TWI264452B - Matte anionic electrodeposition coating composition - Google Patents

Matte anionic electrodeposition coating composition Download PDF

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TWI264452B
TWI264452B TW94108894A TW94108894A TWI264452B TW I264452 B TWI264452 B TW I264452B TW 94108894 A TW94108894 A TW 94108894A TW 94108894 A TW94108894 A TW 94108894A TW I264452 B TWI264452 B TW I264452B
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ethylene
resin
based copolymer
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TW94108894A
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TW200536903A (en
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Shigeki Matsubara
Kensuke Kataoka
Noboru Takoh
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Kansai Paint Co Ltd
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Abstract

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

Description

1264452 九、發明說明: 【發明所屬之技術領域】 本發明係關於一種低溫硬化性、塗膜硬度'模印記隱蔽 性均優異的消光陰離子電鍍塗料。 【先前技術】1264452 IX. Description of the Invention: [Technical Field] The present invention relates to a matte anionic plating coating which is excellent in low-temperature hardenability and coating film hardness, and has excellent masking concealability. [Prior Art]

鋁係具有所謂的量輕且加工性容易、以及耐蝕性均優異 的性質’利用鋁之該等性質而可以被使用於大多數的材料, 特別是建材關連材料。 該鋁之熱間押出之方法,通常是一種將圓柱形的鋁鑄塊 予以加熱熔融,接著再將此種熔融物投入押出機中,予以按 押於具有預定斷面形狀之孔的模具上,使之依序地通過孔而 得到具有預定形成之型材之方法。 又,鋁材本身之防蝕性、耐摩耗性、耐葯品性通常是不 佳的,因而一般是在將鋁予以陽極氧化處理之後,再藉由消 光之陰離子電鍍塗料而被覆一消光之塗膜。 然而,上述之消光陰離子電鍍塗料經電鑛塗裝於陽極氧 化處理後之鋁型材的情況下,素材之鋁型材的模印記容易明 顯化以致會有商品價値低劣化之問題點。 向來,爲使得像這樣的模印記不易明顯化,已有關於一 種陰離子電鑛塗料之發明;其係將溶解性參數不同的2種丙 烯酸系樹脂、以及和彼等之丙烯酸系樹脂不具相溶性的蜜胺 樹脂予以水分散所形成。〔專利文獻1〕。另外之發明爲含 有水分散性樹脂和蜜胺樹脂,並藉由樹脂之S P値的差而得 到之消光塗膜。〔專利文獻2〕。 1264452 此等之發明由於需要1 70 t:以上之燒成,因而不但陽極 氧化皮膜容易產生裂縫、精整性及塗膜性能降低’且消耗能 量變多,所以在經濟上也是有問題的。Aluminum has a so-called light weight, easy processability, and excellent corrosion resistance. It can be used for most materials, particularly building materials related materials, by utilizing these properties of aluminum. The method for extruding the heat between the aluminum is usually a method of heating and melting a cylindrical aluminum ingot, and then putting the molten material into an extruder and pressing it on a mold having a hole having a predetermined sectional shape. A method of sequentially forming a profile is obtained by sequentially passing the holes. Further, since the aluminum itself is generally inferior in corrosion resistance, abrasion resistance, and chemical resistance, it is generally coated with a matte coating film by anodizing the aluminum after anodizing the aluminum. However, in the case where the above-mentioned matte anion plating coating is applied to the aluminum profile after the anodic oxidation treatment by electro-mineral plating, the stamping of the aluminum profile of the material is easily manifested so that there is a problem that the commercial price is deteriorated. In order to make such a stamp imprinting difficult to be apparent, there has been an invention of an anionic electromineral coating which is incompatible with two kinds of acrylic resins having different solubility parameters and their acrylic resins. The melamine resin is formed by water dispersion. [Patent Document 1]. Further, the invention is a matte coating film comprising a water-dispersible resin and a melamine resin and having a difference in S P 树脂 of the resin. [Patent Document 2]. 1264452 In the invention, since the firing of 1 70 t: or more is required, not only the anodic oxide film is liable to cause cracks, the finish property and the coating film performance are lowered, but the energy consumption is increased, so that it is economically problematic.

其他方面,當使用氫氧基及羧基含有樹脂、嵌段化聚異 氰酸酯化合物的塗料之情況下,雖然於1 4 0 °C燒成也可以得 到凝膠分率爲90 %以上之硬化性、及高的塗膜硬度(鉛筆硬 度爲4H以上)之物,然而卻是低光澤(60°光澤爲10以下)、 及模印記隱蔽性也不夠充分〔專利文獻3〕。 另外,一種關於在1分子中具有2個以上之游離異氰酸 酯基的乙烯系共聚物之游離異氰酸酯基的一部分,在1分子 中具有2個以上之氫氧基之丙烯酸樹脂中之該氫氧基的一 部分起反應,接著使全部的殘存之游離異氰酸酯基與嵌段化 劑起反應而成之在1分子中具有倂存的嵌段異氰酸酯基和 氫氧基之樹脂的發明〔專利文獻4〕。就單只將該發明使用 於消光陰離子電鍍塗料而言,是得不到低溫硬化性、塗膜硬 度、模印記隱蔽性均優異的消光塗膜。尙且,消光塗膜之模 印記隱蔽性是優異的。 【專利文獻1】特開平1 0-46065號公報 【專利文獻2】特開2 0 0 1 d 3 1 4 9 4號公報 【專利文獻3】特開平8-4 1 380號公報 【專利文獻4】特開平5-247 1 75號公報 【發明內容】 【發明所欲解決之課題】 所欲解決之問題點在於:發現一種低溫硬化性、塗膜硬 1264452 度、模印記隱蔽性均優異的消光陰離子電鍍塗料。 【用以解決課題之手段】In other cases, when a coating material containing a hydroxyl group and a carboxyl group-containing resin or a blocked polyisocyanate compound is used, it is possible to obtain a curability of a gel fraction of 90% or more at a temperature of 140 ° C, and The coating film hardness (the pencil hardness is 4H or more) is high, but the low gloss (60° gloss is 10 or less) and the masking concealability are insufficient (Patent Document 3). In addition, a part of the free isocyanate group of the ethylene-based copolymer having two or more free isocyanate groups in one molecule, and the hydroxyl group in the acrylic resin having two or more hydroxyl groups in one molecule An invention in which a part of the reaction is carried out, and a resin having a blocked isocyanate group and a hydroxyl group having a ruthenium in one molecule is obtained by reacting all of the remaining free isocyanate groups with a blocking agent (Patent Document 4). In the case of using only the matte anionic plating coating, the matte coating film which is excellent in low-temperature curability, coating hardness, and mold hiding property is not obtained. Moreover, the mold masking property of the matte coating film is excellent. [Patent Document 1] Japanese Laid-Open Patent Publication No. JP-A No. Hei. No. Hei. 】 】 】 】 】 】 】 】 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 Anionic plating coating. [Means to solve the problem]

本發明人等爲了解決上述之問題點,乃刻意地重複地進 行硏究,結果發現藉由使用一種利用將在1分子中具有2個 以上之游離異氰酸酯基的乙烯系共聚物(a 1 )之該游離異氰 酸酯基的一部分,與具有氫氧基、羧基及烷氧矽烷基之乙烯 系共聚物(a 2 )之氫氧基的一部分起反應,接著使全部的殘存 之游離異氰酸酯基與嵌段化劑起反應而成之在彳分子中具 有倂存的嵌段異氰酸酯基和氫氧基之樹脂(A)與硬化觸媒 (B )所形成之消光陰離子電鍍塗料即可以達成,至此乃完成 本發明。 也就是說,本發明係: 1 _ 一種消光陰離子電鍍塗料,其特徵在於:藉由利用將在1 分子中具有2個以上之游離異氰酸酯基的乙烯系共聚物 (a 1 )之該游離異氰酸酯基的一部分,與具有氫氧基、羧基 及烷氧矽烷基之乙烯系共聚物(a2)之氫氧基的一部分起 反應,接著使全部的殘存之游離異氰酸酯基與嵌段化劑 起反應而成之在1分子中具有倂存的嵌段異氰酸酯基和 氫氧基之樹脂,且乙烯系共聚物(a 1 )和乙烯系共聚物(a 2) 之溶解性參數(SP値)的差爲0·4〜1 ·〇之樹脂(A)予以水 分散化,更且進一步添加硬化觸媒(B )予以分散化所形成 的乳化液而構成,且含有相對於樹脂(A)之總量1 00重量 份計爲〇 . 1〜1 0重量份之硬化觸媒(B )。 2.如第1項之消光陰離子電鍍塗料,其中硬化觸媒(B)爲自 1264452 有機錫化合物及胺化合物中所選出之至少1種的化合物。 3.如第1或2項之消光陰離子電鍍塗料,乙烯系共聚物(a 1 ) 爲由含有異氰酸酯基之乙烯系單體及其他的乙烯系單體 所形成的共聚物。 4 . 一種消光塗裝物品,其在經陽極氧化處理的鋁基材上, 塗裝如第1至3項中任一項之消光陰離子電鍍塗料所形 成之塗膜面的60°光澤度係爲10以下。The present inventors have deliberately repeated the above-mentioned problems in order to solve the above-mentioned problems, and as a result, it has been found that a vinyl-based copolymer (a 1 ) having two or more free isocyanate groups in one molecule is used. A part of the free isocyanate group is reacted with a part of the hydroxyl group of the ethylene-based copolymer (a 2 ) having a hydroxyl group, a carboxyl group or an alkoxyalkyl group, and then all the remaining free isocyanate groups are blocked. The matting anion plating coating formed by the resin (A) and the hardening catalyst (B) having a blocked block isocyanate group and a hydroxyl group in the ruthenium molecule can be obtained, and thus the present invention is completed. . That is, the present invention is: 1 - a matting anionic plating coating characterized by using the free isocyanate group of the ethylene-based copolymer (a 1 ) having two or more free isocyanate groups in one molecule. a part of the reaction with a part of the hydroxyl group of the ethylene-based copolymer (a2) having a hydroxyl group, a carboxyl group and an alkoxyalkyl group, and then reacting all the remaining free isocyanate groups with the blocking agent The resin having a blocked block isocyanate group and a hydroxyl group in one molecule, and the difference in solubility parameter (SP値) between the ethylene-based copolymer (a 1 ) and the ethylene-based copolymer (a 2) is 0. 4~1 · The resin (A) is water-dispersed, and further comprises an emulsion formed by dispersing a curing catalyst (B), and contains 100% of the total amount of the resin (A). The parts by weight are 〇. 1 to 10 parts by weight of the hardening catalyst (B). 2. The matte anionic plating coating according to Item 1, wherein the hardening catalyst (B) is at least one selected from the group consisting of an organotin compound and an amine compound. 3. The matte anionic plating coating according to item 1 or 2, wherein the ethylene-based copolymer (a 1 ) is a copolymer of a vinyl monomer containing an isocyanate group and another vinyl monomer. A matte coated article, wherein the 60° gloss of the coating film formed by coating the matte anionic plating coating according to any one of items 1 to 3 on the anodized aluminum substrate is 10 or less.

