TWI224615B - Coating composition for forming titanium oxide film, method of forming titanium oxide film and metal, substrate coated with titanium oxide film - Google Patents
Coating composition for forming titanium oxide film, method of forming titanium oxide film and metal, substrate coated with titanium oxide film Download PDFInfo
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- TWI224615B TWI224615B TW91101041A TW91101041A TWI224615B TW I224615 B TWI224615 B TW I224615B TW 91101041 A TW91101041 A TW 91101041A TW 91101041 A TW91101041 A TW 91101041A TW I224615 B TWI224615 B TW I224615B
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- C09D185/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon; Coating compositions based on derivatives of such polymers
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1224615 A7 ---------B7 _ 五、發明説明(1 ) 本發明係有關於一種新研發之用以形成氧化鈦膜之塗 佈劑、氧化鈦膜形成方法及被覆有氧化鈦膜之金屬基材。 鋼板、铭、鋁合金等金屬基材為使耐蝕性、加工性等 提高,通常進行各種表面處理以作為基底處理。 近年’由於表面處理鋼板需要更優異之耐蝕性,在基 材上之使用,冷軋鋼板已由鉛系鍍敷鋼板取而代之,且正 逐漸增加中。 以往’錯系鍍敷鋼板之表面處理一般係進行鉻酸鹽處 理及磷酸鹽處理。 鉻酸鹽處理中具有鉻化合物之毒性之問題。特別是,6 "ί貝鉻化口物係經以 IARC(International Agency for Research Review) 為首之多數公家機關指定為使人體致癌之物質,乃一種極 為有害之物質。具體言之,鉻酸鹽處理具有如處理程序中 鉻酸鹽煙霧揮發、廢水處理設備需龐大費用、鉻酸將由處 理塗膜溶解析出等問題。 另,磷酸鋅、磷酸鐵等磷酸鹽處理中,經磷酸鹽處理 後,通常因進行鉻酸鹽之後處理,而仍有鉻化合物之毒性 問題,並有磷酸鹽處理劑中之反應加速劑、金屬離子等廢 水處理、由被處理金屬溶解析出金屬離子之污泥處理之問 題。 又,曰本特許公開公報特開昭58—224174號、特開昭 6〇-5(H79號、特開昭60—5咖號等中記載有一種被覆鋼 板,係以辞系鍍敷鋼板作為基材,並使其形成路酸鹽塗膜, 進而於其上形成有機石夕酸鹽塗膜者。該被覆鋼板具有耐姓 本紙張尺度適用中國國家標準(CNS) A4規格(210X297公釐) (請先閲讀背面之注意事項再填寫本頁)1224615 A7 --------- B7 _ V. Description of the invention (1) The present invention relates to a newly developed coating agent for forming a titanium oxide film, a method for forming a titanium oxide film, and coating titanium oxide. Metal substrate of the film. In order to improve the corrosion resistance, workability, and the like of metal substrates such as steel plates, aluminum alloys, and aluminum alloys, various surface treatments are usually performed as a base treatment. In recent years, because surface-treated steel sheets require more excellent corrosion resistance, the use of cold-rolled steel sheets on substrates has been replaced by lead-based plated steel sheets, and is gradually increasing. In the past, the surface treatment of a 'wrapped plated steel sheet was generally performed with chromate treatment and phosphate treatment. Chromate treatment has the problem of toxicity of chromium compounds. In particular, 6 " chrome chromate is an extremely harmful substance that has been designated by most public agencies, including IARC (International Agency for Research Review), as a substance that causes human carcinogenesis. Specifically, the chromate treatment has problems such as the volatilization of chromate fumes in the processing procedure, the large cost of wastewater treatment equipment, and the dissolution of chromic acid from the treatment coating film. In addition, in phosphate treatments such as zinc phosphate and iron phosphate, after the phosphate treatment, the chromate post-treatment usually causes the toxicity of chromium compounds, and there are reaction accelerators and metals in phosphate treatment agents. Wastewater treatment such as ions, sludge treatment in which metal ions are eluted from the treated metal. Also, Japanese Patent Laid-Open Publication No. 58-224174, JP-A 6-0-5 (H79, JP-A 60-5, etc.) describe a coated steel sheet, which is referred to as a coated steel sheet. The base material, and it is formed into a silicate coating film, and then an organic oxalate coating film is formed thereon. The coated steel sheet has a paper size that is resistant to Chinese paper and is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) (Please read the notes on the back before filling this page)
J 、τ .¾. -4- 1224615 A7 B7 五、發明説明(2 性及加工性佳之㈣卜但’由於該被覆鋼板具有鉻酸鹽塗 膜,故仍有鉻化合物之毒性問題。而,自該被覆鋼板去除 鉻酸鹽塗膜後之鋼板,其耐蝕性不足。 此外,鋁或鋁合金基材為使耐蝕性、親水性等提升, 亦大多施有各種表面處理以作為基底處理。 舉例言之,空調機之熱交換器用之葉片,一般係使用 輕量性、加工性、導熱性佳之鋁或鋁合金基材。該空調機 之熱交換器中,由於冷房時產生之凝結水變成水滴而於葉 片間形成水之聯結,並縮小空氣之通風路徑,使通風阻力 變大,而有電力損失、噪音產生、水滴飛散等問題。 為解決此一問題,乃於鋁或鋁合金基材之葉片表面進 行水鋁土處理、水玻璃塗布、水性聚合物塗布等親水化處 理,以防止前述聯結之情形。但,業經親水化處理之鋁或 其合金製之葉片之處理塗膜亦具有親水性,若置於強烈腐 蝕環境下,約數個月左右即受到腐蝕。 防止此般葉片腐敍之方法,以往基於耐餘性、成本等 觀點’大多於鋁或鋁合金基材表面施以鉻酸鹽處理以作為 基底處理。但,鉻酸鹽處理則如前述般具有鉻化合物毒性 之問題。 又,不使用鉻酸鹽之表面處理劑或表面處理方法,舉 例言之,公知者有:將鋁表面以含有鈦鹽、過氧化氫及縮 合磷酸之酸性溶液進行處理之方法(日本特許公開公報特 開昭54 — 24232號);以含有鈦離子及錯合劑之鹼性水溶液 處理銘表面,並於水洗後以磷酸等酸性水溶液處理之方法 (請先閲讀背面之注意事項再填窝本頁)J, τ.¾. -4- 1224615 A7 B7 V. Description of the invention (2) Good and good workability, but 'Because the coated steel sheet has a chromate coating film, there is still a problem of toxicity of chromium compounds. The coated steel sheet has insufficient corrosion resistance after removing the chromate coating film. In addition, in order to improve the corrosion resistance and hydrophilicity of aluminum or aluminum alloy substrates, various surface treatments are often applied as a base treatment. For example In general, the blades of the heat exchanger of the air conditioner generally use aluminum or aluminum alloy substrates with light weight, processability and thermal conductivity. In the heat exchanger of the air conditioner, the condensate generated during the cold room becomes water droplets. The connection of water is formed between the blades, and the ventilation path of the air is narrowed, so that the ventilation resistance is increased, and there are problems such as power loss, noise generation, and water droplets scattering. To solve this problem, the blades are made of aluminum or aluminum alloy substrates. The surface is subjected to hydrophilization treatment such as bauxite treatment, water glass coating, and water-based polymer coating to prevent the aforementioned coupling. However, the blades made of hydrophilized aluminum or its alloys The physical coating film is also hydrophilic, and will be corroded in about several months if it is placed in a strong corrosive environment. The method of preventing such blades from rot is based on the viewpoints of tolerance and cost in the past. The surface of the material is treated with chromate as a base treatment. However, chromate treatment has the problem of toxicity of chromium compounds as described above. Moreover, no surface treatment agent or surface treatment method for chromate is used, for example, Known methods include a method of treating aluminum surface with an acidic solution containing titanium salt, hydrogen peroxide, and condensed phosphoric acid (Japanese Patent Laid-Open Publication No. 54-24232); and an alkaline aqueous solution containing titanium ions and a complexing agent. The method of treating the surface of the Ming and washing it with an acidic aqueous solution such as phosphoric acid after washing (please read the precautions on the back before filling this page)
J .、可丨 .嗓· -5- 1224615 A7 ________B7 五、發明説明(3 ) (日本特許公開公報特開昭54_ 16〇527號);含磷酸離子、 鈦化合物及氟化物之鋁表面處理劑(日本特許公開公報特 (請先閱讀背面之注意事項再填寫本頁) 開平9 一 20984號);含縮合磷酸、鈦鹽、氟化物及亞磷酸 鹽之鋁系金屬表面處理劑(日本特許公開公報特開平9一 143752號)等。 然而,前述使用鈦化合物之表面處理劑或表面處理方 法,有表面處理劑之安定性不足,对辞性不如鉻酸鹽處理, 親水性不佳、耐久性不完全等問題點。 由上述現狀可看出,用於鋼板、鋁、鋁合金等金屬基 材之表面處理劑,需要無毒性問題產生,並可形成耐蝕性 等倶佳之塗膜之無機膜形成材料。 發明之揭示 本發明之目的即在於提供一種可於金屬基材上形成省 餘性、黏附性、加工性等良好之塗膜之新研發之用以形成 氧化鈦膜之塗佈劑及氧化鈦膜形成方法。 本發明之另一目的則在於提供一種被覆有耐蝕性、黏 附性、加工性等倶佳之氧化鈦膜之金屬基材。 本發明之其他目的及特徵由以下記載可明。 本發明係提供以下新研發之用以形成氧化鈦膜之塗佈 劑、氧化鈦膜形成方法及被覆有氧化鈦膜之金屬基材。 1 · 一種用以形成氧化鈦膜之塗佈劑,係包含有: (A)將由水解性鈦化合物、水解性鈦化合物之低 縮合物、氫氧化鈦及氫氧化鈦之低縮合物中選出之至少1 種鈦化合物’與過氧化氫溶液混合而得之含鈦水成液;及 本紙張尺度適用中國國家標準(CNS) A4規格(210X297公釐) -6- 1224615 A7 B7 五、發明説明(4 (B )磷酸系化合物。 2.如前述第1項之用以形成氧化鈦膜之塗佈劑,其中該 含鈦水成液(A)係一種將水解性鈦化合物及/或其低縮合 物與過氧化氫溶液混合而得之過氧化鈦酸水溶液。 3·如則述第2項之用以形成氧化鈦膜之塗佈劑,其中該 水解性鈦化合物係以通式(1)表示之四烷氧基鈦,即·· / Ti (OR) 4 ⑴ (該式中,R係表示碳原子數為i〜5之相同或不同之烷 基)。 4·如前述第2項之用以形成氧化鈦膜之塗佈劑,其中該 水解性鈦化合物之低縮合物係令以通式(丨)表示之四烷氧 基鈦互行縮合反應而組成之縮合率為2〜3〇之化合物; Ti (OR) 4 ⑴ (該式中,R係表示碳原子數為1〜5之相同或不同之 基)。 5 ·如則述第2項之用以形成氧化鈦膜之塗佈劑,其中 X解〖生鈦化合物及/或其低縮合物與過氧化氫溶液之混一 比例,係相對於前者10重量份,後者以過氧化氫換算時約 於〇·1〜100重量份之範圍内。 6·如刖述第2項之用以形成氧化鈦膜之塗佈劑,其中 含鈦水成液(Α)係一種於存有氧化鈦溶膠之狀態下, 水解性鈇化合物及/或其低縮合物與過氧化氫溶液混合 知之過氧化鈇酸水溶液。 7·如刚述第6項之用以形成氧化鈦膜之塗佈劑,其中該 烷 該合 該 將 而 (請先閲讀背面之注意事項再填寫本頁) 、一一一口 -¾. 本紙張尺度適财關家標準(CNS)職格⑵㈣97公箸) 1224615 A7 --—- B7 五、發明説明(5 ) 氧化鈦溶膠係銳鈦礦型氧化鈦之水分散液。 (請先閲讀背面之注意事項再填寫本頁) 8·如前述第6項之用以形成氧化鈦膜之塗佈劑,其中該 氧化欽溶膠之使用量,係相對於水解性鈦化合物及/或其低 縮合物1重量份,以固體成分計約佔0.01〜10重量份。 9. 如前述第1項之用以形成氧化鈦膜之塗佈劑,其中該 填酸系化合物(B )係由單填酸類、單填酸類之衍生物及 鹽類、縮合鱗酸類、縮合磷酸類之衍生物及鹽類所組成之 群中選出之至少1種化合物。 10. 如前述第1項之用以形成氧化鈦膜之塗佈劑,其中 該含钦水成液(A )及磷酸系化合物(B )之含有比例,係 相對於前者之固體成分1〇〇重量份,後者佔約1〜4〇〇重量 份。 11 ·如前述第1項之用以形成氧化鈦膜之塗佈劑,其係 一種pHl〜7之水成液。 12.如前述第1項之用以形成氧化鈦膜之塗佈劑,其進 而包含有由鈦_化物、鈦_化物鹽、锆_化物、锆鹵化物 鹽、石夕_化物、石夕_化物鹽所組成之群中選出之至少1種!| 化物。 13 · —種用以形成氧化鈦膜之塗佈劑,係包含有: (A)將由水解性鈦化合物、水解性鈦化合物之低 縮合物、氫氧化鈦及氫氧化鈦之低縮合物中選出之至少1 種鈥化合物,與過氧化氫溶液混合而得之含鈦水成液; (B ’)由磷酸系化合物、鈦鹵化物、鈦鹵化物鹽、 錯鹵化物、錯鹵化物鹽、石夕鹵化物及石夕1¾化物鹽所組成之 本紙張尺度適用中國國家標準(CNS) A4規格(210X297公釐) -8- 1224615 A7 一· 丨丨——— B7 五、發明説明~ 群中選出之至少1種化合物;及 (c) ΡΗ7以下且安定之水性有機高分子化合物。 14. 如刖述第13項之用以形成氧化鈦膜之塗佈劑,其中 該含鈦水成液(Α)係-種將水解性鈦化合物及/或其低縮 合物與過氧化氫溶液混合而得之過氧化鈦酸水溶液。 15. 如前述第14項之用以形成氧化鈦膜之塗佈劑,其中 該水解性鈦化合物係以通式⑴I示之四烧氧基欽,即:J., Ke 丨. ··· 1224615 A7 ________B7 V. Description of the invention (3) (Japanese Patent Laid-Open Publication No. 54_16〇527); aluminum surface treatment agent containing phosphate ion, titanium compound and fluoride (Special Japanese Patent Publication (please read the precautions on the back before filling this page) Kaiping No. 9-20984); aluminum-based metal surface treatment agent containing condensed phosphoric acid, titanium salt, fluoride and phosphite (Japanese Patent Publication Gazette No. 9-1143752) and so on. However, the aforementioned surface treatment agents or surface treatment methods using titanium compounds have problems such as insufficient stability of the surface treatment agents, inferiority to chromate treatment, poor hydrophilicity, and incomplete durability. From the above situation, it can be seen that surface treatment agents for metal substrates such as steel plates, aluminum, and aluminum alloys need inorganic film forming materials that have no toxicity problems and can form excellent coating films such as corrosion resistance. DISCLOSURE OF THE INVENTION The object of the present invention is to provide a newly developed coating agent for forming a titanium oxide film and a titanium oxide film, which can form a good coating film on metal substrates with good savings, adhesion, and processability. Formation method. Another object of the present invention is to provide a metal substrate coated with a titanium oxide film having excellent corrosion resistance, adhesion, and processability. Other objects and features of the present invention will be made clear by the following description. The present invention provides the following newly developed coating agents for forming a titanium oxide film, a method for forming a titanium oxide film, and a metal substrate coated with a titanium oxide film. 1. A coating agent for forming a titanium oxide film, comprising: (A) one selected from hydrolyzable titanium compounds, low condensates of hydrolyzable titanium compounds, titanium hydroxide, and low condensates of titanium hydroxide; A titanium-containing aqueous solution obtained by mixing at least one titanium compound 'with a hydrogen peroxide solution; and the size of this paper applies the Chinese National Standard (CNS) A4 specification (210X297 mm) -6- 1224615 A7 B7 V. Description of the invention ( 4 (B) Phosphoric acid-based compound 2. The coating agent for forming a titanium oxide film according to the aforementioned item 1, wherein the titanium-containing aqueous solution (A) is a kind of a hydrolyzable titanium compound and / or a low condensation thereof An aqueous solution of peroxytitanic acid obtained by mixing a substance with a hydrogen peroxide solution. 3. The coating agent for forming a titanium oxide film described in item 2 above, wherein the hydrolyzable titanium compound is represented by the general formula (1) Tetraalkoxytitanium, that is, / / Ti (OR) 4 ⑴ (In the formula, R represents an identical or different alkyl group having i to 5 carbon atoms.) 4. Use as described in item 2 above. A coating agent for forming a titanium oxide film, wherein the low condensate of the hydrolyzable titanium compound is represented by the general formula (丨) A compound having a condensation ratio of 2 to 30 as shown in the tetraalkoxytitanium mutual condensation reaction shown; Ti (OR) 4 ⑴ (wherein R represents the same or different carbon atoms having 1 to 5 carbon atoms) 5) As described above, the coating agent for forming a titanium oxide film according to item 2, wherein X solution [the ratio of the raw titanium compound and / or its low condensate to the hydrogen peroxide solution is relative to The former is 10 parts by weight, and the latter is in the range of 0.1 to 100 parts by weight in terms of hydrogen peroxide. 6. The coating agent for forming a titanium oxide film as described in item 2 above, which contains titanium aqueous The liquid (A) is an aqueous solution of perrhenic acid peroxidized by mixing a hydrolyzable amidine compound and / or a low condensate thereof with a hydrogen peroxide solution in the state where a titanium oxide sol is stored. 7. Use as described in item 6 above. In order to form a coating agent for titanium oxide film, the alkane should be appropriate (please read the precautions on the back before filling out this page), one by one-¾. This paper is suitable for financial standards (CNS) Post code: 97) 1224615 A7 ----- B7 V. Description of the invention (5) Titanium oxide sol is anatase type titanium oxide Dispersions. (Please read the precautions on the back before filling in this page) 8. The coating agent used to form the titanium oxide film as described in item 6 above, where the amount of oxidized sol is relative to the hydrolyzable titanium compound and / Or 1 part by weight of the low condensate thereof, and it accounts for about 0.01 to 10 parts by weight as a solid content. 9. The coating agent for forming a titanium oxide film as described in the above item 1, wherein the acid-filling compound (B) is composed of a single-filler acid, a derivative of a single-filler acid and a salt, a condensed linoleic acid, and a condensed phosphoric acid. At least one compound selected from the group consisting of derivatives and salts. 10. The coating agent for forming a titanium oxide film as described in item 1 above, wherein the content ratio of the aqueous solution (A) and the phosphoric acid-based compound (B) containing Qin is relative to the solid content of the former 100. The latter accounts for about 1 to 400 parts by weight. 11 The coating agent for forming a titanium oxide film as described in the above item 1, which is an aqueous solution having a pH of 1 to 7. 12. The coating agent for forming a titanium oxide film according to the above item 1, further comprising a titanium compound, a titanium compound salt, a zirconium compound, a zirconium halide salt, a stone compound, and a stone compound. At least one selected from the group consisting of compound salts! | Chemicals. 13 · A coating agent for forming a titanium oxide film, comprising: (A) selected from a hydrolyzable titanium compound, a low-condensation product of a hydrolyzable titanium compound, titanium hydroxide, and a low-condensation product of titanium hydroxide At least one of the compounds, a titanium-containing aqueous solution obtained by mixing with a hydrogen peroxide solution; (B ') a phosphoric acid-based compound, a titanium halide, a titanium halide salt, a cross halide, a cross halide salt, stone The paper size composed of the halides and the sulfide salts of Xixi is applicable to the Chinese National Standard (CNS) A4 specifications (210X297 mm) -8- 1224615 A7 I · 丨 丨 ———— B7 V. Description of the invention ~ selected from the group At least one compound; and (c) a stable aqueous organic polymer compound having a pH of 7 or less. 14. The coating agent for forming a titanium oxide film as described in item 13, wherein the titanium-containing aqueous solution (A) is a kind of a hydrolyzable titanium compound and / or a low condensation product thereof and a hydrogen peroxide solution. An aqueous solution of peroxytitanic acid obtained by mixing. 15. The coating agent for forming a titanium oxide film as described in the above item 14, wherein the hydrolyzable titanium compound is tetrakis (oxycarbamyl) represented by the general formula (I), namely:
Ti (OR) 4 ⑴ (該式中,R係表示碳原子數為i〜5之相同或不同之烷 基)。 16·如前述第2項之用以形成氧化鈦膜之塗佈劑,其中 該水解性鈦化合物之低縮合物係令以通式(〇表示之四烷 氧基鈦互行縮合反應而組成之縮合率為2〜3〇之化合物;Ti (OR) 4 ⑴ (In the formula, R represents an alkyl group having the same or different carbon number from i to 5). 16. The coating agent for forming a titanium oxide film according to the aforementioned item 2, wherein the low condensate of the hydrolyzable titanium compound is composed of a tetraalkoxytitanium mutual condensation reaction represented by the general formula (0) Compounds with a condensation ratio of 2 ~ 30;
