JPH10218909A - Organic/inorganic composite particle, coating material containing the same and aluminum fin material coated with the coating material - Google Patents
Organic/inorganic composite particle, coating material containing the same and aluminum fin material coated with the coating materialInfo
- Publication number
- JPH10218909A JPH10218909A JP2014897A JP2014897A JPH10218909A JP H10218909 A JPH10218909 A JP H10218909A JP 2014897 A JP2014897 A JP 2014897A JP 2014897 A JP2014897 A JP 2014897A JP H10218909 A JPH10218909 A JP H10218909A
- Authority
- JP
- Japan
- Prior art keywords
- organic
- inorganic composite
- composite particles
- water
- alumina sol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Polymerisation Methods In General (AREA)
- Paints Or Removers (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、有機無機複合粒子
及びこれを含有する塗料に関する。詳しくは、空調機用
熱交換器のアルミニウムフィン表面に高度な親水性の持
続性・耐蝕性を付与し、さらには臭気吸着の極めて少な
く、穴開け加工の際の金型磨耗の少ない好適な高親水性
塗料に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to organic-inorganic composite particles and a paint containing the same. More specifically, the aluminum fin surface of the heat exchanger for air conditioners is provided with a high degree of hydrophilicity and durability and corrosion resistance. It relates to a hydrophilic paint.
【０００２】[0002]
【従来の技術】従来、空調機の熱交換器にはその優れた
加工性・熱伝導性の点からアルミニウムおよびその合金
が広く利用されている。その構成は、基本的に、隣接す
る複数のフィン（比較的薄い板）を有する。空調機の熱
交換器では、冷房時に発生する凝縮水が水滴となってフ
ィンに付着するのは避け難く、その水滴によって、隣接
するフィン間に水のブリッジを形成されやすい。その場
合、水のブリッジが通風を遮り、通風抵抗を増大せし
め、熱交換率を悪化させる。従って、フィン材の表面に
親水化処理を施し、水滴によるブリッジの形成を抑制・
防止し、良好な熱交換率の維持を図っている。一方、近
年、家電製品には小型化が強く求められ、空調機も例外
ではない。特に空調機の中でも大容積を占める熱交換器
には最も強く小型化が求められ、フィン形状の複雑化、
フィン間隔の狭小化が望まれ、フィン材にはより一層の
親水性が求められている。2. Description of the Related Art Conventionally, aluminum and its alloys have been widely used for heat exchangers of air conditioners because of their excellent workability and thermal conductivity. The arrangement basically has a plurality of adjacent fins (relatively thin plates). In a heat exchanger of an air conditioner, it is inevitable that condensed water generated during cooling becomes water droplets and adheres to the fins, and the water droplets tend to form a water bridge between adjacent fins. In that case, the water bridge blocks the ventilation, increases the ventilation resistance, and deteriorates the heat exchange rate. Therefore, the surface of the fin material is subjected to a hydrophilic treatment to suppress the formation of bridges due to water droplets.
Prevention and maintain a good heat exchange rate. On the other hand, in recent years, downsizing of home appliances has been strongly demanded, and air conditioners are no exception. In particular, heat exchangers, which occupy a large volume among air conditioners, are required to be the strongest and are downsized.
It is desired to reduce the fin spacing, and fin materials are required to be more hydrophilic.
【０００３】アルミニウムフィンに親水性を付与する方
法には、化成処理、新水性塗料をとする等の方法があ
る。前者の化成処理は一般的に、冷媒の流れるパイプを
通すために穴空け等のフィン加工をした後に施されるた
め、生産性に劣るという欠点を有していた。Methods for imparting hydrophilicity to aluminum fins include methods such as chemical conversion treatment and use of a new water-based paint. The former chemical conversion treatment is generally performed after performing fin processing such as drilling for passing a pipe through which a refrigerant flows, and thus has a disadvantage of poor productivity.
【０００４】この問題点を解決するために、フィン加工
前にフィンを水ガラスや親水性塗料により被覆する方法
が提案された。このような親水性塗料としては、有機親
水性樹脂からなる塗料や合成シリカ等の無機粒子を含有
する塗料等が挙げられる。[0004] In order to solve this problem, a method has been proposed in which the fins are coated with water glass or a hydrophilic paint before the fins are processed. Examples of such a hydrophilic paint include a paint made of an organic hydrophilic resin and a paint containing inorganic particles such as synthetic silica.
【０００５】しかし、有機親水性樹脂、例えば水性ナイ
ロン、水性アクリル樹脂、ポリビニルアルコール、ポリ
ビニルピロリドン等を用いた場合は、親水性が不十分だ
ったり、親水性と耐蝕性のバランスがとれなかったりと
いった問題点を有していた。一方、親水性を付与するた
めに合成シリカ等を含有する塗料を用いた場合には、親
水性や耐蝕性は有機親水性樹脂を用いた塗料よりは優れ
ているが、塗膜が硬いため穴空け等の加工に用いる金型
・加工工具等の摩耗が激しく工具の寿命が短くなるとい
う問題点や、臭気抑制（防止）効果が不十分だったりと
いった問題点を有していた。However, when an organic hydrophilic resin such as aqueous nylon, aqueous acrylic resin, polyvinyl alcohol, polyvinylpyrrolidone, or the like is used, the hydrophilicity is insufficient, or the hydrophilicity and the corrosion resistance cannot be balanced. Had problems. On the other hand, when a coating containing synthetic silica or the like is used to impart hydrophilicity, hydrophilicity and corrosion resistance are superior to coatings using an organic hydrophilic resin, but since the coating film is hard, a hole is formed. There have been problems such as the severe wear of the molds and processing tools used for processing such as blanking, shortening the service life of the tools, and the problem of insufficient odor control (prevention).
【０００６】また、水ガラス系塗料を塗布した場合に
は、合成シリカ等を含有する塗料を用いた場合と同様
に、金型・加工工具等の摩耗が激しく工具の寿命が短く
なるという問題点、あるいは空調機使用時にシリカ臭が
する等の問題点を有していた。Further, when a water glass based paint is applied, as in the case where a paint containing synthetic silica or the like is used, the abrasion of a mold or a processing tool is severe and the life of the tool is shortened. In addition, there was a problem that silica odor was emitted when the air conditioner was used.
【０００７】上記のような問題点に対し、親水性、防食
性に優れ、工具の寿命を短くしないような比較的軟らか
い塗膜を与える塗料が望まれ、種々の塗料が提案されて
きた。例えば、合成シリカ等を含有しないで、アルミナ
ゾルやアルミナを含有するものが、特開昭５７−１３４
５７２号公報、特開昭５８−７６４６２号公報、特開昭
５９−２０５５９６号公報、特開昭５９−２２９１９７
号公報、特開昭６０−１６４１６８号公報、特開昭６３
−２４９６４３号公報、特開昭６３−２６２２３８号公
報、特開昭６３−２６２２３９号公報、特開平２−２２
０４７号、特開平５−７０７１１号公報、特開平６−１
７２７７７号公報等いくつか提案されているが、親水性
の点でまだ満足のいくものではなかった。In view of the above-mentioned problems, paints which are excellent in hydrophilicity and corrosion resistance and which provide a relatively soft coating film which does not shorten the life of the tool are desired, and various paints have been proposed. For example, the one containing alumina sol or alumina without containing synthetic silica or the like is disclosed in Japanese Patent Application Laid-Open No. 57-134.
572, JP-A-58-76462, JP-A-59-205596, JP-A-59-229197.
