JPH09127303A - Antifogging product having antireflection performance and its production - Google Patents
Antifogging product having antireflection performance and its productionInfo
- Publication number
- JPH09127303A JPH09127303A JP7281690A JP28169095A JPH09127303A JP H09127303 A JPH09127303 A JP H09127303A JP 7281690 A JP7281690 A JP 7281690A JP 28169095 A JP28169095 A JP 28169095A JP H09127303 A JPH09127303 A JP H09127303A
- Authority
- JP
- Japan
- Prior art keywords
- substance
- antireflection
- uppermost layer
- hydrophilic
- layer
- 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.)
- Granted
Links
Landscapes
- Surface Treatment Of Optical Elements (AREA)
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
- Surface Treatment Of Glass (AREA)
- Physical Vapour Deposition (AREA)
Abstract
Description
【0001】[0001]
【発明の属する技術分野】本発明は、防曇性能を有する
メガネ・カメラ等のレンズ、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、または浴室
内で使用する鏡等に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to lenses for spectacles and cameras having anti-fog performance, window glasses, car windshields, helmet shields, underwater glasses, mirrors used in bathrooms, and the like. .
【0002】[0002]
【従来の技術】物品に防曇性能を付与する方法として、
従来から以下に述べる様な種々の方法がとられている。2. Description of the Related Art As a method of imparting antifogging performance to articles,
Conventionally, various methods as described below have been adopted.
【0003】合成樹脂基材自体に界面活性剤を練り込ん
だり、親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は、特開昭51−1078
41,特開昭55−102632,特公昭57−317
35,特開昭58−160325,特開昭60−141
727,特開昭61−114201,特開昭61−11
4202,特開昭62−2202,特開昭62−220
3などに開示されている。A method of imparting an antifogging property by kneading a surfactant into the synthetic resin substrate itself or copolymerizing a hydrophilic monomer to form a synthetic resin substrate is disclosed in JP-A-51- 1078
41, JP-A-55-102632, JP-B-57-317
35, JP-A-58-160325, JP-A-60-141
727, JP-A-61-114201, JP-A-61-11
4202, JP-A-62-2202, JP-A-62-220
3, etc.
【0004】物品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、特公昭45−18972,特公昭
50−1710,特開昭52−146791,特開昭5
3−39347,特開昭55−99930,特開昭55
−750,特開昭55−148283,特開昭57−1
19973,特公昭58−1688,特開昭59−15
473,特公昭62−28986,特開平1−2498
18,特開平2−18048,特開平2−17307
8,などに開示されている。A method of applying a coating having an antifogging property to an article is also well known, and is disclosed in JP-B-45-18972, JP-B-50-1710, and JP-A-52-146791.
3-39347, JP-A-55-99930, JP-A-55.
-750, JP-A-55-148283, JP-A-57-1.
19973, JP-B-58-1688, JP-A-59-15
473, Japanese Patent Publication No. 62-28986, Japanese Patent Laid-Open No. 1-2498
18, JP-A-2-18048, JP-A-2-17307
8, etc.
【0005】以上に示した方法は、基材自体、あるいは
厚いコーティング層に、親水性と吸水性を付与して防曇
性能を達成しようとするものである。The above-mentioned method aims to achieve antifogging performance by imparting hydrophilicity and water absorption to the substrate itself or the thick coating layer.
【0006】吸水性の悪いガラスなどの無機物質に、直
接防曇性能を付与する方法として、最表面を処理して親
水性または疎水性を持たせる方法が知られ、特開昭53
−56177,特公昭57−61294,特開平2−2
52638,特開平4−366140,特開平5−96
679,特開平5−155641,特開昭54−105
120,特開昭60−210641,特開昭62−57
484,特開平2−22341,などに開示されてい
る。As a method for directly imparting antifogging performance to an inorganic substance such as glass having poor water absorption, a method of treating the outermost surface to make it hydrophilic or hydrophobic is known.
-56177, JP-B-57-61294, JP-A-2-2
52638, JP-A-4-366140, and JP-A-5-96.
679, JP-A-5-155641, and JP-A-54-105.
120, JP-A-60-210641, and JP-A-62-57.
484, Japanese Patent Laid-Open No. 223411, etc.
【0007】表面改質の方法としてのグラフト重合は、
特開平1−230644,特開平2−38431,特開
平4−225301に開示されている。Graft polymerization as a method of surface modification is
It is disclosed in JP-A-1-230644, JP-A-2-38431, and JP-A-4-225301.
【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、特開昭49−18910,特公昭52−1132
1,特開昭54−57516,特開昭61−9104
2,特公平1−58481,特開平3−194501が
挙げられる。[0008] Further, as a patent combining the pores and irregularities of an inorganic substance with a hydrophilic substance and a patent utilizing the irregularities on the surface, there are Japanese Patent Laid-Open No. 49-18910 and Japanese Patent Publication No. 52-1132.
1, JP-A-54-57516, JP-A-61-9104
2, Japanese Patent Publication No. 1-58481, and JP-A-3-194501.
