JP2011187445A - Dielectric-coated electrode and plasma-discharge processing device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a dielectric-coated electrode and a plasma-discharge processing device. <P>SOLUTION: Square pillar-shaped dielectric-coated electrodes 36c, 36C are formed by coating conductive base materials (hollow stainless steel pipes) 36b, 36B with dielectrics 36a, 36A, with a porosity of the dielectrics 36a, 36A of ≤10 vol.%. Specifically, spraying of ceramic is accurately performed to the porosity down to ≤10 vol.%, and further, a sealing treatment is performed with an inorganic material cured by sol-gel reaction. Here, thermosetting and UV curing methods are suitable for accelerating the sol-gel reaction. When consecutively repeating coating and curing several times by diluting sealing liquid, an inorganic state of the inorganic material can be further improved, and then, an accurate electrode which is hardly deteriorated can be achieved. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a dielectric coated electrode and a plasma discharge processing apparatus.

  In recent years, many displays provided with an antireflection layer or an antiglare layer for improving visibility have been used. Various types of antireflection layers and antiglare layers have been improved according to the application, and various front plates with these functions are attached to the polarizers of liquid crystal displays 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.

  However, these optical films require, for example, a process of bonding to a polarizing plate or the like, and for that purpose, pretreatment such as surface saponification treatment or application of glue with an alkaline solution for the purpose of improving adhesiveness. The process is essential, and wrinkles and unevenness are easily generated, and the antireflection layer and the antiglare layer are also susceptible to damage. Further, in the pasting step, the antireflection layer or the antiglare layer is liable to be damaged by touching a large number of surface touch rollers.

  In addition, dust adhesion due to static electricity or the like is likely to occur during the optical film laminating step or panel fabrication, which has caused defects and has been desired to be improved.

  In addition, in order to improve the visibility, a display device has been provided with an antiglare layer or an antireflection layer on the surface of the display device. There is a need for a display device.

  An object of the present invention is to provide a dielectric-coated electrode and a plasma discharge processing apparatus.

  The above object of the present invention has been achieved by the following items 1 to 13.

  1. A dielectric-coated electrode, which is a prism-shaped dielectric-coated electrode in which a conductive base material is coated with a dielectric, wherein the porosity of the dielectric is 10% by volume or less.

  2. 2. The dielectric-coated electrode according to 1 above, wherein the dielectric is an inorganic material having a relative dielectric constant of 6 to 45.

  3. 3. The dielectric-coated electrode according to 1 or 2, wherein the dielectric is subjected to sealing treatment with an inorganic material after thermal spraying of ceramics.

  4). 4. The dielectric-coated electrode according to 3 above, wherein the ceramic contains alumina.

  5. 5. The dielectric-coated electrode as described in 3 or 4 above, wherein the sealing inorganic material is cured by a sol-gel reaction.

  6). 6. The dielectric-coated electrode according to 5 above, wherein the sol-gel reaction is promoted by heat or UV.

  7). 7. The dielectric-coated electrode according to any one of 1 to 6, wherein a surface of the dielectric is polished.

  8). 8. The dielectric-coated electrode according to 7, wherein the dielectric has a surface roughness Rmax of 10 μm or less.

  9. 9. The dielectric-coated electrode according to any one of 1 to 8, wherein the dielectric-coated electrode has a cooling means with cooling water.

  10. A substrate is positioned between two types of electrodes facing each other, and a voltage is applied between the electrodes to discharge under atmospheric pressure or a pressure near atmospheric pressure, whereby a reactive gas is brought into a plasma state, and the substrate is In the plasma discharge processing apparatus for forming a thin film on the substrate by exposing the plasma to the reactive gas in the plasma state, at least one of the two kinds of electrodes facing each other is in any one of 1 to 9 above. A plasma discharge treatment apparatus comprising the dielectric-coated electrode described above.

  11. The base material is a long film, and at least one of the two types of electrodes facing each other is one roll electrode that winds the long film and rotates in the conveying direction of the long film, 11. The plasma discharge processing apparatus as described in 10 above, wherein the electrode facing the roll electrode is an electrode group in which a plurality of the dielectric covered electrodes are arranged.

  12 12. The plasma discharge treatment apparatus as described in 11 above, wherein the roll electrode is a dielectric coated electrode obtained by coating a conductive base material with a dielectric.

  13. 13. The plasma discharge treatment apparatus as described in 11 or 12 above, wherein the roll electrode has a surface roughness Rmax of 10 μm or less.

  A dielectric-coated electrode and a plasma discharge processing apparatus are provided.

It is sectional drawing which shows an example of the anti-glare film of this invention. It is sectional drawing which shows an example of the anti-glare film of this invention. It is sectional drawing which shows an example of the anti-glare film of this invention. It is the schematic which shows an example of the plasma discharge processing apparatus used for this invention. It is the schematic which shows an example of the plasma discharge processing apparatus used for this invention. (A), (b) is the schematic which shows an example of the cylindrical roll electrode used for the plasma discharge process which concerns on this invention, respectively. (A), (b) is the schematic which shows an example of the fixed cylindrical electrode used for the plasma discharge process which concerns on this invention, respectively. (A), (b) is the schematic which shows an example of the fixed type | mold prismatic electrode used for the plasma discharge process which concerns on this invention, respectively. It is a conceptual diagram which shows an example of the plasma discharge processing apparatus used for this invention. It is process drawing which shows an example of the manufacturing apparatus of the cellulose-ester film of this invention. Sectional drawing of an example of the slit die | dye used with the manufacturing method of the cellulose-ester film of this invention is shown.

  Hereinafter, the present invention will be described in detail.

  As a result of intensive studies on the above problems, a cellulose ester film characterized in that at least one surface has a fine particle-containing layer as a surface layer and has a haze of 3% to less than 30% is used. Thus, it was found that a cellulose ester film having good scratch resistance and excellent visibility can be obtained.

  In order to further improve the visibility, which is the effect described in the present invention, use an antiglare film in which an active ray curable resin layer is provided directly on the surface layer of the cellulose ester film or via another layer. More preferably, the active ray curable resin layer includes fine particles having a fine particle diameter to form finer irregularities, and particularly preferably, the active ray curable resin layer is reflected on the active ray curable resin layer. It has been found that better visibility can be obtained by forming the prevention layer.

  Further, from the viewpoint of obtaining further excellent scratch resistance, the antireflection layer preferably has a metal oxide layer, and more preferably, the metal oxide layer is formed by atmospheric pressure plasma treatment. .

  Here, the layer structure of the cellulose ester film of the present invention and the antiglare film using the same will be described with reference to FIGS.

  The cellulose ester film of the present invention is a cellulose ester film in which a layer containing fine particles is provided on the surface layer of at least one surface. By providing the surface layer containing fine particles, a cellulose ester film having irregularities on the surface is obtained. It is done. Here, the cellulose ester film having irregularities on the surface is preferably formed by a co-casting film forming method.

  An antiglare film exhibiting antiglare properties is produced by coating an active ray curable resin layer (also referred to as an antiglare layer) on a surface having irregularities on the surface of the cellulose ester film. The centerline average roughness Ra of the actinic radiation curable resin layer is preferably 0.1 μm to 0.5 μm.

  The antiglare film of the present invention can be further provided with an antireflection layer or an actinic ray curable resin layer.

  FIG. 1 is a schematic cross-sectional view showing an example of the antiglare film of the present invention.

  An active ray curable resin layer, an antireflection layer, and an antifouling layer are provided on the surface of a cellulose ester film having a fine particle-containing layer as a surface layer on one surface, and the other surface is intended to prevent blocking. It is preferable to provide a fine particle-containing layer. The fine particle-containing layer provided on the other surface may be formed by a co-casting method or may be formed by coating.

  FIG. 2 is a schematic cross-sectional view showing another example of the antiglare film of the present invention.

  In FIG. 2, in the fine particle-containing layer provided on one surface of the cellulose ester film, unlike the structure of FIG. 1, particles having different particle diameters (here, particles having different particle diameters are primary particle diameters). In this case, the surface layer having finer irregularities is formed by using a different secondary particle size).

  3 (a) and 3 (b) are schematic cross-sectional views showing another example of the antiglare film of the present invention.

  FIG. 3A shows that a cellulose ester film is formed with a surface layer having a large irregularity cycle, and the active ray curable resin layer formed on the surface layer contains fine particles so that the period is longer than that of the cellulose ester film surface layer. Are formed with small irregularities.

  By taking such a structure, the anti-glare film more excellent in anti-glare performance can be obtained. In addition, when an antireflection layer is provided, a layer containing metal oxide fine particles can be provided as an antireflection layer. However, the atmospheric pressure plasma method described later has a uniform thickness even on a surface having fine irregularities. Since a prevention layer can be formed, it is particularly preferably used.

  FIG. 3B is an example in which a surface layer having a large irregularity period is formed on the cellulose ester film, and two active ray curable resin layers are further provided on the surface layer. Fine particles are added to the layer to form fine irregularities with a small period.

  The fine particles according to the present invention will be described.

  It is essential that the cellulose ester film of the present invention contains fine particles in the surface layer of at least one surface. A preferable configuration of the surface layer and the fine particles is as shown below.

  The particle diameter of the fine particles according to the present invention is preferably such that the average particle diameter of the primary particles is in the range of 5 nm to 10 μm, more preferably 10 nm to 5 μm.

  The film thickness of the surface layer containing the fine particles is preferably 1 μm to 20 μm, more preferably 3 μm to 15 μm, and particularly preferably 5 μm to 10 μm.

  Here, it is preferable that the primary particle diameter or secondary particles (aggregates) be 0.5 to 1.5 times the average film thickness of the surface layer, and particles larger than the average film thickness of the surface layer. It is preferable that particles having a diameter are included.

  In the present invention, the surface layer refers to a region having a depth of 20 μm in the center direction from the film surface, and the inside of the film (or the internal region) refers to a region excluding the surface layer.

  The film thickness of the cellulose ester film of the present invention is preferably 30 μm to 1000 μm, more preferably 35 μm to 500 μm, and particularly preferably 40 μm to 300 μm.

  The surface layer according to the present invention preferably has irregularities with an elevation difference of 0.1 μm or more, and the above fine particles are used to provide the irregularities. The height difference according to the present invention is preferably a height difference of 0.1 μm to 10 μm, more preferably 0.2 μm to 5 μm, and still more preferably 0.5 μm to 2 μm. Moreover, it is preferable to have a convex part of 0.1 micrometer-10 micrometers with respect to the average film thickness of a surface layer.

