JP4248562B2 - Water-based treatment agent for hydrophilicity, deodorization and corrosion resistance of aluminum-containing metal materials, and hydrophilicity, deodorization and corrosion resistance treatment method - Google Patents

Description

  The present invention relates to an aqueous treatment agent for making the surface of an aluminum-containing metal material hydrophilic, deodorant, and corrosion resistant, and a hydrophilic, deodorant, and corrosion resistant treatment method using the same. More specifically, the present invention relates to a heat exchanger assembled using an aluminum-containing metal material, and an aqueous system for making the aluminum-containing metal material used in a heat exchanger made of aluminum-containing metal material hydrophilic, deodorizing, and corrosion-resistant. The present invention relates to a treatment agent and a hydrophilic, deodorant, and corrosion resistance treatment method using the same.

  Many heat exchangers that use aluminum-containing metal materials are designed to maximize the surface area of the heat-dissipating part and the cooling part (fins) in order to improve the heat dissipation or cooling effect, and they are also miniaturized. Therefore, the gap between the fins is extremely narrow. For this reason, when this heat exchanger (evaporator) is operated, moisture in the atmosphere is condensed in the fin gap. At this time, the higher the hydrophobicity of the fin surface, the more easily the condensed water becomes water droplets, and clogging occurs in the gap between the fins, so that the ventilation resistance increases and the heat exchange efficiency decreases. There is also a problem that water droplets formed in the fin gaps are scattered on the downstream side of the air.

Conventionally, many heat exchangers have been subjected to chemical conversion treatment such as chromate treatment for the purpose of improving corrosion resistance, but these chemical conversion films have low hydrophilicity and cannot solve the above problems. It was. In addition, such a chemical conversion film has a problem that it emits an unpleasant odor.
Furthermore, there is a problem that microorganisms derived from condensed water adhering to the heat exchanger (evaporator) and dust in the atmosphere propagate in the fin gaps, and a decaying odor is generated by metabolites of these microorganisms.

  A method for making the fin surface hydrophilic is disclosed in Japanese Patent Publication No. 53-48177 as “Chemical conversion of aluminum or the like characterized by treatment with an alkali silicate aqueous solution having a specific composition followed by heat drying at a temperature of 150 ° C. or higher. In Japanese Patent Publication No. 57-46000 (Patent Document 1), there is disclosed an “aluminum heat exchanger characterized by being treated with an organic polymer resin solution containing porous fine particles”. "Surface treatment method" is disclosed, and Japanese Patent Application Laid-Open No. 60-101156 (Patent Document 2) includes "a low-molecular organic compound having an alkali silicate, a carbonyl group, and a water-soluble organic polymer compound". A film forming agent for aluminum ”is disclosed, and a method of applying an inorganic hydrophilic compound such as silica sol or alkali silicate compound to these prior arts is disclosed. It has been proposed.

  However, in the pre-coating method in which molding is performed after various coating treatments are performed, ironing or drilling is performed on the aluminum material treated with the treatment agent containing the inorganic compound having a high hardness as described above. There was a problem that wear of jigs and molds was increased. In addition, these hard coatings have the problem of promoting the generation of off-flavors, rather than having the effect of suppressing the generation of off-flavors.

In order to solve these problems, several methods for applying an organic compound-based treatment not containing an inorganic compound such as an alkali silicate have been proposed.
That is, as means for preventing the scattering of water droplets due to condensed water, Japanese Patent Application Laid-Open No. 60-219285 (Patent Document 3) describes “a polyamide having a tertiary amine and / or a polyamide having a polyalkylene glycol group as a main component. "Anti-fogging and drip-proofing agent" is disclosed. However, the material obtained by using this treatment agent has insufficient hydrophilicity after using it for a long time, and the problem of generation of off-flavors such as rot after use for a long time has not been solved.

  Further, as means for preventing the scattering of water droplets due to condensed water and the generation of a strange odor, Japanese Patent Application Laid-Open No. 61-250495 (Patent Document 4) discloses that “a water-soluble polyamide resin that exhibits a cationic property in an aqueous solution is a main component. A method for forming a hydrophilic film on a chemical film such as chromate is disclosed, and Japanese Patent Application Laid-Open No. 3-72562 (Patent Document 5) discloses “partially saponified polyvinyl acetate, water-soluble nylon and water-soluble”. A hydrophilic surface treatment agent containing an amino resin ”and the like are disclosed. However, these methods and treatment agents have not always been satisfactory in maintaining the hydrophilicity and the effect of preventing odor when used for a long period of time.

