JP5736606B2 - Water-repellent / water-repellent antifouling treatment liquid, water-repellent / water-repellent antifouling film using the same, method for producing the same, and product using them - Google Patents
Water-repellent / water-repellent antifouling treatment liquid, water-repellent / water-repellent antifouling film using the same, method for producing the same, and product using them Download PDFInfo
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Description
本発明は、撥水離水防汚処理液およびそれを用いた撥水離水性防汚膜とその製造方法およびそれらを用いて製造した各種製品に関するものである。 The present invention relates to a water-repellent / water-repellent antifouling treatment liquid, a water-repellent / water-repellent antifouling film using the same, a method for producing the same, and various products produced using them.
さらに詳しくは、フッ化炭素系の撥水離水性防汚膜やアルキルシロキサン系の撥水撥油性防汚膜にさらに炭化水素基を主成分とする第3の物質を添加することにより、撥油性は多少劣るが撥水離水性に優れた防汚膜を製造する際に利用できる撥水離水防汚処理液、およびそれを用いて製造したと基材表面と化学結合した撥水離水性防汚膜およびその製造方法、およびそれらをもちいて製造した各種製品に関するものである。 More specifically, an oil repellency can be obtained by adding a third substance mainly composed of a hydrocarbon group to a fluorocarbon water-repellent and water-repellent antifouling film or an alkylsiloxane water- and oil-repellent antifouling film. Water-repellent and water-repellent antifouling treatment solution that can be used when producing an antifouling film excellent in water repellency and water repellency, and a water-repellent and water-repellent antifouling agent that is chemically bonded to the surface of the substrate. The present invention relates to a film, a manufacturing method thereof, and various products manufactured using them.
なお、ここでいう基材には、金属、半導体、セラミック、ガラス、プラスチック、窯業製品、合成繊維、天然繊維、紙、皮革、毛皮、木材、竹または石等がある。また、撥水離水性防汚膜が形成された物品には、建物の窓ガラス、または自動車等の乗り物の窓ガラス、太陽電池や太陽熱温水器等の太陽エネルギー利用装置のカバーガラス等がある。さらに、それらを装着した製品には、建物、または乗り物、太陽エネルギー利用装置等がある。 Examples of the base material include metals, semiconductors, ceramics, glass, plastics, ceramic products, synthetic fibers, natural fibers, paper, leather, fur, wood, bamboo or stone. Examples of the article on which the water-repellent / water-repellent antifouling film is formed include a window glass of a building, a window glass of a vehicle such as an automobile, a cover glass of a solar energy utilization device such as a solar battery or a solar water heater. Further, the products equipped with them include buildings, vehicles, solar energy utilization devices, and the like.
一般にフッ化炭素基含有クロロシラン系の吸着液と非水系の有機溶媒よりなる化学吸着液を用い、液相で化学吸着して単分子膜状の撥水撥油防汚性化学吸着膜を形成できることはすでによく知られている(例えば、特許文献1参照。)。 Generally, a chemical adsorption solution consisting of a fluorocarbon group-containing chlorosilane-based adsorbent and a non-aqueous organic solvent can be used for chemical adsorption in the liquid phase to form a monomolecular film-like water / oil repellent / antifouling chemical adsorbent film. Is already well known (see, for example, Patent Document 1).
このような溶液中での化学吸着単分子膜の製造原理は、基材表面の水酸基などの活性水素とクロロシラン系の吸着液のクロロシリル基との脱塩酸反応を用いて単分子膜を形成することにある。 The principle of production of a chemisorbed monolayer in such a solution is to form a monolayer by using a dehydrochlorination reaction between active hydrogen such as hydroxyl groups on the substrate surface and chlorosilyl groups of a chlorosilane-based adsorbent. It is in.
しかしながら、従来のフッ化炭素系の撥水撥油防汚化学吸着液は、撥水撥油防汚性に優れた被膜は得られるが、水滴転落角が高いため離水性が悪いという課題があった。 However, conventional fluorocarbon water / oil repellent / antifouling chemical adsorbents can provide coatings with excellent water / oil repellent / antifouling properties, but have the problem of poor water separation due to the high water drop falling angle. It was.
そこで、前記課題解決の手段として提供される、第1の発明群は、撥水離水性に優れ、且つ耐摩耗性や耐水性に優れた撥水離水性防汚膜が形成可能な撥水離水防汚処理液である。 Therefore, a first invention group provided as means for solving the above problems is a water repellent release that can form a water repellent and water-repellent antifouling film that is excellent in water repellent and water repellent properties and excellent in wear resistance and water resistance. It is a water pollution treatment liquid.
第2の発明群は、撥水離水性に優れ、且つ耐摩耗性や耐水性に優れた防汚膜、及び撥水離水性に優れ、且つ耐摩耗性や耐水性に優れた防汚膜の製造方法である。 The second invention group is an antifouling film excellent in water repellency and water resistance and excellent in abrasion resistance and water resistance, and an antifouling film excellent in water repellency and water repellency and excellent in abrasion resistance and water resistance. It is a manufacturing method.
第3の発明群は、前記撥水離水性防汚膜を形成した物品と、それら物品を装着した各種製品である。 A third invention group includes articles formed with the water-repellent and water-repellent antifouling film and various products equipped with the articles.
本発明は、撥水性と離水性に優れた防汚膜を提供するため、フッ化炭素系の撥水離水性防汚膜やジメチルシロキサン基等の官能基を含むアルキルシロキサン系の撥水離水性防汚膜に、さらに第3の物質として、離水性に優れた炭化水素基を主成分とする物質を添加することを最も主要な特徴とする。 In order to provide an antifouling film excellent in water repellency and water separation, the present invention provides a fluorocarbon-based water-repellent / water-repellent antifouling film and an alkylsiloxane-based water / water-repellent / water-repellent film containing a functional group such as a dimethylsiloxane group. The main feature is to add a substance mainly composed of a hydrocarbon group excellent in water separation as a third substance to the antifouling film.
さらに詳しくは、少なくともフッ化炭素基を主成分とする物質1と、炭化水素基を主成分とする物質2と、溶媒とを含む撥水離水防汚処理液を提供する。
また、少なくともフッ化炭素基を主成分とする物質1と、炭化水素基を主成分とする物質2と、シロキサン基を主成分とする物質3と、溶媒とを含む撥水離水防汚処理液を提供する。
More specifically, a water-repellent / water-repellent antifouling treatment liquid comprising at least a substance 1 containing a fluorocarbon group as a main component, a substance 2 containing a hydrocarbon group as a main component, and a solvent is provided.
Further, a water-repellent / water-repellent antifouling treatment liquid comprising at least a substance 1 containing a fluorocarbon group as a main component, a substance 2 containing a hydrocarbon group as a main component, a substance 3 containing a siloxane group as a main component, and a solvent. I will provide a.
さらにまた、少なくともジメチルシロキサン基を主成分とする物質4と、炭化水素基を主成分とする物質2と、溶媒とを含むことを特徴とする撥水離水防汚処理液を提供する。
また、少なくともジメチルシリルキ基を主成分とする物質4と、炭化水素基を主成分とする物質2と、シロキサン基を主成分とする物質3と、非水系有機溶媒とを含む撥水離水防汚処理液を提供する。
Furthermore, the present invention provides a water-repellent and water-repellent antifouling treatment liquid comprising at least a substance 4 containing a dimethylsiloxane group as a main component, a substance 2 containing a hydrocarbon group as a main component, and a solvent.
Further, the water repellent and water-repellent water-proofing material comprising at least a substance 4 having a dimethylsilyl group as a main component, a substance 2 having a hydrocarbon group as a main component, a substance 3 having a siloxane group as a main component, and a non-aqueous organic solvent. Provide a soil treatment solution.
また、少なくとも短鎖のフッ化炭素基を主成分とする物質1’と、長鎖のフッ化炭素基と炭化水素基を主成分とする物質1”と炭化水素基を主成分とする物質2と、溶媒とを含む撥水離水防汚処理液を提供する。
また、少なくとも短鎖のフッ化炭素基を主成分とする物質1’と、長鎖のフッ化炭素基と炭化水素基を主成分とする物質1”と炭化水素基を主成分とする物質2と、シロキサン基を主成分とする物質3と、溶媒とを含む撥水離水防汚処理液を提供する。
Further, at least a substance 1 ′ mainly composed of a short-chain fluorocarbon group, a substance 1 ″ mainly composed of a long-chain fluorocarbon group and a hydrocarbon group, and a substance 2 mainly composed of a hydrocarbon group. And a water-repellent / water-repellent antifouling treatment liquid containing the solvent.
Further, at least a substance 1 ′ mainly composed of a short-chain fluorocarbon group, a substance 1 ″ mainly composed of a long-chain fluorocarbon group and a hydrocarbon group, and a substance 2 mainly composed of a hydrocarbon group. And a water repellent / water-repellent antifouling treatment liquid comprising a substance 3 containing a siloxane group as a main component and a solvent.
このとき、溶媒が非水系有機溶媒であり、物質1〜4および1’と1”がさらにクロロシリル基、またはシアノシリル基、アルコキシシリル基を含むと、基材表面と共有結合で処理物質を固定できて都合がよい。
また、溶媒がシラノール縮合触媒または有機酸を含む非水系有機溶媒であり、物質1〜4および1’と1”がさらにアルコキシシリル基を含むと、反応時間を短縮できて都合がよい。
At this time, if the solvent is a non-aqueous organic solvent and the substances 1 to 4 and 1 ′ and 1 ″ further contain a chlorosilyl group, a cyanosilyl group, or an alkoxysilyl group, the treatment substance can be fixed covalently to the substrate surface. Convenient.
Further, it is convenient that the solvent is a silanol condensation catalyst or a non-aqueous organic solvent containing an organic acid, and the substances 1 to 4 and 1 ′ and 1 ″ further contain an alkoxysilyl group, because the reaction time can be shortened.
さらに、溶媒が水系溶媒であり、物質1〜4および1’と1”がさらにアルコキシシリル基を含むと、有機溶媒による環境汚染を低減する上で都合がよい。
さらにまた、水系溶媒に、アルコールおよび/または陽イオン界面活性剤を含めておくと、水系処理液の安定性を向上できて都合がよい。
Furthermore, when the solvent is an aqueous solvent and the substances 1 to 4 and 1 ′ and 1 ″ further contain an alkoxysilyl group, it is convenient to reduce environmental pollution due to the organic solvent.
Furthermore, it is advantageous to include an alcohol and / or a cationic surfactant in the aqueous solvent because the stability of the aqueous treatment liquid can be improved.
また、撥水離水性防汚膜として、少なくともフッ化炭素基を主成分とする物質1と、炭化水素基を主成分とする物質2とを含む撥水離水性防汚膜を提供する。
さらに、少なくともフッ化炭素基を主成分とする物質1と、炭化水素基を主成分とする物質2と、シロキサン基を主成分とする物質3とを含む撥水離水性防汚膜を提供する。。
さらにまた、少なくともジメチルシロキサン基を主成分とする物質4と、炭化水素基を主成分とする物質2とを含む撥水離水性防汚膜を提供する。
また、少なくともジメチルシリルキ基を主成分とする物質4と、炭化水素基を主成分とする物質2と、シロキサン基を主成分とする物質3とを含む撥水離水性防汚膜を提供する。
Also provided is a water-repellent / water-repellent antifouling film comprising at least a substance 1 mainly composed of a fluorocarbon group and a substance 2 composed mainly of a hydrocarbon group.
