JP2004059953A - Anti-fouling film, anti-fouling reflection-preventive film, and image display device using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an anti-fouling film of excellent film hardness and anti-fouling property and a manufacturing method thereof, to provide a product free from any damages on a plastic film as a base material or any damages on a lower layer thereof if the anti-fouling film is a highest layer, and to provide a method for prolonging the continuous operational time of a manufacturing apparatus thereof. <P>SOLUTION: This film is manufactured by using a chemical vapor deposition (CVD) method for silane compound under the atmosphere containing gaseous hydrogen with the silane compound having both a hydrolytic group and an alkyl group for raw materials. The ratio of silicon, oxygen, and carbon in the anti-fouling film is Si : O : C = 1 : (1.0-1.9) : (0.2-2.0). <P>COPYRIGHT: (C)2004,JPO

Description

上記組成物を撹拌しながら、超音波分散した。
【０１１４】
これを基材試料２とする。
３．反射防止層の設置「塗布法」
中屈折率層の設置
前記基材フィルムのハードコート層の上に、下記中屈折率層組成物Ｍ−１を押し出しコーターで塗布し、８０℃で５分間乾燥させた後、高圧水銀ランプ（８０Ｗ）を用いて紫外線を１７５ｍＪ／ｃｍ^２照射して硬化させ、中屈折率層を有する中屈折率層フィルム１を作製した。
【０１１５】

なお、この中屈折率層フィルムの中屈折率層の厚さは７８ｎｍで、屈折率は１．７０であった。
【０１１６】
高屈折率層の設置
前記中屈折率層フィルム１の上に、下記高屈折率層組成物Ｈ−１を押し出しコーターで塗布し、８０℃で５分間乾燥させた後、高圧水銀ランプ（８０Ｗ）を用いて紫外線を１７５ｍＪ／ｃｍ^２照射して硬化させ、中屈折率層＋高屈折率層を有する基材試料３を作製した。
【０１１７】

なお、この高屈折率層フィルムの高屈折率層の厚さは６６ｎｍで、屈折率は１．８５であった。
【０１１８】
低屈折率層の設置
前記高屈折率層の上に、下記低屈折率層組成物Ｌ−１を押し出しコーターで塗布し、８０℃で５分間乾燥させた後、更に１２０℃で５分間熱硬化させ、さらに紫外線を１７５ｍＪ／ｃｍ^２照射して硬化させ、低屈折率層を有する低反射積層体を作製した。
【０１１９】
〈テトラエトキシシラン加水分解物Ａの調製〉
テトラエトキシシラン３００ｇとエタノール４５５ｇを混合し、これに１．０質量％クエン酸水溶液２９５ｇを添加した後に、室温にて１時間攪拌することでテトラエトキシシラン加水分解物Ａを調製した。
【０１２０】

なお、この低屈折率層フィルムの低屈折率層の厚さは９５ｎｍで、屈折率は１．４５であった。
【０１２１】
これを基材試料４とする。
４．反射防止層の設置「大気圧プラズマ法」
上記ハードコート層を設置した基材（基材試料２）の上に、大気圧プラズマ法により下記の反射防止層の設置を行い、基材試料５〜８を得た。
【０１２２】
高屈折率層＋低屈折率層＋高屈折率層＋低屈折率層・・・・基材試料５
高屈折率層＋後記防汚層２＋高屈折率層・・・・・・・・・基材試料６
高屈折率層＋低屈折率層＋高屈折率層・・・・・・・・・・基材試料７
高屈折率層＋中屈折率層・・・・・・・・・・・・・・・・基材試料８
（高屈折率層）
ガス１・・・アルゴン（９８．９体積％）
ガス２・・・水素（１．００体積％）
ガス３・・・テトライソプロポキシチタン（０．１体積％）
上記「％」は、混合ガス全体に対する体積％
上記ガス１〜３を放電空間直前で均一に混合させて反応ガスとした。
【０１２３】
ガス３はリンテック社製気化器にてアルゴンガスに混合して気化した。
（低屈折率層）
ガス１・・・アルゴン（９８．９０％）
ガス２・・・酸素（１．００％）
ガス３・・・メチルトリエトキシシラン（０．１０％）
上記ガス１〜３を放電空間直前で均一に混合させて反応ガスとした。
【０１２４】
ガス３はリンテック社製気化器にてアルゴンガスに混合して気化した。
（中屈折率層）
ガス１・・・アルゴン（９８．９０％）
ガス２・・・酸素（１．００％）
ガス３・・・二酢酸ジ−ｎ−ブチル錫（０．１０％）
ガス３はリンテック社製気化器にてアルゴンガスに混合して気化した。
【０１２５】
フィルム基材２
ゼオノア（日本ゼオン社製）のフィルム基材で、これを基材試料９とする。
【０１２６】
〔２〕防汚膜の作製
（１）実験１
基材試料５を用いて、その上に防汚膜を成膜した。
【０１２７】
防汚膜は図６に示す如きプラズマ放電処理装置（パール工業社製）を用い、１３．５６ＭＨｚとし、放電出力は表１中に記載した。
【０１２８】
ガス組成
アルゴン、水素、メチルトリエトキシシラン蒸気を用い、その組成比は表１中に記した。
【０１２９】
上記ガス１〜３を放電空間直前で均一に混合させ反応ガスとした。
処理時間
プラズマに曝されている時間・・・３分間
作製した防汚膜試料と特性
下記表１の如く、製膜時条件をコントロールして防汚膜中のＳｉ：Ｏ：Ｃ比を変えたものを作製した。
【０１３０】
【表１】

【０１３１】
特性評価は下記の如く行った。
（接触角）
協和界面化学株式会社製接触角計ＣＡ−Ｘ型を用いて純水、ジヨードメタンの接触角を液滴径１．５ｍｍにて測定した。作製したフィルムを用いて液晶表示装置を作製し、指紋をつけ、ベンコットで拭き取ったあとの接触角（純水）も同様に測定した。
【０１３２】
（耐傷性）
２２ｍｍ角に切断し５００ｇの重りを載せたボンスター＃００００のスチールウールを用い、試料表面を１０回擦って、発生する傷を目視で数える。
【０１３３】
評価基準
Ａ：０本
Ｂ：１〜５本未満
Ｃ：５〜１０本未満
Ｄ：１０〜２０本未満
Ｅ：２０本以上
（ヘイズ）
ＪＩＳ　Ｋ７１０５に準拠し、ヘイズメーターＭＯＤＥＬ　１００１ＤＰ（日本電色工業社製）を用いて、異なる１０箇所を測定した平均値を値とした。
【０１３４】
（装置稼働時間）
膜面に目視で判別できる異物が５個／１００ｃｍ^２以上出現するまでの時間であり、成膜装置の清掃が必要となるまでの時間である。
【０１３５】
尚、膜中のＳｉ：Ｏ：Ｃの比の測定方法は、前記「発明の実施の形態」中に記した方法を用いた。
【０１３６】
（屈折率）
大塚電子社製反射率分光計Ｆｅ３０００により、正反射の状態から５度傾けた条件で４００〜７００ｎｍの範囲の波長（λ）について反射率を測定した。λ／４の値より光学的に膜厚を算出し、これを基に屈折率を算出した。
【０１３７】
本測定では、波長５５０ｎｍでの値を屈折率として表示した。
【０１３８】
【表２】

