JP2002338303A - Low reflection member - Google Patents
Low reflection memberInfo
- Publication number
- JP2002338303A JP2002338303A JP2001151929A JP2001151929A JP2002338303A JP 2002338303 A JP2002338303 A JP 2002338303A JP 2001151929 A JP2001151929 A JP 2001151929A JP 2001151929 A JP2001151929 A JP 2001151929A JP 2002338303 A JP2002338303 A JP 2002338303A
- Authority
- JP
- Japan
- Prior art keywords
- porous film
- reflection member
- substrate
- low reflection
- film
- 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.)
- Pending
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
- C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
- C03C17/23—Oxides
- C03C17/25—Oxides by deposition from the liquid phase
-
- 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
- C03C2217/00—Coatings on glass
- C03C2217/20—Materials for coating a single layer on glass
- C03C2217/21—Oxides
- C03C2217/213—SiO2
-
- 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
- C03C2218/113—Deposition methods from solutions or suspensions by sol-gel processes
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)
- Laminated Bodies (AREA)
- Surface Treatment Of Glass (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、自動車用窓ガラス
に用いる低反射部材に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a low reflection member used for a window glass for an automobile.
【０００２】[0002]
【従来の技術】自動車の内装色を明るい色として開放感
を演出したいという要望は従来から強く、シートやドア
トリムに明るい色を採用した車も増えてきている。しか
し、インストルメントパネルは明るい色を用いるとウィ
ンドシールドにインストルメントパネルの表面が映り込
み、極めて運転がしづらい状況となる。このためほとん
どの車が未だに暗い色調のものが用いられている。2. Description of the Related Art There has been a strong demand for a bright interior color of an automobile to produce a sense of openness, and vehicles employing bright colors for seats and door trims are increasing. However, if a bright color is used for the instrument panel, the surface of the instrument panel is reflected on the windshield, and driving becomes extremely difficult. For this reason, most cars still use dark tones.
【０００３】この問題点を克服する手段として窓ガラス
表面に反射防止処理を施すことが考えられており、従来
はメガネやカメラのレンズに用いられているような屈折
率の異なる透明誘電体を多層膜としてコーティングし、
干渉作用によって入射光の反射率を低減するものがあ
る。このようなものとしては、特開平12−347002号公報
を例示でき、基材上に高屈折率層と中・低屈折率層を6
層交互積層した構成となっている。As a means for overcoming this problem, anti-reflection treatment has been considered to be applied to the surface of the window glass. Conventionally, a transparent dielectric material having a different refractive index, which is conventionally used for glasses or camera lenses, is made of a multilayer. Coated as a membrane,
In some cases, the reflectivity of incident light is reduced by interference. As such a material, JP-A No. 12-347002 can be exemplified, in which a high refractive index layer and a middle / low refractive index layer are formed on a substrate.
The layers are alternately stacked.
【０００４】また、他の方法としてはガラスなどの基材
上に空孔を有する多孔質膜を形成する方法がある。この
ように多孔質膜を利用する方法では現実に存在する材料
よりも見掛け上低屈折率の膜を形成できるため、単層で
あっても優れた反射防止性を発揮することが可能であ
る。このようなものとしては、特開平7−300346号公報
を例示でき、ガラス基材表面を無機酸でエッチングして
表面凹凸を形成して低屈折率層を形成した後、さらにそ
の表面をフルオロアルキルシランで処理して防汚性を持
たせたものとなっている。As another method, there is a method of forming a porous film having pores on a substrate such as glass. As described above, since a method using a porous film can form a film having an apparently lower refractive index than a material that actually exists, it is possible to exhibit excellent antireflection properties even with a single layer. As such a material, JP-A-7-300346 can be exemplified, and after the surface of a glass substrate is etched with an inorganic acid to form surface irregularities to form a low refractive index layer, the surface is further treated with a fluoroalkyl It is treated with silane to provide antifouling properties.
【０００５】優れた反射防止性能を発揮させるためには
基材の両面に反射防止処理を施すことが必須であるが、
自動車のウィンドシールドの場合、室内側の面は比較的
問題は少ないが、室外側は雨天時などにワイパーの摺動
に晒されるため極めて厳しい環境にある。このような環
境では従来の多層干渉膜や多孔質膜では極めて容易に膜
が傷付き、剥離するため、実質的用いることができな
い。In order to exhibit excellent antireflection performance, it is essential to perform antireflection treatment on both surfaces of the substrate.
