JP4356278B2 - Surface treatment method, method for forming antiglare layer, antiglare layer film and antiglare low reflection film - Google Patents

Description

【０１２０】
３．防眩層フィルムの作製
上記の基材フィルム１〜１２に対して、図６に示すプラズマ放電処理装置１０を用い、下記に示すプラズマ処理条件下により、防眩層フィルム１〜２４を作製した。
（プラズマ電源周波数とメーカー）
１３．５６ＭＨｚ（パール工業製）
（放電出力条件）
8W/cm²
（ガス条件１）
ガス１：アルゴン…９８．０体積％
ガス２：酸素…混合ガス全体に対して２．０体積％
上記ガス１〜２を均一に混合させて放電空間に供給し、反応ガスとした。
（ガス条件２）
ガス１：アルゴン…９８．０体積％
ガス２：ＣＦ４…混合ガス全体に対して１．０体積％
ガス３：酸素…混合ガス全体に対して１．０体積％
【０１２１】
上記のようにして作製した防眩層フィルムに対して、中心線平均粗さ（Ra）、防眩性、ギラツキ感、表面均一性、の評価を行ない、結果を表２に示した。
（Raの測定方法）
中心線平均表面粗さＲａ（μｍ）は、非接触３次元表面解析装置（ＷＹＫＯ社ＲＳＴ／ＰＬＵＳ）を用いて、２９９．４μｍ×２３２．４μｍの面積のＲａを測定した。なおＲａの定義は、ＪＩＳ表面粗さ（Ｂ０６０１）に従った。測定は、３０ｃｍ×３０ｃｍの各試料について、３ｃｍ間隔で碁盤目状に１００分割し、各正方形領域の中心について測定を行ない、１００回の測定からその平均値と標準偏差を求めた。中心線平均表面粗さ（Ｒａ）は、得られた粗さ曲線からその中心線の方向に測定長さＬの部分を抜き取り、この抜き取り部分の中心線をＸ軸、縦倍率の方向をＹ軸、粗さ曲線をＹ＝ｆ（Ｘ）で表したとき、下記式によって求められる値をマイクロメートル（μｍ）で表した。
【数１】

【０１２２】
（防眩性の評価方法）
作製した試料面に、ルーバーなしのむき出し蛍光灯（8000cd/m²）を映し、その蛍光灯反射像のボケの程度を、以下に示す基準に従い、目視観察にて防眩性ランクを評価した。
◎：蛍光灯像の輪郭がまったくわからない。
○：蛍光灯像の輪郭が僅かに見える。
△：蛍光灯像はボケてはいるが、輪郭が識別できる。
×：蛍光灯像がほとんどボケない。
【０１２３】
（ギラツキ感の評価方法）
上記により作製した試料面に、ルーバーを有する蛍光灯の拡散光を映し、表面のギラツキ感を、以下に示す基準に従い、目視観察にてギラツキ感ランクを評価した。
◎：ギラツキがまったく認められない。
○：ほとんどギラツキが認められない。
△：僅かにギラツキが認められる。
×：明らかにギラツキが認められる。
【０１２４】
（表面均一性の評価方法）
上記により作製した試料表面を背後よりフラットな拡散光を照射し、以下に示す基準に従い、表面の面状態を目視観察にて表面均一性ランクを評価した。
○：ムラが観察されない。
×：明らかにムラが観察される。
【表２】

【０１２５】
本発明による防眩層フィルムは、防眩性に優れ、ギラツキ感もなく、かつ表面均一性に優れていることが確認された。
【０１２６】
【発明の効果】
本発明によれば、煩雑な工程を経ることなく、基材上に防眩性に対して理想的な凹凸及び空隙を形成する表面処理方法及び防眩層の形成方法を提供でき、また、これら表面処理方法及び防眩層の形成方法により形成された防眩層を有する防眩層フィルム及び防眩性低反射フィルムを提供できる。
【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略図である。
【図２】プラズマ放電処理容器の他の一例を示す概略図である。
【図３】円筒型のロール電極の一例を示す斜視図（ａ）及び（ｂ）である。
【図４】固定型の円筒型電極の一例を示す斜視図（ａ）及び（ｂ）である。
【図５】固定型の角柱型電極の一例を示す斜視図（ａ）及び（ｂ）である。
【図６】プラズマ放電処理装置の一例を示す概略図である。
【符号の説明】
Ｆ 基材
２０ プラズマ放電処理容器
２１、２２、２９ 電極
２１ａ、２１Ａ、２２ａ、２２Ａ、２９ａ、２９Ａ 金属等の導電性母材
２１ｂ、２２ｂ、２９ｂ セラミック被覆処理誘電体
２１Ｂ、２２Ｂ、２９Ｂ ライニング処理誘電体
２３ａ、２３ｂ ニップローラー
２４、２５ ガイドローラー
２６ 仕切板
２７ 給気口
２８ 排気口
４０ ガス発生装置
４１ ガス充填手段
５０ 電源
７０ 電極冷却ユニット[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a surface treatment method for forming a fine shape on the surface of a substrate by forming a reactive gas in a plasma state under atmospheric pressure or a pressure near atmospheric pressure, and exposing the substrate to the substrate, and a method for forming an antiglare layer The present invention relates to an antiglare layer film having an antiglare layer formed and an antiglare low reflection film.
[0002]
[Prior art]
In recent years, development of thin and light notebook computers has been progressing. Along with this, the demand for thinner and higher performance protective films for polarizing plates used in display devices such as liquid crystal display devices is also increasing.
Recently, many displays provided with an antireflection layer or an antiglare layer for improving visibility have been used. Various types and performance improvements have been made to the antireflection layer and antiglare layer depending on the application, and various front plates with these functions are attached to the polarizer of a liquid crystal display, etc., to improve visibility on the display. Therefore, a method of providing an antireflection function or an antiglare function is used. These optical films used as the front plate are provided with an antireflection layer or an antiglare layer formed by coating or sputtering.
[0003]
The anti-glare layer reduces the visibility of the reflected image by blurring the outline of the image reflected on the surface, and reflection of the reflected image is noticeable when using an image display device such as a liquid crystal display, an organic EL display, or a plasma display. It is to prevent it from becoming.
By providing appropriate unevenness on the surface, such a property can be provided. Conventionally, as a method for forming such unevenness, for example, a method of adding fine particles as disclosed in JP-A-59-58036 or the like to a coating solution is used. In addition, an embossing method disclosed in JP-A-6-234175, a method of transferring a mold in advance disclosed in JP-A-63-298201, and the like are known. However, the embossing described above makes it difficult to form fine irregularities, and is therefore insufficient to prevent glare. In addition, the method of adding fine particles to the coating solution requires only fine particles. In order to form such irregularities, it is necessary to add a large amount of fine particles, and scattering is generated inside the coating layer irrespective of the irregularities on the surface. As a result, the transmission image is also blurred. Further, the above-described technique often causes coating unevenness and has a disadvantage that it is inferior in productivity, and there is a demand for the rapid development of improvement means.
[0004]
[Problems to be solved by the invention]
An object of the present invention is to have a surface treatment method for forming an ideal unevenness with respect to anti-glare properties on a substrate, a method for forming an anti-glare layer, and a formed anti-glare layer without going through complicated steps. An object is to provide an antiglare layer film and an antiglare low-reflection film.
[0005]
[Means for Solving the Problems]
  The surface treatment method according to claim 1 of the present invention uses a plurality of substances having different plasma resistance.Non-uniform composition with a carbon content of 5-20%Forms irregularities and voids in the thin film by atmospheric pressure plasma treatment in which an object to be processed, on which the controlled thin film is formed on the surface of the substrate, is exposed to a reactive gas in a plasma state at atmospheric pressure or near atmospheric pressure. The thin film is used as an antiglare layer.
  The surface treatment method according to claim 2 is the surface treatment method according to claim 1,
  At least one of the substances is a substance that is easily gasified by the atmospheric pressure plasma treatment.
[0006]
  The surface treatment method according to claim 3 is the surface treatment method according to claim 1,
  At least one of the substances is an organic substance.
[0007]
  Claim 4The surface treatment method described isClaims 1-3A surface treatment method according to any one of
  The thin film is produced by coating so as to have a non-uniform composition.
  Claim 5The surface treatment method described isClaims 1-3A surface treatment method according to any one of
  The thin film is generated by plasma treatment so as to have a non-uniform composition.
  Claim 6The surface treatment method described isClaims 1-5A surface treatment method according to any one of
  The atmospheric pressure plasma treatment is performed using a mixed gas containing at least one kind of inert gas and the reactive gas.
[0008]
  Claim 7The surface treatment method described isClaim 6A surface treatment method according to claim 1,
  The reactive gas includes a gas composed of a compound containing oxygen or fluorine.
  Claim 8The method for forming the described antiglare layer is:Claims 1-7An antiglare layer is formed on the surface of the substrate by the surface treatment method according to any one of the above.
[0009]
  Claim 9The antiglare layer film described isClaim 8It has the glare-proof layer formed by the formation method of the glare-proof layer of description.
