CN112974185A - Aluminum fin material - Google Patents
Aluminum fin material Download PDFInfo
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- CN112974185A CN112974185A CN202011443414.3A CN202011443414A CN112974185A CN 112974185 A CN112974185 A CN 112974185A CN 202011443414 A CN202011443414 A CN 202011443414A CN 112974185 A CN112974185 A CN 112974185A
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- coating layer
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/50—Multilayers
- B05D7/52—Two layers
- B05D7/54—No clear coat specified
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F28—HEAT EXCHANGE IN GENERAL
- F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
- F28F21/00—Constructions of heat-exchange apparatus characterised by the selection of particular materials
- F28F21/06—Constructions of heat-exchange apparatus characterised by the selection of particular materials of plastics material
- F28F21/067—Details
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- Other Surface Treatments For Metallic Materials (AREA)
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Abstract
The invention provides an aluminum fin material having a hydrophilic coating film which can maintain hydrophilicity for a long period of time and can suppress a decrease in hydrophilicity associated with the adhesion of a volatile organic compound to the fin surface. An aluminum fin material comprising an aluminum plate and a hydrophilic coating layer formed on the aluminum plate in this order, wherein the hydrophilic coating layer comprises a resin composition containing a resin (A) as a polymer or copolymer and a Zr-based crosslinking agent, and the polymer or copolymer of the resin (A) comprises a monomer having at least one group selected from the group consisting of a sulfonic acid group, an alkali metal salt group of a sulfonic acid, and an ammonium salt group of a sulfonic acid.
Description
Technical Field
The present invention relates to an aluminum fin material, and more particularly to an aluminum fin material suitable for use in a heat exchanger of an air conditioner or the like.
Background
Heat exchangers are used in products in various fields such as indoor air conditioners, cabinet air conditioners, refrigerated showcases, refrigerating chambers, oil coolers, and radiators. As a material of the fin of the heat exchanger, aluminum or an aluminum alloy having excellent thermal conductivity, workability, corrosion resistance, and the like is generally used. Plate fin or plate and tube heat exchangers have a configuration in which fins are arranged at narrow intervals.
When the surface temperature of the fins of the heat exchanger is below the dew point, dew condensation water adheres to the fins. When the hydrophilicity of the surface of the fin is low, the contact angle of the adhering dew condensation water becomes large, and therefore scattering called water splash occurs in a living environment. When such dew condensation becomes large, bridges are formed between adjacent fins, and the ventilation path between the fins is blocked, thereby increasing the ventilation resistance.
For the purpose of preventing such water splash and reducing ventilation resistance, a technique of coating the surface of the fin with a hydrophilic coating film to form the hydrophilic coating film has been proposed. As an example of such a hydrophilic coating, patent document 1 discloses a hydrophilic surface treatment agent characterized by containing polyacrylic acid and a zirconium compound in specific amounts with respect to components composed of sodium salt and/or potassium salt of carboxymethyl cellulose, ammonium salt of carboxymethyl cellulose, and N-methylol acrylamide having a specific composition.
Prior art documents
Patent document
Patent document 1: japanese patent No. 2520308 publication
However, when the heat exchanger is operated for a long time, a large amount of components constituting the hydrophilic film are dissolved in the water due to contact between the water and the surface of the hydrophilic film. Therefore, it is difficult to maintain the hydrophilicity of the fin surface for a long time. One of the causes of this is adhesion of Volatile Organic Compounds (VOC) floating in the atmosphere to the surface of the hydrophilic film.
If the hydrophilicity of the hydrophilic coating is lowered, the ventilation resistance due to water bridging between the fins is increased, or water splash of dew condensation water adhering to the surfaces of the fins is generated.
Disclosure of Invention
The present invention has been made in view of the above circumstances, and an object thereof is to provide an aluminum fin material provided with a hydrophilic coating film which can maintain hydrophilicity for a long period of time and can suppress a decrease in hydrophilicity associated with the adhesion of a volatile organic compound to the fin surface.
The present invention relates to the following [1] to [6 ].
[1] An aluminum fin material comprising an aluminum plate and a hydrophilic coating layer formed on the aluminum plate in this order, wherein the hydrophilic coating layer comprises a resin composition comprising a resin A and a Zr-based crosslinking agent as a polymer or copolymer, and the polymer or copolymer of the resin A comprises a monomer having at least one group selected from the group consisting of a sulfonic acid group, an alkali metal salt group of a sulfonic acid, and an ammonium salt group of a sulfonic acid.
[2] The aluminum fin material according to the above [1], wherein the resin composition further contains a resin B as a polymer or copolymer, the polymer or copolymer of the resin B containing a monomer having at least a carboxyl group.
[3] The aluminum fin material according to [2], wherein a ratio of the content of the resin A to the content of the resin B in the resin composition is 20:80 to 80:20 by mass ratio.
[4] The aluminum fin material according to any one of the above [1] to [3], wherein the content of the Zr-based crosslinking agent in the hydrophilic coating layer is 0.05 to 6.0 mass%.
