WO2016170698A1 - 水系表面処理剤、皮膜の製造方法及び表面処理材 - Google Patents
水系表面処理剤、皮膜の製造方法及び表面処理材 Download PDFInfo
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- WO2016170698A1 WO2016170698A1 PCT/JP2015/068637 JP2015068637W WO2016170698A1 WO 2016170698 A1 WO2016170698 A1 WO 2016170698A1 JP 2015068637 W JP2015068637 W JP 2015068637W WO 2016170698 A1 WO2016170698 A1 WO 2016170698A1
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- castor oil
- surface treatment
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- polyoxyethylene
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Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D201/00—Coating compositions based on unspecified macromolecular compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
Definitions
- the present invention is formed by an aqueous surface treatment agent capable of forming a film excellent in moldability and hydrophilic sustainability, a method for producing a film using the aqueous surface treatment agent, and a method for producing the film.
- the present invention relates to a surface treatment material having a film.
- the present invention provides an aqueous surface treatment agent capable of forming a film excellent in molding processability and hydrophilic sustainability without irradiation with energy rays, a method for producing a film using the aqueous surface treatment agent, and It aims at providing the surface treatment material which has a membrane
- the present invention (1) Hydrophilic film forming component (A), polyoxyethylene castor oil or polyoxyethylene hydrogenated castor oil (B), and nonionic surfactant (except polyoxyethylene castor oil and polyoxyethylene hydrogenated castor oil) (C Water-based surface treatment agent containing (2) The aqueous surface treating agent according to the above (1), wherein the hydrophilic film forming component (A) contains at least one water-soluble organic polymer; (3) The aqueous surface treating agent according to (2), wherein the hydrophilic film-forming component (A) further contains a crosslinking agent; (4) A method for producing a film on the surface of an aluminum material, an aluminum alloy material or a plating material thereof, and bringing the aqueous surface treating agent according to any one of (1) to (3) into contact with the surface A method for producing a film, comprising a step and a step of drying the surface in contact with the aqueous surface treatment agent; (5) A surface treatment material having a film formed by the method for producing a film according to (4) above;
- the aqueous surface treating agent can be prepared, for example, by adding the above components (A) to (C) one by one or simultaneously while stirring the solvent (liquid medium).
- water is a main component (for example, water is 70% by mass or more based on the mass of the total solvent).
- water-soluble alcohols such as methanol and ethanol
- water-soluble ketones such as acetone
- water-soluble solvents such as cellosolve such as methyl cellosolve and ethyl cellosolve are within the scope of the present invention and do not impair the film performance. And may be used in any proportion.
- the hydrophilic film forming component (A) is not particularly limited as long as it can form a hydrophilic film, and examples thereof include known water-soluble organic polymers or hydrophilic film forming compositions.
- hydrophilic film-forming composition examples include, but are not limited to, a mixture of two or more water-soluble organic polymers described above, a mixture of one or more water-soluble organic polymers and a crosslinking agent described above, and the like.
- organoalkoxysilicates such as silicate compounds such as alkali silicates, colloidal silica, and colloidal silica having an organic functional group (for example, glycidyl group, vinyl group, amino group, etc.)
- An inorganic compound modified with silane may be blended in the mixture.
- (meth) acrylic acid polymers examples include acrylic acid, methacrylic acid, ethacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, 2-acrylamido-2-methylpropanesulfonic acid, and 2-acrylamidoethylsulfone.
- polyvinyl alcohol examples include polyvinyl alcohol having a saponification degree of 70 mol% or more, preferably 90 mol% to 100 mol%.
- the degree of saponification is a value measured according to JIS K6726.
- cellulose derivatives include carboxymethylcellulose, hydroxyethylcellulose, hydroxypropylmethylcellulose and the like.
- water-soluble organic polymer examples include, in addition to those described above, polymers or copolymers of polyvinylpyrrolidone, polyacrylamide, polyamide, polyethylene glycol, chitosan derivatives, and the like.
- polyvalent carboxylic acid examples include isophthalic acid, adipic acid, pyromellitic acid, maleic acid, itaconic acid, fumaric acid, 1,2,4-trimellitic acid, 1,2,3,4-butanetetracarboxylic acid. , 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic acid, cyclohexane-1,2,4-tricarboxylic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid and other compounds having two or more carboxyl groups Can be mentioned. These may be used alone or in combination.
