JP2006299000A - Surface treatment method, plasma discharge treatment apparatus, anti-glare film and anti-glare low-reflection film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a surface treatment method for forming an anti-glare layer, which requires a short treatment time and no complex step, a plasma discharge treatment apparatus, and an anti-glare film and an anti-glare low-reflection film formed using the surface treatment method and the plasma discharge treatment apparatus. <P>SOLUTION: In the surface treatment method, an electric field with a non-uniform intensity distribution is generated in a region between the opposed electrodes under atmospheric pressure or under a pressure near atmospheric pressure, a mixed gas of a nitrogen gas and a reactive gas is converted into a non-uniform plasma state by the electric field with the non-uniform intensity distribution in the region between the opposed electrodes, and the surface of a substrate to be treated is subjected to the mixed gas in the plasma state to form irregularities and gaps on the surface of the subject to be treated. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention provides a surface treatment method and a plasma discharge treatment apparatus for processing a fine shape on the surface of a substrate by bringing a reactive gas into a plasma state under atmospheric pressure or a pressure near atmospheric pressure and exposing it to the substrate. The present invention relates to an antiglare film and an antiglare low-reflection film formed by these surface treatment methods and plasma discharge treatment apparatuses.

  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.

  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 of forming such irregularities, for example, a method of adding fine particles to a coating solution has been used (see, for example, Patent Document 1). In addition, the embossing method (for example, refer patent document 2). A method of transferring a mold in advance (for example, see Patent Document 3). Etc. are known.
JP 59-58036 A JP-A-6-234175 JP-A-63-298201

  However, the above-described embossing and the method of transferring a mold in advance are difficult to form fine irregularities and are insufficient to prevent glare, and fine particles capable of forming fine irregularities are obtained. In the method of adding to the coating solution, the necessary irregularities are formed only by the fine particles, so it is necessary to add a large amount of fine particles, and scattering is generated inside the coating layer regardless of the irregularities on the surface. The image is blurred and the processing time is long.

  In view of the above problems, an object of the present invention is to provide a surface treatment method and a plasma discharge treatment apparatus for producing an antiglare layer that does not require a complicated process with a short treatment time, as well as these surface treatment method and plasma. An object is to provide an antiglare film and an antiglare low-reflection film formed by an electric discharge treatment apparatus.

  The object of the present invention is achieved by the following means.

  (1) An electric field having a non-uniform intensity distribution is generated in an opposing region of the opposing electrode under atmospheric pressure or a pressure near atmospheric pressure, and a mixed gas of nitrogen gas and reactive gas is generated by the non-uniform intensity distribution electric field. A surface treatment method characterized by forming a non-uniform plasma state in a region facing the electrode and exposing the surface of the object to be processed to the mixed gas in the plasma state to form irregularities and voids on the surface of the object to be processed .

  (2) The substrate of at least one of the opposing electrodes has uneven unevenness on the surface facing the other electrode, and the uneven electric field intensity distribution is not present in the opposing region of the opposing electrode due to the unevenness. The surface treatment method according to claim 1, wherein an electric field is generated.

  (3) At least one of the opposing electrodes has an electrode base material and a dielectric material deposited on the base material, and the dielectric material has unevenness on the surface facing the other electrode. 2. The surface treatment method according to claim 1, wherein an electric field having a non-uniform electric field intensity distribution is generated in an opposing region of the opposing electrodes due to the unevenness.

  (4) The deposited dielectric has projections and depressions on the surface facing the other electrode, and the deposition surface of the dielectric and the substrate has projections and depressions. The surface treatment method according to claim 1, wherein an electric field having a non-uniform electric field intensity distribution is generated in the opposite region of the surface.

  (5) At least one of the opposing electrodes has an electrode base material and a dielectric material deposited on the base material, and the deposited dielectric material faces the other electrode. The surface is a uniform plane, and the deposition surface of the dielectric and the substrate has irregularities, and the irregularities generate an electric field with a non-uniform electric field strength distribution in the opposing regions of the opposing electrodes. The surface treatment method according to claim 1, wherein the surface treatment method is characterized.

  (6) The surface treatment method according to any one of claims 1 to 5, wherein the irregularities are irregularities having a maximum surface roughness defined by JIS-B-0601 of 10 μm or more.

(7) An electric field having a non-uniform intensity distribution is generated in the opposing region of the opposing electrode under atmospheric pressure or a pressure near atmospheric pressure, and a mixed gas of nitrogen gas and reactive gas is generated by the non-uniform intensity distribution electric field. A non-uniform plasma state in the opposing region of the electrode, exposing the surface of the object to be processed to the mixed gas in the plasma state to form irregularities and voids on the surface of the object to be processed,
At least one of the opposing electrodes has a base material of the electrode and a dielectric attached to the base material, and is formed by the applied dielectric and the opposing electrode. 2. The discharge intensity distribution generated between the electrodes is made non-uniform by making the minute electrostatic capacity distribution non-uniform in the opposing region of the electrodes. Surface treatment method.

  (8) The surface treatment method according to claim 7, wherein the minute electrostatic capacity distribution is made non-uniform by making the thickness of the dielectric non-uniform.

  (9) The electric field having a non-uniform intensity distribution is generated between the electrodes by making the distance between the electrodes non-uniform in the opposing region of the opposing electrodes. 2. The surface treatment method according to item 1.

  (10) An electric field having a non-uniform intensity distribution is generated in an opposing region of the opposing electrode, and the object to be processed is exposed to a mixed gas that has become a plasma state due to the electric field having the non-uniform intensity distribution. The surface treatment method according to claim 1, wherein irregularities and voids are formed on the surface of the object to be processed by etching the surface of the object to be processed with a mixed gas.

  (11) An electric field having a non-uniform intensity distribution is generated in the opposing region of the opposing electrode under atmospheric pressure or a pressure near atmospheric pressure, and a mixed gas of nitrogen gas and reactive gas is generated by the electric field having the non-uniform electric field intensity distribution. And forming a thin film having irregularities and voids on the surface of the object to be processed by exposing the surface of the object to be processed to the mixed gas in the plasma state. Surface treatment method.

  (12) A power source that generates an electric field having a non-uniform intensity distribution in an opposing region of opposing electrodes is at least one power source that outputs a voltage of a predetermined frequency connected to at least one of the electrodes. The surface treatment method according to claim 1.

  (13) The power sources for generating an electric field having a non-uniform intensity distribution in the opposing region of the opposing electrodes are two power sources that output voltages of different frequencies respectively connected to the opposing electrodes. The surface treatment method according to any one of 1 to 11.