【0009】以上に示した方法も含め、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)基材表面を撥水性にする。
4)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。In order to impart antifogging performance to articles, including the above-mentioned methods, 1) the substrate is made to absorb water. 2) Make the substrate surface hydrophilic. 3) Make the substrate surface water repellent.
4) Increase the surface temperature of the article so that moisture in the air does not condense on the surface. The following four points have been proposed from the past,
Various attempts have been made.
【0010】[0010]
【発明が解決しようとする課題】しかしながら、従来の
方法では次に述べる様な問題点を有していた。However, the conventional method has the following problems.
【0011】樹脂基材自体や樹脂コーティング層に防曇
性能を付与する方法は、防曇性能としては十分な性能が
得られるが、親水性・吸水性を持つ樹脂は吸水すると柔
らかくなり、非常に傷がつき易いものとなっていた。こ
れでは眼鏡レンズなど耐摩耗性が要求される部分に使用
した場合、傷によって光学特性が劣化し、実用に耐えら
れない。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
あった。Although a method of imparting antifogging performance to the resin base material itself or the resin coating layer can provide sufficient performance as antifogging performance, a resin having hydrophilicity / water absorption becomes soft when water is absorbed, which is extremely high. It was easily scratched. If it is used in a portion such as a spectacle lens that requires abrasion resistance, the optical characteristics deteriorate due to scratches and it cannot be put to practical use. Furthermore, dirt in the air, such as cigarette smoke, is easily adsorbed, and the optical article is colored.
【0012】さらに、これらの方法の最大の欠点は、反
射防止膜などの光学的特性を向上する為の表面処理を最
表面に施すことができないことである。現在広く使用さ
れいて、性能の良い反射防止膜は、無機物質からなる反
射防止膜であり、酸化ケイ素などの無機物質表面に防曇
性能を持たせなければならない。Further, the biggest drawback of these methods is that the outermost surface cannot be subjected to a surface treatment for improving the optical characteristics such as an antireflection film. An antireflection film which is widely used and has a good performance is an antireflection film made of an inorganic material, and the surface of the inorganic material such as silicon oxide must have antifogging performance.
【0013】ガラス表面や無機物質表面に防曇性能を付
与する方法としては、一般に用いられている界面活性剤
を表面に塗布する方法があるが、持続性に問題があり、
水分によって界面活性剤が容易に脱落してしまう。As a method for imparting antifogging performance to the surface of glass or the surface of an inorganic substance, there is a method of applying a generally used surfactant to the surface, but there is a problem in durability.
Surfactant is easily removed by water.
【0014】そのほかに、ガラス表面や無機物質表面に
親水性の物質を用いて極薄い薄膜を形成し、防曇性能を
達成する方法があるが、従来技術に従うとそれらの物質
と表面との結合が弱く、簡単にそれらの物質が脱落して
長期間防曇性能が維持できなかった。In addition, there is a method of forming an extremely thin film by using a hydrophilic substance on the glass surface or the surface of an inorganic substance to achieve antifogging performance. According to the prior art, the binding between these substances and the surface is performed. However, the substances were easily removed and the antifogging performance could not be maintained for a long time.
【0015】逆に撥水性を付与する場合、従来示されて
いる技術では、表面の水に対する接触角が140゜前後
にしかならず十分な防曇性能が得られているとは言いが
たい。On the contrary, in the case of imparting water repellency, it is difficult to say that the conventional techniques show that the contact angle of water on the surface is only about 140 ° and that sufficient antifogging performance is obtained.
【0016】以上に述べた課題を解決する為に、無機物
質表面をシランカップリング剤で処理した後、反応性界
面活性剤を反応させる方法も提案されているが、反応性
界面活性剤の構造によっては十分な防曇効果が得られな
かった。In order to solve the above-mentioned problems, a method has been proposed in which the surface of an inorganic substance is treated with a silane coupling agent and then the reactive surfactant is reacted, but the structure of the reactive surfactant is also proposed. In some cases, a sufficient antifogging effect was not obtained.
【0017】反射防止性能と防曇性能を兼ね備えたもの
として、無機物と親水性物質の組み合わせも提案されて
いる。特に、特開平3−194501は、無機コート膜
の微細間隙と親水性物質を利用した防曇について記載さ
れているが、微細構造及び、反射防止膜の最上層に関し
ての詳細な記述がなかった。さらに、これら無機物質の
表面には、水ヤケが発生したり、汚れやすかった。A combination of an inorganic substance and a hydrophilic substance has also been proposed as having both antireflection properties and antifogging properties. In particular, Japanese Patent Laid-Open No. 3-194501 describes a fine gap in an inorganic coating film and antifogging using a hydrophilic substance, but there is no detailed description about the fine structure and the uppermost layer of the antireflection film. Further, the surface of these inorganic substances was liable to be stained with water or easily stained.
【0018】そこで、本発明は以上の様な問題点を解決
し、物品の反射防止特性などの光学特性、耐摩耗性、耐
水ヤケ、耐汚染性を低下させることなく、優れた防曇性
能、持続性、を有する物品を得ることを目的とする。Therefore, the present invention has solved the above problems and has excellent antifogging performance without deteriorating the optical characteristics such as antireflection characteristics of an article, abrasion resistance, water proof, and stain resistance. The object is to obtain an article having durability.
