201100589 六、發明說明： 【發明所屬之技術領域】 本發明是有關於一種液態組成物，特別是指一種用以 在一金屬基材上形成一皮膜之液態組成物。本發明另有關 於一種藉由該液態組成物來進行的皮膜製備方法，以及一 種被設置在一金屬基材上之皮膜。 【先前技術】 〇 為提升抗蝕性、易潔性，與後續上漆性，常需在一金 屬基材表面披覆上一皮膜，而形成一金屬層疊物；該皮膜 是藉由使一皮膜形成用組成物經過塗佈或浸覆該金屬基材 表面後再被乾燥而獲得。 ' 一般而5皮膜分為有機皮膜與無機皮膜兩類。有機皮 • 膜的材質為高分子聚合物，其缺點是與底下金屬基材之附 著性不足、皮膜較厚且不耐高溫，使得其金屬層疊物的後 續應用受限；氧化矽為一種常見之無機皮膜材質，其所形 Q 成的無機皮膜厚度較上述有機者為薄，但同樣地會有與底 下金屬基材之間的附著性不足之缺點’且用以形成此種皮 膜之液態組成物通常為鹼性，而普遍地以氫氧化鈉或氫氧 化鉀配製’但此等驗性物質的存在不僅使得該液態組成物 容易有膠體沉澱的情形發生，繼而影響到後續皮膜之透明 性與均勻性，同時亦降低了該皮膜的耐水性。 另有一種材質為矽烷類之皮膜，亦在本業界中被廣泛 地使用，然其缺點在於，基於矽烷類之物性本質使得形 • 成該皮膜之液態組成物是以有機溶劑來製備，而容易引發 3 201100589 環保疑慮，也易對所接觸到的人員造成健康上的不良影響 0 含有磷酸鋁之皮膜基於其良好的特性（例如耐溫性、耐 水性、皮膜厚度薄）’而在本業界中漸受重視，其製傷方法 則例如有水熱法與電化學法；然、，此等製備方法卻有步驟 繁靖、處理時間冗長、耗能極大、對環境不夠友善等缺點 0 4另一方面，若欲使皮膜進一步地具有某功能性（例如可 抗菌、抗磨耗等）’ 一般說來都是依序使一特定的功能性奈 米材料（例如奈米銀、奈米氧化紹）與一高分子材料溶液塗佈 於"玄皮膜上’待5¾ tfj分子材料溶液乾燥後，即能固定住其 所披覆之功能性奈米材料，然而高分子材料卻也相對地將 其遮蔽住，而大幅減損了該功能性奈米材料在其作用發揮 時的效益。 是以，本業界目前除了需要一在處理上具有操作簡便 時間紐，且耗能量低等優點的方法以製備品質佳含有磷 馱鋁之皮膜以外，更期待該皮膜與功能性奈米材料間的結 s，可使该功能性奈米材料的效果能更徹底地發揮。 【發明内容】 申請人發現，當一用以形成含磷酸鋁之皮膜的液態組 成物中更含有硝酸根時，其不但可在該濕膜被乾燥的過程 中加速連結劑的氧化，亦會因受高溫分解而使釋出的熱量 協助該濕膜中的溶劑脫除'加速該皮膜之形成，從而達到 快速、簡便地製備該皮膜之目的；另，氧化性未療飽和之 201100589 含磷的酸根（例如亞磷酸根）則在皮膜形成後可與空氣中的氧 作用，因此可有效地加強該皮膜的緻密性。 於是’本發明之第一目的，是在於提供一種用以形成 含填酸铭之皮膜的液態組成物，包含：一連結劑、水、紹 離子、硝酸根，以及一含磷之酸根，其包括磷酸根，與亞 鱗酸根、聚填酸根、焦麟酸根中之至少一者；其中，該連201100589 VI. Description of the Invention: [Technical Field] The present invention relates to a liquid composition, and more particularly to a liquid composition for forming a film on a metal substrate. The invention further relates to a method of preparing a film by the liquid composition, and a film disposed on a metal substrate. [Prior Art] In order to improve corrosion resistance, easy cleanability, and subsequent lacquering, it is often necessary to coat a metal substrate with a film to form a metal laminate; the film is formed by a film. The composition for forming is obtained by coating or immersing the surface of the metal substrate and then drying it. 'Generally, the 5 membranes are divided into organic membranes and inorganic membranes. Organic skin • The material of the membrane is a high molecular polymer. The disadvantage is that the adhesion to the underlying metal substrate is insufficient, the film is thick and not resistant to high temperatures, which makes the subsequent application of the metal laminate limited; cerium oxide is a common Inorganic film material, the shape of the inorganic film formed by Q is thinner than that of the organic one, but similarly, there is a disadvantage of insufficient adhesion to the underlying metal substrate, and the liquid composition for forming such a film Usually alkaline, and generally formulated with sodium hydroxide or potassium hydroxide', but the presence of such an organic substance not only makes the liquid composition susceptible to colloid precipitation, but also affects the transparency and uniformity of the subsequent film. Sex, while also reducing the water resistance of the film. Another type of film which is a decane type is also widely used in the industry. However, the disadvantage is that the liquid composition of the film is prepared by using an organic solvent based on the physical nature of the decane. 3 201100589 Environmental concerns, it is also easy to cause adverse health effects on the people exposed to it. 0 The film containing aluminum phosphate is based on its good characteristics (such as temperature resistance, water resistance, thin film thickness). Gradually pay attention to, the methods of injury are, for example, hydrothermal and electrochemical methods; however, these preparation methods have the disadvantages of complicated steps, long processing time, high energy consumption, and lack of environmental friendliness. In addition, if the film is to have a certain functionality (for example, antibacterial, anti-wear, etc.), it is generally sequential to make a specific functional nanomaterial (such as nano silver, nano-oxidation) and A polymer material solution is coated on the "skin film' After the solution of the 53⁄4 tfj molecular material is dried, the functional nanomaterial coated by the polymer material can be fixed, but the polymer material Also relatively to the shield housing, and significantly detract from the effectiveness when the functional nanomaterial play its role. Therefore, in addition to the need for a process that has a simple operation time and low energy consumption, the present invention is expected to prepare a film containing a high-quality phosphorous-aluminum film, and is expected to be between the film and the functional nanomaterial. The knot s can make the effect of the functional nano material more thoroughly. SUMMARY OF THE INVENTION Applicants have found that when a liquid composition for forming a film containing aluminum phosphate further contains nitrate, it not only accelerates the oxidation of the bonding agent during the drying of the wet film, but also causes Decomposition by pyrolysis causes the released heat to assist the solvent removal in the wet film to accelerate the formation of the film, thereby achieving the purpose of preparing the film quickly and easily. In addition, the oxidative untreated saturated 201100589 phosphate-containing acid radical (for example, phosphite) can react with oxygen in the air after the film is formed, so that the compactness of the film can be effectively enhanced. Thus, the first object of the present invention is to provide a liquid composition for forming a film containing an acid filling, comprising: a linking agent, water, a sulphur ion, a nitrate, and a phosphorus-containing acid group, including Phosphate, at least one of squarate, poly-salt, and sulphate; wherein