【０１３９】
接触角１：純水の接触角
接触角２：ジヨードメタンの接触角
接触角３：拭き取ったあとの純水の接触角
表２より明らかな如く、本発明内の実験番号１−２、１−３及び１−６、１−７は全ての評価で良好な結果が得えられた。
（２）実験２
図８に示す如き大気圧プラズマ放電処理装置を用い、実験１と同様な実験を行った。
【０１４０】
出力密度：第１電極側　１．０Ｗ／ｃｍ^２
第２電極側　３．３Ｗ／ｃｍ^２
尚、膜中の組成を変化させるため条件を変える必要がある場合には、第１電極側は１．０Ｗ／ｃｍ^２に固定し、第２電極側の放電出力を変化させた。この場合、第２電極側は表１の放電出力と同じとした。
【０１４１】
プラズマに曝されている時間・・・３分間
ガス１・・・窒素（９８．９０体積％）
ガス２・・・水素（１．００体積％）
ガス３・・・メチルトリエトキシシラン（０．１０体積％）
ガス組成は、基本的には上記のものを用い、実験１と同様な膜組成となるように、各組成を変量した。
【０１４２】
メチルトリエトキシシランはリンテック社製気化器にて窒素ガスに混合して気化した。
【０１４３】
【表３】

【０１４４】
接触角１：純水の接触角
接触角２：ジヨードメタンの接触角
接触角３：拭き取ったあとの純水の接触角
実験１と同様に、本発明内の実験番号２−２、２−３及び２−６、２−７は全ての評価で良好な結果が得えられた。
（３）実験３
基材試料１〜８を用いて、その上に装置１、２又は３を用いて防汚膜を成膜した。
【０１４５】
装置１
図６に示す如きプラズマ放電処理装置（パール工業社製）を用い、１３．５６ＭＨｚ、放電出力３．３Ｗ／ｃｍ^２にて行った。
【０１４６】
ガス組成
ガス１：・・・アルゴン（９９．００体積％）
ガス２：・・・水素（０．９０体積％）
ガス３：・・・メチルトリエトキシシラン蒸気（０．１０体積％）
上記ガス１〜３を放電空間直前で均一に混合させ反応ガスとした。
【０１４７】
処理時間
プラズマに曝されている時間・・・３分間
尚、表４中、３−４だけはプラズマに曝されている時間を１５秒とした。
【０１４８】
装置２
図８に示す如き大気圧プラズマ放電処理装置を用いた。
【０１４９】
出力密度：第１電極側　１．０Ｗ／ｃｍ^２
第２電極側　３．３Ｗ／ｃｍ^２
尚、膜中の組成を変化させるため条件を変える必要がある場合には、第１電極側は１．０Ｗ／ｃｍ^２に固定し、第２電極側の放電出力を変化させた。
【０１５０】
プラズマに曝されている時間・・・３分間
ガス１・・・窒素（９８．９０体積％）
ガス２・・・水素（１．００体積％）
ガス３・・・メチルトリエトキシシラン（０．１０体積％）
メチルトリエトキシシランはリンテック社製気化器にて窒素ガスに混合して気化した。
【０１５１】
装置３
図９に概略図を示すごとき触媒化学蒸着法の装置を用いた。
【０１５２】
使用原料・・・ジメチルジエトキシシラン
１００ｃｍ^２当たり１ｍの長さのイリジウム線を張り１４００度に熱し、水素を４ＳＬＭ（Ｓｔａｎｄａｒｄ　ｌｉｔｔｅｒ　ｐｅｒ　ｍｉｎｕｔｅ）通し、０．５ＳＬＭのアルゴンと０．００５ＳＬＭで送った原料ガスと混合させて基材上に当たるように流す。
【０１５３】
図９中、２０１は基材Ｆの搬入搬出口、２０２がシャワーヘット、２０３がイリジウム線（又はタングステン線）ホットワイヤー、２０４が原料ガス供給口である。
【０１５４】
比較例
本発明外の比較例として、上記ガス組成において、水素ガスを酸素ガスで置き換えたものを造った。
【０１５５】
作製した防汚膜試料と特性
評価方法等は実験１と同様に行い、下記表４の如き結果を得た。
【０１５６】
【表４】