Ti (OR) 4 ⑴ (忒式中,R係表示碳原子數為j〜5之相同或不同之烷 基)。 17·如前述第14項之用以形成氧化鈦膜之塗佈劑,其中 該水解性鈦化合物及/或其低縮合物與過氧化氫溶液之混 合比例,係相對於前者1 〇重量份,後者以過氧化氫換算時 約於0·1〜100重量份之範圍内。 18·如前述第14項之用以形成氧化鈦膜之塗佈劑,其中 該含鈦水成液(A )係一種於存有氧化鈦溶膠之狀態下, 將水解性鈦化合物及/或其低縮合物與過氧化氫溶液混合 而得之過氧化鈦酸水溶液。 本紙張尺度適用中國國家標準(CNS) A4規格(210X297公釐) (請先閲讀背面之注意事項再填寫本頁)Ti (OR) 4 ⑴ (wherein R represents an alkyl group of the same or different number of carbon atoms of j to 5). 17. The coating agent for forming a titanium oxide film according to the aforementioned item 14, wherein the mixing ratio of the hydrolyzable titanium compound and / or its low condensate with a hydrogen peroxide solution is 10 parts by weight relative to the former, The latter is in the range of about 0.1 to 100 parts by weight in terms of hydrogen peroxide. 18. The coating agent for forming a titanium oxide film according to the foregoing item 14, wherein the titanium-containing aqueous solution (A) is a kind of hydrolyzable titanium compound and / or An aqueous solution of titanic acid is obtained by mixing the low condensate with a hydrogen peroxide solution. This paper size applies to China National Standard (CNS) A4 (210X297 mm) (Please read the precautions on the back before filling this page)
、一叮I -¾. -9- 1224615 A7 ----- B7 __ 五、發明説明(7 ) 19·如前述第18項之用以形成氧化鈦膜之塗佈劑,其中 該氧化鈦溶膠係銳鈦礦型氧化鈦之水分散液。 (請先閱讀背面之注意事項再填寫本頁) 20·如則述第1 8項之用以形成氧化鈦膜之塗佈劑,其中 忒氧化鈦溶膠之使用量,係相對於水解性鈦化合物及/或其 低縮合物1重量份,以固體成分計約佔0 01〜10重量份。 21 ·如前述第13項之用以形成氧化鈦膜之塗佈劑,其中 忒化合物(B ’)中之碌酸系化合物係由單礙酸類、單磷酸 類之衍生物及鹽類、縮合磷酸類、縮合磷酸類之衍生物及 鹽類所組成之群中選出之至少1種化合物。 22. 如前述第13項之用以形成氧化鈦膜之塗佈劑,其中 該化合物(B,)中用以構成鈦鹵化物、鈦函化物鹽、锆_ 化物、錯i化物鹽、矽_化物及矽齒化物鹽之鹵素為氟。 23. 如前述第13項之用以形成氧化鈦膜之塗佈劑,其中 该含鈦水成液(A )及化合物(B,)之含有比例,係相對 於前者之固體成分1〇〇重量份,後者佔約1〜4〇〇重量份。 24. 如前述第13項之用以形成氧化鈦膜之塗佈劑,其中 該水性有機高分子化合物(C ),係由環氧系樹脂、酚系 樹脂、丙烯酸系樹脂、胺曱酸乙酯系樹脂、聚乙烯醇系樹 脂、含聚氧化烯鏈樹脂及烯聚合性不飽和羧酸共聚物系樹 脂所組成之群中選出之至少1種樹脂。 25·如前述第13項之用以形成氧化鈦膜之塗佈劑,其中 该水性有機高分子化合物(C )之含有比例,係相對於含 鈦水成液(A)之固體成分1〇〇重量份佔約10〜2000重量份。 26·如前述第13項之用以形成氧化鈦膜之塗佈劑,其係 本紙張尺度適用中國國家標準(CNS) A4規格(210X297公釐) -10- 1224615 A7 _____B7 五、發明説明(8 ) 一種pHl〜7之水成液。 (請先閱讀背面之注意事項再填寫本頁) 27· —種氧化鈦膜形成方法,係將前述第1或丨3項之用 以形成氧化鈦膜之塗佈劑塗附於金屬基材上並加以乾燥。 28·—種被覆金屬基材,係於一金屬基材表面形成有前 述第1或13項之用以形成氧化鈦膜之塗佈劑之塗膜者。 29.如前述第28項之被覆金屬基材,其中該塗膜之膜厚 係於0.001 μιη〜1 Ομηι之範圍内。 30_如前述第28項之被覆金屬基材,其中該金屬基材係 鋼板。 31.如前述第28項之被覆金屬基材,其中該金屬基材係 銘或紹合金。 本發明人乃進行專門研究以達成前述目的。結果顯 現,依據前述含有含鈦水成液(A )及磷酸系化合物(Β ) 之用以形成氧化鈦膜之塗佈劑I,或前述含有含鈦水成液 (A)、磷酸系化合物及/或鈦!|化物等(& )以及( 水性有機高分子化合物之用以形成氧化鈦膜之塗佈劑π, 則可於金屬基材上形成一耐蝕性、黏附性、加工性等良好 而合適之塗膜,以作為表面處理膜。 前述本發明即基於如此新知而完成者。 J以形成氧化鈦膜之%佑奇丨 本發明之用以形成氧化鈦膜之塗佈劑I ,係前述之含 有(Α)含鈦水成液及(Β)磷酸系化合物之水性塗佈劑。 本發明塗佈劑I中之(Α)成分,即,將由水解性鈦 化合物、水解性鈦化合物之低縮合物、氫氧化鈦及氫氧化 本紙張尺度適用中國國家標準(CNS) Α4規格(210X297公釐) -11- 五、發明説明(9 ) =低ΐ合物中選出之至少1種欽化合物,與過氧化氫溶液 2而传之含敛水成液,係可由公知者中適當選擇而加以 使用。 則述水解性鈦化合物係一種具有可與鈦原子直接結合 之水解性基之鈦化合物,即藉由與水、水蒸氣等水分反應 而產生氳氧化鈦者。又’該水解性鈦化合物中,縱使與鈦 原子結合之基全為水解性基,又縱使部分水解性基變成業 經水解之髮基,盡皆無妨。 作為前述水解性基者,若為可藉與水分反應而生成經 基者即無特別限制,例如可與低級絲基或鈦原子形成鹽 ,基等。可與鈦原子形成鹽之基,則有鹵素原子(氯等)、 氳原子、硫酸離子等。 含有低級烷氧基以作為水解性基之水解性鈦化合物, 係可舉四烷氧基鈦等為例。 具有可與鈦形成鹽之基以作為水解性基之水解性鈦化 合物,代表性者有氯化鈦、硫酸鈦等。 水解性欽化合物之低縮合物係前述水解性鈦化合物間 之低縮合物。該低縮合物,縱使與鈦原子結合之基全為水 解性基,又縱使部分水解性基變成業經水解之羥基,盡皆 無妨。 氫氧化鈦之低縮合物,舉例言之,可使用藉由氯化鈦、 硫酸敛等水溶液與氨、苛性鈉等鹼水溶液產生反應而得之 正飲酸(氫氧化鈦凝膠)等。 前述水解性鈦化合物之低縮合物或氫氧化鈦之低縮合 本紙張尺度適用中國國家標準(CNS) Α4规格(210X297公釐) -12- 1224615 A7 B7 五、發明説明(10 物中之縮合率係可使用2〜30之化合物,特別是以縮合率在 2〜10之範圍内者之使用較為理想。 (請先閲讀背面之注意事項再填寫本頁) 前述水成液(A),若為令前述鈦化合物與過氧化氮 溶液產生反應而得之含鈦水成液,則可使用以往公知者而 無特別限制。具體而言,可使用以下所列者。 (1) 曰本特許公開公報特開昭63-35419號及特開平 1 -224220號中所載,於含氫氧化鈦之凝膠或溶膠中添加過 氧化氫溶液而得之過氧化鈦酸水溶液。 、可| (2) 曰本特許公開公報特開平9一71418號及特開平 1〇-67516號中所載之用以形成氧化鈦膜之水成液,係一種 令氣化鈦、硫酸鈦等水溶液與氨、苛性鈉等鹼水溶液產生 反應而使稱為正鈦酸之氫氧化鈦凝膠沈澱,繼之藉傾析法 为離氫氧化鈦凝膠,經水洗後,再於其中加入過氧化氫溶 液所得之黃色透明黏性液體。 .¾. (3) 日本特許公開公報特開2〇〇〇一247638號及特開 2000-247639號中所載之用以形成氧化鈦膜之水成液,係 一種於氣化鈥、硫酸鈦等無機鈦化合物之水溶液中加入過 氧化氫溶液而形成過氧化鈦水合物,並將於其中添加鹼性 物質所得之溶液進行放置或加熱而形成過氧化鈦水合物聚 合體之沈澱’且於去除水以外之溶解成分後使過氧化氫產 生作用而得者。 含欽水成液(A ),宜使用將水解性鈦化合物及/或其 低縮合物與過氧化氫溶液混合而得之過氧化鈦酸水溶液 (A1 ) 〇Yiding I -¾. -9- 1224615 A7 ----- B7 __ V. Description of the Invention (7) 19 · The coating agent for forming a titanium oxide film as described in the aforementioned item 18, wherein the titanium oxide sol It is an aqueous dispersion of anatase titanium oxide. (Please read the precautions on the back before filling this page.) 20 · As described in item 18 of the coating agent used to form the titanium oxide film, the amount of titanium oxide sol is relative to the hydrolyzable titanium compound. And / or 1 part by weight of the low condensate thereof, occupying about 01 to 10 parts by weight as a solid content. 21 · The coating agent for forming a titanium oxide film as described in item 13 above, wherein the acid compound in the fluorene compound (B ') is composed of mono-acid acids, mono-phosphoric acid derivatives and salts, and condensed phosphoric acid At least one compound selected from the group consisting of derivatives, salts of condensed phosphoric acid, and salts. 22. The coating agent for forming a titanium oxide film according to the aforementioned item 13, wherein the compound (B,) is used to constitute a titanium halide, a titanium halide salt, a zirconium compound, a complex compound salt, and a silicon compound. The halide of the halide and silicide salt is fluorine. 23. The coating agent for forming a titanium oxide film according to the aforementioned item 13, wherein the content ratio of the titanium-containing aqueous solution (A) and the compound (B,) is 100% by weight relative to the former's solid content. The latter accounts for about 1 to 400 parts by weight. 24. The coating agent for forming a titanium oxide film according to the aforementioned item 13, wherein the water-based organic polymer compound (C) is composed of an epoxy resin, a phenol resin, an acrylic resin, and ethyl amino acid ester. At least one resin selected from the group consisting of a series resin, a polyvinyl alcohol resin, a polyoxyalkylene chain resin, and an olefin polymerizable unsaturated carboxylic acid copolymer resin. 25. The coating agent for forming a titanium oxide film according to the aforementioned item 13, wherein the content ratio of the aqueous organic polymer compound (C) is 100% relative to the solid content of the titanium-containing aqueous solution (A). The parts by weight account for about 10 to 2000 parts by weight. 26. The coating agent used to form the titanium oxide film as described in item 13 above, which is the paper size applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) -10- 1224615 A7 _____B7 V. Description of the invention (8 ) An aqueous solution of pH 1 ~ 7. (Please read the precautions on the back before filling in this page) 27 · —A method for forming a titanium oxide film is to apply the coating agent used to form a titanium oxide film in the above item 1 or 3 to a metal substrate And dried. 28. A coated metal substrate is a coating film formed on the surface of a metal substrate with a coating agent for forming a titanium oxide film according to the foregoing item 1 or 13. 29. The coated metal substrate according to the aforementioned item 28, wherein the film thickness of the coating film is in the range of 0.001 μm to 100 μm. 30_ The coated metal substrate according to the aforementioned item 28, wherein the metal substrate is a steel plate. 31. The coated metal substrate according to the aforementioned item 28, wherein the metal substrate is a Ming or Shao alloy. The present inventors have conducted special studies to achieve the foregoing objectives. The results show that according to the coating agent I for forming a titanium oxide film containing the titanium-containing aqueous solution (A) and the phosphoric acid-based compound (B), or the foregoing titanium-containing aqueous solution (A), the phosphoric acid-based compound, and / Or titanium! (&Amp;) and (aqueous organic polymer compound coating agent π for forming a titanium oxide film) can form a good and suitable coating on a metal substrate with good corrosion resistance, adhesion, and processability. The film is used as a surface treatment film. The foregoing invention is completed based on such new knowledge. J is %% of the titanium oxide film. Youqi 丨 The coating agent I of the present invention for forming a titanium oxide film contains the aforementioned ( A) An aqueous coating agent containing a titanium-containing aqueous solution and (B) a phosphoric acid-based compound. The component (A) in the coating agent I of the present invention is composed of a hydrolyzable titanium compound, a low condensate of a hydrolyzable titanium compound, Titanium hydroxide and hydroxide This paper is in accordance with the Chinese National Standard (CNS) A4 specification (210X297 mm) -11- V. Description of the invention (9) = at least one kind of ammonium compound selected from the low sulfonium compounds and peroxide The condensed aqueous solution passed from the hydrogen solution 2 can be appropriately selected and used from known ones. The hydrolyzable titanium compound is a titanium compound having a hydrolyzable group which can be directly bonded to a titanium atom, that is, by combining with a titanium atom. Water, water vapor and other moisture Those who produce titanium oxide should have no problem, even if all the hydrolyzable titanium compounds are hydrolyzable groups, and some hydrolyzable groups become hydrolyzed hair groups, it is not necessary. The sex group is not particularly limited as long as it can be formed by reacting with moisture, for example, it can form a salt with a lower silk group or a titanium atom, a group, etc. A group that can form a salt with a titanium atom has a halogen atom ( (Chlorine, etc.), halogen atoms, sulfate ions, etc. Hydrolyzable titanium compounds containing a lower alkoxy group as a hydrolyzable group, for example, a tetraalkoxy titanium, etc. It has a group capable of forming a salt with titanium for hydrolysis. Typical examples of hydrolyzable titanium compounds include titanium chloride and titanium sulfate. The low-condensation product of the hydrolyzable compound is a low-condensation product between the aforementioned hydrolyzable titanium compounds. Even if the low-condensation product is bonded to a titanium atom, The bases are all hydrolyzable groups, and even if some of the hydrolyzable groups become hydroxyl groups that have been hydrolyzed, it does not matter. Low condensates of titanium hydroxide, for example, can be used water-soluble by titanium chloride, sulfuric acid, etc Orthoacid acid (titanium hydroxide gel) obtained by reacting with alkaline aqueous solutions such as ammonia and caustic soda. The aforementioned low-condensation product of hydrolyzable titanium compound or low-condensation of titanium hydroxide This paper applies Chinese national standards (CNS) ) A4 specification (210X297 mm) -12- 1224615 A7 B7 V. Description of the invention (Condensation ratio of 10 compounds can use 2-30 compounds, especially those with a condensation ratio within the range of 2-10 (Please read the precautions on the back before filling this page) The aqueous solution (A) mentioned above can be used if it is a titanium-containing aqueous solution obtained by reacting the aforementioned titanium compound with a nitrogen peroxide solution. There are no particular restrictions. Specifically, those listed below can be used. (1) The coagulation of titanium hydroxide-containing titanium contained in Japanese Patent Laid-Open Publication Nos. Sho 63-35419 and JP-A Hei 1-224220 An aqueous solution of titanic acid obtained by adding a hydrogen peroxide solution to a gel or sol. , 可 | (2) The aqueous solution for forming a titanium oxide film contained in Japanese Patent Laid-Open Publication Nos. 9-71418 and JP-A No. 10-67516 is a kind of titanium oxide, titanium sulfate, etc. The aqueous solution reacts with alkaline aqueous solutions such as ammonia and caustic soda to precipitate titanium hydroxide gel called orthotitanic acid, followed by decantation method to separate titanium hydroxide gel. After washing with water, peroxide is added to it Yellow transparent viscous liquid obtained from hydrogen solution. .¾. (3) The aqueous solution for forming a titanium oxide film contained in Japanese Patent Laid-Open Publication Nos. 2000-247638 and 2000-247639 is a kind of gasification solution, titanium sulfate Into an aqueous solution of an inorganic titanium compound, a hydrogen peroxide solution is added to form a titanium peroxide hydrate, and a solution obtained by adding an alkaline substance to the solution is left to stand or heated to form a precipitate of a titanium peroxide hydrate polymer. It is obtained by dissolving components other than water and making hydrogen peroxide work. The aqueous solution (A) containing chitin is preferably a peroxytitanic acid aqueous solution (A1) obtained by mixing a hydrolyzable titanium compound and / or a low condensate thereof with a hydrogen peroxide solution.
-13- 1224615-13- 1224615
發明説明 该鈦化合物則以通式(1)所示之四烷氧基鈦特別理想。 Ti ( OR) 4 ⑴ (請先閲讀背面之注意事項再填寫本頁) (该式中,R係表示碳原子數為1〜5之相同或不同之烷 基)。R所不之碳原子數為1〜5之烷基,係可舉甲基、乙 基、正甲基、異丙基、正丁基、異丁基、第二丁基、第三 丁基等為例。 又,前述鈦化合物之低縮合物,宜使用將前述通式(工〕 之化合物互行縮合反應而組成之縮合率為2〜3〇者,且又以 使用縮合率在2〜10範圍内者更為理想。DESCRIPTION OF THE INVENTION The titanium compound is particularly preferably a tetraalkoxytitanium represented by the general formula (1). Ti (OR) 4 ⑴ (Please read the notes on the back before filling out this page) (In this formula, R represents the same or different alkyl group with 1 to 5 carbon atoms). R is an alkyl group having 1 to 5 carbon atoms, which may be methyl, ethyl, n-methyl, isopropyl, n-butyl, isobutyl, second butyl, third butyl, etc. As an example. In addition, as the low-condensation product of the titanium compound, it is preferable to use a compound having a condensation ratio of 2 to 30, which is composed of the compounds of the general formula (engineering) that are subjected to mutual condensation reaction, and the use of the condensation ratio is in the range of 2 to 10 More ideal.
•、可I -嘈· 通式(1 )之水解性鈦化合物及/或其低縮合物(以下, 其等將僅略稱為「水解性鈦化合物(τ )」)與過氧化氫 溶液之混合比例,係相對於前者1〇重量份,後者以過氧化 氫換算時約於0·1〜100重量份之範圍内,又以在1〜2〇重量 份之範圍内特別理想。後者以過氧化氫換算時若未達01 重夏份,則過氧化鈦酸之形成不完全且將產生白濁沈澱, 效果不甚理想。反之,若超過100重量份,則易於殘留未反 應之過氧化氫且將於貯藏中放出危險之活性氧,亦不理想。 過氧化氫之過氧化氫濃度雖無特別限制,但以處理容 易度之觀點而言,則宜於3〜40重量%之範圍内。 又,別述過氧化鈦酸水溶液,通常可藉由將水解性鈦 化合物(Τ)與過氧化氫溶液於溫度1〜70。(:左右之範圍内 攪拌混合約1〇〜2〇小時而調製。進行該混合時,並可視需 要而使用甲醇、乙醇、正丙醇、異丙醇、丁氧基乙醇(ethylene glyC〇1 monobutyl ether )、丙二醇單甲醚(propylene glyc〇1 本紙張尺度適财關家轉(⑽M規格⑽〉〈297公董) -14- 1224615 A7 B7 五、發明説明(l2 monomethyl ether )等水溶性溶媒。 (請先閲讀背面之注意事項再填寫本頁) 刖述過氧化鈦酸水溶液(A1 ),經推測應為藉由令水 解性鈦化合物(T )與過氧化氫溶液混合,使水解性鈦化 合物因水產生水解而生成含羥基之鈦化合物,再藉由過氧 化氫立即與該含羥基之鈦化合物配位而形成過氧化鈦酸後 所得者。該過氧化鈦酸水溶液於室溫範圍内,其安定性高 且可長期保存。• I-Noisy · Hydrolyzable titanium compound of general formula (1) and / or its low condensate (hereinafter, these will be simply referred to as "hydrolyzable titanium compound (τ)") and hydrogen peroxide solution The mixing ratio is 10 parts by weight with respect to the former, and the latter is in the range of about 0.1 to 100 parts by weight when converted to hydrogen peroxide, and particularly preferably in the range of 1 to 20 parts by weight. If the latter is less than 01 weight summer when converted to hydrogen peroxide, the formation of peroxytitanic acid is incomplete and a white turbid precipitate is produced, which is not ideal. Conversely, if it exceeds 100 parts by weight, unreacted hydrogen peroxide is liable to remain and dangerous active oxygen will be released during storage, which is also not desirable. Although the hydrogen peroxide concentration of hydrogen peroxide is not particularly limited, it is preferably within a range of 3 to 40% by weight from the viewpoint of handling ease. In addition, the aqueous solution of a titanic acid may be generally obtained by mixing a hydrolyzable titanium compound (T) and a hydrogen peroxide solution at a temperature of 1 to 70. (: Prepared by stirring and mixing for about 10 to 20 hours in the range of left and right. When performing this mixing, methanol, ethanol, n-propanol, isopropanol, butoxyethanol (ethylene glyC〇1 monobutyl) may be used as necessary. ether), propylene glycerol monomethyl ether (propylene glyc 〇1 paper size suitable for wealth management (家 M specifications)> <297 public directors) -14-1224615 A7 B7 V. Description of the invention (l2 monomethyl ether) and other water-soluble solvents. (Please read the precautions on the back before filling in this page.) Describe the peroxytitanic acid aqueous solution (A1). It is estimated that the hydrolyzable titanium compound (T) should be mixed with the hydrogen peroxide solution to make the hydrolyzable titanium compound. Hydrogen-containing titanium compound is formed by hydrolysis of water, and then hydrogen peroxide is immediately coordinated with the hydroxyl-containing titanium compound to form peroxytitanic acid. The aqueous solution of peroxytitanic acid is in the range of room temperature, It has high stability and can be stored for a long time.
