TW554019B - Aqueous surface-treating agent for metal material and surface treated metal plates - Google Patents

Abstract

The present invention relates to an aqueous surface-treating agent for metal materials to confer excellent corrosion protection on scared area in addition to good alkali-resistance and adhesivity, and also to the surface-treated metal plates. The aqueous metal surface treating agents are composed of water and (A) polyaminoester and/or polyacrylic resins, (B) a firming agent, (C) silica particles, (D) polyethylene with average praticle size of 0.01-0.2 muM, (E) a dispersant represented by the following formula (I), in which R1 and R4 is alkyl, alkenyl, R2 is (CH2CH2-O)m-(CH2CH2CHO)n and R3 is H or sulfonate group.

Description

554019 A7 B7 五、發明說明（ 【發明之詳細說明】 【發明所屬的技術領域】 本發明係有關於金屬材料之表面上為形成平面部耐姓 性、帶有損傷部之耐姓性及塗布附著性優越的樹脂被膜而 用的金屬材料用水性表面處理劑，及使相關的樹脂被膜形 成的表面處理金屬板。 【習用技術】 •長久以來，辞系或鍍鋅系鋼板係被廣泛使用於家庭電 化製品或建材等^面。此等鋼皮在保制狀下，由於耐钱 性或塗布附著性（上塗塗布性）*足，經予施加鉻酸鹽化 學法表面處理或_鹽化學法表面處理，後以施加模壓加 工，折曲加工等的形成加工或塗布等較多"准依所使用的 :途不同，在不進行塗布下保持原狀的使用之情形亦不 在不進行塗布並採用的情形，被稱作鉻酸鹽化學法表 線 面處理鋼板之表面處理劑鋼板係可予經常適用著，惟在成 形加工或組合之際之指紋的附著，具鉻酸鹽被膜量之不同 引起的色凋之分散性等的問題。因此，為解決此等的問題 :、：、於釔fee鹽被膜上使形成有機被膜的耐指紋鋼板乃成為 1被使用的。此耐指紋鋼板係防止指紋之附著為目的，使 =鍍辞系鋼板之表面上鉻酸鹽處理後形成丨“㈤左右的有 機樹脂層者。此耐指紋鋼板，係除耐指紋特性外，被要求 具有耐蝕性、耐溶劑性、塗布附著性、耐帶有傷痕性等的 各種被膜性能。 氏义&翻巾S S家鮮（CNS)A.l 規格（210 X 297公兌） 五、發明說明（） 此等性能之巾，近年對耐帶有傷祕 著’对帶有傷痕性被要求的理由，俜 後的製品之際所生的振動引起’ 由在運达成形加工 P / 5丨起絲物相互間或收容著成 二 楞紙箱等）與成形物間之摩擦，在成形品 之表面上會產生損傷所致。此帶有傷痕之部分，由於一妒 的有機被覆鋼板在㈣性方面較低劣，品f難免會降低。又 因=，與除耐祕、塗布附著性外，亦考慮耐帶有傷 =之表面處理劑鋼板有關的技術已有若干件正被提出伸 明者。此種技術，有日本特開平3 _ 17189號公報、特公 2 6 - 104799號公報、特開平6_烈测號公報所記載的 方法。 對於曰本特開平3 — 17189號公報内，所揭示有盘胺 酯改質聚烯烴樹脂内配合有氟碳系樹絲子及二氧切粒 子之樹脂«有_方法。此方法之频，縣於需使用 亂碳系樹錄子以㈣帶有損傷部之處，惟為使在水溶液 中均勻分散氣碳系樹脂粒子，界面活性劑之使用係必需且 不可欠缺的，由於使用此種界面活性劑，耐蝕性之水準在 整體上較低，未能獲得可滿足的耐蝕性。 取t於日本特公平104799號公報内，所揭示有與含有 聚醋系樹脂及交聯劑與平均分子量2〇〇〇〜_〇之聚乙烯 f犧’被膜有關的方法。在此方法，於基底樹脂内因使用 聚酯樹脂，被膜本身之耐加水分解性並不足夠，未能獲得 々人滿思的而^ 虫性。 本紙張义度適用中關家標準（c^SMm格⑵〇- 297公釐） 554019 經濟部智慧財產局員工消費合作社印沒 A7 --------B7 五、發明說明（） 於日本特開平6_ 292859號公報内，揭示有於分子内 具有活性氫之胺酯樹脂内含有常溫交聯型環氧樹脂的樹脂 内，使含有常溫交聯型環氧樹脂的樹脂的樹脂形成使含有 球形聚乙烯蠟粒子及鏈狀膠體二氧化矽之被膜有關的方 法。膠體二氧化矽，係附著固體表面並具有被稱作提高摩 擦係數之增性的性質，使用此方法之鏈狀膠體二氧化矽的 情形，由於膠體二氧化矽本身之構造性會使耐帶有傷痕性 降低。因此，在此方法係配合著球狀聚乙烯蠟，惟乾燥溫 度較100 C低的溫度，故聚乙烯蠟會埋沒於樹脂被膜中， 潤滑性變成不足，未能獲得可滿足的时帶有傷痕性部分之 耐飯性。 如此，現狀係未能製得塗布附著性_ 部分之耐錄良好㈣面處理鋼板。 ^傷废欧 且，於冷軋鋼板、鑛辞系鋼板或紹系金屬板上 使形成樹職膜之目的下使㈣胺自旨翻及/或 含有聚乙烯㈣的(水性)潤滑性㈣， 已知有如日本特開平5_ 118刷號公報，專 + =專利第261聰號所記載者，惟於其他的構成要= X明之功打®，以下所述的本發㈣與 【發明欲解決的課題】 寻i月不冋。 二問題點而完成者，耐 帶有傷痕部之有:==在 生表面處理劑及採用此而得的表面處理金屬:j目才枓554019 A7 B7 V. Description of the invention ([Detailed description of the invention] [Technical field to which the invention belongs] The present invention relates to the survivability of flat parts on the surface of metal materials, surname resistance with damaged parts, and coating adhesion. Water-based surface treatment agent for metal materials used for resin coatings with excellent properties, and surface-treated metal plates for forming related resin coatings. [Conventional Technology] • For a long time, lexical or galvanized steel sheets have been widely used in households. Electrochemical products or building materials, etc. Under the state of protection, these steel skins have sufficient chromate chemical surface treatment or _salt chemical surface treatment due to money resistance or coating adhesion (top coat coating) *. Treatment, followed by application of molding processing, bending processing, and other forming processing or coating, etc. " Subject to use: different ways, the use of the original state without coating is also not the case without coating and use In some cases, the surface treatment agent steel sheet is called a chromate chemical method. The steel sheet is often used, but the fingerprint is attached during the forming process or combination. There are problems such as color dispersion and dispersion caused by the difference in the amount of chromate coatings. Therefore, in order to solve these problems, the fingerprint-resistant steel sheet that forms the organic coating on the yttrium fee salt coating is made of 1 coating. Used. The purpose of this fingerprint-resistant steel plate is to prevent the adhesion of fingerprints, so that the surface of the plated steel plate is treated with chromate to form an organic resin layer of about 丨. This fingerprint-resistant steel plate is in addition to its fingerprint-resistant properties. In addition, it is required to have a variety of film properties such as corrosion resistance, solvent resistance, coating adhesion, and resistance to scratches. The meaning of the & towels SS home fresh (CNS) Al specifications (210 X 297) Description of the invention () The performance of these scarves, in recent years, the resistance to wear and tear has been 'required for the reason for the scarring, the vibration caused by the subsequent products' is caused by the in-process shape processing P / 5丨 The friction between the filaments or the corrugated cardboard box) and the molded object may cause damage on the surface of the molded product. The part with the scar is caused by an envious organic coated steel sheet. Sexually inferior, product f is inevitable It will be reduced. In addition, a number of technologies related to the surface treatment agent steel plate that are not only resistant to secretion and coating adhesion, but also considered to be resistant to damage, have been proposed. This type of technology is disclosed in Japanese Patent Application Laid-Open The methods described in Japanese Patent Publication No. 3_17189, Japanese Patent Publication No. 2-6-104799, and Japanese Patent Application Laid-Open No. 6_Research No. JP-A No. 3-17189 disclose discontinuous polyester modified polyolefins. Resin mixed with fluorocarbon-based tree filaments and dioxin particles. There are methods. This method requires frequent use of random carbon-based tree records to contain damaged parts. Gaseous carbon-based resin particles are uniformly dispersed in an aqueous solution, and the use of a surfactant is necessary and indispensable. Due to the use of this surfactant, the level of corrosion resistance is generally low, and satisfactory corrosion resistance cannot be obtained. Taken in Japanese Patent Publication No. 104799, there is disclosed a method related to a polyethylene f-sacrifice 'film containing a polyacetate-based resin and a cross-linking agent and an average molecular weight of 2000 to _0. In this method, due to the use of polyester resin in the base resin, the hydrolytic resistance of the film itself is not sufficient, and it is impossible to obtain a satisfactory insecticidal property. The paper's significance applies to the Zhongguanjia standard (c ^ SMm grids 〇-297 mm) 554019 Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economy printed A7 -------- B7 V. Description of the invention () in Japan Japanese Patent Application Laid-Open No. 6_292859 discloses that a resin containing a normal temperature crosslinked epoxy resin is contained in an amine ester resin having an active hydrogen in the molecule, and a resin containing a normal temperature crosslinked epoxy resin is formed into a spherical shape. Method for coating polyethylene wax particles and chain-like colloidal silica. Colloidal silicon dioxide is a substance that adheres to a solid surface and has a property called increasing friction coefficient. In the case of chain-like colloidal silicon dioxide using this method, the structure of colloidal silicon dioxide itself makes it resistant to abrasion. Reduced scarring. Therefore, in this method, spherical polyethylene wax is used, but the drying temperature is lower than 100 C, so the polyethylene wax will be buried in the resin film, the lubricity will be insufficient, and there will be scars when it cannot be satisfied. Sexual resistance to rice. In this way, the current situation is that it has not been possible to produce a coating-resistant good surface-treated steel sheet. ^ Injury and waste, and, in order to form a tree film on cold-rolled steel plates, mineral steel plates or Shao series metal plates, the ammonium amine is intentionally turned over and / or the (aqueous) lubricity of polyethylene rhenium, It is known as described in Japanese Unexamined Patent Publication No. 5_118, exclusively + = Patent No. 261 Satoshi, but other constitutions = X Ming Zhi Gong Da ®, the present invention described below and [invented to solve Subject] I am not looking for a month. For those who completed the two problems, the ones with resistance to scars are: == raw surface treatment agent and surface treatment metal obtained by using this: j 目 才 枓

