201038689 h 六、發明說明： 【發明所屬之技術領域】 本發明係關於對金屬材料，尤其是形狀複雜之金屬構 成體而言’具有較佳的鍍覆均厚能力之電沈積塗料祖成物 及電沈積塗裝方法。 、 【先前技術】 以往，用以對各種金屬材料，尤其是形狀複雜之金屬 構成體賦予較佳的耐蝕性之手法，一般係使用可均勻地使 〇塗膜析出於複雜形狀的各角落之電沈積塗裝。 電沈積塗裝，大致可區分成：在含有陰離子性樹脂乳 化液之水性塗料中，藉由將被塗物進行陽極電解使塗膜析 出之陰離子電沈積塗裝；以及在含有陽離子樹脂乳化液之 水性塗料中，藉由將被塗物進行陰極電解使塗膜析出之陽 離子電沈積塗裂。 陰離子性樹脂乳化液，在驗性區具有分散安定性，在 ο酸性區則失去分散安定性。陽離子樹脂乳化液，相反地在 酸性區具有分散安定性，在驗性區則失去分散安定性。藉 由極電解或陰極電解使樹脂析出者，係利用此性質者。 因此，反應機制上，非離子性樹脂乳化液無法進行析出。 對於鐵系金屬材料的耐姓性提升，不需擔心在電解處 理中基質金屬溶出於塗料中之陽離子電沈積塗裝較為有 利’因此，陽離子電沈積塗裝係廣泛運用在以鐵系材料為 主之金屬構成體的汽車車體、汽車零件、家電製品、建築 材料等。 3 321814 201038689 如剛述般，電沈積塗裝的最大特徵為塗裝的鍍覆均厚 能力，近年來以塗料用旦』蠼復均厚 π 降低及雜性的提升為目的， ^ ’優良的鍍覆均厚能力。針對鍍覆均厚能力的 提升’'已進行種種探討。 年把力的 r4例如專利文獻K日本特Μ 2002-294143號公報）中， 係揭不-齡#水性_、含有分㈣轉財性媒體中 環氧樹脂及封閉型異氰酸酯硬化劑之黏結 劑樹月曰、用以中和陽離子性環氧樹脂之中和酸、有機溶劑、 以及金屬觸媒之無雜陽離子電沈積塗料組成物，直中， 揮發性有機份含量為i重量％以下，金屬離子濃度為5〇〇_ 以下’中和酸的量相對於黏結劑樹脂固形份^，為1〇至 3〇m曰g當量之無純陽離子電沈積塗料組成物，金屬觸媒較 佳是選自由鈽離子、鉍離子、銅離子、鋅離子、鉬離子、 鋁離子所組成之群組的一種以上’中和酸較佳是選自由乙 酸、乳酸、曱酸、胺磺酸所組成之群組的一種以上。 此外’亦有許多揭示使用與此電沈積塗料組成物類似 之組成物來提升鍍覆均厚能力之技術。 專利文獻2(日本特開2002-285391號公報）的特徵是 電沈積浴的溫度控制者，專利文獻3(日本特開2〇〇2_ ^5392號公報）的特徵是具有塗膜的玻螭轉移溫度為不同 之2種電沈積工序者’專利文獻4(日本特開2002-294144 號公報）的特徵是特定出非揮發固形份者，專利文獻5(日 本特開2002-294145號公報）及專利文獻6(日本特開2〇〇2- 约4146號公報）的特徵是特定出陽離子性環氧樹脂#的玻璃 321814 201038689 轉移m·度與分子量者，專利文獻7(日本特開2__294i47 號A報）的特徵疋特定出塗膜的最低製膜溫度者，專利文獻 本特開2005_19侧號公報）的特徵是特定出陽離子 性環氧樹脂的基質樹脂骨架、膜電阻、硬化劑及硬化劑的 玻璃轉移溫度者’專利文獻9(日本特開2__156655號公 報）的特徵仍是特定出膜電阻者。 [先前技術文獻] [專利文獻] 〇 [專利文獻1]日本特開2002-294143號公報 [專利文獻2]日本特開2〇〇2_285391號公報 [專利文獻3]日本特開2002-285392號公報 [專利文獻4]日本特開2002-294144號公報 [專利文獻5]日本特開2002-294145號公報 [專利文獻6]日本特開2002-294146號公報 [專利文獻7]日本特開2〇〇2_294147號公報 〇 [專利文獻8]日本特開2005-194389號公報 [專利文獻9]日本特開2〇〇8_156655號公報 [專利文獻10]日本特開2007_314690號公報 [專利文獻U]日本特開2008-538383號公報 [非專利文獻] [非專利文獻1]前田重義，淺井恆敏，岡田秀彌防蝕 技術：31，268(1982) 【發明内容】 (發明欲解決之課題） 5 321814 201038689 上述習知技術，的確對鍍覆均厚能力具有效果，但市 場需求亦的確要求更進—步㈣覆均厚能力提升。因此， 本發明者們係重新思考陽離子電沈積塗裝的析出機制。 陽離子電沈積塗裝中所用之樹脂乳化液，較多是藉由 胺基的導入來賦予陽離子。文獻i中記載著陽離子樹脂乳 化液，在酸性區具有分散安定性，在鹼性區則失去分散安 疋丨生但貫際上藉由陰極電解使乳化液失去電荷以形成塗 膜之pH ’係到達12前後。 當然，塗膜析出之pH會因樹脂乳化液的性狀，例如乳 化液分子量、所導入之胺基的種類或導入率而有所變化， 但若是未在至少超過pH1〇之區域，則無法開始析出。因 此，當進行陰極電解使pH上升時，起始pH之塗料組成物 的pH成為在樹脂乳化液達到安定化之範圍内儘可能愈高 之PH者，對塗膜的析出性而言可說是有利。 習知技術之專利文獻1〇(日本特開2007-314690號公 報）及專利文獻11(日本特開2008-538383號公報），仍是 關於電沈積塗料组成物者，但此等係以水性塗料組成物的 PH為5至7者較佳’ 5. 5至6. 5者更佳。PH未達5時之缺 失，例如有電沈積塗裝效率及膜外觀的降低。 關於專利文獻1至9，雖然無具體之pH的說明，但為 了改良電沈積塗料的鐵覆均厚能力，較佳是減少塗料組成 物中所含之中和酸的量而將陽離子性環氧樹脂之中和率抑 制在低程度，亦即儘可能將邱保持較高者。事實上，由於 中和酸的量相對於黏結劑樹脂固形份100g為10至30mg當 321814 6 201038689 Μ切料敎獻及專利文 脂乳1:的組成物本身的。Η者、及藉由樹 用除此之外的手沐， ΡΗ者’皆已到達極限，若不使 因此，、、，則無法期待鍍覆均厚能力的改善。 ΡΗ者作Α史本發明者們係探討藉由凝聚劑来降低塗膜析出 ο 致果者新手法。並發現到在種種凝聚劑中，A1為最具 物中，I:使將A1化合物添加於以往的電沈積塗料組成 因時門⑽瞬間水解㈣化為氫氧化物，且氫氧化物會 因時^經過而凝聚，因而失去作為凝聚劑之效果。 <旦由於文獻1至9巾’較佳是含杨離子作為金屬觸媒， 離乂上边理由’推測實際上在電沈積塗料組成物中，紹 Γ瞬間水解而形成氫氧化物。雖然在實施例中未經驗 〇 ’但可考量為氫氧化物雖然維持作為觸媒之作用，卞作 马缝聚劑之效果已無法期待。 (解決課題之手段） =此，本發明者㈣特意地將成為電沈積塗料組成物 吊識之中性附近的pH降低至A1能夠持續以離子狀離存 之範圍為止，來評估A1離子相對於鑛覆均厚能力之效 ，結果發現到儘管降低組成物的pH，仍可獲得極為良好 的鍍覆均厚能力。 此外，本發明者們係發現到此A1離子的效果，對於無 法進行電解析出之非離子性樹脂乳化液亦為有效，且同樣 321814 7 201038689 可藉由陰極電解來析出，因而完成本發明。 亦即’本發明為下列所示之（1)及（2)。 (1) 一種電沈積塗料組成物，其特徵係含有非離子性及 /或陽離子性的水系樹脂以及鋁（A1)離子20至500ppm，並 且當將A1離子濃度設為A[ppm]時’其pH滿足下列計算式； 3. 5SpH$-Log((Axl. 93χ1(Γ15)1/3)。 (2) —種電沈積塗裝方法’其特徵係使用前述之組 成物，將金屬材料施以陰極電解法而析出塗膜。 【實施方式】 本發明之電沈積塗料組成物，係含有非離子性及/或陽 離子性的水系樹脂。在此，並未限定非離子性及陽離子性 的水系樹脂的何種。基質樹脂不論使用何種，均不會損及 本發月之效果’但尤佳為環氧、胺基甲酸g旨（让)、 丙烯酸。在此，本發明的一項特徵，係在於根據嶄新作用 機制（雖然隨著pH的上升使^離子成為氫氧化物膠體而凝 聚，但此時會將周圍的樹脂牽連之作用機制），能夠使用以 往所無法進行電解析出之非離子性樹脂者。如此，由於亦 可使用非離子系樹脂’使選擇性變得寬廣，而能夠將以往 所無法具有之各種性質賦予至覆膜。再者，即使在使用陽 ，子性樹脂時，除了隨著PH#上升使樹脂本身失去分散安 疋性之-般所知的作用機制之外，並可根據前述勒新作用 機制，在較以往還低的PJJ下進行電解析出。 樹脂乳化液的濃度亦無特別規定，當以電沈積塗料組 成物的全體重量為基準時，較佳係含有5至30重量％。更 321814 8 201038689 佳為7至25重量％，最佳為10至20重量％。當樹脂含量過 低時，覆膜析出量不足，當含量過高時，經濟面較為不利。 關於非離子性樹脂乳化液，可採用將環氧乙烷般之非 離子性官能基導入至基質樹脂之方法，亦即自我乳化法， 以及使用非離子界面活性劑進行乳化之方法，亦即強制乳 化法的任一種或兩種手法來製作出。關於陽離子性樹脂乳 化液，可採用將胺基般之陽離子性官能基導入至基質樹脂 之方法，亦即自我乳化法，以及使用陽離子界面活性劑進 ◎行乳化之方法，亦即強制乳化法的任一種或兩種手法來製 作出。此外，在導入陽離子性官能基後，亦可使用非離子 界面活性劑作為乳化輔助劑。此外，當自我乳化乳化液的 分子量較小時，已非粒子狀的乳化液，而成為水溶性樹脂， 但即使是水溶性樹脂，亦不會損及本發明之效果。本發明 之水系樹脂，為形成水分散之乳化液以及水溶性樹脂的總 稱。 ❹ 此外，水系樹脂亦可任意調配以封閉化聚異氰酸酯為 首之硬化劑。 本發明之電沈積塗料組成物中，較佳係含有A1離子 20至500pm。更佳為50至400ppm，最佳為100至300ppm。 當低於下限時，A1離子的塗膜析出提升效果不足，當高於 上限時，組成物的電傳導度過剩，反而使鍍覆均厚能力降 低。 組成物中的A1離子濃度，可藉由超離心機將組成物進 行固液分離，並使用高頻感應耦合電漿發光光譜分析（ICP: 9 321814 201038689201038689 h VI. INSTRUCTIONS OF THE INVENTION: TECHNICAL FIELD OF THE INVENTION The present invention relates to an electrodeposited coating precursor having a better plating thickening ability for a metal material, particularly a metal component having a complicated shape. Electrodeposition coating method. [Prior Art] Conventionally, a method for imparting better corrosion resistance to various metal materials, particularly metal structures having a complicated shape, generally uses electricity which can uniformly separate the ruthenium coating film into various corners of a complicated shape. Deposit coating. The electrodeposition coating can be roughly divided into: an anionic electrodeposition coating which precipitates a coating film by anodic electrolysis of an object to be coated in an aqueous