[5] The aluminum fin material according to any one of the above [1] to [4], further comprising a corrosion-resistant coating layer between the aluminum plate and the hydrophilic coating layer, wherein the hydrophilic coating layer is formed on a surface of the corrosion-resistant coating layer.
[6] The aluminum fin material according to any one of the above [1] to [5], which is used for a heat exchanger.
According to the present invention, it is possible to suppress a decrease in hydrophilicity associated with the adhesion of a volatile organic compound to the surface of the hydrophilic coating layer while maintaining hydrophilicity for a long period of time (durability). This makes it possible to maintain the effect of reducing the air flow resistance of the aluminum fin material and suppressing water splashing for a long period of time. Therefore, when such an aluminum fin material is used for a heat exchanger or the like, a long life of the heat exchanger itself can be expected.
Drawings
Fig. 1 is a schematic cross-sectional view showing one embodiment of the structure of an aluminum fin material.
Fig. 2 is a schematic cross-sectional view showing one embodiment of the structure of an aluminum fin material.
Description of the symbols
1 aluminum plate
2 bottom treatment layer
3 Corrosion-resistant coating layer
4 hydrophilic coating layer
5 lubricating coating layer
10 aluminum fin material
Detailed Description
The mode of the aluminum fin material used for carrying out the present invention will be described in detail below. Further, the term "to" indicating a numerical range is used to include the numerical values mentioned before and after the range as the lower limit value and the upper limit value.
< aluminum Fin sheet >
As shown in fig. 1, the aluminum fin material 10 of the present embodiment includes an aluminum plate 1 and a hydrophilic coating layer 4 on the aluminum plate 1 in this order. Further, it is preferable that the corrosion-resistant coating layer 3 is provided between the aluminum plate 1 and the hydrophilic coating layer 4, and the hydrophilic coating layer 4 is formed on the surface of the corrosion-resistant coating layer 3.
The hydrophilic coating layer 4 contains a resin composition containing a resin a as a polymer or a copolymer and a Zr-based crosslinking agent. The polymer or copolymer of the resin a contains a monomer having at least one group selected from the group consisting of a sulfonic acid group, an alkali metal salt group of a sulfonic acid, and an ammonium salt group of a sulfonic acid.
The aluminum fin material may also have a primer layer 2 between the aluminum plate and the corrosion-resistant coating layer, if necessary. Further, a lubricating coating layer 5 may be further provided on the surface of the hydrophilic coating layer 4.
(hydrophilic coating layer)
The resin composition constituting the hydrophilic coating layer 4 contains a resin A and a Zr-based crosslinking agent. From the viewpoint of maintaining the hydrophilicity of the hydrophilic coating layer more favorably over a long period of time, it is preferable that the hydrophilic coating layer further contains a resin B.
Here, the resin a is a polymer or a copolymer containing a monomer having at least one group selected from the group consisting of a sulfonic acid group, an alkali metal salt group of a sulfonic acid, and an ammonium salt group of a sulfonic acid (hereinafter, simply referred to as "sulfonic acid group or the like"). The resin B is a polymer or copolymer containing a monomer having at least a carboxyl group.
The resin composition containing the resin a can impart a hydrophilic function to the resin composition.
The resin a may be a polymer (homopolymer) composed of only one monomer, or may be a copolymer containing two or more monomers. In the case of the copolymer, an alternating copolymer, a block copolymer, a graft copolymer, a random copolymer, etc. may be used, and the method of arranging the monomers is not particularly limited.
When the resin a is a polymer, it is a polymer composed of a monomer having at least one group selected from the group consisting of a sulfonic acid group, an alkali metal salt group of a sulfonic acid, and an ammonium salt group of a sulfonic acid. When the resin a is a copolymer, 1 or more of the monomers constituting the copolymer may be a monomer having at least one group selected from the group consisting of a sulfonic acid group, an alkali metal salt group of a sulfonic acid, and an ammonium salt group of a sulfonic acid.
The resin composition may contain, as the resin a, only one selected from the group consisting of these polymers and copolymers, or two or more kinds. When two or more kinds are contained, the content of the resin a in the hydrophilic coating layer or the resin composition means the total content of the polymer and the copolymer.
Specific examples of the resin a include the following: a polymer composed of only a monomer having a sulfonic acid group; a polymer composed only of a monomer having an alkali metal salt group of a sulfonic acid; a polymer composed only of a monomer having an ammonium salt group of a sulfonic acid; a copolymer containing a monomer having a sulfonic acid group; a copolymer comprising a monomer having an alkali metal salt group of a sulfonic acid; a copolymer comprising a monomer containing an ammonium salt group of a sulfonic acid.
The monomer constituting the resin a is not particularly limited in its main chain structure if it has a sulfonic acid group, an alkali metal salt group of a sulfonic acid, or an ammonium salt group of a sulfonic acid. Examples of the alkali metal salt group of the sulfonic acid include groups formed into a lithium salt, a sodium salt, a potassium salt, and the like.
The monomer constituting the resin a preferably has an ethylenically unsaturated bond in the structure constituting a part of the main chain. Specific examples of such monomers include the following: an acrylic acid derivative, a methacrylic acid derivative (メタクリル acid guide), an acrylamide derivative (アクリルアミド guide), a methacrylamide derivative (メ タ アクリルアミド guide), a vinyl derivative (ビニル guide), a styrene derivative (スチレン guide) and the like, which have a sulfonic acid group or the like.