- polyvalent carboxylic acid salt examples include salts of sodium, potassium, lithium, ammonium and the like.
- the amount of the crosslinking agent (a1) is such that the solid content mass ratio (a1 / a2) between the crosslinking agent (a1) and the water-soluble organic polymer (a2) is in the range of 0.01 to 0.7. It is preferable. By adjusting the solid content mass ratio (a1 / a2) within this range, the hydrophilic durability and molding processability of the formed film can be further improved.
- the polyoxyethylene castor oil or the polyoxyethylene hydrogenated castor oil (B) is not particularly limited as long as it is obtained by polymerizing and adding ethylene oxide to castor oil, or by polymerizing and adding ethylene oxide to hydrogenated castor oil. Although not necessarily used, it is preferable to use one having an HLB (depending on the Griffin method) of 2.5 to 13.
- HLB depending on the Griffin method
- polyoxyethylene castor oil or polyoxyethylene hydrogenated castor oil whose HLB is within the above numerical range with an aqueous surface treatment agent, molding is performed while maintaining the hydrophilicity of the film formed by the hydrophilic film forming component (A). Workability can be further improved.
- “castor oil” is a non-drying oil extracted from castor bean seeds, and is mainly composed of triglyceride of ricinoleic acid.
- the blending amount of the polyoxyethylene castor oil or the polyoxyethylene hydrogenated castor oil (B) is 1% by mass to 15% by mass in terms of the mass in terms of solid content with respect to the total mass of the solid content in the aqueous surface treatment agent. preferable. By adjusting the blending amount within this range, it is possible to obtain a film with improved moldability while maintaining the hydrophilicity of the film formed by the hydrophilic film forming component (A).
- the nonionic surfactant (C) is not particularly limited as long as it is other than polyoxyethylene castor oil and polyoxyethylene hydrogenated castor oil, but polyalkylene oxide chain [specifically, polyoxyethylene chain ⁇ ( CH 2 CH 2 O) m ⁇ , polyoxypropylene ⁇ (CH 2 CH (CH 3 ) O) n ⁇ and polyoxyethylene ⁇ (CH 2 CH 2 O) i ⁇ , etc.], and an alkyl group ( It is preferably selected from polyoxyalkylene alkyl ethers composed of an ether bond with C n H 2n + 1 ), particularly polyoxyethylene alkyl ethers.
- polyoxyalkylene alkyl ethers examples include polyoxyalkylene branched decyl ether, polyoxyalkylene tridecyl ether, polyoxyalkylene lauryl ether, and the like.
- polyoxyethylene alkyl ethers include polyoxyethylene isopropyl ether. Examples include decyl ether, polyoxyethylene lauryl ether, polyoxyethylene oleyl cetyl ether, and polyoxyethylene tridecyl ether. These may be used alone or in combination of two or more.
- the total solid mass of the polyoxyethylene castor oil or polyoxyethylene hydrogenated castor oil (B) and the nonionic surfactant (C) to be added to the aqueous surface treatment agent is based on the total mass of the solid content in the aqueous surface treatment agent. Thus, it is preferable to adjust the amount so as not to exceed 25% by mass and to blend such that the total HLB is 13 or more. As described above, the storage stability of the water-based surface treatment agent is further improved by adjusting the total solid mass of the component (B) and the component (C) and the total HLB of these components within a predetermined numerical range. Or the hydrophilicity of the film formed by the hydrophilic film forming component (A) can be maintained.
- the total HLB of the component (B) and the component (C) is calculated as a weighted average of each HLB.
- the HLB of the component (B) is 12.5
- the ratio of the solid content converted mass of the component (B) to the total solid mass of the component (B) and the component (C) is 42 mass%
- the hydrophilic film forming component (A), polyoxyethylene castor oil or polyoxyethylene hydrogenated castor oil (B), and nonionic surfactant however, polyoxyethylene castor oil and polyoxyethylene are used).
- the water-based surface treatment agent containing only (C) has been described.
- antioxidants, antifoaming agents, and leveling agents are used.
- An agent, a rust inhibitor, an antibacterial agent, an antifungal agent, an antibacterial antifungal agent, a colorant, and the like may be further blended at an arbitrary ratio as long as the gist of the present invention and the film performance are not impaired.
