CN112262041B - Pre-coated aluminum material - Google Patents
Pre-coated aluminum material Download PDFInfo
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- CN112262041B CN112262041B CN201980039474.8A CN201980039474A CN112262041B CN 112262041 B CN112262041 B CN 112262041B CN 201980039474 A CN201980039474 A CN 201980039474A CN 112262041 B CN112262041 B CN 112262041B
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- resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
- B32B15/082—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising vinyl resins; comprising acrylic resins
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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
- F28F1/00—Tubular elements; Assemblies of tubular elements
- F28F1/10—Tubular elements and assemblies thereof with means for increasing heat-transfer area, e.g. with fins, with projections, with recesses
- F28F1/12—Tubular elements and assemblies thereof with means for increasing heat-transfer area, e.g. with fins, with projections, with recesses the means being only outside the tubular element
- F28F1/24—Tubular elements and assemblies thereof with means for increasing heat-transfer area, e.g. with fins, with projections, with recesses the means being only outside the tubular element and extending transversely
- F28F1/32—Tubular elements and assemblies thereof with means for increasing heat-transfer area, e.g. with fins, with projections, with recesses the means being only outside the tubular element and extending transversely the means having portions engaging further tubular elements
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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
- F28F13/00—Arrangements for modifying heat-transfer, e.g. increasing, decreasing
- F28F13/18—Arrangements for modifying heat-transfer, e.g. increasing, decreasing by applying coatings, e.g. radiation-absorbing, radiation-reflecting; by surface treatment, e.g. polishing
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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
- F28F19/00—Preventing the formation of deposits or corrosion, e.g. by using filters or scrapers
- F28F19/02—Preventing the formation of deposits or corrosion, e.g. by using filters or scrapers by using coatings, e.g. vitreous or enamel coatings
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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
- F28F21/08—Constructions of heat-exchange apparatus characterised by the selection of particular materials of metal
Abstract
The precoated aluminum material (1) has an aluminum sheet (2), a chemical conversion film (3), and a hydrophilic film (4) laminated in this order. The hydrophilic film (4) contains at least an acrylic resin (A), a polyalkylene ether resin (B), a resin (C), and a polyvinyl alcohol (D). The acrylic resin (a) has substantially no repeating unit derived from a monomer having a sulfo group and a monomer having an amide group. The resin (C) has a repeating unit derived from a monomer having an amide group. In the infrared absorption spectrum, the hydrophilic film (4) has a wave number of 1600-1800 cm ‑1 Has 2 peaks in the range of (2). The ratio of absorbance of each peak satisfies a given relationship.
Description
Technical Field
The present invention relates to a precoated aluminum material having a hydrophilic film.
Background
Conventionally, as a heat exchanger to be mounted in an air conditioner, a refrigerator, or the like, a so-called plate-fin tube type heat exchanger having a large number of fins and tubes intersecting the fins has been commonly used. The plate-fin tube heat exchanger may exchange heat between a low-temperature refrigerant and outside air, for example, as in an indoor unit in a cooling operation in an air conditioner.
In this case, if the temperature of the fin is lower than the dew point of the outside air, dew water adheres to the surface of the fin. If the amount of dew condensation water increases, gaps between fins become narrow or, if the case may be, the air flow resistance, that is, resistance when an air flow passes between fins may increase. As a result, there is a possibility that the heat exchange efficiency may be lowered.
In order to solve such a problem, a precoated aluminum material having a hydrophilic film on the surface thereof has been proposed. The precoated aluminum material is subjected to press working or the like, whereby a fin for a heat exchanger having a hydrophilic film on the surface thereof can be produced. By the presence of hydrophilic films on the surface of the fins, the wetting of the water is easily amplified. Therefore, there has been proposed a technique of forming dew condensation water into a film shape having a uniform thickness and a thin film shape, thereby preventing the gaps between fins from being blocked and promoting the drainage of dew condensation water from the gaps between fins.
As such a precoated aluminum material, for example, patent document 1 discloses an aluminum fin material in which a chemical conversion film is formed on the surface and a hydrophilic film is formed on the chemical conversion film. The hydrophilic film contains (meth) acrylic resin, polyvinyl alcohol, at least 1 resin selected from polyethylene oxide and polyethylene glycol; and crosslinkable microparticles.
Prior art literature
Patent literature
Patent document 1: japanese patent No. 5995546
Disclosure of Invention
Technical problem to be solved by the invention
However, the conventional precoated aluminum material tends to adhere to a hydrophilic film. Therefore, for example, in an environment where the air temperature is high in summer, a countermeasure is taken in which the temperature of the precoated aluminum material before winding is suppressed to be low by using a powerful cooling device in order to prevent the occurrence of blocking. Such a countermeasure increases the manufacturing cost of the precoated aluminum material.
In recent years, in order to provide a heat exchanger at a further low cost, further reduction in the cost of the fins has been strongly demanded. If the blending ratio of the (meth) acrylic resin or polyvinyl alcohol, which becomes a skeleton component of the hydrophilic film of the precoated aluminum material, is increased, the occurrence of blocking can be suppressed, but the hydrophilic film is inferior in moisture resistance, and becomes rancid or acidic after being wet, or the wet adhesion is lowered, so improvement is desired.