結劑疋釀類及/或胺基酸’且該組成物中之碟與銘的莫耳數 比值是介於0.3〜2.0之間。 本發明之第二目的，在於提供一種含磷酸鋁之皮膜的 製備方法，該皮膜是披覆於一金屬基材上，而該製備方法 包含：使該金屬基材受如本發明第一目的之用以形成含磷 酸鋁之皮膜的液態組成物所浸覆，而形成出一附著於該金 屬基材表面上之濕膜後，使該濕膜在一介於15〇<)(：〜35〇艺 之間的溫度下被乾燥，而獲得所欲之皮膜。 進一步地，本發明第一目的之液態組成物可被摻入各 種功能性奈米材料’使得該功能性奈米材料在該薄薄的皮 膜形成出之後’即在未受過度遮蔽的型態下被固定，使得 其功能得以發揮。 因此’本發明之第三目&，在於提供一種皮膜，其是 被設置在一金屬基材上，兮由瞪由 这皮膜包含磷酸鋁，與一和磷酸 鋁相互摻雜之一功能性奈米材料。 【實施方式】 本發明各目的之基本要件 目的提供進一步之技術建議； 如上所述，以下將分別就各 需注意的是，倘未特別說明 201100589 本發月在實施上所使用之各條件（例如物料種類與含量）， 基本上並未^特殊限制’而所提出之相關建議則是基於成 本與後續皮膜的品質之合併考量。另，若未特別說明則 下述之各物料在本發明用以形成含麟酸銘之皮臈的液態組 成物中的含量建議，是以本發明液態組成物為i〇〇 wt%來 估計。 需說明的是，就本發明用以形成含磷酸鋁之皮膜的液 態組成物中，基於所必須包含的鋁離子、硝酸根，與含磷 之酸根，本發明液態組成物無庸置疑地，亦允許更包含有 其他用以使該液態組成物達成電荷平衡之抗衡離子 ion);若為使本發明液態組成物所形成出的皮膜中的主要成 份為磷酸鋁，較佳地，該抗衡離子是包括有可在後續濕膜 被乾燥之階段（其溫度是介於15(rc 〜35(rc )中遇熱而分解者 如此即不會殘留在該皮膜中。較佳地，該抗衡離子是包 括有銨根、過氣酸根、氣酸根、有機胺類離子，或此等之 一組合。抗衡離子之所含種類亦可作為在配製本發明液態 組成物時選用物料的參考。 本發明用以形成含磷酸鋁之皮膜的液態組成物令之磷 與紹的莫耳數比值除了基本上是介於〇 3〜2 〇之間以外， 較佳地是介於0.5〜1.5之間，更佳地則是介於〇8〜丨丨之 間。於以下實施例中所示範的，其磷與鋁的莫耳數比值是 介於0.66〜2之間。The binder is brewed and/or the amino acid' and the molar ratio of the dish to the mark in the composition is between 0.3 and 2.0. A second object of the present invention is to provide a method for preparing a film containing aluminum phosphate, which is coated on a metal substrate, and the preparation method comprises: subjecting the metal substrate to the first object of the present invention The liquid composition for forming a film containing aluminum phosphate is immersed to form a wet film attached to the surface of the metal substrate, so that the wet film is between 15 〇 and lt;) (: 〜35 〇) Further, the temperature between the arts is dried to obtain a desired film. Further, the liquid composition of the first object of the present invention can be incorporated into various functional nanomaterials such that the functional nanomaterial is thin. After the film is formed, it is fixed in a state that is not over-masked, so that its function is exerted. Therefore, the third object of the present invention is to provide a film which is disposed on a metal substrate. In the above, a functional nanomaterial is doped with aluminum phosphate and aluminum phosphate and aluminum phosphate. [Embodiment] The basic object of each object of the present invention provides further technical advice; In the following, it should be noted that if the conditions (such as the type and content of materials) used in the implementation of this month are not specified, there is basically no special restriction and the relevant recommendations are Based on the cost and the quality of the subsequent film, if not specified, the following materials are recommended in the liquid composition of the present invention for forming a skin composition containing linonic acid, which is a liquid state of the present invention. The composition is estimated by i〇〇wt%. It is to be noted that, in the liquid composition for forming an aluminum phosphate-containing film of the present invention, based on the aluminum ions, nitrates, and phosphorus-containing acid groups which must be contained, The liquid composition of the present invention is undoubtedly also allowed to further contain other counter ions (ion) for achieving charge balance of the liquid composition; if the main component of the film formed by the liquid composition of the present invention is phosphoric acid Aluminium, preferably, the counter ion is included in a stage in which the subsequent wet film is dried (the temperature is between 15 (rc 〜 35 (rc) and decomposed by heat, so that it does not remain in Preferably, the counter ion comprises ammonium, percarbonate, oleate, organic amine ion, or a combination thereof. The species of the counter ion may also be used in formulating the liquid composition of the present invention. The material is used as a reference for the material. The liquid composition for forming the aluminum phosphate-containing film of the present invention is such that the ratio of phosphorus to molar ratio is substantially between 〇3 and 2 〇, preferably It is between 0.5 and 1.5, and more preferably between 〇8 and 丨丨. As exemplified in the following examples, the molar ratio of phosphorus to aluminum is between 0.66 and 2.
