JP6470548B2 - Aluminum fin material for heat exchanger having antifouling property, method for producing the same, heat exchanger including the aluminum fin material, and air conditioner - Google Patents
Aluminum fin material for heat exchanger having antifouling property, method for producing the same, heat exchanger including the aluminum fin material, and air conditioner Download PDFInfo
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- JP6470548B2 JP6470548B2 JP2014223004A JP2014223004A JP6470548B2 JP 6470548 B2 JP6470548 B2 JP 6470548B2 JP 2014223004 A JP2014223004 A JP 2014223004A JP 2014223004 A JP2014223004 A JP 2014223004A JP 6470548 B2 JP6470548 B2 JP 6470548B2
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- 230000003373 anti-fouling effect Effects 0.000 title claims description 65
- 239000000463 material Substances 0.000 title claims description 48
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims description 38
- 229910052782 aluminium Inorganic materials 0.000 title claims description 37
- 238000004519 manufacturing process Methods 0.000 title claims description 15
- 239000002245 particle Substances 0.000 claims description 127
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 67
- 239000011248 coating agent Substances 0.000 claims description 47
- 238000000576 coating method Methods 0.000 claims description 47
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 36
- 239000003973 paint Substances 0.000 claims description 35
- 229920000178 Acrylic resin Polymers 0.000 claims description 23
- 239000004925 Acrylic resin Substances 0.000 claims description 23
- 229920001223 polyethylene glycol Polymers 0.000 claims description 22
- 239000002202 Polyethylene glycol Substances 0.000 claims description 21
- 239000000178 monomer Substances 0.000 claims description 21
- 239000006185 dispersion Substances 0.000 claims description 16
- 239000011347 resin Substances 0.000 claims description 15
- 229920005989 resin Polymers 0.000 claims description 15
- 239000007787 solid Substances 0.000 claims description 12
- 229910000838 Al alloy Inorganic materials 0.000 claims description 11
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 10
- 229910052731 fluorine Inorganic materials 0.000 claims description 10
- 239000011737 fluorine Substances 0.000 claims description 10
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 10
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 10
- 150000003839 salts Chemical class 0.000 claims description 7
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 6
- 125000002843 carboxylic acid group Chemical group 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 6
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 claims description 5
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 claims description 5
- 230000001476 alcoholic effect Effects 0.000 claims description 5
- 239000008118 PEG 6000 Substances 0.000 claims description 4
- 229920002584 Polyethylene Glycol 6000 Polymers 0.000 claims description 4
- 229920001577 copolymer Polymers 0.000 claims description 4
- 239000000126 substance Substances 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 230000002209 hydrophobic effect Effects 0.000 description 8
- 238000000034 method Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000008119 colloidal silica Substances 0.000 description 5
- 238000011109 contamination Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 3
- -1 aryl sulfonic acid Chemical compound 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 229910001593 boehmite Inorganic materials 0.000 description 2
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- WMYWOWFOOVUPFY-UHFFFAOYSA-L dihydroxy(dioxo)chromium;phosphoric acid Chemical compound OP(O)(O)=O.O[Cr](O)(=O)=O WMYWOWFOOVUPFY-UHFFFAOYSA-L 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 238000011158 quantitative evaluation Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- PRAMZQXXPOLCIY-UHFFFAOYSA-N 2-(2-methylprop-2-enoyloxy)ethanesulfonic acid Chemical compound CC(=C)C(=O)OCCS(O)(=O)=O PRAMZQXXPOLCIY-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 101100008044 Caenorhabditis elegans cut-1 gene Proteins 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 238000004378 air conditioning Methods 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000005660 hydrophilic surface Effects 0.000 description 1
- 238000010191 image analysis Methods 0.000 description 1
- 230000009191 jumping Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 230000001953 sensory effect Effects 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- 150000003755 zirconium compounds Chemical class 0.000 description 1
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- Paints Or Removers (AREA)
Description
本発明は、防汚性を有する熱交換器用アルミニウムフィン材及びその製造方法と前記アルミニウムフィン材を備えた熱交換器及び空気調和機に関する。 The present invention relates to an aluminum fin material for heat exchanger having antifouling property, a method for producing the same, a heat exchanger provided with the aluminum fin material, and an air conditioner .
エアコン用熱交換器のフィン材には、軽量性、加工性、熱伝導性の面で優れるアルミニウムやアルミニウム合金が使用されている。
また、熱交換器において薄板状のフィンが隣接して複数設けられるので結露水がフィンの表面に水滴として付着すると、通風抵抗が増大し、圧力損失が大きくなり、熱交換器としての能力低下を生じる。このため、フィン表面に凝縮した水滴をフィン表面から容易に流下させるために、フィン表面に親水性塗膜を形成している。
熱交換器用フィンの表面に親水性を付与する技術としては、フィン材表面にシリカ粒子を含有する有機高分子樹脂溶液で表面処理する技術や、アクリル系樹脂などからなる有機高分子物質とＳｉＯ２又はＴｉＯ２を含む水性組成物を混合し塗布、乾燥することによって形成される皮膜でアルミニウムフィン材を被覆する技術が知られている。
Aluminum and aluminum alloys that are superior in terms of lightness, workability, and thermal conductivity are used as fin materials for heat exchangers for air conditioners.
In addition, since a plurality of thin plate-like fins are provided adjacent to each other in the heat exchanger, if condensed water adheres to the surface of the fins as water droplets, the ventilation resistance increases, the pressure loss increases, and the capacity of the heat exchanger decreases. Arise. For this reason, a hydrophilic coating film is formed on the fin surface so that water droplets condensed on the fin surface can easily flow down from the fin surface.
As a technique for imparting hydrophilicity to the surface of the fin for heat exchanger, a technique for surface treatment with an organic polymer resin solution containing silica particles on the surface of the fin material, an organic polymer substance composed of an acrylic resin, and SiO 2 is used. or mixed by coating an aqueous composition comprising TiO 2, a technique for coating an aluminum fin material are known in the coating formed by drying.
特許文献１には、Ｚｒ化合物を用いて金属架橋させたポリアクリル酸等の有機樹脂に、シリカ粒子、ポリエチレングリコールを含有した親水性塗膜をアルミニウム合金基材の表面に形成することが開示されている。
特許文献２には、アルミニウム板に、樹脂とジルコニウムを含有する下地皮膜層を形成し、その上に、樹脂、コロイダルシリカ、ジルコニウム化合物を含有する親水性被膜層を形成することが開示されている。
Patent Document 1 discloses that a hydrophilic coating film containing silica particles and polyethylene glycol is formed on the surface of an aluminum alloy substrate on an organic resin such as polyacrylic acid that is metal-crosslinked with a Zr compound. ing.