coating material containing an anionic resin emulsion; and an emulsion containing a cationic resin emulsion In the water-based paint, cation electrodeposition of the coating film is carried out by cathodic electrolysis of the object to be coated. The anionic resin emulsion has dispersion stability in the test area and loses dispersion stability in the acidic region. The cationic resin emulsion, on the contrary, has dispersion stability in the acidic region and loses dispersion stability in the test region. Those who use the extreme electrolysis or cathodic electrolysis to precipitate the resin use this property. Therefore, in the reaction mechanism, the nonionic resin emulsion cannot be precipitated. For the improvement of the resistance of the iron-based metal materials, there is no need to worry about the cationic electrodeposition coating of the matrix metal dissolved in the coating during the electrolytic treatment. Therefore, the cationic electrodeposition coating system is widely used in the iron-based materials. The automobile body, automobile parts, home electric appliances, building materials, etc. of the metal body. 3 321814 201038689 As just mentioned, the most important feature of electrodeposition coating is the ability to coat the coating. In recent years, the coating has been used for the purpose of reducing the average thickness of π and improving the impurity. ^ 'Excellent The ability to plate is thick. Various improvements have been made to the improvement of plating uniformity. In the case of the r4 of the force, for example, the patent document K-Japanese Patent Publication No. 2002-294143, the adhesive tree of the epoxy resin and the blocked isocyanate hardener in the sub-(4)-transferable medium is disclosed. A ruthenium-free electrodeposited coating composition for neutralizing a cationic epoxy resin and an acid, an organic solvent, and a metal catalyst. The content of the volatile organic component is i% by weight or less, metal ion The concentration of the neutralization acid is 5 〇〇 _ or less relative to the solid content of the binder resin, and is a pure cationic electrodeposition coating composition of 1 〇 to 3 〇 m 曰 g equivalent, and the metal catalyst is preferably selected from the group consisting of More than one 'neutralizing acid' of the group consisting of cerium ions, cerium ions, copper ions, zinc ions, molybdenum ions, and aluminum ions is preferably selected from the group consisting of acetic acid, lactic acid, citric acid, and amine sulfonic acid. More than one. In addition, there are many techniques for using a composition similar to this electrodeposition coating composition to enhance the plating uniformity. The temperature of the electrodeposition bath is characterized by a temperature control of the electrodeposition bath, and the feature of the patent document 3 (Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. 2-5539) is a glass transition with a coating film. [Patent Document 4 (Japanese Laid-Open Patent Publication No. 2002-294144) is characterized in that a non-volatile solid portion is specified, Patent Document 5 (JP-A-2002-294145) and a patent. Document 6 (Japanese Unexamined Patent Publication No. Hei No. Hei No. Hei. No. 4146) is characterized in that the glass 321814 201038689 which is specific to the cationic epoxy resin # is transferred to m·degree and molecular weight, and Patent Document 7 (Japanese Patent Laid-Open No. 2__294i47 A) The characteristics of the coating film which is the minimum film forming temperature of the coating film, and the characteristics of the matrix resin skeleton, the film resistor, the hardener and the hardener of the cationic epoxy resin are specified. In the case of the transfer temperature, the patent document 9 (Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. [PRIOR ART DOCUMENT] [Patent Document 1] Japanese Laid-Open Patent Publication No. JP-A-2002-285392 (Patent Document No. JP-A-2002-285392) [Patent Document 5] JP-A-2002-294144 (Patent Document 5) JP-A-2002-294146 (Patent Document 6) JP-A-2002-294146 (Patent Document 7) Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. [Non-patent Document] [Non-Patent Document 1] Maeda Satoshi, Asai Hiroshi, Okada Shoji Anti-corrosion Technology: 31, 268 (1982) [Summary of the Invention] (Problems to be Solved by the Invention) 5 321814 201038689 The conventional technology does have an effect on the ability to thicken the plating, but the market demand does require more advancement (4). Therefore, the inventors rethought the precipitation mechanism of the cationic electrodeposition coating. The resin emulsion used in the cationic electrodeposition coating is often provided with a cation by introduction of an amine group. In document i, a cationic resin emulsion is described, which has dispersion stability in an acidic region, and loses dispersed ampoules in an alkaline