JP4562897B2 - Fin material for heat exchanger having non-chromate reaction type underlayer and heat exchanger provided with the same - Google Patents

Description

【００３９】
表１に示す結果から、必須成分としてのＺｒ又はＴｉを乾燥後の下地層中に１.０〜１００ｍｇ／ｍ²の範囲でこれらの元素を含む試料は親水性に優れ、密着性が良好で、かつ、耐食性にも優れていることが判明した。また、この範囲内でも特に５〜５０ｍｇ／ｍ²の範囲が特に好ましいことも判明した。
【００４０】
次に、先の試験で用いた無機系の親水性皮膜に代えて以下の組成の有機系親水性皮膜を用いた同等の試験結果を以下の表２に示す。
有機系の親水性皮膜とは、ここでは、特開平０８−０８１６５０号明細書に記載の実施例１の親水性皮膜を用いた。
即ち、親水性皮膜の形成のために、まず、〔共重合体Ａ−１〕を製造し、この〔共重合体Ａ−１〕に後述する処理を施した後、後述する耐アルカリ性付与硬化剤を添加し、次いで硬化剤とイオン交換水を後述する重量部混合して有機系の親水性皮膜を得た。
【００４１】
〔共重合体Ａ−１〕の製造
攪拌機、還流冷却器、温度計、滴下ロート及び窒素ガス導入管を付した１Ｌの四つ口フラスコに、イオン交換水４００ｇ、次亜リン酸ソーダ８.１ｇ、過硫酸カリウム５.０ｇ、ライトアクリレートＣＮ（共栄社化字株式会杜製、２−シアノエチルアクリレート）８０ｇ、ライトエステルＨＯ（共栄社化学株式会社製、２−ヒドロキシエチルメタクリレート）２８ｇ、クロトン酸２０ｇ、マレイン酸１００ｇ、メタクリル酸７２ｇ、メチルメタクリレート８ｇ、ライトアクリレートＣＨ（共栄社化学株式会社製、シクロヘキシルアクリレート）４ｇ、ＡＳ（日生化学工業所製、アリールスルホン酸ソーダ）４０ｇ、及びＡＴＢＳ−Ｋ（東亜合成化学工業株式会社製、２−アクリルアミド−２−メチルプロパン−１−スルホン酸カリウム）４８ｇを仕込み、窒素ガス気流下、重合温度４７〜５０℃で１６時間レドックス重合反応を行わせた結果、平均分子量１２０００で、濃度が５１.１％の共重合体Ａ−１を得た。
【００４２】
〔親水性の樹脂イ−１〕の製造
この共重合体Ａ−１にトリエチルアミン及びアンモニア水を加え、４０〜４５℃で１時間撹拌し、２５％アンモニア水でｐＨ調整後、イオン交換水を加えて濃度調節を行い、更に１時間撹拌混合して液状の樹脂を得た。
【００４３】
〔耐アルカリ性付与剤ロ−１〕の製造
これには、攪拌機、温度計、窒素導入管及び還流冷却器を付した５００ｍＬの四ツ口フラスコにＰＥＧ♯６００（ライオン株式会社製、ポリエチレングリコール分子量６００）２００ｇ、及びリカシッドＳＡ（新日本理化株式会社製、無水コハク酸）８７ｇを仕込み、８０℃で２時間、１００℃で１時間、１１０℃で２時間反応させ、無色の液状のジエステル二塩基性酸素酸を得た。これに、トリエチルアミン４４ｇ及び２５％アンモニア水４３．５ｇを加えて１時間４０〜４５℃で攪拌混合し、この後イオン交換水を加えて濃度４０％に調整し、耐アルカリ性付与剤ロ−１を得た。
【００４４】
〔硬化剤ハ−３〕
これは、ユーキコートＥ−３９４（共栄社化学株式会社製、ポリエチレングリコール（エチレングリコール鎖ｎ＝１４）ジグリシジルエーテル、粘度１６０ｃｐｓ、淡黄色透明の液体）である。
これらを用意し、〔親水性の樹脂イ−１〕１００重量部と〔耐アルカリ性付与剤ロ−１〕６０重量部と〔硬化剤ハ−３〕２５重量部とイオン交換水１６０重量部とを混合し、本発明に用いる有機系親水性皮膜を得た。
この有機系親水性皮膜を先の無機系親水性皮膜の代りに利用して表１に示したものと同等の試験に供した。
【００４５】
【表２】

【００４６】
表２に示すように有機系の親水性皮膜を備えたフィン材であっても、無機系の親水性皮膜を備えたフィン材と同等の結果が得られた。
【００４７】
【発明の効果】
以上説明したように本発明は、Ｚｒを必須成分として含む処理液層と金属基材との反応型下地処理法による下地層を有し、その上に親水性皮膜を有するので、Ｚｒを含み、Ｃｒを含んでいないノンクロメート型の下地層を利用することができ、環境汚染の問題を生じないフィン材を提供できる。また、下地層の上に設けられている親水性皮膜がフィン材に親水性を付与し、半球状の凝集水の付着を阻止する。
次に本発明において、前記下地層に含まれる必須成分としてのＺｒが１ｍｇ／ｍ^２以上、１００ｍｇ／ｍ^２以下含有されてなると、下地層として良好な密着性を確保することができ、優れた耐食性を確保でき、フィン材に必要な親水性が確保される。
本発明において、下地層として具体的に、ＡｌＦ _３ とＡｌ _２ Ｏ _３ とＡｌＯＦを含有する基層と、ＡｌＯ _ｘ （ＯＨ） _ｙ ・ｎＨ _２ ＯとＡｌＦ _３ とＡｌＯＦを含有する層と、ＺｒＯ _２ ・ｎＨ ₂ Ｏを有する層と、Ｚｒ _３ （ＰＯ _４ ） _４ ・ｎＨ ₂ Ｏを含有する層の積層構造を採用することができる。
本発明において、前記処理液がフルオロジルコニウム酸またはそのアンモニウム塩に弗化水素酸を添加してなるものを主成分とした処理液を適用できる。
本発明において、前記下地層に、５ｍｇ／ｍ^２以上、５０ｍｇ／ｍ^２以下のＺｒが含有されてなると、下地層としてのより良好な密着性の確保ができ、優れた耐食性とフィン材に必要な親水性が確保される。
【００４８】
次に本発明は、先のいずれかに記載のフィン材を備えたことを特徴とする熱交換器であっても良い。
前記フィン材が設けられた熱交換器であるならば、フィン材の表面に親水性を有するので熱交換器の冷房運転などの際に凝集水が付着してもフィン材周囲において通気性を損なうおそれが少ない。
【図面の簡単な説明】
【図１】 本発明に係るフィン材の第１実施形態の構造を示す断面図。
【図２】 本発明に係るフィン材から構成されたフィンを備えた熱交換器の一例を示す正面図。
【符号の説明】
