JP2011042842A - Substrate treating agent for aluminum fin material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a substrate treating agent which is excellent in hydrophilicity, and further which has excellent processability, adhesiveness, moisture resistance and corrosion resistance. <P>SOLUTION: The substrate treating agent for an aluminum fin material includes: an acrylic modified epoxy resin (A) formed by making a bisphenol type epoxy resin (a1) with number-average molecular weight of 4,000-30,000 and a carboxyl group-containing acrylic resin (a2) react with each other in the presence of an amine compound; an amino resin (B): and 0.1-50 pts.mass of a rust inhibitor (C) with respect to 100 pts.mass of the total solid content of the acrylic modified epoxy resin (A) and the amino resin (B). <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a surface treatment agent suitable for producing a pollution-free aluminum fin material having excellent hydrophilicity and good workability, adhesion, moisture resistance and corrosion resistance.

  Conventionally, as a fin material for a heat exchanger of an air conditioner, an aluminum-based substrate that is excellent in lightness, workability, thermal conductivity, and the like is generally used. However, in the heat exchanger of the air conditioner, the condensed water generated during cooling becomes water droplets, forming a water bridge between the aluminum fin materials, and the ventilation resistance is increased to narrow the air ventilation path, Problems such as power loss, noise generation, and water droplet splashing may occur.

  As a measure for preventing such a problem, for example, the surface of an aluminum fin material (hereinafter referred to as “fin material”) is subjected to a hydrophilization treatment to prevent water droplets or bridge formation due to water droplets.

  However, a fin material formed with a film made of a conventional hydrophilizing agent corrodes in several months if placed in a strong corrosive environment (for example, a coastal area) because the film has hydrophilicity. There was a thing.

  As a method for solving the above problems, there are many methods in which a surface treatment such as chromate treatment is performed on the surface of an aluminum-based substrate in terms of corrosion resistance and cost. However, the chromate treatment has a problem in its use from the environmental aspect because chromium ions are harmful metal ions.

  On the other hand, in Patent Document 1, a surface treatment agent and a treatment method that do not use chromium ions, such as treatment with an acidic solution containing titanium salt (zirconium salt), hydrogen peroxide, and (condensed) phosphoric acid (derivative). A surface treatment method for aluminum is disclosed.

  In addition, Patent Document 2 discloses a surface treatment method for aluminum in which aluminum is treated with an alkaline aqueous solution containing titanium ions (zirconium ions, iron ions) and a complexing agent, washed with water, and then treated with an acidic aqueous solution such as phosphoric acid. Is disclosed.

Patent Document 3 discloses a surface treatment composition for aluminum containing phosphate ions, titanium compounds, fluorides and accelerators.
In addition, Patent Document 4 discloses a surface treatment composition for aluminum containing (condensed) phosphoric acid (salt), titanium salt (zirconium salt), fluoride, and (hypo) phosphorous acid (salt). Yes.

  The surface treatment compositions as described in Patent Documents 1 to 4 above are chromium-free type surface treatment agents, but as the surface treatment for the hydrophilization treatment, any of workability, adhesion, and corrosion resistance may be inferior. there were.

  Therefore, in the case of Patent Document 5, the applicant of the present invention is formed by forming a film of a base treatment agent on a fin material made of aluminum or an aluminum alloy, and forming a hydrophilic treatment film on the base treatment film. The base treatment agent is (A) at least one titanium compound selected from hydrolyzable titanium compounds, hydrolyzable titanium compound low condensates, titanium hydroxide and titanium hydroxide low condensates, and hydrogen peroxide water. An aqueous liquid containing titanium obtained by reacting bismuth, (B) at least one compound selected from phosphoric acid compounds, metal hydrofluoric acids and metal hydrofluorates, and (C) stable at PH7 or lower A heat-exchanger aluminum fin material subjected to hydrophilization treatment characterized by containing an aqueous organic polymer compound was proposed. However, although the above-mentioned surface treatment agent can secure the hydrophilicity of the fin material, the moisture resistance and corrosion resistance are insufficient, and improvement has been demanded.

JP 54-24232 A JP 54-160527 A Japanese Patent Laid-Open No. 9-20984 Japanese Patent Laid-Open No. 9-143752 JP 2002-275650 A

  The problem to be solved by the invention is to provide an undercoat agent for an aluminum fin material which is excellent in hydrophilicity and has good workability, adhesion, moisture resistance and corrosion resistance.

  The inventors have made an acrylic modified epoxy resin (A) obtained by reacting a bisphenol type epoxy resin (a1) having a number average molecular weight of 4,000 to 30,000 with a carboxyl group-containing acrylic resin (a2) in the presence of an amine compound. ), An amino resin (B), and an aluminum containing 0.1 to 50 parts by mass of a rust inhibitor (C) with respect to 100 parts by mass in total of the solid contents of the acrylic-modified epoxy resin (A) and the amino resin (B). The present inventors have found that a ground treatment agent for a fin material can achieve the solution of the above problems, and have completed the present invention.

That is, the present invention
1. Acrylic modified epoxy resin (A) obtained by reacting a bisphenol type epoxy resin (a1) having a number average molecular weight of 4,000 to 30,000 with a carboxyl group-containing acrylic resin (a2) in the presence of an amine compound, an amino resin ( B), and a base for an aluminum fin material containing 0.1 to 50 parts by mass of a rust inhibitor (C) with respect to 100 parts by mass of the total solid content of the acrylic-modified epoxy resin (A) and amino resin (B) Processing agent,
2. The rust inhibitor (C) peroxidizes at least one titanium compound selected from the group consisting of a hydrolyzable titanium compound, a low condensate of hydrolyzable titanium compound, titanium hydroxide and a low condensate of titanium hydroxide. A titanium-containing aqueous liquid (c1) obtained by mixing with hydrogen water, and an organic phosphoric acid compound (c2) are contained. Further, a metavanadate (c3), a zirconium fluoride (c4), and a zirconium carbonate (c5) The surface treatment agent for aluminum fin materials according to claim 1, comprising at least one selected from
3. The rust inhibitor (C) peroxidizes at least one titanium compound selected from the group consisting of a hydrolyzable titanium compound, a low condensate of hydrolyzable titanium compound, titanium hydroxide and a low condensate of titanium hydroxide. Based on 100 parts by mass of the solid content of the titanium-containing aqueous liquid (c1) obtained by mixing with hydrogen water, 1 to 400 parts by mass of the organic phosphate compound (c2), 1 to 400 parts by mass of the metavanadate (c3), The ground treatment agent for an aluminum fin material according to item 1 or 2, comprising 1 to 400 parts by mass of zirconium fluoride (c4) and 1 to 400 parts by mass of zirconium carbonate (c5),
4). 1 to 1 to 40 parts by mass of at least one polymer component (D) selected from polyglycerin and polyvinyl alcohol with respect to 100 parts by mass of the total solid content of the acrylic-modified epoxy resin (A) and amino resin (B) The surface treatment agent for aluminum fin materials according to any one of items 1 to 3,
5). The surface treatment agent according to any one of items 1 to 4 is coated on a fin material made of aluminum or an aluminum alloy, dried, and dried to have a dry film thickness of 0.05 to 5 g / m ² . The present invention relates to a method for producing an aluminum fin material in which a film is formed, and a hydrophilization treatment composition is applied onto the base film to form a hydrophilization treatment film having a dry film thickness of 0.3 to 5 g / m ^2. .

  Since the surface treatment agent of the present invention does not contain chromium, there is no environmental problem, and the surface treatment agent is coated on the fin material made of aluminum or aluminum alloy, and the surface of the lower layer film is hydrophilic. The multi-layered film obtained by forming the upper layer film can provide an aluminum fin material having excellent hydrophilicity and excellent adhesion to an aluminum base material, workability, moisture resistance and corrosion resistance.

