JPH06114334A - Method for forming very fine recessed and projected pattern on base - Google Patents
Method for forming very fine recessed and projected pattern on baseInfo
- Publication number
- JPH06114334A JPH06114334A JP26575092A JP26575092A JPH06114334A JP H06114334 A JPH06114334 A JP H06114334A JP 26575092 A JP26575092 A JP 26575092A JP 26575092 A JP26575092 A JP 26575092A JP H06114334 A JPH06114334 A JP H06114334A
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- JP
- Japan
- Prior art keywords
- film
- substrate
- mold
- metal
- chemical formula
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- Liquid Crystal (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Shaping Of Tube Ends By Bending Or Straightening (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、凹凸パターンを形成す
る方法に関し、とりわけ光ディスク用基板、セルギャッ
プ制御用突起を付与した液晶表示セル用ガラス基板、回
折格子、結像素子、光学部品などに必要な微細な凹凸パ
ターンを形成する方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for forming a concavo-convex pattern, and particularly to an optical disk substrate, a glass substrate for a liquid crystal display cell provided with protrusions for controlling a cell gap, a diffraction grating, an imaging element, an optical component, etc. The present invention relates to a method for forming a necessary fine uneven pattern.
【０００２】[0002]
【従来の技術】従来、微細な凹凸パターンを基板上に形
成する方法としては、金属有機化合物として金属の原子
価数と同じ数の官能基がその金属に直接結合しているた
とえばオルソシリケートを含み、増粘剤としてポリエチ
レングリコールを含む溶液をガラス基板上に塗布して可
塑性塗布膜を形成し、その塗布膜に微細な凹凸パターン
を有する型を押しあて、型の峰形状に対応する溝形状を
転写し、その後凹凸パターンが転写された塗布膜を加熱
焼成して固化させたる方法が、特開昭６２−１０２４４
５号公報、特開昭６２−２２５２７３号公報、特開昭６
３−１５８１６８号公報に開示されている。2. Description of the Related Art Conventionally, as a method for forming a fine uneven pattern on a substrate, a metal organic compound, for example, orthosilicate in which functional groups having the same number as the valence number of the metal are directly bonded to the metal are included. , A solution containing polyethylene glycol as a thickener is applied on a glass substrate to form a plastic coating film, and a mold having a fine uneven pattern is pressed against the coating film to form a groove shape corresponding to the peak shape of the mold. A method of transferring and then heating and baking a coating film on which the concavo-convex pattern is transferred to solidify is described in JP-A-62-10244.
5, JP-A-62-225273, JP-A-6
It is disclosed in Japanese Patent Laid-Open No. 3-158168.
【０００３】[0003]
【発明が解決しようとする課題】しかしながら、上記従
来技術の方法では、金属有機化合物として、金属の結合
手のすべてに官能基が直接結合したものを用いているの
で、３００℃程度の加熱焼成により、凹凸パターンを有
する膜体が無機非晶質になるという利点が有るものの、
溶液に増粘剤を含めているため塗布膜の加熱焼成により
膜が収縮し、形成される凹凸パターンの形状は型のそれ
より凹凸深さが小さくなり、所定の寸法の凹凸パターン
が得にくいという問題点があった。また、増粘剤を用い
ているので、得られる膜は多孔質になり、したがって水
分が吸着しやすく、凹凸を有する膜体の屈折率が変化
し、また膜厚が変化するという問題点があった。さらに
上記従来技術の方法では、凹凸を有する膜の厚みを０.
５μｍ以上にすると膜体にクラックが発生し、基板から
剥離するという問題が発生し、深さが０.５μｍを越え
る凹凸パターンを基板上に形成することは困難であると
いう問題点があった。本発明は、上記の問題点を解決す
るためになされたもので、寸法精度良く凹凸パターンを
形成する、とりわけ凸頂点と凹底部の距離が大きい微細
な凹凸パターンを形成する方法を提供することを目的と
している。However, in the above-mentioned method of the prior art, since the functional group is directly bonded to all the bonding hands of the metal is used as the metal organic compound, it is heated at about 300.degree. Although there is an advantage that the film body having the concavo-convex pattern becomes inorganic amorphous,
Since the solution contains a thickening agent, the film shrinks when the coating film is heated and baked, and the uneven pattern formed has a smaller uneven depth than that of the mold, making it difficult to obtain an uneven pattern of a predetermined size. There was a problem. In addition, since a thickener is used, the obtained film becomes porous, so that water is likely to be adsorbed, the refractive index of the uneven film body changes, and the film thickness also changes. It was Furthermore, in the above-mentioned method of the prior art, the thickness of the film having the unevenness is set to 0.
When the thickness is 5 μm or more, cracks occur in the film body, causing a problem of peeling from the substrate, and it is difficult to form an uneven pattern having a depth of more than 0.5 μm on the substrate. The present invention has been made in order to solve the above problems, and provides a method for forming a concavo-convex pattern with high dimensional accuracy, in particular, for forming a fine concavo-convex pattern in which the distance between the convex vertex and the concave bottom is large. Has an aim.
【０００４】[0004]
【課題を解決するための手段】本発明は、基板上及び／
または微細な凹凸パターンを有する有機樹脂製型上に、
加水分解・縮重合し得る下記化学式１の金属有機化合物
を含む溶液を用いて塗布膜を形成し、該基板及び該型を
接合押圧して該塗布膜を該型の凹凸パターンを有する膜
体とし、その後該型を該膜体から離型し、該膜体を加熱
することにより該有機金属化合物の縮重合体とする、基
板上に微細な凹凸パターンを形成する方法である。The present invention is directed to a substrate and / or
Or on an organic resin mold having a fine uneven pattern,
A coating film is formed by using a solution containing a metal organic compound of the following chemical formula 1 capable of being hydrolyzed and polycondensed, and the substrate and the mold are bonded and pressed to form the coating film as a film body having an uneven pattern of the mold. Then, the mold is released from the film body, and the film body is heated to form a polycondensation polymer of the organometallic compound, which is a method of forming a fine uneven pattern on a substrate.
【０００５】化学式１：ＸkＭAＲm ＭA：原子価数４の金属 Ｘ：重合可能な官能基 Ｒ：アルキル基またはアリール基 （ｋは自然数、ｍは１または２の整数で、ｋ＋ｍ＝４を
満たす） 上記金属有機化合物としては、例えば、（ＣＨ3Ｏ）3Ｓ
ｉＣＨ3，（Ｃ2Ｈ5Ｏ）3ＳｉＣＨ3，（ＣＨ3Ｏ）3Ｓｉ
Ｃ2Ｈ5，（Ｃ2Ｈ5Ｏ）3ＳｉＣ2Ｈ5，（ＣＨ3Ｏ）3Ｓｉ
Ｃ6Ｈ5，（Ｃ2Ｈ5Ｏ）3ＳｉＣ6Ｈ5，Ｃｌ3ＳｉＣＨ3，
Ｃｌ3ＳｉＣ2Ｈ5，Ｃｌ3ＳｉＣ6Ｈ5，（ＣＨ3Ｏ）2Ｓｉ
