JP2002275650A - Hydrophilization treated aluminum fin material for heat exchanger - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a hydrophilization treated aluminum fin material which has excellent corrosion resistance and hydrophilic properties, and has no problems form the view of environmental maintenance. SOLUTION: In the aluminum fin material for the heat exchanger, a film of a substrate treatment agent is formed on a fin material made of aluminum or an aluminum alloy, and a hydrophilization treatment film is formed on the substrate treatment film. The substrate treatment film contains (A) a water based solution containing titanium obtained by reacting at least one kind selected from hydrolyzable titanium compounds, hydrolyzable titanium compound low condensation products, titanium hydroxide and titanium hydroxide low condensation product with a hydrogen peroxide solution (B) at least one kind of compound selected from phosphoric compounds, metallic hydrofluoric acids and metallic hydrofluorides, and (C) a water based organic high molecular compound stable at pH <=7.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat exchanger aluminum fin material subjected to a hydrophilization treatment, and a method for producing the fin material.

[0002]

2. Description of the Related Art As a fin base material for a heat exchanger of an air conditioner, a material obtained by subjecting aluminum or an aluminum alloy, which is excellent in light weight, workability, and heat conductivity, to chemical conversion treatment is generally used. .

In a heat exchanger of an air conditioner, condensed water generated during cooling becomes water droplets to form a water bridge between the fins, and the ventilation passage is narrowed to increase the ventilation resistance, resulting in loss of power and noise. There is a problem that problems such as generation and scattering of water droplets occur.

As a measure for preventing such a phenomenon, for example, the surface of an aluminum fin material (hereinafter, referred to as a "fin material") is subjected to a hydrophilic treatment to prevent water droplets and the formation of bridges due to the water droplets. .

Examples of the hydrophilic treatment include: (1) a boehmite treatment known as a surface treatment of aluminum; and (2) a method of applying a water glass represented by the general formula mSiO ₂ / nNa ₂ O ( (See, for example, JP-B-55-1347, JP-A-58-126989, etc.); (3) Paints prepared by mixing silica, water glass, aluminum hydroxide, calcium carbonate, titania, etc. with an organic resin, or paints thereof. (Japanese Patent Publication No. 57-46000, Japanese Patent Publication No. Sho 5-5)
No. 9-8372, Japanese Patent Publication No. 62-61078,
JP-A-59-229197, JP-A-61-225
(4) A method of applying a paint composed of an organic-inorganic (silica) composite resin and a surfactant (JP-A-59-170170)
(5) A method using a combination of polyvinyl alcohol, a specific water-soluble polymer, and a water-soluble crosslinking agent (Japanese Patent Application Laid-Open (JP-A) No. 3-26)
No. 381, JP-A-1-299877); (6) a block copolymer consisting of a hydrophilic polymer portion composed of a specific hydrophilic monomer and a hydrophobic polymer portion, and a metal chelate type crosslinking agent. (Japanese Unexamined Patent Application Publication No.
(7) A method using a polyacrylamide resin (see JP-A-1-104667 and JP-A-270977); (8) Polyacrylic acid A method using a combination of a polymer such as a polymer and a polymer such as polyethylene oxide or polyvinylpyrrolidone capable of forming a polymer complex by hydrogen bonding with the polymer (Japanese Patent Laid-Open No. 6-322).
292), and some of these methods have already been put to practical use.

[0006] However, the fin material on which the hydrophilized film obtained by these methods is formed may be subjected to a strong corrosive environment because the film has hydrophilicity.
There was a problem that it would be corroded in a few months.

[0007] To solve this problem, corrosion resistance,
From the viewpoint of cost and the like, there are many methods of performing a chromate treatment on the surface of an aluminum or aluminum alloy material as a base material. However, the chromate treatment has a problem in terms of environmental protection because chromium ions are harmful metal ions.

[0008] In addition, the above-mentioned surface treatment agent and treatment method not using chromium ions are also known, for example, an acidic solution containing a titanium salt (zirconium salt), hydrogen peroxide and (condensed) phosphoric acid (derivative). Aluminum surface treatment method (JP-A-54-24232), treating aluminum with an alkaline aqueous solution containing titanium ions (zirconium ions, iron ions) and a complexing agent;
An aluminum surface treatment method of washing with water and treating with an aqueous acidic solution such as phosphoric acid (Japanese Patent Application Laid-Open No. 54-160527), and an aluminum surface treatment composition containing a phosphate ion, a titanium compound, a fluoride and an accelerator (Japanese Patent Application Laid-Open No. No. 20984), an aluminum-based metal surface treatment composition containing (condensed) phosphoric acid (salt), titanium salt (zirconium salt), fluoride, and (next) phosphorous acid (salt) 143
No. 752).

However, the surface treatment agent and the treatment method using the above-mentioned titanium compound are insufficient in stability of the surface treatment agent, insufficient in corrosion resistance as compared with chromate treatment, insufficient in hydrophilicity, and There were problems such as insufficient durability.

An object of the present invention is to provide a hydrophilized aluminum fin material which is excellent in corrosion resistance and hydrophilicity and has no problem in terms of environmental protection.

[0011]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that at least one selected from a hydrolyzable titanium compound, a hydrolyzable titanium compound low-condensate, titanium hydroxide and a titanium hydroxide low-condensate. Aqueous solution containing titanium obtained by reacting a kind of titanium compound with aqueous hydrogen peroxide, at least one compound selected from a phosphoric acid compound, metal hydrofluoric acid and metal hydrofluoride, and an aqueous solution It has been found that the above object can be achieved by using a primer treatment agent containing an organic polymer compound, and the present invention has been completed.

Thus, according to the present invention, a film of a primer is formed on a fin material made of aluminum or an aluminum alloy, and a hydrophilic coating is formed on the primer. The substrate treatment agent is
(A) Titanium obtained by reacting at least one titanium compound selected from a hydrolyzable titanium compound, a hydrolyzable titanium compound low-condensate, titanium hydroxide and a titanium hydroxide low-condensate with hydrogen peroxide water. Aqueous liquid containing (B)
At least one compound selected from a phosphoric acid compound, metal hydrofluoric acid and metal hydrofluoride, and (C) PH
The present invention provides a heat exchanger aluminum fin material which has been subjected to a hydrophilization treatment and which contains a stable aqueous organic polymer compound at 7 or less.

On the surface of the fin material made of aluminum or aluminum alloy, the above-mentioned undercoating agent is dried to a thickness of 0.
After being coated and dried so as to have a thickness of 001 to 10 μm, the hydrophilizing composition is dried on the undercoating agent film in a dry film thickness of 0.1 to 10 μm.
The present invention provides a method for producing a heat exchanger aluminum fin material which has been subjected to a hydrophilization treatment, wherein the fin material is coated with 3 to 5 μm and dried.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION The aluminum fin material subjected to hydrophilic treatment according to the present invention comprises a fin material made of aluminum or an aluminum alloy, which is a base material, and a base treatment agent provided on the base material. It is composed of a base treatment film and a hydrophilic treatment film provided on the base treatment film.

First, the base treating agent will be described.

The surface treating agent used in the present invention is at least one compound selected from the group consisting of aqueous liquid (A) containing titanium, a phosphoric acid compound, metal hydrofluoric acid and metal hydrofluoride. (B) and an aqueous organic polymer compound (C).