就紹離子在本發明用以形成含磷酸鋁之皮膜的液態組 成物中之濃度而言，較佳地，鋁離子的濃度是介於〇 〇5 M 201100589 〜2·0 Μ之間，更佳地則是介於〇丨河〜丨〇 m之間。 本發明用以形成含磷酸鋁之皮膜的液態組成物是以水 為溶劑’ iU匕基本上在配製本發明液態組成物b夺所選用 的㈣皆為可溶於水，或者可溶於酸性水液者。就紹離子 =言，其是源自於一經溶解之鋁化合物，例如硝酸鋁、氫 氧化鋁、過氣酸鋁、氣化鋁、硫酸鋁，或此等之一組合， 其中較佳地則為硝酸鋁、氫氧化鋁、過氣酸鋁，或此等之 〇 .、且a於以下實施例中所示範的，是使用硝酸銘、氣化 鋁來獲得鋁離子，且該鋁離子的濃度，是介於〇.〗Μ〜ι 〇 Μ之間。 另’该含鱗之酸根是包括有構酸根，與亞磷酸根、聚 、 磷酸根【Ρη〇3η+1(η + 2)-，例如Ρ3〇105-、Ρ4〇丨36-】、焦磷酸根【 Ρ2〇7】中之至少一者。在本發明液態組成物中’所需要的 該含碟之酸根的濃度，自可由磷與鋁的莫耳數比值以及 所預定之鋁離子濃度來計算。 在該含磷之酸根中，磷酸根是源自於磷酸或經溶解之 碟酸鹽；亞磷酸根是源自於亞磷酸或一可溶於水之亞磷酸 鹽；該聚磷酸根是源自於聚磷酸或一可溶於水之聚磷酸鹽 ;而該焦磷酸根則是源自於焦磷酸或一可溶於水之焦磷酸 鹽。其中，磷酸鹽較佳地是擇自於磷酸氫銨、磷酸氫二銨 ’或此等之一組合；亞磷酸鹽較佳地是擇自於亞磷酸氫銨 、亞磷酸氫二銨，或此等之一組合；聚磷酸鹽較佳地是擇 自於聚磷酸銨、聚磷酸鈉，或此等之一組合；而焦磷酸鹽 較佳地則是擇自於焦磷酸鈉、焦磷酸鉀，或此等之一組合 201100589 。該含磷之酸根亦可由磷之氧化物來獲得。於以下實施例 中所示範的，是使用磷酸、亞磷酸、聚磷酸、焦磷酸，與 此等之一組合來獲得含磷之酸根。 另就本發明液態組成物中之硝酸根而言，其濃度較佳 地是介於0.15 Μ〜6.0 Μ之間，更佳地是介於0.3 Μ〜3.0 Μ 之間。而該硝酸根是源自於硝酸或一硝酸鹽；該硝酸鹽較 佳地是擇自於硝酸鋁、硝酸銨，或此等之一組合。於以下 實施例中所示範的，是使用硝酸、硝酸鋁來獲得硝酸根， 且硝酸根之濃度是介於0.2 Μ〜3.0 Μ之間。 本發明液態組成物中的連結劑是醣類及/或胺基酸，較 佳地，該連結劑之含量是佔本發明液態組成物之10 wt%以 下但超過0 wt% ，更佳地則是介於0.01 wt%〜5 wt%之間。 而該醣類則是擇自於單醣、雙醣、寡醣、多醣、醣類 衍生物，或此等之一組合。單醣是例如葡萄糖（glucose)、葡 聚七糖（heptaglucose)、果糖（fructose)、半乳糖（galactose)， 或此等之一組合。雙醣則例如乳糖（lactose)、蔑糖（sucrose) 、麥芽糖（maltose)，或此等之一組合。寡醣則例如棉籽糖 (raffinose)、海藻糖（fucose)，或此等之一組合。多醣則例如 阿拉伯膠（arabian gum)、糖原（glycogen)、可溶性澱粉、纖 維素（cellulose)、钻多糖（mucopolysaccharides)、半纖維素 (hemicellulose)、殼糖（chitin，或稱為「幾丁聚質」；其水溶 性商品多半經過去乙醯化）、水蘇糖（stachyose)、菊糖 (inulin)、糊精（dextrin)，或此等之一組合。醣類衍生物則例 如胺糖【amino-sugar，例如N-乙醯-葡萄胺糖（N-acetyl- 201100589 glucosamine)、葡萄胺糖（giucosamine)，或此等之一組人】 就胺基酸而言，較佳地是擇自於甘胺酸、丙胺酸、白 胺酸、絲胺酸、蘇胺酸、半胱胺酸、天冬胺酸、天冬醯胺 酸、麵胺酸、麵醯胺酸、精胺酸、離胺酸、組胺酸、絡胺 酸、色胺酸、脯胺酸，或此等之一組合。於以下實施例中 所示範的，所使用的連結劑包括有甘胺酸、薦糖、殼糖、 ΟIn terms of the concentration of the ion in the liquid composition for forming the aluminum phosphate-containing film of the present invention, preferably, the concentration of the aluminum ion is between 〇〇5 M 201100589 〜2·0 ,, more preferably The land is between the rivers and the rivers. The liquid composition for forming a film containing aluminum phosphate according to the present invention is water as a solvent 'iU 匕 substantially in formulating the liquid composition b of the present invention. (4) are all soluble in water or soluble in acidic water. Liquid. Said ion, which is derived from a dissolved aluminum compound, such as aluminum nitrate, aluminum hydroxide, aluminum percarbonate, aluminum aluminide, aluminum sulfate, or a combination thereof, wherein preferably Aluminum nitrate, aluminum hydroxide, aluminum percarbonate, or the like, and a is exemplified in the following examples, using aluminum nitrate, vaporized aluminum to obtain aluminum ions, and the concentration of the aluminum ions, It is between 〇.〗 Μ ~ι 〇Μ. Another 'the scaly acid root is composed of phytate, with phosphite, poly, phosphate [Ρη〇3η+1 (η + 2)-, such as Ρ3〇105-, Ρ4〇丨36-], pyrophosphate At least one of the roots [Ρ2〇7]. The concentration of the acid-containing acid salt required in the liquid composition of the present invention can be calculated from the molar ratio of phosphorus to aluminum and the predetermined aluminum ion concentration. In the phosphorus-containing acid radical, the phosphate is derived from phosphoric acid or a dissolved disc acid salt; the phosphite is derived from phosphorous acid or a water-soluble phosphite; the polyphosphate is derived from In polyphosphoric acid or a water-soluble polyphosphate; and the pyrophosphate is derived from pyrophosphoric acid or a water-soluble pyrophosphate. Wherein, the phosphate is preferably selected from the group consisting of ammonium hydrogen phosphate, diammonium hydrogen phosphate or a combination thereof; the phosphite is preferably selected from ammonium hydrogen phosphite, diammonium hydrogen phosphite, or One combination; the polyphosphate is preferably selected from the group consisting of ammonium polyphosphate, sodium polyphosphate, or a combination thereof; and the pyrophosphate is preferably selected from sodium pyrophosphate or potassium pyrophosphate. Or one of these combinations 201100589. The phosphorus-containing acid radical can also be obtained from an oxide of phosphorus. Demonstrated in the following examples is the use of phosphoric acid, phosphorous acid, polyphosphoric acid, pyrophosphoric acid, in combination with one of these to obtain a phosphorus-containing acid radical. Further, in the case of the nitrate in the liquid composition of the present invention, the concentration is preferably between 0.15 Μ and 6.0 Μ, more preferably between 0.3 Μ and 3.0 Μ. The nitrate is derived from nitric acid or a nitrate; the nitrate is preferably selected from aluminum nitrate, ammonium nitrate, or a combination thereof. Demonstrated in the following examples is the use of nitric acid, aluminum nitrate to obtain nitrate, and the concentration of nitrate is between 0.2 Μ and 3.0 Μ. The linking agent in the liquid composition of the present invention is a saccharide and/or an amino acid. Preferably, the amount of the linking agent is less than 10% by weight of the liquid composition of the present invention but more than 0% by weight, more preferably It is between 0.01 wt% and 5 wt%. The saccharide is selected from the group consisting of a monosaccharide, a disaccharide, an oligosaccharide, a polysaccharide, a saccharide derivative, or a combination thereof. Monosaccharides are, for example, glucose, heptaglucose, fructose, galactose, or a combination of these. Disaccharides are, for example, lactose, sucrose, maltose, or a combination of these. Oligosaccharides are, for example, raffinose, fucose, or a combination of these. Polysaccharides such as arabic gum, glycogen, soluble starch, cellulose, mucopolysaccharides, hemicellulose, chitin, or chitin Quality; most of its water-soluble products are de-acetated), stachyose, inulin, dextrin, or a combination of these. The saccharide derivative is, for example, an amino sugar (amino-sugar, such as N-acetyl-201100589 glucosamine, giucosamine, or a group thereof). Preferably, it is selected from the group consisting of glycine, alanine, leucine, serine, threonine, cysteine, aspartic acid, aspartic acid, facial acid, and noodles. Proline, arginine, lysine, histidine, lysine, tryptophan, valine, or a combination of these. As exemplified in the following examples, the linking agent used includes glycine, sucrose, chitin, sputum