JP, JP-A-60-164168, JP-A-60-164168
JP-A-249643, JP-A-63-262238, JP-A-63-262239, and JP-A-2-22.
047, JP-A-5-70711, JP-A-6-1
Some proposals have been made, such as 72777, but they have not been satisfactory in terms of hydrophilicity.
【０００８】また親水性架橋重合体微粒子を含有する塗
料が特開平８−３２５１号公報に、親水性架橋重合体微
粒子、水溶性樹脂、架橋剤よりなる組成物が特開平７−
２６８２７４号公報に提案されている。しかし、係る場
合も、親水性やその持続性の点でまだ満足のいくもので
はなかった。A coating containing hydrophilic crosslinked polymer fine particles is disclosed in JP-A-8-3251, and a composition comprising hydrophilic crosslinked polymer fine particles, a water-soluble resin and a crosslinking agent is disclosed in JP-A-7-325.
268274. However, even in such a case, it was not yet satisfactory in terms of hydrophilicity and its persistence.
【０００９】[0009]
【解決しようとする課題】本発明は、親水性・耐蝕性に
優れ、穴開け加工の際に金型磨耗しないような比較的軟
らかい塗膜を与える非シリカ系または非水ガラス系の高
親水性塗料を提供することを目的とする。DISCLOSURE OF THE INVENTION The present invention provides a non-silica-based or non-aqueous glass-based high hydrophilicity which is excellent in hydrophilicity and corrosion resistance and provides a relatively soft coating film which does not wear the mold during drilling. It is intended to provide a paint.
【００１０】[0010]
【課題を解決するための手段】すなわち、第１の発明
は、０．０２〜２μｍのアルミナゾル（ａ）の存在下
に、下記一般式〔１〕または〔２〕で示される親水性単
量体（ｂ）を少なくとも１種類以上と多官能エチレン性
不飽和単量体（ｃ）とを共重合させてなる有機無機複合
粒子である。That is, a first aspect of the present invention relates to a hydrophilic monomer represented by the following general formula [1] or [2] in the presence of 0.02 to 2 μm alumina sol (a). Organic-inorganic composite particles obtained by copolymerizing (b) at least one kind and a polyfunctional ethylenically unsaturated monomer (c).
【化３】 Embedded image
【００１１】第２の発明は、０．０２〜２ｍμのアルミ
ナゾル（ａ）の存在下に、下記一般式〔１〕または
〔２〕で示される親水性単量体（ｂ）を少なくとも１種
類以上と多官能エチレン性不飽和単量体（ｃ）と、上記
（ｂ）（ｃ）と共重合可能なその他のエチレン性不飽和
単量体（ｄ）とを共重合させてなる有機無機複合粒子で
ある。In a second aspect, at least one kind of a hydrophilic monomer (b) represented by the following general formula (1) or (2) is used in the presence of 0.02 to 2 mμ of alumina sol (a). Organic-inorganic composite particles obtained by copolymerizing a polyfunctional ethylenically unsaturated monomer (c) with another ethylenically unsaturated monomer (d) copolymerizable with the above (b) and (c) It is.
【化４】 Embedded image
【００１２】第３の発明は、アルミナゾル（ａ）の一次
粒子が羽毛状、棒状、樹枝状の形状・形態を有すること
を特徴とする第１の発明または第２の発明記載の有機無
機複合粒子である。A third invention is directed to the organic-inorganic composite particles according to the first invention or the second invention, wherein the primary particles of the alumina sol (a) have a feather-like, rod-like, or dendritic shape and form. It is.
【００１３】第４の発明は、有機無機複合粒子の平均粒
径が、０．５〜５μｍであることを特徴とする第１の発
明ないし第３の発明記載の有機無機複合粒子である。A fourth aspect of the present invention is the organic-inorganic composite particles according to the first to third aspects, wherein the average particle size of the organic-inorganic composite particles is 0.5 to 5 μm.
【００１４】第５の発明は、懸濁重合によって得られる
ことを特徴とする第１の発明ないし第４の発明いずれか
記載の有機無機複合粒子である。A fifth invention is the organic-inorganic composite particle according to any one of the first to fourth inventions, which is obtained by suspension polymerization.
【００１５】第６の発明は、多官能エチレン性不飽和単
量体（ｃ）が、ポリオキシエチレンジメタクリレ−ト、
ポリオキシエチレンジアクリレ−ト、メチレンビスアク
リルアミド、メチレンビスメタアクリルアミド、ジビニ
ルベンゼン、ジアリルテレフタレ−トから選ばれる少な
くとも１種または１種以上であることを特徴とする第１
の発明ないし第５の発明いずれか記載の有機無機複合粒
子である。In a sixth aspect, the polyfunctional ethylenically unsaturated monomer (c) is a polyoxyethylene dimethacrylate,
At least one or more selected from polyoxyethylene diacrylate, methylenebisacrylamide, methylenebismethacrylamide, divinylbenzene and diallyl terephthalate;
The organic-inorganic composite particles according to any one of the inventions to the fifth invention.
【００１６】第７の発明は、第１の発明ないし第６の発
明いずれか記載の有機無機複合粒子と、水溶性樹脂とを
含有することを特徴とする高親水性塗料である。A seventh invention is a highly hydrophilic paint containing the organic-inorganic composite particles according to any one of the first invention to the sixth invention, and a water-soluble resin.
【００１７】第８の発明は、第７の発明記載の高親水性
塗料をアルミニウム基材に塗布し、硬化してなるアルミ
ニウムフィン材である。An eighth invention is an aluminum fin material obtained by applying the highly hydrophilic paint according to the seventh invention to an aluminum substrate and curing the coating.
【００１８】[0018]
【発明の実施の形態】アルミナゾルは、アルミナ水和物
の水性分散体であり、アルミナ水和物はアルミナに比べ
て柔らかく、その分散粒子は一般的には０．０２〜０．
２μｍ程度のコロイドの如き大きさを呈することが多い
が、本発明においては一般的なアルミナゾルの分散粒子
に比してかなり大きな０．０２〜２μｍ程度の大きさの
ものまで使い得る。本発明に用いられるアルミナゾルと
しては、具体的には触媒化成工業（株）「カタロイドＡ
Ｓ−１」（平均粒径０．２μｍ）、「カタロイドＡＳ−
２」（平均粒径０．２μｍ）、日産化学工業（株）製
「アルミナゾル−１００」（平均粒径０．２μｍ）、
「アルミナゾル−２００」（平均粒径０．２μｍ）、
「アルミナゾル−５２０」（平均粒径０．０２μｍ）、
川研ファイケミカル（株）製「アルミナクリア−ゾル」
（平均粒径０．０２μｍ）、「アルミゾル−１０」（平
均粒径０．０２μｍ）が挙げられる。また通常のものよ
りかなり大きい粒径を有するものとしては、具体的には
触媒化成工業（株）製「カタロイドＡＳ−３」（平均粒
径０．８μｍ）が挙げられる。触媒化成工業（株）製
「カタロイドＡＰ−３」（乾燥平均粒径２０〜５０μ
ｍ）は、「カタロイドＡＳ−３」をスプレードライ等の
方法によって乾燥せしめたものであり、乾燥時の平均粒
径は上記した通りであるが、容易に水に再分散し、元の
分散粒子の平均粒径０．８μｍを示すので、「カタロイ
ドＡＰ−３」の水分散体は、「カタロイドＡＳ−３」と
同様に用いることができる。DESCRIPTION OF THE PREFERRED EMBODIMENTS Alumina sol is an aqueous dispersion of hydrated alumina. Alumina hydrate is softer than alumina, and its dispersed particles generally have a particle size of 0.02 to 0.1.
