裝時之不揮 發部份濃度至約35重量％以上，以約40〜約80重量％爲佳 ，以約40〜約80重量％更佳之範圍內。 透明塗料（C)可與親水性著色塗料（A)相同地來塗裝， 調整塗裝時之黏度至以福特杯#4約15〜約60秒鐘（20°C) ，特別是約20〜約40秒鐘（2(TC)，塗裝成以硬化塗膜爲 基準，爲約5〜約50//m、特別爲約20〜約45/zm之範圍內 的膜厚爲佳。 以依次重複塗裝如以上所述之親水性著色塗料（A )、水 性著色塗料（B)及透明塗料（C)而形成之塗膜，以3次塗裝 1次烘乾方式或3次塗裝2次烘乾方式，可於約120〜約 180°C、以約130〜約16(TC爲佳之溫度下加熱約15〜約45 分鐘來硬化，可如此依照本發明來形成多層塗膜。 發明之效果 根據以上所述之本發明的方法，得到如以下所述之效 果。 (1)在形成依次塗裝親水性著色塗料（A)、水性著色塗 •16- 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -----------裝--------訂---------^9. (請先閱讀背面之注意事項再填寫本頁) 554016 A7I As the amine resin, for example, a condensation or co-condensation of an amino compound such as melamine, benzoguanamine, a triazine compound, urea, dicyanohydrazine, and formaldehyde, and a melamine formaldehyde resin is particularly preferred. . Suitable for the use of alkyl etherified amino resins having a carbon number of .1-8 units to react with these condensates. The block polyisocyanate compound is a compound that cuts off the isocyanate group of the polyisocyanate compound with a blocking agent. When the blocking agent is heated at the dissociation temperature of the blocking agent (for example, about 100 to about 170 ° C), the blocking agent is dissociated and the free isocyanate is Paper size applies to China National Standard (CNS) A4 (210 X 297 mm) ----------- installed -------- order --------- (please Read the phonetic on the back? Matters and then fill out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 554016 Α7 Β7 V. Description of the invention (7) The radical can be reacted with crosslinkable functional groups. The polyisocyanate compound is a compound having two or more isocyanate groups in one molecule, and examples thereof include aromatic diisocyanates such as toluene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, and naphthalene diisocyanate. ; Aliphatic diisocyanates of tetramethylene diisocyanate, hexamethylene diisocyanate, dimer acid diisocyanate, lysine diisocyanate, etc .; methylene bis (cyclohexyl isocyanate), isophorone diisocyanate, methyl ring Cyclic aliphatic diisocyanates such as hexane diisocyanate, cyclohexane diisocyanate, cyclopentyl diisocyanate, etc .; biuret type, trimeric isocyanate ring type of these polyisocyanate compounds, containing Prepolymers of free isocyanate groups in polyol reactions. Examples of the end-capping agent include phenols, oximes, lactams, reactive methylenes, alcohols, ammoniums, amines, amines, imidazoles, ureas, and carbamates. Acetic acid, imine, thiol, etc. The molecular weight of the block polyisocyanate compound is about 200 to about 10,000, particularly preferably in the range of about 500 to about 5000. The mixing ratio of the carboxyl group-containing resin and the hardener in the hydrophilic coloring paint (A) is based on the total solid weight of the two. Generally speaking, the carboxyl group-containing resin is about 50 to about 90%. It is preferably 60 to about 85%, and then the hardener is about 10 to about 50%, and a range of about 15 to about 40% is suitable. The organic solvent-based hydrophilic coloring paint (A) is added to the neutralizer and hardener of the carboxyl group-containing resin described above, and further contains aluminum powder and a coloring pigment having an average particle diameter of 20 μm or less. This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) --------- II IAW ^ I ------ Order- ----- (Please read the back first Please note this page before filling this page) 554016 A7 a B7 V. Description of the invention (1G) (Please read the notes on the back before filling this page) Hydrophilicity of alcohol, dipropylene glycol and its monoether, acetone, diacetone alcohol, etc. Organic solvents are preferred. These organic solvents are generally at 20 ° C and preferably have a water solubility of 50 parts by weight or more, particularly 70 parts by weight or more, per 100 parts by weight of water. The proportion of the hydrophilic organic solvent with respect to all organic solvents is based on the total weight of the organic solvent of the hydrophilic coloring paint (A) included in the coating, and is more than 20% by weight, particularly 40 to 100. It is suitable to be within the range of% of child quantity. The hydrophilic coloring paint (A) containing each of the above components may have a base concealability of 10 // m or less, particularly in the range of 8 to 5em, based on the cured coating film. Here, the concealment of the undercoating is applying the hydrophilic colored paint (A) on the surface of the black and white checkered pattern, and the film thickness of the thinnest coating film through which the coating film looks can not be visually observed. Although the hydrophilic pigmented coating (A) printed by the employee's consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs can be directly applied to the object to be coated, it can be used as a primer coating for electrodeposition coating (anionic, cationic) and more In further cases, it is better to apply these coating films after hardening. The coating is preferably performed by an atomizing type, and for example, an air sprayer, an airless sprayer, an air atomizing type, or a rotary electrostatic coating machine can be used. The viscosity of the hydrophilic pigmented coating (A) at the