【0019】[0019]
【課題を解決するための手段】請求項1記載の発明は、
基材上に設けられた、無機物質からなる単層及び多層反
射防止膜の最上層が、細孔及び微細な凹凸のどちらか一
方を少なくとも有し、最上層の無機物質の充填率が0.
95以下であり、その細孔及び微細な凹凸に親水性物質
が存在して、最表面が無機物質と親水性物質からなり、
かつ、、無機物質表面の水の静止接触角が90゜以上で
あることを特徴とする。According to the first aspect of the present invention,
The uppermost layer of the single-layer and multi-layered antireflection film made of an inorganic substance provided on the substrate has at least one of pores and fine irregularities, and the filling rate of the inorganic substance of the uppermost layer is 0.
95 or less, a hydrophilic substance is present in the pores and fine irregularities, and the outermost surface is composed of an inorganic substance and a hydrophilic substance,
The static contact angle of water on the surface of the inorganic material is 90 ° or more.
【0020】請求項2記載の発明は、基材上に設けられ
た、無機物質からなる単層及び多層反射防止膜の最上層
を、ガス導入を行いながら真空蒸着によって形成した
後、親水性物質で最上層を処理し、最上層の細孔及び微
細な凹凸に親水性物質を固定し、かつ、撥水性を有する
物質で無機物質表面を処理することを特徴とする。According to a second aspect of the present invention, the uppermost layer of the single layer and the multilayer antireflection film made of an inorganic substance provided on the substrate is formed by vacuum vapor deposition while introducing gas, and then the hydrophilic substance is formed. The uppermost layer is treated with, the hydrophilic substance is fixed to the pores and fine irregularities of the uppermost layer, and the surface of the inorganic substance is treated with a substance having water repellency.
【0021】レンズ、ガラス、鏡等の光学部品には、透
過率の向上や反射率の低減を目的として、単層及び多層
の反射防止膜がしばしば設けられる。これらの反射防止
膜は真空蒸着法やスパッタ法で形成される。真空蒸着の
場合、形成された膜はバルクと比較して充填率が低く、
表面も凹凸のある表面である。一般の蒸着では高密度で
硬い膜を求めるため、充填率を上げる必要がある。従っ
て、蒸着前及び蒸着中の真空度は、高真空度で行うこと
が多い。Optical parts such as lenses, glass, and mirrors are often provided with a single-layer or multi-layer antireflection film for the purpose of improving the transmittance and reducing the reflectance. These antireflection films are formed by a vacuum evaporation method or a sputtering method. In the case of vacuum vapor deposition, the formed film has a lower filling rate than the bulk,
The surface is also uneven. Since a high density and hard film is required in general vapor deposition, it is necessary to increase the filling rate. Therefore, the degree of vacuum before and during vapor deposition is often high.
【0022】一方、本発明ではガスを導入しながら真空
蒸着によって反射防止膜を形成する。蒸着中にガスを導
入し、低真空にすることによって、膜の充填率をさらに
低くすることができる。導入ガスは、膜との反応を避け
るためAr等の不活性ガスが望ましい。このようにして
作成された膜は、ガスを導入しない場合の膜より、サイ
ズの大きな細孔及び微細な凹凸を多数持つ。ガス導入量
は、蒸着前の真空度で2×10-5hPa以上が望まし
い。ちなみに、二酸化珪素膜を例に取るとガス導入しな
いときの屈折率は、1.45、充填率は0.98程度で
あるが、Arガスを真空度が4×10-4hPaになるま
で導入して蒸着を行うと、屈折率1.36充填率0.7
8程度になる。十分な防曇性能を得るためには充填率が
0.95以下であることが大切である。On the other hand, in the present invention, the antireflection film is formed by vacuum vapor deposition while introducing gas. By introducing a gas during vapor deposition and applying a low vacuum, the filling rate of the film can be further lowered. The introduced gas is preferably an inert gas such as Ar to avoid reaction with the film. The film formed in this manner has a large number of pores and fine irregularities, which are larger than those in the case where no gas is introduced. The gas introduction amount is preferably 2 × 10 −5 hPa or more in terms of the degree of vacuum before vapor deposition. Incidentally, taking a silicon dioxide film as an example, the refractive index when gas is not introduced is 1.45 and the filling rate is about 0.98, but Ar gas is introduced until the degree of vacuum reaches 4 × 10 −4 hPa. Then, when vapor deposition is performed, the refractive index is 1.36 and the filling rate is 0.7.
It will be about 8. In order to obtain sufficient antifogging performance, it is important that the filling rate is 0.95 or less.
