JP2006247544A - Method for forming water sliding film containing layer which contains anionic silica fine particles and treatment agent set for forming water sliding film - Google Patents
Method for forming water sliding film containing layer which contains anionic silica fine particles and treatment agent set for forming water sliding film Download PDFInfo
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本発明は、洗車後及び雨天時などの水滴の滑落を良好にするため、ガラス面や塗膜表面に滑水性に優れた皮膜を形成する方法及び滑水性皮膜形成用の処理剤セットに関するものである。 The present invention relates to a method for forming a film having excellent water slidability on a glass surface or a coating film surface, and a treatment agent set for forming the water slidable film, in order to improve the sliding of water droplets after washing a car and in rainy weather. is there.
滑水性や發水性に関して、従来から種々の組成物が提案されている。
例えば、アミノ変性シリコーンオイルとカチオン性界面活性剤とを含有する組成物が提案されており（特許文献１）、該組成物は、単にガラス面に噴霧あるいは塗布するだけで、塗り延ばしや拭き取りが一切不要なため作業が容易であり、優れた撥水を示し、現在最も広く普及されている發水皮膜の形成方法である。しかしながら、この方法は、作業性に優れ、發水生に優れているものの、水滴の滑落、すなわち滑水性は満足のいくものではなかった。
また、末端に加水分解可能な官能基を有するシリコーン化合物、または末端に加水分解可能な官能基を有し他端にフルオロアルキル基を併せ持つシリコーン化合物と、酸と、水とを溶剤に溶解後、混合攪拌によって得られた混合液を、基材表面に塗布し、ついで乾燥させることにより得られる機能層が、基材表面とシロキサン結合により化学的に結合されてなることを特徴とする水滴滑落性に優れた表面処理基材が提案されており（特許文献２）、この基材によれば、５０μｌの水滴が１〜８°程度の傾斜面で落下するものが得られている。この基材は、滑水性、持続性には優れているものの、シリコーンを溶解するための有機溶剤及び加水分解可能な官能基を加水分解するための酸を必要とし、皮膜形成後焼成しなければならず、処理のための設備を必要とし、だれでも簡単に皮膜を形成できるものではなかった。
さらに、（Ａ）疎水化処理された一次平均粒子径１００ｎｍ以下の無機微粒子、（Ｂ）有機ケイ素化合物、（Ｃ）該有機ケイ素化合物が溶解し、１．０１３×１０2ｋＰａにおける沸点が５０〜１５０℃、且つ蒸発潜熱が０．２〜１．３ｋＪ／ｇである有機溶媒を含有する超撥水剤組成物が提案され（特許文献３）、この組成物を、自動車等の塗装面、ガラス面に塗布することにより、無機微粒子が形成する表面のフラクタル構造により、２０μｌの水滴が１０°の斜面で滑落する滑水性を有することが示されている。
しかしながら、この組成物は有機溶剤を必須とするので、塗布に当たり環境汚染を引き起こす可能性があり、一般のユーザが安全に使用することができなかった。
For example, a composition containing an amino-modified silicone oil and a cationic surfactant has been proposed (Patent Document 1), and the composition can be spread or wiped by simply spraying or coating on a glass surface. Since it is unnecessary at all, it is easy to work, exhibits excellent water repellency, and is the most widely used method for forming a water-repellent film. However, this method is excellent in workability and excellent in aquatic life, but the sliding of water droplets, that is, the sliding property is not satisfactory.
In addition, after dissolving a silicone compound having a hydrolyzable functional group at the terminal, or a silicone compound having a hydrolyzable functional group at the terminal and having a fluoroalkyl group at the other end, an acid, and water in a solvent, Water droplet sliding characteristics characterized in that the functional layer obtained by applying the mixed solution obtained by mixing and stirring to the substrate surface and then drying is chemically bonded to the substrate surface by a siloxane bond (Patent Document 2), a substrate in which 50 μl of water droplets fall on an inclined surface of about 1 to 8 ° is obtained. Although this base material is excellent in water slidability and sustainability, it requires an organic solvent for dissolving silicone and an acid for hydrolyzing a hydrolyzable functional group, and must be fired after film formation. In addition, a facility for processing was required, and no one could easily form a film.
Furthermore, (A) inorganic fine particles having a hydrophobized primary average particle diameter of 100 nm or less, (B) an organosilicon compound, (C) the organosilicon compound is dissolved, and a boiling point at 1.013 × 10 2 kPa is 50 to A super water-repellent composition containing an organic solvent having an evaporation latent heat of 0.2 to 1.3 kJ / g has been proposed (Patent Document 3). By applying to the surface, it is shown that 20 μl of water droplets slide on a 10 ° slope due to the fractal structure of the surface formed by the inorganic fine particles.
However, since this composition requires an organic solvent, there is a possibility of causing environmental pollution during application, and it has not been possible for general users to use it safely.
本発明の目的は、自動車などのガラス面や塗装面に、だれでも簡単にしかも環境を汚染することなく、滑水性に優れた皮膜を形成することができる方法を提供することである。
また、本発明の他の目的は、誰にでも簡単に使用可能な、滑水性に優れた皮膜形成用の処理剤セットを提供することである。
An object of the present invention is to provide a method capable of forming a film having excellent water slidability on a glass surface or painted surface of an automobile or the like without any pollution of the environment by anyone.
Another object of the present invention is to provide a treatment agent set for film formation excellent in water slidability that can be easily used by anyone.
本発明者らは、従来から發水剤として知られているシリコーンにアニオン性シリカ微粒子を組み合わせるとシリコーンの滑水性が向上することに着目し本発明に至った。
親水性のアニオン性シリカ微粒子には、シリコーンへの吸着性及びシリコーンの極性基（例えば、アミノ基）を配向させる性質があり、シリコーンの極性基がアニオン性シリカ微粒子に配向することで、水との水素結合力が弱くなり、水滴の転落角が小さくなるものと考えられる。
The inventors of the present invention have reached the present invention by paying attention to the fact that the silicone water-slidability is improved by combining anionic silica fine particles with a silicone conventionally known as a water-repellent agent.