本紙張义度適用中國0家標準 (CNS)A.l 規格⑵〇 x 297 l· --------”訂-—》-------% (請先閲讀背面之注意事項再填寫本頁) 554019 A7 五、發明說明（ 【解決課題而採的方法】 ^本發明人，對為解決上述習知技術之課題而採的手 段，經精心檢討的結果，發現藉由採用胺酯樹及/或丙烯 酸I系樹脂、硬化劑、二氧化石夕粒子、特絲徑之聚乙稀 紙及用作分散劑之特定構造的化合物之水性表面處理 劑，可解決前述課題，以至完成本發明。 /亦即，本發明係以含有（A)胺酯樹脂及//或丙烯酸 醋系樹脂、（B )硬化劑、（c )二氧化石夕粒子、（D )平 均粒子G.Gl〜0.2/zm之聚乙烯堪、（E )分散劑之以下 式（I )表示的化合物及水，成分（A)及（B)係各目 分散或溶解於水，成分（c )及（D )分散於水，成分（ /合解於水，對成分（A)〜（E )之全部固形分，（A ) + ( B )之固形分之比率為5〇〜95重量％（ c )之固 形分之比率為3〜40重量％，（D) + ( E )之固 轉為2〜2G重量％，（A) /⑻固形分重量比在& /1〜4 9/1為特徵的金屬材料用水性表面處理劑· (請先閱讀背面之注意事項再填寫本頁) --------訂--------- 經濟部智慧財產局員工消费舍作社印裂 R1The meaning of this paper applies to China's 0 standard (CNS) Al specifications ⑵〇x 297 l · -------- "Order ---" -------% (Please read the precautions on the back before (Fill in this page) 554019 A7 V. Description of the invention ([Methods adopted to solve the problem] ^ The inventors, through careful review of the means adopted to solve the problems of the conventional technology, found that the use of amine esters Tree and / or acrylic I-based resins, hardeners, silica particles, special silk diameter polyethylene paper, and water-based surface treatment agents for compounds with a specific structure used as dispersants can solve the aforementioned problems and complete the present In other words, the present invention comprises (A) an urethane resin and / or an acrylic resin, (B) a hardener, (c) a silica particle, and (D) an average particle G.Gl ~ 0.2 / zm of polyethylene and (E) a compound represented by the following formula (I) and water as a dispersant, and components (A) and (B) are dispersed or dissolved in water for each item, and components (c) and (D) Dispersed in water, the component (/ combined in water, the ratio of the solid content of components (A) to (E) to (A) + (B) is 5). The solid content ratio of 95% by weight (c) is 3 to 40% by weight, the solid conversion of (D) + (E) is 2 to 2G% by weight, and the weight ratio of (A) / ⑻solid content is between & / 1 ~ 4 9/1 Water-based surface treatment agent for metal materials · (Please read the precautions on the back before filling this page) -------- Order --------- Intellectual Property of the Ministry of Economic Affairs Bureau Employee Consumption House Printing R1

〇 一 R2 — R3 ① 〔式中，R1表示碳數丨〜2〇之烷基或碳數2〜 R2表示⑽⑽n(s中，E表示伸乙基、p表示伸丙^’、 本纸張W適时關家鮮 554019 A7 五、發明說明（) .表示5 ~ 20之整數，n表示。幻〜1〇之整數） 不氫原子或S03MC (式中，μ表示氫原子、驗金屬離、 錄離子）、R4表示氫原子、碳數丨〜4之絲或碳數2 ~ 4 之烯基〕。 (E)之固形分對⑻+ (E)之固形分的比率以 在10〜。40重量％為宜，成分（A )之玻璃轉移溫度以在 -40〜〇°C之範圍為宜’成分（B )以環氧樹脂為宜，成 分（B)以於-分子中具有三個以上的環氧基之環氧 尤宜。 本發明又係有關於金屬材料之表面上具有第一層以金 屬鉻換算計3〜l〇〇mg/m2之鉻酸鹽被膜層，塗布第二層之 上述金屬材料用水性表面處理劑、乾燥並予形成約〇. 3〜 3· Og/m2之樹脂被膜層為特徵之表面處理金屬板。 【發明之實施形態】 以下洋細說明本發明之技術内容。 本發明之第一特徵，係以一定重量比配合適當的種類 之树脂作為基底樹脂。至於樹脂，有作成採取耐钱性、而才 磨耗性、耐藥品性之均衡的構造之必要。因此，在本發明 係使用（A)胺酯樹脂及/或丙烯酸酯系樹脂，此樹脂係 溶解或分散於本金屬材料用性表面處理劑中。 本發明所使用的胺酯樹脂，係採用由具有多元醇成 分、聚異氰酸酯成分、羧酸成分及活性氫三個以上的化合 物所構方的原料予以製造。 本纸張义度家鮮（CNS_)A4規格（210 X 297公 554019〇 一 R2 — R3 ① [In the formula, R1 represents an alkyl group of carbon number 丨 ~ 2〇 or carbon number 2 ~ R2 represents ⑽⑽n (where s, E represents ethylidene, p represents ethylidene ^ ', this paper W Guanjiaxian 554019 A7 in a timely manner V. Description of the invention (). It represents an integer from 5 to 20, n represents. The integer from 1 to 10) is not a hydrogen atom or S03MC (where μ represents a hydrogen atom, metal test ion, record (Ion), R4 represents a hydrogen atom, a silk having a carbon number of 1 to 4 or an alkenyl group having a carbon number of 2 to 4]. The ratio of the solid content of (E) to the solid content of ⑻ + (E) is 10 to. 40% by weight is preferred, and the glass transition temperature of the component (A) is preferably in the range of -40 to 0 ° C. The component (B) is preferably an epoxy resin, and the component (B) has three in the molecule. Above epoxy epoxy groups are particularly preferred. The invention also relates to a surface of a metal material having a first chromate coating layer of 3 to 100 mg / m2 in terms of metal chromium conversion, a water-based surface treatment agent for coating the above-mentioned metal material on the second layer, and drying. A surface-treated metal plate characterized by a resin coating layer of about 0.3 to 3 · Og / m2 is preformed. [Embodiments of the Invention] The technical content of the present invention will be described in detail below. A first feature of the present invention is that a resin of an appropriate type is blended in a certain weight ratio as a base resin. As for the resin, it is necessary to have a balanced structure that is resistant to money and has abrasion and chemical resistance. Therefore, in the present invention, (A) an urethane resin and / or an acrylate resin is used, and this resin is dissolved or dispersed in the surface treatment agent for the present metal material. The amine ester resin used in the present invention is produced from raw materials composed of three or more compounds having a polyol component, a polyisocyanate component, a carboxylic acid component, and active hydrogen. This paper is intended for domestic products (CNS_) A4 (210 X 297 male 554019

經濟部智楚財產局員工消費合作社印製 五、發明說明（) 至於多元醇成分，可列舉出由乙二醇 、二乙二醇、三 乙二醇、1，2-丙二醇、1，3-丙二醇、1，2 - 丁二醇、1，3 -丁二醇、1，4 - 丁二醇、六亞曱二醇、氫化雙酚a、雙酚a、 二羥曱基丙烷、甘油等低分子量之多元醇的環氧乙烷及/ 或環氧丙烷加成物，聚乙二醇、聚丙二醇、聚乙烯/聚丙 烯二酵、聚巳内酯多元醇、聚烯烴多元醇、聚丁二烯多元 醇等的聚醚多元醇，此等的多元醇及琥珀酸、胺基戊二酸、 巳二酸、癸二酸、笨二曱醇、間苯二曱酸、對苯二甲酸、 曱橋四氫苯二曱酸等的多鹼基酸間的反應而得，終端有經 基之聚酯多二醇等。 至於聚異氰酸酯成分，可舉出有：脂肪族、脂環式及 芳香族聚異氰酸酯，宜為可舉出有：四亞曱二異氰酸酯、 六亞甲二異氰酸酯、賴胺酸二異氰酸酯、氫化二曱苯二異 氰酉义、1，4 _環伸巳基二異氰酸酯、4'-二環巳基曱炫 二異氰酸酯、2, 4'-二環巳基甲烷二異氰酸酯、異佛系酮 二異氰S旨、3,3'-二甲氧基_4，4'-聯苯二異氰酸酯、 1,5 -奈一異氰酸酯、1，5 -四氫萘二異氰酸酯、2,4-甲 次笨基二異氰酸酯、2, 6 _曱次苯基二異氰酸酯、4，一 二笨基曱烷二異氰酸酯、2,4'_二苯基曱烷二異氰酸酯、 伸笨基二異氰酸酯、伸二甲笨基二異氰酸酯、四甲基伸二 曱笨基二異氰酸酯等。此等之中在採用四亞甲二異氰酸 酯、六亞甲二異氰酸酯、賴胺酸二異氰酸酯、氫化伸二甲 苯二異氰酸酯、1，4 -環伸巳烷基二異氰酸酯、（4，一二 環巳基甲烷二異氰酸酯、2, 4'-二環巳基甲烷二異氰酸 ----U----j-------------訂---------線^L (請先閱讀背面之注意事項再填寫本頁) 8Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of the invention () As for the polyol component, ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propanediol, 1,3- Propylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, hexamethylene glycol, hydrogenated bisphenol a, bisphenol a, dihydroxymethylpropane, glycerol, etc. Ethylene oxide and / or propylene oxide adducts of molecular weight polyols, polyethylene glycol, polypropylene glycol, polyethylene / polypropylene secondary enzyme, polylactone polyol, polyolefin polyol, polybutadiene Polyether polyols such as olefin polyols, and these polyols and succinic acid, aminoglutaric acid, adipic acid, sebacic acid, succinic acid, isophthalic acid, terephthalic acid, amidine It is obtained by the reaction between polybasic acids such as tetrahydrophthalic acid and the like, and polyester polydiols having a terminal group at the terminal. As for the polyisocyanate component, aliphatic, alicyclic, and aromatic polyisocyanates can be cited, and preferably, they can be: tetramethylene diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, hydrogenated difluorene Benzene diisocyanofluorene, 1,4-cyclohexylene diisocyanate, 4'-dicyclofluorenylfluorene diisocyanate, 2, 4'-dicyclofluorenylmethane diisocyanate, isophorone diisocyanate Purpose, 3,3'-dimethoxy-4,4'-biphenyl diisocyanate, 1,5-naphthalene diisocyanate, 1,5-tetrahydronaphthalene diisocyanate, 2,4-methylbenzyl diisocyanate Isocyanate, 2, 6-fluorenyl diisocyanate, 4, dibenzyl pinane diisocyanate, 2, 4'-diphenylphosphorane di isocyanate, dibenzyl diisocyanate, dibenzyl diisocyanate, Tetramethylene sulfenyl diisocyanate and the like. Among these, tetramethylene diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, hydrogenated xylene diisocyanate, 1,4-cycloalkylene diisocyanate, (4,1-dicyclofluorenyl) Methane diisocyanate, 2, 4'-dicyclofluorenylmethane diisocyanate ---- U ---- j ------------- Order -------- -Line ^ L (Please read the notes on the back before filling in this page) 8