【０１５７】
接触角１：純水の接触角
接触角２：ジヨードメタンの接触角
接触角３：拭き取ったあとの純水の接触角
本発明内の試料番号３−１〜３−１１のものは、皆良好な結果を有するのに対し、本発明外の試料番号３−１２〜３−２２のものは、問題のある特性しか得られないことがわかる。
【０１５８】
【発明の効果】
本発明により、膜の硬度と防汚性が共に良い防汚膜とその製造方法を提供することができ、基材としてのプラスチックフィルムへのダメージや、反射防止膜の最上層とした場合には、その下層へのダメージがない製品を提供することが出来、しかもその製造装置の連続稼働時間を長くすることが出来る。
【図面の簡単な説明】
【図１】プラズマ放電処理容器の一例を示す概念図。
【図２】プラズマ放電処理容器の他の例を示す概略図。
【図３】円筒型のロール電極の一例を示す概略斜視図。
【図４】円筒型の固定電極の一例を示す概略斜視図。
【図５】角柱型の固定電極の一例を示す概略斜視図。
【図６】プラズマ放電処理装置の一例を示す概念図。
【図７】プラズマ放電処理装置の他の例を示す概略図。
【図８】大気圧プラズマ放電処理装置の一例を示した概略図。
【図９】触媒化学蒸着法の装置の概略図。
【符号の説明】
１０　プラズマ放電処理装置
２０　プラズマ放電処理容器
２１　ロール電極
２１ａ、２１Ａ　導電性母材
２１ｂ、２１Ｂ　セラミック被覆処理誘電体
２２、２９　固定電極
２３ａ、２３ｂ　ニップローラ
２４、２５　ガイドローラ
２６　仕切板
２７　給気口
２８　排気口
４０　ガス発生装置
５０　電源
７０　電極恒温ユニット
１０１　高周波電源
１０２　低周波電源
１０３　平板型の電極
１０４ａ、１０４ｂ　角型棒状の電極
Ｆ　基材[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to an antifouling film, an antifouling antireflection film, and an image display device using the same.
[0002]
[Prior art]
Various antifouling technologies have been proposed so that dust or dirt that impairs visibility is easily attached to or removed from the surface of transparent materials such as image display devices such as CRTs and liquid crystal displays, solar cells, and window glasses. Have been.
[0003]
For example, as described in JP-A-2-36921, there is disclosed a method of coating an anti-reflection film with a silanol-terminated organic polysiloxane on the surface to improve the antifouling property on the surface.
[0004]
Although such a film is produced by coating, it is difficult to produce the film because of problems such as inability to apply uniformly depending on the shape and material of the substrate, damage to the substrate by a coating solution, or repelling of the substrate. Was often the case.
[0005]
In addition, when a chemical vapor deposition (CVD) method is used, the plasma CVD method causes plasma damage to the base material, and impairs the transparency of the base material so that desired physical properties cannot be obtained. In the catalytic CVD method, there is a problem that the reaction gas is damaged on the catalyst wire and it is difficult to form a film for a long time.
[0006]
[Problems to be solved by the invention]
An object of the present invention is to provide an antifouling film having both good hardness and antifouling property and a method for producing the same, and damage to a plastic film as a base material, and when the uppermost layer of an antireflection film is used, It is an object of the present invention to provide a method that can provide a product having no damage to the lower layer and can prolong the continuous operation time of the manufacturing apparatus.
[0007]
[Means for Solving the Problems]
The present inventors have made intensive studies and as a result, the object of the present invention has been achieved by adopting one of the following constitutions.
[0008]
[1] A film formed by using a silane compound having both a hydrolyzable group and an alkyl group as a raw material and using a chemical vapor deposition (CVD) method in an atmosphere containing hydrogen gas, wherein silicon, oxygen, An antifouling membrane having a carbon ratio of Si: O: C = 1: (1.0-1.9) :( 0.2-2.0).
[0009]
[2] {characterized by that the ratio of silicon, oxygen and carbon in the film is Si: O: C = 1: (1.0-1.5) :( 0.2-1.5) [1] ] The antifouling film according to the above.
[0010]
[3] The antifouling membrane according to [1] or [2], wherein the hydrolyzable group in the silane compound is an alkoxy group.
[0011]
[4] The antifouling film according to [1], [2] or [3], wherein the alkyl group in the silane compound is a methyl group.
[0012]
[5] The antifouling film according to any one of [1] to [4], wherein the alkoxy group in the silane compound is an ethoxy group.
[0013]
[6] The antifouling film according to any one of [1] to [5], which is produced by an atmospheric pressure plasma chemical vapor deposition method.
[0014]
[7] The antifouling film according to any one of [1] to [5], which is produced by a catalytic chemical vapor deposition method.
[0015]
[8] The film according to any one of [1] to [7], wherein the film is formed on a transparent plastic substrate or on a plastic substrate on which a transparent actinic radiation-curable resin layer (CHC layer) is provided. The antifouling film according to the above.
[0016]
[9] An antifouling antireflection film having the antifouling film according to any one of [1] to [7] on the outermost surface.
[0017]
[10] In an antireflection film composed of two or more layers having different refractive indices, the antifouling film according to any one of [1] to [7] can be used as an antireflection film having a low refractive index of 1.35 to 1.50. An antifouling antireflection film, wherein the antireflection film is used as an outermost surface layer as a refractive index layer.
[0018]
[11] An antifouling antireflection film, wherein the antifouling antireflection film according to [9] or [10] is entirely manufactured by atmospheric pressure plasma-enhanced chemical vapor deposition.
[0019]
[12] An image display device, wherein the antifouling antireflection film according to any one of [9] to [11] is provided on the outermost surface.
[0020]
Incidentally, [1] to [5] relate to a technique for developing antifouling properties, having a required film hardness, and not damaging the base material or the device.
[0021]
[6] discloses that an atmospheric pressure plasma CVD method, which is preferable as the CVD method, is used.
[0022]
[7] discloses the use of a catalytic CVD method as a method for further suppressing damage to a substrate among CVD methods.
[0023]
[8] relates to an antifouling transparent plastic substrate and an antifouling transparent plastic substrate provided with a hard coat, using the method described above.
[0024]
[9] relates to an antifouling antireflection film having an antifouling property imparted to the outermost surface of the antireflection film using the method described above.
[0025]
[10] relates to an antifouling antireflection film produced by utilizing the fact that the film produced by the method described above has a low refractive index.
[0026]
[11] relates to an antifouling antireflection film in which all the layers of the antireflection film are manufactured by using the atmospheric pressure plasma CVD method.
[0027]
[12] relates to an image display device manufactured using the above method, and is preferably a liquid crystal display device, an electroluminescent display device, or a plasma display panel.
[0028]
BEST MODE FOR CARRYING OUT THE INVENTION
Embodiments of the present invention will be further described.
[0029]
(Silane compound having both a hydrolyzable group and an alkyl group)
In order to polymerize a silane compound using a chemical vapor deposition method to form a solid film, the raw material compound needs to have a hydrolyzable functional group (hydrolyzable group). The hydrolyzable group refers to a functional group that can be polymerized by adding water and hydrogen, and is not particularly limited in the present invention, but preferably includes an alkoxy group and an acetyl group. An alkoxy group is preferable, and an ethoxy group is more preferable in terms of reactivity and physical properties of raw materials. However, only by polymerization using such a hydrolyzable group, only silicon oxide is formed, and such a film does not exhibit antifouling properties.
[0030]
In order to exhibit antifouling properties, it is particularly effective to have an alkyl group on the outermost surface of the film, and this object is achieved by using a material having an alkyl group as a raw material. The alkyl group may be a fluoroalkyl group or an alkyl group composed of only carbon and hydrogen, but is preferably an alkyl group composed of only carbon and hydrogen from the viewpoint of environmental suitability after decomposition. It is important that the alkyl group be low in price and maintain the hardness of the film. In this sense, an alkyl group is preferably an ethyl group or a methyl group, and more preferably a methyl group. Further, as long as the above functional group is provided, the compound may contain a plurality of silicon atoms.
[0031]
Preferred compounds corresponding to these conditions include methyltriethoxysilane, dimethyldiethoxysilane, trimethylethoxysilane, ethyltriethoxysilane, diethyldiethoxysilane, triethylethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, and decyltriethoxysilane. Methoxysilane, trifluoropropyltrimethoxysilane and the like can be mentioned, and methyltriethoxysilane and dimethyldiethoxysilane are preferable.
[0032]
[Production of film by chemical vapor deposition (CVD) method]
According to the study of the present inventors, in order to manufacture an antifouling film by a CVD method using such a material, it is necessary to introduce hydrogen into the reaction space. The amount of hydrogen input is required to be at least 0.02% by volume or more of the total amount of the reaction gas including hydrogen gas, and preferably 0.05% by volume. The upper limit may be in a range where vapor deposition or plasma generation is possible, and is preferably 5% by volume or less.
[0033]
The method for introducing hydrogen is not particularly limited in the present invention, but it is preferable to use an apparatus that does not mix with the above-mentioned raw material compounds until they reach the reaction space. Further, a gas other than hydrogen may be contained in the reaction space. However, by using the above-described raw material compound, a desired film can be formed only from the substance in the raw material and the added hydrogen.
[0034]
As a condition for satisfying both the antifouling property and the film hardness of the film produced under such conditions, the ratio of silicon, oxygen, and carbon in the film is as follows: Si: O: C = 1: (1.0 to 1.9). ): (0.2-2.0), preferably Si: O: C = 1: (1.0-1.5) :( 0.2-1.5) is there. When the carbon content is large, the antifouling property is improved, but the film hardness is reduced. Further, when the oxygen content is large, the transmittance of the film is improved and the film hardness is also improved, but the antifouling property is reduced.
[0035]
How to measure silicon, oxygen and carbon content
The silicon, oxygen and carbon contents of the antifouling film of the present invention are measured using an XPS surface analyzer. The XPS surface analyzer is not particularly limited, and any model can be used. In the present invention, ESCALAB-200R manufactured by VG Scientific Inc. was used. The measurement was performed at an output of 600 W (acceleration voltage 15 kV, emission current 40 mA) using Mg as the X-ray anode. The energy resolution was set to be 1.5 to 1.7 eV when defined by the half width of the clean Ag3d5 / 2 peak. Before performing the measurement, it is necessary to etch away a surface layer corresponding to a thickness of 10 to 20% of the film thickness in order to remove the influence of contamination. For removing the surface layer, it is preferable to use an ion gun that can use rare gas ions, and He, Ne, Ar, Xe, Kr, or the like can be used as the ion species.
[0036]
In this measurement, the surface layer was removed using Ar ion etching. First, the range of the binding energy from 0 eV to 1100 eV was measured at a data acquisition interval of 1.0 eV to find out what element was detected. Next, with respect to all the detected elements except for the etching ion species, the data capturing interval was set to 0.2 eV, and a narrow scan was performed for the photoelectron peak giving the maximum intensity, and the spectrum of each element was measured.
[0037]
The obtained spectrum is COMMON DATA PROCESSING SYSTEM (Ver. 2.3 or later is preferable) manufactured by VAMAS-SCA-JAPAN in order to prevent the difference in the content calculation result due to the difference in the measurement device or computer. After the above transfer, the same software was used to perform processing, and the value of each elemental content was determined as the atomic concentration (atomic concentration). Before performing the quantitative processing, a calibration of Count @ Scale was performed for each element, and a 5-point smoothing processing was performed. In the quantitative processing, the peak area intensity (cps * eV) from which the background was removed was used. For the background treatment, a method according to Shirley was used. For the Shirley method, see D.S. A. Shirley, Phys. Rev .. , B5, 4709 (1972).
[0038]
There is a preferable atmospheric pressure plasma CVD method as the CVD method. Regarding the amount of hydrogen gas added as the production condition, it was found that the appropriate ranges of the minimum amount for accelerating the reaction and the maximum amount of hydrogen gas added so as not to adversely affect the discharge were as described above.
[0039]
Among the CVD methods, a catalytic CVD method is preferably used as a method for further suppressing damage to the base material. In this case as well, the amount of hydrogen gas added is at least 0.001% by volume or more of the total amount of reaction gas including hydrogen gas, and the upper limit is vapor deposition in order not to impair the physical properties of the film. It is good to manufacture in an atmosphere in which 5% by volume or less is present.
[0040]
Here, the catalytic CVD method refers to a method in which a gas is brought into contact with a wire catalyst heated to 1000 ° C. or higher to form an active species, and the raw material is decomposed by the active species. In this case, it is preferable to use tungsten or iridium as the wire catalyst, but there is no particular limitation. The raw material silane compound gas is preferably not in contact with the wire as much as possible, but even if it does, there is no problem if the number of hydrolyzable groups in the silane compound is 2 or less, and the raw material is preferable.
[0041]
A plastic (synthetic resin) film having an antifouling film prepared by using the above-described method is preferable as an antifouling transparent plastic film or an antifouling transparent plastic film with a hard coat.
[0042]
Further, an antifouling antireflection film having antifouling properties imparted to the outermost surface of the antireflection film using the above-described method can be obtained, and such an antireflection film having good antifouling properties can be obtained. . Further, since the film produced by using the above-mentioned method has a low refractive index, the antifouling antireflection film produced by using the film as the uppermost layer has good antireflection properties.