In the case of a windshield of an automobile, the surface on the indoor side has relatively few problems, but the outdoor side is exposed to sliding of the wiper in rainy weather or the like, so that the environment is extremely severe. In such an environment, the conventional multilayer interference film or porous film is extremely easily damaged and peeled, and thus cannot be practically used.
【０００６】また、特開平12−347002号公報記載の多層
干渉膜の場合、数層の膜を順次処理して形成することが
必要であり製造コストが高くなってしまう。また、その
表面に数nm程度の撥水処理を行ったとしても、水滴の除
去性能は十分なものとはならず、ワイパーの併用は不可
欠であるため問題点の解決にはならない。Further, in the case of the multilayer interference film described in Japanese Patent Application Laid-Open No. 12-347002, it is necessary to sequentially process and form several layers of film, which increases the manufacturing cost. Further, even if a water repellent treatment of about several nm is performed on the surface, the performance of removing water droplets is not sufficient, and the use of a wiper is indispensable, so that the problem cannot be solved.
【０００７】特に特開平7−300346号公報記載の多孔質
膜の場合には、エッチング処理により空孔を形成してい
るため空孔は連通構造となりやく、かつランダムな構造
となるため、極めて摺動に弱いものとなり易く、爪で擦
っただけで傷付いてしまうことも多い。さらに特開平7
−300346号公報記載のフルオロアルキルシランで多孔質
膜の表面を処理を行うと水に対する接触角は平滑な表面
よりも大きくなって、雨天時のワイパー使用頻度を小さ
くすることができる可能性はあるが、一旦ワイパーで摺
動を行うと容易に膜が破壊されてしまう。In particular, in the case of the porous membrane described in Japanese Patent Application Laid-Open No. 7-300346, since the holes are formed by etching, the holes are likely to have a continuous structure and a random structure. They tend to be vulnerable to movement, and are often damaged by rubbing with nails. In addition,
When the surface of the porous membrane is treated with a fluoroalkylsilane described in -300346, the contact angle to water becomes larger than that of a smooth surface, and there is a possibility that the use frequency of the wiper in rainy weather may be reduced. However, once sliding with the wiper, the film is easily broken.
【０００８】さらにまた特開昭60-175002号公報には光
硬化性樹脂によって形成された、光を通す複数の透光部
と、その透光部間の隔壁となる非透光部とからなる透光
板が提示されているが、本方法では実質的に可視光域で
干渉反射防止を行わせる精度で処理層を形成することは
困難であり、問題となる窓ガラスに入射した光の反射を
抑制する手段として用いることができるものではない。Further, Japanese Patent Application Laid-Open No. Sho 60-175002 discloses a system comprising a plurality of light-transmitting portions formed of a photocurable resin and transmitting light, and a non-light-transmitting portion serving as a partition between the light-transmitting portions. Although a light-transmitting plate is proposed, it is difficult to form a processing layer with the accuracy of substantially preventing interference reflection in the visible light region by this method, and the reflection of light incident on the window glass becomes a problem. Can not be used as means for suppressing
【０００９】[0009]
【発明が解決しようとしている課題】そこで上記したよ
うな従来技術の問題点に鑑み、本発明は優れた反射防止
性能を発揮するとともに、耐摺動性にも優れた低反射部
部材を比較的簡便な手段によって実現することを目的と
している。SUMMARY OF THE INVENTION In view of the above-mentioned problems of the prior art, the present invention provides a low-reflection member which exhibits excellent anti-reflection performance and has excellent sliding resistance. It is intended to be realized by simple means.
【００１０】[0010]
【課題を解決するための手段】本発明者らは上記目的を
解決する手段として、請求項１に示すように、基材とそ
の一方の表面上に形成させた多孔質膜からなり、該多孔
質膜中の空孔が基材に対して略垂直方向に、かつ規則的
に配置させたことを特徴とする低反射部材を見出した。Means for Solving the Problems As means for solving the above-mentioned object, the present inventors have defined a base material and a porous film formed on one surface of the base material. The present inventors have found a low-reflection member characterized in that pores in a porous film are arranged in a direction substantially perpendicular to a substrate and regularly.