More specifically, the resin A is preferably polyvinyl sulfonic acid (ポ リ ビニル ス ル ホ ン acid), polyvinyl sulfonate (ポ リ ビニル ス ル ホ ン acid salt), or acrylic acid-vinyl sulfonic acid copolymer (アクリル acid- ビニル ス ル ホ ン acid co-polymer). Such a resin has high hydrophilicity, and when the resin composition contains the resin B, the compatibility with the resin B is also good.
Specifically, the resin a may be "アクアリック (registered trademark) GL" manufactured by japan catalyst, "ATBS (registered trademark)" manufactured by east asia synthesis, or "VSA-H (trade name)" manufactured by asahi chemical ファインケム.
The resin composition contains, in addition to the resin a, a resin B which is a polymer or copolymer containing at least a monomer having a carboxyl group, and the above-described form is preferable from the viewpoint that the hydrophilicity of the hydrophilic coating layer can be developed for a longer period of time and the durability is excellent.
The resin B may be a polymer (homopolymer) composed of only one monomer, or may be a copolymer containing two or more monomers. When the copolymer is used, it may be an alternating copolymer, a block copolymer, a graft copolymer, a random copolymer, or the like, and the method of arranging the monomers is not particularly limited.
When the resin B is a polymer, it is a polymer containing one monomer having a carboxyl group. When the resin B is a copolymer, 1 or more of the monomers constituting the copolymer may be monomers having a carboxyl group.
The resin B may be one selected from the group consisting of these polymers and copolymers, or two or more types of the resins may be contained in the resin composition. When two or more kinds are contained, the content of the resin B in the hydrophilic coating layer or the resin composition means the total content of these polymers and copolymers.
Specific examples of the resin B include a polymer composed of only a monomer having a carboxyl group, and a copolymer containing a monomer having a carboxyl group.
The monomer constituting the resin B is not particularly limited in structure of the main chain if it has a carboxyl group.
The monomer constituting the resin B preferably has an ethylenically unsaturated bond in the structure constituting a part of the main chain. Specific examples of such monomers include acrylic acid, methacrylic acid, carboxyl group-containing acrylamide derivatives, vinyl derivatives, styrene derivatives, and the like.
More specifically, when the resin B is the same resin as the resin in the corrosion-resistant coating layer, the coating strength of the hydrophilic coating layer and the adhesion between the corrosion-resistant coating layer and the hydrophilic coating layer can be further improved, and therefore, an acrylic resin is preferable as such a resin.
The resin a and the resin B in the resin composition may be mixed in an appropriate ratio in consideration of coatability, workability, physical properties of the coating film, and the like. However, from the viewpoint of sufficiently ensuring the hydrophilicity of the hydrophilic coating layer, the mass ratio of resin a to resin B is preferably 20:80 to 80:20, more preferably 30:70 to 80:20 in terms of solid content. The ratio of the resin a to the resin B in the resin composition is the same as the ratio of the resin a to the resin B in the hydrophilic coating layer.
The resin composition further contains a Zr-based crosslinking agent. By containing the Zr-based crosslinking agent, the hydrophilicity of the resin a can be maintained for a long period of time, and the hydrophilicity sustainability is good. In addition, the decrease in hydrophilicity accompanying the adhesion of the volatile organic compound to the surface of the hydrophilic coating layer can be suppressed, and a good contamination resistance can be achieved.
The Zr-based crosslinking agent may be any compound as long as it contains Zr and functions as a crosslinking agent, and examples thereof include zirconium nitrate, zirconium acetate, zirconium ammonium carbonate, hexafluorozirconic acid, and salts thereof.
By using the Zr-based crosslinking agent, unlike the conventional oxazoline-based crosslinking agent and the like, the effects of hydrophilicity derived from resin a and hydrophilicity derived from resin B can be sustained for a long period of time, and further, adhesion of the volatile organic compound to the surface of the hydrophilic coating layer can be favorably prevented.
The content of the Zr-based crosslinking agent in the hydrophilic coating layer is preferably 0.05 mass% or more, and more preferably 0.1 mass% or more, from the viewpoint of favorably preventing the adhesion of the volatile organic compound to the surface of the hydrophilic coating layer. On the other hand, the content is preferably 8.0 mass% or less, more preferably 6.0 mass% or less, from the viewpoint of preventing an excessive increase in the crosslinking amount, a decrease in the functional groups of the resin a and the resin B, and a decrease in the hydrophilicity of the hydrophilic coating layer.
The resin composition may further contain various aqueous solvents and coating additives for improving the coatability, workability, physical properties of the coating film, and the like, in addition to the above, within a range not to impair the effects of the present embodiment. Examples of the paint additive include a water-soluble organic solvent, a surfactant, a surface conditioner, a wetting dispersant, an anti-settling agent, an antioxidant, an antifoaming agent, a rust inhibitor, and an antibacterial agent. These coating additives may contain one kind or two or more kinds.
