JP2002243901A - Method for imparting anticlouding performance - Google Patents
Method for imparting anticlouding performanceInfo
- Publication number
- JP2002243901A JP2002243901A JP2001042226A JP2001042226A JP2002243901A JP 2002243901 A JP2002243901 A JP 2002243901A JP 2001042226 A JP2001042226 A JP 2001042226A JP 2001042226 A JP2001042226 A JP 2001042226A JP 2002243901 A JP2002243901 A JP 2002243901A
- Authority
- JP
- Japan
- Prior art keywords
- organic
- performance
- imparting
- sulfate
- 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.)
- Withdrawn
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/42—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating of an organic material and at least one non-metal coating
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2218/00—Methods for coating glass
- C03C2218/10—Deposition methods
- C03C2218/11—Deposition methods from solutions or suspensions
- C03C2218/114—Deposition methods from solutions or suspensions by brushing, pouring or doctorblading
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Surface Treatment Of Optical Elements (AREA)
- Surface Treatment Of Glass (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、メガネ・カメラ等
のレンズ、または窓ガラス、車のフロントガラス、ヘル
メットのシールド、水中メガネ等の光学物品、または浴
室内で使用する鏡等表面に酸化物膜を処理した膜上への
防曇性の付与方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an optical article such as a lens for glasses or a camera, a window glass, a windshield of a car, a shield of a helmet, underwater glasses, or a mirror or the like used in a bathroom. The present invention relates to a method for imparting anti-fogging properties to a treated film.
【０００２】[0002]
【従来の技術】物品表面が曇る現象は、表面に微小な水
滴が付着、結露し、この微少水滴が光を乱反射するため
に生じる。この曇りは眼鏡レンズや光学レンズなとの光
学部品ではその性能の著しい低下を引き起こし、自動車
をはじめとする車両用窓ガラスとしては、安全性の点で
大きな問題である。2. Description of the Related Art The phenomenon that the surface of an article is fogged occurs because minute water droplets adhere to the surface and form dew, and the minute water droplets irregularly reflect light. This fogging causes a remarkable decrease in the performance of optical parts such as spectacle lenses and optical lenses, and is a serious problem in terms of safety as a window glass for vehicles such as automobiles.
【０００３】物品に防曇性能を付与するには、１）基材
に吸水性を持たせる、２）基材表面を親水性にする、
３）基材表面を疎水性にする、４）光学物品の表面温度
を高くし、空気中の水分が表面で凝結しない様にする。
の４点の方法が過去から提案され、色々な試みがなされ
ている。[0003] In order to impart antifogging performance to an article, 1) the base material is made to absorb water, 2) the base material surface is made hydrophilic,
3) The surface of the base material is made hydrophobic. 4) The surface temperature of the optical article is increased so that moisture in the air does not condense on the surface.
The above four methods have been proposed in the past, and various attempts have been made.
【０００４】１）の基材に吸水性を持たせる方法につい
て、コーティング組成物または、合成樹脂基材自体に吸
水性材料を混合する、または、親水性、吸水性の単量体
を共重合して吸水性を付与する方法がある。これについ
ては、特開平１０−３１１９０２，特開平０５−１５６
２０２などに開示されている。また、吸水性の悪いガラ
スなどの無機質に吸水性を持たせる方法としては、無機
質を多孔性にして吸水性を持たせる方法が特開平１０−
１１４５４３等で試みられている。Regarding the method of 1) for imparting water absorbency to a substrate, a water absorbent material is mixed with a coating composition or a synthetic resin substrate itself, or a hydrophilic and water absorbent monomer is copolymerized. There is a method of imparting water absorbency by using water. This is described in JP-A-10-311902 and JP-A-05-156.
202 and the like. As a method of imparting water absorbency to an inorganic substance such as glass having poor water absorbency, a method of imparting water absorbency by making the inorganic substance porous is disclosed in
114543.
【０００５】２）の基材表面を親水性にする方法につい
ては、もっとも簡便な手段として、界面活性剤を表面に
塗布することで基材表面を親水性とし、曇りを防ぐ方法
がある。また、連続的な効果を期待するために、前述同
様、合成樹脂基材自体に界面活性剤を混合し、または親
水性、吸水性の単量体を共重合して合成樹脂基材を形成
して防曇性能を付与する方法がある。これについては、
特開平１０−１１４０３５、特開平１０−１３０５１
１、特開平１０−１５８４５３、特開平１０−１８２９
１２、特開平１０−２０２７９８などに開示されてい
る。また、光学樹脂物品の表面に防曇性能を有するコー
ティングを施す方法も良く知られ、特開平８−１７６４
６、特開平８−２７２９１、特開平９−１３６３７４、
特開平９−１５１３６８、特開平９−１５５２８２など
に開示されている。[0005] As the method 2) for making the surface of the substrate hydrophilic, the simplest method is to apply a surfactant to the surface to make the surface of the substrate hydrophilic and prevent fogging. Also, in order to expect continuous effects, as described above, a surfactant is mixed with the synthetic resin base material itself, or a hydrophilic, water-absorbing monomer is copolymerized to form the synthetic resin base material. There is a method of imparting anti-fogging performance by using. For this,
JP-A-10-114035, JP-A-10-13051
1, JP-A-10-158453, JP-A-10-1829
12, and JP-A-10-202798. A method of applying a coating having anti-fog performance to the surface of an optical resin article is also well known.
