JPWO2006049008A1 - Inorganic coating composition, hydrophilic coating film and method for forming hydrophilic coating film - Google Patents
Inorganic coating composition, hydrophilic coating film and method for forming hydrophilic coating film Download PDFInfo
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Abstract
透明性、基材との密着性、親水性等に優れた塗膜を形成できる無機塗料組成物。有機基材上に親水性塗膜を形成することのできる無機塗料組成物であって、（ａ）平均粒子径５〜１００ｎｍのシリカ粒子、（ｂ）界面活性剤、（ｃ）有機基材を膨潤又は溶解することができ、かつ、気圧０．１ＭＰａの状態で沸点１３０℃以上の、水に混和しうる有機溶剤Ａ、（ｄ）有機基材を実質上膨潤又は溶解することがなく、かつ、気圧０．１ＭＰａの状態で沸点５０〜１２０℃の、水に混和しうる有機溶剤Ｂ及び（ｅ）水を含有し、かつ、該無機塗料組成物中において、有機溶剤Ａの含有量が１〜１０質量％であり、有機溶剤Ｂの含有量が０〜９７．２質量％であり、固形分含有量が０．１〜２０質量％であり、固形含有量の３．５〜１７倍の水が含有される無機塗料組成物。An inorganic coating composition capable of forming a coating film excellent in transparency, adhesion to a substrate, hydrophilicity and the like. An inorganic coating composition capable of forming a hydrophilic coating film on an organic substrate, comprising: (a) silica particles having an average particle diameter of 5 to 100 nm, (b) a surfactant, and (c) an organic substrate. An organic solvent A which can swell or dissolve and has a boiling point of 130 ° C. or higher at a pressure of 0.1 MPa and which is miscible with water, (d) substantially does not swell or dissolve the organic substrate, and And an organic solvent B having a boiling point of 50 to 120 ° C. at a pressure of 0.1 MPa and miscible with water and (e) water, and the content of the organic solvent A is 1 in the inorganic coating composition. 10 mass%, the content of the organic solvent B is 0-97.2 mass%, the solid content is 0.1-20 mass%, 3.5 to 17 times the solid content An inorganic coating composition containing water.
Description
本発明は、透明性に優れた親水性塗膜を得ることのできる無機塗料組成物、親水性塗膜及び親水性塗膜の形成方法に関する。 The present invention relates to an inorganic coating composition capable of obtaining a hydrophilic coating film having excellent transparency, a hydrophilic coating film, and a method for forming a hydrophilic coating film.
現在、プラスチック等の有機基材は、透明性に優れていることから各種ランプのカバー、眼鏡レンズ、ゴーグル、各種計器のカバー、農業用フィルム等の様々な用途に使用されている。しかし、一般に、プラスチック等の有機基材は、疎水性であることから結露を生じやすい等の不都合を生じている。特に、常に外気にさらされやすい計器類のカバーの場合は、そのカバーの内面に結露を生じ、曇りが発生するために表示が見えなくなるといった問題が生じることがある。 At present, organic substrates such as plastics are excellent in transparency and are used in various applications such as various lamp covers, spectacle lenses, goggles, various instrument covers, and agricultural films. However, in general, organic base materials such as plastics have a disadvantage that they tend to cause dew condensation because they are hydrophobic. In particular, in the case of a cover of an instrument that is always exposed to the outside air, there may be a problem that dew condensation occurs on the inner surface of the cover and the display becomes invisible due to cloudiness.
有機基材表面に親水性を付与する方法として表面に無機層を形成する方法が知られている。具体的には、アルミナゾルやシリカゾルを含む無機塗料を塗布、乾燥して塗膜を形成する方法（特許文献１）等が挙げられる。しかし、この方法では、形成される塗膜はアルミナ粒子及びシリカ粒子が界面活性剤により有機基材上に接着された状態であるために基材との密着性に欠けるという問題があった。 As a method for imparting hydrophilicity to the organic substrate surface, a method of forming an inorganic layer on the surface is known. Specifically, a method of forming a coating film by applying and drying an inorganic paint containing alumina sol or silica sol (Patent Document 1) and the like can be mentioned. However, this method has a problem that the coating film to be formed is in a state where the alumina particles and the silica particles are adhered to the organic base material by the surfactant, and thus lacks adhesion to the base material.
また、ポリカーボネート等の有機基材に強固なシリカ膜を形成する方法として、疎水処理されたシリカ、水、及び有機基材に対して溶解性のあるセロソルブアセテート等の有機溶剤を含んだ塗料が開示されている（特許文献２）。しかし、この方法では、有機基材に対して溶解性のある有機溶剤を大量に含むことから有機基材への侵食がかなり進み、得られた塗膜品が白濁しやすいという問題があった。また、疎水性のシリカを使用するため親水性の塗膜は得られなかった。 Also, as a method for forming a strong silica film on an organic substrate such as polycarbonate, a paint containing hydrophobically treated silica, water, and an organic solvent such as cellosolve acetate that is soluble in the organic substrate is disclosed. (Patent Document 2). However, this method has a problem that since the organic base material contains a large amount of an organic solvent that is soluble in the organic base material, erosion of the organic base material has progressed considerably, and the obtained coated product is likely to become cloudy. Moreover, since a hydrophobic silica was used, a hydrophilic coating film could not be obtained.
本発明は、高い透明性を有し、有機基材との密着性に優れ、長時間にわたって、親水性、親水性に伴う防曇性、流滴性、防汚性において優れた塗膜を形成できる無機塗料組成物、親水性塗膜及び親水性塗膜の形成方法を提供することを目的とする。 The present invention has high transparency, excellent adhesion to an organic base material, and forms a coating film excellent in hydrophilicity, antifogging property, flowability, and antifouling property associated with hydrophilicity over a long period of time. An object of the present invention is to provide an inorganic coating composition, a hydrophilic coating film, and a method for forming a hydrophilic coating film.