[0043]
In this case, an antifouling antireflection film in which all the layers of the antireflection film are manufactured by using the atmospheric pressure plasma CVD method has high productivity and is therefore advantageous in terms of cost and is therefore preferable.
[0044]
Since the antifouling antireflection film produced as described above has good characteristics and can be practically used in terms of cost, it can be used for an image display device, specifically, a liquid crystal display device, an electroluminescent display device, and a plasma display. It can be preferably applied to panels and the like.
[0045]
[Plasma discharge treatment device]
FIG. 1 is a conceptual diagram showing an example of a plasma discharge processing container 20 used in a plasma discharge processing apparatus 10. In a slightly different embodiment, the plasma discharge processing container 20 shown in FIG. 2 is used.
[0046]
In FIG. 1, a long film-shaped substrate F is transported while being wound around a roll electrode 21 rotating in a transport direction (clockwise in the figure). The fixed electrode 22 is composed of a plurality of cylinders and is installed so as to face the roll electrode 21. The substrate F wound around the roll electrode 21 is pressed by the nip rollers 23a and 23b, regulated by guide rollers 24, transported to a discharge processing space secured by the plasma discharge processing container 20, and subjected to discharge plasma processing. Is conveyed to the next step via the guide roller 25. Further, the partition plate 26 is arranged close to the nip roller 23b, and suppresses the air accompanying the substrate F from entering the plasma discharge processing container 20.
[0047]
The entrained air is preferably suppressed to 1% by volume or less with respect to the total volume of the gas in the plasma discharge processing container 20, and this can be achieved by the nip roller 23b.
[0048]
Note that a mixed gas (an inert gas and an organic gas containing a reactive gas such as an organic fluorine compound, a titanium compound, or a silicon compound) used for the discharge plasma treatment is supplied from the air supply port 27 to the plasma discharge treatment container 20. The gas introduced and processed is exhausted from the exhaust port 28.
[0049]
FIG. 2 is a schematic view showing another example of the plasma discharge processing container 20 as described above. In the plasma discharge processing container 20 of FIG. 1, a cylindrical fixed electrode 22 is used. In the plasma discharge processing container 20 shown in FIG. 1, a prismatic fixed electrode 29 is used.
[0050]
Compared with the columnar fixed electrode 22 shown in FIG. 1, the prismatic fixed electrode 29 shown in FIG. 2 is preferably used in the thin film forming method of the present invention.
[0051]
FIGS. 3A and 3B are schematic perspective views showing an example of the cylindrical roll electrode 21 described above, and FIGS. 4A and 4B are schematic perspective views showing an example of the cylindrical fixed electrode 22. FIGS. 5A and 5B are schematic perspective views showing an example of the prismatic fixed electrode 29. FIG.
[0052]
In FIG. 3A, a roll electrode 21 serving as a ground electrode is formed by spraying ceramic onto a conductive base material 21a such as a metal, and then coating a ceramic-coated dielectric 21b which is sealed with an inorganic material. It is composed of The dielectric material 21b with a ceramic coating is coated with 1 mm of one side, and the roll diameter is made to be 200 mm after coating, and grounded to earth.
[0053]
Further, as shown in FIG. 3 (b), the roll electrode 21 may be formed by combining a conductive base material 21A such as a metal with a ceramic-coated dielectric material 21B provided with an inorganic material by lining. As the lining material, silicate glass, borate glass, phosphate glass, germanate glass, tellurite glass, aluminate glass, vanadate glass and the like are preferably used. Of these, borate glass is more preferably used because it is easy to process. Examples of the conductive base materials 21a and 21A such as metals include metals such as titanium, silver, platinum, stainless steel, aluminum, and iron, and stainless steel or titanium is preferable from the viewpoint of processing. As the ceramic material used for thermal spraying, alumina and silicon nitride are preferably used. Among them, alumina is more preferably used because it is easy to process.
[0054]
In the present embodiment, as the conductive base materials 21a and 21A of the roll electrode, a stainless steel jacket roll base material having a constant temperature means using a liquid is used (not shown).
[0055]
FIGS. 4A and 4B and FIGS. 5A and 5B include a fixed electrode 22 and a fixed electrode 29 which are application electrodes, and are configured in the same combination as the roll electrode 21 described above. .
[0056]
The power source for applying a voltage to the application electrode is not particularly limited, but is a high frequency power source manufactured by Pearl Industries (200 kHz), a high frequency power source manufactured by Pearl Industries (800 kHz), a high frequency power source manufactured by JEOL (13.56 MHz), and a high frequency power source manufactured by Pearl Industries A power supply (150 MHz), a high frequency power supply (2 MHz) manufactured by Pearl Industries, and the like can be used.
[0057]
FIG. 6 is a conceptual diagram illustrating an example of the plasma discharge processing apparatus 10 used in the present invention.
[0058]
6, the portion of the plasma discharge processing container 20 is the same as that shown in FIG. 2, but further includes a gas generator 40, a power supply 50, an electrode constant temperature unit 70, and the like. As a thermostat for the electrode thermostat unit 70, an insulating material such as distilled water or oil is used.
[0059]
The electrodes shown in FIG. 6 are the same as those shown in FIGS. 3 and 5, and the gap between the facing electrodes is set to, for example, about 1 mm.
[0060]
The distance between the electrodes is determined in consideration of the thickness of the solid dielectric placed on the base material of the electrode, the magnitude of the applied voltage, the purpose of using plasma, and the like. The shortest distance between the solid dielectric and the electrode when a solid dielectric is installed on one of the electrodes, and the shortest distance between the solid dielectrics when the solid dielectric is installed on both of the electrodes is uniform in each case. From the viewpoint of performing a proper discharge, the thickness is preferably 0.5 mm to 20 mm, particularly preferably 1 mm ± 0.5 mm.
[0061]
The roll electrode 21 and the fixed electrode 29 are arranged at predetermined positions in the plasma discharge processing container 20, the flow rate of the mixed gas generated by the gas generator 40 is controlled, and the plasma is supplied from the air supply port 27 through the gas filling means 41. The inside of the plasma discharge processing container 20 is filled with a mixed gas used for plasma processing, and the inside of the plasma discharge processing container 20 is exhausted through an exhaust port 28. Next, a voltage is applied to the electrodes by the power supply 50, the roll electrode 21 is grounded to ground, and discharge plasma is generated. Here, the base material F is supplied from the roll-shaped original winding base material 60, and the electrodes in the plasma discharge processing container 20 are in one-side contact (contact with the roll electrode 21) via the guide roller 24. Conveyed. Then, the surface of the base material F is formed by discharge plasma during transport, and a thin film containing an inorganic substance derived from the reactive gas in the mixed gas is formed on the surface. Conveyed. Here, the film is formed only on the surface of the substrate F that is not in contact with the roll electrode 21.
[0062]
The value of the voltage applied to the fixed electrode 29 from the power supply 50 is appropriately determined. For example, the voltage is about 0.5 to 10 kV, and the power supply frequency is adjusted to more than 1 kHz and 150 MHz or less. Regarding the method of applying power, either a continuous sine-wave continuous oscillation mode called a continuous mode or an intermittent oscillation mode in which ON / OFF is intermittently called a pulse mode may be adopted.
[0063]
Although the discharge output depends on the shape of the device, it is preferably 1 W / cm.²5.0 / cm or more²The following discharge density is good.
[0064]
The above is the case where argon, helium, or the like is used. When nitrogen gas is used as the discharge gas, the discharge condition is such that a high-frequency voltage is applied to the discharge space between the opposed first and second electrodes, Is the first frequency ω₁And the first frequency ω₁Higher second frequency ω₂At least a component obtained by superimposing the voltage component of
[0065]
High frequency refers to one having a frequency of at least 0.5 kHz.
The high-frequency voltage has a first frequency ω₁And the first frequency ω₁Higher second frequency ω₂And a waveform component having a frequency ω₁Higher frequency ω on the sine wave of₂Ω with the sine wave of₁Becomes a jagged waveform.
[0066]
In the present invention, the discharge starting voltage refers to a minimum voltage at which a discharge can be caused in a discharge space (such as a configuration of an electrode) and a reaction condition (such as a gas condition) used in an actual thin film forming method. Although the discharge starting voltage varies somewhat depending on the type of gas supplied to the discharge space, the type of dielectric material of the electrode, and the like, it may be considered that the discharge starting voltage is substantially the same as the discharge starting voltage of the discharge gas alone.
[0067]
It is presumed that by applying the high-frequency voltage as described above between the counter electrodes (discharge space), a discharge capable of forming a thin film is generated, and high-density plasma necessary for forming a high-quality thin film can be generated. You. What is important here is that such a high-frequency voltage is applied to each of the opposing electrodes, that is, to the same discharge space from both. The thin film formation of the present invention cannot be achieved by a method in which two application electrodes are juxtaposed and high frequency voltages of different frequencies are applied to different discharge spaces separated from each other.
[0068]
Although superposition of the sine wave has been described above, the present invention is not limited to this, and both may be pulse waves, one may be a sine wave and the other may be a pulse wave. Further, it may have a third voltage component.
[0069]
As a specific method of applying the high frequency voltage of the present invention between the counter electrodes (the same discharge space), a frequency ω is applied to the first electrode constituting the counter electrode.₁And the voltage V₁Is connected to a first power supply for applying a first high-frequency voltage, and a frequency ω is applied to the second electrode.₂And the voltage V₂Is an atmospheric pressure plasma discharge processing apparatus to which a second power supply for applying a second high-frequency voltage is connected.
[0070]
The above-mentioned atmospheric pressure plasma discharge processing apparatus includes a gas supply means for supplying a discharge gas and a thin film forming gas between the opposed electrodes. Further, it is preferable to have an electrode temperature control means for controlling the temperature of the electrode.
[0071]
Further, it is preferable that a first filter is connected to the electrode, the first power supply or any one of them, and a second filter is connected to the electrode, the second power supply or any one of them. It makes it difficult to pass the current of the frequency from the first power supply, makes it easier to pass the current of the frequency from the second power supply, and the second filter, on the contrary, filters the current of the frequency from the second power supply. Each filter having a function of making it difficult to pass the current and facilitating the passage of the current of the frequency from the first power source is used. Here, “hard to pass” means that preferably only 20% or less, more preferably 10% or less of the current is passed. Conversely, passing easily means that 80% or more, more preferably 90% or more of the current is passed.
[0072]
Further, it is preferable that the first power supply of the atmospheric pressure plasma discharge processing apparatus of the present invention has a capability of applying a higher frequency voltage than the second power supply.
[0073]
Further, as another discharge condition in the present invention, a high-frequency voltage is applied between the opposing first electrode and the second electrode, and the high-frequency voltage becomes the first high-frequency voltage V₁And the second high-frequency voltage V₂Are superimposed, and when the discharge starting voltage is IV,
V₁≧ IV> V₂
Or V₁> IV ≧ V₂
Meet. More preferably,
V₁> IV> V₂
It is to satisfy.
[0074]
The definition of the high frequency and the discharge starting voltage, and the specific method of applying the high frequency voltage of the present invention between the counter electrodes (the same discharge space) are the same as those described above.
[0075]
Here, the high-frequency voltage (applied voltage) and the discharge starting voltage referred to in the present invention are those measured by the following method.
[0076]
High frequency voltage V₁And V₂(Unit: kV / mm) Measurement method:
A high-frequency probe (P6015A) for each electrode section is installed, and the high-frequency probe is connected to an oscilloscope (Tektronix, TDS3012B) to measure the voltage.
[0077]
Measuring method of discharge starting voltage IV (unit: kV / mm):
A discharge gas is supplied between the electrodes, the voltage between the electrodes is increased, and a voltage at which discharge starts is defined as a discharge start voltage IV. The measuring device is the same as the above high frequency voltage measurement.