Ａ・・・フィン材、１・・・基材、２・・・下地層、３・・・親水性皮膜、Ｂ・・・熱交換器、１３…チューブ、１４・・・フィン。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a fin material for a heat exchanger having a hydrophilic film with good adhesion and excellent corrosion resistance, and a heat exchanger having the same.
[0002]
[Prior art]
Conventionally, heat exchangers built in air conditioners have been widely used because they are lightweight and require excellent heat exchange characteristics. In these heat exchangers, for example, during cooling operation, moisture in the air around the heat exchanger adheres to the surface of the fins of the heat exchanger as condensed water.
[0003]
As one technique for preventing the adhesion of the condensed water, it is conceivable to coat the surface of the fin with a water-repellent resin film to make the surface of the fin water-repellent. However, if the surface of the fin is made water-repellent, the water adhering to the surface of the fin becomes hemispherical water droplets and adheres between the fins, impairing the air permeability around the fin, and improving the heat exchange efficiency in the fin. May decrease.
Aluminum or aluminum alloy is generally used as a material with excellent corrosion resistance, but in use conditions where condensed water is always attached to the surface of the fin, a kind of density cell is formed on the surface of the fin. This is likely to cause a problem that the corrosion of the fin is accelerated more than expected. From the background as described above, the inventor of the present application considers that it is necessary to form a hydrophilic film on the surface of the fin of the heat exchanger and to further improve the corrosion resistance of the fin itself.
[0004]
A chromate film has been widely studied as a hydrophilic film formed on the surface of this kind of heat exchanger. However, since this chromate film has a composition mainly composed of Cr, there is a possibility that hexavalent chromium, which is regarded as a problem in terms of toxicity, must be used. The film using hexavalent chromium is likely to cause environmental problems. Even if a film in which this hexavalent chromium is replaced with trivalent chromium, which is considered to be high in terms of safety, is oxidized. There is a risk that trivalent chromium may change to hexavalent chromium over time, etc., and even if trivalent chromium is used, there is a need for waste liquid treatment, which may cause environmental chromium contamination problems. ing.
[0005]
[Problems to be solved by the invention]
Therefore, the inventor of the present application conducts research and development of a technology that can be applied to a fin for a heat exchanger by non-chromate processing without using chromium that may cause problems in such an environmental aspect, The present invention has been reached.