【0023】ガス導入を行う層は反射防止膜の最上層に
行う。単層の反射防止膜であれば、単層そのものに行
う。これら最上層は、反射防止膜の設計上、低屈折率層
が用いられる。低屈折率層にガス導入を行って、さらに
低屈折率になるのはかまわないが、高屈折率層にまでガ
ス導入を行って、高屈折率層の屈折率が低下すると、高
性能の反射防止特性が得られにくい。さらに、表面硬度
も得られなくなる。従って、本発明では、最上層の低屈
折率層に対してガス導入を行う。The layer for introducing gas is the uppermost layer of the antireflection film. In the case of a single-layer antireflection film, the single layer itself is used. As the uppermost layer, a low refractive index layer is used due to the design of the antireflection film. It is acceptable to introduce gas into the low-refractive index layer to lower the refractive index, but if gas is introduced into the high-refractive index layer and the refractive index of the high-refractive index layer decreases, high-performance reflection is achieved. It is difficult to obtain prevention properties. Further, the surface hardness cannot be obtained either. Therefore, in the present invention, gas is introduced into the uppermost low refractive index layer.
【0024】基材が合成樹脂の場合、基材の変形を避け
るため高温で蒸着できない。そのため、反射防止膜の低
屈折率層には、低温でも硬い膜が得られる二酸化珪素が
良く用いられる。When the base material is a synthetic resin, vapor deposition cannot be performed at a high temperature in order to avoid deformation of the base material. Therefore, for the low refractive index layer of the antireflection film, silicon dioxide is often used because it gives a hard film even at low temperatures.
【0025】本発明では、以上のようにガス導入して形
成した最上層の細孔及び微細な凹凸に親水性物質を固定
する。親水性物質としては、脂肪酸石鹸、アルキルベン
ゼンスルホン酸塩等の陰イオン界面活性剤、第4アンモ
ニウム基を持つ陽イオン界面活性剤、長鎖アルキルアミ
ノ酸等の両性界面活性剤、ポリオキシエチレンノニルフ
ェニルエーテル等の非イオン界面活性剤、などの界面活
性剤、グルコシルエチルメタクリレート、メタクリル
酸、アクリル酸、2−ヒドロキシルエチルメタクリレー
ト、アクリルアミド、N,N−ジメチルアクリルアミ
ド、N−ビニルピロリドン、N−(2−メタクロイルオ
キシエチル)−2−ピロリドン、グリセリルメタクリレ
ート、ポリエチレングリコールメタクリレート、ポリエ
チレングリコールアクリレート、等のヒドロキシルアル
キル(メタ)アクリレート類、ポリアルキレングリコー
ルモノ(メタ)アクリレート類、(メタ)アクリルアミ
ド類、N−ビニルラクタム類、等の親水性モノマー及び
それらからなるポリマーを挙げることができる。In the present invention, the hydrophilic substance is fixed to the pores and fine irregularities of the uppermost layer formed by introducing the gas as described above. As the hydrophilic substance, fatty acid soap, anionic surfactant such as alkylbenzene sulfonate, cationic surfactant having a quaternary ammonium group, amphoteric surfactant such as long-chain alkylamino acid, polyoxyethylene nonylphenyl ether, etc. Nonionic surfactants such as, surfactants such as, glucosylethylmethacrylate, methacrylic acid, acrylic acid, 2-hydroxylethylmethacrylate, acrylamide, N, N-dimethylacrylamide, N-vinylpyrrolidone, N- (2-methacrolein (Iloxyethyl) -2-pyrrolidone, glyceryl methacrylate, polyethylene glycol methacrylate, polyethylene glycol acrylate, and other hydroxylalkyl (meth) acrylates, polyalkylene glycol mono (meth) acrylate , May be mentioned (meth) acrylamides, N- vinyllactams, the hydrophilic monomers and polymers consisting of equal.
【0026】これらの親水性物質は単体、混合物どちら
で用いても良い。さらに、親水性物質であれば、これら
に限定される事はない。These hydrophilic substances may be used alone or as a mixture. Furthermore, if it is a hydrophilic substance, it is not limited to these.
【0027】親水性のモノマー及びビニル基、アクリル
基、メタクリル基、グリシジル基、アリル基、エポキシ
基、メルカプト基、シアノ基、イソシアノ基、アミノ基
等の反応性末端基とスルホン基、水酸基、アンモニウム
クロライドなどの親水性部分を持つ反応性界面活性剤を
親水性物質として用いる場合、これらの物質を細孔及び
表面の凹凸に付着させた後、熱、紫外線等の電磁波、電
子線等の放射線などによって反応を促進し、強固に固定
させることができる。さらに、最上層が二酸化珪素の場
合、反応性を有する親水性物質と二酸化珪素双方との反
応基を持つシランカップリング剤を一緒に用いれば、膜
との密着性も向上し、防曇の持続性などの耐久性が向上
する。Hydrophilic monomers and reactive terminal groups such as vinyl group, acryl group, methacryl group, glycidyl group, allyl group, epoxy group, mercapto group, cyano group, isocyano group, amino group and sulfone group, hydroxyl group, ammonium. When using a reactive surfactant having a hydrophilic portion such as chloride as a hydrophilic substance, after attaching these substances to the pores and surface irregularities, electromagnetic waves such as heat, ultraviolet rays, radiation such as electron beams, etc. The reaction can be promoted by the and can be firmly fixed. Furthermore, when the uppermost layer is silicon dioxide, if a silane coupling agent having a reactive group with both a reactive hydrophilic substance and silicon dioxide is used together, the adhesion to the film is improved and the anti-fogging property is maintained. The durability such as the property is improved.