Furthermore, a water-repellent and water-repellent antifouling film comprising at least a substance 1 mainly composed of a fluorocarbon group, a substance 2 mainly composed of a hydrocarbon group, and a substance 3 mainly composed of a siloxane group is provided. . .
Furthermore, the present invention provides a water-repellent and water-repellent antifouling film comprising at least a substance 4 mainly composed of dimethylsiloxane groups and a substance 2 mainly composed of hydrocarbon groups.
Also provided is a water-repellent and water-repellent antifouling film comprising at least a substance 4 having a dimethylsilyl group as a main component, a substance 2 having a hydrocarbon group as a main component, and a substance 3 having a siloxane group as a main component. .
また、少なくとも短鎖のフッ化炭素基を主成分とする物質1’と、長鎖のフッ化炭素基と炭化水素基を主成分とする物質1”と炭化水素基を主成分とする物質2とを含む撥水離水性防汚膜を提供する。
また、少なくとも短鎖のフッ化炭素基を主成分とする物質1’と、長鎖のフッ化炭素基と炭化水素基を主成分とする物質1”と炭化水素基を主成分とする物質2と、シロキサン基を主成分とする物質3とを含む撥水離水性防汚膜を提供する。
ここで、撥水離水性防汚膜の基材には、金属、半導体、セラミック、プラスチック、窯業製品、合成繊維、天然繊維、紙、皮革、毛皮、木材、竹または石が利用できる。
Further, at least a substance 1 ′ mainly composed of a short-chain fluorocarbon group, a substance 1 ″ mainly composed of a long-chain fluorocarbon group and a hydrocarbon group, and a substance 2 mainly composed of a hydrocarbon group. And a water-repellent and water-repellent antifouling film.
Further, at least a substance 1 ′ mainly composed of a short-chain fluorocarbon group, a substance 1 ″ mainly composed of a long-chain fluorocarbon group and a hydrocarbon group, and a substance 2 mainly composed of a hydrocarbon group. And a water-repellent / water-repellent antifouling film comprising the substance 3 having a siloxane group as a main component.
Here, metals, semiconductors, ceramics, plastics, ceramic products, synthetic fibers, natural fibers, paper, leather, fur, wood, bamboo, or stone can be used as the base material for the water repellent / water-repellent antifouling membrane.
さらに、撥水離水性防汚膜の製造方法としては、少なくともフッ化炭素基を主成分とする物質1と、炭化水素基を主成分とする物質2と、溶媒とを含む撥水離水防汚処理液に部材表面を接触させて反応させる工程を含む撥水離水性防汚膜の製造方法を提供する。
また、少なくともフッ化炭素基を主成分とする物質1と、炭化水素基を主成分とする物質2と、シロキサン基を主成分とする物質3と、溶媒とを含む撥水離水防汚処理液に部材表面を接触させて反応させる工程を含む撥水離水性防汚膜の製造方法を提供する。
Furthermore, as a method for producing a water-repellent / water-repellent antifouling film, the water-repellent / water-repellent / antifouling method includes at least a substance 1 mainly composed of a fluorocarbon group, a substance 2 composed mainly of a hydrocarbon group, and a solvent. Provided is a method for producing a water-repellent and water-repellent antifouling film comprising a step of bringing a member surface into contact with a treatment liquid and reacting it.
Further, a water-repellent / water-repellent antifouling treatment liquid comprising at least a substance 1 containing a fluorocarbon group as a main component, a substance 2 containing a hydrocarbon group as a main component, a substance 3 containing a siloxane group as a main component, and a solvent. A method for producing a water-repellent and water-repellent antifouling film comprising a step of bringing a member surface into contact with a reaction is provided.
さらに、少なくともジメチルシロキサン基を主成分とする物質4と、炭化水素基を主成分とする物質2と、溶媒とを含む撥水離水防汚処理液に部材表面を接触させて反応させる工程を含む撥水離水性防汚膜の製造方法を提供する。
さらにまた、少なくともジメチルシリルキ基を主成分とする物質4と、炭化水素基を主成分とする物質2と、シロキサン基を主成分とする物質3と、非水系有機溶媒とを含む撥水離水防汚処理液に部材表面を接触させて反応させる工程を含む撥水離水性防汚膜の製造方法を提供する。
また、少なくとも短鎖のフッ化炭素基を主成分とする物質1’と、長鎖のフッ化炭素基と炭化水素基を主成分とする物質1”と炭化水素基を主成分とする物質2と、溶媒とを含む撥水離水防汚処理液に部材表面を接触させて反応させる工程を含む撥水離水性防汚膜の製造方法を提供する。
Furthermore, it includes a step of bringing the surface of the member into contact with a water-repellent / water-repellent antifouling treatment liquid containing at least a substance 4 having a dimethylsiloxane group as a main component, a substance 2 having a hydrocarbon group as a main component, and a solvent. A method for producing a water-repellent / water-repellent antifouling film is provided.
Furthermore, the water-repellent separation containing at least a substance 4 mainly containing a dimethylsilyl group, a substance 2 mainly containing a hydrocarbon group, a substance 3 mainly containing a siloxane group, and a non-aqueous organic solvent. Provided is a method for producing a water-repellent and water-repellent antifouling film comprising a step of bringing a member surface into contact with a water antifouling treatment liquid and causing it to react.
Further, at least a substance 1 ′ mainly composed of a short-chain fluorocarbon group, a substance 1 ″ mainly composed of a long-chain fluorocarbon group and a hydrocarbon group, and a substance 2 mainly composed of a hydrocarbon group. And a method for producing a water-repellent and water-repellent antifouling film comprising a step of bringing a member surface into contact with and reacting with a water-repellent and water-repellent antifouling treatment solution containing a solvent.
また、少なくとも短鎖のフッ化炭素基を主成分とする物質1’と、長鎖のフッ化炭素基と炭化水素基を主成分とする物質1”と炭化水素基を主成分とする物質2と、シロキサン基を主成分とする物質3と、溶媒とを含む撥水離水防汚処理液に部材表面を接触させて反応させる工程を含む撥水離水性防汚膜の製造方法を提供する。
このとき、溶媒が非水系有機溶媒であり、物質1〜4および1’と1”がさらにクロロシリル基、またはシアノシリル基、アルコキシシリル基を含むと、基材表面に結合した撥水離水性防汚膜を製造できて都合がよい。
また、溶媒がシラノール縮合触媒または有機酸を含む非水系有機溶媒であり、物質1〜4および1’と1”がさらにアルコキシシリル基を含むと、製造時間を短縮できて都合がよい。
また、溶媒が水系溶媒であり、物質1〜4および1’と1”がさらにアルコキシシリル基を含むと、環境への負荷を小さくできて都合がよい。
また、水系溶媒がアルコールおよび/または陽イオン界面活性剤を含むと、処理液の凝集分離を押さえ、長時間安定に処理できて都合がよい。
Further, at least a substance 1 ′ mainly composed of a short-chain fluorocarbon group, a substance 1 ″ mainly composed of a long-chain fluorocarbon group and a hydrocarbon group, and a substance 2 mainly composed of a hydrocarbon group. And a method for producing a water-repellent and water-repellent antifouling film comprising a step of bringing a member surface into contact with and reacting with a water-repellent and water-repellent antifouling treatment liquid containing a substance 3 containing siloxane groups as main components and a solvent.
At this time, if the solvent is a non-aqueous organic solvent and the substances 1 to 4 and 1 'and 1 "further contain a chlorosilyl group, a cyanosilyl group or an alkoxysilyl group, the water-repellent and water-repellent antifouling agent bonded to the substrate surface It is convenient to produce a membrane.
In addition, it is advantageous that the solvent is a silanol condensation catalyst or a non-aqueous organic solvent containing an organic acid, and the substances 1 to 4 and 1 ′ and 1 ″ further contain an alkoxysilyl group, because the production time can be shortened.
Moreover, when the solvent is an aqueous solvent and the substances 1 to 4 and 1 ′ and 1 ″ further contain an alkoxysilyl group, it is advantageous because the burden on the environment can be reduced.
In addition, when the aqueous solvent contains an alcohol and / or a cationic surfactant, it is advantageous in that the aggregation and separation of the treatment liquid can be suppressed and the treatment can be performed stably for a long time.
なお、前記撥水離水性防汚膜の製造方法の基材として、金属、半導体、セラミック、プラスチック、窯業製品、合成繊維、天然繊維、紙、皮革、毛皮、木材、竹または石が利用可能である。
さらにまた、この様な撥水離水性防汚膜や撥水離水性防汚膜の製造方法を用いれば、撥水離水防汚性に優れた物品を製造でき、さらに、それらを装着した撥水離水防汚に優れた製品をも提供できる。
In addition, metals, semiconductors, ceramics, plastics, ceramic products, synthetic fibers, natural fibers, paper, leather, fur, wood, bamboo, or stone can be used as the base material for the water repellent / water-repellent antifouling membrane. is there.
Furthermore, by using such a method for producing a water-repellent / water-repellent antifouling membrane or a water-repellent / water-repellent antifouling membrane, an article excellent in water / repellent / water-repellent / antifouling properties can be produced, It can also provide products with excellent water separation and antifouling properties.
以上説明したように、本発明を用いれば、撥水撥油性で、且つ離水性に優れた防汚膜を提供できる効果がある。 As described above, the use of the present invention has an effect of providing an antifouling film that is water and oil repellent and excellent in water separation.
さらに、処理液の主要溶媒として、水系溶媒を用いれば、有機溶液の使用量を削減できることにより、環境負荷を大幅に低減できる効果がある。 Furthermore, if an aqueous solvent is used as the main solvent of the treatment liquid, the amount of the organic solution used can be reduced, which has the effect of greatly reducing the environmental burden.
前記第1の課題を解決するための手段として提供される第1の発明群は、
少なくともフッ化炭素基を主成分とする物質1と、炭化水素基を主成分とする物質2と、溶媒、
または、フッ化炭素基を主成分とする物質1と、炭化水素基を主成分とする物質2と、シロキサン基を主成分とする物質3と、溶媒
または、ジメチルシロキサン基を主成分とする物質4と、炭化水素基を主成分とする物質2と、溶媒
または、ジメチルシリルキ基を主成分とする物質4と、炭化水素基を主成分とする物質2と、シロキサン基を主成分とする物質3と、非水系有機溶媒
とを含む撥水離水防汚処理液を提供する。
The first invention group provided as means for solving the first problem is as follows:
A substance 1 having at least a fluorocarbon group as a main component, a substance 2 having a hydrocarbon group as a main component, a solvent,
Alternatively, a substance 1 containing a fluorocarbon group as a main component, a substance 2 containing a hydrocarbon group as a main component, a substance 3 containing a siloxane group as a main component, and a solvent or a substance containing a dimethylsiloxane group as a main component 4, a substance 2 mainly containing a hydrocarbon group, a substance 4 containing a solvent or a dimethylsilyl group as a main ingredient, a substance 2 containing a hydrocarbon group as a main ingredient, and a siloxane group as a main ingredient Provided is a water-repellent / water-repellent antifouling treatment liquid containing a substance 3 and a non-aqueous organic solvent.