In many cases, the colloid has a size of about 2 μm like a colloid, but in the present invention, a particle having a size of about 0.02 to 2 μm, which is considerably larger than the dispersed particles of general alumina sol, can be used. As the alumina sol used in the present invention, specifically, "Cataroid A"
S-1 "(average particle size 0.2 μm)," Cataloid AS-
2 "(average particle size 0.2 μm)," Alumina Sol-100 "(Nissan Chemical Industries, Ltd.) (average particle size 0.2 μm),
“Alumina sol-200” (average particle size 0.2 μm),
“Alumina sol-520” (average particle size 0.02 μm),
"Alumina clear sol" manufactured by Kawaken Fai Chemical Co., Ltd.
(Average particle diameter 0.02 μm) and “Aluminum sol-10” (average particle diameter 0.02 μm). Further, as a material having a particle size considerably larger than that of a normal product, specifically, "Cataloid AS-3" (average particle size: 0.8 [mu] m) manufactured by Catalyst Chemical Industry Co., Ltd. can be mentioned. "Cataloid AP-3" (Catalyzed Chemical Industry Co., Ltd.)
m) is obtained by drying “Cataloid AS-3” by a method such as spray drying. The average particle size upon drying is as described above. Since the average particle diameter is 0.8 μm, the aqueous dispersion of “Cataloid AP-3” can be used in the same manner as “Cataloid AS-3”.
【００１９】本発明に用いられるアルミナゾル（ａ）
は、一次粒子が羽毛状、棒状、又は樹枝状であることが
好ましい。上記のような形状・形態であると、塗膜表面
の表面積を著しく増大し、さらにまたアルミナゾルの分
散粒子の微少細孔による毛管現象などにより塗膜の親水
性を助長するのでアルミフィン用の塗料として好まし
い。係る形状・形態のアルミナゾル（ａ）としては、日
産化学工業（株）製「アルミナゾル−２００」が挙げら
れる。Alumina sol (a) used in the present invention
It is preferable that the primary particles have a feather shape, a rod shape, or a dendritic shape. With the shape and form as described above, the surface area of the coating film surface is significantly increased, and further, the hydrophilicity of the coating film is promoted by capillary action due to the fine pores of the dispersed particles of alumina sol. Is preferred. Examples of the alumina sol (a) having such a shape and form include “Alumina Sol-200” manufactured by Nissan Chemical Industries, Ltd.
【００２０】本発明に用いられるアルミナゾル（ａ）
は、その分散粒子が不定型ゲルからベーマイトに移行す
る途中の段階にあり、この状態は凝集過程および通常の
塗膜の焼付け条件（例えば、２５０℃×２０秒）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等の分散粒子は、コロイ
ダルシリカやアルミナと比較して軟らかく、従って、こ
のアルミナゾル等の分散粒子を含有する塗膜を加工する
際のプレス加工機の刃の磨耗も極めて少ない。Alumina sol (a) used in the present invention
Is in the middle of the transition of the dispersed particles from the irregular gel to boehmite, and this state does not change during the aggregating process and the normal baking conditions of the coating film (for example, 250 ° C. × 20 seconds). Dispersed particles such as alumina sol during the transition from the irregular gel to boehmite are softer than colloidal silica or alumina, and therefore, are subjected to press working when processing a coating film containing the dispersed particles such as alumina sol. Very little wear on the machine blades.
【００２１】本発明の有機無機複合粒子は、上記アルミ
ナゾル（ａ）の存在下に、下記一般式〔１〕または
〔２〕で示される親水性単量体（ｂ）を少なくとも１種
類以上と多官能エチレン性不飽和単量体（ｃ）とを共重
合させてなるか、あるいは上記（ｂ）（ｃ）と共重合可
能なその他のエチレン性不飽和単量体（ｄ）とを共重合
させてなる有機無機複合粒子である。The organic-inorganic composite particles of the present invention contain as many as at least one hydrophilic monomer (b) represented by the following general formula (1) or (2) in the presence of the alumina sol (a). Either copolymerized with the functional ethylenically unsaturated monomer (c) or copolymerized with the other ethylenically unsaturated monomer (d) copolymerizable with the above (b) and (c). Organic-inorganic composite particles.
【化５】 Embedded image
【００２２】本発明の有機無機複合粒子は、主としてそ
の表面にアルミナゾル（ａ）が分布し、有機無機複合粒
子と水溶性樹脂とを含有する高親水性塗料は、有機無機
複合粒子表面のアルミナゾル（ａ）を連続相である水溶
性樹脂が被覆して親水性官能基を留め、水に対する濡れ
性を発現せしめるものである。さらに有機無機複合粒子
のコア−シエル構造が塗膜の比表面積を大きくするとと
もに、毛細管現象によって水に対する濡れ性の向上に二
重に寄与している。In the organic-inorganic composite particles of the present invention, alumina sol (a) is mainly distributed on the surface thereof, and the highly hydrophilic paint containing the organic-inorganic composite particles and the water-soluble resin is used as the alumina sol (A) on the surface of the organic-inorganic composite particles. a) is coated with a water-soluble resin, which is a continuous phase, to retain hydrophilic functional groups and develop wettability with water. Further, the core-shell structure of the organic-inorganic composite particles increases the specific surface area of the coating film, and double contributes to the improvement of wettability to water by a capillary phenomenon.
【００２３】一般式〔１〕で示される親水性単量体
（ｂ）のうち、Ｒ3 は水素原子又は炭素数１〜４のアル
キレン基であるが、水素原子又は炭素数１のアルキレン
基であることが好ましい。また、Ｒ4 は水素原子又は炭
素数１〜４のアルキル基であるが、水素原子又は炭素数
１のアルキル基であることが好ましい。また、一般式
〔２〕で示される親水性単量体（ｂ）を少なくとも１種
のうち、Ｒ7 は水素原子又は炭素数１〜４のアルキル基
であるが、水素原子又は炭素数１のアルキル基であるこ
とが好ましい。ｎは１〜５０であるが、１〜２０である
ことが好ましい。In the hydrophilic monomer (b) represented by the general formula [1], R 3 is a hydrogen atom or an alkylene group having 1 to 4 carbon atoms, but is a hydrogen atom or an alkylene group having 1 carbon atom. Preferably, there is. R 4 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 carbon atom. Further, among at least one kind of the hydrophilic monomer (b) represented by the general formula [2], R 7 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. It is preferably an alkyl group. n is 1 to 50, preferably 1 to 20.
【００２４】本発明において用いられる多官能エチレン
性不飽和単量体（ｃ）としては、ポリオキシエチレンジ
メタクリレート、ポリオキシエチレンジアクリレート、
メチレンビスアクリルアミド、メチレンビスメタアクリ
ルアミド、ジビニルベンゼン、ジアリルテレフタレート
等が挙げられる。The polyfunctional ethylenically unsaturated monomer (c) used in the present invention includes polyoxyethylene dimethacrylate, polyoxyethylene diacrylate,
Examples include methylene bisacrylamide, methylenebismethacrylamide, divinylbenzene, diallyl terephthalate, and the like.
【００２５】本発明において用いられる（ｂ）（ｃ）と
共重合可能なその他のエチレン性不飽和単量体（ｄ）と
しては、低級アルキルアクリレート又はメタクリレート
が挙げられ、その単独重合体のガラス転移点が比較的高
いものが好ましく、例えばメチルアクリレート、エチル
アクリレート、メチルメタクリレート、エチルメタクリ
レート、またスチレンなどが挙げられる。The other ethylenically unsaturated monomers (d) copolymerizable with (b) and (c) used in the present invention include lower alkyl acrylates or methacrylates. Those having relatively high points are preferable, and examples thereof include methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, and styrene.
