JPWO2008050576A1 - Antiglare film, method for producing antiglare film, polarizing plate and display device - Google Patents

Abstract

An anti-glare film having a fine uneven structure on a transparent substrate, wherein the anti-glare layer has a convex diameter of 15 to 40 μm, a convex height of 2 to 10 μm, and the convex structure The antiglare layer has a surface roughness (Rz) of 0.8 to 4 μm and an average center-to-center distance (Sm) of the protrusions or recesses of the antiglare layer. An antiglare film characterized by having 25 to 100 μm, Rz / Sm of 0.01 to 0.1, and further having 5 to 25 surface shape portions of the convex portions or concave portions per 0.01 mm 2.

Description

  The present invention relates to an antiglare film, a method for producing an antiglare film, a polarizing plate and a display device, and is excellent in transmission sharpness, antiglare property and bending resistance, and has an antiglare material having a desired fine concavo-convex structure formed with good productivity. The present invention relates to a production method for an anti-glare film, an anti-glare film, a polarizing plate and a display device using the anti-glare film.

  In recent years, development of thin and light notebook computers has been progressing. Along with this, the demand for thinner and higher performance protective films for polarizing plates used in display devices such as liquid crystal display devices is also increasing. Also, a computer provided with an anti-glare layer for improving visibility, and also provided with an anti-glare layer that prevents reflections and scatters the reflected light with a rough surface to obtain display performance with less glare. A liquid crystal image display device (also referred to as a liquid crystal display) such as a word processor or the like has been widely used.

  Various types and performance improvements have been made to the antireflection layer and antiglare layer depending on the application, and various front plates with these functions are attached to the polarizer of a liquid crystal display, etc., to improve visibility on the display. Therefore, a method of providing an antireflection function or an antiglare function is used.

  The antiglare layer reduces the visibility of the reflected image by blurring the outline of the image reflected on the surface, and reflection of the reflected image is noticeable when using an image display device such as a liquid crystal display, an organic EL display, or a plasma display. It is to prevent it from becoming.

  By providing an appropriate fine concavo-convex structure on the outermost surface of the front plate of the image display device, the above properties can be provided. For example, there are various methods such as a method using fine particles (for example, refer to Patent Document 1) and a method for embossing the surface (for example, refer to Patent Document 2).

  However, since the method using fine particles forms a fine concavo-convex structure only by including fine particles in the binder layer, it is necessary to disperse the fine particles appropriately, and the desired fine concavo-convex structure can be effectively and stably stabilized. It was difficult to form and had a great obstacle to obtaining a sufficient glare-preventing effect as an antiglare film. In particular, the method using fine particles cannot control the existence density of the fine particles, and the height of the convex portions is higher than the surroundings in a portion where the fine particles overlap, so that a uniform uneven structure cannot be formed stably. The drawback was that the film thickness increased to compensate for this. Moreover, the method of forming a fine concavo-convex structure by embossing is inferior in productivity, and in particular, it is extremely difficult to stably form a fine concavo-convex structure.

  Patent Document 3 describes a method for forming fine irregularities using phase separation of a resin utilizing spinodal decomposition, but the state of phase separation tends to change depending on reaction conditions, and it is difficult to stably produce an antiglare film. Patent Document 4 discloses a technique in which a hard coat layer is provided on a cured resin interspersed in a dot shape so that the surface becomes smooth. The invention does not aim to smooth the film surface.

  In recent years, as image quality has been improved, a display device having anti-glare properties and high contrast has been demanded. For example, the outermost surface of the liquid crystal display device has insufficient contrast with a conventional antiglare film such as a fine particle method, and reflection of external light becomes a problem with a clear hard coat antireflection film. In order to cope with this drawback, many techniques relating to an antiglare antireflection film obtained by coating an antiglare film with an antireflection layer (low refractive index layer) due to light interference have been proposed (for example, Patent Documents 5 to 7). reference.). However, these methods have not yet achieved sufficient anti-glare properties and contrast in obtaining a display device with higher visibility. Further, Patent Document 8 has a description of providing an overcoat layer on an antiglare hard coat film, but it is intended for antifouling properties, easy washing properties, antireflection properties, etc. There is no description about covering the structure and exhibiting antiglare properties.