また、短鎖のフッ化炭素基を主成分とする物質1’と、長鎖のフッ化炭素基と炭化水素基を主成分とする物質1”と炭化水素基を主成分とする物質2と、溶媒
または、短鎖のフッ化炭素基を主成分とする物質1’と、長鎖のフッ化炭素基と炭化水素基を主成分とする物質1”と炭化水素基を主成分とする物質2と、シロキサン基を主成分とする物質3と、溶媒
とを含む撥水離水防汚処理液を提供する。
Further, a substance 1 ′ mainly composed of a short-chain fluorocarbon group, a substance 1 ″ composed mainly of a long-chain fluorocarbon group and a hydrocarbon group, and a substance 2 composed mainly of a hydrocarbon group, , A solvent or a substance 1 'mainly composed of a short-chain fluorocarbon group, a substance 1 "composed mainly of a long-chain fluorocarbon group and a hydrocarbon group, and a substance mainly composed of a hydrocarbon group A water-repellent / water-repellent antifouling treatment liquid comprising 2, a substance 3 containing a siloxane group as a main component, and a solvent is provided.
第2の発明群は、少なくともフッ化炭素基を主成分とする物質1と、炭化水素基を主成分とする物質2と、溶媒とを含む撥水離水防汚処理液に部材表面を接触させて反応させることにより、少なくともフッ化炭素基を主成分とする物質1と、炭化水素基を主成分とする物質2とを含む、
または、少なくともフッ化炭素基を主成分とする物質1と、炭化水素基を主成分とする物質2と、シロキサン基を主成分とする物質3と、溶媒とを含む撥水離水防汚処理液に部材表面を接触させて反応させることにより、少なくともフッ化炭素基を主成分とする物質1と、炭化水素基を主成分とする物質2と、シロキサン基を主成分とする物質3とを含む、
In a second invention group, the surface of a member is brought into contact with a water-repellent / water-repellent antifouling treatment liquid containing at least a substance 1 mainly composed of a fluorocarbon group, a substance 2 mainly composed of a hydrocarbon group, and a solvent. By reacting, the substance 1 containing at least a fluorocarbon group as a main component and the substance 2 containing a hydrocarbon group as a main component are included.
Alternatively, a water-repellent and water-repellent antifouling treatment liquid comprising at least a substance 1 containing a fluorocarbon group as a main component, a substance 2 containing a hydrocarbon group as a main component, a substance 3 containing a siloxane group as a main component, and a solvent. The material surface is brought into contact with and reacted with each other to contain at least a substance 1 mainly composed of a fluorocarbon group, a substance 2 mainly composed of a hydrocarbon group, and a substance 3 mainly composed of a siloxane group. ,
または、少なくともジメチルシロキサン基を主成分とする物質4と、炭化水素基を主成分とする物質2と、溶媒とを含む撥水離水防汚処理液に部材表面を接触させて反応させることにより、少なくともジメチルシロキサン基を主成分とする物質4と、炭化水素基を主成分とする物質2とを含む、
または、少なくともジメチルシロキサン基を主成分とする物質4と、炭化水素基を主成分とする物質2と、シロキサン基を主成分とする物質3と、非水系有機溶媒とを含む撥水離水防汚処理液に部材表面を接触させて反応させることにより、少なくともジメチルシリルキ基を主成分とする物質4と、炭化水素基を主成分とする物質2と、シロキサン基を主成分とする物質3とを含む、
Alternatively, by contacting the surface of the member with a water-repellent / water-repellent antifouling treatment liquid containing at least a substance 4 mainly containing a dimethylsiloxane group, a substance 2 containing a hydrocarbon group as a main ingredient, and a solvent, A substance 4 containing at least a dimethylsiloxane group as a main component and a substance 2 containing a hydrocarbon group as a main component,
Alternatively, a water repellent and water-repellent antifouling containing at least a substance 4 having a dimethylsiloxane group as a main component, a substance 2 having a hydrocarbon group as a main component, a substance 3 having a siloxane group as a main component, and a non-aqueous organic solvent. By bringing the surface of the member into contact with the treatment liquid and reacting it, a substance 4 having at least a dimethylsilyl group as a main component, a substance 2 having a hydrocarbon group as a main component, and a substance 3 having a siloxane group as a main component, including,
または、少なくとも短鎖のフッ化炭素基を主成分とする物質1’と、長鎖のフッ化炭素基と炭化水素基を主成分とする物質1”と炭化水素基を主成分とする物質2と、溶媒とを含む撥水離水防汚処理液に部材表面を接触させて反応させることにより、少なくとも短鎖のフッ化炭素基を主成分とする物質1’と、長鎖のフッ化炭素基と炭化水素基を主成分とする物質1”と炭化水素基を主成分とする物質2とを含む Alternatively, at least a substance 1 ′ mainly composed of a short-chain fluorocarbon group, a substance 1 ″ composed mainly of a long-chain fluorocarbon group and a hydrocarbon group, and a substance 2 composed mainly of a hydrocarbon group. And a water-repellent / water-repellent antifouling treatment solution containing a solvent and contacting the surface of the member to cause a reaction, whereby a substance 1 ′ containing at least a short-chain fluorocarbon group as a main component and a long-chain fluorocarbon group And a substance 1 "mainly containing a hydrocarbon group and a substance 2 mainly containing a hydrocarbon group
または、少なくとも短鎖のフッ化炭素基を主成分とする物質1’と、長鎖のフッ化炭素基と炭化水素基を主成分とする物質1”と炭化水素基を主成分とする物質2と、シロキサン基を主成分とする物質3と、溶媒とを含む撥水離水防汚処理液に部材表面を接触させて反応させることにより、少なくとも短鎖のフッ化炭素基を主成分とする物質1’と、長鎖のフッ化炭素基と炭化水素基を主成分とする物質1”と炭化水素基を主成分とする物質2と、シロキサン基を主成分とする物質3とを含む
撥水離水性防汚膜を提供する。
Alternatively, at least a substance 1 ′ mainly composed of a short-chain fluorocarbon group, a substance 1 ″ composed mainly of a long-chain fluorocarbon group and a hydrocarbon group, and a substance 2 composed mainly of a hydrocarbon group. And a substance mainly composed of at least a short-chain fluorocarbon group by reacting the surface of the member with a water repellent / water-repellent antifouling treatment liquid containing a substance 3 mainly composed of a siloxane group and a solvent. Water repellent comprising 1 ′, a substance 1 ″ mainly composed of a long-chain fluorocarbon group and a hydrocarbon group, a substance 2 mainly composed of a hydrocarbon group, and a substance 3 mainly composed of a siloxane group Provide a water-repellent antifouling film.
第3の発明群は、前記第2の発明群により製造された撥水離水性防汚膜を形成した物品と、それら物品を装着した製品を提供する。 The third invention group provides an article formed with the water repellent and water-repellent antifouling film produced by the second invention group, and a product equipped with the article.
本発明の詳細を、以下、実施例を用いて具体的に説明するが、本願発明は、これら実施例により何ら限定されるものではない。
なお、ここでいう基材には、金属、半導体、セラミック、ガラス、プラスチック、窯業製品、合成繊維、天然繊維、紙、皮革、毛皮、木材、竹または石等がある。また、撥水離水性防汚膜が形成された物品には、建物の窓ガラス、または自動車等の乗り物の窓ガラス、太陽電池や太陽熱温水器等の太陽エネルギー利用装置のカバーガラス等がある。さらに、それらを装着した製品には、建物、または乗り物、太陽エネルギー利用装置等がある。
Details of the present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.
Examples of the base material include metals, semiconductors, ceramics, glass, plastics, ceramic products, synthetic fibers, natural fibers, paper, leather, fur, wood, bamboo or stone. Examples of the article on which the water-repellent / water-repellent antifouling film is formed include a window glass of a building, a window glass of a vehicle such as an automobile, a cover glass of a solar energy utilization device such as a solar battery or a solar water heater. Further, the products equipped with them include buildings, vehicles, solar energy utilization devices, and the like.
以下、一例として、まず、1番目の発明群の撥水離水防汚処理液とその製造方法について説明する。
次に、基材を、表面が親水性の透明基材の代表例であるガラス基板とし、前記処理液を用いた撥水離水防汚膜とその製造方法を詳細に説明する。
なお、本実施例においては、特に記載していない限り分子組成比はモル比を意味する。また、特に記載のない%は、重量%を意味する。
Hereinafter, as an example, the water repellent / fouling and antifouling treatment liquid of the first invention group and the production method thereof will be described first.
Next, the base material is a glass substrate which is a representative example of a transparent base material having a hydrophilic surface, and the water-repellent / water-repellent antifouling film using the treatment liquid and the production method thereof will be described in detail.
In this example, the molecular composition ratio means a molar ratio unless otherwise specified. Further, “%” not particularly described means “% by weight”.
図1は、本発明の撥水離水性防汚膜の概要を分子レベルまで拡大して示したものである。 FIG. 1 shows an outline of the water-repellent / water-repellent and antifouling film of the present invention up to the molecular level.
図2は、本発明の実施例である撥水離水性防汚膜を形成したガラス板の転落角変化を比較例と一緒に示している。 FIG. 2 shows the change in the falling angle of a glass plate on which a water-repellent / water-repellent antifouling film as an example of the present invention is formed together with a comparative example.
例えば、フッ化炭素基と炭化水素基とクロロシリル基を主成分とする物質として、CF3−(CF2)7−(CH2)2−SiCl3、炭化水素基とクロロシリル基を主成分とする物質として、CH3−(CH2)9−SiCl3を、それぞれ0.01mol/Lの濃度(0.1〜0.001mol/L以下の濃度が好ましい。)になるようにヘキサデカンに添加して(この場合、フッ化炭素基を主成分とする物質と炭化水素基を主成分とする物質2の分子組成比は1:2になる。好ましくは、2:1〜1:10、より好ましくは、1:1〜1:5であった。)撥水離水防汚処理液を調整した。その後、さらに、クロロシロキサン基を主成分とする物質として、Cl3Si(OSiCl2)mCl(mは、0または整数、Cl基がメトキシ基であるアルコキシシリル基を主成分とする物質でも、被膜形成後空気中で水分を吸収して加水分解するので問題はなかった。)を添加した。 For example, a material mainly containing hydrocarbon group and a chlorosilyl group and fluorocarbon group, CF 3 - (CF 2) 7 - (CH 2) 2 -SiCl 3, mainly composed of hydrocarbon group and a chlorosilyl group As a substance, CH 3 — (CH 2 ) 9 —SiCl 3 was added to hexadecane so as to have a concentration of 0.01 mol / L (preferably a concentration of 0.1 to 0.001 mol / L or less). (In this case, the molecular composition ratio of the substance mainly composed of a fluorocarbon group and the substance 2 mainly composed of a hydrocarbon group is 1: 2, preferably 2: 1 to 1:10, more preferably 1: 1 to 1: 5.) A water-repellent and water-repellent antifouling treatment solution was prepared. Thereafter, further, as a substance having a chlorosiloxane group as a main component, Cl 3 Si (OSiCl 2 ) m Cl (m is 0 or an integer, and a substance having an alkoxysilyl group whose Cl group is a methoxy group as a main component, After the film was formed, there was no problem because water was absorbed in the air and hydrolyzed.
次に、例えば自動車用窓ガラス(建物用窓ガラスや太陽電池、太陽熱温水器の保護ガラス等にも同様に使用できた。)に用いられる青板ガラス板をよく洗浄し、乾燥後、表面に前記撥水離水防汚処理液を塗布し1〜2時間反応させた。その後、表面に居残った余分な撥水離水防汚処理液をアルコールを用いて洗浄除去するかふき取れば、耐久性に優れ且つ撥水離水性に優れた撥水離水性防汚膜が形成できた。 Next, for example, a blue glass plate used for window glass for automobiles (similarly used for building window glass, solar cells, protective glass for solar water heaters, etc.) was washed well, dried, and the surface was A water repellent / water-repellent antifouling treatment solution was applied and reacted for 1 to 2 hours. After that, if the excess water-repellent water-repellent antifouling treatment liquid remaining on the surface is washed and removed with alcohol, a water-repellent and water-repellent antifouling membrane having excellent durability and water-repellent and water-repellent properties can be formed. It was.