The aluminum fin material using the surface treatment agent of the present invention is formed by coating a surface treatment agent on a fin material made of aluminum or an aluminum alloy to form a surface treatment film, and the hydrophilic treatment composition is formed on the surface film. Is applied to form a hydrophilic treatment film.
The surface treatment agent of the present invention is an acrylic modified epoxy obtained by reacting a bisphenol type epoxy resin (a1) having a number average molecular weight of 4,000 to 30,000 with a carboxyl group-containing acrylic resin (a2) in the presence of an amine compound. It contains a resin (A), an amino resin (B), and a rust inhibitor (C). Details will be described below.

Acrylic modified epoxy resin (A):
The surface treatment agent of the present invention is a specific acrylic-modified epoxy resin (A) described below for the purpose of improving moisture resistance and corrosion resistance, particularly from the viewpoint of workability, adhesion, moisture resistance and corrosion resistance of the resulting coating film. Is used.

  The bisphenol-type epoxy resin (a1) used for the production of the acrylic-modified epoxy resin (A) has a number average molecular weight of 4 from the viewpoints of dispersion stability in an aqueous medium, processability and hygiene of the resulting coating film, and the like. Suitable are those having an epoxy equivalent in the range of 2,000 to 10,000, preferably 2,500 to 10,000, preferably in the range of 5,000 to 30,000, preferably 5,000 to 30,000. Used for.

The bisphenol type epoxy resin (a1) is a resin obtained by a reaction between a polyphenol compound and an epihalohydrin, for example, epichlorohydrin.
Examples of the polyphenol compound include bis (4-hydroxyphenyl) -2,2-propane (bisphenol A), 4,4-dihydroxybenzophenone, bis (4-hydroxyphenyl) methane (bisphenol F), 4,4- Examples include dihydroxydiphenyl sulfone (bisphenol S). Among the bisphenol type epoxy resins (a1), it is preferable to use a bisphenol A type epoxy resin from the viewpoint of corrosion resistance.

The bisphenol A type epoxy resin can be obtained by a polymerization method of bisphenol A and epichlorohydrin. It can also be obtained by a two-stage polymerization method in which bisphenol A is added to a bisphenol A type epoxy resin having a relatively low epoxy equivalent.
The bisphenol A type epoxy resin having a relatively low epoxy equivalent is generally one having an epoxy equivalent of about 160 to about 2,000, and commercially available products thereof include, for example, jER828EL, jER1001, and jER1004 manufactured by Japan Epoxy Resin. , JER1007; Araldite AER250, Araldite AER260, Araldite AER6071, Araldite AER6004, Araldite AER6007, manufactured by Asahi Kasei Epoxy Co., Ltd .; And Adeka Resin EP-5100.

Examples of commercially available bisphenol A type epoxy resins used as the bisphenol type epoxy resin (a1) include jER1010, jER1256B40, and jER1256 manufactured by Japan Epoxy Resin Co., Ltd. The bisphenol A type epoxy resin may be a bisphenol A type modified epoxy resin obtained by modifying a bisphenol A type epoxy resin with a dibasic acid. In this case, as the bisphenol A type epoxy resin to be reacted with the dibasic acid, those having a number average molecular weight of 2,000 to 8,000 and an epoxy equivalent in the range of 1,000 to 4,000 are suitable. Can be used for Examples of the dibasic acid include compounds represented by the general formula HOOC— (CH ₂ ) _n —COOH ( _{where n} represents an integer of 1 to 12), specifically succinic acid, adipic acid, Pimelic acid, azelaic acid, sebacic acid, dodecanedioic acid, hexahydrophthalic acid and the like can be used, and adipic acid can be particularly preferably used.

  The modified bisphenol A type epoxy resin is prepared by reacting a mixture of the bisphenol A type epoxy resin and a dibasic acid in the presence of an esterification catalyst such as tri-n-butylamine or an organic solvent at a reaction temperature of 120 to 180 ° C. And can be obtained by carrying out the reaction for about 1 to 4 hours. In the bisphenol A-modified epoxy resin, the dibasic acid molecular chain introduced into the epoxy resin molecule acts as a plastic component, which is advantageous in improving the processability of the coating film.

  In the present invention, the carboxyl group-containing acrylic resin (a2) (hereinafter abbreviated as “acrylic resin (a2)”) used to produce the acrylic-modified epoxy resin (A) by reacting with the bisphenol-type epoxy resin (a1). Is an acrylic copolymer containing a polymerizable unsaturated carboxylic acid such as acrylic acid, methacrylic acid, maleic acid, itaconic acid and fumaric acid as an essential monomer component.

  The acrylic copolymer has a weight average molecular weight of 5,000 to 100,000, preferably 10,000 to 100,000, and a resin acid value of 150 to 450 mgKOH / g, 200 to 450 mgKOH / g. From the viewpoints of stability in an aqueous medium, processability of the resulting coating film, and adhesion.

  Examples of other monomer components other than the polymerizable unsaturated carboxylic acid used for the polymerization of the acrylic resin (a2) include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n -Butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, benzyl (meth) acrylate, stearyl (meth) acrylate, etc. C1-C22 alkyl ester of acrylic acid or methacrylic acid; cyclohexyl (meth) acrylate, isobornyl (meth) acrylate; aromatic vinyl monomers such as styrene, α-methylstyrene, vinyltoluene; 2-hydroxy Ethyl (meth) acryl , Hydroxyalkyl (meth) acrylates such as hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, hydroxyamyl (meth) acrylate and hydroxyhexyl (meth) acrylate, and hydroxyalkyl such as hydroxyethyl (meth) acrylate ( Hydroxyl group-containing polymerizable unsaturated monomers such as caprolactone-modified alkyl (meth) acrylate having a hydroxyl group obtained by ring-opening addition reaction of 1 to 5 mol of ε-caprolactone with respect to 1 mol of meth) acrylate; acrylamide, meta Acrylamide, N-methoxymethyl (meth) acrylamide, N-ethoxymethyl (meth) acrylamide, Nn-propoxymethyl (meth) acrylamide, N-isopropoxymethyl (meth) acryl Acrylamide monomers such as amide, Nn-butoxymethyl (meth) acrylamide, N-sec-butoxymethyl (meth) acrylamide, N-tert-butoxymethyl (meth) acrylamide; acrylonitrile, methacrylonitrile, vinyl acetate, ethylene And butadiene.

  The acrylic resin (a2) is a monomer mixture of the polymerizable unsaturated carboxylic acid and the other monomer component, for example, in an organic solvent, in the presence of a radical polymerization initiator or a chain transfer agent. And it can obtain by heating and copolymerizing at 80-150 degreeC for 1 to 10 hours.

  As the polymerization initiator, organic peroxides, azos and the like are used, and in the organic peroxides, benzoyl peroxide, t-butylperoxy 2-ethylhexanoate, di-t-butyl peroxide, Examples thereof include t-butyl peroxybenzoate and t-amyl peroxy 2-ethylhexanoate. Examples of azo compounds include azobisisobutyronitrile and azobisdimethylvaleronitrile. Examples of the chain transfer agent include α-methylstyrene dimer and mercaptans.

  In the present invention, the acrylic-modified epoxy resin (A) is obtained by reacting the epoxy resin (a1) with the carboxyl group-containing acrylic resin (a2) in the presence of an amine compound.

  The reaction between the epoxy resin (a1) and the carboxyl group-containing acrylic resin (a2) is a tertiary catalyst such as triethylamine, dimethylethanolamine, triethanolamine, or monomethyldiethanolamine that serves as an esterification catalyst in an organic solvent. An acrylic modified epoxy resin (A) can be obtained by esterifying by heating at 80 to 120 ° C. for 0.5 to 8 hours in the presence of an amine compound.

  The amount of the amine compound used ranges from 1 to 10% by mass based on the total solid content of the epoxy resin (a1) and the carboxyl group-containing acrylic resin (a2), in terms of moisture resistance and corrosion resistance of the resulting film. To preferred.