【發明效果】 本發明之消光陰離子電鍍塗料,係可以藉由在14CTC下 進行低溫燒成乾燥20分鐘而得到塗膜硬度(鉛筆硬度爲4H 以上)、及模印記隱蔽性均優異的60 °光澤度爲1 0以下之消 光塗膜。 本發明之組成物由於具有使用以蜜胺樹脂做爲硬化成 分所不能達成之陰離子電鍍塗料之低溫硬化性,所以能夠解 除習用的藉由在170 °C燒成之陽極氧化皮膜的裂縫、及塗膜 性能下降、以及消耗能量變大等之問題點;又且,可以得到 一種使用習用的嵌段化聚異氰酸酯化合物做爲硬化成分之 陰離子電鍍塗料所不能達成之消光塗膜。 【實施方式】 【用以實施發明之最佳形態】 本發明之消光陰離子電鍍塗料係一種含有包括樹脂(A) 和硬化觸媒(B)並進行水分散而成的乳化液之低溫硬化性良 好的消光陰離子電鍍塗料。以下,詳細說明之。 樹脂(A):樹脂(A)係一種在1分子中具有2個以上之游 1264452 離異氰酸酯基的乙烯系共聚物(a 1 )之該游離異氰酸酯基的 一部分,與在側鏈上具有氫氧基、羧基及烷氧矽烷基之乙烯 系共聚物(a 2 )(以下,簡稱爲水分散乙烯系共聚物(a 2 )之氫氧 基的一部分起反應,接著使全部的殘存之游離異氰酸酯基與 嵌段化劑起反應而成之在1分子中具有倂存的嵌段異氰酸 酯基和氫氧基之樹脂所構成者。 乙烯系共聚物(a 1 )係以含有異氰酸酯基之乙烯系單體 ^ (以下,簡稱爲「含有NCO基之單體」)當做必要成分,並使 | 用其他的乙烯系單體所形成的共聚物,主要是使在直鏈狀之 共聚物的末端及/或側鏈上具有異氰酸酯基。 含有NCO基之單體係爲一種在彳分子中分別具有至少 一個的未嵌段的游離異氰酸酯基、和自由基聚合性雙鍵之化 合物,例如,可以使用自m-或p-異丙烯基-α,α-二甲基苄 基異氰酸酯、2-異氰酸酯乙基甲基丙烯酸酯、含有氫氧基之 乙烯系單體和二異氰酸酯化合物之1 : 1 (莫耳比)加成物等中 所選取的1種或2種以上。[Effect of the Invention] The matte anion plating coating of the present invention can be obtained by drying at a low temperature of 14 CTC for 20 minutes to obtain a coating film hardness (pencil hardness of 4H or more) and excellent 60° gloss of masking concealability. A matte film having a degree of 10 or less. Since the composition of the present invention has low-temperature curability of an anionic plating coating which cannot be achieved by using a melamine resin as a curing component, it is possible to remove the crack of the anodic oxide film which is fired at 170 ° C and apply it. A problem such as a decrease in film properties and an increase in energy consumption can be obtained. Further, a matte coating film which cannot be achieved by using a conventional block-type polyisocyanate compound as an anionic plating coating for a hardening component can be obtained. [Embodiment] [Best Mode for Carrying Out the Invention] The matte anionic plating coating of the present invention is an emulsion containing a resin (A) and a curing catalyst (B) and dispersed in water, and has good low-temperature curability. A matting anionic plating coating. The details are described below. Resin (A): Resin (A) is a part of the free isocyanate group of the ethylene-based copolymer (a 1 ) having two or more of 1,466,452 isocyanate groups in one molecule, and having hydrogen and oxygen on the side chain. a vinyl group-based copolymer (a 2 ) having a group, a carboxyl group and an alkoxyalkyl group (hereinafter, simply referred to as a part of a hydroxyl group of the water-dispersed ethylene-based copolymer (a 2 ), and then all remaining free isocyanate groups A resin composed of a blocked isocyanate group and a hydroxyl group having a enthalpy in one molecule, which is formed by reacting with a blocking agent. The ethylene-based copolymer (a 1 ) is a vinyl monomer containing an isocyanate group. ^ (hereinafter, simply referred to as "the monomer containing NCO group") as a necessary component, and the copolymer formed by using other vinyl monomers is mainly at the end of the linear copolymer and/or The isocyanate group is present on the side chain. The single system containing the NCO group is a compound having at least one unblocked free isocyanate group and a radical polymerizable double bond in the fluorene molecule, for example, may be used from m- P-isopropene -α,α-dimethylbenzyl isocyanate, 2-isocyanate ethyl methacrylate, hydroxyl group-containing vinyl monomer and diisocyanate compound 1: 1 (mole ratio) adduct, etc. One or two or more selected.

在調製含有NCO基之單體上所用的上述含有氫氧基之 乙烯系單體,係爲一種在1分子中分別具有1個以上之氫氧 基和自由基聚合性雙鍵之化合物:舉例來說,例如其可以是 2 -經乙基(甲基)丙烯酸酯、2 -經丙基(甲基)丙烯酸酯、經丁 基丙燒酸酯、2,3-二羥丙基丙烯酸酯、2-羥基_3_苯氧乙基丙 烯酸酯、2-羥基-3-乙氧乙基丙烯酸酯等。更且,舉例來說, 例如其可以是丙烯酸或甲基丙烯酸和二醇(碳原子數爲2〜 2〇)等之莫耳加成物等。 1264452 在調製含有NCO基之單體上所用的上述二異氰酸酯化 合物,係爲在1分子中具有2個異氰酸酯基之物,舉例來說, 例如其可以是伸甲苯基二異氰酸酯、4,4’-二苯基甲烷二異氰 酸酯、伸二甲苯基二異氰酸酯、六亞甲基二異氰酸酯、離氨 酸二異氰酸酯、4,4’·亞甲基雙(環己基異氰酸酯)、甲基環己 烷-2,4 (2,6)-二異氰酸酯、異弗爾酮二異氰酸酯及三甲基己 烷二異氰酸酯等之脂肪族、芳香族及脂環族系的二異氰酸酯 化合物。The hydroxyl group-containing vinyl monomer used for preparing the NCO group-containing monomer is a compound having one or more hydroxyl groups and a radical polymerizable double bond in one molecule: for example For example, it may be 2-ethyl (meth) acrylate, 2- propyl (meth) acrylate, butyl propionate, 2, 3-dihydroxypropyl acrylate, 2 - Hydroxy_3_phenoxyethyl acrylate, 2-hydroxy-3-ethoxyethyl acrylate, and the like. Further, for example, it may be a molar additive such as acrylic acid or methacrylic acid and a diol (having a carbon number of 2 to 2 Å). 1264452 The above diisocyanate compound used in the preparation of a monomer containing an NCO group is a compound having 2 isocyanate groups in one molecule, for example, it may be a tolyl diisocyanate, 4, 4'- Diphenylmethane diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, 4,4'. methylene bis(cyclohexyl isocyanate), methylcyclohexane-2,4 An aliphatic, aromatic or alicyclic diisocyanate compound such as (2,6)-diisocyanate, isophorone diisocyanate or trimethylhexane diisocyanate.

上述含有NCO基之單體中較佳之物,從防止後述的乙 烯系共聚物(a2)間之反應中的凝膠化之觀點來看,特佳爲使 用具有第3級異氰酸酯基之m-異丙烯基,α -二甲基苄基 異氰酸酯。 又,其他的乙烯系單體,較宜是在1分子中具有自由基 聚合性雙鍵、且不具有可以和異氰酸酯基反應的活性氫之化 合物;具體而言,舉例來說,例如其可以是苯乙烯、α -甲 基苯乙烯、乙烯基甲苯等之芳香族乙烯系單體;甲基(甲基) 丙烯酸酯、乙基(甲基)丙烯酸酯、丁基(甲基)丙烯酸酯、2-乙基己基(甲基)丙烯酸酯、月桂基(甲基)丙烯酸酯、十三基 _ (甲基)丙烯酸酯、硬脂酸基(甲基)丙烯酸酯、環己基(甲基) 丙烯酸酯、苄基(甲基)丙烯酸酯等之(甲基)丙烯酸酯類; 必斯可特3 F (大阪有機化學社製、商品名、以下表示同 樣的意義),同上3MF、同上8F、同上8MF、全氟環己基(甲 基)丙烯酸酯、N-2-丙基全氟辛烷磺酸醯胺乙基(甲基)丙烯酸 醋、氟化乙烯、氟化亞乙烯等之含氟乙烯系單體; -11- *1264452 N,N’-二乙基胺基乙基(甲基)丙烯酸酯、ν,Ν,-二乙基胺 基乙基(甲基)丙烯酸酯、Ν,Ν’-二乙基胺基乙基(甲基)丙烯酸 醋、Ν,Ν’-二乙基(甲基)丙烯醯胺等之含氮乙烯系單體;乙烯 基乙基醚、乙烯基丁醚等之乙烯基醚系單體;以及The preferred one of the above-mentioned NCO group-containing monomers is preferably m-isolated with a third-order isocyanate group from the viewpoint of preventing gelation in the reaction between the ethylene-based copolymers (a2) to be described later. Propylene, α-dimethylbenzyl isocyanate. Further, the other vinyl monomer is preferably a compound having a radical polymerizable double bond in one molecule and having no active hydrogen reactive with an isocyanate group; specifically, for example, it may be An aromatic vinyl monomer such as styrene, α-methylstyrene or vinyltoluene; methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2 -ethylhexyl (meth) acrylate, lauryl (meth) acrylate, tridecyl _ (meth) acrylate, stearic acid (meth) acrylate, cyclohexyl (meth) acrylate (Meth) acrylates such as benzyl (meth) acrylate; biscot 3 F (manufactured by Osaka Organic Chemical Co., Ltd., trade name, the following meanings), the same as 3MF, the same as 8F, the same as 8MF , perfluorocyclohexyl (meth) acrylate, N-2-propyl perfluorooctane sulfonate decyl ethyl (meth) acrylate vinegar, fluorinated ethylene, vinyl fluoride, etc. -11- *1264452 N,N'-diethylaminoethyl (methyl) Acrylate, ν, Ν, - diethylaminoethyl (meth) acrylate, hydrazine, Ν'-diethylaminoethyl (meth) acrylate, hydrazine, Ν'-diethyl ( a nitrogen-containing vinyl monomer such as methyl acrylamide; a vinyl ether monomer such as vinyl ethyl ether or vinyl butyl ether;

(甲基)丙烯酸縮水甘油酯、3,4 -環乙氧環己基甲基(甲 基)丙烯酸酯、丙烯酸基縮水甘油醚、羥甲基丙烯醯胺之烷 基醚化物、(甲基)丙烯醯胺、(甲基)丙烯酸氯、氯化乙烯、 氯化亞乙烯、(甲基)丙烯腈、r -甲基丙烯酸氧烷基三甲氧矽 烷等;可以使用此等之中的1種或混合2種以上。Glycidyl (meth)acrylate, 3,4-cycloethoxycyclohexylmethyl (meth) acrylate, acryl glycidyl ether, alkyl etherate of methylol acrylamide, (meth) propylene Hydrazine, (meth)acrylic acid chloride, vinyl chloride, vinylidene chloride, (meth)acrylonitrile, aroxyalkyltrimethoxypropane, etc.; one or a mixture of these may be used. 2 or more types.