[0078]
By taking discharge conditions that apply a high voltage, even with a discharge gas with a high discharge start voltage such as nitrogen gas, the discharge gas is started and a high-density and stable plasma state can be maintained, forming a high-performance thin film. Can be done.
[0079]
When the discharge gas is nitrogen gas according to the above measurement, the discharge starting voltage IV is about 3.7 kV / mm. Therefore, in the above relationship, the first high-frequency voltage is V₁By applying a voltage of ≧ 3.7 kV / mm, the nitrogen gas can be excited to be in a plasma state.
[0080]
Here, the frequency of the first power supply is preferably 200 kHz or less. The electric field waveform may be a sine wave or a pulse wave. The lower limit is desirably about 1 kHz.
[0081]
On the other hand, the frequency of the second power supply is preferably 800 kHz or more. As the frequency of the second power supply is higher, the plasma density is higher, and a dense and high-quality thin film can be obtained. The upper limit is desirably about 200 MHz.
[0082]
Applying a high-frequency voltage from two such power sources requires a first frequency ω₁Side to initiate the discharge of a discharge gas having a higher firing voltage and a second frequency ω₂It is an important point of the present invention that the side is necessary to increase the plasma density to form a dense and high quality thin film.
[0083]
In the present invention, the first filter makes it difficult to pass a current having a frequency from the first power source, and makes it easy to pass a current having a frequency from the second power source. The filter is configured to hardly pass a current having a frequency from the second power source and to easily pass a current having a frequency from the first power source. In the present invention, any filter having such properties can be used without limitation.
[0084]
For example, as the first filter, a capacitor of several tens to several hundreds of pF or a coil of several μH can be used according to the frequency of the second power supply. As the second filter, a coil of 10 μH or more according to the frequency of the first power supply is used, and the ground can be used as a filter by grounding through these coils or a capacitor.
[0085]
As described above, the atmospheric pressure plasma discharge treatment apparatus of the present invention discharges between the opposing electrodes, converts at least the discharge gas and the thin film-forming gas introduced between the opposing electrodes into a plasma state, and places the static electricity between the opposing electrodes. The thin film is formed on the substrate by exposing the substrate to be placed or transferred to the gas in the plasma state (for example, see FIGS. 1 to 7). As another method, an atmospheric pressure plasma discharge treatment apparatus discharges a gas introduced between the opposed electrodes in the same manner as described above to excite the gas introduced between the opposed electrodes or puts the gas into a plasma state, and excites a gas outside the opposed electrode in a jet state. Alternatively, a jet-type apparatus for forming a thin film on a substrate by blowing out a gas in a plasma state and exposing a substrate (which may be left still or transferred) near the counter electrode is exposed. (See FIG. 8 below).
[0086]
The plasma discharge processing container 20 is preferably made of an insulating material such as a processing container made of Pyrex (R) glass, but may be made of metal as long as it can be insulated from the electrodes. For example, a polyimide resin or the like may be adhered to the inner surface of an aluminum or stainless steel frame, and the metal frame may be sprayed with ceramics to obtain insulation.
[0087]
In addition, in order to minimize the influence on the substrate during the discharge plasma treatment, the temperature of the substrate during the discharge plasma treatment may be adjusted to a temperature between room temperature (15 ° C. to 25 ° C.) and less than 200 ° C. Preferably, it is more preferably adjusted to room temperature to 110 ° C. However, these conditions are not limited to these ranges because the upper limit of the temperature is determined depending on the physical properties of the base material, particularly the glass transition temperature. In order to adjust the temperature to the above-mentioned temperature range, the electrodes and the substrate are subjected to a discharge plasma treatment while being cooled by a cooling means, if necessary.
[0088]
In the embodiment of the present invention, the above-described plasma processing is performed at or near atmospheric pressure, but the plasma processing may be performed under vacuum or high pressure. In addition, the vicinity of the atmospheric pressure refers to a pressure of 20 kPa to 110 kPa, and is preferably 93 kPa to 104 kPa in order to preferably obtain the effects described in the present invention.
[0089]
Further, in the electrode for discharge used in the atmospheric pressure plasma treatment, at least the surface of the electrode in contact with the base material F has a maximum surface roughness (Rmax) of 10 μm or less specified in JIS B0601. The surface roughness is preferably adjusted as described above, and the maximum value of the surface roughness is preferably 8 μm or less.
[0090]
The above-described plasma discharge processing apparatus 10 shown in FIGS. 1 and 2 is an apparatus used when the substrate F is a film, but, for example, a substrate having a thickness greater than the film, such as a lens. In such a case, a plasma discharge processing apparatus 10 as shown in FIG. 7 is used. FIG. 7 is a schematic diagram showing another example of the plasma discharge processing apparatus.
[0091]
The plasma discharge processing apparatus 10 uses a plate-shaped electrode 103 as an electrode connected to the high-frequency power supply 101, and mounts a base material (for example, a lens L) on the electrode 103.
[0092]
On the other hand, a rectangular rod-shaped electrode 104b is provided as an electrode connected to the low-frequency power supply 102 so as to face the electrode 103. The square rod-shaped electrode 104a is grounded as ground. In this case, the mixed gas is supplied from above the electrodes 104a and 104b, and is brought into a plasma state in a range from between the electrodes 104a and 104b to the electrode 103.
[0093]
FIG. 8 is a schematic view showing an example of an atmospheric pressure plasma discharge treatment apparatus using a nitrogen gas which is slightly different from the above.
[0094]
The plasma discharge processing apparatus 10 has a counter electrode composed of a first electrode 111 and a second electrode 112, and a first electrode 111 from the first power supply 121 extends between the counter electrodes. Frequency ω₁High frequency voltage V₁Is applied, and a second frequency ω from the second power supply 122 is applied from the second electrode 112.₂High frequency voltage V₂Is applied. The first power supply 121 has a higher frequency voltage (V) than the second power supply 122.₁> V₂), And the first frequency ω of the first power source 121.₁Is the second frequency ω of the second power supply 122₂A lower frequency can be applied.
[0095]
A first filter 123 is provided between the first electrode 111 and the first power supply 121 so that a current from the first power supply 121 flows toward the first electrode 111. , And is designed to make it easier for the current from the second power supply 122 to pass.
[0096]
A second filter 124 is provided between the second electrode 112 and the second power supply 122 so that a current from the second power supply 122 flows toward the second electrode 112. Is designed to make it difficult to pass the current from the first power supply 121.
[0097]
Gas G is introduced from a gas supply unit into a space 113 between the opposing electrodes (discharge space) between the first electrode 111 and the second electrode 112, and a high frequency voltage is applied from the first electrode 111 and the second electrode 112 to generate a discharge Then, the gas G is blown out in a jet state below the counter electrode (lower side of the paper) while the gas G is in a plasma state, and the processing space formed by the lower surface of the counter electrode and the base material F is filled with the gas G ° in the plasma state. A thin film is formed on the material F near the processing position 114.
[0098]
(Formation of a film other than an antifouling film)
The gas used depends on the type of thin film to be provided on the substrate, but is basically a mixed gas of an inert gas and a reactive gas for forming the thin film. The reactive gas is preferably contained at 0.01 to 10% by volume based on the mixed gas. As the thickness of the thin film, a thin film having a thickness in the range of 0.1 nm to 1000 nm is obtained.
[0099]
Examples of the inert gas include Group 18 elements of the periodic table, specifically, helium, neon, argon, krypton, xenon, radon, and nitrogen gas, but in order to obtain the effects described in the present invention. Preferably, helium, argon and nitrogen gas are used.
[0100]
For example, as a reactive gas, zinc acetylacetonate, triethylindium, trimethylindium, diethylzinc, dimethylzinc, etraethyltin, etramethyltin, di-n-butyltin diacetate, tetrabutyltin, tetraoctyltin, indium acetylacetonate and the like By using a reactive gas containing at least one organometallic compound selected from the group consisting of, a metal oxide layer useful as a conductive film, an antistatic film, or a medium refractive index layer of an antireflection film can be formed.
[0101]
Further, by using a reactive gas containing an organic fluorine compound, a silicon compound or a titanium compound, a low refractive index layer or a high refractive index layer of an antireflection film can be provided.
[0102]
When the above-mentioned titanium compound is used in the mixed gas, the content of the titanium compound in the mixed gas is preferably from 0.1 to 10% by volume, and more preferably from 0.1 to 5% by volume. is there.
[0103]
In addition, by containing a component selected from oxygen, ozone, hydrogen peroxide, carbon dioxide, carbon monoxide, hydrogen, and nitrogen in the mixed gas in an amount of 0.01 to 5% by volume, the reaction is promoted and the density is increased. A high-quality thin film can be formed.
[0104]
As the silicon compound and the titanium compound described above, a metal hydrogen compound and a metal alkoxide are preferable from the viewpoint of handling, and a metal alkoxide is preferably used because corrosiveness, no generation of harmful gas, and less contamination in the process are preferred. Can be
[0105]
In order to introduce the above-mentioned silicon compound and titanium compound between the electrodes which are discharge spaces, both may be in a gas, liquid or solid state at normal temperature and normal pressure. In the case of gas, it can be directly introduced into the discharge space, but in the case of liquid or solid, it is used after being vaporized by means such as heating, decompression, and ultrasonic irradiation. When a silicon compound or a titanium compound is vaporized by heating, a metal alkoxide such as tetraethoxysilane or tetraisopropoxytitanium that is liquid at normal temperature and has a boiling point of 200 ° C. or less is suitably used for forming an antireflection film. The metal alkoxide may be used after being diluted with a solvent. As the solvent, an organic solvent such as methanol, ethanol, or n-hexane, or a mixed solvent thereof can be used. Since these diluting solvents are decomposed into molecules and atoms during the plasma discharge treatment, the influence on the formation of the thin film on the base material, the composition of the thin film, and the like can be almost ignored.
[0106]
Examples of the silicon compound described above include organic metal compounds such as dimethylsilane and tetramethylsilane, metal hydrogen compounds such as monosilane and disilane, metal halogen compounds such as silane dichloride and silane trichloride, tetramethoxysilane, and tetraethoxysilane. It is preferable to use an alkoxysilane such as silane, an organosilane, or the like, but it is not limited thereto. These can be used in appropriate combination.
[0107]
When the silicon compound described above is used in the mixed gas, the content of the silicon compound in the mixed gas is preferably from 0.1 to 10% by volume, and more preferably from 0.1 to 5% by volume. is there.
[0108]
Examples of the titanium compound described above include organometallic compounds such as tetradimethylaminotitanium; metal hydrogen compounds such as monotitanium and dititanium; metal halogen compounds such as titanium dichloride, titanium trichloride and titanium tetrachloride; tetraethoxytitanium; It is preferable to use a metal alkoxide such as isopropoxytitanium or tetrabutoxytitanium, but it is not limited thereto.
[0109]
When an organometallic compound is added to the reactive gas, for example, Li, Be, B, Na, Mg, Al, Si, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, Rb, Sr, Y, Zr, Nb, Mo, Cd, In, Ir, Sn, Sb, Cs, Ba, La, Hf, Ta, W, Tl, Pb, Bi, It may include a metal selected from Ce, Pr, Nd, Pm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu. More preferably, these organometallic compounds are preferably selected from metal alkoxides, alkylated metals, and metal complexes.
[0110]
【Example】
Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited to these Examples.
[0111]
[1] A substrate sample having a film substrate and a hard coat layer and an antireflection layer provided thereon
1. Base film
A cellulose triacetate film having a thickness of 80 μm (Konica Cat KC8UX2MW, manufactured by Konica Corp., refractive index 1.49, degree of acetyl group substitution 2.88) was used.
[0112]
The substrate used without any particular processing is referred to as substrate sample 1.
2. Installation of hard coat layer
The following hard coat layer composition (1) was applied to one surface of the base material sample 1 so as to have a dry film thickness of 3.5 μm, and dried at 80 ° C. for 5 minutes. Next, it was irradiated with an 80 W / cm high-pressure mercury lamp from a distance of 12 cm for 4 seconds to be cured, thereby producing a hard coat film 1 having a hard coat layer. The refractive index of the hard coat layer was 1.50.
[0113]