Japanese Patent Laid-Open No. 2-219855 (Patent Document 6) states that “a hydrophilic coating agent obtained by copolymerizing four kinds of α, β unsaturated monomers having specific functional groups” And a hydrophilic coating agent that can reduce wear of a mold or the like during molding. Among them, the use of polyepoxide, which is a glycidyl compound, is specified as one of the crosslinking agents for the copolymer. However, it is difficult to obtain a desired polymer from monomers having four types of functional groups having different ionic properties, and the obtained polymer is unstable, so that the pot of hydrophilic coating agent is used. There was a problem in life. In addition, the film obtained by this treatment has a problem that the effect of suppressing the generation of off-flavor is hardly recognized.
Japanese Patent Publication No.57-46000 JP-A-60-101156 JP 60-219285 A Japanese Patent Laid-Open No. 61-250495 Japanese Patent Laid-Open No. 3-72562 Japanese Patent Laid-Open No. 2-219855

  The present invention solves the problems of heat exchange efficiency due to condensate in the prior art, the problem of water droplet scattering, the problem of off-flavor generation, and the problem of mold wear during molding processing. Provided is an aqueous treatment agent for hydrophilicity, deodorization, and corrosion resistance of an aluminum-containing metal material that can maintain excellent hydrophilicity, off-flavor generation suppression, and antibacterial properties over a long period of time, and a hydrophilic, deodorization, and corrosion resistance treatment method. For the purpose.

  As a result of intensive studies on means for solving the above problems, the present inventors have found that a water-soluble organic compound having a specific structure, a water-soluble organic compound having a specific functional group, and a specific antibacterial agent are included. The present inventors have found that a chemical treatment agent has a remarkable effect in solving the above problems, and have completed the present invention.

That is, the aqueous treatment agent for hydrophilicity, deodorization and corrosion resistance of the aluminum-containing metal material of the present invention has the following components:
(A) a water-soluble organic compound having a glycidyl group,
(B) a water-soluble organic polymer compound having a tertiary amino group and at least one hydrophilic functional group selected from a polyalkylene glycol group and an amide group, and the tertiary amino group and the at least one kind At least one selected from water-soluble organic compounds having a hydrophilic functional group and capable of being polymerized by heating and drying;
(C) an antibacterial agent having no decomposition point at temperatures up to 100 ° C., and (D) Cr (NO ₃ ) ₃ , CrF ₃ , Cr (H ₂ PO ₄ ) ₃ , H ₂ ZrF ₆ and H ₂ TiF ₆ A water / corrosion resistance improver containing at least one selected from the group consisting of:
In the aqueous processing agent of the present invention, 10 to 500 parts by weight of the component (B) and 0.1 to 100 parts by weight of the component (C) are contained with respect to 100 parts by weight of the component (A). It is preferable.
In the aqueous treatment agent of the present invention, it is preferable that the pH value of the aqueous treatment agent is adjusted to 3 to 6.
Moreover, the hydrophilic, deodorant, and corrosion resistance treatment method of the aluminum-containing metal material of the present invention is performed by applying the water-based treatment agent of the present invention to the surface of the aluminum-containing metal material and drying by heating to a thickness of 0.05 to 5 μm. It is characterized by forming a hydrophilic / deodorant / corrosion-resistant film.

  The hydrophilic, deodorant, and corrosion-resistant water-based treatment agent and treatment method of the present invention have excellent durability, anti-odour, antibacterial, and corrosion resistance on the surface of the aluminum-containing metal material, and excellent A film having moldability cannot be formed.

Hereinafter, the water-based treatment agent and the treatment method of the present invention will be described in detail.
The component (A) in the water-based treatment agent for hydrophilicity, deodorization and corrosion resistance of the present invention comprises a water-soluble organic compound having a glycidyl group, and this compound comprises sorbitol polyglycidyl ether, polyglycerol polyglycidyl ether, pentaerythritol poly Organic compounds having a glycidyl group such as glycidyl ether and glycerol polyglycidyl ether, or homopolymers of addition polymerizable monomers such as glycidyl acrylate and glycidyl methacrylate, or copolymers with other monomers, epoxy resins, epoxy-modified resins It can be selected from water-soluble polymer compounds having a glycidyl group such as