6, JP-A-8-27291, JP-A-9-136374,
It is disclosed in JP-A-9-151368 and JP-A-9-155282.
【０００６】光触媒性金属酸化物被膜を形成し、超親水
性を発現させる方法については特開２０００−３０９０
６８、特開２０００−８６９３３、特開平９−７７５３
５、特開平１０−６８０９１、特開平１０−８５１０
０、特開平１０−１６７７２７、特開平１０−２９７９
４０等に開示されている。A method for forming a photocatalytic metal oxide film and exhibiting superhydrophilicity is disclosed in JP-A-2000-3090.
68, JP-A-2000-86933, JP-A-9-7753
5, JP-A-10-68091, JP-A-10-8510
0, JP-A-10-167727, JP-A-10-2979
40 and the like.
【０００７】表面改質の方法としてのグラフト重合は、
基材表面に親水性基を単分子的に導入する方法で、反射
防止特性を有する酸化物膜上に非常に有効な手段であ
る。特開平５−２０２２１６、特開平５−２９５１３
９、特開平８−１７６３２８、特開平９−３０１７４
２、特開平１０−９０５０３等に開示されている。その
他表面改質方法としては特開平１０−１１４５４３、特
開平１０−１６７７６８があげられる。[0007] Graft polymerization as a method of surface modification is
This is a method in which a hydrophilic group is monomolecularly introduced into the substrate surface, and is a very effective means on an oxide film having antireflection properties. JP-A-5-202216, JP-A-5-29513
9, JP-A-8-176328, JP-A-9-30174
2. It is disclosed in JP-A-10-90503 and the like. Other surface modification methods include JP-A-10-114543 and JP-A-10-167768.
【０００８】さらに、無機物質の細孔・凹凸と親水性物
質を組み合わせた特許及び表面の凹凸を利用した特許と
して、特開平９−２０２６５１、特開平９−２９５８３
５、特開平１１−７７８７６が挙げられる。Further, Japanese Patent Application Laid-Open Nos. 9-202651 and 9-29583 disclose a patent in which pores / concavities and convexities of an inorganic substance are combined with a hydrophilic substance and a patent utilizing surface irregularities.
5, JP-A-11-77876.
【０００９】３）は基材表面の接触角を高くして、水滴
をその自重によって落脱させる方法である。これは、特
開２０００−１０３００７、特開平１０−２６７０３、
特開平１０−４５４２９、特開平１１−３２０７４３に
開示されている。Method 3) is a method in which the contact angle on the surface of the base material is increased so that water drops fall off by its own weight. This is disclosed in JP-A-2000-103007, JP-A-10-26703,
It is disclosed in JP-A-10-45429 and JP-A-11-320743.
【００１０】４）光学物品の表面温度を高くし、空気中
の水分が表面で凝結しない様にする。方法については、
特開平７−２４１９３２、特開２０００−８６２９９に
開示されている。4) The surface temperature of the optical article is increased so that moisture in the air does not condense on the surface. For information on how,
It is disclosed in JP-A-7-241932 and JP-A-2000-86299.
【００１１】[0011]
【発明が解決しようとする課題】しかし、これまでの方
法はさまざまな欠点を有している。特に、反射防止特性
を有する光学物品の場合、その反射防止特性を変化させ
ずに最表面に防曇特性を持たせることは困難である。However, the conventional methods have various disadvantages. In particular, in the case of an optical article having antireflection characteristics, it is difficult to provide the outermost surface with antifogging characteristics without changing the antireflection characteristics.
【００１２】１）の基材に吸水性を持たせる方法につい
ては、防曇性能としては十分な性能が得られるが、吸水
した場合、非常に柔らかくなってしまい、傷の付きやす
いものであった。また、これを改善するために、架橋点
を増加させると、吸水率が低下してしまうという。加え
て、飽和吸水量以上になると、曇ってしまうという欠点
がある。さらに、空気中の汚れ、例えばタバコの煙など
も吸着し易く、光学物品が着色してしまうなどの欠点も
ある。また、このような吸水性の膜の場合、ある程度の
膜厚を持たせなければならず、反射防止特性を持つ基材
の上には処方不可能である。In the method of (1) for imparting water absorbency to the base material, sufficient performance is obtained as anti-fog performance, but when water is absorbed, it becomes very soft and easily scratched. . In addition, if the number of cross-linking points is increased to improve this, it is said that the water absorption decreases. In addition, there is a disadvantage that when the water absorption exceeds the saturated water absorption, clouding occurs. Further, there is a drawback that dirt in the air, for example, cigarette smoke is easily adsorbed, and the optical article is colored. Further, in the case of such a water-absorbing film, it is necessary to have a certain thickness, and it is impossible to formulate the film on a substrate having antireflection properties.