The composition was ultrasonically dispersed while stirring.
[0114]
This is designated as a base material sample 2.
3. Installation of anti-reflection layer "Coating method"
Installation of medium refractive index layer
On the hard coat layer of the base film, the following medium refractive index layer composition M-1 was applied by an extrusion coater, dried at 80 ° C. for 5 minutes, and irradiated with ultraviolet rays using a high-pressure mercury lamp (80 W). 175mJ / cm²Irradiation and curing were performed to produce a medium refractive index layer film 1 having a medium refractive index layer.
[0115]

The thickness of the medium refractive index layer was 78 nm, and the refractive index was 1.70.
[0116]
Installation of high refractive index layer
The following high refractive index layer composition H-1 was applied onto the middle refractive index layer film 1 by an extrusion coater, dried at 80 ° C. for 5 minutes, and then irradiated with ultraviolet rays at 175 mJ using a high pressure mercury lamp (80 W). / Cm²Irradiation and curing were performed to produce a base material sample 3 having a middle refractive index layer and a high refractive index layer.
[0117]

The high refractive index layer of the high refractive index layer film had a thickness of 66 nm and a refractive index of 1.85.
[0118]
Installation of low refractive index layer
On the high-refractive-index layer, the following low-refractive-index layer composition L-1 was applied by an extrusion coater, dried at 80 ° C for 5 minutes, thermally cured at 120 ° C for 5 minutes, and further irradiated with ultraviolet rays at 175 mJ. / Cm²Irradiation and curing produced a low reflection laminate having a low refractive index layer.
[0119]
<Preparation of tetraethoxysilane hydrolyzate A>
300 g of tetraethoxysilane and 455 g of ethanol were mixed, 295 g of a 1.0% by mass aqueous citric acid solution was added thereto, and the mixture was stirred at room temperature for 1 hour to prepare a tetraethoxysilane hydrolyzate A.
[0120]