  The blending ratio of the epoxy resin (a1) and the carboxyl group-containing acrylic resin (a2) in the above reaction may be appropriately selected according to the coating workability and the coating film performance, but the resin (a1) / resin (a2) The solid content is preferably in the range of 10/90 to 95/5, more preferably 60/40 to 90/10.

  The acrylic-modified epoxy resin (A) obtained by the esterification reaction has an acid value of 20 to 120 mgKOH / g, preferably 30 to 100 mgKOH / g, and a weight average molecular weight of 1,000 to 40,000, preferably 2,000 to 15,000 is preferable from the viewpoints of stability in an aqueous medium, processability of the obtained coating film, adhesion, moisture resistance, and corrosion resistance.

  The weight average molecular weight in this specification is a value calculated based on the molecular weight of standard polystyrene from the chromatogram measured by gel permeation chromatograph according to the method described in JIS K 0124-83. As the gel permeation chromatograph, “HLC8120GPC” (manufactured by Tosoh Corporation) was used. As the column, four columns of “TSKgel G-4000HXL”, “TSKgel G-3000HXL”, “TSKgel G-2500HXL”, “TSKgel G-2000HXL” (both manufactured by Tosoh Corporation, trade name) were used, Mobile phase: Tetrahydrofuran, measurement temperature: 40 ° C., flow rate: 1 ml / min, detector: under the conditions of RI.

  The acrylic-modified epoxy resin (A) is neutralized and dispersed in an aqueous medium, and amines and ammonia are preferably used as the neutralizing agent used for neutralization. Representative examples of the amines include triethylamine, triethanolamine, dimethylethanolamine, diethylethanolamine, morpholine, and the like. Of these, triethylamine and dimethylethanolamine are particularly preferred. The neutralization of the acrylic-modified epoxy resin (A) is usually preferably in the range of 0.2 to 2.0 equivalent neutralization with respect to the carboxyl group in the resin.

In the present invention, the amount of quaternary ammonium base formed during the esterification reaction and by neutralization is 3.0 × 10 ⁻⁴ mol / g resin or less, preferably 2.5 × 10 ⁻⁴ mol / g resin or less. It is preferable for moisture resistance and corrosion resistance.

Here, the amount of the quaternary ammonium base is measured by using an indicator solution obtained by dissolving an indicator having a sulfonic acid group and a hydroxyl group as functional groups in a sample solution obtained by dissolving a sample after the start of reaction in a solvent. A first step of a titration reaction in which a titration reaction is performed by dropping, and the indicator reacts with a quaternary ammonium chloride epoxy compound to form an indicator and a carboxylic acid in which both sulfonic acid groups and hydroxyl groups are ionized simultaneously; And plotting the relationship between titration and conductivity for the second step of the titration reaction in which the indicator and the ionization indicator react to form an indicator in which only the sulfonic acid group is ionized, and connecting the plots in the first step from titer in the intersection of the straight line connecting the plots in a straight line and the second step, determine the titer t ₁ in the first stage, the equation (1) Ri obtained quaternary ammonium salt of the sample in terms of solid content in 1g of (mol / g).

Quaternary ammonium salt amount (mol / g) = t ₁ (ml) × 2 × indicator concentration (mol / 1) × (1 / 1,000) × {100 / (sample (g) × solid content (%) ) ・ ・ Expression (1)
The aqueous medium in which the acrylic-modified epoxy resin (A) is dispersed may be water alone or a mixture of water and an organic solvent. Any known organic solvent may be used as long as the stability of the acrylic-modified epoxy resin (A) in the aqueous medium is not impaired.

  As the organic solvent, alcohol solvents, cellosolve solvents, carbitol solvents and the like are preferable. Specific examples of the organic solvent include alcohol solvents such as n-butanol; cellosolv solvents such as ethylene glycol monobutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monomethyl ether, and propylene glycol monomethyl ether; diethylene glycol monoethyl ether and the like. Examples thereof include carbitol solvents.

  Moreover, as an organic solvent, the inert organic solvent which is not mixed with water other than the above can also be used as long as the stability in the aqueous medium of the acrylic-modified epoxy resin (A) is not impaired. For example, aromatic hydrocarbons such as toluene and xylene, esters such as ethyl acetate and butyl acetate, and ketones such as methyl ethyl ketone can be used. The amount of the organic solvent in the ground treatment agent for the aluminum fin material of the present invention is desirably 50% by mass or less, preferably 20% by mass or less in the aqueous medium from the viewpoint of environmental protection.

  In order to neutralize and disperse the acrylic-modified epoxy resin (A) in an aqueous medium, a conventional method may be used. For example, the acrylic-modified epoxy resin (A) is gradually added to an aqueous medium containing a neutralizing agent with stirring. After neutralizing the acrylic-modified epoxy resin (A) with a neutralizing agent, an aqueous medium is added to the neutralized product or the neutralized product is added to the aqueous medium with stirring. The method etc. are mentioned.

Amino resin (B):
Examples of the amino resin (B) used as the cross-linking agent of the ground treatment agent of the present invention include melamine resin, urea resin, and benzoguanamine resin, and melamine resin is preferable from the viewpoint of processability and adhesion.

  As the melamine resin, for example, a part or all of the methylol group of methylolated melamine is a monohydric alcohol having 1 to 8 carbon atoms such as methyl alcohol, ethyl alcohol, n-propyl alcohol, i-propyl alcohol, n-butyl. Examples include partially etherified or fully etherified melamine resins etherified with alcohol, i-butyl alcohol, 2-ethylbutanol, 2-ethylhexanol and the like.

  These may be used in which all methylol groups are etherified or partially etherified so that methylol groups or imino groups remain. Examples include alkyl etherified melamines such as methyl etherified melamine, ethyl etherified melamine, and butyl etherified melamine, and only one kind may be used or two or more kinds may be used in combination. Among these, a methyl etherified melamine resin obtained by methyl etherifying at least a part of methylol groups is preferable.

  Examples of commercially available melamine resins that satisfy such conditions include “Cymel 202”, “Cymel 232”, “Cymel 235”, “Cymel 238”, “Cymel 254”, “Cymel 266”, and “Cymel 267”. , “Cymel 272”, “Cymel 285”, “Cymel 301”, “Cymel 303”, “Cymel 325”, “Cymel 327”, “Cymel 350”, “Cymel 370”, “Cymel 701”, “Cymel 703” “Cymel 736”, “Cymel 738”, “Cymel 771”, “Cymel 1141”, “Cymel 1156”, “Cymel 1158”, etc. (above, made by Nippon Cytec Co., Ltd.), “Uban 120”, “Uban 20HS”, “Uban 2021,” “Uban 2028,” “Uban 2061,” etc. ( On, which is commercially available under the trade name manufactured by Mitsui Chemicals, Inc.), and "Melan 522" and the like (manufactured by Hitachi Chemical Co., Ltd.).

  The blending ratio of the acrylic modified epoxy resin (A) and the amino resin (B) is 85/15 to 50/50, particularly 90 / in the solid content mass ratio of the acrylic modified epoxy resin (A) / amino resin (B). The range of 10-80 / 20 is preferable. If the amount of the amino resin (B) is too small, sufficient curability cannot be obtained, and if it is too large, the workability of the aluminum fin material is lowered, which is not preferable.

Rust preventive (C):
The ground treatment agent for the aluminum fin material of the present invention contains 0.1 to 0.1 parts of the rust inhibitor (C) with respect to 100 parts by mass in total of the solid contents of the acrylic-modified epoxy resin (A) and the amino resin (B). By containing 50 parts by mass, a film having excellent moisture resistance and corrosion resistance can be obtained.
Specifically, the antirust agent (C) contains a titanium-containing aqueous liquid (c1), an organic phosphoric acid compound (c2), metavanadate (c3), zirconium fluoride (c4), and zirconium carbonate. It is advantageous for achieving the object of the present invention to contain at least one metal salt selected from (c5). Hereinafter, each component contained in the rust inhibitor (C) will be described in detail.

