JPH10101986A - Fin coating composition improved in lubricity and processability without detriment to hydrophilicity, fin, production of fin, and heat exchanger provided therewith - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a fin coating composition having excellent wettability with water by mixing a specified resin with a specified lubricity improver, a specified processability improver and a specified curing agent. SOLUTION: This composition comprises a hydrophilic resin prepared by neutralizing the acid groups of a copolymer obtained by using an unsaturated hydroxy monomer (A), an unsaturated carboxylic monomer (B), an unsaturated amide monomer, an unsaturated sulfonic acid monomer and a phosphoric acid (salt) with an alkali metal hydroxide (C) and/or an organic amine compound (D), a lubricity improver prepared by neutralizing the acid groups of a dibasic oxoacid diester comprising polyethylene glycol and an organic dibasic oxoacid with D, a processability improver prepared by neutralizing the acid groups of a copolymer obtained by using A, B, an unsaturated monomer having a 1-5C alkyl group and an unsaturated nitride monomer and an aliphatic mercapto compound with C and/or D and at least one curing agent selected among polyglycidyl ethers.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a coating composition suitable for forming a film exhibiting hydrophilicity on the surface of a metal, particularly an aluminum material or an aluminum alloy material (hereinafter, simply referred to as an aluminum alloy material), and a composition thereof. TECHNICAL FIELD The present invention relates to an aluminum or aluminum alloy material fin obtained by applying an object to the surface of an aluminum or aluminum alloy material and thermally curing the same, and a heat exchanger incorporating the same.

[0002]

2. Description of the Related Art Since the surface of a metal material is poor in hydrophilicity, a fin of a heat exchanger and a lithographic printing plate material for printing are coated with a hydrophilic film and used. Hereinafter, in the present specification, a case of a fin of the heat exchanger will be described by taking an air conditioner as an example.

[0003] Recent heat exchangers for air conditioners have been required to have improved thermal efficiency and compactness in order to reduce the weight, and designs have been adopted to make the fin spacing as narrow as possible.
In the air conditioner heat exchanger, during cooling operation, moisture in the air adheres to the surface of the aluminum fins as condensed water. Since the surface of the metal material is generally poor in hydrophilicity, the condensed water exists on the fin surface in a semicircular shape or in a bridge shape between the fins as shown in FIG. This hinders the flow of air between the fins, increases ventilation resistance, and significantly reduces heat exchange efficiency. In order to improve the thermal efficiency of the heat exchanger, it is necessary to quickly remove the condensed water on the fin surface.

As a solution to this problem, (1) a highly hydrophilic film is formed on the surface of the aluminum alloy fin and condensed water is allowed to flow down as a thin water film. Although it is conceivable to prevent water from adhering to the surface, the method (2)
It is extremely difficult at the moment. In order to obtain hydrophilicity, a surface is coated with a coating film.However, a composition that forms a hydrophilic film prevents the formation of dewdrops on the material surface or removes the water film on the material surface. Used to hold.

Conventionally, various methods for forming a hydrophilic film there have been proposed and put to practical use. For example, a method of forming an alkali silicate film on an aluminum surface (Japanese Patent Publication No. 53-48177), applying a composition containing an aqueous paint resin, a surfactant and synthetic silica to form a hydrophilic film. Method (JP-A-55-164264)
No.), a method comprising applying a composition containing a low-molecular organic compound having an alkali silicate and a carbonyl compound and a water-soluble organic high-molecular compound to form a hydrophilic film (JP-A-60-101156). Proposed.

However, in order to impart hydrophilicity, a method of forming a film of an alkali silicate has a problem in that the hydrophilicity is not persistent over time, and when applied to a material to form a fin, The film hardness is high, the wear of the mold is increased, and cracks tend to occur when formed on the fins. In those containing a surfactant, it is impossible to prevent the bleeding phenomenon since the surfactant basically moves toward the surface of the film. As a result, the hydrophilicity of the fin surface decreases with time. In addition, since it contains synthetic silica, when it is applied to a material and processed into fins, it acts like an abrasive and increases the wear of the mold. The method of applying a composition containing a low molecular weight organic compound having an alkali silicate and a carbonyl compound and a water-soluble organic high molecular compound to form a hydrophilic film has been improved in persistence of hydrophilicity. However, in order to provide sufficient wettability to the film, the content of alkali silicate increases, and when it is applied to the material and processed into fins, it acts like an abrasive and molds Increase wear.

[0007]

Accordingly, an object of the present invention is to form a film having good adhesion to aluminum and excellent film properties, no change in hydrophilicity with time, and good wettability to water. An object of the present invention is to provide a coating composition which is applied to a material and which forms a hydrophilic film so as not to increase abrasion of a mold when processed into a fin.

[0008]

Means for Solving the Problems The inventors of the present invention have repeatedly studied to solve the above-mentioned problems. And
In order for the film coated on the aluminum alloy plate to be sufficiently wetted by water, it is necessary that the film itself has excellent hydrophilicity. Conversely, to impart excellent hydrophilicity to the film itself, The glass transition point of the constituent resin will be raised. This increase in the glass transition point decreases the toughness of the film itself, and reduces the lubricity and workability of the surface of the film formed on the surface of the aluminum alloy material. It is important to achieve both. Therefore, as a result of further research, the specific combination of the constituent monomers of the polymer that forms the coating agent, and the addition of a specific substance that maintains hydrophilicity and maintains lubricity and processability, It has been found that it is possible to achieve both the contradictory properties, that is, the compatibility between the wettability of the formed film and other properties.

The gist of the present invention is that an unsaturated monomer having a hydroxy group (a), an unsaturated monomer having a carboxyl group (b), and an unsaturated monomer having an amide group (c) , An unsaturated monomer having a sulfonic acid group (d), and an acid group of a copolymer (A) composed of phosphoric acid and / or a phosphate compound (e), wherein the acid group is a hydroxide of an alkali metal (Α) and / or a hydrophilic resin (a) constituted by neutralization with an organic amine compound (β), and a diester dibasic composed of polyethylene glycol (f) and an organic dibasic oxyacid (g) A lubricity-imparting agent (b) formed by neutralizing an acid group of the carboxylic acid (B) with an organic amine compound (β), an unsaturated monomer having a carboxyl group (h), and a carbon number Unsaturated monomer having 1 to 5 linear or side chain alkyl groups (i A sulfur atom formed by using an unsaturated monomer having a nitrile group (j), an unsaturated monomer having a hydroxy group (k), and an organic compound having an aliphatic mercapto group (l). Having an acid group of the copolymer (C) having an alkali metal hydroxide (α) and / or
Alternatively, a coating composition containing a processability improver (c) constituted by neutralization with an organic amine compound (β) and a curing agent (d) selected from polyglycidyl ether (D) is defined as the first invention. ,

An unsaturated monomer having a hydroxy group (a), an unsaturated monomer having a carboxyl group (b),
Copolymer (A) composed of unsaturated monomer (c) having an amide group, unsaturated monomer (d) having a sulfonic acid group, and phosphoric acid and / or phosphate compound (e) A) a hydrophilic resin (a) constituted by neutralizing an acid group with an alkali metal hydroxide (α) and / or an organic amine compound (β); Diester composed of dibasic oxyacid (g) Lubricity-imparting agent (b) formed by neutralizing acid groups of dibasic oxyacid (g) with organic amine compound (β); Unsaturated monomer having a group (h), having 1 to 5 carbon atoms
Unsaturated monomers having a linear or side chain alkyl group (i), unsaturated monomers having a nitrile group (j), unsaturated monomers having a hydroxy group (k), and aliphatic monomers An acid group of a sulfur atom-containing copolymer (C) composed of an organic compound (I) having a mercapto group has an alkali metal hydroxide (α) and / or an organic amine compound (β) A hydrophilic thermosetting film formed from a workability improver (c) constituted by neutralizing with a solvent and at least one curing agent (d) selected from the group of polyglycidyl ethers (D). A second invention is a fin material provided on the surface of an aluminum or aluminum alloy fin,

An unsaturated monomer having a hydroxy group (a), an unsaturated monomer having a carboxyl group (b),
Copolymer (A) composed of unsaturated monomer (c) having an amide group, unsaturated monomer (d) having a sulfonic acid group, and phosphoric acid and / or phosphate compound (e) A) a hydrophilic resin (a) constituted by neutralizing an acid group with an alkali metal hydroxide (α) and / or an organic amine compound (β); Diester composed of dibasic oxyacid (g) Lubricity-imparting agent (b) formed by neutralizing acid groups of dibasic oxyacid (g) with organic amine compound (β); Unsaturated monomer having a group (h), having 1 to 5 carbon atoms
(I) unsaturated monomer having a linear or side chain alkyl group, (j) unsaturated monomer having a nitrile group, (k) unsaturated monomer having a hydroxy group, and aliphatic An acid group of a sulfur atom-containing copolymer (C) composed of an organic compound (I) having a mercapto group has an alkali metal hydroxide (α) and / or an organic amine compound (β) A paint having a workability improver (c) constituted by neutralizing with a solvent and at least one curing agent (d) selected from the group of polyglycidyl ethers (D) is applied to the surface of the aluminum alloy material. Then, after hardening, the third invention is a method of manufacturing a fin, which is processed into a predetermined shape,

An unsaturated monomer having a hydroxy group (a), an unsaturated monomer having a carboxyl group (b),
Copolymer (A) composed of unsaturated monomer (c) having an amide group, unsaturated monomer (d) having a sulfonic acid group, and phosphoric acid and / or phosphate compound (e) A) a hydrophilic resin (a) constituted by neutralizing an acid group with an alkali metal hydroxide (α) and / or an organic amine compound (β); A diester composed of a dibasic oxyacid (g); a lubricity-imparting agent (b) constituted by neutralizing an acid group of the dibasic oxyacid (B) with an organic amine compound (β); Unsaturated monomer having a group (h), having 1 to 5 carbon atoms
Unsaturated monomers having a linear or side chain alkyl group (i), unsaturated monomers having a nitrile group (j), unsaturated monomers having a hydroxy group (k), and aliphatic monomers The acid group of the sulfur atom-containing copolymer (C) formed using the mercapto group-containing organic compound (l) is an alkali metal hydroxide (α) and / or an organic amine compound (β) A hydrophilic thermosetting film formed from a processability improver (c) constituted by neutralizing with a solvent and at least one curing agent (d) selected from the group of polyglycidyl ethers (D). A fourth aspect of the present invention is a heat exchanger manufactured by molding a fin material provided on the surface of an aluminum or aluminum alloy fin.

Incidentally, the unsaturated monomer having a hydroxy group (a), the unsaturated monomer having a carboxyl group (b), and the unsaturated monomer having an amide group which constitute the copolymer (A) in the above invention are described. The monomer ratio of the monomer (c) / the unsaturated monomer (d) having a sulfonic acid group is 15 to 35/2 by weight.
0 to 45/5 to 15/20 to 45, preferably 19 to 3
It is preferably from 2/25 to 40/7 to 11/28 to 40. Then, the phosphoric acid and / or the phosphate compound (e) is added in an amount of 0.01 to 100 parts by weight of the total amount of the monomers.
-5 to 5 parts by weight in terms of solid content, preferably 0.02 to 3 parts by weight, and the average molecular weight of the copolymer (A) is 2,000 to 50,000, preferably 3,000.
Preferably it is ~ 30,000. Furthermore, hydrophilic resin (a) / lubricity-imparting agent (b) / processability improver (c)
The ratio of the curing agent (d) is 100 parts by weight in terms of solid content.
/ 2 to 50/2 to 30/200 to 500, preferably 1
What is 00 / 5-20 / 5-5 / 300-450 is preferable.