【0028】親水性物質で、細孔や微細な凹凸からはみ
出して無機物質上で膜を形成している物や、反応に寄与
できなかった未反応モノマーを洗浄により洗い流すこと
により、処理前と反射防止特性等の外観が変わらない処
理を行うことができる。By removing the hydrophilic substance, which protrudes from the pores and fine irregularities and forms a film on the inorganic substance, and the unreacted monomer that could not contribute to the reaction, by washing off, it is possible to reflect before treatment. It is possible to perform processing that does not change the appearance such as prevention characteristics.
【0029】本発明では、さらに表面に存在する無機物
質を、撥水性を有する物質で処理する。これは、親水性
物質を固定する前でも後でも良い。処理後の表面の接触
角が90゜以上であれば、十分な耐水ヤケ性、耐汚染性
が得られる。無機物質が二酸化珪素の場合、フッ素を含
むシランカップリング剤が有効である。シランカップリ
ング剤の例としては、ハロゲン化シラン、末端シラノー
ルを有するシラン化合物、アルコキシシラン、アミノシ
ラン、シラザン、珪素官能型シリルイソシアネート等が
挙げられるがこれらに限定されるものではない。これら
の物質は、単体で用いても良いし、混合物で用いても良
い。In the present invention, the inorganic substance existing on the surface is further treated with a substance having water repellency. This may be before or after fixing the hydrophilic substance. When the contact angle of the surface after the treatment is 90 ° or more, sufficient water proofing and stain resistance can be obtained. When the inorganic substance is silicon dioxide, a silane coupling agent containing fluorine is effective. Examples of the silane coupling agent include, but are not limited to, halogenated silanes, silane compounds having terminal silanols, alkoxysilanes, aminosilanes, silazanes, silicon-functional silyl isocyanates, and the like. These substances may be used alone or in a mixture.
【0030】処理は形成された蒸着膜に影響を与えない
低温で行うのが望ましい。処理方法は、処理液を浸漬法
やスピン法で塗布した後、加熱して反応させる方法や、
真空槽内あるいは、大気中でガスとして反応させる方法
をとることができる。反応方法については特に限定され
ない。The treatment is preferably carried out at a low temperature which does not affect the formed vapor deposition film. The treatment method is a method in which the treatment liquid is applied by a dipping method or a spin method and then heated and reacted,
A method of reacting as a gas in a vacuum chamber or in the atmosphere can be used. The reaction method is not particularly limited.
【0031】以上のように形成した最表面は、撥水性を
持つ無機物質と親水性物質が存在する表面となる。The outermost surface formed as described above is a surface on which an inorganic substance having water repellency and a hydrophilic substance are present.
【0032】防曇性の付与される物品はどんな物でも良
いが、特にレンズ・鏡・窓・ゴーグル・水中眼鏡などの
光学物品であれば用途上非常に有効である。The article to which the anti-fog property is imparted may be any article, but it is very effective in use as long as it is an optical article such as a lens, a mirror, a window, goggles, and underwater glasses.
【0033】[0033]
【発明の実施の形態】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。BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail based on Examples, but the present invention is not limited to these Examples.
【0034】〔実施例1〕予め水酸化ナトリウム溶液
(0.1N)に浸漬し、よく水洗、乾燥したジエチレン
グリコールビスアリルカーボネート製レンズに以下に示
すコーティング液をディッピング法で、膜厚が2.5μ
mになる様塗布し、130℃で2時間加熱硬化してハー
ドコート層を設けた。Example 1 A lens made of diethylene glycol bisallyl carbonate, which had been previously immersed in a sodium hydroxide solution (0.1N), washed well with water, and dried, was coated with the following coating solution by a dipping method to give a film thickness of 2.5 μm.
m to obtain a hard coat layer by heating and curing at 130 ° C. for 2 hours.
【0035】(コーティング液の調整)攪拌装置を備え
た、反応容器中に、エタノール206g,エタノール分
散コロイダルシリカ396g(触媒化成工業株式会社製
“オスカル1232”固形分30%),γ−グリシドキ
シプロピルトリメトキシシランの部分加水分解物312
g,フローコントロール剤0.2g(日本ユニカー
(株)製“L−7604”)及び0.05N酢酸水溶液
86gを加え、室温で3時間攪拌をし、コーティング液
とした。(Preparation of coating liquid) In a reaction vessel equipped with a stirrer, 206 g of ethanol, 396 g of ethanol-dispersed colloidal silica (“Oscar 1232” manufactured by Catalysts & Chemicals Co., Ltd., solid content 30%), γ-glycidoxy Partial hydrolyzate of propyltrimethoxysilane 312
g, 0.2 g of a flow control agent (“L-7604” manufactured by Nippon Unicar Co., Ltd.) and 86 g of a 0.05N acetic acid aqueous solution were added, and the mixture was stirred at room temperature for 3 hours to obtain a coating liquid.