含有N C 0基之單體和其他的乙烯系單體間之比例,只 要乙烯系共聚物(a 1 )之1分子中具有2個以上之游離異氰酸 • 酯基的範圍的話即可,並沒有特別地限定,然而以含有NCO ^ 基之單體/其他的乙烯系單體(重量比)爲基準計適宜的範圍 是100/0〜1/99,較宜是在65/35〜30/70之範圍。 又,僅含有NCO基之單體、或者此等以外之其他的乙 烯系單體間之聚合反應,通常較宜是在不具有可以和異氰酸 酯基反應之活性氫的惰性有機溶劑中進行。 此種惰性有機溶劑,例如,可以使用己烷、庚烷、辛烷 等之脂肪族烴系 '酯系、酮系等之單一、或混合溶劑。具體 而言,例如,可以使用甲氧丙基乙酸酯和卜丁基-過氧異丙 ^ 基碳酸酯之混合溶劑。此等之溶劑由於是一種含有水分之 物,因而較宜是視情況需要地預先進行脫水。 此%之聚合反應,通吊是在50〜180 °C之溫度下,使用 自由基聚合起始劑來進行的,乙烯系共聚物(a1)之分子量可 、1264452 以藉由反應濃度、起始劑量等來調整。反應濃度是在聚合物 之20〜80重量%之範圍內進行。 特別是爲了提高聚合率,較宜是使用過氧化物系或碳酸 酯系起始劑,以1 〇 〇 °c以上之反應溫度下進行。更宜是與丙 烯酸酯系單體倂用時,可容易地得到聚合率高之聚合物。聚 起始劑之濃度,雖然可以使用總單體之0.0 1〜1 5重量%之 範圍內者,然而較宜是在0.1〜10重量。/。之範圍內。The ratio between the monomer having an NC 0 group and another vinyl monomer may be in the range of two or more free isocyanate groups in one molecule of the ethylene copolymer (a 1 ). It is not particularly limited, but a suitable range based on the monomer containing NCO^ group/other vinyl monomer (weight ratio) is 100/0 to 1/99, preferably 65/35 to 30/ 70 range. Further, the polymerization reaction between the monomer containing only the NCO group or the other ethylene monomer other than the above is usually carried out in an inert organic solvent which does not have active hydrogen which can react with the isocyanate group. As such an inert organic solvent, for example, a single or mixed solvent of an aliphatic hydrocarbon such as hexane, heptane or octane, such as an ester system or a ketone system, can be used. Specifically, for example, a mixed solvent of methoxypropyl acetate and butylbutyl-peroxyisopropyl carbonate can be used. Since these solvents are water-containing substances, it is preferred to carry out dehydration in advance as occasion demands. The polymerization of this % is carried out by using a radical polymerization initiator at a temperature of 50 to 180 ° C. The molecular weight of the ethylene copolymer (a1) can be 1,264,452 by the reaction concentration, starting. The dose is adjusted to adjust. The reaction concentration is carried out in the range of 20 to 80% by weight of the polymer. In particular, in order to increase the polymerization rate, it is preferred to use a peroxide-based or carbonate-based initiator at a reaction temperature of 1 Torr or higher. More preferably, when it is used in combination with an acrylate monomer, a polymer having a high polymerization rate can be easily obtained. The concentration of the polymerization initiator may be in the range of 0.01 to 15% by weight based on the total monomers, and is preferably 0.1 to 10 by weight. /. Within the scope.

此種乙烯系共聚物(a 1 )之重量平均分子量(註1 )宜是 500〜50000,特佳是在1500〜30000之範圍。又,合適的 異氰酸酯價是30〜200毫克NC 0/10克。又,乙烯系共聚物 (a 1 )雖然是在1分子中具有2個以上之游離的異氰酸酯基, 然而較宜是完全沒有可以和該異氰酸酯基反應之活性氫。 _ (註1)重量平均分子量:以JIS K01 24-83爲基準來進 行,分離管柱係使用 TSK GEL 4000 HXL +G 3000 HXL +G 2500 HXL + G 2000 HXL (東洋曹達(股)公司製),於 40°C、1·0 毫升/分鐘之流速下、使用G P C用四氫呋喃做爲溶離液、以 R1折射計測得色層管柱和聚苯乙烯之檢量線計算而求得。 乙烯系共聚物(a 2 ): 乙烯系共聚物(a2)係適合使用以(1 )含有烷氧矽烷基之 不飽和單體、(2)含有氫氧基之不飽和單體、(3)含有羧基之 ^ 不飽和單體當做必要成分,並視情況需要與(4 )其他的不飽 和單體共聚合而成之物。此等之單體成分,舉例來說,例如 其可以是以下所述者。 (1 )含有烷氧矽烷基之不飽和單體:舉例來說,例如其 1264452 可以是r -(甲基)丙烯醯基氧丙基三甲氧矽烷、r -(甲基)丙 烯醯基氧丙基甲基二甲氧矽烷、r-(甲基)丙烯醯基氧丙基三 乙氧矽烷、乙烯基三甲氧矽烷等。The weight average molecular weight (Note 1) of the ethylene-based copolymer (a 1 ) is preferably from 500 to 50,000, particularly preferably from 1,500 to 30,000. Also, a suitable isocyanate valence is 30 to 200 mg NC 0/10 g. Further, the ethylene-based copolymer (a1) has two or more free isocyanate groups in one molecule, but it is preferred that there is no active hydrogen which can react with the isocyanate group. _ (Note 1) Weight average molecular weight: based on JIS K01 24-83, and the separation column is TSK GEL 4000 HXL + G 3000 HXL + G 2500 HXL + G 2000 HXL (manufactured by Toyo Soda Co., Ltd.) It was obtained by using GPC using tetrahydrofuran as a dissolving solution at 40 ° C and a flow rate of 1.0 ml/min, and measuring the color column and polystyrene by a R1 refractometer. Ethylene-based copolymer (a 2 ): The ethylene-based copolymer (a2) is suitably used as (1) an alkoxyalkyl group-containing unsaturated monomer, (2) a hydroxyl group-containing unsaturated monomer, and (3) The unsaturated monomer containing a carboxyl group is used as an essential component and, if necessary, copolymerized with (4) other unsaturated monomers. The monomer components of these may, for example, be as described below. (1) an alkoxyalkylalkyl group-containing unsaturated monomer: for example, 1,268,452 thereof may be r-(meth)acryloyloxypropyltrimethoxy decane, r-(meth) propylene decyl oxypropylene Methyl dimethoxy decane, r-(methyl) propylene decyl oxypropyl triethoxy decane, vinyl trimethoxy decane, and the like.

(2)含有氫氧基之不飽和單體:舉例來說,例如其可以 是羥乙基(甲基)丙烯酸酯、羥丙基(甲基)丙烯酸酯、以及此 等以外之普拉庫西爾FM1(戴西爾化學製,商品名,己內_ 胺改性(甲基)丙烯酸羥基酯類)、普拉庫西爾F Μ 2 (同左)、普 拉庫西爾FM3(同左)、普拉庫西爾FA1(同左)、普拉庫西爾 FA2(同左)、普拉庫西爾FA3(同左)等之含有氫氧基之不飽和 單體類等。 (3 )含有羧基之不飽和單體:舉例來說,例如其可以是(甲 基)丙烯酸、馬來酸等。 (4 )其他之不飽和單體:舉例來說,例如其可以是(甲基) 丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基) 丙烯酸丁酯、(甲基)丙烯酸己酯、(甲基)丙烯酸辛酯、(甲基) 丙烯酸月桂酯、(甲基)丙烯酸環己酯等之(甲基)丙烯酸的C 1 〜C 1 8之烷酯或環烷酯類、苯乙烯等之芳香族乙烯基單體 類、(甲基)丙烯醯胺、N-丁氧甲基(甲基)丙烯醯胺、N-羥甲 基(曱基)丙烯醯胺等之(甲基)丙烯醯胺及其衍生物類、(甲 基)丙烯腈化合物類等。 此等乙烯系共聚物(a2)之重量平均分子量宜是500〜 50000,特佳爲2000〜35000之範圍,特別合適的氫氧基, 基於羥基價計爲20〜200毫克KOH /克之範圍。 就樹脂(A)之製造而言,乙烯系共聚物(ai)和乙烯系共聚 • 1264452 物(a 2 )間之反應係爲異氰酸酯基和氫氧基間之胺基甲酸酯 化反應,具體而言,可以將乙烯系共聚物(a 2)摻混在乙烯系 共聚物(a1)之有機溶液中,通常是在20〜100 °C、較佳爲在 25〜60t之溫度下進行胺基甲酸酯化反應。 反應是藉由異氰酸酯基的減少量、亦即異氰酸酯價來進 行控制的。又,在此種反應中,爲了得到低溫硬化性及塗膜 * 硬度也較宜是使用有機錫化合物等之硬化觸媒。 . 乙烯系共聚物(a2)之摻混量,只要是每1分子的重量平 S 均分子量爲500〜50000之乙烯系共聚物(a1 )中可以導入至 少平均〇 · 1個胺基甲酸酯鍵的摻混量即可,然而,較佳爲每 1分子的重量平均分子量爲500〜30000之乙烯系共聚物 > (a 1 )中可以導入至少平均〇 . 5〜1 · 5個胺基甲酸酯鍵,特別是 以每彳分子的乙烯系共聚物(a 1 )中可以導入1個胺基甲酸酯 鍵爲最佳。 其次,藉由使如以上所述之乙烯系共聚物(a 2 )起反應而 導入胺基甲酸酯鍵’並使得在加成有水分散性乙烯系共聚物 (a 2 )之乙嫌系共聚物(a 1 )中所含的殘存之游離的異氰酸醋、 和以下之嵌段劑在通常之20〜100 °C的溫度下起反應進行 爰段,即可以得到樹脂(A)。 嵌段劑,舉例來說,例如其可以是酚、曱酚、二甲苯酚、 p-乙酚、〇-異丙酚、P_tert_丁酚、P-tert-辛酚、百里香酚、 p-萘酚、p-硝基酚、P-氯酚等之酚系; 甲醇、乙醇、丙醇、丁醇、乙二醇、甲基溶纖素、乙基 溶纖素、甲基卡必醇、苄基醇、苯基溶纖素、糠基醇、環己 •1264452 醇等之醇系;丙二酸二甲酯、乙醯乙酸酯等之活性亞甲基系; 丁硫醇、硫酚、t e rt -十二基硫醇等之硫醇系;乙醯替苯 胺、乙醯替甲氧基苯胺、醋酸醯胺、苯醯胺等之酸醯胺系; 琥珀酸醯胺、馬來酸醯亞胺等之醯亞胺系;(2) a hydroxyl group-containing unsaturated monomer: for example, it may be hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and the like, FM1 (made by Daisy Chemicals, trade name, _ amine modified (meth) hydroxy acrylate), pracusill F Μ 2 (same left), pracusill FM3 (same left), Hydroxyl-containing unsaturated monomers such as pracusill FA1 (same as left), pracusill FA2 (same as left), and pracusill FA3 (same as left). (3) A carboxyl group-containing unsaturated monomer: for example, it may be (meth)acrylic acid, maleic acid or the like. (4) Other unsaturated monomers: for example, it may be methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, a C 1 ~C 18 alkyl ester of (meth)acrylic acid such as hexyl (meth) acrylate, octyl (meth) acrylate, lauryl (meth) acrylate or cyclohexyl (meth) acrylate or Aromatic vinyl monomers such as cycloalkyl esters and styrene, (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N-hydroxymethyl (decyl) propylene oxime (Meth) acrylamide and its derivatives, (meth) acrylonitrile compounds, etc., such as amines. The weight average molecular weight of the ethylene-based copolymer (a2) is preferably from 500 to 50,000, particularly preferably from 2,000 to 35,000, and particularly preferably a hydroxyl group, in the range of from 20 to 200 mg KOH / gram based on the valence of the hydroxyl group. In the production of the resin (A), the reaction between the ethylene-based copolymer (ai) and the ethylene-based copolymer 1264452 (a 2 ) is an aminoesteration reaction between an isocyanate group and a hydroxyl group, specifically In general, the ethylene-based copolymer (a 2) may be blended in an organic solution of the ethylene-based copolymer (a1), usually at a temperature of from 20 to 100 ° C, preferably from 25 to 60 t. Acidification reaction. The reaction is controlled by the reduced amount of isocyanate groups, i.e., the isocyanate valence. Further, in such a reaction, it is preferred to use a curing catalyst such as an organic tin compound in order to obtain low-temperature curability and coating film * hardness. The blending amount of the ethylene-based copolymer (a2) may be at least an average of 〇·1 urethane in the ethylene-based copolymer (a1) having a weight average S molecular weight of 500 to 50,000 per molecule. The blending amount of the bond may be, however, it is preferably an ethylene-based copolymer having a weight average molecular weight of from 500 to 30,000 per molecule > (a 1 ) at least an average of 5 to 1 · 5 amine groups may be introduced. The formate bond is preferably one in which one urethane bond can be introduced into the vinyl copolymer (a 1 ) per molecule. Next, the urethane bond is introduced by reacting the ethylene-based copolymer (a 2 ) as described above and the ethyl sulphate of the water-dispersible ethylene-based copolymer (a 2 ) is added. The remaining free isocyanuric acid contained in the copolymer (a 1 ) and the following block agent are reacted at a temperature of usually 20 to 100 ° C to carry out a reaction, whereby a resin (A) can be obtained. The block agent may, for example, be phenol, indophenol, xylenol, p-ethylphenol, guanidine-propofol, P_tert-butanol, P-tert-octylphenol, thymol, p-naphthalene Phenols such as phenol, p-nitrophenol, and P-chlorophenol; methanol, ethanol, propanol, butanol, ethylene glycol, methyl cellosolve, ethyl cellosolve, methyl carbitol, benzyl Alcohols such as benzyl alcohol, phenyl cellosolve, mercapto alcohol, cyclohexanol 1268452 alcohol; active methylene groups such as dimethyl malonate and acetamidine acetate; butanol, thiophenol, a thiol group such as te rt-dodecyl thiol; an amide amine such as acetanilide, acetamidine anilide, decylamine or benzoguanamine; guanyl succinate or bismuth maleate An imine or the like of an imine;