このとき、青板ガラス板表面は水酸基すなわち活性水素を多数含み、且つ吸着水で被われているので、前記ガラス板表面で三つの物質のSiCl基と前記水酸基や吸着水とが脱塩酸反応して、フッ化炭素基と炭化水素基とクロロシリル基を主成分とする物質と、炭化水素基とクロロシリル基を主成分とする物質を主成分とする物質と、クロロシロキサン基を主成分とする物質が混合反応し、ポリシロキサン結合を含んだ状態で−SiO−を介して前記ガラス板表面に結合する。 At this time, since the surface of the blue plate glass plate contains a large number of hydroxyl groups, that is, active hydrogen, and is covered with adsorbed water, the SiCl groups of the three substances and the hydroxyl group or adsorbed water undergo a dehydrochlorination reaction on the glass plate surface. A substance mainly composed of a fluorocarbon group, a hydrocarbon group and a chlorosilyl group, a substance mainly composed of a substance mainly composed of a hydrocarbon group and a chlorosilyl group, and a substance mainly composed of a chlorosiloxane group. The mixed reaction causes bonding to the surface of the glass plate via -SiO- in a state including a polysiloxane bond.
すなわち、図1に示すように、フッ化炭素基と炭化水素基とクロロシリル基を主成分とする物質と、炭化水素基とクロロシリル基を主成分とする物質を主成分とする物質と、クロロシロキサン基を主成分とする物質が混合反応し、フッ化炭素基と炭化水素基とクロロシリル基を主成分とする物質は、フッ化炭素基を主成分とする物質1に、炭化水素基とクロロシリル基を主成分とする物質は、炭化水素基を主成分とする物質2に、クロロシロキサン基を主成分とする物質は、ポリシロキサン結合を含んだ物質3にそれぞれ反応変化し、それぞれがシロキサン結合4を介して直接あるいは間接に前記ガラス板5表面に結合したフッ化炭素基を主成分とする物質1と、炭化水素基を主成分とする物質2と、シロキサン基を主成分とする物質3を含んだ耐久性に優れ且つ撥水離水性に優れた撥水離水性防汚膜6を形成できた。 That is, as shown in FIG. 1, a substance mainly composed of a fluorocarbon group, a hydrocarbon group and a chlorosilyl group, a substance mainly composed of a substance mainly composed of a hydrocarbon group and a chlorosilyl group, and a chlorosiloxane A substance mainly composed of a group undergoes a mixed reaction, and a substance mainly composed of a fluorocarbon group, a hydrocarbon group, and a chlorosilyl group, The substance having the main component is changed to the substance 2 containing the hydrocarbon group as the main component, and the substance having the chlorosiloxane group as the main component is changed to the substance 3 containing the polysiloxane bond, respectively. A substance 1 having a fluorocarbon group as a main component, a substance 2 having a hydrocarbon group as a main component, and a substance 3 having a siloxane group as a main component, which are bonded directly or indirectly to the surface of the glass plate 5 via Including It was able to form a water-repellent water separation antifouling 6 excellent excellent and water-repellent water separation durability.
なお、この被膜の水滴接触角は、102.4°であった。また、水滴転落角は、50マイクロリットルで、8°であり、驚異的に低かった。
また、このとき、フッ化炭素基を主成分とする物質1や炭化水素基を主成分とする物質2は、クロロシロキサン基を主成分とする物質が混合反応してできた網目状のポリシロキサン結合7(シロキサン基を主成分とする物質3)で大部分が囲われているため、耐摩耗性も非常に高かった。
布を用いた加重600g/cm2の摩耗試験でも、1万往復で水滴接触角は、100°を維持できた。
The water droplet contact angle of this coating was 102.4 °. The water drop falling angle was 50 microliters and 8 °, which was surprisingly low.
At this time, the substance 1 having a fluorocarbon group as a main component and the substance 2 having a hydrocarbon group as a main component are a network-like polysiloxane formed by mixing and reacting a substance having a chlorosiloxane group as a main component. Since the bond 7 (substance 3 having a siloxane group as a main component) is mostly enclosed, the wear resistance is very high.
Even in a wear test using a cloth at a load of 600 g / cm 2 , the water droplet contact angle could be maintained at 100 ° after 10,000 reciprocations.
実施例1において、クロロシロキサン基を主成分とする物質を除いた他は同条件で試作を行うと、実用レベルではあったが、耐摩耗性は1/3程度まで劣化した。
また、被膜の水滴接触角は、やや高くなり、105°であったが、低転落角度は維持できた。
In Example 1, when a prototype was produced under the same conditions except that the substance containing chlorosiloxane group as a main component was removed, the wear resistance was deteriorated to about 1/3 although it was at a practical level.
Further, the water droplet contact angle of the coating was slightly higher and was 105 °, but the low falling angle could be maintained.
(比較例1)
実施例1において、炭化水素基とクロロシリル基を主成分とする物質を除いた他、同条件で試作を行うと、被膜の水滴接触角は、だいぶ高くなり、116°であったが、転落角が23度と大幅に高くなった。
以上の試作結果から、クロロシロキサン基を主成分とする物質の添加は、耐摩耗性の向上に効果が大きいことが判明した。
また、炭化水素基とクロロシリル基を主成分とする物質の添加は、水滴転落角を小さくする効果が大きいことが判明した。
実施例1で作成した被膜と、比較例1で作成した被膜の水滴量と転落角度の関係を図2に示す。実施例1の被膜では、転落角度が大幅に改善できていることが判る。
(Comparative Example 1)
In Example 1, when the trial production was carried out under the same conditions except for the substance mainly composed of hydrocarbon group and chlorosilyl group, the water droplet contact angle of the coating was considerably high and was 116 °. Was significantly higher at 23 degrees.
From the above trial results, it has been found that the addition of a substance mainly composed of a chlorosiloxane group is highly effective in improving the wear resistance.
It has also been found that the addition of a substance mainly composed of a hydrocarbon group and a chlorosilyl group has a great effect of reducing the water drop falling angle.
FIG. 2 shows the relationship between the amount of water droplets and the falling angle of the coating prepared in Example 1 and the coating prepared in Comparative Example 1. It can be seen that in the coating film of Example 1, the falling angle can be greatly improved.
実施例1において、フッ化炭素基と炭化水素基とクロロシリル基を主成分とする物質の代わりに、アルキルシリルキの代表例であるジメチルシリルキ基とクロロシリル基を主成分とする物質、例えばCH3−[Si(CH3)2O]3−SiCl3を用い、その他を同条件とした場合、水滴接触角は、101°となり、撥油性がやや劣ったが、その他はほぼ同様の結果であった。 In Example 1, instead of a substance mainly composed of a fluorocarbon group, a hydrocarbon group and a chlorosilyl group, a substance mainly composed of a dimethylsilyl group and a chlorosilyl group, which are representative examples of alkylsilyl groups, such as CH When 3- [Si (CH 3 ) 2 O] 3 -SiCl 3 was used and the other conditions were the same, the water droplet contact angle was 101 ° and the oil repellency was slightly inferior, but the other results were almost the same. there were.
実施例3において、クロロシリル基を主成分とする物質を除いた他は同条件で試作を行うと、被膜の水滴接触角は、やや高くなり、103°であったが、低転落角度は維持できた。なお、耐摩耗性は、実施例2と同様に1/3程度まで劣化した。 In Example 3, when the trial production was performed under the same conditions except that the substance having a chlorosilyl group as a main component was removed, the water droplet contact angle of the coating was slightly high and was 103 °, but the low falling angle could be maintained. It was. Note that the wear resistance deteriorated to about 1/3 as in Example 2.
実施例1〜4において、クロロシリル基をシアノシリル基に置き換えて、同様の実験を行ってみたがたが、ほぼ同様の結果を得た。 In Examples 1 to 4, a similar experiment was performed by replacing the chlorosilyl group with a cyanosilyl group, but almost the same result was obtained.
実施例1〜4において、クロロシリル基を全てアルコキシシリルキ基に置き換えて、同様の実験を行ってみたがたが、反応性が悪く、反応時間が2時間以内では実用性のある被膜を形成できなかった。
そこで、さらにシラノール縮合触媒あるいは有機酸を、吸着剤の全体量の0.1%程度添加すると、反応時間が1〜2時間で実施例1〜5と同様に、実用性のある被膜を形成できた。
また、アルコキシシリルキ基の中でも、メトキシシリル基がもっと反応性が高く、量産性に優れていた。なお、この撥水離水防汚処理液は、塩素を含んでおらず、脱アルコール反応であるため、塩酸が発生することもなく普通の大気中での被膜形成が可能であった。
In Examples 1 to 4, the same experiment was conducted by replacing all chlorosilyl groups with alkoxysilyl groups, but the reactivity was poor and a practical film could be formed within 2 hours of reaction time. There wasn't.
Therefore, when a silanol condensation catalyst or an organic acid is further added to about 0.1% of the total amount of the adsorbent, a practical film can be formed in the same manner as in Examples 1 to 5 with a reaction time of 1 to 2 hours. It was.
Of the alkoxysilyl groups, the methoxysilyl group was more reactive and excellent in mass productivity. This water repellent / water-repellent antifouling treatment solution does not contain chlorine and is a dealcoholization reaction, so that it is possible to form a film in ordinary air without generating hydrochloric acid.
実施例6において、溶媒を水とし、アルコール(吸着剤の1乃至10%、より好ましくは3乃至6%。)および/または陽イオン界面活性剤(吸着剤の1乃至10%)を添加して吸着剤を分散しておくと、撥水離水防汚処理液のポットライフを数日にまで延長できた。
なお、陽イオン界面活性剤を添加しない場合には、吸着剤成分が数時間で凝集してしまった。
In Example 6, the solvent is water, and alcohol (1 to 10% of the adsorbent, more preferably 3 to 6%) and / or a cationic surfactant (1 to 10% of the adsorbent) are added. When the adsorbent was dispersed, the pot life of the water repellent / fouling / antifouling treatment liquid could be extended to several days.
In addition, when the cationic surfactant was not added, the adsorbent component was aggregated in several hours.
実施例6において、フッ化炭素基を主成分とする物質1の代わりに、
短鎖のフッ化炭素基を主成分とする物質1’として、
CF3−(CF2)7−(CH2)2−Si(OCH3)3を用い
長鎖のフッ化炭素基と炭化水素基を主成分とする物質1”として、例えば、下記化学式(化1)に示した側鎖にフッ化炭素基と炭化水素基を持つ有機含フッ素エーテル基または有機含フッ素ポリエーテル基およびメトキシシリル基を含む物質を用い、
In Example 6, instead of the substance 1 having a fluorocarbon group as a main component,
As a substance 1 'mainly composed of a short-chain fluorocarbon group,
For example, the following chemical formula (Chemical Formula 1) can be used as the substance 1 ”containing CF 3 — (CF 2 ) 7 — (CH 2 ) 2 —Si (OCH 3 ) 3 and having a long-chain fluorocarbon group and a hydrocarbon group as main components. Using a substance containing an organic fluorine-containing ether group or organic fluorine-containing polyether group having a fluorocarbon group and a hydrocarbon group in the side chain shown in 1) and a methoxysilyl group,
さらに、耐摩耗性は、実施例1乃至4に比べて9倍程度まで改善できた。
Furthermore, the wear resistance was improved up to about 9 times as compared with Examples 1 to 4.