The low refractive index layer had a thickness of 95 nm and a refractive index of 1.45.
[0121]
This is designated as Base Material Sample 4.
4. Installation of anti-reflection layer "Atmospheric pressure plasma method"
The following antireflection layer was set on the base material (base material sample 2) on which the hard coat layer was set by the atmospheric pressure plasma method, and base material samples 5 to 8 were obtained.
[0122]
High refractive index layer + low refractive index layer + high refractive index layer + low refractive index layer: Base material sample 5
High refractive index layer + antifouling layer 2 described later + high refractive index layer.
High refractive index layer + low refractive index layer + high refractive index layer ······· Base material sample 7
High refractive index layer + medium refractive index layer ................. 8
(High refractive index layer)
Gas 1 ... Argon (98.9% by volume)
Gas 2 ... hydrogen (1.00% by volume)
Gas 3 ... tetraisopropoxy titanium (0.1% by volume)
The above “%” is the volume% based on the whole mixed gas
The above gases 1 to 3 were uniformly mixed just before the discharge space to obtain a reaction gas.
[0123]
The gas 3 was mixed with an argon gas by a Lintec vaporizer and vaporized.
(Low refractive index layer)
Gas 1 ... Argon (98.90%)
Gas 2 ... Oxygen (1.00%)
Gas 3 ... Methyltriethoxysilane (0.10%)
The above gases 1 to 3 were uniformly mixed just before the discharge space to obtain a reaction gas.
[0124]
The gas 3 was mixed with an argon gas by a Lintec vaporizer and vaporized.
(Medium refractive index layer)
Gas 1 ... Argon (98.90%)
Gas 2 ... Oxygen (1.00%)
Gas 3 ... di-n-butyltin diacetate (0.10%)
The gas 3 was mixed with an argon gas by a Lintec vaporizer and vaporized.
[0125]
Film substrate 2
This is a film base material of ZEONOR (manufactured by Zeon Corporation), which is used as base material sample 9.
[0126]
[2] Preparation of antifouling film
(1) Experiment 1
Using the base material sample 5, an antifouling film was formed thereon.
[0127]
The antifouling film used was a plasma discharge treatment apparatus (manufactured by Pearl Industries) as shown in FIG. 6 and had a frequency of 13.56 MHz.
[0128]
Gas composition
Argon, hydrogen, and methyltriethoxysilane vapor were used, and their composition ratios are shown in Table 1.
[0129]
The above gases 1 to 3 were uniformly mixed just before the discharge space to obtain a reaction gas.
processing time
Exposure time to plasma: 3 minutes
The prepared antifouling membrane sample and its characteristics
As shown in Table 1 below, a film was prepared in which the conditions at the time of film formation were controlled and the Si: O: C ratio in the antifouling film was changed.
[0130]
[Table 1]

[0131]
The characteristic evaluation was performed as follows.
(Contact angle)
The contact angle of pure water and diiodomethane was measured at a droplet diameter of 1.5 mm using a contact angle meter CA-X manufactured by Kyowa Interface Chemical Co., Ltd. A liquid crystal display device was produced using the produced film, a fingerprint was attached, and the contact angle (pure water) after wiping with a Bencott was measured in the same manner.
[0132]
(Scratch resistance)
The surface of the sample is rubbed 10 times using a Bonstar # 0000 steel wool cut into 22 mm squares and loaded with a 500 g weight, and the generated scratches are visually counted.
[0133]
Evaluation criteria
A: 0
B: 1 to less than 5
C: less than 5 to 10
D: less than 10 to 20
E: 20 or more
(Haze)
According to JIS K7105, using a haze meter MODEL 1001DP (manufactured by Nippon Denshoku Industries Co., Ltd.), an average value measured at 10 different locations was taken as a value.
[0134]
(Equipment operating time)
5 foreign substances / 100 cm that can be visually identified on the film surface²This is the time until the appearance, and the time until the film forming apparatus needs to be cleaned.
[0135]
In addition, as the method of measuring the ratio of Si: O: C in the film, the method described in the “Embodiment of the invention” was used.
[0136]
(Refractive index)
With a reflectance spectrometer Fe3000 manufactured by Otsuka Electronics Co., Ltd., the reflectance was measured at a wavelength (λ) in the range of 400 to 700 nm under a condition inclined at 5 degrees from the state of regular reflection. The film thickness was optically calculated from the value of λ / 4, and the refractive index was calculated based on this.
[0137]
In this measurement, the value at a wavelength of 550 nm was displayed as a refractive index.
[0138]
[Table 2]

