JPH11158434A - Composition and process for hydrophilization treatment - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a composition which can give a coating film excellent in hydrophilicity retention, corrosion resistance, etc., by including a water-soluble polyamide resin, a polyoxyethylene-chain-containing water-soluble resin, and specified hydrophilic crosslinked polymer microparticles. SOLUTION: This composition comprises a water-soluble polyamide resin, a water-soluble resin having at least 40 wt.% polyoxyethylene chains and/or polyoxypropylene chains, and hydrophilic crosslinked polymer microparticles comprising a copolymer comprising 2-50 wt.% hydrophilic monomer having a polymerizable double bond and a polyoxyalkylene chain or a polyvinylpyrrolidone chain, 20-97 wt.% monomer represented by the formula, 1-30 wt.% crosslinking unsaturated monomer selected among compounds having at least two polymerizable double bonds and compounds having a functional group selected among a hydrolyzable silyl group, an epoxy group, an N-methylol group, and an N-alkoxymethyl group and one polymerizable double bond, and 2-50 wt.% COOH-containing polymerizable unsaturated monomer. In the formula, R<1> is H or CH3 ; and R2 and R3 are each H or a 1-5C alkyl (the sum of the C numbers is 5 or below).

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 heat exchanger fin material using the same, and a method for applying the composition. It relates to a heat 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 bridge of water between the fins, thereby narrowing a ventilation passage of air. Problems such as power loss, generation of noise, and scattering of water droplets occur. As a measure for preventing such a phenomenon, for example, the surface of an aluminum fin material (hereinafter, referred to as a fin material) is subjected to a hydrophilic treatment to prevent water droplets and the formation of bridges due to the water droplets.

[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. 55-1)
347, 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. Furthermore, the method of applying water glass of the above (2) shows good hydrophilicity persistence such that the contact angle of water droplets of the fin material-treated plate is 20 ° or less, but the fin material treated with water glass has a powder coating surface over time. And scattered when ventilated, producing 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 so-called after-coat method, in which a fin is formed by molding an aluminum plate, and after assembling this, a surface treatment agent (having a hydrophilic property and a rust inhibitor) is soaked and applied by means such as spraying or showering. There is a so-called pre-coat method in which a surface treatment film is previously formed on an aluminum plate by means of a roll coater or the like, and then the plate is subjected to press molding to form a fin material. In the latter method, when an inorganic component such as silica, water glass, alumina, aluminum hydroxide, calcium carbonate, or titania is mixed in the hydrophilized coating layer, 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] In addition, the press forming method has also been replaced by a more stringent drawless processing method (ironing) from the conventional draw processing method (overhanging and drawing), 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 few problems of poor molding at the time of press molding, but has problems in persistence of hydrophilicity and 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 makes it possible to form a treated film having excellent hydrophilicity persistence, treated film stability and press moldability. However, recently, from the viewpoint of energy saving and improvement in productivity, a coating line has been developed. Shortening the baking time due to the high speed of the baking is being demanded, the above proposed composition, short-time baking, insufficient curability,
There is a problem that sufficient coating film performance cannot be obtained, such as poor adhesion to a substrate. Therefore, the present inventors have intensively studied to obtain a composition for hydrophilization treatment which can solve the above-mentioned problem and can cope with short-time baking by increasing the speed of a coating line. As a result,
It has been found that the above problems can be solved by a composition for hydrophilization treatment in which a water-soluble or water-dispersible polyamide resin, a resin containing a polyoxyalkylene chain, and a specific hydrophilic polymer fine particle are combined, and the present invention. It was completed.