実施例8において、メトキシシロキサン基を主成分とする物質を除いた他は同条件で試作を行うと、被膜の水滴接触角は、やや高くなり、108°であり、低転落角度は維持できたが、やはり、耐摩耗性が1/2程度まで劣化した。 In Example 8, when the trial production was performed under the same conditions except that the substance having a methoxysiloxane group as a main component was removed, the water droplet contact angle of the coating was slightly high, 108 °, and the low falling angle could be maintained. However, the wear resistance deteriorated to about 1/2.
ガラス基材の代わりに、金属、半導体、セラミック、プラスチック、窯業製品、合成繊維、天然繊維、紙、皮革、毛皮、木材、竹または石を用いてみたが、表面に活性水素を全く含まないプラスチック、例えば、ポリエチレンやポリプロピレンを除き、撥水性がほぼ同様の撥水離水製膜を形成できた。
なお、表面に活性水素を全く含まないプラスチック、例えば、ポリエチレンやポリプロピレンの場合でも、前もって、コロナ処理や酸素プラズマ処理を行い表面を親水性に加工しておけば、同様の処理が行え、ほぼ同様の被膜が形成できた。
I tried using metal, semiconductors, ceramics, plastics, ceramic products, synthetic fibers, natural fibers, paper, leather, fur, wood, bamboo or stone instead of glass substrates, but the surface does not contain any active hydrogen. For example, except for polyethylene and polypropylene, a water-repellent / water-repellent film having substantially the same water repellency could be formed.
Even in the case of plastics that do not contain any active hydrogen on the surface, such as polyethylene or polypropylene, if the surface is processed to be hydrophilic by performing corona treatment or oxygen plasma treatment in advance, the same treatment can be performed. A film of
前記実施例1〜9で処理されたガラスを、それぞれ建物の窓ガラスや自動車等の乗り物の窓ガラス、太陽電池や太陽熱温水器等の太陽エネルギー利用装置のカバーガラスに装着して水滴の付着状況を評価してみたが、装着角度が垂直の建物の窓ガラスはもとより、装着角度が水平に対して25°程度以上の自動車等の乗り物の窓ガラス、太陽電池や太陽熱温水器等の太陽エネルギー利用装置のカバーガラスでは、50マイクロリットルの水滴は、滑り落ちてしまい全く残らなかった。
また、水滴接触角が最低でも100°以上あったので、撥油性であり汚れもほとんど付着しなかった。
さらに、乗った埃も、雨滴状の水をかけると、水滴と一緒に流れ落ちてきれいになった。
したがって、建物、および乗り物の雨天時の視認性の向上や、太陽エネルギー利用装置光利用効率の向上に効果があることが確認できた。
The glass treated in Examples 1 to 9 is mounted on a window glass of a building, a window glass of a vehicle such as an automobile, and a cover glass of a solar energy utilization device such as a solar cell or a solar water heater, and the water droplets are attached. However, in addition to the window glass of buildings with a vertical mounting angle, the window glass of vehicles such as automobiles with a mounting angle of about 25 ° or more relative to the horizontal, the use of solar energy such as solar cells and solar water heaters, etc. In the cover glass of the apparatus, 50 microliters of water droplets slipped and did not remain at all.
Further, since the water contact angle was at least 100 ° or more, it was oil-repellent and hardly adhered to dirt.
In addition, when the raindrops were splashed with raindrops, the dust on them flowed down along with the waterdrops and became clean.
Therefore, it has been confirmed that there is an effect in improving the visibility of buildings and vehicles during rainy weather and improving the light utilization efficiency of the solar energy utilization device.
なお、フッ化炭素基を主成分とする物質1を反応形成する物質として、一般には、以下のような物質が挙げられる。
CF3−(CF2)n−(R)m−SiXpCl3-p
(但し、nは0または16以下の整数、Rはアルキル基、フェニル基、ビニル基、エチニル基、シリコン若しくは酸素原子を含む置換基、mは0又は1、XはH,アルキル基,アルコキシル基,シアノシリル基、含フッ素アルキル基又は含フッ素アルコキシ基の置換基、pは0、1または2。さらに、Cl基は、CN基でも良い。)
In addition, as a substance which reacts and forms the substance 1 which has a fluorocarbon group as a main component, the following substances are generally mentioned.
CF 3 - (CF 2) n - (R) m -SiX p Cl 3-p
(However, n is an integer of 0 or 16 or less, R is an alkyl group, phenyl group, vinyl group, ethynyl group, a substituent containing silicon or oxygen atom, m is 0 or 1, X is H, alkyl group, alkoxyl group. , A cyanosilyl group, a fluorine-containing alkyl group or a fluorine-containing alkoxy group substituent, p is 0, 1 or 2. Further, the Cl group may be a CN group.)
さらに、具体的には、以下に示す(1)-(11)が挙げられる。
(1) CF3CH2O(CH2)15SiCl3
(2) CF3(CH2)2Si(CH3)2(CH2 )15SiCl3
(3) CF3(CH2)6Si(CH3)2(CH2 )9 SiCl3
(4) CF3COO(CH2)15SiCl3
(5) CF3(CF2)7−(CH2)2SiCl3
(6) CF3(CF2)5−(CH2)2SiCl3
(7) CF3(CF2)3−(CH2)2SiCl3
(8) CF3(CF2)7−C6H4SiCl3
(9)[CF3(CF2)3(CH2)2]2SiCl2
(10)[CF3(CF2)3(CH2)2]3SiCl
(11) CF3(CF2)7−(CH2)2SiCH3Cl2
More specifically, the following (1) to (11) are mentioned.
(1) CF 3 CH 2 O (CH 2 ) 15 SiCl 3
(2) CF 3 (CH 2 ) 2 Si (CH 3 ) 2 (CH 2 ) 15 SiCl 3
(3) CF 3 (CH 2 ) 6 Si (CH 3 ) 2 (CH 2 ) 9 SiCl 3
(4) CF 3 COO (CH 2 ) 15 SiCl 3
(5) CF 3 (CF 2 ) 7 — (CH 2 ) 2 SiCl 3
(6) CF 3 (CF 2 ) 5- (CH 2 ) 2 SiCl 3
(7) CF 3 (CF 2 ) 3 — (CH 2 ) 2 SiCl 3
(8) CF 3 (CF 2 ) 7 —C 6 H 4 SiCl 3
(9) [CF 3 (CF 2 ) 3 (CH 2 ) 2 ] 2 SiCl 2
(10) [CF 3 (CF 2 ) 3 (CH 2 ) 2 ] 3 SiCl
(11) CF 3 (CF 2 ) 7 - (CH 2) 2 SiCH 3 Cl 2
また、炭化水素基を主成分とする物質2を反応形成する物質として、一般には、以下のような物質が挙げられる。
CH3−(CH2)n−SiXpCl3-p
(但し、nは0または16以下の整数、Rはアルキル基、フェニル基、ビニル基、エチニル基、シリコン若しくは酸素原子を含む置換基、mは0又は1、XはH,アルキル基,アルコキシル基,シアノシリル基、含フッ素アルキル基又は含フッ素アルコキシ基の置換基、pは0、1または2。さらに、Cl基は、CN基でも良い。)
In addition, the following substances are generally exemplified as the substance that forms the substance 2 having a hydrocarbon group as a main component by reaction.
CH 3 - (CH 2) n -SiX p Cl 3-p
(However, n is an integer of 0 or 16 or less, R is an alkyl group, phenyl group, vinyl group, ethynyl group, a substituent containing silicon or oxygen atom, m is 0 or 1, X is H, alkyl group, alkoxyl group. , A cyanosilyl group, a fluorine-containing alkyl group or a fluorine-containing alkoxy group substituent, p is 0, 1 or 2. Further, the Cl group may be a CN group.)
さらに、具体的には、以下に示す(11)-(31)が挙げられる。
(21) CH3CH2O(CH2)15SiCl3
(22) CH3(CH2)2Si(CH3)2(CH2 )15SiCl3
(23) CH3(CH2)6Si(CH3)2(CH2 )9 SiCl3
(24) CH3COO(CH2)15SiCl3
(25) CH3(CH2)17SiCl3
(26) CH3(CH2)10SiCl3
(27) CH3(CH2)18SiCl3
(28) CH3(CH2)7−C6H4SiCl3
(29)[CH3(CH2)5]2SiCl2
(30)[CH3(CH2)7]3SiCl
(31)CH3(CH2)9SiCH3Cl2
More specifically, the following (11) to (31) are mentioned.
(21) CH 3 CH 2 O (CH 2 ) 15 SiCl 3
(22) CH 3 (CH 2 ) 2 Si (CH 3 ) 2 (CH 2 ) 15 SiCl 3
(23) CH 3 (CH 2 ) 6 Si (CH 3 ) 2 (CH 2 ) 9 SiCl 3
(24) CH 3 COO (CH 2 ) 15 SiCl 3
(25) CH 3 (CH 2 ) 17 SiCl 3
(26) CH 3 (CH 2 ) 10 SiCl 3
(27) CH 3 (CH 2 ) 18 SiCl 3
(28) CH 3 (CH 2 ) 7 —C 6 H 4 SiCl 3
(29) [CH 3 (CH 2 ) 5 ] 2 SiCl 2
(30) [CH 3 (CH 2 ) 7 ] 3 SiCl
(31) CH 3 (CH 2 ) 9 SiCH 3 Cl 2
また、シロキサン基を主成分とする物質3として、反応後シロキサン結合を形成するSiCl4、SiHCl3、SiH2Cl2等が利用できた。
一般には、Cl3Si(−OSiCl2)m−Cl(但し、mは整数)で表される化合物が利用できる。
Moreover, SiCl 4 , SiHCl 3 , SiH 2 Cl 2 or the like that forms a siloxane bond after the reaction can be used as the substance 3 having a siloxane group as a main component.
In general, a compound represented by Cl 3 Si (—OSiCl 2 ) m —Cl (where m is an integer) can be used.
さらにまた、クロロシリル基の代わりにメトキシシリルキ基を主成分とする物質として、Si(OCH3)4やSi(OC2H5)4、SiH(OCH3)3、SiH2(OCH3)2等が利用できた。
一般には、(AO)3Si(OSi(OA)2)m2(OA)で表される物質(ここで、mは0または整数、Aはアルキル基を表す。)を用いても同様の結果が得られた。
Furthermore, Si (OCH 3 ) 4 , Si (OC 2 H 5 ) 4 , SiH (OCH 3 ) 3 , SiH 2 (OCH 3 ) 2 can be used as substances having a methoxysilyl group as a main component instead of the chlorosilyl group. Etc. were available.
In general, even when a substance represented by (AO) 3 Si (OSi (OA) 2 ) m 2 (OA) (where m is 0 or an integer and A represents an alkyl group), the same result is obtained. was gotten.
なお、クロロシリル基を主成分とする物質とアルコキシシリル基を主成分とする物質を混合して用いても良いことは言うまでもない。 Needless to say, a substance having a chlorosilyl group as a main component and a substance having an alkoxysilyl group as a main component may be used in combination.