  The height difference is represented by the maximum height (Rmax) defined in JIS B 0601, and the measurement can be performed using an optical interference type surface roughness meter RST / PLUS (manufactured by WYKO). I can do it.

  Examples of the fine particles according to the present invention include inorganic particles and organic particles. As inorganic particles, silicon dioxide, titanium oxide, aluminum oxide, zinc oxide, tin oxide, calcium carbonate, zirconium oxide, calcium carbonate, barium sulfate, talc, kaolin, calcined calcium silicate, hydrated calcium silicate, aluminum silicate , Magnesium silicate, calcium phosphate, calcium sulfate and the like.

  Examples of the fine particles of silicon dioxide include Aerosil R972, R972V, R974, R812, 200, 200V, 300, R202, OX50, TT600 (manufactured by Nippon Aerosil Co., Ltd.), or 250, 250N, 256, 256N, 310. 320, 350, 358, 430, 431, 440, 450, 470, 435, 445, 436, 446, 456, 530, 540, 550, 730, 740, 770 (above, manufactured by Fuji Silysia Co., Ltd.) A commercial product having a trade name can be used.

  As fine particles of zirconium oxide according to the present invention, for example, those commercially available under trade names such as Aerosil R976 and R811 (manufactured by Nippon Aerosil Co., Ltd.) can be used.

  Organic particles include poly (meth) acrylate resins, silicon resins, polystyrene resins, polycarbonate resins, acrylic styrene resins, benzoguanamine resins, melamine resins, polyolefin resins, polyester resins, polyamide resins. Polyimide resin, polyfluorinated ethylene resin, etc. can be used.

  Among these, silicon oxide such as silica is particularly preferably used to achieve visibility, which is one of the objects of the present invention. As the silicon oxide particles preferably used here, ultrafine hydrated silicic acid produced by a wet method is preferred among synthetic amorphous silicas because of its great effect of reducing the glossiness. The wet method is a method in which sodium silicate is reacted with mineral acid and salts in an aqueous solution, and examples thereof include silicia manufactured by Fuji Silysia Chemical Co., Ltd. and Nippon Sil E manufactured by Nippon Silica Co., Ltd.

  Examples of the method for preparing the fine particle dispersion according to the present invention include the following three types, but are not particularly limited thereto.

(Preparation method A)
After stirring and mixing the solvent and the fine particles, dispersion is performed with a disperser. This is a fine particle dispersion. The fine particle dispersion is added to the dope solution and stirred.

(Preparation method B)
After stirring and mixing the solvent and the fine particles, dispersion is performed with a disperser. This is a fine particle dispersion. Separately, a small amount of resin is added to the solvent and dissolved by stirring. The fine particle dispersion is added to this and stirred. This is a fine particle addition solution. The fine particle additive solution is sufficiently mixed with the dope solution using an in-line mixer.

(Preparation method C)
Add a small amount of resin to the solvent and dissolve with stirring. Fine particles are added to this and dispersed by a disperser. This is a fine particle addition solution. The fine particle additive solution is sufficiently mixed with the dope solution using an in-line mixer.

  Preparation method A is excellent in fine particle dispersibility, and preparation method C is excellent in that the fine particles are difficult to re-aggregate. Preparation method B is a preferable preparation method because it is excellent in both dispersibility of the fine particles and the re-aggregation of the fine particles.

(Distribution method)
When the fine particles are mixed with a solvent and dispersed, the concentration of the fine particles is preferably 5% by mass to 30% by mass, more preferably 10% by mass to 25% by mass, and most preferably 15% by mass to 20% by mass.

  Solvents used include ketones such as acetone and methyl ethyl ketone, or esters and alcohols such as methyl acetate and ethyl acetate. Particularly preferred are lower alcohols, such as methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, Examples include but are not limited to butyl alcohol.

  As the disperser, a normal disperser can be used. Dispersers can be broadly divided into media dispersers and medialess dispersers.

  Examples of the media disperser include a ball mill, a sand mill, and a dyno mill.

  Medialess dispersers include ultrasonic, centrifugal, and high pressure types. The high pressure dispersion device is a device that creates special conditions such as high shear and high pressure by passing a composition in which fine particles and a solvent are mixed at high speed through a narrow tube. When processing with a high-pressure dispersion apparatus, for example, the maximum pressure condition inside the apparatus is preferably 10 MPa or more in a thin tube having a tube diameter of 1 to 2000 μm. More preferably, it is 20 MPa or more. At that time, it is preferable that the maximum reaching speed reaches 100 m / second or more, and the heat transfer speed reaches 418 kJ / hour or more.

  The high-pressure dispersion apparatus as described above includes an ultra-high pressure homogenizer (trade name: Microfluidizer) manufactured by Microfluidics Corporation or a nanomizer manufactured by Nanomizer, and other manton gorin type high-pressure dispersion apparatuses such as a homogenizer manufactured by Izumi Food Machinery Co., Ltd. Examples include UHN-01 manufactured by Wako Machine Co., Ltd.

  The haze according to the present invention will be described.

  In order to obtain the effect (improvement of visibility) described in the present invention, it is an essential requirement that the haze of the cellulose ester film of the present invention is 3% to less than 30%.

  Here, although the haze measurement is described in detail in the examples, it can be measured according to ASTM-D1003-52.

  As a means for adjusting the cellulose ester film of the present invention to the above-described range of the haze value, it is preferable to include the organic fine particles and / or inorganic fine particles described above in the surface layer of the cellulose ester film. Silicon dioxide is preferable because it can reduce the haze of the film.

  Moreover, what surface-treated fine particles like a silicon dioxide with organic substance is used preferably in order to adjust the haze of a film to said range.

  The actinic radiation curable resin layer according to the present invention will be described.

  The actinic radiation curable resin layer according to the present invention contains an actinic radiation curable resin as a binder, and more preferably, the actinic radiation curable resin layer containing silicon oxide particles or silicon oxide fine particles is formed by irradiation with actinic radiation after coating. Is preferred.

  The actinic radiation curable resin used in the present invention is defined as 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 UV curable resins include UV curable polyester acrylate resins, UV curable acrylic urethane resins, UV curable acrylate resins, UV curable methacrylate resins, and UV curable polyester acrylate resins. And ultraviolet curable polyol acrylate resins.

  UV curable polyol acrylate resins include trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, alkyl-modified dipentaerythritol pentaerythritol. And the like. These polyol acrylate resins are preferably used because they are highly crosslinkable and have high curability, high hardness, low cure shrinkage, low odor, low toxicity, and relatively high safety.

  The ultraviolet curable polyol acrylate resin may contain other ultraviolet curable resins, for example, an ultraviolet curable epoxy resin as long as the effect is not impaired. A cured coating film obtained by coating a thick film of an acrylate resin has strong curling due to curing shrinkage, which may cause trouble in handling work. Epoxy resins generally have less cure shrinkage and less curling of cured coatings than acrylate resins. The ultraviolet curable epoxy resin referred to here is a compound containing two or more epoxy groups in the molecule, is a epoxy resin containing a cationic polymerization initiator, and undergoes a crosslinking reaction when irradiated with ultraviolet rays.

  Examples of electron beam curable resins are preferably those having an acrylate-based functional group, for example, relatively low molecular weight polyester resins, polyether resins, acrylic resins, epoxy resins, urethane resins, alkyd resins, spiroacetals. Examples thereof include resins, polybutadiene resins, polythiol polyene resins, and the like.

  In order to exert the effects of the present invention remarkably and easily, it is preferable to use an ultraviolet curable resin.

  Examples of the active energy ray-curable resin having an acrylic group or a methacryl group include an ultraviolet curable acrylic urethane resin, an ultraviolet curable polyester acrylate resin, an ultraviolet curable epoxy acrylate resin, and an ultraviolet curable polyol acrylate resin. I can list them.

  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, JP-A-59-151110).

  An ultraviolet curable polyester acrylate resin can be easily obtained by reacting a monomer such as 2-hydroxyethyl acrylate, glycidyl acrylate, or acrylic acid with a hydroxyl group or carboxyl group at the end of the polyester (see, for example, JP-A No. 59-151112).

  The ultraviolet curable epoxy acrylate resin is obtained by reacting a terminal hydroxyl group of an epoxy resin with a monomer such as acrylic acid, acrylic acid chloride, or glycidyl acrylate.

  Examples of ultraviolet curable polyol acrylate resins include ethylene glycol (meth) acrylate, polyethylene glycol di (meth) acrylate, glycerin tri (meth) acrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, and dipenta. Examples include erythritol pentaacrylate, dipentaerythritol hexaacrylate, and alkyl-modified dipentaerythritol pentaerythritol.

  In order to initiate photopolymerization or photocrosslinking reaction of the active energy ray-reactive compound used in the present invention, the active energy ray-reactive compound alone is initiated. Since it may be slow, it is preferable to use a photosensitizer or a photoinitiator, whereby the polymerization can be accelerated. Known photosensitizers and photoinitiators can be used. Specific examples include acetophenone, benzophenone, hydroxybenzophenone, Michler's ketone, α-amyloxime ester, tetramethyluram monosulfide, thioxanthone, and derivatives thereof.

  In the case of an active energy ray-reactive compound having an epoxy acrylate group, a sensitizer such as n-butylamine, triethylamine, or tri-n-butylphosphine can be used. The photoreaction initiator or photosensitizer used for the active energy ray-reactive compound is sufficient to initiate the photoreaction at 0.1 to 15 parts by mass with respect to 100 parts by mass of the ultraviolet-reactive compound, Preferably it is 1-10 mass parts. The sensitizer preferably has an absorption maximum from the near ultraviolet region to the visible light region.