[0006]
Based on the above background, the present invention has a hydrophilic film on the surface portion, has excellent hydrophilicity, has a low risk of causing a decrease in heat exchange efficiency due to adhesion of the condensed water, and the condensed water always adheres. An object of the present invention is to provide a fin material for a heat exchanger that does not cause a problem in terms of corrosion resistance even when used in such an environment. Moreover, it aims at providing the fin material for heat exchangers which has these various characteristics and was excellent also in the adhesiveness of a hydrophilic membrane | film | coat.
Furthermore, this invention aims at provision of the heat exchanger provided with the fin material which has these outstanding characteristics.
[0007]
[Means for Solving the Problems]
  In order to solve the above-mentioned problems, the present invention provides a metal substrate made of aluminum or an aluminum alloy, a non-chromate-type underlayer formed on the metal substrate by a reactive undercoat method, and on the underlayer A hydrophilic film formed, and the underlayerBut ZrIs formed by a reactive base treatment method in which a heated treatment liquid is applied onto a metal substrate, and a part of the treatment liquid layer is reacted with the metal substrate. To do.
ZrHas an undercoat layer by reaction between the treatment liquid layer containing the essential component and the metal substrate, and has a hydrophilic film on it.And ZrA non-chromate-type underlayer containing no Cr can be used, and a fin material that does not cause the problem of environmental pollution can be provided. In addition, the hydrophilic film provided on the underlayer imparts hydrophilicity to the fin material and prevents adhesion of hemispherical condensed water.
[0008]
  In the present invention, as an essential component in the underlayerZr is1mg / m²100 mg / m²It is preferable to be contained below. As an essential ingredientZr1mg / m²100 mg / m or more²By containing below, favorable adhesiveness as a base layer can be ensured, excellent corrosion resistance can be ensured, and hydrophilicity necessary for the fin material is ensured.
  In the present invention, the base layer by the reactive base processing method is AlF ₃ And Al ₂ O ₃ And a base layer containing AlOF, and AlO _x (OH) _y ・ NH ₂ O and AlF ₃ And a layer containing AlOF, ZrO ₂ ・ NH ₂ A layer having O, and Zr ₃ (PO ₄ ) ₄ ・ NH ₂ A special feature is that the layer contains a layer containing O.
  The present invention is characterized in that the treatment liquid is a treatment liquid mainly composed of fluorozirconic acid or an ammonium salt thereof added with hydrofluoric acid.
[0009]
  In the present invention, as an essential component in the underlayerZrIn addition toTi,Among Si, C, V, P, and O, at least one kind or two or more kinds may be contained.
  In the present invention, the base layer includes TiAnd SiAmong them, an oxide of at least one element or two or more elements of V and P may be contained.
[0010]
  In the present invention, the underlayer is 5 mg / m²50 mg / m²Less thanZrIt may be characterized by containing. As an essential ingredient in such a rangeZrAs a foundation layer, better adhesion can be ensured, and excellent corrosion resistance and hydrophilicity necessary for the fin material are ensured.
[0011]
The present invention may be a heat exchanger including any one of the fin materials described above.
If the heat exchanger is provided with the fin material, since the surface of the fin material has hydrophilicity, air permeability around the fin material is impaired even if condensed water adheres during cooling operation of the heat exchanger. There is little fear.
[0012]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, embodiments of the present invention will be described with reference to the drawings, but the present invention is not limited to the following embodiments.
FIG. 1 shows a first embodiment of a fin material for a heat exchanger according to the present invention. A fin material A of the first embodiment includes a plate-shaped metal base 1 made of aluminum or an aluminum alloy, and the metal. The nonchromate reaction type underlayer 2 formed on the surface portion of the substrate 1 and the hydrophilic film 3 coated on the underlayer 2 are formed into a thin plate shape.
[0013]
The metal substrate 1 is made of aluminum or an aluminum alloy, and is made of a JIS 1000 series alloy such as JIS 1050, JIS 1100, JIS 1200, or a JIS 7000 series alloy. However, the constituent material of the metal base 1 is not limited to these materials. Of course, various pure aluminum-based or aluminum alloy-based materials used as the constituent material of the heat exchanger fin material can be applied.
[0014]
The underlayer 2 is formed by performing a reactive non-chromate treatment method, which will be described later, on the metal substrate 1. The underlayer 2 includes at least one of Ti and Zr as an essential component, and further includes one or more of Si, C, V, P, and O as an additive component. Among these elements, O (oxygen) is included in the form of oxides of essential components (Ti or Zr) or in the form of oxides of other additive component elements (Si, C, V, P). .
[0015]
In this underlayer 2, Ti or Zr as an essential component is 1 to 100 mg / m.²It is preferable to contain in the range. Further, Ti or Zn as an essential component of the underlayer 2 is 5 to 50 mg / m.²It is more preferable to contain in the range. These essential components are preferably 10 to 90% by weight of the total amount of the underlayer 2.