葡萄糖胺、離胺酸、甦胺酸、葡萄糖，而該等連結劑之含 量是佔本發明液態組成物的〇 〇〇2 wt%〜〇 15 之間。 除了上述之各種必要組份之外，本發明用以形成含磷 酸鋁之皮膜的液態組成物更可視需要，而另包含有一濕潤 劑、-抗菌劑、一安定劑，或此等之一組合。上述各式添 加劑之使用方式已為本領域所熟知，故相關細節在此不予 贅述。 …：，特別地，本發明用以形成含磷酸鋁之皮膜的液態 組成物可另包含有-功能性奈米材料，藉此可使得當該液 態組成物之後所形成出的皮膜，而能基於該功能性奈米材 料的存在以具有所對應的功效；該功能性奈来材料可例如 為奈米銀（其有抗菌之功效）、鈦氧膠（料光觸媒用）、夺米 氧化⑽以增料隸性）'錢㈣料疏水性與 润滑性)、過渡金屬元素離子(作為表面催化劑或特殊光電材 料）’或此等之一組合。 该功能性奈米材料在本發明用以形成含鱗酸紹之皮膜 的液態組成物之非溶劑部分中所佔的含量，較佳地是介 於0·001 Wt%〜2.〇 Wt%之間，更佳地，是介於0.2 wt%〜 9 201100589 1.0 wt% 之間。 為有助於濕膜的形成，本發明用以形成含磷酸鋁之皮 膜的液態組成物的pH值，較佳地是介於05〜3 5之間，更 佳地則是介於L0〜2.5之間。於以下實施例中所示範的， 本發明用以形成含魏狀皮模的液隸成物的pH值是介 於1’1 2.0之間。於配製本發明液態組成物時，較佳地是 藉氨水與硝酸來調整至所欲之pH值。 有關於本發明之用以製備一披覆於一金屬基材上之皮 膜的方法包3 ·使該金屬基材受上述之本發明用以形成 3 W酸鋁之皮膜的液態組成物所浸覆，而形成出一附著於 該金屬基材表面上之濕膜後，使該濕膜在一介於15〇艺〜 350 C之間的溫度下被乾燥，而獲得所欲之皮膜。 基本上，有確實浸覆到本發明液態組成物之金屬基材 ,、表面P可幵/成出忒濕膜而當該濕膜不再具濕潤感時 ，即表示其已轉化為所欲之皮膜。如欲更精細地判斷，則 可測試該皮膜的表面是否具疏水性與财磨耗性；若是，即 表示該濕膜已被完全地乾燥，若則表示皮膜烘烤不足 ，使得其表面的羥基殘餘過多，而缺乏疏水性。 基於本發明方法之操作，與其所使用之本發明液態纪 成物的成分，較佳地是使所獲得的皮財的主要成分為碟 酸铭’例如使其含量㈣皮膜之95 wt%以上，甚至 wt%以上。 疋 每皮膜的厚度越薄 時所需的時間也就越少 ，或烘乾時所採之溫度越高，乾燥 以厚度為0.5 mm ’材質為不錢鋼 10 201100589 之金屬基材為例，當所獲得之皮膜厚度為i μπι時，於先前 是在150°C〜185°C的溫度範圍下烘乾，則所需時間約是介 於0·8分鐘〜5分鐘不等。 另有關於該金屬基材之材質’並無特殊限制，而可為 鐵、鋁、鎳、辞、錫、鈦、銅，或上述任一金屬之合金。 於以下實施例中所示範的，所使用之金屬基材的材質為不 銹鋼、鋁、銅。 〇 當本發明用以形成含磷酸鋁之皮膜的液態組成物更包 含有功能性奈米材料時’以其所製備而得的皮膜亦為本發 明所欲者。 本發明皮膜’是被設置在一金屬基材上，該皮膜包含 磷酸紹，與一和磷酸鋁相互摻雜之一功能性奈米材料。就 S亥皮膜之成分而S ’在一理想狀態下，碟酸紹即為該皮膜 之主要成分’該功能性奈米材料則為次要成分，甚至本發 明皮膜僅含此兩者；較佳地，磷酸鋁之含量是佔該皮膜之 q 95 wt%以上但未達100 wt% ，該功能性奈米材料之含量則 佔該皮膜之5 wt%以下但超過0 wt% 。 有關於該皮膜中之功能性奈米材料的種類，如先前於 本發明液態組成物中所述’在此不予贅述。而就本發明皮 膜之厚度而言，是較一般的有機皮膜為薄，通常是介於2〇 nm〜5 μιη之間，或者介於50nm〜2 μιη之間。 以下將以實施例來說明本發明各目的之實施方式與功 效。該等實施例將使用下列化學品與設備來進行；若無特 . 別交代，實施例之製備及後續之各項測試與評估，皆是在 11 201100589 常溫常壓的環掊 旧衣境下進仃。須注意的是，該實施例僅為例示 日月 ro τ. ’而不應被解釋為本發明實施之限制。 <實施例> h不銹鋼基材：由健瀚公司所提供，型號為304。 2·鋁基材.由中鋼公司所提供，型號為5052。 3·甘胺酸：由第一化工公司所提供；食品級。 4. 蔗糖·由台糖公司所提供；食品級。 5. 殼糖：由第一化工公司所提供；食品級。 6. 葡萄糖胺：由第一化工公司所提供；食品級。 7·離胺酸：由第一化工公司所提供；食品級。 8·麩胺酸：由第一化工公司所提供；食品級。 9·葡萄糖：由第一化工公司所提供；食品級。 1〇·氣化鋁：由第一化工公司所提供，純度為99°/。。 11. 硝酸鋁：由第一化工公司所提供，型號為工業級。 12. 硝酸：純度為68% ，工業級；由和達公司所提供。 13. 鱗酸.純度為85% ，工業級；由和達公司所提供。 14. 亞磷酸：由第一化工公司所提供，型號為98% 。 15. 聚磷酸（Ηη+2Ρη〇3η+ι):同 105% 磷酸；由 Aldrich 公司 所提供。 16. 焦磷酸（H4P2〇7):同20% h3P〇4 ;由Alddch公司所提 供。 17·氨水：由第一化工公司所提供’型號為28% 。 12 201100589 本發明用以形成含磷酸鋁之皮膜的液熊細忐物· 將各離子源與連結劑摻混於去離子水中以被溶解，並 藉由氣水來使所形成出的液態組成物具有所欲之pH值，而 獲得本發明用以形成含磷酸鋁之皮膜的液態組成物之各實 施例，其等所使用之物料與相關的離子濃度，如表一中所 列，其中，磷酸根、亞磷酸根、聚磷酸根、焦磷酸根的來 源各為麟酸、亞構酸、聚填酸、焦鱗酸。Glucosamine, lysine, threonine, glucose, and the amount of these linkers is between wt 2 wt% and 〇 15 of the liquid composition of the present invention. In addition to the various necessary components described above, the liquid composition of the present invention for forming a film of an aluminum phosphate-containing film is more optionally required, and further comprises a wetting agent, an antibacterial agent, a stabilizer, or a combination thereof. The manner in which the above various additives are used is well known in the art, and the relevant details are not described herein. In particular, the liquid composition for forming a film containing aluminum phosphate according to the present invention may further comprise a functional nanomaterial, whereby the film formed after the liquid composition can be based on The functional nanomaterial is present to have the corresponding efficacy; the functional nai material can be, for example, nano silver (which has antibacterial effect), titanium oxide gel (for photocatalyst), and rice oxidization (10). Material characterization) 'money (four) material hydrophobicity and lubricity), transition metal element ions (as surface catalyst or special photovoltaic material) ' or a combination of these. The content of the functional nanomaterial in the non-solvent portion of the liquid composition of the present invention for forming a film containing serotonic acid is preferably between 0.0001 Wt% and 2. 〇Wt% More preferably, it is between 0.2 wt% and 9 201100589 1.0 wt%. In order to facilitate the formation of the wet film, the pH of the liquid composition for forming the aluminum phosphate-containing film of the present invention is preferably between 05 and 35, and more preferably between L0 and 2.5. between. As exemplified in the following examples, the pH of the liquid component of the present invention for forming a velvet-like skin mold is between 1 and 1 2.0. In formulating the liquid composition of the present invention, it is preferably adjusted to the desired pH by means of aqueous ammonia and nitric acid. A method for preparing a film coated on a metal substrate according to the present invention. 