The thickness of the hydrophilic coating layer is preferably set so that the amount of coating is 0.1mg/dm from the viewpoint of obtaining good hydrophilicity2Above, more preferably 0.5mg/dm2Above, more preferably 1mg/dm2The above. Further, the amount of adhesion is preferably 15mg/dm from the viewpoint of obtaining good film forming properties with suppressed defects such as cracks and high heat exchange efficiency with suppressed heat transfer resistance to be low2Hereinafter, more preferably 10mg/dm2Hereinafter, more preferably 8mg/dm2The following.
The amount of the hydrophilic coating layer to be deposited can be adjusted by, for example, selecting the concentration of the coating composition used for forming the hydrophilic coating layer and the type of the bar coater used for forming the coating layer. The amount of film adhesion of the hydrophilic film layer can be measured by X-ray fluorescence, an infrared film thickness meter, weight measurement based on film peeling, or the like.
(aluminium plate)
The aluminum plate 1 is a concept including a plate made of aluminum and a plate made of an aluminum alloy, and an aluminum plate conventionally used for aluminum fin materials can be used.
As the aluminum sheet, from the viewpoint of excellent thermal conductivity and workability, it is preferable to use JIS H4000: 2014 to 1000 series aluminum. More specifically, as the aluminum plate, aluminum of alloy nos. 1050, 1070, and 1200 is preferably used. However, in the above description, the use of 2000 series to 9000 series aluminum alloys and other aluminum plates as the aluminum plate is not at all excluded.
The aluminum plate can have an appropriate thickness according to the use, specifications, and the like of the fin material. In the fin material for a heat exchanger, the thickness thereof is preferably 0.08mm or more, more preferably 0.1mm or more, from the viewpoint of strength of the fin and the like. On the other hand, from the viewpoint of workability for fins, heat exchange efficiency, and the like, it is preferably 0.3mm or less, more preferably 0.2mm or less.
(bottom treatment layer)
The primer layer 2 is a layer that can be provided between the aluminum plate 1 and the corrosion-resistant coating layer 3 as required. By providing the primer layer 2, the corrosion resistance of the aluminum sheet 1 can be improved, and the adhesion between the aluminum sheet 1 and the corrosion-resistant coating layer 3 can be improved.
The primer layer may be a conventionally known layer, and for example, a layer made of an inorganic oxide or an inorganic-organic composite compound may be used.
The inorganic oxide is preferably an oxide containing chromium (Cr) or zirconium (Zr) as a main component. Specific examples of such inorganic oxides include oxides formed by a phosphate chromate treatment, a zirconium phosphate treatment, a chromate treatment, a zinc phosphate treatment, a titanium phosphate treatment, and the like. However, the kind of the inorganic oxide is not limited to those formed by these treatments.
Examples of the inorganic-organic composite compound include compounds formed by a coating-type chromate treatment, a coating-type zirconium treatment, and the like. Specific examples of such an inorganic-organic composite compound include, for example, an acrylic acid-zirconium composite.
In the primer layer, the amount of adhesion is preferably 0.01 to 1mg/dm in terms of the mass of the metal element such as Cr or Zr2Thereby forming the composite material. By setting the amount of adhesion within the above range, good corrosion resistance can be obtained.
The thickness of the primer layer can be suitably adjusted depending on the use of the fin material, and is preferably 1 to 100nm, for example.
The deposition amount of the bottom treatment layer can be adjusted by adjusting the concentration of the chemical conversion treatment liquid used for forming the bottom treatment layer and the film formation treatment time. The amount of the bottom treatment layer deposited can be measured by X-ray fluorescence, infrared film thickness meter, weight measurement based on elution, or the like.
(Corrosion-resistant coating layer)
The corrosion-resistant coating layer 3 is a layer that can be provided mainly for improving the corrosion resistance of the aluminum plate 1. The corrosion-resistant coating layer 3 prevents water such as dew condensation water, oxygen, ion species such as chloride ions, and the like from entering the aluminum plate 1, and suppresses corrosion of the aluminum plate 1, generation of aluminum oxide which generates odor, and the like.
As the corrosion-resistant coating layer, conventionally known ones can be used, and for example, a resin composition containing an acrylic resin can be mentioned. By using the acrylic resin, a corrosion-resistant coating layer can be formed with good coatability using a water-based paint.
The acrylic resin is crosslinked by dehydration condensation by forming hydrogen bonds and baking at the time of film formation. Therefore, the film strength of the corrosion-resistant film layer and the adhesion to other film layers can be improved.
The acrylic resin specifically includes a polymer or copolymer obtained by polymerizing at least one of acrylic acid and an acrylic acid salt. That is, the polymer may be a polymer (homopolymer) composed of only one kind of monomer, or may be a copolymer containing two or more kinds of monomers. In the case of the copolymer, an alternating copolymer, a block copolymer, a graft copolymer, a random copolymer, etc. may be used, and the method of arranging the monomers is not particularly limited.
When the acrylic resin is a polymer, it is a polymer having acrylic acid or an acrylic acid salt as a monomer. When the acrylic resin is a copolymer, 1 or more of the monomers constituting such a copolymer may be acrylic acid or an acrylic acid salt.