Titanium-containing aqueous liquid (c1)
The titanium-containing aqueous liquid (c1) is obtained by reacting at least one titanium compound selected from hydrolyzable titanium, hydrolyzable titanium low condensate, titanium hydroxide and titanium hydroxide low condensate with hydrogen peroxide. It is the aqueous liquid containing titanium obtained by making it.

The hydrolyzable titanium is a titanium compound having a hydrolyzable group directly bonded to titanium, and produces titanium hydroxide by reacting with water such as water or water vapor. In hydrolyzable titanium, all of the groups bonded to titanium may be hydrolyzable groups, or one part thereof may be a hydrolyzed hydroxyl group. The hydrolyzable group is not particularly limited as long as it produces titanium hydroxide by reacting with moisture as described above. For example, a lower alkoxyl group or a group that forms a salt with titanium (for example, Halogen atoms (such as chlorine), hydrogen atoms, sulfate ions, etc.).
Specifically, as the titanium-containing aqueous liquid (c1), a conventionally known titanium-containing aqueous liquid is used without particular limitation as long as it is an aqueous liquid containing titanium obtained by reacting a titanium compound with hydrogen peroxide water. Examples thereof include those according to the following method (1) to method (3).

  Method (1): titanyl ion hydrogen peroxide complex or titanic acid (peroxotitanium hydrate) aqueous solution obtained by adding hydrogen peroxide water to hydrous titanium oxide gel or sol (for example, JP-A 63-35419 and JP-A-1-224220).

  Method (2): A titania film-forming liquid obtained by synthesizing a titanium hydroxide gel produced from an aqueous solution of titanium chloride or titanium sulfate with a basic solution by allowing a hydrogen peroxide solution to act on the gel (for example, Japanese Patent Application Laid-Open (JP-A)). 9-71418 and JP-A-10-67516).

  Method (3): hydrogen peroxide is added to an aqueous solution of an inorganic titanium compound such as titanium chloride or titanium sulfate to form peroxotitanium hydrate, and then the solution obtained by adding a basic substance is left or heated. To form a precipitate of peroxotitanium hydrate polymer. Thereafter, a solution for forming titanium oxide obtained by allowing hydrogen peroxide to act after removing dissolved components other than water derived from at least the titanium-containing raw material solution (for example, JP 2000-247638 and JP 2000-247639).

In particular, as the titanium-containing aqueous liquid (c1) used in the rust preventive agent (C), it is preferable to use a liquid produced by adding a titanium compound to hydrogen peroxide water. As a titanium compound, hydrolysis containing a group represented by the general formula Ti (OR) ₄ (wherein R is the same or different and represents an alkyl group having 1 to 5 carbon atoms) to become a hydroxyl group. It is preferable to use soluble titanium or its hydrolyzable titanium low condensate.

  The mixing ratio of hydrolyzable titanium and / or its low condensate (hereinafter simply referred to as “hydrolyzable titanium c”) and hydrogen peroxide is 10 parts by mass of hydrolyzable titanium c. It is preferably 0.1-100 parts by mass, particularly 1-20 parts by mass in terms of hydrogen peroxide. When the amount is less than 0.1 parts by mass in terms of hydrogen peroxide, chelate formation is not sufficient and white turbid precipitation occurs.

  On the other hand, if it exceeds 100 parts by mass, unreacted hydrogen peroxide tends to remain, and dangerous active oxygen is released during storage, which is not preferable. The hydrogen peroxide concentration of the hydrogen peroxide solution is not particularly limited, but it is preferably in the range of 3 to 30% by mass in terms of ease of handling and the solid content of the product liquid related to coating workability.

  The titanium-containing aqueous liquid (c1) using hydrolyzable titanium c is obtained by reacting hydrolyzable titanium c with hydrogen peroxide within a reaction temperature range of 1 to 70 ° C. for 10 minutes to 20 hours. Can be manufactured.

  The titanium-containing aqueous liquid (c1) using hydrolyzable titanium c is reacted with hydrolyzable titanium c and hydrogen peroxide solution, so that hydrolyzable titanium is hydrolyzed with water to form a hydroxyl group-containing titanium compound. It is assumed that hydrogen peroxide is then coordinated to the generated hydroxyl group-containing titanium compound, and is obtained by this hydrolysis reaction and coordination by hydrogen peroxide occurring near the same time. It produces a chelate solution that is extremely stable and can withstand long-term storage.

  The titanium hydroxide gel used in the conventional production method is partially three-dimensionalized by Ti—O—Ti bonds, and the product obtained by reacting this gel with hydrogen peroxide is essentially different in terms of composition and stability.

  When a titanium-containing aqueous liquid (c1) using hydrolyzable titanium c is subjected to heat treatment or autoclave treatment at 80 ° C. or higher, a titanium oxide dispersion containing ultrafine particles of crystallized titanium oxide is obtained. Below 80 ° C., the crystallization of titanium oxide does not proceed sufficiently. In the titanium oxide dispersion produced in this way, the particle diameter of the titanium oxide ultrafine particles is 10 nm or less, preferably in the range of 1 nm to 6 nm.

  The appearance of the dispersion is translucent. When the particle diameter is larger than 10 nm, the film forming property is deteriorated (breaking occurs at 1 μm or more), which is not preferable. This dispersion can be used as well.

  The titanium-containing aqueous liquid (c1) using hydrolyzable titanium c can form a dense titanium oxide film with excellent adhesion by itself by applying and drying the steel sheet material or by heat treatment at a low temperature. . As the heat treatment temperature, for example, the titanium oxide film is preferably formed at a temperature of 200 ° C. or lower, particularly 150 ° C. or lower.

  The titanium-containing aqueous liquid (c1) using the hydrolyzable titanium c forms an amorphous titanium oxide film containing some hydroxyl groups at the above temperature.

In addition, a titanium oxide dispersion that has been heat-treated at 80 ° C. or higher can form a crystalline titanium oxide film simply by coating, and thus is useful as a coating material for materials that cannot be heat-treated.
As the titanium-containing aqueous liquid (c1) in the rust preventive agent (C), a hydrolyzable titanium and / or hydrolyzable titanium low condensate similar to the above is further reacted with hydrogen peroxide in the presence of a titanium oxide sol. It is also possible to use an aqueous liquid (c11) containing titanium obtained by heating. Examples of the hydrolyzable titanium and / or hydrolyzable titanium low condensate (hydrolyzable titanium c) include a titanium monomer containing a group represented by the general formula Ti (OR) ₄ and hydrolyzed to become a hydroxyl group. The hydrolyzable titanium low condensate can also be used.

  The above-described titanium oxide sol is a sol in which amorphous titania or anatase titania fine particles are dispersed in water (for example, an alcohol-based or alcohol-ether-based aqueous organic solvent may be contained if necessary).

  A conventionally well-known thing can be used as said titanium oxide sol. Examples of the titanium oxide sol include (1) those obtained by hydrolyzing a titanium-containing solution such as titanium sulfate and titanyl sulfate, (2) those obtained by hydrolyzing an organic titanium compound such as titanium alkoxide, 3) Amorphous titania sol in which titanium oxide aggregates such as those obtained by hydrolyzing or neutralizing titanium halide solutions such as titanium tetrachloride are dispersed in water, and anatase titanium fine particles by firing the titanium oxide aggregates It is possible to use a product obtained by dispersing this in water.