3. The metal substrate is immersed in the liquid composition of the present invention for forming a film of 3 W of aluminum acid. After forming a wet film attached to the surface of the metal substrate, the wet film is dried at a temperature between 15 350 and 350 C to obtain a desired film. Basically, there is a metal substrate which is surely immersed in the liquid composition of the present invention, and the surface P can be formed into a wet film, and when the wet film no longer has a moist feeling, it means that it has been converted into a desired one. Membrane. If you want to judge more finely, you can test whether the surface of the film is hydrophobic and economical; if it means, the wet film has been completely dried, if it means that the film is insufficiently baked, so that the hydroxyl residue on the surface remains. Too much, but lacking in hydrophobicity. Based on the operation of the method of the present invention, it is preferred that the component of the liquid composition of the present invention used is such that the main component of the obtained skin is the acidity of the dish, for example, the content of the film (four) is 95 wt% or more. Even wt% or more.越 The thinner the thickness of each film, the less time it takes, or the higher the temperature at which it is dried. The drying is performed with a thickness of 0.5 mm. The material is a metal substrate of No. 10 201100589. When the obtained film thickness is i μπι, it is previously dried at a temperature ranging from 150 ° C to 185 ° C, and the time required is about 0. 8 minutes to 5 minutes. Further, the material of the metal substrate is not particularly limited, and may be iron, aluminum, nickel, rhodium, tin, titanium, copper, or an alloy of any of the above metals. As exemplified in the following examples, the metal substrate used was made of stainless steel, aluminum or copper. 〇 When the liquid composition for forming a film containing aluminum phosphate of the present invention further contains a functional nanomaterial, the film prepared by the present invention is also desired in the present invention. The film 'is of the present invention' is disposed on a metal substrate comprising phosphoric acid, a functional nanomaterial doped with aluminum and aluminum phosphate. Regarding the composition of the S-film, S' is an essential component of the film in an ideal state. The functional nano-material is a minor component, and even the film of the present invention contains only two of them; The content of aluminum phosphate is more than 95% by weight of the film but less than 100% by weight, and the content of the functional nanomaterial accounts for less than 5% by weight of the film but more than 0% by weight. Regarding the kind of the functional nanomaterial in the film, as described previously in the liquid composition of the present invention, it will not be described herein. As for the thickness of the film of the present invention, it is thinner than a general organic film, usually between 2 Å nm and 5 μm, or between 50 nm and 2 μm. Embodiments and effects of each object of the present invention will be described below by way of examples. These examples will be carried out using the following chemicals and equipment; if not specified, the preparation of the examples and the subsequent tests and evaluations are carried out under the old environment of 11 201100589 normal temperature and pressure. Hey. It should be noted that this embodiment is merely illustrative of the date of the month, ro τ. ' and should not be construed as limiting the implementation of the invention. <Examples> h Stainless steel substrate: supplied by the company, model 304. 2. Aluminum substrate. Provided by China Steel Corporation, model number is 5052. 3. Glycine: supplied by the first chemical company; food grade. 4. Sucrose · provided by Taiwan Sugar Company; food grade. 5. Shell sugar: provided by the first chemical company; food grade. 6. Glucosamine: supplied by the First Chemical Company; food grade. 7. Ionic acid: supplied by the first chemical company; food grade. 8. Glady acid: supplied by the first chemical company; food grade. 9. Glucose: provided by the first chemical company; food grade. 1〇·Gasified Aluminum: Provided by First Chemical Company with a purity of 99°/. . 11. Aluminum nitrate: supplied by the First Chemical Company, model industrial grade. 12. Nitric acid: purity 68%, industrial grade; supplied by Heda. 13. Squaric acid. Purity is 85%, industrial grade; provided by Heda Company. 14. Phosphorous acid: supplied by the First Chemical Company, model number 98%. 15. Polyphosphoric acid (Ηη+2Ρη〇3η+ι): same as 105% phosphoric acid; supplied by Aldrich. 16. Pyrophosphoric acid (H4P2〇7): same as 20% h3P〇4; supplied by Alddch. 17. Ammonia: supplied by the First Chemical Company's model number is 28%. 12 201100589 The invention relates to a liquid bear fine substance for forming a film containing aluminum phosphate. The ion source and the bonding agent are mixed in deionized water to be dissolved, and the formed liquid composition is formed by gas water. Having a desired pH value, and obtaining various embodiments of the liquid composition of the present invention for forming a film containing aluminum phosphate, the materials used and the related ion concentrations, as listed in Table 1, wherein phosphoric acid The sources of root, phosphite, polyphosphate, and pyrophosphate are each a linonic acid, a phthalic acid, a poly-acid, and a pyroic acid.