Hydrophilic anionic silica fine particles have a property of adsorbing to silicone and orienting polar groups (for example, amino groups) of silicone. By aligning polar groups of silicone to anionic silica fine particles, water and It is considered that the hydrogen bonding force of the water becomes weak and the falling angle of the water droplet becomes small.
シリコーンにアニオン性シリカ微粒子を組み合わせ、基材表面に皮膜を形成するには、それぞれ別個に塗布する必要がある。シリコーンとアニオン性シリカ微粒子を混合すると、アニオン性シリカ微粒子が分散不安定となり、所期の効果が得られない。 In order to combine anionic silica fine particles with silicone and form a film on the surface of the substrate, it is necessary to apply them separately. When silicone and anionic silica fine particles are mixed, the anionic silica fine particles become unstable in dispersion, and the desired effect cannot be obtained.
シリコーンやアニオン性シリカ微粒子を塗布するために使用する溶媒として、有機溶媒も使用可能であるが、環境汚染や人体への影響の点から水を使用することが望ましい。 An organic solvent can be used as a solvent used to apply silicone or anionic silica fine particles, but it is desirable to use water from the viewpoint of environmental pollution and influence on the human body.
塗布の順序は問わないが、アニオン性シリカ微粒子は微粒子であるため吸着性も強く、表面の疎水性が弱ければアニオン性シリカ微粒子が塗装面やガラス面に吸着されるので、アニオン性シリカ微粒子を先に塗布することが好ましい。その場合、少量の非イオン界面活性剤を添加すると濡れ性が向上するのでさらに好ましい。
また、アニオン性シリカ微粒子の分散液に樹脂、例えばアルカリ可溶性樹脂の水溶液を少量添加すれば、樹脂の接着力によりアニオン性シリカ微粒子をより強固に基材表面に吸着させることができる。
The order of application is not limited, but the anionic silica fine particles are strong, so the adsorptivity is strong. If the surface hydrophobicity is weak, the anionic silica fine particles are adsorbed on the painted surface or glass surface. It is preferable to apply it first. In that case, it is more preferable to add a small amount of a nonionic surfactant since wettability is improved.
Further, if a small amount of a resin, for example, an aqueous solution of an alkali-soluble resin, is added to the dispersion of the anionic silica fine particles, the anionic silica fine particles can be more firmly adsorbed to the substrate surface by the adhesive force of the resin.
塗装表面やガラス表面は普通、負に帯電しているので、静電気的に吸着されやすいカチオン性有機化合物やカチオン性無機化合物であらかじめ表面をコートしておくと、アニオン性シリカ微粒子はより強く表面に吸着されるのでより好ましい。 Since painted surfaces and glass surfaces are usually negatively charged, anionic silica particles are more strongly applied to the surface if the surface is coated beforehand with a cationic organic compound or cationic inorganic compound that is easily adsorbed electrostatically. It is more preferable because it is adsorbed.
シリコーンとしてカチオン性であるアミノ変性シリコーンオイルを使用する場合には、まずアミノ変性シリコーンオイルを表面に塗布すれば表面と静電気的に結合するので強固な塗膜を形成することができ、その後アニオン性シリカ微粒子を塗布すれば同様な効果が得られる。
この場合、さらにシリコーンエマルジョンを上塗りすれば、滑水性の点で好ましい。
When using an amino-modified silicone oil that is cationic as the silicone, first the amino-modified silicone oil is applied to the surface and electrostatically bonded to the surface, so that a strong coating can be formed. The same effect can be obtained by applying silica fine particles.
In this case, if a silicone emulsion is further applied, it is preferable in terms of water slidability.
本発明の実施の態様は以下のとおりである。
（１）アニオン性シリカ微粒子分散液を基材表面に塗布した後、シリコーンエマルジョンを塗布することにより、１種以上のシリコーンからなる滑水性皮膜を基材表面に形成する方法。
（２）アニオン性シリカ微粒子分散液に界面活性剤を添加したことを特徴とする（１）記載の方法。
（３）アニオン性シリカ微粒子分散液に樹脂を添加したことを特徴とする（１）記載の方法。
（４）アニオン性シリカ微粒子分散液での塗布に先立ち、カチオン性有機化合物の水溶液により基材表面をコートすることを特徴とする（１）記載の方法。
（５）アニオン性シリカ微粒子分散液での塗布に先立ち、カチオン性無機化合物の分散液により基材表面をコートすることを特徴とする（１）記載の方法。
（６）アニオン性シリカ微粒子分散液での塗布に先立ち、カチオン性有機化合物及びカチオン性無機化合物を含む分散液により基材表面をコートすることを特徴とする（１）記載の方法。
（７）アミノ変性シリコーンオイルエマルジョンを基材表面に塗布し、該表面に皮膜を形成した後、アニオン性シリカ微粒子分散液を塗布することにより、シリコーンからなる滑水性皮膜を基材表面に形成する方法。
（８）アミノ変性シリコーンオイルエマルジョンに、カチオン性有機化合物及び／またはカチオン性無機化合物を添加したことを特徴とする（７）記載の方法。
（９）アニオン性シリカ微粒子分散液でアミノ変性シリコーンオイル表面に塗布した後、さらに１種以上のシリコーンエマルジョンを塗布することを特徴とする（７）または（８）記載の方法。
（１０）塗布が、スプレー法で行われることを特徴とする（１）ないし（９）のいずれかに記載の方法。
（１１）アニオン性シリカ微粒子分散液と、１種以上のシリコーンエマルジョンからなる、滑水性皮膜形成用の処理剤セット。
（１２）アニオン性シリカ微粒子分散液に界面活性剤を添加したことを特徴とする（１１）記載の処理剤セット。
（１３）アニオン性シリカ微粒子分散液に樹脂を添加したことを特徴とする（１１）記載の処理剤セット。
（１４）さらに、カチオン性有機化合物の水溶液を組み合わせたことを特徴とする（１１）記載の処理剤セット。
（１５）さらに、カチオン性無機化合物の分散液を組み合わせたことを特徴とする（１１）記載の処理剤セット。
（１６）さらに、カチオン性有機化合物の水溶液及びカチオン性無機化合物の分散液の混合液を組み合わせたことを特徴とする（１１）記載の処理剤セット。
（１７）シリコーンエマルジョンがアミノ変性シリコーンオイルエマルジョンであることを特徴とする（１１）記載の処理剤セット。
（１８）アミノ変性シリコーンオイルエマルジョンにカチオン性有機化合物及び／またはカチオン性無機化合物を添加したことを特徴とする（１７）記載の処理剤セット。
（１９）各組成物がそれぞれ別の容器に収納されていることを特徴とする（１１）ないし（１８）のいずれかに記載の処理剤セット。
（２０）容器がスプレー缶である（１９）記載の処理剤セット。
Embodiments of the present invention are as follows.