Aqueous Liquid Containing Titanium (A) The aqueous liquid containing titanium (A) used in the undercoating agent is:
Aqueous solution containing titanium obtained by reacting at least one titanium compound selected from a hydrolysable titanium compound, a hydrolysable titanium compound low-condensate, titanium hydroxide and a titanium hydroxide low-condensate with hydrogen peroxide water. Liquid. The aqueous liquid is not particularly limited as long as it is as described above, and a conventionally known aqueous liquid can be appropriately selected and used.

The above-mentioned hydrolyzable titanium compound is a titanium compound having a hydrolyzable group directly bonded to titanium, and generates titanium hydroxide by reacting with water such as water or steam. In the hydrolyzable titanium compound, all of the groups bonded to titanium may be hydrolyzable groups, or one part thereof may be a hydrolyzed hydroxyl group.

The hydrolyzable group is not particularly limited as long as it forms titanium hydroxide by reacting with water as described above. For example, a lower alkoxyl group or a group which forms a salt with titanium (for example, , A halogen atom (eg, chlorine), a hydrogen atom, a sulfate ion, etc.).

[0020] The hydrolyzable titanium compounds containing lower alkoxyl groups as hydrolyzable groups, an alkyl group having 1 to 5 carbon atoms, especially the general formula Ti _(OR) 4 (wherein, R are the same or different and ) Is preferred. Examples of the alkyl group having 1 to 5 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an iso-butyl group, a sec-butyl group, and a tert-butyl group. No.

Typical hydrolyzable titanium compounds having a group capable of forming a salt with titanium as a hydrolyzable group include titanium chloride and titanium sulfate.

The hydrolyzable titanium compound low condensate is a low condensate of the above hydrolyzable titanium compounds. The low-condensate may be either a group in which all of the groups bonded to titanium are hydrolyzable or a part of which is a hydrolyzed hydroxyl group.

Also, orthotitanic acid (titanium hydroxide gel) obtained by reacting an aqueous solution such as titanium chloride or titanium sulfate with an alkaline solution such as ammonia or caustic soda can be used as a low condensate.

The degree of condensation of the low condensate of the hydrolyzable titanium compound or titanium hydroxide is 2 to 30.
As the aqueous liquid (A), it is preferable to use a compound having a condensation degree in the range of 2 to 10,
As long as it is an aqueous liquid containing titanium obtained by reacting the above-described titanium compound with aqueous hydrogen peroxide, a conventionally known aqueous liquid can be used without particular limitation.
Specifically, the following can be mentioned.

A titanyl ion hydrogen peroxide complex or a titanic acid (peroxotitanium hydrate) aqueous solution obtained by adding aqueous hydrogen peroxide to a gel or sol of hydrous titanium oxide is disclosed in JP-A-63-35419 and JP-A-1 -224220).

Liquids for forming a titania film obtained by reacting a hydrogen peroxide solution on a titanium hydroxide gel prepared from an aqueous solution of titanium chloride or titanium sulfate and a basic solution (JP-A-9-71418 and JP-A-9-71418) -67516).

In the above liquid for forming a titania film, an aqueous solution of titanium chloride or titanium sulfate having a group capable of forming a salt with titanium is reacted with an alkaline solution such as ammonia or caustic soda to form a hydroxide called orthotitanic acid. Precipitate the titanium gel. Subsequently, the titanium hydroxide gel is separated by decantation using water, washed well with water, and further added with hydrogen peroxide solution to decompose and remove excess hydrogen peroxide, whereby a yellow transparent viscous liquid can be obtained.

The precipitated orthotitanic acid is in a gel state polymerized by polymerization of OH and hydrogen bonding, and cannot be used as an aqueous liquid containing titanium as it is. When hydrogen peroxide solution is added to this gel, a part of OH becomes a peroxidized state and dissolves as peroxotitanate ions, or it becomes a kind of sol in which the polymer chain is divided into low molecules, and excess peroxidation occurs. Hydrogen is decomposed into water and oxygen to be used as an aqueous liquid containing titanium for forming an inorganic film.

Since this sol contains only oxygen atoms and hydrogen atoms in addition to titanium atoms, when it is converted into titanium oxide by drying or firing, only water and oxygen are generated, so it is necessary for the sol-gel method and thermal decomposition of sulfates and the like. It is not necessary to remove a carbon component or a halogen component, and a crystalline titanium oxide film having a relatively high density can be formed even at a lower temperature than before.

Hydrogen peroxide is added to an aqueous solution of an inorganic titanium compound such as titanium chloride or titanium sulfate to form peroxotitanium hydrate, and a basic substance is added thereto. After a precipitate of the titanium hydrate polymer is formed, at least a dissolved component other than water derived from the titanium-containing raw material solution is removed, and a solution for forming titanium oxide obtained by further reacting with hydrogen peroxide (particularly, Kai 2000-247638 and JP 2000-247639
Reference).

As the aqueous liquid (A) used in the present invention, an aqueous liquid containing titanium obtained by the above-mentioned known method can be used. In addition, a method in which a titanium compound is added to a hydrogen peroxide solution for production. The aqueous liquid containing titanium obtained by the above can be used. The titanium compound contains a group which is hydrolyzed by the general formula Ti (OR) ₄ (where R is the same or different and represents an alkyl group having 1 to 5 carbon atoms). It is preferable to use a hydrolyzable titanium compound or a low-condensate of the hydrolyzable titanium compound.

The mixing ratio of the hydrolyzable titanium compound and / or a low-condensate thereof (hereinafter, these are simply referred to as “hydrolyzable titanium compound a”) and hydrogen peroxide water are as follows. It is preferably in the range of 0.1 to 100 parts by weight, particularly 1 to 20 parts by weight in terms of hydrogen peroxide, based on 10 parts by weight of a. If the amount is less than 0.1 part by weight in terms of hydrogen peroxide, chelate formation is not sufficient and cloudy precipitation occurs.
On the other hand, if it exceeds 100 parts by weight, unreacted hydrogen peroxide is apt to remain, and dangerous active oxygen is released during storage.

The hydrogen peroxide concentration of the aqueous hydrogen peroxide solution is not particularly limited, but is preferably in the range of 3 to 30% by weight in view of the ease of handling and the solid content of the product liquid related to coating workability.

The aqueous liquid (A) using the hydrolyzable titanium compound a is prepared by reacting the hydrolyzable titanium compound a with hydrogen peroxide solution at a reaction temperature of 1 to 70 ° C. for 10 minutes to 20 minutes.
It can be produced by reacting for hours.

The aqueous liquid (A) using the hydrolyzable titanium compound a is prepared by reacting the hydrolyzable titanium compound a with a hydrogen peroxide solution, whereby the hydrolyzable titanium compound is hydrolyzed with water. It is presumed that a hydroxyl group-containing titanium compound is generated, and then hydrogen peroxide is coordinated to the generated hydroxyl group-containing titanium compound, and a product obtained by this hydrolysis reaction and coordination by hydrogen peroxide occurring at the same time. And a chelating solution having extremely high stability at room temperature and enduring long-term storage is produced. The titanium hydroxide gel used in the conventional manufacturing method is partially three-dimensionalized by Ti-O-Ti bonds, and is essentially different in composition and stability from a product obtained by reacting this gel with a hydrogen peroxide solution.