Patent Document 2 discloses that a base coating layer containing a resin and zirconium is formed on an aluminum plate, and a hydrophilic coating layer containing a resin, colloidal silica, and a zirconium compound is formed thereon. .
エアコン用熱交換器のフィンには、埃などの親水性の汚れや、油分等の疎水性汚れが付着し、親水性汚れ及び疎水性汚れがフィン表面に付着することによって、フィン表面が撥水化し、結露水が飛散すること、いわゆる露飛びを発生する問題がある。
露飛びを解決するためには、親水性汚れ、疎水性汚れ共にフィンに付着し難くする必要がある。露飛びを解決するための手法の一例として、親水性粒子と疎水性粒子の混合膜をアルミニウムフィンの表面に塗布することが有効であるが、親水性粒子として特許文献２等に記載されているコロイダルシリカを用いると、粒子硬度が高いため、アルミニウム板材からフィン材をプレス加工で作製する場合、金型摩耗を生じ易い問題がある。
Air conditioning heat exchanger fins adhere to hydrophilic dirt such as dust, or hydrophobic dirt such as oil, and the hydrophilic surface and hydrophobic dirt adhere to the fin surface. There is a problem that the condensed water is scattered and the so-called dew is generated.
In order to solve the exposure, it is necessary to make it difficult for both the hydrophilic dirt and the hydrophobic dirt to adhere to the fins. As an example of a technique for solving the exposure, it is effective to apply a mixed film of hydrophilic particles and hydrophobic particles to the surface of the aluminum fin. However, the hydrophilic particles are described in Patent Document 2 and the like. When colloidal silica is used, since the particle hardness is high, there is a problem that mold wear is likely to occur when a fin material is produced from an aluminum plate by press working.
本願発明は、これらの背景に鑑み、親水性汚れと疎水性汚れの両方を付着し難くして防汚性を向上させるとともに、プレス加工時の金型摩耗を生じ難くしたアルミニウムフィン材及びその製造方法の提供を目的とする。本願発明は、これらの背景に鑑み、上述の優れた特徴を備えたアルミニウムフィン材を有する熱交換器及び空気調和機の提供を目的とする。 In view of these backgrounds, the present invention is an aluminum fin material that makes it difficult to attach both hydrophilic and hydrophobic stains to improve antifouling properties and hardly causes mold wear during press working, and the production thereof. The purpose is to provide a method . In view of these backgrounds, an object of the present invention is to provide a heat exchanger and an air conditioner having an aluminum fin material having the above-described excellent characteristics.
本発明の防汚性を有するアルミニウムフィン材は、アルミナゾルと、スルホン酸を含む水溶性アクリル樹脂と、ポリエチレングリコールとフッ素樹脂粒子を含む水系塗料であって、前記アルミナゾル中のアルミナ粒子と前記水溶性アクリル樹脂と前記ポリエチレングリコールと前記フッ素樹脂を含む塗料固形分１００質量％中に、平均粒子径０．０２〜２０μｍのアルミナ粒子を５〜４５質量％、平均粒子径０．１〜０．５μｍのフッ素樹脂粒子を０．０５〜３質量％含有させた水系塗料の焼付塗膜をアルミニウム又はアルミニウム合金からなる板材表面に有し、前記焼付塗膜が、先の尖った凸部を複数有する前記アルミナ粒子と前記フッ素樹脂粒子を樹脂層の内部に複数埋設してなる。 The aluminum fin material having antifouling property of the present invention is a water-based paint containing alumina sol, a water-soluble acrylic resin containing sulfonic acid, polyethylene glycol and fluororesin particles, and the alumina particles in the alumina sol and the water-soluble In 100% by mass of paint solid content containing acrylic resin, polyethylene glycol and fluororesin, 5-45 % by mass of alumina particles having an average particle size of 0.02-20 μm and an average particle size of 0.1-0.5 μm has a baked coating of the fluorine resin particles are contained 0.05 to 3 wt% aqueous coating plate material surface made of aluminum or an aluminum alloy, the alumina the baking coating film, a plurality have a pointed protrusion former A plurality of particles and the fluororesin particles are embedded in the resin layer.
本発明において、前記焼付塗膜表面に分散されているアルミナ粒子の面積占有率が９０％以上であることが好ましい。
本発明において、表面の動摩擦係数が０．２以下であることが好ましい。
本発明において、前記水溶性アクリル樹脂が、スルホン酸基又はその塩を有するα，β不飽和単量体Ａと、カルボン酸基を有するα，β不飽和単量体Ｂと、アルコール性水酸基を有するα，β不飽和単量体Ｃの共重合体であることが好ましい。
本発明において、前記水溶性アクリル樹脂が２−アクリルアミド−２−メチルプロパンスルホン酸であり、前記ポリエチレングリコールがＰＥＧ６０００であり、前記フッ素樹脂粒子がＰＴＦＥディスパージョンまたはＦＥＰディスパージョンに含まれるフッ素樹脂粒子であることが好ましい。
本発明の熱交換器は、先のいずれかに記載のアルミニウムフィン材を備えたものである。
本発明の空気調和機は、先の熱交換器を用いたものである。
In this invention, it is preferable that the area occupation rate of the alumina particle currently disperse | distributed to the said baking coating film surface is 90% or more .
In the present invention, the surface dynamic friction coefficient is preferably 0.2 or less.
In the present invention, the water-soluble acrylic resin comprises an α, β unsaturated monomer A having a sulfonic acid group or a salt thereof, an α, β unsaturated monomer B having a carboxylic acid group, and an alcoholic hydroxyl group. The α, β unsaturated monomer C is preferably a copolymer .
In the present invention, the water-soluble acrylic resin is 2-acrylamido-2-methylpropane sulfonic acid, the polyethylene glycol is PEG 6000, and the fluororesin particles are fluororesin particles contained in PTFE dispersion or FEP dispersion. there it is preferable.
The heat exchanger of this invention is equipped with the aluminum fin material in any one of the above.
The air conditioner of the present invention uses the previous heat exchanger.