至於缓酸成分，可舉出 、 二經f基丁酸、2? ㈣基丙酸、2，卜 丁m二Μ基戊酸等。 至於具有三個以上的活性氫之化合物 聚氰胺、二伸乙三胺、三辩 π牛出.二 一 L甲基丙烷、季戍四醇、丙三醇、 此專的環氧乙烧及/或環氧丙炫加成物等。 二，於製造胺酉旨樹脂時，視必要時以再添加通常所用 的具有二個活性氫之化合物（鏈伸長劑）亦係當然可能的。 至於此種鏈伸長劑，可列舉出有：乙二醇、丙二醇、新戊 二醇、1’6-巳二醇、或此等的環氧乙院加成物及/或環 氧丙烷加成物等之多元醇類、乙二醇、丙二醇、六亞甲二 胺、伸苯基二胺、伸二苯基二胺、二胺基二苯基曱烧、二 胺基二環巳基甲烷、六氫化吡哄、2 -甲基六氫化吡畊、 異佛系酮二胺、琥珀酸二醯胼、己二酸二醯胼，、苯二甲酸 二醯胼等的胺類等。 經濟部智慧財產局員工消費合作社印製 本發明所使用的胺酸樹脂之原料之使用量，對胺酯樹 脂10Q重量分，為多元醇成分30〜7〇重量分，宜為35〜65 重量分、聚異氰酸酯成分20〜50重量分，宜為25〜40重量 分、羧酸成分0.5〜1.0重量分，宜為1〜8重量分，含有活 性氫三個以上的化合物〇·1〜5重量分，宜為〇.2〜3重量分。 又使用時的鏈伸長劑之使用量，對胺酯樹脂1〇〇重量分， 為1〜15重量分，宜為3〜10重量分。 本紙張尺度適用中S國家標準（CNS)A.丨規格（210 X 297公釐） 554019 A7As for the slow-acid component, f-butyric acid, 2? Fluorenyl propionic acid, 2, butylene m di-M-valeric acid, etc. can be mentioned. As for compounds with more than three active hydrogens, such as melamine, diethylene glycol, and triethylene glycol, di-L-methylpropane, quaternary erythritol, glycerol, this special ethylene oxide, and / Or propylene oxide adduct. Second, in the production of amine resins, it is of course possible to add a compound (chain elongation agent) having two active hydrogens usually used if necessary. Examples of such a chain elongating agent include ethylene glycol, propylene glycol, neopentyl glycol, 1'6-fluorene glycol, and ethylene oxide addition products and / or propylene oxide additions. Polyols such as alcohols, ethylene glycol, propylene glycol, hexamethylene diamine, phenylenediamine, phenylenediamine, diaminodiphenyl sulfonium, diamine dicyclofluorinated methane, hexamethylene Pyridoxine, 2-methylhexahydropyridine, isophorone ketone diamine, succinic acid dihydrazone, adipic acid diamine, diamine phthalate, and other amines. The consumption amount of the raw material of the amine acid resin used in the present invention printed by the employees' cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs is 10Q weight points for the amine ester resin, 30 to 70 weight points for the polyol component, and preferably 35 to 65 weight points. Polyisocyanate component 20 to 50 parts by weight, preferably 25 to 40 parts by weight, carboxylic acid component 0.5 to 1.0 part by weight, preferably 1 to 8 parts by weight, compounds containing three or more active hydrogens 0.1 to 5 parts by weight , Preferably 0.2 to 3 weight points. The amount of the chain extender used at the time of use is 1 to 15 parts by weight based on 100 parts by weight of the amine ester resin, and preferably 3 to 10 parts by weight. This paper size is applicable to China National Standard (CNS) A. 丨 specifications (210 X 297 mm) 554019 A7