When the aqueous liquid (A) using the hydrolyzable titanium compound a is subjected to heat treatment or autoclave treatment at 80 ° C. or more, a titanium oxide dispersion containing crystallized ultrafine titanium oxide particles is obtained. If it is lower than 80 ° C., crystallization of titanium oxide does not proceed sufficiently. In the titanium oxide dispersion thus produced, the particle diameter of the ultrafine titanium oxide particles is 10 nm or less, preferably in the range of 1 nm to 6 nm. The appearance of the dispersion is translucent. When the particle diameter is larger than 10 nm, the film forming property is reduced (1 μm).
m or more), which is not preferable. This dispersion can likewise be used.

The aqueous liquid (A) using the hydrolyzable titanium compound a is applied to a steel sheet material and dried or heat-treated at a low temperature to form a dense titanium oxide film having excellent adhesion by itself. it can.

As the heat treatment temperature, it is preferable to form the titanium oxide film at a temperature of, for example, 200 ° C. or lower, particularly 150 ° C. or lower.

The aqueous liquid (A) using the hydrolyzable titanium compound a forms an amorphous titanium oxide film containing some hydroxyl groups at the above-mentioned temperature.

Further, the titanium oxide dispersion liquid which has been heat-treated at 80 ° C. or higher can form a crystalline titanium oxide film only by coating, and thus is useful as a coating material for a material which cannot be subjected to heat treatment.

In the present invention, as the aqueous liquid (A), a hydrolyzable titanium compound and / or a low-condensate of a hydrolyzable titanium compound and hydrogen peroxide water in the presence of a titanium oxide sol are further used. An aqueous liquid containing titanium obtained by the reaction (hereinafter, abbreviated as "aqueous liquid (A-1)") can be used. As the hydrolyzable titanium compound and / or the low-condensate of the hydrolyzable titanium compound (hydrolysable titanium compound a), the above-mentioned general formula Ti (OR)
₄ (wherein R is the same or different and represents an alkyl group having 1 to 5 carbon atoms), a titanium monomer containing a group that becomes a hydroxyl group by hydrolysis and a low-condensate of the hydrolyzable titanium compound. It is preferred to use.

In the above-mentioned titanium oxide sol, amorphous titania and anatase-type titania fine particles contain water (as needed).
For example, a sol dispersed in an aqueous organic solvent such as an alcohol-based or alcohol-ether-based solvent may be used.

As the above-mentioned titanium oxide sol, a conventionally known one can be used. Examples of the titanium oxide sol include (1) those obtained by hydrolyzing a titanium-containing solution such as titanium sulfate or titanyl sulfate;
Titanium oxide aggregates such as those obtained by hydrolyzing an organic titanium compound such as titanium alkoxide and (3) those obtained by hydrolyzing or neutralizing a titanium halide solution such as titanium tetrachloride are dispersed in water. Amorphous titania sol or anatase type titanium fine particles obtained by firing the titanium oxide aggregates and dispersing them in water can be used. Amorphous titania can be converted to anatase-type titania by firing at least at a temperature higher than the crystallization temperature of anatase, for example, at a temperature of 400 ° C. to 500 ° C. or higher. As an aqueous sol of the titanium oxide, for example, TKS-201 (manufactured by Teica Co., Ltd., trade name, anatase crystal form, average particle diameter 6n)
m), TA-15 (manufactured by Nissan Chemical Co., Ltd., trade name, anatase type crystal form), STS-11 (manufactured by Ishihara Sangyo Co., Ltd., trade name, anatase type crystal form) and the like.

The weight ratio of the titanium oxide sol to the titanium hydrogen peroxide reactant when used for reacting the hydrolyzable titanium compound a with aqueous hydrogen peroxide is 1/99 to 9
9/1, preferably in the range of about 10/90 to 90/10. When the weight ratio is less than 1/99, the effect of adding titanium oxide sol such as stability and photoreactivity is not seen, and 99/1
Exceeding the range is not preferred because the film-forming properties are poor.

The mixing ratio of the hydrolyzable titanium compound a and the hydrogen peroxide solution is 0.1 to 100 parts by weight, particularly 1 to 20 parts by weight in terms of hydrogen peroxide, based on 10 parts by weight of the hydrolyzable titanium compound a. Is preferably within the range. If the amount is less than 0.1 part by weight in terms of hydrogen peroxide, chelate formation is not sufficient and cloudy precipitation occurs. On the other hand, if it exceeds 100 parts by weight, unreacted hydrogen peroxide is apt to remain, and dangerous active oxygen is released during storage.

The hydrogen peroxide concentration of the aqueous hydrogen peroxide solution is not particularly limited, but is preferably in the range of 3 to 30% by weight in view of the ease of handling and the solid content of the product liquid related to coating workability.

The aqueous liquid (A-1) is prepared by reacting the hydrolyzable titanium compound a with hydrogen peroxide in the presence of titanium oxide sol at a reaction temperature of 1 to 70 ° C. for 10 minutes to 20 hours. Can be manufactured.

The aqueous liquid (A-1) is obtained by reacting the hydrolyzable titanium compound a with aqueous hydrogen peroxide, whereby the hydrolyzable titanium compound a is hydrolyzed with water to form a hydroxyl group-containing titanium compound. Next, it is presumed that hydrogen peroxide is coordinated to the generated hydroxyl group-containing titanium compound, and the hydrolysis reaction and the coordination by hydrogen peroxide occur at the same time, resulting in stability at room temperature. Produces a chelating solution that is extremely high and can withstand long-term storage. The titanium hydroxide gel used in the conventional manufacturing method is Ti-OT
The gel is partially three-dimensionalized by i-bonds, and the gel and the hydrogen peroxide solution are essentially different in composition and stability. In addition, by using the titanium oxide sol, it is possible to prevent a partial condensation reaction from occurring during the synthesis to increase the viscosity. It is considered that the reason for this is that the condensation reaction product is adsorbed on the surface of the titanium oxide sol, thereby preventing polymerization in a solution state.

Further, the aqueous liquid (A-1) containing titanium was
When a heat treatment or an autoclave treatment is carried out at 0 ° C. or more, a titanium oxide dispersion containing crystallized ultrafine particles of titanium oxide is obtained. If it is lower than 80 ° C., crystallization of titanium oxide does not proceed sufficiently. In the titanium oxide dispersion thus produced, the particle diameter of the ultrafine titanium oxide particles is 10 nm or less, preferably in the range of 1 nm to 6 nm. The appearance of the dispersion is translucent. The particle size is 10
If it is larger than nm, the film-forming property is deteriorated (breakage occurs at 1 μm or more), which is not preferable. This dispersion can likewise be used.

The aqueous liquid (A-1) containing titanium is applied to a steel sheet material by drying or heat treatment at a low temperature, whereby
By itself, a dense titanium oxide film having excellent adhesion can be formed.

As the heat treatment temperature, it is preferable to form the titanium oxide film at a temperature of, for example, 200 ° C. or less, particularly 150 ° C. or less.

The aqueous liquid (A-1) containing titanium forms an anatase-type titanium oxide film containing a small amount of hydroxyl groups at the above-mentioned temperature.

As the aqueous liquid (A) of the present invention, the aqueous liquid and the aqueous liquid (A-1) using the hydrolyzable titanium compound a have excellent properties such as storage stability and corrosion resistance. Preferably, one is used.