As described above, in addition to hydrophilicity and durability, various properties are further required for the precoated aluminum material in recent years. The present invention has been made in view of the above-described background, and it is intended to provide a precoated aluminum material excellent in blocking resistance, odor resistance, acid odor, hydrophilicity continuation, wet adhesion and press formability.
Technical scheme for solving problems
One embodiment of the present invention is a precoated aluminum material characterized in that an aluminum sheet, a chemical conversion coating and a hydrophilic film are laminated in this order,
the hydrophilic film contains at least 15 to 20 mass% of an acrylic resin (A), 30 to 40 mass% of a polyalkylene ether resin (B), 20 to 25 mass% of a resin (C) having a repeating unit derived from a monomer having an amide group, and 22 to 28 mass% of a polyvinyl alcohol (D),
the acrylic resin (A) has substantially no repeating unit derived from a monomer having a sulfo group and no repeating unit derived from a monomer having an amide group,
the acrylic resin (A) has a weight average molecular weight of 20000 ～ 2000000 and an acid value of 100 to 800mgKOH/g,
the weight average molecular weight of the polyalkylene ether resin (B) is 5000 to 500000,
in the infrared absorption spectrum, the hydrophilic film has a wave number of 1600-1800 cm -1 The absorbance a of the peak top in the peak a on the low wave number side of 2 peaks and the absorbance B of the peak top in the peak B on the high wave number side satisfy the relationship of absorbance a/absorbance b=0.6 to 1.3.
Effects of the invention
In the precoated aluminum material, the hydrophilic film contains the acrylic resin (a), the polyalkylene ether resin (B), the resin (C) having a repeating unit derived from a monomer having an amide group, and the polyvinyl alcohol (D) in a predetermined content ratio. And the infrared absorption spectrum of the hydrophilic film is 1600cm in wave number -1 ～1800cm -1 The absorbance a of the peak top in the peak a and the absorbance B of the peak top in the peak B satisfy the above-described given relationship, with 2 peaks in the range.
With the above configuration, the cohesive force of the hydrophilic film of the precoated aluminum material is improved, and the toughness is improved. Therefore, the precoated aluminum material is excellent in blocking resistance. Therefore, even if a strong cooling device is not used, blocking is less likely to occur after winding. As a result, the manufacturing cost can be reduced.
Further, since the hydrophilic film has high cohesive force and high toughness, the hydrophilic film has high barrier property and excellent moisture resistance. Therefore, it is difficult to cause rancidity after being immersed in water. That is, the odor resistance after the moisture resistance test was excellent.
Further, the hydrophilic membrane exhibits excellent hydrophilicity and also excellent hydrophilicity persistence. Further, the precoated aluminum material was excellent in press formability, wet adhesion, and acid odor. Thus, the pre-coated aluminum material is suitable for, for example, fins of a heat exchanger.
As described above, according to the present invention, a precoated aluminum material excellent in blocking resistance, odor resistance, acid odor, hydrophilicity continuation, wet adhesion, and compression moldability can be provided.
Drawings
FIG. 1 is a cross-sectional view of a critical portion of a pre-coated aluminum material in an example.
Fig. 2 is a graph showing an infrared absorption spectrum of the hydrophilic film in example 5.
Fig. 3 is a graph showing an infrared absorption spectrum of the hydrophilic film in comparative example 2.
Detailed Description
[ aluminum plate ]
In the precoated aluminum material, the material of the aluminum plate can be appropriately selected from pure aluminum and aluminum alloys according to desired mechanical properties, corrosion resistance, and the like. The aluminum plate is preferably composed of JIS A1200 or JIS A1050. In this case, the precoated aluminum material is more suitable for the fins of the heat exchanger because of its excellent heat conductivity.
[ chemical conversion film ]
A chemical conversion coating is provided on the surface of the aluminum plate. The chemical conversion coating improves adhesion between the aluminum plate and a hydrophilic film or a corrosion-resistant film described later, or improves corrosion resistance.
The chemical conversion film is formed by a chemical treatment film treatment (i.e., chemical conversion treatment). Specifically, the chemical conversion coating is formed by phosphate chromate treatment (japanese text: swelling treatment). The chemical conversion coating is also formed by non-chromate treatment such as titanium phosphate, zirconium phosphate, molybdenum phosphate, zinc phosphate, and zirconium oxide. The chemical conversion treatment method may be any of a reactive type and a coating type.
The adhesion amount of the chemical conversion coating may be, for example, 5 to 50mg/m from the metal content 2 Is appropriately selected from the range of (a). The amount of the chemical conversion film attached can be measured by a fluorescent X-ray analyzer.
[ hydrophilic film ]
The hydrophilic film is formed on the surface of the chemical conversion film or the surface of a corrosion-resistant film described later. The hydrophilic film contains at least an acrylic resin (A), a polyalkylene ether resin (B), a resin (C) having a repeating unit derived from a monomer having an amide group, and a polyvinyl alcohol (D). The term "repeating unit" refers to a unit of a structure that repeats in a resin, and is sometimes referred to as a repeating structural unit. The repeating unit generally has a structure derived from a monomer used in the production of the resin.