(1) A method of forming a water-slidable film composed of one or more kinds of silicone on the surface of the substrate by applying an anionic silica fine particle dispersion on the surface of the substrate and then applying a silicone emulsion.
(2) The method according to (1), wherein a surfactant is added to the anionic silica fine particle dispersion.
(3) The method according to (1), wherein a resin is added to the anionic silica fine particle dispersion.
(4) The method according to (1), wherein the substrate surface is coated with an aqueous solution of a cationic organic compound prior to coating with the anionic silica fine particle dispersion.
(5) The method according to (1), wherein the substrate surface is coated with a dispersion of a cationic inorganic compound prior to coating with the anionic silica fine particle dispersion.
(6) The method according to (1), wherein the substrate surface is coated with a dispersion containing a cationic organic compound and a cationic inorganic compound prior to coating with the anionic silica fine particle dispersion.
(7) An amino-modified silicone oil emulsion is applied to the surface of the substrate, and after forming a film on the surface, a water-slidable film made of silicone is formed on the surface of the substrate by applying an anionic silica fine particle dispersion. Method.
(8) The method according to (7), wherein a cationic organic compound and / or a cationic inorganic compound is added to the amino-modified silicone oil emulsion.
(9) The method according to (7) or (8), wherein one or more silicone emulsions are further applied after application to the surface of the amino-modified silicone oil with an anionic silica fine particle dispersion.
(10) The method according to any one of (1) to (9), wherein the application is performed by a spray method.
(11) A treatment agent set for forming a water slidable film comprising an anionic silica fine particle dispersion and one or more silicone emulsions.
(12) The treatment agent set according to (11), wherein a surfactant is added to the anionic silica fine particle dispersion.
(13) The treatment agent set according to (11), wherein a resin is added to the anionic silica fine particle dispersion.
(14) The treatment agent set according to (11), which is further combined with an aqueous solution of a cationic organic compound.
(15) The treatment agent set according to (11), further comprising a dispersion of a cationic inorganic compound.
(16) The treatment agent set according to (11), further comprising a combination of an aqueous solution of a cationic organic compound and a dispersion of a dispersion of a cationic inorganic compound.
(17) The treatment agent set according to (11), wherein the silicone emulsion is an amino-modified silicone oil emulsion.
(18) The treatment agent set according to (17), wherein a cationic organic compound and / or a cationic inorganic compound is added to the amino-modified silicone oil emulsion.
(19) The treatment agent set according to any one of (11) to (18), wherein each composition is stored in a separate container.
(20) The treatment agent set according to (19), wherein the container is a spray can.
本発明における、アニオン性シリカ微粒子とは、粒径が４〜２００ｎｍの一次粒子からなるシリカ微粒子で、表面が負に帯電しているものである。
粒径が２００ｎｍを超えると、シリカ微粒子層の透明性が悪くなり、またガラス面や塗装面に吸着しにくくなるので本発明の効果が得られなくなる。
In the present invention, the anionic silica fine particles are silica fine particles composed of primary particles having a particle diameter of 4 to 200 nm, and the surface is negatively charged.
When the particle diameter exceeds 200 nm, the transparency of the silica fine particle layer is deteriorated, and it is difficult to adsorb on the glass surface or the painted surface, so that the effect of the present invention cannot be obtained.
アニオン性シリカ微粒子の分散液とは、負に帯電した４〜１００ｎｍの無定形シリカ粒子が水中に分散したシリカゾル、あるいは負に帯電した粒径２００ｎｍの鱗片状シリカ粒子が水中に分散したシリカ分散液である。 The dispersion of anionic silica fine particles is a silica sol in which negatively charged amorphous silica particles of 4 to 100 nm are dispersed in water, or a silica dispersion in which negatively charged 200 nm-scaled scaly silica particles are dispersed in water. It is.
本発明における、シリコーンとは、従来から發水剤として知られているものでよく、例えばアミノ変性シリコーンオイル、ジメチルシリコーンオイル、アルキル変性シリコーンオイル、アルキルアラキル変性シリコーンオイル、高級脂肪酸エステル変性シリコーンオイル、エポキシ変性シリコーンオイル、カルボキシル変性シリコーンオイル、アミド変性シリコーンオイル、メルカプト変性シリコーンオイル、シリコーンレジンなどの一種もしくは二種以上を使用することができる。
二種以上のシリコーン皮膜を形成するには、二種以上のシリコーンを混合して塗布する方法、それぞれのシリコーンを回分式に塗布する方法、のいずれも採用できる。
In the present invention, the silicone may be a conventionally known water-repellent agent, such as amino-modified silicone oil, dimethyl silicone oil, alkyl-modified silicone oil, alkyl aralkyl-modified silicone oil, and higher fatty acid ester-modified silicone oil. One or more of epoxy-modified silicone oil, carboxyl-modified silicone oil, amide-modified silicone oil, mercapto-modified silicone oil, silicone resin and the like can be used.
