JPH11279540A - Antibacterial transparent water-repellent film and its production - Google Patents
Antibacterial transparent water-repellent film and its productionInfo
- Publication number
- JPH11279540A JPH11279540A JP8175598A JP8175598A JPH11279540A JP H11279540 A JPH11279540 A JP H11279540A JP 8175598 A JP8175598 A JP 8175598A JP 8175598 A JP8175598 A JP 8175598A JP H11279540 A JPH11279540 A JP H11279540A
- Authority
- JP
- Japan
- Prior art keywords
- antibacterial
- repellent film
- fine particles
- water
- transparent water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- Agricultural Chemicals And Associated Chemicals (AREA)
- Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、抗菌性と、ガラス
並の透明性と、フッ素樹脂並の撥水性を併せ持つ抗菌性
透明撥水膜とその製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antibacterial transparent water-repellent film having both antibacterial properties, transparency comparable to glass, and water repellency comparable to fluororesin, and a method for producing the same.
【０００２】[0002]
【従来の技術】抗菌性塗膜は、一般に膜の最表面におい
てのみ抗菌作用を示す。このため、塗膜表面に多量の汚
れが付着すると、膜の抗菌作用は発揮されない。ここ
で、抗菌性と撥水性を併せ持つ抗菌性撥水膜は、汚れが
付きにくいという特徴を持っている。従って、抗菌性撥
水膜は、汚れが付着しやすい環境で使用する場合に有用
である。従来の抗菌性撥水膜には、フッ素樹脂に抗菌性
の粒子を分散したもの（特開平５−１２４９０５号公
報）やシリコーン樹脂に抗菌剤を分散したもの（特開平
６−６５５２７号公報）などがある。2. Description of the Related Art An antibacterial coating generally exhibits an antibacterial effect only on the outermost surface of the film. Therefore, if a large amount of dirt adheres to the coating film surface, the antibacterial action of the film is not exhibited. Here, the antibacterial water-repellent film having both antibacterial properties and water-repellent properties has a feature that dirt is hardly attached. Therefore, the antibacterial water-repellent film is useful when used in an environment where dirt easily adheres. Conventional antibacterial water-repellent films include those obtained by dispersing antibacterial particles in a fluororesin (JP-A-5-124905) and those obtained by dispersing an antibacterial agent in a silicone resin (JP-A-6-65527). There is.
【０００３】[0003]
【発明が解決しようとする課題】従来の抗菌性撥水膜に
使用されているフッ素樹脂やシリコーン樹脂は、不透明
であるため、抗菌性撥水膜で被覆された基材は、その
色、艶、透明性などの素地感を失ってしまうという問題
があった。本発明は、色、艶、透明性など基材の素地感
を保ったまま基材に抗菌性と撥水性を付与できる抗菌性
透明撥水膜とその製造方法を提供することを目的とす
る。The fluororesin and silicone resin used in the conventional antibacterial water-repellent film are opaque. However, there is a problem in that the originality such as transparency is lost. An object of the present invention is to provide an antibacterial transparent water-repellent film capable of imparting antibacterial properties and water repellency to a substrate while maintaining the substrate's base feeling such as color, gloss and transparency, and a method for producing the same.
【０００４】[0004]
【課題を解決するための手段】本発明は、抗菌性透明撥
水膜を実現するために、透明な撥水膜に抗菌性の微粒子
を混入する。すなわち、本発明の抗菌性透明撥水膜は、
酸化珪素を主成分とするガラス、フルオロアルキル鎖を
有する分子、および、粒径１００ｎｍ以下の抗菌性微粒
子からなることを特徴とする。ここにおいて、抗菌性微
粒子は、銀を含むことが望ましい。また、抗菌性微粒子
は、酸化チタンからなり、さらに酸化チタン表面に銀が
付着していることが望ましい。According to the present invention, in order to realize an antibacterial transparent water-repellent film, antibacterial fine particles are mixed into the transparent water-repellent film. That is, the antibacterial transparent water-repellent film of the present invention,
It is characterized by being made of glass containing silicon oxide as a main component, molecules having a fluoroalkyl chain, and antibacterial fine particles having a particle diameter of 100 nm or less. Here, it is desirable that the antibacterial fine particles contain silver. Further, the antibacterial fine particles are preferably made of titanium oxide, and silver is preferably attached to the surface of titanium oxide.