【００１１】さらに請求項2に示すように、前記多孔質
膜厚が10nm〜300nmの範囲にあり、かつ前記多孔質膜中
の空孔が体積率で30%〜75%の範囲にあることを特徴とす
る。Further, as set forth in claim 2, the porous film thickness is in the range of 10 nm to 300 nm, and the pores in the porous film are in the range of 30% to 75% by volume. Features.
【００１２】また請求項3に示すように、前記多孔質膜
がシリカからなることを特徴とする。According to a third aspect of the present invention, the porous membrane is made of silica.
【００１３】また請求項4に示すように、前記基材がソ
ーダライムガラスからなることを特徴とする。According to a fourth aspect of the present invention, the substrate is made of soda lime glass.
【００１４】また請求項5に示すように、前記低反射部
材が自動車用窓ガラスであることを特徴とする。According to a fifth aspect of the present invention, the low reflection member is an automobile window glass.
【００１５】また請求項6に示すように、請求項1ないし
5いずれかに記載の低反射部材の製造方法として、水と
酸とアルキルアンモニウム塩の界面活性剤とアルコキシ
シラン化合物とからなる混合溶液を作製し、該混合溶液
を基材上に塗布するか、該混合溶液に基材を浸漬して薄
膜を形成し、その後加熱焼成することを特徴とする。[0015] As shown in claim 6, claims 1 to
5 As a method of manufacturing the low reflection member according to any one, to prepare a mixed solution comprising a surfactant of water, acid and alkyl ammonium salt and an alkoxysilane compound, or apply the mixed solution on a substrate, The method is characterized in that a base material is immersed in the mixed solution to form a thin film, and then heated and fired.
【００１６】[0016]
【発明の実施の形態】本発明は、基材とその一方の表面
上に形成させた多孔質膜からなり、該多孔質膜の空孔が
基材に対して略垂直方向に、かつ規則的に配置させた構
造となっており、望ましくは膜厚が10nm〜300nmの範囲
にあり、かつ多孔質膜の体積空孔率が30%〜75%の範囲に
あることを特徴とする低反射部材である。BEST MODE FOR CARRYING OUT THE INVENTION The present invention comprises a substrate and a porous film formed on one surface of the substrate, and the pores of the porous film are arranged in a direction substantially perpendicular to the substrate and in a regular manner. The low reflection member characterized in that the film thickness is preferably in the range of 10 nm to 300 nm, and the volume porosity of the porous film is in the range of 30% to 75%. It is.
【００１７】また、本発明の低反射部材は、水と酸とア
ルキルアンモニウム塩の界面活性剤とアルコキシシラン
化合物とからなる混合溶液を作製し、該混合溶液を基材
上に塗布するか、該混合溶液に基材を浸漬して薄膜を形
成し、その後加熱焼成するという製造方法によって実現
できる。In the low reflection member of the present invention, a mixed solution comprising a surfactant of water, an acid, an alkylammonium salt and an alkoxysilane compound is prepared, and the mixed solution is applied to a substrate or This can be realized by a manufacturing method in which a base material is immersed in a mixed solution to form a thin film, and then heated and fired.
【００１８】前記多孔質膜は基材に対して略垂直方向に
形成され、かつ規則性的に配置されることにより、膜は
略ハニカム構造となるため、ランダムな連通孔の多孔質
膜と比較して外部応力に対して強いものとすることがで
きる。The porous film is formed in a direction substantially perpendicular to the base material and is arranged regularly so that the film has a substantially honeycomb structure. As a result, it can be made strong against external stress.