region, but the pH of the coating is lost by cathodic electrolysis to form a coating film. Arrived around 12 years. Of course, the pH at which the coating film is deposited may vary depending on the properties of the resin emulsion, such as the molecular weight of the emulsion, the type of the amine group introduced, or the introduction rate. However, if it is not in the region exceeding at least pH1, the precipitation cannot be started. . Therefore, when the cathode electrolysis is performed to raise the pH, the pH of the coating composition at the initial pH becomes as high as possible in the range in which the resin emulsion reaches a stable level, and the precipitation property of the coating film can be said to be advantageous. The patent document 1 (Japanese Patent Laid-Open Publication No. 2007-314690) and the patent document 11 (JP-A-2008-538383) are still related to the electrodeposition paint composition, but these are water-based paints. The composition having a pH of 5 to 7 is preferably ' 5. 5 to 6. 5 is more preferred. The PH is less than 5 o'clock, such as the efficiency of electrodeposition coating and the appearance of the film. Regarding Patent Documents 1 to 9, although there is no specific pH description, in order to improve the iron coating uniformity of the electrodeposition coating, it is preferred to reduce the amount of the acid contained in the coating composition to form a cationic epoxy. The resin neutralization rate is suppressed to a low level, that is, as high as possible. In fact, since the amount of neutralizing acid is 10 to 30 mg relative to 100 g of the binder resin solid content, the composition itself is 321814 6 201038689 Μ cut material and patented milk 1: The leader and the other hand are used by the tree, and the latter has reached the limit. If it is not, the improvement of the plating uniformity cannot be expected. The inventors of the present inventors explored the use of coagulants to reduce the deposition of coatings. It has been found that among various coagulants, A1 is the most important substance, and I: adding the A1 compound to the conventional electrodeposition coating composition, the time gate (10) is instantaneously hydrolyzed (four) into a hydroxide, and the hydroxide is time-dependent. ^ After the condensation, the effect of being a coagulant is lost. <Due to the fact that the documents 1 to 9 are preferably containing a cation as a metal catalyst, the reason for the above is presumably, in fact, in the electrodeposition paint composition, the hydrazine is instantaneously hydrolyzed to form a hydroxide. Although it has not been empirically studied in the examples, it can be considered that although the hydroxide is maintained as a catalyst, the effect of the smear polymerization agent cannot be expected. (Means for Solving the Problem) = Here, the inventors of the present invention deliberately evaluated the A1 ion relative to the electrodeposition coating composition, and lowered the pH near the neutral state to a range in which A1 can continue to be ion-dissociated. As a result of the uniformity of the ore-covering ability, it was found that although the pH of the composition was lowered, an extremely good plating thickening ability was obtained. Further, the inventors of the present invention have found that the effect of the A1 ion is effective for a nonionic resin emulsion which cannot be electrochemically analyzed, and the same can be carried out by cathodic electrolysis in the same manner as in 321814 7 201038689. Thus, the present invention has been completed. That is, the present invention is the following (1) and (2). (1) An electrodeposition paint composition characterized by containing a nonionic and/or cationic aqueous resin and an aluminum (A1) ion of 20 to 500 ppm, and when the A1 ion concentration is set to A [ppm] The pH satisfies the following formula: 3. 5SpH$-Log((Axl. 93χ1(Γ15)1/3). (2) An electrodeposition coating method 'characterized by applying the aforementioned composition to the metal material The electrodeposition coating composition of the present invention contains a non-ionic and/or cationic water-based resin. Here, the non-ionic and cationic water-based resin is not limited. Whatever the matrix resin is used, it does not impair the effect of the present month, but it is preferably an epoxy, a urethane, or an acrylic acid. Here, a feature of the present invention, It is based on a new mechanism of action (although the ion is agglomerated with a hydroxide colloid due to an increase in pH, but the mechanism of action of the surrounding resin at this time), it is possible to use a non-ion that cannot be electrically analyzed in the past. Resin. So, because it can also The non-ionic resin is used to broaden the selectivity, and various properties that have not been conventionally possessed can be imparted to the film. Further, even when