  In the present invention, an active energy ray reactive epoxy resin is also preferably used. Active energy ray reactive epoxy resins include aromatic epoxy compounds (polyglycidyl ethers of polyhydric phenols), such as hydrogenated bisphenol A or glycidyl ethers of bisphenol A and epichlorohydrin, epoxy novolac resins, aliphatic epoxies. Examples of the resin include polyglycidyl ethers of aliphatic polyhydric alcohols or alkylene oxide adducts thereof, polyglycidyl esters of aliphatic long-chain polybasic acids, homopolymers and copolymers of glycidyl acrylate and glycidyl methacrylate, and typical examples thereof , Ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, Ripropylene glycol glycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, nonapropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, glycerin triglycidyl ether, diglycerol triglycidyl ether , Diglycerol tetraglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol triglycidyl ether, pentaerythritol tetraglycidyl ether, polyglycidyl ether of sorbitol, cycloaliphatic epoxy compounds such as 3,4-epoxycyclohexylmethyl-3 ′ , 4'-Epoxycyclohexanecarboxylate, 2- (3,4-epoxycyclohexyl) 5,5-spiro-3 ', 4'-epoxy) cyclohexane-meta-dioxane, bis (3,4-epoxycyclohexylmethyl) adipate, vinylcyclohexene dioxide, bis (3,4-epoxy-6-methylcyclohexylmethyl) ) Adipate, 3,4-epoxy-6-methylcyclohexyl-3 ', 4'-epoxy-6-methylcyclohexanecarboxylate, methylenebis (3,4-epoxycyclohexane) dicyclopentadiene diepoxide, di (3 , 4-epoxycyclohexylmethyl) ether, ethylenebis (3,4-epoxycyclohexanecarboxylate), dicyclopentadiene diepoxide, diglycidyl ether of tris (2-hydroxyethyl) isocyanurate, tri (2-hydroxyethyl) isocyanurate triglycidyl ether, polyglycidyl acrylate, polyglycidyl methacrylate, glycidyl acrylate or a copolymer of glycidyl methacrylate and other monomers, poly-2-glycidyloxyethyl acrylate, poly-2- Examples include glycidyloxyethyl methacrylate, 2-glycidyloxyethyl acrylate, 2-glycidyloxyethyl acrylate or a copolymer of 2-glycidyloxyethyl methacrylate and other monomers, bis-2,2-hydroxycyclohexylpropane diglycidyl ether, and the like. Or an addition polymer obtained by combining two or more of them individually. The present invention is not limited to these compounds but includes compounds inferred from these compounds.

  In the active energy ray-reactive compound epoxy resin, in addition to those having two or more epoxy groups in the molecule, monoepoxide can be blended and used according to desired performance.

  The active energy ray-reactive compound epoxy resin forms a polymerized, crosslinked structure or network structure not by radical polymerization but by cationic polymerization. Unlike radical polymerization, it is not affected by oxygen in the reaction system, and is therefore a preferred active energy ray reactive resin.

  Silver ethyl sulfonate, silver polyborate and the like can also be preferably used.

  Useful active energy ray-reactive epoxy resins polymerize a compound that releases a substance that initiates cationic polymerization upon irradiation with active energy rays, using a photopolymerization initiator or a photosensitizer. A group of double salts with onium salts that release Lewis acids that are cationically polymerized by irradiation is particularly preferred.

  For example, the compound represented with the following general formula (III) is mentioned as an example.

General formula (III)
[(R ¹ ) _a (R ² ) _b (R ³ ) _c (R ⁴ ) _d Z] ^{+ w} [MeX _v ] ^−w
Wherein the cation is onium, Z is S, Se, Te, P, As, Sb, Bi, O, halogen (eg, I, Br, Cl), or N = N (diazo), R ¹ , R ² , R ³ and R ⁴ are organic groups which may be the same or different. a, b, c, and d are each an integer of 0 to 3, and a + b + c + d is equal to the valence of Z. Me is a metal or metalloid which is a central atom of a halide complex, and B, P, As, Sb, Fe, Sn, Bi, Al, Ca, In, Ti, Zn, Sc, V, Cr, Mn, Co, etc. X is halogen, w is the net charge of the halogenated complex ion, and v is the number of halogen atoms in the halogenated complex ion. The value obtained by subtracting the valence of the central atom Me from v is w.

Specific examples of the anion [MeX _v ] ^-w of the above general formula include tetrafluoroborate (BF ₄ ⁻ ), hexafluorophosphate (PF ₄ ⁻ ), hexafluoroantimonate (SbF ₄ ⁻ ), hexafluoroarsenate. (AsF ₄ ⁻ ), hexachloroantimonate (SbCl ₄ ⁻ ) and the like.

Furthermore, an anion of the general formula MeX _v (OH) ⁻ can also be used. Other anions include perchlorate ion (ClO ₄ ⁻ ), trifluoromethyl sulfite ion (CF ₃ SO ₃ ⁻ ), fluorosulfonate ion (FSO ₃ ⁻ ), toluenesulfonate ion, and trinitrobenzene acid anion. An ion etc. can be mentioned.

  Among these onium salts, it is particularly effective to use an aromatic onium salt as a cationic polymerization initiator. Among them, aromatic haloniums described in JP-A-50-151996, JP-A-50-158680 and the like are particularly effective. Salt, VIA group aromatic onium salts described in JP-A-50-151997, 52-30899, 59-55420, 55-125105, JP-A-56-8428, 56- 149402, 57-192429, etc., oxosulfoxonium salts described in JP-B-49-17040, etc., aromatic diazonium salts described in US Pat. No. 4,139,655, etc. A thiopyrilum salt is preferred. Moreover, an aluminum complex, a photodegradable silicon compound type | system | group polymerization initiator, etc. can be mentioned. The cationic polymerization initiator can be used in combination with a photosensitizer such as benzophenone, benzoin isopropyl ether, or thioxanthone.

  In the active energy ray-curable resin composition useful in the present invention, the polymerization initiator is generally preferably 0.1 to 15 parts by mass with respect to 100 parts by mass of the active energy ray-curable epoxy resin (prepolymer). More preferably, it is added in the range of 1 to 10 parts by mass. An epoxy resin can also be used in combination with the urethane acrylate type resin, polyether acrylate type resin, and the like. In this case, it is preferable to use an active energy ray radical polymerization initiator and an active energy ray cationic polymerization initiator in combination.

In the active energy ray-curable resin-containing layer used in the present invention, a binder such as a known thermoplastic resin, thermosetting resin, or hydrophilic resin such as gelatin can be mixed with the active energy ray-curable resin. . These resins preferably have a polar group in the molecule, and examples of the polar group include —COOM, —OH, —NR ₂ , —NR ₃ X, —SO ₃ M, —OSO ₃ M, —PO ₃ M ₂ , —OPO ₃ M (wherein M represents a hydrogen atom, an alkali metal or an ammonium group, X represents an acid forming an amine salt, R represents a hydrogen atom or an alkyl group), and the like. .

  The actinic radiation curable resin according to the present invention can be cured by irradiation with actinic rays such as electron beams or ultraviolet rays. For example, in the case of electron beam curing, 50 to 1000 KeV emitted from various electron beam accelerators such as a Cockloft Walton type, a bandegraph type, a resonant transformation type, an insulating core transformer type, a linear type, a dynamitron type, and a high frequency type, Preferably, an electron beam or the like having an energy of 100 to 300 KeV is used, and in the case of ultraviolet curing, ultraviolet rays emitted from light rays such as an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a xenon arc, and a metal halide lamp can be used. .

As the amount of energy imparted during the active ray irradiation ^is preferably ^{50mJ / cm 2 ~1000mJ / cm 2} , and more ^preferably from ^{100mJ / cm 2 ~500mJ / cm 2} .

  The thickness of the actinic radiation curable resin layer is preferably 0.3 μm or more and 10 μm or less, and more preferably 0.5 μm or more and 5 μm or less.

  Moreover, it is preferable that centerline average roughness (Ra) prescribed | regulated by JISB0601 of an active ray cured resin layer is 0.1 micrometer-0.5 micrometer, More preferably, it is 0.2 micrometer-0.00. 4 μm.

  The antireflection layer according to the present invention will be described.

In the present invention, an antireflection layer is preferably provided on the active ray curable resin layer of the antiglare film having the actinic ray curable resin layer. As the antireflection layer, a configuration in which 3 to 4 layers of metal oxide thin films or organic polymer thin films having different refractive indexes such as SiO ₂ , TiO ₂ , ZrO ₂ , Y ₂ O _{3 and the} like are usually laminated is preferable. A low refractive index film having a refractive index of 1.25 or less is also preferably used. The antireflection layer may be composed of a plurality of layers, in which case the refractive index and film thickness of each layer are adjusted to optimum values.

  The thickness of the antireflection layer is usually in the range of 1 nm to 200 nm, and an appropriate thickness is selected according to the refractive index of each layer.

  As the structure of the antireflection layer, various types including a single layer and a multilayer are known, but a multilayer structure having a structure in which a high refractive index layer and a low refractive index layer are alternately laminated may be used.

  Examples of the configuration include a high refractive index layer / low refractive index layer in the order of two layers, and three layers having different refractive indexes, a medium refractive index layer (having a higher refractive index than a transparent substrate or a hard coat layer). , A layer having a refractive index lower than that of the high refractive index layer) / high refractive index layer / low refractive index layer, and the like, and more antireflection layers may be laminated.

  On the actinic radiation curable resin layer, an antireflective layer can be applied in the order of a high refractive index layer / medium refractive index layer / low refractive index layer (a layer having a refractive index lower than that of the base film).

  The refractive index is almost determined by the metal or compound contained therein. For example, Ti and Zr are high, Si is low, F-containing compounds are even lower, and the refractive index is set by such a combination.

  The antireflection layer uses metal oxide fine particles such as Ti, Zr, Si, and Sn, or a coating film containing these metal alkoxides or hydrolysates thereof, organic fine particles containing F, polymerizable fluorine-containing compounds, and the like. Each refractive index layer can be coated and provided.

  The antireflection layer provided on the active ray curable resin layer of the antiglare film of the present invention preferably has an average reflectance at 450 nm to 650 nm of 1% or less, particularly preferably 0.5% or less.

  The antireflection layer according to the present invention is preferably formed by plasma treatment, and it is particularly preferable to form an antireflection layer having a metal oxide layer or a fluorine-containing compound layer by an atmospheric pressure plasma method.

In the formation of the metal oxide layer by the atmospheric pressure plasma method, a high-frequency voltage exceeding 100 kHz and a power of 1 W / cm ² or more are supplied between the opposing electrodes to excite the reactive gas and generate plasma. Preferably it is generated.

  By applying such a high power electric field, a dense metal oxide layer with high film thickness uniformity can be obtained with high production efficiency.