【０００５】本発明の抗菌性透明撥水膜の製造方法は、
酸化珪素を主成分とするガラスの前駆体であるメトキシ
シラン化合物またはエトキシシラン化合物、フルオロア
ルキル鎖を含むメトキシシラン化合物またはエトキシシ
ラン化合物、水、酸触媒、粒径１００ｎｍ以下の抗菌性
微粒子、および極性有機溶媒からなるコーティング液を
基材表面に塗布する工程、および塗布された基材を乾燥
した後焼成する工程を有する。ここに用いる抗菌性微粒
子は、銀が表面に付着している酸化チタンであり、さら
に、酸化チタン表面にはアルキル鎖を有する分子、また
はフルオロアルキル鎖を有する分子が付着していること
が望ましい。酸触媒は、水酸基、またはカルボキシル基
を有する有機酸であることが望ましい。[0005] The method for producing the antibacterial transparent water-repellent film of the present invention comprises:
A methoxysilane compound or an ethoxysilane compound which is a precursor of glass containing silicon oxide as a main component, a methoxysilane compound or an ethoxysilane compound having a fluoroalkyl chain, water, an acid catalyst, antibacterial fine particles having a particle size of 100 nm or less, and a polar The method includes a step of applying a coating liquid composed of an organic solvent to the surface of the substrate, and a step of drying and firing the applied substrate. The antimicrobial fine particles used here are titanium oxide having silver adhered to the surface, and it is desirable that a molecule having an alkyl chain or a molecule having a fluoroalkyl chain is adhered to the surface of the titanium oxide. The acid catalyst is desirably an organic acid having a hydroxyl group or a carboxyl group.
【０００６】[0006]
【発明の実施の形態】本発明の抗菌性透明撥水膜は、透
明な撥水膜に抗菌性微粒子が混入されていることを特徴
とする。透明な撥水膜は、ガラスからなる膜にフルオロ
アルキル鎖を有する分子を混入することにより実現でき
る。すなわち、酸化珪素を主成分とするガラスの前駆体
であるメトキシシラン化合物またはエトキシシラン化合
物、および、フルオロアルキル鎖を含むメトキシシラン
化合物またはエトキシシラン化合物を酸性触媒下で加水
分解、脱水重合させたコーティング液を作製し、これを
基材に塗布し、これを焼成することにより作製できる。
従って、このコーティング液に抗菌性微粒子を分散さ
せ、これを基材に塗布することにより抗菌性撥水膜が作
製できる。DESCRIPTION OF THE PREFERRED EMBODIMENTS The antibacterial transparent water-repellent film of the present invention is characterized in that antibacterial fine particles are mixed in a transparent water-repellent film. A transparent water-repellent film can be realized by mixing molecules having a fluoroalkyl chain into a film made of glass. That is, a methoxysilane compound or an ethoxysilane compound which is a precursor of glass containing silicon oxide as a main component, and a coating obtained by hydrolyzing and dehydrating and polymerizing a methoxysilane compound or an ethoxysilane compound having a fluoroalkyl chain under an acidic catalyst. A liquid can be prepared by preparing a liquid, applying the liquid to a substrate, and firing the liquid.
Therefore, an antimicrobial water-repellent film can be prepared by dispersing antimicrobial fine particles in this coating liquid and applying the dispersion to a substrate.
【０００７】本発明の方法によって、前記メトキシシラ
ン化合物またはエトキシシラン化合物の加水分解と縮合
反応の生成物としてＳｉＯ2リッチな膜ーガラスが生成
し、この膜中に抗菌性微粒子、およびフルオロアルキル
鎖を有する分子が分散している。フルオロアルキル鎖を
有する分子は、主として膜の表面に配列される。本発明
の上記製造方法における焼成温度は、コーティング液中
の前記メトキシシラン化合物またはエトキシシラン化合
物の加水分解と縮合反応を起こさせてＳｉＯ2リッチな
膜に変換させるに必要な温度であり、１００〜４００℃
の範囲が適当である。この温度は、前記フルオロアルキ
ル鎖を有する分子が分解ないしは変質しない温度でなけ
ればならず、より好ましくは３００℃までである。な
お、ガラスの前駆体としてフルオロアルキル鎖を含むメ
トキシシラン化合物またはエトキシシラン化合物のみを
用いることも可能ではあるが、フルオロアルキル鎖を有
する分子が多くなり、透明なガラスを得るのが困難とな
る。According to the method of the present invention, a SiO 2 -rich film-glass is produced as a product of the hydrolysis and condensation reaction of the methoxysilane compound or the ethoxysilane compound, and antimicrobial fine particles and fluoroalkyl chains are formed in the film. Molecules are dispersed. Molecules with fluoroalkyl chains are mainly arranged on the surface of the membrane. Firing temperature in the production method of the present invention is a temperature necessary and to cause a hydrolysis and condensation reaction of the silane compound or silane compound in the coating liquid is converted into SiO 2 rich layer, 100 400 ° C
Is appropriate. This temperature must be a temperature at which the molecule having the fluoroalkyl chain does not decompose or deteriorate, and is more preferably up to 300 ° C. Although it is possible to use only a methoxysilane compound or an ethoxysilane compound containing a fluoroalkyl chain as a glass precursor, the number of molecules having a fluoroalkyl chain increases, which makes it difficult to obtain a transparent glass.