  (14) An antiglare film having an antiglare layer formed by the surface treatment method according to any one of claims 1 to 13.

  (15) An antiglare low reflection film comprising an antireflection layer on the top surface of the antiglare film according to claim 14.

(16) At least one pair of electrodes facing each other, a gas supply means for supplying a mixed gas of nitrogen gas and a reactive gas to a region facing the electrodes, and at least one power source for applying a high-frequency voltage to at least one of the electrodes Have
At least one surface of the electrode has unevenness, and the unevenness generates an electric field having a non-uniform intensity distribution in the opposing region of the opposing electrode, and the electric field having the non-uniform intensity distribution in the opposing region of the opposing electrode. A plasma discharge treatment apparatus characterized by generating plasma of the mixed gas and exposing the mixed gas in the plasma state to the surface of the object to be processed to form irregularities and voids on the surface of the object to be processed.

  (17) The plasma discharge processing apparatus according to claim 16, wherein the unevenness of the electrode surface has a maximum surface roughness defined by JIS-B-0601 of 10 μm or more.

  (18) A dielectric is deposited on a surface of at least one of the electrodes facing each other, and at least a surface of the dielectric facing the electrode facing each other has irregularities. 2. A plasma discharge treatment apparatus according to 1.

  (19) The plasma discharge processing apparatus according to claim 18, wherein the unevenness of the dielectric surface has a maximum surface roughness defined by JIS-B-0601 of 10 μm or more.

  (20) The surface treatment method according to any one of claims 16 to 19, wherein the power supply is at least one power supply that outputs a voltage having a predetermined frequency connected to at least one of the electrodes. .

  (21) The surface treatment method according to any one of claims 16 to 19, wherein the power supply is a power supply that outputs voltages of different frequencies respectively connected to opposing electrodes.

  The plasma discharge that generates an electric field having a non-uniform intensity distribution in the opposing region of the opposing electrode using nitrogen as a mixed gas, as described in (1). A surface treatment method shortened to about 2/3 to 1/2 can be provided.

  (2), (3), (4), or (5), the surface of the electrode substrate has irregularities, the dielectric surface has irregularities, or the electrode surface has irregularities And having an uneven surface on the dielectric substrate on the electrode substrate, or having an even surface on the electrode surface and forming an uneven surface on the dielectric substrate surface on the electrode substrate As a result, it is possible to provide a surface treatment method that exhibits the effect described in the item (1) without causing discharge to spread outside from the opposing region of the electrode.

  By setting the maximum surface roughness of the unevenness as described in (6) to 10 μm or more, stable discharge can be achieved without concentration of discharge in a specific portion in the opposing region of the electrode, and the description in (1) It is possible to provide a surface treatment method that exhibits an effect.

  (7) and (8), the capacitance formed by the non-uniform thickness of the dielectric applied to the substrate and the facing electrode, and a very small capacitance in the facing region of the electrode By making the distribution non-uniform, it is possible to provide a surface treatment method that makes the discharge intensity distribution generated between the electrodes non-uniform and exhibits the effect described in the item (1).

  By making the interelectrode distance described in (9) non-uniform, it is possible to provide a surface treatment method that makes the discharge intensity distribution generated between the electrodes non-uniform and exhibits the effect described in (1).

  It is possible to form unevenness on the surface of the object to be processed by etching the surface of the object to be processed by the electric field having a non-uniform intensity distribution in the opposing region of the electrode described in (10), and the item (1) It is possible to provide a surface treatment method that exhibits the above effect.

  (11) Asperities and the like are caused by plasma discharge that generates an electric field having a non-uniform intensity distribution in a facing region of opposing electrodes using at least nitrogen gas and a thin film forming gas for forming a thin film as a mixed gas. It is possible to form a thin film, and it is possible to provide a surface treatment method that exhibits the effect described in item (1).

  By connecting a single frequency power source described in (12) to one electrode, it is possible to provide a surface treatment method that exhibits the effect described in (1).

  By connecting power supplies of different frequencies as described in (13) to different electrodes, the surface having the effect as described in (1), which has a shorter processing time compared to the case of the single power supply described in (12) A processing method can be provided.

  By performing the surface treatment method described in (1) to (13) described in (14), an antiglare film can be obtained.

  By performing the surface treatment method described in (1) to (13) described in (15), an antiglare low reflection film can be obtained.

  According to (16), at least nitrogen is used for the mixed gas, and the opposing surface of at least one of the opposing electrodes has irregularities, and an electric field having a non-uniform intensity distribution is generated in the opposing region of the opposing electrode, resulting in non-uniformity. The surface treatment device that causes plasma discharge by an electric field having a strong intensity distribution and exposes the object to be treated to the plasma discharge reduces the treatment time to about 2/3 to 1/2 compared to a surface treatment device that does not use nitrogen. A surface treatment apparatus can be provided.

  (17), (18), and (19), at least one of the electrodes is coated with a dielectric, and the maximum surface roughness of the electrode (dielectric) surface is set to 10 μm or more so that the electrodes face each other. It is possible to provide a surface treatment apparatus in which discharge does not spread from the region to the outside, and stable discharge is possible without causing the discharge to concentrate on a specific portion in the region facing the electrode.

  By connecting a single frequency power source described in (20) to one electrode, it is possible to provide a surface treatment method that exhibits the effect described in (16).

  By connecting power sources having different frequencies described in (21) to different electrodes, a surface that achieves the effect described in (16), which has a shorter processing time than the case of the single power source described in (20). A processing method can be provided.

  The present invention intends to form surface irregularities and voids for anti-glare on the surface of an object to be processed (base material) by utilizing surface treatment by atmospheric pressure plasma.

  In order to form ideal irregularities and voids for anti-glare on the surface of the substrate, the present inventor actively promotes microscopic non-uniform plasma discharge variation (non-uniformity) in the opposing region of the discharge electrode. Use, that is, slight unevenness on the surface of the electrode that causes non-uniformity in the electric field (discharge) applied between the discharge electrodes, or small unevenness in the thickness of the dielectric deposited on the electrode, and further, the discharge gap is very small It has been found that it is effective to take advantage of non-uniformity.

  Further, it has been found that unevenness and voids can be formed more effectively by converting the mixed gas containing nitrogen into plasma by an electric field in which electric fields of different frequencies are superimposed, thereby providing an antiglare property with a high processing speed. The surface treatment process can be provided, and further, it can be in-lined with other processes required for producing an antiglare film and an antiglare low-reflection film.