本発明は、下記を特徴とする要旨を有する。
（１）有機基材上に親水性塗膜を形成することのできる無機塗料組成物であって、（ａ）平均粒子径５〜１００ｎｍのシリカ粒子、（ｂ）界面活性剤、（ｃ）有機基材を膨潤又は溶解することができ、かつ、気圧０．１ＭＰａの状態で沸点１３０℃以上の、水に混和しける有機溶剤Ａ、（ｄ）有機基材を実質上膨潤又は溶解することがなく、かつ、気圧０．１ＭＰａの状態で沸点５０〜１２０℃の、水に混和しうる有機溶剤Ｂ及び（ｅ）水を含有し、かつ、該無機塗料組成物中における、有機溶剤Ａの含有量が１〜１０質量％であり、有機溶剤Ｂの含有量が０〜９７．２質量％であり、固形分含有量が０．１〜２０質量％であり、固形分含有量の３．５〜１７倍の水が含有される無機塗料組成物。
（２）前記有機基材がポリカーボネート又はアクリル樹脂からなる上記（１）に記載の無機塗料組成物。
（３）前記有機溶剤Ａが、ジグライム、Ｎ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジメチルアセトアミド、アセト酢酸エチル、Ｎ−メチル−２−ピロリジノン、２−ピロリジノン、１，３−ジメチル−２−イミダゾリジノン及びジメチルスルホキシドからなる群より選ばれる少なくとも1種である上記（１）又は（２）に記載の無機塗料組成物。
（４）前記有機溶剤Ｂが、メタノール、エタノール、ｎ−プロパノール、イソプロパノール、ｎ−ブタノール、イソブタノール、ｓｅｃ−ブタノール及びｔ−ブタノールからなる群より選ばれる少なくとも１種である上記（１）〜（３）のいずれかに記載の無機塗料組成物。
（５）前記シリカ粒子が、コロイダルシリカ又は気相法合成シリカである上記（１）〜（４）のいずれかに記載の無機塗料組成物。
（６）上記（１）〜（５）のいずれかに記載の無機塗料組成物を有機基材に塗布することにより得られる親水性塗膜。
（７）前記親水性塗膜の水に対する接触角が２０°以下である上記（６）に記載の親水性塗膜。
（８）（ａ）平均粒子径５〜１００ｎｍのシリカ粒子、（ｂ）界面活性剤、（ｃ）有機基材を膨潤又は溶解することができ、かつ、気圧０．１ＭＰａの状態で沸点１３０℃以上の、水に混和しうる有機溶剤Ａ、（ｄ）有機基材を実質上膨潤又は溶解することがなく、かつ、気圧０．１ＭＰａの状態で沸点５０〜１２０℃の水に混和しうる有機溶剤Ｂ及び（ｅ）水を混合し、該無機塗料組成物中における、有機溶剤Ａの含有量が１〜１０質量％であり、有機溶剤Ｂの含有量が０〜９７．２質量％であり、固形分含有量が０．１〜２０質量％であり、かつ固形分含有量の３．５〜１７倍の水が含有されるように該無機塗料組成物を調製する工程、及び、該無機塗料組成物を有機基材上に塗布、乾燥することにより親水性塗膜を形成する工程、を経る親水性塗膜の形成方法。The present invention has a gist characterized by the following.
(1) An inorganic coating composition capable of forming a hydrophilic coating film on an organic substrate, wherein (a) silica particles having an average particle diameter of 5 to 100 nm, (b) a surfactant, and (c) organic The organic solvent A that can swell or dissolve the substrate and has a boiling point of 130 ° C. or higher at a pressure of 0.1 MPa and is miscible with water, (d) substantially does not swell or dissolve the organic substrate. And an organic solvent B having a boiling point of 50 to 120 ° C. in a state of atmospheric pressure of 0.1 MPa and miscible with water and (e) water, and the content of the organic solvent A in the inorganic coating composition Is 1 to 10 mass%, the content of the organic solvent B is 0 to 97.2 mass%, the solid content is 0.1 to 20 mass%, and the solid content is 3.5 to 3.5%. An inorganic coating composition containing 17 times as much water.
(2) The inorganic coating composition according to the above (1), wherein the organic substrate is made of polycarbonate or acrylic resin.
(3) The organic solvent A is diglyme, N, N-dimethylformamide, N, N-dimethylacetamide, ethyl acetoacetate, N-methyl-2-pyrrolidinone, 2-pyrrolidinone, 1,3-dimethyl-2-imidazo The inorganic coating composition according to the above (1) or (2), which is at least one selected from the group consisting of lysinone and dimethyl sulfoxide.
(4) The above (1) to (1), wherein the organic solvent B is at least one selected from the group consisting of methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol and t-butanol. The inorganic coating composition according to any one of 3).
(5) The inorganic coating composition according to any one of (1) to (4), wherein the silica particles are colloidal silica or vapor-phase synthetic silica.
(6) The hydrophilic coating film obtained by apply | coating the inorganic coating composition in any one of said (1)-(5) to an organic base material.
(7) The hydrophilic coating film according to (6), wherein a contact angle of the hydrophilic coating film with water is 20 ° or less.
(8) (a) silica particles having an average particle diameter of 5 to 100 nm, (b) a surfactant, (c) an organic base material can swell or dissolve, and has a boiling point of 130 ° C. at a pressure of 0.1 MPa. The above organic solvent A miscible with water, (d) an organic solvent which does not substantially swell or dissolve the organic base material and is miscible with water having a boiling point of 50 to 120 ° C. at a pressure of 0.1 MPa. The solvent B and (e) water are mixed, and the content of the organic solvent A in the inorganic coating composition is 1 to 10% by mass, and the content of the organic solvent B is 0 to 97.2% by mass. The step of preparing the inorganic coating composition so that the solid content is 0.1 to 20% by mass and the water content is 3.5 to 17 times the solid content, and the inorganic A process of forming a hydrophilic coating film by applying a coating composition on an organic substrate and drying. Method of forming a hydrophilic coating.
本発明により、高い透明性を有し、有機基材との密着性が高く、親水性の高い、防曇性、防汚性、流滴性にも優れた塗膜を形成できる無機塗料組成物、親水性塗膜及び親水性塗膜の形成方法を得ることができる。 INDUSTRIAL APPLICABILITY According to the present invention, an inorganic coating composition that can form a coating film having high transparency, high adhesion to an organic base material, high hydrophilicity, excellent antifogging properties, antifouling properties, and flowability. A hydrophilic coating film and a method for forming a hydrophilic coating film can be obtained.
本発明の無機塗料組成物は、（ａ）平均粒子径５〜１００ｎｍシリカ粒子、（ｂ）界面活性剤、（ｃ）有機溶剤Ａ、（ｄ）有機溶剤Ｂ及び（ｅ）水を含有する。 The inorganic coating composition of the present invention contains (a) silica particles having an average particle diameter of 5 to 100 nm, (b) a surfactant, (c) an organic solvent A, (d) an organic solvent B, and (e) water.
本発明において、シリカ粒子は、塗膜を形成する主剤としての役割をする。シリカ粒子はコロイダルシリカ又は気相法合成シリカが好ましい。シリカ粒子は、平均粒子径５〜１００ｎｍであることが必要である。これにより、透明性に優れた塗膜を得ることができるので好ましい。シリカ粒子の平均粒子径が５ｎｍ未満であると、細孔容積が小さい緻密な膜が形成され、親水性が低下するおそれがあるので好ましくなく、平均粒子径が１００ｎｍ超であると、得られる塗膜が白濁化して透明性に劣るおそれがあるので好ましくない。シリカ粒子は平均粒子径５〜３０ｎｍであることが好ましく、平均粒子径１０〜２０ｎｍであることが特に好ましい。ここで、平均粒子径とは、質量基準のものとして定義される。 In the present invention, the silica particles serve as a main agent for forming a coating film. The silica particles are preferably colloidal silica or gas phase synthetic silica. The silica particles are required to have an average particle diameter of 5 to 100 nm. Thereby, since the coating film excellent in transparency can be obtained, it is preferable. If the average particle diameter of the silica particles is less than 5 nm, a dense film having a small pore volume is formed, and the hydrophilicity may be lowered. This is not preferable, and if the average particle diameter is more than 100 nm, the resulting coating is obtained. This is not preferable because the film may become cloudy and have poor transparency. The silica particles preferably have an average particle size of 5 to 30 nm, particularly preferably an average particle size of 10 to 20 nm. Here, the average particle size is defined as that based on mass.