、可I .啜· 又,於存有氧化鈦溶膠之狀態下,將水解性鈦化合物 (T )與過氧化氫溶液混合而得之過氧化鈦酸水溶液 (A2 )’其貯藏安定性、所得氧化鈦膜之耐餘性等皆有提 升,效果理想。推測其理由係在於,該水溶液之調製中, 水解性鈦化合物(T )將吸附於氧化鈦溶膠粒子上,而該 吸附之水解性鈦化合物(T )將與該粒子表面產生之經基 行縮合反應而產生化學結合,且該水解性鈦化合物本身亦 行縮合反應而呈高分子化,繼之藉由與過氧化氫溶液混 合,則使所得之該水溶液安定化,並可顯著防止於貯藏中 產生凝膠化或增稠之情形。 前述氧化鈦溶膠,係使非晶形氧化鈦微粒、銳鈦礦型 氧化鈦微粒於水中分散者。該氧化鈦溶膠中,以耐姓性而 言’又以銳鈦礦型氧化鈦之水分散液為佳。氧化鈦溶膠除 水以外’亦可視需要而含有如醇系、醇醚系等水性有機溶 劑。 前述氧化鈦溶膠並可使用以往公知者。舉例言之,可 使用將業已使凝聚物分散於水中之非晶形氧化鈦微粒,或 本紙張尺度適用中國國家標準(CNS) A4規格(210X297公茇) -15- 五、發明説明(l3 ) 焙燒該氧化鈦凝聚物而形成銳銳礦型氧化鈦微粒並將其分 散::中者。非晶形氧化鈦之焙燒若以至少高於銳鈦礦之 結晶溫度之溫度而進行培燒,通常為2GG°C以上之溫度,則 可使非晶形氧化鈦轉變為舰礦型氧化鈦。前述氧化钦凝 聚物’舉例言之有··⑴將硫酸鈦、驗式硫酸鈦等血機欽 化合物水解後所得者,·⑺將鈦絲化物等有機鈦化合物 水解後所得者,(3 )將四氣化敛等自化鈦溶液水解或中和 後所得者等。 刖述氧化鈦溶膠之市售品,舉例言之有··「TKs_2〇i」 (TAYCA(株)製、商品名、平均粒子徑6nm之銳鈦礦型氧 化鈦微粒之水性溶膠);rTKS_2〇3」(tayca(株)製、 商品名、平均粒子徑6nm之銳鈦礦型氧化鈦微粒之水性溶 膠);「TA-15」(曰產化學(株)製、商品名、銳鈦礦型氧 化鈦微粒之水性溶膠);rSTS-11」(石原產業(株)製、 商品名、銳鈦礦型氧化鈇微粒之水性溶膠)等。 水解性鈦化合物(T)與過氧化氫溶液混合時,所具 氧化鈦溶膠之使用量,通常係相對於水解性鈦化合物(T ) 1重里伤’以固體成分计約佔〇 · 〇 1〜1 〇重量份,理想者約佔 0.1〜8重量份之範圍。氧化鈦溶膠之使用量若未達〇〇1重 量份,則無法獲得添加氧化鈦溶膠後應有之提高塗佈劑之 貯藏安定性,及所得氧化鈦膜之耐蝕性之效果,反之若超 過10重量份則使塗佈劑之造膜性差,皆非理想。 含鈦水成液(A ),亦可依需要而於存有氧化鈦溶膠 之狀態下,使將水解性鈦化合物(T )與過氧化氫溶液混 本紙張尺度適用中國國家標準(WS) A4規格(21〇χ297公釐) -16- 1224615 A7 _____B7 五、發縣明(14 ) ^ s 合而得之過氧化鈦酸水溶液,進而以8〇〇Γ 以上之溫度進行 加熱處理或熱壓處理而形成平均粒子徑在1〇nmw下之氧 化欽微粒之分散液後再加以使用。而該分散液之外觀通常 呈半透明狀。 加熱處理或熱壓處理之溫度低於8〇1時,氧化鈦將無 法完全達成結晶化。藉由前述處理所得之氧化鈦微粒,其 粒子徑係在lOnm以下,理想者則在lnm〜6nm之範圍内。 若該粒子徑大於l〇nm則使造膜性降低,且於膜厚大於km 時將產生裂紋,效果並不理想。 含鈦水成液(Α)為前述水成液(Α1)時,於前述乾 燥條件下’通常將形成一含若干經基之非晶形氧化鈦膜。 該非晶形氧化鈦膜係具有氣體阻擋性佳之優點。而,若為 含鈦水成液(Α2 )時,則於前述乾燥條件下,通常將形成 一含若干羥基之銳鈦礦型氧化鈦膜。 本發明塗佈劑I中之磷酸系化合物(Β ),係具有可 使製得塗膜之耐蝕性提升之作用者。該化合物(Β )可舉 例如:亞填酸、多磷酸(polyphosphoric acid )、三鱗酸、 次磷酸、低磷酸、三偏磷酸、二亞磷酸、二磷酸、焦亞磷 酸、焦磷酸、偏亞磷酸、偏磷酸、正磷酸等單磷酸類、單 鱗酸類之衍生物及鹽類;三聚填酸、四磷酸、六磷酸等縮 合磷酸類、縮合磷酸類之衍生物及鹽類· ··等。該等化 合物係可使用1種或2種以上。又,用以形成磷酸系化合物 之鹼化合物,則可舉含有鋰、鈉、銨等之有機或無機驗化 合物為例。 本紙張尺度適用中國國家標準(CNS) A4規格(210X297公釐) -17- -------------------嘹:…——…:-訂.....................啜· (請先閱讀背面之注意事項再填窝本頁) 1224615 A7 _______ B7 五、發明説明(I5 ) 璘酸系化合物(B )宜使用於水中具有溶解性者。 該磷酸系化合物(B )若由可發揮優異之塗佈劑之貯 藏女定性、製得塗膜之耐蝕性等之效果而言,則以焦磷酸 鈉、三聚磷酸鈉、四磷酸鈉、偏磷酸、偏磷酸銨、六偏磷 酸鈉等之使用特別理想。 含鈦水成液(A )及磷酸系化合物(B )之含有比例, 係相對於前者之固體成分100重量份,後者宜佔約1〜4〇〇 重量份。(B )成分若未達1重量份,將使耐蝕性降低,反 之,(B)成分若超過400重量份,則使造膜性低劣,且耐 蝕性降低,效果皆不理想。前述磷酸系化合物(B )更加 理想之含有比例,係相對於含鈦水成液(A) 1〇〇重量份佔 約10〜200重量份。 本發明之用以形成氧化鈦膜之塗佈劑J,係將含鈦水 成液(A)及磷酸系化合物(B)依常用方法混合而製造者。 本發明塗佈劑〗中,磷酸系化合物(B)係藉由使可與該 化合物(B)結合之酸性磷酸基離子與鈦離子配位而於兩 者間形成錯合物構造。如此之錯合物構造僅藉由混合兩成 分即可輕易形成,舉例言之,以常溫(2(rc)放置約5分鐘 〜1小時即可形成。又,加熱該混合物時,舉例言之,以大 約30〜70。(:加熱約1〜30分鐘即形成錯合物構造。 本發明之用以形成氧化鈦膜之塗佈劑I係一種於中性 或酸性領域中呈安定狀態之水成液,其pH通常在丨〜?之範 圍内。特別是於酸性領域中之貯藏安定性佳,且宜於ρΗι 〜5之範圍内。本發明之塗佈劑j亦可依需要而含有如曱 本紙張尺度適用中關家標準⑽)Α4規格⑵QX297公楚) ------------------訂--------------- (請先閲讀背面之注意事項再填寫本頁) -18- 1224615 κι ___ B7 五、發明説明(16 ) 醇、乙醇、異丙醇、乙二醇、丙二醇等親水性溶劑。本發 明塗佈劑I並可視需要以水或親水性溶劑加以稀釋後使 用。 本發明之用以形成氧化鈦膜之塗佈劑〗中,可依需要 而含有由鈦鹵化物、鈦鹵化物鹽、鍅鹵化物、鍅鹵化物鹽、 矽鹵化物、矽鹵化物鹽所組成之群中選出之至少丨種鹵化 物,以使製得塗膜之耐蝕性更加提升。 用以構成該鹵化物之幽素,可舉氟、氣、碘等為例。 而由具優異之塗佈劑之貯藏安定性、塗膜之耐蝕性、耐濕 性等性能之觀點言之,則以氟特別適於作為齒素。又,用 以形成_化物之鹽者,舉例言之有鈉、鉀、鋰、銨等。而 用以形成鹽者,則以鉀、鈉較為理想。 前述鹵化物,宜使用如鈦氫氟酸等鈦_化物;鈦氟化 鉀、鈦氟化銨等鈦i化物鹽;錯氫氟酸等锆齒化物;錯氟 化銨、锆氟化鉀等锆齒化物鹽;矽氫氟酸等矽齒化物;矽 氟化鈉、矽氟化銨、矽氟化鉀等矽齒化物鹽···等。 本發明塗佈劑I中,含有前述鹵化物時之含有比例, 通常係相對於含鈦水成液(A)之固體成分100重量份,佔 約1〜400重量份,又以在10〜200重量份之範圍内特別理 想。 本發明塗佈劑I中,可依需要進而包含有氨、有機鹼 式化合物、鹼金屬氫氧化物、鹼土類金屬氫氧化物等鹼式 中和劑。前述有機鹼式化合物宜使用乙醇胺、三乙胺,而 前述鹼金屬氫氧化物,則宜使用氫氧化鋰、氫氧化鈉、氫 本紙張尺度適用中國國家標準(QJS) A4規格(21〇χ297公釐) —f … (請先閱讀背面之注意事項再填寫本頁) 、? -19- A7 ----------- B7 五、發明説明(17 ) " --- 氧化鉀等。 (請先閲讀背面之注意事項再填寫本頁) 本發明塗佈劑1中,亦可視必要進而含有各種添加 物。該添加物可舉增稠劑、防菌劑、防銹劑、氧化鈦溶膠、 氧化鈦叙纟冑質顏料、防銹顏料、著色顏料、界面活性 劑等為例。前述防銹劑有單寧酸、植酸、苯并三氮唾等。 前述體質顏料則有雲母、滑石、石夕石、硫酸鋇、黏土等。 本發明之用以形成氧化鈦膜之塗佈劑π,係一種含有 前述含1 太水成液(A)、磷酸系化合物及/或鈦_化物等(B,) 及(C)水性有機鬲分子化合物之水性塗佈劑。 本發明塗佈劑π中之含鈦水成液(A )係適當選擇本 發明塗佈劑I中之含鈇水成液及相同者而使用。 本發明塗佈劑Π中,由磷酸系化合物、鈦_化物、鈦 _化物鹽、錘_化物、#鹵化物鹽、矽齒化物、矽_化物 鹽所組成之群中選出之至少丨種化合物(B,),係具有可使 製得塗膜之耐餘性提升之作用者。 前述化合物(B,)中之磷酸系化合物,可舉例如:亞 磷酸、多磷酸、三磷酸、次磷酸、低磷酸、三偏磷酸、二 亞磷酸、二磷酸、焦亞磷酸、焦磷酸、偏亞磷酸、偏磷酸、 正磷酸等單磷酸類、單磷酸類之衍生物及鹽類;三聚磷酸、 四磷酸、六磷酸等縮合磷酸類、縮合磷酸類之衍生物及鹽 類· ··等。又,用以形成磷酸系化合物之鹽之鹼化合物, 可舉含有鋰、鈉、鉀、銨等之有機或無機鹼化合物。 刖述磷酸系化合物,宜使用於水中具有溶解性者。又, 該填酸系化合物若由可發揮優異之塗佈劑之貯藏安定性、 本紙張尺度適用中國國家標準(CNS) A4規格(210X297公釐) -20- 以4615 A7, 可 I. 啜 · In addition, in the state in which a titanium oxide sol is stored, a hydrolyzable titanium compound (T) and a hydrogen peroxide solution are mixed to obtain a titanium peroxide acid aqueous solution (A2). The titanium oxide film has improved residual resistance and the like, and the effect is ideal. The reason is presumably that in the preparation of the aqueous solution, the hydrolyzable titanium compound (T) will be adsorbed on the titanium oxide sol particles, and the adsorbed hydrolyzable titanium compound (T) will be condensed with the radicals generated on the surface of the particles. The reaction results in chemical binding, and the hydrolyzable titanium compound itself undergoes a condensation reaction and becomes polymerized. After mixing with a hydrogen peroxide solution, the obtained aqueous solution is stabilized and can be significantly prevented from being stored. Gelation or thickening occurs. The titanium oxide sol is one in which amorphous titanium oxide particles and anatase titanium oxide particles are dispersed in water. Among the titanium oxide sols, an aqueous solution of anatase-type titanium oxide is preferred in terms of surname resistance. The titanium oxide sol may contain an aqueous organic solvent such as an alcohol-based or alcohol-ether-based solvent, in addition to water. The titanium oxide sol may be a conventionally known one. For example, it is possible to use amorphous titanium oxide particles that have dispersed the aggregates in water, or this paper size applies the Chinese National Standard (CNS) A4 specification (210X297 cm) -15- 5. Description of the invention (l3) roasting The titanium oxide agglomerates to form an anatase-type titanium oxide particle and disperse it :: the medium. Amorphous titanium oxide is calcined at a temperature that is at least higher than the crystallization temperature of anatase, usually at a temperature of 2GG ° C or higher. The aforementioned oxidized agglomerates are exemplified by: ⑴ obtained by hydrolyzing blood organic compounds such as titanium sulfate and titanium sulfate, and ⑺ obtained by hydrolyzing organic titanium compounds such as titanium filaments, (3) Four gasification and other self-chemical titanium solution hydrolyzed or neutralized and so on. The commercially available products of titanium oxide sol are described, for example, "TKs_2〇i" (aqueous sol of anatase-type titanium oxide particles manufactured by TAYCA Corporation, trade name, average particle diameter of 6 nm); rTKS_2. 3 "(aqueous sol of anatase-type titanium oxide particles manufactured by Tayca Co., Ltd. with a trade name and an average particle diameter of 6 nm);" TA-15 "(manufactured by Jassan Chemical Co., Ltd., trade name, anatase type Aqueous sol of titanium oxide particles); rSTS-11 "(aqueous sol of anatase-type hafnium oxide particles, manufactured by Ishihara Industry Co., Ltd., trade name). When the hydrolyzable titanium compound (T) is mixed with a hydrogen peroxide solution, the amount of the titanium oxide sol used is usually 1% of that of the hydrolyzable titanium compound (T), which accounts for about 0.001 ~ 1 in terms of solid content. 10 parts by weight, ideally occupying a range of about 0.1 to 8 parts by weight. If the amount of the titanium oxide sol is less than 0.01 parts by weight, the effects of improving the storage stability of the coating agent and the corrosion resistance of the titanium oxide film obtained after adding the titanium oxide sol cannot be obtained; otherwise, it exceeds 10 Parts by weight make the coating agent poor in film forming properties, which are not ideal. The titanium-containing aqueous solution (A) can also be mixed with a hydrolyzable titanium compound (T) and a hydrogen peroxide solution in the state where a titanium oxide sol is stored as required. The paper size is applicable to Chinese national standard (WS) A4. Specifications (21〇χ297mm) -16- 1224615 A7 _____B7 V. Faxian Ming (14) ^ s The combined aqueous solution of peroxytitanic acid, which is then heated or hot-pressed at a temperature above 80〇Γ A dispersion of oxidized microparticles having an average particle diameter of 10 nmw is formed and then used. The appearance of the dispersion is usually translucent. When the temperature of the heat treatment or hot pressing treatment is lower than 801, the titanium oxide cannot be completely crystallized. The titanium oxide fine particles obtained by the aforementioned treatment have a particle diameter of not more than 10 nm, and are preferably in the range of 1 to 6 nm. If the particle diameter is larger than 10 nm, the film forming property is reduced, and cracks occur when the film thickness is larger than km, and the effect is not satisfactory. When the titanium-containing aqueous solution (A) is the aforementioned aqueous solution (A1), an amorphous titanium oxide film containing several warp groups is usually formed under the aforementioned dry conditions. This amorphous titanium oxide film has the advantage of having good gas barrier properties. In the case of a titanium-containing aqueous solution (A2), an anatase-type titanium oxide film containing several hydroxyl groups will usually be formed under the aforementioned dry conditions. The phosphoric acid-based compound (B) in the coating agent I of the present invention has the effect of improving the corrosion resistance of the obtained coating film. The compound (B) may include, for example, linoleic acid, polyphosphoric acid, triscale acid, hypophosphorous acid, low phosphoric acid, trimetaphosphoric acid, diphosphite, diphosphoric acid, pyrophosphite, pyrophosphoric acid, metaphosphite Derivatives and salts of monophosphates such as phosphoric acid, metaphosphoric acid, orthophosphoric acid, monoscale acids, etc .; Condensed phosphoric acids such as trimer acid, tetraphosphoric acid, hexaphosphate, and derivatives and salts of condensed phosphoric acid ... . These compounds can be used alone or in combination of two or more. Examples of the alkali compound used to form a phosphoric acid-based compound include organic or inorganic test compounds containing lithium, sodium, ammonium, and the like. This paper size applies to China National Standard (CNS) A4 specification (210X297 mm) -17- ------------------- 嘹: ...——...:-Order .. ......... 啜 (Please read the precautions on the back before filling in this page) 1224615 A7 _______ B7 V. Description of the Invention (I5) osmic acid compounds (B) should be used for those who have solubility in water. If the phosphoric acid-based compound (B) exhibits effects such as excellent storage qualitative properties of the coating agent and corrosion resistance of the coating film, sodium pyrophosphate, sodium tripolyphosphate, sodium tetraphosphate, and The use of phosphoric acid, ammonium metaphosphate and sodium hexametaphosphate is particularly desirable. The content ratio of the titanium-containing aqueous solution (A) and the phosphoric acid-based compound (B) is 100 parts by weight relative to the solid content of the former, and the latter preferably accounts for about 1 to 400 parts by weight. If the component (B) is less than 1 part by weight, the corrosion resistance will be reduced. On the other hand, if the component (B) exceeds 400 parts by weight, the film-forming properties will be poor, and the corrosion resistance will be reduced. The phosphoric acid-based compound (B) has a more preferable content ratio, which is about 10 to 200 parts by weight based on 100 parts by weight of the titanium-containing aqueous solution (A). The coating agent J for forming a titanium oxide film of the present invention is produced by mixing a titanium-containing aqueous solution (A) and a phosphoric acid-based compound (B) according to a common method. In the coating agent of the present invention, the phosphoric acid-based compound (B) has an acidic phosphate ion capable of binding to the compound (B) and a titanium ion to form a complex structure between the two. Such a complex structure can be easily formed only by mixing two components. For example, it can be formed by leaving it at room temperature (2 (rc) for about 5 minutes to 1 hour.) When the mixture is heated, for example, It is about 30 ~ 70. (: The complex structure is formed by heating for about 1 ~ 30 minutes. The coating agent I used to form the titanium oxide film of the present invention is a kind of water-based composition which is stable in the neutral or acidic field. The pH of the liquid is generally in the range of 丨 ~ ?. Especially in the acidic field, it has good storage stability and is preferably in the range of ρΗι ~ 5. The coating agent j of the present invention may also contain such as 曱The standard of this paper applies to the Zhongguanjia standard ⑽) A4 size ⑵QX297 public Chu) ------------------ Order --------------- (Please read the notes on the back before filling this page) -18- 1224615 κι ___ B7 V. Description of the invention (16) Alcohol, ethanol, isopropanol, ethylene glycol, propylene glycol and other hydrophilic solvents. The coating agent I of the present invention may be used after being diluted with water or a hydrophilic solvent, if necessary. The coating agent for forming a titanium oxide film according to the present invention may contain titanium halide, titanium halide salt, hafnium halide, hafnium halide salt, silicon halide, silicon halide salt as required. At least one kind of halide is selected from the group to further improve the corrosion resistance of the obtained coating film. The halogen used to form the phantom is exemplified by fluorine, gas, iodine, and the like. From the standpoint of excellent storage stability of the coating agent, corrosion resistance of the coating film, and moisture resistance, fluorine is particularly suitable as the tooth element. Examples of the salts used to form the compounds include sodium, potassium, lithium, and ammonium. For salt formation, potassium and sodium are preferred. The foregoing halides are preferably titanium compounds such as titanium hydrofluoric acid; titanium iide salts such as potassium potassium fluoride and titanium ammonium fluoride; zirconium dental compounds such as hydrofluoric acid; ammonium fluoride and potassium zirconium fluoride, etc. Zirconium dentate salts; Silicon fluoride and other silicon dentate salts; Silicon fluoride and other silicon dentate salts ... In the coating agent I of the present invention, the content ratio when the aforementioned halide is contained is usually 100 parts by weight with respect to the solid content of the titanium-containing aqueous solution (A), accounting for about 1 to 400 parts by weight, and 10 to 200 parts by weight. It is particularly preferable to be in a range of