  As a result, it is possible to perform continuous processing without going through complicated steps, to manufacture an antiglare film and an antiglare low reflection film, and to improve productivity.

  Hereinafter, preferred embodiments of the surface treatment method, plasma discharge treatment apparatus, antiglare film, and antiglare low reflection film forming method according to the present invention will be described with reference to the drawings. In the following description, there are assertive expressions for terms and the like. However, these are examples of preferred embodiments of the present invention and limit the meaning and technical scope of the terms of the present invention. It is not a thing.

  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.

  FIG. 1 is a schematic diagram illustrating an example of a plasma discharge processing apparatus 10.

  In FIG. 1, a long film-like substrate F is conveyed while being wound around a roll electrode 21 rotating in a conveying direction (clockwise in the drawing) from a roll R around which a film-like substrate is wound. The fixed electrode (fixed electrode) 22 is composed of a plurality of prisms or prismatic cylinders, and is installed facing the roll electrode 21. The substrate F wound around the roll electrode 21 is pressed by the nip rollers 23 a and 23 b, is regulated by the guide roller 24, and is conveyed to the discharge processing space secured by the plasma discharge processing container 20. Then, a discharge plasma treatment is performed in the discharge treatment space, and then conveyed to the next process via the guide roller 25. Further, 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.

  In the plasma discharge processing vessel 20, a gas generator 40 that generates a mixed gas, a first power source 50, an electrode cooling unit 70, and the like are arranged.

  The gas generator 40 generates a mixed gas G, which is used for the plasma discharge treatment, and is a mixture of a discharge gas such as nitrogen gas and a reactive gas such as an organic fluorine compound, a titanium compound, or a silicon compound. To do. The mixed gas G is introduced into the plasma discharge processing container 20 from the air supply port 27, and the exhaust gas G ′ after the processing is exhausted from the exhaust port 28.

  The first power supply 50 is not particularly limited, but is a Shinko electric high frequency power supply (3 kHz), a Shinko electric high frequency power supply (5 kHz), a Kasuga electric high frequency power supply (15 kHz), a Shinko electric high frequency power supply (50 kHz). ), A high-frequency power source (100 kHz) manufactured by HEIDEN Laboratory, etc. can be used.

  The high-frequency power supply (100 kHz) manufactured by HEIDEN Laboratories has an intermittent oscillation mode called ON / OFF, which is called a pulse mode, but the voltage waveform supplied from each power supply is continuous like other power supplies. The sine waveform may be an intermittent oscillation waveform such as a high-frequency power source manufactured by HEIDEN Laboratory.

  Moreover, as a coolant for the electrode cooling unit 70, an insulating material such as distilled water or oil is used, and the surface of the roll electrode 21 and the fixed electrode 22 is circulated through the roll electrode 21 and the fixed electrode 22 with a predetermined surface. Adjust to temperature.

  The atmospheric pressure plasma treatment by the plasma discharge treatment apparatus 10 will be described. A roll electrode 21 and a fixed electrode 22 are arranged at predetermined positions in the plasma discharge treatment vessel 20, and a first power supply 50 is connected to the roll electrode 21. The fixed electrode 22 is connected to the ground.

  The flow rate of the mixed gas G generated by the gas generator 40 is controlled and supplied to the plasma discharge processing container 20 from the air supply port 27 via the gas filling means 41. The inside of the plasma discharge processing container 20 is used for the plasma processing. Filled with gas G.

  A high-frequency electric field is applied to the facing region 301 between the roll electrode 21 and the fixed electrode 22 by the first power supply 50 and discharged to generate plasma of the mixed gas G.

  The substrate F is conveyed between the roll electrode 21 and the fixed electrode 22 while being attached to the roll electrode 21. And while conveying between the roll electrode 21 and the fixed electrode 22, an unevenness | corrugation and a space | gap are formed in the surface of the base material F with the generated discharge plasma. Further, a thin film corresponding to the thin film forming gas in the mixed gas may be formed, and irregularities and voids may be formed on the surface of the substrate F.

  The base material F ′ having irregularities formed on the surface by the discharge plasma (discharge-treated) is required for manufacturing an anti-glare film or an anti-glare low reflection film (not shown) via the guide roller 25. It is conveyed to the process.

  In addition, although the value of the voltage applied to the roll electrode 21 from the 1st power supply 50 is determined suitably, for example, a voltage is about 0.5 kV-10 kV, and is adjusted to 200 kHz or less at 1 kHz or more. Here, regarding the voltage waveform of the power supply, either a continuous sine wave continuous oscillation mode called a continuous mode or an intermittent oscillation mode called ON / OFF intermittently called a pulse mode may be adopted. This is preferable because a denser and better quality film can be obtained.

  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 F at the time of the discharge plasma treatment is adjusted to a temperature of room temperature (15 ° C. to 25 ° C.) to less than 200 ° C. It is preferable to adjust to room temperature to 100 ° C. In order to adjust to the above temperature range, if necessary, the roll electrode 21 and the fixed electrode 22 are subjected to discharge plasma treatment while being cooled by an electrode cooling unit 70 which is an electrode cooling means.

  In the present embodiment, the irregularities and voids are formed on the substrate. However, the present invention is not limited to this, and a thin film having irregularities and voids may be formed. The surface of the clear hard coat layer applied to the surface of the substrate F is etched with a plasma state gas using the plasma discharge treatment apparatus 10 to form irregularities and voids on the surface of the substrate F or the hard coat layer. It is good also as what to do.

  FIG. 2 is a schematic view showing an example of another plasma discharge treatment apparatus 30.

  The difference from FIG. 1 is basically only that the second power source 60 is added to the fixed electrode 22, so only the different parts will be described.

  In addition to the above, a second power source 60 is disposed in the plasma discharge processing container 20.

  Although there is no limitation in particular as the 2nd power supply 60, Pearl industrial high frequency power supply (200 kHz), Pearl industrial high frequency power supply (800 kHz), JEOL high frequency power supply (13.56 MHz), Pearl industrial high frequency power supply (150 MHz) ) Etc. can be used.

  The atmospheric pressure plasma processing by the plasma discharge processing apparatus 30 will be described. A roll electrode 21 and a fixed electrode 22 are disposed at predetermined positions in the plasma discharge processing container 20, and a second power source 60 is connected to the fixed electrode 22. The first power supply 50 is connected to the roll electrode 21.