【０００８】一般に、上記の方法で作製される透明撥水
膜の膜厚は１００ｎｍ以下であるため、膜内に混入する
抗菌性微粒子の粒径は１００ｎｍ以下である。そして、
この値は可視光線の波長領域４００〜８００ｎｍよりも
小さいため、抗菌性の微粒子が混入された撥水膜はその
透明性を保持できる。また、一般に微粒子は溶液中で凝
集しやすい。そこで、微粒子表面をアルキル鎖またはフ
ルオロアルキル鎖を有する分子で覆い、さらに、酸触媒
として水酸基またはカルボキシル基を有する有機酸を用
いて微粒子同士の凝集を防ぐことができる。また、抗菌
性微粒子を酸化チタンと銀から構成することにより、３
００℃以上の高温領域にさらされた後でも抗菌性が保持
できる。In general, the thickness of the transparent water-repellent film produced by the above method is 100 nm or less, so that the particle size of the antimicrobial fine particles mixed in the film is 100 nm or less. And
Since this value is smaller than the wavelength region of visible light of 400 to 800 nm, the water-repellent film in which the antibacterial fine particles are mixed can maintain its transparency. Further, generally, the fine particles are easily aggregated in the solution. Thus, the surface of the fine particles can be covered with a molecule having an alkyl chain or a fluoroalkyl chain, and further, aggregation of the fine particles can be prevented by using an organic acid having a hydroxyl group or a carboxyl group as an acid catalyst. In addition, by forming the antibacterial particles from titanium oxide and silver,
Antimicrobial properties can be maintained even after exposure to a high temperature region of 00 ° C. or higher.
【０００９】なお、以下の実施例においては、ガラスの
前駆体としてテトラエトキシシランを用いているが、本
発明はこれに限定されることはなく、たとえば、テトラ
メトキシシランや、これらの誘導体であっても良いこと
は言うまでもない。また、実施例においては、フルオロ
アルキル鎖を有する分子としてＦＭＯＳを用いている
が、これに限定されることはなく、たとえば、フルオロ
アルキル鎖がＦＭＯＳよりも長くても、また、短くても
良いことは言うまでもない。また、実施例においては、
水酸基またはカルボキシル基を有する有機酸としてクエ
ン酸を用いているが、これに限定されることはなく、例
えば、リンゴ酸、乳酸、酒石酸などを用いても良いこと
は言うまでもない。In the following examples, tetraethoxysilane is used as a precursor of glass. However, the present invention is not limited to this. For example, tetramethoxysilane or a derivative thereof may be used. Needless to say, this is acceptable. Further, in the examples, FMOS is used as a molecule having a fluoroalkyl chain. However, the present invention is not limited to this. For example, the fluoroalkyl chain may be longer or shorter than FMOS. Needless to say. In the embodiment,
Although citric acid is used as an organic acid having a hydroxyl group or a carboxyl group, the present invention is not limited to this. Needless to say, malic acid, lactic acid, tartaric acid, and the like may be used.