さらに、吸着剤として、クロロシリル基を含む物質を用いる場合には、非水系溶媒としては、含水率が100ppm以下なら実用に供し得るが、脱水した炭化水素系溶媒やフッ化炭素系溶媒、シリコーン系溶媒を用いることが可能であり、特に沸点が50〜350℃のものが使用に適していた。 Furthermore, when a substance containing a chlorosilyl group is used as the adsorbent, the non-aqueous solvent can be put to practical use if the water content is 100 ppm or less, but dehydrated hydrocarbon solvents, fluorocarbon solvents, silicone-based solvents A solvent can be used, and those having a boiling point of 50 to 350 ° C. are particularly suitable for use.
具体的に使用可能なもとして、石油ナフサ、ソルベントナフサ、石油エーテル、石油ベンジン、イソパラフィン、ノルマルパラフィン、デカリン、ノナン、工業ガソリン、灯油、ジメチルシリコーン、フェニルシリコーン、アルキル変性シリコーン、ポリエーテルシリコーン等を挙げることができる。 Specifically usable are petroleum naphtha, solvent naphtha, petroleum ether, petroleum benzine, isoparaffin, normal paraffin, decalin, nonane, industrial gasoline, kerosene, dimethyl silicone, phenyl silicone, alkyl-modified silicone, polyether silicone, etc. Can be mentioned.
また、フッ化炭素系溶媒には、フロン系溶媒や、フロリナート(3M社製品)、アフルード(旭ガラス社製品)等がある。なお、これらは1種単独で用いても良いし、良く混ざるものなら2種以上を組み合わせてもよい。さらに、クロロホルム等有機塩素系の溶媒を添加しても良い。 Fluorocarbon solvents include fluorocarbon solvents, Fluorinert (product of 3M), Afludo (product of Asahi Glass). In addition, these may be used individually by 1 type and may mix 2 or more types as long as it mixes well. Further, an organic chlorine solvent such as chloroform may be added.
なお、クロロシリル基を主成分とする物質、あるいはアルコキシシリル基を主成分とする物質を添加した場合、フッ化炭素基と炭化水素基とクロロシシリル基を主成分とする物質みで作成した被膜に比べて、膜中のフッ化炭素基と炭化水素基とシリル基を主成分とする物質の密度を2〜3倍向上できた。 In addition, when a substance mainly composed of chlorosilyl groups or a substance mainly composed of alkoxysilyl groups is added, it is compared with a film made of only substances mainly composed of a fluorocarbon group, a hydrocarbon group and a chlorosilyl group. Thus, the density of the substance mainly composed of a fluorocarbon group, a hydrocarbon group, and a silyl group in the film can be improved by 2 to 3 times.
また、上記実施例において、反応後シロキサン基を主成分とする物質3になる、クロロシリル基を主成分とする物質やアルコキシ基を主成分とする物質は、必ずしも添加しなくとも良いが、添加しておいた方が、添加してない場合に比べ、被膜強度を5〜10倍程度強化できた。なお、クロロシリル基を主成分とする物質またはアルコキシ基を主成分とする物質を含まない場合でも、耐摩耗性は多少劣ったが、実用レベルにはあった。 Further, in the above embodiment, the substance 3 mainly composed of siloxane group after reaction and the substance mainly composed of chlorosilyl group and the substance mainly composed of alkoxy group are not necessarily added. The film strength could be enhanced by about 5 to 10 times compared with the case where it was not added. Even when a substance containing chlorosilyl group as a main component or a substance containing alkoxy group as a main component was not included, the wear resistance was somewhat inferior, but it was at a practical level.
また、シラノール縮合触媒として、一般に、カルボン酸金属塩、カルボン酸エステル金属塩、カルボン酸金属塩ポリマー、カルボン酸金属塩キレート、チタン酸エステルチタン酸エステルキレート類、及び酸化チタンを利用できた。
添加量は、吸着剤の1/10〜1/10000程度でよい。より好ましくは、1/100〜1/1000であった。
In general, carboxylic acid metal salts, carboxylic acid ester metal salts, carboxylic acid metal salt polymers, carboxylic acid metal salt chelates, titanate ester titanate chelates, and titanium oxide can be used as silanol condensation catalysts.
The addition amount may be about 1/10 to 1/10000 of the adsorbent. More preferably, it was 1/100 to 1/1000.
なお、上述のシラノール縮合触媒の代わりに、ギ酸、あるいは酢酸、プロピオン酸、ラク酸、マロン酸等の有機酸がシラノール縮合触媒と同様に、同様の濃度で利用できた。 Instead of the above-mentioned silanol condensation catalyst, formic acid or organic acids such as acetic acid, propionic acid, lactic acid and malonic acid could be used at the same concentration as the silanol condensation catalyst.
実施例1に於いて、未反応の余分なフッ化炭素基を主成分として含む物質1や炭化水素基を主成分として含む物質2、シロキサン基主成分として含む物質3を洗浄除去する(あるいはふき取り除去する。)工程を省いても、表面の水滴接触角が略100度で膜厚が数十ナノメートルの被膜が得られ、この条件でも、実用上透明度も全く問題なかった。 In Example 1, the substance 1 containing an unreacted excess fluorocarbon group as a main component, the substance 2 containing a hydrocarbon group as a main component, and the substance 3 containing a siloxane group as a main component are washed away (or wiped off). Even if the process is omitted, a film having a surface water droplet contact angle of about 100 degrees and a film thickness of several tens of nanometers can be obtained.
また、水−アルコール溶媒に、さらに加える陽イオン界面活性剤としては、下記化学式(化2)で表されるテトラアルキルアンモニウム塩があり、0.0005mol/Lになるように調製して水−アルコール−界面活性剤溶媒として使用できた。
この場合、処理液のポットライフが改善され、ほぼ同様の被膜が形成できた。
Further, as a cationic surfactant to be further added to the water-alcohol solvent, there is a tetraalkylammonium salt represented by the following chemical formula (Chemical Formula 2), and the water-alcohol is prepared to 0.0005 mol / L. -It could be used as a surfactant solvent.
In this case, the pot life of the treatment liquid was improved, and almost the same film could be formed.
なお、界面活性剤としては、中性乃至弱アルカリ性の界面活性剤であれば使用できるが、中でも調合処理液のpHが5乃至11になるものでないと高性能の被膜を形成できなかった。pHが5未満の場合、密度の高い被膜が形成できなかった。一方、pHが12を超えると、被膜の一部が破壊された。 As the surfactant, any neutral or weakly alkaline surfactant can be used, but in particular, a high-performance film could not be formed unless the pH of the preparation treatment solution was 5 to 11. When the pH was less than 5, a high-density film could not be formed. On the other hand, when the pH exceeded 12, a part of the coating was destroyed.
また、下記化学式(化3)で表されるテトラアルキルアンモニウム塩の内、特に好ましいものは、R1の炭素数が12〜16であった。
さらにまた、実際に、建物の窓ガラス、電磁誘導調理器用天板、または自動車用窓ガラス、太陽電池および太陽熱温水器用カバーガラスに、テストピースとして試作したガラスを装着してみたが、何れも撥水離水防汚性に優れた性能が得られた。 Furthermore, actually, we tried to install prototype glass as test pieces on building window glass, top plates for electromagnetic induction cookers, or automotive window glass, solar cells and solar water heater covers. The performance which was excellent in water separation water antifouling property was obtained.
さらにまた、長鎖のフッ化炭素基と炭化水素基を主成分とする物質1”である有機含フッ素エーテル基または有機含フッ素ポリエーテル基およびアルコキシシリル基を含む長鎖物質には、下記式(化4または化5)が利用できた。また、耐光性は多少悪くなるが、下記式(化6)で示される物質が利用できたが、何れも平均分子量は1000〜5000程度のものが利用しやすかった。 Furthermore, the long-chain substance containing an organic fluorine-containing ether group or organic fluorine-containing polyether group and an alkoxysilyl group, which is a substance 1 ″ mainly composed of a long-chain fluorocarbon group and a hydrocarbon group, has the following formula: In addition, although the light resistance is somewhat worse, a substance represented by the following formula (Chemical Formula 6) can be used, but each has an average molecular weight of about 1000 to 5000. It was easy to use.
さらに具体的には、下記式(化7)や式(化8)で示される物質が利用できた。
さらにまた、シロキサン基を主成分とする物質として(AO)3Si(OSi(OA)2)pOA(Pは0〜10、Aは、メチル基やチル基のアルキル基、OAはClまたはNCOでも良い。)が挙げられるが、以下に示す物質(41)-(48)が使用しやすかった。 Furthermore, (AO) 3 Si (OSi (OA) 2 ) p OA (P is 0-10, A is an alkyl group of a methyl group or a til group, and OA is Cl or NCO as a substance having a siloxane group as a main component. However, the following substances (41)-(48) were easy to use.
(41)Si(OCH3)4
(42)SiH(OCH3)3
(43)SiH2(OCH3)2
(44)(CH3O)3Si(OSi(OCH3)2)mOCH3
(45)Si(OC2H5)3
(46)SiH(OC2H5)3
(47)SiH2(OC2H5)2
(48)(H5C2O)3Si(OSi(OC2H5)2)mOC2H5
ここで、mは、1〜6整数を表す。
(41) Si (OCH 3 ) 4
(42) SiH (OCH 3 ) 3
(43) SiH 2 (OCH 3 ) 2
(44) (CH 3 O) 3 Si (OSi (OCH 3 ) 2 ) m OCH 3
(45) Si (OC 2 H 5 ) 3
(46) SiH (OC 2 H 5 ) 3
(47) SiH 2 (OC 2 H 5 ) 2
(48) (H 5 C 2 O) 3 Si (OSi (OC 2 H 5 ) 2 ) m OC 2 H 5
Here, m represents an integer of 1 to 6.
なお、このようにして作成したガラス板は、乗用車に装着すると、停止していても雨滴が流れてしまい、走行中にはさらに風を直接受けるので、雨滴はほとんど飛散されてしまい、より安全運転できる。
また、本発明の撥水離水防汚性ガラスでは、耐摩耗性も非常に高いので、ワイパーブレードでこすられるウインドシールド用ガラス板としても適用可能であることは明らかである。
In addition, when the glass plate created in this way is installed in a passenger car, raindrops flow even when stopped, and since the wind is further directly received during traveling, the raindrops are almost scattered and driving more safely. it can.
Moreover, since the water-repellent / water-repellent antifouling glass of the present invention has very high wear resistance, it is clear that it can be applied as a windshield glass plate rubbed with a wiper blade.
さらにまた、以上では言及しなかったが、本発明は、自動車のサイドバックミラーに適用しても、雨天時の後方視認性を大幅に改善できた。 Furthermore, although not mentioned above, the present invention can greatly improve the rear visibility in rainy weather even when applied to a side rearview mirror of an automobile.
なお、本願発明の処理液で処理が可能な物品やそれを用いた製品は、何ら限定されるものではないが、一般に、表面が水に濡れる材料(表面は塗料などで塗装されていても良い。)に適用できる。
一方、表面が水に濡れない材料、例えば、合成樹脂類は、表面をプラズマ処理、あるいはコロナ処理して、親水性に加工すれば適用できる。
The article that can be treated with the treatment liquid of the present invention and the product using the article are not limited at all, but in general, a material whose surface gets wet with water (the surface may be painted with a paint or the like). .).
On the other hand, materials whose surface is not wetted with water, for example, synthetic resins, can be applied if the surface is processed with plasma or corona and processed to be hydrophilic.