Patent Document 9 describes a high-productivity antiglare layer that forms a fine concavo-convex structure by an ink jet method, but further improvement in performance and stability are required.
JP 59-58036 A JP-A-6-234175 JP 2005-227407 A JP 2000-84477 A Japanese Patent Laid-Open No. 2004-4404 JP 2004-125985 A JP 2004-24967 A JP 2003-26832 A JP 2004-151642 A

  Therefore, the present invention has been made in view of the above problems, and its purpose is to effectively capture external light and reduce contrast without deteriorating the sharpness of a high-definition image due to a reduction in pixel size or the like. To provide an antiglare film capable of preventing and forming a desired fine concavo-convex structure effectively and stably with high productivity, a method for producing the antiglare film, and further providing a polarizing plate and a display device using the same. It is in.

  The above object of the present invention is achieved by the following configurations.

1. An anti-glare film having a fine uneven structure on a transparent substrate, wherein the anti-glare layer has a convex diameter of 15 to 40 μm, a convex height of 2 to 10 μm, and the convex structure The antiglare layer has a surface roughness (Rz) of 0.8 to 4 μm and an average center-to-center distance (Sm) of the protrusions or recesses of the antiglare layer. An antiglare film characterized by having 25 to 100 μm, Rz / Sm of 0.01 to 0.1, and further having 5 to 25 surface shape portions of the convex portions or concave portions per 0.01 mm ² .

  2. 2. The antiglare film as described in 1 above, wherein the convex structure is formed by an ink jet method.

  3. 3. The antiglare film as described in 1 or 2 above, wherein the dry film thickness of the antiglare layer formed of the convex structure portion and the transparent resin layer is 3 to 15 μm.

  4). The above-mentioned 1-3, wherein the convex structure part is made of an actinic ray curable resin or a thermosetting resin, and the viscosity of the convex structure-forming ink liquid containing the resin is 5-12 mPa · s. The antiglare film according to any one of the above.

  5. 5. The antiglare film as described in 4 above, wherein a contact angle (θ) between the ink liquid for forming the convex structure portion and the transparent substrate is 45 to 70 °.

  6). 6. The above 4 or 5, wherein the convex structure forming ink liquid contains 60% by mass or more of at least one solvent having a boiling point of 140 to 250 ° C. and a viscosity of 1 to 15 mPa · s. Antiglare film.

  7). 7. The antiglare film as described in 6 above, wherein the solvent is a compound represented by the following general formula (1).

Formula _{(1) R 1 -O- (C} x H 2x -O) n-R 2
In the formula, R ₁ and R ₂ are a hydrogen atom, an aryl group, an alkyl group having 1 to 6 carbon atoms, an alkoxyalkyl group, or an alkylcarbonyl group. The hydrocarbon chain may be linear or branched. However, at least one of R ₁ and R ₂ is a substituent other than a hydrogen atom.

n: an integer of 1 to 3 x: an integer of 2 to 4 8. The antiglare film according to any one of 1 to 7, wherein an antireflection layer or an antifouling layer is further formed on the antiglare layer.

  9. The transparent substrate has a transparent support and at least one cured resin layer or smooth light diffusing layer thereon, and a convex structure is formed on the surface by an inkjet method, and then the convex structure is covered. Thus, the transparent resin layer is formed, and the dry film thickness to the transparent resin layer except this transparent support body is 3-15 micrometers, The manufacturing method of the anti-glare film characterized by the above-mentioned.

  10. A convex resin is formed on the surface of the cured resin layer or light diffusing layer in a half-cured state by an inkjet method, and then a transparent resin layer is formed so as to cover the convex structure. 10. The method for producing an antiglare film as described in 9 above.

  11. 11. The method for producing an antiglare film as described in 9 or 10 above, wherein after forming the convex structure portion, a transparent resin layer is formed so as to cover the convex structure portion by subjecting the surface to plasma treatment.

  12 A polarizing plate using the antiglare film described in any one of 1 to 8 above.

  13. 9. A display device using the antiglare film described in any one of 1 to 8 or the polarizing plate described in 12 above.

  According to the present invention, it is possible to effectively prevent the reflection of external light and a decrease in contrast without deteriorating the sharpness of a high-definition image due to a reduction in pixel size, etc., and a desired fine uneven structure with good flexibility. An antiglare film formed effectively and stably with good productivity and a method for producing an antiglare film can be provided, and a polarizing plate and a display device using the film can be provided.