【００１０】[0010]
【実施例】以下、本発明の実施例を詳細に説明する。 《実施例１》以下の組成を有するＡ液およびＢ液を作製
した。 Ａ液： ２，２，２−トリフオロエタノール １００ｍｌ テトラエトキシシラン ５０ｍｌ ＦＭＯＳ ８ｍｌEmbodiments of the present invention will be described below in detail. << Example 1 >> Liquid A and liquid B having the following compositions were prepared. Solution A: 2,2,2-Trifluoroethanol 100 ml Tetraethoxysilane 50 ml FMOS 8 ml
【００１１】Ｂ液： ２，２，２−トリフオロエタノール １００ｍｌ 水 １４ｍｌ ＨＣｌ ０．８ｍｌ 抗菌性微粒子 １ｍｇSolution B: 2,2,2-trifluoroethanol 100 ml water 14 ml HCl 0.8 ml antibacterial fine particles 1 mg
【００１２】ここで、ＦＭＯＳは、（（２−パーフルオ
ロオクチル）エチル）トリメトキシシランＣＦ3（Ｃ
Ｆ2）7Ｃ2Ｈ4（ＯＣＨ3）3を示す。抗菌性微粒子として
は、粒径約２０ｎｍの酸化チタン表面に銀を吸着させた
もの（大同特殊鋼業製；ギンテック）を用いた。Here, FMOS is represented by ((2-perfluorooctyl) ethyl) trimethoxysilane CF 3 (C
F 2 ) 7 C 2 H 4 (OCH 3 ) 3 is shown. As the antibacterial fine particles, those obtained by adsorbing silver on the surface of titanium oxide having a particle size of about 20 nm (manufactured by Daido Steel Co., Ltd .; Gintech) were used.
【００１３】まず、Ａ液を３００ｍｌのビーカに入れ、
スターラで攪拌しながらＢ液を少しずつ滴下した。滴下
後、１時間攪拌してコーティング液を作製した。その
後、厚さ１ｍｍ、大きさ５ｃｍ角のガラス基材を５ｃｍ
角の面がコーティング液面に対して垂直になるようにゆ
っくりコーティング液に浸漬した。その後、基材を１ｍ
ｍ／ｓの速度でコーティング液から引き上げた。そし
て、基材を室温で１時間乾燥後、１００℃で１０分間、
続いて３００℃で３０分間焼成した。図１は本実施例に
よって作製した塗膜の模式図を示し、図２は化学構造を
示す模式図である。１は基材を表す。基材１上に形成さ
れた膜２は、ガラス３、およびガラス３中に分散してい
る抗菌性微粒子４およびフルオロアルキル鎖含有分子５
からなる。First, put the solution A into a 300 ml beaker,
Solution B was dripped little by little while stirring with a stirrer. After dropping, the mixture was stirred for 1 hour to prepare a coating liquid. Thereafter, a glass substrate having a thickness of 1 mm and a size of 5 cm square is 5 cm.
It was immersed slowly in the coating solution so that the corner surface was perpendicular to the coating solution surface. Then, the base material is 1m
It was withdrawn from the coating solution at a speed of m / s. Then, after drying the substrate at room temperature for 1 hour, 100 ° C. for 10 minutes,
Subsequently, baking was performed at 300 ° C. for 30 minutes. FIG. 1 is a schematic diagram of a coating film produced according to the present example, and FIG. 2 is a schematic diagram showing a chemical structure. 1 represents a substrate. The film 2 formed on the substrate 1 is composed of a glass 3, antimicrobial fine particles 4 dispersed in the glass 3, and a fluoroalkyl chain-containing molecule 5.
Consists of
【００１４】このようにして塗膜を形成した基材の可視
光（波長４００〜８００ｎｍ）に対する透過率は９０％
であり、ガラス基材はその透明性を保っていることが示
された。また、塗膜を形成した基材の撥水性は、基材表
面に滴下された約５０μｌの純水の静的接触角を測定す
ることにより評価した。純水の静的接触角は１０８度あ
り、基材は撥水性を有することが示された。[0014] The transmittance of the substrate on which the coating film is formed with respect to visible light (wavelength: 400 to 800 nm) is 90%.
It was shown that the glass substrate maintained its transparency. The water repellency of the substrate on which the coating film was formed was evaluated by measuring a static contact angle of about 50 μl of pure water dropped on the surface of the substrate. The static contact angle of pure water was 108 degrees, indicating that the substrate had water repellency.