parts by weight. The coating agent I of the present invention may further include a basic neutralizing agent such as ammonia, an organic basic compound, an alkali metal hydroxide, or an alkaline earth metal hydroxide, if necessary. The aforementioned organic basic compounds are preferably ethanolamine and triethylamine, and the aforementioned alkali metal hydroxides are preferably lithium hydroxide, sodium hydroxide, and hydrogen. The paper size is applicable to the Chinese National Standard (QJS) A4 specification (21 × 297). %) —F… (Please read the notes on the back before filling this page),? -19- A7 ----------- B7 V. Description of the invention (17) " --- Potassium oxide Wait. (Please read the precautions on the reverse side before filling out this page) The coating agent 1 of the present invention may contain various additives as necessary. Examples of such additives include thickeners, antibacterial agents, rust inhibitors, titanium oxide sols, titanium oxide pigments, rust inhibitor pigments, coloring pigments, and surfactants. Examples of the rust inhibitor include tannic acid, phytic acid, benzotriazol, and the like. The aforementioned physical pigments include mica, talc, stone spar, barium sulfate, clay, and the like. The coating agent π for forming a titanium oxide film according to the present invention is an aqueous organic compound containing the aforementioned aqueous solution (A), a phosphoric acid-based compound, and / or a titanium compound (B) and (C). Aqueous coating agent for molecular compounds. The titanium-containing aqueous solution (A) in the coating agent π of the present invention is appropriately selected from the rhenium-containing aqueous solution in the coating agent I of the present invention and the same. In the coating agent Π of the present invention, at least one compound selected from the group consisting of a phosphoric acid-based compound, a titanium compound, a titanium compound, a hammer compound, a #halide salt, a silicide, and a silicon compound salt (B,) are those which can improve the remaining resistance of the coating film. Examples of the phosphoric acid-based compound in the compound (B,) include phosphorous acid, polyphosphoric acid, triphosphoric acid, hypophosphorous acid, low phosphoric acid, trimetaphosphoric acid, diphosphite, diphosphoric acid, pyrophosphite, pyrophosphoric acid, and metaphosphoric acid. Monophosphoric acid such as phosphorous acid, metaphosphoric acid, orthophosphoric acid, derivatives and salts of monophosphoric acid; Condensed phosphoric acid such as tripolyphosphoric acid, tetraphosphoric acid, hexaphosphoric acid, and derivatives and salts of condensed phosphoric acid ... . Examples of the alkali compound used to form a salt of a phosphoric acid-based compound include organic or inorganic alkali compounds containing lithium, sodium, potassium, ammonium, and the like. The phosphoric acid-based compound described above is preferably used for those having solubility in water. In addition, if the acid-filling compound exhibits excellent storage stability of the coating agent, the Chinese paper standard (CNS) A4 specification (210X297 mm) applies to this paper size -20- to 4615 A7
製得塗膜之耐蝕性等之效果而言,則以焦磷酸鈉、三聚磷 (請先閲讀背面之注意事項再填寫本頁) 酸鈉、四磷酸鈉、偏磷酸、偏磷酸銨、六偏磷酸鈉等之使 用特別理想。 前述化合物(B’)中,用以構成鈦_化物、鈦_化物 鹽、锆_化物、鍅鹵化物鹽、矽_化物、矽鹵化物鹽之鹵 素,可舉氟、氣、碘等為例。而由具優異塗佈劑之貯藏安 疋性、塗膜之耐蝕性、耐濕性等性能之觀點言之,則以敦 特別適於作為_素。又,用以形成齒化物之鹽者,舉例言 之有鈉、鉀、鋰、銨等。而用以形成鹽者,則以鉀、鈉較 為理想。 #· 則述||化物,宜使用如鈦氫氟酸等鈦鹵化物;鈦氟化 鉀、鈦氟化銨等鈦_化物鹽;鍅氫氟酸等锆齒化物;锆氟 化銨、錯氟化鉀等鍅_化物鹽;矽氫氟酸等矽鹵化物;矽 氟化鈉、矽氟化銨、矽氟化鉀等矽齒化物鹽· ·等。 本發明之用以形成氧化鈦膜之塗佈劑π中,含鈦水成 液(A)與碟酸系化合物、鈦_化物等至少一種(β,), 係於兩者間形成錯合物構造。如此之錯合物構造僅藉由混 口兩成分即可輕易形成,舉例言之,以常溫(2〇艽)放置 約5刀釦〜1小時即可形成。又,加熱該混合物時,舉例言 之,以大約30〜7〇°C加熱約1〜30分鐘即形成錯合物構造。 本發明塗佈劑Π中含鈦水成液(A )及化合物(b,) 之含有比例,係相對於前者之固體成分丨〇〇重量份,後者佔 約1〜400重量份,又以在1〇〜2〇〇重量份之範圍内特別理 想0 本紙張尺度適用巾關豕標準(挪)A4規格⑵QX297公楚) -21- 似 4615 五、發明說明(l9 ▲本發明之用以形成氧化敛膜之塗佈劑n中之水性有機 向分子化合物(C),若為pH在7以下,曰认u 1 丑 P牡/ M下,且於水中溶解或分 政時呈安定狀態而不產生凝聚、增稠、凝膠化等情形者, 即不加以限定,並可使用公知者。 水性有機高分子化合物(c),係可使用具有水溶液、 水分散液或乳液之形態者。而用以使有機高分子化合物於 水中溶化、分散化或乳化之方法,則可以公知之方法進行。 水性有機高分子化合物(c)之具體實例,舉例言之, 可使用含有可單獨溶化或水分散化之官能基(如羥基°、羧 基、胺基、亞胺基、硫離子基、膦基等至少丨種)者,及業 已使該化合物所具之部分或全部官能基中和者等。此時: 中和’若水性有機高分子化合物(c)為含㈣之樹脂等 酸性樹脂,乃以乙醇胺、三乙胺等胺化合物;氨水;氫氧 化鋰、氫氧化鈉、氫氧化鉀等鹼金屬氫氧化物等進行中和, 又若為含胺基之樹脂等鹼性樹脂,則以乙酸、乳酸等脂肪 SiL,峨酸等礦酸等進行中和。 如此之水性有機高分子化合物(C),舉例言之有: %氧系樹脂、酚系樹脂、丙烯酸系樹脂、胺甲酸乙酯系樹 月曰、聚乙烯醇系樹脂、含聚氧化烯鍵樹脂、烯聚合性不飽 和羧酸共聚物系樹脂、耐綸系樹脂、聚甘油、羧甲基纖維 素、羥甲基纖維素、羥乙基纖維素·· ·等。 則述水性有機高分子化合物(C )中,較理想者有環 氧系树脂、紛系樹脂、丙烯酸系樹脂、胺甲酸乙酯系樹脂、 聚乙婦醇系樹脂、含聚氧化烯鍵樹脂、烯聚合性不飽和羧 本紙張尺度適用中國國家標準(CNS) A4規格(210χ297公楚) (請先閲讀背面之注意事項再填寫本頁) 、可| -22- 1224615 五、發明説明(2〇 酸共聚物系樹脂等。 ί 〇又’JT利用親水性高者作為水性有機高分子化合物 (态)之塗佈劑,則可形成-耐㈣與親水性兼備之塗膜’ 且=作為ms合金製葉片之親水化處理劑。 前述環氧系樹脂,係可使用於環氧樹脂中附加胺而組 成之陽離子系環氧樹脂;及丙埽基改質環氧樹脂、胺甲酸 乙醋改質環氧樹脂等„環氧樹脂等。前述陽離子系環氧 樹腊,舉例言之有:環氧化合物與W單胺或聚胺、2級單 胺或聚胺、1,2級混合聚胺等之加成物(參照美國專利第 3984299唬說明書),環氧化合物與具有業經酮亞胺化之工 級胺基的2級單胺或聚胺之加成物(參照美國專利第 4017438號說明書);環氧化合物與具有業經酮亞胺化之i 級胺基的經化合物之醚化反應生成物(參照日本特許公開 公報特開昭59—43013號)等。 前述環氧化合物,係以數量平均分子量在400〜4〇〇〇, 特別是在8 00〜2000之範圍内,且環氧當量在19〇〜2〇〇〇, 特別是在400〜1000之範圍内者為佳。此般環氧化合物,舉 例言之,可藉多紛化合物與表氣醇之反應而得。該多盼化 合物,係可舉例如:雙(4-羥苯基)-2,2-丙烷、4,4-二羥 二苯基酮、雙(4-羥苯基)-1,1-乙烷、雙(4-羥苯基) 異丁烷、雙(4-羥-第三丁基苯基)-2,2-丙烷、雙(2-羥萘 基)甲烷、1,5-二羥萘、雙(2,4_二羥苯基)曱烷、四(4_ 羥苯基)·1,1,2,2-乙烷、4,4-二羥二苯颯、苯酚酚醛樹脂、 曱苯酚酚醛樹脂等。 本紙張尺度適用中國國家標準(CNS) Α4規格U10X297公釐) 頁 訂 脅 -23- 丄以4615 A7 --~-—— _ β7_ 五、發明説明(21 ) 一 々則述酚系樹脂,係可加以使用一將高分子化合物經水 /合化者,而該高分子化合物係令酚成分與甲醚類於反應催 化劑存在下加熱而使其加成、縮合後所得者。而作為起始 原料之前述酚成分,則可使用2官能性酚化合物、3官能性 酚化合物、4官能性以上之酚化合物等。2官能性酚化合物 係可舉鄰甲苯酚、對甲苯酚、對第三丁苯酚、對乙苯酚、 2,夂茬酚、2,5-茬酚等為例,3官能性酚化合物係可舉酚、 間甲苯酚、間乙苯酚、3,5_茬酚、間曱氧苯酚等為例,而4 官能性酚化合物則可舉雙酚Α、雙酚F等為例。該等酚化合 物係可使用其中1種或混合2種以上而使用。 前述丙烯酸系樹脂,係可舉具羧基、胺基、羥基等親 水性基之單體之單獨聚合物或共聚物,及具親水性基之單 體與其他可共聚之單體之共聚物等為例。該等樹脂係行乳 化聚合、懸浮聚合或溶液聚合,及視需要再經中和、水性 化而得者。又,亦可應需要將所得樹脂再加以改質。 前述含羧基單體,係可舉丙烯酸、曱基丙烯酸、順丁 烯二酸、順丁烯二酐、巴豆酸、分解烏頭酸等為例。 作為含氮單體者,舉例言之,有:N,N-二甲胺乙基(間) 丙烯酸酯、N,N-二乙胺乙基(間)丙烯酸酯、N-第三丁基 胺乙基(間)丙稀酸酯等含氮烧基(間)丙烯酸酯;丙稀 醯胺、甲基丙晞醢胺、N_甲基(間)丙稀醯胺、N-乙基(間) 丙烯醯胺、N-羥曱基(間)丙烯醯胺、N-曱氧曱基(間) 丙烯醯胺、N-丁氧曱基(間)丙烯醯胺、N,N-二甲基(間) 丙烯醯胺、N,N-二曱胺丙基(間)丙烯醯胺、n,N-二曱胺 本紙張尺度適用中國國家標準(CNS) A4規格(210X297公釐) ' f (請先閱讀背面之注意事項再填寫本頁) 、τ· A7 -------B7 五、發明説明(22 ) 乙基(間)丙烯醯胺等聚合性醯胺基類;2_乙烯咄啶、卜 乙烯基2-吼口各咬g同、4_乙烯口比口定等芳香族含氮單體;及, 丙烯胺·· ·等。 作為含羥基單體者,舉例言之,有:2_羥乙基(間) 丙烯s文s曰、羥丙基(間)丙烯酸酯、2,3_羥丁基(間)丙 烯馱S曰、4-羥丁基(間)丙烯酸酯及聚乙二醇單(間)丙 烯酸酯等多元醇與丙烯酸或甲基丙烯酸之單酯化物;及, 業已於前述多元醇與丙烯酸或甲基丙烯酸之單酯化物中使 ε-己内酯開環聚合之化合物·· ·等。 其他可共聚之單體,則可舉例如:甲基(間)丙烯酸 酯、乙基(間)丙烯酸酯、正丙基(間)丙烯酸酯、異丙 基(間)丙烯酸酯、正丁基(間)丙烯酸酯、異丁基(間) 丙烯酸酯、第二丁基(間)丙烯酸酯、2_乙基己基(間) 丙烯酸酯、正辛基(間)丙烯酸酯、月桂基(間)丙烯酸 酯、十三烷基(間)丙烯酸酯、十八基(間)丙烯酸酯、 異硬脂基(間)丙烯酸酯等碳原子數SJ〜24之烷基(間) 丙烯酸酯;及,苯乙烯、乙酸乙烯酯等。該等化合物係可 藉1種而使用,或組合2種以上再加以使用。 另,本說明書中,「(間)丙烯酸酯」係意指丙烯酸 酉旨或間丙稀酸酯。 刖述胺甲酸乙酯系樹脂,係可使用將由聚酯多元醇、 多醚多元醇等多元醇與二異氰酸鹽製得之聚胺甲酸酯樹 脂,依需要於存有如二醇、二胺等具2個以上活性氫之低分 子量化合物之增鏈劑之狀態下使其鏈延長,並使之於水中 本紙張尺度適用中國國家標準(CNS) A4規格(210X297公楚) (請先閲讀背面之注意事項再填寫本頁) 、訂— 囔· -25- 1224615 A7 B7 五、發明説明(23 ) 穩定分散或溶解者。如此之胺曱酸乙酯系樹脂,可廣泛使 用如日本特許公告特公昭42—24192號、特公昭42 —24194 號、特公昭42 — 5118號、特公昭49— 986號、特公昭49 — 33 104號、特公昭50 — 15027號、特公昭53 —29175號等所載 之公知者。 使聚胺甲酸酯樹脂於水中穩定分散或溶解之方法,可 利用如下方法。 (1) 藉由在聚胺甲酸酯樹脂之支鏈或末端導入胺基、叛 基等離子性基而賦予親水性,再藉自乳化而於水中分散或 溶解。 (2) 將反應完成後之聚胺甲酸g旨樹脂、或以封阻劑封阻 末端異氰酸基之聚胺曱酸酯樹脂,利用乳化劑與機械剪力 強制於水中分散。該封阻劑係可舉肟、乙醇、酚、硫醇、 胺、亞硫酸氫鈉等為例。 (3) 將具末端異氰酸基之聚胺甲酸酯樹脂與水、乳化劑 及增鏈劑混合,並利用機械剪力同時進行分散化與高分子 量化。 (4) 將使用如聚乙二醇之水溶性多元醇作為聚胺甲酸 酯樹脂之原料多元醇而製得之聚胺甲酸酯樹脂,於水中分 散或溶解。 藉由前述聚胺甲酸酯樹脂之分散或溶解方法而得之水 性樹脂’係可單獨使用或混合二種以上再加以使用。 可用於前述聚胺曱酸酯系樹脂之合成上之二異氰酸 鹽,有芳香族、脂環族及脂肪族之二異氰酸鹽。具體而言, 本紙張尺度翻中國國家標準(CNS) A4規格(210X297公釐) (請先閲讀背面之注意事項再填寫本頁) 訂— 囔· -26- I224615 A7 B7 五、發明說明(24 可舉例如:六亞甲基二異氰酸鹽、四亞甲基二異氰酸鹽、 3’3 -二甲氧基_4,4匕聯苯二異氰酸鹽、對苯二甲基二異氰酸 鹽、間苯二甲基二異氰酸鹽、13-(二異氰酸甲酯)環己 _、1,4-(二異氰酸甲酯)環己酮、4,4’-二異氰酸環己酮、 4,4、亞甲基雙(環己基異氰酸鹽)、異佛爾酮二異氰酸鹽、 2,4-甲伸苯基二異氰酸鹽、2,6-甲伸苯基二異氰酸鹽、對伸 本基一異氰酸鹽、二苯甲烧二異氰酸鹽、間伸苯基二異氰 酸鹽、2,4-萘二異氰酸鹽、3,3,-二甲基_4,4、聯苯二異氰酸 ^ 4,4_聯本^一異乱酸鹽· ··等。其中又以24-甲伸苯 基二異氰酸鹽、2,6-甲伸苯基二異氰酸鹽、六亞甲基二異 氰酸鹽、異佛爾酮二異氰酸鹽特別理想。 前述聚胺甲酸酯系樹脂之市售品,可舉例有:「海得 蘭《音# · /、彳卜7 y》HW_330」、「海得蘭HW-340」、 海得蘭HW-350」(皆為大曰本INK化學工業(株)製、商 品名)、「SUPERFLEX100」、「SUPERFLEX150」、 「SUPERFLEXF-3438D」(皆為第一工業製藥(株)製、商 品名)等。 前述聚乙烯醇系樹脂,宜為皂化度在87%以上之聚乙 婦醇,又以皂化度在98%以上,即所謂之完全皂化聚乙烯 醇特別理想。又,數量平均分子量宜於3〇〇〇〜1〇〇〇〇〇之範 圍内。 前述含聚氧化烯鏈樹脂,可適當使用具有聚氧乙歸鏈 或聚氧丙烯鏈者,舉例言之,有:聚乙二醇、聚丙二醇、 聚氧乙烯鏈與聚氧丙烯鏈結合成塊狀後之成塊聚氧化歸二 本紙張尺度適财關緖準(_ A视格⑽χ297公變) ---------------嚓…:,……——、玎---------------------嘬 (請先閲讀背面之注意事項再填寫本頁) -27- 丄厶厶HO丄:) A7 '^—---- B7 五、發明説明(2τγ -—--〜 醇等。 、則述缔聚合性不飽和㈣共聚物系樹脂,彳善加利用 ;婦6埽等烯烴與(間)丙烯酸、順丁烯二酸等聚合 2不飽和羧酸之共聚物,及該共聚物之水分散液中加入聚 合性不飽和化合物而使其進行乳化聚合,進而於粒子内交 聯而形成之2種樹脂中選出之至少1種水分散性樹脂或水溶 性樹脂。 别述烯烴與聚合性不飽和羧酸之共聚物,係一種以上 之稀烴與一種以上之聚合性不飽和羧酸之共聚物。該共聚 物中,單體含量為前述不合羧酸佔3〜60重量%,理想者於 4〇重里%之範圍内。並藉由以驗性物質中和該共聚物中 之酸基而可於水中分散。 於前述共聚物之水分散液中加入聚合性不飽和化合物 而使其乳化聚合,進而於粒子内交聯而形成之交聯樹脂中 之该聚合性不飽和化合物,可舉前述水分散性或水溶性之 丙烯酸系樹脂之說明中所列舉之乙烯型單體類等為例,並 可適當選擇1種或2種以上進行使用。 水性有機高分子化合物(C )之含有比例,係相對於 含鈦水成液(A )之固體成分100重量份佔約1〇〜2〇〇〇重量 份,而由塗佈劑之安定性、所得氧化鈦膜之耐蝕性等觀點 而言,則以在100〜1000重量份之範圍内特別理想。 本發明之用以形成氧化鈦膜之塗佈劑Π,係可藉一般 方法混合各必須成分而調製。本發明之塗佈劑Π乃一種於 中性或酸性領域中呈安定狀態之水成液,且其pH通常於1 本紙張尺度適用中國國家標準(CNS) A4規格(210X297公董) ......--------------—訂—......... (請先閲讀背面之注意事項再填寫本頁) -28- 五、發明説明(26 ) 〜7之範圍内。特別是’於酸性領域中貯藏安定性佳,並宜 5之圍内。本發明之塗佈劑Π亦可視需要而含有 如f醇、乙醇、異丙醇、乙二醇、丙二醇等親水性溶劑。 本發明之塗_11並可視需要㈣水或親水性溶劑 再使用。 、本發月之塗佈劑][[中,可視需要進而含有氨、有機驗 式化口物鹼金屬氫氧化物、鹼土類金屬氫氧化物等鹼式 中合劑。該有機驗式化合物係可舉乙醇胺、三乙胺為例, 而驗金屬氫氧化物則可舉氫氧化M、氫氧化鈉、氫氧化卸 等為例。 本發明之塗佈劑I[中,亦可視需要再含有各種添加 物。該添加物可舉增稠劑、防菌劑、防銹劑、氧化鈦溶膠、 氧化鈦粉末、體質顏料、防銹顏料、著色顏料、界面活性 劑等為例。前述防銹劑有單寧酸、植酸、苯并三氮唑等。 刖述體質顏料則有雲母、滑石、石夕石、硫酸鋇、黏土等。 本發明之用以形成氧化鈦膜之塗佈劑][及π係具有優 異之貯藏安定性。又,該塗佈劑可於金屬基材上形成一耐 蝕性、黏附性、加工性等倶佳之含氧化鈦之塗膜。 惠....化飲膜形成方法及被覆有氧化鈦膜之金眉某姑 本發明之氧化鈦膜形成方法,係藉由將前述本發明之 塗佈劑I或Π塗布於金屬基材上並加以乾燥而進行。藉此, 即製得被覆有氧化鈦膜之金屬基材。該被覆金屬基材則可 直接作為防銹被覆金屬基材而使用。 本發明之氧化鈦膜形成方法所適用之金屬基材,只要 本紙張尺度適用中國國家標準(CNS) Α4規格(210X297公釐) -29- 1224615 A7 B7 五、發明説明(27 疋至少表面為金屬之基材,即無特別限制。舉例言之,如 表面為鐵、鋁、鋅、銅、錫及含其等中之任一金屬之合金 的基材。特別以使用鋼板基材及鋁或鋁合金基材為宜。 前述鋼板基材,可使用如熱浸鍍鋅鋼板、電鍍鋅鋼板、 鐵-鋅合金鍍敷鋼板、鎳-鋅合金鍍敷鋼板、鋁-鋅合金鍍敷 鋼板等。又,鋁-鋅合金鍍敷鋼板可使用市售名為「佳爾巴 力姆《音譯:twq夕入》」、Γ佳爾方《音譯:方儿 7 7〆》」之商品。此外,鋼板基材亦可使用施有鉻酸鹽 處理、磷酸鋅處理、複合氧化膜處理等轉化處理之鋅系鍍 敷鋼板。進而,鋼板基材若為重疊鋼板者亦無妨。 又’前述鋁或鋁合金基材並無特別限定,但可舉熱交 換裔用之葉片作為代表例。作為該基材之熱交換器用葉 片,可為組裝於熱交換器上之前之構件,亦可為呈裝設於 熱父換器上之狀態者,凡公知者皆可使用。 舉 公 (請先閲讀背面之注意事項再填寫本頁) .訂丨 將本發明之塗佈劑I或Π塗布於金屬基材上之方法, _囔| 例吕之,可藉由浸塗、淋塗、喷塗、輥塗、電沉積法等 知方法進行塗裝。塗佈劑之乾燥條件,通常宜於素材到達 最南/m度約達6 0〜2 5 0 C之加熱條件下使其進行2秒至約3 〇 分鐘之乾燥。 又,塗佈劑之乾燥塗膜膜厚,通常為〇〇〇1μιη〜1〇μιη 左右,而以0·1μηι〜3μιη特別理想。若未達〇 〇〇1μιη,則耐 敍f生耐水性專性能低劣,反之若超過1 〇μηι,則使塗膜破 裂且耐蝕性降低,效果不盡理想。 如此藉由本發明之氧化鈦膜形成方法,則可於金屬For the effect of obtaining the corrosion resistance of the coating film, sodium pyrophosphate and tripolyphosphate (please read the precautions on the back before filling this page) sodium, sodium tetraphosphate, metaphosphoric acid, ammonium metaphosphate, six The use of sodium metaphosphate is particularly desirable. Among the aforementioned compounds (B '), the halogens used to form the titanium halide, titanium halide salt, zirconium halide, hafnium halide salt, silicon halide, silicon halide salt, and examples thereof include fluorine, gas, and iodine. . From the viewpoint of excellent storage stability of coating agent, corrosion resistance of coating film, moisture resistance, etc., it is particularly suitable as a pigment. Examples of the salt used to form the dentate include sodium, potassium, lithium, and ammonium. For salt formation, potassium and sodium are preferred. # · 述 述 || Compounds, titanium halides such as titanium hydrofluoric acid should be used; titanium halides such as potassium fluoride and titanium ammonium fluoride; zirconium dentates such as hafnium hydrofluoric acid; zirconium ammonium fluoride Samarium compound salts such as potassium fluoride; Silicon halide compounds such as hydrofluoric acid; Silicon fluoride compounds such as sodium fluoride, ammonium silicon fluoride, and potassium silicon fluoride. In the coating agent π for forming a titanium oxide film according to the present invention, the titanium-containing aqueous solution (A) and at least one (β,) such as a discic acid-based compound and a titanium compound form a complex between the two. structure. Such a complex structure can be easily formed only by mixing the two components. For example, it can be formed by leaving it at about 5 knives for 1 hour at room temperature (20 ° F). When the mixture is heated, for example, a complex structure is formed by heating at about 30 to 70 ° C for about 1 to 30 minutes. The content ratio of the titanium-containing aqueous solution (A) and the compound (b,) in the coating agent Π of the present invention is relative to the solid content of the former, and the latter accounts for about 1 to 400 parts by weight. The range of 1 ~ 200 parts by weight is particularly ideal. 0 This paper size is suitable for towel standard (Norway) A4 specification (QX297). -21- Like 4615 V. Description of the invention (l9 ▲ This invention is used to form oxidation The water-soluble organic molecular compound (C) in the coating agent n of the convergence film, if the pH is below 7, it is recognized as U 1 / P / M, and it is stable when dissolved in water or divided. Those in the case of agglomeration, thickening, gelation, etc. are not limited, and known ones can be used. The aqueous organic polymer compound (c) can be used in the form of an aqueous solution, an aqueous dispersion, or an emulsion. The method of dissolving, dispersing or emulsifying the organic polymer compound in water can be performed by a known method. Specific examples of the water-based organic polymer compound (c) include, for example, those which can be separately dissolved or water-dispersible. Functional groups (such as hydroxyl °, At least one of the following: an amino group, an amine group, an imine group, a sulfide group, a phosphine group, etc.), and those that have neutralized some or all of the functional groups of the compound. The molecular compound (c) is an acidic resin such as a resin containing rhenium, and is neutralized with amine compounds such as ethanolamine and triethylamine; ammonia water; alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; If it is a basic resin such as an amine group-containing resin, it is neutralized with fatty SiL such as acetic acid and lactic acid, mineral acid such as eelic acid, etc. The aqueous organic polymer compound (C) includes, for example,% oxygen system Resin, phenol-based resin, acrylic resin, urethane-based resin, polyvinyl alcohol-based resin, polyoxyalkylene bond-containing resin, olefin polymerizable unsaturated carboxylic acid copolymer-based resin, nylon-based resin, polymer Glycerin, carboxymethyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, etc .. Among the above-mentioned water-based organic polymer compounds (C), epoxy resins, resins, and acrylic resins are preferred. Resin, urethane resin, poly Women's alcohol-based resins, polyoxyalkylene bond-containing resins, and ethylenically polymerizable unsaturated carboxyl paper standards are applicable to Chinese National Standard (CNS) A4 specifications (210 x 297). (Please read the precautions on the back before filling this page). -22- 1224615 V. Description of the invention (20 acid copolymer resins, etc.) ′ 〇 'JT uses the hydrophilic one as