Acrylic resin (A) >, and process for producing the same
The acrylic resin (a) satisfies the following (1) to (3).
(1) Substantially no repeating units derived from a monomer having a sulfo group and no repeating units derived from a monomer having an amide group. This means that the repeating units constituting the acrylic resin (a) have substantially no sulfo groups and no amide groups.
(2) The weight average molecular weight was 20000 ～ 2000000.
(3) The acid value is 100-800 mgKOH/g.
The acrylic resin (a) improves adhesion between the hydrophilic film and the chemical conversion film, and improves hydrophilicity of the hydrophilic film. In the present specification, the acrylic resin (a) is a concept including not only an acrylic resin but also a methacrylic resin. That is, the acrylic resin (a) is a (meth) acrylic resin. The (meth) acrylic resin means at least one of an acrylic resin and a methacrylic resin.
The acrylic resin (a) contains a repeating unit derived from at least one of an acrylic monomer and a methacrylic monomer. The total content of the repeating units derived from the acrylic acid monomer and the repeating units derived from the methacrylic acid monomer is not particularly limited, but is preferably 50 to 100% by mass.
The acrylic resin (a) may include a repeating unit other than a repeating unit derived from an acrylic monomer and a repeating unit derived from a methacrylic monomer. For example, repeating units derived from acrylic acid monomers or derivatives of methacrylic acid monomers, and the like.
Specifically, there is a monomer having 1 polymerizable unsaturated bond in the molecule. Examples of such monomers include alkyl methacrylates such as methyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, isononyl methacrylate, n-octyl methacrylate, lauryl methacrylate, stearyl methacrylate, and the like; alkyl acrylates such as methyl acrylate, n-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, isononyl acrylate, and n-octyl acrylate; aralkyl methacrylates such as benzyl methacrylate; alkoxyalkyl methacrylates such as butoxyethyl methacrylate; alkoxyalkyl acrylates such as butoxyethyl acrylate and the like. These may be used alone or in combination of 2 or more.
Further, the (meth) acrylic resin (a) may contain components other than the above-described monomers, but substantially contains no repeating unit derived from a monomer having a sulfo group and no repeating unit derived from a monomer having an amide group. If these are contained, it is difficult to suppress the generation of odor and the difference in acid odor when adsorbing acid components in the atmosphere.
(content of acrylic resin (A))
The content of the acrylic resin (A) in the hydrophilic film is 15 to 20 mass%. In this case, the hydrophilicity of the precoated aluminum material can be improved, and the absorbance a/absorbance b can be easily adjusted to a desired range of 0.6 to 1.3. If the content is less than 15 mass%, the wet adhesion is poor, and if the content exceeds 20 mass%, the acid odor is poor. The content of the acrylic resin (a) refers to the content of the entire resin component including the acrylic resin (a), the polyalkylene ether resin (B), the resin (C), and the polyvinyl alcohol (D). The same is true for the contents of the polyalkylene ether resin (B), the resin (C), and the polyvinyl alcohol (D).
(acid value of acrylic resin (A))
The acid value of the acrylic resin (A) is 100 to 800mgKOH/g. If the acid value of the acrylic resin (A) is less than 100mgKOH/g, the adhesion between the hydrophilic film and the metal surface is lowered, and the wet adhesion is poor. If the acid value of the acrylic resin (A) is more than 800mgKOH/g, the hydrophilic film adsorbs acid components in the atmosphere, and the acid odor is reduced. The acid value of the acrylic resin (a) is preferably 500mgKOH/g or more from the viewpoint of further improving the adhesion of the hydrophilic film. The acid value of the acrylic resin (A) is preferably 800mgKOH/g or less as described above from the viewpoint of further improving the odor resistance.
(weight average molecular weight of acrylic resin (A))
The weight average molecular weight of the acrylic resin (a) was 20000 ～ 2000000. If the weight average molecular weight of the acrylic resin (A) is less than 20000, the hydrophilicity is reduced continuously. If the weight average molecular weight of the acrylic resin (a) is more than 2000000, the viscosity of a hydrophilizing agent to be used in the formation of a hydrophilic film becomes high, and workability is poor. If the weight average molecular weight of the acrylic resin (a) is small, the acrylic resin (a) existing in the vicinity of the boundary on the surface side of the aluminum plate moves to the surface side of the hydrophilic film when the hydrophilic film is in contact with moisture. As a result, the adhesion between the hydrophilic film and the metal surface is reduced. If the weight average molecular weight is too small, the acrylic resin is easily eluted into water, and for this reason, the adhesion between the hydrophilic film and the metal surface is lowered. If the weight average molecular weight of the acrylic resin is in the above range, the adhesion between the hydrophilic film and the metal surface does not deteriorate even if water is continuously adhered to the surface of the hydrophilic film. The weight average molecular weight of the acrylic resin (a) is preferably in the range of 20000 to 100000.
The weight average molecular weight was measured by Gel Permeation Chromatography (GPC). Specifically, a solution in which 0.4 parts by mass of the resin sample was dissolved with respect to 100 parts by mass of tetrahydrofuran was used as a sample solution, and this was measured by LC-08 (a-5432) type GPC manufactured by analytical industries, ltd, and calculated by conversion to polystyrene.