【００１９】本発明の低反射部材を自動車用ウィンドシ
ールドに用いる際、通常自動車用ウィンドシールドは水
平面から20°〜40°程度傾斜して設置されている場合が
多く、特に30°近傍で設置されているものが最も多い。
一方、インストルメントパネルのウィンドシールドへの
映り込みは、図1に示すように室内に入射した外光がイ
ンストルメントパネルの上面で反射し、ウィンドシール
ドの法線に対して60°程度の角度で入射、反射してドラ
イバーの目に入ることによって生じている。従って、イ
ンストルメントパネルの映り込みを効果的に低減するに
は、上記60°近傍の入射角での反射率を低減させること
が必要である。When the low reflection member of the present invention is used for a windshield for an automobile, the windshield for an automobile is usually installed at an angle of about 20 ° to 40 ° from a horizontal plane, and especially installed at about 30 °. Most of them are.
On the other hand, the reflection of the instrument panel on the windshield, as shown in Fig. 1, reflects the external light entering the room at the upper surface of the instrument panel, and at an angle of about 60 ° to the normal line of the windshield. It is caused by entering, reflecting and entering the driver's eyes. Therefore, in order to effectively reduce the reflection of the instrument panel, it is necessary to reduce the reflectance at the incident angle near 60 °.
【００２０】単層の光学薄膜における波長λにおける分
光エネルギ反射率Rはフレネルの公式からThe spectral energy reflectance R at a wavelength λ of a single-layer optical thin film is obtained from Fresnel's formula.
【式1】〜[Equation 1] ~
【式５】のように示すことができる。Equation 5 can be expressed as follows.
【００２１】[0021]
【式1】 R = ( Rp + Rs)／2[Formula 1] R = (R p + R s ) / 2
【式２】 Rp = (r1p 2 + r2p 2 + 2r1pr2p cosδ)／(1 +
r1p 2 r2p 2 + 2r1pr2pcosδ)[Equation 2] R p = (r 1p 2 + r 2p 2 + 2r 1p r 2p cosδ) / (1 +
r 1p 2 r 2p 2 + 2r 1p r 2p cosδ)
【式３】 Rs = (r1s 2 + r2s 2 + 2r1sr2s cosδ)／(1 +
r1s 2 r2s 2 + 2r1sr2scosδ) なお、各記号の意味は以下の通りである。 R：分光エネルギ反射率 Rp、 Rs ： p , s偏光成分の分光エネルギ反射率 r1p、 r1s ：多孔質膜と空気の界面におけるp , s偏光
成分の反射光のフレネル係数 r2p、 r2s ：多孔質膜と基材の界面におけるp , s偏光
成分の反射光のフレネル係数 δ：多孔質膜と空気の界面での反射光と多孔質膜と基材
の界面での反射光の位相差[Equation 3] R s = (r 1s 2 + r 2s 2 + 2r 1s r 2s cosδ) / (1 +
r 1s 2 r 2s 2 + 2r 1s r 2s cosδ) The meaning of each symbol is as follows. R: spectral energy reflectance R p, R s: p, s spectral energy reflectance r 1p polarization component, r 1s: porous membrane and p at the interface of air, the Fresnel coefficients of reflection light of the s-polarized component r 2p, r 2s : Fresnel coefficient of reflected light of p and s polarization components at interface between porous film and substrate δ: Reflection light at interface between porous film and air and reflected light at interface between porous film and substrate Phase difference
【００２２】[0022]
【式４】δ = 2πn1d1cosψ1／λ[Equation 4] δ = 2πn 1 d 1 cosψ 1 / λ
【式５】n1＝ p＋n(1-p) n1：多孔質膜の見掛けの屈折率 d1：薄膜の膜厚 ψ1：入射光の薄膜内部での屈折角 λ：入射光の波長 p：多孔質膜の体積空孔率 ｎ：多孔質膜形成材料の真の屈折率N 1 = p + n (1-p) n 1 : Apparent refractive index of porous film d 1 : Thickness of thin film ψ 1 : Refraction angle of incident light inside thin film λ: Wavelength of incident light p : Volume porosity of porous film n: True refractive index of porous film forming material
【００２３】また、実際に人間の目に感じる反射光の強
度は可視光線反射率Rvで表され、JIS Z8722に定められ
た刺激値Yの値と同一で、上記分光エネルギ反射率Rと重
価係数との積の可視域における総和によって求められ
る。Further, the intensity of the reflected light actually feel the human eye is represented by visible light reflectance R v, the same as the value of stimulus value Y stipulated in JIS Z8722, the spectral energy reflectance R and weight It is obtained by summing the product of the valence coefficient and the product in the visible range.