二苯基胺、苯基萘基胺、苯胺、咔唑等之胺系;咪唑、 2 -乙基咪唑等之咪唑系;尿素、硫尿素、伸乙基尿素等之尿 素系;N -苯基胺基甲酸苯酯、2 -腭唑啉酮等之胺基甲酸鹽 系;伸乙基亞胺等之亞胺系; 甲醛肟、乙醛肟、丙酮肟、甲乙酮肟、甲基異丁酮肟、 環己酮肟等之肟系;亞硫酸蘇打、亞硫酸氫鉀等之亞硫酸鹽 系, ε-己內醯胺、(5-戊內醯胺、r -戊內酯、丙內酯等 之內酯系;3,5 -二甲基吡唑、3 -甲基吡唑、4 -硝基3,5 -二甲 基吡唑、以及4_溴-3,5 _二甲基吡唑等之吡唑系等。 樹脂(A)係藉由異氰酸酯基氫氧基間之胺基甲酸酯反 應、透過胺基甲酸酯鍵而將乙烯系共聚物(a1)和乙烯系共聚 物(a2)鍵結在一起。 如此做法所得到的樹脂(A),其在分子中具有平均至少 一個的嵌段異氰酸酯基和至少一個氫氧基,其重量平均分子 量爲1000〜120000左右,特別是5000〜50000左右,合適 的氫氧基價(毫克KOH/克)係25〜250之範圍。 尤其,爲了得到低光澤(60°光澤度爲1〇以下)之消光 塗膜,則乙烯系共聚物(a 1)和乙烯系共聚物(a2)間之溶解性 參數(SP値(註2))之差値宜是在0.4〜1 .0之範圍,較宜是 1264452 〇 · 5 〜〇 . 8 〇 (註2 )溶解性參數:S Ρ値係爲S ο I u b i丨i t y Ρ a r a m e t e r之 簡稱’表示液體分子之分子間相互作用之尺度。就該S P値 而以乙烯系共聚物(a 1 )和水分散性乙烯系共聚物(a2)成 分論’當單體之S P値係爲已知時可以使用下述式(1 )來求得 共聚物單體之S P値,以此之S P値來當做共聚物之S P値使 用0An amine system such as diphenylamine, phenylnaphthylamine, aniline or carbazole; an imidazole system such as imidazole or 2-ethylimidazole; a urea system such as urea, sulfur urea, and ethyl urea; N-phenyl Amino acid salt of phenyl carbamate, 2-oxazolinone, etc.; imine of ethyl imine; formaldehyde oxime, acetald oxime, acetone oxime, methyl ethyl ketone oxime, methyl isobutyl ketone肟, cyclohexanone oxime, etc.; sulfite system such as sulfite soda, potassium hydrogen sulfite, ε-caprolactam, (5-valeroguanamine, r-valerolactone, propiolactone And lactones; 3,5-dimethylpyrazole, 3-methylpyrazole, 4-nitro-3,5-dimethylpyrazole, and 4-bromo-3,5-dimethylpyrazole Pyrazole or the like of azole or the like. Resin (A) is an ethylene-based copolymer (a1) and an ethylene-based copolymer by reacting a urethane between isocyanate-based hydroxyl groups and passing through a urethane bond. (a2) bonded together. The resin (A) obtained in this way has an average of at least one block isocyanate group and at least one hydroxyl group in the molecule, and has a weight average molecular weight of about 1000 to 120,000. It is about 5,000 to 50,000, and the suitable value of the hydroxyl group (mg KOH / gram) is in the range of 25 to 250. In particular, in order to obtain a matte coating film having a low gloss (60° gloss of 1 Å or less), ethylene copolymerization The difference between the solubility parameter (SP値(Note 2)) between the substance (a1) and the ethylene-based copolymer (a2) is preferably in the range of 0.4 to 1.0, more preferably 1,644,452 〇·5 〇. 8 〇 (Note 2) Solubility parameter: S Ρ値 is S ο I ubi丨ity Ρ arameter's abbreviation 'is the scale of the intermolecular interaction of liquid molecules. For this SP値, the ethylene copolymer (a 1 And the water-dispersible ethylene-based copolymer (a2) composition theory. When the SP-based system of the monomer is known, the following formula (1) can be used to determine the SP 値 of the copolymer monomer, and thus the SP 値To use SP as a copolymer, use 0

單體之SP値於油漆技術期刊第42卷第176頁(1 970) 中已有整理。 SP = SP1xfw1+SP2xfW2+......S Pnxfwn 式(1) (SPi、SP2...... f W 1 ' f W 2 ........ w n 之重量分率。) • spn係代表各單體之SP値, 係代表各單體相對於單體總量The SP of the monomer has been collated in the Journal of Paint Technology, Vol. 42, p. 176 (1 970). SP = SP1xfw1+SP2xfW2+...S Pnxfwn Equation (1) (SPi, SP2... f W 1 ' f W 2 ........ wn weight fraction.) • The spn system represents the SP値 of each monomer and represents the total amount of each monomer relative to the monomer.

又’當單體之S P値未知時,則可以藉由濁點滴定來測 定’具體而言’可以依照下述式(2),即κ_ W_ SUH、J_ M_ CORBETT之式(應用高分子科學期刊,第12卷,第2359 頁’ 1968)做爲基準而計算出來。 式⑵In addition, when the SP of the monomer is unknown, it can be determined by cloud point titration to determine 'specifically' according to the following formula (2), ie, κ_W_SUH, J_M_CORBETT (Application of Polymer Science Journal) , Vol. 12, p. 2359 '1968' is calculated as a benchmark. Formula (2)

Vv η * δ·Η ^ Vv ρ ^ δη 7vh (式中’ VH係表示n_己烷之容積分率,vD表示去離子水 -17- 1264452 Z容積分率,(5η係表示η-己烷z SP値” δ、表示去離子水 之s P値。) 濁點滴定係將做爲試樣的樹脂Ο „ 5克(固體物)溶解於1 Ο 毫升之丙酮中,慢慢地加入η -己烷,讀出濁點時之滴定量 Η (毫升)’同樣地讀出將去離子水加入丙酮溶液中之濁點時 的滴定量D(毫升)使用下式而算出VH、VD、5h、5D。另外, 各溶劑之SP値,丙酮:9.75、N-己烷:7.24、去離子水: 23.43 °Vv η * δ·Η ^ Vv ρ ^ δη 7vh (wherein VH represents the volume fraction of n-hexane, vD represents the volume fraction of deionized water -17-1264452 Z, (5η represents η-hexane z SP値” δ, which represents s P値 of deionized water.) The cloud point titration is used as a sample of resin Ο „ 5 g (solid matter) dissolved in 1 毫升 ml of acetone, slowly added η - Hexane, the amount of Η (ml) when the cloud point is read, and the same amount of D (ml) when the deionized water is added to the cloud point in the acetone solution is used to calculate VH, VD, 5h, using the following formula. 5D. In addition, SP値 of each solvent, acetone: 9.75, N-hexane: 7.24, deionized water: 23.43 °