the coating agent for the water-based organic polymer compound (state). A coating film with both hydrophilicity 'and = as a hydrophilizing treatment agent for ms alloy blades. The aforementioned epoxy resin is a cationic epoxy resin that can be used to add an amine to an epoxy resin; Epoxy resin, epoxy urethane modified epoxy resin, etc. „Epoxy resin, etc. The aforementioned cationic epoxy waxes include, for example, epoxy compounds and W monoamines or polyamines, secondary monoamines or Addition of polyamine, grade 1-2 mixed polyamine (refer to US Patent No. 3984299), addition of epoxy compound and grade 2 monoamine or polyamine with ketimated industrial grade amine group Finished product (refer to US Pat. No. 4,017,438) An epoxy compound by etherification with the compound already having a ketiminized amino group of the i-th stage reaction product (refer to Japanese Patent Publication Laid-Open Publication No. Sho 59-43013) and the like. The aforementioned epoxy compound has a number average molecular weight in the range of 400 to 4,000, especially in the range of 800 to 2000, and an epoxy equivalent in the range of 190 to 2000, especially in the range of 400 to 1,000. The insider is better. Such an epoxy compound, for example, can be obtained by the reaction of various compounds with epigasol. Examples of the dopant compound include bis (4-hydroxyphenyl) -2,2-propane, 4,4-dihydroxydiphenyl ketone, and bis (4-hydroxyphenyl) -1,1-ethyl Alkane, bis (4-hydroxyphenyl) isobutane, bis (4-hydroxy-third butylphenyl) -2,2-propane, bis (2-hydroxynaphthyl) methane, 1,5-dihydroxy Naphthalene, bis (2,4-dihydroxyphenyl) pinene, tetrakis (4-hydroxyphenyl) · 1,2,2-ethane, 4,4-dihydroxydiphenylhydrazone, phenol novolac resin, fluorene Phenol novolac resin, etc. This paper size applies to Chinese National Standard (CNS) A4 specification U10X297 mm) Page order -23- 丄 4615 A7-~ -—— _ β7_ V. Description of the invention (21) A description of phenol resins A polymer obtained by subjecting a polymer compound to water / combination is used, and the polymer compound is obtained by heating and adding and condensing a phenol component and methyl ether in the presence of a reaction catalyst. As the aforementioned phenol component as a starting material, a bifunctional phenol compound, a trifunctional phenol compound, a tetrafunctional or higher phenol compound, or the like can be used. Examples of the 2-functional phenol compound system include o-cresol, p-cresol, p-tertiary butylphenol, p-ethylphenol, 2, stubble phenol, and 2,5-stub phenol. Phenol, m-cresol, m-ethylphenol, 3,5-phenol, m-oxyphenol and the like are exemplified, and bisphenol A and bisphenol F are exemplified as the 4-functional phenol compound. These phenol compounds can be used singly or in combination of two or more kinds. The aforementioned acrylic resin may be a single polymer or copolymer of a monomer having a hydrophilic group such as a carboxyl group, an amine group, or a hydroxyl group, and a copolymer of a monomer having a hydrophilic group and other copolymerizable monomers. example. These resins are obtained by emulsion polymerization, suspension polymerization or solution polymerization, and if necessary, neutralization and water-based polymerization. In addition, the obtained resin may be further modified if necessary. Examples of the carboxyl group-containing monomer include acrylic acid, fluorenyl acrylic acid, maleic acid, maleic anhydride, crotonic acid, and decomposed aconitic acid. Examples of the nitrogen-containing monomer include: N, N-dimethylaminoethyl (m) acrylate, N, N-diethylamineethyl (m) acrylate, and N-third butylamine Ethyl (m-) acrylic acid esters and other nitrogen-containing alkyl (m-) acrylates; propylammonium, methacrylamine, N_methyl (m-acryl), N-ethyl (m-) ) Acrylamide, N-Hydroxyfluorenyl (m-acrylamide), N-Phenoxyfluorenyl (m-acrylamide), N-Butoxyfluorenyl (m-) acrylamide, N, N-dimethyl (Intermediate) Acrylamide, N, N-Diamidinopropyl (m) Acrylamide, n, N-Diamidine This paper is sized to the Chinese National Standard (CNS) A4 (210X297 mm) 'f ( Please read the precautions on the back before filling this page), τ · A7 ------- B7 V. Description of the invention (22) Ethyl (m-) acrylamide and other polymerizable amidine groups; 2_ethylene Aromatic nitrogen-containing monomers, such as pyridine, 2-vinyl, and 2-vinyl, respectively; and, acrylamine, etc. As examples of the hydroxyl-containing monomer, there are: 2-hydroxyethyl (m) propylene, hydroxypropyl (m) acrylate, 2,3_hydroxybutyl (m) propylene, S , Monoesters of polyhydric alcohols such as 4-hydroxybutyl (m) acrylate and polyethylene glycol mono (m) acrylate, and acrylic acid or methacrylic acid; and Among the monoesters, compounds that cause ε-caprolactone to undergo ring-opening polymerization ... For other copolymerizable monomers, for example: methyl (m-) acrylate, ethyl (m-) acrylate, n-propyl (m-) acrylate, isopropyl (m-) acrylate, n-butyl ( M) acrylate, isobutyl (m) acrylate, second butyl (m) acrylate, 2-ethylhexyl (m) acrylate, n-octyl (m) acrylate, lauryl (m) acrylate Esters, tridecyl (m) acrylates, octadecyl (m) acrylates, isostearyl (m) acrylates and other alkyl (m) acrylates having a carbon number of SJ to 24; and, styrene , Vinyl acetate and so on. These compounds may be used singly or in combination of two or more kinds. In this specification, "(m) acrylic acid ester" means acrylic acid or m-acrylic acid. The urethane resin is described as a polyurethane resin made from a polyol such as polyester polyol, polyether polyol, and diisocyanate. Chain extension of low molecular weight compounds with more than 2 active hydrogen, such as amines, to extend the chain and make it in water. This paper applies Chinese National Standard (CNS) A4 (210X297). (Please read first Note on the back, please fill out this page again), order — 囔 · -25- 1224615 A7 B7 V. Description of the invention (23) Stable dispersion or dissolution. Such amine ethyl acetate-based resins can be widely used, for example, Japanese Patent Publications No. 42-24192, No. 42-24194, No. 42-5118, No. 49-986, No. 49-33 No. 104, No. 50-5015027, No. 53-29175, etc. As a method for stably dispersing or dissolving the polyurethane resin in water, the following method can be used. (1) Hydrophilicity is imparted by introducing an ionic group such as an amine group or a tertiary group into the branch or end of a polyurethane resin to impart hydrophilicity, and then it is dispersed or dissolved in water by self-emulsification. (2) The polyurethane g resin after completion of the reaction, or a polyurethane resin with terminal isocyanate blocked by a blocking agent, is forcibly dispersed in water using an emulsifier and mechanical shear force. Examples of the blocking agent include oxime, ethanol, phenol, thiol, amine, and sodium bisulfite. (3) A polyurethane resin with a terminal isocyanate group is mixed with water, an emulsifier, and a chain extender, and mechanical dispersion is used to simultaneously disperse and quantify the polymer. (4) A polyurethane resin prepared by using a water-soluble polyol such as polyethylene glycol as a raw material polyol of a polyurethane resin, dispersed or dissolved in water. The water-based resin 'obtained by the method of dispersing or dissolving the aforementioned polyurethane resin can be used alone or in combination of two or more kinds. Diisocyanates which can be used in the synthesis of the aforementioned polyurethane resins include aromatic, alicyclic and aliphatic diisocyanates. Specifically, this paper is translated into Chinese National Standard (CNS) A4 size (210X297 mm) (Please read the precautions on the back before filling out this page) Order — 囔 · -26- I224615 A7 B7 V. Description of the invention (24 Examples include: hexamethylene diisocyanate, tetramethylene diisocyanate, 3'3-dimethoxy-4,4 diphenyl diisocyanate, p-xylylene Diisocyanate, m-xylylene diisocyanate, 13- (methyl diisocyanate) cyclohexyl_, 1,4- (diisocyanate) cyclohexanone, 4,4 '-Cyclohexanone diisocyanate, 4,4, methylenebis (cyclohexyl isocyanate), isophorone diisocyanate, 2,4-methylphenyl diisocyanate , 2,6-Methylphenylene diisocyanate, p-phenylene monoisocyanate, dibenzoyl diisocyanate, m-phenylene diisocyanate, 2,4-naphthalene Diisocyanate, 3,3, -dimethyl_4,4, biphenyl diisocyanate ^ 4,4_biben ^^ isomeric acid salt ... Phenyl diisocyanate, 2,6-methylenephenyl diisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate are particularly desirable. Examples of commercially available polyurethane-based resins include: "Hydra" "Sound # · /, 彳 卜 7 y" HW_330 "," Hydra "HW-340," Hydra "HW-350 "(All are manufactured by Daikoku Ink Chemical Industry Co., Ltd., trade names)," SUPERFLEX100 "," SUPERFLEX150 "," SUPERFLEXF-3438D "(all are manufactured by Daiichi Pharmaceutical Co., Ltd., trade names), etc. Polyvinyl alcohol resin is preferably polyethenol with a degree of saponification of more than 87%, and a degree of saponification of more than 98%, so-called fully saponified polyvinyl alcohol is particularly desirable. Also, the number average molecular weight is preferably 300. Within the range of 0 to 100, 000. As the aforementioned polyoxyalkylene chain-containing resin, those having a polyoxyethylene homing chain or a polyoxypropylene chain can be suitably used, for example, polyethylene glycol, polypropylene glycol, The polyoxyethylene chain and the polyoxypropylene chain are combined to form a block, and the block polyoxidation is reduced to two papers. The standard is suitable for financial affairs. (_ A 视 格 ⑽χ297 public variable) ------------ --- 嚓…:, …… —— 、 玎 --------------------- 嘬 (Please read the precautions on the back before filling this page) -27 -丄 厶 厶 HO 丄) A7 '^ ----- B7 V. Description of the invention (2τγ ----- ~ alcohols, etc., and then mention the polymerizable unsaturated fluorene copolymer resin, which is good to use; olefins such as hydrazone and fluorene 6 and ( (M) A copolymer of a polymerized 2-unsaturated carboxylic acid such as acrylic acid, maleic acid, and the like, and a polymerizable unsaturated compound is added to an aqueous dispersion of the copolymer to perform emulsification polymerization, and then cross-linked within the particles to form At least one water-dispersible resin or water-soluble resin selected from the two resins. The copolymer of an olefin and a polymerizable unsaturated carboxylic acid is a copolymer of one or more dilute hydrocarbons and one or more polymerizable unsaturated carboxylic acids. In this copolymer, the content of the monomer is 3 to 60% by weight of the aforementioned non-combined carboxylic acid, and desirably falls within a range of 40% by weight. It can be dispersed in water by neutralizing the acid groups in the copolymer with a test substance. The polymerizable unsaturated compound is added to the aqueous dispersion of the copolymer to emulsify and polymerize it, and the polymerizable unsaturated compound in the crosslinked resin formed by cross-linking in the particles may be the aforementioned water-dispersible or water-soluble The vinyl monomers and the like listed in the description of the acryl-based acrylic resin are examples, and one or two or more of them may be appropriately selected and used. The content ratio of the aqueous organic polymer compound (C) is about 10 to 2000 parts by weight relative to 100 parts by weight of the solid content of the titanium-containing aqueous solution (A). The stability of the coating agent, From the viewpoints of the corrosion resistance of the obtained titanium oxide film, it is particularly preferable to be in the range of 100 to 1,000 parts by weight. The coating agent Π for forming a titanium oxide film of the present invention can be prepared by mixing the necessary components by a general method. The coating agent Π of the present invention is an aqueous liquid in a stable state in the neutral or acidic field, and its pH is usually 1 paper size applicable to the Chinese National Standard (CNS) A4 specification (210X297 public director) ... ...--------------— Order —......... (Please read the notes on the back before filling out this page) -28- V. Description of the invention ( 26) in the range of ~ 7. In particular, it has good storage stability in the acidic field, and should be within the range of 5 '. The coating agent Π of the present invention may contain a hydrophilic solvent such as f-alcohol, ethanol, isopropanol, ethylene glycol, and propylene glycol, if necessary. The coating 11 of the present invention can be used with water or a hydrophilic solvent if necessary. 2. Coating agent of this month] [[wherein, if necessary, it may further contain basic formulas such as ammonia, organic chemical compounds, alkali metal hydroxides, alkaline earth metal hydroxides and the like. The organic test compounds can be exemplified by ethanolamine and triethylamine, and the test metal hydroxides can be exemplified by M hydroxide, sodium hydroxide, and hydrogen hydroxide. The coating agent I [of the present invention may further contain various additives as necessary. Examples of such additives include thickeners, antibacterial agents, rust inhibitors, titanium oxide sols, titanium oxide powders, extender pigments, rust preventive pigments, coloring pigments, and surfactants. The aforementioned rust inhibitors include tannic acid, phytic acid, benzotriazole and the like. The physical pigments described are mica, talc, stone spar, barium sulfate, clay and so on. The coating agent for forming a titanium oxide film according to the present invention] and π are excellent in storage stability. In addition, the coating agent can form a titanium oxide-containing coating film having excellent corrosion resistance, adhesion, and processability on a metal substrate. Benefit .... Method for forming a chemical drink film and gold eyebrow coated with titanium oxide film The method for forming a titanium oxide film of the present invention is by coating the coating agent I or Π of the present invention on a metal substrate And dried. Thereby, a metal substrate coated with a titanium oxide film is obtained. This coated metal substrate can be used directly as a rust-proof coated metal substrate. As for the metal substrate to which the titanium oxide film forming method of the present invention is applicable, as long as the paper size is in accordance with the Chinese National Standard (CNS) A4 specification (210X297 mm) -29- 1224615 A7 B7 V. Description of the invention (27 疋 At least the surface is metal The substrate is not particularly limited. For example, if the surface is made of iron, aluminum, zinc, copper, tin, or an alloy containing any of these metals, a steel plate substrate and aluminum or aluminum are particularly used. An alloy substrate is preferred. The aforementioned steel substrate may be, for example, a hot-dip galvanized steel plate, an electro-galvanized steel plate, an iron-zinc alloy plated steel plate, a nickel-zinc alloy plated steel plate, an aluminum-zinc alloy plated steel plate, or the like. For the aluminum-zinc alloy plated steel plate, commercially available products called "Jiaerbalim" Transliteration: twq Xiru "and Γ Jiaerfang" Transliteration: Fanger 7 7〆 "can be used. In addition, the steel base As the material, a zinc-based plated steel plate subjected to conversion treatment such as chromate treatment, zinc phosphate treatment, and composite oxide film treatment can be used. Furthermore, if the steel plate base material is an overlapped steel plate, it does not matter. The material is not particularly limited, but can be used for heat exchange The blade is a representative example. The heat exchanger blade used as the base material may be a component before being assembled on the heat exchanger, or may be in a state of being installed on a heat exchanger, and it can be used by any publicly known person. (Please read the precautions on the back before filling this page). Order 丨 The method of coating the coating agent I or Π of the present invention on a metal substrate. _ 吕 | , Spray coating, spray coating, roll coating, electrodeposition and other known methods for coating. The drying conditions of the coating agent are usually suitable for the heating conditions where the material reaches the most south / m degree of about 60 to 2 50 C. It is allowed to dry for 2 seconds to about 30 minutes. In addition, the thickness of the dried coating film of the coating agent is usually about 0.001 μm to 10 μm, and particularly preferably from 0.1 μm to 3 μm. 〇〇〇1μιη, the low water resistance and water resistance are poor, and if it exceeds 10μηι, the coating film is broken and the corrosion resistance is reduced, and the effect is not satisfactory. Thus, by the method for forming a titanium oxide film of the present invention, Available in metal