本発明に係る防汚性を有するアルミニウムフィン材の製造方法は、アルミナゾルと、スルホン酸を含む水溶性アクリル樹脂と、ポリエチレングリコールと、フッ素樹脂粒子を含む水系塗料であって、前記アルミナゾル中のアルミナ粒子と前記水溶性アクリル樹脂と前記ポリエチレングリコールと前記フッ素樹脂粒子を含む塗料固形分１００質量％中に、平均粒子径０．０２〜２０μｍのアルミナ粒子を５〜４５質量％、平均粒子径０．１〜０．５μｍのフッ素樹脂粒子を０．０５〜３質量％含有させた水系塗料をアルミニウム又はアルミニウム合金からなる板材表面に、０.３〜０.８ｇ／ｍ２の塗布量で塗布し、焼成することを特徴とする。
本発明の製造方法において、前記焼付塗膜表面に分散されているアルミナ粒子の面積占有率を９０％以上とすることが好ましい。
本発明の製造方法において、表面の動摩擦係数が０．２以下であることが好ましい。
本発明の製造方法において、前記水溶性アクリル樹脂が、スルホン酸基又はその塩を有するα，β不飽和単量体Ａと、カルボン酸基を有するα，β不飽和単量体Ｂと、アルコール性水酸基を有するα，β不飽和単量体Ｃの共重合体であることが好ましい。
本発明の製造方法において、前記水溶性アクリル樹脂が２−アクリルアミド−２−メチルプロパンスルホン酸であり、前記ポリエチレングリコールがＰＥＧ６０００であり、前記フッ素樹脂粒子がＰＴＦＥディスパージョンまたはＦＥＰディスパージョンに含まれるフッ素樹脂粒子であることが好ましい。
A method for producing an antifouling aluminum fin material according to the present invention is an aqueous sol containing an alumina sol, a water-soluble acrylic resin containing sulfonic acid, polyethylene glycol, and fluororesin particles, the alumina in the alumina sol 5 to 45% by mass of alumina particles having an average particle size of 0.02 to 20 μm and an average particle size of 0.1 % in 100% by mass of the solid content of the paint containing the particles, the water-soluble acrylic resin, the polyethylene glycol and the fluororesin particles . A water-based paint containing 0.05 to 3% by mass of 1 to 0.5 μm of fluororesin particles is applied to the surface of a plate made of aluminum or an aluminum alloy at a coating amount of 0.3 to 0.8 g / m 2 , It is characterized by firing.
In the production method of the present invention, it is preferable that the area occupancy of the alumina particles dispersed on the surface of the baked coating film is 90% or more .
In the production method of the present invention, the surface dynamic friction coefficient is preferably 0.2 or less.
In the production method of the present invention, the water-soluble acrylic resin comprises an α, β unsaturated monomer A having a sulfonic acid group or a salt thereof, an α, β unsaturated monomer B having a carboxylic acid group, and an alcohol. A copolymer of an α, β unsaturated monomer C having a functional hydroxyl group is preferred.
In the production method of the present invention, the water-soluble acrylic resin is 2-acrylamido-2-methylpropanesulfonic acid, the polyethylene glycol is PEG 6000, and the fluororesin particles are fluorine contained in PTFE dispersion or FEP dispersion. Resin particles are preferred.
本発明のアルミニウムフィン材であるならば、アルミナゾルと水溶性アクリル樹脂とポリエチレングリコールとフッ素樹脂粒子を含む水系塗料を焼成した焼付塗膜であって、塗料固形分１００質量％中に、平均粒子径０．０２〜２０μｍのアルミナ粒子を５〜４５質量％、平均粒子径０．１〜０．５μｍのフッ素樹脂粒子を０．０５〜３質量％含有させた水系塗料の焼付塗膜を表面に備えているので、親水性汚れと疎水性汚れの両方を付着し難くすることができ、防汚性を向上できる。このため、本発明のフィン材から形成したフィンであれば、表面に付着した結露水が飛散するという、いわゆる露飛びの発生を抑えることができる。
また、本発明のアルミニウムフィン材であるならば、従来の親水性塗膜を備えたフィン材に用いられていたコロイダルシリカ等の硬質粒子を塗膜中に含まないため、アルミニウムフィン材から金型を用いてフィンを製造する場合、金型摩耗を生じ難くすることができ、金型寿命の低下を抑制できる。
更に、上述の特徴を備えたフィン材を備えた熱交換器または空気調和機であるならば、露飛びの発生を抑えることができるとともに、フィンを金型で製造する場合の金型寿命を延ばすことができる熱交換器または空気調和機を提供できる。
If it is the aluminum fin material of the present invention, it is a baked coating film obtained by baking a water-based paint containing alumina sol, water-soluble acrylic resin, polyethylene glycol, and fluororesin particles , and the average particle diameter is 100% by mass in the solid content of the paint. The surface is provided with a baked coating film of water-based paint containing 0.02 to 20 μm of alumina particles of 5 to 45% by mass and fluororesin particles having an average particle size of 0.1 to 0.5 μm of 0.05 to 3% by mass. Therefore, both hydrophilic dirt and hydrophobic dirt can be made difficult to adhere, and the antifouling property can be improved. For this reason, if it is a fin formed from the fin material of this invention, generation | occurrence | production of what is called dew jumping that the dew condensation water adhering to the surface scatters can be suppressed.
Moreover, if it is the aluminum fin material of this invention, since hard particles, such as colloidal silica used for the fin material provided with the conventional hydrophilic coating film, are not included in a coating film, from aluminum fin material to a metal mold | die. When manufacturing fins using, it is possible to make mold wear less likely to occur and to suppress a decrease in mold life.
Furthermore, if the heat exchanger or the air conditioner is provided with the fin material having the above-described features, it is possible to suppress the occurrence of dew and to extend the mold life when the fin is manufactured by the mold. Can provide a heat exchanger or air conditioner.
以下、添付図面に示す実施形態に基づいて本発明を詳細に説明する。
本実施形態の熱交換器用フィン材１は、図１に断面構造を示すように、アルミニウムまたはアルミニウム合金からなる基材２と、該基材２の表面に被覆された化成皮膜３と、化成皮膜３を覆うように被覆形成された防汚性皮膜５を主体として構成されている。
Hereinafter, the present invention will be described in detail based on embodiments shown in the accompanying drawings.
As shown in the cross-sectional structure of FIG. 1, the heat exchanger fin material 1 of the present embodiment includes a base material 2 made of aluminum or an aluminum alloy, a chemical conversion film 3 coated on the surface of the base material 2, and a chemical conversion film. 3 is mainly composed of an antifouling film 5 formed so as to cover 3.
基材２を構成するアルミニウム又はアルミニウム合金としては、特に限定されず、一般的に熱交換器用の基材に適用されている組成のアルミニウム材を適宜用いて良い。なお、例示するならばＪＩＳ規定Ａ１０５０、Ａ１１００、Ａ１２００、Ａ３００３等が挙げられる。
化成皮膜３としては、クロメート処理された薄いクロメート皮膜などを用いることができる。
It does not specifically limit as aluminum or aluminum alloy which comprises the base material 2, You may use the aluminum material of the composition generally applied to the base material for heat exchangers suitably. For example, JIS rules A1050, A1100, A1200, A3003 and the like can be cited.