time of coating should be adjusted to about 15 to 60 seconds in Ford cup # 4, especially in the range of 15 to about 35 seconds (20 ° C). The thickness of the hardened coating film is thicker than the thickness of the bottom cover film, for example, about 5 to about 25 vm, particularly about 8 to about 20 // m. In the present invention, a hydrophilic coloring paint (A) is applied to the object to be coated, and the coating film is not hardened, so that it can be left at room temperature for 1 to 10 minutes when necessary. Standard (CNS) A4 specification (210 X 297 mm) 554016 A7 B7 ^ ___ Apply the water-based coloring paint (B) to the unhardened material within the time frame printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs on printing the invention statement (n) Better on coated surfaces. (Please read the precautions on the back before filling this page) Water-based pigmented paint (B) is water-based paint with water as the main solvent or dispersant. Specifically, it contains water-based vinyl resin and / or water-based polyester resin. , Hardeners and pigments are suitable for water-based coloring coatings. As the water-based vinyl resin in the water-based coloring paint (B), those known per se can be used. For example, it can be obtained by copolymerizing a carboxyl group-containing polymerizable monomer, a hydroxyl group-containing polymerizable monomer, and other polymerizable monomers. The number average molecular weight is about 3000 to about 40,000, and preferably about 5000 to about 20,000. Water-based vinyl resins having a valence of about 20 to about 100, preferably about 30 to about 80, hydroxyl groups of about 20 to about 200, and preferably about 30 to 150. Examples of the carboxyl polymerizable monomer include monovinyl unsaturated carboxylic acids such as (meth) acrylic acid, maleic acid, and itaconic acid; and examples of the hydroxy polymerizable monomer include (a (Meth) acrylic acid, such as 2-hydroxyethyl acrylate, 2-hydroxypropyl (meth) acrylate, and the like, and hydroxyalkyl esters of monovinyl unsaturated carboxylic acids. Examples of other polymerizable monomers include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, and (meth) Alkyl monovinyl unsaturated carboxylic acids such as 2-ethylhexyl acrylate, lauryl (meth) acrylate, and decyl (meth) acrylate; (meth) acrylamide, N -Acrylamide derivatives such as methylol (meth) acrylamide, diacetone acrylamide; glycidyl esters of monovinyl unsaturated carboxylic acids such as glycidyl (meth) acrylate; acetic acid Vinyl Ester, Ethyl Propionate 13- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 554016 Α7 Β7 5. Description of the invention (12) Ester Such as vinyl esters of saturated carboxylic acids; aromatic unsaturated monomers such as styrene, α-methylstyrene, vinyl toluene and the like. Therefore, the obtained vinyl resin may be an alkali such as ammonia or trimethylamine, monoethanolamine, diethanolamine, triethanolamine, dimethylaminoethanol, or the like, or an alkali metal hydroxide such as sodium hydroxide. Non-'water-soluble water-dispersible substances to neutralize sexual substances. Furthermore, in the case of using or not using a carboxyl group-containing polymerizable monomer, an aqueous dispersion formed by copolymerizing a copolymer containing a hydroxy polymerizable monomer and other polymerizable monomers in water may be used as the aqueous vinyl group. Resin. As the water-based polyester resin, among the polyester resins obtained by condensation reaction of the alcohol component and the acid component exemplified as the carboxylic resin-containing acid-alcohol resin in the hydrophilic coloring paint (A), the It is appropriate to use an acid value in the range of 15 to 100, especially 20 to 80, and then a hydroxyl value in the range of 20 to 200, especially 30 to 150. Examples of the hardening agent in the water-based coloring paint (B) include condensation or co-condensation of melamine, benzoguanamine, triazine-based compounds, urea, dicyanohydrazine, and the like with carbon number 1 Monoalcoholic denaturants of ~ 8 or amine-based resins containing carboxyl groups. Among them, a melamine resin obtained by esterification of an alcohol is particularly preferable. As these hardeners, it is also possible to use hydrophilic and hydrophobic ones. The proportion of water-based vinyl resin and / or water-based polyester resin and hardener in the water-based coloring paint (B) is generally based on the total solid weight of the two, and the resin content is about 50 to 90 weight %, And about -14- This paper size is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) ----------- installed --- I ---- ordered- ------ (Please read the precautions on the back before filling this page) 554016 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (Xi 60 ~ about 85% by weight is better, then hardener The composition is preferably about 10 to about 50% by weight, and preferably in a range of about 15 to about 40% by weight. The water-based coloring paint (B) is a coating film for forming a solid color tone, a metallic color tone, and a light interference color tone. Alternatively, the range of the coloration may be any of the transparency of the hue of the coating film of the