The acrylic resin may contain only one kind selected from the group consisting of these polymers and copolymers, or may contain two or more kinds.
Specific examples of the acrylic resin include the following: a polymer composed only of a monomer as acrylic acid; a polymer composed only of a monomer as an acrylic acid salt; copolymers of acrylic acid as at least one monomer; a copolymer of an acrylate as at least one monomer.
In the case of the copolymer, the other monomer may be acrylic acid or an acrylic acid salt, or may be another compound. The other compound is not particularly limited as long as it is a monomer having a reactive group capable of polymerizing with an acrylic acid, and examples thereof include ethylene, propylene, styrene, and maleic acid.
The acrylic resin may be linear or crosslinked by a crosslinking agent.
Examples of the crosslinking agent include an isocyanate-based crosslinking agent, an epoxy-based crosslinking agent, an oxazoline-based crosslinking agent, a carbodiimide-based crosslinking agent (カルボジイミド -based frame ), an aziridine-based crosslinking agent (アジリジン -based frame ). The acrylic resin may be crosslinked by dehydration condensation caused by baking or the like during film formation. The crosslinking by dehydration condensation may be formed, for example, via a polyol such as carboxymethyl cellulose (カルボキシメチルセルロース), polyvinyl alcohol, or polyethylene oxide (ポリエチレンオキサイド).
More specifically, the acrylic resin is more preferably at least one selected from the group consisting of polyacrylic acid, an alkali metal salt of polyacrylic acid, and ammonium polyacrylate. Examples of the alkali metal salt of polyacrylic acid include sodium polyacrylate, potassium polyacrylate, and the like. These resins can provide high film strength and adhesion.
Specific examples of the acrylic resin include "アクアリック (registered trademark) HL" manufactured by japan catalyst, "ネオクリル (registered trademark) a-614" manufactured by nanmu cost chemical corporation, "パルトップ (registered trademark)" manufactured by japan パーカライジング, "ジュリマー (registered trademark)" manufactured by east asia synthesis corporation, "アロン (registered trademark)" manufactured by east asia synthesis corporation, and "アクリット (registered trademark) AKW" manufactured by university ファインケミカル.
The corrosion-resistant coating layer may contain, in addition to the resin constituting the resin composition, various aqueous solvents and coating additives for improving the coatability, workability, physical properties of the coating, and the like. Examples of the paint additive include a water-soluble organic solvent, a crosslinking agent, a surfactant, a surface conditioner, a wetting dispersant, an anti-settling agent, an antioxidant, an antifoaming agent, a rust inhibitor, and an antibacterial agent. These coating additives may be added singly or in combination.
The thickness of the corrosion-resistant coating layer is preferably 0.3-50 mg/dm of the adhesion amount of the corrosion-resistant coating layer2Is measured. The amount of adhesion is preferably 0.3mg/dm from the viewpoint of obtaining good corrosion resistance and adhesion between layers2Above, more preferably 4mg/dm2Above, more preferably 5mg/dm2Above, more preferably 10mg/dm2The above. On the other hand, the amount of adhesion is preferably 50mg/dm from the viewpoints of good film forming properties, reduced defects such as cracks, suppressed heat transfer resistance of the corrosion-resistant coating layer, and good heat exchange efficiency of the fin2Hereinafter, more preferably 30mg/dm2Hereinafter, more preferably 20mg/dm2The following.
The amount of the corrosion-resistant coating layer to be deposited can be adjusted by, for example, the concentration of the coating composition used for forming the corrosion-resistant coating layer, and the selection of the bar coater No. used for forming the coating layer. The amount of the corrosion-resistant coating layer deposited can be measured by X-ray fluorescence, an infrared film thickness meter, weight measurement based on peeling of the coating, or the like.
(lubricating coating layer)
The lubricating coating layer 5 is mainly used to improve the lubricity of the surface of the fin material, and therefore may be provided on the outermost surface of the aluminum fin material 1. That is, the hydrophilic coating layer 4 can be provided on the surface thereof.
The lubricating coating layer reduces the friction coefficient of the surface of the fin material, and improves the press formability and the like when the fin is processed into a fin.
The lubricating coating layer can be any conventionally known resin composition, but is not particularly limited, and for example, a resin composition containing at least one resin selected from the group consisting of polyethylene glycol (ポリエチレングリコール), carboxymethyl cellulose (カルボキシメチルセルロース), and an alkali metal salt of carboxymethyl cellulose can be used. The alkali metal salt of carboxymethyl cellulose includes sodium salt, potassium salt, calcium salt and the like.
These resins may be modified with a known modifier such as urethane modification or alkyl modification by copolymerization with another monomer.
Among them, a resin obtained by mixing polyethylene glycol and sodium carboxymethylcellulose is preferable. The mass ratio of polyethylene glycol to sodium carboxymethylcellulose is more preferably 50:50 to 90: 10. By having such a composition, the film forming property and the lubricity are further improved.