本発明において、界面活性剤としては、アニオン性界面活性剤、カチオン性界面活性剤、ノニオン性界面活性剤のいずれも使用できる。界面活性剤を含有することにより、有機基材に対して優れた濡れ性を有するので好ましい。界面活性剤としては、−ＣＨ２ＣＨ２Ｏ−、−ＳＯ２−、−ＮＲ−（Ｒは水素原子又は有機基）、−ＮＨ２、−ＳＯ３Ｙ、又は−ＣＯＯＹ（Ｙは水素原子、ナトリウム原子、カリウム原子又はアンモニウムイオン）の構造単位を有するノニオン性界面活性剤が好ましい。なかでも、無機塗料組成物の保存安定性や親水性を損なうおそれのないことから、−ＣＨ２ＣＨ２Ｏ−の構造単位をもつノニオン系の界面活性剤が特に好ましい。
ノニオン系の界面活性剤としては、例えば、アルキルポリオキシエチレンエーテル、アルキルポリオキシエチレン−ポリプロピレンエーテル、脂肪酸ポリオキシエチレンエステル、脂肪酸ポリオキシエチレンソルビタンエステル、脂肪酸ポリオキシエチレンソルビトールエステル、アルキルポリオキシエチレンアミン、アルキルポリオキシエチレンアミド、ポリエーテル変性のシリコーン系界面活性剤等が挙げられる。In the present invention, as the surfactant, any of an anionic surfactant, a cationic surfactant, and a nonionic surfactant can be used. It is preferable to contain a surfactant because it has excellent wettability with respect to the organic substrate. As the surfactant, —CH 2 CH 2 O—, —SO 2 —, —NR— (R is a hydrogen atom or an organic group), —NH 2 , —SO 3 Y, or —COOY (Y is a hydrogen atom, Nonionic surfactants having a structural unit of sodium atom, potassium atom or ammonium ion are preferred. Among these, nonionic surfactants having a structural unit of —CH 2 CH 2 O— are particularly preferred because they do not impair the storage stability and hydrophilicity of the inorganic coating composition.
Nonionic surfactants include, for example, alkyl polyoxyethylene ether, alkyl polyoxyethylene-polypropylene ether, fatty acid polyoxyethylene ester, fatty acid polyoxyethylene sorbitan ester, fatty acid polyoxyethylene sorbitol ester, alkyl polyoxyethylene amine , Alkyl polyoxyethylene amide, polyether-modified silicone surfactants, and the like.
本発明では、無機塗料組成物中に有機溶剤Ａを含有する。これにより、得られる塗膜の密着性を向上させることができる。この有機溶剤Ａを含有することにより、有機基材との密着性が向上する機構については解明できていないが、有機溶剤Ａが有機基材を膨潤又は溶解させることにより、有機基材表面にミクロな欠陥部位を作り出し、そのミクロな欠陥部位にシリカ粒子が浸入した後、有機溶剤Ａが揮発することで有機基板の表面部位で樹脂の収縮が起こり，シリカ粒子が有機基材中に埋め込まれた状態で固定化されるものと考えられる。 In the present invention, the organic solvent A is contained in the inorganic coating composition. Thereby, the adhesiveness of the coating film obtained can be improved. Although the mechanism by which the adhesion with the organic base material is improved by containing the organic solvent A has not been elucidated, the organic solvent A swells or dissolves the organic base material, so that the surface of the organic base material becomes microscopic. After the silica particles infiltrated into the micro-defect site and the organic solvent A volatilized, the resin contracted on the surface of the organic substrate, and the silica particle was embedded in the organic base material. It is considered to be fixed in the state.
有機溶剤Ａは、有機基材を膨潤又は溶解することができ、かつ、気圧０．１ＭＰａの状態で沸点１３０℃以上を有する。有機溶剤Ａは、無機塗料組成物を調製する際、無機塗料組成物中の水と混和して無機塗料組成物が相分離をおこさないものであることが好ましい。このため、有機溶剤Ａは、水に対する溶解度が２以上であることが好ましい。なお、本発明において、水に対する溶解度とは温度２０℃で水１００ｇに溶解する有機溶剤Ａの量（ｇ）をいう。また、有機溶剤Ａが気圧０．１ＭＰａの状態で沸点１３０℃以上であることにより、無機塗料組成物中において、有機溶剤Ｂ及び水に比べて最後まで残存することができ、上述のような効果を示すことができる。
有機溶剤Ａは、気圧０．１ＭＰａの状態で、沸点１６０〜３００℃であることが特に好ましい。有機溶剤Ａは、ジグライム、Ｎ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジメチルアセトアミド、アセト酢酸エチル、Ｎ−メチル−２−ピロリジノン、２−ピロリジノン、１，３−ジメチル−２−イミダゾリジノン及びジメチルスルホキシドからなる群より選ばれる少なくとも１種のものが好ましい。The organic solvent A can swell or dissolve the organic base material, and has a boiling point of 130 ° C. or higher under a pressure of 0.1 MPa. When preparing the inorganic coating composition, the organic solvent A is preferably mixed with water in the inorganic coating composition so that the inorganic coating composition does not cause phase separation. For this reason, it is preferable that the organic solvent A has a solubility in water of 2 or more. In the present invention, the solubility in water means the amount (g) of the organic solvent A dissolved in 100 g of water at a temperature of 20 ° C. Further, when the organic solvent A has a boiling point of 130 ° C. or higher in a state where the atmospheric pressure is 0.1 MPa, it can remain in the inorganic coating composition as compared with the organic solvent B and water, and the above-described effects Can be shown.
The organic solvent A particularly preferably has a boiling point of 160 to 300 ° C. under a pressure of 0.1 MPa. Organic solvent A is diglyme, N, N-dimethylformamide, N, N-dimethylacetamide, ethyl acetoacetate, N-methyl-2-pyrrolidinone, 2-pyrrolidinone, 1,3-dimethyl-2-imidazolidinone and dimethyl At least one selected from the group consisting of sulfoxides is preferred.
また、本発明の無機塗料組成物は有機溶剤Ｂを含有する。有機溶剤Ｂも有機溶剤Ａと同様、無機塗料組成物を調製する際、無機塗料組成物中の水と混和して無機塗料組成物が相分離をおこさないものであることが必要である。このため、有機溶剤Ｂも水に対する溶解度が２以上であることが好ましい。また、有機溶剤Ｂは気圧０．１ＭＰａの状態で沸点５０〜１２０℃であることが必要である。これにより、無機塗料組成物を塗工した後の乾燥の際に有機溶剤Ａより早く蒸発するため有機溶剤Ａが有機基材表面に均一に残り、有機基材表面を均一に膨潤又は溶解することができるので好ましい。
有機溶剤Ｂとしては、メタノール、エタノール、ｎ−プロパノール、イソプロパノール、ｎ−ブタノール、イソブタノール、ｓｅｃ−ブタノール及びｔ−ブタノールからなる群より選ばれる少なくとも１種のものが好ましい。The inorganic coating composition of the present invention contains an organic solvent B. Similarly to the organic solvent A, the organic solvent B must be mixed with water in the inorganic coating composition so that the inorganic coating composition does not cause phase separation when preparing the inorganic coating composition. For this reason, it is preferable that the organic solvent B has a solubility in water of 2 or more. The organic solvent B needs to have a boiling point of 50 to 120 ° C. under a pressure of 0.1 MPa. As a result, the organic solvent A remains uniformly on the surface of the organic base material because it evaporates faster than the organic solvent A during drying after coating the inorganic coating composition, and the organic base material surface uniformly swells or dissolves. Is preferable.