a cationic resin is used, the resin itself is removed in addition to the PH#. In addition to the known mechanism of action for dispersing ampoules, it can be electroanalyzed according to the above-mentioned Lexin action mechanism at a lower PJJ than before. The concentration of the resin emulsion is also not specified. When the total weight of the electrodeposition coating composition is based on, it is preferably 5 to 30% by weight, more preferably 321814 8 201038689, preferably 7 to 25% by weight, most preferably 10 to 20% by weight. When the resin content is too low, The amount of film deposition is insufficient, and when the content is too high, the economic surface is unfavorable. Regarding the nonionic resin emulsion, a method of introducing an ethylene oxide-like nonionic functional group to the matrix resin, that is, self-emulsification, may be employed. The method and the method of emulsifying using a nonionic surfactant, that is, one or two methods of the forced emulsification method. For the cationic resin emulsion, an amine-like cation can be used. The method of introducing a functional group into a matrix resin, that is, a self-emulsification method, and a method of emulsification using a cationic surfactant, that is, one or two methods of forced emulsification, is also introduced. After the cationic functional group, a nonionic surfactant can also be used as the emulsification aid. Further, when the molecular weight of the self-emulsified emulsion is small, the emulsion is non-particulate, and becomes a water-soluble resin, but even water-soluble The water-based resin of the present invention is a general term for forming a water-dispersed emulsion and a water-soluble resin. ❹ In addition, the water-based resin can be optionally blended with a blocked polyisocyanate. The electrodeposition coating composition of the present invention preferably contains A1 ions in an amount of 20 to 500 pm. More preferably 50 to 400 ppm, most preferably 100 to 300 ppm. When the temperature is lower than the lower limit, the coating film of the A1 ion is insufficient to be lifted. When it is higher than the upper limit, the electrical conductivity of the composition is excessive, and the plating uniformity is lowered. The concentration of A1 ions in the composition can be solid-liquid separated by an ultracentrifuge and analyzed by high-frequency inductively coupled plasma luminescence spectroscopy (ICP: 9 321814 201038689)
Inductively Co叩led Plasma)或原子吸收光譜分析（AA: Atomic Absorption)將液相進行定量。 本發明之電沈積組成物的液體媒體，較佳為水性溶 劑，尤佳為水。當液體媒體為水時，亦可含有水以外的水 系溶劑（例如水溶性的醇類）作為液體媒體。 本發明之電沈積塗料組成物的pH，當將A1離子濃度 設為A [ ppm ]時，較佳係滿足下列計算式。 3. 5^pH^-Log((Axl. 93x10 15)1/3) 更佳為滿足下列式。 3. 6^pH^-Log((Axl. 93xl0'15)1/3) 最佳為滿足下列式。 3. 7SpHS-Log((Axl. 93χ1(Γ15)1/3) 當pH低於下限時，析出效率降低而使鍍覆均厚能力降 低。當pH高於上限時，A1離子會發生水解，因而較不佳。 -Log((Axl.93xlO—15)1/3)之項，係從氫氧化 A1 之 25°C 的溶度積：1. 92x10_32中所求取。亦即，當成為此pH以上 時，A1離子沈殿析出成為氫氧化物，而不再為離子。在此， 25°C為組成物之保存時及使用時的典型溫度。 本發明之A1離子的作用效果如下所述。亦即可推測 為，離子狀的A1，由於進行陰極電解使金屬表面的pH上 升而成為細微的氫氧化物膠體，當此氫氧化物膠體在pH為 9的前後完全失去f電荷而急遽地開始凝聚時，亦牵連周 圍的樹脂乳化液而析出。 藉由陰極電解從A1離子至氫氧化物膠體的電荷消失 10 321814 201038689 為止之一連串的反應，必須在瞬間完成。若先成為氫氧化 物時，會隨著時間經過開始凝聚，在ρίί為9的前後凝聚能 力極端衰退。因此，本發明之A1成分，在組成物中必須一 直是離子。 ' 此外’ A1離子可藉由特定的螯合劑進行安定化，但進 行安定化者，亦會卩且礙因pH上升所造成之氫氧化物的生 成，因而較不佳。—般調配於電沈積塗料組成物之乙酸、 甲酸、胺磺酸、乳酸等之有機酸中，並不具有將A1離子進 '行安定化之程度的螯合能力。 AI離子可使用a 1化合物來添加。a 1化合物並無特別 限定’能夠以硝酸鹽、硫酸鹽之無機酸鹽或是乳酸鹽、乙 酸鹽之有機酸鹽的形式來添加。 用以參考’第1圖係顯示A1離子濃度及pH的適當範 圍。 使用本發明之電沈積塗料組成物將塗膜形成於金屬材 ◎料表面之方法，較佳為陰極電解法。以無電解或陽極電解 所進行之塗膜析出較不佳。 陰極電解條件並無特別規定，較佳為施加50至400V 的電壓。更佳為1〇〇至3〇〇v，最佳為15〇至25〇p並不一 疋而為疋電壓，亦可運用逐漸增加電壓之方法或是2段通 電之方法。 本發明之組成物中，更可因應必要來運用顏料、觸媒、 有機溶劑、顏料分散劑、界面活性劑等之塗料領域中一般 所用之添加劑。顏料例如有鈦白、碳黑等之著色顏料；黏 321814 11 201038689 土、滑石、鋇氧等之體質顏料；三聚磷酸鋁、磷酸鋅等之 防鏽顏料；二丁基氧化錫、二辛基氧化錫等之有機錫化合 物；月桂酸二丁基錫、二苯曱酸二丁基錫等之二烷基錫的 脂肪酸或芳香族羧酸鹽等之錫化物等。 本發明之電沈積塗料組成物，可運用在各種金屬材 料。金屬材料並無特別限定，例如有冷壓延鋼板、熱壓延 鋼板、鑄製材、鋼管等之鋼鐵材料，以及在此等鋼鐵材料 上施以鋅系鍍覆處理及/或鋁系鍍覆之材料、鋁合金板、鋁 系鑄製材、鎂合金板、鎂系鑄製材等。此外，即使預先施 以磷酸鋅系化成處理或锆系化成處理，亦不會損及本發明 之效果。尤其適合運用在形狀複雜之金屬構成體，例如以 鐵系材料為主之金屬構成體的汽車車體、汽車零件、家電 製品、建築材料等。 (實施例） 以下舉出實施例及比較例，來更具體地說明本發明之 内容。 實施例中，只要無特別說明，「份」及「％」即為重量 基準。 (陽離子性環氧樹脂的合成） 將2, 4-/2, 6-甲苯二異氰酸酯（重量比=8/2)92份、甲 基異丁酮（以下略稱為MIBK)95份及二月桂酸二丁基錫0. 5 份，饋入至安裝有攪拌機、冷卻管、氮氣導入管、溫度計 及滴液漏斗之燒瓶中。於攪拌下將曱醇21份滴入至反應混 合物。反應係從室溫開始進行，並藉由發熱而升溫至60°C。 12 321814 201038689 接著持續進行30分鐘的反應後，從滴液漏斗將乙二醇 單-2-乙基己醚5了份滴入。然後將雙驗A-環氧丙燒5莫耳 加成物42份添加於反應混合物。反應主要在6〇至65°c的 範圍内進行’並且持續進行反應直到IR光譜測定中依據異 氰酸基的吸收消失為止。 接著將藉由已知的方法從雙酚A與表氯醇所合成之環 氧當量188的環氧樹脂365份加入至反應混合物，並升溫 至125°C。然後添加苯曱基二甲基胺1. 0份，在i3(rc下進 ^ 行反應直到環氧當量成為410為止。 接著加入雙紛A87份並在12(TC下進行反應後，環氧 當量成為1190。然後使反應混合物冷卻，並加入二乙醇胺 11份、N-乙基乙醇胺24份及胺乙基乙醇胺之_亞胺化物 的79重量％MIBK溶液25份，在not：下反應2小時。然後 以MIBK稀釋至非揮發份成為8〇%為止，製得玻璃轉移溫度 為22 C之經胺改質的環氧樹脂（樹脂固形份8〇%)。此製造 〇方法係依據專利文獻1(：日本特開2〇〇2_294143號公報）之 實施例的製造例1。 (封閉型異家i酸目旨硬化劑的製造） 將二苯基甲燒二異氰酸酯1250份及MIBK266. 4份饋入 至反應容器’將此加熱至80t後，加入二月桂酸二丁基錫 2. 5份。然後在8(TC下，於2小時之間，將在丁基溶纖劑 944知中洛解有ε ~己内醯胺226份者滴入於此。在l〇0°c 下加熱4小時後，確認出在IR光譜測定中依據異氰酸基的 吸收已>肖失’放置冷卻後，加入mIBK336.丨份而製得封閉 13 321814 201038689 型異氰酸酯硬化劑。