（ＣＨ3）2，Ｃｌ2Ｓｉ（ＣＨ3）2，（ＣＨ3Ｏ）2Ｓｉ
（ＣＨ2ＣＦ3）2，Ｃｌ2Ｓｉ（ＣＨ2ＣＦ3）2，（ＣＨ3
Ｏ）Ｓｉ（ＣＨ3）3，ＣｌＳｉ（ＣＨ3）3，（ＣＨ
3Ｏ）Ｓｉ（ＣＨ2ＣＦ3）3，ＣｌＳｉ（ＣＨ2Ｃ
Ｆ3）3，（ＣＨ3Ｏ）2Ｓｉ（ＣＨ2ＣＦ3）2，Ｃｌ2Ｓｉ
（ＣＨ2ＣＦ3）2，（ＣＨ3Ｏ）3Ｓｉ（ＣＨ2ＣＦ3），
Ｃｌ3Ｓｉ（ＣＨ2ＣＦ3），（ＣＨ3Ｏ）3ＴｉＣＨ3，
（Ｃ2Ｈ5Ｏ）3ＴｉＣＨ3，（ＣＨ3Ｏ）2Ｔｉ（Ｃ
Ｈ3）2，（Ｃ2Ｈ5Ｏ）2Ｔｉ（ＣＨ3）2，Ｃｌ3ＴｉＣＨ
3，Ｃｌ2Ｔｉ（ＣＨ3）2，（ＣＨ3Ｏ）3Ｔｉ（ＣＨ2Ｃ
Ｆ3），Ｃｌ3Ｔｉ（ＣＨ2ＣＦ3）等が例示できる。なか
でも（ＣＨ3Ｏ）3ＳｉＣＨ3，（Ｃ2Ｈ5Ｏ）3ＳｉＣ
Ｈ3，（ＣＨ3Ｏ）3ＳｉＣ2Ｈ5，（Ｃ2Ｈ5Ｏ）3ＳｉＣ2
Ｈ5，（ＣＨ3Ｏ）3ＳｉＣ6Ｈ5，（Ｃ2Ｈ5Ｏ）3ＳｉＣ6
Ｈ5，Ｃｌ3ＳｉＣＨ3，Ｃｌ3ＳｉＣ2Ｈ5，Ｃｌ3ＳｉＣ6
Ｈ5などの，ＲＳｉＸ3の一般式で表される有機シリコン
化合物が均質な膜体を形成し易いので好ましい。Chemical Formula 1: X k M A R m M A : Metal having a valence of 4 X: Polymerizable functional group R: Alkyl group or aryl group (k is a natural number, m is an integer of 1 or 2, and k + m = 4) As the metal organic compound, for example, (CH 3 O) 3 S
iCH 3 , (C 2 H 5 O) 3 SiCH 3 , (CH 3 O) 3 Si
C 2 H 5, (C 2 H 5 O) 3 SiC 2 H 5, (CH 3 O) 3 Si
C 6 H 5 , (C 2 H 5 O) 3 SiC 6 H 5 , Cl 3 SiCH 3 ,
Cl 3 SiC 2 H 5 , Cl 3 SiC 6 H 5 , (CH 3 O) 2 Si
(CH 3 ) 2 , Cl 2 Si (CH 3 ) 2 , (CH 3 O) 2 Si
(CH 2 CF 3 ) 2 , Cl 2 Si (CH 2 CF 3 ) 2 , (CH 3
O) Si (CH 3 ) 3 , ClSi (CH 3 ) 3 , (CH
3 O) Si (CH 2 CF 3 ) 3 , ClSi (CH 2 C
F 3) 3, (CH 3 O) 2 Si (CH 2 CF 3) 2, Cl 2 Si
(CH 2 CF 3 ) 2 , (CH 3 O) 3 Si (CH 2 CF 3 ),
Cl 3 Si (CH 2 CF 3 ), (CH 3 O) 3 TiCH 3 ,
(C 2 H 5 O) 3 TiCH 3 , (CH 3 O) 2 Ti (C
H 3 ) 2 , (C 2 H 5 O) 2 Ti (CH 3 ) 2 , Cl 3 TiCH
3 , Cl 2 Ti (CH 3 ) 2 , (CH 3 O) 3 Ti (CH 2 C
F 3), Cl 3 Ti ( CH 2 CF 3) and the like. Of these (CH 3 O) 3 SiCH 3 , (C 2 H 5 O) 3 SiC
H 3 , (CH 3 O) 3 SiC 2 H 5 , (C 2 H 5 O) 3 SiC 2
H 5 , (CH 3 O) 3 SiC 6 H 5 , (C 2 H 5 O) 3 SiC 6
H 5, Cl 3 SiCH 3, Cl 3 SiC 2 H 5, Cl 3 SiC 6
An organic silicon compound represented by the general formula of RSiX 3 such as H 5 is preferable because it is easy to form a homogeneous film body.
【０００６】本発明に用いる溶液には、上記化学式１で
表される金属有機化合物に加えて、凹凸パターンを有す
る膜体の屈折率等の光学的性質、硬度等の機械的性質を
調整するための第２の有機金属化合物として、下記化学
式２で表せる金属アルコラートを含ませることができ
る。In the solution used in the present invention, in addition to the metal organic compound represented by the above chemical formula 1, in order to adjust the optical properties such as the refractive index and the mechanical properties such as hardness of the film body having the uneven pattern. As the second organic metal compound, a metal alcoholate represented by the following chemical formula 2 can be included.
【０００７】化学式２：ＭB（ＯＲ）n ＭB：価数ｎを有する金属（ｎは１〜４の整数）、 ＯＲ：アルコキシ基、（Ｒは炭素数が１〜３のアルキル
基） ここで、金属ＭBとして、Ｓｉ，Ｔｉ，Ｚｒ，Ｃａ，Ａ
ｌ，Ｎａ，Ｐｂ，Ｂ，Ｓｎ，Ｇｅ等の金属、アルコキシ
基のＲとしてはメチル，エチル、プロピル等のアルキル
基が用いることができる。また、金属キレート錯体及び
−Ｃｌ，−ＣＯＯＨ，−ＣＯＯＲ，−ＮＨ2， などの官能基を有するものを第２の金属有機化合物とし
て含ませてもよい。なかでも上記化学式２の金属アルコ
ラートが好ましく、そのなかでもＳｉ（ＯＣＨ3）4、Ｓ
ｉ（ＯＣ2Ｈ5）4、Ｔｉ（ＯＣ3Ｈ7）4、Ｔｉ（ＯＣ
4Ｈ9）4，Ｚｒ（ＯＣ3Ｈ7）4，Ｚｒ（ＯＣ4Ｈ9）4，Ａ
ｌ（ＯＣ3Ｈ7）3，Ａｌ（ＯＣ4Ｈ9）3が、得られる膜体
の屈折率を等の光学的性質を制御し、かつ耐候性を向上
させる点から好ましい。また、溶液中の全金属有機化合
物のうち、化学式１の金属有機化合物の割合を６０％以
上１００％未満とすることにより、得られる膜の硬さを
大きく低下させないで、凸頂部と凹底部の距離が大きい
微細な凹凸パターンを、加熱により膜体の収縮率を小さ
くして縮重合を進行させることができる。また、得られ
る膜体の硬さを硬くすることができる。とくに０．５μ
ｍ以上の凹凸段差を有する膜体を形成するには、上記溶
液中に化学式１の金属有機化合物と第２の金属有機化合
物を含ませ、化学式１で表せるものの割合を全金属有機
化合物の６０〜８０％、さらに好ましくは７０〜８０％
とする。Chemical formula 2: M B (OR) n M B : a metal having a valence of n (n is an integer of 1 to 4), OR: an alkoxy group, (R is an alkyl group having 1 to 3 carbon atoms) Then, as the metal M B , Si, Ti, Zr, Ca, A
As a metal such as 1, Na, Pb, B, Sn and Ge, and R of the alkoxy group, an alkyl group such as methyl, ethyl and propyl can be used. The metal chelate complex and -Cl, -COOH, -COOR, -NH 2, Those having a functional group such as may be included as the second metal organic compound. Among them, the metal alcoholate represented by the above chemical formula 2 is preferable, and among them, Si (OCH 3 ) 4 , S
i (OC 2 H 5 ) 4 , Ti (OC 3 H 7 ) 4 , Ti (OC
4 H 9 ) 4 , Zr (OC 3 H 7 ) 4 , Zr (OC 4 H 9 ) 4 , A
l (OC 3 H 7 ) 3 and Al (OC 4 H 9 ) 3 are preferable from the viewpoint of controlling optical properties such as the refractive index of the obtained film body and improving weather resistance. In addition, by setting the ratio of the metal organic compound of the chemical formula 1 to 60% or more and less than 100% of all the metal organic compounds in the solution, the hardness of the obtained film is not significantly decreased, and the convex top and the concave bottom are not significantly reduced. By heating a fine uneven pattern having a large distance, the shrinkage rate of the film body can be reduced to promote polycondensation. Further, the hardness of the obtained film body can be increased. Especially 0.5μ
In order to form a film body having unevenness steps of m or more, the metal organic compound of the chemical formula 1 and the second metal organic compound are contained in the above solution, and the ratio of those represented by the chemical formula 1 is 60 to 60% of the total metal organic compound. 80%, more preferably 70-80%
And
【０００８】本発明に用いる金属有機化合物は、水およ
びアルコール等の有機溶媒、必要に応じて酸またはアル
カリの加水分解触媒と混合された溶液とされる。そし
て、金属有機化合物の溶液全体に占める割合は、溶液の
粘性、形成しょうとする膜体の厚み等により定められ、
２０〜７０％とするのが好ましい。The metal organic compound used in the present invention is a solution mixed with an organic solvent such as water and alcohol and, if necessary, an acid or alkali hydrolysis catalyst. The ratio of the metal organic compound to the entire solution is determined by the viscosity of the solution, the thickness of the film to be formed, etc.
It is preferably 20 to 70%.
【０００９】本発明に用いることのできる基板として
は、ガラス、セラミックス、金属、プラスチック等の任
意の基板を用いることができる。As the substrate that can be used in the present invention, any substrate such as glass, ceramics, metal and plastic can be used.
