JP2008001080A - Aluminum-coated plate and precoat aluminum fin material using this plate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an aluminum-coated plate with excellent properties such as hydrophylicity, contamination resistance, film adhesion, moldability, odorous substance adsorption and bacteriaproofness/fungiproofness, and a precoat aluminum fin material using the aluminum-coated plate. <P>SOLUTION: This aluminum-coated base plate is structured of an aluminum base plate and a hydrophilic film formed on at least one surface of the aluminum base plate. The hydrophiilic film contains at least, either of a urethane-based resin or an acryl-based resin and a carbon black with 12 to 40 nm primary particle diameter. The content of the carbon black is 1 to 200 pts.wt. for 100 pts.wt. hydrophilic resin and the average film thickness of the hydrophilic film is 0.01 to 15 μm. In addition, the precoat aluminum fin material is provided which uses the aluminum-coated plate. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention is an aluminum coated plate in which a hydrophilic film excellent in hydrophilicity, stain resistance, film adhesion, moldability, odorant adsorption, antibacterial and antifungal properties is formed on the surface of an aluminum material or an aluminum alloy material, In addition, the present invention relates to a pre-coated aluminum fin material that is processed and formed from the painted plate, for example, used in a heat exchanger.

  Since the surface of the metal material is poor in hydrophilicity, a fin material of a heat exchanger or a printing lithographic printing plate material having a surface coated with a hydrophilic film is used. Hereinafter, the case of the fin material of the heat exchanger will be described by taking an air conditioner as an example.

  Recent heat exchangers for air conditioners are required to have improved thermal efficiency and compactness in order to reduce weight, and incorporate a design that makes the fin spacing as narrow as possible. In the heat exchanger for an air conditioner, moisture in the air adheres to the surface of the aluminum fin material as condensed water during the cooling operation. Since the surface of the metal material is generally poor in hydrophilicity, this condensed water exists on the surface of the fin material in a semicircular shape or a bridge shape between the fin materials. By preventing the flow of air between the fin materials by such condensed water, the ventilation resistance is increased and the heat exchange efficiency is remarkably lowered. Therefore, in order to improve the thermal efficiency of the heat exchanger, it is necessary to quickly remove the condensed water on the surface of the fin material.

  As a method for quickly eliminating condensed water on the surface of the fin material, (1) a method of forming a highly hydrophilic film on the surface of the aluminum fin material and allowing the condensed water to flow down as a thin water film, (2) the surface of the aluminum fin material Although a method of forming a water-repellent film on the surface and preventing condensed water from adhering to the surface is conceivable, the method (2) is extremely difficult at present. On the other hand, in the method (1), a film is formed on the surface in order to obtain hydrophilicity, and the formation of condensed water droplets on the surface of the aluminum fin material is prevented by such a hydrophilic film. A water film formed on the surface of the material is held on the surface.

Conventionally, various methods for forming a hydrophilic film have been proposed and put into practical use. For example, a method of forming an alkali silicate lubricating film on the surface of an aluminum material (Patent Document 1 below), a method of forming a hydrophilic and lubricating film containing an aqueous paint resin, a surfactant and synthetic silica (described below) Patent Document 2), a method of applying a composition containing a low molecular organic compound having an alkali silicate and a carbonyl compound and a water-soluble organic polymer compound to an aluminum material to form a hydrophilic and lubricious film (the following patent) Document 3) has been proposed.
Japanese Examined Patent Publication No. 53-48177 JP 55-164264 A JP-A-60-101156

  However, in order to impart hydrophilicity, the method of forming a lubricating coating of alkali silicate is poor in sustainability of hydrophilicity over time, and when applied to a material and processed into fins, Since the lubricity film hardness is high, there is a problem that the mold is greatly worn and cracks are likely to occur in the fin material.

There has also been proposed a paint for forming a lubricious coating without such defects as mold wear and crack generation (Patent Documents 4 to 6 below). Examples of such a coating composition include hydrophilic coating compositions containing water-soluble hydrophilic resins such as polyvinyl alcohol resins, polyacrylamide resins, polyacrylic resins, and cellulose resins.
JP 63-173632 A JP-A-5-302042 Japanese Patent Laid-Open No. 9-14889

  By the way, in recent years, interest in the environment has been increasing, and ammonia, acetaldehyde, acetic acid, etc., which cause daily odors and pet odors, are supplemented by the condensed water adhering to the surface of the heat exchanger, and the usage time is increased. At the same time, there is a problem that these odor components are detached from the heat exchanger during operation of the air conditioner and give off an odor from the air outlet. Conventional heat exchangers have insufficient deodorizing performance against these odors and have hardly been expected to have a deodorizing effect on nonpolar molecules and polar molecules that cause tobacco odor.

  In addition, heat exchangers used in air conditioners and the like tend to form condensation on the fins in the summer, and because air passes between the fins, dust, bacteria, and soot easily adhere to the surface. The conditions are easy to generate wrinkles. Once bacteria, sputum, etc. are generated, there are problems such as an unpleasant odor and an effect on allergies. Therefore, it is known to add an antibacterial and antifungal agent to the precoat treatment agent when performing the precoat film treatment. However, the precoat film is extremely thin, and if an antibacterial / antifungal agent is added, the film physical properties such as hydrophilicity are adversely affected, so the amount added cannot be increased. It was not big.

  The inventors of the present invention are aluminum materials for heat exchangers having a hydrophilic and lubricious film such as a pre-coated fin material, which are excellent in hydrophilicity, stain resistance, film adhesion, and formability, and have an odor We have intensively studied the development of aluminum coated plates with hydrophilic and lubricious coatings that are excellent in component adsorption and antibacterial and antifungal properties. As a result, an aluminum coating provided with a hydrophilic film containing a specific resin and a specific carbon black or a hydrophilic film further containing an antibacterial antifungal agent on at least one surface of an aluminum or aluminum alloy substrate The present invention was completed by finding that the plate exhibits excellent performance in any of hydrophilicity, stain resistance, film adhesion, moldability, odor component adsorption and antibacterial and antifungal properties.

  The object of the present invention is to provide a hydrophilic coating that exhibits excellent performance in terms of hydrophilicity, stain resistance, coating adhesion, moldability, odor component adsorption and antibacterial and antifungal properties on the surface of an aluminum or aluminum alloy substrate. Another object of the present invention is to provide an aluminum coated plate, and a precoated aluminum fin material using such an aluminum coated plate, for example, for a heat exchanger.

The present invention is the aluminum coated plate according to claim 1, comprising an aluminum or aluminum alloy base material and a hydrophilic coating formed on at least one surface of the base material,
The hydrophilic coating contains at least one hydrophilic resin of urethane resin and acrylic resin, and carbon black having a primary particle diameter of 12 to 40 nm, and the carbon black is in 100 parts by weight of the hydrophilic resin. On the other hand, 1 to 200 parts by weight of the aluminum coating plate was contained, and the hydrophilic coating had an average film thickness of 0.01 to 15 μm.

  The present invention provides the carbon black according to claim 2, wherein the carbon black has an aromatic compound having at least one selected from a carboxyl group, a hydroxyl group, and a salt thereof attached to the surface, and is based on 100 parts by weight of the carbon black. The aromatic compound was made to adhere to 0.5 to 100 parts by weight. Further, in the present invention according to claim 3, the aromatic compound is a humic acid.

  In the present invention, the hydrophilic resin further contains a polyvinyl alcohol resin, and the polyvinyl alcohol resin is contained in an amount of 5 to 95 parts by weight in 100 parts by weight of the hydrophilic resin.

  According to a fifth aspect of the present invention, in the fifth aspect, the hydrophilic coating further contains 0.1 to 25 parts by weight of an oolong tea component with respect to 100 parts by weight of the hydrophilic resin. Moreover, in Claim 6, in addition to Oolong tea component, the said hydrophilic film further contains 0.1-50 weight part of green tea components and black tea components with respect to 100 weight part of said hydrophilic resins. I made it.