In order to form two or more types of silicone films, either a method in which two or more types of silicones are mixed and applied, or a method in which the respective silicones are applied batchwise can be employed.
本発明においてアニオン性シリカ微粒子に添加される界面活性剤は、濡れ性を向上させるものであれば特に限定されないが、アニオン性シリカ微粒子分散液の分散安定性の点で非イオン界面活性剤が好ましい。 In the present invention, the surfactant added to the anionic silica fine particles is not particularly limited as long as it improves the wettability, but a nonionic surfactant is preferable from the viewpoint of dispersion stability of the anionic silica fine particle dispersion. .
また、同じくアニオン性シリカ微粒子に添加される樹脂も、特に限定されないが、アクリル樹脂、酢酸ビニル樹脂、ウレタン樹脂、エポキシ樹脂などのエマルジョン、あるいはスチレンアクリル樹脂、スチレンマレイン酸樹脂などのアルカリ可溶性樹脂の水溶液が使用できる。 Similarly, the resin added to the anionic silica fine particles is not particularly limited, but emulsions such as acrylic resins, vinyl acetate resins, urethane resins, and epoxy resins, or alkali-soluble resins such as styrene acrylic resins and styrene maleic resins are used. An aqueous solution can be used.
本発明において、予め表面を処理するカチオン性有機化合物としては、モノアルキルアンモニウムクロライド、ジアルキルアンモニウムクロライド、ＥＯ付加型アンモニウムクロライド、アミン酢酸塩類などのカチオン界面活性剤、あるいはポリビニルベンジルトリメチルアンモニウムクロライド、ポリジメチルアミノエチルメタクリレート４級化物、ポリジアリルジメチルアンモニウムクロライド、ポリジアリルジメチルアンモニウムクロライドとアクリルアミドの共重合体、カチオン性セルロース誘導体などのカチオン性高分子化合物の中から選択することができ、これらを水溶液として使用する。
カチオン性無機化合物としては、粒径１０〜１００ｎｍのアルミナ微粒子や、粒径２５〜５０ｎｍのカチオン性シリカ微粒子から選択することができ、これらを水分散液にして使用する。また、シリカの微粒子をカチオン性とするには周知の帯電手段が適用できる。
In the present invention, the cationic organic compound for treating the surface in advance includes a cationic surfactant such as monoalkylammonium chloride, dialkylammonium chloride, EO addition type ammonium chloride, amine acetates, polyvinylbenzyltrimethylammonium chloride, polydimethyl A cationic polymer compound such as aminoethyl methacrylate quaternized product, polydiallyldimethylammonium chloride, polydiallyldimethylammonium chloride and acrylamide copolymer, and cationic cellulose derivative can be selected and used as an aqueous solution. To do.
The cationic inorganic compound can be selected from alumina fine particles having a particle size of 10 to 100 nm and cationic silica fine particles having a particle size of 25 to 50 nm, and these are used as an aqueous dispersion. In order to make the silica fine particles cationic, a known charging means can be applied.
本発明によれば、環境を汚染したり人体に対して有害な有機溶剤を使用しなくて済み、また基材及び人体に対して危険な酸やアルカリを一切使用していないので、一般のユーザが安心して使用することができ、また、2種以上の処理剤を単に塗布するだけで、誰でも簡単に皮膜を形成することができ、しかも形成された皮膜は滑水性に優れているので、洗車時の洗浄水量や洗浄時間を大幅に少なくすることができ、雨天の場合にも水滴が残らないので、窓ガラスの視野を良好に保つことができ、塗装の耐久性も増す。 According to the present invention, it is not necessary to use an organic solvent that pollutes the environment or is harmful to the human body, and since it does not use any dangerous acid or alkali for the base material and human body, Can be used with peace of mind, and by simply applying two or more treatment agents, anyone can easily form a film, and the formed film is excellent in lubricity, The amount of washing water and washing time at the time of car washing can be significantly reduced, and since no water droplets remain even in rainy weather, the field of view of the window glass can be kept good, and the durability of painting is also increased.
本発明の実施例で使用したテスト用基板、噴霧装置及び測定機器は以下のとおりである。
テスト用基板
ガラス板：松浪硝子工業(株)製マイクロスライドガラスＳ−１２１５（76×26ｍｍ）
塗装板：アクリル樹脂塗装鉄板（50×50ｍｍ）
噴霧装置
スプレーノズル：Canyon Corp.製「ＣＨＳ−３ＡＮ−Ｂｕ／Ｗ ストレーナーなし ２Ｃ２２」
測定機器
接触角、転落角：Kyowa Interface Science Co. LTD.製 Model：ＣＡ−ＤＴ
The test substrates, spraying devices, and measuring instruments used in the examples of the present invention are as follows.
Substrate glass plate for testing : Matsunami Glass Industrial Co., Ltd. micro slide glass S-1215 (76 x 26 mm)
Paint plate: Acrylic resin-coated iron plate (50 x 50 mm)
Spray device Spray nozzle: “CHS-3AN-Bu / W without strainer 2C22” manufactured by Canyon Corp.