hydrophilic coloring paint (A) adjacent to the lower layer seen through the coating film, or the opacity of which the hue is not visible, and any of them may be used. The paint of the hue coating film is the same as that exemplified in the above-mentioned hydrophilic pigmented paint (A). It is obtained by mixing color pigments. The paint for forming a coating film with a metallic hue is prepared by mixing with known metal pigments such as aluminum flakes; and the paint for forming a coating film with a light interference tone is prepared with a titanium oxide Metal oxides are prepared by interfering with pigments such as flaky mica powder covering the surface. The water-based coloring paint (B) can be applied in the same manner as the aforementioned hydrophilic coloring paint (A), and the viscosity at the time of painting is usually ford. Cup # 4 is about 10 to 50 seconds (20 ° C), especially about 5 to about 30 seconds (20 ° C), and the thickness of the coating is based on the heat-hardened coating film, in about 5 to about 30 ohms, particularly preferably in the range of about 10 to about 20 vm. In the method of the present invention, the organic solvent-based hydrophilic coloring paint (A) and the water-based coloring paint (B) are applied as described above. Place at room temperature for 1 to 10 minutes, or because of preheating at about 50 to about 100 ° C, and preferably at about 60 to about 80t for 1 to 20 minutes, and apply clear coating (C) as Clear coating (C) is a non-hardened film that is pre-heated if necessary to form a clear coating film. Applicable to China National Standard (CNS) A4 (210 X 297 mm) •-^ ---- r I -------- 11--order --- (Please read the precautions on the back before (Fill in this page) Printed by the Employees ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 554016 A7 B7 V. Description of the invention (14) The coating of the water-based coloring coating (B) can be further enhanced to improve the aesthetics of multi-layer coatings, Retouched appearance, weather resistance, chemical resistance, water resistance, moisture resistance, etc. Specific examples include thermosetting resin compositions made of acrylic resin (base resin) and amine resin (crosslinking). It is an organic solvent-based or non-aqueous dispersion-type paint for adjusting paints. It can also be appropriately blended with ultraviolet absorbers and colorants. The transparent coating (c) is from the viewpoint of pollution prevention and resource saving, and it is preferably a high solid part type. Specifically, for example, it is desired to adjust the concentration of the non-volatile part during coating to about 35% by weight or more and about 40%. It is preferably about 80% by weight, and more preferably about 40 to about 80% by weight. The clear paint (C) can be applied in the same way as the hydrophilic pigmented paint (A). Adjust the viscosity of the paint to Ford Cup # 4 for about 15 to 60 seconds (20 ° C), especially about 20 to About 40 seconds (2 (TC), coating is based on a hardened coating film, and the film thickness is preferably in the range of about 5 to about 50 // m, especially about 20 to about 45 / zm. In order The coating film formed by repeating the coating of the hydrophilic coloring paint (A), water-based coloring paint (B), and clear paint (C) as described above, 3 times of painting, 1 time of drying, or 3 times of painting 2 The secondary drying method can be hardened at about 120 to about 180 ° C at about 130 to about 16 ° C (about 15 to about 45 minutes), and a multi-layer coating film can be formed in accordance with the present invention. Effects According to the method of the present invention described above, the following effects are obtained: (1) A hydrophilic coloring coating (A) and a water-based coloring coating are sequentially applied in the formation of the paper. 16- This paper applies Chinese national standards (CNS) ) A4 size (210 X 297 mm) ----------- install -------- order --------- ^ 9. (Please read the note on the back first (Fill in this page again) 554016 A7
經濟部智慧財產局員工消費合作社印製 五、發明說明（1 (註2):酯化反應新戊二醇ο]莫耳、三羥甲基丙烷 0.3莫耳酞酸酐〇.4莫耳及己二酸ο」莫耳之後，添 加偏苯三酸酐0.03莫耳來進一步反應，然後加入丁基 溶纖劑，並得到酸價40、數量平均分子量約6，〇〇〇及 樹脂固體部份70%之聚酯樹脂溶液。於該聚酯樹脂中 加入二甲胺基乙醇來中和，然後以異丙醇來稀釋（固 體部份50%)。 (註3):三井SAITECH公司製，商品名，水溶性三聚氰 胺樹脂。 (註4):東洋鋁業公司製，商品名，鋁膠。 • 平均粒徑12 μ m (註 5):秒/福特杯（Ford Cup)#4/2(TC。 (註6):塗底隱蔽性係塗裝親水性著色塗料（A)於黑白 之市松模樣表面上，透過該塗膜之模樣而不能目視之 最薄塗膜之膜厚（//m)。 3)水性著色塗料（B) 基於記載於下列表2之成分及配合量來混合得到水性 著色塗料（B)。黏度及固體部份含有比例之調整係加 入去離子水來進行。配合量爲固體部份比。 表2 水性著色塗料（B) B-1 B-2 丙烯酸樹脂中和溶液（註1) 50 50 聚酯樹脂中和溶液（註2) 50 50 丙烯酸懸浮液 （註7) 100 100 SAIMEL370 (註 3) 34 34 鋁膠 （註8) - 2 Blue-G316 5 - 塗料固體部份（％ ) 25 25 黏度 （註5) _ 30 30 -19- 本紙張尺度適角中國國家標準（CNS)A4規格（210 X 297公t ) ------— 裝 — ------訂------ (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 554016 A7 _______ B7 五、發明說明（1 (註7):加入去離子水140份、30%「Newcol 707SF」 (界面活性劑，日本乳化劑（株）製，商品名）2.5份及下 ‘述之單體混合物（1 ) 1份，於氮氣氣流中攪拌混合，於 60°C下加熱，加入3%過硫酸銨水溶液3份。其次，提 高溫度至80°C後，加入由單體混合物（1)79份、 「Newcol 707SF」2.5份、3%過硫化錳水溶液4份及去 離子水42份所構成之單體乳化物於反應容器中進行4小 時。然後進行1小時之熟化。再者，於80°C下同時地將 下述單體混合物（2)20.5份和3%過硫酸銨水溶液4份滴 .入反應容器中進行1 . 5小時。然後，1小時熟化，並以去 離子水30份來稀釋。添加去離子水於過濾液中，以二甲 胺基乙醇調整至PH7.5，得到固體部份含有率20%之丙 烯酸樹脂懸浮液。 單體混合物（1 ):甲基丙烯酸甲酯55份、苯乙烯8份、 丙烯酸正丁酯9份、丙烯酸2-羥基乙酯5份、1，6-己 二醇二丙烯酸酯2份及甲基丙烯酸1份。 