JP2000328038A - Composition and method for improving hydrophilicity - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a hydrophilic coating film excellent in curability, retentivity of hydrophilicity, and anticorrosiveness by mixing a water-soluble or water- dispersible polyamide resin with a water-soluble or water-dispersible resin having a polyoxyalkylene chain in the molecule, a polyacrylamide resin, and hydrophilic crosslinked polymer microparticles made of a copolymer of five monomers. SOLUTION: The hydrophilic crosslinked polymer microparticles are made from a copolymer comprising 2-50 wt.% hydrophilic monomer, particularly, one represented by formula II or III, 20-97 wt.% (meth)acrylamide monomer represented by formula I, 1-30 wt.% crosslinking unsaturated monomer, 2-50 wt.% carboxy-containing polymerizable unsaturated monomer, and 0-50 wt.% other monomers. In the formulae, R1 is H or methyl; R2 and R3 are each H or a 1-5C alkyl; R5, R6, and R7 are each H or methyl; R8 is -OH, -OCH3, -SO3-M+, or the like; M+ is Na+, K+, Li+, NH4+, or an organic ammonium ion; and n is 10-200.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composition for hydrophilizing treatment capable of forming a film having excellent hydrophilicity persistence, a method for hydrophilizing a fin material of a heat exchanger using the same, and a method for applying a hydrophilizing composition. It relates to an exchanger fin material.

[0002]

2. Description of the Related Art In a heat exchanger of an air conditioner, condensed water generated during cooling becomes water droplets to form a water bridge between the fins, and the ventilation resistance increases because the ventilation passage of air is narrowed. Troubles such as loss of noise, generation of noise, and scattering of water droplets occur. As a measure to prevent such a phenomenon, for example, the surface of an aluminum fin material (hereinafter, referred to as a “fin material”) is subjected to a hydrophilic treatment to prevent water droplets and the formation of bridges due to the water droplets.

[0003] As the hydrophilic treatment method, for example, (1)
A boehmite treatment method known as a surface treatment method for aluminum; (2) a method of applying a water glass represented by the general formula mSiO ₂ / nNa ₂ O (for example, Japanese Patent Publication No.
(1) JP-A No. 1347, JP-A-58-126989, etc.); (3) Paints in which silica, water glass, aluminum hydroxide, calcium carbonate, titania, etc. are mixed with an organic resin, or a surfactant is used in combination with these paints (For example, Japanese Patent Publication No. 57-46000,
JP-B-59-8372, JP-B-62-61078
JP, JP-A-59-229197, JP-A-61-229197
(4) a method of applying a paint comprising an organic-inorganic (silica) composite resin and a surfactant (see JP-A-59-170170), and the like. Some of them are already in practical use.

As exemplified above, although the hydrophilization treatment technology of the heat exchanger has been put to practical use, the treatment plate has problems in terms of the continuity of hydrophilicity (water contact angle, overall wettability), corrosion resistance, odor and the like. There are still issues to be improved.

In particular, in recent years, the spacing between the fin materials has been narrowed in order to further reduce the size and weight of the heat exchanger, and thus a higher degree of hydrophilicity has been required. ) And (4) cannot exert sufficient hydrophilic durability.

Further, the boehmite treatment method (1) has a problem in corrosion resistance, and has a problem in press workability because the obtained film is hard. Further, the method of applying water glass of the above (2) shows a good hydrophilic persistence in which the treated fin material has a water droplet contact angle of 20 degrees or less,
The fin material treated with water glass becomes powdery over time with a treated film surface, and is scattered during ventilation to generate a cement odor or a chemical odor. In addition, water glass is hydrolyzed by condensed water generated during operation of the heat exchanger, and the fin material surface becomes alkaline, so that pitting is likely to occur, and aluminum hydroxide powder (white powder), which is a corrosion product, is scattered. It is known that there are also environmental conservation problems.

[0007] As a surface treatment method for a heat exchanger,
A fin is formed by molding an aluminum plate, and after assembling the fin, the surface treatment agent is applied by means of dipping, spraying, showering, etc. There is a so-called pre-coating method in which a fin material is formed by subjecting the plate to press molding after forming a surface treatment film on the substrate. In the latter method, the inorganic component, for example, silica, water glass, alumina, aluminum hydroxide, calcium carbonate, titania, etc. are mixed in the hydrophilized coating layer, and the mold used for press molding is significantly worn, Problems such as poor molding of the fin material, deterioration of corrosion resistance due to destruction of the hydrophilic film, and economic loss due to shortening of the mold life occur.

[0008] The press forming method has also been changed from the conventional draw processing method (extension and drawing) to a more severe drawless processing method (ironing processing), and such a stricter processing method has been adopted. In this case, the conventional one cannot cope.

As the corresponding hydrophilic treatment method, for example, the following method has been proposed.

(1) A method of using a combination of polyvinyl alcohol, a specific water-soluble polymer and a water-soluble crosslinking agent (JP-A-3-26381, JP-A-1-29987)
No. 7), (2) a method of using a combination of a block copolymer composed of a hydrophilic polymer part composed of a specific hydrophilic monomer and a hydrophobic polymer part, and a metal chelate type crosslinking agent (Japanese Patent Laid-Open No. JP-A-2-107678, JP-A-2-107678
No. 202967), (3) a method using a polyacrylamide-based resin (see JP-A-1-104667 and JP-A-1-270977), and (4) a polymer such as a polyacrylic acid polymer, A method in which a molecule is used in combination with a polymer such as polyethylene oxide or polyvinylpyrrolidone which can form a polymer complex by hydrogen bonding (see JP-A-6-322292).

However, the hydrophilized coating film obtained by these methods has a problem in that the problem of poor molding at the time of press molding is considerably improved, but there is a problem in the persistence of hydrophilicity and the water solubility of the processed film.

As described above, many techniques for hydrophilizing fin materials of heat exchangers have been proposed. However, a hydrophilizing method which satisfies all of the continuity of hydrophilicity, stability of a treated film, and press moldability is disclosed. Not yet found.

The present inventors have previously proposed a composition for hydrophilization treatment in which a compound having a polyoxyalkylene chain and specific hydrophilic polymer fine particles are combined as a solution to the above-mentioned problems (see, for example, Japanese Patent Application Laid-Open Publication No. H11-157556). See JP-A-9-87576).

[0014] The composition proposed above can form a treated film having excellent hydrophilicity persistence, treated film stability and press moldability. However, from the viewpoints of energy saving and improvement of productivity, high-speed coating lines are required. Shortening the baking time by the baking has been demanded, and in the above-mentioned proposed composition, in short-time baking, the curability becomes insufficient and the adhesion to the substrate is inferior, such that sufficient coating film performance cannot be obtained. There was a problem.

The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems and to obtain a composition for hydrophilization treatment capable of coping with short-time baking by increasing the speed of a coating line. It has been found that the above problem can be solved by a composition for hydrophilization treatment in which a water-dispersible polyamide resin, a resin containing a polyoxyalkylene chain, a polyacrylamide resin and a specific hydrophilic polymer fine particle are combined, and the present invention is completed. Reached.