Further, in the underlayer 2, in addition to Zr or Ti as an essential element, as additive components, Si is 1 to 20% by weight, C is 10 to 50% by weight, V is 5 to 30% by weight, and P is 5 to 5%. Of these, 30% by weight and 5 to 50% by weight of O are preferably contained singly or in combination of two or more.
[0016]
In the underlayer 2, Zr and Ti are essential components. If they are not contained, adhesion to the metal substrate 1 cannot be obtained, and the corrosion resistance of the metal substrate 1 is also reduced. In the underlayer 2, Si, C, V, P, and O are components that can be added as necessary.
The element constituting the above-described underlayer 2 contains Zr and Ti in a compound state, and the detailed structure will be described later.
[0017]
The hydrophilic film 3 is positioned on the surface of the fin material to ensure hydrophilicity. The hydrophilic film 3 includes a water glass hydrophilic film, an organic hydrophilic film, and a composite hydrophilic film. Any of these may be used.
[0018]
The water glass hydrophilic film is mainly composed of a main component alkali silicate and an aqueous resin as a binder. Among these, for example, a material mainly composed of alkali silicic acid and a low molecular organic compound having a carbonyl group can be used. And it can also be set as the composition formed by adding a water-soluble organic polymer compound with respect to these main components. The alkali silicate constitutes a main component for imparting hydrophilicity to the coating, and SiO₂/ M₂A ratio represented by O (wherein M represents an alkali metal such as lithium, sodium or potassium) is 1 or more, for example, 2 to 5 is preferable. The low-molecular organic compound is, for example, a low-molecular organic compound having a carbonyl group in the molecule, which stabilizes the film made of the alkali silicate, improves hydrophilicity, and gives the film flexibility. is there. Specific examples of such low-molecular organic compounds include aldehyde types, esters, amides, and the like. The water-soluble organic polymer compound is added in order to further improve the hydrophilicity of the film formed from the alkali silicate and the low-molecular organic compound having a carbonyl group, and to improve the flexibility. Specific examples of such water-soluble organic polymer compounds include polysaccharide-based natural polymers, water-soluble protein-based natural polymers, anionic, nonionic, or cationic addition polymerization-based water-soluble synthetic polymers, polycondensation-based water-soluble polymers. An example is a functional polymer.
[0019]
The organic hydrophilic film is composed mainly of a hydrophilic resin such as polyvinyl alcohol, cellulose or acrylic. Among these, for example, conjugated monomers (a) having a nitrile group, conjugated and / or nonconjugated monomers (b) having a hydroxy group, conjugated monomers (c) having a carbonyl group, carbon Acid group of copolymer (A) constituted by using conjugated monomer (d) having a saturated linear and / or alicyclic alkyl group of formulas 1 to 6 and phosphate compound (f) However, it may be a film of hydrophilic resin (A) constituted by partial neutralization or neutralization with a basic compound. Further, an alkali resistance-imparting agent (b) formed by neutralizing the acid group of diester dibasic acid (B) composed of polyethylene glycol and organic dibasic oxygen acid (h) with organic amine compound (γ). ) And polyglycidyl ether (C) at least one curing agent (c) is an organic hydrophilic film obtained by applying and forming a coating material added to the resin of the component described above. May be.
[0020]
In the composition, examples of the monomer (a) include acrylonitrile and methacrylonitrile, and examples of the conjugated and / or non-conjugated monomer (b) include 2-hydroxyethyl methacrylate and 2-hydroxyethyl. Examples thereof include methacrylate, 2-hydroxypropyl ethyl vinyl vinyl ether, and 3-hydroxypropyl vinyl ether. Examples of the conjugated monomer (c) include acrylic acid, methacrylic acid, and crotonic acid, and examples of the conjugated monomer (d) include methyl methacrylate, methyl acrylate, and ethyl methacrylate. it can.
[0021]
As the composite hydrophilic film, those composed of a hydrophilic resin and colloidal silica are widely known. For example, alumina sol, water-soluble acrylic resin and polyethylene glycol, a modified product of polyethylene glycol, a copolymer of ethylene oxide and propylene, and a copolymer of ethylene oxide and propylene oxide and a modified product thereof What can be illustrated.
In the composition constituting the composite hydrophilic film, the alumina sol can be exemplified by a water medium in which alumina hydrate particles are dispersed in water, and the water-soluble acrylic resin is a sulfonic acid group, An acrylic copolymer having a polar group such as a valent salt, a hydroxyl group or a carboxyl group can be exemplified.
[0022]
Any of the various water glass-based hydrophilic coatings, organic hydrophilic coatings, and composite hydrophilic coatings described above can be used as the hydrophilic coating 3 singly or mixed as necessary or as a multilayer.