單體混合物（2):甲基丙烯酸甲酯5份、丙烯酸正丁酯7 份·丙烯酸2-乙基己酯5份、甲基丙烯酸3份及 「Newcol 707SF」0.5 份。 (註8):鋁膠891K :東洋鋁業公司製，商品名。 4)透明塗料（C)= (C-1) 以SWAZOLE#1000(COSMO石油公司製，商品名，芳香烴溶 劑）來調整由丙烯酸樹脂溶液（註9 ) 57份、丙烯酸樹脂非 -20- 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） —1^—k-----·裝--------訂--------- (請先閱讀背面之注意事項再填寫本頁) 554016 A7 B7 五、發明說明（汐 (請先閱讀背面之注音？事項再填寫本頁) 水分散液（註10) 50份、SAIMER303 (註11) 30份、25%十 二烷基苯磺酸溶液4份及BYK- 300(註12)0.5份所構成之 混合物至黏度30秒（福特杯Ford Cup#4/20°C))，得到樹 脂固體部份55%之透明塗料（C-1)。 (註9)丙烯酸樹脂溶液：於反應容器中加入「SWAZ0LE #1000」40份並於12(TC下加熱，其中加入由苯乙烯30 份、丙烯酸丁酯35份、丙烯酸-2-乙基己酯10份、丙嫌 酸羥基乙酯25份及α，α 偶氮二異丁腈4份所構成之 單體混合物聚合3小時而得的樹脂爲羥値120、數量平 均分子量約6,000、樹脂固體部份70%。 經濟部智慧財產局員工消費合作社印製 (註10)丙烯酸樹脂非水分散液：於反應器中置入UVERN 28-60(三井東壓化學（株）製，商品名，三聚氰胺樹脂 溶液，固體部份60% ) 58份、正庚烷30份及苯醯過氧 化物0.15份，從將其加熱至95°C開始，於3小時內滴 入由苯乙烯15份、丙烯腈9份、甲基丙烯酸甲酯13 份、丙烯酸甲酯15份、丙烯酸正丁酯1.8份、丙烯酸 2-乙基己酯10份、丙烯酸1.2份、苯醯過氧化物 〇· 5 份、正丁醇 5 份、「SHELLZOLE 140」（Shel 1 石油公 司製，商品名）30份及正庚烷9份所構成之單體混合 物。然後從此1小時後，在1小時內滴入第三丁基過 0CTATE 0.65 份及「SHELLZOLE 140」3.5 份。然後，在 接著保持95°C之溫度地進行2小時攪拌之後，減壓除去 溶劑，得到樹脂固體部份60%、蠟黏度A(加登納氣泡黏 度）之丙烯酸樹脂非水分散液。 (註11)SAIMER .303 :三井SAITECH日本公司製，商品 -21- 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 554016 A7 _B7_ 五、發明說明（22) 良（7cmx 7cm之測試板上生鏽2個以下）；△:表示稍差 (7cmx 7cm之測試板上生鏽3〜9個）；X :表示劣（7cmx 7cm之測試板上生鏽10個以上）。 — I:---：------·裝--------訂---------MWI (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 4 2 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 554016 修]i1 ^^—-iSA五、發明說明（2) 具有特定平均粒徑之鋁粉末，發現可達致本目的，達成本 發明之完成。 因此，根據本發明，提供一種多層塗膜形成方法，其特 徵爲依序塗布有機溶劑型親水性著色塗料（A )、水性著色 塗料（B )及透明塗料（C )於被塗物上，由於加熱該等塗膜 而硬化來形成多層塗膜的方法，其中親水性著色塗料（A)含有 酸價爲5〜1 00之範圍內之含有羧基之樹脂中和物、 硬化劑、平均粒徑20 // m以下之鋁粉末及著色顏料，然 後該鋁粉末之含有率就相對於樹脂固體部份每100重量份而言 爲在0.1〜10重量份之範圍內。 於本發明中，塗裝水性著色塗料（B )於有機溶劑型親 水性著色塗料（A )之未硬化塗膜面上，並且由於包含於 親水性著色塗料（A )塗膜中的已中和之含有羧基之樹脂 顯示強吸水性，吸收了塗裝於該塗膜之水性著色塗料 (B )塗膜中的水分，由於該黏度急劇地上升，即使在低溼 度氛圍氣體下塗裝該水性著色塗料也少有發生表面粗糙等 缺陷。又，使用水性著色塗料（B )及金屬塗料，不會受塗 裝時的溼度影響，沒有金屬斑點，可形成光澤鮮豔性優異 之塗膜。而且，根據本發明之方法，在親水性著色塗料 中’和著色顏料一起，由於含有特定量之具有特定平均粒 徑之鋁粉末，即使著色顏料之含有率少，也可以薄膜形成 隱蔽性優異之塗膜，而且得到所謂塗膜物理性能不會降低 的顯著效果。 以下，更詳細說明關於本發明之塗裝方法。 554016Printed by the Employees' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (1 (Note 2): Esterification reaction of neopentyl glycol ο] Moore, trimethylolpropane 0.3 Molar phthalic anhydride 0.4 Molar and hexamethylene After the diacid ο ″ Mohr, add 0.03 Molar trimellitic anhydride for further reaction, and then add butyl cellosolve to obtain a polyester resin solution with an acid value of 40, a number average molecular weight of about 6,000, and a resin solids content of 70% Add dimethylaminoethanol to this polyester resin to neutralize it, and then dilute it with isopropyl alcohol (50% solids). (Note 3): Mitsui SAITECH, trade name, water-soluble melamine resin. (Note 4): Made by Toyo Aluminum Co., Ltd., trade name, aluminum glue. • Average particle size 12 μm (Note 5): seconds / Ford Cup # 4/2 (TC. (Note 6): coated The bottom concealment is the thickness of the thinnest coating film (// m) that is coated with a hydrophilic coloring paint (A) on the surface of the black and white Ichimatsu pattern and that cannot be seen through the pattern of the coating film. B) Water-based colored paint (B) is obtained by mixing based on the ingredients and blending amounts described in Table 2 below. Viscosity and solid content Proportional adjustment is performed by adding deionized water. The blending amount is the ratio of solids. Table 2 Water-based coloring paint (B) B-1 B-2 acrylic resin neutralization solution (Note 1) 50 50 polyester resin neutralization Solution (Note 2) 50 50 Acrylic Suspension (Note 7) 100 100 SAIMEL370 (Note 3) 34 34 Aluminum glue (Note 8)-2 Blue-G316 5-Coating solids (%) 25 25 Viscosity (Note 5) _ 30 30 -19- The size of this paper is in accordance with Chinese National Standard (CNS) A4 (210 X 297 metric t) -------- Packing------- Order ------ (Please (Please read the notes on the back before filling this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 554016 A7 _______ B7 V. Invention Description (1 (Note 7): Add 140 parts of deionized water, 30% "Newcol 707SF" ( Surfactant, 2.5 parts by Japan Emulsifier Co., Ltd. and 1 part of the monomer mixture (1) described below. Stir and mix in a nitrogen stream, heat at 60 ° C, and add 3% persulfuric acid. 3 parts of ammonium aqueous solution. Secondly, after raising the temperature to 80 ° C, add 79 parts of monomer mixture (1), 2.5 parts of "Newcol 707SF", and 3% manganese persulfate in water. The monomer emulsion composed of 4 parts of liquid and 42 parts of deionized water was subjected to a reaction container for 4 hours. Then, it was aged for 1 hour. Furthermore, the following monomer mixture (2) was simultaneously prepared at 80 ° C. 20.5 parts and 4% 3% ammonium persulfate aqueous solution were dropped into the reaction vessel for 1.5 hours. Then, it was aged for 1 hour and diluted with 30 parts of deionized water. Deionized water was added to the filtrate, and the pH was adjusted to 7.5 with dimethylaminoethanol to obtain an acrylic resin suspension having a solid content of 20%. Monomer mixture (1): 55 parts of methyl methacrylate, 8 parts of styrene, 9 parts of n-butyl acrylate, 5 parts of 2-hydroxyethyl acrylate, 2 parts of 1,6-hexanediol diacrylate, and formic acid 1 part acrylic. Monomer mixture (2): 5 parts of methyl methacrylate, 7 