此製造方法係依據專利文獻1(日本特 開2002-294143號公報）之實施例的製造例2。 (顏料分散樹脂的製造） 首先’將異佛爾酮二異氰酸酯（以下略稱為IpDI)222. 〇 伤加入於女裝有授拌裝置、冷卻管、氮氣導入管及溫度計 之反應容器内，以MIBK39. 1份進行稀釋後，加入二月桂酸 二丁基錫0.2份。將此升溫至別它後，在攪拌下，於乾燥 氮氣環境中，於2小時之間滴入2-乙基己醇131.5份。藉 由適當的冷卻將反應溫度維持在5(rc。結果可製得經2— 乙基己醇半封閉化的IPDI(樹脂固形份9〇.⑽）。 接著依序將二甲基乙醇胺87· 2份、75%的乳酸水溶液 1Π. 6份及乙二醇單丁醚39. 2份，加入於適當的反應容器 内’在65°C下攪拌約半小時，調製出四級化劑。 然後將 EPON 829(She 11 Chemical Company 製的雙紛 A型環氧樹脂、環氧當量193至203)710.0份與雙酚A 289.6份饋入至適當的反應容器内，在氮氣環境中加熱至 150至16〇°C ’產生初期發熱反應。將反應混合物在150至 160 C下進行約1小時的反應，接著冷卻至120°C後’加入 先前調製之經2-乙基己醇半封閉化的IPDKMIBK溶液） 498. 8 份。 將反應混合物保持在110至12〇。〇約1小時，接著加 入乙二醇單丁醚1390. 2份，將混合物冷卻至85至95〇C， 經均勻化後添加先前調製之四級化劑丨96. 7份。將反應混 合物保持在85至95。(：至酸價成為1為止後，加入去離子 14 321814 201038689 水37. 0 f刀在5衣氧_雙驗A樹脂中結束四級化，而製得具 有四級敍鹽部分之顏料分散用樹脂（樹脂固形份5〇%)。此 衣&方法係依據專利文獻i(日本特開刪MM⑷號公報） 之實施例的製造例3。 (顏料分散膏的製造） 、將，料分散用樹脂12〇份、碳黑2 〇份、高嶺土 1〇〇 〇 伤一氧化鈦80. 〇份、磷酸辞四水合物18. 〇份及離子交 〇換水221. 7份加入於砂磨機，使分散至粒度成為1〇_以 下為止，而製得顏料分散膏（固形份48%)。此製造方法除 了使用麟酸鋅四水合物來取代磷㈣銘之外，其他係依據 專利文獻1(日本特開2002—294143號公報）之實施例的製 造例4。 (陽離子性環氧電沈積塗料紐成物的製造） 以固形份比為70/30均勻地混合陽離子性環氧樹脂與 封閉型異氰酸酯硬化劑。然後以相對於固形份為2重量％ Ο之方式添加乙二醇-2-乙基己醚，以使樹脂固形份每1〇〇g 之S欠的笔克當量（MEQ(A))成為24之方式添加冰醉酸，然後 緩慢地加入離子交換水進行稀釋。於減壓下去除MIBK，藉 此製得固形份為36%之乳化液。 將此乳化液1960份及顏料分散膏197份與二丁基氧化 錫14. 5份與離子交換水1843份混合，而製得固形份為20 重量％之電沈積塗料組成物（以下略稱「R1」）。此製造方法 除了未混合10%乙酸鈽水溶液之外，其他係依據專利文獻1 (曰本特開2002-294143號公報）之實施例的實施例1。 15 321814 201038689 (陽離子性丙烯酸電沈積塗料組成物的製造） 以去離子水來稀釋神東塗料公司製的陽離子性丙烯酸 樹脂「SACSAD# 1000」（固形份：65%)，將固形份調整至18%(以 下略稱「R2」）。 (非離子性胺基甲酸酯電沈積塗料組成物的製造） 以去離子水來稀釋DIC公司製的非離子性胺基甲酸酯 樹脂「V0NDIC 2220」（固形份：40%)，將固形份調整至18%(以 下略稱「R3」）。 關於在實施例及比較例中添加A1離子之水準，A1離 子係使用确酸铭九水合物、硫酸銘十四至十八水合物或乳 酸鋁來添加。此外，可因應必要，使用硝酸或氨水來調整 組成物的pH。組成物的組成如第1表所示。 (試驗板的製作） 試驗板係使用冷壓延鋼板：SPCC(JIS3141)70xl50x 0. 8_，並使用日本帕卡瀨精公司製的強鹼脫脂劑 「FC-E2001」，預先將該表面進行120秒的喷霧處理以進行 脫脂處理。脫脂處理後，進行30秒的喷霧水洗，然後浸潰 於實施例及比較例所示之組成物，實施陰極電解處理。電 解結束後的試驗板，立即以去離子水進行30秒的喷霧水 洗，於電爐中，在170°C下進行20分鐘的燒結。 (鍍覆均厚能力評估） 以「4片盒法」來評估鍍覆均厚能力。將在試驗板上 鑽開直徑8匪的孔，並以2cm的間隔來設置4片鋼板之「附 4片盒法之鍍覆均厚能力試驗用工模（Jig)」（參照第2 16 321814 201038689 圖），以第3圖所示之方式進行配線。第3圖的4片鋼板中， 以面向最左側的鋼板之左側的面為「A面」，以右側的面為 「B面」。同樣的以從左方鼻來弟2片鋼板的左右面分別 為「C面」及「D面」，以從左方算來第3片鋼板的左右面 分別為「E面」及「F面」，以最右側鋼板的左右面分別為 「G面」及「H面」。第2圖的裝置中，係在塗裝浴溫30°C、 A面與電極之極間距離10cm、通電時間3分鐘下.，以使A 面膜厚成為20/zm之方式，藉由電壓進行電沈積塗裝。 Θ 鍍覆均厚能力，係以G面的膜厚來進行評估。以G面 膜厚：未滿5/zm者為X，5/zm以上且未達10/ζιη者為〇， ΙΟ/zm以上者為(§)。 惟關於R3並非使用4片盒法，而是在200V下將1片 試驗板進行3分鐘的陰極電解處理，並評估燒結後的塗膜 厚度，評估結果係一同顯示在第1表中。 從第1表的實施例1至6中可得知，藉由使用本發明 ◎之電沈積塗料組成物，能夠獲得對金屬材料而言為良好的 鍍覆均厚能力。 相對於此，未調配本發明的最大特徵之A1'離子之比較 例1至3，不僅該鍍覆均厚能力不足，且關於非離子性樹 脂乳化液，並無任何析出。 此外，比較例4為A1離子濃度的下限以下者，比較例 5為A1離子濃度過剩且pH的下限以下者，該鍍覆均厚能 力均不足。 再者，比較例6為提高實施例4的pH之組成物，該鍍 17 321814 201038689 覆均厚能力仍不;I’此可考量為在提高邱之中和工 子的絕大部分㈣析出成為氫氧化物，因而無法於揮 離子料果者。貫際上，藉由離⑽職㈣ 確認出A1離子濃度為〇ppm。 1 如此，使用本發明之組成物之金屬材料的陰極電極 理’可獲得峰陽離子電沈餘裝巾所紐獲得之優異^ 鑛覆均厚能力，並且亦可進行峰所無法進行電解析出之 非離子性樹脂乳化液的電解析出，而成為—種_ 術。 (第1表）The liquid phase is quantified by Inductively Co叩led Plasma or Atomic Absorption. The liquid medium of the electrodeposition composition of the present invention is preferably an aqueous solvent, and particularly preferably water. When the liquid medium is water, an aqueous solvent other than water (e.g., a water-soluble alcohol) may be contained as a liquid medium. The pH of the electrodeposition coating composition of the present invention preferably satisfies the following calculation formula when the A1 ion concentration is set to A [ppm]. 3. 5^pH^-Log((Axl. 93x10 15)1/3) It is better to satisfy the following formula. 3. 6^pH^-Log((Axl. 93xl0'15)1/3) The best is to satisfy the following formula. 3. 7SpHS-Log((Axl. 93χ1(Γ15)1/3) When the pH is lower than the lower limit, the precipitation efficiency is lowered and the plating thickness is reduced. When the pH is higher than the upper limit, the A1 ion is hydrolyzed. It is less preferred. -Log((Axl.93xlO-15) 1/3) is obtained from the solubility product of 25 ° C of hydroxide A1: 1. 92x10_32. That is, when it becomes this pH In the above case, the A1 ion sink precipitates as a hydroxide and is no longer an ion. Here, 25 ° C is a typical temperature at the time of storage and use of the composition. The effect of the A1 ion of the present invention is as follows. It is presumed that the ionic A1 is a fine hydroxide colloid due to the cathode electrolysis to raise the pH of the metal surface. When the hydroxide colloid completely loses the f charge before and after the pH 9, it starts to condense eagerly. At the same time, it is also implicated in the surrounding resin emulsion to precipitate. The charge from the A1 ion to the hydroxide colloid disappears by cathodic electrolysis. 10 321814 201038689 A series of reactions must be completed in an instant. If it becomes a hydroxide first, it will Condensed as time passed, condensed before and after ρίί The polycapacity is extremely degraded. Therefore, the component A1 of the present invention must always be an ion in the composition. 