Further, the unsaturated monomer (h) having a carboxyl group constituting the copolymer (C) having a sulfur atom in the above invention / a linear or side chain alkyl group having 1 to 5 carbon atoms. (I) / unsaturated monomer having a nitrile group (j) / unsaturated monomer having a hydroxy group (k) in a weight ratio of 25 to 50/5 to 20/15 to 35
/ 10 to 25, preferably 30 to 45/10 to 18/2
It is preferably 0 to 30/15 to 20. The organic compound (l) having an aliphatic mercapto group is preferably 1 to 15 parts by weight, and more preferably 2.5 to 12 parts by weight, based on 100 parts by weight of the total amount of the monomers. The average molecular weight of the sulfur atom-containing copolymer (C) of the present invention is preferably from 1,000 to 10,000, more preferably from 1,500 to 7,000.

Hereinafter, the present invention will be described in more detail. The unsaturated monomer (a) having a hydroxy group, which is a component of the copolymer (A) constituting the coating film of the present invention, undergoes a crosslinking reaction with the curing agent component, and has an adhesive property to an aluminum alloy and a mechanical property. The resulting coating film has excellent properties such as strength (toughness) and flexibility.

Examples of such an unsaturated monomer having a hydroxy group (a) include 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate,
Hydroxypropyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxybutylyl methacrylate, 2-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 2,3-dihydroxypropyl methacrylate, 2,3-dihydroxypropyl acrylate, 2-
Examples thereof include hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl ether, and 4-hydroxybutyl vinyl ether. Among them, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 2,3-dihydroxypropyl methacrylate, 2,3-dihydroxypropyl acrylate, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether and the like are preferred.

Next, the unsaturated monomer (b) having a carboxyl group, which is a component of the copolymer (A) constituting the coating film, has a function of anionic hydrophilicity, and Neutralized with a hydroxide (α) or an organic amine compound (β) further enhances hydrophilicity. A neutralized product of the alkali metal hydroxide (α) gives lubricity to the formed film, while a neutralized product with the organic amine compound (β) provides a lubricity imparting agent (b) , Causing a cross-linking reaction with the processability improver (c) and the curing agent (d),
The most important object of the present invention is to impart lubricity and workability to an aluminum alloy without impairing hydrophilicity, and to excel in properties such as adhesion to a fin material, mechanical strength (toughness), and flexibility. To form a coated film.

Examples of the unsaturated monomer (b) having a carboxyl group include, for example, acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid and fumaric acid, or itaconic acid, maleic acid and fumaric acid. Half-esters of a linear or side chain alkyl alcohol having 1 to 5 carbon atoms are also included. Among them, acrylic acid, methacrylic acid and maleic acid are preferred.

The amide group-containing unsaturated monomer (c), which is a constituent component of the copolymer (A) constituting the coating film, comprises a lubricity-imparting agent (b) and a processability improver (c). A cross-linking reaction occurs together with the curing agent (d), and the coating film has excellent properties such as adhesion to an aluminum alloy, mechanical strength (toughness), and flexibility. Examples of the unsaturated monomer having such an amide group include acrylamide and methacrylamide, and acrylamide is preferable in terms of cost.

Next, an unsaturated monomer having a sulfonic acid group (d) which is a component of the copolymer (A) constituting the coating film
Is the largest that brings out the hydrophilicity of the hydrophilic resin (a) by neutralizing the acid groups of the copolymer (A) with an alkali metal hydroxide (α) and an organic amine compound (β). It is a component that becomes a factor. Examples of such an unsaturated monomer having a sulfonic acid group (d) include 2-methacryloxyethyl-1-sulfonic acid, 2-acryloxyethyl-1-sulfonic acid, and 3-methacryloxypropyl-1.
-Sulfonic acid, 3-acryloxypropyl-1-sulfonic acid, 3-methacryloxy-2-hydroxypropyl-
1-sulfonic acid, 3-acryloxy-2-hydroxypropyl-1-sulfonic acid and 2-acrylamide-2-
Examples include methylpropane-1-sulfonic acid, arylsulfonic acid, and metharylsulfonic acid. Above all, as the monomer having a sulfonic acid group, an unsaturated monomer such as 2-acrylamido-2-methylpropane-1-sulfonic acid or arylsulfonic acid is preferable. In addition, in addition to the monomers described above, the copolymer (A) may optionally contain alkyl esters of (meth) acrylic acid (eg, methyl (meth) acrylate, ethyl (meth) acrylate, etc.), styrene, and the like. May also be copolymerized.

The phosphoric acid and / or the phosphate compound (e), which is one of the components for determining the average molecular weight of the copolymer (A) constituting the coating film, includes phosphorous acid, hypophosphorous acid, and hypophosphorous acid. Sodium phosphate, potassium hypophosphite, sodium phosphite, potassium phosphite, and the like.
The average molecular weight of the copolymer (A) is determined by the ratio of the phosphate compound (e) to the total amount of the monomers. That is, when producing the copolymer (A), the phosphoric acid and / or
Alternatively, when the phosphate compound (e) is used in combination with a peroxide described later and added to the polymerization reaction system, a redox polymerization reaction occurs and a polymer is formed. In this case, the phosphoric acid and / or the phosphate compound (e) is added to the terminal of the polymer to form a polymer. The bud of the polymerization (called a radical in a radical polymerization reaction, an ion in a redox reaction) Are referred to) and the average molecular weight is determined. Further, since the phosphoric acid and / or the phosphate compound (e) itself is added to the terminal of the polymer, it also has a role of improving the hydrophilicity of the copolymer (A).

An addition polymerization reaction, for example, a usual polymerization reaction in an aqueous medium is carried out using the above-mentioned monomers.
The mixing ratio of the monomers (a), (b), (c) and (d) is 15 to 35/20 to 45 by weight.
/ 5 to 15/20 to 45. The mixing ratio of the phosphoric acid and / or the phosphate compound (e) is 100% by weight of the total of the monomer (a), the monomer (b), the monomer (c) and the monomer (d). The amount is preferably 0.01 to 0.5 part by weight, particularly preferably 0.02 to 3 parts by weight based on parts.

Then, a reaction is carried out by adding a polymerization initiator to such a composition. As the polymerization initiator,
Although what is used for a vinyl type polymerization reaction can be used, water-soluble ammonium persulfate, potassium persulfate, hydrogen peroxide and the like are preferable. Incidentally, such a polymerization initiator is used in an amount of 0.1 to 100 parts by weight of the total of the above monomers.
It is preferably from 10 to 10 parts by weight in terms of solid content. The polymerization temperature is from 0 ° C to 58 ° C in the redox polymerization reaction,
The radical polymerization reaction is preferably carried out at 55 ° C to 110 ° C.

Copolymer (A) obtained as a result of polymerization reaction
Has an average molecular weight of 1,000 to 50,000, especially 2,
It is preferably from 000 to 35,000. The copolymer (A) is neutralized with an alkali metal hydroxide (α) and an organic amine compound (β) to form a hydrophilic resin (A). In this neutralization, all the sulfonic acid groups are neutralized by the alkali metal hydroxide (α), and the carboxylic acid groups are formed by the alkali metal hydroxide (α) and / or the organic amine. It will be neutralized by the system compound (β). The neutralization treatment may be performed after the polymerization operation or in the state of the monomer before the polymerization.

The hydroxide (α) of the alkali metal exhibits a role of increasing the hydrophilicity of the copolymer (A), and the copolymer (A) reacts with the curing agent (d) by a curing reaction. It plays a role of imparting solid lubricity showing workability to the subsequent coating film. Examples of such an alkali metal hydroxide (α) include lithium hydroxide, sodium hydroxide and potassium hydroxide. Among them, potassium hydroxide is preferable. The mixing ratio of the alkali metal hydroxide (α) is 0.1% with respect to 100 parts by weight of the copolymer (A).
It is preferably 1 to 7 parts by weight, preferably 0.5 to 5.5 parts by weight.

The organic amine compound (β) has a role of increasing the hydrophilicity of the copolymer (A) and also has a role of accelerating the reaction with the curing agent (d). Examples of such an organic amine compound (β) include ammonia,
Mono-, di- or trialkyl and / or alkyleneamine having an alkyl group and / or alkylene group having 1 to 3 carbon atoms (methylamine, ethylamine, propylamine, dimethylamine, diethylamine, dipropylamine, trimethylamine, triethylamine, tripropyl Amine, arylamine, diarylamine, triarylami), ammonia and / or alkyl and / or alkylene triamine having an alkyl group and / or alkylene group having 1 to 3 carbon atoms, and having 1 to 2 alkylene oxides having 2 to 3 carbon atoms. 3 moles of monoethanolamine, diethanolamine, triethanolamine, monopropanolamine, dipropanolamine, tripropanolamine, having an alkyl and / or alkylene group having 1 to 3 carbon atoms Trialkanol in which 3 moles of alkylene oxide having 2 to 3 carbon atoms are added to alkyl and / or alkylene triamine and / or alkyl and / or alkylene benzylamine having 2 alkyl and / or 2 alkylene groups having 1 to 3 carbon atoms and ammonia. Hydroxides of quaternary ammonium salts of amines (tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetraarylammonium hydroxide, diaryldimethylammonium hydroxide, diaryldiethylammonium hydroxide, diaryldipropyl Ammonium hydroxide, trimethylbenzylammonium hydroxide, triethylbenzene Ammonium hydroxide, tripropyl benzyl ammonium hydroxide) and the like. Among them, ammonia and hydroxides of quaternary ammonium salts are preferable.

The amount of the organic amine compound (β) is 3 to 1 based on 100 parts by weight of the copolymer (A).
It is preferably 5 parts by weight, more preferably 5 to 12 parts by weight.

The main purpose of the present invention is to simultaneously realize lubricity and workability as well as hydrophilicity in a coating film. This is realized by combining the hydrophilic resin (a) with the lubricity-imparting agent (b), the workability improver (c), and the curing agent (d). That is, an unsaturated monomer having a hydroxy group (a), an unsaturated monomer having a carboxyl group (b), an unsaturated monomer having an amide group (c), and an unsaturated monomer having a sulfonic acid group Isomer (d) and copolymer (A) composed of phosphoric acid and / or phosphate compound (e) are converted to organic amine compound (α) and / or alkali metal hydroxide (β) ), A diester dibasic oxyacid (B) comprising polyethylene glycol (f) and an organic dibasic oxyacid (g) used in combination with a hydrophilic resin (a) constituted by partial or neutralization A) a lubricating agent (b) constituted by neutralizing the acid group with an organic amine compound (β), an unsaturated monomer (h) having a carboxyl group, Unsaturated monomer having a linear and / or side chain alkyl group (i) Having a sulfur atom composed of an unsaturated monomer having a nitrile group (j), an unsaturated monomer having a hydroxy group (k), and an organic compound having an aliphatic mercapto group (l) A processability improver (c) constituted by neutralizing an acid group of the copolymer (C) with a hydroxide (α) of an alkali metal and / or an organic amine compound (β), and polyglycidyl At least one curing agent (d) selected from the group of ethers (D) is a component that constitutes a coating composition that forms a coating film that exhibits lubricity and processability while maintaining hydrophilicity. It is.

In the course of the examination, the present inventors have found that an unsaturated monomer having a hydroxy group (a), an unsaturated monomer having a carboxyl group (b), and an unsaturated monomer having an amide group (c) , An unsaturated monomer having a sulfonic acid group (d), and a copolymer (A) composed of phosphoric acid and / or a phosphate compound (e) are converted into an alkali metal hydroxide (α) ) And a hydrophilic resin (a) constituted by neutralization with an organic amine compound (β), and a polyglycidyl ether (D) used in combination with the hydrophilic resin (a). It was confirmed that a coating film formed from at least one curing agent (d) selected from among them had hydrophilicity but could not obtain a coating film having lubricity and workability proposed by the present invention.