  In the present invention, the frequency of the high-frequency voltage applied between the electrodes is preferably 150 MHz or less.

  Further, the frequency of the high frequency voltage is preferably 200 kHz or more, and more preferably 800 kHz or more.

The power supplied between the electrodes is preferably 1.2 W / cm ² or more, preferably 50 W / cm ² or less, more preferably 20W / cm ² or less. Note that the voltage application area (/ cm ² ) in the electrode refers to the area in which discharge occurs.

  The high-frequency voltage applied between the electrodes may be an intermittent pulse wave or a continuous sine wave. However, in order to obtain the effect of the present invention, it is a continuous sine wave. It is preferable.

  In the present invention, it is preferable to use an electrode capable of maintaining a uniform glow discharge state by applying such a high power voltage in a plasma discharge processing apparatus.

  Such an electrode is preferably a metal base material coated with a dielectric. It is preferable to coat a dielectric on at least one side of the opposed application electrode and the ground electrode, and more preferably coat both the opposed application electrode and the ground electrode with a dielectric. The dielectric is preferably an inorganic substance having a relative dielectric constant of 6 to 45. Examples of such a dielectric include ceramics such as alumina and silicon nitride, silicate glass, borate glass, and the like. There are glass lining materials.

  In addition, when the substrate is placed between the electrodes or conveyed between the electrodes and exposed to plasma, it is preferable to have a roll electrode specification in which the substrate can be conveyed while being in contact with one of the electrodes. By polishing the surface and making the electrode surface roughness Rmax (specified by JIS B 0601) 10 μm or less, the thickness of the dielectric and the gap between the electrodes can be kept constant, and the discharge state is stable. Furthermore, the durability can be greatly improved by coating with a high-precision inorganic dielectric that is not porous and eliminates distortion and cracking due to a difference in thermal shrinkage and residual stress.

  In addition, when manufacturing electrodes with a dielectric coating on a metal base at a high temperature, at least the dielectric on the side in contact with the substrate is polished and the difference in thermal expansion between the metal base and the dielectric of the electrode is as much as possible. Therefore, it is preferable to line an inorganic material on the surface of the base material as a layer capable of absorbing stress by controlling the amount of bubbles mixed in, especially by a melting method known as cocoon as the material. It is preferable that the glass is obtained, and further, the amount of bubbles mixed in the lowermost layer in contact with the conductive metal base material is 20 to 30% by volume, and the subsequent layer and the subsequent layers are 5% by volume or less. A good electrode that does not occur can be produced.

  As another method for coating the base material of the electrode with a dielectric material, ceramic spraying is performed to a porosity of 10% by volume or less, and further, a sealing process is performed with an inorganic material that is cured by a sol-gel reaction. Yes, in order to accelerate the sol-gel reaction, heat curing and UV curing are good. Further, diluting the sealing liquid and repeating coating and curing several times in succession further improves the mineralization, and the denseness without deterioration. A simple electrode.

  A plasma discharge processing apparatus using such an electrode will be described with reference to FIGS. The plasma discharge treatment apparatus shown in FIGS. 4, 5 and 9 discharges between a grounded roll electrode 25 and a fixed electrode 26 or 36 which is an application electrode disposed at an opposing position, and between the electrodes. A reactive gas is introduced from the air supply port 52 to form a plasma state, and a long film-like substrate wound around the roll electrode is exposed to the reactive gas in the plasma state, whereby a thin film is formed on the surface of the substrate. However, the apparatus for carrying out the thin film forming method of the present invention is not limited to this, and it is possible to stably maintain glow discharge and excite reactive gas to form a thin film. Any plasma can be used.

  As another method, there is a jet method in which a base material is placed or transported in the vicinity of an electrode that is not between electrodes and a generated plasma is sprayed onto the base material to form a thin film.

  FIG. 4 is a schematic view showing an example of a plasma discharge processing apparatus used in the thin film forming method of the present invention.

  In FIG. 4, the long film-like substrate F is conveyed while being wound around a roll electrode 25 that rotates in the conveying direction (clockwise in the figure). The fixed electrode 26 is composed of a plurality of cylinders, and is installed facing the roll electrode 25. The substrate F wound around the roll electrode 25 is pressed by the nip rollers 65 and 66, regulated by the guide roller 64, transported to the discharge treatment space secured by the plasma discharge treatment vessel 31, subjected to discharge plasma treatment, and then Then, it is conveyed to the next process via the guide roller 67.

  Further, the partition plate 54 is disposed in the vicinity of the nip rollers 65 and 66 to suppress the air accompanying the base material F from entering the plasma discharge processing container 31.

  The entrained air is preferably suppressed to 1% by volume or less, and more preferably 0.1% by volume or less, with respect to the total volume of gas in the plasma discharge processing vessel 31. This can be achieved by the nip rollers 65 and 66.

  A mixed gas (an inert gas and an organic gas containing an organic fluorine compound, a titanium compound, a silicon compound, or the like, which is a reactive gas) used for the discharge plasma treatment is supplied from the air supply port 52 to the plasma discharge treatment vessel 31. The treated gas is exhausted from the exhaust port 53.

  FIG. 5 is a schematic view showing an example of a plasma discharge processing vessel installed in the plasma discharge processing apparatus used in the manufacturing method of the present invention, as in FIG. In this example, the fixed electrode 26 is a columnar electrode 36, whereas a cylindrical electrode is used.

  Compared with the cylindrical electrode 26 shown in FIG. 4, the prismatic electrode 36 shown in FIG. 5 has an effect of extending the discharge range, and is preferably used for forming a metal oxide layer.

  FIGS. 6A and 6B are schematic views showing examples of the above-described cylindrical roll electrodes, and FIGS. 7A and 7B are examples of electrodes fixed in a cylindrical form. FIGS. 8A and 8B are schematic views showing examples of electrodes fixed in a prismatic shape.

  6 (a) and 6 (b), a roll electrode 25c, which is a ground electrode, is a ceramic-coated dielectric that has been subjected to sealing treatment using an inorganic material after thermal spraying of ceramic on a conductive base material 25a such as metal. It is comprised with the combination which coat | covered the body 25b. A ceramic-coated dielectric is coated 1 mm with a single wall, and the roll diameter is 750 mm after coating, and is grounded to ground. Alternatively, a combination of a conductive base material 25A such as metal covered with a lining dielectric 25B provided with an inorganic material by lining, and a roll electrode 25C may be used. 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 25a and 25A 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 of the roll electrode is a stainless steel jacket roll base material having a cooling means with cooling water (not shown).

  7A, 7B, 8A, and 8B are a fixed electrode 26c, an electrode 26C, an electrode 36c, and an electrode 36C, which are application electrodes, and the roll electrode 25c and the roll electrode described above. It is configured in the same combination as 25C. That is, a hollow stainless steel pipe is covered with the same dielectric as described above, and can be cooled with cooling water during discharge. In addition, it is manufactured so that it becomes 12φ or 15φ after coating with the ceramic coating treated dielectric, and the number of the electrodes is 14 along the circumference of the roll electrode.

  A power source for applying a voltage to the application electrode is not particularly limited, but a high frequency power source (200 kHz) manufactured by Pearl Industry, a high frequency power source (800 kHz) manufactured by Pearl Industrial, a high frequency power source manufactured by JEOL (13.56 MHz), and a high frequency power manufactured by Pearl Industry A power source (150 MHz) or the like can be used.

  FIG. 9 is a conceptual diagram showing an example of a plasma discharge treatment apparatus used in the present invention. In FIG. 9, the portion of the plasma discharge processing vessel 31 is the same as that shown in FIG. 5, but a gas generator 51, a power source 41, an electrode cooling unit 60, and the like are further shown as the device configuration. As a coolant for the electrode cooling unit 60, an insulating material such as distilled water or oil is used.

  The electrodes 25 and 36 shown in FIG. 9 are the same as those shown in FIGS. 6, 7, 8, etc., and the gap between the facing electrodes is set to about 1 mm to 2 mm, for example.

  The distance between the electrodes is determined in consideration of the thickness of the solid dielectric placed on the base material of the electrodes, the magnitude of the applied voltage, the purpose of using plasma, and the like. The shortest distance between the solid dielectric and the electrode when a solid dielectric is placed on one of the electrodes, and the distance between the solid dielectrics when a solid dielectric is placed on both of the electrodes is uniform in any case From the viewpoint of discharging, 0.5 mm to 20 mm is preferable, and 1 mm ± 0.5 mm is particularly preferable.

  A roll electrode 25 and a fixed electrode 36 are arranged in a predetermined position in the plasma discharge processing container 31, and the mixed gas generated by the gas generator 51 is controlled in flow rate, and the plasma discharge processing container is supplied from the air supply port 52. The plasma discharge treatment vessel 31 is filled with a mixed gas used for the plasma treatment and exhausted from the exhaust port 53.

  In particular, it is preferable to supply the mixed gas uniformly so as not to cause unevenness in the concentration, flow rate, and flow rate of the mixed gas in the width direction of the substrate F. Next, a voltage is applied to the electrode 36 by the power source 41, and the roll electrode 25 is grounded to the ground to generate discharge plasma. Here, the base material F is supplied from the roll-shaped original winding base material 61, and the electrodes in the plasma discharge treatment vessel 31 are in a single-sided contact state (in contact with the roll electrode 25) via the guide roller 64. The surface of the base material F is subjected to discharge treatment by discharge plasma during the transport, and then transported to the next process via the guide roller 67. Here, the substrate F is subjected to discharge treatment only on the surface not in contact with the roll electrode 25.

  The value of the voltage applied to the electrode 36 fixed from the power supply 41 is determined as appropriate. For example, the voltage is about 0.5 to 10 kV, and the power supply frequency is adjusted to more than 100 kHz and 150 MHz or less. As for the method of applying power, either a continuous sine wave continuous oscillation mode called continuous mode or an intermittent oscillation mode called ON / OFF intermittently called pulse mode may be adopted. A denser and better quality film can be obtained.

  The plasma discharge treatment vessel 31 is preferably a treatment vessel made of Pyrex (registered trademark) glass or the like, but can be made of metal as long as it can be insulated from the electrodes. For example, polyimide resin or the like may be attached to the inner surface of an aluminum or stainless steel frame, and the metal frame may be subjected to ceramic spraying to provide insulation.