  Amorphous titania can be converted into anatase titania by firing at least at a temperature above the crystallization temperature of anatase, for example, at a temperature of 400 ° C. to 500 ° C. or higher. As an aqueous sol of the titanium oxide, for example, TKS-201 (manufactured by Teika Co., Ltd., trade name, anatase crystal form, average particle diameter 6 nm), TA-15 (manufactured by Nissan Chemical Co., Ltd., trade name, Anatase type crystal form), STS-11 (Ishihara Sangyo Co., Ltd., trade name, anatase type crystal form) and the like.

  The weight ratio of the titanium oxide sol to the titanium hydrogen peroxide reactant when used for reacting hydrolyzable titanium c with aqueous hydrogen peroxide is 1/99 to 99/1, preferably about 10/90 to The range is 90/10. If the weight ratio is less than 1/99, the effect of adding titanium oxide sol is not seen in stability and photoreactivity, and if it exceeds 99/1, the film forming property is inferior.

  The mixing ratio of the hydrolyzable titanium c and the hydrogen peroxide solution is 0.1 to 100 parts by mass, particularly 1 to 20 parts by mass in terms of hydrogen peroxide with respect to 10 parts by mass of the hydrolyzable titanium a. preferable. When the amount is less than 0.1 parts by mass in terms of hydrogen peroxide, chelate formation is not sufficient and white turbid precipitation occurs. On the other hand, if it exceeds 100 parts by mass, unreacted hydrogen peroxide tends to remain, and dangerous active oxygen is released during storage, which is not preferable. The hydrogen peroxide concentration of the hydrogen peroxide solution is not particularly limited, but it is preferably in the range of 3 to 30% by mass in terms of ease of handling and the solid content of the product liquid related to coating workability.

  The aqueous liquid (c11) can be produced by reacting hydrolyzable titanium c with hydrogen peroxide within a reaction temperature range of 1 to 70 ° C. for 10 minutes to 20 hours in the presence of titanium oxide sol.

  In the aqueous liquid (c11), hydrolyzable titanium c was hydrolyzed with water by reacting hydrolyzable titanium c with aqueous hydrogen peroxide to produce a hydroxyl group-containing titanium compound, and then hydrogen peroxide was produced. It is presumed that it coordinates to a hydroxyl group-containing titanium compound, and it was obtained by this hydrolysis reaction and coordination by hydrogen peroxide occurring at the same time. It is extremely stable at room temperature and can be stored for a long time. Produces a chelating solution that can withstand.

  The titanium hydroxide gel used in the conventional production method is partially three-dimensionalized by Ti—O—Ti bond, and the product obtained by reacting this gel with hydrogen peroxide is essentially different in terms of composition and stability. In addition, by using a titanium oxide sol, it is possible to prevent thickening due to partial condensation reaction during synthesis. The reason is considered to be that the condensation reaction product is adsorbed on the surface of the titanium oxide sol and prevents polymerization in the solution state.

  Other pigments and sols can be added and dispersed in the titanium-containing aqueous liquid (c1) as necessary. Examples of the additive include commercially available titanium oxide sol and titanium oxide powder, mica, talc, silica, barita, clay, and the like.

Organophosphate compound (c2)
The organic phosphate compound (c2) is, for example, a hydroxyl group such as 1-hydroxymethane-1,1-diphosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid, 1-hydroxypropane-1,1-diphosphonic acid, etc. Suitable organic phosphorous acid: carboxyl group-containing organic phosphorous acid such as 2-hydroxyphosphonoacetic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, and salts thereof are preferable.

  The organic phosphoric acid compound (c2) has an effect of improving the storage stability of the titanium-containing aqueous liquid (c1). Among them, 1-hydroxyethane-1,1-diphosphonic acid is particularly preferable.

  The addition amount of the organic phosphoric acid compound (c2) is 1 to 400 parts by weight, particularly 20 to 300 parts by weight based on 100 parts by weight of the solid content of the titanium-containing aqueous liquid (c1). It is preferable from the point.

Metavanadate (c3)
Examples of the metavanadate (c3) include lithium metavanadate, potassium metavanadate, sodium metavanadate, and ammonium metavanadate. Among them, ammonium metavanadate is particularly preferable from the viewpoint of corrosion resistance. The addition amount of metavanadate (c3) is preferably 1 to 400 parts by mass, particularly 10 to 400 parts by mass based on 100 parts by mass of the solid content of the titanium-containing aqueous liquid (c1), from the viewpoint of corrosion resistance and the like. .

Zirconium fluoride (c4)
Examples of the zirconium fluoride salt (c4) include salts of zirconium hydrofluoric acid such as sodium, potassium, lithium, and ammonium. Among them, zirconium ammonium fluoride is preferable from the viewpoint of water adhesion resistance. Zirconium fluoride (c4) is added in an amount of 1 to 400 parts by weight, particularly 20 to 400 parts by weight based on 100 parts by weight of the solid content of the titanium-containing aqueous liquid (c1). preferable.

Zirconium carbonate (c5)
Examples of the zirconium carbonate salt (c5) include salts of zirconium carbonate such as sodium, potassium, lithium, and ammonium. Among them, ammonium zirconium carbonate is preferable from the viewpoint of water-resistant adhesion. The addition amount of the zirconium carbonate salt (c5) is preferably 1 to 400 parts by mass, particularly 10 to 400 parts by mass based on 100 parts by mass of the solid content of the titanium-containing aqueous liquid (c1), from the viewpoint of corrosion resistance.

  The compounding ratio of the rust preventive agent (C) in the ground treatment agent of the present invention is 0.1 to 50 parts by mass with respect to 100 parts by mass in total of the solid content in the acrylic-modified epoxy resin (A) and amino resin (B), Preferably 1-30 mass parts, More preferably, 10-20 mass parts is preferable for improving the moisture resistance and corrosion resistance of the obtained coating film.

  In addition to the acrylic-modified epoxy resin (A), amino resin (B), and rust preventive agent (C), the surface treatment agent of the present invention is used for the purpose of improving the hydrophilicity and adhesion of the hydrophilic treatment film as necessary. At least one polymer component (D) selected from polyglycerin and polyvinyl alcohol can be blended.

At least one polymer component (D) selected from polyglycerin and polyvinyl alcohol:
At least one polymer component (D) selected from polyglycerin and polyvinyl alcohol (hereinafter may be abbreviated as “polymer component (D)”) is at least one selected from polyglycerin and polyvinyl alcohol.

  Polyglycerin is a polyether product of glycerin and generally has a number average molecular weight of 200 to 30,000, preferably 300 to 3,000. It is preferable from the viewpoint of adhesion to the upper layer film by the hydrophilic treatment agent and hydrophilicity.

  Polyvinyl alcohol plays a role as a film-forming component and has a large amount of secondary hydroxyl groups in the molecule, so it has a high affinity with water. Furthermore, the interaction between this hydroxyl group and other components makes it water resistant. It exhibits the effect of maintaining hydrophilic durability. The polyvinyl alcohol is a polyvinyl alcohol having a saponification degree of 87% or more, preferably a so-called completely saponified polyvinyl alcohol having a saponification degree of 98% or more, and having a number average molecular weight of 3,000 to 100,000. It is preferable to be within the range.

  Completely saponified polyvinyl alcohol has a low solubility in water at room temperature, and exhibits desirable properties as a film material for a heat exchanger fin material used at room temperature or lower. As the polyvinyl alcohol, a modified polyvinyl alcohol reacted with another organic compound (for example, a copolymer such as acrylamide, unsaturated carboxylic acid, sulfonic acid monomer, cationic monomer or unsaturated silane monomer) can be used.

  The blending amount of the polymer component (D) in the surface treatment agent of the present invention is 1 to 40 parts by mass, preferably 1 with respect to 100 parts by mass of the total solid content in the acrylic-modified epoxy resin (A) and amino resin (B). -25 mass parts, More preferably, 5-20 mass parts is preferable for the adhesiveness and hydrophilic property of the lower layer film | membrane by the surface treating agent of this invention, and the upper layer film | membrane by a hydrophilizing treatment agent.