【００１０】本発明に用いられる型は、塗布溶液の溶媒
に対して耐性があればとくに限定されない。ガラス、セ
ラミックス、金属、プラスチック等の材料を用いること
ができる。膜体と型との離型性を向上させるため、型表
面に離型層を設けてもよい。また、塗布した膜を加熱す
るときの熱膨張による凹凸パターンの寸法精度の劣化を
防ぐために、微細凹凸パターンを表面に形成する基板と
近い熱膨張率を有する型材料を選択することが好まし
い。The mold used in the present invention is not particularly limited as long as it is resistant to the solvent of the coating solution. Materials such as glass, ceramics, metal and plastic can be used. A mold release layer may be provided on the mold surface in order to improve the mold release property between the film body and the mold. Further, in order to prevent deterioration of the dimensional accuracy of the uneven pattern due to thermal expansion when the applied film is heated, it is preferable to select a mold material having a thermal expansion coefficient close to that of the substrate on which the fine uneven pattern is formed.
【００１１】本発明に用いられる型の微細な凹凸パター
ンの形状としては、例えば読みだし専用光ディスク（Ｃ
Ｄ−ＲＯＭ）のピットパターンとして使用可能な０．７
μｍ程度の幅を持ち高さが約１５０ｎｍの凹凸パターン
や、光ディスク用の案内溝として使用可能な１μｍ程度
の幅を持ち、その深さが５０〜２００ｎｍの微細凹凸パ
ターンや、回折格子、グレーティングレンズとして使用
可能な数１００ｎｍ〜数μｍ深さの矩形あるいは鋸歯状
パターンや、液晶表示素子用基板のスペーサーとして使
用可能な深さ１０μｍ程度のものが例示できる。The shape of the fine concavo-convex pattern of the mold used in the present invention is, for example, a read-only optical disk (C
0.7 that can be used as a pit pattern for D-ROM)
An uneven pattern having a width of about 150 μm and a height of about 150 nm, or a fine uneven pattern having a width of about 1 μm and a depth of 50 to 200 nm, which can be used as a guide groove for an optical disc, a diffraction grating, and a grating lens. A rectangular or sawtooth pattern having a depth of several 100 nm to several μm and a depth of about 10 μm which can be used as a spacer of a substrate for a liquid crystal display element can be exemplified.
【００１２】本発明の第２は、基板上に、加水分解・縮
重合し得る化学式１の金属有機化合物を含む溶液をスク
リーン印刷法により塗布して凹凸パターンを有する膜体
とし、その後該膜体を加熱することにより該金属有機化
合物の縮重合体とする、基板上に微細な凹凸パターンを
形成する方法である。A second aspect of the present invention is to apply a solution containing a metal organic compound of chemical formula 1 capable of being hydrolyzed and polycondensed on a substrate by a screen printing method to obtain a film body having an uneven pattern, and then the film body. Is a method for forming a fine concavo-convex pattern on a substrate, which is a condensation polymer of the metal organic compound by heating.
【００１３】化学式１：ＸkＭAＲm ＭA：原子価数４の金属 Ｘ：重合可能な官能基、 Ｒ：アルキル基またはアリール基 （ｋは自然数、ｍは１または２の整数で、ｋ＋ｍ＝４を
満たす） 上記金属有機化合物としては、本発明の第１と同様に
（ＣＨ3Ｏ）3ＳｉＣＨ3，（Ｃ2Ｈ5Ｏ）3ＳｉＣＨ3，
（ＣＨ3Ｏ）3ＳｉＣ2Ｈ5，（Ｃ2Ｈ5Ｏ）3ＳｉＣ2Ｈ5，
（ＣＨ3Ｏ）3ＳｉＣ6Ｈ5，（Ｃ2Ｈ5Ｏ）3ＳｉＣ6Ｈ5，
Ｃｌ3ＳｉＣＨ3，Ｃｌ3ＳｉＣ2Ｈ5，Ｃｌ3ＳｉＣ6Ｈ5，
（ＣＨ3Ｏ）2Ｓｉ（ＣＨ3）2，Ｃｌ2Ｓｉ（ＣＨ3）2，
（ＣＨ3Ｏ）2Ｓｉ（ＣＨ2ＣＦ3）2，Ｃｌ2Ｓｉ（ＣＨ2
ＣＦ3）2，（ＣＨ3Ｏ）Ｓｉ（ＣＨ3）3，ＣｌＳｉ（Ｃ
Ｈ3）3，（ＣＨ3Ｏ）Ｓｉ（ＣＨ2ＣＦ3）3，ＣｌＳｉ
（ＣＨ2ＣＦ3）3，（ＣＨ3Ｏ）2Ｓｉ（ＣＨ2ＣＦ3）2，
Ｃｌ2Ｓｉ（ＣＨ2ＣＦ3）2，（ＣＨ3Ｏ）3Ｓｉ（ＣＨ2
ＣＦ3），Ｃｌ3Ｓｉ（ＣＨ2ＣＦ3），（ＣＨ3Ｏ）3Ｔｉ
ＣＨ3，（Ｃ2Ｈ5Ｏ）3ＴｉＣＨ3，（ＣＨ3Ｏ）2Ｔｉ
（ＣＨ3）2，（Ｃ2Ｈ5Ｏ）2Ｔｉ（ＣＨ3）2，Ｃｌ3Ｔｉ
ＣＨ3，Ｃｌ2Ｔｉ（ＣＨ3）2，（ＣＨ3Ｏ）3Ｔｉ（ＣＨ
2ＣＦ3），Ｃｌ3Ｔｉ（ＣＨ2ＣＦ3）等が例示できる。
なかでも（ＣＨ3Ｏ）3ＳｉＣＨ3，（Ｃ2Ｈ5Ｏ）3ＳｉＣ
Ｈ3，（ＣＨ3Ｏ）3ＳｉＣ2Ｈ5，（Ｃ2Ｈ5Ｏ）3ＳｉＣ2
Ｈ5，（ＣＨ3Ｏ）3ＳｉＣ6Ｈ5，（Ｃ2Ｈ5Ｏ）3ＳｉＣ6
Ｈ5，Ｃｌ3ＳｉＣＨ3，Ｃｌ3ＳｉＣ2Ｈ5，Ｃｌ3ＳｉＣ6
Ｈ5などの，ＲＳｉＸ3の一般式で表される有機シリコン
化合物が、スクリーン印刷により均質な膜体を形成でき
るので好ましい。Chemical Formula 1: X k M A R m M A : Metal having a valence of 4 X: Polymerizable functional group, R: Alkyl group or aryl group (k is a natural number, m is an integer of 1 or 2, k + m = 4) As the above-mentioned metal organic compound, (CH 3 O) 3 SiCH 3 , (C 2 H 5 O) 3 SiCH 3 ,
(CH 3 O) 3 SiC 2 H 5, (C 2 H 5 O) 3 SiC 2 H 5,
(CH 3 O) 3 SiC 6 H 5, (C 2 H 5 O) 3 SiC 6 H 5,
Cl 3 SiCH 3 , Cl 3 SiC 2 H 5 , Cl 3 SiC 6 H 5 ,
(CH 3 O) 2 Si (CH 3 ) 2 , Cl 2 Si (CH 3 ) 2 ,
(CH 3 O) 2 Si ( CH 2 CF 3) 2, Cl 2 Si (CH 2
CF 3 ) 2 , (CH 3 O) Si (CH 3 ) 3 , ClSi (C
H 3) 3, (CH 3 O) Si (CH 2 CF 3) 3, ClSi
(CH 2 CF 3 ) 3 , (CH 3 O) 2 Si (CH 2 CF 3 ) 2 ,
Cl 2 Si (CH 2 CF 3 ) 2 , (CH 3 O) 3 Si (CH 2
CF 3 ), Cl 3 Si (CH 2 CF 3 ), (CH 3 O) 3 Ti
CH 3 , (C 2 H 5 O) 3 TiCH 3 , (CH 3 O) 2 Ti
(CH 3 ) 2 , (C 2 H 5 O) 2 Ti (CH 3 ) 2 , Cl 3 Ti
CH 3 , Cl 2 Ti (CH 3 ) 2 , (CH 3 O) 3 Ti (CH
2 CF 3), Cl 3 Ti (CH 2 CF 3) and the like.
Of these (CH 3 O) 3 SiCH 3 , (C 2 H 5 O) 3 SiC
H 3 , (CH 3 O) 3 SiC 2 H 5 , (C 2 H 5 O) 3 SiC 2
H 5 , (CH 3 O) 3 SiC 6 H 5 , (C 2 H 5 O) 3 SiC 6
H 5, Cl 3 SiCH 3, Cl 3 SiC 2 H 5, Cl 3 SiC 6
Organosilicon compounds represented by the general formula of RSiX 3 such as H 5 are preferable because they can form a uniform film body by screen printing.