As the chemical conversion film 3, a thin chromate film subjected to chromate treatment or the like can be used.
防汚性皮膜５は、アルミナゾルと、スルホン酸を含む水溶性アクリル樹脂と、ポリエチレングリコールもしくはポリエチレングリコールの変性物を含む水系塗料を塗膜として化成皮膜３上に塗布後に１５０〜３００℃で所定時間、例えば、数１０秒〜数分程度焼成してなる。アルミナゾルは、アルミナ粒子を液体の分散媒に分散させた状態のものを意味する。
従って、水系塗料を焼成した後の防汚性皮膜５は、水溶性アクリル樹脂とポリエチレングリコールもしくはポリエチレングリコールの変性物の混合物の焼成体からなる樹脂層６中にアルミナ粒子７が分散された構造となっている。
なお、防汚性皮膜５に対し、フッ素樹脂粒子８を添加した構造を採用してもよい。防汚性皮膜５にフッ素樹脂粒子８を添加するには、フッ素樹脂粒子８を水に分散させたＰＴＦＥディスパージョン、ＦＥＰディスパージョンなどを水系塗料に必要量混合しておけばよい。
水系塗料にＰＴＦＥディスパージョン、ＦＥＰディスパージョンなどの状態でフッ素樹脂粒子８を混合しておき、水系塗料を焼成することで、必要量のフッ素樹脂粒子８を添加した防汚性皮膜５を得ることができる。
The antifouling film 5 is coated on the chemical conversion film 3 with a water-based paint containing alumina sol, a water-soluble acrylic resin containing sulfonic acid, and polyethylene glycol or a modified product of polyethylene glycol for a predetermined time at 150 to 300 ° C. For example, it is fired for about several tens of seconds to several minutes. Alumina sol means a state in which alumina particles are dispersed in a liquid dispersion medium.
Therefore, the antifouling film 5 after firing the water-based paint has a structure in which alumina particles 7 are dispersed in a resin layer 6 made of a fired product of a mixture of a water-soluble acrylic resin and polyethylene glycol or a modified product of polyethylene glycol. It has become.
Note that a structure in which the fluororesin particles 8 are added to the antifouling film 5 may be employed. In order to add the fluororesin particles 8 to the antifouling film 5, a necessary amount of PTFE dispersion, FEP dispersion, etc., in which the fluororesin particles 8 are dispersed in water, may be mixed with the water-based paint.
The antifouling film 5 to which the necessary amount of the fluororesin particles 8 is added is obtained by mixing the fluororesin particles 8 in a state of PTFE dispersion, FEP dispersion or the like in the water-based paint and baking the water-based paint. Can do.
アルミナゾルは、その分散粒子（アルミナ粒子）が不定型ゲルからベーマイト（水和物）に移行する途中の段階にあり、この状態は凝集過程や通常の塗膜の焼付け条件程度では変化しない。この不定型ゲルからベーマイトに移行する途中の段階のアルミナゾルの分散粒子は、コロイダルシリカと比較して軟らかい。例えば、モース硬度が低い。従って、このアルミナゾルに由来する粒子を含有する塗膜を持つ材料をプレス加工する時の加工性は良好であり、かつ、金型の耐久性も高くすることができる。
水溶性アクリル樹脂としては、スルホン酸基、又はその塩を有するα，β不飽和単量体Ａと、カルボン酸基を有するα，β不飽和単量体Ｂと、アルコール性水酸基を有するα，β不飽和単量体Ｃとを（割合：Ａ；１〜８０ｗｔ％（好ましくは３０〜５０ｗｔ％），Ｂ；１〜５０ｗｔ％（好ましくは２０〜５０ｗｔ％），Ｃ；１〜５０ｗｔ％（好ましくは２０〜４０ｗｔ％）が望ましい。Ａ＋Ｂ＋Ｃ＝１００ｗｔ％）共重合したものが好ましい。
The alumina sol is in a stage where the dispersed particles (alumina particles) are transferred from the amorphous gel to boehmite (hydrate), and this state does not change in the aggregation process or the ordinary baking conditions of the coating film. The dispersed particles of alumina sol at the stage of transition from the amorphous gel to boehmite are softer than colloidal silica. For example, the Mohs hardness is low. Therefore, the workability when pressing a material having a coating film containing particles derived from the alumina sol is good, and the durability of the mold can be increased.
Examples of the water-soluble acrylic resin include α, β unsaturated monomers A having a sulfonic acid group or a salt thereof, α, β unsaturated monomers B having a carboxylic acid group, and α, β having an alcoholic hydroxyl group. β unsaturated monomer C (ratio: A; 1 to 80 wt% (preferably 30 to 50 wt%)), B; 1 to 50 wt% (preferably 20 to 50 wt%), C; 1 to 50 wt% (preferably Is preferably 20 to 40 wt%), and A + B + C = 100 wt%) is preferably copolymerized.
スルホン酸基、又はその塩を有するα，β不飽和単量体Ａとしては、例えばビニルスルホン酸、アリールスルホン酸、２−アクリルアミド−２−メチルスルホン酸、スチレンスルホン酸、メタクリロイルオキシエチルスルホン酸、又は前記のナトリウム塩、カリウム塩、リチウム塩などの塩が好ましい。この単量体Ａは、アニオン性の親水性を示し、塗膜の水濡れ性を向上させる。
カルボン酸基を有するα，β不飽和単量体Ｂとしては、例えばアクリル酸、メタクリル酸、マレイン酸、フマル酸、イタコン酸、クロトン酸などが好ましい。この単量体Ｂは、塗膜の水濡れ性と密着性を向上させる。アルコール性水酸基を有するα，β不飽和単量体Ｃとしては、例えば２−ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシプロピル（メタ）アクリレート、Ｎ−メチロール（メタ）アクリルアミド等が好ましい。この単量体Ｃは、塗膜の水濡れ性を向上させると共に、アルミナゾルに由来の粒子を固定する役割を奏する。
Examples of the α, β unsaturated monomer A having a sulfonic acid group or a salt thereof include vinyl sulfonic acid, aryl sulfonic acid, 2-acrylamido-2-methylsulfonic acid, styrene sulfonic acid, methacryloyloxyethyl sulfonic acid, Or salts such as the aforementioned sodium salts, potassium salts and lithium salts are preferred. This monomer A exhibits anionic hydrophilicity and improves the water wettability of the coating film.