As a result of further studies, the present inventor has found that unsaturated monomers (a) having a hydroxy group,
Unsaturated monomer having carboxyl group (b), unsaturated monomer having amide group (c), unsaturated monomer having sulfonic acid group (d), and phosphoric acid and / or phosphate compound The copolymer (A) constituted using (e) is converted into an alkali metal hydroxide (α) and an organic amine compound (β).
(A) hydrophilic resin composed by neutralization with
And at least one curing agent (d) selected from the group of polyglycidyl ethers (D) used in combination with the hydrophilic resin (a), further comprising polyethylene glycol (f) and organic dibasic oxygen A lubricity-imparting agent (b) and a processability improver (c) formed by neutralizing an acid group of a diester dibasic oxyacid (B) composed of an acid (g) with an organic amine compound (β). ), The hydrophilicity is maintained, and excellent lubricity and workability can be simultaneously realized by composing the paint from the four members.

The acid group of diester dibasic oxyacid (B) composed of polyethylene glycol (f) and organic dibasic oxyacid (g) exhibiting lubricity, which is a new finding, is formed by an organic amine compound ( β) having a lubricity imparting agent (b) constituted by neutralization, an unsaturated monomer having a carboxyl group (h), and having a linear and / or side chain alkyl group having 1 to 5 carbon atoms Unsaturated monomer (i), unsaturated monomer having nitrile acid group (j), unsaturated monomer having hydroxy group (k), and organic compound having aliphatic mercapto group (l) Of processability constituted by neutralizing the acid group of the sulfur atom-containing copolymer (C) constituted by using alkali metal hydroxide (α) and organic amine compound (β) Agent (c) is an unsaturated monomer having a hydroxy group a), an unsaturated monomer having a carboxyl group (b), an unsaturated monomer having an amide group (c), an unsaturated monomer having a sulfonic acid group (d), and phosphoric acid and / or phosphorus A hydrophilic resin formed by neutralizing a copolymer (A) formed using an acid salt compound (e) with an organic amine compound (α) and an alkali metal hydroxide (β). The coating film formed by the coating composition composed of the four-component combination with at least one curing agent (d) selected from the group of the polyglycidyl ethers (D) blended in (a) is markedly lubricated. It has good workability and excellent workability, and does not impair the hydrophilicity and toughness required of the fin material.

A hydrophilic resin (a) constituted by neutralizing the copolymer (A) with an alkali metal hydroxide (α) and an organic amine compound (β), and a polyglycidyl ether (D ) Is required for a fin material for a coating film formed only by a coating composition (two-component paint) composed of two components of at least one curing agent (d) selected from the group consisting of: Although it has hydrophilicity, the fin surface has a high dynamic friction coefficient as a controlling factor of the workability of press molding.

Further, a hydrophilic resin (a) constituted by neutralizing the copolymer (A) with an alkali metal hydroxide (α) and an organic amine compound (β), and a polyethylene glycol ( g) and a diester dibasic oxyacid (B) composed of an organic dibasic oxyacid (h), wherein the acid group of the diester dibasic oxyacid (B) is neutralized with an organic amine compound (β) to form a lubricity imparting agent (b) ) And at least one curing agent (d) selected from the group of polyglycidyl ethers (D); It has the hydrophilic property required of the fin material and has a low dynamic friction coefficient on the fin surface, but the severe lubricity required for the drawless processing method, that is, the workability was not recognized.

However, the unsaturated monomer having a hydroxy group (a), the unsaturated monomer having a carboxyl group (b), the unsaturated monomer having an amide group (c), the sulfonic acid group Wherein the acid group of the unsaturated monomer (d) having the formula (I) and the copolymer (A) composed of phosphoric acid and / or the phosphate compound (e) is an alkali metal hydroxide (α) And a hydrophilic resin (a) constituted by neutralization with an organic amine compound (β), and a diester dibasic oxyacid composed of polyethylene glycol (f) and an organic dibasic oxyacid (g) ( B) a lubricity-imparting agent (b) constituted by neutralizing an acid group with an organic amine compound (β), an unsaturated monomer (h) having a carboxyl group, and 1 to 5 carbon atoms An unsaturated monomer (i) having a linear and / or side chain alkyl group of Having a sulfur atom composed of an unsaturated monomer having a tolyl group (j), an unsaturated monomer having a hydroxy group (k), and an organic compound having an aliphatic mercapto group (l) A processability improver (c) constituted by neutralizing an acid group of the copolymer (C) with an alkali metal hydroxide (α) and an organic amine compound (β), and a polyglycidyl ether ( A coating film formed from a coating composition containing at least one curing agent (d) selected from the group of D) maintains the hydrophilicity and toughness required of the fin material. In addition, the fin surface has a low dynamic friction coefficient suitable for press workability, and further has the workability required for the drawless processing method.

Next, the unsaturated monomer having a hydroxy group (a), the unsaturated monomer having a carboxyl group (b), the unsaturated monomer having an amide group (c), sulfonic acid (A) a copolymer composed of an unsaturated monomer having a group (d) and phosphoric acid and a phosphate compound (e)
A) a hydrophilic resin (a) constituted by neutralizing the acid group of (a) with an alkali metal hydroxide (α) and an organic amine compound (β), polyethylene glycol (f) and an organic dibasic Coating composition in combination with a lubricity-imparting agent (b) constituted by neutralizing an acid group of diester dibasic oxyacid (B) composed of oxyacid (g) with an organic amine compound (β) The coating formed from the product was presumed to have a low crosslink density at the time of film formation, and thus the coating was peeled off by water rubbing.

Further, the unsaturated monomer having a hydroxy group (a), the unsaturated monomer having a carboxyl group (b), the unsaturated monomer having an amide group (c), and the sulfonic acid group of the present invention Wherein the acid group of the unsaturated monomer (d) having the formula (I) and the copolymer (A) composed of the phosphoric acid and the phosphate compound (e) is an alkali metal hydroxide (α) A hydrophilic resin (a) constituted by neutralization with an amine compound (β), an unsaturated monomer having a carboxyl group (h), a linear and / or side chain having 1 to 5 carbon atoms An unsaturated monomer having an alkyl group (i), an unsaturated monomer having a nitrile group (j), an unsaturated monomer having a hydroxy group (k), and an organic monomer having an aliphatic mercapto group The acid group of the copolymer (C) having a sulfur atom constituted by using the compound (l) is A coating film formed from a coating composition formed by a combination with a processability improver (c) formed by neutralization with an alkali metal hydroxide (α) and an organic amine compound (β) Although good in lubricity, the essential hydrophilicity was extremely poor, and the lubricity and workability were also poor.

The acid group of the diester dibasic oxyacid (B) comprising polyethylene glycol (f) and the organic dibasic oxyacid (g) is neutralized with an organic amine compound (β). Lubricating agent (b), carboxyl group-containing unsaturated monomer (h), carbon number 1-5
(I) unsaturated monomer having a linear and / or side chain alkyl group, (j) unsaturated monomer having a nitrile group, (k) unsaturated monomer having a hydroxy group, and fat The acid group of a sulfur atom-containing copolymer (C) composed of an organic compound (I) having an aromatic mercapto group has an alkali metal hydroxide (α) and an organic amine compound (β) The coating film formed from the coating composition composed of the workability improver (c) formed by neutralization with a hydrophilic resin (a) and a lubricity-imparting agent (b) Like the coating film formed from the coating composition,
Poor adhesion and poor water rubbing.

Here, the lubricity imparting agent (b) showing the factor of giving the fin surface a low dynamic friction coefficient suitable for press workability will be described. Lubricity imparted by neutralizing the acid group of diester dibasic oxyacid (B) composed of polyethylene glycol (f) and organic dibasic oxyacid (g) with organic amine compound (β) The agent (b) preferably has an average molecular weight of 600 to 20,000 as polyethylene glycol (g). For example, polyethylene glycol PEG # 600, PEG # 1,
000, PEG # 2,000, PEG # 4,000, P
EG # 6,000 and PEG 10,000 # are preferred, and PEG # 2,000, PEG # 4,0 if desired.
00 and PEG # 6,000 are good.

Further, the organic dibasic oxyacid (g) is a saturated or / and unsaturated dibasic oxyacid having 4 to 12 carbon atoms. For example, in an aliphatic system, maleic acid and succinic acid are used. , Glutaric acid, pimelic acid, adipic acid, azelaic acid, sebacic acid, decanoic acid, dodecanoic acid, and phthalic acid, isophthalic acid, terephthalic acid, homophthalic acid and trimellitic acid in the aromatic system, but preferably Is a maleic acid in which each anhydride is sold for industrial use from the viewpoint of producing a diester dibasic oxyacid (B) of polyethylene glycol (f) and these organic dibasic oxyacids (g); Succinic, phthalic and trimellitic anhydrides are preferred.

Further, as a method for producing a diester dibasic oxyacid (B) comprising an organic dibasic oxyacid (g) of polyethylene glycol (f), a prescribed amount of both is put in a reaction vessel, and the reaction is carried out for several hours. It can be manufactured by heating and stirring. However, since most of organic dibasic oxyacids have sublimability, the esterification reaction between polyethylene glycol (f) and the corresponding organic dibasic oxyacid (g) is sufficiently advanced at a sublimation temperature or lower. Need to be kept.
Then, esterification with polyethylene glycol (f) proceeds easily if it is an anhydride of the corresponding organic dibasic oxyacid (g). The reaction temperature and the reaction time are from 80 ° C to 90 ° C.
The reaction is preferably performed at 110 ° C. to 120 ° C. for 1 hour to 3 hours to complete the reaction. 110 ° C., preferably at 80 ° C. to 85 ° C. for 2 hours
1 hour 30 minutes to 2 hours at ~ 115 ° C.

Next, the polyethylene glycol (f)
The organic amine compound (β) in which the acid group of the diester dibasic oxyacid (B) composed of the organic dibasic oxyacid (g) is neutralized,

Has been described.

The compounding amount of the organic amine compound is such that the acid groups of diester dibasic oxyacid (B) composed of polyethylene glycol (f) and organic dibasic oxyacid (g) are neutralized, The amount is such that the pH becomes 7 to 9. When the pH is less than 7, the diester dibasic oxyacid (B) itself of the present invention prevents polyethylene glycol (f) produced by hydrolysis from forming a film later. Furthermore, the storage stability of the coating composition constituted by mixing with the hydrophilic resin (a), the lubricity-imparting agent (ii), the processability improver (iii) and the curing agent (iv) of the present invention is improved. Because of the badness, the adhesion of the film formed therefrom becomes poor.
When the pH exceeds 9, the amount required for neutralizing the acid groups of the diester dibasic oxyacid (B) composed of the polyethylene glycol (f) and the organic dibasic oxyacid (g) Since the organic amine compound (β) is present in excess as described above, the hydrophilic resin (A), lubricity imparting agent (B), workability improver (C) and curing agent (D) of the present invention are used. ) In the coating composition, which reacts with at least one curing agent (d) selected from the group of polyglycidyl ethers (D) to form a film. Before the formation of the film, the organic amine compound (β) of the above does not play the role of the curing agent by opening the epoxy ring which is the reactive group of the polyglycidyl ether (D) which is the curing agent (d). As a result, the adhesion of the formed film becomes poor.