【００１５】次に、塗膜を形成した基材の抗菌性を以下
の方法で評価した。１ｍｌ当たり約１００，０００個の
黄色ブトウ球菌（Stapylococcus aureus IFO12732）ま
たは大腸菌（Escherichia coli IFO 3972）を含む溶液
を調製した。これらの溶液には、菌が生育するために必
要な栄養素が含まれている。これらの溶液０．２ｍｌを
それぞれ塗膜を形成したガラス基板に滴下し、湿度９５
％、温度３５℃の雰囲気下で２４時間放置した。参照と
して、なにも被覆していない基材にも黄色ブドウ球菌お
よび大腸菌が含まれた溶液をそれぞれ滴下して、湿度９
５％、温度３５℃の雰囲気下で２４時間放置した。基材
上に滴下された溶液中の菌は、基材に抗菌性のない場合
には２４時間以内に増殖し、基材に抗菌性がある場合は
死滅していく。２４時間後、基材上の溶液を回収し、そ
の中にいる菌の数を調べた。このために、溶液を寒天培
地に移し、再び、湿度９５％、温度３５℃の雰囲気下で
２４時間放置した。この操作により、１個の菌は増殖し
て菌の集団を作り、寒天上に大きな白い斑点として目視
観察できるようなる。従って、寒天上に現れた斑点の数
が溶液に含まれていた菌の数である。表１に結果を示
す。Next, the antibacterial property of the substrate on which the coating film was formed was evaluated by the following method. A solution containing about 100,000 Staphylococcus aureus IFO12732 or Escherichia coli IFO 3972 per ml was prepared. These solutions contain the nutrients necessary for the bacteria to grow. 0.2 ml of each of these solutions was dropped onto a glass substrate on which a coating film was formed, and a humidity of 95% was applied.
% In a 35 ° C. atmosphere for 24 hours. As a reference, a solution containing Staphylococcus aureus and Escherichia coli was dropped on an uncoated substrate, respectively.
It was left in an atmosphere of 5% and a temperature of 35 ° C. for 24 hours. The bacteria in the solution dropped on the substrate grow within 24 hours when the substrate has no antibacterial properties, and die when the substrate has antibacterial properties. Twenty-four hours later, the solution on the substrate was recovered, and the number of bacteria in the solution was examined. For this purpose, the solution was transferred to an agar medium and left again for 24 hours in an atmosphere at a humidity of 95% and a temperature of 35 ° C. By this operation, one bacterium multiplies to form a bacterium population, and can be visually observed as large white spots on agar. Therefore, the number of spots appearing on the agar is the number of bacteria contained in the solution. Table 1 shows the results.
【００１６】[0016]
【表１】 [Table 1]
【００１７】表１の結果から明らかなように、塗膜を形
成した基材には、大腸菌と黄色ブドウ球菌の増殖を抑え
る抗菌性を有することがわかる。以上から、本実施例で
作製した膜は、撥水性と抗菌性を併せ持つ透明な膜であ
ることが示された。As is clear from the results shown in Table 1, it is understood that the substrate on which the coating film is formed has an antibacterial property for suppressing the growth of Escherichia coli and Staphylococcus aureus. From the above, it was shown that the film produced in this example was a transparent film having both water repellency and antibacterial properties.
【００１８】次に、本実施例の抗菌性透明撥水膜の耐摩
耗性を調べた。すなわち、濡れ布巾（レーヨン３５％、
綿６５％）に１００ｇ重／平方センチメートルの圧力を
かけて基材を往復３０００回擦り、基材の撥水性の低下
の様子を調べた。参照として、抗菌剤を含まない透明撥
水膜の耐摩耗性も調べた。表２にその結果を示す。Next, the abrasion resistance of the antibacterial transparent water-repellent film of this embodiment was examined. That is, a wet cloth (35% rayon,
The substrate was rubbed 3000 times reciprocatingly under a pressure of 100 g weight / square centimeter on 65% cotton), and the state of reduction in the water repellency of the substrate was examined. As a reference, the wear resistance of the transparent water-repellent film containing no antibacterial agent was also examined. Table 2 shows the results.
【００１９】[0019]
【表２】 [Table 2]
【００２０】以上より、抗菌性透明膜の撥水性は、濡れ
布巾に１００ｇ重／平方センチメートルの圧力をかけて
往復３０００回擦ってもほとんど低下しないことが示さ
れた。さらに、抗菌剤の入っている膜の方が、抗菌剤の
入っていない膜よりも耐摩耗性が高いことが示された。From the above, it was shown that the water repellency of the antibacterial transparent film hardly decreased even when the wet cloth was rubbed 3,000 times with a pressure of 100 g weight / square centimeter. Furthermore, it was shown that the film containing the antimicrobial agent had higher abrasion resistance than the film not containing the antimicrobial agent.