The organic solvent B is preferably at least one selected from the group consisting of methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol and t-butanol.
本発明の無機塗料組成物は、適宜必要に応じて、親水性樹脂を含有することができる。この親水性樹脂を含有することにより、得られる塗膜の強度を向上させる効果があるので好ましい。親水性樹脂としては、ポリアクリル酸、ポリビニルアルコール、ポリブチラール、ポリウレタン、セルロース等が挙げられる。親水性樹脂の含有量は、無機塗料組成物の固形分１００質量部に対して１００質量部以下が好ましい。親水性樹脂の含有量が１００質量部超であると、親水性の持続性や耐摩耗性が悪くなるおそれがあるので好ましくない。親水性樹脂の含有量は、無機塗料組成物の固形分１００質量部に対して５０質量部以下であることが特に好ましい。 The inorganic coating composition of the present invention can contain a hydrophilic resin as necessary. By containing this hydrophilic resin, there is an effect of improving the strength of the obtained coating film, which is preferable. Examples of the hydrophilic resin include polyacrylic acid, polyvinyl alcohol, polybutyral, polyurethane, and cellulose. The content of the hydrophilic resin is preferably 100 parts by mass or less with respect to 100 parts by mass of the solid content of the inorganic coating composition. If the content of the hydrophilic resin is more than 100 parts by mass, the hydrophilic durability and wear resistance may be deteriorated. The content of the hydrophilic resin is particularly preferably 50 parts by mass or less with respect to 100 parts by mass of the solid content of the inorganic coating composition.
本発明の無機塗料組成物は、適宜必要に応じて、着色用染料、顔料、紫外線吸収剤、酸化防止剤等の添加剤を含有することができる。 The inorganic coating composition of the present invention can contain additives such as coloring dyes, pigments, ultraviolet absorbers and antioxidants as necessary.
有機溶剤Ａの含有量は、無機塗料組成物の１〜１０質量％であることが必要である。有機溶剤Ａは上述のとおり、有機基材を膨潤化又は溶解させることによりシリカ粒子を基材中に埋め込ませる働きをすると考えられる。したがって、有機溶剤Ａは有機基材の表面を覆う量だけ存在すればよく、無機塗料組成物において、固形分でなく全体の濃度に依存する。有機溶剤Ａの含有量が１質量％未満であると、得られる塗膜の有機基材への密着性が低下するおそれがあるので好ましくない。有機溶剤Ａの含有量が１０質量％超であると、有機基材への侵食の影響が大きくなり、表面の平滑性が損なわれ、塗膜の透明性が低下するおそれがあり、さらに、塗膜の外観が悪くなるおそれがあるので好ましくない。有機溶剤Ａの含有量は３〜７質量％であることが特に好ましい。 The content of the organic solvent A needs to be 1 to 10% by mass of the inorganic coating composition. As described above, it is considered that the organic solvent A functions to embed silica particles in the base material by swelling or dissolving the organic base material. Accordingly, the organic solvent A only needs to be present in an amount that covers the surface of the organic substrate, and depends on the overall concentration, not the solid content, in the inorganic coating composition. If the content of the organic solvent A is less than 1% by mass, the adhesion of the resulting coating film to the organic substrate may be reduced, such being undesirable. When the content of the organic solvent A is more than 10% by mass, the influence of erosion on the organic base material is increased, the surface smoothness may be impaired, and the transparency of the coating film may be reduced. This is not preferable because the appearance of the film may be deteriorated. The content of the organic solvent A is particularly preferably 3 to 7% by mass.
また、有機溶剤Ｂの含有量は、無機塗料組成物において、０〜９７．２質量％であることが必要である。ここで、含有量０質量％とは、有機溶剤Ｂを全く含まないことを意味する。すなわち、本発明の無機塗料組成物においては、有機溶剤Ｂを全く含まなくてもよい。有機溶剤Ｂは無機塗料組成物の有機基材への塗布性を向上させる役割をする。有機溶剤Ｂの含有量は０〜５０質量％であることが特に好ましい。 In addition, the content of the organic solvent B needs to be 0 to 97.2% by mass in the inorganic coating composition. Here, the content of 0% by mass means that no organic solvent B is contained. That is, the inorganic coating composition of the present invention may not contain the organic solvent B at all. The organic solvent B serves to improve the coating property of the inorganic coating composition on the organic substrate. The content of the organic solvent B is particularly preferably 0 to 50% by mass.
本発明の無機塗料組成物の固形分含有量は０．１〜２０質量％であることが必要である。固形分含有量が０．１重量％未満であると、無機塗料組成物を塗布した際、ムラが発生しやすくなるので好ましくなく、固形分含有量が２０重量％超であると、塗布する際の作業性が悪くなるので好ましくない。無機塗料組成物の固形分含有量は０．１〜１０質量％であることが特に好ましい。 The solid content of the inorganic coating composition of the present invention is required to be 0.1 to 20% by mass. When the solid content is less than 0.1% by weight, unevenness is likely to occur when the inorganic coating composition is applied, and this is not preferable. When the solid content is more than 20% by weight, it is not preferable. This is not preferable because the workability of the is deteriorated. The solid content of the inorganic coating composition is particularly preferably 0.1 to 10% by mass.
本発明の無機塗料組成物において、水の含有量は、無機塗料組成物の固形分含有量（質量基準）の３．５〜１７倍であることが必要である。水は，無機塗料組成物において、シリカ粒子の分散性を安定化させる役割をする。水の含有量が無機塗料組成物の固形分含有量の３．５倍未満であると、無機塗料組成物において、シリカ粒子の安定性が低下し凝集が起きて沈降するおそれがあるので好ましくない。水の含有量が無機塗料組成物の固形分含有量の１７倍超であると、無機塗料組成物の濡れ性が低下するため塗布する際の作業性が悪くなるおそれがあるので好ましくない。水の含有量は無機塗料組成物の固形分含有量の５〜１１倍であることが好ましい。 In the inorganic coating composition of the present invention, the water content needs to be 3.5 to 17 times the solid content (mass basis) of the inorganic coating composition. Water plays a role in stabilizing the dispersibility of the silica particles in the inorganic coating composition. If the water content is less than 3.5 times the solid content of the inorganic coating composition, it is not preferable because the stability of the silica particles is reduced in the inorganic coating composition, causing aggregation and sedimentation. . If the water content is more than 17 times the solid content of the inorganic coating composition, the wettability of the inorganic coating composition is lowered, so that the workability during application may be deteriorated, which is not preferable. The water content is preferably 5 to 11 times the solid content of the inorganic coating composition.