【００２６】本発明においては、有機無機複合粒子が粗
大粒子にならないようにするためには、複合粒子中のア
ルミナゾル分散粒子の重量含有率が５〜４０％望ましく
は２０〜３０％であることが好ましい。In the present invention, in order to prevent the organic-inorganic composite particles from becoming coarse particles, the weight content of the alumina sol-dispersed particles in the composite particles is preferably 5 to 40%, more preferably 20 to 30%. preferable.
【００２７】アルミナゾル（ａ）は、その分散粒子が酢
酸・硝酸などの酸イオンにより安定化されているカチオ
ン性水分散体であるので、共重合に際し、構成単量体に
アニオン性物質−例えばカルボキシル基を有する単量
体、スルホン酸やそのナトリウム塩を有する単量体等を
含有すると凝集し粗大粒子を形成し易いので、上記のよ
うな単量体は使用しないことが好ましい。The alumina sol (a) is a cationic aqueous dispersion in which the dispersed particles are stabilized by acid ions such as acetic acid and nitric acid. When a monomer having a group, a monomer having a sulfonic acid or a sodium salt thereof, or the like is contained, it is easy to aggregate and form coarse particles, so that it is preferable not to use the above-mentioned monomer.
【００２８】本発明の高親水性塗料に用いられる有機無
機複合粒子は、平均粒径０．５〜５μｍであることが望
ましいので、懸濁重合によって得ることが好ましい。懸
濁重合によって得られる粒子の粒度分布は、一般に広が
る傾向にあるので、大きな粒子を含有する場合には、遠
心分離または濾過等の手段によって分級してから用いる
ことができる。本発明の高親水性塗料は、上記のような
有機無機複合粒子を用いることによって、膜厚が０．５
〜２μｍ程度の塗膜の表面を粗面化して水との接触表面
積を大きくし、親水性を向上せしめたものである。平均
粒径が０．５μｍより小さい有機無機複合粒子は塗膜に
埋もれてしまい、一方平均粒径が５μｍより大きいもの
はブツ等の塗膜欠陥となり、いずれもアルミニウムフィ
ン用の高親水性塗料使用に適さない。The organic-inorganic composite particles used in the highly hydrophilic paint of the present invention preferably have an average particle size of 0.5 to 5 μm, and are preferably obtained by suspension polymerization. Since the particle size distribution of particles obtained by suspension polymerization generally tends to spread, when large particles are contained, they can be used after being classified by means such as centrifugation or filtration. The highly hydrophilic paint of the present invention has a thickness of 0.5 by using the organic-inorganic composite particles as described above.
The surface of the coating film having a thickness of about 2 μm is roughened to increase the contact surface area with water, thereby improving the hydrophilicity. Organic-inorganic composite particles having an average particle size of less than 0.5 μm are buried in the coating film, while those having an average particle size of more than 5 μm result in coating defects such as bumps, all of which use a highly hydrophilic paint for aluminum fins. Not suitable for
【００２９】本発明に用いられる有機無機複合粒子は、
塗料固形分１００重量部中、０．１〜５０重量部含有す
ることが望ましい。０．１重量部未満だと、親水性の点
で不十分であり、５０重量部を超えると粘度が増大し塗
装性が悪くなる。The organic-inorganic composite particles used in the present invention are:
It is desirable to contain 0.1 to 50 parts by weight based on 100 parts by weight of the solid content of the paint. If the amount is less than 0.1 part by weight, the hydrophilicity is insufficient, and if the amount is more than 50 parts by weight, the viscosity increases and the coatability deteriorates.
【００３０】本発明に用いられる水溶性樹脂は、基材に
本質的に親水性の塗膜を形成し、有機無機複合粒子を該
塗膜中に固定するために配合するものである。例えば、
セルロース系、アクリル系、ポリウレタン系、ポリエス
テル系、ポリエーテルポリオール系、ポリアミド系、エ
ポキシ樹脂系等の水溶性樹脂１種又は２種以上の混合系
が挙げられ、アクリル系樹脂が好適に用いられる。アク
リル系樹脂としては、アニオン系、カチオン系いずれも
使用できる。カチオン系アクリル樹脂は、アルミナゾル
等との相溶性が良い点では好ましいが、樹脂の水溶化に
際し酸を使用するので生産設備の腐食等が懸念される。
一方、アニオン系アクリル系樹脂は、アルミナゾルとの
相溶性の点でカチオン性のものにはやや劣るが、樹脂の
水溶化に際しアンモニアやアミン化合物を使用し、酸を
使用しないので生産設備の保守管理の点からは好まし
い。硬化剤として、イミノ・メチロール型の水溶性メラ
ミン樹脂については多量に添加すると水濡れ性を著しく
悪化させるが、塗料固形分１００重量部に対して１〜１
０部程度であれば混合しても差し支えない。The water-soluble resin used in the present invention is used for forming an essentially hydrophilic coating film on a substrate and fixing the organic-inorganic composite particles in the coating film. For example,
One or a mixture of two or more water-soluble resins such as a cellulose-based, acrylic-based, polyurethane-based, polyester-based, polyether-polyol-based, polyamide-based, and epoxy resin-based resin may be used, and an acrylic resin is preferably used. As the acrylic resin, both anionic and cationic resins can be used. Cationic acrylic resins are preferred in that they have good compatibility with alumina sol and the like, but there is a concern about corrosion of production equipment and the like since an acid is used when the resin is made water-soluble.
On the other hand, anionic acrylic resins are slightly inferior to cationic ones in terms of compatibility with alumina sol, but use ammonia or amine compounds when solubilizing the resin and use no acid, so maintenance of production equipment It is preferable from the point of view. As a curing agent, a large amount of imino-methylol-type water-soluble melamine resin significantly deteriorates water wettability when added in a large amount.
If it is about 0 parts, mixing may be performed.
【００３１】水溶性樹脂は、塗料固形分１００重量部
中、５０〜９９．９重量部含有することが望ましい。５
０重量部未満だと相対的に有機無機複合粒子の含有量が
大きくなると粘度が増大し塗装性が悪くなる。一方、９
９．９重量部を超えると相対的に有機無機複合ゲル粒子
の含有量が小さくなり、親水性が不十分になる。The water-soluble resin is desirably contained in an amount of 50 to 99.9 parts by weight based on 100 parts by weight of the solid content of the paint. 5
If the amount is less than 0 parts by weight, if the content of the organic-inorganic composite particles becomes relatively large, the viscosity increases, and the coating property deteriorates. On the other hand, 9
If it exceeds 9.9 parts by weight, the content of the organic-inorganic composite gel particles becomes relatively small, and the hydrophilicity becomes insufficient.
【００３２】本発明の高親水性塗料には、有機無機複合
粒子、水溶性樹脂以外に、必要に応じて水分散性樹脂、
界面活性剤、親水性の有機粒子または無機粒子、抗菌
剤、滑剤、消泡剤、着色剤、酸化防止剤、溶剤等を配合
しても良い。The highly hydrophilic coating material of the present invention contains, in addition to the organic-inorganic composite particles and the water-soluble resin, a water-dispersible resin, if necessary.
A surfactant, hydrophilic organic or inorganic particles, an antibacterial agent, a lubricant, an antifoaming agent, a coloring agent, an antioxidant, a solvent and the like may be blended.