As the α, β unsaturated monomer B having a carboxylic acid group, for example, acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid and the like are preferable. This monomer B improves the water wettability and adhesion of the coating film. As the α, β unsaturated monomer C having an alcoholic hydroxyl group, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, N-methylol (meth) acrylamide and the like are preferable. This monomer C plays a role of improving the wettability of the coating film and fixing particles derived from the alumina sol.
水系塗料の塗布量は０.３〜０.８ｇ／ｍ２の範囲であることが好ましい。なお、以下の説明において、「〜」を用いて範囲の上限と下限を表記した場合、特に説明のない限り、下限と上限を含むものとする。よって、０.３〜０.８ｇ／ｍ２の範囲は０．３ｇ／ｍ２以上、０．８ｇ／ｍ２以下を意味する。
水系塗料の塗布量を上述の範囲とすることで塗膜密着性、親水性、耐汚染性、防汚性に優れる防汚性皮膜５となる。０.３ｇ／ｍ２未満の塗布量では防汚性皮膜５の親水性不良、耐汚染性不良、防汚性不良となるおそれがある。また、０.８ｇ／ｍ２を超える塗布量では、防汚性皮膜５の密着性不良、コストの上昇になり易い。
The coating amount of the water-based paint is preferably in the range of 0.3 to 0.8 g / m 2. In addition, in the following description, when an upper limit and a lower limit of a range are described using “to”, the lower limit and the upper limit are included unless otherwise specified. Therefore, the range of 0.3 to 0.8 g / m 2 is 0.3 g / m 2 or more, it means a 0.8 g / m 2 or less.
By setting the coating amount of the water-based paint within the above range, the antifouling film 5 having excellent coating film adhesion, hydrophilicity, stain resistance, and antifouling properties is obtained. If the coating amount is less than 0.3 g / m 2 , the antifouling film 5 may have poor hydrophilicity, antifouling resistance, and poor antifouling properties. On the other hand, when the coating amount exceeds 0.8 g / m 2 , the adhesion of the antifouling film 5 is likely to be poor and the cost tends to increase.
アルミナゾルに含まれているアルミナ粒子の平均粒子径は０．０２〜２０μｍの範囲が好ましい。アルミナ粒子の平均粒子径が０．０２μｍ未満では、比表面積が増大することによって吸着臭が発生する問題があり、アルミナ粒子の平均粒子径が２０μｍを超えるようであると、プレス加工時の金型摩耗性が悪化する問題がある。
アルミナ粒子の添加量は塗料中の固形分１００質量％中、５〜４５質量％の範囲であることが望ましい。アルミナ粒子をこの範囲添加することで、塗膜密着性、親水性、耐汚染性、防汚性に優れる防汚性皮膜５となる。アルミナ粒子の添加量を５質量％未満とすると、親水性不良、耐汚染性不良、防汚性不良となるおそれがある。アルミナ粒子の添加量について４５質量％を超える量とすると、防汚性皮膜５の密着性不良、コストの上昇になり易い。
なお、前記水系塗料中には、アルミナ粒子、フッ素樹脂などの固形分の他に、固形分としてスルホン酸を含む水溶性アクリル樹脂４０〜６０％とポリエチレングリコール２０〜４０％程度が含まれる。
The average particle diameter of the alumina particles contained in the alumina sol is preferably in the range of 0.02 to 20 μm. If the average particle diameter of the alumina particles is less than 0.02 μm, there is a problem that an adsorption odor is generated due to an increase in the specific surface area. If the average particle diameter of the alumina particles seems to exceed 20 μm, the mold during press working There is a problem that wear resistance deteriorates.
The addition amount of the alumina particles is desirably in the range of 5 to 45% by mass in 100% by mass of the solid content in the paint. By adding alumina particles in this range, the antifouling film 5 is excellent in coating film adhesion, hydrophilicity, stain resistance, and antifouling properties. If the amount of alumina particles added is less than 5% by mass, there is a risk of poor hydrophilicity, poor stain resistance, and poor antifouling properties. If the amount of the alumina particles added exceeds 45% by mass, the adhesion of the antifouling film 5 is likely to be poor and the cost tends to increase.
In addition to solid content, such as an alumina particle and a fluororesin, the water-based paint contains 40 to 60% water-soluble acrylic resin containing sulfonic acid as a solid content and about 20 to 40% polyethylene glycol.
フッ素樹脂粒子８の平均粒子径は、０．１〜０．５μｍの範囲であることが好ましく、添加量は塗料中の固形分の１００質量％に対し０．０５〜３質量％の範囲であることが望ましい。フッ素樹脂粒子８として、ＰＴＦＥディスパージョン、ＦＥＰディスパージョンなどに含まれている粒子を用いることができる。
フッ素樹脂粒子８の添加量が０．０５〜３質量％の範囲であるならば、良好な防汚性を発揮する。添加量が０．０５質量％未満では防汚性皮膜５の防汚性に劣るようになり、添加量が３質量％を超えるようでは防汚性皮膜５が親水性不良となり易い。
フッ素樹脂粒子８の平均粒子径が０．１μｍ未満では、所定の防汚性を発揮出来ない問題があり、フッ素樹脂粒子８の平均粒子径が０．５μｍを超えると塗料中に均一に分散され難い問題がある。
The average particle diameter of the fluororesin particles 8 is preferably in the range of 0.1 to 0.5 μm, and the addition amount is in the range of 0.05 to 3% by mass with respect to 100% by mass of the solid content in the paint. It is desirable. As the fluororesin particles 8, particles contained in PTFE dispersion, FEP dispersion, or the like can be used.
If the addition amount of the fluororesin particles 8 is in the range of 0.05 to 3% by mass, good antifouling properties are exhibited. When the addition amount is less than 0.05% by mass, the antifouling property of the antifouling coating 5 is inferior, and when the addition amount exceeds 3% by mass, the antifouling coating 5 tends to have poor hydrophilicity.
When the average particle size of the fluororesin particles 8 is less than 0.1 μm, there is a problem that the predetermined antifouling property cannot be exhibited. When the average particle size of the fluororesin particles 8 exceeds 0.5 μm, the fluororesin particles 8 are uniformly dispersed in the paint. There is a difficult problem.