[0015]

That is, the present invention provides:
(A) a water-soluble or water-dispersible polyamide resin,
(B) a water-soluble or water-dispersible resin containing at least one polyoxyalkylene chain of a polyoxyethylene chain and a polyoxypropylene chain in a molecule of 40% by weight or more, and (C) (a) 1 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 the molecule, (b) the following formula (I)

[0016]

Embedded image

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.] 20 to 97% by weight of at least one (meth) acrylamide-based monomer selected from the compounds represented by the following formula: (c) Two or more polymerizable molecules in one molecule A compound having an unsaturated double bond, and 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 unsaturated group in one molecule 1 to 30% by weight of at least one crosslinkable unsaturated monomer selected from compounds having a double bond, (d) 2 to 50% by weight of a carboxyl group-containing polymerizable unsaturated monomer, and (e) one molecule. One Other than the above (a), (b), (c) and (d), having a polymerizable unsaturated group, containing hydrophilic crosslinked polymer fine particles composed of a copolymer of 0 to 50% by weight. It is intended to provide a composition for hydrophilization treatment characterized by the above.

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 having a coating film formed from the composition for hydrophilization treatment as a surface layer.

[0020]

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) The water-soluble or water-dispersible polyamide resin (A) [hereinafter may be abbreviated as "resin (A)"] is not particularly limited as long as it is a water-soluble or water-dispersible amide resin. can do.

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 N-C _1-4 alkyloxymethyl group is introduced. Further, a polyamide resin having water dispersibility by using a dispersing aid such as a surfactant in combination may be used.

As the polyamide resin, for example, 6
-Nylon, 66-Nylon, 6,10-Nylon, 7
-Nylon, 9-nylon, 11-nylon and the like.

The polyamide resin generally has a number average of 3,000 to 200,000, preferably 10,000.
0 to 100,000, more preferably 20,000 to
Preferably it is in the range of 50,000.

Suitable commercial products of the resin (A) include, for example, Tresin FS350, Tresin FS500 (above,
All are water-soluble or water-dispersible nylons manufactured by Teikoku Chemicals Co., Ltd.), AQ nylon P-70, AQ nylon A-90
(All of these are 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.

[0028]

Embedded image

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

(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 alcohol or polyhydric alcohol or phenol which can be used in the above etherification includes
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 which 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, the compound represented by the formula (II) or (III) can be mentioned. Typical examples thereof include Blemmer PME-4000 (manufactured by NOF CORPORATION, methacrylic acid ester having a polyoxyethylene chain), PMA-3
00M (manufactured by Nippon Emulsifier Co., Ltd., methacrylate having a polyoxyethylene chain).

As the other polymerizable unsaturated monomer, any monomer having 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.

Examples of the polybasic acid component to be reacted with the above polyhydric alcohol component include aromatic dicarboxylic acids such as phthalic anhydride, isophthalic acid and terephthalic acid; tetrahydrophthalic anhydride, hexahydrophthalic anhydride, succinic acid and 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 40% by weight of at least one polyoxyalkylene chain of the polyoxyethylene chain and the polyoxypropylene chain in the resin. 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 000, especially 3,000 to 100,000.

Hydrophilic crosslinked polymer fine particles (C): The component (C) in the composition of the present invention comprises the following (a), (b),
It is a hydrophilic crosslinked polymer fine particle comprising a copolymer of the monomers (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 (II):
Compounds represented by (III) or (IV) can be mentioned.

[0044]

Embedded image

[0045] [wherein, R ^5, R ⁶ and R ⁷ are the same or different, each represents a hydrogen atom or a methyl group, R ⁸
Is -OH, -OCH _3, -SO ₃ H or -SO ₃ ^- represents M ^+, wherein M ⁺ is ^{Na +, K +, Li +} , represents NH ₄ ⁺ or an organic ammonium group, n represents 10 to A number of 200 and n expressions

[0046]

Embedded image

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.

[0048]

Embedded image

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

[0050]

Embedded image

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 100
In the above formula (IV), “O,
Specific examples of "a divalent organic group having 5 to 10 carbon atoms which may contain an S or N atom" include a group represented by the following formula.