parts of n-butyl acrylate, 5 parts of 2-ethylhexyl acrylate, 3 parts of methacrylic acid, and 0.5 parts of "Newcol 707SF". (Note 8): Aluminum glue 891K: Made by Toyo Aluminum Co., Ltd., trade name. 4) Clear paint (C) = (C-1) 57 parts of acrylic resin solution (Note 9) and non--20 acrylic resin were adjusted with SWAZOLE # 1000 (trade name, aromatic hydrocarbon solvent, manufactured by COSMO Petroleum Corporation). Paper size applies to China National Standard (CNS) A4 (210 X 297 mm) —1 ^ —k ----- · Installation -------- Order --------- (Please Read the notes on the back before filling this page) 554016 A7 B7 V. Description of the invention (Xi (Please read the note on the back? Matters before filling out this page) Water dispersion (Note 10) 50 parts, SAIMER303 (Note 11) 30 Parts, 4 parts of 25% dodecylbenzenesulfonic acid solution, and 0.5 parts of BYK-300 (Note 12) to a viscosity of 30 seconds (Ford Cup # 4/20 ° C)) to obtain a resin solid part 55% of clear coating (C-1). (Note 9) Acrylic resin solution: Add 40 parts of "SWAZ0LE # 1000" to the reaction vessel and heat at 12 ° C, and add 30 parts of styrene, 35 parts of butyl acrylate, and 2-ethylhexyl acrylate. The resin obtained by polymerizing a monomer mixture composed of 10 parts, 25 parts of hydroxyethyl propionate, and 4 parts of α, α azobisisobutyronitrile for 3 hours is hydroxyamidine 120, the number average molecular weight is about 6,000, and the resin solid part 70%. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs (Note 10) Non-aqueous acrylic resin dispersion: Put UVERN 28-60 (made by Mitsui Toka Chemical Co., Ltd., trade name, melamine resin) in the reactor. Solution, 60% solids) 58 parts, 30 parts of n-heptane and 0.15 parts of phenylhydrazone peroxide, starting from heating to 95 ° C, dripping 15 parts of styrene and 9 parts of acrylonitrile in 3 hours Parts, 13 parts of methyl methacrylate, 15 parts of methyl acrylate, 1.8 parts of n-butyl acrylate, 10 parts of 2-ethylhexyl acrylate, 1.2 parts of acrylic acid, 0.5 parts of phenylhydrazone peroxide, n-butanol 5 parts, "SHELLZOLE 140" (Shel 1 Petroleum Company, trade name) 30 parts, and 9 parts of n-heptane A monomer mixture composed of this. Then, after 1 hour, 0.65 parts of the third butyl peroxide and 3.5 parts of "SHELLZOLE 140" were added dropwise within 1 hour. Then, the mixture was stirred for 2 hours while maintaining the temperature at 95 ° C. The solvent was removed under reduced pressure to obtain an acrylic resin non-aqueous dispersion with a resin solids content of 60% and a wax viscosity A (Gardner bubble viscosity). (Note 11) SAIMER .303: manufactured by Mitsui SAITECH Japan Co., Ltd. The paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 554016 A7 _B7_ V. Description of the invention (22) Good (less than 2 rusts on a 7cmx 7cm test board); △: slightly worse (7cmx 3 ~ 9 pieces of rust on 7cm test board); X: Inferior (more than 10 pieces of rust on 7cmx 7cm test board). — I: ---: ------ · installation ---- ---- Order --------- MWI (Please read the precautions on the back before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 4 2 This paper size applies to Chinese National Standards (CNS) A4 specification (210 X 297 mm) 554016 repair] i1 ^^--iSA 5. Description of the invention (2) Aluminum powder with a specific average particle size, It is found that the present object can be achieved and the invention is completed. Therefore, according to the present invention, a method for forming a multilayer coating film is provided, which is characterized by sequentially coating an organic solvent type hydrophilic coloring paint (A) and an aqueous coloring paint (B) And a method for forming a multilayer coating film by applying a transparent coating (C) on a coating object and curing the coating film by heating, wherein the hydrophilic colored coating (A) contains a carboxyl group having an acid value in the range of 5 to 100 Resin neutralizer, hardener, aluminum powder and color pigment with an average particle size of 20 // m or less, and the content of the aluminum powder is 0.1 to 10 weight per 100 weight parts of the resin solid part Within the range. In the present invention, the water-based coloring paint (B) is applied on the uncured coating film surface of the organic solvent-based hydrophilic coloring paint (A), and is neutralized by the neutralization contained in the coating film of the hydrophilic coloring paint (A). The carboxyl-containing resin exhibits strong water absorption, and absorbs moisture in the coating film of the aqueous coloring coating (B) applied to the coating film. Due to the sharp increase in viscosity, the aqueous coloring is applied even in a low humidity atmosphere. Coatings also rarely have defects such as surface roughness. In addition, the use of water-based coloring paints (B) and metallic paints is not affected by humidity during painting, and there are no metal spots, which can form a coating film with excellent gloss and vividness. In addition, according to the method of the present invention, since a specific amount of aluminum powder having a specific average particle diameter is contained in the hydrophilic coloring paint together with the coloring pigment, even if the content of the coloring pigment is small, the film can be formed with excellent concealability. The coating film has a remarkable effect that the physical properties of the coating film are not reduced. Hereinafter, the coating method of the present invention will be described in more detail. 554016