  The component (B) of the aqueous treating agent of the present invention has a water-soluble polymer compound having a tertiary amino group and at least one hydrophilic functional group selected from a polyalkylene glycol group and an amide group And at least one selected from water-soluble organic compounds having the tertiary amino group and the at least one hydrophilic functional group and capable of being polymerized by heat drying. Polymer compound having a triamino group and at least one of the hydrophilic functional groups, or an oligomer having at least one of a tertiary amino group and the hydrophilic functional group and which is polymerized by heating , Monomers and the like. The water-soluble polymer compound and the water-soluble organic compound to be polymerized include, for example, an addition polymerizable monomer having a tertiary amino group such as dimethylaminoethyl acrylate, dimethylaminopropyl methacrylate, alkyldiallylamine, polyethylene glycol acrylate, polyethylene Copolymers with addition-polymerizable monomers having a hydrophilic functional group selected from polyalkylene glycol groups and amide groups in the molecule, such as glycol acrylate alkylphenyl ethers and acrylamides, containing the tertiary amino group Selected from addition polymerizable monomers, addition polymerizable monomers having the above-mentioned hydrophilic functional groups, alkyl acrylates, alkyl methacrylates, styrene, vinyl toluene, acrylonitrile, vinyl acetate, etc. Polymers having a ternary structure composed of at least three kinds with other addition polymerizable monomers, water-soluble polyamides obtained by ternary condensation polymerization of aminoethylpiperazine, polyethylene glycol diamine, and adipic acid, Mannich reaction or Hoffmann reaction, etc. Can be selected from polyvinylphenols tertiary-aminated by the above, phenol resin oligomers tertiary-aminated in the same manner as above, and bisphenol resin oligomers tertiary-aminated in the same manner as above. In the structure of the water-soluble polymer compound and the organic compound to be polymerized, the functional group introduced in addition to the tertiary amino group is one or two selected from a polyalkylene glycol group and an amide group. It is preferable that when the functional group is 3 or more, the stability of the aqueous treatment agent obtained tends to decrease.

  The component (B) of the water-based treatment agent of the present invention must contain one or more of these water-soluble polymer compounds and organic compounds that can be polymerized, and the component (B) The blending ratio is preferably in the range of 10 to 500 parts by weight, more preferably 50 to 30 parts by weight, relative to 100 parts by weight of the component (A). If the blending ratio of component (B) is less than 10 parts by weight, the hydrophilicity of the resulting film is not sufficient, and if it exceeds 500 parts by weight, the water resistance of the resulting film becomes insufficient.

  Next, the component (C) composed of the antibacterial agent having no decomposition point at a temperature up to 100 ° C. is a solvent for the aqueous treatment agent in the drying step after the aqueous treatment agent is applied to the surface of the aluminum metal material. It is necessary to be able to withstand heating when removing water, and examples of such antibacterial agents include 5-chloro-2-methyl-4-isothiazolin-3-one and 2-methyl-4- Isothiazoline-3-one, 2- (4-thiocyanomethylthio) benzothiazole, 2,2-dibromo-3-nitrilopropionamide, sodium ethylenebis (dithiocarbamate), sodium-2-pyridinethiol-1-oxide, zinc 2-pyridinethiol-1-oxide, 2,2′-dithiobis (pyridine-1-oxide), 2,4,5,6-tetrachloroisophthalate Nitrile, 2-methylcarbonylaminobenzimidazole, 2,3,5,6-tetrachloro-4- (methylsulfonyl) -pyridine, 2- (4-thiazolyl) -benzimidazole, N- (fluorodichloromethylthio) sulfamide, p-chloro-m-xylenol, dehydroacetic acid, o-phenylphenol, 1,2-benzisothiazolin-3-one, 2-bromo-2-nitropropane-1,3-diol, barium metaborate, diiodomethyl-p- Toluene sulfone, 2-n-octyl-4-isothiazolin-3-one, 10,10′-oxybisphenoxyarsine and the like can be mentioned.

  The component (C) composed of the antibacterial agent is preferably blended in the range of 0.1 to 100 parts by weight with respect to 100 parts by weight of the water-soluble organic compound component (A). If the blending ratio of component (C) is less than 0.1 parts by weight, a sufficient antibacterial effect is not seen, and if it is used in excess of 100 parts by weight, the hydrophilicity of the resulting film may be reduced. It is not preferable. Moreover, the antibacterial agent contained in the component (C) of the treatment agent of the present invention is not limited to one type, and two or more types can be used in combination.