'In addition, the A1 ion can be stabilized by a specific chelating agent, but the stability is also caused by the stability. The formation of hydroxide caused by the increase in pH is relatively poor. Generally, it is formulated in the organic acid of acetic acid, formic acid, amine sulfonic acid, lactic acid, etc. of the electrodeposition coating composition, and does not have the A1 ion into the line. The degree of chelating ability of the stability. The AI ion can be added using the a 1 compound. The a 1 compound is not particularly limited to be a mineral acid salt of a nitrate or a sulfate or an organic acid salt of a lactate or an acetate. The form is added. For reference to 'the first figure shows the appropriate range of A1 ion concentration and pH. The method of forming the coating film on the surface of the metal material using the electrodeposition coating composition of the present invention, preferably cathodic electrolysis The deposition of the coating film by electroless or anodic electrolysis is less preferred. The cathode electrolysis conditions are not particularly specified, and it is preferred to apply a voltage of 50 to 400 V, more preferably 1 to 3 Torr, and most preferably 15〇 25〇p is not a 疋 voltage, and it is also possible to use a method of gradually increasing the voltage or a method of energizing two stages. In the composition of the present invention, pigments, catalysts, organic solvents, pigment dispersions may be used as necessary. Additives generally used in the field of coatings such as agents, surfactants, etc. Pigments such as titanium white, carbon black, etc.; pigments 321814 11 201038689 body pigments of talc, talc, etc.; aluminum tripolyphosphate, zinc phosphate Or antirust pigment; an organic tin compound such as dibutyltin oxide or dioctyltin oxide; a fatty acid or an aromatic carboxylate such as dibutyltin laurate or dibutyltin dibenzoate; Tin compounds, etc. The electrodeposition coating composition of the present invention can be applied to various metal materials. The metal material is not particularly limited, and examples thereof include a steel material such as a cold rolled steel sheet, a hot rolled steel sheet, a cast material, a steel pipe, and the like, and a zinc-based plating treatment and/or an aluminum-based plating material on the steel material. , aluminum alloy plate, aluminum-based cast material, magnesium alloy plate, magnesium-based cast material, and the like. Further, even if a zinc phosphate-based chemical conversion treatment or a zirconium-based chemical conversion treatment is applied in advance, the effects of the present invention are not impaired. It is particularly suitable for use in a metal body having a complicated shape, for example, an automobile body, an automobile part, a home appliance product, a building material, and the like which are mainly composed of a metal material of an iron-based material. (Embodiment) Hereinafter, the contents of the present invention will be more specifically described by way of examples and comparative examples. In the examples, "parts" and "%" are the weight basis unless otherwise specified. (Synthesis of cationic epoxy resin) 92 parts of 2,4-/2,6-toluene diisocyanate (weight ratio = 8/2), 95 parts of methyl isobutyl ketone (hereinafter abbreviated as MIBK), and two laurel 0.5 parts of dibutyltin acid was fed into a flask equipped with a stirrer, a cooling tube, a nitrogen introduction tube, a thermometer, and a dropping funnel. 21 parts of sterol was added dropwise to the reaction mixture with stirring. The reaction was started from room temperature and heated to 60 ° C by heating. 12 321814 201038689 Then, after continuing the reaction for 30 minutes, 5 parts of ethylene glycol mono-2-ethylhexyl ether was dropped from the dropping funnel. Then, a double A-glycidazole 5 molar addition product of 42 parts was added to the reaction mixture. The reaction was carried out mainly in the range of 6 Torr to 65 ° C and the reaction was continued until the absorption of the isocyanate group disappeared in the IR spectrum measurement. Next, 365 parts of an epoxy equivalent 188 epoxy resin synthesized from bisphenol A and epichlorohydrin was added to the reaction mixture by a known method, and the temperature was raised to 125 °C. Then, 1.0 part of phenylmercaptodimethylamine was added, and the reaction was carried out under i3 (rc until the epoxy equivalent became 410. Then, A87 was added and the reaction was carried out at 12 (TC), epoxy equivalent. It was made into 1190. Then, the reaction mixture was cooled, and 25 parts of a 79 wt% MIBK solution of 11 parts of diethanolamine, 24 parts of N-ethylethanolamine, and an amine ethylethanolamine-imide was added, and the reaction was carried out for 2 hours under not:. Then, it was diluted with MIBK until the nonvolatile content became 8%, and an amine-modified epoxy resin having a glass transition temperature of 22 C (resin solid content of 8% by weight) was obtained. This method of manufacturing was based on Patent Document 1 ( (Production Example 1 of the Example of JP-A No. 2-294143). (Production of a blocked type of iso-acid-based hardening agent) 1250 parts of diphenylmethane diisocyanate and MIBK266. 