〔Vh = H/(1 O + H)、Vd = D/(1 0 + D)、ά Η = 9·75χ1 0/(1 0 + Η) + 7·24 χΗ/(10 + Η)、(5 〇 = 9.75χ1 0/(1 0 + D) + 23.43xD/(10 + D)] 又,乙烯系共聚物(a1)、及乙烯系共聚物(a2)之玻璃轉 移溫度(Tg)同時爲彳〇 °c以上時,對塗膜性之提昇方面而言較 理想。 硬化觸媒(B ):本發明之陰離子電鍍塗料是一種低溫硬 化性、塗膜硬度均優異之物,且含有硬化觸媒(B )之必要成 分。當做硬化觸媒(B )之有機錫化合物,例如,可以使用辛 酸錫、二丁錫二乙酸鹽、二丁錫二辛酸鹽、二丁錫二月桂酸 鹽、二丁錫二馬來酸鹽、四丁錫、二丁基氧化錫、二丁錫二 苯甲酸鹽氧、二辛錫二苯甲酸鹽氧等: 胺化合物,舉例來說,例如其可以是三甲胺、三乙胺、 二甲基環己胺、N -四甲基己烷_1, 6-二胺、N -五甲基二伸乙 三胺、2-甲基-1,4·二氮雜環〔2,2,2〕辛烷等之3級胺。 此等硬化觸媒(B )係可以單獨使用’較宜是藉由2種以 上之混合使用來提昇低溫硬化性、及塗膜硬度。硬化觸媒之 8 1264452 總量(換算成固體物)雖然是隨著其種類而異,然而從觸媒能 力和塗料安定方面來看,通常相對於樹脂(A)之總量1 0 0重 量份計,硬化觸媒(B)之固體物宜是0»1〜1 〇重量份,較宜 是含有0_5〜8重量份。 製造於本發明之陰離子電鑛塗料使用的乳化液,係可以 藉由在樹脂(A)中加入硬化觸媒(B),並相對於樹脂(A)之羧基 - 摻混〇 1〜1 . 5當量、較宜是0 2〜1 _ 2當量之中和劑(鹼基性 , 化合物)後,再予以混合分散,接著在此物中加入去離子水, ^ 使固體物成爲1 0〜6 0重量。/。、較宜是1 〇〜4 0重量。/。,接著 滴下中和劑將P Η値調整成7 · 0〜8.0來進行。 上述之中和劑,舉例來說,例如其可以是乙基胺、丙基 .. 胺、丁基胺、苄基胺、一乙醇胺 '新戊醇胺、2-胺基丙醇、 3-胺基丙醇等之第1級單胺;二乙胺二乙醇胺、二·η-或二 -iso-丙醇胺、Ν-甲基乙醇胺、Ν-乙基乙醇胺等之第2級單 胺;二甲基乙醇胺、三甲基胺 '三乙基胺、三異丙基胺、甲 基二乙醇胺、二甲基胺乙醇等之第3級單胺;二伸乙基三 Up 胺、羥基乙胺基乙胺、乙胺基乙胺、甲胺基丙胺等之多胺基 三乙胺等。 本發明之消光陰離子電鍍塗料,可以視情況需要添加顏 料、染料、硬化觸媒、流動調劑,進行PH値調整,加入去 ^ 離子水而得到固體物爲5〜2 0重量%之離子型電鍍塗料。又 且,可以更進一步地摻混紫外線吸收劑、光安定劑而得到高 耐候性之塗膜。 上述之紫外線吸收劑,舉例來說,例如其可以是苯基水 -19- 1264452 楊酸酯、辛基苯基水楊酸酯' 4-t-丁苯基水楊酸酯等之水[Vh = H/(1 O + H), Vd = D/(1 0 + D), ά Η = 9·75χ1 0/(1 0 + Η) + 7·24 χΗ/(10 + Η), ( 5 〇 = 9.75 χ 1 0 / (1 0 + D) + 23.43 x D / (10 + D)] Further, the glass transition temperature (Tg) of the ethylene copolymer (a1) and the ethylene copolymer (a2) is simultaneously When 彳〇°c or more, it is preferable in terms of improvement of coating property. Hardening catalyst (B): The anionic plating coating of the present invention is a low-temperature hardening property and an excellent hardness of a coating film, and contains a hardening touch. An essential component of the medium (B). As an organotin compound of the hardening catalyst (B), for example, tin octylate, dibutyltin diacetate, dibutyltin dioctoate, dibutyltin dilaurate, or the like may be used. Butadiene dimaleate, tetrabutyltin, dibutyltin oxide, dibutyltin dibenzoate oxygen, dioctyldibenzoate oxygen, etc.: an amine compound, for example, for example, it may be Trimethylamine, triethylamine, dimethylcyclohexylamine, N-tetramethylhexane_1, 6-diamine, N-pentamethyldiethylenetriamine, 2-methyl-1,4·2 a tertiary amine such as a nitrogen heterocyclic [2,2,2]octane. These hardening catalysts (B) are It is preferable to use it alone or in combination of two or more types to improve low-temperature hardenability and film hardness. The total amount of 8 1264452 (converted into solid matter) of the hardening catalyst varies depending on the type. From the viewpoint of catalyst capacity and paint stability, the solid content of the hardening catalyst (B) is usually 0»1~1 〇 by weight, based on 100 parts by weight of the total amount of the resin (A). It is contained in an amount of 0-5 to 8 parts by weight. The emulsion used in the anionic electromineral coating of the present invention can be obtained by adding a hardening catalyst (B) to the resin (A) and a carboxyl group relative to the resin (A). Mixing 〇1~1. 5 equivalents, preferably 0 2~1 _ 2 equivalents of neutralizer (base, compound), then mixing and dispersing, then adding deionized water to the material, ^ The solid matter is 10 to 60% by weight, more preferably 1 〇 to 40% by weight, and then the neutralizing agent is added to adjust P Η値 to 7 · 0 to 8.0. For example, it may be, for example, ethylamine, propyl: amine, butylamine, benzylamine, monoethanolamine, neopentylamine, a monoamine of a first order such as 2-aminopropanol or 3-aminopropanol; diethylamine diethanolamine, di-n- or di-iso-propanolamine, hydrazine-methylethanolamine, hydrazine-ethyl a second-stage monoamine such as ethanolamine; a third-stage monoamine such as dimethylethanolamine, trimethylamine 'triethylamine, triisopropylamine, methyldiethanolamine or dimethylamine ethanol; A polyaminotriamine such as ethyltri Upamine, hydroxyethylaminoethylamine, ethylaminoethylamine or methylaminopropylamine. In the matting anion plating coating of the present invention, a pigment, a dye, a hardening catalyst, a flow regulating agent may be added as needed, and pH 値 adjustment may be performed, and ionic water is added to obtain an ionic plating coating material having a solid content of 5 to 20% by weight. . Further, a UV absorber and a light stabilizer can be further blended to obtain a coating film having high weather resistance. The above ultraviolet absorber may, for example, be water such as phenyl water -19-1264452 salicylic acid ester or octylphenyl salicylate '4-t-butylphenyl salicylate.

楊酸衍生物,254 -二羥基二苯甲酮、2-羥基-4-甲氧基二苯甲 酮、2,2、二羥基-4-甲氧基二苯甲酮、2-羥基-4-甲氧基-2、 羧基二苯甲酮、2-羥基-4-甲氧基-5-硫二苯甲酮三氫酯、2,2’-二羥基-4,4’-二甲氧基二苯甲酮、2-羥基-4-辛基二苯甲酮、 2-羥基-4-八癸氧基二苯甲酮、2,2,-二羥基-4,4’-二甲氧基- 5-硫二苯甲酮鈉、2,2’,4,4’-四羥基二苯甲酮、4-癸氧基-2-羥 基二苯甲酮、5 -氯-2 -羥基二苯甲酮、間苯二酚單苯甲酸酯、 2,4-二苯甲醯基間苯二酚、4,6-二苯甲醯基間苯二酚、羥基 癸基二苯甲酮、2,2’-二羥基-4(3-甲基丙烯醯氧-2-羥丙氧基) 二苯甲酮等之二苯甲酮系;2-(2’-羥基- 5’-甲基苯基)苯并三 唑之苯并三唑系及其他的(草酸苯胺、胺基丙烯酸酯)的化合 物等。 和紫外線吸收劑混合使用之光安定劑,舉例來說,例如 其可以是受阻胺衍生物,具體而言,例如是雙_(2,2’,6,6’-四甲基-4-哌啶基)癸二酸酯、4-苯甲醯氧基- 2,2’,6,6’-四甲基 哌啶等,而且可以適當地選擇此等中之1種或2種以上來使 用。 就使甩本發明之消光陰離子電鍍塗料來形成塗膜而 言,可以使上述所得到的陰離子電鍍塗料做成浴,將該鋁材 料浸漬在此浴中後,使用著色或無著色陽極氧化鋁材當做被 塗物,進行陰離子電鍍塗裝使所形成之乾燥膜厚度成爲約5 〜30微米,不進行水洗(norwinse)、或進行水洗(「inse), 接著在室溫定型後,再於60〜150 °C、較宜是80〜140 °C下 -20 -Salicylic acid derivative, 254-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,2, dihydroxy-4-methoxybenzophenone, 2-hydroxy-4 -Methoxy-2, carboxybenzophenone, 2-hydroxy-4-methoxy-5-thiobenzophenone trihydrogen ester, 2,2'-dihydroxy-4,4'-dimethoxy Benzophenone, 2-hydroxy-4-octylbenzophenone, 2-hydroxy-4-octadecyloxybenzophenone, 2,2,-dihydroxy-4,4'-dimethoxy Sodium 5-thiobenzophenone sodium, 2,2',4,4'-tetrahydroxybenzophenone, 4-decyloxy-2-hydroxybenzophenone, 5-chloro-2-hydroxyl Benzophenone, resorcinol monobenzoate, 2,4-dibenylhydrazino-resorcinol, 4,6-diphenylmercaptoresorcinol, hydroxydecylbenzophenone, a benzophenone series such as 2,2'-dihydroxy-4(3-methylpropenyloxy-2-hydroxypropoxy)benzophenone; 2-(2'-hydroxy-5'-methyl a benzotriazole-based benzotriazole-based benzotriazole-based compound or other compound (anilinic acid oxalate, amino acrylate). A light stabilizer for use in combination with a UV absorber, for example, it may be a hindered amine derivative, specifically, for example, bis(2,2',6,6'-tetramethyl-4-piperidin Ordinary azelaic acid ester, 4-benzylideneoxy-2,2',6,6'-tetramethylpiperidine, etc., and one or more of these may be appropriately selected and used. . In order to form a coating film by using the matting anionic plating coating of the present invention, the anion plating coating obtained above may be made into a bath, and after the aluminum material is immersed in the bath, a colored or non-colored anodized aluminum material is used. As an object to be coated, an anion plating is applied to form a dried film having a thickness of about 5 to 30 μm, without washing with water (norwinse) or with water washing ("inse", followed by setting at room temperature, and then 60~ 150 ° C, preferably 80 ~ 140 ° C under -20 -

1264452 燒成約2 0〜4 0分鐘並藉由乾燥而使形成塗膜。 藉由消光陰離子電鍍塗料之塗裝所得到的被塗物之塗 膜硬度係顯示出4 Η以上之鉛筆硬度(註3 )、4以上之茲孔 (TUKON)硬度(註4)的高塗膜硬度。 (註3)鉛筆硬度,以JIS Κ 5600-5-4爲基準,使鉛筆芯 以約4 5 °角抵觸試驗塗板面,一邊以約不會折損筆芯左右之 強度按壓試驗塗板面,一邊以均一的速度向前方移動約1 0 毫米。改變試驗處所反復此操作5次,以塗膜不破損情況的 最硬之鉛筆硬度記號當做鉛筆硬度。 (註4)茲孔(TUKON)硬度:將塗板在20°C之恆溫室中放 置4小時後,以美國鏈&纜公司製之TUKON微硬度測試儀 測定而得。 又,消光陰離子電鍍塗料,也可以容易地藉由使用組合 至少2種類的乳化液來調整消光程度。 例如,可以使用含有以相對於乙烯系共聚物(a 1 )和乙烯 系共聚物(a2)之總量1〇〇重量份計,乙烯系共聚物(a 1)/乙烯 系共聚物(a2) =30〜90重量份/1 0〜70重量份之摻混比例, 而以水分散所構成的乙烯系共聚物(a1 )/乙烯系共聚物02) =30〜90重量份/10〜7〇重量份的範圍之乳化液(2)之陰離 子電鍍塗料。 例如,就塗裝線而言’在想要得到變化消光程度之塗裝 物品的情況下,則可以藉由改變乳化液(1 )/乳化液(2)之摻混 比例而適時調整補給到陰離子電鍍塗料。 【實施例】 -21 - 1264452 以下,列舉實施例來更進一步詳細地說明本發明。但是 本發明不僅限定於此等實施例而已。又,「份」及「%」係 表示「重量份」和「重量份」1264452 was fired for about 20 to 40 minutes and dried to form a coating film. The coating film hardness of the coating material obtained by coating the matte anion plating coating shows a pencil hardness of 4 Η or more (Note 3) and a high coating film of 4 or more TUKON hardness (Note 4). hardness. (Note 3) The pencil hardness is based on JIS Κ 5600-5-4, and the pencil lead is pressed against the test coating surface at an angle of about 45°, and the test coating surface is pressed against the strength of the right and left of the refill. The uniform speed moves forward by approximately 10 mm. This operation was repeated 5 times by changing the test place, and the hardest pencil hardness mark in which the film was not damaged was regarded as the pencil hardness. (Note 4) TUKON hardness: The coated plate was placed in a thermostatic chamber at 20 ° C for 4 hours, and then measured by a TUKON microhardness tester manufactured by American Chain & Cable Co., Ltd. Further, in the matte anionic plating coating, it is also possible to easily adjust the degree of extinction by using at least two types of emulsions in combination. For example, the ethylene-based copolymer (a 1)/ethylene-based copolymer (a2) may be used in an amount of 1 part by weight based on the total amount of the ethylene-based copolymer (a 1 ) and the ethylene-based copolymer (a2). = 30 to 90 parts by weight / 10 to 70 parts by weight of the blending ratio, and the ethylene-based copolymer (a1) / ethylene-based copolymer 02) composed of water dispersion = 30 to 90 parts by weight/10 to 7 Torr An anionic plating coating of the emulsion (2) in the range of parts by weight. For example, in the case of a coating line, in the case where a coated article having a varying degree of extinction is desired, the replenishment to the anion can be appropriately adjusted by changing the blending ratio of the emulsion (1) / emulsion (2). Electroplating coatings. [Embodiment] - 21 - 1264452 Hereinafter, the present invention will be described in further detail by way of examples. However, the present invention is not limited to the embodiments. Also, "parts" and "%" mean "parts by weight" and "parts by weight"