【００１３】無機物質を多孔性にして吸水性を持たせる
方法は、その膜厚に制限があるため、吸水量も少なく、
多孔質にすることで表面はもろくなり、耐擦傷性に問題
がある。In the method of making an inorganic substance porous so as to have water absorption, the water absorption is small because the film thickness is limited.
By making it porous, the surface becomes brittle, and there is a problem in scratch resistance.
【００１４】２）の基材表面を親水性にする方法につい
ては、水の付着等により殆どの種類の界面活性剤は流れ
落ちてしまい、連続的な効果は期待できず、都度塗布し
なければならないなどの手間がかかる。しかし、反射防
止特性を有する膜上の防曇性付与には、反射防止特性の
阻害をしない点で非常に有効な手段である。In the method of 2) for making the substrate surface hydrophilic, most kinds of surfactants flow down due to adhesion of water and the like, and a continuous effect cannot be expected. It takes time and effort. However, it is a very effective means for imparting anti-fogging property to a film having anti-reflection properties in that the anti-reflection properties are not hindered.
【００１５】光触媒性金属酸化物被膜を形成し、超親水
性を発現させる方法については、その機構上、紫外線に
暴露される状況になければ、超親水性の発現は困難であ
り、また、曇りの様な極微小な水滴の場合、光触媒性物
質の結晶構造に対して、充分な大きさを持たないため、
水滴の広がりは充分ではなく、曇りが認識される。ま
た、特に反射防止特性を有する光学材料については、最
表面に一般的に屈折率の高い光触媒線物質が存在するこ
とにより、反射がかえって大きくなってしまう。With respect to the method of forming a photocatalytic metal oxide film and exhibiting superhydrophilicity, it is difficult to develop superhydrophilicity unless it is exposed to ultraviolet rays because of its mechanism. In the case of extremely small water droplets like the above, since they do not have a sufficient size for the crystal structure of the photocatalytic substance,
Spread of water droplets is not enough, and cloudiness is recognized. Further, in particular, with respect to an optical material having antireflection properties, the reflection is rather increased due to the presence of a photocatalytic linear substance having a generally high refractive index on the outermost surface.
【００１６】グラフト重合について様々な方法が提案さ
れているが、これは最表面に親水性、疎水性の薄膜を成
膜するものである。従来技術に従うと反応が煩雑であ
り、基材表面に密に防曇成分が反応せずに充分な防曇性
が得られない。[0016] Various methods have been proposed for graft polymerization, in which a hydrophilic and hydrophobic thin film is formed on the outermost surface. According to the prior art, the reaction is complicated, and the antifogging component does not react densely on the surface of the substrate, so that sufficient antifogging property cannot be obtained.
【００１７】３）の基材表面基材表面の接触角を高くし
て、水滴をその自重によって落脱させる方法では、ある
程度の大きさの水滴になってはじめて、水滴は落下す
る。よって、曇りの様な極微小な水滴の場合、自重が不
十分なため、自然に落下しない。In the method of 3), in which the contact angle of the surface of the substrate is increased and the water droplets fall off by their own weight, the water droplets fall only after the water droplets have a certain size. Therefore, in the case of extremely minute water droplets such as cloudy, the water droplets do not fall naturally because of their insufficient weight.
【００１８】４）の方法では、ヒーター部、エネルギー
源は不可欠であり、装置が煩雑になりすぎてしまう。In the method 4), the heater section and the energy source are indispensable, and the apparatus becomes too complicated.
【００１９】そこで、本発明は以上の様な問題点を解決
し、光学物品の光学特性を低下させることなく、防曇性
能を付与することを目的とする。Accordingly, an object of the present invention is to solve the above-mentioned problems and to provide an antifogging property without deteriorating the optical properties of an optical article.
【００２０】[0020]
【課題を解決するための手段】本発明は、表面に酸化物
を含む、例えば反射防止特性を有する光学物品を、有機
硫酸塩及び／または有機スルホン酸塩で処理する工程を
含むことにより、防曇性を付与する方法である。SUMMARY OF THE INVENTION The present invention provides a method for preventing an optical article having an oxide on its surface, for example, having an antireflection property, by treating the optical article with an organic sulfate and / or an organic sulfonate. This is a method for imparting haze.
【００２１】本発明では有機硫酸塩及び／または有機ス
ルホン酸塩が特に真空槽内で成膜された二酸化ケイ素上
に処理されることにより、非常に防曇特性が良く、持続
性が良いことを発見した。有機硫酸塩及び／または有機
スルホン酸塩を処理する場合、有機硫酸塩及び／または
有機スルホン酸塩の防曇特性、及び／または持続性を向
上するための処理として、反射防止特性を損なわない程
度の膜厚であれば、同時、順次に関わらず、いかなる処
理を施していてもよい。In the present invention, the organic sulphate and / or organic sulphonate is treated particularly on the silicon dioxide formed in a vacuum chamber, so that the organic sulphate has a very good antifogging property and a good durability. discovered. When the organic sulfate and / or organic sulfonate is treated, the antifogging property of the organic sulfate and / or organic sulfonate is improved so that the antireflection property is not impaired. As long as the film thickness is, any processing may be performed simultaneously or sequentially.