  According to a seventh aspect of the present invention, a lubricating coating mainly comprising a polyethylene glycol resin is further provided on the hydrophilic resin coating, and the average thickness of the lubricating coating is set to 0.01 to 3 μm.

The present invention according to claim 8, wherein the surface of the substrate is at least one chemical conversion film selected from the group consisting of chromium, zirconium and titanium, and has a metal element conversion of ^{2 to} 50 mg / m ^2. It was assumed that a chemical conversion film containing the above metal was formed. Furthermore, the present invention is the method according to claim 9, wherein the surface of the substrate has an amount of 0.1 to 10 g / m ² consisting of at least one selected from the group consisting of urethane resin, epoxy resin and acrylic resin. It was assumed that a corrosion-resistant organic film was formed.

  In the tenth aspect of the present invention, a precoated aluminum fin material using the aluminum coated plate according to any one of the first to ninth aspects.

The present invention according to claim 11, wherein the hydrophilic coating further contains an antibacterial / antifungal agent, the antibacterial / antifungal agent is contained in an amount of 0.5 to 400 parts by weight based on 100 parts by weight of the hydrophilic resin, and It was supposed to be present in an amount of 0.005 to 10.0 g per unit area (1 m ² ) of the aluminum coated plate.

  The present invention according to claim 12, wherein the antibacterial and antifungal agent is bis- (2-pyridylthio-1-oxide) -zinc, 2,3,5,6-tetrachloro-4- (methylsulfonyl) -pyridine and 2- It contains at least one selected from the group consisting of (4-thiazolyl) benzimidazole.

  In the tenth aspect of the present invention, a precoated aluminum fin material using the aluminum coated plate according to the eleventh or twelfth aspect is provided.

  The aluminum coated plate of the present invention exhibits excellent performance in terms of hydrophilicity, stain resistance, film adhesion, formability, odor component adsorption, and antibacterial and antifungal properties on the surface of an aluminum or aluminum alloy substrate. For example, a heat exchanger using the pre-coated aluminum fin material manufactured by using it exhibits excellent heat exchange efficiency over a long period of time.

Aluminum coating plate The aluminum coating plate according to the present invention includes an aluminum or aluminum alloy base material and a hydrophilic coating formed on at least one surface of the base material.

A. Aluminum substrate The substrate used in the present invention is a substrate made of aluminum or an aluminum alloy. Hereinafter, a base material made of aluminum and an aluminum alloy is simply referred to as “aluminum material”. In addition, metals other than aluminum can also be used for a base material.

  Furthermore, what formed the corrosion-resistant base film in the aluminum material can also be used. Examples of the corrosion-resistant undercoating film include a chemical conversion treatment film, a corrosion-resistant organic film, an anodized film, and a boehmite film, and any corrosion-resistant undercoating film may be used. From the viewpoint of corrosion resistance, adhesion, and economy, it is preferable to use a chemical conversion treatment film and an organic corrosion resistance film.

As the chemical conversion coating, a chromium-based, zirconium-based, or titanium-based chemical conversion coating is used, and a chromium-based chemical conversion coating is preferable from the viewpoint of corrosion resistance and coating adhesion. As a method for forming the chemical conversion treatment film, a coating type, electrolytic type, reaction type chemical conversion treatment method, or the like is used, but any method may be used. The drying temperature is also arbitrary. Of the methods for forming the chemical conversion coating, it is preferable to use a coating-type chromate method excellent in moldability, coating adhesion, and corrosion resistance. The coating amount in this case is ² to 50 mg / m ² in terms of Cr element. If the coating amount is less than 2 mg / m ^{2 in} terms of Cr element, sufficient corrosion resistance and film adhesion cannot be obtained. Moreover, even if it exceeds 50 mg / m < ² >, the effect of corrosion resistance and film adhesion will be saturated, and it will lack economical efficiency. A preferable coating amount is 5 to 15 mg / m ² in terms of Cr element.
In addition, as the corrosion-resistant organic film, a film made of an acrylic resin, a urethane resin, an epoxy resin, or a polyester resin is used, but the hydrophilicity and odor component adsorptivity of the resin film formed thereon are not impaired. As long as any resin film can be used. The formation amount of the corrosion-resistant organic film is 0.1 to 10 g / m ² , preferably 0.5 to 5 g / m ² . If it is less than 0.1 g / m ² , sufficient corrosion resistance cannot be obtained, and if it exceeds 10 g / m ^2, the effect is saturated and uneconomical.

B. Hydrophilic film The hydrophilic film of the present invention contains a urethane resin, an acrylic resin, or both as a hydrophilic resin component. By the urethane-based resin and acrylic resin, in addition to hydrophilicity, film adhesion and corrosion resistance are imparted to the hydrophilic film in a well-balanced manner. In order to further improve hydrophilicity, film adhesion, and corrosion resistance, a polyvinyl alcohol-based resin may be included as a hydrophilic resin component.
The hydrophilic film may be an inorganic film made of an inorganic component such as water glass or colloidal silica, or an organic / inorganic film made of the hydrophilic resin component and these inorganic components.

B-1. Urethane resin The urethane resin is not particularly limited as long as it has a urethane bond in the molecule, and those mainly formed by the reaction of an isocyanate compound and a polyol or a polyether are used.
Specifically, as the isocyanate compound, tolylene diisocyanate, diphenylmethane 4,4 ′ diisocyanate, hexamethylene diisocyanate, trimethylpropane 1-methyl 2-isocyano 4-carbamate, polymethylene polyphenyl isocyanate, metaxylylene diisocyanate, etc. are used. It is done. As the polyols or polyethers, polyethylene glycol, polypropylene glycol, polyether triol and the like are used.

B-2. Acrylic resin Acrylic resins include copolymers and block polymers of α, β monoethylenically unsaturated monomers and monomers polymerizable thereto, or α, β monoethylenically unsaturated monomers. A resin consisting of an amount of polymer itself is used.
Examples of α, β monoethylenically unsaturated monomers include acrylic acid esters (methyl acrylate, ethyl acrylate, isopropyl acrylate, nbutyl acrylate, 2-ethylhexyl acrylate, decyl acrylate, acrylic acid Isooctyl, 2-ethylbutyl acrylate, octyl acrylate, methoxyethyl acrylate, ethoxyethyl acrylate, ethoxypropyl acrylate, etc.); methacrylates (methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, butyl methacrylate, Isobutyl methacrylate, n-hexyl methacrylate, lauryl methacrylate, decyl octyl methacrylate, stearyl methacrylate, 2-methylhexyl methacrylate, 3-methoxybutyl methacrylate, etc.); acrylonitrile; Examples include acrylonitrile, vinyl acetate, vinyl chloride, vinyl ketone, vinyl toluene, and styrene.

  Monomers that can be copolymerized with the α, β monoethylenically unsaturated monomers include styrene, α-methylstyrene, vinyltoluene, t-butylstyrene, ethylene, toluene, propylene, acrylamide, and hydroxypropyl acrylate. , 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, hydroxypropyl methacrylate, N-methylolacrylamide, acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid and the like are used.

B-3. As a hydrophilic resin constituting the resin component of the polyvinyl alcohol-based resin hydrophilic coating, a polyvinyl alcohol-based resin can be contained in addition to at least one of the urethane-based resin and the acrylic resin. As the polyvinyl alcohol-based resin, those having a saponification degree of 90 mol% or more are preferably used, and particularly, a completely saponified polyvinyl alcohol (PVA) is suitably used. From the viewpoint of the degree of polymerization, PVA having an average degree of polymerization of preferably 500 to 4000, more preferably 1500 to 2500 is suitably used.
If the degree of saponification is less than 90 mol% or the average degree of polymerization is less than 500, there is a disadvantage that the hydrophilicity is inferior. On the other hand, if the average degree of polymerization is greater than 4000, the viscosity increases remarkably, and roping or the like may occur during coating, and a uniform film may not be formed.