Polyalkylene ether resin (B) >, and process for producing the same
The polyalkylene ether resin (B) imparts lubricity to the hydrophilic film, and can improve moldability when the surface of the precoated aluminum material is subjected to pressure processing.
Examples of the polyalkylene ether resin (B) include polyethylene oxides, polyethylene glycols and other polyoxyethylene resins; polypropylene oxide, polypropylene glycol and the like.
The weight average molecular weight of the polyalkylene ether resin (B) is 5000 to 500000. By setting the weight average molecular weight to 5000 or more, the occurrence of winding displacement after winding of the precoated aluminum material can be prevented. Further, by setting the viscosity to 500000 or less, it is possible to prevent the viscosity of the coating material for forming a hydrophilic film from becoming too high, and the coatability can be improved.
(content of polyalkylene ether resin (B))
The content of the polyalkylene ether resin (B) is 30 to 40 mass%. If the content is less than 30% by mass, the press formability is lowered. If the content is more than 40% by mass, the membrane component may be eluted in water, resulting in poor hydrophilicity. The content of the polyalkylene ether resin (B) is more preferably 31 to 39% by mass from the viewpoint of further improving the press formability and the hydrophilicity persistence.
< resin (C) >)
The resin (C) is a resin having a repeating unit derived from a monomer having an amide group. That is, the resin (C) has a repeating unit derived from a monomer having an amide group in at least 1 of the repeating structural units of the polymer constituting the resin. The resin (C) can improve the hydrophilic persistence.
As the monomer having an amide group, at least 1 selected from the group consisting of N-methylolacrylamide, N-methylolmethacrylamide, N-hydroxyethyl acrylamide, and N-hydroxyethyl methacrylamide may be used. Preferably, the resin (C) may contain, in at least 1 of the repeating structural units constituting the resin, a repeating unit derived from at least 1 monomer selected from the group consisting of N-methylolacrylamide, N-methylolmethacrylamide, N-hydroxyethyl acrylamide, and N-hydroxyethyl methacrylamide. That is, the resin (C) preferably has at least 1 of these monomers as a repeating unit constituting the polymer. In this case, the effect of improving the cohesion of the coating film and improving the hydrophilicity persistence can be obtained.
The resin (C) is more preferably a copolymer of the (meth) acrylamide monomer described above and the following monomer that can be copolymerized. (meth) acrylamide refers to at least one of acrylamide and methacrylamide. Examples of copolymerizable monomers include monomers having a polyoxyalkylene chain and a polymerizable double bond such as methoxypolyethylene glycol monomethacrylate, methoxypolyethylene glycol monoacrylate, and octoxypolyethylene glycol-polypropylene glycol monoacrylate; vinyl monomers such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, and vinyl acetate; 2-hydroxyethyl acrylate, hydroxypropyl acrylate, and the like.
(content of resin (C))
The content of the resin (C) is 20 to 25 mass%. In this case, the absorbance a/absorbance b is easily adjusted to the above-described desired range while improving the hydrophilicity persistence of the precoated aluminum material. From the viewpoint of further improving the effect, the content of the resin (C) is preferably 21 to 24 mass%. In the case where the content of the resin (C) is less than 20% by mass, the hydrophilicity is inferior in persistence. On the other hand, if the content is more than 25 mass%, the wet adhesion is poor.
Polyvinyl alcohol (D) >, polyvinyl alcohol (A)
The hydrophilic film contains polyvinyl alcohol (D). The polyvinyl alcohol (D) is obtained, for example, by saponifying a polymer obtained by polymerizing polyvinyl acetate.
(content of polyvinyl alcohol (D))
The content of the polyvinyl alcohol (D) is 22 to 28 mass%. When the content of the polyvinyl alcohol (D) is less than 22 mass%, the wet adhesion is poor. On the other hand, when the content is more than 28 mass%, the hydrophilicity and the hydrophilicity-sustaining property are poor.
< other additives >)
To the hydrophilic film, an antifoaming agent, a leveling agent, an anti-shrinkage agent, a dispersing agent, a surfactant, a colorant, an antioxidant, an anti-aging agent, and the like may be added as necessary.
< Infrared absorption Spectrum of hydrophilic film >)
Wave number 1600cm of hydrophilic film in infrared absorption spectrum -1 ～1800cm -1 Has 2 peaks in the range of (2). The peak on the low wave number side is peak a, and the peak on the high wave number side is peak B.
The absorbance a at the peak top of the peak a and the absorbance B at the peak top of the peak B satisfy the relationship of absorbance a/absorbance b=0.6 to 1.3. That is, the ratio of absorbance a to absorbance b (i.e., absorbance a/absorbance b) is 0.6 to 1.3. When the absorbance a/absorbance b is less than 0.6, the component having an amide group is too small, the cohesive force of the coating film is insufficient, and the toughness of the coating film is insufficient. As a result, the odor resistance of the hydrophilic film is deteriorated. On the other hand, when the content is more than 1.3, the content of the component having an ester group or a carboxyl group is too small, and the blocking resistance is deteriorated. The absorbance a/absorbance b is preferably 0.7 to 1.2 from the viewpoint of improving the odor resistance and blocking resistance more in a well-balanced manner.