  Furthermore, the surface treatment agent of the present invention includes antibacterial agents such as 2- (4-thiazolyl) benzimidazole, bis (dimethylthiocarbamoyl) disulfide, and zeolite (aluminosilicate) as necessary; tannic acid, phytin Corrosion inhibitors such as acid and benzotriazole; Oxygen acid salt compounds such as molybdenum, zinc, nickel, cobalt, copper, and iron; Pigments such as colored pigments, extender pigments and rust preventive pigments, and ordinary paints such as waxes and leveling agents Various additives used in can be contained. In particular, it can be confirmed that a base coating is formed on the fin material made of aluminum or aluminum alloy by containing a color pigment.

  Next, in the present invention, a hydrophilic treatment composition is coated on the base film to form a hydrophilic treatment film, the base treatment agent is used as a lower layer film, and the hydrophilic treatment composition is coated on the film. An aluminum fin material having an upper film is produced.

Hydrophilic treatment composition The upper layer film made of the hydrophilic treatment composition has a hydrophilic surface, sufficient film strength, and good workability, adhesion and water resistance. As a hydrophilic treatment agent used for forming such a hydrophilic film, for example, a material containing a hydrophilic film-forming binder can be suitably used.

  As typical examples of the binder used in the above-mentioned hydrophilic treatment composition, (1) an organic resin binder comprising a hydrophilic organic resin as a main component and a crosslinking agent as required; (2) a hydrophilic organic resin And a colloidal silica-based binder comprising a colloidal silica as a main component and, if necessary, a cross-linking agent; (3) a water glass binder that is a mixture of the main component alkali silicate and a nonionic aqueous organic resin Etc. Among these, organic resin binder (1) and organic resin and colloidal silica binder (2) are preferable from the viewpoint of hydrophilicity and corrosion resistance.

  The hydrophilic organic resin in the organic resin binder (1) contains a hydroxyl group, a carboxyl group, or an amino group in the molecule, and is neutralized with an acid or a base as it is or depending on the functional group. Examples thereof include resins that can be dispersed in water. Specific examples of the hydrophilic organic resin include, for example, polyvinyl alcohol, modified polyvinyl alcohol (for example, a copolymer with acrylamide, unsaturated carboxylic acid, sulfonic acid monomer, cationic monomer, unsaturated silane monomer, etc.), polyacrylic Synthetic hydrophilic resins such as acid, polyethylene glycol, carboxyl group-containing acrylic resin, carboxyl group-containing polyester resin, adduct of epoxy resin and amine, copolymer of ethylene and acrylic acid, starch, cellulose, algin, etc. Natural polysaccharides; oxidized starch, dextrin, propylene glycol alginate, carboxymethyl starch, carboxymethylcellulose, hydroxymethyl starch, hydroxymethylcellulose, hydroxyethylcellulose, etc. Mention may be made of the polysaccharide derivatives.

  Examples of the crosslinking agent used as necessary in the organic resin binder (1) include melamine resin, urea resin, phenol resin, blocked polyisocyanate compound, metal chelate compound and the like. In general, the crosslinking agent preferably has water solubility or water dispersibility.

Specific examples of the crosslinking agent include, for example, methyl etherified melamine resin, butyl etherified melamine resin, methyl / butyl mixed etherified melamine resin, methyl etherified urea resin, methyl etherified benzoguanamine resin, polyphenols or aliphatic polyhydric alcohol. Di- or polyglycidyl ether, amine-modified epoxy resin, blocked product of hexamethylene diisocyanate triisocyanurate; metal chelate compound of metal element such as titanium (Ti), zirconium (Zr), aluminum (Al), etc. be able to. The metal chelate compound preferably has at least two or more metal alkoxide bonds in one molecule.

  As the hydrophilic organic resin in the organic resin / colloidal silica binder (2), the same hydrophilic organic resin as in the organic resin binder (1) can be used. The colloidal silica in the binder (2) is a so-called silica sol or finely divided silica, usually having a particle size of about 5 nm to 10 μm, preferably 5 nm to 1 μm, and usually supplied as an aqueous dispersion. Use as it is or use finely divided silica dispersed in water.

  In the organic resin and the colloidal silica-based binder (2), the organic resin and the colloidal silica may be simply mixed, or the organic resin and the colloidal silica are reacted and compounded in the presence of alkoxysilane. It may be.

  As the aqueous organic resin in the water glass-based binder (3), among the hydrophilic organic resins in the organic resin-based binder (1), an anionic or nonionic organic resin can be used.

  The hydrophilic film-forming binder can be dissolved or dispersed in an aqueous medium. This aqueous medium means water or a mixture of water and an organic solvent mainly composed of water. The hydrophilization treatment agent may consist only of an aqueous solution or aqueous dispersion of a hydrophilic film-forming binder, but if necessary, a surfactant for improving the hydrophilicity of the coating film; improving the hydrophilicity Hydrophilic polymer fine particles (usually within an average particle size of 0.03 to 1 μm, preferably 0.05 to 0.6 μm); 2- (4-thiazolyl) benzimidazole, bis (dimethylthio Antibacterial agents such as carbamoyl) disulfide and zeolite (aluminosilicate); anticorrosive agents such as tannic acid, phytic acid and benzotriazole; oxyacid salt compounds such as molybdenum, vanadium, zinc, nickel, cobalt, copper and iron; Various additives used in ordinary paints such as pigments such as coloring pigments, extender pigments and rust preventive pigments, waxes and leveling agents can be contained. Next, the manufacturing method of the hydrophilic treatment aluminum plate of this invention is demonstrated in detail.

Method for Producing Hydrophilized Aluminum Plate The method for producing a hydrophilized aluminum plate is to coat the surface treatment agent of the present invention on the surface of the fin material made of aluminum or aluminum alloy, and after drying to form a lower layer film, A hydrophilic treatment agent is applied to the surface of the lower layer film and dried to form a hydrophilic upper layer film.

  As the fin material made of aluminum or aluminum alloy as the base material, conventionally known ones that can be used as the base material of the heat exchanger aluminum fin material can be used. A material obtained by degreasing, washing with water and drying by a conventionally known method can be preferably used.

  A lower layer film can be formed by coating and drying the surface treatment agent on the aluminum-based substrate. The surface treatment agent is a coating method known per se, such as dip coating, shower coating, spray coating, roll, on an aluminum-based substrate (which may be assembled in a heat exchanger) as a substrate. It can be painted by painting or electrodeposition. The drying condition of the base treatment agent is usually preferably 2 to 30 minutes under the condition that the material reaching maximum temperature is 60 to 250 ° C.

Also, usually, 0.05-5 g / ^{m 2,} is particularly from 0.1 to 3 g / ^{m 2} preferably has a dry film thickness of the ground processing material. When less than 0.05 g / ^{m 2,} corrosion resistance, poor performance such as water resistance, whereas when it exceeds 5 g / ^{m 2,} because such hydrophilic or cracking undercoat poor undesirably.

  On the aluminum-based substrate (which may be assembled in a heat exchanger) provided with the base film, the hydrophilizing agent is applied by a coating method known per se, for example, dip coating, shower coating, It is possible to produce a hydrophilized aluminum plate by painting by spray coating, roll coating, electrodeposition coating, etc., and baking and drying.

The thickness of the hydrophilic treatment film formed from the hydrophilic treatment agent is not particularly limited, but is usually 0.3 to 5 g / m ² , preferably 0. It exists in the range of 5-3 g / m < ² >. Moreover, although the hardening conditions of a hydrophilic treatment agent can be suitably set according to a binder seed | species, a film thickness, etc., it is normally baked for 5 seconds-30 minutes on the conditions that a raw material reach | attainment maximum temperature will be about 80-250 degreeC. Is preferred.