  As such a polyvinyl alcohol-based resin, in addition to the above PVA, for example, a small amount (for example, 5% by weight or less) of allyl glycidyl ether (for example, manufactured by Nagase Kasei Kogyo Co., Ltd., trade name: Denacol EX-III) during polymerization of vinyl acetate ), And a hydroxyl group partially substituted with an epoxy group, or a carboxyl group such as crotonic acid, acrylic acid, maleic anhydride, itaconic acid, MMA (methyl methacrylate) during the polymerization of vinyl acetate. It is also possible to use modified polyvinyl alcohol having a carboxyl group introduced into the main chain by copolymerizing a monomer having

  The polyvinyl alcohol resin is 5 to 95 parts by weight, preferably 25 to 75 parts by weight, based on 100 parts by weight of the entire hydrophilic resin (at least one of urethane resin and acrylic resin, and polyvinyl alcohol resin). It is good to contain by the ratio of a part. If the proportion of the polyvinyl alcohol-based resin is less than 5 parts by weight, hydrophilic sustainability cannot be ensured, and if it exceeds 95 parts by weight, the hydrophilicity is saturated and uneconomical.

B-4. Crosslinking agent It is good also as a crosslinkable resin of a three-dimensional arrangement | sequence by mixing a crosslinking agent in said hydrophilic resin. A crosslinking agent is mix | blended as needed for the purpose of improving the water-soluble solubility of the film obtained. Examples of such a crosslinking agent include metal chelate compounds such as melamine resin, urea resin, phenol resin, polyepoxy compound, blocked polyisocyanate compound, and titanium chelate.

B-5. Carbon black In the present invention, the effect of adsorbing odor components present in the atmosphere is exhibited by incorporating carbon black in the hydrophilic coating. The inside of carbon black has a net-like planar structure and a large number of fine pores exist, so that odor components are adsorbed efficiently. Addition of carbon black increases the irregularities on the surface of the hydrophilic coating, increases the apparent surface area, decreases the water contact angle, further improves the hydrophilicity, and adsorbs odorous components through the intervention of water. There is also a synergistic effect that improves performance.

  The carbon black used in the present invention can be produced by a known method, and the production method is not particularly limited. For example, the carbon black is produced by a channel method, a roller method, a furnace method, or the like. Further, as long as the characteristics of the carbon black in the present invention are met, the manufactured carbon black may be further subjected to further treatment such as a known oxidation reaction.

In the present invention, carbon black having a primary particle size of 12 to 40 nm is used. Moreover, it is one having such a primary particle diameter, and the DBP oil absorption of 30 to 150 ^3/100 g, is preferably used one having a nitrogen adsorption specific surface area of 60~300m ² / g.

  The primary particle size of carbon black strongly affects the odor component adsorption and the carbon black dispersibility. The primary particle diameter of carbon black is 12 to 40 nm, and if it is less than 12 nm, it is difficult for industrial production. On the other hand, when the primary particle diameter exceeds 40 nm, sufficient storage stability and dispersibility of the coating composition cannot be obtained, and thereby, the adsorptivity and hydrophilicity of the odor component are inferior. In addition, a primary particle diameter is measured by well-known methods, such as a microscope method. In the case of ordinary carbon black that is generally used, it is difficult to disperse in the coating composition, and preferably 25 to 40 nm, more preferably 25 to 35 nm. If the primary particle diameter is less than 25 nm, most primary particles form strong aggregates. Since such an aggregate does not dissociate in the solution-like film composition for forming the hydrophilic film, the adsorptivity of the odor component by the hydrophilic film is inferior. 40 nm is preferable.

DBP oil absorption of carbon black also affects strongly adsorbable of odorous, 30~150cm ³ / 100g, preferably is used as the 60~120cm ³ / 100g. Here, the DBP oil absorption is an amount of DPB (dibutyl phthalate) absorbed by 100 g of carbon black expressed by capacity (cm ³ ) in accordance with JIS K6221 A method. The DBP oil absorption is less than 30 cm ^3/100 g, the development degree of the carbon black aggregates too low. As a result, the specific volume of carbon black is reduced and a sufficient adsorption effect of odor components cannot be obtained. On the other hand, DPB oil absorption is more than 150 cm ^3/100 g, the development degree of the carbon black aggregates is increased. As a result, carbon black tends to settle in the solution-like coating composition, and the distribution of carbon black in the formed hydrophilic coating becomes non-uniform, which also provides a sufficient adsorption effect for odor components. Absent.

The nitrogen adsorption specific surface area of carbon black also strongly influences the adsorptivity of odor components, and those having 60 to 300 m ² / g, preferably 50 to 150 m ² / g are used. Here, the nitrogen adsorption specific surface area represents the amount of nitrogen gas adsorbed on 1 g of carbon black in accordance with the method of JIS K6221, and is used as an index of the surface area (m ² ) of carbon black. When the nitrogen adsorption specific surface area is less than 60 m ² / g, sufficient odor adsorption performance cannot be maintained. On the other hand, when the nitrogen adsorption specific surface area is 300 m ² / g, the odor adsorption performance is saturated, which is uneconomical. The nitrogen adsorption amount of carbon black is generally measured by a known method. For example, the BET adsorption method is suitably used.

  Carbon black is contained in an amount of 1 to 200 parts by weight, preferably 5 to 50 parts by weight, based on 100 parts by weight of the hydrophilic resin. If the amount of carbon black is less than 1 part by weight, sufficient adsorptivity of odorous substances and sufficient hydrophilicity cannot be obtained. On the other hand, when the amount of carbon black exceeds 200 parts by weight, carbon black may fall off from the hydrophilic coating when an aluminum coated plate is formed into a fin material or the like.

B-6. In the present invention, carbon black can be used as it is, but carbon black in which an aromatic compound having at least one selected from a carboxyl group, a hydroxyl group and a salt thereof is attached to the surface. May be used. Carbon black with such an aromatic compound attached to the surface has further effects in terms of dispersibility and adsorptivity of odor components compared to non-attached ones.

  Examples of the aromatic compound having a carboxyl group include benzoic acid and phthalic acid. Examples of the aromatic compound having a hydroxyl group include phenol, cresol, 2,4,6-tribromophenol, picric acid, naphthol, catechol, pyrogallol, and oxidized vitamin C. Examples of the aromatic compound having both a carboxylic acid and a hydroxyl group include humic acids and salicylic acid. Furthermore, examples of the salt of a carboxyl group or a hydroxyl group include salts in which an alkali metal, ammonium, or a divalent or higher cation is bonded to these groups.

  As an aromatic compound, a single substance such as benzoic acid or phenol may be attached to the surface of carbon black, but from the viewpoint of adhesion, drug toxicity, water solubility, surface active action, stability during work, Furthermore, it is preferable to attach humic acids to the surface of the carbon black because the dispersibility, odor fixability and hydrophilicity of the carbon black can be greatly improved. Since humic acids have various functional groups (including carboxyl groups and hydroxyl groups) generated from natural substances and a broad spectrum of molecular weight, they are rich in variety as adsorbents.

  In the present invention, humic acids refer to humic acids, humic acid salts, and salts of these derivatives. That is, humic acid extracted from products obtained by oxidative decomposition of sediments and juvenile charcoal with an oxidizing agent with an aqueous alkaline solution, added with an acidic aqueous solution, precipitated and filtered; this humic acid and alkali metal, ammonium Alternatively, a humic acid salt bonded to a divalent or higher cation; an alkali metal salt of a derivative obtained by polycondensation of the humic acid and an aldehyde, an amine or a phenol; Any one of these humic acids can be used in the present invention, but the humic acids are not limited to these.