[0016]

SUMMARY OF THE INVENTION Accordingly, the present invention provides
(A) water-soluble or water-dispersible polyamide resin, (B)
A water-soluble or water-dispersible resin having at least 40% by weight of at least one polyoxyalkylene chain in a polyoxyethylene chain and a polyoxypropylene chain,
(C) a polyacrylamide resin and (D) (a) 2 to 50% by weight of a hydrophilic monomer having at least one polymerizable double bond and a polyoxyalkylene chain or a polyvinylpyrrolidone chain in one molecule, ) The following formula [1]

[0017]

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[In the formula, R ¹ represents a hydrogen atom or a methyl group; R ² and R ³ are the same or different and each represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, provided that R ² is The sum of the number of carbon atoms with R ³ is 5 or less], at least one (meth) acrylamide-based monomer selected from compounds represented by the following formula:
A compound having two or more polymerizable unsaturated double bonds in a molecule, and at least one functional group selected from a hydrolyzable silyl group, an epoxy group, an N-methylol group and an N-alkoxymethyl group in a molecule 1 to 30% by weight of at least one crosslinkable unsaturated monomer selected from a compound having a group and one polymerizable unsaturated double bond, (d) 2 to 50% by weight of a carboxyl group-containing polymerizable unsaturated monomer And (e) a copolymer of 0 to 50% by weight other than the above monomers (a), (b), (c) and (d) having one polymerizable unsaturated group in one molecule. And a hydrophilic cross-linking polymer fine particle comprising:

The present invention also provides a method for hydrophilizing a fin material, which comprises applying the composition for hydrophilization treatment to a fin material made of aluminum heat exchanger.

Further, the present invention provides an aluminum heat exchanger fin material in which a coating film from the composition for hydrophilization treatment is formed as a surface layer.

[0021]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail.

Water-soluble or water-dispersible polyamide resin
(A) water-soluble or water-dispersible polyamide resin (A) [hereinafter,
May be abbreviated as "resin (A)"] as long as it is a water-soluble or water-dispersible amide resin.

The resin (A) may be a polyamide resin in which a group for solubilizing or dispersing in water such as an N-methylol group or an NC _1-4 alkyloxymethyl group is introduced. In addition, a dispersing agent such as a surfactant may be used in combination to impart water dispersibility.

As the resin (A), a water-soluble or water-dispersible nylon is particularly preferable from the viewpoint of the flexibility of a coating film obtained.

The resin (A) has a number average molecular weight of 3,000 to
200,000, preferably 10,000-100,0
Preferably, it has a molecular weight of from 20,000 to 50,000 to 50,000.

Suitable commercial products of the resin (A) include Toresin FS350 and Toresin FS500 (all of which are water-soluble or water-dispersible nylons manufactured by Teikoku Chemicals, Inc.)
AQ nylon P-70, AQ nylon A-90 (or more,
All of them include water-soluble or water-dispersible nylons manufactured by Toray Industries, Inc.).

A water-soluble polyoxyalkylene chain
The water- soluble or water-dispersible resin (B) having a polyoxyalkylene chain (hereinafter sometimes abbreviated as “resin (B)”) is a polyoxyethylene chain and a polyoxypropylene. A water-soluble or water-dispersible resin containing at least one kind of polyoxyalkylene chain in the resin in a proportion of 40% by weight or more, preferably 50% by weight or more, more preferably 80% by weight or more. is there.

In the present invention, the polyoxyalkylene chain is a group represented by the following formula.

[0029]

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[In the formula, R ⁴ represents a hydrogen atom or a methyl group, and k represents an integer of 3 or more, preferably an integer of 5 to 2500.] The following are typical examples of the resin (B). Can be.

(1) Polyethylene glycol, polypropylene glycol, and blocked polyoxyalkylene glycol in which the polyoxyethylene chain and the polyoxypropylene chain are bonded in a block shape.

(2) Either the hydroxyl group at one or both terminals of the above-mentioned polyethylene glycol, polypropylene glycol or blocked polyoxyalkylene glycol is etherified with a monohydric alcohol, a dihydric or higher polyhydric alcohol or a phenol, or A compound that is blocked by esterification with a monobasic acid.

The monohydric alcohols or polyhydric alcohols or phenols that can be used in the above etherification include
For example, methanol, ethanol, isopropanol,
monohydric alcohols such as n-butanol and isobutanol; butanediol, neopentyl glycol, hexanediol, di (hydroxymethyl) cyclohexane,
Polyhydric alcohols such as glycerin, diglycerin, trimethylolethane, trimethylolpropane, and pentaerythritol; phenols such as phenol, bisphenol A and bisphenol F;

Examples of the monobasic acid that can be used in the above esterification include formic acid, acetic acid, propionic acid, butyric acid, hydroxyacetic acid, lactic acid, benzoic acid, pt-butylbenzoic acid and the like.

(3) A polymer of a polymerizable unsaturated monomer having a polyoxyethylene chain or a polyoxypropylene chain, or a copolymer of the monomer and another polymerizable unsaturated monomer.

The polymerizable unsaturated monomer having a polyoxyethylene chain or a polyoxypropylene chain includes:
For example, a compound represented by the formula [2] or [3] can be mentioned, and a typical example thereof is Blemmer PM.
E-4000 (manufactured by NOF Corporation, methacrylate having a polyoxyethylene chain), PMA-300M
(Nippon Emulsifier Co., Ltd., methacrylate having a polyoxyethylene chain).

As the other polymerizable unsaturated monomer, any monomer having a copolymerizability with the above monomer can be used without limitation. Examples thereof include methyl (meth) acrylate and ethyl (meth) acrylate. , Such as propyl (meth) acrylate, butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate
_1-20 alkyl (meth) acrylate; 2-hydroxy-containing, such as hydroxyethyl (meth) acrylate (meth) acrylate; (meth) carboxyl group-containing unsaturated monomers such as acrylic acid; styrene may be mentioned.

(4) Polyester obtained by esterifying a polyhydric alcohol component containing polyethylene glycol or polypropylene glycol and a polybasic acid component.

Polyhydric alcohol components other than polyethylene glycol and polypropylene glycol include, for example, aliphatic diols such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butanediol, neopentyl glycol and hexanediol; Alicyclic diols such as cyclohexanedimethanol and hydrogenated bisphenol A;
Examples include trihydric or higher polyhydric alcohols such as glycerin, trimethylolethane, trimethylolpropane, and pentaerythritol.

The polybasic acid component to be reacted with the polyhydric alcohol component includes, for example, aromatic dicarboxylic acids such as phthalic anhydride, isophthalic acid and terephthalic acid; tetrahydrophthalic anhydride, hexahydrophthalic anhydride, succinic acid, fumaric acid Non-aromatic dicarboxylic acids such as acid, adipic acid, azelaic acid, sebacic acid, dodecanedioic acid, maleic anhydride, cyclohexanedicarboxylic acid; trimellitic anhydride, pyromellitic anhydride, methylcyclohexentricarboxylic acid, pyromellitic anhydride And tribasic or higher polybasic acids, and lower alkyl esters of these acids. Benzoic acid, crotonic acid,
A monobasic acid such as pt-butylbenzoic acid may be used as a part of the acid component for controlling the molecular weight.

The resin (B) must contain at least one kind of polyoxyalkylene chain of the polyoxyethylene chain and the polyoxypropylene chain in the resin in an amount of 40% by weight or more. If the amount is less than 40% by weight, the resulting coating film generally has insufficient hydrophilicity.

The molecular weight of the resin (B) is not particularly limited, but the number average molecular weight is usually 500 to 50.
It is preferably in the range of 0000, especially 3,000 to 100,000.

The polyacrylamide-based resin (C) polyacrylamide-based resin (C) is a copolymer of acrylamide homopolymer or acrylamide and another copolymerizable monomer, in the resin, -CH ₂ - CH
Having the structural unit represented by - (CONH _2). In the copolymer, acrylamide is used as a monomer component constituting the copolymer in an amount of 30 mol% or more, preferably 50 mol% or more.
It is appropriate to contain at least mol%.