Peak a is a peak derived from the stretching vibration of c=o in the amide group. Peak A is located at 1650-1660 cm -1 Within a range of (2). Peak B is a peak of c=o stretching vibration originating from an ester group or a carboxyl group. Peak B is located at 1710-1730 cm -1 Within a range of (2).
The absorbance a/absorbance b is appropriately adjusted depending on the monomer component or the ratio thereof constituting the acrylic resin (a), the monomer component or the ratio thereof constituting the resin (C), the blending ratio of the acrylic resin (a) and the resin (C), the sintering condition, and the like. The infrared absorption spectrum of the hydrophilic film is measured by a total reflection measurement method (i.e., ATR method) of a fourier transform infrared spectrophotometer (i.e., FT-IR), a high sensitivity reflection measurement method (iras), or the like. In the measurement results of at least one of these measurement methods, the absorbance a/absorbance b is preferably within the above-described range, and more preferably at least the absorbance a/absorbance b by FT-IR is within the above-described range.
< hydrophilic film adhesion amount >
The hydrophilic film is preferably attached in an amount of 0.3 to 2.0g/m 2 . If the amount of the adhesion is within this range, the cost increase due to the increase in the amount of the adhesion can be further suppressed, and the press formability of the precoated aluminum material can be further improved. From the viewpoint of further improving the effect, the adhesion amount of the hydrophilic film is more preferably 0.5 to 1.4g/m 2 。
[ Corrosion-resistant film ]
The pre-coated aluminum material may have a corrosion resistant film between the chemical conversion film and the hydrophilic film. The corrosion-resistant film improves the corrosion resistance of the precoated aluminum. The corrosion-resistant film contains at least 1 resin selected from the group consisting of polyurethane-based resins, epoxy-based resins, acrylic-based resins, and polyolefin-based resins.
The adhesion amount of the corrosion-resistant film is preferably 0.3 to 2.0g/m 2 . At less than 0.3g/m 2 In the case of (2), it is difficult to sufficiently obtain the effect of improving the corrosion resistance. If it is greater than 2.0g/m 2 The material cost increases, and it is difficult to obtain an effect of improving corrosion resistance in accordance with the increase in cost.
< method of Forming hydrophilic film >)
First, a coating material is prepared by dispersing an acrylic resin (a), a polyalkylene ether resin (B), a resin (C), and a polyvinyl alcohol (D) as essential components in a liquid such as ion-exchanged water. Such coatings are sometimes referred to as hydrophilizing treatments. Next, the coating material is applied to the aluminum sheet on which the chemical conversion coating film, the corrosion-resistant film, and the like are formed, using a roll coater or a bar coater. Then, the paint is sintered and dried in a hot air drying furnace, a far infrared furnace, a near infrared furnace, or the like. In this case, it is preferable to dry at a temperature of 150 to 300℃for 3 to 20 seconds. In this way, a hydrophilic film can be formed.
The resins (a) to (D) are present as solid components in the coating material. Therefore, from the viewpoint of obtaining a hydrophilic film having the above composition, the coating material may have, for example, a content of the solid component containing the acrylic resin (a) of 15 to 20 mass%, a content of the solid component containing the polyalkylene ether resin (B) of 30 to 40 mass%, a content of the solid component containing the resin (C) of 20 to 25 mass%, and a content of the solid component containing the polyvinyl alcohol (D) of 22 to 28 mass%.
[ use of precoated aluminum Material ]
The precoated aluminum material is preferably used for fins of a plate-fin tube heat exchanger. In this case, the fin including the precoated aluminum material exhibits excellent hydrophilicity. Therefore, dew condensation water accumulation on the fins can be suppressed. Further, the fin exhibits excellent odor resistance, and is less likely to cause rancidity after being immersed in water.
In addition, the precoated aluminum material is excellent in blocking resistance. Therefore, the occurrence of blocking of the precoated aluminum material during winding is easily prevented in an environment with a high temperature such as summer. Specifically, the cooling strength at the time of winding is relaxed, or cooling is not required as the case may be. Therefore, the manufacturing cost of the precoated aluminum material can be reduced. Further, the precoated aluminum material is excellent in press formability. Therefore, the fin-tube heat exchanger can be easily manufactured.
Examples
The following description will be given of examples of the present invention, but the specific embodiment of the precoated aluminum material according to the present invention is not limited to the embodiment, and the configuration may be appropriately changed within the scope of not impairing the gist of the present invention.
Examples 1 to 9
As illustrated in fig. 1, the precoated aluminum material 1 of the example has an aluminum plate 2, a chemical conversion film 3, and a hydrophilic film 4. In the precoated aluminum material 1, an aluminum plate 2, a chemical conversion film 3, and a hydrophilic film 4 are laminated in this order.
Specifically, the chemical conversion film 3 is formed on the surface of the aluminum plate 2, and the hydrophilic film 4 is formed on the surface of the chemical conversion film 3. The chemical conversion coating 3 and the hydrophilic coating 4 may be formed on one surface or both surfaces of the aluminum plate 2.