  As a method for attaching the aromatic compound to the carbon black surface, for example, carbon black powder is added to a solution in which the aromatic compound is dissolved or dispersed (water, an aqueous solution, or an organic solvent is used as a solvent). A method of sufficiently stirring and mixing and uniformly dispersing to form a suspension, followed by filtering and drying carbon black can be mentioned. Also, the carbon black suspension can be uniformly dispersed in the hydrophilic film by adding it to the resin composition for forming the hydrophilic film, but the aromatic compound is eluted in the hydrophilic film. As a result, the hydrophilicity of the hydrophilic film may be lowered.

  The aromatic compound is preferably attached in an amount of 0.5 to 100 parts by weight with respect to 100 parts by weight of carbon black. When the amount of the aromatic compound is less than 0.5 parts by weight, the amount of adhesion to the carbon black is small, the dispersibility of the carbon black at the time of forming the hydrophilic film is insufficient, and the amount of the aromatic compound exceeds 100 parts by weight. And the hydrophilicity of the hydrophilic coating is deteriorated.

B-7. Oolong Tea Component In the present invention, an Oolong tea component can be added to the hydrophilic film component. Oolong tea component has a function of adsorbing odor components such as ammonia and formaldehyde.
The Oolong tea component is contained in an amount of 0.1 to 25 parts by weight, preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the hydrophilic resin. If the Oolong tea component is less than 0.1 parts by weight, it is difficult to obtain sufficient adsorptivity of the odor component, and if it exceeds 25 parts by weight, the desired hydrophilicity cannot be obtained.

  The manufacturing method of the oolong tea component used for this invention is not specifically limited. For example, when oolong tea leaves and stems are heated from room temperature to a predetermined temperature, with a solvent such as water, acidic aqueous solution, aqueous ethanol, ethanol, aqueous methanol, methanol, acetone, ethyl acetate or glycerin aqueous solution or a mixed solvent thereof. The extracted extract is used. In addition to using an extract obtained by removing the solvent from the extract, it can also be used as an extract obtained by extraction (consisting of an oolong tea extract component and an extract solvent) or as a concentrate of the extract. In particular, a method of adding room temperature water or an extract extracted with warm water to the coating composition is preferable from the viewpoint of odor component adsorptivity.

  Oolong tea components obtained by such extraction include catechins (catechin, gallocatechin, epicatechin, epigallocatechin, catechin gallate, epicatechin gallate, gallocatechin gallate, epigallocatechin gallate); tannins. In addition, flavonoids such as kaempferol, quercetin, myricetin; polyphenols such as GOD polyphenol; organic acids such as malonic acid, succinic acid, gallic acid; caffeine; amino acids; sugars; vitamins; ing.

  Inclusion of oolong tea components such as catechins in the hydrophilic film enhances the adsorptivity of odor components. Among oolong tea components, catechins (catechin, gallocatechin, epicatechin, epigallocatechin, catechin gallate, epicatechin gallate, gallocatechin gallate, epigallocatechin gallate) greatly contribute to the adsorptivity of odor components. In particular, a multimer in which these catechins are associated, preferably a catechin dimer and a trimer, effectively acts to enhance the adsorptivity of odor components. Since the catechin dimer and trimer are contained in oolong tea in particular among teas, the oolong tea component is preferably included in the hydrophilic film in order to ensure the adsorptivity of the odor component.

B-8. Green tea component, black tea component Furthermore, in the present invention, in addition to the oolong tea component, at least one of the green tea component and the black tea component is added as a component of the hydrophilic film. These green tea components and black tea components have a function of fixing the odor component adsorbed by the oolong tea component in the film. Therefore, by adding a green tea component or a black tea component as a hydrophilic film component, the desorption rate of the adsorbed odor component is reduced, thereby improving the fixability. As a result, the adsorptivity of the hydrophilic coating is further improved.

At least one of green tea and black tea components is contained in an amount of 0.1 to 50 parts by weight, preferably 0.5 to 20 parts by weight, based on 100 parts by weight of the hydrophilic resin. If the green tea component or black tea component is less than 0.1 part by weight, it is difficult to obtain the adsorptivity of the odor component, and if it exceeds 50 parts by weight, the desired hydrophilicity cannot be obtained.
In addition, these contents are things as a single content, respectively, in the case of the green tea ingredient alone or the black tea ingredient alone, and when using both the green tea ingredient and the black tea ingredient, they are the sum of the contents. is there.

  The methods for producing the green tea component and black tea component used in the present invention are not particularly limited. As a method for producing these green tea components and black tea components, the same method as the method for extracting the oolong tea components is used. Among green tea components and black tea components, polyphenols are particularly excellent in odor component fixing, and therefore it is preferable to add green tea components and black tea components containing more polyphenols.

  The oolong tea component used in the present invention can be used not only for adsorption of ammonia, acetaldehyde, and acetic acid, but also for aldehydes such as butyraldehyde and benzaldehyde, and other types of odor components. The green tea component and black tea component used in the present invention can be used not only for fixing ammonia, acetaldehyde and acetic acid, but also for fixing aldehydes such as butyraldehyde and benzaldehyde, and also for other types of odor components.

  In addition, in order to add the oolong tea component, the green tea component, and the black tea component to the hydrophilic resin, they are previously mixed with carbon black and then added to the hydrophilic resin, or added to the hydrophilic resin simultaneously with the carbon black. Is preferred. By selectively adhering these tea components to the surface of carbon black having a large surface area, the adsorptivity of odor components can be greatly improved. In addition, since carbon black to which the tea component is adhered is present on the surface of the hydrophilic film, a large number of functional groups of the tea component can act on pollutants in the atmosphere, thereby improving the stain resistance. The contamination resistance referred to here means that a decrease in hydrophilicity can be prevented when a higher fatty acid such as stearic acid present in the atmosphere adheres to the surface of the hydrophilic coating.

B-9. Antibacterial / antifungal component In the present invention, an antibacterial / antifungal agent is added for the purpose of imparting antibacterial / antifungal properties to the resulting hydrophilic coating. The antibacterial and antifungal agent in the present invention has at least one of antibacterial and antifungal properties, and preferably has both antibacterial and antifungal properties. Antibacterial and antifungal agents include isothiazoline, aldehyde, benzimidazole, halogen, carboxylic acid, sulfamide, thiazole, triazole, phenol, phthalimide, naphthenic acid, pyridine, and other organic systems, Examples include inorganic systems such as Ag, Cu, Zn, etc. Among them, zinc pyrithione, that is, bis- (2-pyridylthio-1-oxide) -zinc, 2,3,5,6-tetrachloro-4- (methylsulfonyl) ) -Pyridine and 2- (4-thiazolyl) benzimidazole are preferred because they hardly affect the film properties such as hydrophilicity, are water-insoluble and are excellent in thermal stability. Accordingly, at least one of bis- (2-pyridylthio-1-oxide) -zinc, 2,3,5,6-tetrachloro-4- (methylsulfonyl) -pyridine and 2- (4-thiazolyl) benzimidazole is substituted. It is preferable to use it.

  The antibacterial and antifungal agent is contained in an amount of 0.5 to 400 parts by weight, preferably 5 to 50 parts by weight, based on 100 parts by weight of the hydrophilic resin. If it is less than 0.5 part by weight, the content of the antibacterial / antifungal agent is small and sufficient antibacterial / antifungal properties cannot be obtained. On the other hand, when the amount of the antibacterial / antifungal agent exceeds 400 parts by weight, the physical properties of the coating such as hydrophilicity are deteriorated when the aluminum coated plate is formed into a fin material or the like, and cannot be used as a fin agent.