  A high-frequency electric field in which voltages having different frequencies are superimposed by the first power supply 50 and the second power supply 60 is applied to the facing region 301 between the roll electrode 21 and the fixed electrode 22 to cause discharge to generate plasma of the mixed gas G Let

  The value of the voltage applied from the second power supply 60 to the fixed electrode 22 is appropriately determined. For example, the voltage is about 0.1 kV to 10 kV, and the power supply frequency is adjusted to 100 kHz or more and 150 MHz or less. Here, as a method of applying power, either a continuous sine wave continuous oscillation mode called a continuous mode or an intermittent oscillation mode that performs ON / OFF intermittently called the pulse mode described above may be employed.

Note that a first filter 51 is installed between the roll electrode 21 and the first power supply 50 to facilitate passage of current from the first power supply 50 to the roll electrode 22, and current from the second power supply 60. , The current from the second power source 60 to the first power source 50 becomes difficult to pass through,
A second filter 61 is installed between the fixed electrode 22 and the second power source 60 to facilitate passage of current from the second power source 60 to the fixed electrode 22 and to ground the current from the first power source 50. Thus, it is difficult to pass current from the first power supply 50 to the second power supply 60.

The first high-frequency power supply 50 can apply the frequency ω ₁ , the output current I ₁ per unit area of the discharge surface of the electrode, and the electric field strength V ₁ between the fixed electrode 22 and the roll electrode 22. The high frequency power supply 60 can apply a frequency ω ₂ , an output current I ₂ per unit area of the discharge surface of the electrode, and an electric field strength V ₂ between the fixed electrode 22 and the roll electrode 22.

Then, a high-frequency electric field in which the frequency ω ₁ and the frequency ω ₂ are superimposed is generated in the opposing region 301 between the fixed electrode 22 and the roll electrode 21 by both power sources.

When the discharge gas is nitrogen, if the electric field strength applied between the electrodes for starting discharge with respect to nitrogen is IV, the discharge starts stably, and the thin film forming gas and the like are stably excited even after the discharge starts. to be able to do,
Each power source has a relationship of ω ₂ > ω ₁ and V ₁ ≧ IV> V ₂ or V ₁ > IV ≧ V ₂ , and the electric field intensity capable of starting the discharge of nitrogen is 3.7 kV / mm. When the electric field intensity at which nitrogen discharge can be started is IV, the electric field intensity V ₁ applied from at least the first high-frequency power supply 50 is 3.7 kV / mm or more, and the electric field applied from the second high-frequency power supply 60 is The strength V ₂ is preferably 3.7 kV / mm or less.

The current is preferably I ₁ <I ₂ per unit area of the discharge surface of the electrode. Current I ₁ is preferably ^{0.3mA / cm 2 ~20mA / cm 2} , more preferably at ^{1.0mA / cm 2 ~20mA / cm 2} . The current I ₂ is preferably ^{10mA / cm 2 ~100mA / cm 2} , more preferably ^{20mA / cm 2 ~100mA / cm 2} .

The relationship between the frequencies ω ₁ and ω ₂ and the applied electric field strengths V ₁ and V ₂ related to the first high frequency power supply 50 and the second high frequency power supply 60 is ω ₁ > ω ₂ and V ₁ ≦ IV <. V ₂ or V ₁ <may IV ≦ V _2.

  FIG. 3 is a schematic view showing an example of the cylindrical roll electrode 21 described above.

The structure of the roll electrode 21 will be described. In FIG. 3A, the roll electrode 21 is an inorganic material after thermal spraying ceramics on a conductive base material 21a (hereinafter also referred to as “electrode base material”) such as metal. And a ceramic coating treated dielectric 21b (hereinafter, also simply referred to as “dielectric”) that has been subjected to sealing treatment.
Further, as shown in FIG. 3B, the roll electrode 21 may be configured by a combination in which a conductive base material 21A such as metal is covered with a lining dielectric 21B provided with an inorganic material by lining.

  In the roll electrode 21, the conductive base material 21a is connected to the ground in the plasma discharge processing apparatus 10, and the plasma discharge processing apparatus 30 is connected to the second high-frequency power source 60 through a filter.

  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).

  FIG. 4 is a schematic diagram showing an example of a prismatic fixed electrode 22.

  In FIG. 4 (a), the fixed electrode 22 of a prism or a rectangular cylinder is sealed with an inorganic material after thermal spraying ceramics on a conductive base material 22a such as metal, like the roll electrode 21 described above. The ceramic coating treatment dielectric 22b is applied in combination. As shown in FIG. 4 (b), the prismatic or prismatic fixed electrode 22 is composed of a combination of a conductive base material 22A such as metal coated with a lining dielectric 22B provided with an inorganic material by lining. May be.

  In order to generate an electric field having a non-uniform intensity distribution in the opposing region 301 between the roll electrode 21 and the fixed electrode 22 and to make the plasma discharge intensity non-uniform, the following process is performed.

  FIG. 5 is a conceptual diagram of an electrode having an uneven surface.

  FIG. 5 is a partial cross-sectional perspective view of the facing surface 211 of the roll electrode 21 and the fixed electrode 22 facing the facing electrode, and at least the discharge portion of the electrode (roll electrode 21 and / or fixed electrode 22) provided with irregularities on the surface. Are provided with a plurality of uneven unevenness 29 or a plurality of uneven unevenness 29 and a plurality of gaps (not shown).

  The uneven unevenness means the unevenness 29 whose position, height, and shape of the unevenness are indefinite, and in particular, the maximum height of the surface roughness in which the roughness of the unevenness is defined by JIS B 0601. (Rmax) refers to 10 μm or more, and the non-uniform surface refers to a surface having irregularities with a maximum height (Rmax) of surface roughness of 10 μm or more.

  The uniform or uniform plane is a plane having a maximum roughness (Rmax) of the surface roughness specified by JIS B 0601 having only irregularities of less than 10 μm, or a plane having only irregularities having an Rmax of less than 10 μm. pointing.

  In the present invention, Rmax is preferably 10 μm or more for the plurality of uneven unevenness.

  In addition, a plurality of non-uniformities on the non-uniform surface of the dielectric applied to the electrode base material to be described later have the same shape.

  FIG. 6 is a partial cross-sectional view of an electrode having irregularities on the surface. FIG. 7 is a partial cross-sectional view of an electrode in which irregularities are provided on a surface without a dielectric. FIG. 8 is a partial cross-sectional view of another form of electrode having a uniform surface.

  Hereinafter, the structure of the electrode will be described, but a description will be given by taking, as an example, a case where a plurality of uneven unevenness is provided on the roll electrode 21, for example.