In the aqueous liquid (A) containing titanium, other pigments and sols can be added and dispersed as needed. Examples of the additives include commercially available titanium oxide sol, titanium oxide powder, and the like, mica, talc, silica, barita, clay, and the like.

Compound (B) The compound which is the component (B) of the undercoating agent is at least one compound selected from a phosphoric acid compound, a metal hydrofluoric acid and a metal hydrofluoride.

Examples of the phosphoric acid compound include phosphorous acid, strong phosphoric acid, triphosphoric acid, hypophosphorous acid, hypophosphoric acid,
Monophosphoric acids such as trimetaphosphoric acid, diphosphoric acid, diphosphoric acid, pyrophosphoric acid, pyrophosphoric acid, metaphosphoric acid, metaphosphoric acid, phosphoric acid (orthophosphoric acid), and phosphoric acid derivatives, and salts thereof, and tripolyphosphoric acid , Tetraphosphoric acid, hexaphosphoric acid, condensed phosphoric acids such as condensed phosphoric acid derivatives, and salts thereof. These compounds can be used alone or in combination of two or more. Also,
Examples of the alkali compound forming the above-mentioned salt include organic or inorganic alkali compounds such as lithium, sodium, potassium, and ammonium. further,
It is preferable to use a water-soluble phosphoric acid compound.

Examples of the phosphoric acid compound include sodium pyrophosphate, sodium tripolyphosphate, sodium tetraphosphate, metaphosphoric acid, ammonium metaphosphate,
It is preferable to use sodium hexametaphosphate, since sodium hexametaphosphate and the like exhibit excellent effects such as storage stability of the coating agent and rust prevention of the coating film.

In the present invention, the above-mentioned blend of the aqueous liquid (A) containing titanium and the phosphate compound is prepared by coordinating the acidic phosphate group ion bound to the phosphate compound with the titanium ion. It is considered that a complex structure is formed between the two.

Such a reaction can be easily carried out by simply mixing the two components. For example, the mixture is allowed to stand at normal temperature (20 ° C.) for about 5 minutes to about 1 hour, When forcibly heating, for example, heating can be performed at about 30 to about 70 ° C. for about 1 minute to about 30 minutes.

The above-mentioned metal hydrofluoric acid and metal hydrofluoride include, for example, zirconium hydrofluoric acid, titanium hydrofluoric acid, hydrosilicofluoric acid, zirconium fluoride, titanium fluoride, Examples thereof include silicofluoride. Examples of the metal hydrofluoric acid salt include, for example, sodium, potassium, lithium, and ammonium. Among them, potassium and sodium are preferable, and specific examples thereof include potassium zirconium fluoride, potassium titanium fluoride, Examples thereof include sodium silicofluoride and potassium silicofluoride.

The phosphoric acid compound, the metal hydrofluoric acid and the metal hydrofluoride can be used singly or in combination of two or more. The compounding ratio of the compound (B) is determined based on the aqueous liquid containing titanium. The amount is preferably from 1 to 400 parts by weight, particularly preferably from 10 to 200 parts by weight, based on 100 parts by weight of the solid content of (A).

[0062] aqueous organic high molecular compound (C) ground processing material is an aqueous organic high molecular compound (C) is blended in addition to components described above. The aqueous organic polymer compound (C) itself is free from aggregation and sedimentation of the organic resin component dissolved or dispersed in water at a pH of 7 or less, and does not cause thickening or abnormal gelation. Any conventionally known aqueous liquid can be used as long as the aqueous liquid has excellent stability.

The aqueous organic polymer compound (C) is water-soluble,
Those having a form of water dispersibility or emulsion can be used. Water soluble organic polymer compound in water,
As a method of dispersing and emulsifying, a conventionally known method can be used. In particular,
As the organic polymer compound, a compound containing a functional group (for example, at least one kind of a hydroxyl group, a carboxyl group, an amino (imino) group, a sulfide group, a phosphine group, etc.) which can be made water-soluble or water-dispersible by itself, and if necessary. When some or all of these functional groups are acidic resins (such as carboxyl group-containing resins), amine compounds such as ethanolamine and triethylamine; ammonia water; lithium hydroxide;
Those neutralized with an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide, or a basic resin (such as an amino group-containing resin), a fatty acid such as acetic acid or lactic acid; A sum can be used.

Examples of the aqueous organic polymer compound (C) include an epoxy resin, a phenol resin, an acrylic resin, a urethane resin, an olefin-carboxylic acid resin, a nylon resin, and a polyoxyalkylene chain. Resins, polyvinyl alcohol, polyglycerin, carboxymethylcellulose, hydroxymethylcellulose, hydroxyethylcellulose and the like can be mentioned.

As the epoxy resin, a cationic epoxy resin obtained by adding an amine to an epoxy resin; a modified epoxy resin such as an acrylic-modified or urethane-modified epoxy resin can be preferably used. As a cationic epoxy resin,
For example, an adduct of an epoxy compound with a primary mono- or polyamine, a secondary mono- or polyamine, a mixed primary and secondary polyamine, and the like (for example, U.S. Pat.
No. 99); an adduct of an epoxy compound and a secondary mono- or polyamine having a ketiminated primary amino group (see, for example, U.S. Pat. No. 4,017,438); And etherification reaction products with a hydroxyl compound having a secondary amino group (for example, see JP-A-59-43013).

The epoxy compound has a number average molecular weight of 4
In the range of from 0.00 to 4,000, in particular from 800 to 2,000, and the epoxy equivalent is in the range from 190 to 2,000, in particular 4
Those in the range of 00 to 1,000 are suitable. Such an epoxy compound can be obtained, for example, by reacting a polyphenol compound with epilurylhydrin. Examples of the polyphenol compound include bis (4-hydroxyphenyl) -2,2-propane,
4-dihydroxybenzophenone, bis (4-hydroxyphenyl) -1,1-ethane, bis (4-hydroxyphenyl) -1,1-isobutane, bis (4-hydroxy-tert-butylphenyl) -2,2-propane ,
Bis (2-hydroxynaphthyl) methane, 1,5-dihydroxynaphthalene, bis (2,4-dihydroxyphenyl) methane, tetra (4-hydroxyphenyl)-
Examples thereof include 1,1,2,2-ethane, 4,4-dihydroxydiphenylsulfone, phenol novolak, and cresol novolak.

As the above-mentioned phenolic resin, those obtained by making a polymer compound obtained by heating and adding and condensing a phenol component and formaldehydes in the presence of a reaction catalyst into water, can be suitably used. As the phenol component as a starting material, a bifunctional phenol compound, a trifunctional phenol compound, a phenol compound having four or more functional groups, and the like can be used. For example, as the bifunctional phenol compound, o-cresol, As trifunctional phenol compounds such as p-cresol, p-tert-butylphenol, p-ethylphenol, 2,3-xylenol, and 2,5-xylenol, phenol, m-cresol, m-ethylphenol, 3,5-
Bifunctional phenol compounds such as xylenol and m-methoxyphenol include bisphenol A and bisphenol F. These phenol compounds can be used alone or in combination of two or more.