- the surface treatment material according to the present invention can be obtained by producing a film on the surface of a metal substrate such as a heat exchanger fin material using the aqueous surface treatment agent.
- the method for producing the film is particularly limited as long as it includes a step of bringing the aqueous surface treatment agent into contact with the surface of the metal substrate and a step of drying the metal substrate surface in contact with the aqueous surface treatment agent.
- a step of performing a degreasing treatment, a step of forming a corrosion-resistant film, and the like may be included.
- Examples of the method for bringing the aqueous surface treatment agent into contact include methods such as roll coater treatment, spray treatment, airless spray treatment, roller coating, brush coating, bar coater treatment, shower squeezing, and dipping treatment.
- the drying of the surface of the metal substrate can be performed by, for example, a convection type using hot air or a radiation type oven using an electric heating tube.
- the drying temperature it is preferable that the maximum temperature reached by the metal substrate is 150 ° C. to 250 ° C.
- Examples of the metal substrate include an aluminum material, an aluminum alloy material, or a plating material thereof.
- Examples of the aluminum material include a 1000 series pure aluminum material defined in JIS H4000, and examples of the aluminum alloy material include a 3000 series or 8000 series aluminum alloy material, but are not limited thereto. Is not to be done.
- Examples of the type of aluminum or aluminum alloy plated material include a hot-dip aluminum-plated steel sheet specified in JIS G3314, a molten 55% aluminum-zinc alloy-plated steel sheet specified in JIS G3321, and the like. It is not limited to these.
- the degreasing treatment on the surface of the metal substrate there is no repellency, so long as the oil on the surface of the metal substrate can be removed to such an extent that the aqueous surface treatment agent and the surface treatment agent for forming a corrosion-resistant film can be applied.
- Any method may be applied.
- a known degreasing treatment method using an alkaline or acid degreasing agent may be applied.
- Examples of the method of forming the corrosion-resistant film include a chemical conversion treatment method such as a coating type chromate treatment, a phosphoric acid chromate treatment, a zirconium chemical conversion treatment, a titanium chemical conversion treatment, or a surface containing an acrylic resin, a urethane resin, an epoxy resin, or the like.
- a known method such as a method of applying a treatment agent can be used, but it is not limited to these methods.
- a surface treatment material having both hydrophilic sustainability and molding processability can be obtained.
- the method for producing a film according to the present invention can produce a surface treatment material excellent in hydrophilic sustainability and molding processability without forming a lubricating film on the upper layer of the hydrophilic film.
- the fin material can be manufactured efficiently.
- Test material By spraying JIS A1050, aluminum material with a plate thickness of 0.26 mm with an alkaline degreasing agent (2% aqueous solution of Fine Cleaner FC-4477: manufactured by Nihon Parkerizing Co., Ltd.) at 60 ° C. for 15 seconds. Degreasing was performed. Then, it washed with water, drained, and what dried the surface was used as a test material.
- an alkaline degreasing agent 2% aqueous solution of Fine Cleaner FC-4477: manufactured by Nihon Parkerizing Co., Ltd.
- Table 1 shows the composition of each aqueous surface treatment agent used for preparing test plates of Examples 1 to 19 and Comparative Examples 1 to 3 described later.
- the compounding amount of each component in Table 1 indicates a mass ratio (%) to the total solid mass of the aqueous surface treatment agent.
- each symbol shown in the type column in Table 1 means the substance shown in Table 2.
- all the solid content in an aqueous surface treating agent was 10 mass%.
- the aqueous surface treatment agent was prepared by sequentially adding each component while stirring water as a solvent.
- the examples of the present invention are superior to the comparative examples (Comparative Examples 1 to 3) in storage stability, and are comparable to those immediately after preparation even after being stored for a certain period of time.
- a film excellent in molding processability and hydrophilic sustainability can be formed.