  The pH of the aqueous treatment agent of the present invention is adjusted to 3 to 6 by at least one selected from phosphoric acid, nitric acid and zirconium hydrofluoric acid. When this pH is less than 3 or exceeds 6, the glycidyl group of the water-soluble organic compound in the component (A) is changed to water in the treatment agent or in the component (B) by aging for 5 to 10 days. It may react with the tertiary amino group in the water-soluble polymer compound or the tertiary amino group in the organic compound to be polymerized, so that sufficient performance may not be imparted to the material to be treated.

  The solvent for the water-based treatment agent of the present invention is mainly water, but water-soluble solvents such as alcohols, ketones and cellosolves are used for adjusting the drying rate and improving the coating state and for improving the solubility of the components. It does not prevent the combined use. The total content of components (A), (B) and (C) in the aqueous processing agent of the present invention is preferably 0.5 to 20% by weight, more preferably 1 to 10% by weight.

Further, in order to improve the water resistance and corrosion resistance of the film formed on the metal material, as a component (D) in the aqueous treatment agent, a metal compound such as Cr, Zr, Ti, that is, Cr (NO ₃ ) ₃ , CrF ₃ , Cr (H ₂ PO ₄ ) ₃ , H ₂ ZrF _6, H ₂ TiF _6, etc.), in addition to rust preventives, leveling agents, fillers, colorants, surfactants, An antifoaming agent etc. can be added in the range which does not impair the main point and film | membrane performance of this application.

  About the density | concentration and viscosity of the aqueous processing agent of this invention, it sets suitably according to the coating method to be used, a desired film thickness, etc. The thickness of the film formed after coating and drying is 0.05 to 5 μm, preferably 0.1 to 2 μm. If the film thickness is less than 0.05 μm, it is difficult to impart sufficient hydrophilicity and prevention of off-flavor generation to the formed film, and if it exceeds 5 μm, the thermal conductivity of the resulting film is reduced. Reduce.

Next, the hydrophilic / deodorizing treatment method of the present invention will be described.
The surface of the aluminum-containing metal material is preliminarily degreased, then subjected to a known chemical conversion treatment or an organic polymer primer treatment, and then the aqueous treatment agent of the present invention is applied and dried. Examples of the chemical conversion treatment include chromate chromate treatment, phosphate chromate treatment, and zirconium phosphate treatment.

In the method of the present invention, the method for applying the aqueous treatment agent is not particularly limited, and dipping, spraying, brushing, roll coating, flow coating, and the like are used.
Although there is no particular limitation on the drying method after the application of the aqueous treatment agent, it is usually dried using a hot air drying furnace or the like, and the temperature is 80 to 300 ° C, more preferably 100 to 250 ° C. The temperature at which the efficacy of component (C)) is not impaired.

  The hydrophilic film formed on the surface of the aluminum-containing metal material by the treatment method using the water-based treatment agent of the present invention has excellent hydrophilicity, off-flavor generation suppression and antibacterial properties over a long period of time. It is suitable as a film for a heat exchanger made of a metal material.

  When the water-soluble organic compound-containing component (A) having a glycidyl group used in the present invention is heated and dried, the water-soluble polymer compound or organic compound of the component (B) has a catalytic action of a tertiary amino group. Resin to form a dense three-dimensional structure. The tertiary amino group in component (B) not only promotes the polymerization between glycidyl groups catalytically, but also reacts with the glycidyl group, so that component (B) is immobilized in the film. The water-soluble polymer compound of component (B) has a hydrophilic functional group such as a polyalkylene glycol group and an amide group together with a tertiary amino group, and these hydrophilic groups that are fixed in the film are long-term. It exhibits excellent hydrophilicity throughout. In addition, the film formed of the component (A) and the component (B) as described above has excellent water resistance, so that the film does not deteriorate over a long period of time, so that the underlying aluminum or chemical conversion film is exposed on the surface. There is no. Accordingly, it is possible to prevent the generation of a strange odor by suppressing the scattering of aluminum hydroxide, which is considered to be a cause of dusty odor, or the like, or a deterioration product of the chemical conversion film over a long period of time.

In addition, the component (C) composed of the antibacterial agent contained in the aqueous composition of the present invention is uniformly dispersed in the film formed by the component (A) and the component (B), and is prevented for a long time. It has an excellent effect of sustaining fungi and suppressing rot odor caused by bacterial metabolites and mold.
Moreover, since the aqueous composition of the present invention forms an organic polymer film, it is excellent in forming processability.