The unsaturated monomer having a hydroxy group (a), the unsaturated monomer having a carboxyl group (b), the unsaturated monomer having an amide group (c), and the sulfonic acid group according to the present invention. The acid group of the copolymer (A) constituted by using the unsaturated monomer (d) and the phosphate compound (e) is
A hydrophilic resin (a) constituted by neutralization with an alkali metal hydroxide (α) and an organic amine compound (β), and an organic dibasic oxyacid (g) of polyethylene glycol (f) A diester dibasic oxyacid (B) acid group consisting of a lubricating agent (b) constituted by neutralization with an organic amine compound (β) and an unsaturated monomer having a carboxyl group ( h) an unsaturated monomer having a straight-chain and / or side-chain alkyl group having 1 to 5 carbon atoms (i), an unsaturated monomer having a nitrile group (j), an unsaturated monomer having a hydroxy group The acid group of the copolymer (C) having a sulfur atom, which is formed by using the polymer (k) and the organic compound (l) having an aliphatic mercapto group, is an alkali metal hydroxide (α). And organic amine compounds (β)
Processability improver composed by neutralizing with (c)
And a fin material paint comprising four components of at least one curing agent (d) selected from the group of polyglycidyl ethers (D), applied to an aluminum alloy material, and applied to a coating film formed by baking. The mixing ratio of the lubricity-imparting agent (b) to the hydrophilic resin (a) for imparting lubricity of the present invention is 2 to 100 parts by weight of the hydrophilic resin (a) in terms of solids content. It is preferable to use 50 parts by weight. Particularly, 5 to 20 parts by weight is preferable.

Next, hydrophilicity required of the fin material,
A workability improver (c) which maintains toughness, has a low dynamic friction coefficient suitable for press workability on the fin surface, and further imparts the workability required for the drawless working method will be described. Unsaturated monomer having a carboxyl group (h), unsaturated monomer having a linear and / or side chain alkyl group having 1 to 5 carbon atoms (i), unsaturated monomer having a nitrile group ( j), an unsaturated monomer having a hydroxy group (k), and an acid group of a sulfur atom-containing copolymer (C) composed of an organic compound (l) having an aliphatic mercapto group , A processability improver (C) constituted by neutralization with an alkali metal hydroxide (α) and an organic amine compound (β) is used as an unsaturated monomer (h) having a carboxyl group. And the same as the component (b) in the copolymer (A), among which acrylic acid, methacrylic acid and maleic acid are preferred.

Next, the unsaturated monomer (i) having a straight-chain and / or side-chain alkyl group having 1 to 5 carbon atoms is a hydrophilic resin (A) composed only of the copolymer (A). B) the glass transition temperature is too high, and the adhesion, toughness and flexibility are inferior, so that the characteristics of adhesion, toughness and flexibility that lower the glass transition temperature are improved, In addition to improving the coating properties, the workability of the formed film is improved.

Examples of such a monomer (i) include methyl methacrylate, methyl acrylate, ethyl methacrylate, ethyl acrylate, propyl methacrylate, propyl acrylate, butyl methacrylate, butyl acrylate, amyl methacrylate, amyl acrylate, dimethyl maleate, Examples thereof include diethyl maleate, methyl crotonate, ethyl crotonate, propyl crotonate, butyl crotonate, and amyl crotonate. Among them, methyl methacrylate, ethyl acrylate, dimethyl maleate, methyl crotonate and the like are preferable.

Next, since the nitrile group in the unsaturated monomer (j) having a nitrile group has a dipole efficiency extremely high due to the nitrile group, that is, the π electron in the triple bond between the carbon element and the nitrogen element. Increase the hydrophilicity of the resin. However, on the contrary, there is not enough force (polarity or dipole efficiency) to cause the phenomenon of water-solubilization that lowers the adhesion of the resin itself to the aluminum alloy. Therefore, the presence of the nitrile group having a large dipole efficiency improves the adhesion to the aluminum alloy, and consequently increases the adhesion between the aluminum alloy and the coating composed of the coating composition of the present invention. It doubles the function of strengthening itself and increasing workability.

Examples of such a monomer (j) include acrylonitrile, methacrylonitrile, 2-cyanoethyl methacrylate and 2-cyanoethyl acrylate. Among them, acrylonitrile is a preferred example.

Next, the unsaturated monomer (k) having a hydroxy group causes a cross-linking reaction with the curing agent component, and the processability such as adhesion to aluminum alloy, mechanical strength (toughness), flexibility and the like. It has the role of giving excellent properties to the coating film.

The inner conjugated monomer of the conjugated and / or non-conjugated monomer (k) having such a hydroxy group includes:
Same as the component (a) in the copolymer (A), and among them, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 2,3-dihydroxypropyl methacrylate, 2,3-dihydroxypropyl acrylate, 2-hydroxyethyl Vinyl ether and 4
-Hydroxybutyl vinyl ether and the like are preferred.

Next, prior to the description of the organic compound (l) having an aliphatic mercapto group, the load-bearing additive of the lubricating oil will be described. The lubricating properties of lubricating oils can be roughly divided into two categories: hydrodynamic effects due to the viscosity of the liquid, and other effects due to the adsorption of organic polar compounds to the metal surface and the formation of a solid lubricating film by reaction with the metal surface. . Hydrodynamic effects are influenced by the molecular weight, molecular structure and association of the lubricating oil molecules in relation to viscosity-temperature, viscosity-pressure, and adhesion to metal surfaces. Lubricity during boundary lubrication and extreme pressure lubrication, that is, the lubricating oil is provided with a load bearing capacity is an oil agent, an antiwear agent, and an extreme pressure agent. According to this classification, the processability improver (c) included in the coating composition of the present invention falls under extreme pressure agents, and in particular, the organic compound (l) having an aliphatic mercapto group
Is the main raw material of this extreme pressure agent. The organic compound (l) having an aliphatic mercapto group used in the processability improver (c) of the present invention provides the processability required for the press working of aluminum alloy fin materials, particularly the drawless processing method. I discovered that.

The organic compound (l) having an aliphatic mercapto group is represented by the general formula: HSR ₁ OH HSR ₁ OCOR ₂ HSR ₃ COOH HSR ₃ COOR ₄ HSR ₅ Wherein R ₁ is an alkyl or alkylene group having 1 to 15 carbon atoms, R ₂ is hydrogen or an alkyl group having 1 to 11 carbon atoms, R ₃ is an alkylene group having 1 to 2 carbon atoms, and R ₄ is 1 to 16 carbon atoms. alkyl group, R ₅ is an alkyl group or an alkylene group having 1 to 18 carbon atoms. For example, mercaptoalkyl or alkylene glycol such as 2-mercaptoethanol and an ester of an aliphatic organic acid having 1 to 12 carbon atoms, mercaptoalkanoic acid such as α-mercaptoacetic acid and β-mercaptopropionic acid and 1 to 16 carbon atoms thereof
Alkyl or alkylene ester having, 1-mercaptomethane, 1-mercaptoethane, 1-mercaptobutane, 1-mercaptooctane, 1-mercaptododecane or a straight-chain or side-chain 1-mercaptoalkane having 1 to 18 carbon atoms No. In particular, 2-mercaptoethanol, β-mercaptopropionic acid, and 1-mercaptododecane are generally used industrially for production and resin production, and are advantageous in terms of cost. Two or more organic compounds having a group may be used in combination.

Further, the unsaturated monomer having a hydroxy group (a), the unsaturated monomer having a carboxyl group (b), the unsaturated monomer having an amide group (c), the sulfonic acid group Wherein the acid group of the unsaturated monomer (d) having the formula (I) and the copolymer (A) composed of phosphoric acid and / or the phosphate compound (e) is an alkali metal hydroxide (α) And a hydrophilic resin (a) constituted by neutralization with an organic amine compound (β) and a diester dibasic oxyacid composed of an organic dibasic oxyacid (g) of polyethylene glycol (f) ( B) a lubricating agent (b) in which an acid group is neutralized with an organic amine compound (β), an unsaturated monomer having a carboxyl group (h), Unsaturated monomers (i) having a linear and / or side chain alkyl group, Having a sulfur atom constituted by using an unsaturated monomer having a luyl group (j), an unsaturated monomer having a hydroxy group (k), and an organic compound having an aliphatic mercapto group (l) A processability improver (c) constituted by neutralizing an acid group of the copolymer (C) with a hydroxide (α) of an alkali metal and an organic amine compound (β), and a polyglycidyl ether ( A coating material for a fin material comprising a quaternary component and at least one curing agent (d) selected from the group of D) is applied to an aluminum alloy material and baked to form a coating film, which exhibits the workability of the present invention. The mixing ratio of the processability improver (c) to the hydrophilic resin (a) to be applied is 2 to 30 parts by weight in 100 parts by weight of the hydrophilic resin (a) in terms of solid content weight ratio. Is preferred. Particularly, 5 to 15 parts by weight is preferable.

Further, when the workability improver (c) used here is less than 2 with respect to the hydrophilic resin (a), the workability of the film is not exhibited due to insufficient extreme pressure, and conversely, To 30
If the amount exceeds parts by weight, the amount of sulfur atoms is large,
As a result, the atomization against salt water was poor for aluminum alloy materials.

The unsaturated monomer having a hydroxy group (a), the unsaturated monomer having a carboxyl group (b), the unsaturated monomer having an amide group (c), and the unsaturated monomer having a sulfonic acid group Saturated monomer (d), phosphoric acid and / or
Alternatively, the acid group of the copolymer (A) formed using the phosphate compound (e) is neutralized with an alkali metal hydroxide (α) and an organic amine compound (β). Hydrophilic resin (a), polyethylene glycol (g)
And a diester dibasic oxyacid (B) composed of an organic dibasic oxyacid (h) and a lubricity-imparting agent (b) formed by neutralizing with an organic amine compound (β). Unsaturated monomer having carboxyl group (h), carbon number 1
To 5 unsaturated monomer having a linear and / or side chain alkyl group (i), unsaturated monomer having a nitrile group (j), unsaturated monomer having a hydroxy group (k), And the acid group of the sulfur atom-containing copolymer (C) formed by using the organic compound (I) having an aliphatic mercapto group has an alkali metal hydroxide (α) and an organic amine compound ( β) at least one curing agent (d) selected from the group of polyglycidyl ethers (D) used in combination with the processability improver (c) constituted by neutralization is hydrophilic, It functions to cure the coating film while maintaining its porosity and lubricity.

Such a polyglycidyl ether (D)
At least one curing agent (d) selected from the group consisting of ethylene oxide and ethylene oxide
0 to 91 moles of diglycidyl ether of polyethylene glycol and propylene glycol and / or butylene glycol are added with 10 to 9 ethylene oxide.
Examples thereof include diglycidyl ether of polyalkylene ethylene glycol with one mole added, and polyethylene glycol diglycidyl ether obtained by adding 10 to 91 moles of ethylene oxide to ethylene glycol is preferable.

At least one curing agent (d) selected from the group of polyglycidyl ethers (D) is used in an amount of 200 to 200 parts by weight of the above hydrophilic resin (a) in terms of solid content. It is preferable to use 500 parts by weight, particularly 300 to 480 parts by weight. The above-mentioned hydrophilic resin (a), lubricity-imparting agent (ii), workability improver (iii)
And a coating composition formed by applying the coating composition comprising the curing agent (d) to the surface of the coil material made of an aluminum alloy, thereby forming a coating having a thickness of 0.5 to 5 μm.
Desirably, the thickness is 1-2 μm. As an application means, an appropriate means such as brush coating, dipping, spraying, electrostatic coating, and a roll coater can be used. For drying, known means can be used.
It is preferable to maintain the temperature of 280 ° C. for 10 seconds to 90 seconds.

Then, predetermined processing is performed on the aluminum alloy coil to which the coating material comprising the coating composition according to the present invention is applied to form a fin. At the time of this processing, since the coating film having the above characteristics is provided on the surface of the aluminum alloy material, the mold has good durability. That is, since the coating film formed on the surface of the aluminum alloy material has a lubricating function, damage to the mold is less likely to occur. Moreover, since no component such as silica is added to the coating film, the mold is less likely to be damaged.

Further, the coating film formed on the surface of the obtained fin has hydrophilicity, lubricity and workability, and is excellent in water wettability. Moreover, the formation of a coating film having lubricity and workability on the aluminum alloy material can be performed only once, and is extremely simple, so that the production cost of the fin is low. Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples.