Abstract
Description
(1)親水皮膜形成成分(A)と、ポリオキシエチレンひまし油又はポリオキシエチレン硬化ひまし油(B)と、非イオン性界面活性剤(但しポリオキシエチレンひまし油及びポリオキシエチレン硬化ひまし油を除く)(C)とを含有する水系表面処理剤;
(2)前記親水皮膜形成成分(A)が、少なくとも1種の水溶性有機高分子を含む上記(1)に記載の水系表面処理剤;
(3)前記親水皮膜形成成分(A)が、架橋剤をさらに含む上記(2)に記載の水系表面処理剤;
(4)アルミニウム材若しくはアルミニウム合金材又はそれらのめっき材の表面に皮膜を製造する方法であって、上記(1)~(3)のいずれかに記載の水系表面処理剤を前記表面に接触させる工程と、前記水系表面処理剤を接触させた前記表面を乾燥させる工程を含む皮膜の製造方法;
(5)上記(4)に記載の皮膜の製造方法により形成された皮膜を有する表面処理材;
などである。
本発明に係る水系表面処理剤は、親水皮膜形成成分(A)と、ポリオキシエチレンひまし油又はポリオキシエチレン硬化ひまし油(B)と、ポリオキシエチレンひまし油及びポリオキシエチレン硬化ひまし油以外の非イオン性界面活性剤(C)とを含有する。本発明に係る水系表面処理剤は、これらの成分を含むことにより、液安定性に優れ、長期間(少なくとも3ヶ月)の貯蔵が可能となる。また、調製直後の水系表面処理剤を用いても、一定期間(例えば3ヶ月)貯蔵した水系表面処理剤を用いても同様に、成型加工性及び親水持続性に優れた皮膜を金属基材上に形成することができる。それゆえ、本発明に係る水系表面処理剤は、水系の金属表面処理剤として有用である。
(12.5×0.42)+(16.8×0.58)=15.0
本発明に係る表面処理材は、上記水系表面処理剤を用いて、熱交換器用フィン材等の金属基材の表面上に皮膜を製造することにより得る事ができる。
(1)供試材
JIS A1050、板厚0.26mmのアルミニウム材に、アルカリ脱脂剤(ファインクリーナーFC-4477の2%水溶液:日本パーカライジング株式会社製)を、60℃で15秒間スプレーすることにより脱脂を行った。その後、水洗して水切りし、表面を乾燥させたものを供試材として使用した。
後述の実施例1~19及び比較例1~3の試験板を作製するために用いた各水系表面処理剤の組成を表1に示す。表1中の各成分の配合量は、水系表面処理剤の固形分合計質量に対する質量割合(%)を示す。また、表1中の種類の欄に示す各記号は、表2に示す物質をそれぞれ意味する。なお、水系表面処理剤における固形分は全て10質量%とした。また、水系表面処理剤は、溶媒である水を攪拌しながら、各成分を順次添加することにより調製した。
供試材の表面に、アクリル系樹脂及び炭酸ジルコニウムアンモニウムを含むアクリル系耐食塗料をバーコーター#5で塗布し、熱風循環式乾燥炉で乾燥して耐食皮膜を形成した。続いて、耐食皮膜の上に各水系表面処理剤をバーコーター#5で塗布し、熱風循環式乾燥炉で乾燥して親水性皮膜を形成させ、実施例1~19及び比較例1~3の試験板を作製した。これらの試験板を用いて以下の性能評価を行った。
(1)親水性
実施例1~19及び比較例1~3の試験板の表面に10μLの純水を滴下し、水滴の接触角を協和界面科学株式会社製自動接触角計「DM-501」を用いて測定した後、以下の評価基準に基づいて親水性を評価した。この評価は、親水性皮膜形成直後の各試験板(初期親水性)、及び「0.5L/minの流水に8時間浸漬した後、80℃で16時間乾燥する処理」を1サイクルとして5サイクル繰り返して行った各試験板(サイクル後親水性)に対し実施した。
<評価基準>
◎・・・接触角10°未満
○・・・10°以上30°未満
△・・・30°以上40°未満
×・・・40°以上
成型加工性を評価するために下記の評価を実施した。
各試験板表面の動摩擦係数を、新東科学株式会社製表面性測定器「HEYDON TYPE:14FW」を用いて測定し、以下の評価基準に基づいて潤滑性を評価した。
<試験条件>
荷重:200g、鋼球:3mmφ、ストローク:10mm、摺動速度:10mm/sec、摺動回数:30往復
<評価基準>
◎・・・摩擦係数0.2未満
○・・・0.2以上0.3未満
△・・・0.3以上0.5未満
×・・・0.5以上
試験板の取り扱い(加工を含む)において問題となる表面のベタツキを以下の評価基準に基づいて評価した。具体的には、水平に置いた各試験板表面に軽く指を押し当て、そのまま指を水平方向に動かしたときの感触にて判定した。
<評価基準>
○・・・粘着感を感じる事無く、なめらかに指を動かせる。
△・・・指触直後にやや粘着感を感じるが、ほとんど抵抗無く指を動かせる。
×・・・指に粘着感があり、指が移動し難い。
実施例1~19及び比較例1~3の試験板を作製するために用いた各水系表面処理剤を、ポリ容器に封入し、25℃で3ヶ月静置した後の状態を観察し、以下の評価基準に基づいて貯蔵安定性を評価した。
<評価基準>
○・・・凝集又は沈殿が認められない。
×・・・凝集又は沈殿が認められた。
Claims (5)