554019 經濟部智慧財產局員工消費合作社印製 Α7 Β7 五、發明說明（) 基（曱基）烯丙醚、4 -羥基丁基（甲基）烯丙醚、烯丙 醇、甲基丙烯酸縮水甘油酯、丙烯酸2- (1 -氮雜環烷基) 乙酯、乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷烯丙基 縮水甘油基醚、甲基丙烯酸亞胺醇、丙烯醯基嗎啉、N-羥曱基（曱基）丙烯醯胺、N -甲氧基甲基（曱基）丙烯 醯胺、N -乙氧基曱基（曱基）丙烯醯胺、N - 丁氧基甲基 (曱基）丙烯醯胺、（曱基）丙烯醯胺、N -甲基（曱基） 丙烯醯胺、N，N -二甲基（曱基）丙烯醯胺、二甲基胺 基丙基（甲基）丙烯酿胺、甲酸乙烯酯、乙酸乙稀酯、丁 酸乙稀酯、丙稀酸乙烯酯、苯乙稀、α -曱基苯乙稀、第 三丁基苯乙烯、乙烯基曱苯、（曱基）丙烯腈、桂皮酸腈、 (曱基）丙烯氧基乙基磷酸酯、雙（甲基）丙烯氧基乙基 磷酸酯、（曱基）丙烯氧基乙基苯基酸磷酸酯等。 (曱基）丙烯酸之使用量，對本發明所使用的丙稀酸 酯系樹脂100重量分，宜為1〜20重量分，以2〜15重 量分為較宜。 •至於本發明所使用的丙烯酸酯系樹脂之製造方法並未 予特別限制，惟使被稱作乳化劑之界面活性劑及單體均勻 分散於水中並使單體成為乳化狀態後使聚合反應進行的乳 化聚合法，使單體分散於完全或幾乎不溶解單體的溶劑（例 如水）内並採用難溶於溶劑而可溶於單體之聚合引發劑使 在已懸浮的單體之水滴内進行聚合反應的懸浮聚合法等的 工業基礎上有實績的方法為宜。 本紙張尺/艾適用中囚國家標準規格（LM〇x 297公兌） (請先閱讀背面之注意事項再填寫本頁) --------訂---------線座 554019 五、發明說明（ 又 特別限樹脂之分子量並未予 萬〜⑽萬為;；轉滲透色相層析法測㈣情形，以約！ 本^月所使用的（A )樹脂，以玻璃移轉、、θ 0t者為宜，以-40 „-度在-40〜 4〇t低的5C：者為較宜。玻璃移轉溫度較_ 劣敎耐疊㈣（antibi〇cking)低 而右^4·又’祕脂之被膜物性係有以玻璃移轉溫度 二Γ變化之傾向。通常，成形加工後之製品 予处里的》皿度，雖在10〜50t之 範圍内有玻璃移轉溫产 图’、、、而在此/皿度 _會引起變ί 氣溫不同，樹脂之被 古 ^化被膜之耐Τ有傷痕性低劣的可能性較 低，i多轉溫度超過5〇t之情形，由於被膜之 Π @4_之乾燥溫度的必要。在經濟 =為宜因此，樹脂— 其次’說明樹脂之玻璃移轉溫度之測定方法， :=溫度時’採用測定裝置:(股）東洋精機製作所 錢的Rhe〇graphsolid s _卜試片：採用已在副。c乾 燥30分鐘的膜厚100㈣、寬度_、長度編之薄膜， 在頻率1_進行測定’由彈性損失率之轉折點求取。 在本發明，為較能發揮（A )則旨之特性，乃配合（B ) 硬化劑。至於本發明所使用的（B)硬化劑，以異氛酸酯 化合物，氮雜丙烷化合物、環氧樹氧為宜，以一分子中 三個以上的環氧基之環氧樹脂為較宜。由於本發明所使用 12 554019 A7 B7 五 、發明說明（ ，樹月曰由於具有絲，藉由此缓基與硬化劑之官能基 t酸醋基、氮雜環丙絲、環氧基等）間之反應而ί的樹 月含曰之構造會形成三維的網目構造，被膜性能乃呈大幅提 ^。至於相關的環氧樹脂，可舉出祕清涞型環氧樹脂、 ^具有三個以上的Η基之化合物及表氯醇間之 壤氧樹脂等。X，本發明所使用的上述環氧樹脂之分= 亚未予特別限制，惟以凝膠渗透色相層析法測定的情形， 以在3, 000以下為宜。 y 在上述的ί衣氧樹脂係在本發明之水性表面處理 解或分散於水中。 / 訂 本發明所使用的（Α)胺酷樹脂及/或丙烯酸醋系樹 脂與（Β)硬化劑間之固形分重 卜49/i為宜，以1〇…1〇/1為較宜4/ ^ A ) / ( B )之比未滿4//工之情形，（a )樹脂未能 發揮特’ X，未反應的硬化劑殘留著，為達成可塑性的角 色’对蝕性會降低’並不合適。另一方面（a)/(b) =超過4 9/1之情形’硬化劑之配合效果欠缺，未能 獲得可令人滿意的耐钱性。 本發明之水性表面處理劑之成分（A)+(B)之固 形分對⑷+ (B)(C) + (D) + (E)之固形分 、(以下稱全固形分）之比率，以在5〇〜95重量％為必要， 以60〜85重1%為宜。此比率未滿5〇重量％時，被膜 本身之耐水性會降低，故並不宜。另一方面，此比率若超 過9〇重量％時’帶有傷痕部分之耐姓性會降低，故並不 佳0 I________13 本纸張尺度適用中關家標準（CNS)A‘l規格（210 X 297公楚 554019 A7 B7 五、發明說明（ 本發明所使用的（c)_ 狀、種類並未予特別限制老石夕粒子，係在粒徑、形 之範圍為宜。二氧化石夕粒 ^輕有關以在3〜30測 中正分散於水中。-氧在本發明之水性表面處理劑 未滿3蝴之情形，卿里:為且。此比率在 超過40重找時，樹脂成之“效果缺乏，另一方面 耐飯性降低，故並不宜。 ◎結劑效果變小’ 性之的，聚乙烯壤，係為使耐帶有傷痕 Γ_0.01〜0.2"，以 係數，有壤粒徑變大時即二傾：作:滑性指標之摩擦 及m有1 疋一致者’摺動次數（或摺動距離） 數間之關係較重要的。本發明人等經精心檢討堪 之^粒徑與摺動次數間之關係的結果，發現藉由設定蠟 =均粒輕成0·0卜0.2//m，可得優越的耐帶有傷痕性。 二之平均粒徑’係使虫鼠之溶融黏度能分散，故受使用的機 械之性能所影響。因此，蠟之平均粒徑未滿〇 〇1則， ^有使用較高性能之機械的必要，在成本上並不經濟，另 二方面，超過〇.2#m時，由被膜表面突出的蠟在摺動時 變成容易取下，結果連續摺動性會降低，並不合適。 且，在本發明，對（D)聚乙烯蠟之分子量，熔點並 未予別限制，惟酸價以5〜50之範圍為宜，以10〜3〇 之範圍為較佳。酸價未滿5時，蠟及樹脂幾乎不相溶，故 14 0^ ^訂--------- 1-言先閱讀背面之注意事項再填寫衣f) 經濟部智慧財產局員工消費合作社印製 本紙浪用甲國國家標準（cNS)A4規格（210 ： 554019 A7 B7554019 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention () (Allyl) allyl ether, 4-hydroxybutyl (meth) allyl ether, allyl alcohol, glycidyl methacrylate Ester, 2- (1-azacycloalkyl) acrylate, vinyltrimethoxysilane, vinyltriethoxysilyl allyl glycidyl ether, iminyl methacrylate, allyl acryl N-Hydroxy (fluorenyl) acrylamide, N-methoxymethyl (fluorenyl) acrylamide, N-ethoxyfluorenyl (fluorenyl) acrylamide, N-butoxy Methyl (fluorenyl) acrylamide, (fluorenyl) acrylamide, N-methyl (fluorenyl) acrylamide, N, N-dimethyl (fluorenyl) acrylamide, dimethylamine Propyl (meth) acrylamide, vinyl formate, ethyl acetate, ethyl butyrate, vinyl acrylic acid, styrene, α-fluorenyl styrene, tertiary butyl styrene, Vinylbenzene, (fluorenyl) acrylonitrile, cinnamic acid nitrile, (fluorenyl) acryloxyethyl phosphate, bis (meth) acryloxyethyl phosphate, (fluorenyl) Propenyloxy ethylphenyl acid phosphate. The amount of (fluorenyl) acrylic acid is preferably 1 to 20 weight parts, and more preferably 2 to 15 weight parts, based on 100 weight parts of the acrylic resin used in the present invention. The manufacturing method of the acrylate resin used in the present invention is not particularly limited, but the polymerization reaction proceeds after the surfactant and the monomer called emulsifier are uniformly dispersed in water and the monomer is in an emulsified state. The emulsification polymerization method disperses the monomers in a solvent (such as water) that completely or almost does not dissolve the monomers, and uses a polymerization initiator that is hardly soluble in the solvents and soluble in the monomers to make the water droplets of the suspended monomers A method based on industrial performance, such as a suspension polymerization method for carrying out a polymerization reaction, is preferred. This paper ruler / Ai applies to the national standard specification for prisoners (LM〇x 297). (Please read the precautions on the back before filling this page) -------- Order --------- Thread stand 554019 V. Description of the invention (but the molecular weight of the resin is not particularly limited to 10,000 to 10,000); the determination of tritium by osmosis chromatography, to about! (A) resin used this month, glass It is better to transfer, and θ 0t, and 5C which is lower than -40 ¡° to -40 ~ 40t is more suitable. The glass transition temperature is lower than that Right ^ 4. Also, the physical properties of the coating of secret oil tend to change with the glass transition temperature of two Γ. Generally, the products after forming and processing have a glass temperature of 10%, although there is a glass shift in the range of 10 ~ 50t. Turning temperature production map ',, and here / plate temperature _ will cause changes. At different temperatures, the resin ’s ancient coating film is less likely to have poor scratch resistance, and the temperature is more than 50 ° In this case, due to the necessity of the drying temperature of the film Π @ 4_. In the economic = is appropriate, therefore, the resin — Secondly, the method of measuring the glass transition temperature of the resin is explained. Measuring device: Rheograph solid s from Toyo Seiki Co., Ltd. _ Test piece: A film with a film thickness of 100㈣, width _, and length which has been dried for 30 minutes at the sub.c is measured at a frequency of 1_. Calculated from the turning point of the elastic loss rate. In the present invention, in order to better display the characteristics of the purpose of (A), a (B) hardener is blended. As for the (B) hardener used in the present invention, an isocyanate is used. Compounds, azapropane compounds, and epoxy resins are preferred, and epoxy resins with more than three epoxy groups in one molecule are more suitable. Since the present invention is used 12 554019 A7 B7 V. Description of the invention () Due to the presence of silk, the structure of the tree structure will form a three-dimensional mesh structure by the reaction between the retarder and the functional group of the hardener (acid group, aziridine, epoxy group, etc.) The coating performance has been greatly improved. As for the related epoxy resins, there may be mentioned the secret type epoxy resin, the compound having three or more fluorenyl groups, and the oxygen resin between epichlorohydrin. X, Points of the above-mentioned epoxy resin used in the present invention = Yawei In the case of gel permeation chromatographic measurement, it is preferable to be less than 3,000. Y The above-mentioned oxyhydrogen resin is dissolved or dispersed in water in the aqueous surface treatment of the present invention. / Order the present invention The solid weight between the (A) amine resin and / or acrylic resin and (B) hardener is preferably 49 / i, and 10… 1/10/1 is more suitable 4 / ^ A) When the ratio of (/) (B) is less than 4 // process, (a) the resin fails to exhibit the characteristics of 'X, and the unreacted hardener remains, and in order to achieve the role of plasticity,' corrosion will decrease 'is not appropriate. On the other hand, when (a) / (b) = more than 4 9/1, the compounding effect of the hardener is insufficient, and satisfactory money resistance cannot be obtained. The ratio of the solid content of the component (A) + (B) to the solid content of ⑷ + (B) (C) + (D) + (E) of the water-based surface treatment agent of the present invention, (hereinafter referred to as the total solid content), It is necessary to be 50 to 95% by weight, and 60 to 85% by weight is suitable. If the ratio is less than 50% by weight, the water resistance of the coating film itself is lowered, which is not suitable. On the other hand, if this ratio exceeds 90% by weight, the surname resistance of the part with a scar will be reduced, so it is not good. 0 I________13 This paper standard applies the CNS A'l specification (210 X 297 Gongchu 554019 A7 B7 V. Description of the Invention (The shape and type of (c) _ used in the present invention are not particularly limited to old stone eve particles, and it is appropriate to fall within the range of particle size and shape. Stone dioxide eve ^ It is related to the fact that it is being dispersed in water in the test of 3 ~ 30. -Oxygen in the case of the aqueous surface treatment agent of the present invention is less than 3 butterfly, Qingli: Yes and. When this ratio is more than 40 rediscovery, the resin becomes "effective The lack of rice resistance on the other hand, it is not suitable. ◎ The effect of the cement becomes smaller. Of course, the polyethylene soil is resistant to scarring Γ_0.01 ~ 0.2 " When the diameter becomes larger, it becomes dip: as: the friction of the slippage index and m has a unity of 1 ', the relationship between the number of times of turning (or the distance of turning) is more important. The present inventors and others have carefully reviewed it ^ As a result of the relationship between the particle size and the number of folds, it was found that by setting the wax = average particle size to be 0 · 0 to 0.2 // m, It has excellent resistance to scratches. The average particle size of two is to disperse the melt viscosity of pests and rats, so it is affected by the performance of the machinery used. Therefore, the average particle size of the wax is less than 0.001, ^ It is necessary to use a high-performance machine, which is not economical in terms of cost. On the other hand, when it exceeds 0.2 # m, the wax protruding from the surface of the film becomes easy to remove when it is folded, resulting in continuous folding. In addition, in the present invention, the molecular weight and melting point of (D) polyethylene wax are not limited, but the acid value is preferably in the range of 5 to 50, and the range of 10 to 30 is preferred. When the acid value is less than 5, wax and resin are almost incompatible, so 14 0 ^ ^ Order --------- 1- Read the precautions on the back before filling in clothes f) Intellectual property of the Ministry of Economic Affairs Bureau National Consumer Cooperative Co., Ltd. Printed Paper A National Standard (cNS) A4 Specification (210: 554019 A7 B7