【００２４】これらより、多孔質膜表面への入射角60゜
においては、基材が屈折率1.52のソーダライムガラスの
場合には、膜厚が10nmよりも小さいと、いくら体積空孔
率を変えても未処理ガラスに対して十分な反射率の低減
ができず、反射防止性能としては不十分となる。また、
多孔質膜の膜厚が300nmよりも大きいと、成膜時にクラ
ックが発生しやすくなるとともに外部応力によって膜が
壊れやすくなるため、膜厚は300nm以下とすることが必
要である。From the above, when the substrate is made of soda lime glass having a refractive index of 1.52 at an incident angle of 60 ° on the porous film surface, if the film thickness is smaller than 10 nm, the volume porosity changes. However, the reflectance cannot be sufficiently reduced with respect to the untreated glass, and the antireflection performance becomes insufficient. Also,
If the film thickness of the porous film is larger than 300 nm, cracks are likely to occur at the time of film formation and the film is easily broken by external stress. Therefore, the film thickness needs to be 300 nm or less.
【００２５】また、体積空孔率が30%より小さいと未処
理ガラスに対して実質的に有意な反射低減が困難であ
り、75%より大きいと多孔質膜は外部応力によって壊れ
やすくなるため、体積空孔率は30%〜75%の間とすること
が望ましい。上記膜厚、体積空孔率の範囲で、可視光線
反射率Rvが最も小さくなるような組み合わせを選択する
ことによって有効な低反射膜とすることができる。If the volume porosity is less than 30%, it is difficult to substantially reduce the reflection of the untreated glass, and if the porosity is more than 75%, the porous film is easily broken by external stress. The volume porosity is desirably between 30% and 75%. The film thickness in the range of volumetric porosity, can be an effective low-reflection film by selecting a combination that the visible light reflectance R v is minimized.
【００２６】なお多孔質膜を形成する材料は、屈折率が
比較的小さく取り扱いも容易であることからシリカを用
いるのが好ましい。It is preferable to use silica as the material for forming the porous film because it has a relatively small refractive index and is easy to handle.
【００２７】さらに必要に応じて上記多孔質膜の表面を
フルオロアルキルシランやアルコキシ基を有するシリコ
ーンなどで疎水化処理を行い、撥水性を付与することも
できる。本発明のように基材に対して略垂直方向に空孔
があいた多孔質膜の場合、大きな比表面積のために水滴
接触角は平滑な面の場合に比較して増大し、さらに空孔
の途中までしか水が侵入できない状態となるため、水滴
接触角は極めて大きな値となり、いわゆる超撥水性を示
すことになる。Further, if necessary, the surface of the porous film may be subjected to a hydrophobic treatment with a fluoroalkylsilane or a silicone having an alkoxy group to impart water repellency. In the case of a porous film having holes in a direction substantially perpendicular to the substrate as in the present invention, the contact angle of water droplets is larger than that of a smooth surface due to a large specific surface area. Since water can enter only halfway, the contact angle of the water droplet becomes extremely large, indicating a so-called super water repellency.
【００２８】このような状態となると、降雨時でも落下
してきた雨は表面でバウンドするようになり、走行中は
風によって吹き飛ばされるため、視界確保のためにワイ
パーを使う必要がほとんどなくなる。このため、ワイパ
ー摺動による膜の劣化速度を非常に小さいものとできる
というメリットも生まれる可能性がある。In such a state, the rain that has fallen even during rainfall bounces on the surface, and is blown off by the wind during traveling, so that there is almost no need to use a wiper to secure a view. For this reason, there is a possibility that a merit that the rate of deterioration of the film due to the sliding of the wiper can be made extremely small may be produced.
【００２９】なお基材は製造時の高温焼成に耐えるもの
なら仕様可能であるが、安価であることからソーダライ
ムガラスが最も好適に用いられる。The substrate can be used as long as it can withstand high-temperature sintering at the time of production, but soda-lime glass is most preferably used because it is inexpensive.