【００２１】次に、抗菌性撥水膜を形成したガラス基材
は、撥水性を有するため、基材に付着した汚れは除去し
易いはずである。そこで、基材の防汚耐久性を調べた。
このために、ガラス基材に砂糖と醤油の混合物（重量比
に対して１：１）を０．２ｍｌ滴下して３００℃で２０
分焼き付けた後、これが濡れた布巾で擦り取ることがで
きるかを調べた。そして、この操作を繰り返し、砂糖醤
油の除去できなくなる回数を調べた。表３にその結果を
示す。Next, since the glass substrate on which the antibacterial water-repellent film is formed has water repellency, dirt attached to the substrate should be easily removed. Then, the antifouling durability of the substrate was examined.
For this purpose, 0.2 ml of a mixture of sugar and soy sauce (1: 1 by weight ratio) is dropped on a glass substrate and the mixture is heated at 300 ° C. for 20 minutes.
After baking, it was determined whether it could be scraped off with a wet cloth. Then, this operation was repeated, and the number of times that the sugar soy sauce could not be removed was examined. Table 3 shows the results.
【００２２】[0022]
【表３】 [Table 3]
【００２３】以上の結果から、本実施例で作製した抗菌
性透明撥水膜上には、砂糖、醤油がこびりつきにくく、
これらを簡単に除去でき、さらに抗菌剤が入っていない
透明撥水膜よりも防汚耐久性が高いことがわかる。本実
施例では、フルオロアルキル鎖を含む分子として、鎖長
の長いパーフルオロオクチル基を有するＦＭＯＳを用い
ているので、作製された膜は高い撥水性を有する。From the above results, sugar and soy sauce hardly stick on the antibacterial transparent water-repellent film produced in this example.
It can be seen that these can be easily removed and the antifouling durability is higher than that of the transparent water-repellent film containing no antibacterial agent. In this embodiment, as a molecule containing a fluoroalkyl chain, an FMOS having a long-chain perfluorooctyl group is used, so that the formed film has high water repellency.
【００２４】《実施例２》以下のＡ，Ｂ液を作製した。 Ａ液： ２，２，２−トリフオロエタノール １００ｍｌ テトラエトキシシラン ５０ｍｌ ＦＭＯＳ ８ｍｌExample 2 The following liquids A and B were prepared. Solution A: 2,2,2-Trifluoroethanol 100 ml Tetraethoxysilane 50 ml FMOS 8 ml
【００２５】Ｂ液： ２，２，２−トリフオロエタノール １００ｍｌ 水 １４ｍｌ クエン酸 ６０ｍｇ 抗菌性微粒子を２ｗｔ％含むエタノール ２．５ｍｌSolution B: 2,2,2-trifluoroethanol 100 ml water 14 ml citric acid 60 mg ethanol containing 2 wt% of antibacterial fine particles 2.5 ml
【００２６】抗菌性微粒子としては、粒径約１０ｎｍの
酸化チタン表面に、銀を付着し、さらに、エチルトリエ
トキシシランを反応させて吸着させたものを用いた。As the antimicrobial fine particles, those obtained by adhering silver to the surface of titanium oxide having a particle diameter of about 10 nm and further reacting and reacting with ethyltriethoxysilane were used.
【００２７】Ａ液を３００ｍｌのビーカに入れ、スター
ラで攪拌しながらＢ液を少しずつ滴下した。滴下後、１
時間攪拌してコーティング液を作製した。その後、厚さ
１ｍｍ、大きさ５ｃｍ角のガラス基材をその表面がコー
ティング液面に対して垂直になるようにゆっくりコーテ
ィング液に浸漬した。その後、基材を１ｍｍ／ｓの速度
でコーティング液から引き上げた。そして、基材を室温
で１時間乾燥後、１００℃で１０分間、続いて３００℃
で３０分間焼成した。実施例１と同様の方法により、上
記の塗膜を形成したガラスの特性を評価したところ、こ
の塗膜は、可視光に対する透明性、撥水性、および、抗
菌性を有することが分かった。The solution A was put into a 300 ml beaker, and the solution B was dropped little by little while stirring with a stirrer. After dripping, 1
After stirring for a time, a coating liquid was prepared. Thereafter, a glass substrate having a thickness of 1 mm and a size of 5 cm square was slowly immersed in the coating liquid so that its surface was perpendicular to the coating liquid surface. Thereafter, the substrate was pulled up from the coating liquid at a speed of 1 mm / s. Then, the substrate was dried at room temperature for 1 hour, then at 100 ° C. for 10 minutes, and then at 300 ° C.