【0036】以上のようにして得られたコーティング済
みレンズを真空槽内にセットし、真空蒸着により、基板
温度50℃で、コーティング表面に反射防止処理を行っ
た。膜構成は、光学膜厚でレンズ側から、二酸化ケイ素
層がλ/4,酸化ジルコニウム層と二酸化ケイ素層の合
成膜厚が、λ/4,酸化ジルコニウム層がλ/4,最上
層の二酸化ケイ素層がλ/4とした。(λは520nm)
ここで、最上層の二酸化珪素層を形成する際に、アルゴ
ンガスを導入し、真空度を2×10−4hPaにした状
態で蒸着を行った。最上層の屈折率は、1.41、充填
率は、0.89であった。このように形成した反射防止
膜付きレンズを、次の手順で調整した防曇処理用反応液
で処理した。The coated lens obtained as described above was set in a vacuum chamber, and the coating surface was subjected to antireflection treatment at a substrate temperature of 50 ° C. by vacuum vapor deposition. The film structure is such that, from the lens side in terms of optical film thickness, the synthetic film thickness of the silicon dioxide layer is λ / 4, the zirconium oxide layer and the silicon dioxide layer is λ / 4, the zirconium oxide layer is λ / 4, and the uppermost silicon dioxide layer. The layer was λ / 4. (Λ is 520 nm)
Here, when forming the uppermost silicon dioxide layer, argon gas was introduced and vapor deposition was performed in a state where the degree of vacuum was 2 × 10 −4 hPa. The uppermost layer had a refractive index of 1.41 and a filling rate of 0.89. The lens with the antireflection film thus formed was treated with the reaction solution for antifogging treatment prepared by the following procedure.
【0037】アクリルアミド2g、アゾビスイソブチロ
ニトリル0.1g、界面活性剤0.01gを純水98g
に加え、均一な水溶液とし、コーテイング反応液とし
た。98 g of pure water containing 2 g of acrylamide, 0.1 g of azobisisobutyronitrile and 0.01 g of a surfactant.
In addition to the above, a uniform aqueous solution was prepared to obtain a coating reaction solution.
【0038】このコーテイング反応液に、先に形成した
反射防止膜付きレンズを液温15℃で1分間浸漬した。
その後、湿度60%、温度25℃の雰囲気で、1cm/
分の速度でレンズを引き上げた。引き上げ後、窒素気流
中、高圧水銀灯を用いて、紫外線照射と50℃まで加熱
を行った。その後、トリクロロエチレンにより洗浄を行
った。洗浄後のレンズの外観、反射防止特性に、大きな
変化は見られなかった。The lens with the antireflection film formed above was immersed in this coating reaction solution at a liquid temperature of 15 ° C. for 1 minute.
After that, in an atmosphere with a humidity of 60% and a temperature of 25 ° C., 1 cm /
The lens was pulled up at the speed of a minute. After pulling up, UV irradiation and heating to 50 ° C. were performed in a nitrogen stream using a high pressure mercury lamp. Then, it wash | cleaned by trichloroethylene. No significant change was observed in the appearance and antireflection property of the lens after washing.
【0039】次に、上記のように作製したレンズを2−
(パーフルオロオクチル)エチルトリアミノシラン3g
をC6F14を主成分としたC5F12及びC7F16の混合溶
剤 (住友3M製FX3250)97gに溶解した液温
20℃の液に5分間浸漬し、浸漬後、相対湿度50%、
温度50℃雰囲気中に取り出し、10分間放置した。そ
の後、アセトンによりレンズを拭きあげた。Next, the lens produced as described above is
(Perfluorooctyl) ethyltriaminosilane 3g
Is immersed in 97 g of a mixed solvent of C 5 F 12 and C 7 F 16 containing C 6 F 14 as a main component (FX3250 manufactured by Sumitomo 3M) for 5 minutes at a liquid temperature of 20 ° C., and after the immersion, a relative humidity of 50 %,
It was taken out in an atmosphere at a temperature of 50 ° C. and left for 10 minutes. Then, the lens was wiped off with acetone.
【0040】得られた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
くもり止め性に従って1〜4級で評価した。(1級が一
番防曇性能が良く、4級が一番悪い。) さらに、防曇
性能の耐久性の評価として、反射防止膜表面を、布で1
kgの荷重をかけ、500回摩擦した後、防曇性の低下
の程度を上記防曇性評価方法で評価した。耐水ヤケ性の
試験は、水道水をレンズ表面にたらし乾燥させた後、布
で残留物を拭き取った。残留物が残ればC、完全に拭き
取れればA、一部残ればBと評価した。The method for evaluating the antifogging property of the obtained article is "JIS
-S4030 Grade 1 to 4 were evaluated according to the anti-fog property at low temperature part of "Test method for anti-fog agent for eyeglasses" (1st grade is the best antifogging performance, 4th grade is the worst). To evaluate the durability of the
After applying a load of kg and rubbing 500 times, the degree of deterioration of the antifogging property was evaluated by the above antifogging evaluation method. For the test of water resistance, the surface of the lens was dried by tap water, and the residue was wiped off with a cloth. The residue was evaluated as C when remaining, A as completely wiped, and B as partially remaining.
【0041】評価結果は、表1に実施例と比較例をまと
めて示した。The evaluation results are shown in Table 1 together with Examples and Comparative Examples.