五、發明說明（8) ——— 作爲銘粉末者’可使用鱗片狀之金屬鋁粉末，該平均 粒徑通常爲20 // m以下，特別以1 5〜5 // rri之範圍內爲 佳。 此處’ 「平均粒徑」係表示以雷射折射散射法（LA- 500 ) 所測定之中間數。又，其厚度爲〇 . 〇〇 1〜〇 . 5 // m，特別 以0 · 0 1〜0 · 3 // m之範圍內爲適。於相關於鋁粉末之親水 性著色顏料（A )中的配合比例，一般在樹脂固體部份每 1 〇〇重量份’爲0 · 1〜1 〇重量份，特別以〇 . 5〜7重量份、 更特別以1〜5重量份之範圍內爲適。 由以上述比例配合該大小之鋁粉末的塗料所形成之塗 膜，大體上沒有顯示出閃爍的光亮感，可顯著地改善其 隱蔽性，該結果爲可減少倂用之著色顏料的配合量。例 如，在含有鈦白顏料作爲著色顏料之塗料的情況下，以 鈦白顏料之配合量約一半範圍可達到同等隱蔽性之顏料 。該結果爲比較於僅使用著色顏料的情況下，可格外地 提昇塗膜之物理性能，例如，抗碎裂·剝離性（耐衝擊性） 等。 配合於親水性著色塗料（A )之著色顏料，係爲了於塗膜 上賦予所希望之色調及隱蔽性者，亦爲不僅包含通常之 顏料而且包含染料者‘，舉例有二氧化鈦、碳黑、酞菁藍 、献菁綠、咔1:1坐紫、蒽吡啶酮、偶氮橙、黃色素、黃蒽 酮黃、異吲哚滿黃、偶氮黃、吲唑酮藍、二溴安噻紅、 紫蘇烯紅、偶氮紅、蒽醌紅、喹吖酮紅、紫等之有機或 無機系之著色顏料；單偶氮染料、多偶氮染料、金屬偶 氮錯合物染料、吡唑啉-5 -酮偶氮染料、1，2 -二苯乙烯 -10- 554016 a； 五、發明說明（9) 偶氮染料、噻唑偶氮染料等之偶氮染料；萬酸衍生體、 蒽酮衍生體等之蒽醌染料；酞菁染料、二苯基甲院染料 、三苯基甲烷染料、咕噸染料、吖啶染料等之碳金鏺染 料；吖嗪染料、噁嗪染料、噻嗪染料等之醌亞胺染料； 聚甲炔（或喹啉藍）染料、重氮甲川染料等之甲川染料； 喹啉染料、硝酸靈染料、對苯醌、萘醌染料、萘二甲H 亞胺染料、周萘酮染料等之染料類，該等可個別單獨使 用或合倂2種以上使用。該等著色顏料之在親水性著色塗 料（A )中的配合比例並無特別之限制，可於能形成所希望 之色調的塗膜之範圍內來配合。 親水性著色塗料（A)可由溶解或分散於以上所述之含有 羧基之樹脂的中和物、硬化劑、鋁粉末及著色顏料於有 機溶劑中來調製，調整於塗裝時之固體部份濃度至約3 5 重量％以上，特別以約40〜約60重量％之所謂高固體含量 型爲佳。 作爲有機溶劑者，舉例有用於塗料之酯系、醚系、醇 系、醯胺系、酮系、脂肪族烴系、脂環族烴系、芳香族烴 系等之溶劑，其可個別單獨地或2種以上合倂使用。其 中，以使用如醋酸乙二醇單甲醚酯、醋酸二乙二醇單甲酿 酯、醋酸二乙二醇單乙醚酯、二噁烷、二乙醇單甲醚、二 乙醇一乙醚、二乙醇一 丁基酸、二乙二醇單甲醚、二乙二 醇單乙醚、二乙二醇二乙醚、二乙二醇單丁基酸、甲醇、 乙醇、烯丙醇、正丙醇、異丙醇、三級丁醇、二乙醇、 1 ,2-丙二醇及其單醚、1 ,3-丁二醇、2,3-丁二醇、己二醇、己二 -1 1 - 554016V. Description of the invention (8) ——— As a Ming powder, scaly metal aluminum powder can be used. The average particle size is usually 20 // m or less, especially in the range of 1 5 to 5 // rri. . Here, "the average particle diameter" means an intermediate number measured by a laser refraction scattering method (LA-500). In addition, the thickness is preferably 0.001 to 0.55 m, and it is particularly suitable to be within a range of 0 · 0 1 to 0 · 3 // m. As for the mixing ratio of the hydrophilic coloring pigment (A) related to the aluminum powder, it is generally 0. 1 to 1 0 parts by weight, especially 0.5 to 7 parts by weight, per 100 parts by weight of the solid portion of the resin. More preferably, it is in the range of 1 to 5 parts by weight. The coating film formed by coating the aluminum powder of this size in the above proportion does not show a glittering luster, and concealability is significantly improved. As a result, it is possible to reduce the amount of colored pigments used. For example, in the case of a paint containing a titanium white pigment as a coloring pigment, a pigment having the same concealability can be achieved with a compounding amount of the titanium white pigment in a range of about half. The result is that the physical properties of the coating film, such as chipping resistance and peeling resistance (impact resistance), can be significantly improved compared to the case where only a coloring pigment is used. The coloring pigment blended with the hydrophilic coloring paint (A) is for imparting the desired hue and concealment to the coating film. It also includes those containing not only ordinary pigments but also dyes. Examples include titanium dioxide, carbon black, and phthalic acid. Cyanine blue, cyanine green, 1: 1 sitting purple, anthrapyridone, azo orange, yellow pigment, yellow anthrone yellow, isoindolin yellow, azo yellow, indazolone blue, dibromoanthine red Organic or inorganic colored pigments such as perillene red, azo red, anthraquinone red, quinacridone red, and violet; monoazo dyes, polyazo dyes, metal azo complex dyes, pyrazolines -5 -Ketoazo dyes, 1,2-stilbene-10-554016 a; V. Description of the invention (9) Azo dyes such as azo dyes, thiazole azo dyes, etc. Anthraquinone dyes, such as phthalocyanine dyes, diphenylmethane dyes, triphenylmethane dyes, gutton dyes, acridine dyes, etc .; azine dyes, oxazine dyes, thiazine dyes, etc. Quinone imine dye; polymethine (or quinoline blue) dye, diazomethine dye, etc. Morpholine dyes, spirit dyes nitric acid, p-benzoquinone, naphthoquinone dyes, naphthalimide H imine dyes, quinophthalone dyes, etc. circumferential naphthalene dyes, such individual may be used singly or two or more kinds Merger. The mixing ratio of these color pigments in the hydrophilic coloring paint (A) is not particularly limited, and they can be blended within a range capable of forming a coating film of a desired color tone. The hydrophilic coloring paint (A) can be prepared by dissolving or dispersing the neutralized product of the carboxyl group-containing resin, the hardener, the aluminum powder, and the coloring pigment in an organic solvent, and adjusting the concentration of the solid portion during the coating. It is more preferably about 35 wt% or more, and particularly preferably a so-called high solid content type of about 40 to about 60 wt%. Examples of the organic solvent include solvents such as ester-based, ether-based, alcohol-based, ammonium-based, ketone-based, aliphatic hydrocarbon-based, alicyclic hydrocarbon-based, and aromatic hydrocarbon-based solvents which can be used individually and individually. Or use 2 or more types together. Among them, for example, ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl acetate, diethylene glycol monoethyl ether acetate, dioxane, diethanol monomethyl ether, diethanol monoethyl ether, and diethanol are used. Monobutyl acid, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol monobutyl acid, methanol, ethanol, allyl alcohol, n-propanol, isopropyl Alcohol, tertiary butanol, diethanol, 1,2-propanediol and its monoethers, 1,3-butanediol, 2,3-butanediol, hexanediol, adipylene-1 1-554016