For 30 minutes. When the properties of the glass on which the above-mentioned coating film was formed were evaluated by the same method as in Example 1, it was found that this coating film had transparency to visible light, water repellency, and antibacterial properties.
【００２８】本実施例では、表面がエチル基で覆われた
抗菌剤を用いているため、抗菌剤はエタノール系溶媒の
コーティング液に均一に分散することができる。さら
に、本実施例で用いた酸触媒のクエン酸は、金属に対す
る腐食性の低い弱酸であるため、塗膜を工業生産する場
合に取り扱い易いという利点を持っている。In this embodiment, since the antibacterial agent whose surface is covered with an ethyl group is used, the antibacterial agent can be uniformly dispersed in a coating solution of an ethanol solvent. Furthermore, citric acid as the acid catalyst used in this example is a weak acid having low corrosiveness to metals, and thus has an advantage that it is easy to handle when industrially producing a coating film.
【００２９】[0029]
【発明の効果】以上のように本発明によれば、抗菌性と
撥水性を併せ持つ透明な膜を得ることができる。本発明
の膜は、３００℃以上の雰囲気にさらしても特性が変化
しないガラス、フルオロアルキル鎖を有する分子、およ
び酸化チタンと銀からなる抗菌性微粒子を含むので、高
温にさらされる調理機器などへの応用が可能である。さ
らに、本発明では、無機物である抗菌剤を撥水性膜に混
入していることから、これが撥水膜の充填剤の役割を果
たし、撥水性膜の硬度を向上し、実用耐久性が向上する
という効果がある。As described above, according to the present invention, a transparent film having both antibacterial properties and water repellency can be obtained. Since the film of the present invention contains glass whose properties do not change even when exposed to an atmosphere of 300 ° C. or more, molecules having a fluoroalkyl chain, and antibacterial fine particles composed of titanium oxide and silver, the film of the present invention can be used for cooking equipment exposed to high temperatures. Is applicable. Furthermore, in the present invention, since the inorganic antibacterial agent is mixed in the water-repellent film, this serves as a filler for the water-repellent film, improves the hardness of the water-repellent film, and improves the practical durability. This has the effect.
【図１】本発明の一実施例における抗菌性透明撥水膜の
構成を示す模式図である。FIG. 1 is a schematic diagram showing a configuration of an antibacterial transparent water-repellent film in one example of the present invention.
【図２】同要部の化学構造を示す模式図である。FIG. 2 is a schematic view showing the chemical structure of the relevant part.
１ 基材 ２ 膜 ３ ガラス ４ 抗菌性微粒子 ５ フルオロアルキル鎖含有分子 DESCRIPTION OF SYMBOLS 1 Base material 2 Film 3 Glass 4 Antimicrobial fine particle 5 Fluoroalkyl chain containing molecule
Claims (6)
ロアルキル鎖を有する分子、および粒径１００ｎｍ以下
の抗菌性微粒子からなる抗菌性透明撥水膜。1. An antibacterial transparent water-repellent film comprising glass having silicon oxide as a main component, molecules having a fluoroalkyl chain, and antibacterial fine particles having a particle diameter of 100 nm or less.
抗菌性透明撥水膜。2. The antibacterial transparent water-repellent film according to claim 1, wherein the antibacterial fine particles contain silver.
化チタンからなる請求項１記載の抗菌性透明撥水膜。3. The antibacterial transparent water-repellent film according to claim 1, wherein the antibacterial fine particles are made of titanium oxide having silver adhered to the surface.
であるメトキシシラン化合物またはエトキシシラン化合
物、フルオロアルキル鎖を含むメトキシシラン化合物ま
たはエトキシシラン化合物、水、酸触媒、粒径１００ｎ
ｍ以下の抗菌性微粒子、および極性有機溶媒からなるコ
ーティング液を基材表面に塗布する工程、および塗布さ
れた基材を乾燥した後焼成する工程からなる抗菌性透明
撥水膜の製造方法。4. A methoxysilane compound or an ethoxysilane compound which is a precursor of glass containing silicon oxide as a main component, a methoxysilane compound or an ethoxysilane compound containing a fluoroalkyl chain, water, an acid catalyst, and a particle diameter of 100 n.
