JPH08232078A - Hydrophilic aqueous processing agent of aluminum-containing metallic material and hydrophilic treatment - Google Patents

Abstract

PURPOSE: To obtain an aq. processing agent excellent in formability and maintaining hydrophilicity, capability of suppressing the development of a nasty smell and antibacterial effect for a long period by incorporating a compd. including a glycidyl group and a hydrophilic functional group and an antibacterial agent which is not decomposed at high temp. CONSTITUTION: A water-soluble org. compd. A having a glycidyl group, a water- soluble high molecular compd. B having a hydrophilic functional group such as tertiary amino, sulfonic, phosphonic, polyalkylene glycol, hydroxyl and amido groups, etc., and 1 kind of water-soluble org. compd. capable of being polymerized by heating and drying and an antibacterial agent C not having a decomposition point below 100 deg.C are incorporated to obtain an aq. hydrophilic processing agent. The agent consists preferably of 100 pts.wt. of the compd. A, 10-500 pts.wt. of the compd. B and 0.1-100 pts.wt. of the agent C. The agent is applied on the surface of an Al-contg. metallic material, heated and dried to form a high-performance hydrophilic film rich in durability.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an aqueous treatment agent for rendering the surface of an aluminum-containing metal material hydrophilic, and a hydrophilic treatment method using the same. More specifically, the present invention relates to a heat exchanger assembled using an aluminum-containing metal material, and a water-based treatment agent that makes the aluminum-containing metal material used in the aluminum-containing metal material heat exchanger hydrophilic. And a hydrophilic treatment method using the same.

[0002]

2. Description of the Related Art Many heat exchangers made of aluminum-containing metal materials are designed to maximize the surface area of the heat radiating portion and the cooling portion (fin) in order to improve the heat radiation or cooling effect. In addition, the space between the fins is extremely narrow for downsizing.
Therefore, when operating this heat exchanger (evaporator),
Water 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 fin gap, so that ventilation resistance increases and heat exchange efficiency decreases. Further, there is also a problem that water droplets formed in the fin gap are scattered to the air downstream side.

Conventionally, many heat exchangers have been subjected to chemical conversion treatment such as chromate treatment for the purpose of improving corrosion resistance.
Since these chemical conversion coatings have low hydrophilicity, the above problems could not be solved. Further, such a chemical conversion film has a problem that it emits an unpleasant odor. Further, 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 metabolites of the microorganisms generate a rotten odor.

As a method of making the fin surface hydrophilic,
Japanese Patent Publication No. 53-48177 discloses "a chemical conversion treatment method for aluminum or the like characterized by treating with an aqueous alkali silicate solution having a specific composition and then heating and drying at a temperature of 150 ° C. or higher". Japanese Unexamined Patent Publication No. 57-46000 discloses "a surface treatment method for an aluminum heat exchanger characterized by treating with an organic polymer resin solution containing porous fine particles", and JP-A-Sho 60 -10
Japanese Patent No. 1156 discloses "a film forming agent of aluminum characterized by containing a low-molecular organic compound having an alkali silicate and a carbonyl group and a water-soluble organic polymer compound". , A method of applying an inorganic hydrophilic compound such as an alkali silicate compound has been proposed.

However, in the pre-coating method in which various coating treatments are performed and then molding is performed, the aluminum material treated with the treatment agent containing the inorganic compound having a high hardness as described above is ironed or punched. However, there is a problem in that the jig and the die are greatly worn. Further, these hard coatings have a problem that they not only have the effect of suppressing the generation of offensive odors, but also promote the generation of offensive odors.

In order to solve these problems, there have been proposed some methods of applying an organic compound treatment containing no inorganic compound such as alkali silicate. That is, as means for preventing water droplets from scattering due to condensed water, there is disclosed in Japanese Patent Laid-Open No. 60-21.
No. 9285 discloses "Anti-fog and drip-proofing agent mainly containing a polyamide having a tertiary amine and / or a polyamide having a polyalkylene glycol group". However, the material obtained by using this treatment agent has insufficient hydrophilicity after long-term use, and the problem of generation of offensive odor such as putrid odor after long-term use has not been solved.