Examples of the acrylic resin include a homopolymer or a copolymer of a monomer having a hydrophilic group such as a carboxyl group, an amino group and a hydroxyl group, and a copolymer of a monomer having a hydrophilic group with another monomer. And copolymers with possible monomers. These are resins obtained by emulsion polymerization, suspension polymerization or solution polymerization, and, if necessary, neutralized and made aqueous or modified resins.

Examples of the carboxyl group-containing monomer include acrylic acid, methacrylic acid, maleic acid, maleic anhydride, crotonic acid, and itaconic acid.

Examples of the nitrogen-containing monomer include nitrogen-containing alkyl (meth) acrylates such as N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, and Nt-butylaminoethyl (meth) acrylate. ) Acrylate; acrylamide, methacrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-methylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide,
N, N-dimethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, N, N
Polymerizable amides such as -dimethylaminoethyl (meth) acrylamide; 2-vinylpyridine, 1-vinyl-2-
Aromatic nitrogen-containing monomers such as pyrrolidone and 4-vinylpyridine; and allylamine.

As the hydroxyl group-containing monomers, 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 2,3-dihydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth)
Acrylate and polyethylene glycol mono (meth)
Monoesters of polyhydric alcohols such as acrylates with acrylic acid or methacrylic acid; compounds obtained by ring-opening polymerization of ε-caprolactone with monoesters of the polyhydric alcohols with acrylic acid or methacrylic acid, and the like.

Other monomers include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl C1-C24 such as (meth) acrylate, 2-ethylhexyl acrylate, n-octyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, octadecyl (meth) acrylate, and isostearyl (meth) acrylate Alkyl (meth) acrylate; styrene, vinyl acetate and the like. These compounds can be used alone or in combination of two or more. In the present invention, “(meth) acrylate” means acrylate or methacrylate.

As the urethane resin, a polyurethane composed of a polyol such as a polyester polyol or a polyether polyol and a diisocyanate may be a low molecular weight compound having two or more active hydrogens such as a diol or a diamine, if necessary. Those obtained by elongating a chain in the presence of an elongating agent and stably dispersing or dissolving in water can be suitably used, and known ones can be widely used (for example, JP-B-42-24192, JP-B-42-24194, No. 42-5118, No. 49-986, No. 4
9-33104, JP-B-50-15027 and JP-B-53-29175). As a method for stably dispersing or dissolving the polyurethane resin in water, for example, the following method can be used.

(1) A method of imparting hydrophilicity by introducing an ionic group such as a hydroxyl group, amino group or carboxyl group into a side chain or a terminal of a polyurethane polymer, and dispersing or dissolving in water by self-emulsification.

(2) The reaction-completed polyurethane polymer or terminal isocyanate group is replaced with an oxime, alcohol,
A method in which a polyurethane polymer blocked with a blocking agent such as phenol, mercaptan, amine, and sodium bisulfite is forcibly dispersed in water using an emulsifier and mechanical shearing force. Further, a method of mixing a urethane polymer having a terminal isocyanate group with water / emulsifier / chain extender and simultaneously dispersing and increasing the molecular weight using mechanical shearing force.

(3) A method in which a water-soluble polyol such as polyethylene glycol is used as a polyol as a main raw material of polyurethane and dispersed or dissolved in water as a water-soluble polyurethane.

The polyurethane resin is not limited to a single dispersion or dissolution method as described above, and a mixture obtained by each method can also be used.

Examples of the diisocyanate that can be used for synthesizing the above polyurethane resin include aromatic, alicyclic and aliphatic diisocyanates, and specifically, hexamethylene diisocyanate, tetramethylene diisocyanate, and 3,3′-dimethoxy-diisocyanate. 4,4′-biphenylene diisocyanate, p-xylylene diisocyanate,
m-xylylene diisocyanate, 1,3- (diisocyanatomethyl) cyclohexanone, 1,4- (diisocyanatomethyl) cyclohexanone, 4,4'-diisocyanatocyclohexanone, 4,4'-methylenebis (cyclohexyl isocyanate) , Isophorone diisocyanate, 2,4-tolylene diisocyanate, 2,6-
Tolylene diisocyanate, p-phenylene diisocyanate, diphenylmethane diisocyanate, m-phenylene diisocyanate, 2,4-naphthalene diisocyanate, 3,3'-dimethyl-4,4'-biphenylene diisocyanate, 4,4'-biphenylene diisocyanate, and the like. . Of these, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate are particularly preferred.

Commercially available polyurethane resins include Hydran HW-330, HW-340 and HW-340.
-350 (all manufactured by Dainippon Ink and Chemicals, Incorporated),
Superflex 100, 150, F-3438
D (all manufactured by Daiichi Kogyo Seiyaku Co., Ltd.).

As the above polyvinyl alcohol resin,
It is preferably polyvinyl alcohol having a saponification degree of 87% or more, and particularly preferably so-called completely saponified polyvinyl alcohol having a saponification degree of 98% or more, and having a number average molecular weight of 3,000 to 100,000.
Is preferably within the range.

As the resin having a polyoxyalkylene chain, those having a polyoxyethylene chain or a polyoxypropylene chain can be suitably used. For example, polyethylene glycol, polypropylene glycol, the above polyoxyethylene chain and the above polyoxypropylene chain can be used. Blocked polyoxyalkylene glycol in which a chain is bonded in a block shape can be exemplified.

Examples of the olefin-carboxylic acid resin include a copolymer of an olefin such as ethylene and propylene and a polymerizable unsaturated carboxylic acid, and a polymerizable unsaturated compound added to a dispersion of the copolymer to emulsify the copolymer. At least one kind of water-dispersible or water-soluble resin selected from two kinds of resins which are polymerized and crosslinked in the particles can be used.

The above copolymer comprises olefin and (meth)
It is a copolymer with one or more of unsaturated carboxylic acids such as acrylic acid and maleic acid. In the copolymer, the content of the unsaturated carboxylic acid is 3 to 60% by weight,
The content is preferably in the range of 5 to 40% by weight, and the copolymer can be dispersed in water by neutralizing the acid group in the copolymer with a basic substance.

The above resin is added to an aqueous dispersion of a copolymer,
It is a crosslinked resin formed by adding a polymerizable unsaturated compound, performing emulsion polymerization, and further performing intra-particle crosslinking. Examples of the polymerizable unsaturated compound include the vinyl monomers listed in the description of the water-dispersible or water-soluble acrylic resin.
The species or two or more species can be appropriately selected and used.

The mixing ratio of the aqueous organic polymer compound (C) is 10 to 2,000 parts by weight, particularly 100 to 1,000 parts by weight, per 100 parts by weight of the solid content of the aqueous liquid (A) containing titanium.
The amount within the range of 0 parts by weight is preferable from the viewpoints of stability of the liquid, anticorrosion property and the like.

The undercoating agent becomes a stable liquid in a neutral or acidic region, and therefore preferably has a pH of 1 to 7, particularly 1 to 5.

For the undercoating agent, if necessary, for example,
In addition to the above-mentioned components, it contains a thickener, a surfactant, an antibacterial agent, a rust preventive (tannic acid, phytic acid, benzotriazole, etc.), a pigment such as a coloring pigment, an extender pigment, and a rust preventive pigment. be able to.

The undercoating agent may be diluted with a hydrophilic solvent such as methanol, ethanol, isopropyl alcohol, ethylene glycol, or propylene glycol as necessary.