[0052]

Embedded image

As the monomer (a), from the viewpoint of dispersion stability when a large amount of the monomer (b) is used,
Among them, Formula (II) or (II) wherein n is 50 to 200.
Compounds of I) are preferred.

(Meth) acrylamide monomer
(B): (meth) acrylamide-based monomer (b)
It is at least one compound selected from the compounds represented by the following general formula (I).

[0055]

Embedded image

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 The sum of the number of carbon atoms with ³ is 5 or less.] In the above formula (I), the “alkyl group having 1 to 5 carbon atoms” represented by R ² or R ³ is a straight-chain or Any of branched ones, for example,
Examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, amyl and the like.

Representative examples of the monomer (b) represented by the above general formula (I) 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 crosslinking of the particles, and is a compound having two or more polymerizable double bonds in one molecule; At least one compound selected from a compound 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. Species of compound.

Of the above 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-mentioned 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.

[0061]

Embedded image

Wherein 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): As the carboxyl group-containing polymerizable unsaturated monomer (d), a compound having at least one carboxyl group and one polymerizable unsaturated group in one molecule can be used without particular limitation. Representative examples include acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, monobutyl itaconate, and monobutyl maleate. The monomer (d) is
The carboxyl group contained therein is hydrogen-bonded with the compound (A) having a polyoxyalkylene chain, and contributes to the curability of the composition for hydrophilization treatment of the present invention.

Another monomer (e): a monomer used as needed, having one polymerizable unsaturated group in one molecule, and having the above-mentioned monomers (a), (b), (c) and The monomers (a), (b), which are copolymerizable with (d);
Compounds other than (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.

[0068]

[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, for example, an amino group, is used as the monomer (e) in order to obtain crosslinked polymer fine particles. 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 cross-linked polymer fine particles (C) : The hydrophilic cross-linked polymer fine particles (C) are prepared by using the hydrophilic monomer (a), (meth) acrylamide-based monomer (b), A copolymer formed by dissolving a saturated monomer (c), a carboxyl group-containing polymerizable unsaturated monomer (d) and, if necessary, another monomer (e) in the absence of a dispersion stabilizer, wherein the above monomer is dissolved. Can be produced by polymerizing in a water-miscible organic solvent which does not substantially dissolve 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. For example, it can be as follows.

Hydrophilic monomer (a): 2 to 50% by weight, preferably 2 to 40% by weight, (meth) acrylamide monomer (b): 20 to 97% by weight, preferably 30 to 97% by weight, crosslinkability Unsaturated monomer (c): 1 to 30% by weight, preferably 2 to 20% by weight, carboxyl group-containing polymerizable unsaturated monomer (d): 2 to 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 (C) has a highly hydrophilic polyoxyalkylene chain or polyvinylpyrrolidone chain in the molecule. Since the monomer (a) plays a role of stabilizing the dispersion of the produced polymer, the use of a dispersion stabilizer is not required in the production of the polymer fine particles (B).

In the production of the polymer fine particles (C), a water-miscible organic solvent or a water-miscible organic solvent / water which dissolves the raw material monomer mixture 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. Any water-miscible organic solvent can be used as long as it satisfies the above requirements. In particular, the solubility parameter (SP) generally ranges from 9 to 11, especially from 9.5 to 1,
Those containing at least 50% by weight, especially 70% by weight or more of an organic solvent in the range of 0.7 are preferred from the viewpoint of polymerization stability. The “solubility parameter (SP) value” in the present specification refers to “Journal of Paint Technol”
ogy, Vol. 42, No. 541, 76-118 (February 1970).

Examples of the water-miscible organic solvent having an SP value within the above range include 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 selected from the group consisting of 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 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 the polymerization initiator used and the like.
A temperature in the range of 0 ° C, more preferably 90 to 160 ° C, is appropriate, 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 (C) produced as described above is not particularly limited, but is not limited to the stability of the polymer fine particles (C) and the suppression of generation of aggregates. From the viewpoint, it is generally 0.03 to 1 μm, preferably 0.0
Suitably, it has an average particle size in the range of 5-0.6 μm. The average particle size can be measured by a particle size measuring device, for example, a Coulter model N4MD (manufactured by Coulter).