【００２２】本発明はさらに、真空槽内で成膜された二
酸化ケイ素膜そのもの、または真空槽内で成膜された二
酸化ケイ素膜を有機硫酸塩及び／または有機スルホン酸
塩で処理された膜を、有機硫酸塩及び／または有機スル
ホン酸塩を含ませた布または紙で拭くことで防曇性を付
与する、容易かつメンテナンスしやすい方法を考案し
た。The present invention further provides a silicon dioxide film formed in a vacuum chamber itself or a silicon dioxide film formed in a vacuum chamber treated with an organic sulfate and / or an organic sulfonate. An easy and easy-to-maintain method of imparting anti-fog properties by wiping with a cloth or paper impregnated with an organic sulfate and / or an organic sulfonate has been devised.
【００２３】以下に本発明の詳細を示す。本発明で用い
る有機硫酸塩及び／または有機スルホン酸塩は、例えば
アルキルスルホコハク酸塩、アルキルスルホ酢酸塩、ア
ルキルスルホン酸塩、アルキル硫酸塩、ポリオキシエチ
レンアルキルエーテル硫酸塩、ポリオキシエチレンアル
キルフェニルエーテル硫酸塩、またはこれらの変性化合
物等があげられる。The details of the present invention will be described below. The organic sulfate and / or organic sulfonate used in the present invention includes, for example, alkyl sulfosuccinate, alkyl sulfoacetate, alkyl sulfonate, alkyl sulfate, polyoxyethylene alkyl ether sulfate, polyoxyethylene alkyl phenyl ether Sulfates and modified compounds thereof are exemplified.
【００２４】有機硫酸塩及び／または有機スルホン酸塩
の処理として、例えば、酸化物膜上に有機硫酸塩及び／
または有機スルホン酸塩を塗布等によって処理したも
の、または、有機硫酸塩及び／または有機スルホン酸塩
をカップリング剤で処理し、これを基材にグラフト重合
する方法、または基材をカップリング剤で処理し、これ
に有機硫酸塩及び／または有機スルホン酸塩をグラフト
重合する方法、または、オルガノシラン基を含む有機硫
酸塩及び／または有機スルホン酸塩アニオンシラン（米
国特許第４，２３５，６３８に開示されているスルホナ
ートオルガノシラノールなど）を反応させる方法など、
光学特性を損なうことなく、防曇性能を付与する方法で
あれば、これらに限定するものではない。As the treatment of the organic sulfate and / or the organic sulfonate, for example, the organic sulfate and / or the organic sulfonate may be formed on the oxide film.
Or a method in which an organic sulfonate is treated by coating or the like, or a method in which an organic sulfate and / or an organic sulfonate is treated with a coupling agent and graft-polymerized to a substrate, or the substrate is a coupling agent And graft polymerization of an organic sulfate and / or an organic sulfonate thereto, or an organic sulfate and / or an organic sulfonate anion silane containing an organosilane group (US Pat. No. 4,235,638). Reaction of sulfonate organosilanol disclosed in
The method is not limited to these, as long as it is a method for imparting anti-fog performance without impairing optical characteristics.
【００２５】本発明では、防曇性能を付与する方法とし
て有機硫酸塩及び／または有機スルホン酸塩を含ませた
布または紙で拭くことにより、防曇成分を供給する。前
述したような有機硫酸塩及び／または有機スルホン酸塩
は常温で固体のものが主であり、使用時の落脱が少な
い。またこれらの界面活性剤を布または紙に含ませた場
合もその柔軟性を損なわず、払拭性を損なうことがな
い。In the present invention, as a method for imparting anti-fogging performance, the anti-fogging component is supplied by wiping with a cloth or paper impregnated with an organic sulfate and / or an organic sulfonate. The above-mentioned organic sulfates and / or organic sulfonates are mainly solid at room temperature, and are less likely to fall off during use. Also, when these surfactants are contained in cloth or paper, their flexibility is not impaired and their wiping properties are not impaired.
【００２６】本発明で用いる布または紙は、一般的にレ
ンズ拭きとして用いられているものが、払拭性に優れて
いるため、好適である。また、このような布または紙は
その極細繊維故に界面活性剤を保持しやすく、より多量
の界面活性剤を含み、防曇性付与能力が高くなる。As the cloth or paper used in the present invention, those generally used for wiping lenses are preferable because of their excellent wiping properties. Further, such a cloth or paper easily retains a surfactant because of its ultrafine fibers, contains a larger amount of the surfactant, and has a high ability to impart antifogging property.
【００２７】本発明によって得られる防曇性能の付与方
法によって、光学物品の光学特性を損なうことなく、長
期にわたって物品を使用することが可能である。この方
法は、眼鏡レンズ、カメラレンズ、浴室内の鏡、水中眼
鏡、窓ガラス、電子レンジの窓、車の窓ガラス、望遠鏡
のレンズ、スキーのゴーグル、湿気の多い所で使用する
光学機器のレンズ、ミラーなどに適用することが可能で
ある。According to the method for imparting anti-fogging performance obtained by the present invention, the article can be used for a long time without impairing the optical properties of the optical article. This method is used for spectacle lenses, camera lenses, bathroom mirrors, underwater glasses, window glasses, microwave oven windows, car window glasses, telescope lenses, ski goggles, and optical equipment lenses used in humid places. , Mirrors and the like.