The antibacterial / antifungal agent needs to be present in an amount of 0.005 to 10.0 g per unit area (1 m ² ) of the aluminum coated plate. If the amount per 1 m ² is less than 0.005 g, the antibacterial and antifungal properties are insufficient, and if it exceeds 10.0 g, the coating film adhesion is insufficient.
The antibacterial / antifungal agent has a particle size of 5 μm or less, preferably 0.5 to 4.0 μm. By setting the thickness to 5 μm or less, the antibacterial / antifungal agent in the film is easily retained, and the antibacterial / antifungal effect is easily maintained.

B-10. Additives In the hydrophilic coating of the present invention, if necessary, rust preventives such as tannic acid, gallic acid, phytic acid, and phosphinic acid; leveling agents such as alkyl esters of polyalcohols and polyethylene oxide condensates; Fillers such as polyacrylamide and polyvinylacetamide added within a range that does not impair the solubility; Colorants such as phthalocyanine compounds; Surfactants such as alkyl sulfates and alkyl sulfosuccinates; Zinc oxide, Silicon oxide (silica) Inorganic oxides such as aluminum oxide (alumina) and titanium oxide can be added.

B-11. Formation of hydrophilic coating In order to form a hydrophilic coating on the surface of the aluminum material of the present invention, a liquid coating composition for the hydrophilic coating is applied to the surface of the aluminum material or the surface of the corrosion resistant base coating formed on the surface of the aluminum material ( Apply) and bake.

  Such a coating composition is prepared by dissolving and dispersing a hydrophilic resin, carbon black, tea components such as oolong tea, antibacterial and antifungal agents, and the above-described additives as necessary. Such a solvent is not particularly limited as long as each component can be dissolved or dispersed. For example, an aqueous solvent such as water, a ketone solvent such as acetone, an alcohol solvent such as ethanol, ethylene glycol, etc. Ethylene glycol alkyl ether solvents such as monoethyl ether; diethylene glycol alkyl ether solvents such as diethylene glycol monobutyl ether, propylene glycol alkyl ether solvents such as propylene glycol monomethyl ether, and a series of glycol alkyl ethers such as ethylene glycol monoethyl ether acetate Examples include esterified products of system solvents, among which aqueous solvents are preferable, and water is particularly preferable.

  As a coating method of the coating composition, a roll coater method, a roll squeeze method, a chemicoater method, an air knife method, a dipping method, a spray method, an electrostatic coating method, and the like are used. A good roll coater method is preferred. As the roll coater method, a gravure roll method with easy coating amount management, a natural coating method suitable for thick coating, a reverse coating method suitable for giving an aesthetic appearance to the coated surface, and the like can be employed. For drying the coating, a general heating method, dielectric heating method, or the like is used.

  Baking at the time of forming the film is preferably performed under the conditions that the baking temperature (reached surface temperature) is 180 to 300 ° C. and the baking time is 1 to 60 seconds. When the baking temperature in film formation is less than 180 ° C. or when the baking time is less than 1 second, the film is not sufficiently formed, and the film adhesion is lowered. When the baking temperature exceeds 300 ° C. or the baking temperature exceeds 60 seconds, the coating component is modified and the hydrophilicity is remarkably lowered.

For example, when the film thickness is formed on an aluminum coating plate for a heat exchanger, the film thickness is set to 0.01 to 15 μm. In order to obtain sufficient hydrophilicity, stain resistance, moldability, odor adsorbability and antibacterial and antifungal properties, the thickness is preferably 0.1 μm or more. When the antibacterial / antifungal agent is contained at a high level of 5 to 10 g / m ^2, it needs to be as thick as ² to 15 μm. When the content of the antibacterial / antifungal agent is not as high as described above, or when the content of the antibacterial / antifungal agent is not included, it is not necessary to increase the thickness of the coating. It is preferable to set it to -1.2 micrometers, especially 0.1-1.0 micrometer. If the film thickness is less than 0.01 μm, the desired hydrophilicity, stain resistance, moldability, odor adsorption and antibacterial and antifungal properties cannot be obtained, and if it is thicker than 15 μm, these characteristics are saturated and uneconomical. .

C. Lubricating film In the aluminum coating plate according to the present invention, the formability can be improved by forming a lubricating film mainly comprising a polyethylene glycol resin on the hydrophilic film. As the polyethylene glycol-based resin, polyethylene glycol (PEG), ethylene glycol / propylene glycol copolymer and the like having a weight average molecular weight of preferably 1000 to 20000, more preferably 4000 to 11000 are used. The thickness of the lubricating coating is 0.01 to 3 μm, preferably 0.05 to 2 μm, more preferably 0.05 to 1 μm. If it is less than 0.01 μm, sufficient moldability cannot be obtained, and if it exceeds 3 μm, the moldability is saturated and uneconomical.

  The lubricious film may contain an additive in addition to the polyethylene glycol resin as the main component. In such additives, carbon black, oolong tea component, green tea component, black tea component, antibacterial and antifungal agent contained in the hydrophilic film listed above are contained, thereby adsorbing odor components, hydrophilicity, Antibacterial and antifungal properties can be further improved.

  The lubricating coating is formed by coating (applying) a liquid coating composition for the lubricating coating on the surface of the hydrophilic coating and baking it. The coating composition for the lubricating coating is applied and baked in the same manner as the hydrophilic coating. This coating composition is prepared by dissolving and dispersing a polyethylene glycol resin and, if necessary, a tea component such as carbon black and oolong tea, an antibacterial antifungal agent and the above additives in a solvent. As such a solvent, the same solvents as those used for the coating composition for hydrophilic coating can be used, and an aqueous solvent is preferably used, and water is particularly preferably used.

  The lubricating coating is formed in a separate process from the formation of the hydrophilic coating. That is, the hydrophilic coating composition is applied to the surface of the aluminum material or the corrosion-resistant base coating surface on the aluminum material and baked, and then the lubricating coating composition is applied to the hydrophilic coating and baked. Is used (hereinafter referred to as “twice coating twice baking method”).

  Alternatively, the lubricating coating may be formed simultaneously with the hydrophilic coating. That is, a mixed solution of a coating composition for a hydrophilic coating and a coating composition for a lubricous coating is applied to the surface of an aluminum material or the surface of a corrosion-resistant base coating on the aluminum material and baked. When the above mixed solution is applied, it is separated into a hydrophilic coating component on the lower layer side (base material side) and a lubricating coating component on the upper layer side (outer side) before baking. By baking this, a two-layer structure consisting of a hydrophilic coating on the substrate side and a lubricating coating thereon is obtained (hereinafter referred to as “one coating once baking method”).

  Further, a method for forming a two-layer structure by applying a hydrophilic coating composition on a substrate, then applying a lubricating coating composition on the hydrophilic coating composition, and baking these compositions ( Hereinafter, it may be referred to as “twice coating once baking method”.

  Since the “double coating twice baking method” and the “double coating once baking method” are less economical than the “once coating once baking method”, it is preferable to adopt a film forming method by once coating once baking. .

  The aluminum coated plate thus produced is precoated with a desired fin shape by applying volatile press oil for press forming to the surface and then forming such as slit processing and corrugation processing. An aluminum fin material is produced. Such a pre-coated aluminum fin material is preferably used as, for example, a fin material of a heat exchanger for an air conditioner, but is limited to a heat exchanger for an air conditioner as long as it is used to prevent condensation between the fin materials. It is not a thing.

  Hereinafter, preferred embodiments of the present invention will be specifically described based on Examples and Comparative Examples, but the present invention is not limited to these Examples.