The polymer fine particles (C) are oriented outward with a polyoxyalkylene chain or a 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.

The polymer fine particles (C) are cross-linked in the particles due to the presence of the monomer (c) component, maintain their form even in an organic solvent type paint, and are easily melted by heating. Instead, when the processing film is formed from the paint, fine irregularities can be formed on the processing film.

Composition for Hydrophilizing Treatment In the composition of the present invention, the mixing ratio of the resin (A), the resin (B) and the polymer fine particles (C) depends on the performance desired for the obtained composition. Although it can be appropriately selected and is not particularly limited, usually, the ratio of component (A) / component (B) is 10/90 to 90/1 in terms of solids weight ratio.
0, and particularly preferably in the range of 20/80 to 70/30, and the ratio of the total of component (A) and component (B) / component (C) is from 10/90 to solid weight ratio. 90/1
0, and particularly preferably in the range of 40/60 to 80/20.

In the composition of the present invention, the components (A), (B) and (C) are components having excellent hydrophilicity, and the amide group of the component (A) and the polyoxy group of the component (B) are used. The alkylene chain and the amide group, polyoxyalkylene chain and carboxyl group of the component (C) are bonded to each other by a hydrogen bond. Above all, the components (A) and (C) have similar solubility parameters, have good compatibility with each other, and are effectively bonded by hydrogen bonding.

The composition of the present invention can form a coating film having excellent continuous film forming property and curability in a short period of time. Strong cohesive force, usually being a high molecular weight resin, the effect of the hydrogen bond, and in a short bake,
It is presumed that the component (A) contributes to better volatility of water as compared to the component (B).

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 that each of (A), (B) and (C) The component is a component having excellent hydrophilicity, the component (C) is a fine particle polymer, and the effect of improving hydrophilicity by forming fine irregularities on the coating film surface. The difference in solubility parameter is large, and the effect of both components gives
It is presumed that this is due to the fact that irregularities more effective for improving the hydrophilicity can be formed.

The composition of the present invention may contain a crosslinking agent as a component (D), if necessary, in order to further improve the water solubility of the treated film obtained from the composition. Good. Examples of the crosslinking agent (D) 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 (E).

The surfactant (E) may be any of anionic, cationic, amphoteric and nonionic surfactants as long as they have a surface wetting action.
Representative examples of the surfactant (E) 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 amount of the surfactant (E) can be usually 20 parts by weight or less based on 100 parts by weight in total of the resin (A), the resin (B), and the polymer fine particles (C), and is preferably. 0.5
It is in the range of 10 to 10 parts by weight, more preferably 1 to 5 parts by weight.

The composition of the present invention may further contain a bactericidal agent as a component (F), if necessary, in order to prevent the generation and propagation of microorganisms. As the antibacterial agent (F), 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) germicidal at a low concentration or capable of inhibiting the growth of bacteria; (4) not to be reduced in efficacy even when blended with paint, and not to impair the stability of paint. (5) not to impair the hydrophilicity and corrosion resistance of the formed film.

The antibacterial agent meeting such conditions can be selected from 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 above antibacterial agent include 2- (4-
Thiazolyl) -benzimidazole, N- (fluorodichloromethylthio) phthalimide, N-dimethyl-N '
-Phenol-N '-(fluorodichloromethylthio)
-Sulfamide, O-phenylphenol, 10,1
0'-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 properties, hydrophilicity of the coating film and the corrosion resistance of the coated plate are not impaired, the resin (A), the resin (B) and the polymer fine particles (C) are added to 100 parts by weight in total. It is preferably 20 parts by weight or less, more preferably 3 to 15 parts by weight.