五、發明說明（15) 料（B )及透明塗料（C )之多層塗膜的方法中，由於親水性 著色塗料（A )中之被中和的含有羧基之樹脂爲親水性的， 塗裝於該塗面之水性著色塗料（B )優異的親密性，而且 吸收水性著色塗料（B )塗膜中的水分，由於塗膜黏度急劇 地上升，於低溼度氛圍氣體下塗裝水性著色塗料亦不會 產生表面粗糙等之缺陷。 (2)使用金屬型水性著色塗料（B)，亦由於不會受其塗 裝時之溼度影響，可形成無金屬斑痕、光澤鮮豔性優異 之金屬塗膜。 (3 )有機溶劑型親水性著色塗料（A )含有特定之鋁粉末 及著色顏料，特別是由於含有特定量鋁粉末，該塗膜大 致上不會顯示閃爍的光亮感，由於可顯著地改善其隱蔽 性，可減少所倂用之著色顏料之配合量，該結果爲可提 升親水性著色塗料（A )之物理性能，例如，抗碎裂·剝離 性（耐衝擊性）等。 (4 )作爲節省資源、有利於公害對策上的塗裝方法，以 本發明之方法中所形成的多層塗膜，對於潤飾的外觀、 設計性、塗裝作業性等方面極爲優異，可廣泛地利用在 汽車、腳踏車、電氣製品等之塗裝中。 實例 以下以實例及比較例來更具體地說明本發明。份及％ 均以重量爲基準，而塗膜之膜厚係關於硬化塗膜之厚度。 1 .試料之調製 1 )被塗物 -17- 554016V. Description of the invention (15) In the method of multi-layer coating of material (B) and transparent coating (C), since the neutralized carboxyl-containing resin in the hydrophilic coloring coating (A) is hydrophilic, the coating The water-based coloring paint (B) on the coating surface has excellent intimacy, and absorbs moisture in the coating film of the water-based coloring paint (B). Since the viscosity of the coating film rises sharply, it is also possible to apply the water-based coloring paint in a low humidity atmosphere No defects such as rough surface. (2) The metallic water-based coloring paint (B) is used, and it is not affected by the humidity at the time of painting, so it can form a metal coating film with no metal marks and excellent gloss and vividness. (3) The organic solvent-based hydrophilic coloring paint (A) contains a specific aluminum powder and a coloring pigment, and in particular, because it contains a specific amount of aluminum powder, the coating film does not show a flickering and bright feeling, and it can be significantly improved. Concealment can reduce the amount of coloring pigments used. The result is that the physical properties of the hydrophilic coloring paint (A) can be improved, such as chipping resistance and peeling resistance (impact resistance). (4) As a coating method that saves resources and contributes to pollution countermeasures, the multilayer coating film formed in the method of the present invention is extremely excellent in the appearance, design, and coating workability of the finish, and can be widely used. Used in the coating of automobiles, bicycles, electrical products, etc. Examples Hereinafter, the present invention will be described more specifically with examples and comparative examples. Parts and% are based on weight, and the film thickness of the coating film is about the thickness of the hardened coating film. 1. Preparation of sample 1) Coating object -17- 554016
五、發明說明（16) a :於進行過脫脂及磷酸鋅處理的酮板上，以平常方法 來電極沉積塗裝「ELACURONE #9400」（關西塗料（株）製 ’商品名，陽離子電極沉積塗料），並於1 7 5 °C下加熱3 〇 分鐘來使塗膜硬化。膜厚爲20 μ m。其次，於該塗面塗裝 中塗層塗料「RUGAPAKE中塗層，淡灰色」（關西塗料（株） 製’商品名），並於1 4 0 °C下加熱3 0分鐘來使塗膜硬化（月莫 厚20 // m )，將其作爲被塗物。 2 )有機溶劑型親水性著色塗料（A ) 基於記載於下列表1之成分及配合量來混合得到有機溶 劑型親水性著色塗料（A )。黏度及固體部份含有比例之調 整係加入異丙醇來進行。配合量爲固體部份比。 表1 親水性著色塗) 料(A) Α·1 Α-2 A-3 A-4 丙烯酸樹脂中和溶液(註1) 70 - 70 - 聚酯樹脂中和溶液（註2) - 70 - 70 SAIMEL370 (註 3) 30 30 30 30 A1 Paste891K (註 4) 5 5 - - 鈦白顏料 50 50 55 r 95 塗料固體部份(％) 35 35 35 35 黏度 （註5) 25 25 25 25 塗底隱蔽膜厚 （註6) 10 10 25 10 (註1 ):共聚合丙烯酸甲酯3 0份、丙烯酸乙酯2 3份、 丙烯酸丁酯3 0份、甲基丙烯酸羥基乙酯1 2份及丙烯酸 5份，得到酸價4 0、羥値5 2及數量平均分子量約 1 0,000之丙烯酸樹脂有機溶劑溶液（固體部份60%)。 於該溶液中加入二甲胺基乙醇來中和，接著以異丙醇 來稀釋（固體部份50%)。 -18- 554016V. Description of the invention (16) a: Electrode deposition coating "ELACURONE # 9400" (trade name, manufactured by Kansai Paint Co., Ltd., cationic electrode deposition coating) on a ketone plate subjected to degreasing and zinc phosphate treatment in a usual manner. ) And heated at 17 5 ° C for 30 minutes to harden the coating film. The film thickness was 20 μm. Next, the intermediate layer coating "RUGAPAKE intermediate layer, light gray" ("trade name" manufactured by Kansai Paint Co., Ltd.) was applied to this coating surface, and the coating film was hardened by heating at 140 ° C for 30 minutes. (Month Mo thickness 20 // m), use it as the coating object. 2) Organic solvent-based hydrophilic colored paint (A) Based on the components and blending amounts described in Table 1 below, an organic solvent-based hydrophilic colored paint (A) is obtained by mixing. The viscosity and solids content were adjusted by adding isopropanol. The blending amount is the solid portion ratio. Table 1 Hydrophilic pigmented coating) Material (A) A · 1 A-2 A-3 A-4 Neutralization solution of acrylic resin (Note 1) 70-70-Neutralization solution of polyester resin (Note 2)-70-70 SAIMEL370 (Note 3) 30 30 30 30 A1 Paste891K (Note 4) 5 5--Titanium white pigment 50 50 55 r 95 Solid content of coating (%) 35 35 35 35 Viscosity (Note 5) 25 25 25 25 Undercover concealed Film thickness (Note 6) 10 10 25 10 (Note 1): 30 parts of copolymerized methyl acrylate, 23 parts of ethyl acrylate, 30 parts of butyl acrylate, 12 parts of hydroxyethyl methacrylate, and 5 parts of acrylic acid Parts to obtain an acrylic resin organic solvent solution (solid content 60%) with an acid value of 40, hydroxyamidine 52, and a number average molecular weight of about 10,000. To this solution was added dimethylaminoethanol for neutralization, followed by dilution with isopropanol (50% solids). -18- 554016