The thickness of the lubricating coating layer is preferably 0.1-8.0 mg/dm of the adhesion amount of the lubricating coating layer2Is measured. From the viewpoint of obtaining good lubricity, the amount of adhesion is preferably 0.1mg/dm2Above, more preferably 0.2mg/dm2The above. On the other hand, the amount of adhesion is preferably 8.0mg/dm from the viewpoint of obtaining sufficient lubricity and suppressing the heat transfer resistance to be low2From the viewpoint of reducing the amount of adhesion as quickly as possible, the amount of adhesion is more preferably 4.0mg/dm2The following.
The amount of the lubricating coating layer to be deposited can be adjusted by, for example, the concentration of the coating composition used for forming the lubricating coating layer, and the selection of the bar coater No. used for forming the coating layer. The amount of the lubricating coating layer deposited can be measured by X-ray fluorescence, infrared film thickness meter, weight measurement based on peeling of the coating, and the like.
(constitution of aluminum Fin)
As shown in fig. 1, in the aluminum fin material 10 of the present embodiment, the foregoing coating layers, that is, the base treatment layer 2, the corrosion-resistant coating layer 3, the hydrophilic coating layer 4, and the lubricating coating layer 5, which are formed as necessary, are formed in this order on one main surface of the aluminum plate 1. As shown in fig. 2, each of the coating layers may be formed on the other principal surface of the aluminum plate 1, and when each of the coating layers is formed on both principal surfaces of the aluminum plate 1, the configuration of each of the coating layers on both principal surfaces may be the same or different.
The preferred thickness of the aluminum fin material varies depending on the application, but when used in a heat exchanger, for example, is preferably 0.08mm or more, more preferably 0.1mm or more, from the viewpoint of strength that can be tolerated during processing. From the viewpoint of workability and heat exchange efficiency, it is preferably 0.3mm or less, and more preferably 0.2mm or less.
Aluminum fin materials are preferably used when the fin pitch (the interval between fin materials) is narrow. This is because, as the fin pitch becomes narrower, the increase in ventilation resistance due to water bridging between the fins and the water splash of dew condensation water adhering to the fin surfaces are more likely to occur, and the effects of the present embodiment can be exerted particularly effectively.
Applications for forming such a fin pitch include heat exchangers for air conditioners and the like, heat exchangers for automobiles, and the like. Among them, aluminum fin materials are preferably used for heat exchangers of air conditioners and the like.
Method for producing aluminum fin material
Next, an example of a method for manufacturing the aluminum fin material 10 will be described, but the method is not limited to this, and the aluminum fin material can be manufactured by other manufacturing methods as long as the effects of the present embodiment are not impaired.
The aluminum fin material 10 of the present embodiment can be manufactured, for example, through a substrate manufacturing step and a coating layer forming step.
(substrate production Process)
In the substrate manufacturing step, the aluminum plate 1 is manufactured.
For example, an ingot is melted, and the molten metal is solidified into an arbitrary shape to obtain an ingot containing a chemical component such as Al in a specific amount. Then, the ingot is subjected to surface cutting as necessary, and hot rolling and cold rolling are performed to obtain an aluminum plate. In the production of an aluminum plate, the ingot may be subjected to a homogenizing heat treatment, or an intermediate annealing may be performed during rolling. Further, the rolled plate material may be subjected to solution heat treatment, tempering, or the like.
(film layer Forming step)
In the coating layer forming step, a coating layer is formed on the surface of the aluminum plate 1. Specifically, the surface is cleaned and degreased as necessary, and the hydrophilic coating layer 4 is formed on the aluminum plate 1 in a clean state. Further, as required, a corrosion-resistant coating layer 3 may be formed on the surface of the aluminum plate 1, and then a hydrophilic coating layer 4 may be sequentially formed. Between the aluminum plate 1 and the corrosion-resistant coating layer 3, a base treatment layer 2 is preferably further formed as necessary. The lubricating coating layer 5 is preferably formed on the surface of the hydrophilic coating layer 4, i.e., the outermost surface of the aluminum fin material 10, as needed.
The primer layer 2 can be formed by applying a chemical conversion treatment liquid to the aluminum plate 1 by spraying or the like, or by immersing the aluminum plate 1 in the chemical conversion treatment liquid and then heating and drying it.
The corrosion-resistant coating layer 3 and the lubricating coating layer 5 can be formed by dispersing a resin constituting such a coating layer in a solvent to obtain a coating composition, applying the coating composition using an application device such as a bar coater or a roll coater, and then baking the coating composition. The baking temperature for coating is not particularly limited, but is usually in the range of about 100 to 300 ℃. When the corrosion-resistant coating layer further contains a paint additive, the paint additive may be blended with the paint composition and applied, and the coating composition may be baked at a temperature not higher than a temperature at which the paint additive does not decompose.
The hydrophilic coating layer 4 is a hydrophilic coating layer made of a resin composition, which is obtained by dispersing a resin a and a Zr-based crosslinking agent in an aqueous solvent at an arbitrary ratio together with a resin B added as required, applying the coating composition to the surface of the corrosion-resistant coating layer using a coating apparatus such as a bar coater or a roll coater, and then baking the coating composition.