Other copolymerizable monomers constituting the copolymer include acrylic acid, methacrylic acid, styrene sulfonic acid, ethylene sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid, and dimethylamino methacrylate. Ethyl ester, dimethylaminopropyl methacrylate, dimethylaminoethyl acrylate,
Dimethylaminopropyl acrylate, diallyldimethylammonium chloride and their quaternary salts and the like; methyl (meth) acrylate, ethyl (meth) acrylate,
C of acrylic acid such as butyl (meth) acrylate
_Examples include _{1 to 24} alkyl esters.

The polyacrylamide-based resin (C) is prepared by adding a monomer component constituting the resin (C) in the presence of a polymerization initiator (azo, peroxide, oxidation-reduction type, etc.) to water, an organic solvent or the like. Can be produced by a polymerization reaction in a solvent of

The polyacrylamide resin (C) is preferably a nonionic or anionic resin from the viewpoint of the stability of the resulting paint.

Commercially available polyacrylamide-based resins (C) include, for example, Santax (registered trademark) series manufactured by Mitsui Chemicals, Inc., and Polymer Set (trade name) series manufactured by Arakawa Chemical Industries, Ltd. Can be mentioned.

Hydrophilic crosslinked polymer fine particles (D) The component (D) in the composition of the present invention comprises the following (a):
These are hydrophilic crosslinked polymer fine particles comprising a copolymer of monomers (b), (c), (d) and (e).

The hydrophilic monomer (a) is a compound having at least one polymerizable double bond and a polyoxyalkylene chain or a polyvinylpyrrolidone chain in one molecule. Typical examples thereof include the following general formula [2]:
The compound represented by [3] or [4] can be mentioned.

[0050]

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Wherein R ⁵ , R ⁶ and R ⁷ are the same or different and each represent a hydrogen atom or a methyl group;
⁸ -OH, -OCH _3, -SO ₃ H or -SO ₃ ^- M
⁺ , Where M ⁺ is Na ⁺ , K ⁺ , Li ⁺ , NH
₄ ⁺ or an organic ammonium group, n represents 10 to 20
A number of 0 and n expressions

[0052]

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Each R ⁷ in the unit may be the same or different from each other, wherein the organic ammonium group may be any of primary, secondary, tertiary and quaternary. The nitrogen atom is preferably a compound in which at least one organic group and 0 to 3 hydrogen atoms are bonded to each other, and the organic group may include O, S, N atoms and the like. Examples thereof include 1 to 8 alkyl groups, aryl groups, and aralkyl groups.

[0054]

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[Wherein R ⁵ , R ⁶ , R ⁷ , R ⁸ and n
Has the same meaning as above.]

[0056]

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Wherein R ⁵ and R ⁶ have the same meaning as described above, and X represents a divalent organic group having 5 to 10 carbon atoms which may contain O, S or N atoms; m is 10 to 10
In the above formula [4], "O, S represented by X
Specific examples of the "divalent organic group having 5 to 10 carbon atoms that may contain an N atom" include a group represented by the following formula.

[0058]

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As the monomer (a), from the viewpoint of dispersion stability and the like when a large amount of the monomer (b) is used,
Among them, a compound of the formula [2] or [3] wherein n is 50 to 200 is preferable.

(Meth) acrylamide-based monomer (b) The (meth) acrylamide-based monomer (b) is at least one compound selected from the compounds represented by the following general formula [1].

[0061]

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[Wherein R ¹ represents a hydrogen atom or a methyl group, R ² and R ³ are the same or different and each represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, provided that R ² and R The sum of the number of carbon atoms with ³ is 5 or less.] In the above formula [1], the “alkyl group having 1 to 5 carbon atoms” represented by R ² or R ³ may be a straight-chain or Any of branched ones, for example, methyl, ethyl, n-propyl, isopropyl, n
-Butyl, isobutyl, t-butyl, amyl and the like.

Thus, typical examples of the monomer (b) represented by the general formula [1] include acrylamide, methacrylamide, N-methylacrylamide, N-methylmethacrylamide, N, N-dimethylacrylamide,
N, N-dimethylmethacrylamide, N-ethylacrylamide, N-ethylmethacrylamide, Nn-propylacrylamide, Nn-propylmethacrylamide, N-isopropylacrylamide, N-isopropylmethacrylamide, Nn-butyl Acrylamide and the like can be mentioned.

Crosslinkable Unsaturated Monomer (c) The crosslinkable unsaturated monomer (c) is a component that contributes to the crosslinking of the particles, and includes a compound having two or more polymerizable double bonds in one molecule, A hydrolyzable silyl group in the molecule,
At least one selected from compounds having at least one functional group selected from an epoxy group, an N-methylol group and an N-alkoxymethyl group and one polymerizable double bond
Species of compound.

Of the above-mentioned crosslinkable unsaturated monomers (c),
Examples of the compound (c-1) having two or more polymerizable double bonds in one molecule include methylene bisacrylamide, ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, and tetraethylene glycol Di (meth) acrylate, 1,3-
Butylene glycol di (meth) acrylate, 1,6-
Examples thereof include hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, divinylbenzene, and allyl (meth) acrylate. Among these, methylenebisacrylamide and methylenebismethacrylamide are preferred from the viewpoints of dispersion stability and hydrophilicity of the obtained polymer fine particles.

Among the above crosslinkable unsaturated monomers (c),
Compound (c-2) having at least one functional group selected from a hydrolyzable silyl group, an epoxy group, an N-methylol group and an N-alkoxymethyl group and one polymerizable double bond in one molecule. The following compounds can be mentioned as typical examples. In addition, in this specification, a "hydrolysable silyl group" means the silicon-containing group which produces | generates a silanol group (Si-OH) by hydrolyzing, for example,
Examples include groups represented by the following formulas.

[0067]

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[Wherein the two R ⁹ are the same or different,
Each represents a hydrogen atom, a hydrocarbon group having 1 to 18 carbon atoms, an alkoxy group having 1 to 4 carbon atoms or an alkoxyl group substituted with 2 to 4 carbon atoms, and R ¹⁰ has 1 to 1 carbon atoms.
Represents an alkoxyl group of 4 or an alkoxyl group substituted with an alkoxyl group having 2 to 4 carbon atoms.] However, typical examples of the compound (c-2) include γ
-Methacryloyloxypropyltrimethoxysilane,
γ-acryloyloxypropyltrimethoxysilane,
Unsaturated compounds having a hydrolyzable silyl group such as vinyltriethoxysilane, vinyltrimethoxysilane, 2-styrylethyltrimethoxysilane, and vinyltris (methoxyethoxy) silane; epoxy groups such as glycidyl (meth) acrylate and allyl glycidyl ether An unsaturated compound having the formula: N-methylolacrylamide,
Unsaturated compounds having an N-methylol group such as N-methylol methacrylamide; N-methoxymethyl acrylamide, N-methoxymethyl methacrylamide, N-ethoxymethyl acrylamide, N-ethoxymethyl methacrylamide, N-butoxymethyl acrylamide, N
And unsaturated compounds having an N-alkoxymethyl group such as -butoxymethyl methacrylamide. Among these, unsaturated compounds having an N-methylol group or an alkoxymethyl group having 1 to 7 carbon atoms are preferred from the viewpoint of the stability of the polymer fine particles in an organic solvent.