【００１４】本発明の第２に用いる溶液には、上記化学
式１で表される金属有機化合物に加えて、凹凸パターン
を有する膜体の屈折率等の光学的性質、硬度等の機械的
性質を調整するために、Ｓｉ（ＯＣＨ3）4、Ｓｉ（ＯＣ
2Ｈ5）4、Ｔｉ（ＯＣ3Ｈ7）4、Ｔｉ（ＯＣ4Ｈ9）4， Ｚ
ｒ（ＯＣ3Ｈ7）4，Ｚｒ（ＯＣ4Ｈ9）4，Ａｌ（ＯＣ
3Ｈ7）3，Ａｌ（ＯＣ4Ｈ9）3、Ｃ2Ｈ5ＯＮａ等の化学式
２で表せる金属アルコラートＭ（ＯＲ）n（ＭはＳｉ，
Ｔｉ，Ｚｒ，Ｃａ，Ａｌ，Ｎａ，Ｐｂ，Ｂ，Ｓｎ，Ｇｅ
等の金属、Ｒはメチル，エチル等のアルキル基、ｎは
１、２、３または４）、金属キレート錯体及び−Ｃｌ，
−ＣＯＯＨ，−ＣＯＯＲ，−ＮＨ2， 等の重縮合あるいは架橋反応を行う官能基を含む金属有
機化合物を含めることができる。これらの有機金属化合
物のうちＭ（ＯＲ）n（ｎは１〜４の整数）で表される
金属アルコラートがスクリーン印刷法を用いるときに
も、得られる膜体の光学的性質、機械的性質を制御し耐
候性を向上させるので好ましい。また、溶液中の金属有
機化合物のうち、化学式１で表せる金属有機化合物の割
合を重量比で６０〜９０％とすることにより、得られる
膜の硬さを大きく低下させないで、凹凸の深さが大き
く、かつ、膜の加熱により収縮する割合が小さい、した
がって寸法精度がよい凹凸パターンを有する膜体を形成
することができる。特に０．５μｍ以上の凹凸段差を有
する膜体を形成するには、上記溶液中に化学式１と化学
式２で表される金属有機化合物を含ませ、化学式１で表
せるものの割合を全金属有機化合物の６０〜８０％、さ
らに好ましくは７０〜８０％とする。In addition to the metal-organic compound represented by the above chemical formula 1, the solution used in the second embodiment of the present invention has optical properties such as refractive index of a film body having an uneven pattern and mechanical properties such as hardness. To adjust, Si (OCH 3 ) 4 , Si (OC
2 H 5 ) 4 , Ti (OC 3 H 7 ) 4 , Ti (OC 4 H 9 ) 4 , Z
r (OC 3 H 7 ) 4 , Zr (OC 4 H 9 ) 4 , Al (OC
3 H 7 ) 3 , Al (OC 4 H 9 ) 3 , C 2 H 5 ONa, and the like, metal alcoholates M (OR) n (M is Si,
Ti, Zr, Ca, Al, Na, Pb, B, Sn, Ge
Etc., R is an alkyl group such as methyl and ethyl, n is 1, 2, 3 or 4), a metal chelate complex and -Cl,
-COOH, -COOR, -NH 2, A metal organic compound containing a functional group that undergoes polycondensation or cross-linking reaction can be included. Among these organometallic compounds, the metal alcoholate represented by M (OR) n (n is an integer of 1 to 4) exhibits optical and mechanical properties of the obtained film body even when the screen printing method is used. It is preferable because it is controlled to improve weather resistance. Further, by setting the weight ratio of the metal organic compound represented by Chemical Formula 1 to 60 to 90% of the metal organic compound in the solution, the hardness of the obtained film is not significantly lowered, and the depth of the unevenness is increased. It is possible to form a film body which is large and has a small rate of shrinkage due to heating of the film, and therefore has a concavo-convex pattern with good dimensional accuracy. In particular, in order to form a film body having unevenness steps of 0.5 μm or more, the above solution should contain the metal organic compound represented by the chemical formula 1 and the chemical formula 1, and the proportion of the metal organic compound represented by the chemical formula 1 should be changed to the total metal organic compound. 60 to 80%, and more preferably 70 to 80%.
【００１５】本発明の第２に用いる金属有機化合物は、
水およびアルコール等の有機溶媒、必要に応じて酸また
はアルカリの加水分解触媒と混合して微細凹凸パターン
を形成するための溶液とされる。そして、有機金属化合
物の溶液全体に占める割合は、溶液の粘性、形成する膜
体の厚みにより定められ、５０〜８０％とするのが好ま
しい。The metal organic compound used in the second of the present invention is
It is mixed with water and an organic solvent such as alcohol and, if necessary, an acid or alkali hydrolysis catalyst to form a solution for forming a fine uneven pattern. The proportion of the organometallic compound in the entire solution is determined by the viscosity of the solution and the thickness of the film to be formed, and is preferably 50-80%.
【００１６】本発明の第２に用いることのできる基板と
しては、ガラス、セラミックス、金属、プラスチック等
の任意の基板を用いることができる。As the substrate that can be used in the second aspect of the present invention, any substrate such as glass, ceramics, metal and plastic can be used.
【００１７】[0017]
【作用】本発明に用いられる溶液中に含まれる金属有機
化合物は加水分解縮重合性を有し、それにより溶液を基
板上に厚く塗布することができる。さらに本発明に用い
られる有機金属化合物の金属に直接結合しているアルキ
ル基およびアリール基は、塗布膜を柔軟にし型押合によ
る成形およびスクリーン印刷による凹凸パターンを有す
る膜体の可能にするとともに、塗布後の加熱に際しては
膜体の収縮を生じさせない。したがって、ポリエチレン
グリコールなどの粘度調整剤を塗布溶液に含ませること
が不要となり、基板上に形成する凹凸を有する膜体の形
状の寸法精度を向上させることができる。この有機金属
化合物が有する柔軟性付与と収縮量低下の作用により、
凸頂部と凹底部の距離が大きい微細な凹凸パターンを寸
法精度良く基板上に形成することができる。The metal organic compound contained in the solution used in the present invention has a hydrolytic polycondensation property, whereby the solution can be applied thickly on the substrate. Further, the alkyl group and the aryl group directly bonded to the metal of the organometallic compound used in the present invention make the coating film flexible and enable the formation of a film body having a concavo-convex pattern by molding and screen printing. The film body does not shrink during subsequent heating. Therefore, it is not necessary to include a viscosity adjusting agent such as polyethylene glycol in the coating solution, and the dimensional accuracy of the shape of the film body having irregularities formed on the substrate can be improved. Due to the flexibility imparted by this organometallic compound and the effect of reducing the amount of shrinkage,
A fine concavo-convex pattern having a large distance between the convex top and the concave bottom can be formed on the substrate with high dimensional accuracy.
【００１８】[0018]
【実施例】以下に本発明を実施例に基づいて説明する。
図１は本発明により得られる微細凹凸パターンが表面に
形成された基板の一部断面図で、図１（ａ）、図１
（ｂ）はそれぞれ実施例１および実施２で得られた微細
凹凸パターン付き基板の一部断面図である。 実施例１ メチルトリエトキシシラン（ＣＨ3Ｓｉ（ＯＣ2Ｈ5）3）
０．０５モルを秤量し、これに０．０５モルのエタノー
ルと０．２モルの水（０．１ｗｔ％の塩酸（ＨＣｌ）を
含む）を加え、室温で３０分間攪拌したものを塗布溶液
１とした。ここで、ＨＣｌのメチルトリエトキシシラン
に対するモル比は、０.００２である。塗布溶液１を、
ソーダ石灰ガラス基板（１００ｍｍ×１００ｍｍ×２ｍ
ｍ）上に４ｍｌ滴下し、１ｒｐｍでガラス基板を回転さ
せることにより被膜をガラス基板上に形成した。次い
で、直径１０μｍ、高さ５μｍの半球凸パターン多数を
有する樹脂製型（１００ｍｍ×１００ｍｍ×１ｍｍ）と
このガラス基板とを空気の入らないように大気中で押合
した。その後このままの状態で１２０℃で１０分間加熱
し、その後型とガラス基板との離型を行い、凹凸を有す
る膜体が表面に形成されたガラス基板を３５０℃で１５
分間加熱した。この加熱焼成操作により、被膜はエタノ
ール及び水分等が飛散して膜厚約１０μｍのメチル基含
有ＳｉＯ2ガラス類似膜体となっていた。EXAMPLES The present invention will be described below based on examples.