本発明の無機塗料組成物において、界面活性剤の含有量は、１〜５００ｐｐｍであることが好ましい。界面活性剤の含有量が１ｐｐｍ未満であると、無機塗料組成物の濡れ性が低下するため塗布する際の作業性が悪くなるおそれがあるので好ましくなく、界面活性剤の含有量が５００ｐｐｍ超であると、得られる塗膜の外観の品質が低下するおそれがあるので好ましくない。界面活性剤の含有量は１０〜４００ｐｐｍであることが特に好ましい。 In the inorganic coating composition of the present invention, the surfactant content is preferably 1 to 500 ppm. If the content of the surfactant is less than 1 ppm, the wettability of the inorganic coating composition is lowered, so that the workability at the time of application may be deteriorated, so that the surfactant content is more than 500 ppm. When it exists, since there exists a possibility that the quality of the external appearance of the coating film obtained may fall, it is unpreferable. The content of the surfactant is particularly preferably 10 to 400 ppm.
本発明の無機塗料組成物は、有機基材に塗布することにより、親水性の塗膜を形成することができる。有機基材としては、適宜必要に応じて、様々なものが使用することができるが、ポリカーボネート又はアクリル樹脂からなる基板を使用することが好ましい。また、基材の形状は平板に限らず、全面又は一部に曲率を有していてもよい。得られる塗膜の親水性は、水に対する接触角で評価することができる。得られる塗膜の接触角は２０°以下であることが好ましい。接触角が２０°超であると、得られる塗膜の親水性が不充分となり好ましくない。接触角は１０°以下が特に好ましく、５°以下が最も好ましい。 The inorganic coating composition of this invention can form a hydrophilic coating film by apply | coating to an organic base material. As the organic base material, various materials can be used as appropriate, but it is preferable to use a substrate made of polycarbonate or acrylic resin. Further, the shape of the substrate is not limited to a flat plate, and may have a curvature on the entire surface or a part thereof. The hydrophilicity of the coating film obtained can be evaluated by the contact angle with water. The contact angle of the obtained coating film is preferably 20 ° or less. When the contact angle is more than 20 °, the hydrophilicity of the resulting coating film is insufficient, which is not preferable. The contact angle is particularly preferably 10 ° or less, and most preferably 5 ° or less.
また、得られる塗膜は透明性にも優れているので、特に有機基材が透明である場合は、使用に適している。透明性については、ＪＩＳ Ｋ７１５０の規格に則り、ヘイズ値で評価することが好ましい。得られた塗膜のヘイズ値は１％以下であることが好ましい。ヘイズ値が１％超であると、塗膜の透明性が悪くなり、透過率が低下するので好ましくない。得られる塗膜のヘイズ値は０．５％以下が特に好ましい。 Moreover, since the obtained coating film is excellent also in transparency, especially when an organic base material is transparent, it is suitable for use. About transparency, it is preferable to evaluate by a haze value according to the specification of JIS K7150. The haze value of the obtained coating film is preferably 1% or less. When the haze value is more than 1%, the transparency of the coating film is deteriorated and the transmittance is lowered, which is not preferable. The haze value of the obtained coating film is particularly preferably 0.5% or less.
また、得られる塗膜の細孔容積としては、０．３〜１．５ｍｌ／ｇであることが好ましい。これにより、塗膜中に空気を含有することができ、得られる塗膜の屈折率を低くすることができるので光が散乱しにくくなり、透明性に優れた塗膜が得られるので好ましい。細孔容積が０．３ｍｌ／ｇ未満であると、細孔が小さくなるため親水基の量が減少し、得られる塗膜の防曇性が低下するため好ましくない。細孔容積が１．５ｍｌ／ｇ超であると、塗膜の透明性が損なわれ、また、塗膜の機械的強度が低下するおそれがあるので好ましくない。細孔容積は０．５〜１．２ｍｌ／ｇであることが特に好ましい。なお、塗膜の細孔容積は、窒素吸脱着法により測定することが好ましい。 Moreover, as a pore volume of the coating film obtained, it is preferable that it is 0.3-1.5 ml / g. Thereby, air can be contained in the coating film, and the refractive index of the resulting coating film can be lowered, so that light is hardly scattered and a coating film having excellent transparency is obtained, which is preferable. When the pore volume is less than 0.3 ml / g, the pores become small, the amount of hydrophilic groups decreases, and the antifogging property of the resulting coating film decreases, which is not preferable. When the pore volume is more than 1.5 ml / g, the transparency of the coating film is impaired, and the mechanical strength of the coating film may be lowered, which is not preferable. The pore volume is particularly preferably 0.5 to 1.2 ml / g. The pore volume of the coating film is preferably measured by a nitrogen adsorption / desorption method.
本発明では、（ａ）平均粒子径５〜１００ｎｍのシリカ粒子、（ｂ）界面活性剤、（ｃ）有機溶剤Ａ、（ｄ）有機溶剤Ｂ及び（ｅ）水を混合し、有機溶剤Ａの含有量が１〜１０質量％で、有機溶剤Ｂの含有量が０〜９７．２質量％で、固形分含有量が０．１〜２０質量％であり、固形分含有量の３．５〜１７倍の水が含有されるように無機塗料組成物を調製する工程、及び、該無機塗料組成物を有機基材上に塗布、乾燥することにより親水性塗膜を形成する工程、を経ることが好ましい。これにより、有機基材との密着性が高い親水性塗膜を形成することができる。 In the present invention, (a) silica particles having an average particle diameter of 5 to 100 nm, (b) a surfactant, (c) an organic solvent A, (d) an organic solvent B and (e) water are mixed, The content is 1 to 10% by mass, the content of the organic solvent B is 0 to 97.2% by mass, the solid content is 0.1 to 20% by mass, and the solid content is 3.5 to 3.5%. Steps of preparing an inorganic coating composition so as to contain 17 times as much water and a step of forming a hydrophilic coating film by applying and drying the inorganic coating composition on an organic substrate Is preferred. Thereby, the hydrophilic coating film with high adhesiveness with an organic base material can be formed.
本発明において、無機塗料組成物の塗布方法としては従来より公知の方法で行うことができる。例えば、はけ塗り、ローラー塗布、手塗り、回転塗布、浸漬塗布、各種印刷方式による塗布、カーテンフロー、ダイコート、フローコート、スプレーコート等が挙げられる。また、乾燥方法としては、塗膜の機械的強度を高める目的で、必要に応じて、加熱や電磁波（紫外線や電子線等）の照射を行ってもよい。加熱は有機基材の耐熱性を加味して決定すればよいが、６０〜１００℃が好ましい。本発明の無機塗料組成物を塗布するにあたり、有機基材に対して特に前処理は必要としないが、塗膜の密着性をより高める目的で、プラズマ処理、コロナ処理、ＵＶ処理、オゾン処理等の放電処理、水、酸やアルカリ等の化学処理、または研磨剤を用いた物理的処理を施すことができる。 In the present invention, the inorganic coating composition can be applied by a conventionally known method. Examples include brush coating, roller coating, hand coating, spin coating, dip coating, coating by various printing methods, curtain flow, die coating, flow coating, spray coating, and the like. Moreover, as a drying method, you may perform a heating and irradiation of electromagnetic waves (an ultraviolet ray, an electron beam, etc.) as needed for the purpose of raising the mechanical strength of a coating film. The heating may be determined in consideration of the heat resistance of the organic base material, but is preferably 60 to 100 ° C. In applying the inorganic coating composition of the present invention, no pretreatment is required for the organic substrate, but for the purpose of further improving the adhesion of the coating film, plasma treatment, corona treatment, UV treatment, ozone treatment, etc. Discharge treatment, chemical treatment such as water, acid or alkali, or physical treatment using an abrasive.