[0023]
Next, a method for manufacturing the non-chromate reaction type underlayer 2 by the above-described reaction type undercoat method for forming the underlayer 2 will be described.
Basically, the reaction type ground treatment method is performed by applying a treatment liquid having a necessary composition on the metal substrate 1 by a spray coating method or the like, and performing a heat treatment as necessary. In this method, the component of the treatment liquid and the metal substrate 1 are reacted at the surface portion to form a reaction product layer, and the portion other than the reaction product layer is washed and removed to form the base layer 2. The method for applying the treatment liquid onto the metal substrate 1 may be any method such as spray coating, dipping, or brushing.
[0024]
The treatment liquid to be applied here is based on a Zr or Ti compound, and the Zr-based treatment liquid is fluorozirconic acid (H₂ZrF₆) Or an ammonium salt thereof added with hydrofluoric acid as a main component, or those further added with phosphoric acid. The fluorozirconic acid (H₂ZrF₆) Or its ammonium salt to which hydrofluoric acid is added, and tannin, phosphoric acid ester and silica, or a water-soluble polymer or the like may be used.
Next, the reaction with the Al metal substrate 1 in the above-described fluorozirconic acid / phosphoric acid processing solution can be simply expressed as follows.
2Al + H₂ZrF_Four+ 2H₂O → ZrO₂+ 2AlF_Three+ 3H₂
3H₂ZrF₆+ 4H_ThreePO_Four  → Zr_Three(PO_Four)_Four+ 18HF
[0025]
As is apparent from this reaction formula, the underlayer 2 is mainly composed of zirconium oxide and zirconium phosphate, and AlF_ThreeIs included. Therefore, the underlayer 2 having this composition has a composition containing P in addition to Zr as an essential component.
In the above formula, HF is generated, but HF reacts with Al and is consumed. In addition to the basic composition, in the case of a composition containing Ti, H₂TiF₆In the case of a composition containing Si, H₂SiF₆It is preferable to use those containing. Further, the surfactant and the resin added contain C, and vanadium oxide (V₂O_Five) And ammonium vanadate (NH_FourVO_Three) Is added to V.
As the structure of the base layer 2 obtained using the treatment liquid of the basic composition system, AlF is formed on the upper surface side of the metal substrate 1._Three, Al₂O_Three, There is a base layer containing AlOF, on which AlO_x(OH)_y・ NH₂O, AlF_ThreeA layer containing AlOF, and ZrO₂・ NH₂A layer having O, and Zr_Three(PO_Four)_Four・ NH₂A layer structure in which layers containing O are sequentially laminated can be exemplified.
[0026]
In order to form the underlayer 2 more specifically, the following steps can be employed as an example.
First, a rolled Al thin plate having a thickness of about 100 μm is prepared, and this is subjected to an alkaline degreasing treatment to clean the surface, followed by washing with water to remove the alkaline solution. Here, for example, the alkaline degreasing treatment is performed by immersing an Al thin plate in an alkaline solution for several seconds at a temperature of 50 to 70 ° C. and then pulling it out.
[0027]
Next, a non-chromate treatment solution is sprayed (sprayed) on the Al thin plate with a spray device at a temperature higher than room temperature, for example, about 50 ° C. to 80 ° C. to form a coating layer, and then the reaction solution is washed with water. After removing, heating in a range of 120 ° C. to 200 ° C., drying and baking are performed for several seconds to 30 seconds, and a reactive non-chromate treatment is performed.
In the above non-chromate treatment, when the non-chromate treatment liquid is sprayed onto the Al thin plate at 50 to 80 ° C., the reaction between Al and the non-chromate treatment solution proceeds on the surface of the Al thin plate, and the surface of the Al thin plate. A reaction layer is formed in the part. The reaction also proceeds in the drying process and baking process performed after spraying the non-chromate treatment liquid, and a base layer having a desired thickness is formed on the Al thin plate.
[0028]
The underlayer 2 formed by the above non-chromate treatment method contains Ti or Zr as an essential component, and in addition to these essential components, one or more of Si, C, V, P, and O Therefore, the adhesion of the base layer 2 to the metal substrate 1 can be improved, and the corrosion resistance of the metal substrate 1 can also be improved.
In addition, since the hydrophilic film 3 formed on the underlayer 2 exhibits good hydrophilicity, the hydrophilic film 3 is excellent in hydrophilicity, and no hemispherical water droplets adhere to the hydrophilic film 3. There is no risk of impairing the surrounding air permeability.
[0029]
Next, one form of the heat exchanger B provided with the fin material having the above-described structure is shown in FIG.
FIG. 2 shows an example of a heat exchanger for an air conditioner provided with fins obtained by using the fin material A according to the present invention. The heat exchanger B of this example has a large number of fin materials A and is fine. A meandering tube 13 is arranged so as to pass through the fins 14 having a structure in which the layers are stacked with an interval (an interval of about 1 mm to several mm).