Measuring instrument contact angle, sliding angle: manufactured by Kyowa Interface Science Co. LTD. Model: CA-DT
（１）ガラス板を非イオン界面活性剤「ＩＤ２０６」（日本油脂(株)製）を０．０１％添加したアニオン性シリカゾル「スノーテックスS」（日産化学工業(株)製、粒径８〜１１ｎｍ、ＳｉＯ２ ３０％）の０．７％水分散液に浸漬し、常温で乾燥させる。
（２）上記ガラス板をアミノ変性シリコーンオイルエマルジョン「ＢＹ２２−８３０」（東レ・ダウコーニング・シリコーン(株)製、有効成分１５％）の０．３％水溶液に浸漬し水洗する操作を２回繰り返し、常温で乾燥した後、接触角と転落角を測定した。
(1) Anionic silica sol “Snowtex S” (Nissan Chemical Industry Co., Ltd., particle size 8˜8) with non-ionic surfactant “ID206” (manufactured by NOF Corporation) added to glass plate by 0.01% 11 nm, SiO 2 30%) in a 0.7% aqueous dispersion and dried at room temperature.
(2) The operation of immersing the glass plate in a 0.3% aqueous solution of amino-modified silicone oil emulsion “BY22-830” (manufactured by Toray Dow Corning Silicone Co., Ltd., 15% active ingredient) and washing with water twice is repeated. After drying at room temperature, the contact angle and the falling angle were measured.
（１）ガラス板をアニオン性シリカゾル「クレボゾール３０Ｒ２５」（ＡＺエレクトロニクス・マテリアルズ(株)製、粒径２５ｎｍ、ＳｉＯ２ ３０％）の１．３％水分散液に浸漬し、常温で乾燥させる。
（２）上記ガラス板をジメチルシリコーンオイルエマルジョン「ＬＥ−４５」（東レ・ダウコーニング・シリコーン(株)製、有効成分３５％）の０．３％水溶液に浸漬し水洗する操作を２回繰り返し、常温で乾燥した後、接触角と転落角を測定した。
(1) The glass plate is immersed in a 1.3% aqueous dispersion of anionic silica sol “Crebosol 30R25” (manufactured by AZ Electronics Materials Co., Ltd., particle size 25 nm, SiO 2 30%) and dried at room temperature.
(2) The operation of immersing the glass plate in a 0.3% aqueous solution of dimethyl silicone oil emulsion “LE-45” (manufactured by Toray Dow Corning Silicone Co., Ltd., active ingredient 35%) and washing with water is repeated twice. After drying at room temperature, the contact angle and the sliding angle were measured.
（１）ガラス板を非イオン界面活性剤「ＩＤ２０６」を０．０１％添加したアニオン性シリカゾル「スノーテックスS」の０．７％水分散液に浸漬し、常温で乾燥させる。
（２）上記ガラス板をアミノ変性シリコーンオイルエマルジョン「ＢＹ２２−８３０」の０．３％水溶液に浸漬し水洗する操作を２回繰り返す。
（３）上記ガラス板をジメチルシリコーンエマルジョン「LE−４５」の０．２％水溶液に浸漬し水洗し、常温で乾燥した後、接触角と転落角を測定した。
(1) A glass plate is immersed in a 0.7% aqueous dispersion of anionic silica sol “Snowtex S” to which 0.01% of a nonionic surfactant “ID206” is added and dried at room temperature.
(2) The operation of immersing the glass plate in a 0.3% aqueous solution of amino-modified silicone oil emulsion “BY22-830” and washing with water is repeated twice.
(3) The glass plate was immersed in a 0.2% aqueous solution of dimethyl silicone emulsion “LE-45”, washed with water, dried at room temperature, and then contact angle and sliding angle were measured.
（１）ガラス板を非イオン界面活性剤「ＩＤ２０６」を０．０１％添加したアニオン性シリカゾル「スノーテックスS」の０．７％水分散液に浸漬し、常温で乾燥させる。
（２）上記ガラス板をアミノ変性シリコーンオイルエマルジョン「ＢＹ２２−８３０」の０．３％水溶液とジメチルシリコーンエマルジョン「LE−４５」の０．２％水溶液の混合溶液（１：１重量比）に浸漬し水洗する操作を２回繰り返し、常温で乾燥した後、接触角と転落角を測定した。
(1) A glass plate is immersed in a 0.7% aqueous dispersion of anionic silica sol “Snowtex S” to which 0.01% of a nonionic surfactant “ID206” is added and dried at room temperature.
(2) The glass plate is immersed in a mixed solution (1: 1 weight ratio) of a 0.3% aqueous solution of amino-modified silicone oil emulsion “BY22-830” and a 0.2% aqueous solution of dimethyl silicone emulsion “LE-45”. The operation of washing with water was repeated twice, and after drying at room temperature, the contact angle and the falling angle were measured.
（１）塗装板をアルカリ可溶性樹脂水溶液「アクリスＧＳＡ−４０４Ｌ」（(株)岐阜セラック製造所製、スチレンアクリル樹脂水溶液、有効成分２５％）を０．０１２５％添加したアニオン性シリカゾル「スノーテックスＮ」（日産化学工業(株)製、粒径１０〜２０ｎｍ、ＳｉＯ２ ２０％）の１．０％水分散液に浸漬し、常温で乾燥させる。
（２）上記塗装板をアミノ変性シリコーンオイルエマルジョン「ＢＹ２２−８３０」の０．３％水溶液に浸漬し水洗する操作を２回繰り返し、常温で乾燥した後、接触角と転落角を測定した。
(1) Anionic silica sol “Snowtex N” containing 0.0125% of an aqueous solution of alkali-soluble resin “Acrys GSA-404L” (manufactured by Gifu Shellac Manufacturing Co., Ltd., styrene acrylic resin aqueous solution, 25% active ingredient) It is dipped in a 1.0% aqueous dispersion (manufactured by Nissan Chemical Industries, Ltd., particle size 10-20 nm, SiO 2 20%) and dried at room temperature.
(2) The operation of immersing the above-mentioned coated plate in a 0.3% aqueous solution of amino-modified silicone oil emulsion “BY22-830” and washing with water was repeated twice. After drying at room temperature, the contact angle and the falling angle were measured.