  Hereinafter, the present invention will be described in more detail with reference to Production Examples, Examples, and Comparative Examples, but the present invention is not limited thereto. In the examples, “parts” represents parts by mass, and “%” represents mass%.

Production Example 1 Carboxyl group-containing acrylic resin 1 Preparation of Solution 850 parts of n-butanol was heated to 100 ° C. under a nitrogen stream, and the monomer mixture and polymerization initiator “450 parts of methacrylic acid, 450 parts of styrene, 100 parts of ethyl acrylate, t-butylperoxy-2” -40 parts of ethylhexanoate "was added dropwise over 3 hours, and the mixture was aged for 1 hour after the addition. Next, a mixed solution of 10 parts of t-butylperoxy-2-ethylhexanoate and 100 parts of n-butanol was added dropwise over 30 minutes, followed by aging for 2 hours. Subsequently, 933 parts of n-butanol and 400 parts of ethylene glycol monobutyl ether were added, and carboxyl group-containing acrylic resin No. 1 having a solid content of about 30% was added. 1 was obtained. The obtained resin had a resin acid value of 300 mgKOH / g and a weight average molecular weight of about 17,000.

Production Example 2 Carboxyl group-containing acrylic resin 2. Preparation of solution 1,400 parts of n-butanol were heated to 100 ° C. under a nitrogen stream, and the monomer mixture and the polymerization initiators “670 parts of methacrylic acid, 250 parts of styrene, 80 parts of ethyl acrylate, t-butylperoxy” 2-ethylhexanoate 50 parts "was added dropwise in 3 hours, and the mixture was aged for 1 hour. Next, a mixed solution of 10 parts of t-butylperoxy-2-ethylhexanoate and 100 parts of n-butanol was added dropwise over 30 minutes, followed by aging for 2 hours. Subsequently, 373 parts of n-butanol and 400 parts of ethylene glycol monobutyl ether were added, and a carboxyl group-containing acrylic resin No. 1 having a solid content of about 30% was added. 2 was obtained. The obtained resin had a resin acid value of 450 mg KOH / g and a weight average molecular weight of about 14,000.

Production and Production Example 3 of Acrylic Modified Epoxy Resin (A) 1
jER828EL (manufactured by Japan Epoxy Resin Co., Ltd., epoxy resin, epoxy equivalent of about 190, number average molecular weight of about 380) 513 parts, bisphenol A 287 parts, tetramethylammonium chloride 0.3 parts and methyl isobutyl ketone 89 parts, nitrogen stream The resultant was heated to 140 ° C. and reacted for about 4 hours to obtain an epoxy resin solution. The resulting epoxy resin had an epoxy equivalent of 3,700 and a number average molecular weight of about 1,7000.
Subsequently, carboxyl group-containing acrylic resin No. 30 having a solid content of about 30% obtained in Production Example 1 was added to the obtained epoxy resin solution. 1 was charged in 667 parts and heated to 90 ° C. to dissolve uniformly, then 40 parts of deionized water was added dropwise at the same temperature over 30 minutes, then 30 parts of dimethylethanolamine was added and stirred for 1 hour. Reaction was performed.
Further, 2380 parts of deionized water was added over 1 hour to obtain an acrylic modified epoxy resin No. having a solid content of about 25%. 1 aqueous dispersion was obtained. The obtained resin had a resin acid value of 48 mgKOH / g and a quaternary ammonium salt amount (according to the conductivity titration method in the specification) of 1.2 × 10 ⁻⁴ mol / g.

Production Example 4 Acrylic modified epoxy resin no. 2
jER828EL (manufactured by Japan Epoxy Resin Co., Ltd., epoxy resin, epoxy equivalent of about 190, number average molecular weight of about 380) 519 parts, bisphenol A 281 parts, tetramethylammonium chloride 0.3 parts and methyl isobutyl ketone 89 parts, nitrogen stream The resultant was heated to 140 ° C. and reacted for about 4 hours to obtain an epoxy resin solution. The resulting epoxy resin had an epoxy equivalent of 2,800 and a number average molecular weight of about 12,000.
Subsequently, carboxyl group-containing acrylic resin No. 30 having a solid content of about 30% obtained in Production Example 2 was added to the obtained epoxy resin solution. No. 2 was charged in 667 parts and heated to 90 ° C. to dissolve uniformly, then 40 parts of deionized water was added dropwise at the same temperature over 30 minutes, and then 53 parts of dimethylethanolamine was added and stirred for 1 hour. Reaction was performed. Further, 2,350 parts of deionized water was added over 1 hour to obtain an acrylic modified epoxy resin No. 1 having a solid content of about 25%. An aqueous dispersion of 2 was obtained. The obtained resin had a resin acid value of 75 mgKOH / g and a quaternary ammonium salt amount (result of conductivity titration) of 1.8 × 10 ⁻⁴ mol / g.

Production Example 5 Acrylic resin no. 1 Production of aqueous solution (for comparative example)
80 parts of polyacrylic acid “AC10LP” (manufactured by Nippon Pure Chemicals Co., Ltd., polyacrylic acid, weight average molecular weight 25,000, acid value 779 mg KOH / g) is dissolved in 535 parts of water and acrylic resin No. 13% solid content . 1 aqueous solution was obtained.

Production Example 6 Acrylic resin no. 2Production of aqueous solution (for comparative example)
A four-necked flask equipped with a reflux tube, a thermometer, a dropping funnel, and a stirrer is charged with 406 parts of ethylene glycol monobutyl ether, heated and held at 100 ° C. under a nitrogen stream, 196 parts of acrylic acid, 2-hydroxyethyl acrylate A mixture of 49 parts, 35 parts of ethylene glycol monobutyl ether and 14 parts of 2,2′-azobisisobutyronitrile was added dropwise from the dropping funnel over 3 hours. After the addition, stirring was continued at the same temperature for 2 hours. Then, the mixture was cooled to obtain an acrylic resin solution having a solid content of 35%. The obtained resin (solid content) had an acid value of 623 mgKOH / g and a weight average molecular weight of 25,000. Water was gradually added to the obtained 35% acrylic resin solution and stirred to obtain an acrylic resin No. 13 having a solid content of 13%. Two aqueous solutions were obtained.

Production and production example 7 of rust inhibitor (C)
Ammonia water (1: 9) was added dropwise to a solution in which 5 ml of a titanium tetrachloride 60% solution was made 500 ml with distilled water to precipitate titanium hydroxide. After washing with distilled water, 10 ml of a 30% hydrogen peroxide solution was added and mixed to obtain a yellow translucent viscous titanium-based aqueous liquid T1 containing titanium.

Production Example 8
A mixture of 10 parts of tetraiso-propoxytitanium and 10 parts of iso-propanol was dropped into a mixture of 10 parts of 30% hydrogen peroxide and 100 parts of deionized water at 20 ° C. with stirring for 1 hour. Thereafter, aging was carried out at 25 ° C. for 2 hours to obtain a yellow transparent and slightly viscous titanium-based aqueous liquid T2.

Production Example 9
In Production Example 8, production was carried out under the same production conditions as in Production Example 8 except that tetra-n-butoxytitanium was used instead of tetraiso-propoxytitanium to obtain a titanium-based aqueous liquid T3. Production Examples 10-15
The blending contents shown in Table 1 below were adjusted to a solid content with deionized water, and each rust inhibitor No. 1-No. 6 was obtained.

Production and Production Example 16 of Polymer Component (D) Polyvinyl alcohol No. 16 1 Preparation of aqueous solution Denkapoval K-05 (manufactured by Denki Kagaku Kogyo Co., Ltd., saponification degree 99%, polymerization degree 550) was dissolved in water and polyvinyl alcohol No. 14 having a solid content of 14%. 1 aqueous solution was obtained.