具体的には、
(a)刃物の例:
包丁、鋏、ナイフ、カッター、彫刻刀、剃刀、バリカン、鋸、カンナ、ノミ、錐、千枚通し、バイト、ドリルの刃、ミキサーの刃、ジューサーの刃、製粉機の刃、芝刈り機の刃、パンチ、押切り、ホッチキスの刃、缶切りの刃、または手術用メス等。
In particular,
(A) Examples of blades :
Kitchen knife, scissors, knife, cutter, carving knife, razor, clipper, saw, canna, chisel, cone, awl, cutting tool, drill blade, mixer blade, juicer blade, flour mill blade, lawn mower blade, Punch, press cut, staple blade, can open blade, or surgical knife.
(b)針の例:
鍼術用の針、縫い針、ミシン針、畳針、注射針、手術用針、安全ピン等。
(B) Examples of needles :
Acupuncture needles, sewing needles, sewing needles, tatami needles, injection needles, surgical needles, safety pins, etc.
(c)窯業製品の例:
陶磁器製、ガラス製、セラミックス製またはほうろうを含む製品等。例えば衛生陶磁器(例えば便器、洗面器、風呂等)、食器(例えば、茶碗、皿、どんぶり、湯呑、コップ、瓶、コーヒー沸かし容器、鍋、すり鉢、カップ等)、花器(水盤、植木鉢、一輪差し等)、水槽(養殖用水槽、鑑賞用水槽等)、化学実験器具(ビーカー、反応容器、試験管、フラスコ、シャーレ、冷却管、撹拌棒、スターラー、乳鉢、バット、注射器)、瓦、タイル、ほうろう製食器、ほうろう製洗面器、ほうろう製鍋、各種コンクリート製品。
(C) Examples of ceramic products :
Products made of ceramic, glass, ceramics or enamel. For example, sanitary ceramics (for example, toilet bowls, washbasins, baths, etc.), tableware (for example, tea bowls, dishes, bowls, cups, cups, bottles, coffee-boiled containers, pots, mortars, cups, etc.) Etc.), aquarium (aquaculture tank, appreciation aquarium, etc.), chemical laboratory equipment (beaker, reaction vessel, test tube, flask, petri dish, cooling tube, stir bar, stirrer, mortar, vat, syringe), tile, tile, Enamel tableware, enamel basin, enamel pan, various concrete products.
(d)鏡の例:
手鏡、姿見鏡、浴室用鏡、洗面所用鏡、自動車用鏡(バックミラー、サイドミラー)、ハーフミラー、ショーウィンドー用鏡、デパートの商品売り場の鏡等。
(D) Example of mirror :
Hand mirrors, sight mirrors, bathroom mirrors, bathroom mirrors, automotive mirrors (back mirrors, side mirrors), half mirrors, show window mirrors, department store product mirrors, etc.
(e)成形用部材の例:
プレス成形用金型、注型成形用金型、射出成形用金型、トランスファー成形用金型、真空成形用金型、吹き込み成形用金型、押し出し成形用ダイ、インフレーション成形用口金、繊維紡糸用口金、カレンダー加工用ロールなど。
(E) Examples of molding members :
Press mold, cast mold, injection mold, transfer mold, vacuum mold, blow mold, extrusion mold, inflation mold, fiber spinning Base, calendar processing roll, etc.
(f)装飾品の例:
腕時計、メガネフレームや真珠、真珠、ルビー、エメラルド、ガーネット、キャッツアイ、ダイヤモンド、トパーズ、ブラッドストーン、アクアマリン、サードニックス、トルコ石、瑪瑙、大理石、アメジスト、カメオ、オパール、水晶、ガラス等の宝石、さらに白金、金、銀、銅、アルミ、チタン、錫あるいはそれらの合金やステンレス製の指輪、腕輪、ブローチ、ネクタイピン、イヤリング、ネックレス等の貴金属装飾製品等。
(F) Examples of ornaments :
Jewelry such as watches, eyeglass frames and pearls, pearls, pearls, rubies, emeralds, garnets, cat's eyes, diamonds, topaz, bloodstone, aquamarine, sardonyx, turquoise, jade, marble, amethyst, cameo, opal, crystal, glass, etc. Furthermore, platinum, gold, silver, copper, aluminum, titanium, tin or their alloys and stainless steel rings, bracelets, brooches, tie pins, earrings, necklaces and other precious metal decoration products.
(g)食品成形用型の例:
ケーキ焼成用型、クッキー焼成用型、パン焼成用型、チョコレート成形用型、ゼリー成形用型、アイスクリーム成形用型、オーブン皿、製氷皿等。
(G) Examples of food molds :
Cake baking mold, cookie baking mold, bread baking mold, chocolate molding mold, jelly molding mold, ice cream molding mold, oven dish, ice tray, etc.
(h)調理器具の例:
鍋、釜、やかん、ポット、フライパン、ホットプレート、焼き物調理用網、油切り、タコ焼きプレート等。
(H) Examples of cookware :
Pots, kettles, kettles, pots, frying pans, hot plates, grilled nets, oil drainers, octopus grilled plates, etc.
(i)紙の例:グラビア紙、撥水撥油紙、ポスター紙、高級パンフレット紙 (I) Examples of paper : gravure paper, water / oil repellent paper, poster paper, high-grade brochure paper
(j)樹脂の例:
ポリプロピレン、ポリエチレン等のポリオレフィン、ポリ塩化ビニル、ポリ塩化ビニリデン、ポリアミド、ポリイミド、ポリアミドイミド、ポリエステル、アラミド、ポリスチレン、ポリスルホン、ポリエーテルスルホン、ポリフェニレンスルフィド、フェノール樹脂、フラン樹脂、ユリア樹脂、エポキシ樹脂、ポリウレタン、ケイ素樹脂、ABS樹脂、メタクリル樹脂、アクリル酸エステル樹脂、ポリアセタール、ポリフェンレンオキサイド等
(J) Examples of resins :
Polyolefins such as polypropylene and polyethylene, polyvinyl chloride, polyvinylidene chloride, polyamide, polyimide, polyamideimide, polyester, aramid, polystyrene, polysulfone, polyethersulfone, polyphenylene sulfide, phenol resin, furan resin, urea resin, epoxy resin, polyurethane , Silicon resin, ABS resin, methacrylic resin, acrylate resin, polyacetal, polyphenylene oxide, etc.
(k)家庭電化製品の例:
テレビジョン、ラジオ、テープレコーダー、オーディオ、CD、冷凍関係機器の冷蔵庫、冷凍庫、エアコン、ジューサー、ミキサー、扇風機の羽根、照明器具、文字盤、パーマ用ドライヤー等。
(K) Examples of home appliances :
Television, radio, tape recorder, audio, CD, refrigeration equipment refrigerators, freezers, air conditioners, juicers, mixers, fan blades, lighting equipment, dials, permanent hair dryers, etc.
(l)スポーツ用品の例:
スキー、釣竿、棒高跳び用のポール、ボート、ヨット、ジェットスキー、サーフボード、ゴルフボール、ボーリングのボール、釣糸、魚網、釣り浮き等。
(L) Examples of sports equipment :
Skis, fishing rods, pole vaulting poles, boats, yachts, jet skis, surfboards, golf balls, bowling balls, fishing lines, fishnets, fishing floats, etc.
(m)乗り物部品に適用する例:
(1) ABS樹脂:ランプカバー、インストルメントパネル、内装部品、オートバイのプロテクター、(2) セルロースプラスチック:自動車のマーク、ハンドル(3) FRP(繊維強化樹脂):外板バンパー、エンジンカバー、(4)フェノール樹脂:ブレーキ(5) ポリアセタール:ワイパーギヤ、ガスバルブ、キャブレター部品(6) ポリアミド:ラジエータファン(7) ポリアリレート:方向指示レンズ、計器板レンズ、リレーハウジング(8) ポリブチレンテレフタレート:リヤエンド、フロントフェンダ(9) ポリアミノビスマレイミド:エンジン部品、ギヤボックス、ホイール、サスペンジョンドライブシステム(10)メタクリル樹脂:ランプカバーレンズ、計器板とカバー、センターマーク(11)ポリプロピレン:バンパー(12)ポリフェニレンオキシド:ラジエーターグリル、ホイールキャップ(13)ポリウレタン:バンパー、フェンダー、インストルメントパネル、ファン(14)不飽和ポリエステル樹脂:ボディ、燃料タンク、ヒーターハウジング、計器板
(M) Examples applied to vehicle parts :
(1) ABS resin: lamp cover, instrument panel, interior parts, motorcycle protector, (2) Cellulose plastic: car mark, handle (3) FRP (fiber reinforced resin): outer bumper, engine cover, (4 ) Phenolic resin: Brake (5) Polyacetal: Wiper gear, gas valve, carburetor parts (6) Polyamide: Radiator fan (7) Polyarylate: Direction indicator lens, instrument panel lens, relay housing (8) Polybutylene terephthalate: Rear end, front Fender (9) Polyamino bismaleimide: Engine parts, gear box, wheel, suspension drive system (10) Methacrylic resin: Lamp cover lens, instrument panel and cover, Center mark (11) Polypropylene: Bumper (12) Polyphenylene oxide: Radiator Guriru, wheel cap (13) polyurethane: a bumper, fender, instrument panel, a fan (14) Unsaturated polyester resin: body, fuel tank, heater housing, instrument panel
(n)事務用品の例:
万年筆、ボールペン、シャ−プペンシル、筆入れ、バインダー、机、椅子、本棚、ラック、電話台、物差し、製図用具等。
(N) Examples of office supplies :
Fountain pens, ballpoint pens, sharp pencils, brush holders, binders, desks, chairs, bookshelves, racks, telephone stands, rulers, drafting tools, etc.
(o)建材の例:
屋根材、外壁材、内装材。屋根材として窯瓦、スレート瓦、トタン(亜鉛メッキ鉄板)など。外壁材としては木材(加工木材を含む)、モルタル、コンクリート、ケイカル板、窯業系サイジング、金属系サイジング、レンガ、石材、プラスチック材料、アルミ等の金属材料など。内装材としては木材(加工木材を含む)、アルミ等の金属材料、プラスチック材料、紙、繊維など。
(O) Examples of building materials :
Roofing materials, outer wall materials, interior materials. Roof tiles include kiln tiles, slate tiles, and tin (galvanized iron plate). Outer wall materials include wood (including processed wood), mortar, concrete, calcite board, ceramic sizing, metal sizing, brick, stone, plastic material, aluminum and other metal materials. Interior materials include wood (including processed wood), metal materials such as aluminum, plastic materials, paper, and fibers.
(p)石材の例:
花コウ岩、大理石、みかげ石等。たとえば建築物、建築材、芸術品、置物、風呂、墓石、記念碑、門柱、石垣、歩道の敷石など。
(P) Examples of stone :
Flower kite, marble, granite, etc. For example, buildings, construction materials, works of art, figurines, baths, tombstones, monuments, gateposts, stone walls, paving stones, etc.
(q)楽器および音響機器の例:
打楽器、弦楽器、鍵盤楽器、木管楽器、金管楽器などの楽器、およびマイクロホン、スピーカなどの音響機器等。具体的には、ドラム、シンバル、バイオリン、チェロ、ギター、琴、ピアノ、フルート、クラリネット、尺八、ホルンなどの打楽器、弦楽器、鍵盤楽器、木管楽器、金管楽器などの楽器、およびマイクロホン、スピーカ、イヤホーンなどの音響機器。
(Q) Examples of musical instruments and audio equipment :
Percussion instruments, string instruments, keyboard instruments, woodwind instruments, brass instruments, and other acoustic equipment such as microphones and speakers. Specifically, drums, cymbals, violins, cellos, guitars, kotos, pianos, flutes, clarinets, shakuhachi, horns and other percussion instruments, stringed instruments, keyboard instruments, woodwinds, brass instruments, etc., microphones, speakers, Sound equipment such as earphones.