【００３３】本発明の高親水性塗料は、アルミニウムフ
ィン材に塗装するプレコート塗料として用いられること
ができるほかに、加工されたフィンに塗装するポストコ
ート塗料としても使用することができる。The highly hydrophilic paint of the present invention can be used not only as a precoat paint applied to an aluminum fin material, but also as a postcoat paint applied to a processed fin.
【００３４】[0034]
【実施例】次に実施例により本発明を説明する。 合成例１（有機無機複合粒子の合成例） １０００ｃｃの三つ口フラスコにエタノール３４４ｇ、
イオン交換水８６ｇを仕込み、攪拌しながらアルミナゾ
ル−２００（日産化学（株）製：平均粒径０．２μｍ）
１２０ｇ（不揮発分１２ｇ）を３０分間かけて滴下す
る。アクリルアミド２６ｇとエチレンビスアクリルアミ
ド２２ｇを仕込み８０℃に加熱する。アゾビスイソブチ
ロニトリル１．０ｇ添加して重合を開始し、２時間後に
アゾビスイソブチロニトリル０．５ｇを添加し４時間反
応後重合を終了し、有機無機複合粒子を得た。得られ
た有機無機複合粒子の平均粒径を日機装（株）製マイ
クロトラックＭＫ−II型粒度分析計にて求めたところ、
３．０μｍであった。Next, the present invention will be described by way of examples. Synthesis Example 1 (Synthesis example of organic-inorganic composite particles) In a 1000 cc three-necked flask, 344 g of ethanol was added.
86 g of ion-exchanged water is charged and alumina sol-200 (manufactured by Nissan Chemical Co., Ltd .: average particle size 0.2 μm) with stirring.
120 g (12 g of non-volatile components) are added dropwise over 30 minutes. 26 g of acrylamide and 22 g of ethylenebisacrylamide are charged and heated to 80 ° C. Polymerization was started by adding 1.0 g of azobisisobutyronitrile, and after 2 hours, 0.5 g of azobisisobutyronitrile was added, and after 4 hours of reaction, the polymerization was terminated to obtain organic-inorganic composite particles. The average particle size of the obtained organic-inorganic composite particles was determined using a Nikkiso Co., Ltd. Microtrac MK-II type particle size analyzer.
It was 3.0 μm.
【００３５】合成例２〜６（有機無機複合粒子〜の
合成例） 表１に示す組成（重量比）で合成例１同様に懸濁重合を
行い、有機無機複合粒子〜を得た。得られた有機無
機複合粒子の平均粒径を合成例１と同様にして求めた。
結果を表１に示す。Synthesis Examples 2 to 6 (Synthesis Examples of Organic-Inorganic Composite Particles) Suspension polymerization was carried out in the same manner as in Synthesis Example 1 with the composition (weight ratio) shown in Table 1 to obtain organic-inorganic composite particles. The average particle size of the obtained organic-inorganic composite particles was determined in the same manner as in Synthesis Example 1.
Table 1 shows the results.
【００３６】合成例７〜９（有機無機複合粒子〜の
合成例） 表１に示す組成（重量比）で合成例１同様に懸濁重合を
行なったところ、合成例７、合成例８は平均粒径２０μ
以上の粗大粒子になり、合成例９は重合中にゲル化し
た。Synthesis Examples 7 to 9 (Synthesis Examples of Organic-Inorganic Composite Particles) When suspension polymerization was carried out in the same manner as in Synthesis Example 1 with the composition (weight ratio) shown in Table 1, Synthesis Examples 7 and 8 were averaged. Particle size 20μ
The particles became coarse particles as described above, and in Synthesis Example 9, gelation occurred during the polymerization.
【００３７】合成例１０（有機無機複合粒子(10)の合成
例） 表１に示す組成（重量比）で、エタノール３４４ｇ及び
イオン交換水８６ｇをイソプロピルアルコ−ル４３０ｇ
に置き換えた以外は合成例１同様にして懸濁重合を行
い、有機無機複合粒子(10)を得た。得られた有機無機複
合粒子の平均粒径を合成例１と同様にして求めた。結果
を表１に示す。Synthesis Example 10 (Synthesis example of organic-inorganic composite particles (10)) With the composition (weight ratio) shown in Table 1, 344 g of ethanol and 86 g of ion-exchanged water were mixed with 430 g of isopropyl alcohol.
The suspension polymerization was carried out in the same manner as in Synthesis Example 1 except that the above was replaced with the above, to obtain organic-inorganic composite particles (10). The average particle size of the obtained organic-inorganic composite particles was determined in the same manner as in Synthesis Example 1. Table 1 shows the results.
【００３８】合成例１１（水溶性アクリル樹脂例） ５００ｃｃの三つ口フラスコに、イオン交換水２２０ｇ
を６０℃に保ち攪拌する。過硫酸アンモニウム０．４ｇ
を仕込み、２−アクリルアミド−２−メチルプロパンス
ルホン酸（２ＡＡ２ＭＰＳＡ）の５０％水溶液１６０ｇ
と２−ヒドロキシエチルアクリレート（ＨＥＡ）１０
ｇ、アクリル酸（ＡＡ）１０ｇ、次亜燐酸ソ−ダの１０
％水溶液２０ｇの混合溶液を１時間かけて滴下する。５
０分毎に過硫酸アンモニウムの１０％水溶液０．４ｇを
４回添加し、２回目の添加時に反応系を８０℃に昇温す
る。不揮発分が２４％なった時点で重合を終了させ、水
溶性アクリル樹脂を得た。Synthesis Example 11 (Example of water-soluble acrylic resin) In a 500 cc three-necked flask, 220 g of ion-exchanged water was added.
Is kept at 60 ° C. and stirred. 0.4 g of ammonium persulfate
And 160 g of a 50% aqueous solution of 2-acrylamido-2-methylpropanesulfonic acid (2AA2MPSA)
And 2-hydroxyethyl acrylate (HEA) 10
g, acrylic acid (AA) 10 g, sodium hypophosphite 10
A mixed solution of 20 g of a 20% aqueous solution is dropped over 1 hour. 5
0.4 g of a 10% aqueous solution of ammonium persulfate is added four times every 0 minutes, and the temperature of the reaction system is raised to 80 ° C. at the time of the second addition. When the nonvolatile content became 24%, the polymerization was terminated, and a water-soluble acrylic resin was obtained.
【００３９】合成例１２〜１４（水溶性アクリル樹脂
〜の合成例） 表１に示す組成（重量比）で合成例１１同様に水溶液重
合を行い、水溶性アクリル樹脂〜を得た。Synthesis Examples 12 to 14 (Synthesis Examples of Water-Soluble Acrylic Resin) Aqueous polymerization was carried out in the same manner as in Synthesis Example 11 with the composition (weight ratio) shown in Table 1 to obtain a water-soluble acrylic resin.
【００４０】[0040]
【表１】 [Table 1]
【００４１】実施例１ 合成例１で得られた有機無機複合粒子を乾燥重量で６
０部、合成例１１で得られた水溶性アクリル樹脂を乾
燥重量で４０部を攪拌下で混合し、イオン交換水で希釈
して不揮発分１０％の親水性塗料を調整した。塗料化し
た後の平均粒径は１．５μｍであった。予め燐酸クロメ
ート処理を施したアルミ板に、バーコーターNo. ６によ
り塗布後、２５０℃のガスオーブン（風速毎秒２ｍ）に
て２０秒間焼き付けして約１μｍの塗膜厚のアルミニウ
ム塗装材を得た。Example 1 The organic-inorganic composite particles obtained in Synthesis Example 1 were dried at a dry weight of 6%.