Examples 1-14 and Comparative Examples 1-7
As shown in Table 1, the resin component is composed of at least one of urethane resin and acrylic resin, or acrylic resin and polyvinyl alcohol (PVA) having a saponification degree of 92 to 99 mol% and an average polymerization degree of 1800. For a hydrophilic coating containing carbon black having a predetermined primary particle size, DPB oil absorption, nitrogen adsorption specific surface area, and tea ingredient having oolong tea extract, green tea extract, black tea extract A composition was prepared.
In Examples 1 to 6, 14 and Comparative Examples 1 to 7, no tea component was added. In Example 7, only the oolong tea component was added, and in Examples 8 to 13, in addition to oolong tea, either green tea or black tea was added. In Comparative Example 3, a cellulose resin was used as the resin component.
Furthermore, in Examples 10 to 13, a composition for a lubricating coating containing polyethylene glycol having a weight average molecular weight of 9300 was prepared.
Water was used as a solvent for the hydrophilic coating composition and the lubricating coating composition. Content of each component shown in Table 1 shows the weight part in 1 liter of water which is a solvent. Here, 100 parts by weight shown in Table 1 is specifically 100 g.

  For the oolong tea extract, green tea extract and black tea extract, eluates prepared with the components shown in Table 2 were used. Oolong tea extract is a commercially available Oolong tea extract, green tea extract is a commercially available green tea extract, and black tea extract is an extract from commercially available tea leaves. Each component such as polyphenol was measured by high performance liquid chromatography. The polyphenol, catechin, caffeine, and other tea components shown in Table 2 are extracts obtained by removing the extraction solvent from the extract, and the weight% of each component represents a numerical value when the entire extract is 100%. .

A hydrophilic film was formed on the surface of the aluminum material as follows. An aluminum alloy plate (1100-H24 material, 0.100 mm thickness) was weakly alkaline degreased, washed with water and then dried. Next, a coating type chromate (SAT427 manufactured by Nippon Paint Co., Ltd.) was applied to the surface of the aluminum alloy plate thus treated, and baked at 180 ° C. for 10 seconds. The amount of chromium deposited was 10 mg / m ^{2 in} terms of metallic chromium. A coating-type chromate-based chemical film was formed as a base film. Next, each hydrophilic coating composition shown in Table 1 was applied to this aluminum alloy plate with a roll coater, and baked at a reaching plate surface temperature (PMT) of 250 ° C. for 20 seconds to obtain an aluminum-coated plate. In Examples 10 to 13, an aluminum coated plate was obtained by applying and baking in the same manner as in Examples 1 to 9 and 14 using a mixed solution of the hydrophilic coating composition and the lubricating coating composition. .

  The aluminum coated plate thus obtained was measured for hydrophilicity, stain resistance, moldability, carbon black dispersibility, and odor component adsorption (ammonia, formaldehyde) by the methods described below. The results are shown in Table 3.

Examples 15-31 and Comparative Examples 8-13
As shown in Table 4, the resin component is made of an acrylic resin, or the resin component is made of an acrylic resin and polyvinyl alcohol (PVA) having a saponification degree of 92 to 99 mol% and an average polymerization degree of 1800, and a predetermined carbon black. With a primary particle size of 28 nm and a nitrogen adsorption specific surface area of 79 g / m ² , with a predetermined amount of humic acid attached to the surface, and with oolong tea extract, green tea extract and black tea extract as tea components A composition for a hydrophilic film was prepared.
For humic acid adhesion, humic acid was dissolved in water to prepare 1 liter of a 5% by weight humic acid aqueous solution, and 0.59 to 25 g of carbon black powder was added thereto, and the mixture was thoroughly stirred and mixed. To form a suspension. Next, carbon black was filtered from the suspension and dried at 100 ° C. for 1 hour.

In Examples 15 to 26 and Comparative Examples 8 to 13, no tea component was added. In Example 27, only the oolong tea component was added, and in Examples 28-31, either green tea or black tea was added in addition to oolong tea. In Comparative Examples 8 and 10, a cellulose resin was used as the resin component.
Further, in Examples 30 and 31, compositions for lubricating coatings containing polyethylene glycol having a weight average molecular weight of 9300 were prepared.
Water was used as a solvent for the hydrophilic coating composition and the lubricating coating composition. Content of each component shown in Table 4 shows the weight part in 1 liter of water which is a solvent. Here, 100 parts by weight shown in Table 4 is specifically 100 g.

  For the oolong tea extract, green tea extract and black tea extract, eluates prepared with the components shown in Table 2 were used.

A hydrophilic film was formed on the surface of the aluminum material as follows. In Examples 15 to 22, 27 to 31, and Comparative Examples 8 to 13, a coating-type chromate-based chemical conversion film having a chromium adhesion amount of 20 mg / m ² was formed as a base film in the same manner as Example 1. Baking conditions: 180 ° C. for 10 seconds). In Example 23, instead of the coating type chromate of Example 1, a coating type zirconium-based undercoat was formed so that the zirconium adhesion amount was 25 mg / m ² (baking conditions: 180 ° C. for 10 seconds). In Examples 24 to 26, in place of the coating type chromate of Example 1, an epoxy film, a urethane film, and an acrylic film, which are corrosion-resistant organic films, were respectively formed to have a base film of 3.0 mg / m ² ( Baking conditions: 240 ° C. for 10 seconds).
Next, each hydrophilic coating composition shown in Table 4 was applied to this aluminum alloy plate with a roll coater and baked at a final plate surface temperature (PMT) of 250 ° C. for 20 seconds to obtain an aluminum coated plate.
In Examples 30 and 31, application and baking were performed in the same manner as in Example 1 using a mixed solution of the hydrophilic coating composition and the lubricating coating composition to obtain an aluminum coated plate.

  The aluminum coated plate thus obtained was measured for hydrophilicity, moldability, film adhesion, carbon black dispersibility, and odor component adsorptivity (ammonia, acetaldehyde) by the methods described below. The results are shown in Table 5.

  First, the sample was pretreated as follows. Each sample was immersed in volatile press oil (Daphni AF-2A manufactured by Idemitsu Kosan Co., Ltd.) for 1 minute. After removing the sample, the sample was held vertically at room temperature for 30 seconds to drain the oil. Subsequently, it was placed in a hot air oven (atmosphere) at 180 ° C. for 2 minutes and then cooled to room temperature.

The contact angle of pure water was measured with a hydrophilic goniometer. The hydrophilicity immediately after producing the aluminum coating plate and the hydrophilicity after the wet and dry cycle were evaluated. In the dry / wet cycle, the manufactured aluminum coated plate was immersed in tap water having a flow rate of 1 liter / min for 8 hours, and then dried at 80 ° C. for 16 hours, and this was performed 20 cycles. The meanings of the symbols in Table 3 are as follows.
(Double-circle): A contact angle is 20 degrees or less, and shows that it is very favorable.
◯: The contact angle exceeds 20 ° and is 30 ° or less, indicating that it is good.
(Triangle | delta): A contact angle exceeds 30 degrees and is 40 degrees or less, and it shows that it is inferior.
X: Indicates that the contact angle exceeds 40 ° and is very poor.

The prepared aluminum coated plate was pretreated and then subjected to a contamination cycle treatment. The contamination cycle treatment is to adsorb palmitic acid in the gas phase by exposing the aluminum coating plate to air at 50 ° C. containing palmitic acid vapor for 1 hour, then immersing in tap water for 6 hours and then drying in a dryer. Was one cycle and this was carried out for 10 cycles. The contact angle on the surface of the hydrophilic coating after 10 cycles was measured by the same method as in the hydrophilicity evaluation. The meanings of the symbols in Table 3 are as follows, and “◎”, “◯”, and “Δ” were regarded as acceptable.
(Double-circle): A contact angle is 20 degrees or less, and shows that it is very favorable.
A: The contact angle exceeds 20 ° and is 40 ° or less, indicating that it is good.
(Triangle | delta): A contact angle exceeds 40 degrees and is 60 degrees or less, and it shows that it is inferior.
X: Indicates that the contact angle exceeds 60 ° and is very poor.