(r)繊維製品の例:
帽子、コート、手袋、スーツ、ズボン、ベスト、呉服、毛皮、靴、鞄、手術着、作業着、レインコート、壁用クロス、カーテンなどのアパレル製品。
(R) Examples of textile products :
Apparel products such as hats, coats, gloves, suits, trousers, vests, kimonos, furs, shoes, bags, surgical clothes, work clothes, raincoats, wall cloths, curtains.
(s)その他:
魔法瓶、真空系機器、電力送電用碍子またはスパークプラグ等の撥水離水防汚効果の高い高耐電圧性絶縁碍子等からなる基材に適用できる。
(S) Other :
The present invention can be applied to a base material made of a high voltage-resistant insulator such as a thermos, a vacuum device, a power transmission insulator or a spark plug, which has a high water-repellent / water-repellent and antifouling effect.
1 フッ化炭素基を含む化学吸着分子
2 炭化水素基を含む化学吸着分子
3 ポリシロキサン結合を含んだ物質
4 シロキサン結合
5 ガラス基材
6 撥水離水性防汚膜
7 網目状のポリシロキサン結合
DESCRIPTION OF SYMBOLS 1 Chemisorption molecule | numerator containing fluorocarbon group 2 Chemisorption molecule | numerator containing hydrocarbon group 3 Substance containing polysiloxane bond 4 Siloxane bond 5 Glass substrate 6 Water repellent water-repellent antifouling film 7 Reticulated polysiloxane bond
Claims (26)
フッ化炭素基を主成分とする物質1として、
CF3−(CF2)n−(R)m−SiXpCl3-p
(但し、nは0または16以下の整数、Rはアルキレン基もしくはフェニレン基、mは0又は1、XはH,アルキル基,アルコキシル基,シアノシリル基、含フッ素アルキル基又は含フッ素アルコキシ基の置換基、pは0、1または2。さらに、Cl基は、CN基でも良い。)で表される化合物、炭化水素基を主成分とする物質2として、
CH3−(CH2)n−SiXpCl3-p
(但し、nは0または16以下の整数、XはH,アルキル基,アルコキシル基,シアノシリル基、含フッ素アルキル基又は含フッ素アルコキシ基の置換基、pは0、1または2。さらに、Cl基は、CN基でも良い。)で表される化合物、
さらに、シロキサン基を主成分とする物質3として、
Cl3Si(−OSiCl2)m−Cl(但し、mは0または整数)で表される化合物、あるいは(AO)3Si(OSi(OA)2)m(OA)(ここで、mは0または整数、Aはアルキル基を表す。)で表される化合物を用いることを特徴とする撥水離水防汚処理液。 In a water-repellent and water-repellent antifouling treatment liquid comprising at least a substance 1 mainly containing a fluorocarbon group, a substance 2 containing a hydrocarbon group as a main ingredient, a substance 3 containing a siloxane group as a main ingredient, and a solvent,
As a substance 1 mainly composed of a fluorocarbon group,
CF 3 - (CF 2) n - (R) m -SiX p Cl 3-p
(Where n is an integer of 0 or 16 or less, R is an alkylene group or a phenylene group, m is 0 or 1, X is a substitution of H, an alkyl group, an alkoxyl group, a cyanosilyl group, a fluorine-containing alkyl group, or a fluorine-containing alkoxy group. Group, p is 0, 1 or 2. Further, the Cl group may be a CN group.)
CH 3 - (CH 2) n -SiX p Cl 3-p
(Where n is an integer of 0 or 16 or less , X is H, an alkyl group, an alkoxyl group, a cyanosilyl group, a fluorine-containing alkyl group or a substituent of a fluorine-containing alkoxy group, p is 0, 1 or 2. Further, a Cl group Can be a CN group.)
Furthermore, as the substance 3 having a siloxane group as a main component,
A compound represented by Cl 3 Si (—OSiCl 2 ) m —Cl (where m is 0 or an integer), or (AO) 3 Si (OSi (OA) 2 ) m (OA) (where m is 0 Or an integer, A represents an alkyl group).
ジメチルシロキサン基を主成分とする物質4として、
CH3−[Si(CH3)2O]3−SiCl3で表される化合物、
炭化水素基を主成分とする物質2として、
CH3−(CH2)n−SiXpCl3-p
(但し、nは0または16以下の整数、XはH,アルキル基,アルコキシル基,シアノシリル基、含フッ素アルキル基又は含フッ素アルコキシ基の置換基、pは0、1または2。さらに、Cl基は、CN基でも良い。)で表される化合物を用いることを特徴とする撥水離水防汚処理液。 In a water-repellent and water-repellent antifouling treatment liquid comprising at least a substance 4 having a dimethylsiloxane group as a main component, a substance 2 having a hydrocarbon group as a main component, and a solvent,
As a substance 4 having a dimethylsiloxane group as a main component,
A compound represented by CH 3 — [Si (CH 3 ) 2 O] 3 —SiCl 3 ,
As a substance 2 mainly composed of a hydrocarbon group,
CH 3 - (CH 2) n -SiX p Cl 3-p
(Where n is an integer of 0 or 16 or less , X is H, an alkyl group, an alkoxyl group, a cyanosilyl group, a fluorine-containing alkyl group or a substituent of a fluorine-containing alkoxy group, p is 0, 1 or 2. Further, a Cl group May be a CN group.) A water-repellent / water-repellent antifouling treatment liquid characterized by using a compound represented by:
ジメチルシロキサン基を主成分とする物質4として、
CH3−[Si(CH3)2O]3−SiCl3で表される化合物、
炭化水素基を主成分とする物質2として、
CH3−(CH2)n−SiXpCl3-p
(但し、nは0または16以下の整数、XはH,アルキル基,アルコキシル基,シアノシリル基、含フッ素アルキル基又は含フッ素アルコキシ基の置換基、pは0、1または2。さらに、Cl基は、CN基でも良い。)で表される化合物、
さらに、シロキサン基を主成分とする物質3として、
Cl3Si(−OSiCl2)m−Cl(但し、mは0または整数)で表される化合物、あるいは(AO)3Si(OSi(OA)2)m(OA)(ここで、mは0または整数、Aはアルキル基を表す。)で表される化合物を用いることを特徴とする撥水離水防汚処理液。 A water-repellent / water-repellent antifouling treatment liquid comprising at least a substance 4 mainly containing a dimethylsiloxane group, a substance 2 mainly containing a hydrocarbon group, a substance 3 mainly containing a siloxane group, and a non-aqueous organic solvent. In
As a substance 4 having a dimethylsiloxane group as a main component,
A compound represented by CH 3 — [Si (CH 3 ) 2 O] 3 —SiCl 3 ,
As a substance 2 mainly composed of a hydrocarbon group,
CH 3 - (CH 2) n -SiX p Cl 3-p
(Where n is an integer of 0 or 16 or less , X is H, an alkyl group, an alkoxyl group, a cyanosilyl group, a fluorine-containing alkyl group or a substituent of a fluorine-containing alkoxy group, p is 0, 1 or 2. Further, a Cl group Can be a CN group.)
Furthermore, as the substance 3 having a siloxane group as a main component,
A compound represented by Cl 3 Si (—OSiCl 2 ) m —Cl (where m is 0 or an integer), or (AO) 3 Si (OSi (OA) 2 ) m (OA) (where m is 0 Or an integer, A represents an alkyl group).
短鎖のフッ化炭素基を主成分とする物質1’として、
CF3−(CF2)n−(R)m−SiXpCl3-p
(但し、nは0または16以下の整数、Rはアルキレン基もしくはフェニレン基、mは0又は1、XはH,アルキル基,アルコキシル基,シアノシリル基、含フッ素アルキル基又は含フッ素アルコキシ基の置換基、pは0、1または2。さらに、Cl基は、CN基でも良い。)で表される化合物、
長鎖のフッ化炭素基と炭化水素基を主成分とする物質1” として、
有機含フッ素エーテル基または有機含フッ素ポリエーテル基およびアルコキシシリル基を含む下記式(化4または化5または6)で表される化合物、
炭化水素基を主成分とする物質2として、
CH3−(CH2)n−SiXpCl3-p
(但し、nは0または16以下の整数、XはH,アルキル基,アルコキシル基,シアノシリル基、含フッ素アルキル基又は含フッ素アルコキシ基の置換基、pは0、1または2。さらに、Cl基は、CN基でも良い。)で表される化合物を用いることを特徴とする撥水離水防汚処理液。
As a substance 1 'mainly composed of a short-chain fluorocarbon group,
CF 3 - (CF 2) n - (R) m -SiX p Cl 3-p
(Where n is an integer of 0 or 16 or less, R is an alkylene group or a phenylene group, m is 0 or 1, X is a substitution of H, an alkyl group, an alkoxyl group, a cyanosilyl group, a fluorine-containing alkyl group, or a fluorine-containing alkoxy group. Group, p is 0, 1 or 2. Further, the Cl group may be a CN group.)
As a material 1 ”mainly composed of a long-chain fluorocarbon group and a hydrocarbon group,
A compound represented by the following formula (chemical formula 4 or chemical formula 5 or 6) containing an organic fluorine-containing ether group or an organic fluorine-containing polyether group and an alkoxysilyl group;
As a substance 2 mainly composed of a hydrocarbon group,
CH 3 - (CH 2) n -SiX p Cl 3-p
(Where n is an integer of 0 or 16 or less , X is H, an alkyl group, an alkoxyl group, a cyanosilyl group, a fluorine-containing alkyl group or a substituent of a fluorine-containing alkoxy group, p is 0, 1 or 2. Further, a Cl group May be a CN group).
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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JP2010039843A JP5736606B2 (en) | 2010-02-25 | 2010-02-25 | Water-repellent / water-repellent antifouling treatment liquid, water-repellent / water-repellent antifouling film using the same, method for producing the same, and product using them |
Applications Claiming Priority (1)
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JP2015117147A (en) * | 2013-12-18 | 2015-06-25 | 国立大学法人 東京大学 | Production method of glass member, and glass member |
CN107109124B (en) | 2014-10-31 | 2021-07-09 | 住友化学株式会社 | Transparent coating film |
US10370546B2 (en) | 2014-10-31 | 2019-08-06 | Sumitomo Chemical Company, Limited | Water/oil-repellent coating composition |
US11203674B2 (en) | 2014-10-31 | 2021-12-21 | Sumitomo Chemical Company, Limited | Transparent film |
KR102478714B1 (en) | 2014-11-12 | 2022-12-16 | 스미또모 가가꾸 가부시키가이샤 | Water-repellant/oil-repellant coating composition and transparent film |
JP6735232B2 (en) * | 2014-11-12 | 2020-08-05 | 住友化学株式会社 | Transparent film |
US9359386B1 (en) * | 2015-02-19 | 2016-06-07 | Gelest Technologies, Inc. | Silanes and silicones with distinct hydrophilic and oleophobic substitution |
JP7124525B2 (en) * | 2018-07-31 | 2022-08-24 | 住友ゴム工業株式会社 | Golf ball |
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JP7354760B2 (en) * | 2019-03-27 | 2023-10-03 | 住友ゴム工業株式会社 | Golf ball |
KR102494419B1 (en) | 2019-04-18 | 2023-02-02 | 주식회사 엘지에너지솔루션 | Nonaqueous electrolyte additive for lithium secondary battery, nonaqueous electrolyte for lithium secondary battery comprising the same, and lithium secondary battery |
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