【００３０】次に本発明の多孔質膜の作成方法について
述べる。水と酸とアルキルアンモニウム塩の界面活性剤
とアルコキシシラン化合物とからなる混合溶液は基材上
に塗布層を形成し、静置すると、アルコキシシラン化合
物は酸を触媒として水と反応してゲル化が進行する。同
時にアルキルアンモニウム塩の界面活性剤は自己組織化
を起こし、ほぼ一定間隔で規則的に並び、膜面に垂直方
向に凝集したミセルを形成する。このようにして、界面
活性剤をテンプレートとした自己組織化膜が形成され
る。Next, a method for producing the porous film of the present invention will be described. A mixed solution composed of water, an acid, a surfactant of an alkylammonium salt and an alkoxysilane compound forms a coating layer on a substrate, and when left standing, the alkoxysilane compound reacts with water using the acid as a catalyst to gel. Progresses. At the same time, the surfactant of the alkylammonium salt causes self-organization, and is regularly arranged at substantially constant intervals to form micelles which are aggregated in a direction perpendicular to the film surface. Thus, a self-assembled film using the surfactant as a template is formed.
【００３１】これを80℃程度の低温で乾燥させた後に水
洗し、さらに炉中で500℃程度の高温でゲル状のシリカ
の部分加水分解物を焼成するとともに、有機物の界面活
性剤を分解除去することで、空孔が基材に対してほぼ垂
直方向に形成され、かつ多孔質膜表面において規則性を
持った配置となったものが得られる。なお、焼成の際の
昇温やその後の常温までの降温は急激に行うと膜にクラ
ックが入りやすいので、ゆっくりと行うよう注意が必要
である。This is dried at a low temperature of about 80 ° C. and then washed with water. Further, the partial hydrolyzate of the gel silica is baked at a high temperature of about 500 ° C. in an oven, and the organic surfactant is decomposed and removed. By doing so, it is possible to obtain one in which pores are formed in a direction substantially perpendicular to the base material and are arranged with regularity on the surface of the porous film. Note that if the temperature is raised at the time of firing and then the temperature is lowered to room temperature rapidly, cracks are likely to be formed in the film.
【００３２】アルキルアンモニウム塩の界面活性剤とし
ては、自己組織化を起こしやすいことから、As a surfactant of an alkyl ammonium salt, self-assembly tends to occur.
【式６】で表されるものを用いることが好ましい。It is preferable to use one represented by the following formula:
【００３３】[0033]
【式６】CnH2n+1N(CH3)2X （nは10以上30以下の整数、XはCl, Brなどのハロゲン原
子） アルコキシシラン化合物はテトラエトキシシラン、メチ
ルトリエトキシシラン、エチルトリエトイシシラン、テ
トラメトキシシラン、メチルトリメトキシシラン、エチ
ルトリエトキシシランなどを用いることができる。[Equation 6] C n H 2n + 1 N ( CH 3) 2 X (n is 10 to 30 integer, X is Cl, a halogen atom such as Br) alkoxysilane compounds tetraethoxysilane, methyltriethoxysilane, Ethyltriethoxysilane, tetramethoxysilane, methyltrimethoxysilane, ethyltriethoxysilane, or the like can be used.
【００３４】[0034]
【実施例】以下実施例により本発明を具体的に説明す
る。ただし本発明は係る実施例に限定されるものではな
い。The present invention will be described in detail with reference to the following examples. However, the present invention is not limited to such an embodiment.
【００３５】実施例1 水、塩酸、界面活性剤C18H37N(CH3)2Br、テトラエトキ
シシランがモル比で100：7.5：0.1：0.2となるようにし
て混合溶液を作成し、ソーダライムガラスをこの混合溶
液中に1時間浸漬した後、ゆっくりと引き上げて取り出
し、1時間風乾した。その後、80℃のオーブン中で3時間
乾燥させ、続いて純水で洗浄した。これを炉に移し、1
時間かけて常温から500℃まで昇温して3時間この温度下
に保持した後、1時間かけて常温まで降温し、多孔質性
膜を得た。 Example 1 A mixed solution was prepared so that the molar ratio of water, hydrochloric acid, surfactant C 18 H 37 N (CH 3 ) 2 Br, and tetraethoxysilane was 100: 7.5: 0.1: 0.2. After soda lime glass was immersed in this mixed solution for 1 hour, it was slowly pulled up and taken out, and air-dried for 1 hour. Then, it was dried in an oven at 80 ° C. for 3 hours, and subsequently washed with pure water. Transfer this to the furnace, 1
After the temperature was raised from room temperature to 500 ° C. over a period of time and kept at this temperature for 3 hours, the temperature was lowered to room temperature over 1 hour to obtain a porous film.