The coating baking temperature of the hydrophilic coating layer can be appropriately set depending on the type of the resin a, the type of the resin B, the type of the Zr-based crosslinking agent, the mixing ratio thereof, and the like, but is usually in the range of 150 to 300 ℃. From the viewpoint of improving the film strength and adhesion of the hydrophilic film layer, the coating baking temperature is preferably 190 ℃ or higher, and more preferably 200 ℃ or higher. On the other hand, the coating baking temperature is preferably 260 ℃ or lower, more preferably 250 ℃ or lower, from the viewpoint of avoiding thermal decomposition of the resin.
Through the above steps, the aluminum fin material of the present embodiment can be manufactured.
[ examples ] A method for producing a compound
The present invention will be described more specifically below with reference to examples and comparative examples, but the present invention is not limited to these examples, and can be modified and practiced within the scope that meets the spirit of the present invention, and all of these are included in the technical scope of the present invention.
(examples 1 to 13 and comparative examples 1 to 5)
As the aluminum plate, a plate having a thickness of 0.1mm, JIS H4000: 2014 the specification of alloy braid 1200. On the surface of one side of the aluminum plate, a primer layer was formed by a phosphate chromate treatment. Then, a coating composition containing a resin for a corrosion-resistant coating layer (acrylic resin, manufactured by imperial and jews industries) was applied by a bar coater and baked to form a coating amount of 4mg/dm2The corrosion-resistant coating layer of (2).
Next, the composition shown in table 1 was dispersed in water to obtain a coating composition, and the coating composition was applied to the surface of the corrosion-resistant coating layer using a bar coater so that the amount of the hydrophilic coating layer was the value shown in table 1. Then, the resultant was baked at 200 ℃ to form a hydrophilic coating layer made of a resin composition.
Finally, the surface of the obtained hydrophilic coating layer was coated with a bar coater so that the amount of adhesion was 1.0mg/dm2In the embodiment of (1), a coating composition containing a resin for a lubricating coating layer (パスコール, manufactured by Mingchito chemical Co., Ltd.) was applied and baked to form a lubricating coating layer, thereby obtaining an aluminum fin material.
The resin a in table 1 is a polymer containing a monomer having a sulfonic acid group, the resin B is a polymer containing a monomer having a carboxyl group, and the crosslinking agent is a Zr-based crosslinking agent. However, エポクロス (registered trademark) (manufactured by Japan catalyst Co., Ltd.) was used as the oxazoline-based crosslinking agent in the crosslinking agent of comparative example 5.
The obtained aluminum fin sheets were evaluated for stain resistance and durability of hydrophilicity by the following methods.
(anti-contamination property)
The aluminum fin material was immersed in tap water at a flow rate of 1L/min for 16 hours. Next, 5 kinds of paraffin, palmitic acid, stearic acid, dioctyl phthalate (DOP) and stearyl alcohol were put into a 5L glass dryer as volatile organic compounds (VOPs) in an amount of 0.5g each, and an aluminum fin material was sealed therein. Subsequently, the procedure of heating the glass dryer at 100 ℃ for 8 hours was performed for 5 cycles each as 1 cycle, and VOP was attached to the surface. Thereafter, the aluminum fin was returned to room temperature, and about 0.5. mu.L of pure water was dropped onto the surface of the fin, and the contact angle was measured by using a contact angle measuring instrument (CA-05, manufactured by Kyowa Kagaku Co., Ltd.).
The evaluation criteria are as follows. Thus, the decrease in hydrophilicity (contamination resistance) of the surface of the aluminum fin material accompanying the adhesion of VOP to the surface of the hydrophilic coating layer was evaluated. The results are shown together in Table 1.
< evaluation Standard >
Very good: the contact angle is less than 26 DEG
Good (acceptable) Δ: the contact angle is higher than 26 DEG and below 30 DEG
X bad (failed): contact angle higher than 30 °
(persistence of hydrophilicity)
The aluminum fin material was exposed to ion-exchanged water at a flow rate of 0.1 mL/min for 8 hours, and then dried at 80 ℃ for 16 hours, and the above steps were performed in 14 cycles, taking 1 cycle as the above step. Thereafter, the aluminum fin material was returned to room temperature, and about 0.5. mu.L of pure water was dropped onto the surface of the fin material, and the contact angle was measured by using a contact angle measuring instrument (CA-05, manufactured by Kyowa Kagaku Co., Ltd.).
The evaluation criteria are as follows. Thus, the durability of hydrophilicity (hydrophilicity persistence) of the surface of the aluminum fin material can be evaluated. The results are shown together in Table 1.
< evaluation criteria >
Very good: contact angle lower than 40 °
Good (acceptable) Δ: contact angle "40 ° -60 °"
X bad (failed): contact angle higher than 60 °
[ TABLE 1]
TABLE 1
Using oxazoline-based crosslinking agents
According to the results of example 1 and comparative example 1, the hydrophilic coating layer was excellent in the contamination resistance by using the resin a and the Zr-based crosslinking agent. This effect is not seen in the combination of the resin B and the Zr-based crosslinking agent (comparative example 4), and is also not seen in the case where the oxazoline-based crosslinking agent conventionally used is used for the aluminum fin material (comparative example 5), so that it can be said that the effect is obtained only when the resin A is combined with the Zr-based crosslinking agent.