It is a figure which shows the glare-proof improvement effect by coating | cover of a transparent resin layer. It is sectional drawing which shows an example of the inkjet head which can be used for the inkjet system used for this invention. It is the schematic which shows an example of the inkjet head part and nozzle plate which can be used by this invention. It is a schematic diagram which shows an example of the inkjet system which can be preferably used by this invention. It is the schematic diagram which showed a mode that gentle unevenness | corrugation was formed by covering both the convex structure part and the part without a convex structure part with a transparent resin layer. It is a schematic diagram of the fine concavo-convex structure preferable for the present invention. It is a flow of contact angle measurement. It is an example of a method for forming a fine concavo-convex structure on a base film by an inkjet method. It is the figure which showed typically the environment at the time of observation when an anti-glare antireflection film is applied to a liquid crystal display device.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 Base film 11 Board | substrate 12 Piezoelectric element 13 Flow path plate 13a Ink flow path 13b Wall part 14 Common liquid chamber structural member 15 Ink supply pipe 16 Nozzle plate 16a Nozzle 17 Drive circuit printed board 18 Lead part 19 Drive electrode 20 Groove 21 Protective plate 22 Fluid resistance 23, 24 Electrode 25 Upper partition wall 26 Heater 27 Heater power supply 28 Heat transfer member 29 Actinic ray irradiation unit 30 Inkjet head 31 Liquid droplet 32 Nozzle 35 Back roll 101 Laminated roll 103 First coater 104A-D Back roll 105A ~ D Drying zone 107 Plasma processing unit 108 Ink supply tank 109 Inkjet emitting unit 110 Heating unit 113 Winding roll

  The best mode for carrying out the present invention will be described in detail below, but the present invention is not limited thereto.

  As a result of intensive studies on the above problems, the present inventors have found that when the dots are separated from each other as described in Patent Document 8 and the space between the dots is a planar substrate, the planar substrate is not obtained by using only dots. It does not show satisfactory anti-glare properties depending on the part, but by overcoating the dots, the flat substrate part between the dots is covered with an overcoat in an inclined state, so that the anti-glare property is remarkably improved. It is what I found. Hereinafter, in this application, a dot and a convex structure part are demonstrated as synonymous.

  FIG. 1 is a characteristic diagram showing the effect of improving the antiglare property by covering the transparent resin layer.

(Anti-glare evaluation method)
The reflection angle distribution is measured using a goniophotometer GP-1-3D manufactured by Optec Co., Ltd., using as a sample an antiglare film containing only dots and an antiglare film obtained by coating the dots with a transparent resin layer. Light projection diameter φ = 10 mm, light reception diameter φ = 3 mm.

  The numerical value of the anti-glare property is represented by a logarithmic value of an integral value of scattered light intensity at a scanning angle of ± 1 to 3.5 ° (excluding a regular reflection region).

  From the results shown in FIG.

Logarithm of scattered light intensity integral value Antiglare dots only -1.5 Low Cover the dots with a transparent resin layer -0.48 High Therefore, the antiglare film of the present invention has a fine uneven structure on a transparent substrate. The antiglare layer has a convex structure portion having a convex portion diameter of 15 to 40 μm, a convex portion height of 2 to 10 μm, and a transparent resin layer so as to cover the convex structure portion; and The surface roughness (Rz) of the antiglare layer is 0.8 to 4 μm, the average center-to-center distance (Sm) of the protrusions or recesses of the antiglare layer is 25 to 100 μm, and Rz / Sm is 0.01 to 0. 1 and further having 5 to 25 surface shape portions of the convex portion or the concave portion per 0.01 mm ² .

  Further, the formation of the convex structure is not particularly limited, but it is preferably formed by a pattern preparation method such as a gravure method, a screen printing method, a flexographic printing method, an ink jet method, etc. It is preferable.

  Next, the anti-glare layer is cured by actinic rays or heating after the convex structure portion, and then a microgravure method, an extrusion coating method, a wire bar method, a spray coating method, a flexographic printing method, an ink jet method, etc. It is produced by uniformly applying a transparent resin layer by a thin film uniform application method.

  FIG. 2 is a cross-sectional view showing an example of an ink jet head used in an ink jet system suitable for the present invention.