Carboxyl group-containing polymerizable unsaturated monomer
(D) The carboxyl group-containing polymerizable unsaturated monomer (d) can be used without particular limitation as long as it has at least one carboxyl group and one polymerizable unsaturated group in one molecule. Examples include acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, monobutyl itaconate, monobutyl maleate and the like. In the monomer (d), the carboxyl group of the monomer (d) forms a hydrogen bond with the compound (A) having a polyoxyalkylene chain, and contributes to the curability of the composition for hydrophilization treatment of the present invention.

Other Monomer (e) The other monomer (e) is a monomer used as necessary, and has one polymerizable unsaturated group in one molecule. Compounds other than the monomers (a), (b), (c) and (d), which are copolymerizable with b), (c) and (d).

Representative examples of the monomer (e) include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, lauryl (meth) acrylate, Alkyl or cycloalkyl esters of acrylic acid or methacrylic acid having 1 to 24 carbon atoms, such as cyclohexyl (meth) acrylate;
C2-8 hydroxyalkyl esters of acrylic acid or methacrylic acid such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate and hydroxybutyl (meth) acrylate; polymerizable unsaturated such as acrylonitrile and methacrylonitrile Nitrile; aromatic vinyl compounds such as styrene, α-methylstyrene, vinyltoluene, α-chlorostyrene;
N, N-dimethylaminoethyl (meth) acrylate,
C3-8 nitrogen-containing alkyl esters of acrylic acid or methacrylic acid such as N, N-dimethylaminopropyl (meth) acrylate; α such as ethylene and propylene
-Olefin; diene compounds such as butadiene and isoprene; vinyl esters such as vinyl acetate and vinyl propionate; vinyl ethers such as ethyl vinyl ether and n-propyl vinyl ether. These compounds can be used singly or as a mixture of two or more. However, care must be taken because the use of a large amount of a hydrophobic compound impairs the hydrophilicity of the polymer particles.

As the monomer (e), the monomer (c)
When a compound having a functional group that reacts complementarily with the functional group in -2) is used, crosslinking can be performed by the reaction between the functional group in the monomer (c-2) and the functional group in the monomer (e). When the functional group in the monomer (c-2) is a hydrolyzable silyl group, an N-methylol group or an N-alkoxymethyl group, these groups may react with each other and crosslink. it can. in this case,
A siloxane bond is formed by the hydrolyzable silyl groups, and N
- methylol group or N- alkoxymethyl group by dehydration condensation reaction or dealcoholation (= N-CH ₂ -O
—CH ₂ —N =) bonds can be formed and crosslinked.

Examples of the functional group which the monomer (e) having reactivity with the functional group in the monomer (c-2) may have include those shown in Table 1 below.

[0074]

[Table 1]

When a compound (c-2) having an epoxy group is used as the monomer (c), a functional group having a reactivity with the epoxy group as the monomer (e), for example, amino A compound having a group or a hydroxyl group can be used as all or a part of the compound (d), and the carboxyl group in the monomer (d) can be obtained by using a compound having an epoxy group as the compound (c-2). Crosslinking can also be performed by reaction with the epoxy group.

Production of hydrophilic crosslinked polymer fine particles (D) The hydrophilic crosslinked polymer fine particles (D) are prepared by mixing the hydrophilic monomer (a), the (meth) acrylamide monomer (b), and the crosslinkable unsaturated A monomer (c), a carboxyl group-containing polymerizable unsaturated monomer (d) and, if necessary, another monomer (e) are dissolved in the absence of a dispersion stabilizer to form a copolymer which is dissolved but produced. It can be produced by polymerizing in a water-miscible organic solvent that is substantially insoluble or in a water-miscible organic solvent / water mixed solvent.

The proportion of each monomer used at this time can be the same as the proportion of the desired monomer in the copolymer to be formed, and can be, for example, as follows.

Hydrophilic monomer (a): 2 to 50% by weight,
Preferably 2 to 40% by weight, (meth) acrylamide-based monomer (b): 20 to 97
%, Preferably 30 to 97% by weight, crosslinkable unsaturated monomer (c): 1 to 30% by weight, preferably 2 to 20% by weight, carboxyl group-containing polymerizable unsaturated monomer (d):
50% by weight, preferably 5 to 40% by weight, other monomer (e): 0 to 50% by weight, preferably 0 to
30% by weight.

When the amount of the hydrophilic monomer (a) is less than 2% by weight, it is generally difficult to sufficiently stabilize the resulting polymer particles, and aggregates are easily formed during polymerization or storage. On the other hand, when the content exceeds 50% by weight, the polymer particles to be produced are easily dissolved in the reaction solvent, and most of the polymer is dissolved, so that it is impossible to satisfactorily form the polymer fine particles.

(Meth) acrylamide monomer (b)
If the amount is less than 20% by weight, the polymer formed by the polymerization is generally easily dissolved in the reaction solvent and it becomes difficult to form polymer fine particles. The polymer fine particles have insufficient stability and tend to form aggregates.

When the amount of the crosslinkable unsaturated monomer (c) is less than 1% by weight, the degree of crosslinking of the resulting polymer fine particles generally becomes small. It becomes easy to dissolve and swell. On the other hand, if it exceeds 30% by weight, the generation of aggregates during polymerization increases, and it becomes extremely difficult to stably produce desired polymer fine particles.

When the amount of the carboxyl group-containing polymerizable unsaturated monomer (d) is less than 2% by weight, the ability to form a hydrogen bond with the compound (A) is reduced, and the curability of the resulting film becomes insufficient. On the other hand, when the content exceeds 50% by weight, the stability of the obtained composition for hydrophilization treatment becomes poor.

The hydrophilic monomer (a) used in the production of the hydrophilic crosslinked polymer fine particles (D) has a polyoxyalkylene chain or a polyvinylpyrrolidone chain rich in hydrophilicity in the molecule. Since the monomer (a) plays a role of stabilizing the dispersion of the produced polymer, the production of the polymer fine particles (D) does not require the use of a dispersion stabilizer.

In the production of the polymer fine particles (D), a water-miscible organic solvent or a water-miscible organic solvent / water which dissolves the monomer mixture of the raw material but does not substantially dissolve the produced copolymer is used as a reaction solvent. A mixed solvent is used. Here, “water-miscible” or “miscible with water” means that it can be dissolved in water at an arbitrary ratio at a temperature of 20 ° C.

As the water-miscible organic solvent, any one can be used as long as the above requirements are satisfied.
In particular, solubility parameter (SP) values are generally 9-11,
In particular, those containing at least 50% by weight, especially 70% by weight or more of an organic solvent in the range of 9.5 to 10.7,
It is suitable from the viewpoint of polymerization stability. The “solubility parameter (SP) value” in the present specification refers to the Journal of P
aint Technology, Vol. 42 No. 541, 76-11
8 (February 1970).

The water-miscible organic solvent having an SP value within the above range includes, for example, ethylene glycol monobutyl ether, propylene glycol monomethyl ether,
Examples thereof include alkylene glycol monoalkyl ethers such as ethylene glycol monoethyl ether, diethylene glycol monoethyl ether, and diethylene glycol monobutyl ether. Of these, ethylene glycol monobutyl ether and propylene glycol monomethyl ether are particularly preferable.

The water-miscible organic solvent is S
In addition to the organic solvent having a P value in the range of 9 to 11, other water-miscible or water-immiscible organic solvent can be contained. Such organic solvents include water-miscible organic solvents,
For example, methanol, ethanol, isopropyl alcohol and the like are suitable. The other organic solvent is desirably used in an amount of 50% by weight or less, particularly 30% by weight or less of the total amount of the organic solvent.