防汚性皮膜５の表面の動摩擦係数は０．２０以下であることが望ましい。防汚性皮膜５の動摩擦係数が０．２０を超える値では金型摩耗不良となり易い。防汚性皮膜５の動摩擦係数が０．２０以下であるならば、プレス加工性に優れ、金型摩耗不良を生じ難い。
防汚性皮膜５の表面に占めるアルミナ粒子の面積率は、９０％以上であることが望ましい。アルミナ粒子は、防汚性皮膜５に分散した状態にする必要があり、分散させるためには、アルミナ粒子添加量を塗料固形分１００質量中４０質量％以下にする必要がある。４０質量％以下にすることによって、塗料表面アルミナ粒子の面積率を９０％以上にすることが可能で、これにより動摩擦係数を低減でき、かつ、金型摩耗を低減することが可能となる。防汚性皮膜５の表面に存在するアルミナ粒子の面積率が９０％未満では防汚性皮膜５の表面においてアルミナ粒子が凝集状態となり易く、凝集により動摩擦係数が増大し、０．２を超えるようになり、金型摩耗性が悪化する。
The coefficient of dynamic friction on the surface of the antifouling film 5 is preferably 0.20 or less. When the dynamic friction coefficient of the antifouling film 5 exceeds 0.20, mold wear tends to be poor. If the coefficient of dynamic friction of the antifouling film 5 is 0.20 or less, it is excellent in press workability and hardly causes mold wear defects.
The area ratio of the alumina particles in the surface of the antifouling film 5 is desirably 90% or more. The alumina particles need to be dispersed in the antifouling film 5, and in order to disperse, it is necessary that the amount of alumina particles added be 40% by mass or less based on 100 masses of the solid content of the paint. By setting it to 40% by mass or less, it is possible to make the area ratio of the coating surface alumina particles 90% or more, thereby reducing the dynamic friction coefficient and reducing die wear. If the area ratio of the alumina particles present on the surface of the antifouling film 5 is less than 90%, the alumina particles are likely to be in an aggregated state on the surface of the antifouling film 5, and the dynamic friction coefficient increases due to aggregation so that it exceeds 0.2. As a result, the wear resistance of the mold deteriorates.
以上説明の防汚性皮膜５を表面に備えたフィン材１であるならば、密着性に優れ、親水性に優れ、耐汚染性に優れ、動摩擦係数が小さく、フィンを形成するためのプレス加工において金型摩耗を少なくし、金型寿命を長くできる特徴を有する。
これは、親水性に優れた防汚性皮膜５について、モース硬度が従来材のコロイダルシリカよりも低いアルミナ粒子を含むアルミナゾルを用い、更に疎水性粒子としてのフッ素樹脂粒子８を混合することによって、親水性汚れ、疎水性汚れの両方を付着し難くして防汚性を向上させ、かつ、防汚性皮膜５の表面に面積率で９０％以上のアルミナ粒子を存在させることでプレス加工時の金型摩耗を低減できることによる。
The fin material 1 having the antifouling film 5 described above on the surface is excellent in adhesion, excellent in hydrophilicity, excellent in contamination resistance, has a small coefficient of dynamic friction, and is pressed to form fins. Has features that the mold wear can be reduced and the mold life can be extended.
This is about the antifouling film 5 having excellent hydrophilicity, by using an alumina sol containing alumina particles whose Mohs hardness is lower than that of the colloidal silica of the conventional material, and further mixing the fluororesin particles 8 as hydrophobic particles. Improves antifouling properties by making it difficult to attach both hydrophilic and hydrophobic soils, and the presence of alumina particles having an area ratio of 90% or more on the surface of the antifouling coating 5 allows This is because mold wear can be reduced.
前記構造のフィン材１は、ルームエアコンの熱交換器、パッケージエアコンの熱交換器、自動販売機用熱交換器、冷凍ショーケース用熱交換器、冷蔵庫用熱交換器などに広く適用することができる。 The fin material 1 having the above structure can be widely applied to heat exchangers for room air conditioners, heat exchangers for packaged air conditioners, heat exchangers for vending machines, heat exchangers for refrigeration showcases, heat exchangers for refrigerators, and the like. it can.
触媒化成工業株式会社製商品名（カタロイドAS-3）のアルミナゾル（アルミナ粒子の平均粒子径０．８μｍ）と、水溶性アクリル樹脂（２−アクリルアミド−２−メチルプロパンスルホン酸）と、ポリエチレングリコール（ＰＥＧ＃６０００）と、旭硝子株式会社製商品名（PTFE AD911E）のフッ素樹脂（ＰＴＦＥフッ素ディスパージョン）を以下の表１に示す割合で混合し水系塗料を作製した。表１ではＰＴＦＥフッ素ディスパージョンに含まれるフッ素樹脂粒子の量で添加量を表示している。
ＪＩＳ規定Ａ１０５０合金からなる厚さ１００μｍのアルミニウム合金板をリン酸クロメート処理して厚さ０．３μｍの化成皮膜を形成後、この化成皮膜上に以下の表１に示す種々の組成の水系塗料を表１に示す塗布量にてバーコーターにて塗布し、オーブンを用いて２２０℃（設定温度）にて３０秒間焼き付けて防汚性塗膜を形成した。
得られた複数のフィン材について、塗膜の密着性、流水後親水性、乾湿サイクル後接触角、耐汚染性、動摩擦係数、粉体付着率、金型摩耗、アルミナ粒子面積率を測定し、以下の表１に示す。
Alumina sol (average particle diameter of alumina particles 0.8 μm) of a product name (Cataloid AS-3) manufactured by Catalyst Chemical Industry Co., Ltd., water-soluble acrylic resin (2-acrylamido-2-methylpropanesulfonic acid), polyethylene glycol ( PEG # 6000) and a fluororesin (PTFE fluorine dispersion) manufactured by Asahi Glass Co., Ltd. (PTFE AD911E) were mixed at a ratio shown in Table 1 to prepare a water-based paint. In Table 1, the addition amount is indicated by the amount of fluororesin particles contained in the PTFE fluorine dispersion.
A 100 μm thick aluminum alloy plate made of JIS standard A1050 alloy is subjected to phosphoric acid chromate treatment to form a 0.3 μm thick chemical film, and water-based paints having various compositions shown in Table 1 below are formed on this chemical film. It apply | coated with the bar coater with the application quantity shown in Table 1, and baked for 30 seconds at 220 degreeC (setting temperature) using oven, and formed the antifouling coating film.
For the obtained fin materials, measure the adhesion of the coating film, hydrophilicity after running water, contact angle after dry and wet cycle, contamination resistance, dynamic friction coefficient, powder adhesion rate, mold wear, alumina particle area ratio, It is shown in Table 1 below.