形成被膜時，蠟會完全定向於被膜表面上，引起耐帶有傷 痕性及塗布附著性之降低，並不合適。另一方面，酸價超 過50時，蠟之親水性變強，故蠟本身所具的潤滑性降低， 耐T有傷痕性會降低，故並不合適。 本發明所使用的（E)分散劑係以前述式（I )表 的化合物。 、上述中R1係碳數5〜20之烷基或碳數2〜5之烯美 ，宜1係8〜20之整數為宜，n係〇或！〜5之整數^ 宜，R3係氫原子或s〇3NH4為宜。r4係氫原子或碳數2〜4. 之烯基為宜。 本發明所使用的（D)聚乙烯犧，通常係使用作採用 (E)分散劑並予製備的水分散體。對聚乙烯蠟之分散方 法並未予特別限制，若依工業上所用的方法即可。月 且前述的（D) $乙烯螺之平均粒徑係在此水分散體 中的值。 (E )之固形分對上述水分散體之固形分（亦即（d + )之固形分）之比率為5〜4〇重量％為宜，以5〜％ 重量％為較宜。上述比率在未滿1〇重量％時，採用所得 的水性表面處理劑所得的被膜之耐水性會降低，並不宜^ 上述水分散體對本發明之水性表面處理劑 (亦即成分⑷+⑻+ (c) + (D)+== 固形分）之比率，以（D) + ( e )之固形分之比率 需”〜20重量％，以3〜15重量％為宜，以3〜；〇’ 重f%為更宜。此比率未滿2重量％時’耐帶有傷痕性之 15 本纸張尺度適用中國國家標準（CNS)A·!規格（210 X 297公楚 "h --------•訂 ί·------- (請先閱讀背面之注意事項再填寫本頁) 554019 A7 五、發明說明（） 改善效果缺乏，另一方面超過2〇重量％時，上 會降低，並不宜。 作性 、於本發明之水性表面處理劑内，使含有可於被塗面形 成均勻的被膜而狀被稱作濕漂性提高劑的界面活性劑，/ f提高賴性而用的導電性物f，提高外觀設計性而^的 著色顏料，提高造膜性而用的溶劑等作為任意成分亦可。 上述成分（A)、（B)、（C)及水分散體（亦即（D) + ( E ))’及藉由將上述任意成分混合於水並使溶解、分 政了付本务明之金屬材料用水性表面處理劑。成分之添 加順序亚未予特別限定，惟混合例如可採用螺旋槳式攪拌 機等，藉由攪拌予以進行較合適。 訂 所得的本發明之水性表面處理劑，係以固形分濃度在 5 : 50重量％之範圍内為宜，以在5〜4〇重量％之範圍 内為車乂且。固形分濃度未滿5重量％時，乾燥時間會變長， 並不合適。另一方面，固形分濃度超過50重量％時，1 理劑本身的黏度高，處理上導致障礙的顧慮。 、，至於塗布本發明之水性表面處理劑的金屬材料（原材 料）’可舉出有：冷軋鋼板、鍍鋅系鋼板、鍍鋁系鋼板'、 鋁板等金屬板。 本發明之水性表面處理劑，亦可直接塗布於相關的金 屬材料，惟為使能充分發揮本發明之功效，首先利用由常 用方法進行的鉻酸鹽處理，形成鉻酸鹽被膜，於其上塗布 本發明之水性表面處理劑並形成樹脂被膜即可。 16 本紙張尺度適用中關家標準（CNS)A‘丨規格⑵Q χ 297公楚 554019 A7 Β7 濟 部 智 慧 財 產 局 消 費 合 社 印 製 五、發明說明（ 至於絡酸鹽處理’有刺用電解形成絡酸鹽被膜之電解 鉻酸鹽，利用與原材料間之反應使形成被膜，其後洗去多 餘的處理液之反應型鉻酸鹽，將處理液塗布於被處理物上 在不予水洗下乾燥使形成被膜之塗布型鉻酸鹽，本發明係 亦可採用任一種處理方法。 於利用上述鉻酸鹽處理所形成的基底被膜之上，在10 〜50t塗布本發明之水性表面處理劑，藉由在到達板6〇〜 2〇〇°C使予乾燥，可形成樹脂被膜，至於塗布方法，可採 用常法，例如輥輪塗布器法、浸潰法、靜電塗布法等。 利用相關的二階段處理而得之本發明的表面處理金屬 板’係於金屬材料之表面上，具有以金屬路換算計第丄層 之3〜l〇〇mg/m2之鉻酸鹽被膜層，塗布本發明之 ς 用水性表面處理劑並乾驗形成的Q.3〜3 Qg/m2^^4 J膜層2為第2層為特徵之表面處理金屬板。鉻酸鹽二 =!以金屬鉻換算計3〜5〇mg/m2為宜，以5〜4。_2 鉻附著量未滿3 mg/m2時，耐钱性之 之提高效果飽和，並不二 樹脂被膜量未滿G.3 g/“之情形 性二 效不亚不足，超過3·〇 g/m2時，耐蝕 性如回 不經濟。 棱阿效果會飽和並 …塗布本發明之錢表面處理劑並予 被膜、接著表面處理金屬板’在平面部耐蝕、帶傷二:旨 耐純及塗布附著性優越。至塗布於樹脂被膜上的Γίί ---——__17 本紙張尺/i適用中ϋ國家標举（CNS)A4 公发 (請先閲讀背面之注意事項再填寫本頁) i·^.------ —訂--------- 554019 A7 B7 五、發明說明（） 料，並未予特別限制，惟例如可舉出：常溫乾燥型三聚氰 胺醇酸系塗料、烘烤型三聚氰胺醇酸系塗料、丙烯酸酯樹 脂系塗料、紫外線硬化型樹脂系塗料等。 【實施例】 以下採用製造例、實施例及比較例、具體的說明本 發明，此案實施例系供說本發明而記載者並非用以限定 本發明者。 試板之製作 (1)供試材 使用下示的市售之原材料作為供試材。 •電鍍鋅鋼板（EG) 板厚0· 8mm、單位面積重量=20/20(g/m2) •含有5%鋁之鍍鋅鋼板（GF) 板厚0· 8mm、單位面積重量=90/90(g/m2) •鋁板（AL) 板厚 1. 0mm、5182 系 (2) 脫脂處理 以上述的各供試材料石夕酸鹽系驗脫脂劑之Fine cleaner4336 (註冊商標··日本Parkerizing股份有限公 司製造）進行脫脂處理。且在濃度20g/L、溫度60°C喷布 處理2分鍾後，以自來水清洗。 (3) 底材處理 (3_1)反應型鉻酸鹽化學法表面處理（原材料：EG、GF) 採用 Zinchrome 357 (註冊商標：日本 Parkerizing 本紙掁尺度適用中Θ國家標準（CNS)A‘l規格（210 X 297公釐） -----ί---U---- (請先閱讀背面之注意事項再填寫本頁) 訂-------. 經濟部智慧財產局員工消費合作社印製 554019 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明（） 股份有限公司製造）’在液溫501進行5秒鐘噴布處理， 用自來水清洗後風乾，製作試板。 (3-2)塗布型鉻酸鹽化學法表面處理（原材料：阢、gf) 採用 Zinchrome 1300AN(註冊商標：日本 Parkerizir^ 股份有限公司製造），用輥輪塗布器法塗布，不予水洗下 立即在200°C之空氣溫度下乾燥1〇秒鐘並製作試板。且 此際之到達溫度為l〇〇°C。 (3-3)反應型鉻酸鹽處理（原材料：AL) 採用Alchr〇me71；3 (註冊商標：日 股份有限公司製造），在液溫50t進行噴布處理5秒鐘， 用自來水清洗後風乾，製作試板。 〔水性表面處理劑之製備〕 在室溫，在採用螺旋槳攪拌機依序攪拌表丨之樹脂， 表2之硬化劑，表3之一氧化叾夕粒子，表4之蠛水分散體 並予混合，加入蒸餾水並調整固形分濃度，製備表5所示 的實施例之水性表面處理劑及表6所示的比較例之水性表 面處理劑。且蠟水分散體，係將表4所示的蠟，化合物（工〕 及水全量放入高壓釜内，如熱至溫度13〇〜14〇t並予攪 拌予以製備。 〔水性表面處理劑對試板之塗布方法〕 採用塗布桿塗布器，將上述製備的各水性表面處理 劑，塗布於上述各試板上，在24〇。〇之空氣溫度乾燥1〇 秒鐘。此劑之到達板溫度為1〇〇1。且附著量之調整係適 19 本氏又週用Τ四四木準（CNS)A·丨規格（21〇 X 297公·^ ) (請先閱讀背面之注意事項再填寫本頁) --------^訂 i — %| 554019When the film is formed, the wax is completely oriented on the surface of the film, which causes a reduction in scratch resistance and coating adhesion, which is not suitable. On the other hand, if the acid value exceeds 50, the hydrophilicity of the wax becomes strong, so the lubricity of the wax itself is reduced, and the resistance to T and scratches is reduced, which is not suitable. The (E) dispersant used in the present invention is a compound represented by the aforementioned formula (I). In the above, R1 is an alkyl group having 5 to 20 carbon atoms or olefinic group having 2 to 5 carbon atoms, preferably an integer of 8 to 20 is suitable, and n is 0 or! An integer of ~ 5 is preferred, and R3 is a hydrogen atom or so3NH4. r4 is a hydrogen atom or an alkenyl group having 2 to 4 carbon atoms. The polyethylene (D) used in the present invention is usually used as an aqueous dispersion prepared using the (E) dispersant. The method for dispersing polyethylene wax is not particularly limited, and it may be any method as long as it is industrially used. The average particle diameter of the aforementioned (D) $ vinyl snail is the value in this aqueous dispersion. The ratio of the solid content of (E) to the solid content of the above-mentioned aqueous dispersion (that is, the solid content of (d +)) is preferably 5 to 40% by weight, and more preferably 5 to 5% by weight. When the above ratio is less than 10% by weight, the water resistance of the film obtained by using the obtained aqueous surface treatment agent is reduced, and the above-mentioned aqueous dispersion is not suitable for the aqueous surface treatment agent of the present invention (that is, the component ⑷ + ⑻ + ( c) + (D) + == solid content) ratio, the ratio of (D) + (e) solid content needs to be "~ 20% by weight, preferably 3 ~ 15% by weight, 3 ~; 0 ' The weight f% is more suitable. When the ratio is less than 2% by weight, the paper size of 15 is resistant to scratches. This paper standard applies to China National Standard (CNS) A ·! Specifications (210 X 297) " h --- ----- • Order ί · ------- (Please read the notes on the back before filling in this page) 554019 A7 V. Description of the invention () The improvement effect is lacking, on the other hand, when it exceeds 20% by weight It will be lower, which is not suitable. In the water-based surface treatment agent of the present invention, the surfactant containing a surfactant which can form a uniform film on the coated surface and is called a wet-bleaching improver is increased. The conductive material f, which is used for the purpose, may be an optional component, such as a colored pigment that improves the design property, and a solvent for improving the film forming property. The ingredients (A), (B), (C), and water dispersion (ie (D) + (E)) 'and mixing and dissolving any of the above-mentioned ingredients in water and dissolving, divide the matter Water-based surface treatment agent for metal materials. The order of adding components is not particularly limited, but mixing can be performed by stirring, for example, using a propeller mixer, etc. The water-based surface treatment agent of the present invention is obtained in a solid form. The concentration is preferably within a range of 5: 50% by weight, and is preferably within a range of 5 to 40% by weight. When the solid content concentration is less than 5% by weight, the drying time becomes longer, which is not suitable. On the other hand, when the solid content concentration exceeds 50% by weight, the viscosity of the physical agent itself is high, which may cause trouble in handling. As for the metal material (raw material) to which the aqueous surface treatment agent of the present invention is applied, examples thereof include: : Cold-rolled steel sheet, galvanized steel sheet, aluminized steel sheet, and aluminum sheet. The water-based surface treatment agent of the present invention can also be directly applied to related metal materials, but in order to fully exert the effects of the present invention, First use by The chromate treatment by a common method is to form a chromate film, and the aqueous surface treatment agent of the present invention can be coated thereon to form a resin film. 16 This paper size is applicable to Zhongguanjia Standard (CNS) A '丨 Specifications⑵Q χ 297 Gongchu 554019 A7 B7 Printed by the Consumer Cooperative of the Ministry of Intellectual Property of the Ministry of Economic Affairs of the People's Republic of China. 5. Description of the invention Form a coating, and then wash away the reactive chromate of the excess treatment solution, apply the treatment solution to the object to be treated and dry without washing to form a coating type of chromate. The present invention can also use any A processing method. On the base film formed by the above chromate treatment, the aqueous surface treatment agent of the present invention is applied at 10 to 50 t, and it is dried at a temperature of 60 to 200 ° C. to form a resin film. As for the coating method, conventional methods such as a roll coater method, a dipping method, an electrostatic coating method, and the like can be used. The surface-treated metal plate of the present invention obtained by using the related two-stage processing is on the surface of a metal material, and has a chromate coating layer of 3 to 100 mg / m2 of the third layer in terms of metal circuit conversion. The Q.3 ~ 3 Qg / m2 ^^ 4 J film layer 2 coated with the aqueous surface treatment agent of the present invention and dried is a surface-treated metal plate characterized by the second layer. Chromate 2 =! It is preferably 3 ~ 50mg / m2 in terms of metal chromium conversion, and 5 ~ 4. _2 When the amount of chromium is less than 3 mg / m2, the effect of improving the money resistance is saturated, and the amount of resin coating is less than G.3 g / ". At m2, the corrosion resistance is not economical. The edge effect will be saturated and ... coated with the surface treatment agent of the present invention and coated, and then the surface-treated metal plate will be corrosion-resistant and damaged in the plane part 2: purpose of pure resistance and coating adhesion Excellent performance. To the Γίί coated on the resin film ---——__ 17 This paper rule / i is suitable for China National Standards (CNS) A4 public announcement (please read the precautions on the back before filling this page) i · ^ .------ —Order --------- 554019 A7 B7 5. Description of the invention () Materials are not particularly limited, but examples include: dry-temperature melamine alkyd paint, Baking-type melamine alkyd paint, acrylic resin paint, UV-curable resin paint, etc. [Examples] The following uses manufacturing examples, examples, and comparative examples to specifically explain the present invention. The person who writes about the present invention is not intended to limit the present inventor. The test materials used the commercially available raw materials shown below as test materials: • Galvanized steel (EG) plate thickness 0 · 8mm, unit area weight = 20/20 (g / m2) • Galvanized steel plate containing 5% aluminum ( GF) plate thickness 0 · 8mm, weight per unit area = 90/90 (g / m2) • aluminum plate (AL) plate thickness 1.0mm, 5182 series (2) degreasing treatment with the above test materials Fine cleaner 4336 (registered trademark, manufactured by Japan Parkerizing Co., Ltd.) for degreasing agent was degreased. After spraying at a concentration of 20 g / L and a temperature of 60 ° C for 2 minutes, it was washed with tap water. (3) Substrate treatment (3_1) Reactive chromate chemical method surface treatment (raw materials: EG, GF) Zinchrome 357 (registered trademark: Japan Parkerizing) This paper's standard is applicable to Θ national standard (CNS) A'l specification (210 X 297 mm) ----- ί --- U ---- (Please read the notes on the back before filling this page) Order -------. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 554019 Wisdom of the Ministry of Economic Affairs Printed by A7, B7, Consumer Cooperatives of the Property Bureau V. Description of Invention () Co., Ltd.) '5 seconds at liquid temperature 501 Clock spraying, washing with tap water, and air-drying to make test plates. (3-2) Coating type chromate chemical surface treatment (raw material: 阢, gf) Zinchrome 1300AN (registered trademark: made by Japan Parkerizir ^ Co., Ltd.) ), Coated with a roller coater method, immediately dried at 200 ° C air temperature for 10 seconds without washing, and made a test plate. The temperature reached at this time was 100 ° C. (3-3) Reactive chromate treatment (raw material: AL): Alchrome 71; 3 (registered trademark: manufactured by Nissho Co., Ltd.), spray-treated for 5 seconds at a liquid temperature of 50 t, washed with tap water, and air-dried , Making test panels. [Preparation of water-based surface treatment agent] At room temperature, using a propeller stirrer, sequentially stir the resins in Table 丨, the hardener in Table 2, one of Table 3 oxide particles, and the water dispersion in Table 4 and mix, Distilled water was added and the solid content concentration was adjusted to prepare the aqueous surface treatment agents of the examples shown in Table 5 and the aqueous surface treatment agents of the comparative examples shown in Table 6. The wax water dispersion is prepared by putting the entire amount of wax, compound (engineering) and water shown in Table 4 in an autoclave, and heating it to a temperature of 13 to 14 t and stirring to prepare it. [Aqueous surface treatment agent pair Coating method of test plate] Using a coating bar coater, each of the above-mentioned aqueous surface treatment agents was coated on each of the above test plates, and dried at an air temperature of 24.0 ° C for 10 seconds. The agent reached the plate temperature It is 1001. And the adjustment of the attachment amount is suitable for 19 Benshi and weekly TT Sisiquan (CNS) A · 丨 specifications (21〇X 297 public · ^) (Please read the precautions on the back before filling (This page) -------- ^ Order i —% | 554019