The composition of the present invention comprises, for example, the resin (A), the resin (B), polymer fine particles (C) and, if necessary, a crosslinking agent (D) and / or a surfactant (E) and / or The antibacterial agent 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 within a range of 3 to 5 μm, particularly 0.5 to 3 μm. Generally, baking has a maximum temperature of about 8
The baking is carried out at a temperature of 0 to about 250 ° C. for a baking time of about 30 minutes to 15 seconds. However, the composition of the present invention can form a good cured coating film under the conditions of 15 to 5 seconds. .

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 or the like, and baking.

[0104]

As described above, according to the composition of the present invention, the curability is excellent even in short-time baking due to an increase in the speed of the coating line, and the hydrophilicity persistence, which has been a conventional problem, has been achieved. (Whole surface wetting property and contact angle with water 20 ° or less), while maintaining continuous moldability (abrasion resistance of mold)
A hydrophilic film having excellent corrosion resistance can be formed on a substrate, and the addition of a bactericidal agent in the composition has the effects of greatly reducing the generation of odor due to mold.

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.

[0106]

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 Crosslinked Polymer Fine Particles Production Example 1 200 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 heated 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).

Blenmer 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.

[0110]

Embedded image

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 at 90 ° C. for 1 hour after the completion of the dropwise addition, 1 part of 2,2′-azobis (2,4-dimethylvaleronitrile) and 1 part of propylene glycol monomethyl ether
0 part of the solution was added dropwise over 1 hour, stirred for 1 hour, and then 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.

[0113]

Embedded image

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.

Blenmer PME-4000 20 parts Acrylamide 50 parts N-methylol acrylamide 15 parts Acrylic acid 10 parts Methylenebisacrylamide 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 ° C. 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 resulting dispersion 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.degree. 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 dispersion obtained is milky white, solid content 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 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.

[0125]

Embedded image

Production of Resin Having Polyoxyalkylene Chain
Concrete Production Example 7 of water was charged 150 parts in a four-necked flask, flaky PEG20000 stirring at 50 ° C. (Sanyo Chemical Industries, Ltd., polyethylene glycol, number average molecular weight 2
0000) was added and dissolved, and the solid content was 40%.
A polyethylene glycol aqueous solution (g) was obtained.

Production Example 8 Production Example 7 was carried out in the same manner as in 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 instead of PEG 20,000, and polyethylene glycol monomethyl having a solid content of 40% was used. An aqueous ether solution (i) was obtained.

Production Example 10 200 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 ° C. 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 further maintained at 140 ° C. for 1 hour to obtain a polymer solution (j). The number average molecular weight of the obtained polymer was about 20,000.

Blemma-PME-4000 60 parts Acrylamide 30 parts 2-hydroxyethyl methacrylate 10 parts 2,2'-azobis (2-methylbutyronitrile) 1.5 parts Propylene glycol monomethyl ether 200 parts Production Example 11 Thermometer The following components were charged into a flask equipped with a stirrer and a water separator.

PEG 400 (polyethylene glycol having a number average molecular weight of about 400) 720 parts Glycerin 18 parts Succinic anhydride 170 parts Then, the contents were heated to 220 ° C. over 4 hours while stirring. After maintaining at 220 ° C. for 2 hours, 4% of toluene was added to the total charged amount to promote the removal of by-product condensed water, and the reaction was advanced. A solvent (propylene glycol monomethyl ether / water = 1/1 (weight ratio)) was added and diluted,
A polyester resin solution (k) having a solid content of about 80% was obtained.
The resulting resin has 81% polyoxyethylene chains.

Production Example 12 (Comparative Example) A polyester resin (l) was obtained in the same manner as in Production Example 11, except that the components charged into the flask were changed to the following components.

PEG 400 160 parts 1,6-hexanediol 165 parts Glycerin 18 parts Succinic anhydride 170 parts The obtained resin had 33% of polyoxyethylene chains.