FIG. 1 is a partial cross-sectional view of a substrate having a fine concavo-convex pattern obtained according to the present invention on its surface.
(B) is a partial cross-sectional view of the substrate with a fine concavo-convex pattern obtained in Example 1 and Example 2, respectively. Example 1 Methyl triethoxysilane (CH 3 Si (OC 2 H 5) 3)
0.05 mol was weighed, 0.05 mol of ethanol and 0.2 mol of water (containing 0.1 wt% hydrochloric acid (HCl)) were added thereto, and the mixture was stirred at room temperature for 30 minutes to obtain a coating solution 1. And Here, the molar ratio of HCl to methyltriethoxysilane is 0.002. Coating solution 1
Soda-lime glass substrate (100mm x 100mm x 2m
A coating film was formed on the glass substrate by dropping 4 ml onto m) and rotating the glass substrate at 1 rpm. Then, a resin mold (100 mm × 100 mm × 1 mm) having a large number of hemispherical convex patterns having a diameter of 10 μm and a height of 5 μm was pressed against this glass substrate in the atmosphere so that air could not enter. Then, in this state, it is heated at 120 ° C. for 10 minutes, and then the mold and the glass substrate are released from each other, and the glass substrate having a film body having unevenness formed on the surface is heated at 350 ° C. for 15 minutes.
Heated for minutes. By this heating and firing operation, ethanol and water were scattered to form a methyl group-containing SiO 2 glass-like film having a film thickness of about 10 μm.
【００１９】上記により作製した半球状凹パターンが多
数表面に設けられたレンズ作用を有するガラス基板をＳ
ＥＭ（走査型電子顕微鏡）で観察したところ、直径１０
μｍ、深さ約４．５μｍの凹パターンが多数形成されて
いた。ソーダ石灰ガラス基板の代わりに、無アルカリガ
ラス及び石英ガラスを用いた場合も同様の結果が得られ
た。 実施例２ 実施例１で調製した塗布溶液１を用いて凹凸を有する膜
体を導電性透明電極付きソーダ石灰ガラス基板上に形成
した。導電性透明電極付きソーダ石灰ガラス基板（１０
０ｍｍ×１００ｍｍ×１ｍｍ）に直径１０μｍの細孔を
多数有する樹脂製メッシュ（厚み２、５、１０、２０μ
ｍ）を密着させ、このメッシュに塗布溶液１を数回塗布
し６０℃で乾燥させた。その後メッシュを導電性透明電
極付きソーダ石灰ガラス基板から剥し、凹凸パターンを
有する膜体を形成したガラス基板を２００℃１５分間の
加熱焼成を行った。A glass substrate having a lens function having a large number of hemispherical concave patterns produced as described above on the surface is formed into an S-shaped glass substrate.
When observed with an EM (scanning electron microscope), a diameter of 10
A large number of concave patterns having a size of μm and a depth of about 4.5 μm were formed. Similar results were obtained when non-alkali glass and quartz glass were used instead of the soda-lime glass substrate. Example 2 Using the coating solution 1 prepared in Example 1, a film body having irregularities was formed on a soda-lime glass substrate with a conductive transparent electrode. Soda-lime glass substrate with conductive transparent electrode (10
Resin mesh (thicknesses 2, 5, 10, 20μ) having a large number of pores with a diameter of 10 μm in 0 mm × 100 mm × 1 mm)
m) was brought into close contact, the coating solution 1 was applied to this mesh several times and dried at 60 ° C. After that, the mesh was peeled off from the soda-lime glass substrate with a conductive transparent electrode, and the glass substrate on which the film having the uneven pattern was formed was heated and baked at 200 ° C. for 15 minutes.
【００２０】上記により作成した微細なパターン付き導
電性透明電極付きガラス基板の表面をＳＥＭで観察した
ところ、直径１０μｍ、深さはメッシュの厚みに応じて
約２、約５、約１０、約２０μｍの凸パターンが形成さ
れていた。When the surface of the glass substrate with a conductive transparent electrode having a fine pattern formed as described above was observed by SEM, the diameter was 10 μm, and the depth was about 2, about 5, about 10, and about 20 μm depending on the thickness of the mesh. No convex pattern was formed.
【００２１】このガラス基板は、液晶表示装置のセルギ
ャップ付き透明電極付き基板として用いることができ
る。 実施例３ メチルトリエトキシシラン（ＣＨ3Ｓｉ（ＯＣ2Ｈ5）3）
０．０５モルを秤量し、これに０．２モルのエタノール
と０．２モルの水（０．１ｗｔ％のＨＣｌを含む）を加
え、室温で３０分間攪拌し、その後エタノールをさらに
０．２モル加えて５分間攪拌したものを塗布溶液２とし
た。ＨＣｌのメチルトリエトキシシランに対するモル比
は、０.００２である。塗布溶液２を、化学強化ガラス
ディスク基板（外径１３０ｍｍ、内径１５ｍｍ、厚さ
１．２ｍｍ）に４ｍｌ滴下し、エタノール雰囲気の槽内
で８００ｒｐｍで２５秒間回転させ、基板上に塗布膜を
形成した。次いで、ピッチ１．６μｍ、深さ１００ｎ
ｍ、溝幅０．５μｍの光ディスク用溝パターンを半径２
５ｍｍから６０ｍｍの範囲に有する外径１３０ｍｍ、厚
さ１．２ｍｍのポリカーボネート製型と、このガラス基
板とを、５×１０-6Ｔｏｒｒの減圧下で５０ｋｇｆ／ｃ
ｍ2の圧力で押合した。その後押圧した状態でガラスデ
イスク基板を大気圧中に取り出し、クリーンオーブン中
で１２０℃１０分間の加熱を行い、その後型とガラスデ
ィスク基板の離型を行い、さらに凹凸を有する膜体が形
成されたガラスディスク基板を３５０℃１５分間の加熱
を行った。この加熱操作により、塗布膜はエタノール及
び水分等が飛散して膜厚約０．３μｍのメチル基含有Ｓ
ｉＯ2ガラス類似膜体となっていた。This glass substrate can be used as a substrate with a transparent electrode having a cell gap in a liquid crystal display device. Example 3 methyltriethoxysilane (CH 3 Si (OC 2 H 5) 3)
0.05 mol was weighed, 0.2 mol ethanol and 0.2 mol water (containing 0.1 wt% HCl) were added thereto, stirred at room temperature for 30 minutes, and then ethanol was further added to 0.2 mol. A coating solution 2 was obtained by adding a mole and stirring for 5 minutes. The molar ratio of HCl to methyltriethoxysilane is 0.002. 4 ml of the coating solution 2 was dropped on a chemically strengthened glass disk substrate (outer diameter 130 mm, inner diameter 15 mm, thickness 1.2 mm) and rotated at 800 rpm for 25 seconds in a tank in an ethanol atmosphere to form a coating film on the substrate. . Next, pitch 1.6 μm, depth 100 n
m, groove width 0.5 μm for optical disk groove pattern with radius 2
A polycarbonate mold having an outer diameter of 130 mm and a thickness of 1.2 mm in the range of 5 mm to 60 mm and this glass substrate were subjected to a reduced pressure of 5 × 10 −6 Torr and a pressure of 50 kgf / c.
Pressed with a pressure of m 2 . After that, the glass disk substrate was taken out to the atmospheric pressure in a pressed state, heated at 120 ° C. for 10 minutes in a clean oven, and then the mold and the glass disk substrate were separated from each other, and a film body having irregularities was formed. The glass disk substrate was heated at 350 ° C. for 15 minutes. By this heating operation, ethanol, water and the like are scattered to the coating film, and a methyl group-containing S having a film thickness of about 0.3 μm.
It was an iO 2 glass-like film body.
【００２２】上記操作により作製された光ディスク用ガ
ラスディスク基板をＳＴＭで観察したところ、ピッチ
１．６μｍ、深さ９０ｎｍ、峰幅０．５μｍの均一な微
細溝パターンが基板に形成されていた。When the glass disk substrate for an optical disk manufactured by the above operation was observed by STM, a uniform fine groove pattern having a pitch of 1.6 μm, a depth of 90 nm and a peak width of 0.5 μm was formed on the substrate.