當變更該組成物之固形濃度及塗布桿塗布器之種類予次進 〔塗布板性能試驗〕 (請先閱讀背面之注音？事項再填寫本頁} (1) 千面性耐性 對eg板之情形進行24〇小時，GF板之情形進行· $時，AL材之情形進行6〇〇小時之利用Jis_ z237i規 疋的疏水噴式驗，觀察白錄姓發生狀況，依 進行評估。 〈評估基準〉 ◎:白銹蝕發生面積率未滿全面積之3% Ο .•白銹蝕發生面積率在全面積之3%以上未滿1〇% ^ •白銹蝕發生面積率在全面積之10%以上未滿30% 册白銹蝕發生面積率在全面積之3〇%以上 (2) 帶有傷痕部之耐|虫性 經濟部智慧財產局員工消费合作社印製 將試片裁切成30_χ300_之尺度，進行落珠試驗 drop bead test，珠粒前端lmmR、珠粒高度4_、骰 形小方塊肩部1_R、壓著負載5⑼kg、溫度加。㈡。至 於此試片之摺動部分，對EG材之情形進行12〇小時，gf 材之f月形進行240小時，AL材之情形進行刻小時，利 IS 22371規疋的鹽水噴霧試驗，觀察白銹蝕發生 狀況，依下述基準進行評估。 〈評估基準〉 ◎:白銹蝕發生面積率未滿全面積之3% 白銹蝕發生面積率在全面積之抓以上未滿1⑽ 20 554019 A7 B7 五、發明說明（ $ ··白銹餘發生面積率在全面積之⑽以上未滿3〇% 白錄钱發生面積率在全面積之30%以上 (3)塗布附著性 將三聚氰氨醇酸系塗料塗布至烘烤乾燥後 心m，在125烘烤20分鐘。烘烤後採用經過24^為 的4片依JIS - Z5400規定描繪imm棋盤方格刪個 後，利用赛珞仿膠帶剝離塗膜，依下述基準進行評估。 〈評估基準〉 ◎ •無塗膜剝離、塗膜殘存個數1 〇〇個 〇 極夕σ卩分塗膜剝離，塗膜殘存個數1 〇〇個 △ ••塗膜殘存個數95〜99個 X ··塗膜殘存個數94個以下 試驗結果示於表7及表8。在採用本發明之水性表面 處理劑的實施例卜2卜在平面部耐錄，帶有傷痕部 雜性及塗布附著性之任—者均係良好。另—方面，在 採用本發明之範®外的水性表面處關之比較例， 平面D卩耐姓性、π有傷痕部耐飯性及塗布附著性之至少 兩個性能係低劣的。 ^ 21 本纸張义度適用中舀國家標準（CNS)A-!规格（210 X 297公£When changing the solid concentration of the composition and the type of the coating rod applicator to the secondary [coating plate performance test] (Please read the note on the back? Matters and then fill out this page} (1) Situation of thousand-face resistance to eg board For 24 hours, the condition of the GF board is performed. At the time of the AL material, the water spray test using the Jis_z237i standard is performed for 6,000 hours. The occurrence of Bailu surname is observed, and the evaluation is performed. 〈Evaluation Standard〉 ◎ : The area ratio of white rust occurrence is less than 3% of the total area 〇. • The area ratio of white rust occurrence is more than 3% and less than 10% of the total area ^ • The area ratio of white rust occurrence is more than 10% and less than 30% of the total area % The area ratio of white rust occurrence is more than 30% of the total area. (2) The resistance of the damaged part | Insect resistance Ministry of Economics and Intellectual Property Bureau Staff Consumer Cooperatives Printed and cut the test piece to a size of 30_χ300_ Bead test drop bead test, the bead tip 1mmR, bead height 4_, dice small shoulder 1_R, pressing load 5⑼kg, temperature plus. ㈡. As for the bending part of this test piece, the situation of EG material is 12 〇hour, f moon shape of gf material for 240 hours, AL material In the case where the situation lasts for an hour, the salt spray test according to IS 22371 is observed, and the occurrence of white rust is observed, and the evaluation is performed according to the following criteria. <Evaluation Criteria> ◎: The white rust occurrence area ratio is less than 3% of the total area. The rate above the full area is less than 1⑽ 20 554019 A7 B7 V. Description of the invention ($ ·· The rate of the area where the white rust is generated is not less than 30% of the total area. The area rate of the white recorded money is 30% of the total area. % Or more (3) Coating adhesion Apply the melamine alkyd paint to the core m after baking and drying, and bake for 20 minutes at 125. After baking, use 4 pieces that have passed through 24 ^ for drawing in accordance with JIS-Z5400. After the imm checkerboard is deleted, the coating film is peeled off using a siphon tape and evaluated according to the following criteria. 〈Evaluation Criteria〉 ◎ • There is no peeling of the coating film, and the number of remaining coating films is 1,000. The coating film was peeled off, and the number of remaining coating films was 100. △ • The number of remaining coating films was 95 to 99. The number of remaining coating films was 94 or less. The test results are shown in Tables 7 and 8. When the present invention was used, Example 2 of the water-based surface treatment agent is resistant to recording on the flat surface, Either the scratched part is heterogeneous or the coating adhesion is good. On the other hand, in a comparative example using an aqueous surface outside the scope of the present invention, the flat surface is resistant to surnames, and the scratched part is resistant to π. At least two properties of food and coating adhesion are inferior. ^ 21 The meaning of this paper applies to China National Standard (CNS) A-! Specifications (210 X 297 kg).