  First, FIG. 6 will be described. In FIG. 6A, the electrode base material 21a of the roll electrode 21 has a uniform thickness, and the deposition surface 212 of the dielectric 21b on the electrode base material 21a is a uniform plane. The formed dielectric 21b has a plurality of non-uniform irregularities having a non-uniform thickness on the surface. For this reason, the opposed surface 211 of the roll electrode 21 to the fixed electrode has a plurality of unevenness.

  In FIG. 6B, the electrode base material 21a of the roll electrode 21 has a plurality of non-uniform irregularities having a non-uniform thickness, and the surface 212 of the dielectric 21b applied to the electrode base material 21a is non-uniform. A plurality of irregularities are formed, and the dielectric 21b has a uniform thickness. For this reason, the surface 211 facing the fixed electrode of the roll electrode 21 has a plurality of unevenness due to the influence of the unevenness of the electrode base material 21a.

  In FIG. 6C, the electrode base material 21a and the dielectric 21b of the roll electrode 21 have a plurality of non-uniform irregularities having a non-uniform thickness, and the dielectric 21b is attached to the electrode base 21a. The surface 212 forms a plurality of uneven unevenness, and the surface 211 facing the fixed electrode of the roll electrode 21 has a plurality of uneven unevenness.

  Next, with reference to FIG. 7, the roll electrode 21 does not deposit a dielectric, and the surface 211 facing the fixed electrode of the electrode base material 21a is a surface having a plurality of unevenness.

  Next, referring to FIG. 8, the electrode base material 21a and the dielectric 21b of the roll electrode 21 have a plurality of non-uniform irregularities having a non-uniform thickness, and the dielectric 21b on the electrode base 21a The adherend surface 212 forms a plurality of uneven unevenness, and the facing surface 211 of the roll electrode 21 facing the fixed electrode is a uniform flat surface.

  The distance between the fixed electrode and the roll electrode, that is, the discharge gap is a concave portion and a convex portion due to a plurality of non-uniform irregularities on the facing surface 211 of the fixed electrode (not shown) facing the roll electrode 21 described in FIGS. Therefore, it is possible to generate an electric field having a non-uniform intensity distribution between the electrodes. As a result, it is considered possible to generate a discharge having a non-uniform discharge intensity distribution between the electrodes.

  The same can be said even when unevenness is provided on the surface of the fixed electrode.

Further, in the dielectric 21b having uneven unevenness described with reference to FIGS. 8, 6A, and 6C, the roll electrode 21 and the fixed electrode 22 (not shown) are replaced with the fixed electrode and the roll electrode. When the capacitor is considered as a capacitor with a dielectric 21b sandwiched between them, the capacitance in a distributed constant sense differs between the concave and convex portions of the dielectric 21b due to the non-uniform thickness of the dielectric 21b.
As a result, it is considered that a discharge current corresponding to a capacity (impedance) in a distributed constant sense flows through the concave and convex portions, and as a result, non-uniform discharge can be generated between the electrodes.

  The same can be said even if a plurality of non-uniform irregularities are provided on the surface of the fixed electrode 22.

  For these reasons, when Rmax of a plurality of uneven unevenness increases, discharge concentrates on that portion, and it becomes difficult to form fine unevenness uniformly on the substrate, and when Rmax is 5 μm or less. The discharge intensity distribution becomes uniform and it becomes difficult to make it non-uniform.

  6 and 8, the thickness of the dielectric 21b is not particularly limited, but for example, ± 20 with respect to the average thickness in the front-rear direction (about 1 mm in the present embodiment). It has a thickness variation in the range of about%.

  In the plasma discharge treatment apparatuses 10 and 30 according to the present invention, at least one of the roll electrode 21 and the fixed electrode 22 disposed to face each other is the one shown in FIGS. 6 to 8. Any one of the configurations may be provided. For example, both the roll electrode 21 and the fixed electrode 22 may have one of the configurations shown in FIGS. 6 to 8, or either one of the roll electrode 21 and the fixed electrode 22 What is necessary is just to provide one structure among the structures shown in FIGS.

  With such a configuration, it is possible to generate an electric field having a non-uniform electric field intensity distribution between the electrodes as described above, and to generate a discharge having a non-uniform discharge intensity distribution between the electrodes.

  FIG. 9 is a conceptual diagram of unevenness and voids on the surface of the workpiece.

  FIG. 9 is a partial cross-sectional perspective view of the surface of the object 100 to be processed, and has a plurality of uneven portions 101 and a plurality of gaps (not shown) on the surface.

  The uneven unevenness 101 refers to a concave portion 101a that is deeply etched by a strong discharge portion, and a convex portion 101b that is a shallow etched portion and a portion that is not etched.

  It is deeply etched by strong discharge and shallowly etched by weak discharge.

  And the position, height (depth), and shape of the unevenness | corrugation 101 are indefinite by the electric field (strong discharge / weak discharge) of non-uniform intensity distribution.

  Moreover, the maximum height (Rmax) of the surface roughness defined by the roughness of the surface according to JIS B 0601 is 10 μm or more.

  Below, the gas used for the plasma discharge treatment apparatus 10 and 30 of this invention shown in FIG.1 and FIG.2 is demonstrated.

  In the present invention, the gas supplied from the gas generator 40 to the plasma discharge treatment apparatuses 10 and 30 varies depending on the type of thin film desired to be provided on the substrate, but basically forms a discharge gas for performing discharge and a thin film. It is a mixed gas of reactive gas for.

  Examples of the discharge gas include nitrogen and 18th group elements of the periodic table, specifically helium, neon, argon, krypton, xenon, radon, etc., but the effect of increasing the processing speed of the present invention. In order to obtain it, nitrogen is particularly preferably used.

  The reactive gas is preferably contained in an amount of 0.01 to 10% by volume with respect to the mixed gas, and a thin film having a thickness in the range of 0.1 nm to 1000 nm is obtained.

  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.

  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.

  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.

  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.

  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.

  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.

  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.

  Further, when the organic fluorine compound is a gas at normal temperature and 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 performed most easily. 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. .

  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. Moreover, reaction can be promoted by containing 0.01-5 volume% of components selected from oxygen, ozone, hydrogen peroxide, a carbon dioxide, carbon monoxide, and hydrogen in mixed gas.

  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.

  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.

  Titanium compounds 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, tetraisopropoxy titanium It is preferable to use a metal alkoxide such as tetrabutoxytitanium, but is not limited thereto.

  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 a thin film can be formed on the surface thereof, such as a film-like material or a three-dimensional shape such as a lens shape, but in order to improve productivity. In the case where the steps shown in FIGS. 1 and 2 are assembled, a film-like one is particularly preferable.