  Moreover, in order to suppress the influence on the base material at the time of the discharge plasma treatment to a minimum, the temperature of the base material at the time of the discharge plasma treatment may be adjusted to a temperature from room temperature (15 ° C. to 25 ° C.) to less than 200 ° C. More preferably, the temperature is adjusted to room temperature to 120 ° C. In order to adjust to the above temperature range, the electrode and the substrate are subjected to discharge plasma treatment while being cooled by a cooling means as necessary.

  In the atmospheric pressure plasma treatment according to the present invention, the discharge plasma treatment is performed at or near atmospheric pressure. Here, “near atmospheric pressure” represents a pressure of 20 kPa to 200 kPa. In order to obtain it preferably, 90 kPa to 110 kPa is preferable, and 93 kPa to 107 kPa is particularly preferable.

  Further, in the discharge electrode related to the formation of the metal oxide layer, the maximum height (Rmax) of the surface roughness defined by JIS B 0601 on the side in contact with the base material of the electrode is adjusted to 10 μm or less. Although it is preferable, the maximum value of the surface roughness is more preferably 8 μm or less, and particularly preferably adjusted to 7 μm or less.

  The mixed gas relating to the formation of the metal oxide layer according to the present invention will be described.

  In forming the metal oxide layer, the gas used is preferably a mixed gas of an inert gas and a reactive gas for forming a thin film, and the reactive gas is 0.01% relative to the mixed gas. It is preferable to contain 10 to 10 volume%. As the thickness of the metal oxide layer, a thin film in the range of 0.1 nm to 1000 nm is preferably obtained.

  Examples of the inert gas include Group 18 elements of the periodic table, specifically helium, neon, argon, krypton, xenon, radon, etc. In order to obtain the effects described in the present invention, helium Argon is preferably used.

  When an organometallic compound is added as a 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.

  Various highly functional metal oxide layers can be obtained by appropriately selecting a reactive gas other than the above or other than the above and using it for forming a metal oxide layer used for the antireflection layer. One example is shown below, but the present invention is not limited thereto.

Electrode film Au, Al, Ag, Ti, Ti, Pt, Mo, Mo-Si
Dielectric protective film _{SiO 2, SiO, Si 3 N} 4, Al 2 O 3, Al 2 O 3, Y 2 O 3
Transparent conductive film In ₂ O ₃ , SnO ₂
Electrochromic film WO ₃ , IrO ₂ , MoO ₃ , V ₂ O ₅
Fluorescent film ZnS, ZnS + ZnSe, ZnS + CdS
Magnetic recording film Fe—Ni, Fe—Si—Al, γ-Fe ₂ O ₃ , Co, Fe ₃ O ₄ , Cr, SiO ₂ , AlO ₃
Superconductive film Nb, Nb-Ge, NbN
Solar cell film a-Si, Si
Reflective film Ag, Al, Au, Cu
Selective absorption membrane ZrC-Zr
Selective permeable membrane In ₂ O ₃ , SnO ₂
Antireflection film SiO ₂ , TiO ₂ , SnO ₂
Shadow mask Cr
Abrasion resistant film Cr, Ta, Pt, TiC, TiN
Corrosion resistant film Al, Zn, Cd, Ta, Ti, Cr
Heat resistant film W, Ta, Ti
Lubricating film MoS ₂
Decorative film Cr, Al, Ag, Au, TiC, Cu
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.

  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. In the present invention, it is preferable to provide an antifouling layer on the antireflection layer.

  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.

As the organic fluorine compound, a fluorocarbon gas, a fluorinated hydrocarbon gas, or the like is preferably used. As the fluorocarbon gas, carbon tetrafluoride, carbon hexafluoride, specifically, tetrafluoromethane, tetrafluoroethylene, hexafluoropropylene (CF ₃ CF═CF ₂ ), octafluorocyclobutane, C ₄ F _{8 and the} like can be mentioned. 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.

  When the organic fluorine compound described above is used in the mixed gas, the content of the organic fluorine compound in the mixed gas is 0.1% by volume to 10% from the viewpoint of forming a uniform thin film on the substrate by discharge plasma treatment. Although it is preferable that it is volume%, More preferably, it is 0.1 volume%-5 volume%.

  Further, when the organic fluorine compound according to the present invention is a gas at normal temperature and normal pressure, it can be used as it is as a component of the mixed gas, so that the method of the present invention can be most easily performed. However, when the organic fluorine compound is liquid or solid at normal temperature and normal pressure, it may be used after being vaporized by a method such as heating or decompression, or may be used after being dissolved in an appropriate solvent. .

  Alternatively, a hydrophilic polymer film can be deposited by performing plasma 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.

  When the titanium compound described above is used in the mixed gas, the content of the titanium compound in the mixed gas is 0.1% by volume to 10% by volume from the viewpoint of forming a uniform thin film on the substrate by discharge plasma treatment. Although it is preferable, it is 0.1 volume%-5 volume% more preferably.

  Moreover, the hardness of a thin film can be improved remarkably by containing 0.1 volume%-10 volume% of hydrogen gas in the said 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.

  When using the above-mentioned silicon compound in the mixed gas, the content of the silicon compound in the mixed gas is 0.1 to 10% by volume from the viewpoint of forming a uniform thin film on the substrate by discharge plasma treatment. However, it is more preferably 0.1 to 5% by volume.

  Examples of the titanium compounds described above include organometallic compounds such as tetradimethylaminotitanium, metal hydrogen compounds such as monotitanium and dititanium, metal halogen compounds such as titanium dichloride, titanium trichloride, and titanium tetrachloride, tetraethoxy titanium, tetra Metal alkoxides such as isopropoxy titanium and tetrabutoxy titanium are preferably used, but are not limited thereto.

  Further, the reaction is promoted by containing 0.01 vol% to 5 vol% of a component selected from oxygen, ozone, hydrogen peroxide, carbon dioxide, carbon monoxide, hydrogen, and nitrogen in the mixed gas, and A dense and high-quality thin film can be formed.

  In the present invention, the carbon content of the high-refractive index layer and the low-refractive index layer of the antireflection layer (which may be the metal oxide layer itself) is both 0.2% by mass to 5% by mass and is in close contact with the lower layer. It is preferable for its flexibility and film flexibility, and more preferably 0.3% by mass 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 preferable because the adhesion of the film is improved. The atmospheric pressure plasma treatment can be preferably used because a thin film having a uniform film thickness can be formed on the antiglare film of the present invention having particularly fine irregularities.

  The cellulose ester used for manufacture of the cellulose ester film of the present invention will be described.

  As the cellulose ester according to the present invention, the cellulose ester is preferably a lower fatty acid ester. The lower fatty acid in the lower fatty acid ester of cellulose ester means a fatty acid having 6 or less carbon atoms. For example, cellulose acetate, cellulose propionate, cellulose butyrate and the like are preferable examples of the lower fatty acid ester of cellulose. .

  In addition to the above, mixed fatty acid esters such as cellulose acetate propionate and cellulose acetate butyrate described in JP-A Nos. 10-45804, 08-231761, and US Pat. No. 2,319,052 are used. I can do it.

  In the above description, the lower fatty acid ester of cellulose particularly preferably used is cellulose triacetate.

  Further, from the viewpoint of base strength, a degree of polymerization of 250 to 400 and a bound acetic acid amount of 54 to 62.5% are preferably used, and more preferable is cellulose triacetate having a bound acetic acid amount of 58 to 62.5%. .

  As the cellulose triacetate according to the present invention, either cellulose triacetate synthesized from cotton linter or cellulose triacetate synthesized from wood pulp can be used alone or in combination. If peelability from the belt or drum becomes a problem, it is preferable to use a large amount of cellulose triacetate synthesized from a cotton linter that has good peelability from the belt or drum.

  When cellulose triacetate synthesized from wood pulp is mixed and used, the ratio of cellulose triacetate synthesized from cotton linter is preferably 40% by mass or more, and the effect of releasability becomes remarkable, more preferably 60% by mass or more. Most preferably, it is used alone.

  Depending on the properties of the resin, there are a method of forming a film by a solution casting method and a method of forming a film by extruding a resin in a molten state by melt extrusion using an extruder or the like. In order to obtain high film thickness accuracy and surface quality, it is more preferable to form a film by a solution casting method.

  The cellulose ester film of the present invention 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 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.

  Moreover, it is preferable that the cellulose-ester film of this invention contains a ultraviolet absorber.

  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 oxybenzophenone compounds, benzotriazole compounds, salicylic acid ester compounds, benzophenone compounds, triazine compounds, cyanoacrylate compounds, nickel complex compounds, and the like. However, it is not limited to these. 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 as described in Japanese Patent Application No. 11-295209, so that contamination of the plasma treatment process is prevented. In addition, it is preferable because various coating layers have excellent coating properties, and it is particularly preferable to use an ultraviolet absorber having a distribution coefficient of 10.1 or more.

  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 necessary 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 being treated at 80 ° C. and 90% RH for 48 hours. Preferred (retention). 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 cellulose ester film of the present invention, in-plane retardation R ₀ is preferably ₀ to 1000 nm, and thickness direction retardation R _t is preferably ₀ to 300 nm depending on the application. It is done. As wavelength dispersion characteristics, R ₀ (600) / R ₀ (450) is preferably 0.7 to 1.3, and more preferably 1.0 to 1.3.

Here, R ₀ (450) is an in-plane retardation based on a three-dimensional refractive index measurement with light having a wavelength of 450 nm, and R ₀ (600) is an in-plane retardation based on a three-dimensional refractive index measurement with light having a wavelength of 600 nm. Represents.

  The manufacturing method of the cellulose-ester film of this invention is demonstrated.

  In order to produce a film having a haze of 3% to less than 30% by using at least two kinds of dopes and simultaneously or sequentially casting the dopes on a support and then drying them after peeling, It is necessary to add fine particles to at least one of the dope B used on the support side (B side) and the dope A used on the air side (A side). The content is preferably adjusted so as to be more than 0.5% by mass and 70% by mass or less per solid content, more preferably more than 1% by mass and 50% by mass or less.

  The manufacturing method of the cellulose ester film of this invention is demonstrated referring process drawing shown by FIG.10 and FIG.11.

  FIG. 10 is a process diagram showing an example of the cellulose ester film production apparatus of the present invention, and FIG. 11 is a sectional view of the slit die 6 of FIG.