(請先閱讀背面之注意事項再填寫本頁) -I I I . II線 丨. 554019 A7 B7 五、發明說明（) 【表1】 實施例及比較所用的樹脂 樹脂 品名 製造廠名 樹脂系 玻璃移 轉溫度 固形分 濃度 請求 範圍 理由 A1 Super flex 107M 第一工業製藥(股） 胺酯 -40°C 25% 〇 A2 Adecarixnti^iter HUX-580 旭電化工業(股） 胺酯 -14°C 62% 〇 A3 Primal K-3 R0HM&amp;HAAS 丙婦酸S旨 -27〇C 46% 〇 A4 Primal NW-1715 R0HM&amp;HAAS 丙烯酸酯 -6°C 44% 〇 A5 VironalMD-1930 東洋紡織(股） 酯 -10°C 30% X 樹脂系 不同 【表2】實施例及比較所用的硬化劑 硬化劑 品名 製造廠名 官能基 固形分濃度 B1 Dinacore EX-512 Negas(長瀨）化成(股） 環氧 100% B2 Elastron BN-69 第一工業製藥(股） 異氰酸酯 40% (請先閱讀背面之注意事項再填寫本頁) - Γ I m ϋ ·ϋ 1! ϋ ϋ ϋ 1 β ·ϋ ϋ ϋ ^1 ϋ ϋ ^1 _ 經濟部智慧財產局員工消費合作社印製 【表3】 實施例及比較所用的二氧化石夕 二氧化矽 品 名 製造廠名 固形分濃度 C1 Snowtex-N 曰產化學工業（股） 20% C2 Snowtex-0 曰產化學工業（股） 20% 22 本紙張尺度適用中a S家標準（CNS)A.l規格（210 X 297公H ) 554019 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明說明（ 【表4】 實施例及比較所用的蠟水分散體（固形分濃度20% ) 蠛 化練（I) 平均 粒徑 jum 請求 範圍 麵* 1 配合量*2 R1 R2 R3 R4 酉量*2 Μ η W1 三牛it#(股)製 Hi 丽 4202E 酸價17 75 C 2H 19- 12 0 -Η -CH 二 CHCH 3 25 0.08 〇 W 三井^谢股)製 Hiwax 42203A 酸價30 95 C 1 8只 3 7- 20 0 -so3nh4 -Η 5 0.12 〇 W3 三和谢股)製 Hi丽 4202E 酸價17 90 C 8 Η 丨 7 - 10 5 -Η 10 0.15 〇 W4 三和谢股)製 ta 4051E mt i2 80 (Ή 2 = och2- 10 5 - Η -Η 20 0.15 〇 % 三(股)製 Hiwox 4202Ε 酸價17 85 C 9Η 1 9- 12 0 -Η -Η 15 0.45 X*3 W6 三井ί谢股)製 Hi腿 _55 酸價0 90 Q 8^ 37 ~ 20 0 -so3nh4 -Η 10 0.10 X*4 *1 : W^W5為聚乙烯蠟，W6為聚丙烯蠟。 *2 :配合量之數值為對蠟水分散體之全固形分的固形分重量％。 *3:粒徑在範圍外。 *4 :蠟之種類在範圍外。 23 (請先閱讀背面之注意事項再填寫本頁) -0 mmM9 11 in ϋ 1 n ^ ^ I I w· ws I 凿 本紙張尺度適用中a 0家標準（CNS)A.l規格（210 X 297公坌） 554019 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明說明（） 【表5】 實施例所用的水性表面處理劑 水性表面處理劑 水丨 生表面處理齊 之固形分濃方 [氺1 (A)/(B) 之比 水性表面處理劑之 固形分濃度 樹脂 硬化劑 二氧化矽粒 子 蠟水分散體 1 AK72) BK3) CK20) Wl(5) 24.0 12.0% 2 A2(72) BK3) C1C20) Wl(5) 24.0 12.0% 3 A3C72) BK3) CK20) Wl(5) 24.0 12.0% 4 A4(72) BK3) Cl(20) W1⑸ 24.0 12.0% 5 AK72) B2⑶ Cl(20) Wl(5) 24.0 12.0% 6 AK72) BK3) C2(20) W1⑸ 24.0 12.0% 7 AK82) BK3) CK10) Wl(5) 27.3 12.0% 8 AK63) BK2) CK30) Wl(5) 31.5 12.0% 9 AK61) BK4) Cl(20) W1⑸ 15.3 12.0% 10 Al(80) BK2) Cl(10) Wl(8) 40.0 12.0% 11 AK70) BK7) Cl(20) Wl(3) 10.0 12.0% 12 AK72) BK3) Cl(20) W2(5) 24.0 12.0% 13 AK72) BK3) CK20) W3(5) 24.0 12.0% 14 AK72) BK3) Cl(20) W4(5) 24.0 12.0% 15 AK72) BK3) Cl(20) Wl(5) 24.0 40.0% 16 AK72) BK3) Cl(20) W1⑸ 24.0 5.0% *1:()内之數值係對水性表面處理劑之全固形分的固形分重量％ 24 (請先閱讀背面之注意事項再填寫本頁) '裝------l· I訂 --------線 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 554019 A7 B7 五、發明說明（ 經濟部智慧財產局員工消費合作社印製 ί#1ϊ^νθ&lt;±1、^忘 κ^ί冬 【9裕】 理由 樹脂之種類不同 蠟之粒徑在範圍外 犧之種類在範圍外 (Α)/(Β)之比在範圍外 (Α)/(Β)之比在範圍外 二氧化石夕量較少 二氧化矽量較多 蝶量較少 壤量較多 Ηλ㈣ « 2 12.0% 12.0% 12.0% 12.0% 12.0% i 12.0% 12.0% 12.0% 12.0% (Α)/(Β)之比 24.0 〇 寸· οα 24.0 ◦ CD oi 26.7 ◦ 寸· CO LO OCI CD 水性表面處理劑之固形分濃度*1 1 蠟水分散體 W1⑸ W5⑸ W6⑸ | W1C5) 1 1 Wl(5) 1 1 Wl(15) 1 W1⑸ 1 W1(1) 1 | Wl(25) I 二氧化矽 粒子 | Cl(20) 1 [Cl(20) 1 Cl(20) | Cl(20) I οα 1 C2 ⑵ 1 | Cl(45) | | Cl(20) I | Cl(20) | 硬化劑 | ΒΚ3) I | ΒΚ3) | | ΒΚ3) | | Β1(3) I Β2(25) 1 BK3) 1 | ΒΚ32 | I Bl(3) 1 Bl(5) 樹脂 | A5C72) | ΑΚ72) | ΑΚ72) | | Α1(74) I Α1(50) 1 A1C80) 1 ΑΚ48) | A1C76) I | AK50) | 卜 〇〇 οα οο CO οα 寸 CM LO 〇〇 V0 Hill W w ^ V ^ ^ ^ )： I* -----i.---1------------訂---------線^^· (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中因國家標準（CNSMI规格（210 x 297公釐） 554019 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明說明（ 【表7 實施例之試驗水準及被膜性能(Please read the precautions on the back before filling this page) -III. II line 丨. 554019 A7 B7 V. Description of the invention () [Table 1] Resin resin name used in the examples and comparisons Manufacturer name Resin-based glass transfer Temperature solid content concentration request range reason A1 Super flex 107M First Industrial Pharmaceutical Co., Ltd. -40 ° C 25% 〇A2 Adecarixnti ^ iter HUX-580 Asahi Denki Chemical Co., Ltd. -14 ° C 62% 〇A3 Primal K-3 R0HM &amp; HAAS Hyaluronic acid S-27 ° C 46% 〇A4 Primal NW-1715 R0HM &amp; HAAS Acrylate-6 ° C 44% 〇A5 VironalMD-1930 Toyobo MD-1930 Ester-10 ° C 30% X Resin is different [Table 2] Hardener used in the examples and comparison Hardener Product name Manufacturer name Functional group solid content concentration B1 Dinacore EX-512 Negas (Nase) Chemical conversion (share) Epoxy 100% B2 Elastron BN -69 First Industrial Pharmaceutical Co., Ltd. 40% isocyanate (Please read the precautions on the back before filling out this page)-Γ I m ϋ · ϋ 1! Ϋ ϋ ϋ 1 β · ϋ ϋ ϋ ^ 1 ϋ ^ 1 _ Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs [Table 3] Examples and Comparison Solid dioxide concentration of the used silica dioxide and silica dioxide product manufacturer name C1 Snowtex-N Chemical Industry (stock) 20% C2 Snowtex-0 Chemical Industry (stock) 20% 22 This paper is applicable to a S Home Standard (CNS) Al Specification (210 X 297 male H) 554019 A7 B7 Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (Table 4) Wax dispersions (solid content concentration) for the examples and comparisons 20%) 蠛 chemical training (I) average particle size jum request range surface * 1 blending amount * 2 R1 R2 R3 R4 酉 量 * 2 Μ η W1 Sanniu it # (share) Hi Li 4202E acid value 17 75 C 2H 19- 12 0 -Η-CH di-CHCH 3 25 0.08 〇W Mitsui ^ Xiegu) system Hiwax 42203A Acid value 30 95 C 1 8 3 7- 20 0 -so3nh4-Η 5 0.12 〇W3 Sanwa Xiegu) system Hi Li 4202E acid value 17 90 C 8 Η 丨 7-10 5 -Η 10 0.15 〇W4 Sanhe Xie shares) system ta 4051E mt i2 80 (Ή 2 = och2- 10 5-Η -Η 20 0.15 ％% three ( Stock) Hiwox 4202E acid value 17 85 C 9Η 1 9- 12 0 -Η -Η 15 0.45 X * 3 W6 Mitsui 谢 stock) Hi leg _55 acid value 0 90 Q 8 ^ 37 ~ 20 0 -so3nh4- Η 10 0.10 X * 4 * 1: W ^ W5 is polyethylene wax, W6 is polypropylene wax. * 2: The numerical value of the blending amount is the solid content weight% of the total solid content of the aqueous wax dispersion. * 3: The particle diameter is outside the range. * 4: The type of wax is outside the range. 23 (Please read the precautions on the back before filling out this page) -0 mmM9 11 in ϋ 1 n ^ ^ II w · ws I Chiseled paper sizes are applicable a 0 Standards (CNS) Al (210 X 297 cm) ) 554019 A7 B7 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention () [Table 5] Water-based surface treatment agent used in the examples Water-based surface treatment agent Water surface treatment solid solid concentration formula [氺 1 (A) / (B) Specific solid content concentration of water-based surface treatment agent Resin hardener Silicon dioxide particle wax aqueous dispersion 1 AK72) BK3) CK20) Wl (5) 24.0 12.0% 2 A2 (72) BK3) C1C20 ) Wl (5) 24.0 12.0% 3 A3C72) BK3) CK20) Wl (5) 24.0 12.0% 4 A4 (72) BK3) Cl (20) W1⑸ 24.0 12.0% 5 AK72) B2⑶ Cl (20) Wl (5) 24.0 12.0% 6 AK72) BK3) C2 (20) W1⑸ 24.0 12.0% 7 AK82) BK3) CK10) Wl (5) 27.3 12.0% 8 AK63) BK2) CK30) Wl (5) 31.5 12.0% 9 AK61) BK4) Cl () 20) W1⑸ 15.3 12.0% 10 Al (80) BK2) Cl (10) Wl (8) 40.0 12.0% 11 AK70) BK7) Cl (20) Wl (3) 10.0 12.0% 12 AK72) BK3) Cl (20) W2 (5) 24.0 12.0% 13 AK72) BK3) CK20) W3 (5) 24.0 12.0% 14 AK72) BK3) Cl (20) W4 (5) 24.0 12.0% 15 AK72) BK3) Cl (20) Wl (5) 24.0 40.0% 16 AK72) BK3) Cl (20) W1⑸ 24.0 5.0% * 1 :() Within The value is the solid content weight% of the total solid content of the water-based surface treatment agent. 24 (Please read the precautions on the back before filling this page) 'Packing ------ l · I order ------- -The paper size of the paper is in accordance with the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 554019 A7 B7 V. Description of the invention (printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs) κ ^ ί 冬 【9 裕】 Reasons The type of the resin is different. The particle size of the wax is outside the range. The type of the sacrifice is outside the range. The ratio of (A) / (B) is outside the range. The ratio of (A) / (B) is outside the range. Less amount of dioxide, more amount of silica, more butterflies, less soil, more Ηλ㈣ «2 12.0% 12.0% 12.0% 12.0% 12.0% i 12.0% 12.0% 12.0% 12.0% (Α) / (Β) Ratio 24.0 〇 Inch · οα 24.0 ◦ CD oi 26.7 ◦ Inch · CO LO OCI CD Solid content concentration of water-based surface treatment agent * 1 1 Wax water dispersion W1⑸ W5⑸ W6⑸ | W1C5) 1 1 Wl (5) 1 1 Wl ( 15) 1 W1⑸ 1 W1 (1) 1 | Wl (25) I Dioxide Particles | Cl (20) 1 [Cl (20) 1 Cl (20) | Cl (20) I οα 1 C2 ⑵ 1 | Cl (45) | | Cl (20) I | Cl (20) | Hardener | ΒΚ3 ) I | ΒΚ3) | | ΒΚ3) | | Β1 (3) I Β2 (25) 1 BK3) 1 | ΒΚ32 | I Bl (3) 1 Bl (5) resin | A5C72) | ΑΚ72) | ΑΚ72) | (74) I Α1 (50) 1 A1C80) 1 ΑΚ48) | A1C76) I | AK50) | Bu 〇〇οα οο CO οα Inch CM LO 〇VOV Hill W w ^ V ^ ^ ^): I * --- --i .--- 1 ------------ Order --------- line ^^ · (Please read the precautions on the back before filling this page) This paper size Applicable national standards (CNSMI specifications (210 x 297 mm) 554019 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of the invention (Table 7 Test levels of the examples and film performance