【００３６】このサンプル表面の多孔質膜の体積空孔率
を窒素吸着法で測定したところ55%であった。また、原
子間力顕微鏡(AFM)でサンプル表面の形状を測定したと
ころ、直径5nm〜7nmの空孔が規則性をもって並んでいる
ことが分かった。また、破断面を高解像度の走査型電子
顕微鏡(SEM)で観察したところ、空孔は基材のガラスに
対してほぼ垂直方向にあいており膜厚は150nmであっ
た。The volume porosity of the porous film on the sample surface was measured by a nitrogen adsorption method and found to be 55%. In addition, when the shape of the sample surface was measured with an atomic force microscope (AFM), it was found that pores having a diameter of 5 nm to 7 nm were regularly arranged. When the fracture surface was observed with a high-resolution scanning electron microscope (SEM), the pores were almost perpendicular to the glass substrate and the film thickness was 150 nm.
【００３７】このサンプルの裏面を煤で覆い、表面から
入射角60゜で光が入射するようにして片面の分光反射率
を分光光度計により可視光線反射率を求めたところ、1.
16%と極めて優れた低反射性を示した。またこのサンプ
ルの表面を底面積1cm2の圧子に100gの荷重をかけながら
100回往復運動を行わせて摺動試験を行った後に表面を
目視にて観察したが、特に傷や膜の剥がれは観察されな
かった。The back surface of this sample was covered with soot, and the light was incident at an incident angle of 60 ° from the front surface. The spectral reflectance of one surface was measured with a spectrophotometer to determine the visible light reflectance.
It exhibited extremely excellent low reflectivity of 16%. Applying a load of 100 g to the indenter with a bottom area of 1 cm 2
After a sliding test was performed by reciprocating 100 times, the surface was visually observed, but no particular damage or peeling of the film was observed.
【００３８】実施例2 混合溶液の塗布方法をスピンコートとし、回転数1000rp
mにて基材上に塗布した以外は実施例1と同様にして多孔
質性膜を得た。膜特性の測定を実施例1と同様にして行
った結果、空孔率70%、空孔直径直径5nm〜8 nm、膜厚20
0nmで、サンプルの片面の可視光線反射率は0.82%であっ
た。また、摺動試験後の目視観察で傷や膜の剥がれは観
察されなかった。 Example 2 The application method of the mixed solution was spin coating, and the number of rotations was 1000 rp.
A porous membrane was obtained in the same manner as in Example 1, except that the composition was applied to the substrate at m. As a result of measuring the film properties in the same manner as in Example 1, the porosity was 70%, the pore diameter was 5 nm to 8 nm, and the film thickness was 20.
At 0 nm, the visible light reflectance of one side of the sample was 0.82%. Further, no scratches or peeling of the film were observed by visual observation after the sliding test.
【００３９】[0039]
【発明の効果】以上説明したように、本発明の低反射部
材は、優れた反射防止性能を発揮するとともに、耐摺動
性にも優れたものとなり、自動車用窓ガラスなどの外表
面にも好適に利用できる。As described above, the low-reflection member of the present invention exhibits excellent anti-reflection performance and also has excellent sliding resistance, and can be applied to the outer surface of an automobile window glass or the like. It can be suitably used.
【図1】自動車の室内に外光が入射し、インストルメン
トパネル表面で反射した光がウィンドシールドで反射し
てドライバーの目に入る様子の説明図である。FIG. 1 is an explanatory diagram showing a state in which external light enters a vehicle interior, and light reflected on an instrument panel surface is reflected by a windshield and enters a driver's eyes.