Hydrophilic treatment film The hydrophilic treatment film formed on the undercoat film is
The surface is hydrophilic, has sufficient film strength, and has good water resistance and good adhesion to the undercoat film. As the hydrophilic treatment composition used for forming the hydrophilic treatment film, for example, a composition containing a hydrophilic film-forming binder can be suitably used.

Representative examples of the hydrophilic film-forming binder include: (1) an organic resin-based binder comprising a hydrophilic organic resin as a main component and, if necessary, a crosslinking agent; (2) a hydrophilic organic resin; An organic resin / colloidal silica-based binder comprising colloidal silica as a main component and optionally a crosslinking agent; (3) a water glass-based binder which is a mixture of an alkali silicate as a main component and a nonionic aqueous organic resin. And the like. Among them, the organic resin binder (1) and the organic resin / colloidal silica binder (2) are preferable.

The hydrophilic organic resin in the organic resin-based binder (1) contains a hydroxyl group, a carboxyl group or an amino group in the molecule and can be neutralized as it is or by neutralization with an acid or a base depending on the functional group. And water-soluble or water-dispersible resins. Specific examples of the hydrophilic organic resin include, for example, polyvinyl alcohol, modified polyvinyl alcohol (for example, copolymers with acrylamide, unsaturated carboxylic acid, sulfonic acid monomer, cationic monomer, unsaturated silane monomer, etc.), polyacrylic Synthetic hydrophilic resins such as acid, polyethylene glycol, carboxyl group-containing acrylic resin, carboxyl group-containing polyester resin, adduct of epoxy resin and amine, copolymer ionomer of ethylene and acrylic acid; starch, cellulose, algin, etc. Natural polysaccharides; oxidized starch, dextrin, propylene glycol alginate, carboxymethyl starch, carboxymethyl cellulose, hydroxymethyl starch,
Derivatives of natural polysaccharides such as hydroxymethylcellulose and hydroxyethylcellulose can be mentioned.

Examples of the crosslinking agent optionally used in the organic resin binder (1) include melamine resins, urea resins, phenol resins, polyepoxy compounds,
Examples include a blocked polyisocyanate compound and a metal chelate compound. It is generally preferred that the crosslinking agent has water solubility or water dispersibility.

Specific examples of the cross-linking agent include, for example, methyl etherified melamine resin, butyl etherified melamine resin, methyl / butyl mixed etherified melamine resin, methyl etherified urea resin, methyl etherified benzoguanamine resin, polyphenols or aliphatic compounds. Blocked product of di- or polyglycidyl ether of polyhydric alcohol, amine-modified epoxy resin, triisocyanurate of hexamethylene diisocyanate; metal chelate compound of metal element such as titanium (Ti), zirconium (Zr), aluminum (Al) And the like.
The metal chelate compound preferably has at least two or more metal alkoxide bonds in one molecule.

As the hydrophilic organic resin in the organic resin / colloidal silica binder (2), the same hydrophilic organic resin as in the organic resin binder (1) can be used. The colloidal silica in the binder (2) is a so-called silica sol or finely divided silica, usually having a particle diameter of about 5 nm to 10 μm, preferably 5 nm to 1 μm, and usually supplied as an aqueous dispersion. It can be used as it is or by dispersing finely divided silica in water. In the organic resin / colloidal silica binder (2),
The organic resin and colloidal silica may be simply mixed, or the organic resin and colloidal silica may be reacted and complexed in the presence of alkoxysilane.

As the aqueous organic resin in the water glass-based binder (3), an anionic or nonionic organic resin among the hydrophilic organic resins in the organic resin-based binder (1) can be used.

Examples of the hydrophilic film-forming binder include:
Among them, the organic resin binder (1) and the organic resin / colloidal silica binder (2) are preferable.

[0097] The hydrophilic film-forming binder can be dissolved or dispersed in an aqueous medium. The aqueous medium means water or a mixture of water mainly composed of water and an organic solvent. The hydrophilic treatment composition may be composed of only an aqueous solution or aqueous dispersion of a hydrophilic film-forming binder, but if necessary, a surfactant for improving the hydrophilicity of the coating film; Hydrophilic polymer fine particles for improvement (usually having an average particle size of 0.03 to 1 μm, preferably 0.05 to 0.6 μm); 2- (4-thiazolyl) benzimidazole, bis (dimethyl) Antibacterial agents such as thiocarbamoyl) disulfide and zeolite (aluminosilicate); Rust inhibitors such as tannic acid, phytic acid, and benzotriazole; oxyacid compounds such as molybdenum, vanadium, zinc, nickel, cobalt, copper, and iron A pigment such as a coloring pigment, an extender pigment, or a rust-preventive pigment;

Next, the heat exchanger aluminum fin material subjected to the hydrophilic treatment and the method for producing the same according to the present invention will be described in detail.

Method for Producing Heat Exchanger Aluminum Fin Material The heat exchanger aluminum fin material subjected to the hydrophilic treatment according to the present invention comprises a fin material made of aluminum or an aluminum alloy as a base material and a fin material provided on the base material. It comprises a base treatment film from the base treatment agent and the hydrophilic treatment film provided on the base treatment film.

As the base material, aluminum or an aluminum alloy material, a material known per se which can be used as a base material of a heat exchanger aluminum fin can be used.

The undercoating film can be formed by coating and drying the undercoating agent on the aluminum fin material. The surface treating agent is applied to a base material, an aluminum fin material (which may be assembled in a heat exchanger), by a known coating method, for example, dip coating, shower coating, spray coating, roll coating. , Can be coated by electrodeposition coating or the like. The drying condition of the undercoating agent is generally such that the maximum temperature at which the material reaches is about 60 to 250 ° C.
It is preferable to dry under the following conditions for about 2 seconds to about 30 minutes.

The dry film thickness of the undercoating agent is usually preferably in the range of 0.001 to 10 μm, particularly preferably in the range of 0.1 to 3 μm. When the thickness is less than 0.001 μm, the performance such as corrosion resistance and water resistance is deteriorated. On the other hand, when the thickness is more than 10 μm, the base treatment film is cracked or the hydrophilicity is deteriorated.

The above-mentioned hydrophilizing composition is applied on an aluminum fin material provided with the above-mentioned undercoating film (which may be assembled in a heat exchanger) by a known coating method, for example, dip coating, It is possible to produce a heat exchanger aluminum fin material that has been subjected to a hydrophilic treatment by painting and baking by shower coating, spray coating, roll coating, electrodeposition coating and the like. Although the film thickness of the hydrophilic treatment film formed from the hydrophilic treatment composition is not particularly limited, it is generally 0.3 to 5 μm, preferably 0.1 to 5 μm.
Preferably, it is in the range of 5 to 3 μm. In addition, the curing conditions of the hydrophilic treatment composition can be appropriately set according to the kind of the binder, the thickness of the coating film, and the like. 3
Baking for 0 minutes is preferred.

[0104]

According to the present invention having the above-described structure, the following effects are considered to be obtained.