【００２３】得られた基板は、溝形状均一性、物理的特
性、機械的特性、信号特性とも光ディスク用基板として
の規格を十分に満足するものであった。ポリカーボネー
ト製型の代わりに、光反応硬化性樹脂をエポキシ基板と
ニッケル製スタンパーの間に展開し露光する２Ｐ製法で
作製した２Ｐ／エポキシ型を用いて微細な凹凸パターン
を転写により行った場合も、射出成形ポリオレフィン型
を用いた場合も、上記と同様の光デイスク基板として良
好な特性を有する基板が得られた。The obtained substrate satisfied the standards for an optical disk substrate in terms of groove shape uniformity, physical characteristics, mechanical characteristics, and signal characteristics. In the case of using a 2P / epoxy mold prepared by a 2P manufacturing method in which a photoreactive curable resin is spread between an epoxy substrate and a nickel stamper and exposed instead of the polycarbonate mold, a fine uneven pattern is also transferred. When the injection-molded polyolefin mold was used, a substrate having good characteristics as an optical disc substrate similar to the above was obtained.
【００２４】また、光ディスク用溝パターンの代わり
に、ピッチ１．６μｍ，高さ１１０ｎｍ、幅０．７μｍ
の微細なピットパターンを多数、半径２５ｍｍから６０
ｍｍの範囲の表面に有する外径１３０ｍｍ、厚さ１．２
ｍｍのポリカーボネート製型を用いて、ガラス基板上に
凹凸を有する膜体を形成した。上記操作により作製され
た基板を用いた読みだし専用光ディスクは、ピッチ１．
６μｍ，深さ１００ｎｍ、ピット幅０．７μｍの均一な
微細ピットパターンが基板に形成されており、低いエラ
ーレートを示し、溝形状均一性、物理的特性、機械的特
性、信号特性とも光ディスク用基板としての規格を十分
に満足するものであった。 実施例４ メチルトリエトキシシラン（ＣＨ3Ｓｉ（ＯＣ2Ｈ5）3）
０．０４モルとテトラエトキシシラン（Ｓｉ（ＯＣ
2Ｈ5）4）０．０１モルを秤量し、これに０．０５モル
のエタノールと０．２モルの水（０．１ｗｔ％のＨＣｌ
を含む）を加え、室温で３０分間攪拌したものを塗布溶
液３とした。ここで、ＨＣｌのメチルトリエトキシシラ
ンに対するモル比は、０.００２である。塗布溶液３
を、用いて実施例１及び２と同様の微細凹凸パターンを
基板上に形成した。Further, instead of the groove pattern for the optical disk, the pitch is 1.6 μm, the height is 110 nm, and the width is 0.7 μm.
Many fine pit patterns, radius 25mm to 60
Outer diameter 130 mm, thickness 1.2 on the surface in the range of mm
A film body having irregularities was formed on a glass substrate by using a polycarbonate mold of mm. The read-only optical disc using the substrate manufactured by the above operation has a pitch of 1.
A uniform fine pit pattern of 6 μm, depth of 100 nm, and pit width of 0.7 μm is formed on the substrate, showing a low error rate, and the groove shape uniformity, physical characteristics, mechanical characteristics, and signal characteristics are all substrates for optical disks. Was sufficiently satisfied. Example 4 Methyl triethoxysilane (CH 3 Si (OC 2 H 5) 3)
0.04 mol and tetraethoxysilane (Si (OC
2 H 5 ) 4 ) 0.01 mol was weighed, and 0.05 mol of ethanol and 0.2 mol of water (0.1 wt% HCl) were added to this.
Was added, and the mixture was stirred at room temperature for 30 minutes to prepare a coating solution 3. Here, the molar ratio of HCl to methyltriethoxysilane is 0.002. Coating solution 3
Was used to form a fine concavo-convex pattern similar to those in Examples 1 and 2 on the substrate.
【００２５】直径１０μｍ、高さ５μｍの半球凸パター
ン多数を有する樹脂製型を用いた場合は、直径１０μ
ｍ、深さ約４．５μｍの凹パターンがガラス基板上に形
成されていた。When a resin mold having a large number of hemispherical convex patterns having a diameter of 10 μm and a height of 5 μm is used, the diameter is 10 μm.
A concave pattern having a depth of m and a depth of about 4.5 μm was formed on the glass substrate.
【００２６】直径１０μｍの細孔を多数有する樹脂製メ
ッシュ（厚み１０μｍ）を用いた場合は、直径１０μ
ｍ、深さ約１０μｍの凸パターンが導電性透明電極付き
ガラス基板形成されていた。メチルトリエトキシシラン
にテトラエトキシシランを加えることにより、最終的に
得られる微細な凹凸パターンの屈折率が向上した。上記
塗布溶液の調製条件において、テトラエトキシシランの
代わりにチタニウムテトラメトキシド０．０１モルある
いはジルコニウムテトラメトキシド０．０１モルを加え
た場合も、良好な微細凹凸パターン付き基板が得られ
た。チタニウムテトラメトキシドを加えた場合もジルコ
ニウムテトラメトキシドを加えた場合も最終的に得られ
る微細凹凸パターンの屈折率が大きくなったが、膜体の
加熱前後の収縮量はわずかであった。 実施例５ メチルトリエトキシシラン（ＣＨ3Ｓｉ（ＯＣ2Ｈ5）3）
０．０４モルとテトラエトキシシラン（Ｓｉ（ＯＣ
2Ｈ5）4）０．０１モルを秤量し、これに０．２モルの
エタノールと０．２モルの水（０．１ｗｔ％のＨＣｌを
含む）を加え、室温で３０分間攪拌し、その後エタノー
ルをさらに０．２モル加えて５分間攪拌したものを塗布
溶液４とした。ここで、ＨＣｌのメチルトリエトキシシ
ランに対するモル比は、０.００２である。塗布溶液４
を用いて実施例３と同様の微細凹凸パターンを基板上に
形成した。ピッチ１．６μｍ，深さ１００ｎｍ、溝幅
０．５μｍの光ディスク用溝パターンを半径２５ｍｍか
ら６０ｍｍの範囲に有する外径１３０ｍｍ、厚さ１．２
ｍｍのポリカーボネート製型を用いた場合、ピッチ１．
６μｍ，深さ９０ｎｍ、峰幅０．５μｍの均一な微細溝
パターンがガラスディスク基板上に形成されていた。When a resin mesh (thickness 10 μm) having a large number of pores with a diameter of 10 μm is used, the diameter is 10 μm.
A glass substrate with a conductive transparent electrode was formed with a convex pattern of m and a depth of about 10 μm. By adding tetraethoxysilane to methyltriethoxysilane, the refractive index of the finally obtained fine concavo-convex pattern was improved. Even when 0.01 mol of titanium tetramethoxide or 0.01 mol of zirconium tetramethoxide was added in place of tetraethoxysilane under the above-mentioned conditions for preparing the coating solution, a fine patterned substrate having fine irregularities was obtained. Both when titanium tetramethoxide and zirconium tetramethoxide were added, the refractive index of the finally obtained fine concavo-convex pattern increased, but the amount of shrinkage before and after heating the film was slight. Example 5 Methyl triethoxysilane (CH 3 Si (OC 2 H 5) 3)
0.04 mol and tetraethoxysilane (Si (OC
2 H 5 ) 4 ) 0.01 mol was weighed, 0.2 mol of ethanol and 0.2 mol of water (containing 0.1 wt% HCl) were added thereto, and the mixture was stirred at room temperature for 30 minutes, then Coating solution 4 was prepared by further adding 0.2 mol of ethanol and stirring for 5 minutes. Here, the molar ratio of HCl to methyltriethoxysilane is 0.002. Coating solution 4
Using, the fine concavo-convex pattern similar to that in Example 3 was formed on the substrate. An optical disk groove pattern having a pitch of 1.6 μm, a depth of 100 nm, and a groove width of 0.5 μm in a radius of 25 mm to 60 mm, an outer diameter of 130 mm, and a thickness of 1.2.
When using a polycarbonate mold of 1 mm, the pitch is 1.
A uniform fine groove pattern of 6 μm, depth of 90 nm and peak width of 0.5 μm was formed on the glass disk substrate.
【００２７】ピッチ１．６μｍ，高さ１１０ｎｍ、幅
０．７μｍの微細ピットパターン多数を半径２５ｍｍか
ら６０ｍｍの範囲に有する外径１３０ｍｍ、厚さ１．２
ｍｍのポリカーボネート製型を用いて成形を行った場合
は、ピッチ１．６μｍ，深さ１００ｎｍ、ピット幅０．
７μｍの均一な微細ピットパターンが基板上に形成され
ていた。メチルトリエトキシシランにテトラエトキシシ
ランを加えることで、最終的に得られる凹凸パターンを
有する膜体の屈折率が向上した。An outer diameter of 130 mm and a thickness of 1.2 having a large number of fine pit patterns having a pitch of 1.6 μm, a height of 110 nm and a width of 0.7 μm within a radius of 25 mm to 60 mm.