1 外光 2 ウィンドシールド 3 インストルメントパネル 4 ドライバーのアイポイント 1 Outside light 2 Wind shield 3 Instrument panel 4 Driver's eye point
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｇ０２Ｂ 1/11 Ｇ０２Ｂ 1/10 Ａ ──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 7 Identification symbol FI Theme coat ゛ (Reference) G02B 1/11 G02B 1/10 A
Claims (6)
孔質膜からなり、該多孔質膜中の空孔が基材に対して略
垂直方向に、かつ規則的に配置させたことを特徴とする
低反射部材。A porous film formed on one surface of the substrate, wherein pores in the porous film are arranged in a direction substantially perpendicular to the substrate and regularly. A low reflection member characterized by the above-mentioned.
あり、かつ前記多孔質膜中の空孔が体積率で30%〜75%の
範囲にあることを特徴とする請求項１記載の低反射部
材。2. The porous film according to claim 1, wherein the thickness of the porous film is in the range of 10 nm to 300 nm, and the porosity of the porous film is in the range of 30% to 75% by volume. Low reflection member.
徴とする請求項1ないし2いずれかに記載の低反射部材。3. The low reflection member according to claim 1, wherein the porous film is made of silica.
ことを特徴とする請求項1ないし3いずれかに記載の低反
射部材。4. The low reflection member according to claim 1, wherein said substrate is made of soda lime glass.
ることを特徴とする請求項1ないし4いずれかに記載の低
反射部材。5. The low reflection member according to claim 1, wherein the low reflection member is an automobile window glass.
活性剤とアルコキシシラン化合物とからなる混合溶液を
作製し、該混合溶液を基材上に塗布するか、該混合溶液
に基材を浸漬して薄膜を形成し、その後加熱焼成するこ
とを特徴とする請求項1ないし5いずれかに記載の低反射
部材の製造方法。6. A mixed solution comprising a surfactant of water, an acid and an alkylammonium salt and an alkoxysilane compound is prepared, and the mixed solution is applied on a base material or the base material is immersed in the mixed solution. 6. The method for producing a low-reflection member according to claim 1, wherein a thin film is formed by heating, followed by heating and firing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001151929A JP2002338303A (en) | 2001-05-22 | 2001-05-22 | Low reflection member |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001151929A JP2002338303A (en) | 2001-05-22 | 2001-05-22 | Low reflection member |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2002338303A true JP2002338303A (en) | 2002-11-27 |
Family
ID=18996679
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2001151929A Pending JP2002338303A (en) | 2001-05-22 | 2001-05-22 | Low reflection member |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2002338303A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005221911A (en) * | 2004-02-09 | 2005-08-18 | Pentax Corp | Optical element having reflection preventing film |
| JP2009221050A (en) * | 2008-03-17 | 2009-10-01 | National Institute Of Advanced Industrial & Technology | Self-standing mesoporous carbon thin film |
| CN105314884A (en) * | 2014-07-08 | 2016-02-10 | 上海交通大学 | Antireflection film and making method thereof |
| US11422294B2 (en) | 2017-10-10 | 2022-08-23 | Central Glass Company, Limited | Durable functional coatings |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000037374A1 (en) * | 1998-12-21 | 2000-06-29 | Saint-Gobain Vitrage | Glazing with functional mesoporous, in particular hydrophobic, coating |
-
2001
- 2001-05-22 JP JP2001151929A patent/JP2002338303A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000037374A1 (en) * | 1998-12-21 | 2000-06-29 | Saint-Gobain Vitrage | Glazing with functional mesoporous, in particular hydrophobic, coating |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005221911A (en) * | 2004-02-09 | 2005-08-18 | Pentax Corp | Optical element having reflection preventing film |
| JP4495476B2 (en) * | 2004-02-09 | 2010-07-07 | Ｈｏｙａ株式会社 | Method for manufacturing optical element having antireflection film |
| JP2009221050A (en) * | 2008-03-17 | 2009-10-01 | National Institute Of Advanced Industrial & Technology | Self-standing mesoporous carbon thin film |
| CN105314884A (en) * | 2014-07-08 | 2016-02-10 | 上海交通大学 | Antireflection film and making method thereof |
| CN105314884B (en) * | 2014-07-08 | 2017-12-08 | 上海交通大学 | Antireflective coating and preparation method thereof |
| US11422294B2 (en) | 2017-10-10 | 2022-08-23 | Central Glass Company, Limited | Durable functional coatings |
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