  2A is a cross-sectional view of the inkjet head, and FIG. 2B is an enlarged view taken along the line AA in FIG. 2A. In the figure, 11 is a substrate, 12 is a piezoelectric element, 13 is a flow path plate, 13a is an ink flow path, 13b is a wall, 14 is a common liquid chamber constituent member, 14a is a common liquid chamber, 15 is an ink supply pipe, 16 Is a nozzle plate, 16a is a nozzle, 17 is a drive circuit printed board (PCB), 18 is a lead portion, 19 is a drive electrode, 20 is a groove, 21 is a protective plate, 22 is a fluid resistance, 23 and 24 are electrodes, 25 Is an upper partition, 26 is a heater, 27 is a heater power source, 28 is a heat transfer member, and 30 is an ink-jet head.

  In the integrated inkjet head 30, the laminated piezoelectric element 12 having the electrodes 23 and 24 is grooved in the direction of the flow path 13a corresponding to the flow path 13a, so that the groove 20 and the driving piezoelectric element 12b. And non-driving piezoelectric element 12a. The groove 20 is filled with a filler. The flow path plate 13 is joined to the piezoelectric element 12 subjected to the groove processing through the upper partition wall 25. That is, the upper partition 25 is supported by the non-driving piezoelectric element 12a and the wall 13b that separates the adjacent flow path. The width of the driving piezoelectric element 12b is slightly narrower than the width of the flow path 13a. When the driving piezoelectric element 12b selected by the driving circuit on the driving circuit printed board (PCB) is applied with a pulsed signal voltage, the driving piezoelectric element 12b. The element 12b changes in the thickness direction, the volume of the flow path 13a changes via the upper partition 25, and as a result, ink droplets are ejected from the nozzles 16a of the nozzle plate 16.

  Heaters 26 are bonded to the flow path plate 13 via heat transfer members 28, respectively. The heat transfer member 28 is provided around the nozzle surface. The heat transfer member 28 is intended to efficiently transfer the heat from the heater 26 to the flow path plate 13, carry the heat from the heater 26 to the vicinity of the nozzle surface, and warm the air in the vicinity of the nozzle surface. A material with good conductivity is used. For example, metals such as aluminum, iron, nickel, copper, and stainless steel, or ceramics such as SiC, BeO, and AlN are preferable materials.

  When the piezoelectric element is driven, the piezoelectric element is displaced in a direction perpendicular to the longitudinal direction of the flow path, and the volume of the flow path is changed. By the change in volume, ink droplets are ejected from the nozzle. The piezoelectric element is given a signal that keeps the flow path volume constantly reduced, and after the displacement of the selected flow path in the direction of increasing the flow volume, the displacement that reduces the flow volume again is applied. By applying a pulse signal to be applied, ink is ejected as ink droplets from a nozzle corresponding to the flow path.

  FIG. 3 is a schematic view showing an example of an inkjet head unit and a nozzle plate that can be used in the present invention.

  3, (a) of FIG. 3 is a sectional view of the head portion, and (b) of FIG. 3 is a plan view of the nozzle plate. In the figure, 10 is a substrate film, 31 is an ink droplet, 32 is a nozzle, and 29 is an actinic ray irradiation part. The ink droplet 31 ejected from the nozzle 32 flies in the direction of the base film 10 and adheres. The ink droplets that have landed on the substrate film 10 are immediately irradiated with actinic rays from the actinic ray irradiating unit disposed upstream thereof, and are cured. Reference numeral 35 denotes a back roll for holding the base film 10.

  In the present invention, as shown in FIG. 3B, the nozzles of the inkjet head unit are preferably arranged in a staggered manner, and provided in multiple stages in parallel in the transport direction of the base film 10. preferable. Further, it is preferable that fine vibrations are applied to the ink jet head portion during ink ejection so that ink droplets land randomly on the transparent substrate. Thereby, generation | occurrence | production of an interference fringe can be suppressed. The fine vibration can be given by a high frequency voltage, a sound wave, an ultrasonic wave or the like, but is not particularly limited thereto.

  As the method for forming the convex structure portion used in the present invention, it is preferable to use an ink jet method in which small droplets of ink are formed from multiple nozzles. FIG. 4 shows an example of an ink jet system that can be preferably used in the present invention.

  4, (a) of FIG. 4 is a method (line) in which the inkjet head 30 is arranged in the width direction of the transparent substrate film 10 and a convex structure portion is formed on the surface of the transparent substrate film 10 while being conveyed. 4B is a method (flat head method) in which the inkjet head 30 moves in the sub-scanning direction to form a convex structure portion on the surface thereof, and FIG. 8C) is an inkjet head. 30 is a method of forming a convex structure portion on the surface of the transparent substrate film 10 while scanning in the width direction (capstan method), and any method can be used. The line head method is preferable from the viewpoint of productivity. In addition, you may attach the actinic ray irradiation part used when the below-mentioned actinic ray curable resin is used as an ink like 29 of (a)-(c) of FIG.