In the case of molding using a polycarbonate mold having a diameter of 1.0 mm, the pitch is 1.6 μm, the depth is 100 nm, and the pit width is 0.
A uniform fine pit pattern of 7 μm was formed on the substrate. By adding tetraethoxysilane to methyltriethoxysilane, the refractive index of the finally obtained film body having an uneven pattern was improved.
【００２８】上記塗布溶液の調製条件において、テトラ
エトキシシランの代わりにチタニウムテトラエトキシド
０．０１モルあるいはジルコニウムテトラエトキシド
０．０１モルを加えた場合も、良好な微細凹凸パターン
付き基体が得られた。チタニウムテトラエトキシドを加
えた場合もジルコニウムテトラエトキシドを加えた場合
も最終的に得られる凹凸パターンを有する膜体の屈折率
が大きくなったが、加熱前後の収縮量はわずかであっ
た。Even when 0.01 mol of titanium tetraethoxide or 0.01 mol of zirconium tetraethoxide is added in place of tetraethoxysilane under the above-mentioned conditions for preparing the coating solution, a finely patterned substrate having fine irregularities can be obtained. It was In both cases of adding titanium tetraethoxide and zirconium tetraethoxide, the refractive index of the finally obtained film body having an uneven pattern increased, but the amount of shrinkage before and after heating was small.
【００２９】実施例４および５において、テトラエトキ
シシラン、チタニウムテトラメトキシド、ジルコニウム
テトラメトキシド、チタニウムテトラエトキシド、ジル
コニウムテトラエトキシドの化学式２で表せる金属有機
化合物を化学式１で表せる有機金属化合物であるメチル
トリエトキシシランに対するモル比をそれぞれ１より多
くすると、凹凸を有する膜体の厚みを１０μｍ以上にす
ることが困難であった。比較例１ テトラエトキシシラン（Ｓｉ（ＯＣ2Ｈ5）4）０．０５
モルを秤量し、これに０．０５モルのエタノールと０．
２モルの水（０．１ｗｔ％のＨＣｌを含む）を加え、室
温で３０分間攪拌したものを塗布溶液５とした。ここ
で、ＨＣｌのメチルトリエトキシシランに対するモル比
は、０.００２である。塗布溶液５を、ソーダ石灰ガラ
ス基板（１００ｍｍ×１００ｍｍ×２ｍｍ）上に４ｍｌ
滴下し、１ｒｐｍで基板を回転させることにより塗布膜
をガラス基板上に形成した。次いで、樹脂製型を塗布膜
に押合させようとしたところ、塗布膜にクラックが発生
し、良好なパターン成形は行えなかった。 比較例２ テトラエトキシシラン（Ｓｉ（ＯＣ2Ｈ5）4）０．０５
モルを秤量し、これに０．２モルのエタノールと０．２
モルの水（０．１ｗｔ％のＨＣｌを含む）を加え、室温
で３０分間攪拌し、その後エタノールをさらに０．２モ
ル加えて５分間攪拌したものを塗布溶液６とした。ＨＣ
ｌのメチルトリエトキシシランに対するモル比は、０．
００２である。塗布溶液６を、化学強化ガラスディスク
基板（外径１３０ｍｍ、内径１５ｍｍ、厚さ１．２ｍ
ｍ）上に４ｍｌ滴下し、エタノール雰囲気の槽内で８０
０ｒｐｍで２５秒間回転させ、基板上に塗布膜を形成し
た。次いで、ピッチ１．６μｍ，深さ１００ｎｍ、溝幅
０．５μｍの光ディスク用溝パターンを半径２５ｍｍか
ら６０ｍｍの範囲に有する外径１３０ｍｍ、厚さ１．２
ｍｍのポリカーボネート製型と、上記塗布膜を表面に形
成したガラス基板を５×１０-6Ｔｏｒｒの減圧下で５０
ｋｇｆ／ｃｍ2の圧力で押合した。その後押合体を大気
圧中に取り出して観察したところ塗布膜が硬いために、
型と塗布膜の押合が十分になされず、微細な凹凸パター
ンを有する膜体を形成することができなかった。型と塗
布膜の押合圧力を５０ｋｇｆ／ｃｍ2から２００ｋｇｆ
／ｃｍ2に増大させても、型と塗布膜の押合が十分にな
されず、凹凸パターンを塗布膜に転写することはできな
かった。 比較例３ 塗布溶液６にポリエチレングリコールを３ｇ添加したも
のを塗布溶液７とした。塗布溶液７を用いて、比較例２
と同様の凹凸パターンをガラス基板上に形成した。上記
操作により作製された光ディスク用ガラスディスク基板
をＳＴＭ（走査型透過電子顕微鏡）で観察したところ、
ピッチ１．６μｍ，深さ５０ｎｍ、峰幅０．５μｍの均
一な溝パターンが基板に形成されていた。上記光ディス
ク用ガラス基板は、溝形状均一性、物理的特性、機械的
特性、信号特性とも光ディスク用基板としての規格を満
足するものであったが、溝深さが型の溝深さの約５０％
程度になっており、また溝形状にも鈍りが観察された。
さらに膜の気孔率が高く、吸着水の量が多くなってい
た。In Examples 4 and 5, the tetraethoxysilane, titanium tetramethoxide, zirconium tetramethoxide, titanium tetraethoxide, and zirconium tetraethoxide metal organic compounds represented by the chemical formula 2 were replaced by organometallic compounds represented by the chemical formula 1. When the molar ratio to a certain methyltriethoxysilane was more than 1, it was difficult to make the thickness of the film having irregularities 10 μm or more. Comparative Example 1 Tetraethoxysilane (Si (OC 2 H 5 ) 4 ) 0.05
The moles were weighed and added to this with 0.05 mole of ethanol and 0.
Coating solution 5 was prepared by adding 2 mol of water (containing 0.1 wt% HCl) and stirring the mixture at room temperature for 30 minutes. Here, the molar ratio of HCl to methyltriethoxysilane is 0.002. 4 ml of coating solution 5 on a soda-lime glass substrate (100 mm x 100 mm x 2 mm)
A coating film was formed on the glass substrate by dropping and rotating the substrate at 1 rpm. Next, when an attempt was made to press the resin mold against the coating film, cracks were generated in the coating film and good pattern formation could not be performed. Comparative Example 2 Tetraethoxysilane (Si (OC 2 H 5 ) 4 ) 0.05
Weigh mol and add 0.2 mol of ethanol and 0.2
Molar water (containing 0.1 wt% HCl) was added, and the mixture was stirred at room temperature for 30 minutes, and then 0.2 mol of ethanol was further added and stirred for 5 minutes to obtain coating solution 6. HC
The molar ratio of 1 to methyltriethoxysilane is 0.1.
002. The coating solution 6 is a chemically strengthened glass disk substrate (outer diameter 130 mm, inner diameter 15 mm, thickness 1.2 m).
m) 4 ml was dripped on and 80 in a tank of ethanol atmosphere.
The coating film was formed on the substrate by rotating at 0 rpm for 25 seconds. Then, an optical disk groove pattern having a pitch of 1.6 μm, a depth of 100 nm and a groove width of 0.5 μm is provided in a radius of 25 mm to 60 mm, an outer diameter of 130 mm, and a thickness of 1.2.
mm polycarbonate mold and a glass substrate having the coating film formed on the surface thereof under reduced pressure of 5 × 10 −6 Torr.
They were pressed together at a pressure of kgf / cm 2 . After that, when the pressed body was taken out into the atmospheric pressure and observed, the coating film was hard,
The mold and the coating film were not pressed against each other sufficiently to form a film having a fine concavo-convex pattern. Pressing pressure between mold and coating film is 50kgf / cm 2 to 200kgf
Even if the pressure was increased to / cm 2 , the pressing force between the mold and the coating film was not sufficient, and the concavo-convex pattern could not be transferred to the coating film. Comparative Example 3 Coating solution 7 was prepared by adding 3 g of polyethylene glycol to coating solution 6. Comparative Example 2 using the coating solution 7
An uneven pattern similar to that was formed on a glass substrate. When the glass disk substrate for an optical disk manufactured by the above operation was observed with an STM (scanning transmission electron microscope),
A uniform groove pattern having a pitch of 1.6 μm, a depth of 50 nm and a peak width of 0.5 μm was formed on the substrate. The above-mentioned glass substrate for an optical disk satisfies the standards as an optical disk substrate in terms of groove shape uniformity, physical characteristics, mechanical characteristics, and signal characteristics, but the groove depth is about 50 times the groove depth of the die. %
However, the groove shape was also blunt.
Furthermore, the porosity of the membrane was high and the amount of adsorbed water was large.