本発明において、得られる塗膜の膜厚は３０〜３０００ｎｍが好ましい。塗膜の膜厚が３０ｎｍ未満であると、親水性やその効果持続性が低下するおそれがあるので好ましくなく、塗膜の膜厚が３０００ｎｍ超であると、クラックが入りやすくなったり、干渉縞が発生したり、傷が入った場合にはその傷が目立ちやすくなるので好ましくない。塗膜は膜厚５０〜１０００ｎｍが特に好ましい。 In the present invention, the thickness of the obtained coating film is preferably 30 to 3000 nm. If the thickness of the coating film is less than 30 nm, the hydrophilicity and sustainability of the effect may be lowered, and it is not preferable. If the coating film thickness is more than 3000 nm, cracks are likely to occur or interference fringes may occur. If a crack occurs or a scratch is formed, the scratch is easily noticeable, which is not preferable. The film thickness is particularly preferably 50 to 1000 nm.
以下に、実施例として、例１、２、５、７、８、９、１０を示す。また、比較例として、例３、４、６を示す。以下、特に断らない限り、質量％を単に％で示す。 Examples 1, 2, 5, 7, 8, 9, and 10 are shown below as examples. In addition, Examples 3, 4, and 6 are shown as comparative examples. Hereinafter, unless otherwise specified, mass% is simply indicated by%.
［例１］
容量２００ｍｌガラス製反応容器に、シリカゾル（触媒化成工業社製、商品名：カタロイドＳ、型式：ＳＩ−３０、平均粒子径：１２ｎｍ、固形分含有量３０％）を３０ｇ、水を５５ｇ、Ｎ，Ｎ−ジメチルアセトアミド（圧力０．１ＭＰａでの沸点１６６℃、水に対する溶解度：任意の割合で溶解する）５ｇを加え、混合した後、含有量０．１％のノニオン性界面活性剤（日本ユニカー社製、商品名：Ｌ−７７）エタノール溶液を１０ｇ添加して、２０℃で１時間撹拌して、固形分含有量９％の無機塗料組成物を得た。なお、Ｎ，Ｎ−ジメチルアセトアミドの含有量は５％であり、エタノールの含有量は１０％であり、水の無機塗料組成物の固形分に対する含有量は８．４４倍であった。[Example 1]
In a reaction vessel made of glass having a capacity of 200 ml, 30 g of silica sol (manufactured by Catalyst Kasei Kogyo Co., Ltd., trade name: Cataloid S, model: SI-30, average particle size: 12 nm, solid content 30%), 55 g of water, N, After adding and mixing 5 g of N-dimethylacetamide (boiling point 166 ° C. at a pressure of 0.1 MPa, solubility in water: dissolve in an arbitrary ratio), a nonionic surfactant (Nihon Unicar Co., Ltd.) having a content of 0.1% (Product name: L-77) 10 g of an ethanol solution was added and stirred at 20 ° C. for 1 hour to obtain an inorganic coating composition having a solid content of 9%. The N, N-dimethylacetamide content was 5%, the ethanol content was 10%, and the water content relative to the solid content of the inorganic coating composition was 8.44 times.
［評価試験］
得られた無機塗料組成物３ｇを、エタノール拭きしたポリカーボネート板（１００ｍｍ×１００ｍｍ、厚さ３．５ｍｍ）上に、塗布して、回転数１５０ｒｐｍで７０秒間スピンコートした後、１００℃で１０分間乾燥し、厚さ３００ｎｍの塗膜を形成した。なお、塗膜の厚さは、触針式膜厚計（Ｓｌｏａｎ社製、型式：Ｄｅｋｔａｋ３０３０）で測定した。
以下、塗膜の形成されたサンプルについて、下記に示す方法で評価を行った。評価結果を表１、表２に示す。なお、例２〜１０においても、得られた無機塗料組成物を使用して、例１と同様の操作を行い、塗膜を形成し、評価を行った。評価結果を併せて表１、表２に示す。[Evaluation test]
3 g of the obtained inorganic coating composition was applied onto a polycarbonate plate (100 mm × 100 mm, thickness 3.5 mm) wiped with ethanol, spin-coated at 150 rpm for 70 seconds, and then dried at 100 ° C. for 10 minutes. Then, a coating film having a thickness of 300 nm was formed. In addition, the thickness of the coating film was measured with a stylus type film thickness meter (manufactured by Sloan, model: Dektak 3030).
Hereinafter, the sample in which the coating film was formed was evaluated by the method shown below. The evaluation results are shown in Tables 1 and 2. In Examples 2 to 10, the obtained inorganic coating composition was used, and the same operation as in Example 1 was performed to form a coating film and evaluated. The evaluation results are also shown in Tables 1 and 2.
外観評価として、得られた塗膜の塗布ムラを目視により判断した。塗布ムラがなく外観上良好なものを〇、塗布ムラがあり実用的でないものを×として評価した。 As appearance evaluation, the coating unevenness of the obtained coating film was judged visually. The case where there was no coating unevenness and the appearance was good was evaluated as ◯, and the case where there was coating unevenness and impractical was evaluated as x.
透明性評価として、ヘイズ値により評価を行った。ヘイズ測定はＪＩＳ Ｋ７１５０の規格に則り、評価を行った。基板上の塗膜のヘイズ値をヘーズコンピューター（スガ試験機社製、型名：ＨＧＭ−３ＤＰ）で測定した。ヘイズ値が１％以下のものは合格、１％を超えるものは不合格とした。 As the transparency evaluation, evaluation was performed using a haze value. The haze measurement was evaluated according to the standard of JIS K7150. The haze value of the coating film on the substrate was measured with a haze computer (manufactured by Suga Test Instruments Co., Ltd., model name: HGM-3DP). Those having a haze value of 1% or less were accepted and those exceeding 1% were rejected.
親水性評価として、塗膜の水に対する接触角により評価を行った。塗膜の表面における水の接触角を、接触角計（協和界面科学社製、型式：ＣＡ−Ｘ１５０）で測定した。測定は任意の異なる５つの箇所で行い、その平均値を算出した。 As hydrophilicity evaluation, it evaluated by the contact angle with respect to the water of a coating film. The contact angle of water on the surface of the coating film was measured with a contact angle meter (manufactured by Kyowa Interface Science Co., Ltd., model: CA-X150). The measurement was performed at five different points, and the average value was calculated.
親水性の持続性評価として、サンプルを温度２５℃、湿度５０％の環境下で、１ヶ月間放置し、放置後の塗膜の親水性を評価した。 As a hydrophilicity evaluation, the sample was allowed to stand for 1 month in an environment of a temperature of 25 ° C. and a humidity of 50%, and the hydrophilicity of the coating film after being left was evaluated.
防曇性の評価として、塗膜表面に息を吹きかけ、曇らない場合を◎、息を吹きかけると一部曇るがすぐ透明になる場合を○、息を吹きかけると大部分が曇るがすぐに透明になる場合を△、息を吹きかけると曇りが発生し透明になるまでに時間がかかる場合を×とした。なお、実用上使用できるのは◎、○、△である。 As an evaluation of anti-fogging properties, blow on the surface of the paint film and ◎ if it is not cloudy, ○ if it is partly cloudy but immediately becomes transparent when blown, ○ if it is blown, most part is cloudy but immediately becomes transparent The case where it becomes becomes (triangle | delta) and cloudiness generate | occur | produces when blowing and it takes time to become transparent is set as x. In practice, ◎, ○, and Δ can be used.