The resins having a polyoxyalkylene chain obtained in Production Examples 7 to 12 are all water-soluble or water-dispersible resins.

Production Example 13 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-shaped particles were dissolved, the mixture was cooled to obtain a polyamide resin aqueous solution (m).

Production of composition for hydrophilization treatment Example 1 Toresin FS-500 (manufactured by Teikoku Chemical Industry Co., Ltd., water-soluble nylon, indicated as "FS-500" in Table 2)
In an amount of 30 parts as a solid content, and the aqueous solution of polyethylene glycol (g) obtained in Production Example 7 was 40 parts in a solid content.
Parts and the amount of the hydrophilic crosslinked polymer fine particle dispersion (a) obtained in Production Example 1 as a solid content of 30 parts were mixed, and water was added to the composition for hydrophilization treatment at a solid content of 10%. I got something.

Examples 2 to 11 and Comparative Examples 1 to 5 A water-soluble or water-dispersible polyamide resin, a resin solution having a polyoxyalkylene chain obtained in Production Examples, a dispersion of hydrophilic crosslinked polymer fine particles, and if necessary A crosslinking agent,
The same operation as in Example 1 was carried out except that the surfactant and the antibacterial compound were used and mixed so as to obtain the composition shown in Table 2 below, and each of the compositions for hydrophilization treatment having a solid content of 10% was used. Obtained. The compounding amounts in Table 2 are based on the solid content. Further, the types of the cross-linking agent, surfactant and antibacterial compound in Table 2 are as follows.

Crosslinking agent A: trade name “Cymel 370”, manufactured by Mitsui Cytec Co., Ltd., methylated melamine resin.

Crosslinking agent B: trade name “Symel UFR6”
5 ", manufactured by Mitsui Cytec Co., Ltd., methylated urea resin.

Surfactant a: trade name "Newcol 29"
0M ", manufactured by Nippon Emulsifier Co., Ltd., sodium salt of dialkyl sulfosuccinate.

Surfactant b: trade name "Sylwet L-
77 ", manufactured by Nippon Unicar Co., Ltd., an alkylene oxide silane compound.

Bactericidal Compound I: 2- (4-thiazolyl) benzimidazole Comparative Example 6 614 parts of water was charged into a four-necked flask, and the mixture was stirred at 85.degree. Product name “Poval PVA” manufactured by Kuraray Co., Ltd.
-117 ") 100 parts and dissolved to give a solid content of about 1
A 4% aqueous polyvinyl alcohol solution was obtained. An effective amount of Titabond 50 [a titanium chelate solution containing diisopropoxybis (acetylacetonato) titanium (IV) as an active ingredient, manufactured by Nippon Soda Co., Ltd.] is used in an amount of 100 parts of the solid content of the aqueous polyvinyl alcohol solution. The components were mixed in an amount of 5 parts, and water was added to obtain a composition for hydrophilization treatment having a solid content of 10%.

Comparative Example 7 The hydrophilic crosslinked polymer fine particle dispersion (a) obtained in Production Example 1 was added to the amount of 65 parts of the solid content of the aqueous polyvinyl alcohol solution having a solid content of about 14% obtained in Comparative Example 6. In solids
5 parts were added, and further, titabond 50 was mixed in an amount of 5 parts in terms of the active ingredient, and water was added to obtain a composition for hydrophilization treatment having a solid content of 10%.

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, a plate thickness of 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.

[0145] 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. In Table 3, the coated plate to which the composition of Comparative Example 1 was applied had insufficient curability, had a sticky surface, and was not tested for hydrophilicity and corrosion resistance. These results were indicated as (-).

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 ○.

Water-philicity: One cycle of a wet-dry process in which a test coated plate is immersed in running tap water (flowing amount: 15 kg / h per 1 m ² of 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 was wet with water, and there was no unevenness of water even after 10 seconds of pulling.