- 親水皮膜形成成分(A)と、ポリオキシエチレンひまし油又はポリオキシエチレン硬化ひまし油(B)と、非イオン性界面活性剤(但しポリオキシエチレンひまし油及びポリオキシエチレン硬化ひまし油を除く)(C)とを含有する水系表面処理剤。
- 前記親水皮膜形成成分(A)が、少なくとも1種の水溶性有機高分子を含む請求項1に記載の水系表面処理剤。
- 前記親水皮膜形成成分(A)が、架橋剤をさらに含む請求項2に記載の水系表面処理剤。
- アルミニウム材若しくはアルミニウム合金材又はそれらのめっき材の表面に皮膜を製造する方法であって、
請求項1~3のいずれか一項に記載の水系表面処理剤を前記表面に接触させる工程と、前記水系表面処理剤を接触させた前記表面を乾燥させる工程を含む皮膜の製造方法。 - 請求項4に記載の皮膜の製造方法により形成された皮膜を有する表面処理材。
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JPH08302277A (ja) * | 1995-04-28 | 1996-11-19 | Mitsubishi Alum Co Ltd | フィン用塗料組成物、フィン及びその製造方法 |
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JP2002285140A (ja) * | 2001-03-27 | 2002-10-03 | Nippon Paint Co Ltd | 親水化処理剤、親水化処理方法及び親水化処理されたアルミニウム材又はアルミニウム合金材 |
JP2005232269A (ja) * | 2004-02-18 | 2005-09-02 | Mitsubishi Alum Co Ltd | 耐汚染性に優れた親水性コーティング塗料及びアルミニウム材料並びに熱交換器 |
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ATE286403T1 (de) * | 1997-03-12 | 2005-01-15 | Abbott Lab | Hydrophile binäre systeme zur verabreichung von cyclosporin |
JP4942251B2 (ja) * | 2001-03-27 | 2012-05-30 | 日本ペイント株式会社 | 親水化処理剤、親水化処理方法及び親水化処理されたアルミニウム材又はアルミニウム合金材 |
CN100584908C (zh) * | 2007-04-10 | 2010-01-27 | 大连工业大学 | 环保型镀锌金属表面处理剂 |
CN103333571B (zh) * | 2013-06-24 | 2015-12-02 | 广州慧谷化学有限公司 | 用于热交换器翅片表面处理的水性抗菌防霉亲水涂料 |
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- 2015-06-29 CN CN201580078937.3A patent/CN107969132B/zh active Active
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JPH07109436A (ja) * | 1993-10-14 | 1995-04-25 | Dainippon Toryo Co Ltd | 塗料組成物及び被覆アルミニウム材 |
JPH08302277A (ja) * | 1995-04-28 | 1996-11-19 | Mitsubishi Alum Co Ltd | フィン用塗料組成物、フィン及びその製造方法 |
JPH09176521A (ja) * | 1995-12-22 | 1997-07-08 | Nisshinbo Ind Inc | 塗料組成物および被覆材 |
JP2002285140A (ja) * | 2001-03-27 | 2002-10-03 | Nippon Paint Co Ltd | 親水化処理剤、親水化処理方法及び親水化処理されたアルミニウム材又はアルミニウム合金材 |
JP2005232269A (ja) * | 2004-02-18 | 2005-09-02 | Mitsubishi Alum Co Ltd | 耐汚染性に優れた親水性コーティング塗料及びアルミニウム材料並びに熱交換器 |
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JPWO2016170698A1 (ja) | 2017-04-27 |
CN107969132B (zh) | 2020-08-25 |
CN107969132A (zh) | 2018-04-27 |
KR20170129905A (ko) | 2017-11-27 |
JP6064088B1 (ja) | 2017-01-18 |
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