4 parts were fed. To the reaction vessel, after heating to 80t, add 2.5 parts of dibutyltin dilaurate. Then, at 8 (TC), within 2 hours, it will be dissolved in butyl cellosolve 944. 226 parts of guanamine were added here. After heating at l〇0 °c for 4 hours, it was confirmed by IR spectroscopy. According to the absorption of the isocyanate group, the mixture is cooled, and then mIBK336 is added to obtain a blocked isocyanate hardener. The manufacturing method is based on Patent Document 1 (Japanese Patent Laid-Open No. 2002-294143) Production Example 2 of the Example of the Invention (Production of Pigment Dispersion Resin) First, 'isophorone diisocyanate (hereinafter abbreviated as IpDI) 222. 〇 加入 加入 加入 女装 女装 女装 加入 加入 加入 加入 加入 加入 加入 加入 加入In a reaction vessel of a nitrogen gas introduction tube and a thermometer, diluted with MIBK 39.1 parts, and then added 0.2 parts of dibutyltin dilaurate. The temperature was raised to another temperature, and the mixture was stirred under a dry nitrogen atmosphere for 2 hours. 131.5 parts of 2-ethylhexanol were added dropwise. The reaction temperature was maintained at 5 (rc) by appropriate cooling. As a result, IPDI semi-blocked with 2-ethylhexanol was obtained (resin solid fraction 9 〇. (10) Then, 87 parts of dimethylethanolamine, 75% of a 75% aqueous solution of lactic acid, and 39.2 parts of ethylene glycol monobutyl ether were added to a suitable reaction vessel to stir at 65 ° C. About half an hour, the quaternization agent is prepared. Then EPON 829 710.0 parts of double-type A epoxy resin (epoxy equivalent of 193 to 203) prepared by She 11 Chemical Company and 289.6 parts of bisphenol A were fed into a suitable reaction vessel and heated to 150 to 16 〇 in a nitrogen atmosphere. C 'generates an initial exothermic reaction. The reaction mixture is subjected to a reaction at 150 to 160 C for about 1 hour, followed by cooling to 120 ° C and then 'addition of the previously prepared 2-ethylhexanol semi-blocked IPDKMIBK solution) 498 8. 8 servings. The reaction mixture was maintained at 110 to 12 Torr. 5份。 After aging, the mixture was cooled to 85 to 95 ° C, after homogenization, the previously prepared quaternizing agent 丨 96. 7 parts. The reaction mixture was maintained at 85 to 95. (: After the acid value becomes 1, add deionized 14 321814 201038689 water 37. 0 f knife ends the quaternization in 5 coat oxygen_double test A resin, and obtains pigment dispersion with four-stage salt fraction Resin (resin solid content: 5% by weight). This coating & method is based on the production example 3 of the example of the patent document i (Japanese Patent Laid-Open Publication No. MM(4)). (Production of Pigment Dispersion Paste) 12 parts of resin, 2 parts of carbon black, 1 part of kaolin and 1 part of titanium oxide 80. 〇, phosphoric acid tetrahydrate 18. 〇 and ion exchange water exchange 221. 7 parts added to the sand mill, so that Disperse to a particle size of 1 〇 Å or less, and obtain a pigment dispersion paste (solid content 48%). This manufacturing method is based on the use of zinc linoleate tetrahydrate instead of phosphorus (four), other based on Patent Document 1 (Japan) Production Example 4 of the Example of JP-A-2002-294143. (Production of Cationic Epoxy Electrodeposition Coating New Material) The cationic epoxy resin and the blocked isocyanate were uniformly mixed at a solid ratio of 70/30. a hardener. Then it is 2% by weight relative to the solid content. Add ethylene glycol-2-ethylhexyl ether, add the ice-toxic acid in such a manner that the solid content of the resin per gram of S ticks (MEQ (A)) becomes 24, and then slowly add ion exchange 5份与离子交换水。 I. The mixture was diluted with water to remove the MIBK, to obtain a solid content of 36% of the emulsion. 1960 parts of the emulsion and pigment dispersion 197 parts and dibutyl tin oxide 14. 5 parts with ion exchange water 1843 parts were mixed to obtain an electrodeposition coating composition (hereinafter abbreviated as "R1") having a solid content of 20% by weight. This production method is based on Patent Document 1 except that 10% aqueous solution of cerium acetate is not mixed. Example 1 of the embodiment of JP-A-2002-294143. 15 321814 201038689 (Manufacture of cationic acrylic electrodeposition coating composition) Diluted cationic acrylic resin "SACSAD" manufactured by Shendong Coating Co., Ltd. with deionized water #1000" (solid content: 65%), the solid content is adjusted to 18% (hereinafter abbreviated as "R2"). (Manufacture of nonionic urethane electrodeposition coating composition) Dilute with deionized water DIC company's non-ionic urethane resin "V0ND IC 2220" (solid content: 40%), the solid content was adjusted to 18% (hereinafter abbreviated as "R3"). For the addition of the A1 ion level in the examples and comparative examples, the A1 ion system was made using the acid IX hydrate. Add the substance, sulphate tetradecyl octahydrate or aluminum lactate. In addition, nitric acid or ammonia water may be used to adjust the pH of the composition as necessary. The composition of the composition is shown in Table 1. (Production of test plate The test plate was cold-rolled steel plate: SPCC (JIS3141) 70xl50x 0. 