五、發明說明（20 ) - ^ 名，單分子三劑氰胺樹脂。 (註12)BYK- 3 00 : PICK CHEMIE日本公司製，商品名， 表面調整劑。 2 .實例及比較例 於相對溼度75% RH中，將親水性著色塗料（^丨）〜 (A - 4 )之任一個以空氣噴霧法塗裝於被塗物上成膜厚 1 〇 // m，於室溫下放置5分鐘。其次，於其未硬化塗面上 ，在相對溼度75% RH中，將水性著色塗料（B-1)或（B_2) 以空氣噴霧法塗裝成膜厚約1 5 // m，於60°C下預加熱5分 鐘後，將透明塗料（C - 1 )以空氣噴霧法塗裝成膜厚約3 5 # m ’從於室溫下放置5分鐘至於1 40°C下加熱30分鐘，同時 地交聯硬化3層塗膜。於下述表3顯示該等之塗裝步驟及 所得之多層塗膜之性能測試結果。 表3 實例 比較例 1 2 3 4 1 2 親水性著色塗料(A) A-1 A-2 A-1 A-2 A-3 A-4 水性著色塗料(B) B-1 B-1 B-2 B-2 B-1 B-2 透明塗料(C C-1 C-1 C-1 C-1 C-1 C-1 性能測試結果 平滑性 18 17 18 17 18 18 鮮豔性 1.0 1.0 1.0 1.0 1.0 1.0 耐水性 〇 〇 〇 〇 〇 〇 附著性 〇 〇 〇 〇 〇 〇 耐衝擊性 〇 〇 〇 〇 △ X 抗碎裂性 〇 〇 〇 〇 Δ X 平滑性：於拉伸測試計（Tension Meter)(RENAULTY公 測試方法 司製）測試。數値在大的範圍則表示平滑性優異。 -22- 年月q 年月q5. Description of the invention (20)-^ Name, single-molecule three-dose cyanamide resin. (Note 12) BYK- 3 00: PICK CHEMIE Japan Co., Ltd. trade name, surface conditioner. 2. Examples and Comparative Examples In a relative humidity of 75% RH, any of the hydrophilic coloring paints (^ 丨) to (A-4) was applied to the coated object by the air spray method to form a film thickness of 1 〇 // m, let stand at room temperature for 5 minutes. Secondly, on its unhardened coating surface, the water-based coloring paint (B-1) or (B_2) was applied by air spraying to a film thickness of about 1 5 // m at 60 ° in a relative humidity of 75% RH. After preheating at C for 5 minutes, the transparent coating (C-1) was applied by air spraying to a film thickness of about 3 5 # m 'from standing at room temperature for 5 minutes to heating at 1 40 ° C for 30 minutes, Cross-linking and hardening 3 layers of coating film. Table 3 below shows these coating steps and the performance test results of the resulting multilayer coating film. Table 3 Examples Comparative Examples 1 2 3 4 1 2 Hydrophilic pigmented paint (A) A-1 A-2 A-1 A-2 A-3 A-4 Water-based pigmented paint (B) B-1 B-1 B- 2 B-2 B-1 B-2 clear coating (C C-1 C-1 C-1 C-1 C-1 C-1 C-1 performance test results smoothness 18 17 18 17 18 18 vividness 1.0 1.0 1.0 1.0 1.0 1.0 Water resistance 0.00000 Adhesion 100,000 Impact resistance △ △ X Fracture resistance 〇 △ △ Smoothness: Tension Meter (RENAULTY) Public Test Method Division) test. A large range indicates excellent smoothness. -22- year month q year month q
五、發明說明（21 ) 鮮豔性：於鮮豔性測試機NAI C(SUGA試驗機公司製）測 試。數値在大的範圍則表示鮮豔性優異。 耐水性：於40°C之水溫中浸漬試料塗板240小時後， 以目視由下述之標準來評估塗面之狀態。〇：表示沒看 到異常；△:表示稍微看見消光、起泡等缺陷；X :表 示消光、起泡等缺陷顯著。 耐水附著性：於40°C之水溫中浸漬試料塗板1 0日後， 乾燥塗膜，於塗面上以分割刀達到底材地、間隔2mm地 切割1 1道割痕，並以與其垂直而相同地間隔2mm地切割 11道割痕，作成100個2mmX2mrri之圍棋盤網目，於20°C 下貼著黏著玻璃紙膠帶，在急劇地將其剝離之中，檢查 殘存之圍棋盤網目塗膜數。〇：表示殘存1 00個；△: 表示殘存99〜90個；X :表示殘存89個以下。 耐衝擊性：依照]13 1(- 5400 8.3.2 ( 1 900 )來進行。目 視觀察進行將所使用尖端半徑6. 3mni之衝擊型的之500公 克重錘從30公分之高度落下之塗膜之裂痕及剝落的狀態 。〇：表示完全不見裂痕及剝落；△:表示在落下地點 及其周圍部分部分地產生裂痕及剝落；X :表示在落下 地點及其周圍部分大部分地產生裂痕及剝落。 抗碎裂性：使用Q-G-R礫石計（Q PANEL公司製），以 4kg / cm2之空壓送入7號碎石0.5公斤。在20°C之溫度條 件下，吹入碎石於測試板上，施加衝擊於塗膜之後，依照 規定於〗IS Z- 237 1之方法實施鹽水噴霧測試48小時。總 合地評估生鏽的狀態，以以下之標準表示。◦:表示優 -23-V. Description of the invention (21) Vividness: Tested on the vividness tester NAI C (manufactured by SUGA Testing Machinery Co., Ltd.). A large range indicates excellent vividness. Water resistance: After dipping the sample coating plate at a water temperature of 40 ° C for 240 hours, the condition of the coating surface was evaluated visually from the following criteria. ○: No abnormality was seen; △: Defects such as extinction and foaming were slightly seen; X: Defects such as extinction and foaming were significant. Water resistance: After immersing the sample coating board in a water temperature of 40 ° C for 10 days, the coating film was dried, and 11 cuts were cut on the coating surface with a dividing knife to reach the substrate at an interval of 2 mm, and perpendicular to it. Eleven cuts were cut at the same interval of 2mm to make 100 Go board meshes of 2mmX2mrri. Adhesive cellophane tape was attached at 20 ° C. While peeling them sharply, check the number of remaining Go board mesh coatings. ○: Remaining 100 pieces; △: Remaining 99 to 90 pieces; X: Representing 89 pieces or less. Impact resistance: According to] 13 1 (-5400 8.3.2 (1 900). Visually observe the coating film that dropped the impact weight of a 500-gram weight hammer with a tip radius of 6.3 mm from a height of 30 cm. The state of cracks and peeling. 〇: indicates that cracks and peeling are not seen at all; △: indicates that cracks and peeling are partially generated at the dropping point and its surroundings; X: indicates that cracks and peeling are mostly generated at the dropping point and its surrounding Chip resistance: Use QGR gravel meter (manufactured by Q PANEL) to feed 0.5 kg of crushed stone No. 7 at a pressure of 4 kg / cm2. Blow the crushed stone on the test board at a temperature of 20 ° C. After applying an impact to the coating film, a salt spray test was performed for 48 hours in accordance with the method prescribed in IS Z-237 1. The overall evaluation of the state of rust was expressed by the following standards. ◦: Excellent 23-