【0042】上述のような構成によれば、表面に親水性
物質と撥水性を有する二酸化珪素が存在し、反射防止性
能と耐水ヤケ性、耐汚染性を有する耐久性のある防曇を
同時に実現することができる。According to the above-mentioned constitution, the hydrophilic substance and the silicon dioxide having water repellency are present on the surface, and at the same time, the anti-reflection performance, the water proofing resistance, and the durable anti-fogging having the stain resistance are realized. can do.
【0043】[0043]
【表1】 [Table 1]
【0044】〔実施例2〕実施例1で作成した、コーテ
イング済みレンズに反射防止膜を形成した後、出力40
0WのアルゴンRFプラズマで処理を行いながら、真空
槽内に2−ヒドロキシエチルメタクリレートを導入し、
気体の状態で反射防止表面と接触させ、表面に皮膜が形
成されない程度にプラズマ重合を行った。その後、真空
槽内にビス(パーフルオロプロピルメチル)ジアミノシ
ランを導入し、表面の二酸化珪素と反応させた。Example 2 After forming an antireflection film on the coated lens prepared in Example 1, output 40
Introducing 2-hydroxyethyl methacrylate into the vacuum chamber while performing treatment with 0 W argon RF plasma,
It was brought into contact with the antireflection surface in a gas state, and plasma polymerization was carried out to the extent that no film was formed on the surface. Then, bis (perfluoropropylmethyl) diaminosilane was introduced into the vacuum chamber and reacted with silicon dioxide on the surface.
【0045】得られたレンズは、実施例1と同様の評価
方法で評価した。結果は、表1に示した。The obtained lens was evaluated by the same evaluation method as in Example 1. The results are shown in Table 1.
【0046】上述のような構成によれば、表面に親水性
物質と撥水性を持つ二酸化珪素が存在し、反射防止性能
と耐水ヤケ性、耐汚染性を持つ耐久性のある防曇を同時
に実現することができる。According to the above-mentioned constitution, the hydrophilic substance and the silicon dioxide having water repellency are present on the surface, and at the same time, the anti-reflection performance and the water proofing resistance and the stain-proofing and the durable anti-fog are realized. can do.
【0047】〔実施例3〕防曇処理用反応液を、次の手
順で調整した。即ち、2−ヒドロキシエチルアクリレー
ト1g、N,N−ジメチルアクリルアミド、0.5g、
50%エタノール水溶液198g、アゾビス(2,4−
ジメチルバレロニトリル)0.001g、ポリエチレン
グリコール系界面活性剤0.02gを加え、均一な水溶
液とし、コーテイング液とした。Example 3 A reaction liquid for antifogging treatment was prepared by the following procedure. That is, 1 g of 2-hydroxyethyl acrylate, 0.5 g of N, N-dimethylacrylamide,
198 g of 50% aqueous ethanol solution, azobis (2,4-
0.001 g of dimethyl valeronitrile) and 0.02 g of a polyethylene glycol-based surfactant were added to form a uniform aqueous solution, which was used as a coating liquid.
【0048】この液に、実施例1で作製した反射防止膜
付きレンズを浸漬し、10cm/分で引き上げた後、6
0℃で1時間加熱した。その後、レンズを水洗し、アセ
トンで拭きあげた。The lens with the antireflection film prepared in Example 1 was dipped in this solution and pulled up at 10 cm / min.
Heated at 0 ° C. for 1 hour. Then, the lens was washed with water and wiped with acetone.
【0049】次に、上記のように作製したレンズをヘキ
サメチルジシラザン蒸気の充満した容器に釣り下げ、蒸
気にさらすことによって表面を処理した。処理後、アセ
トンにより拭きあげた。Next, the lens produced as described above was suspended in a container filled with hexamethyldisilazane vapor and exposed to the vapor to treat the surface. After the treatment, it was wiped off with acetone.
【0050】得られたレンズは、実施例1と同様の評価
方法で評価した。結果は、表1に示した。The obtained lens was evaluated by the same evaluation method as in Example 1. The results are shown in Table 1.
【0051】上述のような構成によれば、表面に親水性
物質と撥水性を持つ二酸化珪素が存在し、反射防止性能
と耐水ヤケ性、耐汚染性を持つ耐久性のある防曇を同時
に実現することができる。According to the above construction, the hydrophilic substance and the silicon dioxide having water repellency are present on the surface, and at the same time, the anti-reflection performance, the water proofing resistance, and the stain-proofing with the durability are realized. can do.
【0052】〔比較例1〕実施例1で形成した反射防止
膜付きレンズで、2−(パーフルオロオクチル)エチル
トリアミノシランによる処理を行わないレンズを比較例
1とした。Comparative Example 1 A lens having an antireflection film formed in Example 1 and not treated with 2- (perfluorooctyl) ethyltriaminosilane was used as Comparative Example 1.
【0053】〔比較例2〕実施例1で最上層の二酸化珪
素をアルゴンガス導入を行わずに形成し、ビス(パーフ
ルオロプロピルメチル)ジアミノシランで処理を行わな
いレンズを比較例2とした。Comparative Example 2 A lens in which the uppermost layer of silicon dioxide in Example 1 was formed without introducing an argon gas and was not treated with bis (perfluoropropylmethyl) diaminosilane was used as Comparative Example 2.