  The material constituting the substrate is not particularly limited, but a resin can be preferably used because it is under atmospheric pressure or pressure near atmospheric pressure. 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.

  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.

  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, a support body is not limited to said description. A film thickness of 10 μm to 1000 μm is preferably used as the film thickness.

  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.

  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.

  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, pyromellitic acid ester Examples of plasticizers include tetrabutyl pyromellitate, tetraphenyl pyromellitate, tetraethyl pyromellitate, In acid ester type, triacetin, tributyrin, ethyl phthalyl ethyl glycolate, methyl phthalyl ethyl glycolate, butyl phthalyl butyl glycolate, etc., citrate ester plasticizers such as triethyl citrate, tri-n-butyl citrate 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.

  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.

  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. 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.

  As the ultraviolet absorber, those excellent in the ability to absorb ultraviolet rays having a wavelength of 370 nm or less and having little 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.

  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 described in Japanese Patent Application No. 11-225209, so that the 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.

  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.

  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.

  Here, R0 (450) represents in-plane retardation based on three-dimensional refractive index measurement using light with a wavelength of 450 nm, and R0 (600) represents in-plane retardation based on three-dimensional refractive index measurement using light with a wavelength of 600 nm. .

  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.

  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.

  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.

  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).

  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). .

  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.

  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.

  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.

  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.

  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, UVECRYL22201, UVECRYL22202 (above, Daicel UCB), 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.

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. The irradiation conditions vary depending on individual lamps, but the amount of light irradiated may be any degree 20~10000mJ / cm ^2, preferably from 50~2000mJ / cm ^2. It can be used by using a sensitizer having an absorption maximum in the near ultraviolet region to the visible light region.

  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.

  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.

  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.

  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.

  Even if the layer formed by curing the ultraviolet curable resin thus formed is a clear hard coat layer having a center line surface roughness Ra of 1 to 50 nm, the center line surface roughness Ra is about 0.1 to 1 μm. It may be an antiglare layer. As described above, a layer obtained by curing an ultraviolet curable resin is applied to the surface of the substrate, and further, plasma treatment is performed on the upper surface by the plasma discharge treatment apparatus 10 or 30 described with reference to FIGS. Thus, irregularities and voids can be formed in the ultraviolet curable resin layer to form an antiglare layer.

  Here, it is preferable to use nitrogen gas as the discharge gas in order to shorten the processing time. In this case, it is preferable to perform plasma processing by the plasma discharge processing apparatus 30.

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) Backcoat 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 / Anti-glare layer / Medium refractive index layer / High refractive index layer / Low refractive index layer In order to facilitate wiping, an antifouling layer is preferably provided on the outermost low refractive index layer.

  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: 13.56 MHz (made by Pearl Industry)
Discharge output density: 4 W / cm ²
Gas conditions: Gas 1: Argon 99.8% by volume, Gas 2: Propylene hexafluoride 0.2% by volume
Moreover, the antistatic layer shown in the structural examples iv and v) can also 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: 13.56 MHz (made by Pearl Industry)
Discharge output density: 4 W / cm ²
Gas conditions: Gas 1: Argon 9.5% by volume, Gas 2: Bubbling argon into tetrabutyltin, Bubbling argon into triethylindium, and a mixture of tetrabutyltin and triethylindium vapor contained by these two bubblings 0 .5% by volume
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 was applied on the above-described antiglare film, dried at 100 ° C. for 5 minutes, and then irradiated with ultraviolet light at 180 mJ / hr using a high pressure mercury lamp (80 W). A medium refractive index layer (thickness: 77 nm, refractive index: 1.70) is provided by curing with cm ² irradiation.

Middle refractive index layer composition: Tetra (n) butoxytitanium 250 parts by mass, terminal-reactive dimethyl silicone oil (N-Unicar L-9000) 0.5 parts by mass, aminopropyltrimethoxysilane (Shin-Etsu Chemical KBE903) 22 parts by mass, UV curable epoxy resin (KR500, manufactured by Asahi Denka Co., Ltd.) 21 parts by mass, 4850 parts by mass of propylene glycol monomethyl ether, 4900 parts by mass of isopropyl alcohol: Coating of high refractive index layer: above formed middle refractive index layer The following high-refractive index layer composition was applied, dried at 100 ° C. for 5 minutes, and then cured by irradiating with UV light at 180 mJ / cm ² using a high-pressure mercury lamp (80 W). The thickness was 65 nm and the refractive index was 1.85).

High refractive index layer composition: 310 parts by mass of tetra (n) butoxytitanium, terminal-reactive dimethyl silicone oil (L-9000, manufactured by Nihon Unicar Company) 0.4 parts by mass, aminopropyltrimethoxysilane (KBE903, manufactured by Shin-Etsu Chemical Co., Ltd.) 4.8 parts by mass, UV curable epoxy resin (KR500 manufactured by Asahi Denka Co., Ltd.) 4.6 parts by mass, propylene glycol monomethyl ether 4800 parts by mass, isopropyl alcohol 4900 parts by mass Application of low refractive index layer: high refractive index formed above On the 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 irradiated with ultraviolet rays at 180 mJ / hour using a high-pressure mercury lamp (80 W). Irradiated with cm ² , a low refractive index layer (thickness is 95 nm and refractive index is 1.45) was provided.

  Low refractive index layer composition: tetraethoxysilane hydrolyzate (* 1) 1020 parts by mass, terminal reactive dimethyl silicone oil (L-9000, manufactured by Nippon Unicar Company) 0.42 parts by mass, propylene glycol monomethyl ether 2700 parts by mass, 6300 parts by mass of isopropyl alcohol, * 1: Preparation of tetraethoxysilane hydrolyzate 300 g of tetraethoxysilane and 455 g of ethanol were mixed, and 225 g of a 0.5% by mass citric acid aqueous solution was added thereto, followed by stirring at room temperature for 1 hour. Thus, a tetraethoxysilane hydrolyzate was prepared.

  Moreover, the film formation method by the plasma processing of an optical interference layer uses the plasma discharge processing apparatus 10 shown in FIG. 1 on the above-mentioned anti-glare layer, and follows the following procedures.

High refractive index layer: discharge gas: argon, hydrogen gas (1% with respect to argon), reaction gas: tetraisopropoxy titanium vapor (heated to 100 ° C. and bubbled with argon gas)
Discharge density: 450 W · min / m ² , processing speed: 30 m / min
Low refractive index layer: discharge gas: argon, hydrogen gas (1% with respect to argon), reaction gas: tetraethoxysilane vapor (bubbled with argon gas)
Discharge density: 400 W · min / m ² , processing speed: 30 m / min
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.