皮膜之製備： 將所使用之各金屬基材分別以其之一部分，浸覆在本 發明用以形成含磷酸鋁之皮膜的液態組成物的實施例中， 歷時10秒’取出後各金屬基材上之受浸覆的區域皆形成有 一附著於其表面上之濕膜，繼而移至一溫度設定為180£)(::之 火、箱中供烤60秒，以乾燥該濕膜，而各自獲得一被設置於 該金屬基材之局部表面上的皮膜。所形成出之部分受到皮 膜披覆的金屬基材，即如圖1(其基材之右側部分有皮膜披 覆）與圖2(其基材之左側部分有皮膜披覆），並接續被施以下 述各項功效測試，其等之測試結果記錄於以下表一中。 功效測試 皮膜表面觀察與皮膜成分測試： 使該皮膜表面藉一由HITACHI公司製造，型號為 S3〇〇〇n的掃描式電子顯微鏡/能量散射光譜儀（SC_ing icroscope/ energy dispersive spectr〇rneter，以下 簡稱為「SEM/EDS_j 於400倍、4000倍之放大倍率下 進行觀察’另亦分析所形成出之皮膜的成分。 13 201100589 2_金屬基材耐蝕性測試： 將以各實施例之液態組成物所處理過的銘基材施以 編號為ASTM B-m的中性鹽霧測試（NSST)，藉此試驗 各皮膜對其彼覆之基材部分所提供的㈣性其中，越 晚出現腐㈣者’表示其耐純越佳，同時並比較該金 屬基材之受皮膜披覆部分，與未受皮膜《部分之錢 狀況。另考量各皮膜組成之差異性，各實施例所形成出 之皮膜的耐録是在相對比較之下，以等級來呈現；未 又皮膜披覆部分之金屬的耐钱性設為G，實施例5、8、 10之！呂基材受皮膜披覆部分的耐触時間達72小時，其耐 蝕性設為5。 3.易潔性測試： 以市售油性筆任意地塗寫於以各實施例之液態組成 物處理過的各金屬基材表面上，使用微濕的衛生紙輕拭 後估該基材表面之未受皮膜披覆部分，與受皮膜披 覆^分之將所附著污潰清潔掉的難易程度；最容易去除 者才不不為5’ |材之未受皮膜披覆部分上的污潰則最難去 除‘不為〇。若同一實施例中對不同基材與附著於其等 之上的各皮膜具有相同的測試結果，即在表一中以該功 效所對應之特^數字’來共同表示該等相同結果。 各實把例之液態組成物的成分，與其等之功能性測 試結果，如以下表一所列。 201100589 表一 實 施 例 連結劑 铭離子 硝酸根 含磷之酸根(M) pH值 磷/鋁 莫耳數 比值 基材 材質 功1 測試 M·生 結果 種類 含量 (wt % ) 來源 濃度 (M) 來源 濃度 (M) 磷酸 根 0.2 亞磷 酸根 聚磷 酸根 焦磷 酸根 財钱性 易潔性 1 甘胺酸 0.002 硝酸鋁 0.4 硝酸鋁 1.2 0.2 - - 1.5 1 不銹鋼 鋁 4 4 2 甘胺酸 蔗糖 0.02 0.05 硝酸鋁 0.4 硝酸 1.5 0.1 0.2 - - 1.2 0.75 不錢鋼 鋁 3 4 3 殻糖 0.1 硝酸鋁 0.6 硝酸鋁 1.8 _ 0.2 0.2 - 1.3 〜0.66 鋁 3 5 4 葡萄糖胺 0.05 硝酸鋁 0.4 硝酸鋁 1.2 0.2 0.2 - - 1.5 不錄鋼 鋁 4 4 1 甘胺酸 蔗糖 0.02 0.05 硝酸鋁 0.4 硝酸鋁 1.2 0.2 0.2 - - 1.5 1 不銹鋼 鋁 5 4 6 離胺酸 般糖 0.005 0.02 硝酸鋁 0.2 硝酸鋁 0.6 0.1 0.05 0.05 - 1.8 〜1 鋁 4 5 7 麩胺酸 0.005 氣化鋁 0.1 硝酸 0.2 0.15 0.05 - - 2.0 2 鋁 3 2 δ 甘胺酸 蔗糖 0.05 0.1 硝酸鋁 1.0 硝酸鋁 3.0 0.6 0.4 - - 1.1 1 鋁 5 3 9 甘胺酸 蔗糖 0.002 0.01 硝酸鋁 0.4 硝酸鋁 1.2 - 0.4 - - 1.4 1 鋁 4 4 10 甘胺酸 蔗糖 0.002 0.01 硝酸鋁 0.3 硝酸 1.2 - 0.2 - 0.1 1.5 1.33 鋁 5 2 11 甘胺酸 蔗糖 0.002 0.01 硝酸鋁 0.4 硝酸鋁 1.2 - 0.4 - - 1.4 1 銅 不銹鋼 鋁 4 4 ¥ 葡萄糖 0.05 硝酸鋁 0.4 硝酸鋁 1.2 0.2 0.2 - - 1.5 1 不錄鋼 紹 2 4 13 甘胺酸 0.02 硝酸鋁 0.8 硝酸鋁 2.4 0.5 0.5 - - 1.5 1.25 銘 4 4 14 離胺酸 0.02 硝酸鋁 0.6 硝酸鋁 1.8 0.25 0.25 - - 1.5 0.83 不鎸鋼 銘 3 5 15 甘胺酸 0.01 硝酸鋁 0.75 硝酸 2.4 0.25 0.25 - - 1,5 0.67 1 不銹鋼 4 4 比 較 例 甘胺酸 0.002 氣化鋁 0.4 _ - - 0.2 0.2 - - 1.5 不銹鋼 鋁 - - 就上述15個成份各有不同之實施例的測試結果，顯示 所獲得之本發明用以形成含磷酸鋁之皮膜的液態組成物， 在多種金屬基材上都可順利地形成出皮膜，且該等皮膜亦 確實為其所覆蓋之基材提供了良好的耐蝕性與易潔性。 15 201100589 參見比較例’該液態組成物之成份類似於實施例1者 ’但其铭離子是源自於氣化鋁，且未含有硝酸根離子；經 試驗結果’發現比較例之液態組成物在金屬基材上所形成 的皮膜’結構極為鬆散且不耐水洗，而未進行耐蝕性與易 潔性之測試。由表一之各實施例與比較例之結果看來，可 證實硝酸根離子之存在，對於本發明用以形成含磷酸鋁之 皮膜的液態組成物的重要性。 就上述本發明用以形成含磷酸鋁之皮膜的液態組成物 的實施例1在一不銹鋼基材上所形成之皮膜，以sem/eds 將其表面放大400倍與4000倍來加以觀察，其等狀況分別 如圖3、4所示，顯然該皮膜之表面甚為均勻。 另’以實施例1之各物料投入量的2.5倍再配製另一本 發明液態組成物，並以其在一不銹鋼基材上形成皮膜後， 同樣地以SEM/EDS將其表面放大400倍與4〇〇〇倍來加以 觀察，其等狀況則分別如圖5、6所示。 因所使用之組成物的物料濃度較高，形成出的皮膜也 較厚，經乾燥之後難免會因其與基材間之熱膨脹係數的差 異’而導致皮膜微微地有裂痕形成。該皮膜進一步以 SEM/EDS進行其成分測試，所得的結果如圖7所示；其中 ，Fe和Cr之訊號係來自於該皮膜所披覆之金屬基材，另就 其他元素所得之訊號結果並扣除掉源自於環境與該基材之 訊號，可推知磷酸鋁是在該皮膜中佔有一極大比例的最主 要成分，另因未觀察到N之訊號，顯示皮膜中並無硝酸根 殘留。 16 201100589 圖1之經本發明用以形成含磷酸鋁之皮膜的液態組成 物的實施例4處理過的金屬基材右側部分，其耐蝕性測試 之結果則如圖8所示。該金屬基材之未受皮膜披覆的左側 部分在48小時之測試時間下，即呈現如圖8所示之銹蝕的 狀况，然受皮膜披覆的右側部分仍完好如初而未被錢姓， 因而可確認該金屬基材之右側部分的耐蝕時間可達48小時 以上。 〇 圖2之經本發明用以形成含磷酸鋁之皮膜的液態組成 物的實施例1處理過的部分金屬基材，其易潔性測試之結 果則如圖9所示。該金屬基材之受皮膜披覆部分經微濕衛 生紙輕拭後即完全不留任何油性筆的痕跡，相對地右側部 . 刀顯然因為未受皮膜披覆，而使得痕跡不易被微濕衛生紙 ‘ 拭除；由此可知，該皮膜具有極佳的易潔性。 由此可證實，本發明用以形成含磷酸鋁之皮膜的液態 組成物，可適用於多種不同材質之金屬基材，且所形成出 〇 的皮膜不但確實含有磷酸鋁，甚至是以其為主要成分；再 者，該皮膜更可對其所披覆的基材，提供良好的抗蝕性與 易潔性。 另一方面，本發明液態組成物在其使用上並不需要耗 費大量能源，僅需使所欲處理之金屬基材浸覆於其中，繼 而乾燥形成於其表面上的濕膜，即可獲得所欲之皮膜，操 作上極為方便。 進一步地，若該液態組成物中更摻有功能性奈米材料 時，則形成出之皮膜除了原有的優異性質外，更能藉助該 17 201100589 功能性奈米材料而一併發揮其功效，進而成為一複合式且 具有更廣泛用途的功能性皮膜。 惟以上所述者，僅為本發明之較佳實施例而已，當不 能以此限定本發明實施之範圍，即大凡依本發明申請專利 範圍及發明說明内容所作之簡單的等效變化與修飾，皆仍 屬本發明專利涵蓋之範圍内。 【圖式簡單說明】 圖1是一照片，說明一材質為鋁之金屬基材，藉由本 發明用以形成含磷酸鋁之皮膜的液態組成物的實施例4,而 於其3/5之右側表面部分地形成一皮膜； 圖2是另一照片，說明一材質為不銹鋼之金屬基材， 藉由本發明用以形成含磷酸鋁之皮膜的液態組成物的實施 例1，而於其3/4之左側表面部分地形成一皮膜； 圖3、4各是一 SEM圖，說明本發明用以形成含磷酸鋁 之皮膜的液態組成物的實施例丨所形成出的皮膜，其表面 刀另丨在400倍、4000倍之放大倍率下所呈現的情況； 圖5、6各是一 SEM圖，說明—其物料濃度為本發明用 以形成含磷酸鋁之皮膜的液態組成物的實施例丨之2 5倍的 液態組成物，所形成出的皮膜表面分別在4〇〇倍' 4〇〇〇倍 之放大倍率下所呈現的情況； 圖7疋一 EDS圖，說明本發明用以形成含磷酸鋁之皮 膜的液態組成物的實施例i之2.5倍的液態組成物，所形成 出的皮膜之所含成分為麟酸紹； 圖8是一照片，說明以圖丄之表面部分彼覆皮膜的金 18 201100589 屬基材進行耐蝕性測試的結果；及 之表面部分披覆皮膜的 圖9是另一照片，說明以圖2 金屬基材進行易潔性測試的結果。 【主要元件符號說明】 益Preparation of a film: Each of the metal substrates used is partially immersed in an embodiment of the liquid composition for forming an aluminum phosphate-containing film of the present invention, and each metal substrate is taken out after 10 seconds. The upper impregnated area is formed with a wet film attached to the surface thereof, and then moved to a temperature of 180 £) (:: fire, in the box for baking for 60 seconds to dry the wet film, and each Obtaining a film disposed on a partial surface of the metal substrate, and forming a metal substrate covered by the film, that is, as shown in FIG. 1 (the right side portion of the substrate is covered with a film) and FIG. 2 ( The left side of the substrate is coated with a film), and the following efficacy tests are performed successively, and the test results are recorded in the following Table 1. Efficacy test film surface observation and film component test: The surface of the film is borrowed A scanning electron microscope/energy scattering spectrometer (SC_ing icroscope/energy dispersive spectr〇rneter) manufactured by HITACHI, model S3〇〇〇n, hereinafter referred to as "SEM/EDS_j at 400x, 4000x magnification Observations were made. The composition of the formed film was also analyzed. 