Further, as means for preventing the scattering of water droplets due to condensed water and the generation of offensive odor, JP-A-61-250495 has been proposed.
Japanese Unexamined Patent Publication No. 3-72562 discloses a method of forming a hydrophilic film containing a water-soluble polyamide resin that is cationic in an aqueous solution as a main component on a chemical conversion film such as chromate. Discloses "hydrophilic surface treatment agent containing partially saponified polyvinyl acetate, water-soluble nylon and water-soluble amino resin". However, these methods and treatment agents were not always satisfactory in terms of hydrophilicity and sustaining of an offensive odor-preventing effect after long-term use.

Japanese Unexamined Patent Publication (Kokai) No. 2-219875 relates to "a hydrophilic coating agent characterized by being obtained by copolymerizing four kinds of α, β unsaturated monomers having a specific functional group". It discloses a hydrophilic coating agent that can reduce wear of a mold or the like during molding. Among them, it is specified to use polyepoxide, which is a glycidyl compound, as one of the crosslinking agents for copolymers. However, it is difficult to obtain a target polymer from monomers having four types of functional groups having different ionicities, and the obtained polymer is unstable, so that the pot of the hydrophilic coating agent is I had a problem with my life. Further, there is a problem that the effect of suppressing the generation of offensive odor is hardly recognized in the film obtained by this treatment.

[0009]

DISCLOSURE OF THE INVENTION The present invention has a problem in that the heat exchange efficiency due to condensed water, the problem of water droplets scattering, the problem of offensive odor, and the problem of die wear during molding process, which the prior art has. A hydrophilic water-based treatment agent for an aluminum-containing metal material, which can solve the above-mentioned problems, and can retain the hydrophilicity, the generation of offensive odor, and the antibacterial property, which are superior to those of the prior art, and a hydrophilic treatment method. The purpose is to do.

[0010]

Means for Solving the Problems As a result of extensive studies on means for solving the above problems, the present inventors have identified a water-soluble organic compound having a specific structure, a water-soluble organic compound having a specific functional group, and a specific functional group. It was found that a water-soluble treatment agent containing the antibacterial agent described above has a remarkable effect in solving the above problems, and has completed the present invention.

That is, the hydrophilic aqueous treatment agent for an aluminum-containing metal material of the present invention comprises 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 sulfonic acid group, a phosphonic acid group, a carboxyl group, a polyalkylene glycol group, a hydroxyl group and an amide group, and the above. At least one selected from water-soluble organic compounds having a tertiary amino group and the above-mentioned at least one hydrophilic functional group and capable of being polymerized by heating and drying, and (C) 1
It is characterized by containing an antibacterial agent having no decomposition point at temperatures up to 00 ° C.

In the aqueous treatment agent of the present invention, with respect to 100 parts by weight of the component (A), 10 to 500 parts by weight of the component (B) and 0.1 to 100 parts by weight of the component (C) are used. Is preferably contained.

Further, the hydrophilic treatment method for an aluminum-containing metal material of the present invention is characterized in that the surface of the aluminum-containing metal material is coated with the aqueous treatment agent of the present invention and dried.

[0014]

The aqueous treatment agent and treatment method of the present invention will be described in detail below. The component (A) in the hydrophilic aqueous treatment agent of the present invention is
A water-soluble organic compound having a glycidyl group, which is an organic compound having a glycidyl group such as sorbitol polyglycidyl ether, polyglycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, glycerol polyglycidyl ether,
Alternatively, it may be selected from homopolymers of addition-polymerizable monomers such as glycidyl acrylate and glycidyl methacrylate, or copolymers with other monomers, water-soluble polymer compounds having a glycidyl group such as epoxy resins and epoxy-modified resins. it can.

Component (B) of the aqueous treatment agent of the present invention has a tertiary amino group and is at least one selected from a sulfonic acid group, a carboxyl group, a polyalkylene glycol group, a hydroxyl group and an amide group. A water-soluble polymer compound having a hydrophilic functional group, and at least a water-soluble organic compound having the tertiary amino group and the at least one hydrophilic functional group and capable of being polymerized by heating and drying. A polymer compound having a tertiary amino group and at least one kind of the hydrophilic functional group in one molecule, or having a tertiary amino group and at least one kind of the hydrophilic functional group. And also includes oligomers and monomers that are polymerized by heating. Examples of the water-soluble polymer compound and the water-soluble organic compound to be polymerized include addition-polymerizable monomers having a tertiary amino group such as dimethylaminoethyl acrylate, dimethylaminopropyl methacrylate, and alkyldiallylamine, vinyl sulfonic acid, and sulfo. Ethyl methacrylate, 2-acrylamido-2-methylpropanesulfonic acid, vinylphosphonic acid, acid phosphooxyethyl methacrylate, acrylic acid, methacrylic acid, itaconic acid, polyethylene glycol acrylate, polyethylene glycol acrylate alkylphenyl ether, hydroxyethyl methacrylate, allyl alcohol And acrylamide, etc., such as sulfonic acid group, phosphonic acid group, carboxyl group, polyalkylene glycol group, hydroxyl group in the molecule. Copolymer with an addition polymerizable monomer having a hydrophilic functional group selected from a group and an amide group, the tertiary amino group-containing addition polymerizable monomer, and the addition functional monomer having a hydrophilic functional group, Polymer of ternary structure consisting of at least three kinds of other addition polymerizable monomers selected from alkyl acrylate, alkyl methacrylate, styrene, vinyltoluene, acrylonitrile, vinyl acetate, etc., aminoethylpiperazine, polyethylene Glycol diamine and water-soluble polyamide obtained by ternary condensation polymerization of adipic acid, polyvinylamine tertiary aminated by Mannich reaction or Hoffmann reaction, tertiary aminated phenol resin oligomer similar to the above, and As well as tertiary aminated It can be selected from the scan phenolic resin oligomer. Further, the water-soluble polymer compound and the organic compound to be polymerized,
In the structure, the functional group introduced in addition to the tertiary amino group is preferably one or two selected from a sulfonic acid group, a phosphonic acid group, a carboxyl group, a polyalkylene glycol group, a hydroxyl group and an amide group. However, when the number of the functional groups is 3 or more, the stability of the resulting water-based treatment agent 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 capable of polymerizing, and The blending ratio of (B) is preferably in the range of 10 to 500 parts by weight, and more preferably 50 to 30 parts by weight, relative to 100 parts by weight of the component (A). When the compounding ratio of the component (B) is less than 10 parts by weight, the hydrophilicity of the obtained film is not sufficient, and the hydrophilicity is 500.
When it exceeds the amount by weight, the water resistance of the resulting coating becomes insufficient.

Next, the component (C) consisting of the antibacterial agent having no decomposition point at a temperature of up to 100 ° C. is added to the aqueous treatment agent in the drying step after the aqueous treatment agent is applied to the surface of the aluminum-based metal material. It is necessary to withstand heating when removing water as a solvent, and examples of such an antibacterial agent include 5-chloro-2-methyl-4-isothiazolin-3-one and 2-methyl. -4-isothiazoline-3
On, 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-tetrachloroisophthalonitrile, 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.

The component (C) consisting of the antibacterial agent is 0.1 to 10 parts by weight based on 100 parts by weight of the water-soluble organic compound component (A).
It is preferably blended in the range of 0 parts by weight. When the compounding ratio of the component (C) is less than 0.1 part by weight, sufficient antibacterial effect is not observed, and when it is used in excess of 100 parts by weight, the hydrophilicity of the obtained film may be deteriorated. Not preferable. Further, 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.

It should be noted that before using the water-based treating agent of the present invention,
When storing for 10 days or more, it is preferable to adjust the pH of the treating agent to 3 to 7, and when the pH is lower than 3 or higher than 7, the component (A ), The glycidyl group of the water-soluble organic compound is water in the treating agent, or the tertiary amino group in the water-soluble polymer compound in component (B), or the tertiary amino group in the organic compound to be polymerized. In some cases, it may not be possible to impart sufficient performance to the material to be treated. The pH of the treatment liquid is adjusted by inorganic acids such as phosphoric acid, nitric acid, sulfuric acid, and zirconium hydrofluoric acid, organic acids having a carboxyl group, alkali metals such as sodium hydroxide, and hydroxides of alkaline earth metals, Alternatively, it is performed using an oxide, ammonia, an amine compound, or the like.

The solvent of the water-based treating agent of the present invention is mainly composed of water, but for the purpose of adjusting the drying rate, improving the state of the coating film, and improving the solubility of the components, alcohols, ketones,
It does not prevent the combined use of water-soluble solvents such as cellosolve. The total content of components (A), (B) and (C) in the water-based treatment 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, Cr is contained in the hydrotreating agent.
Metal compounds such as Zr and Ti (for example, Cr (NO ₃ ) ₃ ,
_{CrF 3, Cr (H 2 PO} 4) 3, H 2 ZrF like ₆ and H ₂ TiF ₆₎ can be contained, in addition, rust inhibitors, leveling agents, fillers, colorants, surfactants A defoaming agent or the like may be added within a range not impairing the gist of the present application or the film performance.

The concentration and viscosity of the water-based treating agent of the present invention are appropriately set according to the coating method used, the desired film thickness and the like. The thickness of the film formed after coating and drying is 0.0
It is preferably 5 to 5 μm, more preferably 0.
It is 1 to 2 μm. When the film thickness is less than 0.05 μm,
It is difficult to impart sufficient hydrophilicity and prevention of offensive odor to the formed film, and if it exceeds 5 μm, the thermal conductivity of the obtained film may be lowered, which is not suitable.

Next, the hydrophilic treatment method of the present invention will be described. After degreasing the surface of the aluminum-containing metal material in advance, a known chemical conversion treatment or an organic polymer-based primer treatment is performed, and then the aqueous treatment agent of the present invention is applied and dried. Examples of the chemical conversion treatment include chromate chromate treatment, chromate phosphate treatment, and zirconium phosphate treatment.

In the method of the present invention, the method of applying the aqueous treatment agent is not particularly limited, and dipping, spraying, brushing, roll coating, flow coating and the like are used. The method of drying after applying the aqueous treatment agent is not particularly limited, but it is usually dried using a hot air drying oven or the like, and the temperature thereof is 80 to 300 ° C, more preferably 100 to 250 ° C, and the antibacterial agent ( This is the temperature at which the potency of component (C) is not compromised.

The hydrophilic film formed on the surface of the aluminum-containing metal material by the treatment method using the aqueous treatment agent of the present invention has excellent hydrophilicity, offensive odor generation inhibiting property and antibacterial property for a long period of time. It is suitable as a film for a heat exchanger made of an aluminum-based metal material.

The component (A) containing a water-soluble organic compound having a glycidyl group used in the present invention is a catalyst for the tertiary amino group contained in the water-soluble polymer compound or organic compound of the component (B) when heated and dried. It is resinified by a mechanical action to form a dense three-dimensional structure. The tertiary amino group in the component (B) not only catalytically promotes the polymerization between the glycidyl groups, but also reacts with the glycidyl group to immobilize the component (B) in the film. The water-soluble polymer compound as the component (B) has a hydrophilic functional group such as a sulfonic acid group, a phosphonic acid group, a carboxyl group, a polyalkylene glycol group, and / or a hydroxyl group together with the tertiary amino group. The hydrophilic groups fixed in the film exhibit excellent hydrophilicity for a long period of time. In addition, since the film formed by the components (A) and (B) as described above has excellent water resistance, the film does not deteriorate over a long period of time, and therefore the underlying aluminum or chemical conversion film is exposed on the surface. There is no. Therefore, it is possible to suppress the scattering of aluminum hydroxide, which is considered to be the cause of dusty odor, or the like, oxides, deterioration products of the chemical conversion film, and the like, for a long period of time, and prevent the generation of offensive odors.

The component (C) consisting of the antibacterial agent contained in the aqueous composition of the present invention is the component (A) and the component (B).
It is evenly dispersed in the film formed by, and has an excellent effect of maintaining antibacterial properties for a long period of time and suppressing the odor of spoilage due to bacterial metabolites and mold. Also,
Since the water-based composition of the present invention forms an organic polymer film, it has excellent processability for forming.

[0028]

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

Example 1 Aluminum plate (JIS-A1100, 70 mm × 150)
mm, plate thickness: 0.12 mm) is immersed 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. for 90 seconds, and the surface of oil etc. Of the chromic acid chromate treatment liquid (trademark: Alchrome 713, manufactured by Nihon Parkerizing Co., Ltd.) kept at 50 ° C. for 60 seconds, and then tapped. It was washed with water to form a chromate film.

An aqueous plate containing the following composition at a nonvolatile content of 2% (by weight) and adjusted to pH 4.5 with phosphoric acid was coated with the chromate film on an aluminum plate at 25 ° C. Soaked for a second. Ingredient Amount (parts by weight) ──────────────────────────────── Component (A): Pentaerythritol tetra glycidyl ether 100 ( Solid content) Component (B): dimethylaminoethylmethacrylate (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 treating agent, and the temperature was 180 ° C.
It was heated and dried for 5 minutes in a hot air circulation type oven adjusted to.

Example 2 The same process as in Example 1 was performed. However, the water-based treatment agent used was one containing the following composition at a nonvolatile content of 2% (weight) and adjusted to pH 5.0 with zirconium hydrofluoric acid. Ingredient parts by weight ──────────────────────── ──────── Component (A): Water-soluble epoxy-modified polyamide 100 (solid content) component (B): water-soluble nylon (*) ₁ 200 (solids) component (C): zinc 2-pyridine thiol-1-10 (solids) oxide surfactant (*) ₂ 0.5 [Note] (*) ₁ ... Polycondensation product of aminoethylpiperazine, polyethylene glycol diamine, and adipic acid (*) ₂ ... Trademark: Adecanol B-4009, manufactured by Asahi Denka Kogyo Co., Ltd.

Example 3 Al-Mn alloy (JIS-A3004, 70 mm x 15)
0 mm, plate thickness: 0.12 mm was degreased by the same method as in Example 1, and phosphoric acid chromate treatment liquid (alchrome 702, manufactured by Nippon Parkerizing Co., Ltd., 47 g / l, hydrofluoric acid) kept at 50 ° C. After dipping in 500 ppm) for 30 seconds, it was washed with tap water to form a phosphoric acid chromate film.

An aluminum alloy plate having the chromate film formed thereon was dipped in an aqueous treatment solution containing the following composition at a non-volatile content of 2% by weight and adjusted to pH 3.5 with nitric acid at 25 ° C. for 10 seconds. The resultant was heated and dried in a hot air circulation oven adjusted to 140 ° C. for 5 minutes. Ingredient parts by weight ──────────────────────── ───────── Component (A): Glycerol polyglycidyl ether 100 (solid content) Component (B): Copolymer of 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

Example 4 The same process as in Example 3 was performed. However, as a water treatment agent,
A composition containing the following composition at a non-volatile content of 5% by weight and adjusted to pH 6.0 with phosphoric acid was used. Ingredients By weight ──────────────────────── ──────── Component (A): Sorbitol polyglycidyl ether 100 (solid content) Component (B): a copolymer 30 (solids) water-soluble nylon and dimethylaminopropyl acrylate (50 mole%) and 2-hydroxyethyl methacrylate (50 mole%) (*) ₃ 70 (solids) component (C) : 2-n-octyl-4-isothiazolin-3-one 2 (solid content) [Note] (*) ₃ ... A condensate of aminoethylpiperazine, adipic acid and ε-caprolactam

Example 5 Aluminum plate (JIS-A1100, 70 mm × 150)
mm, plate thickness: 0.12 mm) in an aqueous solution of 20 g / liter of a medium alkaline degreasing agent (trademark: Fine Cleaner 4306, manufactured by Nippon Parkerizing Co., Ltd.) kept at 70 ° C.
It was immersed for 0 seconds to remove surface contaminants such as oil, washed with tap water, and dried at 80 ° C. for 30 seconds. Next, on this aluminum plate, 70 g of an acrylic resin-based primer (trademark: Paltop 3977-2A, manufactured by Nippon Parkerizing Co., Ltd.) and the same primer (trademark: Paltop 397).
7-2B, manufactured by Nihon Parkerizing Co., Ltd.) and a water-based pretreatment agent composed of a mixture of
Bar coating with a coating amount of 1.5 g / m ² using
It was dried by heating at 0 ° C. for 10 seconds.

Next, an aqueous treatment solution containing the following composition at a non-volatile 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. Bar coating, and heat-dried at 200 ° C. for 10 seconds. Ingredients By weight ──────────────────────── ──────── Component (A): Sorbitol polyglycidyl ether 100 (solid content) Component (B): Water-soluble nylon (*) ₁ 100 (solid content) Water-soluble phenolic resin having a tertiary amino group 200 (solid content) Component (C): 2- (4-thiocyanomethylthio) benzothiazole 4 (solid content) Minutes)

Example 6 The same treatment as in Example 5 was carried out. However, as a water treatment agent,
A composition containing the following composition in a nonvolatile content of 7% by weight and adjusted to pH 4.0 with phosphoric acid was used. Ingredient parts by weight ──────────────────────── ──────── Component (A): Water-soluble epoxy-modified polyamide 50 (solid content) : Copolymer of glycidyl methacrylate (30 mol%) and acrylamide (70 mol%) 50 (solid content) Component (B): Copolymer of dimethylaminoethyl methacrylate (40 mol%) and acrylic acid (60 mol%) 20 (solid content) Component (C): 5-chloro-2-methyl-4-isothiazolin-3-one 1 (solid content): 2-methyl-4-isothiazolin-3-one 1 (solid content) Surfactant ADEKA NOL B-4009 0.5

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

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

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

Comparative Example 4 The same treatment as in Example 5 was performed. However, as a water 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 AC10N, Nippon Pure Chemical ( Made) 5
An aqueous treatment agent containing a non-volatile component consisting of 0 parts by weight (solid content) at a concentration of 5% was used.

The following tests and evaluations were performed on the treated plates prepared in Test Examples 1 to 6 and Comparative Examples 1 to 4. (1) Hydrophilicity The test piece was immersed in running water at room temperature for 8 hours and then dried at 80 ° C. for 16 hours, and the cycle was treated for 5 cycles. The measurement was performed using a FACE contact angle meter CA-P type (manufactured by Kyowa Interface Science Co., Ltd.).

(2) Inhibition of offensive odor generation The test piece obtained by subjecting the test piece to immersion in running water at room temperature for 8 hours and then drying at 80 ° C. for 16 hours was treated for 5 cycles, and the resulting test piece was obtained. It was exposed to deionized water vapor for about 1 second and its odor was evaluated quickly. Display of evaluation results:
◯: No odor is felt △: Some odor is felt ×: Obvious odor is felt

(3) Antibacterial property The test piece obtained after being subjected to 5 cycles of treatment was one cycle in which the test piece was immersed in running water at room temperature for 8 hours and then dried at 80 ° C. for 16 hours. Cut into 3 cm squares, and on the surface of the test plate, Nutr
ient Broth, and in the case of mold test, a 1: 1 mixture of peptone and glucose.
Spray a mixed suspension of the bacteria shown below and apply 30 ± 2
Culture was performed at 14 ° C for 14 days. Bacteria were extracted from sterilized water from the test pieces after culturing, and the number of bacteria was measured using the 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 ×: Number of bacteria 10 ⁵ or more / m ² Used bacteria: Bacteria: Escherichia coli, Bacil
lus subtilis, Pseudomanos
aeruginosa fungus: Aspergillus niger, Peni
cillium citrinum, Cladospo
riom cladosporioides

(4) Molding workability A volatile press oil (trademark: AF-2A, manufactured by Idemitsu Petrochemical Co., Ltd.) was applied to the surface of the test piece, and this was subjected to continuous punching press 100,000 times, and thereafter. The wear condition of the piercing punch surface was observed and evaluated with a scanning electron microscope. Display of evaluation results: ○: Almost no wear, △: Little wear,
×: Large wear

The preparation conditions of the samples prepared in Examples 1 to 6 are summarized in Tables 1 and 2, and the preparation conditions of the samples prepared in Comparative Examples 1 to 4 are summarized in Table 3. Further, Examples 1 to
Table 4 shows the evaluation results of the samples prepared in No. 4 and Comparative Examples 1 to 3.

[0047]

[Table 1]

[0048]

[Table 2]

[0049]

[Table 3]

[0050]

[Table 4]

As is clear from the results shown in Table 4, the hydrophilized samples prepared in Examples 1 to 6 using the aqueous treatment agent and treatment method of the present invention have excellent hydrophilicity even under the durability test conditions. It had an offensive odor generation control property, a bacteriostatic property, 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 Comparative Example 2 in which the water-soluble polymer compound component (B) was not used, the films obtained were obtained. The durability was low, and the hydrophilicity, the off-odor prevention property, and the antibacterial property were poor. Further, in Comparative Example 3 in which the antibacterial agent component (C) was not used, the antibacterial property of the obtained film was poor. Further, in Comparative Example 4 containing silica, silicate and the like, the moldability of the obtained product was poor.

[0052]

EFFECT OF THE INVENTION The hydrophilic water-based treatment agent and treatment method of the present invention are applied to the surface of an aluminum-containing metal material, and are excellent in hydrophilicity for a long period of time, suppression of offensive odor, antibacterial property,
And a film having moldability can be formed,
It is extremely useful industrially.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location // C09D 163/00 PKC C09D 163/00 PKC

Claims (3)

[Claims] 1. The following components: (A) a water-soluble organic compound having a glycidyl group, (B) a tertiary amino group, and a sulfonic acid group, a phosphonic acid group, a carboxyl group, a polyalkylene glycol group, a hydroxyl group and an amide group. At least one selected from
At least selected from water-soluble polymer compounds having one kind of hydrophilic functional group and the above-mentioned tertiary amino group and at least one kind of hydrophilic functional group, and water-soluble organic compounds capable of being polymerized by heating and drying. A hydrophilic water-based treatment agent for an aluminum-containing metal material, characterized in that it contains one type and (C) an antibacterial agent having no decomposition point at a temperature of up to 100 ° C. 2. 100 to 100 parts by weight of the component (A), 10 to 500 parts by weight of the component (B), and 0.
The water-based treatment agent according to claim 1, which contains 1 to 100 parts by weight of the component (C). 3. A hydrophilic treatment method for an aluminum-containing metal material, which comprises coating the surface of the aluminum-containing metal material with the water-based treatment agent according to claim 1 and heating and drying.