  Moreover, in this invention, you may provide another actinic ray irradiation part in the downstream of the conveyance direction of the base film of (a) of FIG. 4, (b), (c).

  In the present invention, in order to form a fine uneven structure, the ink droplet is preferably 0.1 to 20 pl, more preferably 0.5 to 10 pl, and particularly preferably 0.5 to 5 pl. Also, different ink droplet amounts may be ejected from different ink jet head portions, and ink may be ejected from the same ink jet head portion while changing the amount of liquid droplets. It may be.

  The convex structure portion has a convex major axis of 15 to 40 μm, more preferably 15 to 30 μm, and the convex portion has a constant size and height of 2 to 10 μm, more preferably 2 to 8 μm. It is preferable that the protrusions are arranged at random by a method such as FM screening. Here, the diameter of the convex portion represents the diameter when the convex portion is circular, and the diameter converted into the same area when the convex portion is triangular, quadrangular, polygonal, or indefinite. The height of a convex part means the difference of the height of the highest part of a dot from a base film surface.

  The FM screening method is a method for expressing light and shade by modulating the interval between dots, that is, the frequency, and the frequency of hitting the basic dots (dot density). The FM screening method is sometimes called a random screening method or a stochastic screening method. The FM screening method refers to a method of modulating the interval between dots, that is, periodicity. Specifically, the crystal raster screening method (Agfa Gebalt), the diamond screen method (Rhinotype Hell), the class screening method and the full-tone screening method (Cytex), the velvet screening method ( Ugura Cohan), Accutone Screening (Dannery), Megadot Screening (American Color), Clear Screening (Seacolor), Monet Screening (Barco) Yes. Although all of these methods have different dot generation algorithms, it is a method of expressing shading by changing the dot density, and can be said to be various aspects of the FM screening method.

  In FM screening, the size of dots on which ink is placed is constant, and the frequency of dot appearance changes according to the density of the image. Since the size of each dot in FM screening is smaller than a so-called halftone dot, a required pattern can be reproduced with high resolution. Unlike so-called halftone dots, dots in FM screening are not periodically arranged. The FM screening has a feature that moire does not occur because the dot arrangement is not periodic.

  Next, the ink composition for the convex structure and the liquid composition for the transparent resin layer according to the present invention will be described.

  The ink liquid and the liquid composition of the present invention are preferably an actinic ray curable resin, a thermoplastic resin, a thermosetting resin, a metal alkoxide, or a hydrolyzate thereof.

  First, the actinic ray curable resin that is preferably used in the ink composition for the convex structure portion and the liquid composition of the transparent resin layer of the present invention will be described.

  The actinic ray curable resin is a resin that is cured through a crosslinking reaction or the like by irradiation with actinic rays such as ultraviolet rays or electron beams. Typical examples of the actinic ray curable resin include an ultraviolet curable resin, an electron beam curable resin, and the like, but a resin that is cured by irradiation with actinic rays other than ultraviolet rays and electron beams may be used.

  Examples of the ultraviolet curable resin include an ultraviolet curable acrylic urethane resin, an ultraviolet curable polyester acrylate resin, an ultraviolet curable epoxy acrylate resin, an ultraviolet curable polyol acrylate resin, and an ultraviolet curable epoxy resin. be able to.

  UV curable acrylic urethane resins generally include 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate (hereinafter referred to as acrylates) in 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, a mixture of 100 parts Unidic 17-806 (Dainippon Ink Co., Ltd.) and 1 part Coronate L (Nihon Polyurethane Co., Ltd.) described in JP-A-59-151110 is preferably used. .

  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 the ultraviolet curable polyol acrylate resin 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 pentaacrylate.

  As examples of the ultraviolet curable epoxy acrylate resin and the ultraviolet curable epoxy resin, preferred examples of the epoxy actinic ray reactive compound are shown.