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 ultraviolet irradiation is preferably 50 to 2000 mJ / cm ² . If it is less than 50 mJ / cm ² , the effect is not sufficient, and if it exceeds 2000 mJ / cm ² , deformation of the substrate may occur, which is not preferable. 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.

For this reason, it is preferable to irradiate a plasma processing surface after plasma processing as 50-2000 mJ / cm < ² > as ultraviolet irradiation light quantity. 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.

  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.

  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.

  The high refractive index layer is particularly preferably composed mainly of titanium oxide and having a refractive index of 2.2 or more.

  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.

  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 Substrate Film (Cellulose Ester Film) A cellulose ester film as a substrate was produced according to the following method.

(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 dispersion device.

(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.

(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 and allowed to stand overnight, and after defoaming operation, the solution was added to Azumi Filter Paper No. 1 manufactured by Azumi Filter Paper Co., Ltd. A dope stock solution C was prepared by filtration using 244.

  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.

(2) Preparation of dope E (Preparation of silicon oxide dispersion A)
Aerosil R972V (Nippon Aerosil Co., Ltd.) 1kg
(Average diameter of primary particles 16 nm)
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 dispersion device.

(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
40 kg of ethanol
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.

(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 and allowed to stand overnight, and after defoaming operation, the solution was added to Azumi Filter Paper No. 1 manufactured by Azumi Filter Paper Co., Ltd. A dope stock solution E was prepared by filtration using 244.

  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.

(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 dispersion device.

(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.

(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 and allowed to stand overnight, and after defoaming operation, the solution was added to Azumi Filter Paper No. 1 manufactured by Azumi Filter Paper Co., Ltd. A dope stock solution G was prepared by filtration using 244.

  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.

(4) Production of Cellulose Ester Film A cellulose ester film was produced as follows using the dopes C, E, and G prepared above.

  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%.

  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.

  About the cellulose-ester film obtained above, the retentivity was measured with 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%.

(5) Measuring method of retentivity A sample is cut into a size of 10 cm × 10 cm, and the mass after being left for 24 hours in an atmosphere of 23 ° C. and 55% RH is measured. Under the conditions of 80 ° C. and 90% RH Left for 48 hours. 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
2. Formation of clear hard coat layer The following clear hard coat layer coating composition was coated on a cellulose ester film having a film thickness of 80 μm with an extrusion coater so as to have a wet film thickness of 13 μm, and then a drying section set at 80 ° C. After drying, the sample was irradiated with ultraviolet rays at 120 mJ / cm ² to prepare a clear hard coat layer having a dry film thickness of 4 μm and an arithmetic average roughness (Ra) of 15 nm.

(Clear hard coat layer coating composition)
Dipentaerythritol hexaacrylate monomer 60 mass parts Dipentaerythritol hexaacrylate dimer 20 mass parts Dipentaerythritol hexaacrylate trimer or higher component 20 mass parts Dimethoxybenzophenone photoinitiator 4 mass parts Ethyl acetate 50 mass parts 2. 50 parts by mass of methyl ethyl ketone 50 parts by mass of isopropyl alcohol Formation of antiglare films 1 to 20 Using the plasma discharge treatment apparatus 10 or 30 shown in FIG. 1 or 2 for the prepared clear hard coat layer, atmospheric pressure plasma treatment (etching surface) under the following plasma treatment conditions Processing) to produce an antiglare film.

Plasma Treatment Conditions Table 1 shows the treatment conditions and evaluation results of the produced antiglare film.

(Gas condition)
Gas 1: Gas shown in the condition column of Table 1 ... 98.00 vol%
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
(electrode)
As the fixed electrode 22 (rod-shaped electrode), one having the configuration shown in FIGS.

  In Table 1, the electrode 1 indicates a conventional electrode without unevenness, the electrode 2 indicates an electrode having the configuration shown in FIG. 6A, and the electrode 3 has the configuration shown in FIG. The electrode 4 is an electrode having the configuration shown in FIG. 6C, and the electrode 5 is an electrode having the configuration shown in FIG.

  Further, a case where argon gas was used as the discharge gas, and a case where the conventional electrode 1 without unevenness was used even when nitrogen gas was used were used as comparative examples.

4). Evaluation of anti-glare films 1 to 20 Anti-glare property was evaluated after performing plasma treatment for 5 seconds, and anti-glare property was evaluated after performing plasma treatment for 5 seconds again. This was repeated, and the antiglare property was evaluated until the plasma treatment time was up to 40 seconds. The results are shown in the result column of Table 1.

(Anti-glare evaluation method)
An exposed fluorescent lamp (8000 cd / m ² ) without a louver was projected on the prepared sample surface, and the degree of blur 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.

  It was confirmed that the antiglare film according to the present invention has excellent antiglare properties in a short time.

5. Formation of antiglare films 21 to 40 On a cellulose ester film having a film thickness of 80 μm, plasma discharge treatment apparatuses 10 and 30 shown in FIGS. 1 and 2 are used to perform atmospheric pressure plasma treatment under the following plasma treatment conditions. Thus, an antiglare layer was directly formed on the cellulose ester film to produce an antiglare film.

Plasma treatment conditions Table 2 shows the treatment conditions and evaluation results of the produced antiglare film.

(Gas condition)
Gas 1: Gas shown in the condition column of Table 2 ... 98.75% by volume
Gas 2: Oxygen: 1% by volume with respect to the entire mixed gas
Gas 3: Tetraethoxysilane vapor: 0.25% by volume with respect to the total gas mixture
The above gases 1 to 3 were mixed uniformly to obtain a mixed gas (reactive gas).

(electrode)
As the fixed electrode 22 (rod-shaped electrode), one having the configuration shown in FIGS.

  Further, a case where argon gas was used as the discharge gas, and a case where the conventional electrode 1 without unevenness was used even when nitrogen gas was used were used as comparative examples.

6). Evaluation of anti-glare films 21-40 Anti-glare property was evaluated after performing plasma treatment for 5 seconds, and anti-glare property was evaluated after performing plasma treatment for 5 seconds again. This was repeated, and antiglare properties were evaluated until the plasma treatment time was up to 40 seconds. The results are shown in the result column of Table 2.

  It was confirmed that the antiglare film according to the present invention has excellent antiglare properties in a short time.

1 is a schematic view showing an example of a plasma discharge treatment apparatus 10. It is the schematic which shows an example of the other plasma discharge processing apparatus. It is the schematic which shows an example of the above-mentioned cylindrical roll electrode. 3 is a schematic view showing an example of a prismatic fixed electrode 22. FIG. It is a conceptual diagram of the electrode which provided the unevenness | corrugation in the surface. It is a fragmentary sectional view of the electrode which provided unevenness on the surface. It is a fragmentary sectional view of the electrode of the form which provided unevenness in the surface without a dielectric. It is a fragmentary sectional view of the electrode of other forms of a plane with a uniform surface. It is a conceptual diagram of the unevenness | corrugation and space | gap of a to-be-processed object surface.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 Plasma discharge processing apparatus 21 Roll electrode 21a Electrode base material 21b Dielectric 22 Fixed electrode 29 Concavity and convexity 40 Gas generator 50 First power supply 60 Second power supply 211 Opposing surface 212 Adhering surface 301 Opposing region F Substrate G Mixed gas

Claims (21)

Under an atmospheric pressure or a pressure near atmospheric pressure, an electric field having a non-uniform intensity distribution is generated in an opposing region of the opposing electrode, and a mixed gas of nitrogen gas and reactive gas is generated by the electric field having the non-uniform intensity distribution. A surface treatment method comprising forming a non-uniform plasma state in a facing region and exposing the surface of the object to be processed to the mixed gas in the plasma state to form irregularities and voids on the surface of the object to be processed. The substrate of at least one of the opposing electrodes has uneven unevenness on the surface facing the other electrode, and the unevenness generates an electric field with uneven electric field strength distribution in the opposing region of the opposing electrode. The surface treatment method according to claim 1, wherein: At least one of the opposing electrodes has an electrode base material and a dielectric attached to the base material, and the dielectric has irregularities on the surface facing the other electrode, 2. The surface treatment method according to claim 1, wherein an electric field having a non-uniform electric field intensity distribution is generated in an opposing region of the opposing electrodes due to the unevenness. The deposited dielectric has irregularities on the surface facing the other electrode, and the deposition surface of the dielectric and the substrate has irregularities, and the opposing region of the electrode facing by the two irregularities The surface treatment method according to claim 1, wherein an electric field having a non-uniform electric field strength distribution is generated. At least one of the opposing electrodes has an electrode base material and a dielectric material applied to the base material, and the applied dielectric material has a uniform surface facing the other electrodes. And the dielectric and the substrate have irregularities, and the irregularities generate an electric field having a non-uniform electric field intensity distribution in the opposing region of the opposing electrodes. The surface treatment method according to claim 1. The surface treatment method according to claim 1, wherein the irregularities are irregularities having a maximum surface roughness defined by JIS-B-0601 of 10 μm or more. Under an atmospheric pressure or a pressure near atmospheric pressure, an electric field having a non-uniform intensity distribution is generated in the opposing region of the opposing electrode, and the mixed gas of nitrogen gas and reactive gas is generated by the electric field having the non-uniform intensity distribution. In the opposite region, the plasma state is non-uniform, the surface of the object to be processed is exposed to the mixed gas in the plasma state to form irregularities and voids on the surface of the object to be processed,
At least one of the opposing electrodes has a base material of the electrode and a dielectric attached to the base material, and is formed by the applied dielectric and the opposing electrode. 2. The discharge intensity distribution generated between the electrodes is made non-uniform by making the minute electrostatic capacity distribution non-uniform in the opposing region of the electrodes. Surface treatment method. The surface treatment method according to claim 7, wherein the minute capacitance distribution is made non-uniform by making the thickness of the dielectric non-uniform. The electric field having a non-uniform intensity distribution is generated between the electrodes by making the distance between the electrodes non-uniform in the opposing region of the opposing electrodes. The surface treatment method as described. An electric field having a non-uniform intensity distribution is generated in the opposing region of the opposing electrode, and the object to be processed is exposed to a mixed gas that has been brought into a plasma state by the electric field having a non-uniform intensity distribution. The surface treatment method according to claim 1, wherein irregularities and voids are formed on the surface of the object to be processed by etching the surface of the object to be processed. Under an atmospheric pressure or a pressure near atmospheric pressure, an electric field having a non-uniform intensity distribution is generated in the opposing region of the opposing electrode, and the mixed gas of nitrogen gas and reactive gas is opposed by the electric field of the non-uniform electric field intensity distribution. A surface having a non-uniform plasma state in a region facing an electrode, and exposing the surface of the object to be processed to the mixed gas in the plasma state to form a thin film having irregularities and voids on the surface of the object to be processed Processing method. 2. The power source that generates an electric field having a non-uniform intensity distribution in an opposing region of opposing electrodes is at least one power source that outputs a voltage of a predetermined frequency connected to at least one of the electrodes. The surface treatment method of any one of -11. 12. The power source that generates an electric field having a non-uniform intensity distribution in the opposing region of the opposing electrodes is two power sources that output voltages of different frequencies respectively connected to the opposing electrodes. The surface treatment method according to any one of the above. It has an anti-glare layer formed by the surface treatment method of any one of Claims 1-13, The anti-glare film characterized by the above-mentioned. An anti-glare low-reflection film comprising an anti-reflection layer on the upper surface of the anti-glare film according to claim 14. At least one pair of electrodes opposed to each other, a gas supply means for supplying a mixed gas of nitrogen gas and a reactive gas to an opposed region of the electrodes, and at least one power source for applying a high frequency voltage to at least one of the electrodes. ,
At least one surface of the electrode has unevenness, and the unevenness generates an electric field having a non-uniform intensity distribution in the opposing region of the opposing electrode, and the electric field having the non-uniform intensity distribution in the opposing region of the opposing electrode. A plasma discharge treatment apparatus characterized by generating plasma of the mixed gas and exposing the mixed gas in the plasma state to the surface of the object to be processed to form irregularities and voids on the surface of the object to be processed. The plasma discharge processing apparatus according to claim 16, wherein the unevenness of the electrode surface has a maximum surface roughness defined by JIS-B-0601 of 10 µm or more. The dielectric material is deposited on the surface of at least one of the electrodes facing each other, and at least a surface of the dielectric facing the electrode facing each other has irregularities. Plasma discharge treatment equipment. 19. The plasma discharge processing apparatus according to claim 18, wherein the unevenness of the dielectric surface has a maximum surface roughness defined by JIS-B-0601 of 10 [mu] m or more. The surface treatment method according to claim 16, wherein the power source is at least one power source that outputs a voltage having a predetermined frequency connected to at least one of the electrodes. 20. The surface treatment method according to claim 16, wherein the power source is a power source that outputs voltages having different frequencies respectively connected to opposing electrodes.

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