13 201100589 2_Metal substrate corrosion resistance test: The inscription substrate treated with the liquid composition of each example was subjected to the neutral numbered ASTM Bm. Salt spray test (NSST), by which the film is tested for the (four) properties provided by the substrate portion of the film. The later, the later occurrence of rot (four) indicates that the purity is better, and the metal substrate is compared. The film coating part, and the unaffected film "partial money situation. Another difference in the composition of each film, the film formation of each example is recorded in a relative comparison, presented in grades; no film The durability of the metal of the covering portion was set to G, and Examples 5, 8, and 10 were used; the contact resistance time of the exposed portion of the film was 72 hours, and the corrosion resistance was set to 5. 3. Easyness test: A commercially available oil-based pen was arbitrarily applied to the surface of each of the metal substrates treated with the liquid composition of each of the examples, and the surface of the substrate was evaluated by light wiping with a slightly wet toilet paper. The coating of the film will be attached to the stain The ease of rinsing; the easiest to remove is not the 5' | the material on the uncoated portion of the coating is the most difficult to remove 'not 〇. If the same substrate in the same substrate and attached Each of the films on the same has the same test result, that is, in Table 1, the same result is represented by the specific number corresponding to the effect. The components of the liquid composition of each example, and the like The functional test results are listed in the following Table 1. 201100589 Table 1 Example connection agent ionic nitrate phosphate phosphorus acid (M) pH phosphorus / aluminum molar ratio substrate material work 1 test M · results Content (wt %) Source concentration (M) Source concentration (M) Phosphate 0.2 Phosphate polyphosphate pyrophosphate Feasibility Easy to clean 1 Glycine 0.002 Aluminum nitrate 0.4 Aluminum nitrate 1.2 0.2 - - 1.5 1 Stainless steel Aluminum 4 4 2 Glycine sucrose 0.02 0.05 Aluminum nitrate 0.4 Nitric acid 1.5 0.1 0.2 - - 1.2 0.75 No money steel aluminum 3 4 3 Shell sugar 0.1 Aluminum nitrate 0.6 Aluminum nitrate 1.8 _ 0.2 0.2 - 1.3 ～0.66 Aluminum 3 5 4 Glucosamine 0.05 aluminum nitrate 0.4 Aluminum nitrate 1.2 0.2 0.2 - - 1.5 Unrecorded steel aluminum 4 4 1 Glycine sucrose 0.02 0.05 Aluminum nitrate 0.4 Aluminum nitrate 1.2 0.2 0.2 - - 1.5 1 Stainless steel aluminum 5 4 6 Amino acid-like sugar 0.005 0.02 Aluminum nitrate 0.2 Aluminum nitrate 0.6 0.1 0.05 0.05 - 1.8 〜1 aluminum 4 5 7 glutamic acid 0.005 vaporized aluminum 0.1 nitric acid 0.2 0.15 0.05 - - 2.0 2 aluminum 3 2 δ glycine sucrose 0.05 0.1 aluminum nitrate 1.0 aluminum nitrate 3.0 0.6 0.4 - - 1.1 1 Aluminum 5 3 9 Glycine sucrose 0.002 0.01 Aluminum nitrate 0.4 Aluminum nitrate 1.2 - 0.4 - - 1.4 1 Aluminum 4 4 10 Glycine sucrose 0.002 0.01 Aluminum nitrate 0.3 Nitric acid 1.2 - 0.2 - 0.1 1.5 1.33 Aluminum 5 2 11 Glycine Sucrose 0.002 0.01 Aluminum nitrate 0.4 Aluminum nitrate 1.2 - 0.4 - - 1.4 1 Copper stainless steel aluminum 4 4 ¥ Glucose 0.05 Aluminum nitrate 0.4 Aluminum nitrate 1.2 0.2 0.2 - - 1.5 1 Not recorded steel 2 4 13 Glycine 0.02 Aluminum nitrate 0.8 Nitric acid Aluminum 2.4 0.5 0.5 - - 1.5 1.25 Ming 4 4 14 Amino acid 0.02 Aluminum nitrate 0.6 Aluminum nitrate 1.8 0.25 0.25 - - 1.5 0.83 Stainless steel Ming 3 5 15 Glycine 0.01 Aluminum nitrate 0.75 Nitric acid 2.4 0.25 0.25 - - 1, 5 0.67 1 stainless steel 4 4 comparison Glycine 0.002 vaporized aluminum 0.4 _ - - 0.2 0.2 - - 1.5 stainless steel aluminum - - Test results of the examples in which the above 15 components are different, showing that the obtained invention is used to form an aluminum phosphate-containing film The liquid composition can form a film smoothly on a variety of metal substrates, and the film also provides good corrosion resistance and cleanability to the substrate it covers. 15 201100589 See the comparative example 'The composition of the liquid composition is similar to that of Example 1' but the imide ion is derived from vaporized aluminum and does not contain nitrate ions; the test results show that the liquid composition of the comparative example is The film formed on the metal substrate is extremely loose and water-resistant, and has not been tested for corrosion resistance and cleanability. From the results of the respective examples and comparative examples of Table 1, it is confirmed that the presence of nitrate ions is important for the liquid composition of the present invention for forming a film containing aluminum phosphate. The film formed on a stainless steel substrate of Example 1 of the present invention for forming a liquid composition containing an aluminum phosphate film was observed by sem/eds by a magnification of 400 times and 4000 times, and the like. The conditions are shown in Figures 3 and 4, respectively, and it is apparent that the surface of the film is very uniform. Further, another liquid composition of the present invention was reconstituted by 2.5 times the amount of each material input of Example 1, and after forming a film on a