[0060]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Prior to the description of Examples and Comparative Examples,
The method for producing the parent component of the present invention will be described together with comparative examples.

(Copolymer A-1) Stirrer, reflux condenser,
In a 1 liter four-necked flask equipped with a thermometer, a dropping funnel and a nitrogen gas inlet tube, 400 g of ion-exchanged water and 2.1 g of sodium hypophosphite were charged, stirred and dissolved, and then light ester HO (Kyoeisha Chemical Co., Ltd.) 2-hydroxyethyl methacrylate), 50 g of light ester HOA
50 g of 2-hydroxyethyl acrylate (manufactured by Kyoeisha Chemical Co., Ltd.), acrylic acid (manufactured by Nippon Shokubai Co., Ltd.) 7
5 g, methacrylic acid (Mitsubishi Gas Chemical Industry Co., Ltd.) 5
0 g, acrylamide (manufactured by Mitsubishi Chemical Corporation) 35 g,
AS (Nissei Chemical Industry, sodium aryl sulfonate)
115 g, and ATBS-K (manufactured by Toa Gosei Chemical Industry Co., Ltd., 2-acrylamide-2-methylpropane-1-)
25 g of potassium sulfonate) and a solution of 3.7 g of potassium persulfate in 9.3 g of 35% aqueous hydrogen peroxide were added at a polymerization temperature of 47 ° C. to 50 ° C. under a nitrogen gas stream at 12 ° C.
After dropping over a period of time, a redox polymerization reaction was further performed at 50 to 52 ° C. for 2 hours. As a result, the average molecular weight was 10,000.
At 0, a copolymer (A-1) having a concentration of 50.3% was obtained.

(Copolymer A-2) In the same production method as for (Copolymer A-1), 400 g of ion-exchanged water and 1.2 g of sodium phosphite were charged and dissolved by stirring.
40 g, light ester HOA 20 g, 2-hydroxyethyl vinyl ether (manufactured by Nippon Carbide Industry Co., Ltd.) 20 g, light acrylate POA (manufactured by Kyoeisha Chemical Co., Ltd., 2-hydroxypropyl acrylate) 25
g, 40 g of acrylic acid, 40 g of methacrylic acid, 60 g of crotonic acid, 40 g of acrylamide, 80 g of AS (manufactured by Nissei Chemical Co., Ltd., sodium metharyl sulfonate) and ATB
S-K (40 g) was charged, and potassium persulfate (3.8 g) was added to 35
Solution dissolved in 8.2 g of 1% hydrogen peroxide solution
After the dropwise addition over 5 hours, the redox polymerization reaction was further performed for 2 hours. As a result, a copolymer (A-2) having an average molecular weight of 12,600 and a concentration of 50.5% was obtained.

(Copolymer A-3) In the same manner as in (Copolymer A-1), 400 g of ion-exchanged water and 4.9 g of sodium phosphite were charged and dissolved by stirring.
A (manufactured by Kyoeisha Chemical Co., Ltd., 2-hydroxyethyl acrylate) 40 g, 2-hydroxyethyl vinyl ether 40 g, light ester POA 16 g, methacrylic acid 40 g, crotonic acid 40 g, maleic acid 40 g, acrylamide 44 g, AS 80 g, and ATBS-K 60 g
Was added, and a solution of 3.7 g of potassium persulfate dissolved in 6.5 g of 35% aqueous hydrogen peroxide was similarly added dropwise over 20 hours, and further subjected to a redox polymerization reaction for 2 hours. As a result, the average molecular weight was determined. A copolymer (A-3) having a 16,400 concentration of 50.5% was obtained.

(Copolymer A-4) In the same manner as in (Copolymer A-1), 400 g of ion-exchanged water and 9.5 g of sodium hypophosphite were charged, and after stirring and dissolving, light ester H was dissolved.
O40g, light ester HOA40g, 2-hydroxyethyl vinyl ether 8g, light acrylate PO
A8 g, acrylic acid 80 g, methacrylic acid 72 g, acrylamide 36 g, AS 16 g, and ATBS-K80
g of potassium persulfate and 10 g of hydrogen peroxide solution.
g for 3 hours, and the polymerization temperature is 75-77 ° C.
After the dropwise addition, a redox polymerization reaction was further carried out at 82 to 82 ° C. for 13 hours. As a result, a copolymer (A-4) having an average molecular weight of 5,400 and a concentration of 50.8% was obtained.

(Copolymer A-5) In the same manner as in (Copolymer A-1), 400 g of ion-exchanged water, 7.1 g of sodium hypophosphite, 40 g of light ester HO, and 48 g of 2-hydroxyethyl vinyl ether were used. , Acrylic acid 40 g,
A solution prepared by dissolving 80 g of crotonic acid, 40 g of methacrylic acid, 32 g of acrylamide, 80 g of AS and 40 g of ATBS-K, and dissolving 5 g of potassium persulfate in 15 g of hydrogen peroxide solution was added dropwise over 3 hours at a polymerization temperature of 70/72 ° C.
Further, as a result of performing a redox polymerization reaction at 70 to 72 ° C. for 15 hours, the average molecular weight was 8,200 and the concentration was 50.9.
% Copolymer (A-5) was obtained.

These copolymers (A-1) to (A-5)
The hydrophilic resin (a) formed by neutralizing the acid group of (a) with an alkali metal hydroxide (α) and an organic amine compound (β) will be described in detail below. (Hydrophilic resin (A-1)) (Copolymer (A-1)) 1
5g of 25% aqueous ammonia was added to
After stirring and mixing at 0 ° C. to 45 ° C. for 1 hour, adjusting the pH, adjusting the concentration by adding ion-exchanged water, stirring and mixing for another 1 hour to produce a colorless transparent liquid having a heating residue of 10.1% and a pH of 7.0. As a result, a hydrophilic resin (a-1) was obtained.

According to the method for producing (hydrophilic resin (a-2)) (hydrophilic resin (a-1)), (copolymer (A-2))
To 100 g, 59.4 g of 25% aqueous ammonia was added, and the same production was performed.
As a result, a colorless transparent liquid hydrophilic resin (a-2) having a heating residue of 10.3% and a pH of 7.0 was obtained.

According to the method for producing (hydrophilic resin (a-3)) (hydrophilic resin (a-1)), (copolymer (A-3))
56.6 g of 25% aqueous ammonia was added to 100 g, and the same production was performed.
As a result, a colorless transparent liquid hydrophilic resin (a-3) having a heating residue of 10.0% and a pH of 7.0 was obtained.

According to the method for producing (hydrophilic resin (a-4)) (hydrophilic resin (a-1)), (copolymer (A-4))
To 100 g, 71.7 g of 25% ammonia water was added, and the same production was performed. When ion-exchanged water was added to adjust the concentration,
A colorless transparent liquid hydrophilic resin (a-4) having a heating residue of 10.1% and a pH of 7.0 was obtained.

According to the method for producing (hydrophilic resin (a-5)) (hydrophilic resin (a-1)), (copolymer (A-5))
To 100 g, 68.2 g of 25% ammonia water was added, and the same production was performed.
A colorless transparent liquid hydrophilic resin (A-5) having a heating residue of 10.4% and a pH of 7.0 was obtained.

According to the method for producing (hydrophilic resin (a-6)) (hydrophilic resin (a-1)), (copolymer (A-1))
To 100 g, 10 g of triethylamine and 42.7 g of 25% aqueous ammonia were added, and the same production was performed. When the concentration was adjusted by adding ion-exchanged water, the heating residue was 10.1%, PH
A colorless transparent liquid hydrophilic resin (7.2) of 7.2 was obtained.

According to the method for producing (hydrophilic resin (a-7)) (hydrophilic resin (a-1)), (copolymer (A-2))
10 g of triethylamine and 45.4 g of 25% aqueous ammonia were added to 100 g, and the same production was performed. When the concentration was adjusted by adding ion-exchanged water, the heating residue was 10.5%, P
A colorless transparent liquid hydrophilic resin of H7.2 (a-7) was obtained.

According to the method for producing (hydrophilic resin (a-8)) (hydrophilic resin (a-1)), (copolymer (A-3))
To 100 g, 10 g of triethylamine and 42.6 g of 25% aqueous ammonia were added, and the same production was performed. When the concentration was adjusted by adding ion-exchanged water, the heating residue was 10.0%, PH
A colorless transparent liquid hydrophilic resin (7.2) of 7.2 was obtained.

According to the method for producing (hydrophilic resin (a-9)) (hydrophilic resin (a-1)), (copolymer (A-4))
To 100 g, 10 g of triethylamine and 57.7 g of 25% aqueous ammonia were added, and the same production was performed. When the concentration was adjusted by adding ion-exchanged water, the heating residue was 10.0%, P
A colorless transparent liquid hydrophilic resin (H-9) of H7.2 was obtained.

According to the method for producing (hydrophilic resin (a-10)) and (hydrophilic resin (a-1)), the copolymer (A-
5)) To 100 g, 10 g of triethylamine and 25%
Ammonia water (54.2 g) was added, the mixture was produced in the same manner, and ion exchanged water was added to adjust the concentration.
%, PH 7.2, a colorless transparent liquid hydrophilic resin (a-1)
0) was obtained.

According to the method for producing (hydrophilic resin (a-11)) (hydrophilic resin (a-1)), the copolymer (A-
1)) To 100 g, 5.6 g of potassium hydroxide (manufactured by Wako Pure Chemical, first grade reagent) and 42.7 g of 25% ammonia water were added, and the same production was performed. As a result, a colorless transparent liquid hydrophilic resin (a-11) having a residue of 10.4% and a pH of 7.5 was obtained.

According to the method for producing (hydrophilic resin (a-12)) (hydrophilic resin (a-1)), the copolymer (A-
2)) To 100 g, 5.6 g of potassium hydroxide and 45.3 g of 25% aqueous ammonia were added, and the mixture was produced in the same manner.
A colorless transparent liquid hydrophilic resin having a pH of 7.5 (a-1)
2)) was obtained.

According to the method for producing (hydrophilic resin (a-13)) (hydrophilic resin (a-1)), the copolymer (A-
3)) To 100 g, 5.6 g of potassium hydroxide and 42.5 g of 25% aqueous ammonia were added, and the mixture was produced in the same manner.
PH7.5 colorless transparent liquid hydrophilic resin (A-13)
was gotten.

According to the method for producing (hydrophilic resin (a-14)) (hydrophilic resin (a-1)), the copolymer (A-
4)) To 100 g, 5.6 g of potassium hydroxide and 57.6 g of 25% aqueous ammonia were added, and the same production was performed. When the concentration was adjusted by adding ion-exchanged water, the heating residue was 10.1%.
PH7.5 colorless transparent liquid hydrophilic resin (A-14)
was gotten.

According to the method for producing (hydrophilic resin (a-15)) (hydrophilic resin (a-1)), the copolymer (A-
5)) To 100 g, 5.6 g of potassium hydroxide and 54.1 g of 25% aqueous ammonia were added, and the mixture was produced in the same manner.
PH7.5 colorless transparent liquid hydrophilic resin (A-15)
was gotten.

According to the method for producing (hydrophilic resin (a-16)) (hydrophilic resin (a-1)), the copolymer (A-
1)) To 100 g, 5.6 g of potassium hydroxide, 7.5 g of triethanolamine and 35.7 of 25% aqueous ammonia.
g in the same manner, and ion-exchanged water was added to adjust the concentration. As a result, a colorless transparent liquid hydrophilic resin (A-16) having a heating residue of 10.0% and a pH of 7.3 was obtained. .