The heat exchanger B having this structure is constituted by a fin 14 formed by plastic working the fin material A described above.
[0030]
When the fins 14 of the heat exchanger B are configured from the fin material A in this way, the hydrophilic coating 2 is uniformly provided on the entire surface of the fins 14, so that the uniform hydrophilicity is provided on the entire surface of the fins 14 of the heat exchanger B. Even if the heat exchanger B is provided in the air conditioner and the cooling operation is performed, there is a possibility that condensed water may be generated on the surface portion of the fin material A. Since the aggregated water does not adhere in the form of droplets on the surface, and the aggregated water is generated on the surface of the fin material A in a thin film shape, the fin material A, The possibility that the condensed water closes or narrows the gap between A can be eliminated.
[0031]
Therefore, if it is the heat exchanger B provided with the above-mentioned fin material A, a favorable heat exchange characteristic can be maintained even when condensed water is generated during the cooling operation. Further, since the fin material A has the base layer 2, the fin material A has excellent adhesion and corrosion resistance.
[0032]
【Example】
A plurality of aluminum metal substrates having a thickness of 100 μm made of a JIS specified pure aluminum alloy (JIS1050) were prepared.
These metal substrates were subjected to alkaline degreasing (a 3% solution of Surf Cleaner 330 manufactured by Nippon Paint, soaked at 50 ° C. for several seconds), and then washed with water at room temperature. Next, these metal substrates were sprayed with various amounts of a 50 ° C. Zr compound-based treatment liquid using a spray coating apparatus, and were similarly sprayed with various amounts of a 50 ° C. Ti-based compound treatment liquid, Zr and Ti. Three types of treatment solutions sprayed in various amounts in the same manner were prepared.
[0033]
The treatment liquid used here is based on a Zr or Ti compound, and the Zr-based treatment liquid is a zirconium fluoride salt (NH_Four)₂ZrF₆And phosphoric acid H_ThreePO_FourAnd hydrofluoric acid HF having the following composition were used. "(NH_Four)₂ZrF₆: 100 ppm, H_ThreePO_Four: 100 ppm, hydrofluoric acid HF 50 ppm. Next, as a Ti-based treatment liquid, “titanium fluoride salt H”₂TiF₆A mixture of “phosphoric acid and hydrofluoric acid” was used. In addition to these, in the case of a composition containing Si, H₂SiF₆In which C is added, in which surfactant or resin is included, and in the case where V is included, vanadium oxide (V₂O_Five) Or ammonium vanadate (NH_FourVO_Three) Was used.
[0034]
The metal substrate sprayed with the treatment liquid was allowed to stand for about 10 seconds, then washed with water, heated to 120 ° C., dried and baked to form an underlayer formed by reaction with the treatment liquid on the metal substrate.
Next, a hydrophilic resin was applied on the base layer. This hydrophilic resin is inorganic, and as the inorganic hydrophilic film, a water glass-based paint (trade name: Surfal Coat 131 manufactured by Nippon Paint Co., Ltd.) is applied in an amount of SiO.₂200mg / m in quantity²And then baked in an oven at 260 ° C. for 30 seconds.
[0035]
The content of Ti or Zr as an essential component contained in the underlayer of each sample obtained is measured, and the hydrophilicity and adhesion (adhesion of the hydrophilic film) and corrosion resistance (corrosion resistance of the metal substrate) of these samples. The results of testing for) are shown in Table 1 below.
[0036]
In Table 1, the weight in the film indicates the weight percentage of Ti or Zr as an essential component contained in the film of the underlying layer after drying.
In addition to Zr and Ti, the film contains additive elements such as C, O, Si, V, and P.
In Table 1, only the essential components Zr and Ti are shown. For example, in an underlayer containing 23 wt% Zr, O is 33 wt%, Si is 2 wt%, C is 35 wt%, V 6% by weight, the balance is inevitable impurities, and in the underlayer having 28% by weight of Zr, O was 27% by weight, Si was 2% by weight, C was 36% by weight, and V was 7% by weight.
Further, in the sample to which Zr and Ti were mixed and added, O was 24% by weight, Si was 2% by weight, C was 54% by weight, and V was 4% by weight.
[0037]
In Table 1, “hydrophilic A” indicates the result of measuring the contact angle of water droplets after the sample was immersed in volatile press oil for 60 seconds and then heat-treated at 150 ° C. for 3 minutes. The results of measurement of the contact angle of water droplets after the immersion for a period of time and drying in an oven at 80 ° C. for 16 hours and after repeating the above cycle for 14 cycles are shown.