表１に示す密着性とは、１ポンドのハンマーに貼り付けたキムタオル（登録商標）を試料の防汚性皮膜の表面に載置し、往復１０回擦った後の防汚性皮膜の密着状態を観察した結果である。防汚性皮膜が剥離しない試料を◎、表層は剥離するが一層残る試料を○で示し、５０％程度剥離する試料を△で示し、１００％剥離が認められた試料を×で示した。
流水後親水性とは、試料に対し流量３Ｌ／ｍｉｎの常温流水に２４時間浸漬した後の防汚性皮膜表面の接触角を測定した結果である。接触角が２０゜以下の試料を○で示し、接触角が２０゜を超えた試料を×で示した。
乾湿サイクル後接触角とは、試料に対し流量３Ｌ／ｍの常温流水に２４時間浸漬した後、８０℃×１６時間乾燥を交互に１４サイクル行った後の防汚性皮膜表面の接触角を測定した結果である。接触角４０゜以下の試料を○で示し、接触角４０゜を超える試料を×で示した。
The adhesion shown in Table 1 refers to the adhesion state of the antifouling film after the Kim Towel (registered trademark) affixed to a 1 pound hammer is placed on the surface of the antifouling film of the sample and rubbed 10 times. It is the result of having observed. A sample in which the antifouling film was not peeled was indicated by ◎, a sample that peeled off the surface layer but remained was indicated by ◯, a sample that was peeled about 50% was indicated by Δ, and a sample in which 100% peeling was observed was indicated by ×.
The hydrophilicity after running water is the result of measuring the contact angle of the antifouling film surface after being immersed in room temperature running water at a flow rate of 3 L / min for 24 hours. A sample having a contact angle of 20 ° or less is indicated by ◯, and a sample having a contact angle exceeding 20 ° is indicated by ×.
The contact angle after dry / wet cycle is the contact angle of the surface of the antifouling film after 14 cycles of alternating drying at 80 ° C. for 16 hours after being immersed in normal temperature flowing water at a flow rate of 3 L / m. It is the result. Samples having a contact angle of 40 ° or less were indicated by ◯, and samples having a contact angle of 40 ° or more were indicated by x.
耐汚染性を評価する耐汚染試験は、汚染物質としてバルミチン酸６ｇと試料とをビーカーの中に入れ、１００℃で６日間加熱暴露後の防汚性皮膜表面の接触角を測定した。接触角６０゜以下の試料を○で示し、接触角６０゜を超える試料を×で示した。
動摩擦係数は、バウデン式摩擦試験機を用い、プレス油を塗布しないで試料の防汚性皮膜表面に鋼球サイズφ９／３２の接触子を２００ｇの荷重で押し付け、試料を摺動（１サイクル）させたときの摩擦力を測定して。動摩擦係数を求めた。動摩擦係数が０．２以下の試料を○で示し、動摩擦係数が０．２を超えた試料を×で示した。
粉体付着率は、１００ｍｍ×１００ｍｍの試料（アルミニウムフィン材）を流量３Ｌ／ｍｉｎの常温流水に１時間浸漬後、ＪＩＳＺ８９０１で定められる試験用粉体１１種、１２種のそれぞれを試料の防汚性皮膜の表面に付着させて、画像解析により付着面積率を測定した。付着面積率が３％以下の試料を○で示し、付着面積率が３％を超える試料を×で示した。
In the stain resistance test for evaluating the stain resistance, 6 g of valmitic acid as a contaminant and a sample were placed in a beaker, and the contact angle of the antifouling film surface after exposure to heating at 100 ° C. for 6 days was measured. Samples having a contact angle of 60 ° or less are indicated by ◯, and samples having a contact angle of 60 ° or more are indicated by ×.
The dynamic friction coefficient was measured by using a Bowden friction tester, pressing a contact of steel ball size φ9 / 32 against the antifouling film surface of the sample with a load of 200 g without applying press oil, and sliding the sample (1 cycle) Measure the friction force when you let it go. The coefficient of dynamic friction was determined. A sample having a dynamic friction coefficient of 0.2 or less is indicated by ◯, and a sample having a dynamic friction coefficient exceeding 0.2 is indicated by ×.
The powder adhesion rate was determined by immersing a 100 mm x 100 mm sample (aluminum fin material) in room-temperature flowing water at a flow rate of 3 L / min for 1 hour, and then using 11 types and 12 types of test powders defined by JISZ8901 for antifouling of the sample. The adhesion area ratio was measured by image analysis. A sample having an adhesion area ratio of 3% or less is indicated by ◯, and a sample having an adhesion area ratio exceeding 3% is indicated by ×.
金型摩耗は、プレス加工で１００万回試料（アルミニウムフィン材）を切断し、金型（スリット刃）の摩耗状態を観察した。スリット刃の硬度はＨＲＣ３７〜４１のものを使用し、定量評価としてレーザー顕微鏡にて金型（スリット刃）の刃先の摩耗面積を測定し、２次元断面での摩耗面積が１００μｍ２以下の試料を○で示し、摩耗面積が１００μｍ２を超えた試料を×で示した。
アルミナ粒子の面積率は、定量評価としてレーザー顕微鏡にて防汚性皮膜の表面を対物レンズ１００倍で観察し、５０μｍ×５０μｍの視野での２値化した画像にて粒子解析によりアルミナ粒子の面積率を測定し、アルミナ粒子の面積率が９０％以上の試料を○印で示し、面積率が９０％未満の試料を×で示した。
For die wear, a sample (aluminum fin material) was cut 1 million times by press working, and the wear state of the die (slit blade) was observed. The hardness of the slit blade is HRC 37-41, and the wear area of the cutting edge of the die (slit blade) is measured with a laser microscope for quantitative evaluation. A sample with a wear area in a two-dimensional cross section of 100 μm 2 or less is used. A sample having a wear area exceeding 100 μm 2 is indicated by ×.
The area ratio of the alumina particles is determined by observing the surface of the antifouling film with a laser microscope with a 100 × objective lens as a quantitative evaluation, and analyzing the area of the alumina particles by binarized images in a 50 μm × 50 μm field of view. The sample with an area ratio of alumina particles of 90% or more was indicated by ◯, and the sample with an area ratio of less than 90% was indicated by x.
表１に示す結果から水系塗料の塗布量が０.３〜０.８ｇ／ｍ２の範囲となっているＮｏ.１〜Ｎｏ.１８の実施例試料は、塗膜の密着性に優れるとともに、流水後親水性と乾湿サイクル後接触角と耐汚染性と動摩擦係数と粉体付着率と金型摩耗と粒子面積率の試験のうち、多くの試験結果において優れ、バランスの良い特性を発揮した。
試料Ｎｏ.１〜１８において、水系塗料塗布量が０.３〜０.８ｇ／ｍ２の範囲であり、アルミナ添加量が塗料固形分中５〜４５質量％であり、フッ素樹脂添加量が塗料固形分中０.０５〜３.０質量％であるＮｏ.１〜１４の試料は全ての試験項目において優れた結果を示した。
From the results shown in Table 1, the examples of No. 1 to No. 18 in which the coating amount of the water-based paint is in the range of 0.3 to 0.8 g / m 2 are excellent in the adhesion of the coating film, Among the tests of hydrophilicity after running water, contact angle after dry / wet cycle, contamination resistance, dynamic friction coefficient, powder adhesion rate, mold wear and particle area rate, many of the test results showed excellent and well-balanced characteristics.