According to the method for producing (hydrophilic resin (a-17)) (hydrophilic resin (a-1)), the copolymer (A-
2)) To 100 g, 5.6 g of potassium hydroxide, 7.5 g of triethanolamine and 38.4 of 25% aqueous ammonia.
g, and the mixture was adjusted in the same manner by adding ion-exchanged water to obtain a colorless transparent liquid hydrophilic resin (a-17) having a heating residue of 10.1% and a pH of 7.3. .

According to the method for producing (hydrophilic resin (a-18)) (hydrophilic resin (a-1)), the copolymer (A-
3)) To 100 g, 5.6 g of potassium hydroxide, 7.5 g of triethanolamine, and 35.25% aqueous ammonia.
When 6 g was added and the mixture was prepared in the same manner and ion-exchanged water was added to adjust the concentration, a colorless transparent liquid hydrophilic resin (B-18) having a heating residue of 10.5% and a pH of 7.3 was obtained. .

According to the method for producing (hydrophilic resin (a-19)) (hydrophilic resin (a-1)), the copolymer (A-
4)) To 100 g, 5.6 g of potassium hydroxide, 7.5 g of triethanolamine, and 50.25% aqueous ammonia.
When 7 g was added and the mixture was prepared in the same manner and ion-exchanged water was added to adjust the concentration, a colorless transparent liquid hydrophilic resin (A-19) having a heating residue of 10.0% and a pH of 7.3 was obtained. .

According to the method for producing (hydrophilic resin (a-20)) (hydrophilic resin (a-1)), (copolymer A-5) 1
5.6 g of potassium hydroxide, 7.5 g of triethanolamine, and 47.2 g of 25% aqueous ammonia were similarly added to 00 g, and the concentration was adjusted by adding ion-exchanged water. A colorless transparent liquid hydrophilic resin (a-20) having a pH of 7.3 and 1% was obtained.

(Lubricity imparting agent (B-1)) PEG 2,000 # (Lion Co., Ltd., polyethylene glycol) Molecular weight 2,000
0) 200 g, and 26.1 g of succinic anhydride (reagent first grade, manufactured by Wako Pure Chemical Industries, Ltd.) were charged, and the mixture was heated at 80 ° C. for 2 hours.
The reaction was carried out at 100 ° C. for 1 hour and further at 110 ° C. for 2 hours to obtain a white solid diester dibasic oxyacid (B-1). In addition, 15 g of triethanolamine and 25 g
% Ammonia water, and mixed and stirred at 40 ° C. to 45 ° C. for 1 hour.
Was adjusted. As a result, heating residue 40.3%, PH7.
As a result, a lubricity imparting agent (b-1) represented by the following formula (1) as a colorless transparent liquid of No. 5 was obtained.

[0087]

Embedded image

(Lubricity imparting agent (B-2)) By the same production method as (Lubricity imparting agent (B-1)), PEG 2,000 #
200 g and 25.6 g of maleic anhydride were charged and reacted in the same manner to obtain a diester dibasic oxyacid (B-2) as a pale yellow solid. When adjusted, a lubricating agent (b-2) represented by the following formula (2) as a pale yellow transparent liquid having a heating residue of 40.5% and a pH of 7.5 was obtained.

[0089]

Embedded image

(Lubricity imparting agent (II-3)) PEG 2,000 #
200 g and 38.6 g of phthalic anhydride were charged and reacted in the same manner to obtain a white solid diester dibasic oxyacid (B-
3), and 15 g of triethanolamine and 25%
Add 10 g of ammonia water and adjust in the same manner.
A lubricity imparting agent (b-3) represented by the following formula (3) as a colorless transparent liquid having a pH of 7.5 and 0.1% was obtained.

[0091]

Embedded image

(Lubricity-imparting agent (II-4)) PEG 2,000 #
200 g and 50 g of trimellitic anhydride were charged and reacted in the same manner to give a diester dibasic oxyacid (B-
4) and 15 g of triethanolamine and 25%
By adding 10 g of aqueous ammonia and adjusting similarly, a lubricating agent (b-4) represented by the following formula (4) as a pale yellow liquid having a heating residue of 40.5% and a pH of 7.5 was obtained.

[0093]

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(Lubricity imparting agent (II-5)) PEG 4,000 #
200 g of polyethylene glycol molecular weight (Lion Co., Ltd., 4,000) and 13 g of succinic anhydride were charged to obtain diester dibasic oxyacid (B-5) as a white solid, and further 15 g of triethanolamine and 10 g of 25% aqueous ammonia. , And the concentration was adjusted to 40% by further adding ion-exchanged water. As a result, a lubricating agent (B-5) represented by the following formula (5) as a colorless transparent liquid having a heating residue of 40.1% and a pH of 7.5 was obtained.

[0095]

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(Lubricity imparting agent (B-6)) PEG600 # 4,
000) and 12.8 g of maleic anhydride were charged and reacted in the same manner to obtain a diester dibasic oxyacid (B-6) as a brown solid.
g and 5 g of 25% aqueous ammonia, and the mixture was adjusted in the same manner to obtain a lubricating agent (b-6) represented by the following formula (6) as a pale brown liquid having a heating residue of 40% and a pH of 7.5.

[0097]

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(Lubricity imparting agent (II-7)) PEG 4,000 #
200 g and 19.3 g of phthalic anhydride were charged and reacted in the same manner to obtain a diester dibasic oxyacid (B-
7) and 7.5 g of triethanolamine and 25
% Ammonia water was added and adjusted similarly to obtain a lubricating agent (b-7) represented by the following formula (7) as a pale brown liquid having a heating residue of 40.4% and a pH of 7.5.

[0099]

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(Lubricity-imparting agent (B-8)) PEG 4,000 # by the same production method as (Lubricity-imparting agent (B-1))
200 g and trimellitic anhydride (manufactured by Wako Pure Chemical Industries, Ltd.
25 g of reagent primary) was charged and reacted in the same manner to obtain diester dibasic oxyacid (B-8) as a white solid, and 7.5 g of triethanolamine and 5 g of 25% aqueous ammonia.
To adjust the heating residue to 40.1%, PH
As a result, a lubricating agent (B-8) represented by the following formula (8) was obtained as a colorless transparent liquid of 7.5.

[0101]

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(Lubricity-imparting agent (II-9)) By the same production method as (Lubricity-imparting agent (II)), PEG 6,000 was obtained.
200 g of polyethylene glycol molecular weight (manufactured by Lion Corporation) and 8.7 g of succinic anhydride were charged and reacted in the same manner to obtain a diester dibasic oxyacid (B-9) as a white solid. When 5 g and 3.4 g of 25% aqueous ammonia were added and adjusted similarly, a lubricating agent (b-9) represented by the following formula (9) of a colorless transparent liquid having a heating residue of 40.5% and a pH of 7.5 was obtained. Obtained.

[0103]

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(Lubricity-imparting agent (II-10)) PEG6,000 was produced by the same production method as (Lubricity-imparting agent (II-1)).
#, 200 g and 8.5 g of maleic anhydride were charged and reacted in the same manner to obtain diester dibasic oxyacid (B-10) as a white solid, and 5 g of triethanolamine and 3.4 g of 25% aqueous ammonia were further added. In the same manner, a lubricating agent (B-10) represented by the following formula (10) as a colorless transparent liquid having a heating residue of 40.0% and a pH of 7.5 was obtained.

[0105]

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(Lubricity-imparting agent (II-11)) PEG6,000 was produced by the same production method as (Lubricity-imparting agent (II-1)).
#, 200 g and 12.9 g of phthalic anhydride were charged and reacted in the same manner to obtain a diester dibasic oxyacid (B-11) as a white solid. Further, 5 g of triethanolamine and 3.4 g of 25% aqueous ammonia were added. In the same manner, a lubricating agent (b-11) represented by the following formula (11) was obtained as a colorless transparent liquid having a heating residue of 40.5% and a pH of 7.5.

[0107]

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(Lubricity-imparting agent (II-12)) (Lubricity-imparting agent (II-1))
#, 200 g and trimellitic anhydride 6.4 g,
The same reaction was performed to obtain a diester dibasic oxyacid (B-12) as a white solid, and further adjusted by adding 5 g of triethanolamine and 3.4 g of 25% aqueous ammonia to obtain a heating residue of 40.0%, A lubricity imparting agent (b-12) represented by the following formula (12) as a colorless transparent liquid having a pH of 7.5 was obtained.

[0109]

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Next, the third component, a processability improver (c)
Will be described below. (Processability improver (c-1)) In a 1-liter four-necked flask equipped with a stirrer, thermometer, nitrogen inlet tube and reflux condenser, 100 g of ion-exchanged water and phosphorous acid (Wako Pure Chemical Industries, Ltd.) , First grade reagent), and after 16 g of sufficient stirring and dissolution,
Further, 250 g of methyl alcohol, 80 g of acrylic acid,
100 g of methacrylic acid, 40 g of maleic acid, 20 g of ethyl acrylate, 12 g of light ester NA (n-amyl methacrylate, manufactured by Kyoeisha Chemical Co., Ltd.), 8 g of light ester NB (n-butyl methacrylate, manufactured by Kyoeisha Chemical Co., Ltd.), 80 g of acrylonitrile, light 40 g of ester HOA (manufactured by Kyoeisha Chemical Co., Ltd., 2-hydroxyethyl acrylate) and 20 g of 2-hydroxyethyl vinyl ether (manufactured by Nippon Carbide Chemical Industry Co., Ltd.)
g, 2-mercaptoethanol (manufactured by Toyo Kasei Kogyo Co., Ltd.) (19 g), and while bubbling nitrogen, a solution consisting of potassium persulfate (15 g), 35% hydrogen peroxide solution (20 g) and ion-exchanged water (50 g) was heated to 55 ° C. to 57 ° C. After 12 hours, the mixture was polymerized at 60 ° C. to 62 ° C. for 1 hour to obtain a copolymer (C-1). This copolymer (C-1) 2
To 50 g, 11.2 g of potassium hydroxide, 14.9 g of triethanolamine and 61.9 g of 25% aqueous ammonia were added, and mixed and stirred at 40 ° C. to 45 ° C. for 1 hour. Was adjusted. As a result,
A workability improver (c-1) as a pale yellow liquid having a heating residue of 40.1% and a pH of 7.5 was obtained.

According to the process for preparing (processability improver (c-2)) and (processability improver (c-1)), 100 g of ion-exchanged water was used.
After 26 g of phosphorous acid was charged and sufficiently stirred and dissolved, 250 g of methyl alcohol, 20 g of acrylic acid, 80 g of methacrylic acid, 40 g of maleic acid, and 20 g of ethyl acrylate
g, light ester NA 20 g, light ester NB8
g, acrylonitrile 92 g, light ester HOA8
0 g, 20 g of light ester HO, 20 g of 2-hydroxyethyl vinyl ether, and 30 g of 1-mercapto-2-octacarboxyethane (manufactured by Kyoeisha Chemical Co., Ltd.).
Using a solution consisting of 20 g of a 5% hydrogen peroxide solution and 50 g of ion-exchanged water, the copolymer (C-
2) was obtained. To 250 g of this copolymer (C-2),
5.6 g of potassium hydroxide, 7.5 of triethanolamine
g, and 40.8 g of 25% aqueous ammonia were added to obtain a workable improver (c-2) as a pale yellow liquid having a heating residue of 40.5% and a pH of 7.8.