-30- 1224615 A7 I----------------B7 _ 五、發明説明(28 ) 基材上形成-财蚀性、黏附性、加工性、耐指紋性等良好 之氧化鈦塗膜。 X,本發明之塗佈劑I或]!亦可藉由塗布於金屬基材以 外之基材上並使其乾燥,而形成氧化鈦塗膜。 该金屬基材以外之基材並無特別限制。舉例言之,如: 由聚氣乙稀樹脂、聚對苯二甲酸乙二酉旨、丙稀酸系樹脂、 矽系樹脂、聚酯系樹脂、氟系樹脂、環氧系樹脂、聚乙烯 樹脂、耐論樹脂、丁酸樹脂、纖維素樹脂、齡樹脂等中之2 種以上樹脂組合成之樹脂所構成之塑料基材;玻璃、水泥 等無機基材,紙、纖維等紙漿基材;及,於該等塑料基材、 無機基材、紙漿基材上施有表面處理或底漆之基材等。 前述基材塗布方法,舉例言之,可藉由浸塗、淋塗、 喷塗、輥塗、電沉積法等公知方法進行塗裝。塗佈劑之乾 燥條件’通常宜於素材到達最高溫度約達2〇〜25〇〇c之加熱 條件下使其進行2秒至約30分鐘之乾燥。又,塗佈劑之乾燥 塗膜膜厚,通常宜為〇·〇〇1μιη〜1〇μηι左右。 經本發明之塗佈劑I或π而形成有氧化鈦塗膜之基材 上,亦可視需要形成一上層塗膜。用以形成該上層塗膜之 組成物可隨目的而適當選擇,並可使用各種塗料組成物。 该塗料組成物可舉潤滑塗膜形成組成物、該耐餘性塗膜形 I 成組成物、底漆塗料、著色頂層塗料等為例。亦可於塗附 潤滑塗膜形成組成物、高耐蝕性塗膜形成組成物或底漆塗 料並俟乾燥後,再於其上塗附著色頂層塗料。 被覆有本發明之塗佈劑I或π之鋁或鋁合金基材係具 本紙張尺度適用中國國家標準(CNS) Α4規格(210Χ297公釐)-30- 1224615 A7 I ---------------- B7 _ 5. Description of the invention (28) Formation on substrate-corrosion, adhesion, processability, fingerprint resistance, etc. Good titanium oxide coating. X, the coating agent I of the present invention or]! A titanium oxide coating film can also be formed by coating on a substrate other than a metal substrate and drying it. The substrate other than the metal substrate is not particularly limited. For example, such as: Polyethylene resin, polyethylene terephthalate, acrylic resin, silicon resin, polyester resin, fluorine resin, epoxy resin, polyethylene resin , Plastic substrates made of resins consisting of two or more resins such as resistant resins, butyric acid resins, cellulose resins, and ageing resins; inorganic substrates such as glass and cement; pulp substrates such as paper and fiber; and , Substrates with surface treatment or primer applied to these plastic substrates, inorganic substrates, and pulp substrates. The substrate coating method can be performed by a known method such as dip coating, shower coating, spray coating, roll coating, or electrodeposition method, for example. The drying condition of the coating agent is generally suitable for drying the material for 2 seconds to about 30 minutes under heating conditions where the maximum temperature reaches about 20 to 2500c. In addition, the thickness of the dry coating film of the coating agent is generally preferably about 0.001 μm to 10 μm. On the substrate on which the titanium oxide coating film is formed through the coating agent I or π of the present invention, an upper coating film may be formed as required. The composition for forming the upper coating film can be appropriately selected according to the purpose, and various coating compositions can be used. The coating composition can be exemplified by a lubricating coating film-forming composition, the residual coating film-forming composition, a primer coating, and a colored top coating. It is also possible to apply a lubricious coating film-forming composition, a highly corrosion-resistant coating film-forming composition, or a primer coating and then dry it, and then apply a color-coated top coating thereon. Aluminum or aluminum alloy base material covered with the coating agent I or π of the present invention The paper size is applicable to China National Standard (CNS) A4 specification (210 × 297 mm)
囔… (請先閲讀背面之注意事項再填寫本頁) 、一叮 — -31- 五、發明説明(29 ) 有耐餘性、親水性、黏附性、加工性等俱佳之塗膜,而 藉由對其進行光照射,則可使親水性更加提升。 又,於鋁或鋁合金基材上被覆有本發明塗佈劑之被覆 土材於作為熱父換器用葉片而使用時,可視需要於該塗 膜上再形成一親水化處理塗膜。 前述親水化處理塗膜係一表面因親水性而具有充分之 塗膜強度,且耐水性、對表面處理覆膜之黏附性倶佳者。 刖述親水化處理塗膜之形成,通常可藉由塗布親水化處理 組成物並使之乾燥而適當進行。 該親水化處理組成物宜為含有親水性塗膜形成性黏結 劑者。理想之親水性塗膜形成性黏結劑,舉例言之,有: (1)以親水性有機樹脂為主成分,並視需要與交聯劑組合而 形成之有機樹脂系黏結劑;(2)以親水性有機樹脂與膠體二 氧化矽為主成分,並視需要與交聯劑組合而形成之有機樹 脂·膠體二氧化矽系黏結劑;(3)主成分之鹼金屬矽酸鹽與 陰離子系或非離子系水性有機樹脂之混合物之水玻璃系黏 結劑等。該等黏結劑中,以有機樹脂系黏結劑(1)、有機樹 脂·膠體二氧化矽系黏結劑交為理想。 用以實施發明之畢祛裉能 其次,舉製造例、實施例及比較例再更具體說明本發 明。唯,本發明並未受以下舉例所限。而各例中記載之「份」 及「%」乃重量基準。 含鈦水成液(A )之調製 製造例1 本紙張尺度適用中國國家標準(CNS) A4规格(210X297公釐) -32- 1224615 A7 ___ B7 五、發明説明(3〇 ) 於使四氣化鈦60%水溶液5cc與蒸餾水調成500CC之水 溶液中,滴下10%氨水.,並使氫氧化鈦沈澱。以蒸餾水洗 淨沈澱後’加入10cc過氧化氫溶液3〇%溶液並攪拌混合, 而製得一含過氧鈦酸且固體成分2%之黃色半透明黏性液 體之含鈦水成液(1 ) 70cc。 製造例2 將四異丙氧基鈦10份與異丙醇1〇份之混合物,以2〇t 並費1小時邊攪拌邊滴落於30%過氧化氫溶液1〇份與去離 子水100份之混合物中。其後以25。〇進行2小時之熟成,而 製得一黃色透明之具少許黏性且固體成分2%之過氧鈦酸 水溶液之含鈦水成液(2 )。 製造例3 除將製造例2中四異丙氧基鈦改為使用同量之四正丁 氧基鈦外,以同於製造例2之方式製得一固體成分2%之含 鈦水成液(3 )。 製造例4 除將製造例2中四異丙氧基鈦改為使用同量之四異丙 氧基鈦之三聚物外,以同於製造例2之方式製得一固體成分 2%之含鈦水成液(4)。 製造例5 除於製造例2中使用3倍量之過氧化氫溶液並以5(Γ(:耗 費1小時加以滴落,其後再以6(rc進行3小時之熟成外’以 同於製造例2之方式製得一固體成分2%之含鈦水成液⑸。 製造例6 本紙張尺度適用中國國家標準(CNS) A4規格(21〇><297公釐) (請先閲讀背面之注意事項再填寫本頁) 訂· -囔- -33- 1224615 A7 B7 ___ 五、發明説明(31 ) 一 (請先閲讀背面之注意事項再填寫本頁) 將製造例3製得之含鈦水成液進而以95°C進行6小時之 加熱處理’而製得一白黃色半透明氧化鈦分散液之固體成 分2%之含鈦水成液(6)。 製造例7 將四異丙氧基鈦10份與異丙醇10份之混合物,以10°C 並費1小時邊攪拌邊滴於「TKS-203」(TAYCA(株)製、商 品名、平均粒子徑6nm之銳鈦礦型氧化鈦微粒之水性溶膠) 5份(固體成分)、3〇%過氧化氫溶液1〇份及去離子水1〇〇 份之混合物中。其後以忉艽進行24小時之熟成,而製得一 黃色透明之具少許黏性且固體成分2%之含鈦水成液(7)。 主發.明之用以形成氧化鈦膜之塗佈劑〗之例 實施例1 混合以製造例1製得之含鈦水成液(1) 5〇份、1〇%偏 磷酸5份及去離子水45份後,製得本發明之用以形成氧化鈦 膜之塗佈劑。 實施例2〜16及比較例1〜2 依據表1所示之組成,並以同於實施例1之方式,製得 本發明之塗佈劑及比較用之塗佈劑。 本紙張尺度適用中國國家標準(CNS) A4規格(210X297公釐) -34· 1224615 A7B7 五、發明説明(32 ) 表1 實施例 1 2 3 4 5 6 7 8 9 (A )成分 (1) (2) (3) (4) (5) (6) ⑺ 50 50 50 50 50 50 50 50 50 (B)成分 10%偏磷酸 5 5 10 5 5 10%焦磷酸鈉 5 10%三聚磷酸鈉 5 10%四磷酸鈉 5 10%六偏磷酸鈉 5 40%锆氰靡 L酸 10%锆氟化銨 10%氨水 10%氫氧化鋰 去離子水 45 45 45 45 45 45 45 45 45 (請先閲讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準(CNS) A4規格(210X297公釐) -35- 1224615 A7B7 五、發明説明(33 ) 表1 (續) 實施例 比較例 10 11 12 13 14 15 16 1 2 (A)成分 ⑴ 50 (2) 50 50 50 50 50 (3) (4) (5) 50 (6) 50 ⑺ 50 (B)成分 10%偏磷酸 5 5 5 5 5 5 5 10%焦磷酸鈉 10%三聚磷酸鈉 10%四磷酸鈉 10%六偏磷酸鈉 40%锆氰氟酸 2 2 2 10%锆氟化銨 1 10%氨水 1 10%氫氧化鋰 3 去離子水 45 45 45 45 45 45 45 45 45 (請先閲讀背面之注意事項再填寫本頁) 本發明之用以形成氧化鈦膜之塗佈劑I之性能試驗 利用實施例1〜16及比較例1〜2所得之各塗佈劑進行 金屬基材之被覆處理,並查驗製得之被覆基材之耐蝕性。 (1 )鋁板之被覆處理 將板厚0.1mm之鋁板(A1050 ),以溶有鹼去脂劑(曰 本C.B.CHEMICAL(株)製、商品名「ChemiCleaner561B」) 之濃度2%之水溶液去脂,經水洗後,以軋輥塗附各塗佈劑 而使乾燥塗膜重量達〇.2g/m2,並焙燒20秒以使素材到達溫 本紙張尺度適用中國國家標準(CNS) A4規格(210X297公釐) -36- 1224615 A7 B7 五、發明説明(34 ) 度達100°C,而形成氧化鈦塗膜。 (2)被覆板之耐蝕性 (請先閲讀背面之注意事項再填寫本頁) 針對前述各被覆板,依據JIS Z2371之鹽水喷霧試驗法 進行測定。試驗時間分為120小時、240小時、360小時及480 小時4階段,並依以下基準加以評價。 a. ..塗面無白銹、氣泡產生; b. ..產生少許白銹或氣泡; c. ..明顯產生白銹或氣泡。 試驗結果顯示於表2。 表2 塗佈劑 試驗時間 120hr 240hr 360hr 480hr 實施例1 a a b c 實施例2 a a a b 實施例3 a a b b 實施例4 a a b b 實施例5 a a a b 實施例6 a a a b 實施例7 a a a b 實施例8 a a a b 實施例9 a a a b 實施例10 a a a b 實施例11 a a b c 實施例12 a a b c 實施例13 a a a b 實施例14 a a a b 實施例15 a a a b 實施例16 a a a b 比較例1 b c c c 比較例2 b b c c 本紙張尺度適用中國國家標準(CNS) A4規格(210X297公釐) -37- 1224615 A7 ____B7 五、發明説明(35 ) (3 )鋼板之被覆處理 將板厚0.6腿之電鏡鋅鋼板(單面之艘敷附著量為 20g/m2),以溶有鹼去脂劑(日本C.B CHEMICAL(株)製、 商品名「ChemiCleaner561B」)之濃度2%之水溶液去脂, 經水洗後,以軋輥塗附各塗佈劑而使乾燥塗膜重量達 l.〇g/m,並焙燒20秒以使素材到達溫度達1〇〇。[,而形成 氧化鈦塗膜。 (4 )被覆板之耐餘性 針對將前述各被覆板之端面部及裏面部密封之試驗塗 板,依據JIS Z2371之鹽水喷霧試驗法進行測定。試驗時間 分為24小時、48小時及72小時3階段,並依以下基準加以評 價。 a···無白銹產生; b…白銹之產生程度未達塗膜面積之5% ; c…白錄之產生程度超過塗膜面積之但未達; d…白錄之產生程度超過塗膜面積之但未達; e…白鱗之產生程度超過塗膜面積之50%。 试驗結果顯不於表3。 本紙張尺度適用中國國家標準(CNS) A4規格(210X297公釐) (請先閲讀背面之注意事項再填寫本頁) 訂— -38- 1224615 A7 B7 五、發明説明(36 ) 表3 塗佈劑 試驗時間 24hr 48hr 72hr 實施例1 a b c 實施例2 a a b 實施例3 a b b 實施例4 a b b 實施例5 a a b 實施例6 a a b 實施例7 a a b 實施例8 a a b 實施例9 a a b 實施例10 a a b 實施例11 a b c 實施例12 a b c 實施例13 a a b 實施例14 a a b 實施例15 a a b 實施例16 a a b 比較例1 c b d 比較例2 c c d (請先閲讀背面之注意事項再填寫本頁) (5 )鋼板之被覆處理 將板厚0.6丽之電鍍鋅鋼板(單面之鍍敷附著量為 20g/m2)以鹼去脂後,喷塗「普雷帕倫《音譯:」 (曰本PAKERIZING(株)製、商品名)並進行表面調整。 繼之,於噴塗「PALBOND3308」(日本PARKERIZING(株) 製、商品名、磷酸鋅水溶液)後,經水洗並加以乾燥,而 製得一施有磷酸鋅處理之鍍敷鋼板。該磷酸鋅處理塗膜之 附著量為1.5g/m2。 於前述施有磷酸鋅處理之鍍敷鋼板表面,喷塗前述各 塗佈劑而使乾燥塗膜重量達1 .〇g/m2,並焙燒20秒以使素材 本紙張尺度適用中國國家標準(CNS) A4規格(210X297公釐) -39- 1224615 A7 B7 五、發明説明(37 到達溫度達100°C,而形成氧化鈦塗膜。 (6 )被覆板之耐蝕性 針對將前述各被覆板之端面部及裏面部密封之試驗塗 板,依據JIS Z2371之鹽水喷霧試驗法進行測定。試驗時間 分為24小時、48小時及72小時3階段,並依以下基準加以評 價。 a···無白銹產生; b…白銹之產生程度未達塗膜面積之5% ; c…白銹之產生程度超過塗膜面積之5%但未達1〇% ; d…白銹之產生程度超過塗膜面積之10%但未達5〇% ; e…白錄之產生程度超過塗膜面積之。 試驗結果顯示於表4。 (請先閲讀背面之注意事項再填寫本頁) •訂— .管_ 本紙張尺度適用中國國家標準(CNS) A4規格(21〇χ297公釐) -40- ^4615 A7 B7 五、發明説明(38 ) 表4 塗佈劑 試驗時間 24hr 48hr 72hr 實施例1 a b c 實施例2 a a b 實施例3 a b b —實施例4 a b b _實施何5 a a b 實施例6 a a b 實施例7 a a b 實施例8 a a b 實施例9 a a b 實施例10 a a b 實施例11 a b c 實施例12 a b c 實施例13 a a b 實施例14 a a b — 實施例15 a a b 實施例16 a a 卜b 比較例1 h b c c 比較例2 b b c 达A有機高分手化合物(C)之調 製造例8 (請先閲讀背面之注意事項再填寫本頁) 訂| -管- 於具有溫度計、攪拌器、冷凝器、滴液漏斗之丨L之四 口燒瓶中,放入異丙醇180份,並於氮取代後,將燒瓶内之 溫度調整為85°C,且將由乙基丙烯酸酯140份、曱基丙烯酸 甲酯68份、苯乙烯15份、N_正丁氧基甲基丙烯醯胺15份、 2 _經乙基丙烯酸g旨3 8份及丙烯酸2 4份所組成之單體混合 物,與催化劑2,2-偶氮雙(2,4_二甲基戊腈)6份一併費時 約2小時加以滴入。滴液完畢後若以同溫度再持績5小時反 應,則可製得聚合率幾近100%、固體成分約63%、酸值約 本紙張尺度適用中國國家標準(CNS) A4規格(210X297公釐) -41- 1224615 A7 __B7_ 五、發明説明(39 ) 67mgKOH/g之無色透明樹脂溶液。藉由相對於該樹脂溶液 5 0 0伤而混合二曱胺乙醇1 〇 8份,並加水充分攪拌,則製得 固體成分30%之丙烯酸樹脂水分散液(ci)。 製造例9 於具有授拌裝置、回流冷凝器、溫度計、液滴裝置之 反應裝置中,加入「EPIKOTE1009」(SHELL化學社製、 商品名、分子量3750之環氧樹脂)i880g ( 0.5莫耳)與甲 基異丁基酮/苯二甲基=1/1 (重量比)之混合溶媒1〇〇〇g 後,加以攪拌加熱並均勻溶解。其後冷卻至7(rc,並將均 分於液滴裝置中之二(正丙醇)胺70g費30分鐘加以滴落。 其間,反應溫度保持於70°C。滴液完成後以120°C保持2小 時’並藉由結束反應’而製得固體成分66%之胺改質環氧 樹脂。藉由相對於所得樹脂l〇〇〇g而混合88%之曱酸25份, 並加水充分攪拌,則製得固體成分30%之胺改質環氧樹脂 水分散液(C2)。 主普明之用以形成氣化鈦膜之沴佈劑π之例 實施例17 將以製造例1製得之含鈦水成液(D 50份、2〇%錯氫 氟酸、30%丙烯酸樹脂水分散液(ci ) 1〇份及去離子水35 份加以混合,則製得本發明之用以形成氧化鈦膜之塗佈劑。 實施例18〜27及比較例3〜5 依據表5所示之組成,並以同於實施例17之方式,製得 本發明之塗佈劑及比較用之塗佈劑。 本紙張尺度適用中國國家標準(CNS) M規格(2lox297公釐) ——.....—9^------------------訂—--------*線· (請先閲讀背面之注意事項再填寫本頁) -42- 1224615 A7B7 五、發明説明(4〇 ) 表5 實施> 例 17 18 19 20 21 22 23 (A)成分 (1) 50 50 50 50 50 ⑵ 50 (3) 50 (4) (5) ⑹ ⑺ (B)成分 20%锆氫氟酸 5 2.5 10 40%鈦氫氟酸 10 20 40%矽氟化酸 2.5 10%偏磷酸 10 (C)成分 30%丙烯酸樹脂 水分散液(C1) 10 20 30%胺改質環氧樹 脂水分散液(C2) 15 25 「SaranLatex L-411」 10 20 「KURARAYRS 聚合物 RS-105」 25 去離子水 35 25 37.5 15 37.5 15 10 (請先閲讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準(CNS) A4規格(210X297公釐) -43- 1224615 A7 B7 五、發明説明(41 ) 表5 (續)囔… (Please read the precautions on the back before filling out this page), Yiding—-31- V. Description of the Invention (29) There is a coating film with excellent durability, hydrophilicity, adhesion, processability, etc., and By irradiating it with light, hydrophilicity can be further improved. When the coated earth material coated with the coating agent of the present invention on an aluminum or aluminum alloy substrate is used as a blade for a heat exchanger, a hydrophilic treatment coating film may be formed on the coating film as needed. The above-mentioned hydrophilized coating film is one having a surface having sufficient coating film strength due to hydrophilicity, water resistance, and excellent adhesion to the surface-treated coating. The formation of the hydrophilized coating film is generally carried out appropriately by applying and drying the hydrophilized composition. The hydrophilizing composition is preferably one containing a hydrophilic coating film-forming adhesive. The ideal hydrophilic coating film-forming adhesives include, for example: (1) organic resin-based adhesives composed of a hydrophilic organic resin as the main component and combined with a crosslinking agent as needed; (2) Organic resin · colloidal silica based binder formed by hydrophilic organic resin and colloidal silica as the main component and combined with a crosslinking agent as needed; (3) alkali metal silicate and anionic or Water glass-based adhesives such as mixtures of non-ionic water-based organic resins. Among these adhesives, an organic resin-based adhesive (1) and an organic resin-colloidal silica-based adhesive are preferably used. The ability to implement the invention Next, the present invention will be described more specifically with reference to manufacturing examples, examples, and comparative examples. However, the present invention is not limited by the following examples. The "parts" and "%" described in each example are based on weight. Preparation example of titanium-containing aqueous solution (A) 1 This paper size is in accordance with Chinese National Standard (CNS) A4 specification (210X297 mm) -32- 1224615 A7 ___ B7 V. Description of the invention (3〇) 5cc of titanium 60% aqueous solution and distilled water were adjusted to 500CC, 10% ammonia water was dropped, and titanium hydroxide was precipitated. After washing the precipitate with distilled water, 10cc of a 30% solution of hydrogen peroxide solution was added and stirred to prepare a yellow translucent viscous liquid containing titanium peroxytitanic acid and 2% solids (1 ) 70cc. Production Example 2 A mixture of 10 parts of titanium tetraisopropoxide and 10 parts of isopropanol was dripped into 10 parts of a 30% hydrogen peroxide solution and deionized water 100 at 20 t while stirring for 1 hour. Parts of the mixture. Then 25. 