In the present invention, phosphoric acid which is a component (B) constituting the undercoating agent is prepared by applying the undercoating agent having the above-mentioned structure to an aluminum substrate and heating to form a titanium-based anticorrosion film. Compound, metal hydrofluoric acid,
Metal hydrofluoride or the like acts as a metal etchant. On the other hand, the aqueous liquid (A) containing titanium and the aqueous organic polymer compound (C) provide excellent adhesion to the material, oxygen permeability, It is presumed that a film having low water vapor permeability is formed, and exhibits a remarkable effect on corrosion resistance and durability.
By forming a hydrophilic treatment film on the undercoating film, it is possible to obtain a hydrophilization treatment aluminum material which is excellent in corrosion resistance and hydrophilicity, does not contain chromium, and has no problem in terms of environmental protection. It is suitable as a heat exchanger aluminum fin material.

[0106]

The present invention will be described more specifically below with reference to examples and comparative examples. Hereinafter, “parts” and “%” mean “parts by weight” and “% by weight”, respectively. The present invention is not limited to the following examples.

Production Example 1 of Titanium-Based Aqueous Liquid Ammonia water (1: 9) was added dropwise to a solution prepared by diluting 5 cc of a 60% titanium tetrachloride solution with 500 cc of distilled water to precipitate titanium hydroxide. After washing with distilled water, hydrogen peroxide water 30
% Solution was added and stirred to obtain a titanium-based aqueous liquid (A1) containing titanium and containing a translucent yellowish solid having a solid content of 2%.

Production Example 2 A mixture of 10 parts of tetra-iso-propoxytitanium and 10 parts of iso-propanol was stirred at 20 ° C. for 1 hour in a mixture of 10 parts of 30% hydrogen peroxide and 100 parts of deionized water. It was dropped. Thereafter, the mixture was aged at 25 ° C. for 2 hours, and was a yellowish, transparent, slightly viscous titanium-based aqueous liquid having a solid content of 2% (A
2) was obtained.

Production Example 3 Preparation of Titanium-Based Aqueous Liquid (A2) Titanium-n-butoxytitanium was used in place of tetra-iso-propoxytitanium in the same production conditions as in the production example of titanium-based aqueous liquid (A3). ) Got.

Production Example 4 A titanium-based aqueous liquid (A2) was prepared in the same manner as in the production example of the titanium-based aqueous liquid (A2) except that the tetraiso-propoxytitanium trimer was used instead of the tetraiso-propoxytitanium trimer. An aqueous liquid (A4) was obtained.

Production Example 5 In the production example of the titanium-based aqueous liquid (A2), hydrogen peroxide was added dropwise at 50 ° C. over 1 hour using a three-fold amount of aqueous hydrogen peroxide, and further added at 60 ° C.
For 3 hours to obtain a titanium-based aqueous liquid (A5) having a solid content of 2%.

Production Example 6 A titanium-based aqueous solution (A3) was heated at 95 ° C. for 6 hours.
White-yellow translucent titanium-based aqueous liquid having a solid content of 2% (A6)
I got

Production Example 7 A mixture of 10 parts of tetra-iso-propoxytitanium and 10 parts of iso-propanol was mixed with TKS-203 (Taika).
1 part in a mixture of 5 parts (solid content), 10 parts of 30% hydrogen peroxide solution and 100 parts of deionized water.
The mixture was added dropwise with stirring at 0 ° C. for 1 hour. Then 10
Aged at 24 ° C. for 24 hours, yellow transparent, slightly viscous solid 2
% Titanium-based aqueous liquid (A7).

Production Example 8 of Acrylic Resin 180 parts of isopropyl alcohol was placed in a 1 L four-necked flask equipped with a thermometer, a stirrer, a cooler, and a dropping funnel. C. and adjusted to a monomer mixture consisting of 140 parts of ethyl acrylate, 68 parts of methyl methacrylate, 15 parts of styrene, 15 parts of Nn-butoxymethylacrylamide, 38 parts of 2-hydroxyethyl acrylate and 24 parts of acrylic acid. Dropwise over about 2 hours with a catalyst consisting of 6 parts of 2,2'-azobis (2,4-dimethylvaleronitrile). When the reaction was continued at the same temperature for 5 hours after the completion of the dropwise addition, the polymerization rate was almost 100%, the solid content was about 63%, and the acid value was about 67.
A colorless and transparent resin solution is obtained. This resin solution 500
To this part, 108 parts of dimethylaminoethanol was mixed, and after adding water, the mixture was sufficiently stirred to obtain an aqueous acrylic resin dispersion (C1) having a solid content of 30%.

Production Example 9 of Amine-Modified Epoxy Resin A reactor equipped with a stirrer, a reflux condenser, a thermometer and a liquid dropping device was charged with Epicoat 1009 resin (epoxy resin manufactured by Shell Chemical Co .; molecular weight 3,750), 880g
(0.5 mol) and methyl isobutyl ketone / xylene =
After adding 1,000 g of a 1/1 (weight ratio) mixed solvent,
The mixture was stirred and heated to dissolve uniformly. Thereafter, the temperature was cooled to 70 ° C., and 70 g of di (n-propanol) amine collected in the liquid dropping device was dropped over 30 minutes. During this time, the reaction temperature was maintained at 70 ° C. After completion of the dropwise addition, the mixture was maintained at 120 ° C. for 2 hours to complete the reaction, whereby the solid content was 66%
An amine-modified epoxy resin was obtained. The obtained resin 1,0
25 parts of 88% formic acid was mixed with 00 g, and the mixture was sufficiently stirred after the addition of water to obtain an aqueous dispersion of an amine-modified epoxy resin (C2) having a solid content of 30%.

[0116] hydrophilized aluminum plate prepared in Example 1 2% titanium-based aqueous solution (A1) 50 parts, 5 parts of 20% zirconium hydrofluoric acid, 30% acrylic resin water dispersion (C
1) 10 parts and 35 parts of deionized water were blended to obtain a surface treating agent.

A 0.1 mm thick aluminum plate (A10
50) was degreased and washed with a 2% concentration aqueous solution in which an alkali degreasing agent (trade name “Chem Cleaner 561B” manufactured by CB Chemical Co., Ltd.) was dissolved. Was applied so as to be 0.2 g / m ^2, and baked for 5 seconds so that the temperature at which the material reached reached 100 ° C. to form an undercoating film. Then, “Cosmer 1310” (manufactured by Kansai Paint Co., Ltd., a hydrophilic treatment composition containing hydrophilic organic resin and colloidal silica as main components, trade name) was applied on the obtained undercoating film to a dry film thickness of 1 μm. And baked for 10 seconds at a raw material temperature of 230 ° C. to obtain a hydrophilized aluminum plate.

Examples 2 to 11 and Comparative Examples 1 to 3 The same procedure as in Example 1 was repeated except that the composition of the undercoating agent was as shown in Table 1 below. I got a board.

A test was carried out on each of the hydrophilically treated aluminum plates obtained above according to the following test methods. Table 1 shows the obtained results.

Test Method Appearance of coating film: The test plate was visually evaluated. When no abnormality was observed in the coating film, it was evaluated as ○.

Dry rubbing property: about 4 kg / kg of Kimwipe (paper, trade name, manufactured by Jujo Kimberly Co., Ltd.)
It was rubbed back and forth over a distance of about 5 cm with a pressure of cm ² . The number of times until the coating film was removed and the aluminum plate surface was exposed was measured and evaluated according to the following criteria. …: The aluminum plate surface is not exposed even after 10 reciprocations.…: The aluminum plate surface is exposed after 5 to 10 reciprocations. X: The aluminum plate surface is exposed after less than 5 reciprocations.