(Processability improver (C-3)) According to the production method of (Processability improver (C-1)), 100 g of ion-exchanged water,
After 22.5 g of phosphorous acid was charged and sufficiently stirred and dissolved, 250 g of methyl alcohol, 40 g of acrylic acid, 80 g of methacrylic acid, 40 g of maleic acid, 28 g of ethyl acrylate, 20 g of light ester NA, and 20 g of light ester N
B8 g, acrylonitrile 104 g, light ester H
40 g of OA, 20 g of light ester HO, 20 g of 2-hydroxyethyl vinyl ether, and 26 g of β-mercaptopropionic acid (manufactured by Tomioka Chemical Co., Ltd.) were charged. When a solution composed of 50 g was polymerized in the same manner, a copolymer (C-3) was obtained. To 250 g of this copolymer (C-3), 8.4 g of potassium hydroxide, 11.9 g of triethanolamine, and 2
When 39.2 g of 5% aqueous ammonia was added and the same procedure was performed, a processability improver (c-3) as a pale yellow liquid with a heating residue of 40.2% and a pH of 8.2 was obtained.

(Processability improver (c-4)) According to the process for producing (processability improver (c-1)), 100 g of ion-exchanged water
After 34 g of phosphorous acid was charged and sufficiently stirred and dissolved, 250 g of methyl alcohol, 40 g of acrylic acid, 80 g of methacrylic acid, 40 g of maleic acid, and 36 g of ethyl acrylate were added.
g, light ester NA 20 g, light ester NB8
g, acrylonitrile 96 g, light ester HOA4
0 g, light ester HO 20 g, 2-hydroxyethyl vinyl ether 20 g, β-mercaptopropionic acid n-butyl ester (first grade reagent, manufactured by Wako Pure Chemical Industries, Ltd.)
39.5 g was charged, and while bubbling with nitrogen, a copolymer consisting of 10 g of potassium persulfate, 15 g of 35% hydrogen peroxide solution and 50 g of ion-exchanged water was similarly polymerized to obtain a copolymer (C-4). Was done. This copolymer (C-4)
250 g, 8.4 g of potassium hydroxide, 11.9 g of triethanolamine, and 37.1 g of 25 g% aqueous ammonia
g, add 40.2% of heating residue, PH
8.5 was obtained as a pale yellow liquid processability improver (c-4).

According to the production method of (Processability improver (C-5)) (Processability improver (C-1)), 100 g of ion-exchanged water,
After 45 g of phosphorous acid was charged and sufficiently stirred and dissolved, 250 g of methyl alcohol, 100 g of acrylic acid, 40 g of methacrylic acid, 40 g of maleic acid, and ethyl acrylate 2 were added.
8 g, light ester NB12 g, acrylonitrile 1
20 g, light ester HOA 60 g, 1-mercaptododecane (Wako Pure Chemical Industries, Ltd., first grade reagent) 52 g were charged, and while blowing nitrogen, potassium persulfate 3 g, 35 g
Polymerization was carried out in the same manner using a solution consisting of 5 g of a 5% hydrogen peroxide solution and 50 g of ion-exchanged water to obtain a copolymer (C-5). To 250 g of this copolymer (C-5), 9.5 g of potassium hydroxide, 13.4 g of triethanolamine,
Then, 42.3 g of 25% aqueous ammonia was added to obtain a workability improver (c-5) as a pale yellow liquid having a heating residue of 40.2% and a pH of 7.1.

(Curing Agent D-1) As the curing agent D-1, Yukicoat E-195 (manufactured by Kyoeisha Chemical Co., Ltd., polyethylene glycol (n = 4) diglycidyl ether) represented by the following formula (13) is used. And a colorless and transparent liquid having a viscosity of 40 cps.

[0116]

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(Curing Agent D-2) As the curing agent D-2, Yukicoat E-305 (polyethylene glycol (n = 9) diglycidyl ether manufactured by Kyoeisha Chemical Co., Ltd.) represented by the following formula (14) is used. And a colorless and transparent liquid having a viscosity of 40 cps.

[0118]

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(Curing Agent D-3) The curing agent D-3 is a Yukicoat E-394 (manufactured by Kyoeisha Chemical Co., Ltd., polyethylene glycol (n = 14)) represented by the following formula (15).
Diglycidyl ether) and is a pale yellow transparent liquid having a viscosity of 160 cps.

[0120]

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(Curing Agent D-4) Curing agent D-4 was prepared from Yukicoat E-587 (Kyoeisha Chemical Co., Ltd., polyethylene glycol (n = 22)) represented by the following formula (16).
Diglycidyl ether) and is a pale yellow solid with a melting point of 45 ° C.

[0122]

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(Curing Agent N-5) Hardening agent N-5 was obtained from Yukicoat E-1080 (manufactured by Kyoeisha Chemical Co., Ltd., polyethylene glycol (n = 4) represented by the following formula (17).
5) Diglycidyl ether) is a pale yellow solid having a melting point of 52 ° C.

[0124]

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(Curing Agent N-6) The curing agent N-6 is a Yukicoat E-140 (Kyoeisha Chemical Co., Ltd., glycerol diglycidyl ether) represented by the following formula (18).
Is a colorless and transparent liquid having a viscosity of 145 cps.

[0126]

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(Curing Agent N-7) As the curing agent N-7, Yukicoat E-170 (manufactured by Kyoeisha Chemical Co., Ltd., polyglycerol (n = 2) polyglycidyl ether) represented by the following formula (19) is used. And a pale yellow liquid having a viscosity of 1500 cps.

[0128]

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Next, a fin coating composition having hydrophilicity, good lubricity and excellent workability according to the present invention, which is obtained by combining the components constituting the base of the present invention, is produced.
This will be described as Examples 1 to 120. Examples 1 to 120 A hydrophilic resin (A), a lubricity-imparting agent (B) and a processability improver (C) and ion-exchanged water were added, and the mixture was sufficiently stirred and mixed. In addition, mix well with stirring,
% Of a paint was prepared, and this was used in Examples 1 to 120.
And The results are shown in Tables 1-1 to 1-5 below.

Next, hydrophilic resin for comparative example (e1 to 4)
The production method was used, and this was used as a raw material resin for a comparative example. (Hydrophilic resin (e-1) for comparative example) 1 equipped with a stirrer, a reflux condenser, a thermometer, a dropping funnel and a nitrogen gas inlet tube.
In a liter four-necked flask, 280 g of ion-exchanged water,
Using 7.2 g of sodium hypophosphite, 9 g of potassium persulfate, 40 g of light ester HO, 120 g of acrylic acid, and 120 g of acrylamide as raw materials, a redox polymerization reaction was carried out at a polymerization temperature of 65 to 68 ° C. for 15 hours under a nitrogen gas stream. With an average molecular weight of 14,500 and a concentration of 51.0
% Copolymer (D-1) was obtained. According to the method for producing (hydrophilic resin (a-1)), the copolymer (D-1) 50
0 g, 8.4 g of potassium hydroxide and 6 ammonia water.
When 2.3 g was added and the mixture was prepared in the same manner and ion exchange water was added to adjust the concentration, a light yellow liquid hydrophilic resin (e-1) having a heating residue of 20.1% and a pH of 7.5 was obtained. Was done.

(Hydrophilic resin for comparative example (e-2)) In a 1-liter four-necked flask equipped with a stirrer, a reflux condenser, a thermometer, a dropping funnel and a nitrogen gas inlet tube, 440 g of ion-exchanged water was added. Using 4.5 g of sodium hypophosphite, 3.1 g of potassium persulfate, 60 g of acrylonitrile, 80 g of light ester HOA, 148 g of acrylic acid, and 52 g of methyl methacrylate as raw materials, at a polymerization temperature of 68 to 72 ° C. for 12 hours under a nitrogen gas stream. A redox polymerization reaction was performed to obtain a copolymer (B-2) having an average molecular weight of 10,900 and a concentration of 50.7%. This is referred to as a hydrophilic resin (a-
According to the production method of 1)), 500 g of the copolymer (D-2)
8.4 g of potassium hydroxide and 63.7 g of 25% aqueous ammonia were added to the mixture, and the mixture was adjusted in concentration by adding ion-exchanged water to obtain a heating residue of 20.5% and a pH of 7.5.
A light yellow liquid hydrophilic resin (e-2) was obtained.

(Hydrophilic resin for comparative example (e-3)) In a 1-liter four-necked flask equipped with a stirrer, a reflux condenser, a thermometer, a dropping funnel and a nitrogen gas inlet tube, 300 g of ion-exchanged water was added. Using, as raw materials, 12.5 g of sodium hypophosphite, 5.3 g of ammonium persulfate, 120 g of acrylonitrile, 175 g of acrylic acid, and 5 g of light acrylate NA, at a polymerization temperature of 48 to 52 ° C.
The redox polymerization reaction is carried out for an
At 0, a copolymer (D-3) having a concentration of 50.1% was obtained.
According to the method for producing (hydrophilic resin (a-1)), 500 g of copolymer (D-3), 8 g of sodium hydroxide,
And 85.4 g of 25% aqueous ammonia, and then the concentration was adjusted by adding ion-exchanged water. As a result, a hydrophilic resin of a pale yellow liquid having a heating residue of 20.7% and a pH of 7.5% ( E-3) was obtained.

(Hydrophilic resin for comparative example (e-4)) In a 1-liter four-necked flask equipped with a stirrer, a reflux condenser, a thermometer, a dropping funnel and a nitrogen gas inlet tube, 370 g of ion-exchanged water was added. 7.2 g of sodium hypophosphite, 6 g of potassium persulfate, 120 g of acrylic acid, 120 g of ATBS-K,
And 120 g of acrylamide as raw materials, a redox polymerization reaction was carried out at a polymerization temperature of 65 to 68 ° C. for 15 hours under a nitrogen gas stream, and the average molecular weight was 14,500 and the concentration was 5
1.0% of a copolymer (D-4) was obtained. According to the method for producing (hydrophilic resin (a-1)), the copolymer (D-
4) To 500 g, 8.4 g of potassium hydroxide and 25%
The same production was performed by adding 43.8 g of ammonia water, and the concentration was adjusted by adding ion-exchanged water.
%, PH7.5 light yellow liquid hydrophilic resin (e-4)
was gotten.

Next, using these hydrophilic resins (e-1) to (e-4) for comparative example and the hydrophilic resins (a-1) to (a-20) of the present invention, Comparative Example Paint No. 1 to paint No. 1 96, and this was compared with Comparative Examples 1 to
A description will be given as a comparative example 96.

Comparative Example A hydrophilic resin (e), a lubricity imparting agent (b) for a comparative example,
Add the processability improver (c) and ion-exchanged water and mix well with stirring, then add the curing agent (d) and mix well with this to produce a 20% concentration paint for comparative examples. Are described in Tables 2-1 to 2-3.

[0136]

[Table 1]

[0137]

[Table 2]

[0138]

[Table 3]

[0139]

[Table 4]

[0140]

[Table 5]

[0141]

[Table 6]

[0142]

[Table 7]

[0143]

[Table 8]

Characteristics of Examples The paints obtained in the above examples were applied to the surface of an aluminum alloy material, and the wettability (hydrophilic contact angle), adhesion, lubricity and press workability of the surface were examined. The results are shown in Tables 3-1 to 3-4 below for Examples 1 to 120.
Shown in Tables 4-1 and 4-1 below show Comparative Examples 1 to 96.
To 4-3.