When a water-miscible organic solvent / water mixed solvent is used as the reaction solvent, the content of water in the mixed solvent is usually from the viewpoint of polymerization stability and the like. 60 parts by weight or less per 100 parts by weight, especially 4
It is preferably 0 parts by weight or less.

The copolymerization of the hydrophilic monomer (a), the (meth) acrylamide monomer (b), the crosslinkable unsaturated monomer (c), the carboxyl group-containing polymerizable unsaturated monomer (d) and the other monomer (e) The polymerization is usually performed in the presence of a radical polymerization initiator. As the radical polymerization initiator, those known per se can be used, and the amount of the radical polymerization initiator can be usually in the range of 0.2 to 5% by weight based on the total amount of the monomers.

The polymerization temperature can be varied depending on the type of polymerization initiator used, etc., but is usually from about 50 to about 16
A temperature in the range of 0 ° C, more preferably 90 to 160 ° C, is suitable, and the reaction time can be about 0.5 to 10 hours. Further, in order to promote the crosslinking by the monomer (c) after the polymerization reaction, it may be heated to a higher temperature. Further, a crosslinking reaction catalyst may be added, if necessary, so that the intraparticle crosslinking reaction during or after the polymerization reaction proceeds more quickly. Examples of the crosslinking reaction catalyst include strong acid catalysts such as dodecylbenzenesulfonic acid and paratoluenesulfonic acid; and base catalysts such as triethylamine, and may be appropriately selected depending on the crosslinking reaction species.

The particle size of the polymer fine particles (D) produced as described above is not particularly limited, but is not limited to the stability of the polymer fine particles (D) and the suppression of generation of aggregates. From the viewpoint, it is generally 0.03 to 1 μm, preferably 0.1 to 1 μm.
Suitably, it has an average particle size in the range of from 0.05 to 0.6 μm. The average particle diameter can be measured by a particle diameter measuring device, for example, a Coulter model N4MD (manufactured by Coulter).

The polymer fine particles (D) are oriented outward with the polyoxyalkylene chain or polyvinylpyrrolidone chain derived from the monomer (a) chemically bonded to the surface of the polymer fine particles. Even in the absence of a dispersion stabilizer, the polymerization stability and dispersion stability over time (storage stability) are extremely excellent, and the surface is rich in hydrophilicity.

Further, the polymer fine particles (D) are crosslinked in the particles due to the presence of the monomer (c) component, and maintain the form even in the organic solvent type paint, and are easily heated. When the treatment film is formed from the paint without melting, fine irregularities can be formed on the treatment film.

Composition for hydrophilization treatment In the composition of the present invention, the mixing ratio of the resin (A), the resin (B), the resin (C) and the polymer fine particles (D) is determined by the performance desired for the composition to be obtained. Although it is not particularly limited and can be appropriately selected depending on, for example, the mixing ratio of the resin (A), the resin (B), and the resin (C) is usually the same as that of the resin (A) and the resin (B). It is appropriate that the solid content is within the following range based on 100 parts by weight of the total amount of the resin and the resin (C).

Resin (A): 5 to 60 parts by weight, preferably 10 to 40 parts by weight, Resin (B): 10 to 80 parts by weight, preferably 20 to 70 parts by weight
Parts by weight, resin (C): 5 to 80 parts by weight, preferably 20 to 70 parts by weight
Parts by weight.

The ratio of the total amount of the resin (A), the resin (B), and the resin (C) / the ratio of the polymer fine particles (D) is from 10/90 to 90/10, particularly 40/90, by weight based on the solid content. 60-8
A range of 0/20 is preferred.

The composition of the present invention comprises (A), (B) and (C)
And each component of (D) is a component having excellent hydrophilicity, and the amide group of the component (A), the polyoxyalkylene chain of the component (B), the amide of the component (C), and the amide group of the component (D) , A polyoxyalkylene chain and a carboxyl group are bonded to each other by a hydrogen bond. Among them, the components (A), (C) and (D) have similar solubility parameters, have good compatibility with each other, and are effectively bonded by hydrogen bonding.

The composition of the present invention makes it possible to form a coating film which is excellent in continuous coating film forming property and curability in a short time. (B) that the resin is generally a high molecular weight resin, the effect of the hydrogen bonding, and that in the short-time baking, the component (A) has better moisture volatility than the component (B), It is considered that the fact that the component (C) is a polymer resin like the component (A) contributes.

Further, the composition of the present invention can form a coating film having excellent hydrophilicity. The reason for this is that the present inventors have considered (A), (B), (C) and (D) Is a component having excellent hydrophilicity, component (D) is a fine-particle polymer, and the effect of improving hydrophilicity by forming fine irregularities on the coating film surface; component (B) and component (D) The difference between the solubility parameters is large, and the effect of both components can form irregularities more effectively on the surface of the coating film to improve the hydrophilicity, and the component (C) has excellent moisture retention. Believe in things.

The composition of the present invention may optionally contain a crosslinking agent as the component (E) in order to further improve the water solubility of the treated film obtained from the composition. Good. Examples of the crosslinking agent (E) include a melamine resin, a urea resin, a phenol resin, a polyepoxy compound,
Examples thereof include a blocked polyisocyanate compound and a metal chelate compound such as a titanium chelate.
Generally, the crosslinking agent preferably has water solubility or water dispersibility.

In the heat exchanger fin material treated with the composition of the present invention, for example, the fin pitch of the heat exchanger is 1.
When it is 2 mm or less, it is desirable that the contact angle between the fin and water is so-called extended wetting of 5 degrees or less. For this purpose, the composition of the present invention may optionally contain a surfactant having a wetting action as the component (F).

The surfactant (F) may be any of anionic, cationic, amphoteric and nonionic surfactants as long as they have a surface wetting action.
Representative examples of the surfactant (F) that can be used include a dialkyl sulfosuccinate salt and an alkylene oxide silane compound. These surfactants can be used alone or in combination of two or more. The compounding amount of the surfactant (F) is usually 20 parts by weight or less based on 100 parts by weight of the total of the resin (A), the resin (B), the resin (C), and the polymer fine particles (D). And preferably in the range of 0.5 to 10 parts by weight, more preferably 1 to 5 parts by weight.

The composition of the present invention may further contain, if necessary, a bactericidal agent as a component (G) for inhibiting the generation and propagation of microorganisms. As the antibacterial agent (G), those having the following conditions (1) to (5) are particularly suitable.

(1) Low toxicity and high safety; (2) Stable to heat, light, acid, alkali, etc., soluble in water and excellent in durability (3) It has a bactericidal property at a low concentration or has an ability to inhibit the growth of fungi; (5) not to impair the hydrophilicity and corrosion resistance of the formed film.

The antibacterial agent meeting such conditions can be selected from among aliphatic and aromatic organic compounds having a known antibacterial and bactericidal action. For example, haloallyl sulfone, iodopropane Gil, N-haloalkylthio, benzothiazole, nitrile, pyridine, 8
Oxyquinoline, benzothiazole, isothiazoline, phenol, quaternary ammonium salt, triazine, thiazine, anilide, adamantane,
Bactericidal agents such as dithiocarbamate type and bromine indanone type are exemplified.

Specific examples of the antibacterial agent include 2- (4-
Thiazolyl) -benzimidazole, N- (fluorodichloromethylthio) phthalimide, N-dimethyl-N '
-Phenol-N '-(fluorodichloromethylthio)
-Sulfamide, O-phenylphenol, 10,10
'-Oxybisphenoxyarsine, 2,3,5,6-
Tetrachloro-4- (methylsulfonyl) pyridine,
2,4,5,6-tetrachloroisophthalonitrile, diiodomethyl-p-toluylsulfone, methyl 2-benzimidazolecarbamate, bis (dimethylthiocarbamoyl) disulfide, N- (trichloromethylthio) -4-cyclohexene-1 , 2-dicarboximide and the like. In addition, an inorganic salt-based antibacterial agent can be used, and examples thereof include barium metaborate, copper borate, zinc borate, and zeolite (aluminosilicate).