Water rubbing property: A gauze impregnated with deionized water, applying a pressure of about 4 kg / cm ² to the coated surface for about 5
Rubbed back and forth over a distance of cm. The number of times until the coating film was removed and the aluminum plate surface was exposed was measured and evaluated according to the following criteria. …: The aluminum plate surface is not exposed even after 10 reciprocations.…: The aluminum plate surface is exposed after 5 to 10 reciprocations. X: The aluminum plate surface is exposed after less than 5 reciprocations.

[0123] Hydrophilic: initial test plate, and the test plate in running tap water (water flow is painted panels 1 m ² per 15 kg / h) 7
The test plate was immersed for a period of time, pulled up, and dried in a room for 17 hours, and the drying and wetting process was performed in one cycle.

Water Wettability: The coated plate is immersed in a beaker containing tap water for 10 seconds, and the state of water dripping on the surface of the coated plate when pulled up is visually determined. ○: The entire surface of the coated plate is wet with water and there is no unevenness of water even after 10 seconds of pulling. △: The entire surface of the coated plate is wet immediately after pulling, but water is applied from the edge of the coated plate to the center after 10 seconds of pulling. Closed state ×: Polka dots are formed immediately after pulling, and water is not wet on the entire coated plate.

Water contact angle: After drying each test plate at 80 ° C. for 5 minutes, 0.03 cc was applied on the coated surface of each test plate with a syringe.
Was added dropwise to form a water droplet, and the contact angle of the water droplet was measured with a contact angle meter DCAA type manufactured by Kyowa Chemical Industry Co., Ltd.

Corrosion resistance: according to JIS-Z-2371 salt spray test method. The test time was set in three stages of 120 hours, 240 hours and 360 hours, and evaluated according to the following criteria. …: No white rust or swelling was observed on the coated surface.…: Little white rust or swelling was generated. ×: White rust or swelling was remarkably generated.

[0127]

[Table 1]

[0128]

[Table 2]

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Osamu Isozaki 4-171-1, Higashiyawata, Hiratsuka-shi, Kanagawa F-term (reference) in Kansai Paint Co., Ltd. 4D075 AE16 AE27 BB24Y BB24Z BB91Z BB92Y BB92Z CA13 CA33 CA37 DA03 DA06 DA23 DB07 DC16 DC19 EA06 EA10 EA12 EB07 EB13 EB19 EB20 EB22 EB32 EB33 EB35 EB37 EB38 EB39 EB45 EB47 EB52 EB56 EC01 EC08 EC52 EC54 4K026 AA09 AA22 BA03 CA13 CA23 CA25 CA26 CA02 BA03 BA03 DA03 DA02 DA

Claims (14)

[Claims] 1. A fin material made of aluminum or an aluminum alloy, on which a film of an undercoating agent is formed, and a hydrophilizing film is formed on the undercoating film. The agent is obtained by reacting (A) at least one titanium compound selected from a hydrolyzable titanium compound, a hydrolysable titanium compound low-condensate, titanium hydroxide and a titanium hydroxide low-condensate with hydrogen peroxide water. Aqueous solution containing titanium obtained, (B) at least one selected from phosphoric acid compounds, metal hydrofluoric acid and metal hydrofluoride
An aluminum fin material subjected to hydrophilization treatment, comprising: a compound of the type described above; and (C) an aqueous organic polymer compound having a pH of 7 or less and being stable. 2. The aqueous liquid (A) contains a titanium obtained by reacting a hydrolyzable titanium compound and / or a low-condensate of a hydrolyzable titanium compound with a hydrogen peroxide solution in the presence of a titanium oxide sol. The heat exchanger aluminum fin material according to claim 1, which is an aqueous liquid (A-1). 3. The heat exchanger aluminum fin material according to claim 1, wherein the aqueous liquid (A) is produced by adding a titanium compound to a hydrogen peroxide solution. 4. The heat exchanger aluminum fin according to claim 1, wherein the hydrolyzable titanium compound is a titanium monomer containing a group that is hydrolyzed to become a hydroxyl group. Wood. 5. The method according to claim 1, wherein the low-condensation product of the hydrolyzable titanium compound is a low-condensation product of a titanium monomer having a group that becomes a hydroxyl group by hydrolysis. The heat exchanger aluminum fin material described. 6. The hydrolyzable titanium compound represented by the general formula Ti
(OR) _{4 wherein} R is the same or different and has 1 carbon atom
The aluminum fin material according to any one of claims 1 to 4, wherein the aluminum fin material has an alkyl group of from 1 to 5. 7. The heat exchanger aluminum fin material according to claim 1, wherein the low-condensate has a degree of condensation of 2 to 30. 8. The method according to claim 1, wherein the mixing ratio of the titanium compound to the hydrogen peroxide solution is 0.1 to 100 parts by weight of hydrogen peroxide per 10 parts by weight of the titanium compound.
4. The heat exchanger aluminum fin material according to any one of claims 1 to 3. 9. Compound (B) is phosphoric acid, metaphosphoric acid,
Condensed phosphoric acid, condensed metaphosphoric acid, phosphate, metaphosphate, condensed phosphate, condensed metaphosphate, zirconium hydrofluoric acid, titanium hydrofluoric acid, hydrofluorosilicic acid, zirconium fluoride, titanium The heat exchanger aluminum fin material according to claim 1, wherein the aluminum fin material is at least one compound selected from a fluoride salt and a silicofluoride salt. 10. The compounding ratio of the compound (B) is 1 to 4 with respect to 100 parts by weight of the solid content of the aqueous liquid (A) containing titanium.
The heat exchanger aluminum fin material according to claim 1 or 9, which is 00 parts by weight. 11. The aqueous organic polymer compound (C) is at least one of an epoxy resin, a phenol resin, an acrylic resin, a urethane resin, a polyvinyl alcohol resin, a polyalkylene glycol resin, and an olefin-carboxylic acid resin. The heat exchanger aluminum fin material according to claim 1, which is an aqueous organic polymer compound selected from one kind of resin. 12. The compounding ratio of the aqueous organic polymer compound (C) is 10 to 2,000 parts by weight based on 100 parts by weight of the solid content of the aqueous liquid (A) containing titanium. Item 12. The heat exchanger aluminum fin material according to item 1 or 11. 13. The heat exchanger aluminum fin material according to claim 1, wherein the base treating agent is an aqueous liquid having a pH of 1 to 7. 14. At least one selected from the group consisting of (A) a hydrolyzable titanium compound, a low-condensation product of a hydrolyzable titanium compound, titanium hydroxide and a low-condensation product of titanium hydroxide, on a fin material made of aluminum or an aluminum alloy. An aqueous liquid containing titanium obtained by reacting a titanium compound with hydrogen peroxide water, (B) at least one compound selected from phosphoric acid compounds, metal hydrofluoric acid and metal hydrofluoride, And (C) a base film containing a stable aqueous organic polymer compound having a pH of 7 or less,
After coating and drying to a thickness of 0.3 μm, the hydrophilic treatment composition is coated on the base treatment in a dry film thickness of 0.3 to 5 μm and dried, and then subjected to a hydrophilic heat treatment. Method of manufacturing aluminum fin material.