The chemical conversion film 3 is a phosphate chromate treatment film. The hydrophilic film 4 contains an acrylic resin (a), a polyalkylene ether resin (B), a resin (C) and a polyvinyl alcohol (D) as essential components.
The acrylic resin (a) is a resin having no repeating unit derived from a monomer having a sulfo group and a monomer having an amide group. Further, the resin (C) is a resin having a repeating unit derived from a monomer having an amide group.
Specifically, in this example, the following (1) to (9) are used as the acrylic resin (a). As the polyalkylene ether resin (B), the following a to c were used. As the resin (C), the following α to γ are used. The polyvinyl alcohol (D) used was as follows.
Acrylic resin (A) "
( 1) Polyacrylic acid (weight average molecular weight: 20000, acid number: 780mgKOH/g )
( 2) Polyacrylic acid (weight average molecular weight: 2000000, acid number: 800mgKOH/g )
( 3) Copolymers of polyacrylic acid and hydroxyethyl methacrylate (weight average molecular weight: 400000, acid number: 400mgKOH/g )
( 4) Polyacrylic acid (weight average molecular weight: 20000, acid number: 100mgKOH/g )
( 5) Polyacrylic acid (weight average molecular weight: 6000, acid number: 780mgKOH/g )
( 6) Polyacrylic acid (weight average molecular weight: 20000, acid number: 40mgKOH/g )
( 7) Polyacrylic acid (weight average molecular weight: 20000, acid number: 820mgKOH/g )
( 8) Polyacrylic acid (polyethylene sulfonate) (weight average molecular weight: 20000, acid number: 200mgKOH/g )
( 9) Polyacrylamide (weight average molecular weight: 20000, acid number: 200mgKOH/g )
Polyalkylene ether resin (B) "
a: polyethylene glycol, weight average molecular weight: 5000
b: polyethylene oxide, weight average molecular weight: 500000
c: polyethylene glycol, weight average molecular weight: 1000
"resin (C)", resin (C) "
Alpha: copolymers of N-methylolacrylamide with acrylic acid
Beta: copolymers of N-methylolmethacrylamide and methacrylic acid
Gamma: copolymers of N-hydroxyethyl acrylamide and methacrylic acid
Polyvinyl alcohol (D) "
Degree of polymerization: 500, saponification degree: 98.0mol%
In producing the precoated aluminum materials of examples 1 to 9, first, an aluminum sheet of JIS A1200P and 0.10mm in thickness was prepared. After alkaline degreasing, the aluminum sheet was subjected to a phosphate chromate treatment. Thus, a phosphate chromate treatment film was formed as a chemical conversion film on the surface of the aluminum plate.
Next, the acrylic resin (a), the polyalkylene ether resin (B), the resin (C), and the polyvinyl alcohol (D) were dispersed in pure water at the ratio shown in table 1 below. Thus, a coating material for forming a hydrophilic film was produced. Next, the coatings of the respective examples adjusted in accordance with the formulation shown in table 1 were applied to the chemical conversion films using a roll coater. Thereafter, the dope is sintered by heating. Thereby, a hydrophilic film is formed. The precoated aluminum materials of the respective examples were produced in this manner.
Next, the infrared absorption spectrum of the hydrophilic film of each precoated aluminum material was measured by the ATR method of FT-IR. The measurement device and measurement conditions are as follows.
Measurement device: FT-IR Microscope (Fourier transform type infrared spectrometer) manufactured by Bruker Optics Inc
Measurement conditions: number of scans 15 times, resolution 4
The results of example 5 are shown in FIG. 2 as representative examples of the infrared absorption spectrum of the hydrophilic film in the examples. As shown in FIG. 2, in the infrared absorption spectrum of example 5, the wave number is 1600 to 1800cm -1 In the range of (2) peaks were confirmed. In fig. 2, the horizontal axis represents wave numbers, the right side in the horizontal axis direction represents small wave numbers, and the left side represents large wave numbers. Among the 2 peaks, the peak on the right side in the horizontal axis direction (i.e., the low wave number side) is "peak a", and the peak on the left side in the horizontal axis direction (i.e., the high wave number side) is "peak B". The absorbance at the peak top of peak a is "absorbance a", and the absorbance at the peak top of peak B is "absorbance B". The "peak a", "peak B", "absorbance a" and "absorbance B" in the infrared absorption spectrum of fig. 3 described later are also similar to those of fig. 2. Based on the infrared absorption spectrum of the hydrophilic film of each example, the absorbance a of the peak a and the absorbance B of the peak B were measured, and the ratio (specifically, absorbance a/absorbance B) was calculated. The results are shown in Table 1.
Next, the precoated aluminum material of each example was evaluated for blocking resistance, odor resistance, acid odor, hydrophilicity continuation, wet adhesion, and press formability by the following methods. Note that A, B was acceptable and C was unacceptable. The results are shown in Table 1.
< antiblocking Property >
The coated surfaces of the precoated aluminum materials were superimposed, and heated under hot pressure at 50℃and 10MPa for 15 minutes. Thereafter, the precoated aluminum materials were peeled off from each other, and the attached state was evaluated according to the following criteria.