〇Curing for 2 hours to prepare a yellow transparent titanium peroxytitanate aqueous solution (2) with a slight viscosity and a solid content of 2%. Manufacturing Example 3 A titanium-containing aqueous solution having a solid content of 2% was prepared in the same manner as in Manufacturing Example 2 except that tetraisopropoxy titanium in Manufacturing Example 2 was replaced with tetra-n-butoxy titanium in the same amount. (3). Manufacturing Example 4 A solid content of 2% was obtained in the same manner as in Manufacturing Example 2 except that the tetraisopropoxy titanium in Manufacturing Example 2 was changed to a terpolymer using the same amount of titanium tetraisopropoxy titanium. The titanium aqueous solution (4). Manufacturing Example 5 The same manufacturing method as in Manufacturing Example 2 was carried out except that a three-fold amount of a hydrogen peroxide solution was used and dripped at 5 (Γ (: it took 1 hour to drip, and then matured at 6 (rc for 3 hours). A titanium-containing aqueous hydrazone with a solid content of 2% was prepared in the manner of Example 2. Manufacturing Example 6 The paper size is applicable to the Chinese National Standard (CNS) A4 specification (21〇 > < 297mm) (Please read the back first Please pay attention to this page and fill in this page) Order ·-囔--33- 1224615 A7 B7 ___ V. Description of the invention (31) I (Please read the precautions on the back before filling this page) The titanium-containing material obtained in Manufacturing Example 3 The aqueous solution was further subjected to a heating treatment at 95 ° C for 6 hours to obtain a titanium yellow aqueous solution (6) having a solid content of 2% as a white-yellow translucent titanium oxide dispersion. Production Example 7 Tetraisopropoxy A mixture of 10 parts of base titanium and 10 parts of isopropanol was dropped at 10 ° C and stirring for 1 hour to an anatase type of "TKS-203" (manufactured by TAYCA Corporation) with a trade name and an average particle diameter of 6 nm. Aqueous sol of titanium oxide microparticles) in a mixture of 5 parts (solid content), 10 parts of 30% hydrogen peroxide solution and 100 parts of deionized water. The maturation was carried out for 24 hours, and a yellow transparent titanium-containing aqueous solution (7) with a little viscosity and a solid content of 2% was prepared. The main application is a coating agent for forming a titanium oxide film. Example 1 After mixing 50 parts of the titanium-containing aqueous solution (1) obtained in Manufacturing Example 1, 50 parts of 10% metaphosphoric acid and 45 parts of deionized water, a coating for forming a titanium oxide film according to the present invention was prepared. Cloth agent. Examples 2 to 16 and Comparative Examples 1 to 2 According to the composition shown in Table 1, the coating agent of the present invention and a comparative coating agent were prepared in the same manner as in Example 1. This paper The scale is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) -34 · 1224615 A7B7 V. Description of the invention (32) Table 1 Example 1 2 3 4 5 6 7 8 9 (A) Composition (1) (2) (3) (4) (5) (6) ⑺ 50 50 50 50 50 50 50 50 50 (B) 10% metaphosphoric acid 5 5 10 5 5 10% sodium pyrophosphate 5 10% sodium tripolyphosphate 5 10% Sodium tetraphosphate 5 10% Sodium hexametaphosphate 5 40% Zirconium cyanide L acid 10% Zirconium ammonium fluoride 10% Ammonia water 10% Lithium hydroxide deionized water 45 45 45 45 45 45 45 45 45 (Please read the notes on the back before filling in this page) This paper size applies to Chinese National Standard (CNS) A4 (210X297 mm) -35- 1224615 A7B7 V. Description of the invention (33) Table 1 (continued) ) Examples Comparative Example 10 11 12 13 14 15 16 1 2 (A) component ⑴ 50 (2) 50 50 50 50 50 (3) (4) (5) 50 (6) 50 ⑺ 50 (B) component 10% Metaphosphoric acid 5 5 5 5 5 5 5 10% sodium pyrophosphate 10% sodium tripolyphosphate 10% sodium tetraphosphate 10% sodium hexametaphosphate 40% zirconium cyanofluoric acid 2 2 2 10% ammonium zirconium fluoride 1 10% ammonia 1 10% lithium hydroxide 3 Deionized water 45 45 45 45 45 45 45 45 45 45 (Please read the precautions on the back before filling out this page) Performance test utilization of coating agent I for forming titanium oxide film of the present invention Each coating agent obtained in Examples 1 to 16 and Comparative Examples 1 to 2 was subjected to coating treatment on a metal substrate, and the corrosion resistance of the prepared coating substrate was examined. (1) Coating treatment of aluminum plate The aluminum plate (A1050) with a thickness of 0.1 mm is degreased with an aqueous solution having a concentration of 2% by dissolving an alkali degreaser (produced by CBCHEMICAL Co., Ltd. under the trade name "ChemiCleaner561B"). After washing with water, each coating agent is applied with a roller to make the dry coating weight reach 0.2 g / m2, and it is fired for 20 seconds to make the material reach the temperature of the paper. The Chinese national standard (CNS) A4 specification (210X297 mm) is applied. ) -36- 1224615 A7 B7 5. Description of the invention (34) The temperature reaches 100 ° C, and a titanium oxide coating film is formed. (2) Corrosion resistance of coated panels (Please read the precautions on the back before filling in this page.) For each of the aforementioned coated panels, measure in accordance with the salt spray test method of JIS Z2371. The test time is divided into 120 hours, 240 hours, 360 hours, and 480 hours, and is evaluated according to the following criteria. a. .. There is no white rust or air bubbles on the coating surface; b .. A little white rust or air bubbles are generated; c. .. White rust or air bubbles are obviously generated. The test results are shown in Table 2. Table 2 Coating agent test time 120hr 240hr 360hr 480hr Example 1 aabc Example 2 aaab Example 3 aabb Example 4 aabb Example 5 aaab Example 6 aaab Example 7 aaab Example 8 aaab Example 9 aaab Example 10 aaab example 11 aabc example 12 aabc example 13 aaab example 14 aaab example 15 aaab example 16 aaab comparative example 1 bccc comparative example 2 bbcc This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) -37- 1224615 A7 ____B7 V. Description of the invention (35) (3) Coating treatment of steel plate The thickness of 0.6-leg SEM zinc steel plate (single-sided boat coating amount is 20g / m2), with alkali degreaser dissolved (CB Chemical Co., Ltd., Japan, product name: "ChemiCleaner561B") degreasing solution with a concentration of 2%, after washing with water, each coating agent is applied with a roller to make the dry coating weight reach 1.0 g / m. And baked for 20 seconds so that the temperature of the material reached 100. [While forming a titanium oxide coating film. (4) Residual resistance of coated panels The test coated panels that sealed the end and inner surfaces of the aforementioned coated panels were measured in accordance with the salt water spray test method of JIS Z2371. The test time is divided into three stages of 24 hours, 48 hours, and 72 hours, and the evaluation is based on the following criteria. a ... no white rust is generated; b ... the degree of white rust is less than 5% of the area of the coating film; c ... the degree of white record exceeds the area of the coating film but not yet reached; d ... the degree of white record exceeds the coating The area of the film is less than that; e. The generation of white scale exceeds 50% of the area of the coating film. The test results are not shown in Table 3. This paper size applies to China National Standard (CNS) A4 specification (210X297 mm) (Please read the precautions on the back before filling this page) Order — -38- 1224615 A7 B7 V. Description of the invention (36) Table 3 Coating agent Test time 24hr 48hr 72hr Example 1 abc Example 2 aab Example 3 abb Example 4 abb Example 5 aab Example 6 aab Example 7 aab Example 8 aab Example 9 aab Example 10 aab Example 11 abc Implementation Example 12 abc Example 13 aab Example 14 aab Example 15 aab Example 16 aab Comparative example 1 cbd Comparative example 2 ccd (Please read the precautions on the back before filling out this page) (5) Covering the steel sheet 0.6 Li of galvanized steel sheet (plating adhesion amount of 20g / m2 on one side) is degreased with alkali, and sprayed with "Preparan" transliteration: (produced by PAKERIZING Co., Ltd., trade name) and then Surface adjustment. Next, "PALBOND3308" (trade name, zinc phosphate aqueous solution, manufactured by PARKERIZING Co., Ltd.) was spray-washed, washed with water, and dried to obtain a zinc phosphate-treated plated steel sheet. The adhesion amount of the zinc phosphate-treated coating film was 1.5 g / m2. Spray each coating agent on the surface of the aforementioned plated steel plate with zinc phosphate treatment to make the dry coating weight reach 1.0 g / m2, and bake for 20 seconds so that the paper size of the material applies the Chinese national standard (CNS ) A4 specification (210X297 mm) -39- 1224615 A7 B7 V. Description of the invention (37 When the temperature reaches 100 ° C, a titanium oxide coating film is formed. (6) Corrosion resistance of the covering plate The test coated plate sealed at the inner part and the inner part was measured according to the salt water spray test method of JIS Z2371. The test time was divided into three stages of 24 hours, 48 hours, and 72 hours, and evaluated according to the following criteria. A ... No white rust Produced; b ... the generation of white rust is less than 5% of the coating film area; c ... the generation of white rust is more than 5% but less than 10% of the coating film area; d ... the generation of white rust exceeds the coating film area 10% but less than 50%; e ... The degree of white recording exceeds the area of the coating film. The test results are shown in Table 4. (Please read the precautions on the back before filling this page) • Order —. 管 _ 本Paper size applies to China National Standard (CNS) A4 (21〇297mm) -4 0- ^ 4615 A7 B7 V. Description of the invention (38) Table 4 Test time of coating agent 24hr 48hr 72hr Example 1 abc Example 2 aab Example 3 abb — Example 4 abb _ implementation He 5 aab Example 6 aab implementation Example 7 aab Example 8 aab Example 9 aab Example 10 aab Example 11 abc Example 12 abc Example 13 aab Example 14 aab — Example 15 aab Example 16 aa bb Comparative Example 1 hbcc Comparative Example 2 bbc Da A Organic High Breaking Compound (C) Preparation Example 8 (Please read the precautions on the back before filling this page) Order | -Tube-In a thermometer with a stirrer, condenser, dripping funnel Put 180 parts of isopropanol in a mouth flask, and after nitrogen substitution, the temperature in the flask was adjusted to 85 ° C, and 140 parts of ethyl acrylate, 68 parts of methyl methacrylate, and 15 parts of styrene , 15 parts of N-n-butoxymethacrylamide, 2 monomer mixture consisting of 38 parts of ethyl acrylic acid and 24 parts of acrylic acid, and catalyst 2,2-azobis (2, 4_dimethylvaleronitrile) 6 parts together takes about 2 hours plus After dripping, if the reaction is continued for another 5 hours at the same temperature, a polymerization rate of nearly 100%, a solid content of about 63%, and an acid value of about this paper are applicable to China National Standard (CNS) A4 specifications. (210X297mm) -41- 1224615 A7 __B7_ V. Description of the invention (39) 67mgKOH / g colorless transparent resin solution. By mixing 108 parts of diammonium alcohol with respect to 500 to the resin solution, and adding water and stirring well, an acrylic resin aqueous dispersion (ci) having a solid content of 30% was prepared. Production Example 9 To a reaction device having a mixing device, a reflux condenser, a thermometer, and a droplet device, "EPIKOTE1009" (epoxy resin manufactured by SHELL Chemical Co., Ltd., trade name, molecular weight 3750) i880g (0.5 mol) and After 1000 g of a mixed solvent of methyl isobutyl ketone / xylylene = 1/1 (weight ratio), the mixture was heated with stirring and uniformly dissolved. After that, it was cooled to 70 ° C., and 70 g of bis (n-propanol) amine, which was evenly divided in the droplet device, was dropped for 30 minutes. Meanwhile, the reaction temperature was maintained at 70 ° C. After the completion of the drop, the temperature was 120 °. C was held for 2 hours and the reaction was completed to prepare an amine-modified epoxy resin with a solid content of 66%. 25 parts of 88% osmic acid was mixed with 1,000 g of the obtained resin, and water was added sufficiently By stirring, an amine-modified epoxy resin aqueous dispersion (C2) having a solid content of 30% is prepared. Example 17 of the main puming used to form a fluorinated cloth agent π of a vaporized titanium film Example 17 will be prepared in Production Example 1 The titanium-containing aqueous solution (D 50 parts, 20% hydrofluoric acid, 30% acrylic resin aqueous dispersion (ci) 10 parts, and deionized water 35 parts were mixed to prepare the invention for forming Coating agents for titanium oxide films. Examples 18 to 27 and Comparative Examples 3 to 5 According to the composition shown in Table 5, the coating agent of the present invention and a comparative coating were prepared in the same manner as in Example 17. Cloth agent. This paper size is applicable to Chinese National Standard (CNS) M specification (2lox297 mm) ——.....— 9 ^ ------------------ Order— -------- * line · (please first Read the notes on the back and fill in this page) -42- 1224615 A7B7 V. Description of the invention (4〇) Table 5 Implementation &Example; Example 17 18 19 20 21 22 23 (A) Ingredient (1) 50 50 50 50 50 ⑵ 50 (3) 50 (4) (5) ⑹ ⑺ (B) 20% zirconium hydrofluoric acid 5 2.5 10 40% titanium hydrofluoric acid 10 20 40% silicic acid 2.5 10% metaphosphoric acid 10 (C) 30 % Acrylic resin water dispersion (C1) 10 20 30% amine modified epoxy resin water dispersion (C2) 15 25 "SaranLatex L-411" 10 20 "KURARAYRS polymer RS-105" 25 DI water 35 25 37.5 15 37.5 15 10 (Please read the notes on the back before filling out this page) This paper size applies to Chinese National Standard (CNS) A4 (210X297 mm) -43- 1224615 A7 B7 V. Description of the invention (41) Table 5 ( Continued)
實施例 比較例 24 25 26 27 3 4 5 (A)成分 0) 50 (2) (3) 50 (4) 50 (5) 50 ⑹ 50 (7) 50 (B)成分 20%锆氫氟酸 5 10 5 40%鈦氫氟酸 5 40%矽氫氟酸 5 5 10%偏磷酸 (C)成分 30%丙烯酸樹脂 水分散液(C1) 20 20 30%胺改質環氧樹 脂水分散液(C2) 20 80 「SaranLatex L-411」 45 「KURARAYRS 聚合物 RS-105」 25 40 去離子水 20 25 20 5 30 15 前述表5中,「SaranLatexL-411」及「KURARAYRS (請先閲讀背面之注意事項再填寫本頁) 聚合物RS-105」係以下所示者。Examples Comparative Example 24 25 26 27 3 4 5 (A) component 0) 50 (2) (3) 50 (4) 50 (5) 50 ⑹ 50 (7) 50 (B) component 20% zirconium hydrofluoric acid 5 10 5 40% titanium hydrofluoric acid 5 40% silicon hydrofluoric acid 5 5 10% metaphosphoric acid (C) component 30% acrylic resin aqueous dispersion (C1) 20 20 30% amine modified epoxy resin aqueous dispersion (C2 ) 20 80 "SaranLatex L-411" 45 "KURARAYRS Polymer RS-105" 25 40 Deionized water 20 25 20 5 30 15 In the aforementioned Table 5, "SaranLatex L-411" and "KURARAYRS (Please read the precautions on the back first) Fill out this page again) Polymer RS-105 "is shown below.