  The dope liquid tank 1 for preparing the cellulose ester dope liquid is charged with the dope liquid 1a, and the fine particle additive liquid tanks 2 and 2 'are respectively charged with the fine particle additive liquids 2a and 2a'. (Here, the fine particle addition liquids 2a and 2a 'may have the same composition or different compositions).

  The dope solution 1a is sent to the inline mixers 5a, 5b5c by the liquid feed pumps 4b, 4c, 4e, the fine particle additive solution 2a is sent to the inline mixer 5a by the pump 4a, and the fine particle additive solution 2a 'is sent to the inline mixer 5c by the pump 4f. Each is sent. The dope liquid 1 a and the fine particle addition liquid 2 a are sufficiently mixed by the in-line mixer 5 a and sent to the slit a of the slit die 6. Further, the dope liquid 1 a and the fine particle addition liquid 2 a ′ are sufficiently mixed by the in-line mixer 5 c and sent to the slit c of the slit die 6.

  Similarly, the dope liquid 1 a and the ultraviolet absorbent additive liquid 3 a are sufficiently mixed by the in-line mixer 5 b and sent to the slit b of the slit die 6.

  By the slit die 6, the middle layer is composed of a mixed liquid of the dope liquid 1a and the fine particle addition liquid 2a, and the upper and lower surface layers are a mixed liquid of the dope liquid 1a and the fine particle addition liquid 2a, and the dope liquid 1a and the fine particle addition liquid. Co-cast from the casting port 11 while being mixed with the mixed liquid 2a ′, and cast on the casting belt 8 that continuously moves from the drum 7. The three-layer cast cellulose ester dope layer is peeled off from the casting belt by the roller 9 as the cellulose ester film 10 after drying.

  In the present invention, the dope solution in which the resin is dissolved is a state in which a resin such as cellulose ester is dissolved in a solvent (solvent), and an additive such as a plasticizer can be added to the dope solution. Desirably, of course, other additives may be added if necessary. The concentration of the resin in the dope liquid is preferably 10% by mass to 30% by mass, and more preferably 15% by mass to 25% by mass.

  The solvent used in the present invention may be used alone or in combination, but it is preferable to use a mixture of a good solvent and a poor solvent from the viewpoint of production efficiency, and more preferably, the mixing ratio of the good solvent and the poor solvent is good. A solvent is 70 mass%-95 mass%, and a poor solvent is 30-5 mass%.

  With the good solvent and the poor solvent used in the present invention, those that dissolve the resin used alone are defined as good solvents, and those that swell or do not dissolve alone are defined as poor solvents. Therefore, depending on the substitution degree of the cellulose ester, the good solvent and the poor solvent change. For example, when acetone is used as the solvent, the cellulose acetate is a good solvent at an acetylation degree of 55%, and the acetylation degree is 60%. End up.

  Examples of the good solvent used in the present invention include organic halogen compounds such as methylene chloride, methyl acetate, acetone, and dioxolanes.

  Moreover, as a poor solvent used for this invention, methanol, ethanol, n-butanol, a cyclohexane etc. are used preferably, for example.

  As a method for dissolving the cellulose ester when preparing the dope described above, a general method can be used. However, as a preferable method, the cellulose ester is mixed with a poor solvent and wetted or swollen. A method of mixing with a good solvent is preferably used. At this time, under pressure, the method of heating at a temperature above the boiling point of the solvent at a normal temperature and in a range where the solvent does not boil and dissolving while stirring prevents the generation of massive undissolved substances called gels and mamaco, More preferred.

  As the support in the casting step, a support obtained by mirror-finishing belt-shaped or drum-shaped stainless steel is preferably used. The temperature of the support in the casting process can be cast at a general temperature range of 0 ° C. to a temperature lower than the boiling point of the solvent, but the dope is better cast on a support at 0 ° C. to 30 ° C. In order to increase the peeling limit time, it is preferable to cast on a support at 5 to 15 ° C. The peeling limit time is the time during which the cast dope is on the support at the limit of the casting speed at which a transparent and flat film can be continuously obtained. A shorter peeling limit time is preferable because of excellent productivity.

  The surface temperature of the support on the side to be cast (cast) is 10 to 55 ° C., the temperature of the solution is 25 to 60 ° C., and the temperature of the solution is preferably higher than the temperature of the support by 0 ° C. or more, More preferably, it is set to 5 ° C. or higher. The higher the solution temperature and the support temperature, the higher the drying speed of the solvent, which is preferable. However, when the temperature is too high, foaming or flatness may be deteriorated.

  A more preferable range of the temperature of the support is 20 ° C. to 40 ° C., and a more preferable range of the solution temperature is 35 ° C. to 45 ° C.

  Moreover, since the adhesive force of a film and a support body can be reduced by making the support body temperature at the time of peeling into 10 to 40 degreeC, More preferably, 15 to 30 degreeC, it is preferable.

  In order for the cellulose ester film during production to exhibit good flatness, the residual solvent amount when peeling from the support is preferably 10% to 150%, more preferably 20% to 120%, especially Preferably, it is 30% to 110%.

  In the present invention, the amount of residual solvent is defined by the following formula.

Residual solvent amount = (mass before heat treatment−mass after heat treatment) / (mass after heat treatment) × 100%
The heat treatment for measuring the residual solvent amount means that the film is heat treated at 115 ° C. for 1 hour.

  The peeling tension when peeling the support and the film is usually 200 N / m to 250 N / m (Newton) / m), but the content of the UV absorber per unit mass of the cellulose ester is large. In addition, since the cellulose ester film of the present invention that has been made thinner than the conventional film is likely to wrinkle at the time of peeling, the cellulose ester film is preferably peeled at a minimum tension of 170 N / m that can be peeled, more preferably the minimum tension is It is peeling at 140 N / m.

  Moreover, in the drying process of the cellulose ester film, the film peeled off from the support is further dried, and the residual solvent amount is preferably 3% by mass or less, more preferably 0.5% by mass or less.

  In the film drying process, generally, a method of drying while transporting the film by a roll suspension method or a pin tenter method is adopted. For the liquid crystal display member, it is preferable to dry while maintaining the width by a pin tenter method in order to improve the dimensional stability.

  In particular, it is particularly preferable to maintain the width in a large amount of residual solvent immediately after peeling from the support because the effect of improving dimensional stability is more exhibited. The means for drying the film is not particularly limited, and is generally performed with hot air, infrared rays, a heating roll, microwaves, or the like. It is preferable to carry out with hot air in terms of simplicity. The drying temperature is preferably in the range of 40 ° C. to 150 ° C. and divided into 3 to 5 stages, and it is preferable to increase the temperature step by step, and it is more preferable to carry out in the range of 80 ° C. to 140 ° C. in order to improve the dimensional stability. .

  A small amount of fine particles can be added to the dope used on the support side (B side) to be cast or the dope used on the air side (A side), and the effect of increasing the slipperiness of the film surface is also expected. The Although the slip property is expressed by a dynamic friction coefficient, the dynamic friction coefficient is a dynamic friction coefficient between the film surface and the back surface, and when measured according to JIS-K-7125 (1987), it is further 1.5 or less. Preferably, it is 1.0 or less, more preferably 0.5 or less. The dynamic friction coefficient can be lowered by increasing the amount of matting agent added.

  In the production of the cellulose ester film of the present invention, the film is preferably peeled after casting and then stretched in the transverse direction by means such as a tenter. This is preferable because high flatness can be maintained. As a result, an antiglare film that does not warp over a long period of time can be obtained. The tenter is preferably applied in the range of 3% to 40% by weight of the residual solvent. More preferably, it is 10 mass%-35 mass%. The amount of residual solvent can be obtained from the mass change before and after the film containing the solvent is treated at 115 ° C. for 1 hour and the mass of the film after the heat treatment according to the above formula.

  In addition, the cellulose ester film produced by the method of the present invention is excellent in optical isotropy, and a light diffusion film having a retardation (Rt) value in the film thickness direction of 100 nm or less is obtained, and a light diffusion film of 50 nm or less. Further, it is excellent in that a light diffusion film of 0 nm to 30 nm can also be obtained. Furthermore, the method of the present invention is excellent in that uniform retardation can be obtained.

  The retardation (Rt) value is represented by the following formula.

R _t = ((Nx + Ny) / 2−Nz) × d
In the formula, Nx is the refractive index of the film in the direction parallel to the film forming direction, Ny is the refractive index of the film in the direction perpendicular to the film forming direction, Nz is the refractive index of the film in the thickness direction, and d is the thickness of the film. (Nm) respectively.

For example, the retardation is measured using an automatic birefringence meter KOBRA-21ADH (manufactured by Oji Scientific Instruments) at a wavelength of 590 nm in an environment of 23 ° C. and 55% RH. , measured Nx, Ny, and Nz, thereby to calculate the _{R t} values.

  Production of the polarizing plate and the polarizing plate of the present invention will be described.

  The polarizing plate of this invention is produced using the cellulose-ester film of Claim 1, or the anti-glare film of any one of Claims 2-5, or Claim 13. First, the antiglare film is subjected to a surface saponification treatment using an aqueous solution of sodium hydroxide. Here, the surface of the antiglare film provided with the antireflection layer or antifouling layer is pasted with a protective film that can be removed again. It is preferable to protect from alkali using a method such as combining.

  Prepare a polarizing film prepared separately, and paste it on the surface of the antiglare film that has been saponified (the surface on the opposite side of the antireflection layer or antifouling layer) using an adhesive. On the other side of the polarizing film, A cellulose ester film is appropriately bonded to produce the polarizing plate of the present invention.

  In addition, the detail of polarizing plate preparation is described in an Example.

  EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to these.

Example 1
<< Preparation of Dope F >>
First, 4 kg of silicon oxide fine particles (primary average particle size 1.0 μm) and 6 kg of silicon oxide fine particles (primary average particle size 2.5 μm) were added and dispersed in 10 kg of ethanol to prepare a fine particle dispersion. Next, materials other than the remaining ethanol and silicon oxide fine particles used for the preparation of the fine particle dispersion were put into a sealed container, kept at 80 ° C. under pressure, dissolved completely with stirring, filtered, and filtered here. It was prepared with. After adding the fine particle dispersion and mixing well, filtration was performed again to prepare Dope F.