As the criteria for determining hydrophilicity, ◎ indicates less than 20 °, ○ indicates less than 30 °, Δ indicates less than 40 °, and X indicates 40 ° or more.
In Table 1, “Adhesion” means that a dried “trade name made by Crecia Co., Ltd .: Kim Towel” was placed on the hydrophilic film, and the tile was rubbed 50 times with a load of 500 g. ◎ for those with no damage, △ for those with only a few damages, △ for those with 2-3 damages, and X for those with more damage .
In Table 1, corrosion resistance A is a salt spray test (SST: 240 hours) defined in JISZ2371, and corrosion resistance B is a moisture resistance test (240 hours) defined in JISH4001. The x mark indicates that corrosion marks have been confirmed at multiple locations, the △ mark indicates that corrosion marks have been confirmed at multiple locations, the ○ mark indicates that corrosion marks have been confirmed at 1 to 2 locations, and the ◎ mark indicates corrosion. This indicates that no traces could be confirmed.
[0038]
[Table 1]

[0039]
From the results shown in Table 1, 1.0 to 100 mg / m2 of Zr or Ti as an essential component in the underlying layer after drying.²It was found that a sample containing these elements in the range of 1 to 2 has excellent hydrophilicity, good adhesion, and excellent corrosion resistance. Also within this range, especially 5 to 50 mg / m.²It has also been found that this range is particularly preferred.
[0040]
Next, Table 2 below shows equivalent test results using an organic hydrophilic film having the following composition in place of the inorganic hydrophilic film used in the previous test.
As the organic hydrophilic film, here, the hydrophilic film of Example 1 described in Japanese Patent Application Laid-Open No. 08-081650 was used.
That is, in order to form a hydrophilic film, first, [Copolymer A-1] is produced, the [Copolymer A-1] is subjected to the treatment described later, and then the alkali resistance-improving curing agent described later. Then, a hardener and ion exchange water were mixed in parts by weight described later to obtain an organic hydrophilic film.
[0041]
Production of [Copolymer A-1]
In a 1 L four-necked flask equipped with a stirrer, reflux condenser, thermometer, dropping funnel and nitrogen gas introduction tube, 400 g of ion-exchanged water, 8.1 g of sodium hypophosphite, 5.0 g of potassium persulfate, light acrylate CN (Kyoeisha Chemical Co., Ltd., 2-cyanoethyl acrylate) 80 g, Light Ester HO (Kyoeisha Chemical Co., Ltd., 2-hydroxyethyl methacrylate) 28 g, Crotonic acid 20 g, Maleic acid 100 g, Methacrylic acid 72 g, Methyl methacrylate 8 g , Light acrylate CH (manufactured by Kyoeisha Chemical Co., Ltd., cyclohexyl acrylate), 4 g of AS (manufactured by Nissei Chemical Industry Co., Ltd., aryl sulfonic acid soda), and ATBS-K (manufactured by Toa Gosei Chemical Co., Ltd., 2-acrylamide-2- 48g methylpropane-1-sulfonate They were charged, under a stream of nitrogen gas, polymerization temperature 47 to 50 results were performed for 16 hours redox polymerization reaction at ° C., an average molecular weight of 12,000, the concentration to obtain a copolymer A-1 51.1%.
[0042]
Production of [Hydrophilic Resin A-1]
Triethylamine and aqueous ammonia are added to this copolymer A-1, stirred at 40 to 45 ° C. for 1 hour, pH adjusted with 25% aqueous ammonia, ion-exchanged water is added to adjust the concentration, and further stirred and mixed for 1 hour. Thus, a liquid resin was obtained.
[0043]
Manufacture of [alkali resistance imparting agent b-1]
For this, a 500 mL four-necked flask equipped with a stirrer, thermometer, nitrogen inlet tube and reflux condenser was added to 200 g of PEG # 600 (manufactured by Lion Corporation, polyethylene glycol molecular weight 600), and Ricacid SA (Nippon Nippon Chemical Co., Ltd.). 87 g of succinic anhydride (manufactured by company) were charged and reacted at 80 ° C. for 2 hours, 100 ° C. for 1 hour, and 110 ° C. for 2 hours to obtain a colorless liquid diester dibasic oxygen acid. To this, 44 g of triethylamine and 43.5 g of 25% ammonia water were added and stirred and mixed at 40 to 45 ° C. for 1 hour, and then ion-exchanged water was added to adjust the concentration to 40%. Obtained.
[0044]
[Curing agent C-3]
This is Yuki Coat E-394 (manufactured by Kyoeisha Chemical Co., Ltd., polyethylene glycol (ethylene glycol chain n = 14) diglycidyl ether, viscosity 160 cps, light yellow transparent liquid).
These were prepared, and 100 parts by weight of [Hydrophilic resin A-1], 60 parts by weight of [Alkali resistance imparting agent B-1], 25 parts by weight of [Curing agent C-3], and 160 parts by weight of ion-exchanged water. By mixing, an organic hydrophilic film used in the present invention was obtained.
This organic hydrophilic film was used in place of the inorganic hydrophilic film and subjected to a test equivalent to that shown in Table 1.
[0045]
[Table 2]

[0046]
As shown in Table 2, even if the fin material was provided with an organic hydrophilic film, the same results as the fin material provided with an inorganic hydrophilic film were obtained.
[0047]
【The invention's effect】
  As described above, the present inventionZrBetween the treatment liquid layer and the metal substrateBy reactive surface treatmentIt has an underlayer and a hydrophilic film on itAnd ZrA non-chromate-type underlayer containing no Cr can be used, and a fin material that does not cause the problem of environmental pollution can be provided. In addition, the hydrophilic film provided on the underlayer imparts hydrophilicity to the fin material and prevents adhesion of hemispherical condensed water.
  Next, in the present invention, as an essential component contained in the underlayerZr1mg / m²100 mg / m²When it is contained below, good adhesion as the underlayer can be ensured, excellent corrosion resistance can be ensured, and hydrophilicity necessary for the fin material is ensured.
  In the present invention, as the underlayer, specifically, AlF ₃ And Al ₂ O ₃ And a base layer containing AlOF, and AlO _x (OH) _y ・ NH ₂ O and AlF ₃ And a layer containing AlOF, ZrO ₂ ・ NH ₂ A layer having O, and Zr ₃ (PO ₄ ) ₄ ・ NH ₂ A laminated structure of layers containing O can be employed.
  In the present invention, a treatment liquid mainly composed of fluorozirconic acid or an ammonium salt thereof added with hydrofluoric acid can be applied.
  In the present invention, the underlayer is 5 mg / m²50 mg / m²Less thanZrIf it is contained, better adhesion as the underlayer can be ensured, and excellent corrosion resistance and hydrophilicity necessary for the fin material are ensured.
[0048]
Next, the present invention may be a heat exchanger including any one of the fin materials described above.
If the heat exchanger is provided with the fin material, since the surface of the fin material has hydrophilicity, air permeability around the fin material is impaired even if condensed water adheres during cooling operation of the heat exchanger. There is little fear.
[Brief description of the drawings]
FIG. 1 is a cross-sectional view showing the structure of a first embodiment of a fin material according to the present invention.
FIG. 2 is a front view showing an example of a heat exchanger provided with fins made of a fin material according to the present invention.
[Explanation of symbols]
DESCRIPTION OF SYMBOLS A ... Fin material, 1 ... Base material, 2 ... Underlayer, 3 ... Hydrophilic film, B ... Heat exchanger, 13 ... Tube, 14 ... Fin.

Claims (8)

A metal base material made of aluminum or an aluminum alloy, a non-chromate reaction type base layer formed on the metal base material by a reactive base processing method, and a hydrophilic film formed on the base layer. becomes Te, the underlying layer comprises a Zr as an essential component, a treatment liquid was heated on a metal substrate coated, Zr by reactive surface treatment method of reacting with the metal substrate a portion of the processing liquid layer A fin material for a heat exchanger, characterized in that it is formed so as to have an oxide of the above . ^{2. The} fin material for a heat exchanger according to claim 1, wherein Zr is contained in the underlayer as an essential component in an amount of 1 mg / m ² to 100 mg / m ² . The base layer formed by the reactive base processing method is AlF. ₃ And Al ₂ O ₃ And a base layer containing AlOF, and AlO _x (OH) _y ・ NH ₂ O and AlF ₃ And a layer containing AlOF, ZrO ₂ ・ NH ₂ A layer having O, and Zr ₃ (PO ₄ ) ₄ ・ NH ₂ The fin material for a heat exchanger according to claim 1 or 2, wherein the fin material has a laminated structure of layers containing O. 4. The heat exchanger according to claim 1, wherein the treatment liquid is a treatment liquid mainly composed of fluorozirconic acid or an ammonium salt thereof added with hydrofluoric acid. Fin material. In addition to Zr as essential components in the underlying layer, Ti, Si, C, V , P, of the O, more of claims 1-3, characterized in that at least one or more, two or, which are contained heat exchanger fin stock according to any one of claims. 6. The fin material for a heat exchanger according to claim 5 , wherein the underlayer contains an oxide of at least one element or two or more elements of Ti , Si , V, and P. Wherein the base layer, 5 mg / ^{m 2} or more, the heat exchanger fin stock according to any one of claims 2-6 that 50 mg / ^{m 2} or less of Zr is characterized by comprising been contained. A heat exchanger comprising the fin material according to any one of claims 1 to 7 .

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