(A) Glycidyl ether of bisphenol A (this compound is obtained as a mixture having different degrees of polymerization by reaction of epichlorohydrin and bisphenol A)
(B) A compound having a glycidyl ether group by reacting epichlorohydrin, ethylene oxide and / or propylene oxide with a compound having two phenolic OHs such as bisphenol A. (c) Glycidyl ether of 4,4'-methylenebisphenol (D) Epoxy compound of phenol formaldehyde resin of novolak resin or resol resin (e) Compound having alicyclic epoxide, for example, bis (3,4-epoxycyclohexylmethyl) oxalate, bis (3,4-epoxycyclohexylmethyl) ) Adipate, bis (3,4-epoxy-6-cyclohexylmethyl) adipate, bis (3,4-epoxycyclohexylmethyl pimelate), 3,4-epoxycyclohexylmethyl-3,4-epoxy Rhohexanecarboxylate, 3,4-epoxy-1-methylcyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate, 3,4-epoxy-1-methyl-cyclohexylmethyl-3', 4'-epoxy-1 '-Methylcyclohexanecarboxylate, 3,4-epoxy-6-methyl-cyclohexylmethyl-3', 4'-epoxy-6'-methyl-1'-cyclohexanecarboxylate, 2- (3,4-epoxycyclohexyl- 5 ', 5'-spiro-3 ", 4" -epoxy) cyclohexane-meta-dioxane (f) diglycidyl ethers of dibasic acids such as diglycidyl oxalate, diglycidyl adipate, diglycidyl tetrahydrophthalate, di Glycidyl hexahydrophthalate, diglycidyl Phthalate (g) Diglycidyl ether of glycol, such as ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, copoly (ethylene glycol-propylene glycol) di Glycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether (h) Glycidyl ester of polymer acid, for example, polyglycidyl ester of polyacrylic acid, polyester diglycidyl ester (i) Polyhydric alcohol Glycidyl ethers such as glycerin triglycidyl ether, trimethylolpropane triglyceride Dil ether, pentaerythritol diglycidyl ether, pentaerythritol triglycidyl ether, pentaerythritol tetraglycidyl ether, glucose triglycidyl ether (j) As diglycidyl ether of 2-fluoroalkyl-1,2-diol, the low refractive index substance (K) Examples of the fluorine-containing alkane-terminated diol glycidyl ether include fluorine-containing epoxy compounds of the fluorine-containing resin of the low refractive index material, and the like. it can.

  The molecular weight of the said epoxy compound is 2000 or less as an average molecular weight, Preferably it is 1000 or less.

  When the above epoxy compound is cured with actinic rays, it is effective to use a compound having a polyfunctional epoxy group (h) or (i) in order to increase the hardness.

  The photopolymerization initiator or photosensitizer for cationically polymerizing an epoxy actinic light-reactive compound is a compound capable of releasing a cationic polymerization initiating substance upon irradiation with actinic light, and particularly preferably, cationic polymerization is initiated by irradiation. A group of double salts of onium salts that release potent Lewis acids.

  The actinic 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 a preferable actinic ray reactive resin because it is not affected by oxygen in the reaction system.

  The actinic ray-reactive epoxy resin useful in the present invention is polymerized by a photopolymerization initiator or a photosensitizer that releases a substance that initiates cationic polymerization upon irradiation with actinic rays. As the photopolymerization initiator, a group of double salts of onium salts that release a Lewis acid that initiates cationic polymerization by light irradiation is particularly preferable.

  A typical example is a compound represented by the following general formula (a).

Formula (a)
[(R1) a (R2) b (R3) c (R4) dZ] w ⁺ [MeXv] w ⁻
Wherein cation is onium, Z is S, Se, Te, P, As, Sb, Bi, O, halogen (eg, I, Br, Cl), or N = N (diazo), R1, R2, R3 and R4 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.

Specific examples of the anion [MeXv] w− of the general formula (a) include tetrafluoroborate (BF ₄ ⁻ ), tetrafluorophosphate (PF ₄ ⁻ ), tetrafluoroantimonate (SbF ₄ ⁻ ), tetrafluoro Examples include arsenate (AsF ₄ ⁻ ) and tetrachloroantimonate (SbCl ₄ ⁻ ).