【0054】[0054]
【発明の効果】請求項1記載の発明によれば、物品表面
は、撥水性を有する無機物質と親水性物質が存在する表
面となり、反射防止性能、耐摩耗性、耐水ヤケ性、耐汚
染性、防曇性を兼ね備えることができる。According to the invention of claim 1, the surface of the article is a surface on which an inorganic material having water repellency and a hydrophilic material are present, and the antireflection performance, abrasion resistance, water proofing resistance, and stain resistance. , And can also have anti-fogging properties.
【0055】請求項2記載の発明によれば、充填率の低
い膜に親水性物質を固定することが可能となり、親水性
物質の密度が高まり、さらに、表面に露出した無機物質
に撥水性を付与することができ、十分な防曇性能と反射
防止性能、耐摩耗性、耐水ヤケ性、耐汚染性を兼ね備え
ることができる。According to the second aspect of the present invention, the hydrophilic substance can be fixed to the film having a low filling rate, the density of the hydrophilic substance is increased, and the inorganic substance exposed on the surface is made water repellent. It can be imparted, and can have sufficient antifogging performance and antireflection performance, abrasion resistance, water stain resistance, and stain resistance.
Claims (9)
層及び多層反射防止膜の最上層が、細孔及び微細な凹凸
のどちらか一方を少なくとも有し、最上層の無機物質の
充填率が0.95以下であり、その細孔及び微細な凹凸
に親水性物質が存在して、最表面が無機物質と親水性物
質からなり、かつ、無機物質表面の水の静止接触角が9
0゜以上であることを特徴とする反射防止性能を有する
防曇性物品。1. An uppermost layer of a single-layer or multi-layered antireflection film made of an inorganic material, which is provided on a substrate, has at least one of pores and fine irregularities, The filling rate is 0.95 or less, a hydrophilic substance is present in the pores and fine irregularities, the outermost surface is composed of an inorganic substance and a hydrophilic substance, and the static contact angle of water on the surface of the inorganic substance is 9
An antifogging article having an antireflection property, which is characterized in that it is 0 ° or more.
層及び多層反射防止膜の最上層を、ガス導入を行いなが
ら真空蒸着によって形成した後、親水性物質で最上層を
処理し、最上層の細孔及び微細な凹凸に親水性物質を固
定し、かつ、撥水性を有する物質で無機物質表面を処理
することを特徴とする反射防止性能を有する防曇性物品
の製造方法。2. An uppermost layer of a single layer and a multilayer antireflection film made of an inorganic substance, which is provided on a substrate, is formed by vacuum vapor deposition while introducing gas, and then the uppermost layer is treated with a hydrophilic substance. A method for producing an antifogging article having an antireflection property, which comprises fixing a hydrophilic substance to the pores and fine irregularities of the uppermost layer and treating the surface of the inorganic substance with a substance having water repellency.
を特徴とする請求項1記載の反射防止性能を有する防曇
性物品。3. The antifogging article having antireflection performance according to claim 1, wherein the base material is a synthetic resin lens.
を主成分とする物質であることを特徴とする請求項1記
載の反射防止性能を有する防曇性物品。4. The antifogging article having antireflection properties according to claim 1, wherein the uppermost layer is made of silicon dioxide and a substance containing silicon dioxide as a main component.
を特徴とする請求項2記載の反射防止性能を有する防曇
性物品の製造方法。5. The method for producing an antifogging article having antireflection performance according to claim 2, wherein the base material is a synthetic resin lens.
を主成分とする物質であることを特徴とする請求項2記
載の反射防止性能を有する防曇性物品の製造方法。6. The method for producing an antifogging article having antireflection performance according to claim 2, wherein the uppermost layer is made of silicon dioxide and a substance containing silicon dioxide as a main component.
とする請求項2記載の反射防止性能を有する防曇性物品
の製造方法。7. The method for producing an antifogging article having antireflection performance according to claim 2, wherein the gas is an inert gas.
あって、最上層を親水性物質で処理後、加熱及び電磁波
・放射線の照射によって反応を促進することを特徴とす
る請求項2記載の反射防止性能を有する防曇性物品の製
造方法。8. The hydrophilic substance is a reactive substance, and the reaction is promoted by heating and irradiating electromagnetic waves / radiation after treating the uppermost layer with the hydrophilic substance. A method for producing an antifogging article having the antireflection performance as described.
むシラン化合物であることを特徴とする請求項2記載の
反射防止性能を有する防曇性物品の製造方法。9. The method for producing an antifogging article having antireflection performance according to claim 2, wherein the substance having water repellency is a silane compound containing fluorine.
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JP28169095A JP3694882B2 (en) | 1995-10-30 | 1995-10-30 | Antifogging article having antireflection performance and method for producing the same |
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Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP28169095A JP3694882B2 (en) | 1995-10-30 | 1995-10-30 | Antifogging article having antireflection performance and method for producing the same |
Publications (2)
Publication Number | Publication Date |
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JPH09127303A true JPH09127303A (en) | 1997-05-16 |
JP3694882B2 JP3694882B2 (en) | 2005-09-14 |
Family
ID=17642631
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