〈製造例1〉 編號1之乙烯系共聚物(a 1 )溶液之製造例 在備有攪拌機、迴流冷卻器及溫度計之反應器中裝入 6 5份之甲氧丙基乙酸酯,加熱並保持於1 3 〇 〇c,以3小時滴 下25份m-異丙烯基- α,α_二甲基苄基異氰酸酯(m_TM|)、 4〇份之iso -丁基甲基丙烯酸酯、4份之η·丁基丙烯酸醋、 3 1份之甲氧乙基丙烯酸酯的混合物。 接著以1小時滴下3 5份之甲氧丙基乙酸酯、5 · 〇份之 卜丁基過氧異丙基碳酸酯的混合液,進一步熟成3小時,而 得到固體物爲50%之編號1之乙烯系共聚物(a彳)溶液。 編號1之乙烯系共聚物(a 1 )溶液中之乙烯系共聚物(a1 ) 之重量平均分子量爲約5000,SP値爲9.0,Tg爲24.1 °C。 〈製造例2〜5 &gt; 和製造例1同樣地按照表1之摻混內容,以溶劑調整固 體物而得到編號2〜5之乙烯系共聚物(a彳)溶液。 -22 - 1264452 製造例5 編號5 LO CD Ο) CO LO C0 LO 5000 寸 οό 00 LO 1 製造例4 編號4 L〇 CD 〇 卜 LT) 00 IT) g 5000 00 〇6 LO CD 製造例3 編號3 L〇 CD L〇 CvJ CvJ 寸 卜 CD LO C0 LT) g 5000 〇〇 00 24.4 製造例2 編號2 ΙΟ CD L〇 CM 33.4 CO T— 寸 LO C0 LO s 5000 00 00 00 C0 製造例1 編號1 L〇 CD ΙΟ CvJ o 寸 寸 LT) C0 LO s 5000 〇 σ&gt; 24.1 乙烯系共聚物(a1)溶液 甲氧丙基乙酸酯 ll 義 - am ?瀣 Ml i|l K峨 «ν W E tf iso-丁基甲基丙烯酸酯 η-丁基丙烯酸酯 甲氧乙基丙烯酸酯 2-乙基己基丙烯酸酯 甲基丙烯酸甲酯 甲基丙烯酸乙酯 甲氧丙基乙酸酯 卜丁基過氧異丙基碳酸酯 固體物(%) 重量平均分子量 SP値 Tg(°c) 摻混 特徵<Production Example 1> Production Example of Ethylene-Based Copolymer (a 1 ) Solution No. 1 In a reactor equipped with a stirrer, a reflux condenser, and a thermometer, 65 parts of methoxypropyl acetate was charged and heated. While maintaining at 1 3 〇〇c, 25 parts of m-isopropenyl-α, α-dimethylbenzyl isocyanate (m_TM|), 4 parts of iso-butyl methacrylate, 4 parts of η were added dropwise over 3 hours. a mixture of butyl acrylate and 31 parts of methoxyethyl acrylate. Then, a mixture of 35 parts of methoxypropyl acetate and 5 parts of butyl peroxyisopropyl carbonate was added dropwise over 1 hour, and further matured for 3 hours to obtain a solid matter of 50%. A vinyl copolymer (a) solution. The ethylene-based copolymer (a1) in the ethylene-based copolymer (a1) solution of No. 1 had a weight average molecular weight of about 5,000, an SP値 of 9.0, and a Tg of 24.1 °C. <Production Examples 2 to 5 &gt; In the same manner as in Production Example 1, the solid content was adjusted with a solvent in accordance with the blending contents of Table 1, and a vinyl-based copolymer (a) having a number of 2 to 5 was obtained. -22 - 1264452 Manufacturing Example 5 No. 5 LO CD Ο) CO LO C0 LO 5000 Inch οό 00 LO 1 Manufacturing Example 4 No. 4 L〇CD 〇 LT) 00 IT) g 5000 00 〇6 LO CD Manufacturing Example 3 No. 3 L〇CD L〇CvJ CvJ Inch CD LO C0 LT) g 5000 〇〇00 24.4 Manufacturing Example 2 No. 2 ΙΟ CD L〇CM 33.4 CO T-inch LO C0 LO s 5000 00 00 00 C0 Manufacturing Example 1 No. 1 L 〇CD ΙΟ CvJ o inch LT) C0 LO s 5000 〇σ> 24.1 Vinyl copolymer (a1) solution methoxypropyl acetate ll - am ? Ml i|l K峨 «ν WE tf iso-butyl Acrylate η-butyl acrylate methoxyethyl acrylate 2-ethylhexyl acrylate methyl methacrylate ethyl methacrylate methoxypropyl acetate butyl peroxy isopropyl carbonate solid ( %) Weight average molecular weight SP値Tg(°c) Blending characteristics

〈製造例6〉 編號6之乙烯系共聚物(a2)溶液 -23 - 1264452 在反應器中投入2 7 5份之甲氧丙基乙酸酯,並保持於 8 (TC,以3小時向其中滴下7 5份之苯乙烯、1 5 5份之甲基 丙烯酸甲酯、9 5份之η - 丁基丙烯酸酯、5 0份之乙基丙烯酸 酯、7 5份之2 -羥乙基丙烯酸酯、3 5份之丙烯酸、1 5份之r -甲基丙烯醯氧丙基三甲氧基矽烷、以及1份之疊氮聯二甲<Production Example 6> No. 6 ethylene-based copolymer (a2) solution -23 - 1264452 275 parts of methoxypropyl acetate was placed in a reactor and kept at 8 (TC, 3 hours) 7 5 parts of styrene, 155 parts of methyl methacrylate, 9.5 parts of η-butyl acrylate, 50 parts of ethyl acrylate, and 7 parts of 2-hydroxyethyl acrylate , 35 parts of acrylic acid, 15 parts of r-methacryloxypropyltrimethoxydecane, and 1 part of azide

基戊腈的混合物,接著添加3份之疊氮聯二甲基戊腈,保持 於8 0 °C進行反應3小時,而得到具有烷氧矽烷基之固體物 爲65重量%之編號1之水分散性乙烯系共聚物(a2)溶液。該 編號1之溶液中之水分散性乙烯系共聚物(a2)的SP値爲 9_54,Tg 爲 25〇C。 〈製造例7〉 編號1之樹脂(A)溶液之製造 在備有攪拌機、迴流冷卻器及溫度計之反應器中加入 700份(固體物爲350份)之固體物爲50%之編號1之乙烯系 共聚物(a 1 )溶液、以及1 000份(固體物爲650份)之在製造 例6所得到的編號1之水分散性乙烯系共聚物(a2)溶液,於 室溫(25°C )下攪拌15分鐘,測定異氰酸酯價。混合清漆之 異氰酸酯價爲4 7 · 6。 接著,邊攪拌邊加熱維持於4 0 °C,約進行反應3小時 後,在異氰酸酯價變爲4 5.8的時點加入3 0 0份之甲乙酮肟, 於60°C下熟成2小時,而得到固體物爲50.0%、重量平均分 孑量爲約1 6000之編號1之樹脂(A)溶液。 〈製造例8〜1 2〉 和製造例7同樣地按照表2之摻混內容,製得編號2 -24- 1264452 Z樹脂(A)溶液〜編號6之樹脂(A)溶液。在表2中,括弧內 之表示固體物量。 表2 製造例12 編號6 700 (350) 1000 (650) 300 2000 (1000) 1.14 製造例11 編號5 r 700 I (350) I 1000 (650) 300 I 2000 (1000) 1.24 製造例10 編號4 600 (300) 1077 (700) 323 2000 (1000) 0.54 製造例9 編5虎3 700 (350) 1000 (650) 300 2000 (1000) 0.74 製造例8 編號2 700 (350) 1000 (650) 300 2000 (1000) 0.74 製造例7 編號1 700 (350) I 1000 (650) I 300 2000 (1000) j 0.54 : 樹脂(A)溶液(種類) 編號1之乙烯系共聚物(a1)溶液 編號2之乙烯系共聚物(a1)溶液 編號3之乙烯系共聚物(a1)溶液 編號4之乙烯系共聚物(a1)溶液 編號5之乙烯系共聚物(a1)溶液 ΦΚ 讓 甲乙酮肟 樹脂(A)溶液(摻混量) |她I nn Q. 我⑺ K]孔 〈製造例1 3〉 在反應器中投入5 5份之異丙醇並保持於8 0 °C,以3小 -25 - 1264452a mixture of valeronitrile, followed by the addition of 3 parts of azide dimethyl valeronitrile, and maintaining the reaction at 80 ° C for 3 hours to obtain a water having an alkoxyalkyl group as a solid content of 65% by weight. A solution of a dispersible ethylene-based copolymer (a2). The water-dispersible ethylene-based copolymer (a2) in the solution of No. 1 had an SP値 of 9 to 54 and a Tg of 25 °C. <Production Example 7> Production of Resin (A) Solution No. 1 In a reactor equipped with a stirrer, a reflux condenser, and a thermometer, 700 parts (350 parts of solid matter) of solid matter was added as 50% of ethylene of No. 1 a copolymer (a 1 ) solution and 1 000 parts (650 parts by weight) of the water-dispersible ethylene-based copolymer (a2) solution of No. 1 obtained in Production Example 6, at room temperature (25 ° C) The mixture was stirred for 15 minutes, and the isocyanate valence was measured. The isocyanate price of the mixed varnish is 4 7 · 6. Next, heating was maintained at 40 ° C while stirring, and after about 3 hours of reaction, 300 parts of methyl ethyl ketone oxime was added at a time when the isocyanate value became 45.8, and it was aged at 60 ° C for 2 hours to obtain a solid. A resin (A) solution having a weight of 50.0% and a weight average of about 16,000. <Production Examples 8 to 1 2> A resin (A) solution of No. 2 -24 to 1264452 Z resin (A) solution to No. 6 was obtained in the same manner as in Production Example 7 in accordance with the blending contents of Table 2. In Table 2, the amount of solid matter is indicated in brackets. Table 2 Manufacturing Example 12 No. 6 700 (350) 1000 (650) 300 2000 (1000) 1.14 Manufacturing Example 11 No. 5 r 700 I (350) I 1000 (650) 300 I 2000 (1000) 1.24 Manufacturing Example 10 No. 4 600 (300) 1077 (700) 323 2000 (1000) 0.54 Manufacturing Example 9 Series 5 Tiger 3 700 (350) 1000 (650) 300 2000 (1000) 0.74 Manufacturing Example 8 No. 2 700 (350) 1000 (650) 300 2000 ( 1000) 0.74 Production Example 7 No. 1 700 (350) I 1000 (650) I 300 2000 (1000) j 0.54 : Resin (A) solution (type) No. 1 ethylene copolymer (a1) Solution No. 2 of ethylene Copolymer (a1) Solution No. 3 of ethylene-based copolymer (a1) Solution No. 4 of ethylene-based copolymer (a1) Solution No. 5 of ethylene-based copolymer (a1) solution ΦΚ Let methyl ethyl ketone oxime resin (A) solution (doped Mixing) |She I nn Q. I (7) K]Hole <Manufacturing Example 1 3> Put 5 5 parts of isopropanol in the reactor and keep at 80 °C, 3 small -25 - 1264452