防曇持続性評価として、塗膜品を温度２５℃、湿度５０％の環境下で、１ヶ月間放置した後、上記防曇性評価を行った。 As the anti-fogging durability evaluation, the above-mentioned anti-fogging evaluation was performed after the coating film product was left for 1 month in an environment of a temperature of 25 ° C. and a humidity of 50%.
防汚性評価として、塗膜品を４５度傾斜して、屋外に１ヶ月間曝露した。その後、サンプルを回収し、サンプルの塗膜表面に蒸留水をかけ、親水性が保持されている面積を肉眼観察した。９０％以上の面積で親水性が保持されている場合を○、５０％以上の面積で親水性が保持されている場合を△、５０％以下の面積しか親水性が保持されていない場合を×として評価した。 As an antifouling property evaluation, the coated film product was inclined 45 degrees and exposed outdoors for one month. Thereafter, the sample was recovered, distilled water was applied to the surface of the sample coating film, and the area where the hydrophilicity was maintained was visually observed. A case where hydrophilicity is maintained in an area of 90% or more, a case where hydrophilicity is maintained in an area of 50% or more, and a case where hydrophilicity is maintained only in an area of 50% or less. As evaluated.
密着性評価として、サンプルにおいて塗膜にセロハンテープを接着し、このセロハンテープを剥がした時の塗膜の剥離状況を肉眼で観察した。塗膜が全く剥がれない場合を○、一部が剥がれたが半分以上の面積が残っている場合を△、半分以上が剥離した場合を×とした。 As adhesion evaluation, the cellophane tape was adhere | attached on the coating film in the sample, and the peeling condition of the coating film when this cellophane tape was peeled off was observed with the naked eye. The case where the coating film was not peeled at all was marked as ◯, the case where a part was peeled off but more than half of the area remained was Δ, and the case where more than half was peeled was marked as x.
耐磨耗性評価として、サンプルの塗膜表面を、綿布で１００回往復磨耗した後、塗膜の剥離状況を肉眼で観察した。塗膜が全く剥がれない場合を○、一部が剥がれたが半分以上の面積が残っている場合を△、半分以上が剥離した場合を×とした。 As an evaluation of abrasion resistance, the surface of the coating film of the sample was worn back and forth 100 times with a cotton cloth, and the peeling state of the coating film was observed with the naked eye. The case where the coating film was not peeled at all was marked as ◯, the case where a part was peeled off but more than half of the area remained was Δ, and the case where more than half was peeled was marked as x.
屈折率は、サンプルを分光エリプソメーター（大塚電子製、型式：ＦＴＭ７７００Ｗ）で測定した。 The refractive index was measured with a spectroscopic ellipsometer (manufactured by Otsuka Electronics, model: FTM7700W).
細孔容積は、サンプルをガス吸着測定装置（カンタクローム社製、型式：オートソーブ３Ｂ型）で測定した。 The pore volume was measured with a gas adsorption measuring device (manufactured by Cantachrome, model: Autosorb 3B type).
［例２］
例１において、シリカゾル（触媒化成工業社製、商品名：カタロイドＳ、型式：ＳＩ−４５Ｐ、平均粒子径：４５ｎｍ、固形分含有量４０％）２２．５ｇを使用し、水を６２．５ｇとした以外は例１と同様にして操作を行い、無機塗料組成物を得た。なお、Ｎ，Ｎ−ジメチルアセトアミドの含有量は５％であり、エタノールの含有量は１０％であり、水の無機塗料組成物の固形分に対する含有量は８．４４倍であった。[Example 2]
In Example 1, 22.5 g of silica sol (manufactured by Catalyst Kasei Kogyo Co., Ltd., trade name: Cataloid S, model: SI-45P, average particle size: 45 nm, solid content 40%) was used, and water was 62.5 g. An inorganic coating composition was obtained by operating in the same manner as in Example 1 except that. The N, N-dimethylacetamide content was 5%, the ethanol content was 10%, and the water content relative to the solid content of the inorganic coating composition was 8.44 times.
［例３］
例１において、水を４０ｇ、Ｎ−ジメチルアセトアミドを２０ｇとした以外は、例１と同様にして操作を行い、無機塗料組成物を得た。なお、Ｎ，Ｎ−ジメチルアセトアミドの含有量は２０％であり、エタノールの含有量は１０％であり、水の無機塗料組成物の固形分に対する含有量は６．７８倍であった。[Example 3]
An inorganic coating composition was obtained in the same manner as in Example 1 except that 40 g of water and 20 g of N-dimethylacetamide were used in Example 1. In addition, the content of N, N-dimethylacetamide was 20%, the content of ethanol was 10%, and the content of water with respect to the solid content of the inorganic coating composition was 6.78 times.
［例４］
例１において、水を６５ｇ、Ｎ−ジメチルアセトアミドを添加しない以外は、例１と同様にして操作を行い、無機塗料組成物を得た。なお、エタノールの含有量は１０％であり、水の無機塗料組成物の固形分に対する含有量は９．５６倍であった。[Example 4]
An inorganic coating composition was obtained in the same manner as in Example 1 except that 65 g of water and N-dimethylacetamide were not added. The ethanol content was 10%, and the water content relative to the solid content of the inorganic coating composition was 9.56 times.
［例５］
例１において、水を５８ｇとし、Ｎ−ジメチルアセトアミドの代わりに２−ピロリジノン（圧力０．１ＭＰａでの沸点２４５℃、水に対する溶解度：任意の割合で溶解する）を２ｇとした以外は、例１と同様にして操作を行い、無機塗料組成物を得た。なお、２−ピロリジノンの含有量は２％であり、エタノールの含有量は１０％であり、水の無機塗料組成物の固形分に対する含有量は８．７８倍であった。[Example 5]
Example 1 except that in Example 1, 58 g of water was used and 2 g of 2-pyrrolidinone (boiling point 245 ° C. at a pressure of 0.1 MPa, solubility in water: soluble at any ratio) was used instead of N-dimethylacetamide. In the same manner as described above, an inorganic coating composition was obtained. The content of 2-pyrrolidinone was 2%, the content of ethanol was 10%, and the content of water relative to the solid content of the inorganic coating composition was 8.78 times.
［例６］
例１において、界面活性剤を添加しない以外は、例１と同様にして操作を行い、無機塗料組成物を得た。[Example 6]
In Example 1, except that the surfactant was not added, an operation was performed in the same manner as in Example 1 to obtain an inorganic coating composition.