【００３０】[0030]
【発明の効果】本発明によれば、微細形状でかつ表面凹
凸の深さが大きい膜体を基板上に形成することができ
る。これにより基板自体を溝加工することなく、表面に
微細な凹凸パターンを有する光デイスク用基板、液晶表
示セル用のスペーサー付き基板、回折格子や結像素子等
の光学部品を製造することができる。According to the present invention, a film body having a fine shape and a large depth of surface irregularities can be formed on a substrate. As a result, it is possible to manufacture optical components such as a substrate for an optical disc having a fine concavo-convex pattern on the surface, a substrate with a spacer for a liquid crystal display cell, a diffraction grating and an imaging element, without grooving the substrate itself.
【図１】図１（ａ）および図１（ｂ）は、それぞれ実施
例１および実施例２で得られた基板の一部断面図であ
る。1 (a) and 1 (b) are partial cross-sectional views of substrates obtained in Example 1 and Example 2, respectively.
１・・・微細な凹凸パターンを有する膜体、２・・・ガ
ラス基板、３・・・微細な凹凸パターン付き基板DESCRIPTION OF SYMBOLS 1 ... Film body having a fine uneven pattern, 2 ... Glass substrate, 3 ... Substrate with fine uneven pattern
───────────────────────────────────────────────────── フロントページの続き (72)発明者 三橋 慶喜 大阪府大阪市中央区道修町３丁目５番11号 日本板硝子株式会社内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Yoshiki Mitsuhashi 3-5-11 Doshomachi, Chuo-ku, Osaka City, Osaka Prefecture Nippon Sheet Glass Co., Ltd.
Claims (4)
有する有機樹脂製型上に、加水分解・縮重合し得る化学
式１の金属有機化合物を含む溶液を用いて塗布膜を形成
し、該基板及び該型を接合押圧して該塗布膜を該型の凹
凸パターンを有する膜体とし、その後該型を該膜体から
離型し、該膜体を加熱することにより該有機金属化合物
の縮重合体とする、基板上に微細な凹凸パターンを形成
する方法。 化学式１：ＸkＭAＲm ＭA：原子価数４の金属 Ｘ：重合可能な官能基 Ｒ：アルキル基またはアリール基 （ｋは自然数、ｍは１または２の整数で、ｋ＋ｍ＝４を
満たす）1. A coating film is formed on a substrate and / or an organic resin mold having a fine concavo-convex pattern by using a solution containing a metal organic compound of the chemical formula 1 capable of being hydrolyzed and polycondensed, and the substrate is formed. And pressing the mold to form the coating film as a film having an uneven pattern of the mold, and then releasing the mold from the film and heating the film to degenerate the organometallic compound. A method of forming a fine concavo-convex pattern on a substrate to be united. Chemical Formula 1: X k M A R m M A : Metal having a valence of 4 X: Polymerizable functional group R: Alkyl group or aryl group (k is a natural number, m is an integer of 1 or 2, and k + m = 4 Fulfill)
１の金属有機化合物を含む溶液をスクリーン印刷法によ
り塗布して凹凸パターンを有する膜体とし、その後該膜
体を加熱することにより該金属有機化合物の縮重合体と
する、基板上に微細な凹凸パターンを形成する方法。 化学式１：ＸkＭAＲm ＭA：原子価数４の金属 Ｘ：重合可能な官能基、 Ｒ：アルキル基またはアリール基 （ｋは自然数、ｍは１または２の整数で、ｋ＋ｍ＝４を
満たす）2. A solution containing a metal-organic compound of the chemical formula 1 capable of being hydrolyzed and polycondensed is applied onto a substrate by a screen printing method to form a film body having an uneven pattern, and then the film body is heated. A method of forming a fine concavo-convex pattern on a substrate, which is a condensation polymer of the metal organic compound. Chemical Formula 1: X k M A R m M A : Metal having a valence of 4 X: Polymerizable functional group, R: Alkyl group or aryl group (k is a natural number, m is an integer of 1 or 2, and k + m = 4) Meet)
徴とする請求項１または２に記載の基板上に微細な凹凸
パターンを形成する方法。3. The method for forming a fine concavo-convex pattern on a substrate according to claim 1, wherein the metal M of Chemical Formula 1 is Si.
物と化学式２の金属有機化合物を含ませ、全金属有機化
合物のうち化学式１で表せるものの割合を６０％以上と
したことを特徴とする、請求項１乃至３のいずれかの項
に記載の基板上に微細な凹凸パターンを形成する方法。 化学式２：ＭB（ＯＲ）n ＭB：価数ｎを有する金属（ｎは１〜４の整数）、 ＯＲ：アルコキシル基、（Ｒは炭素数が１〜３のアルキ
ル基）4. The solution contains the metal organic compound represented by the chemical formula 1 and the metal organic compound represented by the chemical formula 2, and the ratio of the total metal organic compound represented by the chemical formula 1 is 60% or more. A method for forming a fine concavo-convex pattern on the substrate according to any one of claims 1 to 3. Chemical formula 2: M B (OR) n M B : metal having valence n (n is an integer of 1 to 4), OR: alkoxyl group, (R is an alkyl group having 1 to 3 carbon atoms)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26575092A JP3381945B2 (en) | 1992-10-05 | 1992-10-05 | Method of forming fine uneven pattern on substrate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26575092A JP3381945B2 (en) | 1992-10-05 | 1992-10-05 | Method of forming fine uneven pattern on substrate |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2002281332A Division JP2003227915A (en) | 2002-09-26 | 2002-09-26 | Method for forming fine rugged pattern on substrate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06114334A true JPH06114334A (en) | 1994-04-26 |
| JP3381945B2 JP3381945B2 (en) | 2003-03-04 |
Family
ID=17421489
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|---|---|---|---|
| JP26575092A Expired - Fee Related JP3381945B2 (en) | 1992-10-05 | 1992-10-05 | Method of forming fine uneven pattern on substrate |
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| JP (1) | JP3381945B2 (en) |
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| JP2002542021A (en) * | 1999-04-16 | 2002-12-10 | インスティトゥート フィア ノイエ マテリアーリエン ゲマインニュッツィゲ ゲゼルシャフト ミット ベシュレンクタ ハフトゥンク | Substrate having a microstructured surface, method of making the same and use thereof |
| US6849209B2 (en) | 2000-02-25 | 2005-02-01 | Nippon Sheet Glass Co., Ltd. | Article having predetermined surface shape and method for production thereof |
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|---|---|---|---|---|
| JP2002542021A (en) * | 1999-04-16 | 2002-12-10 | インスティトゥート フィア ノイエ マテリアーリエン ゲマインニュッツィゲ ゲゼルシャフト ミット ベシュレンクタ ハフトゥンク | Substrate having a microstructured surface, method of making the same and use thereof |
| US6849209B2 (en) | 2000-02-25 | 2005-02-01 | Nippon Sheet Glass Co., Ltd. | Article having predetermined surface shape and method for production thereof |
| WO2002068183A1 (en) * | 2001-02-28 | 2002-09-06 | Nippon Sheet Glass Co., Ltd. | Article having predetermined surface shape and method for preparation thereof |
| US6849350B2 (en) | 2001-02-28 | 2005-02-01 | Nippon Sheet Glass Co., Ltd. | Article having a predetermined surface shape and method for preparation thereof |
| JP2006168147A (en) * | 2004-12-15 | 2006-06-29 | Aitesu:Kk | Manufacturing method of fine structure using organic/inorganic hybrid material and nano-imprinting technique and fine structure |
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| WO2008010330A1 (en) * | 2006-07-21 | 2008-01-24 | Nippon Sheet Glass Company, Limited | Transfer mold, method for manufacturing transfer mold, and method for manufacturing transferred product using the transfer mold |
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| JP2010052408A (en) * | 2008-08-30 | 2010-03-11 | Nagaoka Univ Of Technology | Ceramic calcined body with fine uneven pattern on surface and method for manufacturing the same |
| JP2012099731A (en) * | 2010-11-04 | 2012-05-24 | Ulvac Japan Ltd | Method of manufacturing substrate |
| JP2013042124A (en) * | 2011-07-19 | 2013-02-28 | Tokuyama Corp | Pattern manufacturing method using photocurable nanoimprint composition |
| WO2015011980A1 (en) * | 2013-07-26 | 2015-01-29 | Ｊｘ日鉱日石エネルギー株式会社 | Method for manufacturing substrate having textured structure |
| JPWO2015011980A1 (en) * | 2013-07-26 | 2017-03-02 | Ｊｘエネルギー株式会社 | Manufacturing method of substrate having concavo-convex structure |
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