  EXAMPLES The present invention will be described below with reference to examples, but these examples illustrate the present invention and do not limit the scope of the present invention.

Reference example 1
An aluminum plate (JIS-A1100, 70 mm × 150 mm, plate thickness: 0.12 mm) was dissolved in an aqueous solution of 30 g / liter of a weak alkaline degreasing agent (trademark: Fine Cleaner 315, manufactured by Nihon Parkerizing Co., Ltd.) kept at 60 ° C. Immerse in seconds to remove contaminants on the surface such as oil, wash with tap water, and then chromate chromate treatment solution (trademark: Alchrome 713, Nihon Parkerizing Co., Ltd.) 72 g / liter kept at 50 ° C. Was immersed in an aqueous solution for 60 seconds and washed with tap water to form a chromate film.

An aluminum plate coated with the chromate film was immersed in an aqueous treatment agent containing the following composition at a nonvolatile content of 2% (by weight) and adjusted to pH 4.5 with phosphoric acid at 25 ° C. for 10 seconds. .
Ingredient Amount (parts by weight)
──────────────────────── ────────
Component (A): Pentaerythritol tetra
Glycidyl ether 100 (solid content)
Component (B): Dimethylaminoethyl methacrylate
(30 mol%) /
Sodium vinyl sulfonate (30 mol%) /
Acrylamide (40 mol%) terpolymer 20 (solid content)
Component (C): 2-bromo-2-nitropropane-1,3-
Diol 0.5 (solid content)
Next, the aluminum plate was pulled up from the treatment agent and dried by heating in a hot air circulation oven adjusted to 180 ° C. for 5 minutes.

Example 1
The same processing as in Reference Example 1 was performed. However, an aqueous treatment agent containing the following composition at a non-volatile content of 2% (weight) and a component (D) adjusted to pH 5.0 with zirconium hydrofluoric acid was used.
Ingredient Weight part ──────────────────────── ────────
Component (A): Water-soluble epoxy-modified polyamide 100 (solid content)
Component (B): Water-soluble nylon (*) ₁ 200 (solid content)
Component (C): zinc-2-pyridinethiol-1-10 (solid content)
Oxide surfactant (*) ₂ 0.5
[註] (*) ₁ ... aminoethylpiperazine, polyethylene glycol diamine and azimuth
Condensation product of pinic acid (*) ₂ ... Trademark: Adecanol B-4009, manufactured by Asahi Denka Kogyo Co., Ltd.

Reference example 2
An Al-Mn alloy (JIS-A3004, 70 mm x 150 mm, plate thickness: 0.12 mm) was degreased in the same manner as in Reference Example 1 and maintained at 50 ° C for a phosphate chromate treatment solution (Alchrome 702, Japan) After dipping in Parkerizing Co., Ltd. (47 g / l, hydrofluoric acid 500 ppm) for 30 seconds, it was washed with tap water to form a phosphate chromate film.

An aluminum alloy plate on which the chromate film was formed was immersed in an aqueous treatment solution containing the following composition at a nonvolatile content of 2% by weight and adjusted to pH 3.5 with nitric acid at 25 ° C. for 10 seconds, It was heated and dried for 5 minutes in a hot air circulating oven adjusted to 140 ° C.
Ingredient Weight part ──────────────────────── ────────
Component (A): Glycerol polyglycidyl ether 100 (solid content)
Component (B): Dimethylaminopropyl acrylate
(40 mol%) and acrylic acid (60 mol%)
100 (solid content)
Component (C): 1,2-benzisothiazolin-3-one 10 (solid content)
Surfactant Adecanol B-4009 0.5

Reference example 3
The same treatment as in Reference Example 2 was performed. However, as the aqueous treatment agent, the following composition containing a non-volatile content of 5% by weight and adjusted to pH 6.0 with phosphoric acid was used.
Ingredient Weight part ──────────────────────── ────────
Component (A): Sorbitol polyglycidyl ether 100 (solid content)
Component (B): Dimethylaminopropyl acrylate
(50 mol%)
2-hydroxyethyl methacrylate
Copolymerized with (50 mol%) 30 (solid content)
Water-soluble nylon (*) ₃ 70 (solid content)
Component (C): 2-n-octyl-4-isothiazoline
-3-one 2 (solid content)
[註] (*) ₃ ... condensation of aminoethylpiperazine, adipic acid and ε-caprolactam
object