【００２８】以下、本発明を実施例に基づき詳細に説明
するが、本発明はこれら実施例に限定されるものではな
い。Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples.
【００２９】[0029]
【発明の実施の形態】Ｉ．防曇性能付与用レンズ拭きの
作製 １．レンズ拭き洗浄 メガネ拭きとして市販されている東レ（株）製、トレシ
ー（メガネ拭き）をエタノール中に２５℃で２時間浸漬
した後、４０℃で２時間乾燥させた。次にこれを１００
℃の蒸留水中で３０分間煮沸し、６０℃で２時間乾燥さ
せた。これをレンズ拭きＤとした。DETAILED DESCRIPTION OF THE INVENTION Preparation of lens wipe for imparting anti-fog performance Lens Wipe Cleaning Toraysee (glass wipes) manufactured by Toray Industries, Inc., which is commercially available for cleaning glasses, was immersed in ethanol at 25 ° C. for 2 hours, and then dried at 40 ° C. for 2 hours. Then add this to 100
Boiled in distilled water at 30 ° C for 30 minutes and dried at 60 ° C for 2 hours. This was designated as lens wipe D.
【００３０】２．防曇成分の含浸 ａ．レンズ拭きＡ ラウリル硫酸ナトリウム１ｇを９９ｇの蒸留水中に溶解
し、この中に、レンズ拭きＤをつけ、充分しみこませた
後、６０℃で２時間乾燥させた。これをレンズ拭きＡと
した。2. Impregnation of anti-fog component a. Lens wipe A 1 g of sodium lauryl sulfate was dissolved in 99 g of distilled water, and lens wipe D was applied thereto, thoroughly soaked, and dried at 60 ° C. for 2 hours. This was designated as lens wipe A.
【００３１】ｂ．レンズ拭きＢ ラウリルスルホ酢酸ナトリウム１ｇを９９ｇの蒸留水中
に溶解し、この中に、レンズ拭きＤをつけ、充分しみこ
ませた後、６０℃で２時間乾燥させた。これをレンズ拭
きＢとした。B. Lens wipe B Sodium lauryl sulfoacetate (1 g) was dissolved in 99 g of distilled water, and lens wipe D was applied thereto, thoroughly soaked, and dried at 60 ° C. for 2 hours. This was designated as lens wipe B.
【００３２】ｃ．レンズ拭きＣ ポリオキシエチレン（４）ラウリルエーテル硫酸ナトリ
ウムの２５％水溶液４ｇを９６ｇの蒸留水中に溶解し、
この中に、レンズ拭きＤをつけ、充分しみこませた後、
６０℃で２時間乾燥させた。これをレンズ拭きＡとし
た。C. Lens wipe C Dissolve 4 g of a 25% aqueous solution of sodium polyoxyethylene (4) lauryl ether sulfate in 96 g of distilled water,
In this, apply the lens wipe D and soak thoroughly.
Dry at 60 ° C. for 2 hours. This was designated as lens wipe A.
【００３３】ｄ．レンズペーパーＡ ラウリル硫酸ナトリウム１ｇを９９ｇの蒸留水中に溶解
し、この中に、小津産業（株）製クリーニングワイパー
ダスパーを浸漬し、充分しみこませた後、６０℃で２時
間乾燥させた。これをレンズペーパーＡとした。 II．防曇性光学物品の準備D. Lens paper A 1 g of sodium lauryl sulfate was dissolved in 99 g of distilled water, and a cleaning wiper daspar manufactured by Ozu Sangyo Co., Ltd. was immersed in the solution, thoroughly immersed, and dried at 60 ° C. for 2 hours. This was designated as lens paper A. II. Preparation of anti-fog optical article
【００３４】１．コーティング液の調整 撹拌装置を備えた、反応容器中に、イソプロピルアルコ
ール１１８．８ｇ，蒸留水３００．０ｇ、γ−グリシド
キシプロピルトリエトキシシラン１３９．４ｇ、０．０
５規定塩酸水溶液３８．２ｇを投入し、６０分攪拌し
た。次に酸化チタン・酸化ジルコニウム・酸化珪素の複
合ゾル(触媒化成工業(株)製“オプトレイク１１２０Ｚ
（Ｕ２５Ａ８）”)４０３．３ｇシリコーン系界面活性
剤（日本ユニカー（株）製“Ｌ−７６０４”）０．３ｇ
添加し、十分攪拌した後コーティング液とした。1. Preparation of Coating Solution In a reaction vessel equipped with a stirrer, 118.8 g of isopropyl alcohol, 300.0 g of distilled water, 139.4 g of γ-glycidoxypropyltriethoxysilane, 0.0
38.2 g of a 5 N aqueous hydrochloric acid solution was added, and the mixture was stirred for 60 minutes. Next, a composite sol of titanium oxide / zirconium oxide / silicon oxide ("Optreak 1120Z" manufactured by Kata Kasei Kogyo Co., Ltd.)