Further, since a specific amount of the resin B is present in addition to the resin a and the Zr-based crosslinking agent, this stain resistance is very good and the hydrophilic durability is also very good (examples 1 to 5).
Even if the Zr-based crosslinking agent is added in a trace amount of 0.2 mass% (0.2 parts by mass), the effect of the stain resistance and the hydrophilic durability is significant (example 4 and comparative example 3).
The thickness of the hydrophilic coating layer, i.e., the amount of coating deposited, is 1mg/dm2Even in such a small amount, the effect thereof was confirmed to be sufficiently exhibited (example 10).
Claims (10)
1. An aluminum fin material comprising, in this order, an aluminum plate and a hydrophilic coating layer formed on the aluminum plate,
the hydrophilic coating layer comprises a resin composition containing a resin A as a polymer or a copolymer and a Zr-based crosslinking agent,
the polymer or copolymer of the resin A contains a monomer having at least one group selected from the group consisting of a sulfonic acid group, an alkali metal salt group of a sulfonic acid, and an ammonium salt group of a sulfonic acid.
2. The aluminum fin material according to claim 1,
the resin composition further contains a resin B as a polymer or a copolymer,
the polymer or copolymer of the resin B contains a monomer having at least a carboxyl group.
3. The aluminum fin material according to claim 2, wherein a content ratio of the resin A to the resin B in the resin composition is 20:80 to 80:20 in terms of a mass ratio.
4. The aluminum fin material according to any one of claims 1 to 3, wherein the Zr-based crosslinking agent is contained in the hydrophilic coating layer in an amount of 0.05 to 6.0 mass%.
5. The aluminum fin material according to any one of claims 1 to 3, further comprising a corrosion-resistant coating layer between the aluminum sheet and the hydrophilic coating layer, wherein the hydrophilic coating layer is formed on a surface of the corrosion-resistant coating layer.
6. The aluminum fin material according to claim 4, wherein a corrosion-resistant coating layer is further provided between the aluminum sheet and the hydrophilic coating layer, and the hydrophilic coating layer is formed on a surface of the corrosion-resistant coating layer.
7. An aluminum fin material according to any one of claims 1 to 3, for use in a heat exchanger.
8. The aluminum fin material of claim 4, for use in a heat exchanger.
9. The aluminum fin material of claim 5, for use in a heat exchanger.
10. The aluminum fin material of claim 6, for use in a heat exchanger.
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Citations (4)
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|---|---|---|---|---|
| JP2011042842A (en) * | 2009-08-21 | 2011-03-03 | Kansai Paint Co Ltd | Substrate treating agent for aluminum fin material |
| CN103555114A (en) * | 2013-10-25 | 2014-02-05 | 广州慧谷化学有限公司 | Coating composition for hydrophilic treatment of air-conditioning parallel flow heat exchanger |
| CN106634389A (en) * | 2016-12-30 | 2017-05-10 | 广州慧谷化学有限公司 | Coating for preparing lubricating hydrophilic coating and application thereof |
| JP2019073749A (en) * | 2017-10-12 | 2019-05-16 | 株式会社Uacj | Hydrophilic surface treatment aluminum containing metal material and heat exchanger |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US4973359A (en) * | 1989-01-04 | 1990-11-27 | Nippon Paint Co., Ltd. | Surface treatment chemical and bath for forming hydrophilic coatings and method of surface-treating aluminum members |
| JP3717205B2 (en) * | 1995-06-29 | 2005-11-16 | 株式会社デンソー | Aluminum-containing metal heat exchanger and manufacturing method |
| JPH11131254A (en) * | 1997-10-24 | 1999-05-18 | Nippon Parkerizing Co Ltd | Surface treatment of aluminum-containing metallic material |
| JP2000191419A (en) * | 1998-12-28 | 2000-07-11 | Toyobo Co Ltd | Microbicidal composition used for laminating heat exchanger fins and heat exchanger fin |
| KR20150106230A (en) * | 2014-03-11 | 2015-09-21 | 삼성전자주식회사 | Heat exchanger and method for manufacturing the same, and outdoor unit for air-conditioner having the heat exchanger |
| JP6941465B2 (en) * | 2017-04-07 | 2021-09-29 | 日本ペイント・サーフケミカルズ株式会社 | Hydrophilization treatment agent and method for forming a hydrophilic film |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011042842A (en) * | 2009-08-21 | 2011-03-03 | Kansai Paint Co Ltd | Substrate treating agent for aluminum fin material |
| CN103555114A (en) * | 2013-10-25 | 2014-02-05 | 广州慧谷化学有限公司 | Coating composition for hydrophilic treatment of air-conditioning parallel flow heat exchanger |
| CN106634389A (en) * | 2016-12-30 | 2017-05-10 | 广州慧谷化学有限公司 | Coating for preparing lubricating hydrophilic coating and application thereof |
| JP2019073749A (en) * | 2017-10-12 | 2019-05-16 | 株式会社Uacj | Hydrophilic surface treatment aluminum containing metal material and heat exchanger |
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