[0145]

[Table 9]

[0146]

[Table 10]

[0147]

[Table 11]

[0148]

[Table 12]

[0149]

[Table 13]

[0150]

[Table 14]

[0151]

[Table 15]

Water wettability A: Contact angle of water droplet measured after leaving the baked and dried sample for 24 hours at room temperature O mark: Contact angle of 20 or less △ mark; Contact angle of 20 to 40 × mark; Contact angle of 40 or more Property B: Contact angle of water droplet after immersing sample in ion-exchanged water for 240 hours O mark; contact angle of 20 or less △ mark; contact angle of 20 to 40 x mark; contact angle of 40 or more Water wettability C: volatilization of sample 6 for neutral press oil (RF-190)
After immersion for 0 second and heat treatment at 150 ° C. for 3 minutes, the contact angle of a water drop after immersion in pure water for 24 hours was measured. O mark: contact angle of 20 or less △ mark; contact angle of 20 to 40 × mark; contact angle of 40 water or less Rubbing property: Immerse water in gauze and rub 10 times with a load of 3 kg to evaluate coating film appearance O mark; no peeling △ mark; partial peeling × mark; many peeling Film coating property of film: 5 samples are superimposed The presence or absence of adhesion of this sample at a load of 600 kg / cm ² was determined. O mark; no adhesion Δ mark; some adhesion × mark; adhesion Adhesion: Volatile press oil was applied to the sample, and degreased with Triclean. Thereafter, it was determined by a JISH4001 cross cut test. Lubricity: A volatile press oil was applied to the sample, and the dynamic friction coefficient of the surface was measured with a Bowden friction tester (× 1/100).
0) O mark; 0.15 or less △ mark; 0.16 or more and 0.25 or less X mark; 0.26 or more Press workability A: The sample was continuously processed using volatile press oil, and the molded product was defective and gold Observation of baking on the mold O mark: 5% or less molding failure, no baking on the mold △ mark: 5-15% molding failure, a little baking on the mold × mark: 15% or more molding failure, on the mold Pressing property B: Continuous processing of the sample without volatile press oil, observing defective molded products and seizure to the mold O mark: 5% or less molding failure, no seizure to the mold △ mark: molding Defective 5-15%, slightly burned to mold × mark; Molding failure 15 ° C or more, many burns to mold ------ × ----: Unable to measure

[0153]

As described above, the coating composition according to the present invention is rich in water wettability. Therefore, since the coating composition is applied to the fin surface, even if water droplets adhere, the water droplets will It can be understood that the expansion and the remarkable increase of the ventilation resistance are solved, and therefore the heat exchange efficiency is improved. Also, because it has excellent lubricity,
Even if a coating film is formed in advance and then subjected to press working or the like, the die is less likely to be damaged, so that the manufacturing cost is reduced accordingly. Furthermore, the excellent lubricity makes it possible to reduce the amount of lubricating oil used during press working, and if the amount of lubricating oil is further reduced, the lubricating oil used in the subsequent process can be reduced. This is not only easy to remove, but also makes it possible to prevent a decrease in water wettability, which is extremely advantageous.
And, the rich adhesion of the coating film means that it has high durability. Therefore, the water wettability can be maintained for that long, and the corrosion resistance is also high. The heat exchanger will be more durable. In addition, since the coating film has lubricity and workability, it can be formed by the drawless processing method, and the wear of the mold is small.

[Brief description of the drawings]

FIG. 1 is a diagram illustrating a state in which water droplets adhere between fins of a conventional heat exchanger.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Akihiro Kiyotani 5-11-3 Shimbashi, Minato-ku, Tokyo Sumitomo Sumitomo Building Inside Sumitomo Light Metal Industries Co., Ltd. (72) Inventor Kiju Isomura 5-11- Shimbashi, Minato-ku, Tokyo 3. Shimbashi Sumitomo Building Sumitomo Light Metal Industry Co., Ltd. (72) Inventor Tsukasa Kasuga 5-11-3 Shimbashi, Minato-ku, Tokyo Shimbashi Sumitomo Building Sumitomo Light Metal Industry Co., Ltd. (72) Inventor Chihiro Masago 5 Suzaku, Nara City, Nara Prefecture Chome 1-1-48-203 (72) Inventor Rieko Kawahara 1-7-7 Hinokizaka, Haibara-cho, Uda-gun, Nara Prefecture (72) Tachi Akiyama 33-1, Kanzakicho, Amagasaki-shi, Hyogo Kansai Paint Co., Ltd. (72) Inventor Shinichiro Nitta 33-1, Kanzakicho, Amagasaki City, Hyogo Prefecture Kansai Paint Co., Ltd.

Claims (13)

[Claims] 1. An unsaturated monomer having a hydroxy group (a), an unsaturated monomer having a carboxyl group (b),
Copolymer composed of unsaturated monomer having an amide group (c), unsaturated monomer having a sulfonic acid group (d), and phosphoric acid and / or phosphate compound (e) ( A) a hydrophilic resin (a) constituted by neutralizing an acid group of A) with an alkali metal hydroxide (α) and / or an organic amine compound (β); and polyethylene glycol (f).
A diester dibasic oxyacid (B) comprising an organic dibasic oxyacid (g) and a lubricity-imparting agent (b) formed by neutralizing with an organic amine compound (β). ,
Unsaturated monomer having carboxyl group (h), carbon number 1
To 5 unsaturated monomer having a linear and / or side chain alkyl group (i), unsaturated monomer having a nitrile group (j), unsaturated monomer having a hydroxy group (k), And the acid group of the sulfur-containing copolymer (C) formed using the organic compound (I) having an aliphatic mercapto group is a hydroxide (α) of an alkali metal and / or an organic amine-based compound. It is characterized by containing a processability improver (c) constituted by neutralization with the compound (β) and at least one curing agent (d) selected from the group of polyglycidyl ethers (D). Paint composition. 2. The copolymer (A) constituting the hydrophilic resin (a) is an unsaturated monomer having a hydroxy group (a) /
The ratio of the unsaturated monomer having a carboxyl group (b) / the unsaturated monomer having an amide group (c) / the unsaturated monomer having a sulfonic acid group (d) is from 15 to 35 / weight ratio. 20
The coating composition according to claim 1, wherein the ratio is from 45/15 to 15/20 to 45. 3. An unsaturated monomer having a hydroxy group (a), an unsaturated monomer having a carboxyl group (b), and an unsaturated monomer having an amide group, which constitute the hydrophilic resin (a). (C) a phosphoric acid and / or a phosphate compound (e) in an amount of 0.01 to 5 parts by solid content based on 100 parts by weight of the total amount of the unsaturated monomer having a sulfonic acid group (d). The coating composition according to claim 1, wherein 4. The copolymer (A) in the hydrophilic resin (A) has an average molecular weight of 2,000 to 50,000, and the lubricating agent (B) and the processability improver (C) 2. The coating composition according to claim 1, wherein the sum is from PH7 to PH9. 5. The lubricating agent (b) is a diester dibasic oxyacid (B) composed of polyethylene glycol (f) and an organic dibasic oxyacid (g), wherein the acid group of the diester dibasic oxyacid (B) is an organic amine compound (B). 2. The coating composition according to claim 1, which is constituted by neutralizing with β). 6. The ratio of hydrophilic resin (a) / lubricity-imparting agent (b) is 2 to 50 parts by weight based on 100 parts by weight of hydrophilic resin (a) in terms of solid content weight ratio. The coating composition according to claim 1, wherein 7. The ratio of hydrophilic resin (a) / processability improver (c) is 2 to 30 parts by weight based on 100 parts by weight of hydrophilic resin (a) in terms of solid content weight ratio. The coating composition according to claim 1, wherein 8. The ratio of hydrophilic resin (a) / hardener (d) is 100 parts by weight of hydrophilic resin (a) in terms of solid content weight ratio.
2. The coating composition according to claim 1, wherein the amount is 200 to 500 parts by weight based on parts by weight. 9. The processability improver (c) is an unsaturated monomer (h) having a carboxyl group / an unsaturated monomer (i) having a linear or side chain alkyl group having 1 to 5 carbon atoms. ) / Unsaturated monomer having a nitrile group (j) / unsaturated monomer having a hydroxy group (k) in a weight ratio of 25 to 50.
The coating composition according to claim 1, wherein the ratio is from / 5 to 20/15 to 35/10 to 25. 10. An average molecular weight of 1,000 to 10,000.
A processability improver (c), wherein the unsaturated monomer (h) having a carboxyl group and a carbon number of 1 to 5;
A total of 100 parts by weight of an unsaturated monomer (i) having a linear or side chain alkyl group, an unsaturated monomer (j) having a nitrile group, and an unsaturated monomer (k) having a hydroxy group The coating composition according to claim 1, wherein the organic compound (l) having an aliphatic mercapto group is 1 to 15 parts by weight in terms of solid content. 11. An unsaturated monomer having a hydroxy group (a), an unsaturated monomer having a carboxyl group (b),
Copolymer composed of unsaturated monomer having an amide group (c), unsaturated monomer having a sulfonic acid group (d), and phosphoric acid and / or phosphate compound (e) ( A) a hydrophilic resin (a) constituted by neutralizing an acid group of A) with an alkali metal hydroxide (α) and / or an organic amine compound (β); and polyethylene glycol (f).
A diester dibasic acid (B) composed of an organic dibasic acid (g) and a diluent dibasic acid (g), wherein the acid group of the diester dibasic acid (B) is neutralized with an organic amine compound (β); An unsaturated monomer having a group (h), an unsaturated monomer having a linear or branched alkyl group having 1 to 5 carbon atoms (i),
Having a sulfur atom composed of an unsaturated monomer having a nitrile group (j), an unsaturated monomer having a hydroxy group (k), and an organic compound having an aliphatic mercapto group (l) A workability improver (c) constituted by neutralizing the acid group of the copolymer (C) with an alkali metal hydroxide (α) and / or an organic amine compound (β);
A fin material comprising a coating film formed by reacting at least one curing agent (d) selected from the group of polyglycidyl ethers (D) on the surface. 12. An unsaturated monomer having a hydroxy group (a), an unsaturated monomer having a carboxyl group (b),
Copolymer composed of unsaturated monomer having an amide group (c), unsaturated monomer having a sulfonic acid group (d), and phosphoric acid and / or phosphate compound (e) ( A) a hydrophilic resin (a) constituted by neutralizing an acid group of A) with an alkali metal hydroxide (α) and / or an organic amine compound (β); and polyethylene glycol (f).
A diester dibasic acid (B) composed of a diester dibasic acid (B) composed of an organic dibasic acid (h) and a lubricating agent (b) formed by neutralizing the acid group with an organic amine compound (β); An unsaturated monomer having a group (h), an unsaturated monomer having a linear or branched alkyl group having 1 to 5 carbon atoms (i),
Having a sulfur atom composed of an unsaturated monomer having a nitrile group (j), an unsaturated monomer having a hydroxy group (k), and an organic compound having an aliphatic mercapto group (l) A workability improver (c) constituted by neutralizing the acid group of the copolymer (C) with an alkali metal hydroxide (α) and / or an organic amine compound (β);
A paint containing at least one curing agent (d) selected from the group of polyglycidyl ethers (D) is applied to the surface of aluminum or an aluminum alloy material and then processed into a predetermined shape. Fin manufacturing method. 13. An unsaturated monomer having a hydroxy group (a), an unsaturated monomer having a carboxyl group (b),
Copolymer composed of unsaturated monomer having an amide group (c), unsaturated monomer having a sulfonic acid group (d), and phosphoric acid and / or phosphate compound (e) ( A) a hydrophilic resin (a) constituted by neutralizing an acid group of A) with an alkali metal hydroxide (α) and / or an organic amine compound (β); and polyethylene glycol (f).
A diester dibasic acid (B) composed of an organic dibasic acid (g) and a diluent dibasic acid (g), wherein the acid group of the diester dibasic acid (B) is neutralized with an organic amine compound (β); An unsaturated monomer having a group (h), an unsaturated monomer having a linear or branched alkyl group having 1 to 5 carbon atoms (i),
An unsaturated monomer having a sulfur atom constituted by using an unsaturated monomer having a nitrile group (j), an unsaturated monomer having a hydroxy group (k), and an organic compound having an aliphatic mercapto group (l) A processability improver (c) constituted by neutralizing an acid group of the polymer (C) with a hydroxide (α) of an alkali metal and / or an organic amine compound (β), and a polyglycidyl ether A heat exchanger comprising a fin having a coating film formed by reacting at least one curing agent (d) selected from the group (D) on its surface.