（１）塗装板をカチオン性高分子化合物の水溶液「リポフローＭＮ」(ライオン(株)製、ポリジアリルジメチルアンモニウムクロライドとアクリルアミドの共重合体水溶液、濃度５．５％)の０．２％水溶液に浸漬し、水洗する。
（２）上記塗装板をアニオン性シリカゾル「スノーテックスＮ」の２．０％水分散液に浸漬し、常温で乾燥させる。
（３）上記塗装板をアミノ変性シリコーンオイルエマルジョン「ＢＹ２２−８３０」の０．３％水溶液に浸漬し水洗する操作を２回繰り返し、常温で乾燥した後、接触角と転落角を測定した。
(1) Apply the coated plate to a 0.2% aqueous solution of a cationic polymer compound aqueous solution “Lipoflow MN” (manufactured by Lion Corporation, polydiallyldimethylammonium chloride / acrylamide copolymer aqueous solution, concentration 5.5%). Immerse and wash with water.
(2) The coated plate is immersed in a 2.0% aqueous dispersion of anionic silica sol “Snowtex N” and dried at room temperature.
(3) The operation of immersing the above-mentioned coated plate in a 0.3% aqueous solution of amino-modified silicone oil emulsion “BY22-830” and washing with water was repeated twice. After drying at room temperature, the contact angle and the falling angle were measured.
（１）ガラス板をアルミナゾル「アルミナゾル−２００」(日産化学工業(株)製、粒径１００ｎｍ×１０ｎｍ、Ａｌ２Ｏ３ １０％)の４．０％水分散液に浸漬し、水洗する。
（２）上記ガラス板をアニオン性シリカゾル「スノーテックスＮ」の２．０％水分散液に浸漬し、常温で乾燥させる。
（３）上記ガラス板をアミノ変性シリコーンオイルエマルジョン「ＢＹ２２−８３０」の０．３％水溶液に浸漬し水洗する操作を２回繰り返し、常温で乾燥した後、接触角と転落角を測定した。
(1) The glass plate is immersed in a 4.0% aqueous dispersion of alumina sol “Alumina sol-200” (manufactured by Nissan Chemical Industries, Ltd., particle size 100 nm × 10 nm, Al 2 O 3 10%) and washed with water.
(2) The glass plate is immersed in a 2.0% aqueous dispersion of anionic silica sol “Snowtex N” and dried at room temperature.
(3) The operation of immersing the glass plate in a 0.3% aqueous solution of amino-modified silicone oil emulsion “BY22-830” and washing it with water was repeated twice, dried at room temperature, and then contact angle and sliding angle were measured.
（１）ガラス板をカチオン性シリカゾル「クレボゾール３０ＣＡＬ２５」(ＡＺエレクトロニクス・マテリアルズ(株)製、粒径２５ｎｍ、ＳｉＯ２ ３０％)の１．３％水分散液に浸漬し、水洗する。
（２）上記ガラス板をアニオン性シリカゾル「クレボゾール３０Ｒ２５」の１．３％水分散液に浸漬し、常温で乾燥させる。
（３）上記ガラス板をアミノ変性シリコーンオイルエマルジョン「ＢＹ２２−８３０」の０．３％水溶液に浸漬し水洗する操作を２回繰り返し、常温で乾燥した後、接触角と転落角を測定した。
(1) The glass plate is immersed in a 1.3% aqueous dispersion of cationic silica sol “Crebosol 30CAL25” (manufactured by AZ Electronics Materials, particle size 25 nm, SiO 2 30%) and washed with water.
(2) The glass plate is immersed in a 1.3% aqueous dispersion of anionic silica sol “Crebosol 30R25” and dried at room temperature.
(3) The operation of immersing the glass plate in a 0.3% aqueous solution of amino-modified silicone oil emulsion “BY22-830” and washing it with water was repeated twice, dried at room temperature, and then contact angle and sliding angle were measured.
（１）塗装板をアミノ変性シリコーンオイルエマルジョン「ＢＹ２２−８３０」の０．３％水溶液に浸漬した後、常温で乾燥させる。
（２）上記塗装板をアニオン性シリカゾル「スノーテックスＳ」の０．７％水分散液に浸漬し、常温で乾燥した後、接触角と転落角を測定した。
(1) The coated plate is immersed in a 0.3% aqueous solution of amino-modified silicone oil emulsion “BY22-830” and then dried at room temperature.
(2) The coated plate was immersed in a 0.7% aqueous dispersion of anionic silica sol “Snowtex S”, dried at room temperature, and then contact angle and sliding angle were measured.
（１）塗装板をアミノ変性シリコーンオイルエマルジョン「ＢＹ２２−８３０」の０．３％水溶液に浸漬した後、常温で乾燥させる。
（２）上記塗装板を非イオン界面活性剤「ＩＤ２０６」を０．０５％添加したアニオン性シリカゾル「スノーテックスＮ」の２．０％水分散液に浸漬した後、水洗する。
（３）上記塗装板をアミノ変性シリコーンオイルエマルジョン「ＢＹ２２−８３０」の０．３％水溶液に浸漬し、水洗する操作を２回繰り返し、常温で乾燥した後、接触角と転落角を測定した。
(1) The coated plate is immersed in a 0.3% aqueous solution of amino-modified silicone oil emulsion “BY22-830” and then dried at room temperature.
(2) The coated plate is immersed in a 2.0% aqueous dispersion of anionic silica sol “Snowtex N” to which 0.05% of a nonionic surfactant “ID206” is added, and then washed with water.
(3) The coating plate was immersed in a 0.3% aqueous solution of amino-modified silicone oil emulsion “BY22-830” and washed with water twice. After drying at room temperature, the contact angle and the sliding angle were measured.