0 parts and 40 parts by weight of the water-soluble acrylic resin obtained in Synthesis Example 11 were mixed under stirring and diluted with ion-exchanged water to prepare a hydrophilic paint having a nonvolatile content of 10%. The average particle size after coating was 1.5 μm. After coating on an aluminum plate previously treated with phosphoric acid chromate using a bar coater No. 6, it was baked for 20 seconds in a gas oven at 250 ° C. (wind speed 2 m / s) to obtain an aluminum coating material having a coating thickness of about 1 μm. .
【００４２】実施例２〜６ 合成例２〜６で得られた有機無機複合粒子〜を乾燥
重量で６０部、合成例１１で得られた水溶性アクリル樹
脂を乾燥重量で４０部を攪拌下で混合し、以下実施例
１と同様に親水性塗料を調整し、アルミニウム塗装材を
得た。Examples 2 to 6 The organic-inorganic composite particles obtained in Synthesis Examples 2 to 6 were mixed with 60 parts by dry weight of the water-soluble acrylic resin obtained in Synthetic Example 11, and 40 parts by dry weight of the particles were stirred. After mixing, a hydrophilic coating material was prepared in the same manner as in Example 1 to obtain an aluminum coating material.
【００４３】実施例７〜９ 実施例７は、水溶性アクリル樹脂の代わりに合成例１
２で得た水溶性アクリル樹脂を用い、実施例８は、水
溶性アクリル樹脂の代わりに合成例１３で得た水溶性
アクリル樹脂を用い、実施例９は、水溶性アクリル樹
脂の代わりに合成例１３で得た水溶性アクリル樹脂
を用いた以外は、それぞれ実施例１と同様にして親水性
塗料を調整し、アルミニウム塗装材を得た。Examples 7 to 9 Example 7 is a synthesis example 1 in place of the water-soluble acrylic resin.
Example 8 uses the water-soluble acrylic resin obtained in Synthesis Example 13 in place of the water-soluble acrylic resin obtained in Step 2, and Example 9 uses the water-soluble acrylic resin in place of the water-soluble acrylic resin in Example 9. A hydrophilic coating material was prepared in the same manner as in Example 1 except that the water-soluble acrylic resin obtained in 13 was used, to obtain an aluminum coating material.
【００４４】実施例１０ 合成例１で得た有機無機複合粒子を乾燥重量で１０
部、合成例１１で得た水溶性アクリル樹脂を乾燥重量
で９０部を攪拌下で混合し、以下実施例１と同様に親水
性塗料を調整し、アルミニウム塗装材を得た。Example 10 The organic-inorganic composite particles obtained in Synthesis Example 1 were dried at a weight of 10%.
Of the water-soluble acrylic resin obtained in Synthesis Example 11, 90 parts by dry weight were mixed under stirring, and a hydrophilic coating material was prepared in the same manner as in Example 1 to obtain an aluminum coating material.
【００４５】実施例１１ 合成例１で得た有機無機複合粒子を乾燥重量で７０
部、合成例１１で得た水溶性アクリル樹脂を乾燥重量
で３０部を攪拌下で混合し、以下実施例１と同様に親水
性塗料を調整し、アルミニウム塗装材を得た。Example 11 The organic-inorganic composite particles obtained in Synthesis Example 1 were dried at a dry weight of 70%.
Of the water-soluble acrylic resin obtained in Synthesis Example 11, 30 parts by dry weight were mixed with stirring, and a hydrophilic coating material was prepared in the same manner as in Example 1 to obtain an aluminum coating material.
【００４６】実施例１２ 合成例１で得た有機無機複合粒子を乾燥重量で５０
部、合成例１１で得た水溶性アクリル樹脂を乾燥重量
で４０部、ダイセル化学工業（株）製「ＨＥＣダイセル
ＳＰ−２５０」（ヒドロキシエチルセルロースの水溶
液）を乾燥重量で１０部、攪拌下で混合し、以下実施例
１と同様に親水性塗料を調整し、アルミニウム塗装材を
得た。Example 12 The organic-inorganic composite particles obtained in Synthesis Example 1 were dried at a dry weight of 50%.
Parts, 40 parts by weight of the water-soluble acrylic resin obtained in Synthesis Example 11, and 10 parts by weight of "HEC Daicel SP-250" (aqueous solution of hydroxyethyl cellulose) manufactured by Daicel Chemical Industries, Ltd. under stirring and mixed. Then, a hydrophilic coating material was prepared in the same manner as in Example 1 to obtain an aluminum coating material.
【００４７】実施例１３ 合成例１で得た有機無機複合粒子を乾燥重量で５０
部、合成例１１で得た水溶性アクリル樹脂を乾燥重量
で４０部、日本合成化学（株）製「ゴーセノールＧＬ−
Ｏ５」（ポリビニルアルコールの水溶液）を乾燥重量で
１０部、攪拌下で混合し、以下実施例１と同様に親水性
塗料を調整し、アルミニウム塗装材を得た。Example 13 The organic-inorganic composite particles obtained in Synthesis Example 1 were dried at a dry weight of 50%.
Part, the water-soluble acrylic resin obtained in Synthesis Example 11 is 40 parts by dry weight, "Gohsenol GL-" manufactured by Nippon Synthetic Chemical Co., Ltd.
O5 "(an aqueous solution of polyvinyl alcohol) was mixed with 10 parts by dry weight under stirring, and a hydrophilic coating material was prepared in the same manner as in Example 1 to obtain an aluminum coating material.
【００４８】実施例１４ 合成例１で得た有機無機複合粒子を乾燥重量で５０
部、合成例１１で得たによる水溶性アクリル樹脂を乾
燥重量で４０部、第一工業製薬（株）製「スーパーフレ
ックス１１０」（ポリウレタンの水分散体）を乾燥重量
で１０部、攪拌下で混合し、以下実施例１と同様に親水
性塗料を調整し、アルミニウム塗装材を得た。Example 14 The organic-inorganic composite particles obtained in Synthesis Example 1 were dried at a dry weight of 50%.
Parts, the dry weight of the water-soluble acrylic resin obtained in Synthesis Example 11 was 40 parts, and the “Superflex 110” (aqueous dispersion of polyurethane) manufactured by Daiichi Kogyo Seiyaku Co., Ltd. was 10 parts by dry weight under stirring. After mixing, a hydrophilic coating material was prepared in the same manner as in Example 1 to obtain an aluminum coating material.
【００４９】実施例１５ 合成例１で得た有機無機複合粒子を乾燥重量で５５
部、合成例１１で得た水溶性アクリル樹脂を乾燥重量
で４０部、日清紡（株）製「アルギン酸カルシウムビー
ズ」（水分散体）を乾燥重量で５部、攪拌下で混合し、
以下実施例１と同様に親水性塗料を調整し、アルミニウ
ム塗装材を得た。Example 15 The organic-inorganic composite particles obtained in Synthesis Example 1 were dried at a dry weight of 55%.
Parts, 40 parts by weight of the water-soluble acrylic resin obtained in Synthesis Example 11 by dry weight, and 5 parts by weight of “calcium alginate beads” (aqueous dispersion) manufactured by Nisshinbo Co., Ltd. under dry weight, and mixed under stirring.
Thereafter, a hydrophilic coating material was prepared in the same manner as in Example 1 to obtain an aluminum coating material.