捺_其中滴π 1 5份之苯乙烯,3 ·〗份之甲基丙烯酸甲酯' 1 5 份之丁基丙烯酸酯'10份之乙基丙烯酸酯、15份之2〜 羥乙基丙烯酸酯' 7份之丙烯酸、7份之Ν = 丁氧甲基丙烯醯 胺 '以及1。0份之疊氮聯二甲基戊腈之混合物5滴下終了後 於此溫度下保持1小時,接著滴下1份之疊氮聯二甲基戊腈 和4 5份之丁基溶纖素,進一步於8 0 °C持續進行反應4小 時,而得到固體物爲50重量。/。、重量平均分子量爲30〇〇〇、 S P値爲9.6 0,T g爲1 6 _ 5。(:之編號7之樹脂溶液。 〈製造例1 4〉 編號1之乳化液之製造 在摻混相對於200份(固體物爲100份)之在製造例7所 製作的編號1之樹脂(A)溶液的羧基計爲〇 _ 4當量之三乙胺 後,再予以混合分散,並混合〇·5份(固體物)之SCAT-7(註 5)予以分散後,再邊攪拌邊慢慢地滴下去離子水’更進一步 添加三乙胺、以去離子水調使P Η値成7 · 5而得到固體物爲 1 0 %之編號1之乳化液。 和製造例1 4同樣地按照表3之摻混內容,製得編號2 〜〜編號6之固體物爲1 〇%的乳化液。 〈製造例20〉 在1 40份(固體物爲70份)之在製造例1 3所製作的編號 7之樹脂溶液中,混合37,5份(固體物爲30份)之杜拉內特 MF-B80M(註 6)、〇·5 份(固體物爲 0.5 份)之 SCAT-7(註 5), 邊進行攪拌邊慢慢滴下去離子水,更進一步添加三乙胺、以 -26 - 1264452 去離子水調使ρ Η値成7.5而得到固體物爲1 Ο %之編號7之 乳化液。捺_ π 1 5 parts of styrene, 3 · gram of methyl methacrylate '15 parts of butyl acrylate '10 parts of ethyl acrylate, 15 parts of 2 ~ hydroxyethyl acrylate A mixture of '7 parts of acrylic acid, 7 parts of hydrazine = butoxy methacryl decylamine' and 1.0 part of azide dimethyl valeronitrile was left at this temperature for 1 hour, followed by dropping 1 A portion of azide dimethyl valeronitrile and 45 parts of butyl cellosolve were further subjected to a reaction at 80 ° C for 4 hours to obtain a solid matter of 50 parts by weight. /. The weight average molecular weight is 30 〇〇〇, S P 値 is 9.6 0, and the T g is 16 _ 5 . (Production No. 7 of the resin solution. <Production Example 1 4> The emulsion of No. 1 was produced by blending the resin of No. 1 produced in Production Example 7 with respect to 200 parts (100 parts of solid matter). After the carboxyl group of the solution is 〇 4 equivalents of triethylamine, it is mixed and dispersed, and 5 parts (solid matter) of SCAT-7 (Note 5) is mixed and dispersed, and then slowly dripped while stirring. The ionized water was further added with triethylamine, and the deionized water was adjusted to make P 7.5 to obtain an emulsion having a solid content of 10% of No. 1. The same as in Production Example 1 4, according to Table 3 In the case of the mixing, the emulsion of No. 2 to No. 6 was obtained in an amount of 1% by weight. <Production Example 20> In the number of 7 of 40 parts (solid content: 70 parts), the number 7 was produced in Production Example 13. In the resin solution, 37,5 parts (30 parts of solids) of Duranet MF-B80M (Note 6), and 5 parts (0.5 parts of solid matter) of SCAT-7 (Note 5) were mixed. While stirring, slowly drip the ionized water, further add triethylamine, adjust ρ Η値 to 7.5 with -26 - 1264452 deionized water to obtain a solid content of 1 Ο % 7 The emulsion.

製造例20 編號7 140(70) 0.5(0.5) 37.5(30) 調整成爲1 〇 %固體物 製造例19 _I 編號6 | | 200(100) | 0.5(0.5) !___ 1 製造例18 j _ 編號5 200(100) 0.5(0.5) 製造例17 編號4 200(100) 0.5(0.5) c\T τ— ^ T— 製造例16 編號3 200(100) 0.5(0.5) 0.4(0.4) 製造例15 編號2 200(100) 0.5(0.5) 1 製造例14 編號1 200(100) 0.5(0.5) ^7.5 乳化液 編號1之樹脂(A)溶液 編號2之樹脂(A)溶液 編號3之樹脂(A)溶液 編號4之樹脂(A)溶液 編號5之樹脂(A)溶液 編號6之樹脂(A)溶液 編號7之樹脂溶液 SCAT-7(註 5) 杜拉內特MF-80M(註6) U-CAT18X(註 7) 汽內畢328(註8) 汽內畢292(註9) 三乙胺 去離子水 (鬆瀏画) -27 - 1264452 (註5 )S CAT-7 :三共有機合成(股)公司製,商品名,二 丁錫雙氫硫基羧酸酯; (註6)杜拉內特MF-B80M :旭化成(股)公司製,商品名, 六亞甲基異氰酸酯之異氰酸酯型、甲乙酮肟嵌段化劑、固體 物爲8 0 % ; (註7)U-CAT18X :三洋化成公司製,商品名,胺系之硬 化觸媒;Manufacturing Example 20 No. 7 140 (70) 0.5 (0.5) 37.5 (30) Adjustment to 1 〇% solid matter Production Example 19 _I No. 6 | | 200 (100) | 0.5 (0.5) !___ 1 Manufacturing Example 18 j _ No. 5 200 (100) 0.5 (0.5) Manufacturing Example 17 No. 4 200 (100) 0.5 (0.5) c \T τ - ^ T - Manufacturing Example 16 No. 3 200 (100) 0.5 (0.5) 0.4 (0.4) Manufacturing Example 15 No. 2 200 (100) 0.5 (0.5) 1 Production Example 14 No. 1 200 (100) 0.5 (0.5) ^7.5 Resin No. 1 Resin (A) Solvent No. 2 Resin (A) Solution No. 3 Resin (A) Solution No. 4 Resin (A) Solution No. 5 Resin (A) Solution No. 6 Resin (A) Solution No. 7 Resin Solution SCAT-7 (Note 5) Duranet MF-80M (Note 6) U -CAT18X(Note 7) 汽内毕328(Note 8) 汽内毕292(Note 9) Triethylamine deionized water (Song Liuhua) -27 - 1264452 (Note 5) S CAT-7: Sankyo Organic Synthesis (Stock) company, trade name, dibutyltin dihydrothiocarboxylate; (Note 6) Duranet MF-B80M: Asahi Kasei Co., Ltd., trade name, hexamethylene isocyanate isocyanate type, methyl ethyl ketone Barium block The chemical agent and the solid matter are 80%; (Note 7) U-CAT18X: Sanyo Chemical Co., Ltd., trade name, amine hardening catalyst;

(註8)汽內畢328 :汽巴蓋記股份有限公司製,商品名, 紫外線吸收劑; (註9)汽內畢292 :汽巴蓋記股份有限公司製’商品名, 光安定劑; 【實施例1】 於1 000份(固體物爲100份)的編號1之固體物爲1 〇% 之乳化液中,添加三乙胺使P Η値成爲8 · 5,而得到編號1 之陰離子電鍍塗料。(Note 8) Vapor Completion 328: manufactured by Ciba Bags Co., Ltd., trade name, UV absorber; (Note 9) Vapor Bi 292: Commodity name, light stabilizer; [Example 1] In 1 000 parts (100 parts of solid matter), the emulsion of No. 1 solid matter was 1% by weight, and triethylamine was added to make P Η値 8.5, and an anion of No. 1 was obtained. Electroplating coatings.

藉由和實施例1同樣之操作,而得到如表4之內容的實 施例2〜5之編號2〜編號5之陰離子電鍍塗料。 【比較例1〜4】 藉由和實施例1同樣之操作,而得到如表5之內容的比 較例1〜4之編號6〜編號9之陰離子電鍍塗料。 【比較例5】 使用艾雷庫龍AG-300(關西油漆公司製’商品名’丙烯 -28 - 1264452 酸樹脂•蜜胺硬化型之陰離子電鍍塗料)。 試驗板之作成_ 將在實施例及比較例所得到的陰離子電鍍塗料做成 浴,將已實施2次處理(脫脂-蝕刻-中和-陽極氧化處理-封孔) 之被膜厚度爲約1 〇微米的陽極氧化錦材(銀:大小爲1 5 〇 ^ 7 0x0.5毫米)之被塗物浸漬於此浴中,進行電鍍塗裝使乾燥 膜厚度成爲1〇微米,水洗後再於140 °C燒成20分鐘。An anionic plating coating of Nos. 2 to 5 of Examples 2 to 5 as shown in Table 4 was obtained by the same operation as in Example 1. [Comparative Examples 1 to 4] An anionic plating coating of Nos. 6 to 9 of Comparative Examples 1 to 4 as shown in Table 5 was obtained by the same operation as in Example 1. [Comparative Example 5] Aerecuron AG-300 (manufactured by Kansai Paint Co., Ltd.) propylene -28 - 1264452 acid resin/melamine hardening type anion plating coating) was used. Preparation of test plate _ The anion plating coatings obtained in the examples and the comparative examples were bathed, and the thickness of the film which had been subjected to two treatments (degreasing-etching-neutralizing-anodizing-sealing) was about 1 〇. The micron anodized bismuth material (silver: 1 5 〇^ 7 0x0.5 mm) is immersed in the bath to make the dried film thickness 1 〇 micron, washed and then 140 ° C is baked for 20 minutes.