(U25A8) ") 403.3 g Silicone surfactant (" L-7604 "manufactured by Nippon Unicar Co., Ltd.) 0.3 g
After adding and stirring sufficiently, a coating liquid was obtained.
【００３５】２．基材の準備 予め水酸化ナトリウム溶液（０.１Ｎ） に浸漬し、よく
水洗、乾燥したプラスチックレンズ(セイコーエプソン
(株)製、セイコースーパーソブリン用レンズ生地、屈折
率１．６７)に上述したコーティング液をディッピング
法で、膜厚が２.５μｍ になる様塗布し、１３５℃で
２．５時間加熱硬化した。このようにして得られたレン
ズの表面に、プラズマ処理(アルゴンプラズマ４００W×
６０秒)を行った後、無機物質の酸化ケイ素、酸化ジル
コニウムからなる反射防止膜を真空蒸着法で多層被覆
し、ハードコート、反射防止付プラスチックレンズ、基
材Ａを作成した。この基材Ａの水に対する静的接触角は
５°であった。2. Preparation of base material A plastic lens (Seiko Epson) immersed in sodium hydroxide solution (0.1N) in advance, washed well with water and dried
The above-mentioned coating solution was applied by dipping to a thickness of 2.5 μm on a lens fabric for Seiko Super Sovereign (manufactured by Seiko Super Sovereign Co., Ltd.) and cured by heating at 135 ° C. for 2.5 hours. . The surface of the lens thus obtained is subjected to plasma treatment (argon plasma 400 W ×
After 60 seconds), an anti-reflection film made of an inorganic substance, silicon oxide and zirconium oxide, was multi-layer coated by a vacuum deposition method to prepare a hard coat, a plastic lens with anti-reflection, and a substrate A. The static contact angle of the substrate A with water was 5 °.
【００３６】３．防曇処理 ａ．試料Ａ 真空装置から取り出した基材Ａを、ラウリル硫酸ナトリ
ウムの０．５％水溶液１００ｇに２５℃で２時間浸漬
し、２時間風乾した。これを試料Ａとした。得られたレ
ンズの外観・反射防止の特性に大きな変化は見られなか
った。また、この時の水に対する接触角は３°であり、
初期防曇性能が確認された。3. Anti-fog treatment a. Sample A The substrate A taken out of the vacuum apparatus was immersed in 100 g of a 0.5% aqueous solution of sodium lauryl sulfate at 25 ° C. for 2 hours and air-dried for 2 hours. This was designated as Sample A. No significant change was observed in the appearance and antireflection characteristics of the obtained lens. At this time, the contact angle with water is 3 °,
Initial anti-fog performance was confirmed.
【００３７】ｂ．試料Ｂ メタクリロキシエチルトリメトキシシラン１５ｇ、メタ
クリロキシプロピル硫酸ナトリウム３０ｇ、ベンゾイル
パーオキサイド２ｇ、イソプロパノール１００ｇを混合
し、６０℃で３時間攪拌しながら重合を行った。次に、
得られた溶液に蒸留水を３．３ｇ添加し、塩酸でｐＨ３
に調整した後、室温で２時間攪拌することによってシラ
ンカップリング剤の加水分解を行った。このスルホン酸
塩化合物の固形分濃度が５重量部となるように蒸留水を
加え、真空装置から取り出した基材Ａを引き上げ速度２
０ｃｍ毎分でディッピングした。次にこれを７０℃で５
時間反応させ、試料Ｂを得た。得られたレンズの外観・
反射防止の特性に大きな変化は見られなかった。また、
この時の水に対する接触角は５°であり、初期防曇性能
が確認された。B. Sample B 15 g of methacryloxyethyltrimethoxysilane, 30 g of sodium methacryloxypropyl sulfate, 2 g of benzoyl peroxide and 100 g of isopropanol were mixed, and polymerization was carried out at 60 ° C. with stirring for 3 hours. next,
3.3 g of distilled water was added to the obtained solution, and the solution was adjusted to pH 3 with hydrochloric acid.
Then, the mixture was stirred at room temperature for 2 hours to hydrolyze the silane coupling agent. Distilled water was added so that the solid content concentration of the sulfonate compound was 5 parts by weight, and the substrate A taken out of the vacuum device was pulled up at a speed of 2%.
Dipping was performed at 0 cm per minute. Then, at 70 ° C,
After reacting for a time, sample B was obtained. The appearance of the obtained lens
No significant change was observed in the antireflection characteristics. Also,
At this time, the contact angle with water was 5 °, and the initial antifogging performance was confirmed.