△: The entire surface is wet immediately after pulling,
10 seconds after lifting, the water has been drawn from the edge to the center of the coated plate.

X: A polka dot is 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 was measured as follows.
After the coated plate is dried at 80 ° C. for 5 minutes, the measurement is performed with a contact angle meter DCAA type manufactured by Kyowa Chemical Industry Co., Ltd. Corrosion resistance: According to JIS-Z-2371 salt spray test method. The test time was 500 hours.

A case where no white rust and blistering occurred was evaluated as good (○).

Those with a little white rust or blistering were judged to be slightly defective (不良).

Further, a test was conducted on the test coated plates of Examples 7 and 9 under the following conditions, and the occurrence of mold on the coated surface after a predetermined time was visually judged. No mold was observed at all.

Antifungal property: A peptone glucose medium is prepared in a sterilized petri dish, a test coated plate is placed thereon, and Cladosporium (Gradosporium) is used as a bacterium to be used.
sp, Penicillum sp, A
ltarnaria (Alternaria) sp, Asper
gillus sp and Trich
A suspension of mixed spores of P. odama (Trichoderma) sp in peptone glucose was sprayed and cultured at a temperature of 26 ± 2 ° C. for 28 days.

[0158]

[Table 2]

[0159]

[Table 3]

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08L 71/02 C08L 71/02 77/00 77/00 C09D 5/00 C09D 5/00 Z 5/14 5/14 7/12 7/12 Z 9/04 9/04 133/24 133/24 155/00 155/00 167/07 167/07 171/00 171/00 B 171/02 171/02 C23C 22/00 C23C 22/00 Z 22/66 22/66 22/74 22/74 F28F 13/18 F28F 13/18 B // C08F 290/06 C08F 290/06

Claims (11)

[Claims] 1. A (A) water-soluble or water-dispersible polyamide resin, and (B) a polyoxyalkylene chain of at least one of a polyoxyethylene chain and a polyoxypropylene chain in a molecule of 40% by weight or more. A water-soluble or water-dispersible resin, and (C) (a) a hydrophilic monomer having at least one polymerizable double bond and a polyoxyalkylene chain or a polyvinylpyrrolidone chain in one molecule.
50% by weight, (b) the following formula (I) 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 The sum of the number of carbon atoms is 5 or less.] 20 to 97% by weight of at least one (meth) acrylamide-based monomer selected from the compounds represented by the following formula: (c) two or more polymerizable unsaturated diamines in one molecule. A compound having a heavy 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 composition for hydrophilic treatment according to claim 1, wherein the polyamide resin (A) has a number average molecular weight of 3,000 to 200,000. 3. The method according to claim 1, wherein the hydrophilic monomer (a) has the following formula (II):
Or (III) [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, —OC
Represents H 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 composition for hydrophilization treatment according to claim 3, wherein n in the formula (II) or (III) is 30 to 200. 5. The hydrophilic crosslinked polymer fine particles (C) 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). 5) 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. 6. The compounding ratio of the polyamide resin (A) and the resin (B) containing a polyoxyalkylene chain is (A)
/ (B) is in the range of 10/90 to 90/10 in terms of the solid content weight ratio, and is the mixing ratio of the total of the resin (A) and the resin (B) and the hydrophilic crosslinked polymer fine particles (C). But (A) +
(B) / (C) solid content weight ratio of 10/90 to 90 /
The composition for hydrophilization treatment according to any one of claims 1 to 5, which is within the range of 10. 7. The composition for hydrophilic treatment according to claim 1, further comprising (D) a crosslinking agent. 8. The composition for hydrophilization treatment according to claim 1, further comprising (E) a surfactant having a wetting action. 9. The composition for hydrophilization treatment according to claim 1, further comprising (F) an antibacterial agent. 10. A method for hydrophilizing a fin material, comprising applying the composition for hydrophilization treatment according to claim 1 to a fin material made of aluminum heat exchanger. 11. 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.