A method for producing an antibacterial transparent water-repellent film, comprising: a step of applying a coating liquid comprising m or less of antibacterial fine particles and a polar organic solvent to the surface of a substrate, and a step of drying and firing the applied substrate.
化チタンであり、さらに、酸化チタン表面にはアルキル
鎖またはフルオロアルキル鎖を含む有機分子が付着して
いる請求項４記載の抗菌性透明撥水膜の製造方法。5. The antibacterial property according to claim 4, wherein the antibacterial fine particles are titanium oxide having silver attached to the surface, and organic molecules containing an alkyl chain or a fluoroalkyl chain are attached to the titanium oxide surface. A method for producing a transparent water-repellent film.
有する有機酸である請求項４記載の抗菌性透明撥水膜の
製造方法。6. The method according to claim 4, wherein the acid catalyst is an organic acid having a hydroxyl group or a carboxyl group.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8175598A JPH11279540A (en) | 1998-03-27 | 1998-03-27 | Antibacterial transparent water-repellent film and its production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8175598A JPH11279540A (en) | 1998-03-27 | 1998-03-27 | Antibacterial transparent water-repellent film and its production |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH11279540A true JPH11279540A (en) | 1999-10-12 |
Family
ID=13755268
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8175598A Pending JPH11279540A (en) | 1998-03-27 | 1998-03-27 | Antibacterial transparent water-repellent film and its production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH11279540A (en) |
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| WO2002081588A1 (en) * | 2001-04-02 | 2002-10-17 | Matsushita Electric Industrial Co., Ltd. | Water-repellent film and method for preparing the same, and ink-jet head and ink-jet type recording device using the same |
| WO2005091070A1 (en) * | 2004-03-19 | 2005-09-29 | Daikin Industries, Ltd. | Surface treating agent for substrate for use in lithography |
| WO2008004677A1 (en) * | 2006-07-07 | 2008-01-10 | Nippon Soda Co., Ltd. | Liquid antimicrobial composition capable of forming transparent films |
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| WO2016186051A1 (en) * | 2015-05-15 | 2016-11-24 | 富士フイルム株式会社 | Antibacterial solution, antibacterial film and wet wipe |
| JP2017043599A (en) * | 2015-08-25 | 2017-03-02 | 富士フイルム株式会社 | Antibacterial solution, antibacterial film, spray and cloth |
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-
1998
- 1998-03-27 JP JP8175598A patent/JPH11279540A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2002081588A1 (en) * | 2001-04-02 | 2002-10-17 | Matsushita Electric Industrial Co., Ltd. | Water-repellent film and method for preparing the same, and ink-jet head and ink-jet type recording device using the same |
| US7141305B2 (en) | 2001-04-02 | 2006-11-28 | Matsushita Electric Industrial Co., Ltd. | Water-repellent film and method for producing the same, and ink jet head and ink jet type recording apparatus using the same |
| CN100411752C (en) * | 2001-04-02 | 2008-08-20 | 松下电器产业株式会社 | Water-repellent film and method for preparing the same, and ink-jet head and ink-jet type recording device using the same |
| WO2005091070A1 (en) * | 2004-03-19 | 2005-09-29 | Daikin Industries, Ltd. | Surface treating agent for substrate for use in lithography |
| WO2008004677A1 (en) * | 2006-07-07 | 2008-01-10 | Nippon Soda Co., Ltd. | Liquid antimicrobial composition capable of forming transparent films |
| CN107529745A (en) * | 2015-05-15 | 2018-01-02 | 富士胶片株式会社 | Antimicrobial fluid, antibacterial film and wet mop towel |
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| WO2016186051A1 (en) * | 2015-05-15 | 2016-11-24 | 富士フイルム株式会社 | Antibacterial solution, antibacterial film and wet wipe |
| EP3295792A4 (en) * | 2015-05-15 | 2018-03-21 | FUJIFILM Corporation | Antibacterial solution, antibacterial film and wet wipe |
| US10433541B2 (en) | 2015-05-15 | 2019-10-08 | Fujifilm Corporation | Antibacterial liquid, antibacterial film, and wet wipe |
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| JP2017043599A (en) * | 2015-08-25 | 2017-03-02 | 富士フイルム株式会社 | Antibacterial solution, antibacterial film, spray and cloth |
| WO2017033926A1 (en) * | 2015-08-25 | 2017-03-02 | 富士フイルム株式会社 | Antibacterial solution, antibacterial film, spray and cloth |
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