【００３８】ｃ．試料Ｃ オクタデシルトリクロロシラン０．５ｇをｎ−ヘキサン
１９９．５ｇに溶解した液中に前述の基材Ａを２５℃で
１時間浸漬した。その後、基材を取り出し、ｎ−ヘキサ
ンで洗浄を行った。これにより酸化物表面にオルガノシ
ランを反応させた。この時のレンズの外観・反射防止の
特性に大きな変化は見られなかった。また、この時の水
に対する接触角は８３°であり、オルガノシランが表面
に固定化されている事が確認された。次に、ラウリル硫
酸ナトリウム０．５ｇを蒸留水１９９．５ｇ中に溶解
し、界面活性剤溶液を調合した。２５℃に保ったこの液
中に、上述のオルガノシラン処理した基材を１時間浸漬
し、風乾した。この時のレンズの外観・反射防止の特性
に大きな変化は見られなかった。また、この時の水に対
する接触角は３°であり、初期防曇性能が確認された。C. Sample C The above-described substrate A was immersed in a solution of 0.5 g of octadecyltrichlorosilane dissolved in 199.5 g of n-hexane at 25 ° C. for 1 hour. Thereafter, the substrate was taken out and washed with n-hexane. Thereby, the organosilane was reacted with the oxide surface. At this time, no significant change was observed in the appearance and antireflection characteristics of the lens. At this time, the contact angle with water was 83 °, and it was confirmed that the organosilane was immobilized on the surface. Next, 0.5 g of sodium lauryl sulfate was dissolved in 199.5 g of distilled water to prepare a surfactant solution. The above-mentioned organosilane-treated substrate was immersed in this liquid kept at 25 ° C. for 1 hour and air-dried. At this time, no significant change was observed in the appearance and antireflection characteristics of the lens. At this time, the contact angle with water was 3 °, and the initial antifogging performance was confirmed.
【００３９】ｄ．試料Ｄ ３−スルホプロピルメトキシナトリウムオキシシラン５
ｇをイソプロパノール１００ｇに溶解し、０．５Ｎの塩
酸１ｇを加え、室温で２時間攪拌、加水分解を行った。
このスルホン酸塩化合物処理液に、真空装置から取り出
した基材Ａを引き上げ速度２０ｃｍ毎分でディッピング
した。次にこれを７０℃で５時間反応させ、試料Ｄを得
た。得られたレンズの外観・反射防止の特性に大きな変
化は見られなかった。また、この時の水に対する接触角
は５°であり、初期防曇性能が確認された。 III．防曇性能評価方法 光学物品の防曇性評価方法は“ＪＩＳ−Ｓ４０３０ 眼
鏡用くもり止め剤試験方法”の低温部くもり止め性を参
考にして１〜４級で評価した。（１級の一番防曇性能が
良く、４級が一番悪い。）ここで、１級のみを実用可能
なレベルとした。また、水に対する接触角を協和科学
（株）製、接触角系にて測定した。D. Sample D 3-Sulfopropylmethoxy sodium oxysilane 5
g was dissolved in 100 g of isopropanol, 1 g of 0.5N hydrochloric acid was added, and the mixture was stirred and hydrolyzed at room temperature for 2 hours.
The substrate A taken out of the vacuum device was dipped in the sulfonate compound-treated solution at a pulling rate of 20 cm / min. Next, this was reacted at 70 ° C. for 5 hours to obtain a sample D. No significant change was observed in the appearance and antireflection characteristics of the obtained lens. At this time, the contact angle with water was 5 °, and the initial antifogging performance was confirmed. III. Anti-fogging performance evaluation method The anti-fogging property evaluation method of the optical article was evaluated in the first to fourth grades with reference to the low-temperature part anti-fogging property of "JIS-S4030 Test method for anti-fog agent for spectacles". (The first grade has the best anti-fog performance, and the fourth grade is the worst.) Here, only the first grade was set to a practical level. The contact angle with water was measured by a contact angle system manufactured by Kyowa Kagaku Co., Ltd.
【００４０】防曇性能付与性評価は、基材をサンシャイ
ンウェザーメーターで２４時間劣化させた後、蒸留水に
て洗浄した。その後、処理を行ったレンズ拭きを用い
て、荷重２００ｇ２０往復払拭し、同様に防曇性評価を
行った。In the evaluation of the antifogging property imparting property, the substrate was aged for 24 hours with a sunshine weather meter, and then washed with distilled water. Thereafter, using a treated lens wiper, a load of 200 g was reciprocated for 20 times, and the antifogging property was evaluated in the same manner.
【００４１】〔実施例〕上述の方法で作製された試料Ａ
〜Ｄについて、レンズ拭きＡ〜Ｃ、レンズペーパーＡを
用いて、防曇性能付与性評価を行った。評価結果を表１
に示した。[Embodiment] Sample A prepared by the above method
About -D, antifogging performance imparting property evaluation was performed using lens wipes A-C and lens paper A. Table 1 shows the evaluation results.
It was shown to.
【００４２】〔比較例〕上述の方法で作製された試料Ａ
〜Ｄについて、レンズ拭きＤ及び小津産業（株）製クリ
ーニングワイパーダスパーを用いて、防曇性能付与性評
価を行った。評価結果を表１に示した。Comparative Example Sample A prepared by the above method
About -D, antifogging performance imparting property evaluation was performed using lens wipe D and Ozu Sangyo Co., Ltd. cleaning wiper daspar. Table 1 shows the evaluation results.