SaranLatex L-411 :旭化成工業(株)製,商品名,雙氯 亞乙烯樹脂,固體成分50%。 KURARAY RS 聚合物 RS-105 : KURARY(株)製,商品 名、聚乙烯醇,固體成分10%。 本發明之用以形成氧化鈦膜之塗佈劑Π之性能試驗 利用實施例17〜27及比較例3〜5所製得之各塗佈劑進 行鋼板基材之防銹被覆處理,並查驗所得被覆鋼板之塗膜 外觀、黏附性及耐蝕性。 (1)鋼板基材之防銹被覆處 使用板厚0.8之各種鍍敷鋼板作為基材。使用過之鍍敷 本紙張尺度適用中國國家標準(CNS) A4規格(210X297公釐) -44- 1224615 A7 B7 五、發明説明(42 ) 鋼板有以下6種。 ⑴電鐘辞鋼板:鑛敷附著量2〇g/m2,並稱「EG」; (⑴熱^:鑛辞鋼板:鑛敷附著量6〇g/m2,並稱「HDG」· (Hi)鋅鐵合金鑛敷鋼板:鑛層中之Fe量10%,鍍敷附 著量60g/m2,並稱「Zn-Fe」; (iv) 鋅-鎳合金鍍敷鋼板:鍍層中之见量12%,鍍敷附 著量30g/m2,並稱「Zn-Ni」; (v) 鋅-鋁合金鍍敷鋼板:鍍層中之八丨量12%,鍍敷附 著量 150g/m2,並稱「Zn-12%A1」; (vi) 鋅-鋁合金鑛敷鋼板··鍍層中之Ai量55%,鍵敷附 著量 250g/m2,並稱「Ζη·55%Α1」。 將前述各鍍敷鋼板表面,以液溫65°C之溶有鹼去脂劑 (曰本C.B.CHEMICAL(株)製、商品名「ChemiCleaner561B」) 之濃度2%之水溶液喷灑20秒而去脂後,再噴灑6〇°c之溫水 2 0秒以將其洗淨。於該經去脂之鑛敷鋼板上,喷塗各塗佈 劑且使乾燥塗膜重量達〇.5g/m2,並於環境溫度250°C下乾 燥15秒(素材到達溫度為i〇〇°c ),而形成一防銹塗膜,旅 製得被覆鋼板。 (2 )被覆鋼板之性能試驗 針對前述製得之各被覆鋼板,而依據以下試驗方法進 行塗膜外觀、黏附性及耐蝕性之試驗。 试驗方法 塗膜外觀··憑目視並依據以下基準而對塗膜之均勻性 加以評價。 本紙張尺度適用中國國家標準(CNS) A4規格(210X297公釐) (請先閲讀背面之注意事項再填寫本頁) 訂| -45- 1224615 A7 五、發明説明(43 ) (請先閲讀背面之注意事項再填寫本頁) a:無凹凸不平並呈均勻之外觀; b :部分有凹凸不平情形; c :全面呈凹凸不平之狀態。 黏附性·對塗膜進行jIS〖54〇〇之8 5.2所載之棋盤格附 著法(空隙間隔1mm ),並依以下基準評價黏附性。 a :塗膜完全無剝離現象; b :塗膜產生剝離,但剝離面積未達5% ; c:剝離面積超過5%但未達2〇% ; d:剝離面積超過20%但未達50% ; e :剝離面積超過50%。 耐鍅性:將被覆鋼板之端面部及裏面部密封,並分24 小時、48小時及72小時3階段進行JIS Z2371規定之鹽水喷 霧試驗,且藉由以下基準評價耐蝕性。 a :塗面無白銹及氣泡產生; b :白銹或氣泡之產生程度未達塗膜面積之1〇% ; c:白銹或氣泡之產生程度超過塗膜面積之1〇%但未達 30% ; d:白銹或氣泡之產生程度超過塗膜面積之3〇%但未達 50% ; e:白銹或氣泡之產生程度超過塗膜面積之5〇%。 试驗結果顯示於表6。 本紙張尺度適用中國國家標準(CNS) A4规格(210X297公釐) -46- 1224615 A7 B7 五、發明説明(44 ) 表6 塗佈劑 鍍敷鋼板 塗膜外觀 黏附性 财餘性 24hr 48hr 72hr 實施例17 EG a a a b c 實施例18 EG a a a b c 實施例19 EG a a a a b 實施例20 HDG a a a a a 實施例21. HDG a a a a a 實施例22 Zn-Fe a a a a b 實施例23 Zn-Fe a a a a b 實施例24 Zn-Ni a a a a b 實施例25 Zn-12%A1 a a a a a 實施例26 Zn-55%A1 a a a a a 實施例27 Zn-55%A1 a a a a a 比較例3 EG a b b c d 比較例4 HDG a b a b c 比較例5 Zn-Fe a b b c d (請先閱讀背面之注意事項再填寫本頁) 本發明之用以形成氧化鈦膜之塗佈劑Π之例 實施例28 混合製造例1所得之含鈦水成液(1) 50份、20%锆氫 氟酸5份、「AC10LP」(曰本化藥(株)製、聚丙烯酸水溶 液、重量平均分子量25000、酸值779mgKOH/g、固體成分 10%) 30份及去離子水15份,則製得本發明之用以形成氧 化鈦膜之塗佈劑。 實施例2 9〜3 3及比較例6〜7 依據表7所示之組成,並以同於實施例28之方式,製得 本發明之塗佈劑及比較用之塗佈劑。 本紙張尺度適用中國國家標準(CNS) A4規格(210X297公釐) -47- 1224615 A7B7 五、發明説明(45 ) 表7 實施例 比較例 28 29 30 31 32 33 6 7 (A)成分 (1) 50 50 (2) 50 ⑶ 50 (4) 50 (5) 50 (6) 50 (B)成分 20%锆氫氟酸 5 40%鈦氫氟酸 10 40%矽氫氟酸 2.5 5 10%偏磷酸 10 5 (C)成分 「AC10LP」 30 50 「DENKAPOVALK-05」 20 30 「PEG6000S」 40 30 40 85 去離子水 15 20 7.5 10 10 5 15 前述表7中,「AC10LP」、「DENKAPOVALK-05 (請先閲讀背面之注意事項再填寫本頁) 及「PEG6000S」乃以下所示者。 AC10LP:曰本化藥(株)製、商品名、聚丙烯酸水溶液、 重量平均分子量25000、酸值779mgKOH/g、固體成分10%。 DENKA POVAL K-05:電氣化學工業(株)製、商品名、 聚乙烯醇、皂化度99%、聚合度550、固體成分10%。 PEG6000S:三洋化成工業(株)製、商品名、聚乙二醇、 平均分子量8300、固體成分10%。 本發明之用以形成氧化鈦膜之塗佈劑U之性能試驗 利用實施例28〜33及比較例6〜7製得之各塗佈劑進行 鋁基材之防銹被覆處理,並查驗所得之被覆鋁板之塗膜外 觀、親水性及耐#性。 (1 )鋁基材之防銹被覆處理 將板厚〇·1丽之鋁板(A1050 )以溶有鹼去脂劑(曰本 本紙張尺度適用中國國家標準(CNS) A4規格(210X297公釐) -48- 1224615 A7 ___ B7 五、發明説明(46 ) I C.B.CHEMICAL(株)製、商品名「chemiCleaner561B」) 之濃度2%之水溶液進行去脂,經水洗後,於3〇t:之各塗佈 劑中浸塗30秒以達乾燥膜厚5μηι,並以160°C焙燒1〇分鐘而 形成防銹塗膜,則製成被覆鋁板。 (2 )試驗塗板之性能試驗 針對前述各被覆鋁板,而依據以下試驗方法進行塗膜 外觀、親水性及耐餘性之試驗。 塗膜外觀:憑目視並依據以下基準而對防銹塗膜之均 句性加以評價。 a:無凹凸不平並呈均勻之外觀; b :部分有凹凸不平情形; c :全面呈凹凸不平之狀態。 親水性:依據將被覆鋁板浸潰於自來水流水(流水量 係每塗板lm2為15kg/hr)中72小時後之水接觸角而評價親 水性。又,為做比較,則並對進行該試驗前之初期試驗板 做水接觸角之測定(初期親水性)。水接觸角係於w8〇t: 使被覆紹板乾燥5分鐘後,於被覆鋁板之塗面上以注射器滴 下0.04cc之去離子水並形成水滴,再以協和科學(株)製「康 達克坦格爾計《音譯:3^夕夕夕>夕、、小夕一夕一》]:)(::八八型」 測疋水滴之接觸角。而水接觸角越大,則親水性越大。 耐餘性:針對前述各被覆鋁板,並依據;13 Z2371規定 之鹽水噴霧試驗法進行測定。試驗時間分為120小時及240 小時2階段,且依以下基準評價耐蝕性。 a :塗面無白銹及氣泡產生; ------------ 本紙張尺度適财關緖準(CNS)A4規格(210X297公釐) ~ - -49-SaranLatex L-411: manufactured by Asahi Kasei Corporation, trade name, vinylidene chloride resin, solid content 50%. KURARAY RS polymer RS-105: manufactured by Kurary Co., Ltd., trade name, polyvinyl alcohol, solid content 10%. The performance test of the coating agent Π for forming a titanium oxide film of the present invention uses each coating agent prepared in Examples 17 to 27 and Comparative Examples 3 to 5 to perform a rust-proof coating treatment on a steel plate substrate, and inspects the obtained results. Coating film appearance, adhesion and corrosion resistance of coated steel plates. (1) Anti-rust coating place of steel plate base material Various plated steel plates having a plate thickness of 0.8 were used as the base material. Used plating This paper is sized for Chinese National Standard (CNS) A4 (210X297 mm) -44-1224615 A7 B7 5. Description of the invention (42) There are 6 types of steel plates. ⑴Dianzhong Zhongci steel plate: 20g / m2 of mineral deposits, and is called "EG"; (⑴) ^: Minci steel plate: 60g / m2 of mineral deposits, and is called "HDG" · (Hi) Zinc-iron alloy cladding steel sheet: 10% Fe in the ore layer, 60g / m2 plating deposit, and is called "Zn-Fe"; (iv) Zinc-nickel alloy cladding steel sheet: 12% in the coating, (G) Zinc-aluminum alloy plated steel plate: 8% of the amount of the coating, 150g / m2, and called "Zn-12" "% A1"; (vi) Zinc-aluminum alloy coated steel plate · The amount of Ai in the coating is 55%, the bond adhesion amount is 250g / m2, and it is referred to as "Zη · 55% Α1". Spray a 20% solution of alkali degreaser ("ChemiCleaner561B", manufactured by CBCHEMICAL Co., Ltd.) at a liquid temperature of 65 ° C for 20 seconds to remove fat, and then spray 60 ° C. It was washed in warm water for 20 seconds. On the degreased mineral-coated steel plate, each coating agent was sprayed so that the dry coating film weight reached 0.5 g / m2, and the ambient temperature was 250 ° C. Dry for 15 seconds (the material reaches a temperature of 100 ° C) to form an anti-rust coating film. Coated steel sheet. (2) Performance test of coated steel sheet For each coated steel sheet prepared as described above, the coating film appearance, adhesion, and corrosion resistance were tested according to the following test methods. Test method Coating film appearance ·· Visually and according to The following standards are used to evaluate the uniformity of the coating film. This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) (Please read the precautions on the back before filling this page) Order | -45- 1224615 A7 5 、 Explanation of invention (43) (Please read the notes on the back before filling in this page) a: No unevenness and uniform appearance; b: Some unevenness; c: All unevenness. Adhesion · The coating film was subjected to the checkerboard adhesion method (space interval 1 mm) described in jIS [5400-85.2], and the adhesion was evaluated according to the following criteria: a: the coating film was completely free of peeling; b: the coating film was peeling, but The peeling area is less than 5%; c: The peeling area is more than 5% but less than 20%; d: The peeling area is more than 20% but less than 50%; e: The peeling area is more than 50%. End face and inside are sealed and divided into 24 The salt spray test specified in JIS Z2371 was performed at three stages of hours, 48 hours, and 72 hours, and the corrosion resistance was evaluated according to the following criteria: a: No white rust or air bubbles on the coating surface; b: Less than white rust or air bubbles 10% of the area of the coating film; c: The degree of white rust or air bubbles exceeds 10% but not more than 30% of the area of the coating film; d: The degree of white rust or air bubbles exceeds 30% of the area of the coating film but not more Up to 50%; e: the degree of white rust or air bubbles exceeds 50% of the area of the coating film. The test results are shown in Table 6. This paper size applies to Chinese National Standard (CNS) A4 (210X297 mm) -46- 1224615 A7 B7 V. Description of the invention (44) Table 6 Coating agent plating steel sheet coating film appearance adhesiveness surplus 24hr 48hr 72hr Implementation Example 17 EG aaabc Example 18 EG aaabc Example 19 EG aaaab Example 20 HDG aaaaa Example 21. HDG aaaaa Example 22 Zn-Fe aaaab Example 23 Zn-Fe aaaab Example 24 Zn-Ni aaaab Example 25 Zn -12% A1 aaaaa Example 26 Zn-55% A1 aaaaa Example 27 Zn-55% A1 aaaaa Comparative example 3 EG abbcd Comparative example 4 HDG ababc Comparative example 5 Zn-Fe abbcd (Please read the notes on the back before filling (This page) Example 28 of the coating agent Π for forming a titanium oxide film of the present invention Example 28 The titanium-containing aqueous solution (1) obtained in the mixed production example 1 50 parts, 20 parts zirconium hydrofluoric acid 5 parts, "AC10LP "(Made by Benhwa Pharmaceutical Co., Ltd., an aqueous polyacrylic acid solution, a weight average molecular weight of 25,000, an acid value of 779 mgKOH / g, and a solid content of 10%) and 30 parts of deionized water. Titanium film Coating agent. Example 2 9 to 3 3 and Comparative Examples 6 to 7 According to the composition shown in Table 7, the coating agent of the present invention and a comparative coating agent were prepared in the same manner as in Example 28. This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) -47- 1224615 A7B7 V. Description of the invention (45) Table 7 Examples Comparative Examples 28 29 30 31 32 33 6 7 (A) Ingredients (1) 50 50 (2) 50 ⑶ 50 (4) 50 (5) 50 (6) 50 (B) 20% zirconium hydrofluoric acid 5 40% titanium hydrofluoric acid 10 40% silicon hydrofluoric acid 2.5 5 10% metaphosphoric acid 10 5 (C) Ingredients "AC10LP" 30 50 "DENKAPOVALK-05" 20 30 "PEG6000S" 40 30 40 85 Deionized water 15 20 7.5 10 10 5 15 In the aforementioned Table 7, "AC10LP", "DENKAPOVALK-05 (Please Please read the notes on the back before filling out this page) and "PEG6000S" are shown below. AC10LP: manufactured by Japan Chemical Co., Ltd., trade name, polyacrylic acid aqueous solution, weight average molecular weight 25000, acid value 779 mgKOH / g, solid content 10%. DENKA POVAL K-05: manufactured by Denki Chemical Industry Co., Ltd., trade name, polyvinyl alcohol, saponification degree of 99%, polymerization degree of 550, and solid content of 10%. PEG6000S: manufactured by Sanyo Chemical Industries, Ltd., trade name, polyethylene glycol, average molecular weight 8300, and solid content 10%. The performance test of the coating agent U for forming a titanium oxide film of the present invention uses each coating agent prepared in Examples 28 to 33 and Comparative Examples 6 to 7 to perform an antirust coating treatment on an aluminum substrate, and inspects the obtained Coating film appearance, hydrophilicity and #resistance of coated aluminum plate. (1) The rust-proof coating treatment of the aluminum base material is made of aluminum plate (A1050) with a thickness of 0.1 liters with an alkali degreasing agent (the paper size of this paper applies the Chinese National Standard (CNS) A4 specification (210X297 mm)- 48- 1224615 A7 ___ B7 V. Description of the invention (46) I CBCHEMICAL Co., Ltd. (trade name "chemiCleaner561B") in a concentration of 2% aqueous solution for degreasing, after washing with water, each coating at 30t: It was dip-coated in the agent for 30 seconds to achieve a dry film thickness of 5 μm, and baked at 160 ° C. for 10 minutes to form a rust-preventive coating film, and a coated aluminum plate was prepared. (2) Performance test of the test coated plate For each of the foregoing coated aluminum plates, the test of the appearance, hydrophilicity and resistance of the coating film was performed according to the following test methods. Coating film appearance: The uniformity of the anti-rust coating film was evaluated visually and based on the following criteria. a: No unevenness and uniform appearance; b: Partial unevenness; c: Full unevenness. Hydrophilicity: Hydrophilicity was evaluated based on the water contact angle after the coated aluminum plate was immersed in running water (flowing amount was 15 kg / hr per 1 lm2 of coated plate) for 72 hours. For comparison, an initial test plate before the test was measured for water contact angle (initial hydrophilicity). The water contact angle is at 80 ° C: After drying the coated plate for 5 minutes, 0.04cc of deionized water was dripped on the coated surface of the coated aluminum plate with a syringe to form water droplets. Then, the product was manufactured by Kyowa Scientific Co., Ltd. The Tanger meter "Transliteration: 3 ^ Xixi Xi > Xi ,, Xiaoxi Yixiyi"]:) (:: type of eight or eight "measures the contact angle of water droplets. The larger the water contact angle, the more hydrophilic The larger the remaining resistance: For each of the foregoing coated aluminum plates, and measured in accordance with the salt spray test method specified in 13 Z2371. The test time is divided into two stages of 120 hours and 240 hours, and the corrosion resistance is evaluated according to the following criteria. A: Coating There is no white rust and air bubbles on the surface; ------------ This paper is suitable for standard size (CNS) A4 (210X297 mm) ~--49-
......----- (請先閲讀背面之注意事項再填寫本頁) 訂— 1224615 A7 B7 五、發明説明(47 b :白銹或氣泡之產生程度未達塗膜面積之1〇% ; 白銹或氣泡之產生程度超過塗膜面積之1〇%但未達 30% ; d·白錄或氣泡之產生程度超過塗膜面積之但未達 50% ; e:白銹或氣泡之產生程度超過塗膜面積之5〇% 試驗結果顯示於表8。 表8 塗佈劑 塗膜 外觀 初期親水性 水接觸角 親水性 水接觸角 对钱性 120hr 240hr 實施例28 a < 5° 20-30° a a 實施例29 a < 5° 20-30° a a 實施例30 a < 5° 20-30° a b 實施例31 a < 5° 20-30° a b 實施例32 a < 5° 20-30° a a 實施例33 a < 5° 20-30° a b 比較例6 a < 5° 40-50° b c 比較例7 a < 5° >50° c e (請先閲讀背面之注意事項再填寫本頁) 、可| -管· 形成方法及被覆有氧化鈦膜之金屬基材,則可致下列之特 殊效果。 (1) 本發明之塗佈劑係具有優異之貯藏安定性。其理 由在於’含鈦水成液(A)本身即呈安定狀態,且該水成 液(A )與磷酸系化合物、鈦齒化物等(b )或(B,)可形 成安定之錯合物。 (2) 依據使用本發明之用以形成氧化鈦膜之塗佈劑之 氧化鈦膜形成方法,則可於金屬基材上形成一耐餘性、黏 附性、耐久性、加工性、親水性等倶佳,且含氧化鈦之塗 本紙張尺度適用中國國家標準(CNS) A4規格(210X297公釐) -50- ^24615 A7 ^ -----—---— B7 五、發明説明(48) ~~ ---- 膜。 議之耐餘性或耐久性佳,理由有:其對基材之黏 附性佳,而因其為細密之氧化鈦膜故氧透過性或水蒸氣透 過性小,且鱗酸系化合物、鈦齒化物等⑻<(B,)對 金屬具有作為餘刻劑及腐餘抑制劑之機能,以及鱗酸系化 合物、鈦鹵化物等(B或B,)可受氧化鈦保護· ·等。 (3 )運用本發明之氧化鈦膜形成方法所得之被覆金屬 基材係可作為防銹被覆基材而直接加以使用。 (4 )利用將本發明之塗佈劑塗附於鋁或鋁合金基材之 表面而形成塗膜之熱交換器用葉片,則可防止於冷房時產 生之凝結水於葉片間形成水之聯結。因此,乃可防止鋁或 鋁合金製之葉片腐蝕。 (請先閲讀背面之注意事項再填寫本頁) ir— 旁 本紙張尺度適用中國國家標準(CNS) A4規格(210X297公釐) -51-......----- (Please read the precautions on the back before filling this page) Order — 1224615 A7 B7 V. Description of the invention (47 b: The degree of white rust or air bubbles does not reach the area of the coating film 10%; the degree of white rust or air bubbles exceeds 10% but less than 30% of the area of the coating film; d. The degree of white rust or air bubbles exceeding the area of the film but not more than 50%; e: white rust or The degree of air bubble generation exceeds 50% of the area of the coating film. The test results are shown in Table 8. Table 8 Hydrophilic water contact angle at the initial stage of the appearance of the coating film of the hydrophilic water contact angle 120hr 240hr Example 28 a < 5 ° 20-30 ° aa example 29 a < 5 ° 20-30 ° aa example 30 a < 5 ° 20-30 ° ab example 31 a < 5 ° 20-30 ° ab example 32 a & lt 5 ° 20-30 ° aa Example 33 a < 5 ° 20-30 ° ab Comparative Example 6 a < 5 ° 40-50 ° bc Comparative Example 7 a < 5 ° > 50 ° ce (please first Read the precautions on the back and fill in this page again),-| Tubes, forming methods, and metal substrates coated with titanium oxide film can cause the following special effects. (1) The coating agent of the present invention has excellent Store Stability. The reason is that the titanium-containing aqueous solution (A) itself is in a stable state, and the aqueous solution (A) and phosphoric acid-based compounds, titanium dental compounds (b) or (B,) can form a stable (2) According to the method for forming a titanium oxide film using the coating agent for forming a titanium oxide film of the present invention, a metal substrate can be formed with a residue resistance, adhesion, durability, and processability. And hydrophilicity, and the size of coated paper containing titanium oxide is applicable to Chinese National Standard (CNS) A4 specification (210X297 mm) -50- ^ 24615 A7 ^ ----------------- B7 V. Invention Explanation (48) ~~ ---- Film. The recommended residual resistance or durability is good. The reasons are: its adhesion to the substrate is good, and because it is a fine titanium oxide film, it has oxygen permeability or water vapor. Permeability is low, and 鳞 < (B,), such as scaly acid-based compounds, titanium dendrites, has a function as a preservative and corrosion inhibitor for metals, and scaly acid-based compounds, titanium halides, etc. (B or B, ) Can be protected by titanium oxide, etc. (3) The coated metal substrate obtained by using the titanium oxide film forming method of the present invention can be It is directly used for rust-proof coating the substrate. (4) The heat exchanger blades formed by applying the coating agent of the present invention to the surface of an aluminum or aluminum alloy substrate to form a coating film can be prevented from occurring in a cold room. The condensed water forms a water connection between the leaves. Therefore, it is possible to prevent corrosion of the blade made of aluminum or aluminum alloy. (Please read the precautions on the back before filling out this page) ir—next This paper size applies to China National Standard (CNS) A4 (210X297 mm) -51-
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JP4737868B2 (en) * | 2000-07-25 | 2011-08-03 | 関西ペイント株式会社 | Inorganic film forming coating agent, inorganic film forming method, surface treatment agent for aluminum-containing metal material, hydrophilized heat exchanger aluminum fin material, and method for producing heat exchanger aluminum fin material |
JP2004076024A (en) * | 2002-08-09 | 2004-03-11 | Nippon Paint Co Ltd | Aluminum base material treatment method and product |
JP2005206708A (en) * | 2004-01-23 | 2005-08-04 | Nippon Paint Co Ltd | Method for producing titanium oxide membrane |
JP4575047B2 (en) * | 2004-06-29 | 2010-11-04 | 関西ペイント株式会社 | Metal surface treatment composition and metal surface treatment steel plate |
JP2007022844A (en) * | 2005-07-15 | 2007-02-01 | Sustainable Titania Technology Inc | Oxide composite film, coating liquid for forming the film, method of manufacturing the coating liquid and method of forming the film |
JP4612533B2 (en) * | 2005-11-30 | 2011-01-12 | Jsr株式会社 | Method for forming aluminum film |
JP2007177142A (en) * | 2005-12-28 | 2007-07-12 | Furukawa Co Ltd | Titania film-forming liquid and method for producing the same |
JP2007327001A (en) * | 2006-06-09 | 2007-12-20 | Yamada Fumitaka | Inorganic coating composition |
JP2007327000A (en) * | 2006-06-09 | 2007-12-20 | Koji Yamada | Inorganic coating composition |
CA2801420C (en) * | 2010-06-09 | 2019-07-23 | Chemetall Gmbh | Inorganic chromium-free metal surface treatment agent |
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US20200216963A1 (en) * | 2019-01-03 | 2020-07-09 | The Boeing Company | Titanium-based coatings and methods for making coatings |
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