金屬鉻換算附著量* 2:乾燥樹脂被膜附著量 26 (請先閱讀背面之注意事項再填寫本頁) —訂---------^ 本紙張尺度適用中0國家標準（CNS)A·丨規格（210 X 297公釐） 554019 _B7 五、發明說明（) 經濟部智慧財產局員工消费合作社印製 A7 【表8】 比較例之試驗水準及被膜性能 原材 料 鉻酸鹽化与 s法表面處理 水性表面處理劑 塗布板性能 種類 附著量氺1 ng/tf 種類 附著量*2 ng/tf 财ϋ性 塗布附 著性 平面部 帶有傷 痕部 1 EG 反應型 20 17 1.0 Δ X Δ 比 2 EG 反應型 20 18 1.0 Δ Δ Δ 3 EG 反應型 20 19 1.0 Δ Δ X 4 EG 反應型 20 20 1.0 Δ Δ Δ 較 5 EG 反應型 20 21 1.0 Δ Δ Δ 6 EG 反應型 20 22 * 1.0 Δ X Δ 7 EG 反應型 20 23 1.0 Δ X Δ 例 8 EG 反應型 20 24 1.0 Δ X Δ 9 EG 反應型 20 25 1.0 Δ Δ Δ * 1 :金屬鉻換算附著量* 2:乾燥樹脂被膜附著量 【發明之功效】 如上述般，藉由本發明水性表面處理劑塗布於以施 以鉻酸鹽處理之金屬板的表面上並予乾燥，可得平面部 耐蝕性，帶有傷痕部耐蝕性及塗布附著性優越的表面處 理金屬板。 本紙張尺度適用中S 0家標準（CNS)A4規格（210 X 297公；？| ) (請先閱讀背面之注意事項再填寫本頁)Metal chromium conversion adhesion amount * 2: Dry resin coating adhesion amount 26 (Please read the precautions on the back before filling out this page) — Order --------- ^ This paper is applicable to 0 national standards (CNS) A · 丨 Specifications (210 X 297 mm) 554019 _B7 V. Description of the invention () Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, printed A7 [Table 8] Test levels and film properties of comparative examples Raw materials chromate and s method Surface treatment Aqueous surface treatment agent coated plate Performance type Adhesion amount 氺 1 ng / tf Kind adhesion amount * 2 ng / tf Financial coating adhesion Adhesive flat part with a scar part 1 EG Reactive type 20 17 1.0 Δ X Δ ratio 2 EG Reactive type 20 18 1.0 Δ Δ Δ 3 EG reactive type 20 19 1.0 Δ Δ X 4 EG reactive type 20 20 1.0 Δ Δ Δ than 5 EG reactive type 20 21 1.0 Δ Δ Δ 6 EG reactive type 20 22 * 1.0 Δ X Δ 7 EG reactive type 20 23 1.0 Δ X Δ Example 8 EG reactive type 20 24 1.0 Δ X Δ 9 EG reactive type 20 25 1.0 Δ Δ Δ * 1: Metal chromium equivalent adhesion amount * 2: Dry resin film adhesion amount [Invention of Efficacy] As described above, with the aqueous surface treatment agent of the present invention Applied to the cloth to the upper surface of the chromate-treated metal plate and to dried to give corrosion resistance flat portion, with a flaw portion corrosion resistance and coating adhesion surface treatment of the metal plate superior. This paper size is applicable to S 0 Standards (CNS) A4 (210 X 297 male;? |) (Please read the precautions on the back before filling this page)

Claims (1)

554019 /.V -b/-¾ 口 斗v Ma-nix a.. ,..u -^ -----•丨·ι --六、申請專利範圍 【申請專利範圍】 1. 一，金屬材料用水性表面處理劑，特徵在於含有 (A) 胺酯樹脂及/或丙烯酸酯系樹脂、（B )硬化劑 ，氧化梦粒子、（D)平均粒子Q.㈣，婦 堪、（£)分散劑之以下式（I ) t ，R4 R 一^\〇V~ Ο — R2— r3 ⑴ 〈式内R1表示碳數1〜20之烷基或碳數2〜2〇之烯基，R2表 示(一Ε〇)「(Ρ〇)η (式中E表示伸乙基、p表示伸丙基、m 表不5〜20之整數、n表示〇或h〇之整數），❹示氯原 ^或so 3 Μ(式中Μ表示氩原子、鹼金屬離子或銨離子）， R4表示氫原子、碳數丨〜4之烷基或碳數2〜4之烯基〉表示 的化合物及水，成分（Α)及（Β)係各自分散或溶解於 水，成分（C )及（D )分散於水，成分（Ε )溶解於水， 對成分（A )〜（Ε )之全部固形分，（A ) + ( Β )之固 形^之比率為50〜95重量％，（ C )之固形分之比率為3〜4〇 重里％，（D) + (£)之固形分之比率為2〜2〇重量％，（ a ) /(B)固形分重量比在4/；[〜4 g/ι。 2·如申請專利範圍第1項之金屬材料用水性表面處理 劑，其中（E)之固形分對（D) + (E)之固形分的 比率為5〜40重量％。 訂 本纸張尺度適用中關家標準(CNS)A丨規格(2Ϊ0 X 297 iV 6(公告本 申請曰期 案 號 ^ ί〇33〇^ 類 別 (以上各欄由本局填註）554019 /.V -b / -¾ 口 斗 v Ma-nix a .., .. u-^ ----- • 丨 · ι-6. Scope of patent application [Scope of patent application] 1. Metal Water-based surface treatment agent for materials, characterized by containing (A) urethane resin and / or acrylate resin, (B) hardener, dream oxide particles, (D) average particles Q.㈣, Fukan, (£) dispersion The following formula (I) t of the agent, R4 R — ^ \ 〇V ~ 〇 — R2— r3 〈<wherein R1 represents an alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 2 carbon atoms, and R2 represents ( -E〇) "(PO) η (where E represents ethylene, p represents propyl, m represents an integer of 5 to 20, n represents an integer of 0 or h0), and chloro represents ^ or so 3 M (where M represents an argon atom, an alkali metal ion, or an ammonium ion), R 4 represents a hydrogen atom, an alkyl group having a carbon number of from 4 to 4 or an alkenyl group having a carbon number of 2 to 4, and water, and a component ( A) and (B) are each dispersed or dissolved in water, the components (C) and (D) are dispersed in water, the component (E) is dissolved in water, and for all solid components of the components (A) to (Ε), (A ) + (Β) solid ratio ^ ratio is 50 ~ 95% by weight, (C) The ratio of the solid content is 3 to 40% by weight, the ratio of the solid content of (D) + (£) is 2 to 20% by weight, and the weight ratio of (a) / (B) solid content is 4 /; [~ 4 g / ι. 2. If the water-based surface treatment agent for metal materials according to item 1 of the scope of patent application, the ratio of the solid content of (E) to the solid content of (D) + (E) is 5 to 40% by weight. This paper size is applicable to Zhongguanjia Standard (CNS) A 丨 specifications (2Ϊ0 X 297 iV 6 (announcement of this application's issue case number ^ 〇〇〇〇) category (the above columns are filled out by the Bureau) 554019554019 專利説明書 中 文 金屬材料用水性表面處理劑及表面處理金屬板 發明新型 名稱 英 文 Aqueous Surface Treating Agents for Metal Materials And Surface-treated Metal Plates 姓名 國 籍 (U木下 (2) 上野 (3) 小山 均日本 弘一康圭隆 發明創作/ 住、居所 均日本國東京都中央區日不橋卜丨5 □本巴卡萊近沽股份有限公司內Patent Specification Chinese Metal Materials Water-based Surface Treatment Agent and Surface-treated Metal Plate Invention New Name English English Aqueous Surface Treating Agents for Metal Materials And Surface-treated Metal Plates Name Nationality (U Kinoshita (2) Ueno (3) Koyama Jun Japan Hiroichi Kanguilong Invention, creation, residence and residence, Hibashibashi, Chuo-ku, Tokyo, Japan 丨 5 □ In the Bakalai Kingu Co., Ltd. 姓 名 (名稱） 日本巴卡萊近沽股份有限公司 線 經濟部智^57是^;吕：工消費合作社印％ 國 籍 日本 三、申請人 住、居所(事務所） 代表人 姓 名 彐:i：國栗曱都屮央區日本橋卜丨5 -丨 垔昆菊雄 太纸張尺度適用中國國家標准：CNS ) A4規格（2H)X297公釐）Name (Name) Japan Bakalai Kingu Co., Ltd., Ministry of Economic Affairs, Chi ^ 57 Yes ^; Lu: Industrial and consumer cooperative seals% Nationality Japan III. Applicant's residence, residence (office) Representative name 彐: i: country Japanese Bridge in Liyang District, Liyang District 丨 5-丨 The size of the paper for Kunxiong Xiongtai paper is applicable to Chinese national standards: CNS) A4 size (2H) X297 mm)