The Dolores molded at moldability actual fin press was evaluated in situations was conducted. The molding conditions are as follows. Volatile press oil: AF-2C (Idemitsu Kosan) was used, the ironing rate was 58%, and the molding speed was 250 spm. The meanings of the symbols in Table 3 which are the evaluation results are as follows, and “◎” and “◯” are considered acceptable.
(Double-circle): It shows that it is very favorable.
◯: Indicates that it is good.
(Triangle | delta): It shows that a crack generate | occur | produces on the inner surface of a color part and is defective.
X: Indicates that buckling or color jump occurs and is defective.

Carbon black dispersibility The dispersibility of carbon black in the hydrophilic coating was evaluated by SEM observation in a 2000 × (2400 μm ² ) field of view. The meanings of the symbols in Table 3 which are the evaluation results are as follows, and “◎” and “◯” are considered acceptable.
○: No aggregation of carbon black was observed in the visual field, indicating that the dispersibility was good.
Δ: Some aggregation of carbon black is observed in the field of view, indicating that the dispersibility is slightly poor.
X: Aggregation of carbon black occurs frequently in the visual field, indicating that the dispersibility is poor.

Film adhesion The adhesion test according to JIS H4001 was performed, and the number of remaining tapes after peeling at the grid was measured. The case where all remained (100/100) was regarded as acceptable.

Ammonia adsorptivity Adsorption test Each aluminum coating board was arrange | positioned in the container of ammonia atmosphere, and the ammonia concentration (Ca) in the container after making ammonia adsorb | suck was measured. Ca is a concentration corresponding to the amount of unadsorbed ammonia. The measurement conditions were as follows. In addition, the density | concentration (Cb) which deducted said ammonia density | concentration Ca from the following ammonia initial density | concentration (20 ppm) is a density | concentration corresponding to the ammonia adsorption amount by an aluminum coating plate. The adsorption rate (%) of ammonia is represented by (Cb / 20) × 100.
Sample area: 100 × 200 mm ²
Sample container: 5 liter desiccator Gas amount of container: 5 liter Initial gas concentration: 20 ppm of ammonia
Gas measurement method: ammonia detector tube Laboratory temperature: 20 ° C
Measurement time: 24 hours

2. Desorption test Each aluminum coating plate that adsorbed ammonia was placed in a container in an atmospheric atmosphere, and the ammonia concentration (Cc) in the container after ammonia was desorbed was measured. The measurement conditions were as follows. The concentration (Cd) obtained by subtracting the ammonia concentration Cc from the ammonia concentration Cb is a concentration corresponding to the ammonia fixing amount by the aluminum coating plate. Therefore, the ammonia fixing rate (%) is expressed by (Cd / Cb) × 100.
Sample area: 100 × 200 mm ²
Sample container: 5 liter desiccator Gas amount in container: 5 liter Gas initial concentration: Ammonia 0 ppm
Gas measurement method: ammonia detector tube Laboratory temperature: 20 ° C
Measurement time: 24 hours

  A case where the ammonia adsorption rate was 35% or more and the fixing rate was 80% or more was determined to be acceptable to satisfy the ammonia adsorption property.

Formaldehyde adsorption property, acetaldehyde adsorption property In the above ammonia adsorption test, the initial concentration of formaldehyde was set to 15 ppm, acetaldehyde was set to 20 ppm, and a gas measurement method was the same as the ammonia adsorption test except that a formaldehyde adsorption tube or an acetaldehyde adsorption tube was used. A formaldehyde adsorption test or an acetaldehyde adsorption test was performed, and the adsorption rate of formaldehyde or acetaldehyde was measured. Furthermore, in the ammonia desorption test, a formaldehyde desorption test or an acetaldehyde desorption test is performed in the same manner as the ammonia desorption test, except that a formaldehyde adsorption tube or an acetaldehyde adsorption tube is used as a gas measurement method, and the fixation rate of formaldehyde or acetaldehyde is measured. did.

  The case where the adsorption rate of formaldehyde is 40% or more and the fixing rate is 30% or more, the case where the adsorption rate of acetaldehyde is 55% or more and the fixing rate is 90% or more, and pass that satisfies formaldehyde adsorption property or acetaldehyde adsorption property did.

As shown in Table 3, in Examples 1 to 14, all of the initial and post-cycle test hydrophilicity, stain resistance, moldability, carbon black dispersibility, and adsorption rate using ammonia and formaldehyde as odor components. And the adsorptivity regarding the fixing rate was good. In particular, those containing oolong tea extract are excellent in stain resistance and adsorptivity of odor components. Among them, the example containing the green tea component or the black tea component in addition to the oolong tea component is excellent in the adsorptivity of the odor component, and the example including the green tea component is particularly excellent in the adsorptivity of the odor component.
Moreover, what formed the lubricous film is remarkably excellent in a moldability.

  On the other hand, in Comparative Examples 1 and 2, since the carbon black was not contained in the hydrophilic coating film, the adsorptivity of the odor component could not be satisfied. Moreover, since the hydrophilic resin of the hydrophilic film of the comparative example 3 is a cellulose type, it was not able to satisfy hydrophilicity. In Comparative Example 4, since the carbon black content was too small, the adsorptivity of odor components could not be satisfied. In Comparative Examples 5 and 6, since the primary particle diameter was too large, aggregates of carbon black were generated in the hydrophilic film, and the adsorptive property and desorption property of the odor component could not be satisfied. In Comparative Example 7, since the film thickness of the hydrophilic coating was too thin, the hydrophilicity after the cycle test and the adsorptivity of the odor component could not be satisfied.

As shown in Table 5, in all of Examples 15 to 31, no problems were found in hydrophilicity, moldability, film adhesion, carbon black dispersibility, and adsorptivity of odor components (ammonia / acetaldehyde). We were satisfied with.
Among these Examples, Examples 27 to 31 containing oolong tea extract were excellent in odor substance adsorption. Among them, in Examples 28 to 31 which further contained a green tea component or a black tea component, the adsorptivity and fixability of the odor substance were excellent. Regarding formability, Examples 30 and 31 provided with a lubricious coating were particularly excellent.

  On the other hand, in Comparative Examples 8 and 9, since carbon black was not contained in the hydrophilic film, the adsorptivity of odor components could not be satisfied. Moreover, in Comparative Example 10, although the adsorptivity of odorous substances was good by containing carbon black with humic acid attached to the surface in the hydrophilic film, a cellulose resin was used as the hydrophilic resin. The hydrophilicity could not be satisfied. In Comparative Example 11, the content of carbon black was too small, so that the adsorptivity of odorous substances could not be satisfied. Since the comparative example 12 had too much carbon black content, film adhesiveness was not able to be ensured. In Comparative Example 13, since the film thickness of the hydrophilic coating was too thin, the hydrophilicity and the adsorptivity of odor components could not be satisfied.

Examples 32-48 and Comparative Examples 14-22
As shown in Table 6, the resin component is composed of at least one of urethane resin and acrylic resin, or acrylic resin and polyvinyl alcohol (PVA) having a saponification degree of 92 to 99 mol% and an average polymerization degree of 1800. Carbon black having a predetermined primary particle size, antibacterial and antifungal agents, zinc pyrithione (ZPT), 2,3,5,6-tetrachloro-4- (methylsulfonyl) -pyridine, 2- (4 -A composition for hydrophilic coatings containing thiazolyl) benzimidazole (TBZ) was prepared. In Example 48, a hydrophilic film was used in which oolong tea component and green tea component were added in addition to carbon black and antibacterial and antifungal agent.

  Water was used as a solvent for the hydrophilic coating composition and the lubricating coating composition. Content of each component shown in Table 6 shows the weight part in 1 liter of water which is a solvent. Here, 100 parts by weight shown in Table 6 is specifically 100 g.