【００５０】実施例１６ 合成例１で得た有機無機複合粒子を乾燥重量で５５
部、合成例１１で得た水溶性アクリル樹脂を乾燥重量
で４０部、住友化成工業（株）製「スミマール４０Ｗ」
（メラミン樹脂の水溶液）を乾燥重量で５部、攪拌下で
混合し、以下実施例１と同様に親水性塗料を調整し、ア
ルミニウム塗装材を得た。Example 16 The organic-inorganic composite particles obtained in Synthesis Example 1 were dried at a dry weight of 55%.
Parts, 40 parts by weight of the water-soluble acrylic resin obtained in Synthesis Example 11 by dry weight, "Sumimar 40W" manufactured by Sumitomo Chemical Co., Ltd.
(Aqueous solution of melamine resin) was mixed with 5 parts by dry weight under stirring, and a hydrophilic coating material was prepared in the same manner as in Example 1 to obtain an aluminum coating material.
【００５１】実施例１７ 合成例１で得た有機無機複合粒子を乾燥重量で５０
部、合成例１１で得た水溶性アクリル樹脂を乾燥重量
で４０部、東レ（株）製「ＡＱナイロンＡ−９０」（ナ
イロンの水溶液）を乾燥重量で１０部、攪拌下で混合
し、以下実施例１と同様に親水性塗料を調整し、アルミ
ニウム塗装材を得た。Example 17 The organic-inorganic composite particles obtained in Synthesis Example 1 were dried at a dry weight of 50%.
Parts, 40 parts by weight of the water-soluble acrylic resin obtained in Synthesis Example 11 by dry weight, and 10 parts by weight of “AQ nylon A-90” (aqueous solution of nylon) manufactured by Toray Industries, Ltd. A hydrophilic coating material was prepared in the same manner as in Example 1 to obtain an aluminum coating material.
【００５２】比較例１ 合成例１１で得た水溶性アクリル樹脂を実施例１同様
に、燐酸クロメート処理アルミ板に塗布・焼き付けをし
てアルミニウム塗装材を得た。Comparative Example 1 The water-soluble acrylic resin obtained in Synthesis Example 11 was applied and baked on a phosphoric acid chromate-treated aluminum plate in the same manner as in Example 1 to obtain an aluminum coating material.
【００５３】比較例２〜４ 比較例２では、合成例１で得た有機無機複合粒子の代
わりに合成例７で得た有機無機複合粒子を用い、比較
例３では合成例１で得た有機無機複合粒子の代わりに
合成例８で得た有機無機複合粒子を用い、比較例４で
は、合成例１０で得た有機無機複合粒子(10)を用いた以
外は、それぞれ実施例１と同様に親水性塗料を調整し、
アルミニウム塗装材を得た。Comparative Examples 2 to 4 In Comparative Example 2, the organic-inorganic composite particles obtained in Synthesis Example 7 were used instead of the organic-inorganic composite particles obtained in Synthesis Example 1, and in Comparative Example 3, the organic and inorganic composite particles obtained in Synthesis Example 1 were used. In the same manner as in Example 1 except that the organic-inorganic composite particles obtained in Synthesis Example 8 were used instead of the inorganic composite particles, and in Comparative Example 4, the organic-inorganic composite particles (10) obtained in Synthesis Example 10 were used. Adjust the hydrophilic paint,
An aluminum coating was obtained.
【００５４】以上実施例１〜１７、比較例１〜４の親水
性塗料の組成を表２に記載した。The compositions of the hydrophilic paints of Examples 1 to 17 and Comparative Examples 1 to 4 are shown in Table 2.
【００５５】[0055]
【表２】 [Table 2]
【００５６】得られた各アルミニウム塗装材（親水性塗
膜）に対して、下記の通り親水持続試験、密着性試験、
耐蝕性試験を行った。For each of the obtained aluminum coating materials (hydrophilic coating films), a hydrophilicity sustaining test, an adhesion test,
A corrosion resistance test was performed.
【００５７】（１）親水持続試験 塗装されたアルミニウム板を水道水（３０リットルのプ
ラスチック製容器に対して毎分３リットル／分の流水量
で）に８時間浸漬した後、５０℃の電気オーブンで１６
時間乾燥させる事を１サイクルとして、２０サイクル迄
続けて水接触角を測定した。水接触角の測定は、サンプ
ルを水平に置きその上に純水５μl を滴下し、接触角計
（ＣＡ−Ｚ：協和界面科学（株）製）により測定した。
評価は以下の通りである。 ◎：５°未満 ○：５°以上２０°未満 △ ２０°以上３０°未満 ×：３０°以上(1) Sustained Hydrophilicity Test The coated aluminum plate was immersed in tap water (at a flow rate of 3 liters / minute per minute in a 30 liter plastic container) for 8 hours, and then heated at 50 ° C. in an electric oven. At 16
The drying for one hour was defined as one cycle, and the water contact angle was measured continuously until 20 cycles. The water contact angle was measured by placing a sample horizontally and dropping 5 μl of pure water on it, and measuring the contact angle with a contact angle meter (CA-Z: Kyowa Interface Science Co., Ltd.).
The evaluation is as follows. ◎: less than 5 ° ○: 5 ° to less than 20 ° △ 20 ° to less than 30 ° ×: 30 ° or more
【００５８】（２）密着性試験 塗装されたアルミニウム板を水で湿したペーパータオル
で拭き、評価した。 ◎：拭き取れない ○：表層が拭き取れるが基材の上に一層残る △：最大５０％まで拭き取れる。 ×：完全に拭き取れる(2) Adhesion test The coated aluminum plate was wiped with a paper towel moistened with water and evaluated. ◎: Cannot be wiped off ：: Surface layer can be wiped off, but still remains on substrate △: Can be wiped up to 50%. ×: Completely wiped off
【００５９】（３）耐蝕性試験 塗装されたアルミニウム板に対して塩水噴霧試験を４０
０時間行い、腐食部分の面積の割合を評価した。 ◎：０％以上１％未満 ○：１％以上５％未満 ×：５％以上(3) Corrosion resistance test A salt spray test was performed on the painted aluminum plate for 40 minutes.
This was performed for 0 hour, and the ratio of the area of the corroded portion was evaluated. ：: 0% or more and less than 1% ： １: 1% or more and less than 5% ×: 5% or more
【００６０】（４）臭気 塗装されたアルミニウムを水に濡らして、乾燥する過程
で直接臭気を嗅ぐごとにより臭気の評価を行った。 ◎：全く臭気を感じない ○：殆ど臭気を感じない ×：明らかに臭気を感じる。(4) Odor The coated aluminum was wetted with water, and the odor was evaluated by directly smelling the odor during the drying process. ◎: No odor is felt at all. ○: Almost no odor is felt. ×: Odor is clearly felt.
【００６１】試験（１）〜（４）の結果を表３に示す。Table 3 shows the results of the tests (1) to (4).