<< Preparation of Dopes A to E and Dopes G to I >>
Dopes A to E and Dopes G to I were prepared in the same manner as Dope F, except that the materials used for dope preparation were changed as shown in Table 1.

  The compositions of the obtained dopes A to I are shown in Table 1.

<< Production of Cellulose Ester Films 1-9 >>
Next, each of the dopes A to I is cooled and kept at 33 ° C., and as shown in Table 2, the three dopes are combined to form a three-layer structure using the die shown in FIG. A web formed by uniformly casting on a stainless steel band was dried at 33 ° C. for 5 minutes. The thickness (μm) of each layer after drying is shown in Table 2.

  After peeling the web from the stainless steel band, it was dried in a roll conveyance drying zone at 80 ° C., then adjusted using a tenter maintained at 100 ° C. so that the residual solvent amount was 5% by mass, and the width direction The film was stretched to 1.06 times.

  Furthermore, it was made to dry while conveying with many rolls at 120 degreeC, and as shown in Table 2, the cellulose-ester films 1-8 were obtained. A cellulose ester film 9 was obtained in the same manner except that only the dope I was used to form a single layer structure. The haze was measured according to ASTM-D1003-52.

<< Preparation of antiglare films 1-12 >>
The following coating composition on each B surface of the cellulose ester films 1 to 9 obtained above (the surface that was on the stainless steel band side during casting was the B surface of the film and the opposite side was the A surface) The product (1) was extruded and coated so that the wet film thickness was 13 μm, and dried at a drying temperature of 80 ° C. to provide a backcoat layer. Each layer was provided, and furthermore, an antireflection layer was provided as described below on the actinic radiation curable resin layer described below to obtain antiglare films 1 to 12.

Coating composition (1) (coating composition for backcoat layer)
Acetone 30 parts by mass Ethyl acetate 45 parts by mass Isopropyl alcohol 10 parts by mass Diacetylcellulose 0.5 part by mass Ultrafine silica 2% acetone dispersion (Aerosil 200V:
Nippon Aerosil Co., Ltd.) 0.11 parts by mass << Coating of actinic radiation curable resin layer >>
Coating of the actinic radiation curable resin layer on each cellulose ester film described in Table 3 was performed as described below.

(Preparation of active ray curable resin layer 1)
The following coating composition (2) was extruded and coated on the A-side of the cellulose ester film, then dried in a drying section set at 80 ° C., and then irradiated with ultraviolet rays at 120 mJ / cm ² to obtain an active ray having a thickness of 3 μm. A cured resin layer 1 was provided.

Coating composition (2)
Dipentaerythritol hexaacrylate monomer 60 parts by mass Dipentaerythritol hexaacrylate dimer 20 parts by mass Components of dipentaerythritol hexaacrylate trimer or more
20 parts by mass Dimethoxybenzophenone photoinitiator 4 parts by mass Methyl ethyl ketone 75 parts by mass Propylene glycol monomethyl ether 75 parts by mass (Coating of actinic radiation curable resin layer 2)
The following coating composition (3) was extruded and coated on the A side of the cellulose ester film, and then dried in a drying section set at 80 ° C., and then irradiated with ultraviolet rays at 120 mJ / cm ² to give a film thickness of 2.5 μm. An actinic radiation curable resin layer 2 was provided.

Coating composition (3)
Dipentaerythritol hexaacrylate monomer 60 parts by mass Dipentaerythritol hexaacrylate dimer 20 parts by mass Components of dipentaerythritol hexaacrylate trimer or more
20 parts by mass Dimethoxybenzophenone photoinitiator 4 parts by mass Methyl ethyl ketone 75 parts by mass Propylene glycol monomethyl ether 75 parts by mass Silicon oxide fine particles (Aerosil R972V:
Nippon Aerosil Co., Ltd., primary average particle size 0.016 μm) 3 parts by mass << Formation of antireflection layer: formed by atmospheric pressure plasma discharge treatment >>
Using a plasma discharge treatment apparatus as shown in FIG. 9 (however, in FIG. 9, only one plasma discharge treatment vessel is installed, but three are used in this embodiment), the following reactive gases are used. Atmospheric pressure plasma discharge treatment was performed to form an antireflection layer on the actinic radiation curable resin layer.

  The specific installation conditions of the plasma discharge treatment apparatus are shown below.

  As the roll electrode 25, a stainless steel jacket roll base material having a cooling function with cooling water (the cooling function is not shown in FIG. 9) is coated with 1 mm of alumina by ceramic spraying, and then tetramethoxysilane is coated with ethyl acetate. After the diluted solution was applied and dried, a roll electrode having a dielectric material which was cured by ultraviolet irradiation and sealed was manufactured and grounded.

  On the other hand, as the fixed electrode 36 used as the application electrode, a hollow rectangular stainless steel is coated with the same dielectric material under the same conditions as described above, and an opposing electrode group is required for both the low refractive index layer and the high refractive index layer. The film thickness was adjusted to obtain each.

The power source used for generating discharge plasma was a high frequency power source (800 kHz) manufactured by Pearl Industry, and supplied with 12 W / cm ² of power. However, the roll electrode was rotated in synchronization with the conveyance of the substrate using a drive.

《Reactive gas》
The composition of the mixed gas (reactive gas) used for the plasma treatment is described below.

(For tin oxide layer formation)
Inert gas: Argon (98.7% by volume)
Reaction gas 1: Hydrogen gas (1% by volume)
Reaction gas 2: Tetrabutyltin vapor (0.3% by volume)
(For titanium oxide layer formation)
Inert gas: Argon (98.7% by volume)
Reaction gas 1: Hydrogen gas (1% by volume)
Reaction gas 2: Tetraisopropoxytitanium vapor (0.3% by volume)
(For silicon oxide layer formation)
Inert gas: Argon (98.7% by volume)
Reaction gas 1: Hydrogen gas (1% by volume)
Reaction gas 2: Tetramethoxysilane vapor (0.3% by volume)
As the antireflection layer, it is subjected to continuous atmospheric pressure plasma treatment on the actinic radiation curable resin layer, and in order, a tin oxide layer (refractive index 1.7, film thickness 67 nm, carbon content 0.3 mass%), Three layers of titanium oxide layer (refractive index 2.14, film thickness 110 nm, carbon content 0.4 mass%), silicon oxide layer (refractive index 1.44, film thickness 87 nm, carbon content 0.2 mass%) Was provided. The carbon content was measured as follows.

<Measurement of carbon content>
The carbon content of each of the tin oxide layer, titanium oxide layer, and silicon oxide layer, which are constituent layers of the antireflection layer, was measured using an XPS (X-ray photoelectron spectroscopy) surface analyzer. There are no particular limitations on the XPS (X-ray photoelectron spectroscopy) surface analyzer, and any model can be used. In the present invention, ESCALAB-200R manufactured by VG Scientific, Inc. was used.

  In the measurement, Mg was used for the X-ray anode, and measurement was performed at an output of 600 W (acceleration voltage: 15 kV, emission current: 40 mA). The energy resolution was set to be 1.5 eV to 1.7 eV when defined by the half width of a clean Ag3d5 / 2 peak.

  Moreover, in order to remove the influence by contamination before the measurement, the surface layer corresponding to the thickness of 10 to 20% of the film thickness of each antiglare film sample was removed by etching.

  For removing the surface layer, it is preferable to use an ion gun using rare gas ions, and He, Ne, Ar, Xe, Kr, etc. can be appropriately used as ion species. In this measurement, Ar ion etching is used. Used to remove the surface layer.

  First, the range of binding energy from 0 eV to 1100 eV was measured at a data acquisition interval of 1.0 eV to determine what elements were detected.

  Next, with respect to all the detected elements except the etching ion species, the data acquisition interval was set to 0.2 eV, and the photoelectron peak giving the maximum intensity was subjected to narrow scan, and the spectrum of each element was measured.

  The obtained spectrum is transferred onto COMMON DATA PROCESSING SYSTEM (Ver. 2.3) manufactured by VAMAS-SCA-JAPAN in order not to cause a difference in the content calculation result due to a difference in measuring apparatus or computer. After that, processing was performed with the same software, and the value of the carbon content was determined as atomic concentration.

  Before performing the quantitative process, a calibration of the Scale Scale was performed for each element, and a 5-point smoothing process was performed.

  In the quantitative process, the peak area intensity (cps * eV) from which the background was removed was used. For the background treatment, the method by Shirley was used. For the Shirley method, see D.C. A. Shirley, Phys. Rev. , B5, 4709 (1972).

<< Preparation of antiglare films 13-15 >>
The following reactive gas was used for the preparation of the antifouling layer, and antireflection was applied in the same manner as in the above antiglare films 1 to 12 except that plasma discharge treatment was performed by applying a power of 11 W / cm ² in all layers. Antiglare films 13 to 15 having an antifouling layer on the layer were produced.

  Here, the refractive index, the film thickness (μm), and the carbon content of each layer formed on the active ray curable resin layer by the atmospheric pressure plasma treatment are as follows in order: 7, film thickness 68 nm, carbon content 0.4 mass%), titanium oxide layer (refractive index 2.14, film thickness 106 nm, carbon content 0.5 mass%), silicon oxide layer (refractive index 1.46, A film thickness of 75 nm, a carbon content of 0.4 mass%), and an antifouling layer (refractive index of 1.33, film thickness of 10 nm).

《Reactive gas》
The composition of the mixed gas (reactive gas) used for the plasma treatment is described below.

(For tin oxide layer formation)
Inert gas: Argon (98.7% by volume)
Reaction gas 1: Hydrogen gas (1% by volume)
Reaction gas 2: Tetrabutyltin vapor (0.3% by volume)
(For titanium oxide layer formation)
Inert gas: Argon (98.7% by volume)
Reaction gas 1: Hydrogen gas (1% by volume)
Reaction gas 2: Tetraisopropoxytitanium vapor (0.3% by volume)
(For silicon oxide layer formation)
Inert gas: Argon (98.7% by volume)
Reaction gas 1: Hydrogen gas (1% by volume)
Reaction gas 2: Tetramethoxysilane vapor (0.3% by volume)
(For antifouling layer formation)
Inert gas: Argon (98.7% by volume)
Reaction gas 1: Hydrogen gas (1% by volume)
Reaction gas 2: 6-propylene fluoride (0.3 vol%)
The antifouling layer was formed on the silicon oxide layer provided on the A side of the cellulose ester film 3 or 5 (the side having the uneven surface). A high frequency power source manufactured by JEOL was used as a power source, a continuous frequency of 13.56 MHz and power of 15 W / cm ² were supplied, and the composition of the mixed gas (reactive gas) used for the plasma treatment was as described above. In the same manner, an antifouling layer was formed.