  Claim 10The antiglare and low reflection film described isClaim 9An antireflection layer is provided on the upper surface of the described antiglare layer film.
[0010]
Hereinafter, the present invention will be described in detail.
In order to form an ideal unevenness with respect to anti-glare properties, the present inventor uses a base material containing an organic substance derived from a carbon component in the composition of the base material (object to be processed) surface. It has been found that unevenness and voids can be formed uniformly by performing atmospheric pressure plasma treatment with a high plasma density.
In addition, as a mechanism for forming irregularities and voids by atmospheric pressure plasma, organic components such as carbon are broken by the energy of the plasma and combined with oxygen in the atmosphere, oxygen in the substrate, carbon dioxide, etc. This is thought to be due to the separation of the base material.
[0011]
In addition, the present invention is characterized in that a film forming process is performed in which an organic component such as carbon that is easily gasified intentionally remains in the vicinity of the surface of the base material by plasma processing or coating.
As a method of forming a thin film that intentionally leaves organic components near the surface of the substrate, the frequency of the high-frequency voltage applied to the electrode and the plasma input power density are controlled using coating or a well-known plasma discharge treatment device. It is easy to operate because it can be done most easily. Other methods include a method of adjusting gas conditions such as gas concentration and a method of reducing the net input power by pulsing the plasma applied voltage. It is not limited to.
[0012]
By applying atmospheric pressure plasma processing (preferably processing conditions different from the film forming conditions) to the substrate on which the organic component is intentionally left in this manner, an ideal surface unevenness as an antiglare layer is obtained. The surface which has can be formed.
Also, plasma treatment (atmospheric pressure plasma treatment) is performed under atmospheric pressure or near atmospheric pressure to form irregularities and voids on the surface of the thin film, so that the thin film surface treatment process can be performed with an antiglare layer film or antiglare property. It can be inlined with other processes required for manufacturing a low reflection film. Therefore, an anti-glare layer film and an anti-glare low-reflection film can be produced by continuous continuous processing without going through complicated steps, and productivity can be improved.
In the surface treatment method according to claim 1, the surface of the workpiece having a non-uniform composition of a plurality of substances having different plasma resistances at least in the vicinity of the surface is subjected to plasma state reactivity under atmospheric pressure or pressure near atmospheric pressure. Unevenness and voids are formed on the surface of the object to be processed by atmospheric pressure plasma treatment exposed to gas.
[0013]
And it is preferable that at least one of the plurality of substances having different plasma resistance is a substance that is easily gasified by atmospheric pressure plasma treatment, for example, an organic substance derived from a carbon component.
Moreover, when performing an atmospheric pressure plasma process, it is preferable that the temperature of a base material shall be below a glass transition temperature.
If the carbon content in the organic material is controlled, the amount of formation of irregularities and voids on the substrate surface by atmospheric pressure plasma treatment can be controlled.
Note that the plasma processing is not limited to the pressure of the processing atmosphere, and includes plasma processing not only under atmospheric pressure but also under vacuum or high pressure.
In addition, the non-uniform composition refers to a composition of a plurality of substances having different plasma resistance (etching resistance to plasma).
[0014]
Hereinafter, the surface treatment method of the substrate according to the present invention, the formation method of the antiglare layer, the antiglare layer film having the formed antiglare layer, and the antiglare low reflection film will be described with reference to the preferred embodiments. However, the present invention is not limited to these examples, and in the following description, there are assertive expressions for terms and the like, but they show preferred examples of the present invention. It is not intended to limit the significance or technical scope.
In the present embodiment, a thin film containing an organic substance derived from a carbon component that is easily gasified is formed on the surface of the base material, and the surface of this thin film is subjected to atmospheric pressure plasma treatment, whereby an antiglare layer having uniform unevenness is formed. An anti-glare layer film is formed. As will be described in detail later, examples of the type of thin film include a thin film containing SiO2, TiO2, or the like. In addition, before forming a thin film on the base material surface, it is preferable to apply | coat a clear hard-coat layer to the surface of a base material beforehand using well-known methods, such as an extrusion coater and a gravure coater.
[0015]
FIG. 1 is a schematic view showing an example of a plasma discharge treatment container 20, and the plasma discharge treatment apparatus 10 (see FIG. 6) used in the present embodiment uses the plasma discharge treatment container 20 shown in FIG. .
[0016]
In FIG. 1, a long film-like substrate F is conveyed while being wound around a roll electrode 21 that rotates in the conveying direction (clockwise in the figure). The fixed electrode 22 is composed of a plurality of cylinders, and is installed facing the roll electrode 21. The substrate F wound around the roll electrode 21 is pressed by the nip rollers 23a and 23b, is regulated by the guide roller 24, is transported to the discharge treatment space secured by the plasma discharge treatment vessel 20, is subjected to discharge plasma treatment, and then Then, it is conveyed to the next process via the guide roller 25. In addition, the partition plate 26 is disposed in the vicinity of the nip roller 23 b and suppresses the air accompanying the base material F from entering the plasma discharge processing container 20.
[0017]
The entrained air is preferably suppressed to 1% by volume or less, and more preferably 0.1% by volume or less, with respect to the total volume of the gas in the plasma discharge treatment vessel 20. This can be achieved by the nip roller 23b.
[0018]
A mixed gas (an inert gas and an organic gas containing an organic fluorine compound, a titanium compound, a silicon compound, or the like, which is a reactive gas) used for the discharge plasma treatment is supplied from the air supply port 27 to the plasma discharge treatment vessel 20. The introduced and treated gas is exhausted from the exhaust port 28.
[0019]
FIG. 2 is a schematic view showing another example of the plasma discharge processing container 20 as described above, and the plasma discharge processing container 20 of FIG. 1 uses the cylindrical fixed electrode 22 whereas FIG. The plasma discharge processing container 20 shown in FIG. 1 uses a prismatic fixed electrode 29.
[0020]
Compared with the cylindrical electrode 22 shown in FIG. 1, the prismatic electrode 29 shown in FIG. 2 has an effect of widening the discharge range, and thus is preferably used in the surface treatment method of the present invention.
[0021]
3A and 3B are schematic views showing an example of the above-described cylindrical roll electrode 21, and FIGS. 4A and 4B are schematic views showing an example of the cylindrical fixed electrode 22. 5A and 5B are schematic views showing an example of a prismatic fixed electrode 29. FIG.
[0022]
In FIG. 3 (a), a roll electrode 21 as a ground electrode is a combination in which a ceramic coating is applied to a conductive base material 21a such as a metal, and then a ceramic coating treatment dielectric 21b that is sealed with an inorganic material is coated. It is composed of. The ceramic-coated dielectric material 21b is coated with 1 mm in one piece, manufactured so that the roll diameter becomes 200φ after coating, and is grounded to the ground. Further, as shown in FIG. 3B, the roll electrode 21 may be constituted by a combination of a conductive base material 21A such as metal covered with a lining dielectric 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 preferred because it is easy to process. Examples of the conductive base materials 21a and 21A such as metal include metals such as silver, platinum, stainless steel, aluminum, and iron. Stainless steel is preferable from the viewpoint of processing. As the ceramic material used for thermal spraying, alumina, silicon nitride, or the like is preferably used. Among these, alumina is more preferable because it is easily processed. In the present embodiment, the base material 21a, 21A of the roll electrode uses a stainless steel jacket roll base material having cooling means by cooling water (not shown).
[0023]
4 (a), 4 (b), 5 (a), and 5 (b) are a fixed electrode 22 and an electrode 29 that are application electrodes, and are configured in the same combination as the roll electrode 21 described above. .
[0024]
A power source for applying a voltage to the application electrode is not particularly limited, but a high frequency power source (200 kHz) manufactured by Pearl Industry, a high frequency power source (800 kHz) manufactured by Pearl Industry, a high frequency power source manufactured by JEOL (13.56 MHz), and a high frequency power source manufactured by Pearl Industry. A power source (150 MHz) or the like can be used.
[0025]
FIG. 6 is a conceptual diagram showing an example of a plasma discharge treatment apparatus 10 used in the present invention.
. In FIG. 6, the portion of the plasma discharge treatment vessel 20 is the same as that shown in FIG. 2, but a gas generator 40, a power source 50, an electrode cooling unit 70, and the like are further arranged as the device configuration. As a coolant for the electrode cooling unit 70, an insulating material such as distilled water or oil is used.
[0026]
The electrodes 21 and 29 shown in FIG. 6 are the same as those shown in FIGS. 3 and 5, and the gap between the opposing electrodes is set to about 1 mm, for example.
The distance between the electrodes is determined in consideration of the thickness of the solid dielectric placed on the base material of the electrodes, 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 placed on one of the electrodes, and the distance between the solid dielectrics when a solid dielectric is placed on both of the electrodes is uniform in any case From the viewpoint of discharging, 0.5 mm to 20 mm is preferable, and 1 mm ± 0.5 mm is particularly preferable.
[0027]
In the plasma discharge treatment vessel 20, a roll electrode 21 and a fixed electrode 29 are provided.
Is placed at a predetermined position, the flow rate of the mixed gas generated by the gas generator 40 is controlled, and the gas mixture is introduced into the plasma discharge treatment vessel 20 from the air supply port 27 via the gas filling means 41. Is filled with a mixed gas used for plasma processing and exhausted through an exhaust port 28. Next, a voltage is applied to the electrodes 21 and 29 by the power source 50, and the roll electrode 21 is grounded to the ground to generate discharge plasma. Here, the base material F is supplied from the roll-shaped original winding base material 60, and the electrodes in the plasma discharge treatment container 20 are in a single-sided contact state (in contact with the roll electrode 21) via the guide roller 24. Be transported. And the surface of the base material F is subjected to a discharge treatment by discharge plasma during conveyance, and after the thin film containing the organic substance derived from the reactive gas in the mixed gas is formed on the surface, the substrate F is passed through the guide roller 25 to the next process. Be transported. Here, the substrate F is subjected to discharge treatment only on the surface not in contact with the roll electrode 21.
[0028]
The value of the voltage applied to the fixed electrode 29 from the power supply 50 is determined as appropriate.
However, for example, the voltage is about 0.5 to 10 kV, and the power supply frequency is adjusted to more than 100 kHz and not more than 150 MHz. As for the method of applying power, either a continuous sine wave continuous oscillation mode called continuous mode or an intermittent oscillation mode called ON / OFF intermittently called pulse mode may be adopted. A denser and better quality film can be obtained.
[0029]
The plasma discharge treatment vessel 20 is preferably a treatment vessel made of Pyrex (R) glass or the like, but may be made of metal as long as it can be insulated from the electrodes. For example, polyimide resin or the like may be attached to the inner surface of an aluminum or stainless steel frame, and the metal frame may be subjected to ceramic spraying to provide insulation.
[0030]
Moreover, in order to suppress the influence on the base material at the time of the discharge plasma treatment to a minimum, the temperature of the base material at the time of the discharge plasma treatment may be adjusted to a temperature from room temperature (15 ° C. to 25 ° C.) to less than 200 ° C. More preferably, the temperature is adjusted to room temperature to 100 ° C. In order to adjust to the above temperature range, the electrode and the substrate are subjected to discharge plasma treatment while being cooled by a cooling means as necessary.
[0031]
In the present embodiment, the plasma treatment is performed at or near atmospheric pressure, but as described above, the plasma treatment may be performed under vacuum or high pressure. In addition, although the atmospheric pressure vicinity represents the pressure of 20 kPa-110 kPa, in order to acquire the effect as described in this invention preferably, 93 kPa-104 kPa are preferable. Moreover, you may form a thin film by well-known means, such as application | coating.
[0032]
In the discharge electrode according to the thin film forming method of the present invention, the maximum height (Rmax) of the surface roughness defined by JIS B 0601 on the side in contact with at least the substrate is adjusted to 10 μm or less. Although it is preferable from the viewpoint of obtaining the effects described in the present invention, the maximum value of the surface roughness is more preferably 8 μm or less, and particularly preferably adjusted to 7 μm or less.
[0033]
The centerline average surface roughness (Ra) specified by JIS B 0601 is preferably 0.5 μm or less, more preferably 0.1 μm or less.
[0034]
The gas used in the present invention is basically a mixed gas of an inert gas and a reactive gas for forming a thin film, although it varies depending on the type of thin film to be provided on the substrate. It is preferable to contain 0.01-10 volume% of reactive gas with respect to mixed gas. As the thickness of the thin film, a thin film in the range of 0.1 nm to 1000 nm is obtained.
[0035]
Examples of the inert gas include Group 18 elements of the periodic table, specifically helium, neon, argon, krypton, xenon, radon, etc. In order to obtain the effects described in the present invention, helium Argon is preferably used.
[0036]
For example, at least selected from zinc acetylacetonate, triethylindium, trimethylindium, diethylzinc, dimethylzinc, etraethyltin, etramethyltin, di-n-butyltin diacetate, tetrabutyltin, tetraoctyltin and the like as the reactive gas A reactive gas containing one organometallic compound can be used to form a metal oxide layer useful as a middle refractive index layer of a conductive film, an antistatic film, or an antireflection film.
[0037]
Moreover, by using a fluorine-containing compound gas, a water-repellent film can be obtained in which a fluorine-containing group is formed on the surface of the substrate to reduce the surface energy and obtain a water-repellent surface. Examples of the fluorine element-containing compound include fluorine / carbon compounds such as hexafluoropropylene (CF3CFCF2) and octafluorocyclobutane (C4F8). From the viewpoint of safety, propylene hexafluoride and cyclobutane octafluoride that do not generate hydrogen fluoride, which is a harmful gas, are used.
[0038]
Moreover, a hydrophilic polymer film can be deposited by performing the treatment in an atmosphere of a monomer having a hydrophilic group and a polymerizable unsaturated bond in the molecule. Examples of the hydrophilic group include a hydroxyl group, a sulfonic acid group, a sulfonate group, a primary or secondary or tertiary amino group, an amide group, a quaternary ammonium base, a carboxylic acid group, and a carboxylic acid group. Can be mentioned. Similarly, a hydrophilic polymer film can be deposited using a monomer having a polyethylene glycol chain.
[0039]
Examples of the monomer include acrylic acid, methacrylic acid, acrylamide, methacrylamide, N, N-dimethylacrylamide, sodium acrylate, sodium methacrylate, potassium acrylate, potassium methacrylate, sodium styrenesulfonate, allyl alcohol, allylamine, polyethylene. Examples thereof include glycol dimethacrylic acid ester and polyethylene glycol diacrylic acid ester, and at least one of them can be used.
[0040]
Further, by using a reactive gas containing an organic fluorine compound, a silicon compound, or a titanium compound, the low refractive index layer or the high refractive index layer of the antireflection film can be provided.
[0041]
As the organic fluorine compound, a fluorocarbon gas, a fluorinated hydrocarbon gas, or the like is preferably used. Examples of the fluorocarbon gas include carbon tetrafluoride and carbon hexafluoride, specifically, tetrafluoromethane, tetrafluoroethylene, hexafluoropropylene, octafluorocyclobutane, and the like. Examples of the fluorinated hydrocarbon gas include difluoromethane, tetrafluoroethane, tetrafluoropropylene, and trifluoride propylene.
[0042]
Furthermore, a halogenated fluoride compound such as trichloromethane monochloride, methane difluoride methane, or cyclobutane tetrachloride, or a fluorine-substituted product of an organic compound such as alcohol, acid, or ketone may be used. Yes, but not limited to these. Moreover, these compounds may have an ethylenically unsaturated group in the molecule. The above compounds may be used alone or in combination.
[0043]
When the organic fluorine compound described above is used in the mixed gas, the content of the organic fluorine compound in the mixed gas is 0.1 to 10% by volume from the viewpoint of forming a uniform thin film on the substrate by discharge plasma treatment. Although it is preferable, it is 0.1-5 volume% more preferably.
[0044]
Further, when the organic fluorine compound is a gas at normal temperature and normal pressure, it can be used as it is as a component of the mixed gas, so that the method of the present invention can be most easily performed. However, when the organic fluorine compound is liquid or solid at normal temperature and normal pressure, it may be used after being vaporized by a method such as heating or decompression, or may be used after being dissolved in an appropriate solvent. .
[0045]
When using the titanium compound described above in the mixed gas, the content of the titanium compound in the mixed gas is 0.1 to 10% by volume from the viewpoint of forming a uniform thin film on the substrate by discharge plasma treatment. However, it is more preferably 0.1 to 5% by volume.
[0046]
Moreover, the hardness of a thin film can be remarkably improved by containing 0.1-10 volume% of hydrogen gas in the said mixed gas.
In addition, by containing 0.01 to 5% by volume of a component selected from oxygen, ozone, hydrogen peroxide, carbon dioxide, carbon monoxide, hydrogen and nitrogen in the mixed gas, the reaction is promoted and dense. A high-quality thin film can be formed.
[0047]
As the silicon compounds and titanium compounds described above, metal hydrides and metal alkoxides are preferable from the viewpoint of handling, and metal alkoxides are preferably used because they are not corrosive, do not generate harmful gases, and have little contamination in the process. It is done.
Further, in order to introduce the silicon compound and the titanium compound described above between the electrodes which are the discharge spaces, both of them may be in the state of gas, liquid or solid at normal temperature and pressure. In the case of gas, it can be introduced into the discharge space as it is, but in the case of liquid or solid, it is used after being vaporized by means such as heating, decompression or ultrasonic irradiation. When a silicon compound or a titanium compound is vaporized by heating, a metal alkoxide that is liquid at room temperature and has a boiling point of 200 ° C. or lower, such as tetraethoxysilane or tetraisopropoxytitanium, is preferably used for forming the antireflection film. The metal alkoxide may be used after being diluted with a solvent. As the solvent, an organic solvent such as methanol, ethanol, n-hexane, or a mixed solvent thereof can be used. Since these diluted solvents are decomposed into molecular and atomic forms during the plasma discharge treatment, the influence on the formation of the thin film on the substrate, the composition of the thin film, etc. can be almost ignored.
[0048]
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 tetraethoxy. It is preferable to use alkoxysilane such as silane or dimethyldiethoxysilane, organosilane, or the like, but the invention is not limited to these. Moreover, these can be used in combination as appropriate.
[0049]
When using the above-mentioned silicon compound in the mixed gas, the content of the silicon compound in the mixed gas is 0.1 to 10% by volume from the viewpoint of forming a uniform thin film on the substrate by discharge plasma treatment. However, it is more preferably 0.1 to 5% by volume.
[0050]
Examples of the titanium compounds 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, tetraethoxy titanium, tetra Metal alkoxides such as isopropoxy titanium and tetrabutoxy titanium are preferably used, but are not limited thereto.
[0051]
When adding an organometallic compound 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, A metal selected from Ce, Pr, Nd, Pm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu can be included. More preferably, those organometallic compounds are selected from metal alkoxides, alkylated metals, and metal complexes.
Next, the base material that can be used in the present invention will be described.
The substrate that can be used in the present invention is not particularly limited as long as it can form a thin film on the surface thereof, such as a film-like material or a three-dimensional shape such as a lens shape. If the substrate can be placed between the electrodes, it can be placed between the electrodes, and if the substrate cannot be placed between the electrodes, the generated plasma can be blown against the substrate to blow the thin film. What is necessary is just to form.
[0052]
The material constituting the substrate is not particularly limited, but a resin can be preferably used because it is under atmospheric pressure or a pressure near atmospheric pressure and low-temperature glow discharge. Preferably, cellulose esters such as film-like cellulose triacetate, polyester, polycarbonate, polystyrene, and those coated with gelatin, polyvinyl alcohol (PVA), acrylic resin, polyester resin, cellulose resin, etc. are used. I can do it. Moreover, these base materials can use what coated the anti-glare layer and the clear hard-coat layer on the support body, and coated the back-coat layer and the antistatic layer.
[0053]
As the above support (also used as a base material), specifically, polyester films such as polyethylene terephthalate and polyethylene naphthalate, polyethylene film, polypropylene film, cellophane, cellulose diacetate film, cellulose acetate butyrate film, Cellulose acetate propionate film, cellulose acetate phthalate film, cellulose triacetate, cellulose ester film such as cellulose nitrate, or derivatives thereof, polyvinylidene chloride film, polyvinyl alcohol film, ethylene vinyl alcohol film, syndiotactic polystyrene series Film, polycarbonate film, norbornene resin film, polymethylpen Film, polyetherketone film, polyimide film, polyethersulfone film, polysulfone film, polyetherketoneimide film, polyamide film, fluororesin film, nylon film, polymethylmethacrylate film, acrylic film or polyarylate film Can be mentioned.
[0054]
These materials can be used alone or in combination as appropriate. Among these, commercially available products such as ZEONEX (manufactured by Nippon Zeon Co., Ltd.) and ARTON (manufactured by Nippon Synthetic Rubber Co., Ltd.) can be preferably used. Furthermore, even for materials with a large intrinsic birefringence, such as polycarbonate, polyarylate, polysulfone, and polyethersulfone, conditions such as solution casting and melt extrusion, as well as stretching conditions in the longitudinal and lateral directions are set as appropriate. Can be obtained. Moreover, the support body which concerns on this invention is not limited to said description. A film thickness of 10 μm to 1000 μm is preferably used as the film thickness.
[0055]
Moreover, when the thin film provided on a base material is an antireflection film, it is preferable to use a cellulose ester film as a support because a laminate having a low reflectance can be obtained. From the viewpoint of preferably obtaining the effects described in the present invention, as the cellulose ester, cellulose acetate, cellulose acetate butyrate, and cellulose acetate propionate are preferable, and among them, cellulose acetate butyrate and cellulose acetate propionate are preferably used.
[0056]
In the present invention, when the cellulose ester film is used as a substrate having an antireflection film, the cellulose ester film preferably contains a plasticizer.
[0057]
The plasticizer is not particularly limited, but is a phosphate ester plasticizer, a phthalate ester plasticizer, a trimellitic ester plasticizer, a pyromellitic acid plasticizer, a glycolate plasticizer, or a citrate ester plasticizer. An agent, a polyester plasticizer, or the like can be preferably used. For phosphate esters, triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, octyl diphenyl phosphate, diphenyl biphenyl phosphate, trioctyl phosphate, tributyl phosphate, etc. For phthalate esters, diethyl phthalate, dimethoxyethyl phthalate, dimethyl Trimellitic plasticizers such as phthalate, dioctyl phthalate, dibutyl phthalate, di-2-ethylhexyl phthalate, butyl benzyl phthalate, etc. Tributyl trimellitate, triphenyl trimellitate, triethyl trimellitate, etc. Examples of plasticizers include tetrabutyl pyromellitate, tetraphenyl pyromellitate, tetraethyl pyromellitate, Acid ester-based triacetin, tributyrin, ethyl phthalyl ethyl glycolate, methyl phthalyl ethyl glycolate, butyl phthalyl butyl glycolate, etc. Acetyl triethyl citrate, acetyl tri-n-butyl citrate, acetyl tri-n- (2-ethylhexyl) citrate and the like can be preferably used.
Examples of other carboxylic acid esters include butyl oleate, methylacetyl ricinoleate, dibutyl sebacate, and various trimellitic acid esters.
[0058]
A copolymer of a dibasic acid such as an aliphatic dibasic acid, an alicyclic dibasic acid, or an aromatic dibasic acid and a glycol can be used as the polyester plasticizer. The aliphatic dibasic acid is not particularly limited, and adipic acid, sebacic acid, phthalic acid, terephthalic acid, 1,4-cyclohexyl dicarboxylic acid and the like can be used. As the glycol, ethylene glycol, diethylene glycol, 1,3-propylene glycol, 1,2-propylene glycol, 1,4-butylene glycol, 1,3-butylene glycol, 1,2-butylene glycol and the like can be used. These dibasic acids and glycols may be used alone or in combination of two or more.
[0059]
It is preferable that the usage-amount of these plasticizers is 1-20 mass% with respect to a cellulose ester at points, such as film performance and workability.
[0060]
Further, when the thin film is an antireflection film, an ultraviolet absorber is preferably used as the base material (which may be a support alone) from the viewpoint of preventing deterioration of liquid crystals and the like.
[0061]
As the ultraviolet absorber, those excellent in the ability to absorb ultraviolet rays having a wavelength of 370 nm or less and having a small absorption of visible light having a wavelength of 400 nm or more are preferably used from the viewpoint of good liquid crystal display properties. Specific examples of preferably used ultraviolet absorbers include, but are not limited to, oxybenzophenone compounds, benzotriazole compounds, salicylic acid ester compounds, benzophenone compounds, cyanoacrylate compounds, nickel complex compounds, and the like. Not. Further, a polymeric ultraviolet absorber described in JP-A-6-148430 is also preferably used.
[0062]
In addition, the ultraviolet absorber that can be used for the support of the present invention contains an ultraviolet absorber having a distribution coefficient of 9.2 or more as described in Japanese Patent Application No. 11-295209, so that contamination of the plasma treatment process is prevented. In addition, it is preferable because various coating layers have excellent coating properties, and it is particularly preferable to use an ultraviolet absorber having a distribution coefficient of 10.1 or more.
[0063]
When cellulose ester films containing plasticizers and UV absorber absorbers are used as the base material, they may contaminate the process by attaching to the plasma processing part due to bleed-out, etc., which may adhere to the film Can be considered. In order to solve this problem, it is preferable to use a support having a cellulose ester and a plasticizer and having a mass change of less than ± 2% by mass before and after the time treatment at 80 ° C. and 90% RH. (Holding). As such a cellulose ester film, a cellulose ester film described in Japanese Patent Application No. 2000-338883 is preferably used. For this purpose, high molecular weight ultraviolet absorbers (or ultraviolet absorbing polymers) described in JP-A-6-148430 and Japanese Patent Application No. 2000-156039 can be preferably used. As a polymer ultraviolet absorber, PUVA-30M (manufactured by Otsuka Chemical Co., Ltd.) and the like are commercially available. The polymer ultraviolet absorbers described in the general formula (1) or general formula (2) of JP-A-6-148430 or the general formulas (3), (6) and (7) of Japanese Patent Application No. 2000-156039 are particularly preferably used.
[0064]
As the optical properties of the substrate when the thin film is an antireflection film, the in-plane retardation R0 is preferably 0 to 1000 nm, and the thickness direction retardation Rt is 0 to 300 nm depending on the application. Are preferably used. Further, as wavelength dispersion characteristics, R0 (600) / R0 (450) is preferably 0.7 to 1.3, and more preferably 1.0 to 1.3.
[0065]
Here, R0 (450) represents in-plane retardation based on three-dimensional refractive index measurement with light having a wavelength of 450 nm, and R0 (600) represents in-plane retardation based on three-dimensional refractive index measurement with light having a wavelength of 600 nm. .
[0066]
In the case where the thin film is an antireflection film, from the viewpoint of improving the adhesion between the substrate and the thin film formed by the discharge plasma treatment, a layer formed by polymerizing a component containing one or more ethylenically unsaturated monomers The discharge plasma treatment is preferably formed by the discharge plasma treatment described above, and in particular, the discharge plasma treatment is performed after treating the layer formed by polymerizing the component containing the ethylenically unsaturated monomer with a solution having a pH of 10 or more. This is preferable because the adhesion is further improved. As a solution having a pH of 10 or more, a 0.1 to 3 mol / L sodium hydroxide or potassium hydroxide aqueous solution is preferably used.
[0067]
As the resin layer formed by polymerizing a component containing an ethylenically unsaturated monomer, a layer containing an actinic ray curable resin or a thermosetting resin as a constituent component is preferably used, but an actinic ray curable resin is particularly preferably used. Is a layer.
[0068]
Here, the actinic radiation curable resin layer refers to a layer mainly composed of a resin that cures through a crosslinking reaction or the like by irradiation with actinic rays such as ultraviolet rays or electron beams. Typical examples of the actinic radiation curable resin include an ultraviolet curable resin and an electron beam curable resin, but a resin that is cured by irradiation with an actinic ray other than ultraviolet rays or an electron beam may be used. Examples of the ultraviolet curable resin include an ultraviolet curable acrylic urethane resin, an ultraviolet curable polyester acrylate resin, an ultraviolet curable epoxy acrylate resin, an ultraviolet curable polyol acrylate resin, and an ultraviolet curable epoxy resin. I can do it.
[0069]
UV curable acrylic urethane resins generally include 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate (hereinafter referred to as acrylate) to products obtained by reacting polyester polyols with isocyanate monomers or prepolymers. It can be easily obtained by reacting an acrylate monomer having a hydroxyl group such as 2-hydroxypropyl acrylate (for example, see JP-A-59-151110).
[0070]
The UV curable polyester acrylate resin can be easily obtained by reacting polyester polyol with 2-hydroxyethyl acrylate or 2-hydroxy acrylate monomer (see, for example, JP-A-59-151112). .
[0071]
Specific examples of the ultraviolet curable epoxy acrylate resin include those obtained by reacting epoxy acrylate with an oligomer, a reactive diluent and a photoinitiator added thereto (for example, JP-A-1- No. 105738). As the photoreaction initiator, one or more kinds selected from benzoin derivatives, oxime ketone derivatives, benzophenone derivatives, thioxanthone derivatives and the like can be selected and used.
[0072]
Specific examples of ultraviolet curable polyol acrylate resins include trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, alkyl-modified dipentaerythritol pentaacrylate. Etc. can be mentioned.
[0073]
These resins are usually used together with known photosensitizers. Moreover, the said photoinitiator can also be used as a photosensitizer. Specific examples include acetophenone, benzophenone, hydroxybenzophenone, Michler's ketone, α-amyloxime ester, thioxanthone, and the like. Further, when using an epoxy acrylate photoreactant, a sensitizer such as n-butylamine, triethylamine, or tri-n-butylphosphine can be used. It is preferable that the photoreaction initiator or photosensitizer contained in the ultraviolet curable resin composition excluding the solvent component that volatilizes after coating and drying is 2.5 to 6% by mass of the composition.
[0074]
Examples of the resin monomer include general monomers such as methyl acrylate, ethyl acrylate, butyl acrylate, vinyl acetate, benzyl acrylate, cyclohexyl acrylate, and styrene as monomers having one unsaturated double bond. In addition, monomers having two or more unsaturated double bonds include ethylene glycol diacrylate, propylene glycol diacrylate, divinylbenzene, 1,4-cyclohexane diacrylate, 1,4-cyclohexyldimethyl adiacrylate, and the above trimethylolpropane. Examples thereof include triacrylate and pentaerythritol tetraacryl ester.
[0075]
For example, as an ultraviolet curable resin, Adekaoptomer KR / BY series: KR-400, KR-410, KR-550, KR-566, KR-567, BY-320B (above, manufactured by Asahi Denka Kogyo Co., Ltd.) Or Koei hard A-101-KK, A-101-WS, C-302, C-401-N, C-501, M-101, M-102, T-102, D-102, NS-101, FT -102Q8, MAG-1-P20, AG-106, M-101-C (manufactured by Guangei Chemical Industry Co., Ltd.), Seika Beam PHC2210 (S), PHC X-9 (K-3), PHC2213, DP- 10, DP-20, DP-30, P1000, P1100, P1200, P1300, P1400, P1500, P1600, SCR900 (above Manufactured by Dainichi Seika Kogyo Co., Ltd.), or KRM7033, KRM7039, KRM7130, KRM7131, UVECRYL29201, UVECRYL29202 (above, Daicel UCB Corporation), or RC-5015, RC-5016, RC-5020, RC-5031, RC -5100, RC-5102, RC-5120, RC-5122, RC-5152, RC-5171, RC-5180, RC-5181 (manufactured by Dainippon Ink & Chemicals, Inc.) or Aulex No. 340 clear (manufactured by China Paint Co., Ltd.), or Sun Rad H-601 (manufactured by Sanyo Chemical Industries, Ltd.), SP-1509, SP-1507 (manufactured by Showa Polymer Co., Ltd.), or RCC-15C (Grace Japan Co., Ltd.) (Manufactured by company), Aronix M-6100, M-8030, M-8060 (above, manufactured by Toagosei Co., Ltd.) or other commercially available ones can be used.
[0076]
The actinic radiation curable resin layer used in the present invention can be applied by a known method. As the light source for forming the cured film layer of the actinic radiation curable resin by photocuring reaction, any light source that generates ultraviolet rays can be used. For example, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, or the like can be used. Irradiation conditions vary depending on each lamp, but the amount of irradiation light is 20-10000 mJ / cm.²About 50 to 2000 mJ / cm.²It is. It can be used by using a sensitizer having an absorption maximum in the near ultraviolet region to the visible light region.
[0077]
Solvents for coating the above-mentioned back coat layer or resin layer containing conductive fine particles as a solvent for coating an actinic radiation curable resin layer, such as hydrocarbons, alcohols, ketones, esters, glycol ethers In addition, the solvent can be appropriately selected from among other solvents or can be used by mixing them. Preferably, propylene glycol mono (alkyl group having 1 to 4 carbon atoms) alkyl ether or propylene glycol mono (alkyl group having 1 to 4 carbon atoms) alkyl ether ester is 5% by mass or more, more preferably 5 to 80% by mass or more. The containing solvent is used.
[0078]
As a method for applying the ultraviolet curable resin composition coating solution, a known method such as a gravure coater, a spinner coater, a wire bar coater, a roll coater, a reverse coater, an extrusion coater, or an air doctor coater can be used. The coating amount is suitably 0.1 to 30 μm, preferably 0.5 to 15 μm in terms of wet film thickness. The coating speed is preferably 10 to 60 m / min.
[0079]
The UV curable resin composition is applied and dried, and then irradiated with UV light from a light source. The irradiation time is preferably 0.5 seconds to 5 minutes, and 3 seconds to 2 from the curing efficiency and work efficiency of the UV curable resin. Minutes are more preferred.
[0080]
It is preferable to add inorganic or organic fine particles to the cured film layer thus obtained in order to prevent blocking and to improve scratch resistance. Examples of the inorganic fine particles include silicon oxide, titanium oxide, aluminum oxide, tin oxide, zinc oxide, calcium carbonate, barium sulfate, talc, kaolin, calcium sulfate, and the like, and examples of the organic fine particles include polymethacrylic acid. Methyl acrylate resin powder, acrylic styrene resin powder, polymethyl methacrylate resin powder, silicon resin powder, polystyrene resin powder, polycarbonate resin powder, benzoguanamine resin powder, melamine resin powder, polyolefin resin powder, polyester resin powder , Polyamide resin powder, polyimide resin powder, polyfluoroethylene resin powder, and the like, and can be added to the ultraviolet curable resin composition. The average particle diameter of these fine particle powders is preferably 0.005 μm to 1 μm, and particularly preferably 0.01 to 0.1 μm. The proportion of the ultraviolet curable resin composition and the fine particle powder is desirably blended so as to be 0.1 to 10 parts by mass with respect to 100 parts by mass of the resin composition.
[0081]
Even if the layer formed by curing the ultraviolet curable resin thus formed is a clear hard coat layer having a centerline surface roughness Ra of 1 to 50 nm, it is an antiglare layer having an Ra of about 0.1 to 1 μm. May be.
As described above, a layer obtained by curing an ultraviolet curable resin is applied to the surface of the base material, and further, a plasma treatment is performed on the upper surface by the plasma discharge treatment apparatus 10 to form a thin film in which organic components remain. Then, by subjecting the surface of the thin film to atmospheric pressure plasma treatment, the organic component in the thin film is gasified, and uniform unevenness and voids ideal for anti-glare properties are formed on the thin film surface.
As described above, the atmospheric pressure plasma treatment condition applied to the surface of the thin film is different from the plasma treatment condition when forming the thin film in which the organic component remains using the plasma discharge treatment apparatus. It is preferable.
[0082]
In addition, an optical interference layer such as a low refractive index layer or a high refractive index layer is laminated on the surface of a thin film (antiglare layer film) on which irregularities are formed by atmospheric pressure plasma treatment, thereby providing antiglare and low reflection. A film may be formed.
Below, the preferable structural example i)-v) of an anti-glare low reflection film is shown. In addition, / indicates that they are stacked.
i) Back coat layer / support / antiglare layer / high refractive index layer / low refractive index layer
ii) Backcoat layer / support / antiglare layer / medium refractive index layer / high refractive index layer / low refractive index layer
iii) Backcoat layer / support / antiglare layer / high refractive index layer / low refractive index layer / high refractive index layer / low refractive index layer
iv) Backcoat layer / support / antistatic layer / antiglare layer / medium refractive index layer / high refractive index layer / low refractive index layer
v) Antistatic layer / support / antiglare layer / medium refractive index layer / high refractive index layer / low refractive index layer
It is preferable to provide an antifouling layer on the outermost low refractive index layer so that dirt and fingerprints can be easily wiped off.
[0083]
For example, the antifouling layer can be formed by atmospheric pressure plasma treatment under the following treatment conditions using the plasma discharge treatment apparatus 10 shown in FIG.
(Power frequency and manufacturer)
13.56MHz (Made by Pearl Industry)
(Discharge output density)
4W / cm²
(Gas condition)
Gas 1: Argon: 99.8% by volume
Gas 2: Propylene hexafluoride 0.2% by volume
[0084]
Further, the antistatic layer shown in the structural examples iv) and v) can be formed by atmospheric pressure plasma treatment under the following treatment conditions using, for example, the plasma discharge treatment apparatus 10 shown in FIG. .
(Power frequency and manufacturer)
13.56MHz (Made by Pearl Industry)
(Discharge output density)
4W / cm²
(Gas condition)
Gas 1: Argon: 99.5% by volume
Gas 2: Bubbling argon into tetrabutyltin
Bubble argon into triethylindium
A mixture of tetrabutyltin and triethylindium vapor contained by these two bubbling. 0.5% by volume
[0085]
The film formation method by application of the optical interference layer is according to the following procedure.
(Coating of medium refractive index layer)
The following medium refractive index layer composition is applied onto the above antiglare film, dried at 100 ° C. for 5 minutes, and then irradiated with ultraviolet rays at 180 mJ / cm using a high pressure mercury lamp (80 W).²Irradiate and cure to provide a medium refractive index layer (thickness is 77 nm, refractive index is 1.70).
(Medium refractive index layer composition)
250 parts by mass of tetra (n) butoxytitanium
End-reactive dimethyl silicone oil (Ni-Unicar L-9000) 0.5 parts by mass
22 parts by mass of aminopropyltrimethoxysilane (KBE903, manufactured by Shin-Etsu Chemical Co., Ltd.)
21 parts by mass of UV curable epoxy resin (KR500 manufactured by Asahi Denka Co., Ltd.)
4850 parts by mass of propylene glycol monomethyl ether
Isopropyl alcohol 4900 parts by mass
[0086]
(Coating of high refractive index layer)
The following high refractive index layer composition is applied on the medium refractive index layer formed above, dried at 100 ° C. for 5 minutes, and then irradiated with ultraviolet rays at 180 mJ / cm using a high pressure mercury lamp (80 W).²Irradiated and cured to provide a high refractive index layer (thickness 65 nm, refractive index 1.85).
(High refractive index layer composition)
Tetra (n) butoxytitanium 310 parts by mass
Terminal reactive dimethyl silicone oil (Ni-Unicar L-9000) 0.4 parts by mass
4.8 parts by mass of aminopropyltrimethoxysilane (KBE903, manufactured by Shin-Etsu Chemical Co., Ltd.)
4.6 parts by mass of UV curable epoxy resin (KR500 manufactured by Asahi Denka Co., Ltd.)
4800 parts by mass of propylene glycol monomethyl ether
Isopropyl alcohol 4900 parts by mass
[0087]
(Coating of low refractive index layer)
On the formed high refractive index layer, the following low refractive index layer composition is applied, dried at 100 ° C. for 5 minutes, thermally cured at 120 ° C. for 5 minutes, and further using a high pressure mercury lamp (80 W). UV light 180mJ / cm²Irradiated to provide a low refractive index layer (thickness 95 nm, refractive index 1.45).
(Low refractive index layer composition)
Tetraethoxysilane hydrolyzate (* 1) 1020 parts by mass
Terminal reactive dimethyl silicone oil (Ni-Unicar L-9000) 0.42 parts by mass
2700 parts by mass of propylene glycol monomethyl ether
Isopropyl alcohol 6300 parts by mass
* 1: Preparation of tetraethoxysilane hydrolyzate
After mixing 300 g of tetraethoxysilane and 455 g of ethanol and adding 295 g of 0.5% by mass aqueous citric acid solution thereto, the mixture was stirred at room temperature for 1 hour to prepare a tetraethoxysilane hydrolyzate.
[0088]
Moreover, the film formation method by the plasma processing of an optical interference layer uses the plasma discharge processing apparatus 10 shown in FIG. 6 on the above-mentioned anti-glare layer, and follows the following procedures.
(High refractive index layer)
Noble gas: Argon
Reaction gas: Hydrogen gas (1% of argon)
Reaction gas: Tetraisopropoxy titanium vapor (heated to 100 ° C and then bubbled with argon gas)
Discharge density: 450 W · min / m²
Processing speed: 30m / min
(Low refractive index layer)
Noble gas: Argon
Reaction gas: Hydrogen gas (1% of argon)
Reaction gas: Tetraethoxysilane vapor (bubbled with argon gas)
Discharge density: 400 W · min / m²
Processing speed: 30m / min
[0089]
In addition, when providing a thin film with respect to a base-material surface, it is preferable to provide so that the film thickness deviation with respect to an average film thickness may be +/- 10%, More preferably, it is less than +/- 5%, Especially preferably, it is less than +/- 1% It is preferable to provide so that.
[0090]
In addition, it is preferable to irradiate the plasma-treated surface with ultraviolet rays before plasma-treating the thin film on the surface of the substrate because the adhesion of the formed film is excellent. The amount of UV irradiation is 50 to 2000 mJ / cm²It is preferable that 50 mJ / cm²Less than 2000mJ / cm, the effect is not sufficient.²Exceeding the range is not preferred because the substrate may be deformed. It is preferable to perform plasma treatment within 1 hour after ultraviolet irradiation, and it is particularly preferable to perform plasma treatment within 10 minutes after ultraviolet irradiation. The ultraviolet irradiation before the plasma treatment may be performed simultaneously with the ultraviolet irradiation for curing the above-described ultraviolet curable resin, and in that case, it is preferable to increase the ultraviolet irradiation amount necessary for the curing.
In addition, irradiation with ultraviolet light after performing plasma treatment is also effective in stabilizing the formed film at an early stage.
[0091]
For this reason, 50-2000 mJ / cm as the amount of ultraviolet irradiation light²Is preferably irradiated to the plasma-treated surface after the plasma treatment. These treatments are preferably performed after the plasma treatment and before the winding process. Moreover, it is preferable that the base material after a plasma process is processed for 1 to 30 minutes in the drying zone adjusted to 50-130 degreeC.
[0092]
A base material having an antireflection film is preferably subjected to plasma treatment on both surfaces because curling after treatment is reduced. Although the plasma treatment on the back surface may be performed separately, it is preferable to perform the plasma treatment on both sides simultaneously, and it is preferable to perform the back surface processing by plasma processing on the back surface side on the low reflection processing side. Examples thereof include easy adhesion processing described in Japanese Patent Application No. 2000-273066 and antistatic processing described in Japanese Patent Application No. 2000-80043, but are not particularly limited thereto.
[0093]
The base material having the antireflection film is mainly composed of a high refractive index layer mainly composed of titanium oxide having a refractive index of 1.6 to 2.3 and silicon oxide having a refractive index of 1.3 to 1.5. It is preferable to continuously provide the low refractive index layer on the surface of the long film substrate. Thereby, the adhesiveness between each layer becomes favorable. Preferably, it is more preferable to provide the high refractive index layer and the low refractive index layer by plasma treatment immediately after providing the ultraviolet curable resin layer on the base film.
[0094]
The high refractive index layer is particularly preferably composed mainly of titanium oxide and having a refractive index of 2.2 or more.
[0095]
The carbon content of the high-refractive index layer and the low-refractive index layer of the antireflection film is preferably 0.2 to 5% by mass for the adhesion to the lower layer and the flexibility of the film. More preferably, the carbon content is 0.3 to 3% by mass. That is, since the layer formed by the plasma treatment contains an organic substance (carbon atom), the range gives flexibility to the film, which is excellent in film adhesion. If the carbon ratio is too high, the refractive index tends to fluctuate with time, which is not preferable.
[0096]
【Example】
EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.
1. Production of base film (cellulose ester film)
According to the method shown below, a cellulose ester film as a substrate was produced.
(1) Preparation of dope C
(Preparation of silicon oxide dispersion A)
Aerosil 200V (Nippon Aerosil Co., Ltd.) 1kg
Ethanol 9kg
The above material was stirred and mixed with a dissolver for 30 minutes, and then dispersed using a Manton Gorin type high-pressure dispersing device.
[0097]
(Preparation of additive solution B)
Cellulose triacetate (acetyl substitution degree: 2.65) 6kg
Methylene chloride 140kg
The material was put into a sealed container, heated, and completely dissolved and filtered while stirring. To this, 10 kg of the above silicon oxide dispersion A was added with stirring, followed by further stirring for 30 minutes, followed by filtration to prepare additive liquid B.
[0098]
(Preparation of dope stock solution C)
440 kg of methylene chloride
Ethanol 35kg
Triacetyl cellulose (acetyl substitution degree: 2.65) 100 kg
Triphenyl phosphate 8kg
Ethyl phthalyl ethyl glycolate 3kg
Tinuvin 326 (Ciba Specialty Chemicals) 0.4kg
Tinuvin 109 (Ciba Specialty Chemicals) 0.9kg
Tinuvin 171 (Ciba Specialty Chemicals) 0.9kg
The solvent was put into an airtight container, the raw material was added while stirring, and completely dissolved and mixed while heating and stirring. The dope was lowered to the temperature at which the dope was cast, allowed to stand overnight, and subjected to a defoaming operation. A dope stock solution C was prepared by filtration using 244.
[0099]
Further, 2 kg of the additive solution B was added per 100 kg of the solution, sufficiently mixed with an in-line mixer (Toray static type in-pipe mixer H-Mixer, SWJ), and filtered to prepare a dope C.
[0100]
(2) Preparation of dope E
(Preparation of silicon oxide dispersion A)
Aerosil R972V (manufactured by Nippon Aerosil Co., Ltd.)
(Average diameter of primary particles 16nm) 1kg
Ethanol 9kg
The above material was stirred and mixed with a dissolver for 30 minutes, and then dispersed using a Manton Gorin type high-pressure dispersing device.
[0101]
(Preparation of additive solution D)
Cellulose acetate propionate (acetyl substitution degree: 2.0, propionyl group substitution degree: 0.8) 6 kg
100 kg of methyl acetate
Ethanol 40kg
The above materials were put into a sealed container, heated, and completely dissolved and filtered while stirring. To this, 10 kg of the above silicon oxide dispersion A was added with stirring, and the mixture was further stirred for 30 minutes, followed by filtration to prepare additive solution D.
[0102]
(Preparation of dope stock solution E)
Cellulose acetate propionate (acetyl substitution degree: 2.0, propionyl group substitution degree: 0.8) 100 kg
290 kg of methyl acetate
Ethanol 85kg
KE-604 (Arakawa Chemical Industries) 15kg
PUVA-30M (Otsuka Chemical Co., Ltd.) 5kg
The solvent was put into an airtight container, the raw material was added while stirring, and completely dissolved and mixed while heating and stirring. The dope was lowered to the temperature at which the dope was cast, allowed to stand overnight, and subjected to a defoaming operation. A dope stock solution E was prepared by filtration using 244.
[0103]
Further, 2 kg of the additive solution D was added per 100 kg of the solution, sufficiently mixed with an in-line mixer (Toray static type in-pipe mixer Hi-Mixer, SWJ), and filtered to prepare Dope E.
[0104]
(3) Preparation of dope G >>
(Preparation of silicon oxide dispersion F)
Aerosil 200V (Nippon Aerosil Co., Ltd.) 1kg
Ethanol 9kg
The above material was stirred and mixed with a dissolver for 30 minutes, and then dispersed using a Manton Gorin type high-pressure dispersing device.
[0105]
(Preparation of additive solution E)
Cellulose triacetate (acetyl substitution degree: 2.88) 6kg
Methylene chloride 140kg
The material was put into a sealed container, heated, and completely dissolved and filtered while stirring. To this, 10 kg of the above silicon oxide dispersion F was added with stirring, and the mixture was further stirred for 30 minutes, followed by filtration to prepare additive E.
[0106]
(Preparation of dope stock solution G)
440 kg of methylene chloride
Ethanol 35kg
Triacetyl cellulose (acetyl substitution degree: 2.88) 100 kg
9 kg of triphenyl phosphate
Ethyl phthalyl ethyl glycolate 4kg
Tinuvin 326 (Ciba Specialty Chemicals) 0.4kg
Tinuvin 109 (Ciba Specialty Chemicals) 0.9kg
Tinuvin 171 (Ciba Specialty Chemicals) 0.9kg
The solvent was put into an airtight container, the raw material was added while stirring, and completely dissolved and mixed while heating and stirring. The dope was lowered to the temperature at which the dope was cast, allowed to stand overnight, and subjected to a defoaming operation. A dope stock solution G was prepared by filtration using 244.
[0107]
Further, 2 kg of the additive solution E was added per 100 kg of the solution, sufficiently mixed with an in-line mixer (Toray static type in-pipe mixer Hi-Mixer, SWJ), and filtered to prepare a dope G.
In addition, the measurement of the substitution degree of the cellulose ester used for preparation of each of said dope C, E, and G was performed according to the method prescribed | regulated to ASTM-D817-96.
[0108]
(4) Preparation of cellulose ester film
A cellulose ester film was produced as follows using the dopes C, E, and G prepared above.
[0109]
After the dope E was filtered, it was uniformly cast on a stainless steel band support having a dope temperature of 35 ° C. and a temperature of 30 ° C. using a belt casting apparatus. Then, after drying to the peelable range, the web was peeled from the stainless steel band support body. At this time, the residual solvent amount of the web was 35%.
[0110]
After peeling from the stainless steel band support, drying at 115 ° C while holding in the width direction, releasing the width holding, finishing drying in a 120 ° C drying zone while carrying the roll, and having a width of 10 mm at both ends of the film Then, a knurling process having a height of 5 μm was applied to produce a cellulose ester film having a thickness of 80 μm. The film width was 1300 mm, and the winding length was 1500 m.
[0111]
About the cellulose-ester film obtained above, the holdability was evaluated by the following method. As a result, the retentivity determined from the mass change before and after being left for 48 hours at 80 ° C. and 90% RH was 0.4%.
[0112]
(5) Reservation evaluation method
The sample was cut into a size of 10 cm × 10 cm, the mass after being allowed to stand for 24 hours in an atmosphere of 23 ° C. and 55% RH was measured, and left for 48 hours under the conditions of 80 ° C. and 90% RH. The surface of the sample after the treatment was lightly wiped, the mass after standing for 1 day at 23 ° C. and 55% RH was measured, and the retention (mass%) was calculated by the following method.
Retention property = {(mass before being left−mass after being left) / mass before being left} × 100
[0113]
2. Film formation by plasma treatment
Using the plasma discharge treatment apparatus 10 shown in FIG. 6 on the cellulose ester film having a film thickness of 80 μm obtained as described above, a film mainly composed of SiO 2 having a film thickness of 4 μm is used under the following plasma treatment conditions. The base film 1-6 was produced.
[0114]
Plasma processing conditions
(Plasma power frequency and manufacturer)
13.56 MHz (made by Pearl Industry)
800 kHz (made by Pearl Industry)
100 kHz (manufactured by HEIDEN Laboratory)
50kH (made by Shinko Electric)
(Discharge output condition)
2W / cm², 4W / cm², 8W / cm²
Where unit W / cm²The applied output (unit: W) is the discharge area (cm²) Divided by.
(Gas condition)
Gas 1: Argon: 99.25% by volume
Gas 2: Oxygen: 0.5% by volume with respect to the entire mixed gas
Gas 3: Tetraethoxysilane vapor: 0.25% by volume based on the entire mixed gas
The above gases 1 to 3 were uniformly mixed immediately before the discharge space to obtain a reaction gas.
The gas 3 can supply tetraethoxysilane vapor | steam by bubbling the tetraethoxysilane (liquid) heated at 60 degreeC using a part of gas 1. FIG.
[0115]
The roll electrode 21 of the plasma discharge treatment apparatus 10 was coated with 1 mm of alumina by ceramic spraying on a stainless steel jacket roll base material having cooling means with cooling water, and then tetramethoxysilane was diluted with ethyl acetate. After the solution was applied and dried, it was cured by ultraviolet irradiation and sealed, and a roll electrode 25 having a dielectric (relative dielectric constant 10) having a smooth surface and an Rmax of 5 μm was produced and grounded. On the other hand, as an application electrode, a hollow square stainless steel pipe was covered with the same dielectric as described above under the same conditions to form an opposing electrode group.
[0116]
Next, the following clear hard coat layer was applied onto the cellulose ester film, and film formation was performed on the clear hard coat layer in the same manner as the base films 1 to 6 to prepare base films 7 to 12.
(Generation method of clear hard coat layer)
The following clear hard coat layer coating composition was coated with an extrusion coater to a wet film thickness of 13 μm, then dried in a drying section set at 80 ° C., and then 120 mJ / cm²Then, a clear hard coat layer having a dry film thickness of 4 μm and an arithmetic average roughness (Ra) of 15 nm is produced.
(Clear hard coat layer coating composition)
60 parts by mass of dipentaerythritol hexaacrylate monomer
Dipentaerythritol hexaacrylate dimer 20 parts by mass
Dipentaerythritol hexaacrylate trimer or higher component 20 parts by mass
4 parts by weight of dimethoxybenzophenone photoinitiator
50 parts by mass of ethyl acetate
50 parts by mass of methyl ethyl ketone
50 parts by mass of isopropyl alcohol
[0117]
Next, the carbon content of the produced base films 1 to 12 was measured by the following measuring method.
(1) The carbon content is measured using an XPS surface analyzer.
There is no particular limitation on the XPS surface analyzer, and any model can be used. In this example, ESCALAB-200R manufactured by VG Scientific, Inc. was used. Mg was used for the X-ray anode, and measurement was performed at an output of 600 W (acceleration voltage: 15 kV, emission current: 40 mA).
The energy resolution was set to be 1.5 to 1.7 eV when defined by the half width of a 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 thickness of the thin film in order to eliminate the influence of contamination. For the removal of the surface layer, it is preferable to use an ion gun that can use rare gas ions. As the ion species, He, Ne, Ar, Xe, Kr, or the like can be used. In this measurement, the surface layer was removed using Ar ion etching.
[0118]
(2) The range of binding energy from 0 eV to 1100 eV was measured at a data acquisition interval of 1.0 eV to determine what elements were detected.
(3) Next, with respect to all the detected elements except the etching ion species, the data capture interval was set to 0.2 eV, and the photoelectron peak giving the maximum intensity was subjected to narrow scan, and the spectrum of each element was measured. .
The obtained spectrum is COMMON DATA PROCESSING SYSTEM (Ver. 2.3 or later is preferable) manufactured by VAMAS-SCA-JAPAN in order not to cause a difference in the content calculation result due to a difference in measuring apparatus or computer. After being transferred to the top, the process was performed with the same software, and the value of carbon content was determined as atomic concentration.
[0119]
Before performing the quantitative process, a calibration of the Scale Scale was performed for each element, and a 5-point smoothing process was performed. In the quantitative process, the peak area intensity (cps * eV) from which the background was removed was used. For the background treatment, the method by Shirley was used. For the Shirley method, see D.C. A. Shirley, Phys. Rev. , B5, 4709 (1972).
[Table 1]

[0120]
3. Production of anti-glare layer film
Antiglare layer films 1 to 24 were produced on the base films 1 to 12 using the plasma discharge treatment apparatus 10 shown in FIG. 6 under the following plasma treatment conditions.
(Plasma power frequency and manufacturer)
13.56 MHz (made by Pearl Industry)
(Discharge output condition)
8W / cm²
(Gas condition 1)
Gas 1: Argon: 98.0% by volume
Gas 2: Oxygen: 2.0% by volume with respect to the entire mixed gas
The above gases 1 and 2 were uniformly mixed and supplied to the discharge space to obtain a reaction gas.
(Gas condition 2)
Gas 1: Argon: 98.0% by volume
Gas 2: CF4: 1.0% by volume with respect to the entire mixed gas
Gas 3: Oxygen: 1.0% by volume with respect to the entire mixed gas
[0121]
The antiglare layer film produced as described above was evaluated for center line average roughness (Ra), antiglare property, glare feeling, and surface uniformity, and the results are shown in Table 2.
(Ra measurement method)
For the centerline average surface roughness Ra (μm), Ra with an area of 299.4 μm × 232.4 μm was measured using a non-contact three-dimensional surface analyzer (RST / PLUS manufactured by WYKO). Ra was defined according to JIS surface roughness (B0601). The measurement was performed by dividing each sample of 30 cm × 30 cm into 100 grids at intervals of 3 cm, measuring the center of each square region, and calculating the average value and standard deviation from 100 measurements. For the centerline average surface roughness (Ra), a portion of the measurement length L is extracted from the obtained roughness curve in the direction of the centerline, the centerline of this extracted portion is the X axis, and the direction of the vertical magnification is the Y axis. When the roughness curve is represented by Y = f (X), the value obtained by the following formula is represented by micrometers (μm).
[Expression 1]

[0122]
(Anti-glare evaluation method)
Exposed fluorescent lamp (8000cd / m without louver) on the prepared sample surface²), And the degree of blurring of the reflected image of the fluorescent lamp was evaluated by visual observation according to the criteria shown below.
A: The outline of the fluorescent lamp image is not known at all.
○: The outline of the fluorescent lamp image is slightly visible.
Δ: The fluorescent lamp image is blurred, but the outline can be identified.
X: The fluorescent lamp image is hardly blurred.
[0123]
(Evaluation method for glare feeling)
The diffused light of a fluorescent lamp having a louver was projected on the sample surface produced as described above, and the glare sensation rank was evaluated by visual observation according to the criteria shown below.
A: No glare is recognized.
○: Almost no glare is observed.
Δ: Slight glare is observed.
X: Glare is clearly recognized.
[0124]
(Evaluation method of surface uniformity)
The sample surface prepared as described above was irradiated with flat diffused light from behind, and the surface uniformity was evaluated by visual observation of the surface state of the surface according to the following criteria.
○: Unevenness is not observed.
X: Unevenness is clearly observed.
[Table 2]

[0125]
It was confirmed that the antiglare layer film according to the present invention has excellent antiglare properties, no glare, and excellent surface uniformity.
[0126]
【The invention's effect】
According to the present invention, it is possible to provide a surface treatment method and a method for forming an antiglare layer that form ideal irregularities and voids for antiglare properties on a substrate without going through complicated steps. An antiglare layer film and an antiglare low reflection film having an antiglare layer formed by a surface treatment method and an antiglare layer forming method can be provided.
[Brief description of the drawings]
FIG. 1 is a schematic view showing an example of a plasma discharge treatment container.
FIG. 2 is a schematic view showing another example of a plasma discharge treatment container.
FIGS. 3A and 3B are perspective views showing an example of a cylindrical roll electrode. FIGS.
4A and 4B are perspective views showing an example of a fixed cylindrical electrode.
FIGS. 5A and 5B are perspective views showing an example of a fixed prismatic electrode. FIG.
FIG. 6 is a schematic view showing an example of a plasma discharge treatment apparatus.
[Explanation of symbols]
F base material
20 Plasma discharge treatment vessel
21, 22, 29 electrodes
21a, 21A, 22a, 22A, 29a, 29A Conductive base material such as metal
21b, 22b, 29b Ceramic coating dielectric
21B, 22B, 29B Lined dielectric
23a, 23b Nip roller
24, 25 Guide roller
26 Partition plate
27 Air supply port
28 Exhaust vent
40 Gas generator
41 Gas filling means
50 power supply
70 Electrode cooling unit

Claims (10)

The object to be processed carbon content plasma resistance Ri by the different substances was formed in 5-20% of non-uniform controlled surface of the thin film substrate to the composition, a pressure of atmospheric pressure or a pressure near atmospheric pressure A surface treatment method characterized by forming irregularities and voids in the thin film by atmospheric pressure plasma treatment exposed to a reactive gas in a plasma state to form the thin film as an antiglare layer. The surface treatment method according to claim 1,
At least one of the substances is a substance that is easily gasified by the atmospheric pressure plasma treatment. The surface treatment method according to claim 1,
A surface treatment method, wherein at least one of the substances is an organic substance. It is the surface treatment method as described in any one of Claims 1-3 ,
A surface treatment method, wherein the thin film is produced by coating so as to have a non-uniform composition. It is the surface treatment method as described in any one of Claims 1-3 ,
The surface treatment method, wherein the thin film is generated by plasma treatment so as to have a non-uniform composition. It is the surface treatment method as described in any one of Claims 1-5 ,
A surface treatment method, wherein the atmospheric pressure plasma treatment is performed using a mixed gas containing at least one kind of inert gas and the reactive gas. The surface treatment method according to claim 6 ,
The surface treatment method according to claim 1, wherein the reactive gas contains a gas composed of a compound containing oxygen or fluorine. A method for forming an antiglare layer, comprising forming an antiglare layer on the surface of the substrate by the surface treatment method according to claim 1 . An antiglare layer film comprising the antiglare layer formed by the method for forming an antiglare layer according to claim 8 . An anti-glare low-reflection film comprising an anti-reflection layer on the upper surface of the anti-glare layer film according to claim 9 .

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