A hydrophilic film was formed on the surface of the aluminum material as follows. An aluminum alloy plate (1100-H24 material, 0.100 mm thickness) was weakly alkaline degreased, washed with water and then dried. Next, a coating type chromate (SAT427 manufactured by Nippon Paint Co., Ltd.) was applied to the surface of the aluminum alloy plate thus treated, and baked at 180 ° C. for 10 seconds. The amount of chromium deposited was 10 mg / m ^{2 in} terms of metallic chromium. A coating-type chromate-based chemical film was formed as a base film. Next, each hydrophilic coating composition shown in Table 1 was applied to this aluminum alloy plate with a roll coater and baked at a final plate surface temperature (PMT) of 200 ° C. for 20 seconds to obtain an aluminum-coated plate. In Examples 46 to 48, an aluminum coated plate was obtained by applying and baking in the same manner as in Example 1 using a mixed solution of the hydrophilic coating composition and the lubricating coating composition.

  The aluminum coated plate thus obtained was measured for hydrophilicity, stain resistance, moldability, film adhesion, carbon black dispersibility, and antibacterial and antifungal properties by the methods described below. The results are shown in Table 7.

  First, the sample was pretreated as follows. Each sample was immersed in volatile press oil (Daphni AF-2A manufactured by Idemitsu Kosan Co., Ltd.) for 1 minute. After removing the sample, the sample was held vertically at room temperature for 30 seconds to cut off the oil. Subsequently, it was placed in a hot air oven (atmosphere) at 180 ° C. for 2 minutes and then cooled to room temperature.

  The hydrophilicity, stain resistance, moldability, and carbon black dispersibility were evaluated in the same manner as in Example 1, and the film adhesion was evaluated in the same manner as in Example 15. The antibacterial and antifungal properties were evaluated by the following methods.

Antibacterial and antifungal properties Antibacterial test The sample was subjected to an antibacterial test (film adhesion method) according to JIS Z2801, and the antibacterial activity value was determined using the formula R = log (A / B). Here, R, A, and B are as follows.
R: Antibacterial activity value A: Average number of viable cells after culturing of blank sample B: Average number of viable cells after culturing of antibacterial processed sample The meanings of symbols in Table 2 which are evaluation results are as follows, ○ is regarded as a pass that satisfies the performance.
○: R is 2.0 or more, indicating that it is good.
X: R is less than 2.0, indicating a failure.

2. Antifungal test The sample was subjected to a fungus resistance test in accordance with JIS Z2911, and the growth of the mycelium was observed with the naked eye. The meanings of the symbols in Table 2, which are the evaluation results, are as follows.
3: Mycelial growth is not observed in the inoculated part of the sample.
2: The area of the growing part of the mycelium observed in the inoculated part of the sample does not exceed 1/3 of the total surface area.
1: The area of the growth part of the mycelium recognized in the inoculated part of the sample exceeds 1/3 of the total surface area.

  As shown in Table 2, each of Examples 32-48 had good hydrophilicity, stain resistance, moldability, film adhesion, carbon black dispersibility, and antibacterial and antifungal properties after the initial and cycle tests. It was. In Examples 33 to 36, 38, 40, 41 and 45 to 47, even when an antibacterial antifungal agent was added, the hydrophilicity was particularly excellent. Further, in Examples 46 and 47 in which the lubricious coating was formed, the moldability was remarkably excellent.

  On the other hand, in Comparative Examples 14 and 15, since carbon black and an antibacterial / antifungal agent were not contained in the hydrophilic coating film, the stain resistance and the antibacterial / antifungal property could not be satisfied. Further, in Comparative Example 16, the hydrophilic resin of the hydrophilic film is a cellulosic resin and does not contain an antibacterial and antifungal agent, so that hydrophilicity, stain resistance and antibacterial and antifungal properties can be satisfied. There wasn't. In Comparative Example 17, the content of carbon black was too small, and in Comparative Example 18, no carbon black was contained. Therefore, none of them satisfied the hydrophilicity and the stain resistance after the cycle test. In Comparative Example 19, the antibacterial and antifungal properties could not be satisfied because the amount of the antibacterial and antifungal agent per coating plate area was too small. In Comparative Example 20, since the coating content of the antibacterial / antifungal agent was too small, the antifungal property could not be satisfied. In Comparative Example 21, since the coating content of the antibacterial / antifungal agent was too large, the coating properties such as hydrophilicity, contamination resistance, moldability, and coating adhesion could not be satisfied. In Comparative Example 22, since the film thickness was too thin, the film properties of hydrophilicity, stain resistance, and moldability could not be satisfied, and the amount of antibacterial / antifungal agent per unit area of the coated plate was too small. Therefore, antibacterial and antifungal properties could not be satisfied.

  According to the present invention, there can be obtained an aluminum coated plate having a hydrophilic film on its surface that exhibits excellent performance in hydrophilicity, stain resistance, moldability, film adhesion, odor component adsorption, antibacterial and antifungal properties, A heat exchanger such as a heat exchange fin of an air conditioner obtained by processing and molding this aluminum coated plate exhibits excellent heat exchange efficiency over a long period of time.

Claims (13)

An aluminum coated plate provided with a base material of aluminum or an aluminum alloy and a hydrophilic film formed on at least one surface of the base material,
The hydrophilic coating contains at least one hydrophilic resin of urethane resin and acrylic resin, and carbon black having a primary particle diameter of 12 to 40 nm, and the carbon black is in 100 parts by weight of the hydrophilic resin. 1 to 200 parts by weight of the aluminum coating plate, wherein the hydrophilic coating has an average film thickness of 0.01 to 15 μm.   The carbon black is one in which an aromatic compound having at least one selected from a carboxyl group, a hydroxyl group, and a salt thereof is attached to the surface, and the aromatic compound is 0.5 parts per 100 parts by weight of the carbon black. The aluminum coating plate according to claim 1, which is attached to -100 parts by weight.   The aluminum coating board of Claim 2 whose said aromatic compound is humic acids.   The said hydrophilic resin further contains a polyvinyl alcohol-type resin, and 5-95 weight part of said polyvinyl alcohol-type resins are contained in 100 weight part of said hydrophilic resin, The Claim 1 1-3. Aluminum painted plate.   The aluminum coating plate as described in any one of Claims 1-4 in which the said hydrophilic film further contains 0.1-25 weight part Oolong tea component with respect to 100 weight part of said hydrophilic resins.   The aluminum coating board of Claim 5 in which the said hydrophilic film further contains at least one of 0.1-50 weight part of green tea components and black tea components with respect to 100 weight part of said hydrophilic resins.   The lubricant film further comprising a polyethylene glycol resin as a main component on the hydrophilic film, and an average film thickness of the lubricant film is 0.01 to 3 μm. The aluminum paint plate of description. The surface of the base material is at least one chemical conversion coating selected from the group consisting of chromium, zirconium and titanium, and contains ^{2 to} 50 mg / m ² of metal in terms of metal element. The aluminum coating plate as described in any one of Claims 1-7 in which was formed. The organic film of the amount of 0.1-10 g / m < ² > which consists of at least 1 type selected from the group which consists of a urethane type resin, an epoxy resin, and an acrylic resin was formed in the surface of the said base material. The aluminum coating plate as described in any one of -7.   The precoat aluminum fin material using the aluminum coating plate as described in any one of Claims 1-9. The hydrophilic coating further contains an antibacterial / antifungal agent, the antibacterial / antifungal agent is contained in an amount of 0.5 to 400 parts by weight with respect to 100 parts by weight of the hydrophilic resin, and the unit area ( The aluminum coating plate as described in any one of Claims 1-9 which exists in the quantity of 0.005-10.0g per 1m < ² >).   The antibacterial / antifungal agent is bis- (2-pyridylthio-1-oxide) -zinc, 2,3,5,6-tetrachloro-4- (methylsulfonyl) -pyridine and 2- (4-thiazolyl) benzimidazole. The aluminum coating plate according to claim 11, comprising at least one selected from the group consisting of:   The precoat aluminum fin material using the aluminum coating plate of Claim 11 or 12.