stainless steel substrate, the surface thereof was magnified 400 times by SEM/EDS. 4 times to observe, and the other conditions are shown in Figures 5 and 6, respectively. Since the composition of the composition to be used has a high material concentration, the formed film is also thick, and after drying, it is inevitable that the film is slightly cracked due to the difference in thermal expansion coefficient between the substrate and the substrate. The film is further tested by SEM/EDS, and the results obtained are shown in FIG. 7. The signals of Fe and Cr are derived from the metal substrate coated by the film, and the signal results obtained by other elements are After deducting the signal originating from the environment and the substrate, it can be inferred that aluminum phosphate is the most important component in the film, and since no signal of N is observed, there is no nitrate residue in the film. 16 201100589 The right side portion of the metal substrate treated in Example 4 of the present invention for forming a liquid composition containing an aluminum phosphate film of Fig. 1 has a corrosion resistance test result as shown in Fig. 8. The left side portion of the metal substrate which was not covered by the film showed a rust condition as shown in Fig. 8 at the test time of 48 hours, but the right portion of the film was still intact as before and was not surnamed by the money. Therefore, it can be confirmed that the corrosion resistance time of the right portion of the metal substrate can be more than 48 hours. Fig. 2 shows a portion of the metal substrate treated in Example 1 for forming a liquid composition of an aluminum phosphate-containing film of the present invention, and the results of the cleanability test are shown in Fig. 9. The coated surface of the metal substrate is lightly wiped by the micro-wet toilet paper, and no trace of the oily pen is left at all, and the right side portion. The knife is obviously not covered by the film, so that the trace is not easily wetted by the micro-wet toilet paper. Wiping; thus, it is known that the film has excellent cleanability. It can be confirmed that the liquid composition for forming a film containing aluminum phosphate of the present invention can be applied to a metal substrate of a plurality of different materials, and the film formed by the invention not only contains aluminum phosphate, but even mainly In addition, the film can provide good corrosion resistance and cleanability to the substrate to which it is coated. On the other hand, the liquid composition of the present invention does not require a large amount of energy in its use, and it is only necessary to immerse the metal substrate to be treated therein, and then dry the wet film formed on the surface thereof, thereby obtaining the obtained The desired film is extremely convenient to operate. Further, if the liquid composition is further doped with a functional nano material, the formed film can exert its efficacy together with the functional nano material by using the 17 201100589 functional nano material in addition to the original excellent properties. Further, it becomes a composite functional film having a wider range of uses. The above is only the preferred embodiment of the present invention, and the scope of the invention is not limited thereto, that is, the simple equivalent changes and modifications made by the scope of the invention and the description of the invention are All remain within the scope of the invention patent. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a photograph showing a metal substrate made of aluminum, which is the liquid composition of the aluminum phosphate-containing film of the present invention, and is on the right side of 3/5. The surface partially forms a film; FIG. 2 is another photograph illustrating a metal substrate made of stainless steel, which is used in the present invention to form a liquid composition of an aluminum phosphate-containing film, and 3/4 thereof A film is partially formed on the left side surface; FIGS. 3 and 4 are each an SEM image showing the film formed by the embodiment of the present invention for forming a liquid composition containing an aluminum phosphate film, the surface of which is further 400 times, 4000 times the magnification presented; Figures 5 and 6 are each an SEM image, illustrating that the material concentration is the embodiment of the present invention for forming a liquid composition containing an aluminum phosphate film. 5 times the liquid composition, the surface of the formed film is respectively presented at a magnification of 4 ' 4 4 times; Figure 7 is an EDS diagram illustrating the formation of aluminum phosphate containing the present invention. Example i of the liquid composition of the film 2.5 times the liquid composition, the formed film contains the component of linonic acid; Figure 8 is a photograph showing the corrosion resistance test of the substrate of the gold film of the surface of the film The results; and FIG. 9 of the surface portion covering the film are another photograph showing the results of the easy-cleanness test conducted on the metal substrate of FIG. 2. [Main component symbol description]
1919