A: the precoated aluminum materials can be peeled from each other after heating.
C: the precoated aluminum materials cannot be peeled from each other after heating.
< odor resistance >)
For each precoated aluminum material, the production method was carried out in accordance with JIS K5600-7-2:1999, moisture resistance test was performed for 144 hours. Thereafter, the odor of the hydrophilic film surface was evaluated by the functional evaluation according to the following criteria. The average value was taken by 10 persons specializedly.
A: the occurrence of odor was hardly confirmed.
B: the occurrence of odor was slightly confirmed.
C: the occurrence of odor was significantly confirmed.
< acid odor >)
After immersing each precoated aluminum material in pure water for 1 hour, 0.5g of acetic acid was added to the vessel, and the vessel was contaminated at room temperature for 72 hours. Taken out and left in the atmosphere, and after 5 hours, the odor was evaluated according to the following evaluation criteria. The average value of the 10 evaluations of the evaluators was recorded as the evaluation result.
A: no odor.
B: the malodor was slightly felt.
C: a strong odor was perceived.
< hydrophilicity >
The hydrophilicity was evaluated by measuring the contact angle of water using an automatic contact angle meter. As the automatic contact angle meter, FACE automatic contact angle meter "CA-Z" manufactured by Kyowa Kagaku Co., ltd. Specifically, in an environment where the room temperature is controlled to be within a range of 20±5 ℃, water droplets are dropped on the hydrophilic film of each precoated aluminum material. The contact angle of the water drop after 30 seconds from the drop was measured by an automatic contact angle meter, and evaluated according to the following criteria.
A: the contact angle is 20 DEG or less
C: case of contact angle of more than 20 DEG
In the evaluation of hydrophilicity, the case where the evaluation result is "a" is high in hydrophilicity, and the increase in ventilation resistance due to dew condensation water can be suppressed, and therefore, the evaluation is judged to be acceptable, and the case where the evaluation result is "C" is low in hydrophilicity, and the increase in ventilation resistance due to dew condensation water is difficult to be suppressed, and therefore, the evaluation is judged to be unacceptable.
< hydrophilic persistence >)
After each of the precoated aluminum materials was immersed in pure water for 240 hours, the contact angle with water drops was evaluated. The contact angle was measured in the same manner as in the above-described evaluation of hydrophilicity. The evaluation was performed according to the following criteria.
A: the contact angle is 30 DEG or less
C: case of contact angle of more than 30 DEG
< wetting adhesion >
Pure water was sprayed on each of the precoated aluminum materials, and the precoated aluminum materials were rubbed slightly with a finger. The number of 1 round trip was counted as 1 time, and the number of times until the hydrophilic film was peeled was evaluated.
A: more than 5 times.
C: less than 4 times.
< compression moldability >)
A processing oil is applied to the surface of each precoated aluminum material. Then, a single pressurization was performed so that the elongation rate reached 48%, and a colored portion was formed on the precoated aluminum material. Thereafter, the degree of peeling of the hydrophilic film in the colored portion was observed, and the press formability was evaluated based on the following criteria.
A: no change was observed at all.
B: peeling was slightly observed.
C: vertical stripping was observed.
Comparative examples 1 to 16
The same operations as in examples 1 to 9 were carried out except that a coating material obtained by dispersing the acrylic resin (a), the polyalkylene ether resin (B), the resin (C), and the polyvinyl alcohol (D) in pure water in the proportions shown in table 1 described below was used. The results of comparative examples 1 to 16 are shown in Table 2. The results of comparative example 2 are shown in fig. 3 as representative examples of the infrared absorption spectrum of the hydrophilic film in the comparative example.
[ Table 1 ]
(Table 1)
[ Table 2 ]
As shown in table 1, the hydrophilic membranes in examples 1 to 9 do not have repeating units derived from a monomer having a sulfo group and a monomer having an amide group, and contain an acrylic resin (a) having a weight average molecular weight and an acid value in a given range, a polyalkylene ether resin (B) having a weight average molecular weight in a given range, a resin (C) having repeating units derived from a monomer having an amide group, and a polyvinyl alcohol (D) in a given ratio. In the hydrophilic films of examples 1 to 9, the absorbance a/absorbance b in the infrared absorption spectrum was in the range of 0.6 to 1.3. Examples 1 to 9 having such hydrophilic films showed good results for all of blocking resistance, odor resistance, acid odor, hydrophilicity continuation, wet adhesion, and press formability.
On the other hand, in comparative examples 1 and 3, absorbance a/absorbance b in the infrared absorption spectrum of the hydrophilic film was lower than 0.6. Such hydrophilic films have poor odor resistance. Further, since the acrylic resin (a) is more than 20 mass%, the acid odor is poor. Next, in comparative examples 2 and 4, a/B of absorbance a/absorbance B in the infrared absorption spectrum of the hydrophilic film was greater than 1.3. Such hydrophilic films have poor blocking resistance. Further, since the resin (C) is more than 25 mass%, the wet adhesion is poor.