Reference example 4
An aluminum plate (JIS-A1100, 70 mm × 150 mm, plate thickness: 0.12 mm) was added to a 20 g / liter aqueous solution of a medium alkaline degreasing agent (trademark: Fine Cleaner 4306, manufactured by Nihon Parkerizing Co., Ltd.) kept at 70 ° C. It was immersed for 2 seconds to remove contaminants on the surface such as oil, washed with tap water, and dried at 80 ° C. for 30 seconds. Next, on this aluminum plate, a mixture of 70 g of an acrylic resin primer (trademark: Paltop 3997-2A, manufactured by Nihon Parkerizing Co., Ltd.) and 30 g of the same primer (trademark: Paltop 3777-2B, manufactured by Nihon Parkerizing Co., Ltd.) The aqueous pretreatment agent consisting of was coated with a bar coater No. 3 at a coating amount of 1.5 g / m ² and heat-dried at 200 ° C. for 10 seconds.

Next, an aqueous treatment liquid containing the following composition at a nonvolatile content of 10% by weight and adjusted to pH 5.0 with phosphoric acid was applied to the pretreated aluminum plate using a bar coater No3. And dried by heating at 200 ° C. for 10 seconds.
Ingredient Weight part ──────────────────────── ────────
Component (A): Sorbitol polyglycidyl ether 100 (solid content)
Component (B): Water-soluble nylon (*) ₁ 100 (solid content)
Water-soluble phenolic resin having tertiary amino group 200 (solid content)
Component (C): 2- (4-thiocyanomethylthio) benzo
Thiazole 4 (solid content)

Reference Example 5
The same treatment as in Reference Example 4 was performed. However, as the aqueous treatment agent, a composition containing the following composition with a nonvolatile content of 7% by weight and adjusted to pH 4.0 with phosphoric acid was used.
Ingredient Weight part ──────────────────────── ────────
Component (A): Water-soluble epoxy-modified polyamide 50 (solid content)
: Glycidyl methacrylate (30 mol%) and
Copolymer of acrylamide (70 mol%) 50 (solid content)
Component (B): Dimethylaminoethyl methacrylate
(40 mol%) and acrylic acid (60 mol%)
Copolymer 20 (solid content)
Component (C): 5-chloro-2-methyl-4-isothiazoline-
3-one 1 (solid content)
: 2-methyl-4-isothiazolin-3-one 1 (solid content)
Surfactant Adecanol B-4009 0.5

Comparative Example 1
The same treatment as in Reference Example 1 was performed. However, pentaerythritol tetraglycidyl ether (component (A)) was not used in the aqueous processing solution.

Comparative Example 2
The same treatment as in Example 1 was performed. However, water-soluble nylon (component (B)) was not used in the aqueous processing solution.

Comparative Example 3
The same treatment as in Example 1 was performed. However, 1,2-benzisothiazolin-3-one (component (C)) was not used in the aqueous processing solution.

Comparative Example 4
The same treatment as in Reference Example 4 was performed. However, as an aqueous treatment agent, colloidal silica (trademark: manufactured by Snowtex C Nissan Chemical Co., Ltd.) 50 parts by weight (solid content), No. 3 sodium silicate 50 parts by weight (solid content), sodium polyacrylate (trademark: Julimer) An aqueous treatment agent containing a non-volatile component consisting of 50 parts by weight (solid content) of AC10N, manufactured by Nippon Pure Chemical Co., Ltd. at a concentration of 5% was used.

The following test and evaluation were performed about the processing board produced in Test Example 1, Reference Examples 1-5, and Comparative Examples 1-4.
(1) Hydrophilicity The test piece was immersed in flowing water at room temperature for 8 hours, and then dried at 80 ° C. for 16 hours. One cycle of the test piece was subjected to 5 cycles, and the water contact angle of the obtained test piece was determined. The measurement was performed using a FACE contact angle meter CA-P type (manufactured by Kyowa Interface Chemical Co., Ltd.).