These antibacterial agents may be used alone or in combination, and the amount of the antibacterial agents may be varied depending on the kind of the antibacterial agent. In consideration of the fact that the film forming property, the hydrophilicity of the coating film, and the corrosion resistance of the coated plate are not impaired, the total of the resin (A), the resin (B), the resin (C), and the polymer fine particles (D) is 10 in total.
The amount is preferably 20 parts by weight or less, more preferably 3 to 15 parts by weight, based on 0 parts by weight.

The composition of the present invention comprises, for example, the above resin (A), resin (B), resin (C) and polymer fine particles (D), and if necessary, a crosslinking agent (E) and a surfactant (F). ) And / or the antibacterial agent (G) can be prepared by dissolving or dispersing in an aqueous medium. The aqueous medium contains water as a main component, and may further contain an organic solvent, a neutralizing agent, and the like.

The composition of the present invention may also contain, if necessary, a coloring pigment, a rust-preventive pigment known per se (for example, chromate-based, lead-based, molybdic acid-based, etc.), a rust-preventive agent (for example, tannic acid, Phenolic carboxylic acids such as gallic acid and salts thereof, organic phosphoric acids such as phytic acid and phosphinic acid, metal salts of biphosphoric acid, nitrites, etc.).

The composition of the present invention can be used for metal, glass, wood,
It can be applied on a substrate such as plastics or cloth, and a hydrophilic cured coating film can be formed by baking this coating film. The cured film has a cured film thickness of 0.
It is preferably in the range of 3 to 5 μm, more preferably 0.5 to 3 μm. Baking is generally carried out under conditions where the maximum temperature at which the material reaches the temperature is about 80 to about 250 ° C. and the baking time is about 30 minutes to 15 seconds. It is possible to form a coating.

The composition of the present invention is particularly useful for hydrophilizing aluminum heat exchange fins. The hydrophilization treatment of the aluminum heat exchanger fin material can be performed by applying the composition of the present invention to the fin material.
For example, the composition of the present invention may be applied to a sufficiently degreased and optionally converted aluminum plate (which may be assembled in a heat exchanger) by a method known per se,
For example, it can be carried out by coating by dipping coating, shower coating, spray coating, roll coating, electrophoretic coating and the like, followed by baking.

[0112]

The present invention will now be described more specifically with reference to examples and comparative examples. These examples serve to illustrate the invention in more detail and do not limit the scope of the invention in any way. “Parts” and “%” indicate “parts by weight” and “% by weight”, respectively.

Production Example 1 of Hydrophilic Cross- Linked Polymer Fine Particles 200 parts of propylene glycol monomethyl ether was placed in a flask equipped with a nitrogen inlet tube, a condenser with balls, a dropping funnel and a mechanical stirrer, and the temperature was raised to 118 ° C. Next, a mixture of the following monomer, solvent and initiator was added dropwise to the flask over 5 hours, and after the completion of the addition, the mixture was kept at 118 ° C. for 1 hour to obtain a hydrophilic crosslinked polymer fine particle dispersion (a).

Blemmer PME-4000 (Note 1) 20 parts Acrylamide 50 parts N-methylolacrylamide 20 parts Acrylic acid 10 parts Propylene glycol monomethyl ether 200 parts 2,2'-azobis (2-methylbutyronitrile) 1.5 parts The resulting dispersion was a milky white, stable dispersion having a solid content of 20%, and the particle size of the resin particles was 345 nm.

(Note 1) Blemmer PME-4000:
A compound represented by the following formula, manufactured by NOF Corporation.

[0116]

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Production Example 2 60 parts of propylene glycol monomethyl ether was charged into a flask equipped with a nitrogen inlet tube, a condenser with balls, a dropping funnel and a mechanical stirrer, and the temperature was raised to 90 ° C.
Next, 100 parts of N-vinylpyrrolidone, 2,
A solution consisting of 2 parts of 2'-azobisisobutyronitrile and 5 parts of propylene glycol monomethyl ether and a solution consisting of 5 parts of mercaptoacetic acid and 30 parts of propylene glycol monomethyl ether were simultaneously added dropwise over 2 hours. After maintaining the temperature at 90 ° C. for 1 hour after the completion of the dropwise addition, a solution comprising 1 part of 2,2′-azobis (2,4-dimethylvaleronitrile) and 10 parts of propylene glycol monomethyl ether was added dropwise over 1 hour. After stirring for an hour, the mixture was cooled to obtain a polyvinylpyrrolidone solution having a solid content of 50%.

The obtained polyvinylpyrrolidone solution 800
26.6 parts of glycidyl methacrylate and 1.8 parts by weight of tetraethylammonium bromide were added to
The mixture was stirred at 0 ° C for 7 hours, and the solid content represented by the following formula was about 52%
A solution of polyvinylpyrrolidone macromonomer was obtained.

[0119]

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In Preparation Example 1, polymerization was carried out in the same manner as in Preparation Example 1 except that a mixed solution of the following monomer, solvent and initiator was used as a mixed solution to be dropped, and a dispersion of hydrophilic crosslinked polymer fine particles (b) was used. I got

A solution of the polyvinylpyrrolidone macromonomer having a solid content of about 52% obtained above 38.5 parts Acrylamide 50.0 parts N-methylolacrylamide 20.0 parts Methacrylic acid 10.0 parts Propylene glycol monomethyl ether 181.5 parts 1.5 parts of 2,2′-azobis (2-methylbutyronitrile) The resulting dispersion was a milky white, stable dispersion having a solid content of 20%, and the particle size of the resin particles was 254 nm.

Production Example 3 200 parts of propylene glycol monomethyl ether was placed in a flask equipped with a nitrogen inlet tube, a condenser with balls, a dropping funnel and a mechanical stirrer, and the temperature was raised to 80.degree. Next, the following mixture was added dropwise to the flask over 5 hours, and after completion of the addition, the mixture was kept at 80 ° C. for 2 hours to obtain a dispersion liquid (c) of hydrophilic crosslinked polymer fine particles.

Blemmer PME-4000 20 parts Acrylamide 50 parts N-methylol acrylamide 15 parts Acrylic acid 10 parts Methylene bisacrylamide 5 parts Propylene glycol monomethyl ether 150 parts Deionized water 50 parts Ammonium persulfate 1.5 parts It was a milky white, stable dispersion having a solid content of 20%, and the particle size of the resin particles was 320 nm.

Production Example 4 170 parts of propylene glycol monomethyl ether was placed in a flask equipped with a nitrogen inlet tube, a condenser with balls, a dropping funnel and a mechanical stirrer, and the temperature was raised to 80.degree. Next, the following mixture was added dropwise to the flask over 5 hours, and after completion of the addition, the mixture was maintained at 80 ° C. for 2 hours to obtain a hydrophilic crosslinked polymer fine particle dispersion (d).

Blemmer PME-4000 30 parts Acrylamide 45 parts Acrylic acid 15 parts Glycidyl methacrylate 10 parts Propylene glycol monomethyl ether 150 parts Deionized water 80 parts Ammonium persulfate 1.5 parts The dispersion obtained is milky white, solid content 20% And the particle size of the resin particles was 163 nm.