8_, and the surface was subjected to a spray treatment for 120 seconds using a strong alkali degreasing agent "FC-E2001" manufactured by Paccarat Co., Ltd., Japan. Degreasing treatment. After the degreasing treatment, spray washing was carried out for 30 seconds, and then the compositions shown in the examples and the comparative examples were impregnated, and cathodic electrolysis treatment was carried out. The test plate after completion of the electrolysis was immediately spray-washed with deionized water for 30 seconds, and sintered in an electric furnace at 170 ° C for 20 minutes. (Evaluation of plating blanketing ability) The "4 piece box method" was used to evaluate the plating thickness uniformity. A hole having a diameter of 8 inches was drilled on the test plate, and the "plate for the thickness of the plating method of the four-piece box method (Jig) was attached to the four sheets at intervals of 2 cm" (refer to 2160 321814 201038689). Fig.), wiring is performed as shown in Fig. 3. In the four steel sheets in Fig. 3, the surface on the left side facing the leftmost steel sheet is "A surface", and the surface on the right side is "B surface". Similarly, the left and right sides of the two steel sheets from the left side are "C side" and "D side", and the left and right sides of the third steel sheet are "E side" and "F side", respectively. The left and right sides of the rightmost steel plate are "G surface" and "H surface". In the apparatus of Fig. 2, the coating bath temperature is 30 ° C, the distance between the A surface and the electrode is 10 cm, and the energization time is 3 minutes. The thickness of the A mask is 20 / zm, and the voltage is made by voltage. Electrodeposition coating.镀 The plating thickness is evaluated by the film thickness of the G surface. G-film thickness: X, 5/zm or less and less than 10/ζιη are 〇, and ΙΟ/zm or more is (§). However, R3 was not subjected to a cathodic electrolysis treatment at 200 V for 3 minutes, and the thickness of the coating film after sintering was evaluated. The evaluation results are shown together in Table 1. As is apparent from Examples 1 to 6 of the first table, by using the electrodeposition paint composition of the present invention, it is possible to obtain a plating thickening ability which is good for a metal material. On the other hand, in Comparative Examples 1 to 3 in which the A1' ions of the greatest feature of the present invention were not formulated, not only the plating thickening ability was insufficient, but also no precipitation was observed with respect to the nonionic resin emulsion. Further, Comparative Example 4 is equal to or lower than the lower limit of the A1 ion concentration, and Comparative Example 5 is that the A1 ion concentration is excessive and the lower limit of the pH or lower, and the plating uniformity is insufficient. In addition, Comparative Example 6 is a composition for improving the pH of Example 4, and the plating thickness of the coating of 321814814 201038689 is still not; I's considered to be the most (4) precipitation in the improvement of Qiuzhong and the workman. Hydroxide, and therefore can not be used for the ion. In a continuous manner, the A1 ion concentration was confirmed to be 〇ppm by the (10) position (4). 1 Thus, the cathode electrode of the metal material of the composition of the present invention can obtain the excellent uniformity of the mineralization obtained by the peak cation ion sink, and the peak can not be electrically analyzed. The nonionic resin emulsion is electrolyzed and becomes a kind of technique. (Table 1)
【圖式簡單說明】 第1圖係顯示A1離子濃度及pH的適當範圍之圖。 321814 18 201038689 m 第2圖係鍍覆均厚能力試驗中所用之「附4片盒之鑛 覆均厚能力試驗用工模」的模型圖。 第3圖係顯示鍍覆均厚能力試驗之電沈積塗裝狀態。 【主要元件符號說明】 1 直徑8mm的孔 2 4片盒法之鍍覆均厚能力試驗用工模的外板（A面） 3 4片盒法之鍍覆均厚能力試驗用工模的内板（G面） 4 電沈積塗料浴 ❹ 〇 19 321814BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a view showing an appropriate range of A1 ion concentration and pH. 321814 18 201038689 m Fig. 2 is a model diagram of the "model for the uniform thickness test of the four-piece box" used in the plating uniformity test. Figure 3 shows the electrodeposition coating state of the plating blanketing ability test. [Explanation of main component symbols] 1 Hole of 8 mm diameter 2 Plated method of coating thickness of the test piece of the outer plate (A side) of the test piece 3 4 piece of box method G face) 4 Electrodeposition paint bath 〇19 321814