<< Preparation of antiglare film 16 >>
A tin oxide layer having a thickness of 100 nm was formed as an antistatic layer by atmospheric pressure plasma treatment using the following reactive gas for forming a tin oxide layer. The active ray curable resin layer 1 was coated thereon so that the film thickness was 2 μm. Furthermore, a titanium oxide layer (refractive index 2.2, film thickness 13 nm, carbon content 0.3% by mass) and a silicon oxide layer (refractive index 1.46, film thickness 35 nm, carbon content 0.3 in order) Mass%), titanium oxide layer (refractive index 2.2, film thickness 122 nm, carbon content 0.3 mass%), silicon oxide layer (refractive index 1.46, film thickness 88 nm, carbon content 0.3 mass%) ) Was provided as an antireflection layer. Furthermore, an antifouling layer having a film thickness of 10 nm was provided thereon to obtain an antiglare film 16. The specific resistance of the surface of this film was 10 ¹⁰ Ω / cm ² .

(For tin oxide layer formation)
Inert gas: Argon (97.7% by mass)
Reaction gas 1: Oxygen gas (2% by mass)
Reaction gas 2: Tetrabutyltin vapor (0.3% by mass)
(For titanium oxide layer formation)
Inert gas: Argon (97.7% by mass)
Reaction gas 1: Oxygen gas (2% by mass)
Reaction gas 2: Tetraisopropoxytitanium vapor (0.3% by mass)
(For silicon oxide layer formation)
Inert gas: Argon (97.7% by mass)
Reaction gas 1: Oxygen gas (2% by mass)
Reaction gas 2: Tetramethoxysilane vapor (0.3% by mass)
(For antifouling layer formation)
Inert gas: Argon (98.7% by mass)
Reaction gas 1: Hydrogen gas (1% by mass)
Reaction gas 2: 6-propylene fluoride (0.3% by mass)
<Surface specific resistance>
After the antiglare film 16 was conditioned for 6 hours under the conditions of 23 ° C. and 55% RH, the surface specific resistance value of the surface of the coating film was measured under the same conditions by using an insulation resistance measuring instrument (VE-30 manufactured by Kawaguchi Electric Co., Ltd.). Type).

The electrodes used for the measurement were measured by placing two electrodes (parts in contact with the sample at 1 cm × 5 cm) in parallel with an interval of 1 cm, contacting the sample with the electrodes, and multiplying the measured value by five times. The value was a surface specific resistance value Ω / cm ² .

  About said anti-glare films 1-16, the following evaluation was performed.

<Measurement of haze (turbidity)>
Measurement was performed on one film sample according to ASTM-D1003-52.

<Measurement of reflectance>
Spectral reflectance was measured using spectrophotometer U-4000 type (manufactured by Hitachi, Ltd.) under the condition of regular reflection at 5 degrees. In the measurement, the back surface on the observation side is roughened and then light absorption processing is performed using a black spray to prevent reflection of light on the back surface of the film and reflectivity (for wavelengths of 400 nm to 700 nm). Measurements were made. Moreover, the average reflectance of 450 nm-650 nm was calculated | required.

<Measurement of scratch resistance>
Steel wool # 000 was pressed under a load of 250 g / cm ² and after 10 reciprocating motions, the number of scratches was measured, and the rank was evaluated as follows.

A: 0 to 3 B: 4 to 10 (practical)
C: 11 to 20 D: 21 or more << Center line average roughness (Ra) >>: Numerical values specified in JIS B 0601 Using an optical interference type surface roughness meter RST / PLUS (manufactured by WYKO), 1 The center line average roughness Ra of the active ray curable resin layer surface was determined for an area of 0.2 mm × 0.9 mm.

<Visibility evaluation>
About the visibility of an anti-glare film, the polarizing plates 1-16 were each produced as follows using the anti-glare films 1-16, those polarizing plates were built in the liquid crystal display panel, and visibility was evaluated.

(Preparation of polarizing plate 1)
(A) A 120 μm thick polyvinyl alcohol film was immersed in 100 kg of an aqueous solution containing 1 kg of iodine, 2 kg of potassium iodide, and 4 kg of boric acid, and stretched 4 times at 50 ° C. to prepare a polarizing film.

  (B) Samples of the antiglare film 1 and the cellulose ester film 9 cut in a longitudinal direction of 30 cm and a lateral direction of 18 cm were immersed in a 2 mol / l sodium hydroxide solution at 60 ° C. for 1 minute, further washed with water and dried. The antireflection layer or antifouling layer surface of the antiglare film was protected from alkali by applying a polyester protective film (film thickness: 30 μm).

  (C) The polarizing film having the same size as the antiglare film was immersed in a polyvinyl alcohol adhesive tank having a solid content of 2% by mass for 1 to 2 seconds.

  (D) Gently remove excess adhesive adhered to the polarizing film and place it on the opposite surface of the antireflection layer of the antiglare film sample, and further laminate so that the cellulose ester film 9 and the adhesive are in contact with each other. And arranged.

  (E) Excess adhesive and bubbles are removed and bonded from the end of the laminate of the polarizing film, the antiglare film and the cellulose ester film laminated with a hand roller. The pressure of the hand roller was about 0.2 MPa to 0.3 MPa, and the roller speed was about 2 m / min.

  (F) The sample obtained in (e) was allowed to stand in a dryer at 80 ° C. for 2 minutes to produce a polarizing plate 1.

  Polarizing plates 2 to 16 using the antiglare films 2 to 16 were produced in the same manner except that the antiglare film 1 was changed to the antiglare films 2 to 16. Here, the comparative polarizing plates are the polarizing plates 8 and 9 produced using the antiglare films 8 and 9 (comparative).

  The obtained polarizing plates 1-16 were evaluated as follows.

  The outermost polarizing plate of MultiSync LCD1525J type name LA-1529HM was carefully peeled off, and polarizing plates 1 to 16 of the present invention having the polarization directions were attached thereto.

  As a result of visual observation of each liquid crystal display panel, the liquid crystal display panel using the polarizing plate of the present invention has no unevenness of reflected light with respect to the liquid crystal display panel using the polarizing plates 8 and 9 of the comparative example. It was confirmed that it was easy to read even fine characters as shown in FIG. In particular, the comparative polarizing plates 8 and 9 were difficult to read characters due to glare.

(Visibility evaluation method)
Change the character font size on the screen using a word processor software (MS Word (manufactured by Microsoft)), and read the character 50 cm away from the angle of 50 ° to the horizontal direction of the screen. The rank was evaluated as follows.

A: Clearly read up to font size 8 B: Somehow read at font size 8 C: Somehow read at font size 10 D: Some characters could not be read at font size 10 3 shows.

  From Table 3, it is clear that the sample of the present invention has good scratch resistance and excellent visibility.

DESCRIPTION OF SYMBOLS 1 Dope liquid tank 1a Dope liquid 2, 2 'Fine particle additive liquid tank 2a, 2a' Fine particle additive liquid 3 Tank 3a Ultraviolet absorber additive liquid 4a, 4b, 4c, 4d, 4e, 4f Pump 5a, 5b, 5c In-line mixer 6 Slit die 7 Drum 8 Casting belt 9 Roller 10 Cellulose ester film 11 Casting port 12 Slit 13 Slit 25, 25c, 25C Roll electrode 26, 26c, 26C, 36, 36c, 36C Electrode 25a, 25A, 26a, 26A, 36a , 36A Conductive base material such as metal 25b, 26b, 36b Ceramic-coated dielectric 25B, 26B, 36B Lining dielectric 31 Plasma discharge treatment vessel 41 Power supply 51 Gas generator 52 Air supply port 53 Exhaust port 60 Electrode cooling unit 61 Original roll base 65, 66 D Prora 64 and 67 guide rollers

Claims (13)

  A dielectric-coated electrode, which is a prism-shaped dielectric-coated electrode in which a conductive base material is coated with a dielectric, wherein the porosity of the dielectric is 10% by volume or less.   2. The dielectric-coated electrode according to claim 1, wherein the dielectric is an inorganic material having a relative dielectric constant of 6 to 45.   The dielectric-coated electrode according to claim 1, wherein the dielectric is subjected to sealing treatment with an inorganic material after thermal spraying of ceramics.   The dielectric-coated electrode according to claim 3, wherein the ceramic contains alumina.   5. The dielectric-coated electrode according to claim 3, wherein the sealing inorganic material is cured by a sol-gel reaction.   The dielectric-coated electrode according to claim 5, wherein the sol-gel reaction is promoted by heat or UV.   The dielectric-coated electrode according to claim 1, wherein a surface of the dielectric is polished.   The dielectric-coated electrode according to claim 7, wherein the dielectric has a surface roughness Rmax of 10 μm or less.   The dielectric-coated electrode according to any one of claims 1 to 8, wherein the dielectric-coated electrode has a cooling means with cooling water.   A substrate is positioned between two types of electrodes facing each other, and a voltage is applied between the electrodes to discharge under atmospheric pressure or a pressure near atmospheric pressure, whereby a reactive gas is brought into a plasma state, and the substrate is In the plasma discharge processing apparatus which forms a thin film on the said base material by exposing to the reactive gas of the said plasma state, at least one of the said 2 types of opposing electrodes is any one of Claims 1-9. A plasma discharge treatment apparatus, characterized in that it is a dielectric-coated electrode described in (1).   The base material is a long film, and at least one of the two types of electrodes facing each other is one roll electrode that winds the long film and rotates in the conveying direction of the long film, 11. The plasma discharge processing apparatus according to claim 10, wherein the electrode facing the roll electrode is an electrode group in which a plurality of the dielectric-coated electrodes are arranged.   The plasma discharge processing apparatus according to claim 11, wherein the roll electrode is a dielectric-coated electrode obtained by coating a conductive base material with a dielectric.   The plasma discharge treatment apparatus according to claim 11, wherein the roll electrode has a surface roughness Rmax of 10 μm or less.

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