Production Example 5 170 parts of propylene glycol monomethyl ether was placed in a flask equipped with a nitrogen inlet tube, a condenser with balls, a dropping funnel and a mechanical stirrer, and the temperature was raised to 80 ° C. Next, the following mixture was dropped into the flask over 5 hours. After the completion of the dropping, the mixture was kept at 80 ° C. for another 2 hours to obtain a hydrophilic crosslinked polymer fine particle dispersion (e).

Blenmer PME-4000 30 parts Acrylamide 60 parts γ-methacryloxypropyltrimethoxysilane 10 parts Propylene glycol monomethyl ether 150 parts Deionized water 80 parts Ammonium persulfate 1.5 parts The resulting dispersion is milky white, solid It was a 20% stable dispersion, and the particle size of the resin particles was 128 nm.

Production Example 6 200 parts of ethylene glycol monobutyl ether was placed in a flask equipped with a nitrogen inlet tube, a condenser with balls, a dropping funnel and a mechanical stirrer, and the temperature was raised to 140.degree. Next, a mixture of the following monomer, solvent and initiator was dropped into the flask over 5 hours, and after completion of the dropping, the mixture was kept at 140 ° C. for 1 hour to obtain a hydrophilic crosslinked polymer fine particle dispersion (f).

RMA-300M (Note 2) 15 parts Acrylamide 55 parts N-butoxymethylacrylamide 15 parts 2-hydroxyethyl methacrylate 15 parts Ethylene glycol monobutyl ether 200 parts 2,2′-azobis (2-methylbutyronitrile) 1 0.5 part The obtained dispersion was a milky white, stable dispersion having a solid content of 20%, and the particle size of the resin particles was 441 nm.

(Note 2) RMA-300M: a compound represented by the following formula, manufactured by Nippon Emulsifier Co., Ltd.

[0131]

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Preparation of Resin Having Polyoxyalkylene Chain
Water was charged 150 parts during granulation Production Example 7 A four-neck flask, flaky PEG20000 stirring at 50 ° C. (Sanyo Chemical Industries, Ltd., polyethylene glycol, number average molecular weight of about 20,000) 100 parts Add and dissolve, solids 4
A 0% polyethylene glycol aqueous solution (g) was obtained.

Production Example 8 Production Example 7 was the same as Production Example 7 except that Sannics PE-75 (produced by Sanyo Chemical Industries, Ltd., propylene oxide / ethylene oxide copolymer) was used instead of PEG20000. The operation was performed to obtain a polyalkylene glycol aqueous solution (h) having a solid content of 40%.

Production Example 9 The same operation as in Production Example 7 was carried out except that polyethylene glycol monomethyl ether (number average molecular weight: about 4,000) was used in place of PEG 20000, and a polyethylene having a solid content of 40% was obtained. An aqueous solution of glycol monomethyl ether (i) was obtained.

Production Example 10 In a flask equipped with a thermometer and a stirrer, 250 parts of AQ nylon A-90 (water-soluble nylon manufactured by Toray Industries, Inc.)
750 parts of deionized water were charged, heated to 40 ° C., and held for 5 hours. Thereafter, stirring was started, and after confirming that the pellet-like particles were dissolved, the mixture was cooled to obtain a polyamide resin aqueous solution (k).

Production of Hydrophobizing Composition Example 1 Tresin FS-500 (manufactured by Teikoku Chemical Industry Co., Ltd., water-soluble nylon, abbreviated as “FS500” in Table 2) was used as a solid content of 10 parts. Amount, the amount of the aqueous solution of polyethylene glycol (g) obtained in Production Example 7 was 20 parts as a solid content, and the amount of the hydrophilic crosslinked polymer fine particle dispersion (a) obtained in Production Example 1 was 30 parts as a solid content. The amount and the amount of Santax CS-18 (manufactured by Mitsui Chemicals, Inc., trade name, polyacrylamide, abbreviated as “CS-18” in Table 2) to give a solid content of 40 parts were mixed, and water was mixed. In addition, a composition for hydrophilic treatment having a solid content of 10% was obtained.

Examples 2 to 10 and Comparative Examples 1 to 2 Water-soluble or water-dispersible polyamide resin, resin solution having polyoxyalkylene chain obtained in Production Example, hydrophilic crosslinked polymer fine particle dispersion, polyacrylamide resin And, if necessary, the same operation as in Example 1 was carried out except that a crosslinking agent, a surfactant and a bacteriostatic compound were used and mixed so as to have a composition shown in Table 2 below. %
Was obtained.

The blending amounts in Table 2 are based on the solid content. In Table 2, “Polymer set” in the column of polyacrylamide resin (C) means “Polymer set 512” manufactured by Arakawa Chemical Industries, Ltd. Further, the types of the cross-linking agent, surfactant and antibacterial compound in Table 2 have the following meanings.

Crosslinking agent A: trade name "Cymel 370", manufactured by Mitsui Cytec Co., Ltd., methylated melamine resin, crosslinker B: trade name "Cymel UFR65", manufactured by Mitsui Cytec Co., Ltd., methylated urea resin, interface Surfactant a: brand name “Newcol 290M”, manufactured by Nippon Emulsifier Co., Ltd., sodium salt of dialkyl sulfosuccinate, surfactant b: brand name “Silwet L-77”, manufactured by Nippon Unicar Co., Ltd., alkylene oxide silane Compound, antibacterial compound I: 2- (4-thiazolyl) benzimidazole.

The compositions for hydrophilization treatment obtained in the above Examples and Comparative Examples were used in an aqueous solution having a concentration of 2% in which an alkali degreasing agent (trade name “Chem Cleaner 561B” manufactured by Nippon CB Chemical Co., Ltd.) was dissolved. After degreased, an aluminum plate (A1) subjected to a chromate treatment (a coating amount of metal chromium is 30 mg / m ² ) with a chromate treating agent (trade name “Alchrome 712” manufactured by Nippon Parkerizing Co., Ltd.)
050, plate thickness 0.1 mm) so as to have a dry film thickness of 1 micron and baked with hot air of 240 ° C. for 6 seconds so that the maximum temperature of the material reached 230 ° C. to obtain a coated plate.

A volatile press oil was applied to this coated plate,
What was dried at 50 ° C. for 5 minutes was used as a test coated plate, and the coating film appearance, hydrophilicity, and corrosion resistance were tested. The test results are shown in Table 3 below.

The tests in Table 3 were performed according to the following test methods.

Coating appearance: The test coated plate was visually evaluated.
When no abnormality was observed in the coating film, it was evaluated as ○.

Dry rubbing property: about 4 kg / kg on Kimwipe (trade name, paper, manufactured by Juzen Kimberly Co., Ltd.)
It was rubbed back and forth over a distance of about 5 cm with a pressure of cm ² . The number of times until the coating film was removed and the aluminum plate surface was exposed was measured and evaluated according to the following criteria.

…: The aluminum plate surface is not exposed even after 10 reciprocations. Δ: The aluminum plate surface is exposed after 5 to 10 reciprocations. X: The aluminum plate surface is exposed after less than 5 reciprocations.

Water rubbing property: Gauze impregnated with deionized water, applying a pressure of about 4 kg / cm ² to the coating surface for about 5
Rubbed back and forth over a distance of cm. The number of times until the coating film was removed and the aluminum plate surface was exposed was measured and evaluated according to the following criteria.

…: The aluminum plate surface is not exposed even after 10 reciprocations. Δ: The aluminum plate surface is exposed after 5 to 10 reciprocations. X: The aluminum plate surface is exposed after less than 5 reciprocations.