In sample Nos. 1 to 18, the amount of water-based paint applied is in the range of 0.3 to 0.8 g / m 2 , the amount of alumina added is 5 to 45% by weight in the solid content of the paint, and the amount of fluororesin added is paint Samples Nos. 1 to 14 having a solid content of 0.05 to 3.0% by mass showed excellent results in all test items.
これらの実施例試料に対し、アルミナ粒子添加量の多すぎる試料Ｎｏ.１９、２０は、動摩擦係数が大きく、金型摩耗、粒子面積率で結果が悪く、水系塗料塗布量が少ない比較例試料Ｎｏ.２１は、流水後親水性と乾湿サイクル後接触角と耐汚染性が悪化した。また、水系塗料塗布量が多すぎる比較例試料Ｎｏ.２３、２４は密着性に問題を生じた。 Sample Nos. 19 and 20 in which the amount of alumina particles added is too large compared to these example samples. Comparative Sample No. 19 and 20 have a large dynamic friction coefficient, poor results in mold wear and particle area ratio, and a small amount of aqueous paint coating. .21 deteriorated hydrophilicity after running water, contact angle after wet / dry cycle, and contamination resistance. Moreover, comparative example sample No. 23 and 24 with too much water-system paint application amount produced the problem in adhesiveness.
図２は表１の実施例Ｎｏ.３の試料表面に形成した防汚性皮膜に含まれているアルミナ粒子とフッ素粒子を示す顕微鏡写真である。
先の尖った凸部を複数有する不定形の多数のアルミナ粒子が米粒状のフッ素樹脂粒子とともに混在された状態を呈している。これらの粒子が樹脂層の内部に埋設された構造が防汚性皮膜の概略構造となっていることがわかる。
FIG. 2 is a photomicrograph showing alumina particles and fluorine particles contained in the antifouling film formed on the sample surface of Example No. 3 in Table 1.
A large number of amorphous alumina particles having a plurality of pointed convex portions are mixed together with rice-like fluororesin particles. It can be seen that the structure in which these particles are embedded in the resin layer is a schematic structure of the antifouling film.
次に、先の実施例において用いた平均粒子径０．８μｍのアルミナ粒子に替えて、平均粒子径の異なるアルミナ粒子を含む複数のアルミナゾルを用い、各アルミナゾルに前記実施例と同等の水溶性アクリル樹脂とポリエチレングリコールとフッ素樹脂粒子を混合して水系塗料を作製した。これらの塗料を用いて先の実施例と同等のリン酸クロメート処理済みのアルミニウム合金板に塗膜を形成し、先の実施例と同等の条件で焼き付けて防汚性塗膜を形成した。水系塗料の塗布量を０．６ｇ／ｍ２、アルミナ粒子添加量を３０質量％、フッ素樹脂粒子添加量を１．０％に設定した。
得られた各防汚性塗膜の防汚性、臭気性、金型摩耗性について試験した。それらの結果を以下の表２に記載する。
Next, instead of the alumina particles having an average particle diameter of 0.8 μm used in the previous examples, a plurality of alumina sols containing alumina particles having different average particle diameters were used, and each of the alumina sols had the same water-soluble acrylic as in the previous examples. A water-based paint was prepared by mixing resin, polyethylene glycol, and fluororesin particles. Using these paints, a coating film was formed on a phosphoric acid chromate-treated aluminum alloy plate equivalent to the previous example, and baked under the same conditions as in the previous example to form an antifouling coating film. The coating amount of the water-based paint was set to 0.6 g / m 2 , the alumina particle addition amount was set to 30% by mass, and the fluororesin particle addition amount was set to 1.0%.
Each antifouling coating film thus obtained was tested for antifouling properties, odor properties, and mold wear properties. The results are listed in Table 2 below.
臭気性については、熱交換器組み付け後に１０人のパネラーにて官能臭気評価を実施した。判定は６段階評価（０：無臭、１：やっと臭い感知、２：何の臭いかわかる、３：楽に臭い感知、４：臭い強い、５：臭い強烈）して、評価基準２以下が○、２以上を×とし、１０人の平均値にて評価した。
表２に示すように、臭気性については、粒子径が最も小さい０．０１μｍのものが臭気性が悪く、粒子径が最も小さいものは比表面積が大きいことによって、吸着臭が発生したと思われる。また、金型摩耗性については、粒子径が大きいもので悪い結果を示したが、粒子径が大きいことによって、ブツ等の塗膜欠陥や粒子の凝集が生じたことによって、金型摩耗性が悪化した。
About odor property, sensory odor evaluation was implemented in 10 panelists after the heat exchanger assembly | attachment. Judgment is made on a 6-point scale (0: no odor, 1: finally smell detection, 2: what the smell is, 3: easy smell detection, 4: strong smell, 5: strong smell), the evaluation criteria 2 and below are ○, Two or more were evaluated as x, and the average value of 10 people was evaluated.
As shown in Table 2, regarding the odor, the one with the smallest particle size of 0.01 μm has poor odor, and the one with the smallest particle size has a large specific surface area, which seems to have caused an adsorption odor. . In addition, as for mold wear, the particle size was large and showed a bad result. However, due to the large particle size, coating film defects such as bumps and agglomeration of particles occurred, resulting in mold wear. It got worse.
表２に示す結果から、アルミナ粒子平均粒子径に係わらず防汚性の面で優れた結果を得られるものの、アルミナ粒子の平均粒子径が小さすぎる場合は臭気性に問題を生じ、アルミナ粒子の平均粒子径が大きすぎる場合は金型摩耗の面で問題を生じた。 From the results shown in Table 2, although excellent results in terms of antifouling properties can be obtained regardless of the average particle size of alumina particles, if the average particle size of the alumina particles is too small, there is a problem in odor, When the average particle size was too large, there was a problem in terms of mold wear.
１…熱交換器用フィン材、２…基材、３…化成皮膜、５…防汚性皮膜。 DESCRIPTION OF SYMBOLS 1 ... Fin material for heat exchangers, 2 ... Base material, 3 ... Chemical conversion film, 5 ... Antifouling film.
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