【００６２】[0062]
【表３】 [Table 3]
【００６３】[0063]
【発明の効果】本発明の高親水性塗料を乾燥・硬化せし
めた塗膜は、極めて良好な親水持続性を有しており、密
着性、耐蝕性、臭気も良好である。粒子の外側にアルミ
ナゾルを配したゲル粒子は複雑なフラクタル表面を形成
し、不定型ゲル状態であるアルミナゾルの添加は、金型
の磨耗を極めて少なくし、金型の寿命を延ばすという効
果も有しており、該高親水性塗料は熱交換器用アルミニ
ウム製フィン材等に好適な親水性塗膜を提供するもので
ある。The coating film obtained by drying and curing the highly hydrophilic coating material of the present invention has extremely good hydrophilicity persistence, and has good adhesion, corrosion resistance and odor. Gel particles with alumina sol arranged outside the particles form a complex fractal surface, and the addition of alumina sol, which is in an irregular gel state, has the effect of extremely reducing mold wear and extending mold life. The highly hydrophilic paint provides a hydrophilic coating suitable for an aluminum fin material for a heat exchanger.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 ＦＩ Ｃ０９Ｄ 7/12 Ｃ０９Ｄ 7/12 Ｚ 125/02 125/02 131/08 131/08 133/14 133/14 133/26 133/26 Ｆ２８Ｆ 1/32 Ｆ２８Ｆ 1/32 Ｈ ──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. 6 Identification code FI C09D 7/12 C09D 7/12 Z 125/02 125/02 131/08 131/08 133/14 133/14 133/26 133 / 26 F28F 1/32 F28F 1/32 H
Claims (8)
の存在下に、下記一般式〔１〕または〔２〕で示される
親水性単量体（ｂ）を少なくとも１種類以上と多官能エ
チレン性不飽和単量体（ｃ）とを共重合させてなる有機
無機複合粒子。 【化１】 1. Alumina sol of 0.02 to 2 μm (a)
In the presence of a copolymer of at least one hydrophilic monomer (b) represented by the following general formula [1] or [2] and a polyfunctional ethylenically unsaturated monomer (c). Organic-inorganic composite particles. Embedded image
の存在下に、下記一般式〔１〕または〔２〕で示される
親水性単量体（ｂ）を少なくとも１種類以上と多官能エ
チレン性不飽和単量体（ｃ）と、上記（ｂ）（ｃ）と共
重合可能なその他のエチレン性不飽和単量体（ｄ）とを
共重合させてなる有機無機複合粒子。 【化２】 2. Alumina sol of 0.02 to 2 μm (a)
In the presence of at least one hydrophilic monomer (b) represented by the following general formula [1] or [2], a polyfunctional ethylenically unsaturated monomer (c), and the above (b) Organic / inorganic composite particles obtained by copolymerizing (c) with another copolymerizable ethylenically unsaturated monomer (d). Embedded image
状、棒状、樹枝状の形状・形態を有することを特徴とす
る請求項１または２記載の有機無機複合粒子。3. The organic-inorganic composite particles according to claim 1, wherein the primary particles of the alumina sol (a) have a feather-like, rod-like, or dendritic shape and form.
〜５μｍであることを特徴とする請求項１ないし３記載
の有機無機複合粒子。4. An organic-inorganic composite particle having an average particle size of 0.5
The organic-inorganic composite particles according to any one of claims 1 to 3, wherein the particle diameter is from 5 to 5 µm.
する請求項１ないし４いずれか記載の有機無機複合粒
子。5. The organic-inorganic composite particle according to claim 1, which is obtained by suspension polymerization.
が、ポリオキシエチレンジメタクリレ−ト、ポリオキシ
エチレンジアクリレ−ト、メチレンビスアクリルアミ
ド、メチレンビスメタアクリルアミド、ジビニルベンゼ
ン、ジアリルテレフタレ−トから選ばれる少なくとも１
種または１種以上であることを特徴とする請求項１ない
し５いずれか記載の有機無機複合粒子。6. A polyfunctional ethylenically unsaturated monomer (c).
Is at least one selected from polyoxyethylene dimethacrylate, polyoxyethylene diacrylate, methylenebisacrylamide, methylenebismethacrylamide, divinylbenzene and diallyl terephthalate
The organic-inorganic composite particles according to any one of claims 1 to 5, wherein the organic-inorganic composite particles are at least one species.
機複合粒子と、水溶性樹脂とを含有することを特徴とす
る高親水性塗料。7. A highly hydrophilic paint comprising the organic-inorganic composite particles according to claim 1 and a water-soluble resin.
ウム基材に塗布し、硬化してなるアルミニウムフィン
材。8. An aluminum fin material obtained by applying the highly hydrophilic paint according to claim 7 to an aluminum substrate and curing the coating.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2014897A JPH10218909A (en) | 1997-02-03 | 1997-02-03 | Organic/inorganic composite particle, coating material containing the same and aluminum fin material coated with the coating material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2014897A JPH10218909A (en) | 1997-02-03 | 1997-02-03 | Organic/inorganic composite particle, coating material containing the same and aluminum fin material coated with the coating material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH10218909A true JPH10218909A (en) | 1998-08-18 |
Family
ID=12019078
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2014897A Pending JPH10218909A (en) | 1997-02-03 | 1997-02-03 | Organic/inorganic composite particle, coating material containing the same and aluminum fin material coated with the coating material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH10218909A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104830193A (en) * | 2014-02-06 | 2015-08-12 | 东亚合成株式会社 | High hydrophilic coating composition and use thereof |
-
1997
- 1997-02-03 JP JP2014897A patent/JPH10218909A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104830193A (en) * | 2014-02-06 | 2015-08-12 | 东亚合成株式会社 | High hydrophilic coating composition and use thereof |
| JP2015147852A (en) * | 2014-02-06 | 2015-08-20 | 東亞合成株式会社 | Highly hydrophilic coating composition and use thereof |
| CN104830193B (en) * | 2014-02-06 | 2019-02-22 | 东亚合成株式会社 | High-hydrophilic coating composition and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR940007204B1 (en) | Heat exchanger | |
| EP2862634B1 (en) | Method for covering aluminum fin material with hydrophilic film, aluminum fin material, and aluminum heat exchanger | |
| JP4464076B2 (en) | Crosslinkable fine particles, hydrophilic treatment agent, hydrophilic film coating method and hydrophilic film | |
| JPWO2016002484A1 (en) | Method for coating hydrophilic film of aluminum fin material, aluminum fin material, and aluminum heat exchanger | |
| JPH08313191A (en) | Aluminum fin material for heat exchanger | |
| JP2857343B2 (en) | Method for producing resin-based precoated fin material for heat exchanger having excellent hydrophilicity | |
| JP3430482B2 (en) | Heat exchange material | |
| JP2512452B2 (en) | Method for hydrophilic treatment of aluminum | |
| JP3225793B2 (en) | Highly hydrophilic paint | |
| JP3430483B2 (en) | Heat exchange material | |
| JP5180145B2 (en) | Crosslinkable fine particles, hydrophilic treatment agent, hydrophilic film coating method and hydrophilic film | |
| JPH0747329A (en) | Metallic substrate subjected to hydrophilic treatment | |
| JPH10218909A (en) | Organic/inorganic composite particle, coating material containing the same and aluminum fin material coated with the coating material | |
| JPH10219191A (en) | Highly hydrophilic coating material and aluminum fin material made by using it | |
| JP3403906B2 (en) | Manufacturing method of highly hydrophilic paint | |
| JP2009179811A5 (en) | ||
| JP3671339B2 (en) | Manufacturing method of precoat fin material for heat exchanger | |
| JPH09272819A (en) | Composition for hydrophilic treatment of fin material for heat exchanger | |
| JP2507070B2 (en) | Method for hydrophilizing aluminum fin coil material | |
| JPH0978002A (en) | Highly hydrophilic coating material | |
| JP3141703B2 (en) | Highly hydrophilic paint | |
| JP4467264B2 (en) | Fin coating composition and fin material | |
| JPS61225044A (en) | Aluminum fin material for heat exchanger | |
| JPH0718206A (en) | Highly hydrophilic coating material | |
| JPH02105873A (en) | Highly hydrophilic coating material |