［例７］
例１において、非イオン系界面活性剤「Ｌ−７７」の代わりに、含フッ素ノニオン系界面活性剤（Ｃ８Ｆ１７ＣＨ２ＣＨ２ＣＨ（ＣＨ３）Ｏ（ＣＨ２ＣＨ２Ｏ）ｘ（ＣＨ２ＣＨ（ＣＨ３）Ｏ）ｙＨ、ｘ：ｙ＝７０：３０、ｘ＋ｙ＝５．７２、平均分子量８００）を使用した以外は、例１と同様にして操作を行い、無機塗料組成物を得た。[Example 7]
In Example 1, instead of the nonionic surfactant “L-77”, a fluorine-containing nonionic surfactant (C 8 F 17 CH 2 CH 2 CH (CH 3 ) O (CH 2 CH 2 O) x ( An inorganic coating composition was prepared in the same manner as in Example 1 except that CH 2 CH (CH 3 ) O) y H, x: y = 70: 30, x + y = 5.72, average molecular weight 800) was used. Got.
［例８］
ポリビニルアルコール（クラレ社製、商品名：ポバール１２４）に水を混合して、含有量３％のポリビニルアルコール水溶液を得た。
例１において、シリカゾルを２５ｇ、含有量３％のポリビニルアルコール水溶液を５０ｇ、水を１０ｇ、Ｎ−ジメチルアセトアミドを５ｇ、界面活性剤溶液を１０ｇとした以外は例１と同様の操作を行い、固形分含有量９％の無機塗料組成物を得た。なお、Ｎ，Ｎ−ジメチルアセトアミドの含有量は５％で、エタノールの含有量は１０％であり、水の無機塗料組成物の固形分に対する含有量は８．４４倍であった。[Example 8]
Water was mixed with polyvinyl alcohol (trade name: POVAL 124, manufactured by Kuraray Co., Ltd.) to obtain a polyvinyl alcohol aqueous solution having a content of 3%.
In Example 1, the same operation as in Example 1 was performed except that 25 g of silica sol, 50 g of a 3% polyvinyl alcohol aqueous solution, 10 g of water, 5 g of N-dimethylacetamide, and 10 g of a surfactant solution were used. An inorganic coating composition having a content of 9% was obtained. In addition, the content of N, N-dimethylacetamide was 5%, the content of ethanol was 10%, and the content of water with respect to the solid content of the inorganic coating composition was 8.44 times.
［例９］
アクリル酸エステル共重合体の分散液（日本純薬社製、商品名：ジュリマーＡＰＯ−６０１Ｎ、固形分含有量１７％）に水を混合して、含有量３％のアクリル酸エステル共重合体分散液を得た。
例８において、含有量３％のポリビニルアルコール水溶液の代わりに、含有量３％のアクリル酸エステル共重合体分散液を使用した以外は例１と同様の操作を行い、固形分含有量９％の無機塗料組成物を得た。なお、Ｎ，Ｎ−ジメチルアセトアミドの含有量は５％で、エタノールの含有量は１０％であり、水の無機塗料組成物の固形分に対する含有量は８．４４倍であった。[Example 9]
Dispersion of acrylic ester copolymer (manufactured by Nippon Pure Chemicals Co., Ltd., trade name: Julimer APO-601N, solid content 17%) is mixed with water to disperse acrylic ester copolymer with a content of 3%. A liquid was obtained.
In Example 8, the same operation as in Example 1 was carried out except that an acrylic ester copolymer dispersion having a content of 3% was used instead of the polyvinyl alcohol aqueous solution having a content of 3%, and the solid content was 9%. An inorganic coating composition was obtained. In addition, the content of N, N-dimethylacetamide was 5%, the content of ethanol was 10%, and the content of water with respect to the solid content of the inorganic coating composition was 8.44 times.
［例１０］
例１において、基材をポリメチルメタクリレートに変更した以外は、例１と同様にして操作を行い、塗膜を形成した。[Example 10]
In Example 1, except that the base material was changed to polymethyl methacrylate, the same operation as in Example 1 was performed to form a coating film.
本発明の無機塗料組成物を使用することにより、各種ランプのカバー、眼鏡レンズ、ゴーグル、各種計器のカバー等の有機基材を有する様々な物品に親水性の膜を付与することができる。
なお、２００４年１１月８日に出願された日本特許出願２００４−３２３８５３号の明細書、特許請求の範囲、及び要約書の全内容をここに引用し、本発明の明細書の開示として、取り入れるものである。By using the inorganic coating composition of the present invention, hydrophilic films can be imparted to various articles having an organic substrate such as various lamp covers, spectacle lenses, goggles, and various instrument covers.
The entire contents of the specification, claims and abstract of Japanese Patent Application No. 2004-323853 filed on Nov. 8, 2004 are incorporated herein as the disclosure of the specification of the present invention. Is.
Claims (8)
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| PCT/JP2005/019064 WO2006049008A1 (en) | 2004-11-08 | 2005-10-17 | Inorganic coating composition, hydrophilic coating film and method for forming hydrophilic coating film |
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| JP4840899B2 (en) * | 2005-03-25 | 2011-12-21 | 石原薬品株式会社 | Hydrophilic antifouling coating composition, film forming method using the same and use thereof |
| DE102007032886A1 (en) | 2007-07-14 | 2009-01-15 | Bayer Materialscience Ag | Hydrophilic hardcoat coatings |
| DE102008004622A1 (en) | 2008-01-16 | 2009-07-23 | Bayer Materialscience Ag | Silica-containing UV-curable hardcoat coatings with urethane acrylates |
| EP2396373B1 (en) | 2009-02-12 | 2014-06-18 | Bayer Intellectual Property GmbH | Anti-reflex/anti-fog coatings |
| CN101798781A (en) * | 2010-03-25 | 2010-08-11 | 西安三业精细化工有限责任公司 | Silicone defoaming agent for papermaking and pulping and preparation method thereof |
| US20150010748A1 (en) * | 2012-02-27 | 2015-01-08 | Xue-hua Chen | Basic compositions including inorganic oxide nanoparticles and an organic base, coated substrates, articles and methods |
| JP2012166195A (en) * | 2012-03-27 | 2012-09-06 | Asahi Kasei Chemicals Corp | Method for forming stain-proof layer |
| JP5804996B2 (en) * | 2012-03-27 | 2015-11-04 | 中央自動車工業株式会社 | Anti-fogging and antifouling agent for organic substrate and method for coating organic substrate with said anti-fogging and antifouling agent |
| TWI483848B (en) * | 2012-09-24 | 2015-05-11 | 3M Innovative Properties Co | Hydrophilic film, and preparation method and use thereof |
| CN107400387A (en) * | 2017-06-06 | 2017-11-28 | 东莞唯智美新材料科技有限公司 | The underwater eyeglass of preventing atomization hydrophilic coating, preventing atomization and application method for underwater eyeglass |
| US20200186685A1 (en) * | 2018-12-07 | 2020-06-11 | Canon Kabushiki Kaisha | Transparent member and image pickup apparatus, and method of manufacturing transparent member |
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| JPS6430681A (en) * | 1987-07-24 | 1989-02-01 | Matsushita Electric Works Ltd | Formation of porous inorganic coated film |
| JP4374793B2 (en) * | 2001-03-26 | 2009-12-02 | パナソニック電工株式会社 | Forming method of coating film |
| JP2004099647A (en) * | 2002-09-05 | 2004-04-02 | Toto Ltd | Coating composition for forming photocatalytic and hydrophilic film, photocatalytic and hydrophilic member and method for producing the same |
| JP2005298570A (en) * | 2004-04-07 | 2005-10-27 | Asahi Glass Co Ltd | Inorganic coating composition and hydrophilic film |
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