In comparative example 5, the absorbance a/absorbance b in the infrared absorption spectrum of the hydrophilic film was more than 1.3, and thus the blocking resistance was poor. Further, since the acrylic resin (a) is less than 15 mass%, the wet adhesion is poor.
The content of the polyalkylene ether resin (B) of comparative example 6 is less than 30 mass%, and thus the press moldability is poor. The content of the polyalkylene ether resin (B) of comparative example 7 is more than 40 mass%, and thus the hydrophilic persistence is poor. The polyvinyl alcohol (D) content of comparative example 8 was less than 22 mass%, and thus the wet adhesion was poor.
The polyvinyl alcohol (D) of comparative example 9 has a content of more than 28 mass% and thus has poor hydrophilicity and hydrophilicity persistence. The absorbance a/absorbance b in the infrared absorption spectrum of the hydrophilic film of comparative example 10 was lower than 0.6, and thus the odor resistance was poor. Further, the content of the resin (C) is less than 20 mass%, and thus the hydrophilicity persistence is poor.
The acrylic resin (a) of comparative example 11 has a weight average molecular weight of less than 20000, and thus has poor hydrophilicity persistence. The acrylic resin (A) of comparative example 12 has an acid value of less than 100mgKOH/g, and thus has poor wet adhesion. The acrylic resin (A) of comparative example 13 has an acid value of more than 800mgKOH/g, and thus has a poor acid odor.
Since the weight average molecular weight of the polyalkylene ether resin (B) of comparative example 14 was less than 5000, winding displacement occurred at the time of winding. This means that the precoated aluminum material cannot be produced. The acrylic resin (a) of comparative example 15 has a repeating unit derived from a monomer having a sulfo group, and thus has a poor acid odor. The acrylic resin (a) of comparative example 16 has a repeating unit derived from a monomer having an amide group, and thus has a poor acid odor.
Claims (2)
1. A precoated aluminum material is characterized in that an aluminum plate, a chemical conversion film and a hydrophilic film are sequentially laminated and formed,
the hydrophilic film contains at least 15 to 20 mass% of an acrylic resin (A), 31 to 39 mass% of a polyalkylene ether resin (B), 21 to 24 mass% of a resin (C) having a repeating unit derived from a monomer having an amide group, and 22 to 28 mass% of a polyvinyl alcohol (D),
the acrylic resin (A) has substantially no repeating unit derived from a monomer having a sulfo group and no repeating unit derived from a monomer having an amide group,
the acrylic resin (A) has a weight average molecular weight of 20000 ～ 2000000 and an acid value of 100 to 800mgKOH/g,
the weight average molecular weight of the polyalkylene ether resin (B) is 5000 to 500000,
in the infrared absorption spectrum, the hydrophilic film has a wave number of 1600-1800 cm -1 The absorbance a of the peak top in the peak a on the low wave number side of 2 peaks and the absorbance B of the peak top in the peak B on the high wave number side satisfy the relationship of absorbance a/absorbance b=0.6 to 1.3.
2. The pre-coated aluminum product of claim 1, wherein the pre-coated aluminum product is used in fins of a heat exchanger.
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| JP2023009820A (en) * | 2021-07-08 | 2023-01-20 | 株式会社Uacj | Precoat fin material and its manufacturing method |
| JP2023009821A (en) * | 2021-07-08 | 2023-01-20 | 株式会社Uacj | Precoat fin material and its manufacturing method |
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| WO2013191149A1 (en) * | 2012-06-19 | 2013-12-27 | 日本ペイント株式会社 | Method for covering aluminum fin material with hydrophilic film, aluminum fin material, and aluminum heat exchanger |
| WO2016002484A1 (en) * | 2014-06-30 | 2016-01-07 | 日本ペイント・サーフケミカルズ株式会社 | Method for coating aluminum fin material with hydrophilic film, aluminum fin material, and aluminum heat exchanger |
| JP2016222879A (en) * | 2015-06-03 | 2016-12-28 | 日本ペイント・サーフケミカルズ株式会社 | Hydrophilization treatment agent, hydrophilic film forming method, and hydrophilic film |
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| JP2006321965A (en) * | 2005-02-02 | 2006-11-30 | Furukawa Sky Kk | Hydrophilic coating composition, coated aluminum plate and precoated aluminum fin material |
| JP2018023932A (en) * | 2016-08-10 | 2018-02-15 | 日本ペイント・サーフケミカルズ株式会社 | Hydrophilic film coating method of aluminum fin material, aluminum fin material, and heat-exchanger made of aluminum |
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| WO2013191149A1 (en) * | 2012-06-19 | 2013-12-27 | 日本ペイント株式会社 | Method for covering aluminum fin material with hydrophilic film, aluminum fin material, and aluminum heat exchanger |
| WO2016002484A1 (en) * | 2014-06-30 | 2016-01-07 | 日本ペイント・サーフケミカルズ株式会社 | Method for coating aluminum fin material with hydrophilic film, aluminum fin material, and aluminum heat exchanger |
| JP2016222879A (en) * | 2015-06-03 | 2016-12-28 | 日本ペイント・サーフケミカルズ株式会社 | Hydrophilization treatment agent, hydrophilic film forming method, and hydrophilic film |
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