（１）ガラス板に、非イオン界面活性剤「ＩＤ２０６」を０．０１％添加したアニオン性シリカゾル「スノーテックスS」の０．７％水分散液をスプレーノズルより噴霧し、常温で乾燥させる。
（２）上記ガラス板に、アミノ変性シリコーンオイルエマルジョン「ＢＹ２２−８３０」の０．３％水溶液をスプレーノズルより噴霧し、スプレーノズルで水洗する操作を２回繰り返し、常温で乾燥した後、接触角と転落角を測定した。
(1) A 0.7% aqueous dispersion of anionic silica sol “Snowtex S” to which 0.01% of a nonionic surfactant “ID206” is added is sprayed on a glass plate from a spray nozzle and dried at room temperature.
(2) A 0.3% aqueous solution of amino-modified silicone oil emulsion “BY22-830” is sprayed from the spray nozzle on the glass plate and washed with the spray nozzle twice, dried at room temperature, and then contact angle. And the falling angle was measured.
（１）塗装板に、アミノ変性シリコーンオイルエマルジョン「ＢＹ２２−８３０」の０．３％水溶液をスプレーノズルより噴霧した後、常温で乾燥させる。
（２）上記塗装板に、非イオン界面活性剤「ＩＤ２０６」を０．０５％添加したアニオン性シリカゾル「スノーテックスＮ」の２．０％水分散液をスプレーノズルより噴霧した後、スプレーノズルで水洗する。
（３）上記塗装板に、アミノ変性シリコーンオイルエマルジョン「ＢＹ２２−８３０」の０．３％水溶液をスプレーノズルより噴霧し、スプレーノズルで水洗する操作を２回繰り返し、常温で乾燥した後、接触角と転落角を測定した。
(1) A 0.3% aqueous solution of amino-modified silicone oil emulsion “BY22-830” is sprayed on a coated plate from a spray nozzle and then dried at room temperature.
(2) A 2.0% aqueous dispersion of anionic silica sol “Snowtex N” containing 0.05% nonionic surfactant “ID206” is sprayed from the spray nozzle onto the above-mentioned coated plate, and then the spray nozzle is used. Wash with water.
(3) A 0.3% aqueous solution of amino-modified silicone oil emulsion “BY22-830” is sprayed from the spray nozzle on the coated plate and washed with water twice with the spray nozzle, dried at room temperature, and then contact angle. And the falling angle was measured.
（１）塗装板に、カチオン性高分子化合物の水溶液「リポフローＭＮ」の０．２％水溶液をスプレーノズルより噴霧し、スプレーノズルで水洗する。
（２）上記塗装板に、アニオン性シリカゾル「スノーテックスＮ」の２．０％水分散液をスプレーノズルより噴霧し、常温で乾燥させる。
（３）上記塗装板に、アミノ変性シリコーンオイルエマルジョン「ＢＹ２２−８３０」の０．３％水溶液をスプレーノズルより噴霧し、スプレーノズルで水洗する操作を２回繰り返し、常温で乾燥した後、接触角と転落角を測定した。
(1) A 0.2% aqueous solution of an aqueous solution of a cationic polymer compound “Lipoflow MN” is sprayed from a spray nozzle onto a coated plate, and washed with a spray nozzle.
(2) A 2.0% aqueous dispersion of anionic silica sol “Snowtex N” is sprayed from the spray nozzle onto the coated plate and dried at room temperature.
(3) A 0.3% aqueous solution of amino-modified silicone oil emulsion “BY22-830” is sprayed from the spray nozzle on the coated plate and washed with water twice with the spray nozzle, dried at room temperature, and then contact angle. And the falling angle was measured.
（１）塗装板に、アルカリ可溶性樹脂水溶液「アクリスＧＳＡ−４０４Ｌ」を０．０１２５％添加したアニオン性シリカゾル「スノーテックスＮ」の１．０％水分散液をスプレーノズルより噴霧し、常温で乾燥させる。
（２）上記塗装板に、アミノ変性シリコーンオイルエマルジョン「ＢＹ２２−８３０」の０．３％水溶液をスプレーノズルより噴霧し、スプレーノズルで水洗する操作を２回繰り返し、常温で乾燥した後、接触角と転落角を測定した。
(1) A 1.0% aqueous dispersion of an anionic silica sol “Snowtex N” containing 0.0125% of an alkali-soluble resin aqueous solution “Acris GSA-404L” is sprayed from a spray nozzle onto a coated plate and dried at room temperature. Let
(2) The operation of spraying a 0.3% aqueous solution of amino-modified silicone oil emulsion “BY22-830” on the above-mentioned coated plate from a spray nozzle and washing with a spray nozzle twice is performed after drying at room temperature, and then the contact angle. And the falling angle was measured.
［比較例］
（１）ガラス板及び塗装板をアミノ変性シリコーンオイルエマルジョン「ＢＹ２２−８３０」の０．３％水溶液に浸漬する。
（２）上記ガラス板及び塗装板を水洗し、常温で乾燥した後、接触角と転落角を測定した。
[Comparative example]
(1) The glass plate and the coated plate are immersed in a 0.3% aqueous solution of amino-modified silicone oil emulsion “BY22-830”.
(2) The glass plate and the coated plate were washed with water and dried at room temperature, and then the contact angle and the falling angle were measured.
上記各実施例及び比較例における接触角と転落角の測定値を表１に示す。
表の結果から明らかなように、アニオン性シリカ微粒子を併用しない比較例と比べ本発明の実施例では転落角が小さく、特に２種類のシリコーンオイルを使用した実施例では転落角が非常に小さくなった。また、実施例２に見られるように接触角、すなわち發水性と、転落角とは必ずしも関係しない。
As is clear from the results of the table, compared to the comparative example in which the anionic silica fine particles are not used in combination, the falling angle is small in the example of the present invention, and in particular, the falling angle is very small in the example using two kinds of silicone oils. It was. Further, as seen in Example 2, the contact angle, that is, the hydrophobicity and the falling angle are not necessarily related.