依照下述之試驗條件進行試驗。實施例示於表4,而比 較例則示於表5。 表4 實施例1 實施例2 實施例3 實施例4 實施例5 陰離子電鍍塗料 編號1 編號2 編號3 編號4 編號5 摻 混 乳化液 種 編號1 編號2 編號3 編號4 編號1 摻混量 1000 1000 1000 1000 500 種 編號2 摻混量 500 三乙胺 調整成 pH=8_5 &lt;— &lt;— &lt;— &lt;— 塗 膜 性 能 凝膠分率(註10) 95 95 98 93 95 鉛筆硬度(註11) 4H 4H 5H 4H 4H 茲孔硬度(註12) 4 5 6 4 4.5 60°光澤度(註13) 4 8 5 7 6 模印記隱蔽性(註14) 〇 〇 〇 〇 〇 摩擦附著性(註15) ◎ ◎ ◎ ◎ 〇 耐候性(註16) 90 94 91 96 92 -29- 1264452 表5 —----— ---------- ______ 比較例1 比較例2 比較例3 比較例4 比較例5 陰離子電鍍塗料 ----_______ ________ - 編號6 編號7 編號8 編號9 種 編號5 編號6 編號5 編號7 掺 乳化液 摻混量 1000 1000 500 1000 艾雷 種 編號6 庫龍 混 摻混量 500 AG-300 三乙胺 調整成 ρΗ=8·5 &lt;— &lt;— &lt;— 凝膠分率(註10) 91 93 92 90 84 塗 膜 性 能 鉛筆硬度(註11) 2Η 2Η 2Η 2Η 2Η 茲孔硬度(註12) 3 3 3 2 2 60°光澤度(註13) 23 35 27 38 5 模印記隱蔽性(註14) Δ Δ Δ Δ X 摩擦附著性(註15) 〇 〇 〇 Δ X 耐候性(註16) 87 88 87 91 53 (I主10)凝膠分率:The test was carried out in accordance with the test conditions described below. The examples are shown in Table 4, and the comparative examples are shown in Table 5. Table 4 Example 1 Example 2 Example 3 Example 4 Example 5 Anion plating material No. 1 No. 2 No. 3 No. 4 No. 5 Mixed emulsion type No. 1 No. 2 No. 3 No. 4 No. 1 Blending amount 1000 1000 1000 1000 500 Kind No. 2 Blending amount 500 Triethylamine adjusted to pH=8_5 &lt;- &lt;- &lt;- &lt;- Coating film performance gel fraction (Note 10) 95 95 98 93 95 Pencil hardness (Note 11) 4H 4H 5H 4H 4H Buchhole hardness (Note 12) 4 5 6 4 4.5 60° gloss (Note 13) 4 8 5 7 6 Imprinting concealability (Note 14) 〇〇〇〇〇 Friction adhesion (Note) 15) ◎ ◎ ◎ ◎ 〇 weather resistance (Note 16) 90 94 91 96 92 -29- 1264452 Table 5 —----— ---------- ______ Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Anionic Electroplating Coating----__________________ - No.6 No.7 No.8 No.9 No.5 No.6 No.5 No.7 Mixed Emulsion Mixing 1000 1000 500 1000 Ai Lei Type No.6 Coulomb Mixing amount 500 AG-300 Triethylamine adjusted to ρΗ=8·5 &lt;- &lt;- &lt;- Gel fraction (Note 10) 9 1 93 92 90 84 Coating performance Pencil hardness (Note 11) 2Η 2Η 2Η 2Η 2Η Dielectric hardness (Note 12) 3 3 3 2 2 60° Gloss (Note 13) 23 35 27 38 5 Imprinting concealment (Note) 14) Δ Δ Δ Δ X Friction adhesion (Note 15) 〇〇〇Δ X Weather resistance (Note 16) 87 88 87 91 53 (I main 10) Gel fraction:

將從塗裝馬口鐵板之馬口鐵板剝離的塗膜裝入3 0 0篩 目之不銹鋼製的網狀容器中,使用丙酮/甲醇=彳/1之溶劑、 於迴流溫度下萃取6小時後,依照下式算出凝膠分率。 凝膠分率(%)=(萃取後之塗膜重量)/(萃取前之塗膜重量)χ1〇〇 (註1 1 )鉛筆硬度: 以J IS Κ 56 0 0-5-4爲基準,使鉛筆芯以約45。角抵觸試 驗塗板面’ 一邊以約不會折損筆芯左右之強度按壓試驗塗板 面’一邊以均一的速度向前方移動約1 0毫米。改變試驗處 所反復此操作5次,以塗膜不破損情況的最硬之鉛筆硬度記 號當做鉛筆硬度。 -30-The coating film peeled from the tinplate coated with the tinplate is placed in a mesh container made of stainless steel of 300 mesh, and extracted with a solvent of acetone/methanol=彳/1 at reflux temperature for 6 hours. The gel fraction was calculated by the following formula. Gel fraction (%) = (weight of coating film after extraction) / (weight of coating film before extraction) χ 1 〇〇 (Note 1 1 ) Pencil hardness: Based on J IS Κ 56 0 0-5-4, Make the pencil lead at about 45. The angle of the test is applied to the surface of the test plate, and the test plate surface is pressed about the strength of the left and right sides of the refill, and the front side is moved at a uniform speed by about 10 mm. The test was repeated five times, and the hardest pencil hardness mark with no damage to the film was used as the pencil hardness. -30-

1264452 (註12)茲孔(TUKON)硬度: 將塗板在2 0 °C之恆溫室中放置4小時後 公司製之TUKON微硬度測試儀測定而得。數 塗膜愈硬。 (註13)60°光澤度: 塗膜之光澤的程度係依照JIS K-5400 7· 度鏡面光澤度,分別測定60度時之入射角和 率,以鏡面光澤度之基準面的光澤度做爲1 0 0 表示。 (註14)模印記隱蔽性: 以目視評價來評價。 〇:模印記隱蔽性良好。 △:模印記隱蔽性不佳。 X :模印記隱蔽性顯著低劣。 (註1 5)摩擦附著性: 在試驗板之中央部長度方向上’切割覓 行線(到達鋁面)。從一方之端面剝離約僅90 彎曲1 8 0度(參照第1圖)。 使用自動繪圖S - D型(島津製作所社製、 恆溫槽之萬能拉伸試驗機),以50毫米/分鐘 行拉伸約30毫米(氛圍氣溫度爲25°C ±5它)、 剝離強度。 ◎:剝離強度爲39.2 N (4公斤重)以上。 〇:剝離強度爲2 9 _ 4〜3 9 · 2 N。 以美國鏈&amp;纜 値愈高則表示 6(1 990)之 60 受光角的反射 時之百分率來 25毫米之平 米之薄膜層, 商品名、附有 之拉伸速度進 並測定薄膜之 1264452 △:剝離強度爲20〜29„4N。 X :剝離強度爲小於20N。 (註16)耐候性: 藉由利用陽光氣候計,評量照射2 0 0 0小時之光澤保持 率(%)。 【產業利用可能性】1264452 (Note 12) TUKON hardness: The coated plate was placed in a thermostatic chamber at 20 °C for 4 hours and then determined by a TUKON microhardness tester. The harder the film is. (Note 13) 60° gloss: The degree of gloss of the coating film is measured according to JIS K-5400 7 · degree specular gloss, and the incident angle and rate at 60 degrees are respectively measured, and the gloss of the reference surface of the specular gloss is made. It is represented by 1 0 0. (Note 14) Mold imprint concealability: Evaluation by visual evaluation. 〇: The stamp is well concealed. △: The impression is poorly concealed. X: The imprinting of the stamp is significantly inferior. (Note 1 5) Friction adhesion: Cut the 觅 line (to reach the aluminum surface) in the longitudinal direction of the center portion of the test plate. It is peeled off from the end face of one side by only 90 bends by 180 degrees (refer to Fig. 1). Using an automatic drawing S-D type (manufactured by Shimadzu Corporation, a universal tensile tester for a constant temperature bath), the product was stretched at a distance of 50 mm/min for about 30 mm (ambient gas temperature was 25 ° C ± 5 rpm), and peel strength. ◎: The peel strength was 39.2 N (4 kg weight) or more. 〇: Peel strength is 2 9 _ 4~3 9 · 2 N. The higher the US chain & cable, the higher the percentage of 6 (1 990) 60 reflected by the light angle to the film layer of 25 mm square meters, the trade name, the attached tensile speed and the measurement of the film 1644452 △ : Peeling strength is 20 to 29 „4N. X: Peeling strength is less than 20 N. (Note 16) Weather resistance: The gloss retention rate (%) of 2000 hours is measured by using a sunlight climatometer. Utilization possibility

藉由利用本發明之消光陰離子電鍍塗料,可以得到低溫 硬化性、塗膜硬度、模印記隱蔽性均優異的60。光、澤g ] 〇 以下之消光塗膜、及消光塗裝物品。 【圖式簡單說明】 第1圖爲摩擦附著性試驗之模式圖。 【元件符號說明】 1 塗膜 2 3By using the matte anionic plating coating of the present invention, 60 which is excellent in low-temperature hardenability, coating film hardness, and mold-blocking concealability can be obtained. Light, ze g ] 〇 The following matte coating film, and matte coated items. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic view of a frictional adhesion test. [Component Symbol Description] 1 Coating film 2 3

被塗物之鋁 副板 用以固定試驗板之部分 -32 -The aluminum plate of the object to be coated is used to fix the part of the test plate -32 -

Claims (1)

126.4452 十、申請專利範圍:126.4452 X. Patent application scope: 1 _ 一種消光陰離子電鍍塗料,其特徵在於:藉由利用將在1 分子中具有2個以上之游離異氰酸酯基的乙烯系共聚物 (a1)之該游離異氛酸醋基的一部分,與具有氯氧基、竣基 及烷氧矽烷基之乙烯系共聚物(a2)之氫氧基的一部分起 反應,接著使全部的殘存之游離異氰酸酯基與嵌段化劑起 反應而成之在1分子中具有倂存的嵌段異氰酸酯基和氫 氧基之樹脂,且乙烯系共聚物(a1)和乙烯系共聚物(a2)之 溶解性參數(SP値)的差爲0.4〜1·0之樹脂(A)予以水分 散化,更且進一步添加硬化觸媒(Β)予以分散化所形成的 乳化液而構成,且含有相對於樹脂(Α)之總量100重量份 計爲〇」〜10重量份之硬化觸媒(Β)。 2 ·如申請專利範圍第1項之消光陰離子電鍍塗料,其中硬 化觸媒(Β)爲自有機錫化合物及胺化合物中所選出之至少 1種的化合物。 3 _如申請專利範圍第1或2項之消光陰離子電鍍塗料,乙 烯系共聚物(a 1)爲由含有異氰酸酯基之乙烯系單體及其 他的乙烯系單體所形成的共聚物。 4 _ 一種消光塗裝物品,其在經陽極氧化處理的鋁基材上,塗 裝如申請專利範圍第1至3項中任一項之消光陰離子電 鍍塗料所形成之塗膜面的6 0 °光澤度係爲1 〇以下。 -33 -1 - a matte anionic plating coating characterized by using a part of the free isocyanate group of the ethylene-based copolymer (a1) having two or more free isocyanate groups in one molecule, and having chlorine a part of the hydroxyl group of the ethylene-based copolymer (a2) of the oxy group, the mercapto group and the alkoxyalkyl group is reacted, and then all the remaining free isocyanate groups are reacted with the blocking agent to form one molecule. a resin having a blocked block isocyanate group and a hydroxyl group-containing resin, and a difference in solubility parameter (SP値) between the ethylene-based copolymer (a1) and the ethylene-based copolymer (a2) is 0.4 to 1.0% ( A) The water is dispersed, and further, an emulsion formed by dispersing a curing catalyst (Β) is further added, and is contained in an amount of 〇 10 parts by weight based on 100 parts by weight of the total amount of the resin. Hardening catalyst (Β). 2. The matte anionic plating coating according to the first aspect of the invention, wherein the hardening catalyst (Β) is at least one selected from the group consisting of an organotin compound and an amine compound. 3. The matte anionic plating coating according to claim 1 or 2, wherein the ethylene copolymer (a1) is a copolymer of a vinyl monomer containing an isocyanate group and another vinyl monomer. 4 _ A matte coated article which is coated on an anodized aluminum substrate with a coating surface formed by a matte anionic plating coating according to any one of claims 1 to 3; The gloss is 1 〇 or less. -33 -
TW94108894A 2004-03-29 2005-03-23 Matte anionic electrodeposition coating composition TWI264452B (en)

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