(2) Suppression of off-flavor generation The test piece is immersed in flowing water for 8 hours at room temperature and then dried at 80 ° C. for 16 hours. The treatment is performed for 5 cycles, and the obtained test piece is deionized water vapor. The odor was quickly evaluated.
Evaluation result display: ○: No odor △: Some odor
×: Obvious odor

(3) Antibacterial property After the test piece was immersed in flowing water at room temperature for 8 hours and then dried at 80 ° C. for 16 hours, one cycle was performed, and after 5 cycles of treatment, the obtained test piece was 3 cm square. In the case of a bacterial test, Nutrient Broth is attached to the surface of the test plate as a nutrient source, and in the case of a mold test, a 1: 1 mixture of peptone and glucose is attached. The suspension was sprayed and this was incubated at 30 ± 2 ° C. for 14 days. Bacteria were extracted from sterilized test pieces into sterilized water, and the number of bacteria was measured using a dilution culture method.
Display of evaluation results: ○: Number of bacteria less than 10 ² / m ²
Δ: Number of bacteria 10 ² or more and less than 10 ⁵ / m ²
×: 10 ⁵ or more bacteria / m ²
Bacteria used:
Bacteria: Escherichia coli, Bacillus subtilis, Pseudomanos aeruginosa
Mold: Aspergillus niger, Penicillium citrinum, Cladosporium cladosporioides

(4) Molding workability Volatile press oil (trademark: AF-2A, manufactured by Idemitsu Petrochemical Co., Ltd.) is applied to the surface of the test piece, and 100,000 punching presses are continuously applied thereto. Surface wear was observed and evaluated with a scanning electron microscope.
Display of evaluation results: ○: almost no wear, △: low wear, ×: high wear

  The production conditions of the samples produced in Example 1 and Reference Examples 1 to 5 are collectively shown in Tables 1 and 2, and the production conditions of the samples produced in Comparative Examples 1 to 4 are collectively shown in Table 3. Table 4 shows the evaluation results of the samples prepared in Example 1, Reference Examples 1 to 3, and Comparative Examples 1 to 3.

  As is apparent from the results in Table 4, the hydrophilic and deodorized samples prepared in Examples 1 to 6 using the aqueous treatment agent and the treatment method of the present invention are excellent in hydrophilicity and odor. It had generation inhibition and antibacterial properties and good moldability. On the other hand, in Comparative Example 1 in which the water-soluble organic compound component (A) having a glycidyl group was not used and in Comparative Example 2 in which the water-soluble polymer compound component (B) was not used, the obtained film The durability was low, and the hydrophilicity, the off-flavor generation prevention property and the antibacterial property were inferior. Further, in Comparative Example 3 in which the antibacterial component (C) was not used, the antibacterial properties of the obtained film were poor. Moreover, in the comparative example 4 containing a silica, a silicate, etc., the moldability of the obtained product was inferior.

  The hydrophilic / deodorant / corrosion-resistant water-based treatment agent and the hydrophilic / deodorant / corrosion-resistant treatment method of the present invention are applied to the surface of an aluminum-containing metal material, and have excellent hydrophilicity, off-flavor generation suppression, and antibacterial properties over a long period of time. And a film having molding processability can be formed, which is extremely useful industrially.

Claims (4)

The following components (A), (B), (C) and (D):
(A) a water-soluble organic compound having a glycidyl group,
(B) a water-soluble polymer compound having a tertiary amino group and at least one hydrophilic functional group selected from a polyalkylene glycol group and an amide group, and the tertiary amino group and the at least one hydrophilic group. At least one selected from water-soluble organic compounds having a functional functional group and capable of being polymerized by heat drying,
(C) an antibacterial agent having no decomposition point at temperatures up to 100 ° C., and (D) Cr (NO ₃ ) ₃ , CrF ₃ , Cr (H ₂ PO ₄ ) ₃ , H ₂ ZrF ₆ and H ₂ TiF ₆ An aqueous treatment agent for improving hydrophilicity, deodorization, and corrosion resistance of an aluminum-containing metal material, comprising a water / corrosion resistance improver containing at least one selected from the group consisting of:   The component (A) is contained in 10 to 500 parts by weight of the component (B) and 0.1 to 100 parts by weight of the component (C) with respect to 100 parts by weight of the component (A). Water-based treatment agent.   The aqueous treatment agent according to claim 1 or 2, wherein a pH value of the aqueous treatment agent is adjusted to 3 to 6.   The water-based treatment agent according to any one of claims 1 to 3 is applied to the surface of an aluminum-containing metal material and dried by heating to form a hydrophilic, deodorant, and corrosion-resistant film having a thickness of 0.05 to 5 µm. A method for imparting hydrophilicity, deodorization, and corrosion resistance to an aluminum-containing metal material, comprising: