JPH09316434A - Aqueous treating agent for converting metal material into hydrophilic metal material and treatment therefor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject treating agent containing a specific water-soluble organic compound, a specific hydrophilic polymer and a water-soluble polymer and capable of forming coating films excellent in corrosion resistance, hydrophilicity, foreign smell prevention and moldability for a long period on metal materials such as aluminum-containing metal materials. SOLUTION: This aqueous treating agent contains (A) a water-soluble organic compound having a polyoxyethylene chain, such as polyethylene glycol (ester), (B) a hydrophilic polymer having sulfonic acid (salt) groups, phosphonic acid (salt) groups, primary to tertiary amino groups or quaternary ammonium groups, and (C) a water-soluble polymer comprising a polyvinyl alcohol (water-soluble derivative) or the (co)polymer of a compound of the formula (R<1> is H, methyl; R<2> , R<3> are each H, a 1-4C alkyl, benzyl, a 1-3C hydroxyalkyl).

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a surface treatment agent for metal materials and a surface treatment method. More specifically, the present invention provides an aqueous surface treatment agent that forms a hydrophilic film on the surface of a metal material, for example, an aluminum-containing metal material, and the aqueous surface treatment agent forms a hydrophilic film on a metal material. The present invention relates to a surface treatment method. The aqueous surface treatment agent for metal materials and the surface treatment method according to the present invention form a hydrophilic film on the surface of a fin coil of a heat exchanger formed by using a metal material, for example, an aluminum-containing metal material to form water droplets. It is extremely effective in preventing heat generation and improving its heat exchange efficiency.

[0002]

2. Description of the Related Art In a heat exchanger made of a metal material such as an aluminum-containing metal material, when the moisture in the atmosphere is condensed on the fin surface as a cooling portion during the cooling operation, the fin surface is exposed to high humidity. It When the condensed water stays and dries repeatedly, as a result, the surface of the metal material corrodes, and the corrosion products (white powder) accumulated between the fins are scattered into the room that is being cooled during the operation of the heat exchanger. It causes inconvenience. In order to solve this problem, conventionally, a surface treatment for coating the fin surface with an anticorrosive oxide film, a boehmite film, a chromate film, or a resin film for the purpose of preventing white rust is used.

On the other hand, in many heat exchangers made of aluminum-containing metal materials, the surface areas of the heat radiating portion and the cooling portion are designed to be as large as possible in order to improve the heat radiation or cooling effect. In order to reduce the size, the space between the fins is extremely narrow. Therefore, when the evaporator is operated, water in the atmosphere is condensed in the fin gaps, and the more hydrophobic the fin surfaces are, the more easily the condensed water becomes water droplets, which easily causes clogging in the fin gaps. Therefore, there is a problem that ventilation resistance in the fin gap increases, heat exchange efficiency is reduced, and water droplets are scattered downstream of the air.

In order to solve these problems, it is desired to make the fin surface hydrophilic as a method for promptly draining the condensed water adhering to the fin surface without forming water droplets. However, the conventional coatings for the purpose of imparting the above-mentioned corrosion resistance show hydrophobicity rather than hydrophilicity, or even if they have some hydrophilicity at the initial stage, they are hydrophobic after being left for a short period of time. It will be
The above problems cannot be solved by the conventional corrosion-resistant coating.

Therefore, as a method of making the surface of the fins more hydrophilic, the method disclosed in JP-B-53-48177, "15 after treating with an aqueous solution of alkali silicate having a specific composition,
A method for chemical conversion treatment of aluminum or the like characterized by heating and drying at a temperature of 0 ° C. or higher ”, and treatment with an organic polymer resin solution containing porous fine particles in Japanese Patent Publication No. 57-46000. Surface treatment method for aluminum heat exchanger ", JP-A-60-101156," Alkaline silicate, a low-molecular organic compound having a carbonyl group, and a water-soluble organic polymer compound, characterized in that the film of aluminum. "Forming agent", and "organic-inorganic composite reaction product of" specific vinylic double bond-containing aqueous silica dispersion and polymerizable unsaturated monomer "in JP-A-3-269072.
A curing agent and a hydrophilic treatment composition containing a water-dispersible silica in a specific blending amount, and a treatment method ", and the like, a method of forming a film containing an inorganic hydrophilic compound such as silica sol and an alkali silicate compound. was suggested.

However, in the precoating method in which the above-mentioned surface treatment is followed by molding, the metal material treated with the treatment agent containing these inorganic compounds, particularly the aluminum-containing metal material, is subjected to ironing, perforation and the like. Also, due to the high hardness of the inorganic compound-containing coating, the jigs and dies are largely worn, and the flexibility of the coating or the lubricity of the coating surface is insufficient, which causes problems such as peeling and cracking of the coating. Was occurring. In addition, a heat exchanger treated with these inorganic compound-containing treatment agents is used as a car air conditioner,
Alternatively, when it is applied to a room air conditioner, there is a problem that dust tools (also expressed as inorganic odor, chalk odor, cement odor, etc.) are generated.

In order to solve these problems, many methods have been proposed in which surface treatment is performed with a treatment liquid containing no inorganic compound such as silica or alkali silicate, for example, a treatment liquid containing an organic compound. For example, in JP-A-2-258874, "A hydrophilic surface treating agent having a specific amount of sodium salt and / or potassium salt of carboxymethyl cellulose, ammonium salt of carboxymethyl cellulose and N-methylol acrylamide", JP-A-3-72562. "Hydrophilic surface treatment agent containing partially saponified polyvinyl acetate, water-soluble nylon, and water-soluble amino resin" in JP-A-5-302042, "PVA having a specific degree of saponification and a specific degree of polymerization," Two types of PVP having a specific degree of polymerization, water-soluble nylon, and a treatment agent containing a water-soluble phenol, and a treatment method ", JP-A-7-18206," hydrophilic resin fine particles having a water swelling ratio below a specific level, " Hydrophilic coating consisting of water-soluble or water-dispersible resin and zirconium carbonate alkali metal or ammonium salt "And the like have been disclosed. These are effective in reducing dust odor and tool wear during molding, but the hydrophilicity of the resulting coating is inferior to that using an inorganic hydrophilized material such as alkali silicate, and its action The effect was insufficient.

In the conventional molding process of a pre-coated fin material, a press oil is applied to the surface of the fin material for imparting lubricity before press molding, and after the molding process, it is removed by halogen-based solvent degreasing such as freon. Was common. However, in recent years, as the use of these solvents has been regulated due to environmental problems, a highly volatile press oil is used as a type of press oil that does not require cleaning, and there is a method of volatilizing and removing by heat after molding. Has been adopted. However, this volatile press oil has a drawback that the effect of imparting lubricity is lower than that of conventional press oils, and in order to compensate for this, it is necessary to impart higher lubricity to the lubricating film itself. Is desired.

Regarding the means for imparting lubricity, Japanese Patent Laid-Open No.
No. 322469, "Fin material having a film formed by sequentially laminating an undercoat resin coating layer and a hydrophilic resin coating layer, wherein the undercoat resin coating layer contains a specific amount of wax" No. 4-251193, "Al fin material for self-lubricating heat exchange, characterized in that a hydrophilic coating made of a dispersible silica mixed with microcapsules containing a lubricating oil and a hydrophilic organic resin is formed", Kaihei 5-70711 "Hydrophilic treatment agent containing a siloxane compound having a specific hydrophilic functional group" and JP-A 6-346248 "Inorganic system containing a specific weight of phosphate ester salt" A fin material having a hydrophilic film "and the like are disclosed. Although these techniques have improved lubricity and made it possible to perform good molding processing, the lubricants used for these have poor hydrophilicity, which causes the problem of inhibiting the hydrophilicity of the metal surface. occured.

As a method for applying a lubricant after the surface of a metal material is subjected to a hydrophilic treatment, there is a method disclosed in Japanese Patent Laid-Open No. 2781/1992.
Japanese Unexamined Patent Publication No. Hei 7-43092, which discloses a fin material characterized by providing a hydrophilic polymer layer having a specific film thickness on a silica-based hydrophilic film treated on the surface of aluminum.
Japanese Patent Laid-Open Publication "Aluminum fin material characterized in that a hydrophilic film containing a specific silicon compound is formed on aluminum, and a film of a lubricating resin composition which is easily released by washing with water is coated on the hydrophilic film". Etc. are known. However, these have a large number of processing steps, and therefore have problems such as a decrease in productivity and an increase in costs related to capital investment and energy. Further, the lubricating resin composition disclosed in JP-A-7-43092 contains a polyolefin wax, a fluororesin and the like, and these inhibit the hydrophilicity of a film formed on the surface of a metal material. .

[0011]

DISCLOSURE OF THE INVENTION The present invention is directed to a heat exchanger formed of a metal material, in which heat exchange efficiency is reduced by condensed water, which is a problem of the prior art, a problem of water droplet scattering, a problem of offensive odor, and a molding process. A water-based surface treatment agent that solves problems such as mold wear and film cracking and peeling, and that imparts hydrophilicity, offensive odor generation prevention, and molding processability superior to conventional technologies for metal materials, and surface treatment It is intended to provide a method.

[0012]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that a water-soluble organic compound having a polyethylene oxide chain is added with a hydrophilic polymer and a water-soluble polymer having a specific structure. It has been found that the above problems can be solved by using them in combination.

That is, the aqueous treating agent for hydrophilizing a metal material of the present invention comprises the following components: (A) a component comprising at least one water-soluble organic compound having a polyoxyethylene chain, (B) a sulfonic acid group,
Sulfonate group, phosphonate group, phosphonate group, 1-
A component composed of at least one hydrophilic polymer having at least one member selected from a tertiary amino group and a quaternary ammonium group, and (C) polyvinyl alcohol,
Water-soluble derivatives of polyvinyl alcohol, and the following general formula (I):

Embedded image [Wherein R ¹ represents a hydrogen atom or a —CH ₃ group, and R 1
² and R ³ are each independently a hydrogen atom, C _1-4
Representing an alkyl group, a benzyl group, or a C _1-3 hydroxyalkyl group], the component comprising at least one water-soluble polymer selected from homopolymers and copolymers of acrylamide compound monomers. It is what

In the aqueous treatment agent of the present invention, the polyoxyethylene compound for the component (A) is polyethylene glycol, polyethylene oxide, polyethylene glycol ester, block copolymer of propylene glycol and ethylene glycol, polyethylene glycol diamine, polyethylene glycol. It is preferably selected from diisocyanates, polyethylene glycol diglycidyl ether, water-soluble polyamides of dibasic acids and polyethylene glycol diamines, polyethylene glycol acrylates, and polyethylene glycol acrylate alkylphenyl ethers. In the aqueous treatment agent of the present invention, the polyvinyl alcohol for component (C) and the water-soluble derivative of vinyl alcohol are represented by the following formula (II):

Embedded image [Wherein, in the above formula (II), X represents a copolymerization unit different from vinyl acetate and vinyl alcohol, and l, m, and n are vinyl acetate polymerization unit, vinyl alcohol polymerization unit, and copolymerization unit X, respectively. Copolymerization molar ratio (percent)
And 1 + m + n = 100, and 1 and n may be 0]. Furthermore, in the aqueous treatment agent of the present invention, each of the water-soluble organic compound component (A), the hydrophilic polymer component (B) and the water-soluble polymer component (C) independently of each other, these components (A), The content is preferably 5 to 90% by weight based on the total weight of (B) and (C).

The method for making a metal material hydrophilic according to the present invention comprises:
It is characterized in that an aqueous surface treatment liquid containing an aqueous treatment agent for hydrophilicizing a metal material as described above is adhered to the surface of a metal material and dried to form a hydrophilic film.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION The aqueous treating agent for aqueous solution of a metal material according to the present invention comprises a component (A) comprising at least one water-soluble organic compound having a polyoxyethylene chain, a sulfonic acid group and a sulfone group. Component (B) comprising at least one hydrophilic polymer having at least one member selected from an acid group, a phosphonic acid group, a phosphonic acid group, a primary to tertiary amino group, and a quaternary ammonium group, and polyvinyl alcohol. It contains a water-soluble derivative of polyvinyl alcohol and at least one component (C) selected from homopolymers and copolymers of the acrylamide compound represented by the general formula (I).

The component (A) comprises 1 in the polymer molecular structure.
It is composed of at least one water-soluble organic compound having at least one polyoxyethylene chain structure. Hereinafter, the water-soluble organic compound constituting this component (A) will be referred to as a polyoxyethylene compound. Examples of the polyoxyethylene compound useful as the component (A) of the aqueous treatment agent of the present invention include polyethylene glycol, polyethylene oxide, polyethylene glycol ester, block copolymers of propylene glycol and ethylene glycol, polyethylene glycol diamine, polyethylene glycol. Diisocyanate, polyethylene glycol diglycidyl ether, 2
It can be selected from water-soluble polyamides of basic acid and polyethylene glycol diamine, polyethylene glycol acrylate, polyethylene glycol acrylate alkylphenyl ether and the like. Such a polyoxyethylene compound preferably has a molecular weight of 100 to 4 million, and the polyoxyethylene chain contained therein preferably has a degree of polymerization of 2 to 90,000.

The aqueous polymer (hereinafter referred to as the hydrophilic polymer for the component (B)) constituting the component (B) in which the aqueous treating agent of the present invention is used is a sulfonic acid group, a sulfonate group or a phosphonic acid group. , Phosphonate groups, primary to
It is selected from hydrophilic polymers having a tertiary amino group and a quaternary ammonium group.

The hydrophilic polymer for component (B) is (B-
1) A polymer having at least one member selected from anionic groups consisting of a sulfonate group, a sulfonate group, a phosphonate group, and a phosphonate group, and having no cationic group, and (B- 2) primary to tertiary amino groups and 4
Have at least one member selected from a quaternary ammonium group,
It can be classified as a polymer having no anionic group. In the component (B) used in the present invention, it is preferable that the anionic hydrophilic polymer (B-1) and the cationic hydrophilic polymer (B-2) are not used in combination.

Anionic monomer (b-1) forming the anionic hydrophilic polymer (B-1) for component (B)
Is vinyl sulfonic acid, styrene sulfonic acid, sulfoethyl acrylate, sulfoethyl methacrylate, N-
It can be selected from methylene sulfonic acid acrylamide, 2-acrylamido-2-methylpropane sulfonic acid, vinylphenol sulfonic acid acid phosphooxyethyl methacrylate, and salts thereof. Further, the cationic monomer (b-2) forming the cationic hydrophilic polymer (B-2) for the component (B) is aminoethyl (meth) acrylate, N, N-dimethylaminoethyl acrylate, N-hydroxypropylamino. Ethyl (meth) acrylate, hydroxymethylaminoethyl methacrylate, vinyl imidazole, vinyl pyridine, N, N-diallylamine, N, N-diallyl-N,
It can be selected from N-dimethylammonium chloride and the like. These, the monomer (b-1), and (b-
Each of 2) may form a hydrophilic homopolymer for component (B), or may be copolymerized with a polymerizable comonomer containing no polyoxyethylene chain to form a hydrophilic polymer for component (B). May be formed.

The above comonomer is the monomer (b-
1) and (b-2) and another monomer (b-3),
For example, acrylamide, N-methylol (meth) acrylamide, hydroxyethyl (meth) acrylate,
Vinylpyrrolidone, acroylmorpholine, polyethylene glycol acrylate, polyethylene glycol acrylate alkylphenyl ether, acrylic acid, methacrylic acid, itaconic acid, maleic acid, salts thereof, styrene, acrylonitrile, vinyl ether, acrylic esters (for example, methyl methacrylate), Including vinyl acetate and the like. The comonomer may be a low hydrophilic monomer such as styrene, acrylonitrile, vinyl ether, (meth) acrylic acid ester (for example, methyl acrylate), but when such a low hydrophilic monomer is used, the copolymerization ratio is It is set so as not to impair the desired water solubility of the resulting copolymer.

The water-soluble polymer for component (C) is (C-
1) Polyvinyl alcohol, water-soluble derivatives of polyvinyl alcohol, and (C-2) homopolymers and copolymers of acrylamide compound monomers of general formula (I).

The polyvinyl alcohol for component (C) and its water-soluble derivative (C-1) can be selected from the polyvinyl alcohol compounds of formula (II). That is, the polyvinyl alcohol compound of the formula (II) includes a partially saponified product and a completely saponified product of polyvinyl acetate, and a partially saponified product and a completely saponified product of a copolymer of vinyl acetate and another monomer. The comonomer copolymerized with vinyl acetate is not particularly limited, and examples thereof include acrylic acid, methacrylic acid, itaconic acid, maleic acid or salts thereof as anionic comonomers, and styrene as a nonionic monomonomer. , Acrylonitrile, vinyl ether, (meth) acrylamide, N-methylol (meth) acrylamide, methyl (meth) acrylate, hydroxyethyl (meth) acrylate, vinylpyrrolidone, acroylmorpholine, vinyl acetate and the like, and as a cationic comonomer, amino. Ethyl (meth) acrylate, N-hydroxypropylaminoethyl (meth) acrylate, vinylimidazole, N, N-dimethyldiallylamine and the like can be used.

In the polyvinyl alcohol compound of the general formula (II), the copolymerization molar ratio of the copolymerization units (X) (n /
(L + m + n)) is preferably 0 to 0.4, and more preferably 0 to 0.3. Moreover, in the polyvinyl alcohol compound of the general formula (II), the copolymerization molar ratio of vinyl acetate copolymerization units (l / (l + m +
n)) is preferably 0 to 0.2, and 0 to 0.1
Is more preferable. If the copolymerization ratio of these is too large, the water solubility of the obtained polyvinyl alcohol compound may be lowered and may be insufficient.

The homopolymer and copolymer (C-2) of the acrylamide compound of the general formula (I) used as the component (C) are the same as those of the acrylamide compound of the general formula (I) (monomer (ca)). Polymer (homopolymer), two or more copolymers, and one or more acrylamide monomers (c-a) of the general formula (I) and one or more other comonomers (c-b). And copolymers thereof. Comonomers (c-b) used here
Is selected from an acrylamide monomer (ca) and a polymerizable anionic, nonionic or cationic addition-polymerizable monomer. Such comonomer (bb)
Are, for example, (meth) acrylic acid, itaconic acid, maleic acid, vinyl sulfonic acid, styrene sulfonic acid, sulfoethyl acrylate, sulfoethyl methacrylate, N
-Anionic unsaturated monomers such as methylenesulfonic acid acrylamide, 2-acrylamido-2-methylpropanesulfonic acid, acid phosphooxyethyl methacrylate or salts thereof, (meth) acrylamide, N-
Nonionic unsaturated monomers such as methylol (meth) acrylamide, hydroxyethyl (meth) acrylate, vinylpyrrolidone, acroylmorpholine, polyethylene glycol acrylate, polyethylene glycol acrylate alkylphenyl ether, and aminoethyl (meth) acrylate, N, N -Dimethylaminoethyl acrylate, N-hydroxypropylaminoethyl (meth) acrylate, hydroxymethylaminoethyl methacrylate, vinylimidazole, vinylpyridine, N, N-diallylamine, N, N-diallyl-
It can be selected from cationic unsaturated monomers such as N, N-dimethylammonium chloride. Further, the comonomer (c-b) may be selected from addition-polymerizable monomers having low hydrophilicity such as styrene, acrylonitrile, vinyl ether, acrylic esters (eg methyl methacrylate), vinyl acetate, etc. It is used in a copolymerization ratio such that the water solubility of the resulting copolymer is maintained at a desired level.

One polymer (homopolymer) of the acrylamide monomer (c-a), two or more copolymers thereof, and one or more acrylamide monomer (c-a) and one or more comonomers. A copolymer obtained by subjecting the copolymer of (c-b) to post-treatment or post-reaction to change its structure can also be used as the hydrophilic polymer for the component (B). For example, the amide group converted to a carboxyl group by hydrolysis, the amide group treated with amines and formalin and converted to an aminoalkyl group (Mannich reaction), the amide group treated with alkali and bromine. By decarboxylation (Hoffmann reaction) to convert an amide group to an amino group, or a side chain ester group converted to an amino group by an ester-amide exchange reaction in which an alkyldiamine acts on a side chain ester group, or an amino group A quaternary group or the like can also be used as the component (B).

In the aqueous treating agent of the present invention, the respective contents of the water-soluble organic compound component (A), the hydrophilic polymer component (B) and the water-soluble polymer component (C) are independent of each other. The total weight of (A), (B) and (C) is preferably 5 to 90% by weight, more preferably 10 to 80% by weight, further preferably 15 to 70% by weight. preferable. If the content of the component (A) is less than 5% by weight, the moldability of the resulting film may be insufficient, and the component (B) may be insufficient.
Is less than 5% by weight, the hydrophilicity of the resulting coating may be insufficient, and if the content of component (C) is less than 5% by weight, the water resistance of the resulting coating may be reduced. To
It becomes difficult to adjust to the desired value.

To the aqueous treatment agent of the present invention, a fungicide and / or fungicide is added unless the effect is impaired, to prevent the generation of spoilage odor due to the growth of mold, bacteria and yeast. You can The antibacterial and antifungal agent that can be used in the present invention,
In a drying step after applying the treatment agent of the present invention, one that can withstand heating when removing water which is a solvent of the treatment agent,
That is, it is desirable that the antibacterial and antifungal agent has no decomposition point at temperatures up to 100 ° C. Examples of the antibacterial / antifungal agent contained in the aqueous surface treatment agent of the present invention include 5-chloro-2-methyl-4-isothiazolin-3-one, 2-methyl-4-isothiazolin-3-one and 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-
It can be selected from n-octyl-4-isothiazolin-3-one, 10,10'-oxybisphenoxyarsine and the like. The addition amount of the antibacterial / antifungal agent is 0.1 to 7 with respect to the total amount of the components (A), (B) and (C).
It is preferably 0% by weight, more preferably 0.3
˜50% by weight, more preferably 0.5 to 30% by weight.

In the present invention, a water-soluble crosslinking agent can be used for the purpose of improving the water resistance of the film. The crosslinking agent used in the present invention includes a water-soluble organic crosslinking agent and a water-soluble inorganic crosslinking agent. As the water-soluble organic cross-linking agent,
Water-soluble blocked polyisocyanate, polymethylol, polyglycidyl, polyaziridyl compounds and aldehydes can be used. That is, the organic crosslinking agent is a bisulfite-blocked polyisocyanate, methylolmelamine, methylolurea, methylolated polyacrylamide, polyethylene glycol diglycidyl ether,
It can be selected from diaziridylated polyethylene oxide, glyoxal, furfural and the like. The water-soluble inorganic cross-linking agent is a metal compound capable of forming a complex compound, and is a compound of a metal having four or more coordination numbers, particularly Cr, Zr,
Ti compounds are preferably used. For example, chromic acid compounds such as chromic anhydride and dichromic acid, or salts thereof, or partial reduction products thereof, chromium compounds such as chromium sulfate, chromium nitrate, chromium diphosphate, chromium fluoride, chromium acetate and chromium formate. A zirconium compound such as ammonium zirconium carbonate, zirconyl nitrate, zirconyl sulfate, zirconyl acetate, zircon hydrofluoric acid or a salt thereof, a titanium compound such as diisoproepoxy titanium bisacetylacetone, titanium hydrofluoric acid or a salt thereof can be used as an inorganic crosslinking agent. .

The cross-linking agent used in the aqueous treating agent of the present invention is preferably 5 to 200% by weight, more preferably the organic cross-linking agent, based on the total weight of the components (A), (B) and (C). 10 to 150, particularly preferably 20 to 80% by weight, the inorganic crosslinking agent is preferably 0.1 to 70% by weight,
It is more preferably used in an amount of 0.3 to 50% by weight, particularly preferably 0.5 to 30% by weight. If the amount is less than the above value, the crosslinking effect is poor, and if the amount is more than the above value, the coating becomes too hard and brittle, which is not preferable in terms of workability and adhesion.

Further, in the aqueous treatment agent of the present invention, if necessary, for the purpose of further improving the surface lubricity of the coating film formed, or for the purpose of improving the coating property of the treatment agent, a surface active agent may be added. Agents can be included. The surfactant used for this purpose may be any of anionic, cationic, nonionic and amphoteric surfactants, but the surfactant (A), (B) or (C) used is ionic. It is not preferable to use a paired ionic substance, because it may impair the stability of the treatment liquid. Surfactants that can be used in the present invention include, for example, nonionic ones such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether and other polyoxyethylene alkyl ethers, and polyoxyethylene nonylphenyl ether and other polyoxyethylene alkyl ethers. Phenyl ether, block copolymer of oxyethylene and oxypropylene (Pluronic), sorbitan monolaurate, sorbitan monostearate and other sorbitan fatty acid esters, polyoxyethylene laurate, polyoxyethylene stearate, polyoxyethylene oleate and other poly There are oxyethylene fatty acid ester, glycerin fatty acid ester, polyoxyethylene polypropylene glycol alkylphenol ether, etc., anionic interface Examples of the sexing agent include fatty acid salts such as sodium laurate, sodium stearate, and sodium oleate, alkyl sulfates such as sodium dodecyl sulfate, alkylbenzene sulfonates such as sodium dodecylbenzenesulfonate, alkylsulfosuccinates, and dialkylsulfosuccinic acid. Examples thereof include salts, alkenyl sulfosuccinates, polyoxyethylene alkyl sulfates, and the like. Examples of the cationic surfactant include alkylamine salts such as stearylamine acetate, quaternary ammonium salts such as stearyltrimethylammonium, alkylbetaines such as laurylbetaine, and amine oxides.
Examples thereof include alkylaminopropionate and alkyldimethylbetaine, and fluorine-based surfactants, silicon-based surfactants and the like can also be used. The amount of the surfactant used is preferably 0.1 to 70% by weight, more preferably 0.3 to 50% by weight, particularly preferably 0.3 to 50% by weight, based on the total weight of the components (A), (B) and (C). Preferably 0.5
３０30% by weight.

The solvent used in the aqueous treating agent of the present invention is
Although it is mainly composed of water, it does not prevent the combined use of water-soluble solvents such as alcohols, ketones and cellosolves in order to adjust the drying rate, improve the state of the coating film, and improve the solubility of the components. In addition to the above, a rust preventive agent, a leveling agent, a filler, a coloring agent, an antifoaming agent and the like may be added to the aqueous treatment agent of the present invention within a range that does not impair the performance of the film obtained by the present invention.

The aqueous surface-treating agent of the present invention is used as it is or as a surface-treating solution diluted with water. The concentration and viscosity of this treating solution are appropriately selected depending on the coating method used, the desired film thickness and the like. Adjusted to.

In the method of the present invention, an aqueous treatment liquid containing the above-mentioned aqueous surface treatment agent of the present invention is adhered to the surface of a metal material and dried to form a film. The thickness of this dry film is preferably 0.05 to 5 μm, more preferably 0.1 to 2 μm. The film thickness is 0.0
If it is less than 5 μm, it is difficult to impart sufficient hydrophilicity, lubricity, molding processability, and offensive odor prevention property to the coating, and if it is more than 5 μm, during copper tube welding in the assembly process after precoating. The heating tends to increase the tendency of the film to be colored, which is not preferable.

Next, the surface treatment method of the present invention will be further described. The type of metal material to which the method of the present invention is applied,
Although there is no limitation in size and shape, it is preferably applied to heat exchangers and aluminum-containing metal materials (plates, rods, pipes, etc.), particularly aluminum-containing metal materials. Aluminum-containing metal materials include aluminum materials and aluminum alloys (Al-Mn, Al-Mg, A
materials such as 1-Si alloys).

When the method of the present invention is applied, for the purpose of removing rust-preventing oil, processing oil, dirt and the like adhering to the surface of the metal material, and for removing the oxide film on the surface,
A degreasing treatment is performed, and then an aqueous treatment liquid is applied to the surface of the metal material by coating or dipping, and dried. The degreasing agent used in the pretreatment is phosphoric acid, sulfuric acid, nitric acid,
Inorganic acids such as hydrofluoric acid, acid-based degreasing agents containing these inorganic acids and surfactants, alkali hydroxides or alkali salts such as sodium hydroxide, sodium phosphate, sodium carbonate, sodium silicate, etc., or alkalis thereof. It may be any of an alkali degreasing agent containing a builder and a surfactant, and a solvent degreasing agent such as trichloroethane or trichlorethylene. Further, after degreasing, desmutting by pickling, surface adjustment, etc. may be performed as necessary.

The surface of the metal material to be surface-treated according to the present invention is preferably subjected to pretreatment such as pre-formation chemical treatment for the purpose of improving corrosion resistance and the like. As a pretreatment agent for improving corrosion resistance, chromate chromate, chromate phosphate, zirconium phosphate-based, titanium phosphate-based, organic acid zirconium-based, organic acid titanium-based chemical conversion agents, chromium compounds are applied and baked. Examples thereof include coating type chromating agents, organic coating type chromating agents containing an organic binder, and resin primers.

In the method of the present invention, the aqueous treatment liquid is adhered onto the surface of the metal material after degreasing and washing, or after pretreatment as required, and this is heated and dried to form a film. The method for applying the treatment liquid is not particularly limited, and dipping, spraying, brushing, roll coating, flow coating, spin coating and the like are used. For sheet metal materials such as fin coils, a roll coating method and a flow coating method are more suitable. In addition, the dipping method and the spraying method are suitable for metal materials having a heat exchanger having a complicated shape.To prevent nonuniform treatment such as liquid pool, air blow or centrifugal separation should be performed after the coating operation. Alternatively, it is preferable to sufficiently drain the liquid by physical impact or the like.

In the method of the present invention, the method of drying after applying the treatment liquid is not particularly limited, but it is usually dried using a hot air drying oven or the like, and the temperature is preferably 80 to 350 ° C., more preferably Is 100 to 300 ° C. It does not prevent the combined use of water-soluble solvent such as cellosolve together with water in the preparation of the treatment liquid. In addition to the above, a rust preventive agent, a leveling agent, a filler, a coloring agent, a surfactant, an antifoaming agent and the like may be added to the treatment liquid within a range not impairing the gist of the present application and the film performance.

The film formed on the surface of the metal material by the treatment method using the aqueous treatment agent of the present invention has excellent hydrophilicity,
It has an offensive odor suppressing property, a bacteriostatic property, and a molding processability, and is particularly suitable for forming a surface film of a heat exchanger made of an aluminum-containing metallic material. In the method of the present invention,
When the aqueous treatment liquid layer attached to the surface using the metal agent is heated and dried, the organic compound component (A) having a polyoxyethylene chain reacts with the component (C) (radical hydrogen transfer reaction).
And form a three-dimensional network structure. The film thus formed has excellent hydrophilicity and flexibility, and has excellent water resistance. Further, the combined use of the water-soluble crosslinking agent is effective in improving the water resistance of the film. The hydrophilic polymer component (B) is a polymer having a highly hydrophilic group, the polymer molecule of which is entangled or confined in the three-dimensional network structure formed by the component (A) and the component (C). IPN (Inter
A Penetrating Network) structure is formed. In such a three-dimensional structure, the strongly hydrophilic polymer (B) always migrates to the surface of the film, or a very small part of the polymer dissolves and is flushed away with the foreign substances adhering to the surface of the film, maintaining the hydrophilicity for a long time. It is thought that it contributes to. Further, the antibacterial agent used in the present invention is uniformly dispersed and retained in the film formed by the components (A), (B) and (C), and maintains the antibacterial property for a long period of time. It can also exhibit the effect of suppressing the generation of spoilage odor due to bacterial metabolites and mold.

[0041]

The present invention is further described by the following examples. However, these examples do not limit the scope of the present invention.

[0042] In each of Examples 1-8 and Comparative Examples 1-3 Examples 1-8 and Comparative Examples 1-3, using the following aqueous treating agent, and by the following processing method, surface treated metallic material, For the obtained surface-treated metal material,
The tests described below were performed.

(1)surface treatment For various metal materials, the surface treatment by the following surface treatment method
It was given. The used surface treatment method is shown in Tables 1 and 2.Substrate processing method (A) Aluminum plate (JIS-A1100, 70mm x 150
mm, plate thickness: 0.12 mm), a weak arc kept at 60 ° C.
Degreasing agent, Fine cleaner 315 (Trademark, Nippon Par
30 g / liter aqueous solution of Kalizing Co., Ltd.)
Dip for 90 seconds to remove surface contaminants such as oil,
This was washed with tap water. Surface-cleaned aluminum
Chromate chromate treatment solution (day)
This Parkerizing Co., Ltd., Alchrome 713 (commercial
72 g / liter aqueous solution)) for 30 seconds and then water
Rinse with running water and dry at 60 ° C for 40 seconds.
A chromate film was formed on the surface of the aluminum plate.Substrate processing method (B) Al-Mn alloy plate (JIS-A3004, 70 mm x 1
50mm, plate thickness: 0.12mm)
Potassium degreaser, fine cleaner 4306 (trademark, Japan
20 g / liter water solution of Parkerizing Co., Ltd.)
Immerse in liquid for 10 seconds to remove surface contaminants such as oil
Then, it was washed with tap water and dried at 80 ° C. for 30 seconds. this
Chromate phosphoric acid with surface cleaned alloy plate kept at 50 ℃
Treatment liquid (Alchrome, manufactured by Nihon Parkerizing Co., Ltd.)
702 (trademark), 47 g / liter, hydrofluoric acid 50
0ppm) for 30 seconds, then rinse with tap water at 80 ℃
After drying for 30 seconds, phosphoric acid on the surface of the Al-Mn alloy plate
A chromate film was formed. Base treatment method (C) Aluminum plate (JIS-A1100, 70mm x 150
mm, plate thickness: 0.12 mm)
Degreasing agent, Fine cleaner 4306 (Trademark, Japan
-Kalizing Co., Ltd.) 20 g / liter aqueous solution
Soak for 10 seconds inside to remove surface contaminants such as oil
Then, it was washed with tap water and dried at 80 ° C. for 30 seconds. this
Surface-cleaning Aluminum plate surface coated organic chrome
250g of Paltop 3978A (trademark)
Prepared by mixing with 250 g of Top 3978B ™
The treated aqueous treatment agent was applied to Barco using No. 3 bar coater.
And heat-dry at 220 ° C for 10 seconds and chromate
A film was formed.

(2) Hydrophilic treatment The pretreated metallic material was subjected to a hydrophilic treatment by the following method. The treatment methods used are shown in Tables 1 and 2. Hydrophilic treatment method (A) It was immersed for 5 seconds at room temperature in an aqueous treatment solution adjusted to a total nonvolatile content of 3%, set for about 20 seconds, and then dried by heating at 180 ° C for 5 minutes. Hydrophilic treatment method (B) Aqueous treatment liquid adjusted to have a total nonvolatile content of 7% was bar-coated using a bar coater No.
Heat dried for 0 seconds.

(3) Components of Aqueous Surface Treatment Agent A treatment liquid was prepared using the following ingredients and additives. The composition of the treatment liquid is shown in Tables 1 and 2. Water-soluble polyoxyethylene organic compound component (A) polyethylene oxide (molecular weight: 200,000) adipic acid, polyethylene glycol diamine, and ε-
Block polymer of caprolactam (molecular weight: 10,000) Hydrophilic polymer component (B) acrylic acid / sulfoethyl methacrylate (80/2
0) Copolymer (molecular weight: 70,000) Acrylic acid / sodium vinyl sulfonate (60/4
0) Copolymer (molecular weight: 30,000) Sodium polystyrene sulfonate (molecular weight: 50,000) Water-soluble polymer component (C-1) PVA (Saponification degree: 90 mol%, molecular weight: 100,000) 5 mol% -diketene-treated PVA (Saponification degree: 90 mol
%, Molecular weight 50,000) Additive (D) (antibacterial agent) Zinc-2-pyridinethiol-1-oxide 2-n-octyl-4-isothiazolin-3-one 2,2-dibromo-3-nitrilopropionamide (Crosslinking agent) Glyoxal Sodium sulfite blocked polyethylene glycol-based polyisocyanate prepolymer (isocyanate content: 5.0 to 5.5) (Surfactant) Discol R-612 (trademark), Dai-ichi Kogyo Seiyaku Co., Ltd. Made

(4) Test The following tests and evaluations were performed on the treated plates produced in each of Examples 1 to 8 and Comparative Examples 1 to 3. The test results are shown in Tables 1 and 2. (Hydrophilicity) After the test treated material was immersed in running water at room temperature for 8 hours,
One cycle consists of 5 hours of drying at 0 ° C for 5 hours
The cycle treatment was performed, and the contact angle of water on the surface of the obtained sample was measured using a FACE contact angle meter CA-P type (manufactured by Kyowa Interface Science Co., Ltd.). (Prevention of generation of offensive odor) The treated material under test was immersed in running water for 8 hours at room temperature and then dried at 80 ° C for 16 hours. This treatment was defined as one cycle, and the treatment material was subjected to 5 cycles of deionization. It was exposed to water vapor for about 1 second, and its odor was quickly sniffed and evaluated. Evaluation criteria: ◎: No odor was felt, ○: Almost no odor was felt, △: Some odor was felt, x: Clear odor was felt (antibacterial property), after the test treated material was immersed in running water for 8 hours at room temperature, 8
After drying at 0 ° C for 16 hours, this treatment is treated as 1 cycle, 5 cycles of treatment are performed, the obtained treated plate is cut into 3 cm squares, and Nutrient Broth as a nutrient source on the surface of the sample plate is used as a nutrient source. , For mold, attach a 1: 1 mixture of peptone and glucose,
A mixed suspension of the following bacteria was sprayed thereon and cultured at 30 ± 2 ° C. for 14 days. The bacteria were extracted from the treated plate after culturing into sterilized water, and the number of the bacteria was measured using the dilution culture method. Bacteria used: Bacteria Escherishia coli, Bacillus subtilis, Pseudoma
nos aeruginosa mold Aspergillus niger, Penicillium citrinum, Clad
osporium cladosporioides (molding processability) A volatile press oil (AF-2A manufactured by Idemitsu Petrochemical Co., Ltd.) was applied to the surface of the test treated material, and punching press was applied to this to examine the damage state of the coating with a scanning electron microscope. Observed at. Evaluation criteria: ◯: Almost no change, Δ: Film peeling, small crack, ×: Film peeling, large crack

[0047]

[Table 1]

[0048]

[Table 2]

As is clear from the results of Tables 1 and 2, the aqueous treatment agents of the present invention and the treatment materials obtained in Examples 1 to 8 using the treatment method exhibited excellent parent transition even under the durability test conditions. It had an offensive odor-preventing property and a bacteriostatic property, and had good moldability. On the other hand, in Comparative Example 1 in which the hydrophilic polymer component (B) was not used, the hydrophilicity of the obtained film was insufficient and the comparative example in which the polyvinyl alcohol-based polymer component (C-1) was not used In No. 2, the durability of the film was poor and the hydrophilicity, the offensive odor preventing property and the antibacterial property were poor. Further, in Comparative Example 3 in which the water-soluble compound component (A) having a polyoxyethylene chain was not used, the moldability of the obtained film was inferior.

[0050] Examples 9-16 and Comparative Examples 4-6 Examples 9-16 and in each of Comparative Examples 4 to 6, the same base treatment as in Example 1~8 (A), (B) and (C) , And hydrophilic processing methods (A) and (B) were used. The base treatment method and hydrophilic treatment method used are shown in Tables 3 and 4.

The components of the aqueous treating agent were as follows. Tables 3 and 4 show the compositions of the aqueous surface treatment solutions used in the respective examples and comparative examples. (1) Component of aqueous surface treatment agent Water-soluble polyoxyethylene organic compound component (A) Polyethylene oxide (molecular weight: 200,000) Adipic acid, polyethylene glycol diamine and ε-
Block polymer of caprolactam (molecular weight: 10,000) Hydrophilic polymer component (B) acrylic acid / sulfoethyl methacrylate = 80/2
0 (Molecular weight: 70,000) Sodium polystyrene sulfonate (Molecular weight: 50,000) Polydimethyldiallylammonium chloride (Molecular weight: 20,000) Block polymer of adipic acid, aminoethylpiperazine and ε-caprolactam Water-soluble polymer component (C-2 ) Acrylamide homopolymer (molecular weight: 70,000) Acrylamide / acrylic acid = 50/50 (molecular weight:
50,000) (antibacterial agent) zinc-2-pyridinethiol-1-oxide 2-n-octyl-4-isothiazolin-3-one 2,2-dibromo-3-nitrilopropion acid (crosslinking agent) glyoxal chromium sulfate ( Surfactant) Discol R-612 (trademark), manufactured by Daiichi Kogyo Seiyaku Co., Ltd.

With respect to the obtained surface treatment agent,
The same test as 8 was performed. The test results are shown in Tables 3 and 4.

[0053]

[Table 3]

[0054]

[Table 4]

As is clear from the results shown in Table 3, Examples 9 to 16 using the aqueous surface treatment agent and treatment method of the present invention
The surface-treated product of No. 1 showed excellent hydrophilicity, prevention of offensive odor, and antibacterial property even under each endurance test. Also,
These had excellent moldability. On the other hand, as is clear from Table 4, Comparative Examples 4 to 6 were inadequate in any of hydrophilicity, moldability, and prevention of offensive odor.

[0056]

INDUSTRIAL APPLICABILITY The aqueous surface treatment agent and treatment method of the present invention, when applied to the surface of a metal material, particularly an aluminum-containing metal material, provides excellent corrosion resistance over a long period of time.
A film having hydrophilicity, prevention of offensive odor, and moldability can be formed on the surface of the metal material.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C09D 133/26 PFW C09D 133/26 PFW C23C 22/00 C23C 22/00 Z

Claims (5)

[Claims] 1. The following components: (A) a component comprising at least one water-soluble organic compound having a polyoxyethylene chain, (B) a sulfonate group, a sulfonate group, a phosphonate group,
A component composed of at least one hydrophilic polymer having at least one member selected from a phosphonate group, a primary to tertiary amino group, and a quaternary ammonium group; and (C) polyvinyl alcohol, a water-soluble derivative of polyvinyl alcohol, And the following general formula (I): [Wherein R ¹ represents a hydrogen atom or a —CH ₃ group, and R 1
² and R ³ are each independently a hydrogen atom, C _1-4
An alkyl group, a benzyl group, or a C _1-3 hydroxyalkyl group], which is a component of at least one water-soluble polymer selected from homopolymers and copolymers of acrylamide compound monomers represented by Aqueous treatment agent for hydrophilicity. 2. The polyoxyethylene compound for the component (A) is polyethylene glycol, polyethylene oxide, polyethylene glycol ester, block copolymer of propylene glycol and ethylene glycol, polyethylene glycol diamine, polyethylene glycol diisocyanate, polyethylene glycol diglycidyl. The aqueous treatment agent according to claim 1, which is selected from water-soluble polyamides of ethers, dibasic acids and polyethylene glycol diamines, polyethylene glycol acrylates, and polyethylene glycol acrylate alkylphenyl ethers. 3. The polyvinyl alcohol for component (C) and the water-soluble derivative of vinyl alcohol are represented by the following formula (I
I): [Wherein, in the above formula (II), X represents a copolymerization unit different from vinyl acetate and vinyl alcohol, and l, m, and n are vinyl acetate polymerization unit, vinyl alcohol polymerization unit, and copolymerization unit X, respectively. Copolymerization molar ratio (percent)
And 1 + m + n = 100, and 1 and n may be 0], the aqueous treating agent according to claim 1. 4. The water-soluble organic compound component (A), the hydrophilic polymer component (B) and the water-soluble polymer component (C).
Of each of these components (A) and (B) independently of each other.
The aqueous treatment agent according to claim 1, wherein the content is 5 to 90% by weight based on the total weight of (C). 5. An aqueous surface treatment solution containing the aqueous treatment agent for hydrophilizing a metal material according to claim 1, which is adhered to the surface of the metal material and dried to obtain hydrophilicity. A hydrophilic treatment method for a metal material, which comprises forming a hydrophilic film.