Production Example 17 Polyvinyl alcohol No. 2 Preparation of aqueous solution Denkapoval B-05 (manufactured by Denki Kagaku Kogyo Co., Ltd., saponification degree 88%, polymerization degree 550) was dissolved in water, and polyvinyl alcohol No. 14 having a solid content of 14% was dissolved. Two aqueous solutions were obtained.

Production Examples 1 to 15 of Ground Treatment Agent
Each component was sufficiently mixed with a stirrer according to the formulation shown in Table 2 and Table 3 below, and deionized water was added to adjust the solid content, thereby preparing a base treatment agent No. 1 having a solid content of 10%. 1-No. 15 was created.

比較例１〜９
下記表４に示す配合に従って配合して、各成分を攪拌機で十分に混合し、脱イオン水を加えて固形分を調整して固形分１０％の下地処理剤Ｎｏ．１６〜Ｎｏ．２４を作成した。

Comparative Examples 1-9
Blended according to the formulation shown in Table 4 below, each component was thoroughly mixed with a stirrer, deionized water was added to adjust the solid content, and a surface treatment agent No. 10 having a solid content of 10% was prepared. 16-No. 24 was created.

(Note 1) Cymel 350: manufactured by Nippon Cytec Industries, trade name, methyl etherified melamine resin, solid content 100%.
(Note 2) Cymel 370: manufactured by Nippon Cytec Industries, trade name, methyl etherified melamine resin, solid content 82%.
(Note 3) Polyglycerin # 750: manufactured by Sakamoto Pharmaceutical Co., Ltd., trade name, polyglycerin mainly composed of decaglycerin, hydroxyl value of about 900 mg KOH / g, solid content of 100% by mass.

Production and performance evaluation of hydrophilized aluminum plate Example 16
No treatment with a thickness of 0.11 mm. A 1000 series aluminum plate is degreased, washed with water and dried, and then each of the above surface treatment agents is applied to the surface so that the dry film mass becomes 1.0 g / m ^2, and then the material maximum temperature (PMT) reaches 100 ° C. Then, the film was baked and dried for 10 seconds to obtain an undercoat.
After applying the hydrophilizing agent shown in Table 5 on the base film so that the dry film mass is 1.2 g / m ² , baking is performed for 10 seconds so that the maximum material temperature (PMT) is 220 ° C. Hydrophilized aluminum plate No. 1 was obtained.

Examples 17-34
Tables 5 to 6 show examples of the combination of the base film and the hydrophilic treatment agent and the performance results.

Hydrophilic treatment agent (Note 4) Treatment agent A: Cosmer 9600, trade name, manufactured by Kansai Paint Co., Ltd., a hydrophilization treatment agent mainly composed of highly oxidized acrylic resin and polyvinyl alcohol.

  (Note 5) Treatment agent B: Cosmer 9400, trade name, manufactured by Kansai Paint Co., Ltd., a hydrophilization treatment agent mainly composed of polyoxyalkylene glycol and hydrophilic crosslinked polymer fine particles.

  (Note 6) Treatment agent C: Cosmer 1310, trade name, manufactured by Kansai Paint Co., Ltd., a hydrophilic treatment agent mainly comprising a hydrophilic organic resin and colloidal silica.

Comparative Examples 8-18
Table 7 shows a comparative example in the combination of the base film and the hydrophilizing agent and the performance results.

Hydrophilized aluminum plate No. 31
Comparative Example 19
A hydrophilization treatment agent A is applied onto a phosphate chromate treatment aluminum plate, and the hydrophilization treatment aluminum plate No. 1 is applied. 31 was created.

Evaluation method (Note 7) Coating film adhesion: Cut the coating film on each test plate with a cutter so that it reaches the base, make 100 1mm x 1mm size gobangs, and apply adhesive tape to the surface. The remaining number of Gobang eyes coatings after the tape was peeled off rapidly at 20 ° C. was examined.

(Note 8) Corrosion resistance: After each test plate is cut to a size of 70 mm x 150 mm, the end face is sealed, the test is conducted for 240 hours in accordance with the JIS Z-2371 salt spray test method, and then each test piece is corroded. Was evaluated according to the following criteria.
○: Corrosion occurrence area is less than 5%.
Δ: Corrosion occurrence area of 5% or more and less than 20%.
X: Corrosion generation area 20% or more.

(Note 9) Moisture resistance: Each test plate was allowed to stand in an environment with a temperature of 50 ° C. and a relative humidity of 95% for 10 days, and then the degree of discoloration of the coating film was evaluated according to the following criteria.
○: Discoloration is less than 5% of the area of the flat surface.
Δ: Discolored at 5% or more and less than 80% of the area of the plane part.
X: Discolored at 80% or more of the area of the plane part.

(Note 10) Hydrophilicity: 0.03 cc of deionized water was dropped onto the coated surface of each test plate with a syringe to form water droplets, and the contact angle of the water droplets was measured with a Kyowa Chemical Co., Ltd. CA-X150 type measuring instrument. Measured.
○: The contact angle is less than 20 °.
Δ: The contact angle is 20 ° or more and less than 40 °.
X: A contact angle is 40 degrees or more.

(Note 11) Color tone sustainability: The change in color tone of each test plate before and after being immersed in running tap water for 72 hours was visually evaluated according to the following criteria.
○: Almost no color change is observed.
Δ: Color change is slightly recognized.
X: The color change is remarkable.

  Fin materials for heat exchangers such as condensers, radiators, evaporators and the like having excellent hydrophilicity and good workability, adhesion, moisture resistance and corrosion resistance can be obtained.

Claims (5)

Acrylic modified epoxy resin (A) obtained by reacting a bisphenol type epoxy resin (a1) having a number average molecular weight of 4,000 to 30,000 with a carboxyl group-containing acrylic resin (a2) in the presence of an amine compound, an amino resin ( B), and a base for an aluminum fin material containing 0.1 to 50 parts by mass of a rust inhibitor (C) with respect to 100 parts by mass of the total solid content of the acrylic-modified epoxy resin (A) and amino resin (B) Processing agent. The rust inhibitor (C) peroxidizes at least one titanium compound selected from the group consisting of a hydrolyzable titanium compound, a low condensate of hydrolyzable titanium compound, titanium hydroxide and a low condensate of titanium hydroxide. A titanium-containing aqueous liquid (c1) obtained by mixing with hydrogen water, and an organic phosphoric acid compound (c2) are contained. Further, a metavanadate (c3), a zirconium fluoride (c4), and a zirconium carbonate (c5) The surface treatment agent for an aluminum fin material according to claim 1, comprising at least one selected from the group consisting of: The rust inhibitor (C) peroxidizes at least one titanium compound selected from the group consisting of a hydrolyzable titanium compound, a low condensate of hydrolyzable titanium compound, titanium hydroxide and a low condensate of titanium hydroxide. Based on 100 parts by mass of the solid content of the titanium-containing aqueous liquid (c1) obtained by mixing with hydrogen water, 1 to 400 parts by mass of the organic phosphate compound (c2), 1 to 400 parts by mass of the metavanadate (c3), The ground treatment agent for an aluminum fin material according to claim 1 or 2, comprising 1 to 400 parts by mass of zirconium fluoride (c4) and 1 to 400 parts by mass of zirconium carbonate (c5). Claims containing 1 to 40 parts by mass of at least one polymer component (D) selected from polyglycerin and polyvinyl alcohol with respect to 100 parts by mass of the total solid content of the acrylic-modified epoxy resin (A) and amino resin (B). Item 4. A ground treatment agent for an aluminum fin material according to any one of Items 1 to 3. A ground treatment agent according to any one of claims 1 to 4 is applied onto a fin material made of aluminum or an aluminum alloy, and dried to have a dry film thickness of 0.05 to 5 g / m ² . forming a coating on the lower ground film, manufacturing method of an aluminum fin stock hydrophilized coating 0.3 to 5 g / m ² on a dry film thickness was applied to a hydrophilic treatment composition is formed.