[0139]
Contact angle 1: Contact angle of pure water
Contact angle 2: Contact angle of diiodomethane
Contact angle 3: Contact angle of pure water after wiping
As is clear from Table 2, good results were obtained in all evaluations of Experiment Nos. 1-2, 1-3 and 1-6, 1-7 in the present invention.
(2) Experiment 2
An experiment similar to Experiment 1 was performed using an atmospheric pressure plasma discharge treatment apparatus as shown in FIG.
[0140]
Output density: 1st electrode side @ 1.0W / cm²
The second electrode side 3.3 W / cm²
When it is necessary to change the conditions in order to change the composition in the film, the first electrode side is set to 1.0 W / cm.², And the discharge output on the second electrode side was changed. In this case, the second electrode side had the same discharge output as in Table 1.
[0141]
Exposure time to plasma: 3 minutes
Gas 1 ... Nitrogen (98.90% by volume)
Gas 2 ... hydrogen (1.00% by volume)
Gas 3 ... Methyltriethoxysilane (0.10% by volume)
The gas composition was basically the same as that described above, and each composition was varied so as to have the same film composition as in Experiment 1.
[0142]
Methyltriethoxysilane was mixed with nitrogen gas and vaporized by a Lintec vaporizer.
[0143]
[Table 3]

[0144]
Contact angle 1: Contact angle of pure water
Contact angle 2: Contact angle of diiodomethane
Contact angle 3: Contact angle of pure water after wiping
As in Experiment 1, in Experiment Nos. 2-2, 2-3 and 2-6, 2-7 in the present invention, good results were obtained in all evaluations.
(3) Experiment 3
Using the substrate samples 1 to 8, an antifouling film was formed thereon using the apparatus 1, 2 or 3.
[0145]
Apparatus 1
13.56 MHz, discharge power 3.3 W / cm using a plasma discharge treatment apparatus (manufactured by Pearl Industries) as shown in FIG.²I went in.
[0146]
Gas composition
Gas 1: ... Argon (99.00% by volume)
Gas 2: ... hydrogen (0.90% by volume)
Gas 3: ... Methyltriethoxysilane vapor (0.10% by volume)
The above gases 1 to 3 were uniformly mixed just before the discharge space to obtain a reaction gas.
[0147]
processing time
Exposure time to plasma: 3 minutes
In Table 4, only the period of exposure to the plasma was set to 15 seconds for only 3-4.
[0148]
Device 2
An atmospheric pressure plasma discharge treatment apparatus as shown in FIG. 8 was used.
[0149]
Output density: 1st electrode side @ 1.0W / cm²
The second electrode side 3.3 W / cm²
When it is necessary to change the conditions in order to change the composition in the film, the first electrode side is set to 1.0 W / cm.², And the discharge output on the second electrode side was changed.
[0150]
Exposure time to plasma: 3 minutes
Gas 1 ... Nitrogen (98.90% by volume)
Gas 2 ... hydrogen (1.00% by volume)
Gas 3 ... Methyltriethoxysilane (0.10% by volume)
Methyltriethoxysilane was mixed with nitrogen gas and vaporized by a Lintec vaporizer.
[0151]
Device 3
An apparatus of the catalytic chemical vapor deposition method as shown in the schematic diagram of FIG. 9 was used.
[0152]
Raw material used: dimethyldiethoxysilane
100cm²A iridium wire having a length of 1 m per wire is stretched and heated to 1400 ° C., hydrogen is passed through 4 SLM (Standard litter per minute), mixed with 0.5 SLM argon and the raw material gas sent at 0.005 SLM so as to hit the substrate. Shed.
[0153]
9, reference numeral 201 denotes a loading / unloading port of the base material F, 202 denotes a shower head, 203 denotes an iridium wire (or tungsten wire) hot wire, and 204 denotes a source gas supply port.
[0154]
Comparative example
As a comparative example outside the present invention, a gas composition was prepared in which hydrogen gas was replaced with oxygen gas in the above gas composition.
[0155]
The prepared antifouling membrane sample and its characteristics
The evaluation method and the like were performed in the same manner as in Experiment 1, and the results shown in Table 4 below were obtained.
[0156]
[Table 4]

[0157]
Contact angle 1: Contact angle of pure water
Contact angle 2: Contact angle of diiodomethane
Contact angle 3: Contact angle of pure water after wiping
Samples Nos. 3-1 to 3-11 in the present invention all have good results, whereas samples Nos. 3-12 to 3-22 out of the present invention have only problematic characteristics. You can see that it can not be done.
[0158]
【The invention's effect】
According to the present invention, it is possible to provide an antifouling film having both good hardness and antifouling property and a method for producing the same. Thus, it is possible to provide a product having no damage to the lower layer, and to extend the continuous operation time of the manufacturing apparatus.
[Brief description of the drawings]
FIG. 1 is a conceptual diagram showing an example of a plasma discharge processing container.
FIG. 2 is a schematic view showing another example of the plasma discharge processing container.
FIG. 3 is a schematic perspective view showing an example of a cylindrical roll electrode.
FIG. 4 is a schematic perspective view showing an example of a cylindrical fixed electrode.
FIG. 5 is a schematic perspective view showing an example of a prismatic fixed electrode.
FIG. 6 is a conceptual diagram illustrating an example of a plasma discharge processing apparatus.
FIG. 7 is a schematic view showing another example of the plasma discharge processing apparatus.
FIG. 8 is a schematic view showing an example of an atmospheric pressure plasma discharge processing apparatus.
FIG. 9 is a schematic view of an apparatus for catalytic chemical vapor deposition.
[Explanation of symbols]
10 ° plasma discharge processing equipment
20 plasma discharge processing vessel
21 roll electrode
21a, 21A conductive base material
21b, 21B ceramic-coated dielectric
22, 29 ° fixed electrode
23a, 23b @ nip roller
24, 25 guide roller
26mm divider
27 air inlet
28mm exhaust port
40 gas generator
50 power supply
70 ° electrode constant temperature unit
101 high frequency power supply
102 low frequency power supply
103 flat electrode
104a, 104b square rod-shaped electrode
F substrate

Claims (12)

A film formed by using a silane compound having both a hydrolyzable group and an alkyl group as a raw material and using a chemical vapor deposition (CVD) method in an atmosphere containing a hydrogen gas. , Si: O: C = 1: (1.0 to 1.9) :( 0.2 to 2.0). The ratio of silicon, oxygen, and carbon in the film is as follows: Si: O: C = 1: (1.0-1.5) :( 0.2-1.5). Antifouling membrane. The antifouling film according to claim 1, wherein the hydrolyzable group in the silane compound is an alkoxy group. The antifouling film according to claim 1, wherein the alkyl group in the silane compound is a methyl group. The antifouling film according to any one of claims 1 to 4, wherein the alkoxy group in the silane compound is an ethoxy group. The antifouling film according to any one of claims 1 to 5, wherein the antifouling film is produced by an atmospheric pressure plasma chemical vapor deposition method. The antifouling film according to any one of claims 1 to 5, which is produced by a catalytic chemical vapor deposition method. The antifouling film according to any one of claims 1 to 7, wherein a film is formed on a transparent plastic substrate or on a plastic substrate on which a transparent actinic radiation-curable resin layer (CHC layer) is provided. . An antifouling antireflection film having the antifouling film according to claim 1 on the outermost surface. In an antireflection film composed of two or more layers having different refractive indices, the antifouling film according to any one of claims 1 to 7 is most preferably used as a low refractive index layer having a refractive index of 1.35 to 1.50. An antifouling antireflection film, which is used for a surface layer. An antifouling antireflection film, wherein the antifouling antireflection film according to claim 9 or 10 is all produced by an atmospheric pressure plasma-enhanced chemical vapor deposition method. An image display device, wherein the antifouling antireflection film according to claim 9 is provided on the outermost surface.

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