Hydrophilicity: A test wet plate was immersed in running tap water (flowing amount: 15 kg / h per 1 m ² of the coated plate) for 7 hours, pulled up, and dried in the coating for 17 hours. The water wetting property and the contact angle of water droplets were measured for each of the coated plates subjected to 5 cycles by the following methods.

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

Contact Angle: The contact angle between the coated plate and water is measured by drying the coated plate at 80 ° C. for 5 minutes and using a contact angle meter DCAA type manufactured by Kyowa Chemical Industry Co., Ltd.

Corrosion resistance: according to JIS-Z-2371 salt spray test method. The test time was 500 hours, and evaluated according to the following criteria. …: No white rust or swelling was observed on the coated surface.…: White rust or swelling was slightly generated.

Water wetting during dew condensation: A 20 × 15 × 5 cm stainless steel container was placed in a thermostat at 30 ° C. and 75% RH, and a test coated plate was stuck to the side surface. Next, an antifreeze solution at 0 ° C. was circulated in a stainless steel container, and the state of water wetting due to dew on the surface of the test coated plate after circulating for 10 hours was visually observed and evaluated according to the following criteria. …: The entire surface of the coated plate is wet with water, and the diameter of the water droplet is 1 mm or less.…: 50 to 100% of the surface of the coated plate is wet with water, and the diameter of the water droplet is more than 1 mm and less than 2 mm. The area is less than 50%.

Further, a test for the antifungal property of the test coated plate of Example 8 was performed under the following conditions, and the state of generation of mold on the coating film surface after a predetermined time was visually judged. No generation of mold was observed on the coated surface. I couldn't.

Antifungal property: A peptone glucose medium was prepared in a sterilized petri dish, a test coated plate was placed thereon, and Cladosporium (gradosporium) s was used as a bacterium to be used.
p, Penicillum sp, Al
tarnaria (Alternaria) sp, Asperg
illus sp and Tricho
A suspension of mixed spores of derma (Trichoderma) sp. in peptone glucose is sprayed on at a temperature of 26 ± 2 ° C.
Cultured for 8 days.

[0155]

[Table 2]

[0156]

[Table 3]

In Table 3, those excellent in both dry rubbing properties and water rubbing properties (○) are excellent in curability.

[0158]

The composition of the present invention can form a coating film having excellent curability even when baked for a short time, and maintains hydrophilicity even when baked for a short time (overall water wetting and a contact angle with water of 2).
0 ° or less), and a hydrophilic film excellent in drawless type continuous molding processability (mold abrasion resistance) and also excellent in corrosion resistance can be formed on a substrate.

Further, by adding a bactericidal agent to the composition of the present invention, there is an effect that the generation of odor due to mold can be greatly improved.

Thus, by using the aluminum heat exchanger fin material treated with the composition of the present invention, energy saving and resource saving of the heat exchanger can be achieved.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09D 171/02 C09D 171/02 177/00 177/00 C09K 3/18 C09K 3/18 F28F 1/32 F28F 1/32 H 13/18 13/18 B // C08F 220/54 C08F 220/54 290/06 290/06 F term (reference) 4D075 CA37 CA45 DB07 DC19 EA06 EB22 EB39 EB52 EB56 EC35 4H020 AA03 AB02 AB05 4J027 AC02 AC03 AC04 AC05 AC06 AC09 BA02 BA04 BA05 BA06 BA07 BA08 BA14 BA20 BA21 BA26 CA20 CA25 CA26 CC02 CD08 4J038 CG141 CG142 CG171 CG172 CH141 CH142 DF021 DF022 DH002 GA02 GA04 GA07 GA08 GA15 KA03 KA09 MA14 NA04 NA02 A02 AB03 AB03 AB03 AB03 AB08T AB16R AE02T AE04T AE09Q AE09R AG04T AJ01S AJ02S AJ08S AJ09S AL03T AL04T AL05T AL08Q AL08R AL08T AL09T AL10R AL36S AL44S AL61R AL63R AL66R AL75R AM01T AM 02T AM17P AM19P AM21R AM24R AN04Q AP01Q AP16R AS02T AS03T BA03Q BA03R BA04R BA05Q BA06R BA08Q BA08R BA32T BA56Q BA77R BC04T BC54R BC68Q CA03 CA06 JA01

Claims (9)

[Claims] 1. A (A) water-soluble or water-dispersible polyamide resin; and (B) a water-soluble or water-soluble polyamide resin having at least one polyoxyalkylene chain of at least 40% by weight in the molecule. Monomer having a water-dispersible or water-dispersible resin, (C) a polyacrylamide resin, and (D) (a) at least one polymerizable double bond in one molecule and a polyoxyalkylene chain or a polyvinylpyrrolidone chain 2 to 50% by weight, (b) the following formula [1] [Wherein, R ¹ represents a hydrogen atom or a methyl group, R ² and R ³ are the same or different and each represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, provided that R ² and R ³
And at least one (meth) acrylamide-based monomer selected from the group consisting of 20 to 97% by weight, and (c) two or more polymerizable monomers per molecule. A compound having a saturated double bond, and a hydrolyzable silyl group in one molecule,
At least one type of crosslinkable unsaturated monomer selected from a compound having at least one functional group selected from an epoxy group, an N-methylol group and an N-alkoxymethyl group and one polymerizable unsaturated double bond; (D) carboxyl group-containing polymerizable unsaturated monomer
50% by weight, and (e) 0 to 50% by weight of another monomer other than (a), (b), (c) and (d) having one polymerizable unsaturated group in one molecule. A composition for hydrophilization treatment, comprising hydrophilic crosslinked polymer fine particles composed of a copolymer. 2. The hydrophilic treatment composition according to claim 1, wherein the polyamide resin (A) is a water-soluble nylon having a number average molecular weight of 3,000 to 200,000. 3. The method according to claim 1, wherein the hydrophilic monomer (a) is represented by the following formula [2] or [3]: [Wherein, R ⁵ , R ⁶ and R ⁷ are the same or different and each represent a hydrogen atom or a methyl group, and R ⁸ represents —OH, —O
CH ₃ , —SO ₃ H or —SO ₃ ⁻ M ⁺ , wherein M ⁺ represents Na ⁺ , K ⁺ , Li ⁺ , NH ₄ ⁺ or an organic ammonium group, and n is a number from 10 to 200 , And n formulas Wherein each R ⁷ in the unit may be the same or different from each other].
Or the composition for hydrophilization treatment according to 2. 4. The hydrophilic crosslinked polymer fine particles (D) are composed of 2 to 40% by weight of a hydrophilic monomer (a), 30 to 97% by weight of a (meth) acrylamide monomer (b), and a crosslinkable unsaturated monomer (c). 4) A copolymer of 2 to 20% by weight, 5 to 40% by weight of a carboxyl group-containing polymerizable unsaturated monomer (d), and 0 to 30% by weight of another monomer (e). The composition for hydrophilization treatment according to claim 1. 5. The composition for hydrophilization treatment according to claim 1, further comprising (E) a crosslinking agent. 6. The composition for hydrophilization treatment according to claim 1, further comprising (F) a surfactant having a wetting action. 7. The composition for hydrophilization treatment according to claim 1, further comprising (G) an antibacterial agent. 8. A method for hydrophilizing a fin material, comprising applying the composition for hydrophilization treatment according to any one of claims 1 to 7 to a fin material made of aluminum heat exchanger. 9. A heat exchanger fin material made of aluminum, comprising a coating film formed from the composition for hydrophilization treatment according to claim 1 as a surface layer.