【００４３】[0043]
【表１】 [Table 1]
【発明の効果】本発明によれば、真空槽内で成膜された
酸化物膜上に有機硫酸塩及び／または有機スルホン酸塩
を処理する工程を含むことにより持続性の良い防曇性能
を有する表面を得ることが可能となった。また、真空槽
内で成膜された酸化物膜上に防曇性能を付与する方法の
一つとして有機硫酸塩及び／または有機スルホン酸塩を
含ませた布または紙で基材を拭くことにより、容易に防
曇性を付与することが可能となった。これらの方法によ
って物品の使用期間を長期化することが可能となった。According to the present invention, a process for treating an organic sulfate and / or an organic sulfonate on an oxide film formed in a vacuum chamber can be carried out to provide a long-lasting anti-fog performance. It has become possible to obtain a surface having. Further, as one of methods for imparting anti-fog performance to an oxide film formed in a vacuum chamber, a substrate is wiped with a cloth or paper impregnated with an organic sulfate and / or an organic sulfonate. Thus, the anti-fogging property can be easily provided. These methods have made it possible to extend the use period of the article.
フロントページの続き Ｆターム(参考） 2K009 AA02 AA15 BB02 CC03 CC42 DD03 DD04 DD17 EE02 4G059 AA01 AA11 AB01 AB11 AC21 EA01 EA05 EB03 FA04 FA05 FA22 FA28 FA30 FB06 GA02 GA04 GA16 Continued on front page F term (reference) 2K009 AA02 AA15 BB02 CC03 CC42 DD03 DD04 DD17 EE02 4G059 AA01 AA11 AB01 AB11 AC21 EA01 EA05 EB03 FA04 FA05 FA22 FA28 FA30 FB06 GA02 GA04 GA16
Claims (4)
スルホン酸塩で処理する工程を含むことにより、防曇性
を付与することを特徴とする防曇性能付与方法。1. A method for imparting anti-fogging performance, comprising a step of treating an oxide surface with an organic sulfate and / or an organic sulfonate to impart anti-fogging property.
得られた防曇性酸化物表面を、有機硫酸塩及び／または
有機スルホン酸塩を含ませた布または紙で拭くことによ
り、有機硫酸塩及び／または有機スルホン酸塩を供給し
て防曇性を付与することを特徴とする請求項１記載の防
曇性能付与方法。2. An organic compound obtained by wiping the surface of an antifogging oxide obtained by the method for imparting antifogging performance according to claim 1 with a cloth or paper containing an organic sulfate and / or an organic sulfonate. The method for imparting anti-fogging performance according to claim 1, wherein the anti-fogging property is imparted by supplying a sulfate and / or an organic sulfonate.
スルホン酸塩を含ませた布または紙で拭くことにより、
有機硫酸塩及び／または有機スルホン酸塩を供給して防
曇性を付与することを特徴とする防曇性能付与方法。3. An oxide surface is wiped with a cloth or paper impregnated with an organic sulfate and / or an organic sulfonate,
A method for imparting anti-fogging performance, comprising supplying an organic sulfate and / or an organic sulfonate to impart anti-fogging properties.
ッタなどの真空槽内で成膜されることを特徴とする請求
項１から３のいずれかに記載の防曇性能付与方法。4. The method according to claim 1, wherein the oxide surface is formed in a vacuum chamber such as vacuum deposition, CVD, and sputtering.
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|---|---|---|---|
| JP2001042226A JP2002243901A (en) | 2001-02-19 | 2001-02-19 | Method for imparting anticlouding performance |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001042226A JP2002243901A (en) | 2001-02-19 | 2001-02-19 | Method for imparting anticlouding performance |
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ID=18904555
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010067122A1 (en) * | 2008-12-12 | 2010-06-17 | Pilkington Group Limited | Apparatus and method for applying a stain inhibitor |
| WO2010067121A1 (en) * | 2008-12-12 | 2010-06-17 | Pilkington Group Limited | Glass with improved stain resistance |
| JP2018509369A (en) * | 2015-03-13 | 2018-04-05 | 華為技術有限公司Ｈｕａｗｅｉ Ｔｅｃｈｎｏｌｏｇｉｅｓ Ｃｏ．，Ｌｔｄ． | Exterior zirconia ceramic parts and manufacturing method thereof |
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| JPH1081953A (en) * | 1996-09-06 | 1998-03-31 | Olympus Optical Co Ltd | Production of spectacle lens made of synthetic resin and spectacles made of synthetic resin |
| JPH11174205A (en) * | 1997-12-08 | 1999-07-02 | Seiko Epson Corp | Synthetic resin lens with antireflection film |
| JP2000262368A (en) * | 1999-01-14 | 2000-09-26 | Toto Ltd | Hydrophilic mirror, hydrophilizatopm method therefor and hydrophilizatopm method of glass |
| JP2000239045A (en) * | 1999-02-17 | 2000-09-05 | Asahi Glass Co Ltd | Antifogging vehicular glass and its production |
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