本発明の滑水性皮膜は、アニオン性シリカ微粒子のシリコーンに対する吸着力及びシリコーンの極性基のアニオン性シリカ微粒子への配向を利用しているので、単に両者を塗布するだけでよく、加水分解などの反応や焼成などの処理を必要としないので誰でも簡単に皮膜を形成することができる。
また、処理剤セットは水系組成物で、有機溶剤を使用しなくて済み、強アルカリ性、強酸性でもないことから環境、塗装面、人体に対し安全であり、洗車機を利用して塗布する場合や、スプレー缶を利用して塗布する場合にも安心して使用できるものであり、産業上の利用性は高い。
Since the water-slidable coating of the present invention utilizes the adsorption force of anionic silica fine particles to silicone and the orientation of polar groups of silicone to anionic silica fine particles, it is only necessary to apply both of them, such as hydrolysis. Since no treatment such as reaction or firing is required, anyone can easily form a film.
In addition, the treatment agent set is an aqueous composition that does not require the use of organic solvents, and is not strongly alkaline or strongly acidic, so it is safe for the environment, painted surface, and human body, and is applied using a car wash machine. In addition, it can be used with peace of mind when applying using a spray can, and its industrial applicability is high.
Claims (20)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005068707A JP4535440B2 (en) | 2005-03-11 | 2005-03-11 | Method for forming water slidable film including layer containing anionic silica fine particles and treatment agent set for forming water slidable film |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005068707A JP4535440B2 (en) | 2005-03-11 | 2005-03-11 | Method for forming water slidable film including layer containing anionic silica fine particles and treatment agent set for forming water slidable film |
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| Publication Number | Publication Date |
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| JP2006247544A true JP2006247544A (en) | 2006-09-21 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009185201A (en) * | 2008-02-07 | 2009-08-20 | Soft99 Corporation | Water-repellent treatment composition for aerosol, and aerosol type water-repellent treatment agent |
| JP2012508108A (en) * | 2008-11-12 | 2012-04-05 | ヒェメタル ゲゼルシャフト ミット ベシュレンクテル ハフツング | Method for coating surfaces with particles and use of coatings formed by this method |
| WO2012157635A1 (en) | 2011-05-18 | 2012-11-22 | 株式会社スリーボンド | Coating layer and method for forming coating layer |
| JP2016104481A (en) * | 2010-03-15 | 2016-06-09 | ロス テクノロジー コーポレーション．Ｒｏｓｓ Ｔｅｃｈｎｏｌｏｇｙ Ｃｏｒｐｏｒａｔｉｏｎ | Plunger and method for obtaining hydrophobic surface |
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| JPH05295354A (en) * | 1992-04-01 | 1993-11-09 | Idemitsu Kosan Co Ltd | Water-repellent emulsion composition and its production |
| JPH1150006A (en) * | 1997-06-04 | 1999-02-23 | Toto Ltd | Pretreatment of surface forming photocalytic hydrophilic coating film and cleaning agent and unedrcoating composition used therefor |
| JP2002210876A (en) * | 2001-01-19 | 2002-07-31 | Nippon Soda Co Ltd | Water repellent layer supporting structure and its manufacturing method |
| JP2003236977A (en) * | 2002-02-19 | 2003-08-26 | Matsushita Electric Works Ltd | Stainproof member |
| JP2005028337A (en) * | 2003-07-11 | 2005-02-03 | Wacker Asahikasei Silicone Co Ltd | Method of applying water-repellent agent for vehicle |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH05295354A (en) * | 1992-04-01 | 1993-11-09 | Idemitsu Kosan Co Ltd | Water-repellent emulsion composition and its production |
| JPH1150006A (en) * | 1997-06-04 | 1999-02-23 | Toto Ltd | Pretreatment of surface forming photocalytic hydrophilic coating film and cleaning agent and unedrcoating composition used therefor |
| JP2002210876A (en) * | 2001-01-19 | 2002-07-31 | Nippon Soda Co Ltd | Water repellent layer supporting structure and its manufacturing method |
| JP2003236977A (en) * | 2002-02-19 | 2003-08-26 | Matsushita Electric Works Ltd | Stainproof member |
| JP2005028337A (en) * | 2003-07-11 | 2005-02-03 | Wacker Asahikasei Silicone Co Ltd | Method of applying water-repellent agent for vehicle |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009185201A (en) * | 2008-02-07 | 2009-08-20 | Soft99 Corporation | Water-repellent treatment composition for aerosol, and aerosol type water-repellent treatment agent |
| JP4682213B2 (en) * | 2008-02-07 | 2011-05-11 | 株式会社ソフト９９コーポレーション | Water-repellent treatment composition for aerosol and aerosol-type water-repellent treatment agent |
| JP2012508108A (en) * | 2008-11-12 | 2012-04-05 | ヒェメタル ゲゼルシャフト ミット ベシュレンクテル ハフツング | Method for coating surfaces with particles and use of coatings formed by this method |
| JP2016104481A (en) * | 2010-03-15 | 2016-06-09 | ロス テクノロジー コーポレーション．Ｒｏｓｓ Ｔｅｃｈｎｏｌｏｇｙ Ｃｏｒｐｏｒａｔｉｏｎ | Plunger and method for obtaining hydrophobic surface |
| WO2012157635A1 (en) | 2011-05-18 | 2012-11-22 | 株式会社スリーボンド | Coating layer and method for forming coating layer |
| US9334408B2 (en) | 2011-05-18 | 2016-05-10 | Threebond Fine Chemical Co., Ltd. | Coating layer and method for forming coating layer |
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| JP4535440B2 (en) | 2010-09-01 |
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