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 such onium salts, it is particularly effective to use an aromatic onium salt as a cationic polymerization initiator. Among them, aromatic halonium salts described in JP-A-50-151996, 50-158680, etc. VIA group aromatic onium salts described in Kaisho 50-151997, 52-30899, 59-55420, 55-125105, JP-A-56-8428, 56-149402, Preference is given to oxosulfoxonium salts described in JP-A-57-192429, aromatic diazonium salts described in JP-B-49-17040, thiopyrilum salts described in US Pat. No. 4,139,655, and the like. 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 case of an actinic ray reactive compound having an epoxy acrylate group, a photosensitizer such as n-butylamine, triethylamine, or tri-n-butylphosphine can be used. The photosensitizer and photoinitiator used for the actinic ray reactive compound are 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 they are 1 mass part-10 mass parts. The sensitizer preferably has an absorption maximum from the near ultraviolet region to the visible light region.

  In the ink liquid and the liquid composition containing the actinic ray curable resin useful in the present invention, the photopolymerization initiator is generally added in an amount of 0.1% by mass with respect to 100 parts by mass of the actinic ray curable epoxy resin (prepolymer). The use of 1 to 15 parts by mass is preferred, and the addition in the range of 1 to 10 parts by mass is more preferred.

  An epoxy resin can be used in combination with the urethane acrylate type resin, polyether acrylate type resin, or the like. In this case, it is preferable to use an actinic ray radical polymerization initiator and an actinic ray cationic polymerization initiator in combination.

  Moreover, in this invention, an oxetane compound can also be used as a photoinitiator. The oxetane compound used is a compound having a three-membered oxetane ring containing oxygen or sulfur. Among them, a compound having an oxetane ring containing oxygen is preferable. The oxetane ring may be substituted with a halogen atom, a haloalkyl group, an arylalkyl group, an alkoxyl group, an allyloxy group, or an acetoxy group. Specifically, 3,3-bis (chloromethyl) oxetane, 3,3-bis (iodomethyl) oxetane, 3,3-bis (methoxymethyl) oxetane, 3,3-bis (phenoxymethyl) oxetane, 3-methyl -3 chloromethyloxetane, 3,3-bis (acetoxymethyl) oxetane, 3,3-bis (fluoromethyl) oxetane, 3,3-bis (bromomethyl) oxetane, 3,3-dimethyloxetane and the like. In the present invention, any of a monomer, an oligomer and a polymer may be used.

  Specific examples of the ultraviolet curable resin that can be used in the present invention include, for example, Adekaoptomer KR, BY series KR-400, KR-410, KR-550, KR-566, KR-567, BY-320B. (Asahi Denka Kogyo Co., Ltd.), Koeihard A-101-KK, A-101-WS, C-302, C-401-N, C-501, M-101, M-102, T -102, D-102, NS-101, FT-102Q8, MAG-1-P20, AG-106, M-101-C (manufactured by Guangei Chemical Industry Co., Ltd.), Seika Beam PHC2210 (S), PHCX -9 (K-3), PHC2213, DP-10, DP-20, DP-30, P1000, P1100, P1200, P1300, P1400, P1500, P1600, CR900 (above, manufactured by Dainichi Seika Kogyo Co., Ltd.), KRM7033, KRM7039, KRM7130, KRM7131, UVECRYL29201, UVECRYL29202 (above, Daicel UCB), RC-5015, RC-5016, RC-5020, RC -5031, RC-5100, RC-5102, RC-5120, RC-5122, RC-5152, RC-5171, RC-5180, RC-5181 (above, Dainippon Ink & Chemicals, Inc.), Aurex No. 340 clear (manufactured by China Paint Co., Ltd.), Sunrad H-601, RC-750, RC-700, RC-600, RC-500, RC-611, RC-612 (above, Sanyo Chemical Industries, Ltd.) , SP-1509, SP-1507 (above, manufactured by Showa Polymer Co., Ltd.), RCC-15C (produced by Grace Japan Co., Ltd.), Aronix M-6100, M-8030, M-8060 (above, Toagosei Co., Ltd.) (Made by Co., Ltd.), or other commercially available products.

  The solid content concentration of the actinic ray curable resin in the ink liquid and the liquid composition is preferably 10 to 95% by mass, and the optimum concentration is selected depending on the coating method and the like.

  Further, when an ultraviolet curable resin is used as the actinic ray curable resin, an ultraviolet absorber may be included in the ultraviolet curable resin composition to the extent that does not hinder the photocuring of the ultraviolet curable resin. 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 ultraviolet absorbers preferably used in the present invention include, for example, oxybenzophenone compounds, benzotriazole compounds, salicylic acid ester compounds, benzophenone compounds, cyanoacrylate compounds, triazine compounds, nickel complex compounds, and the like. However, it is not limited to these.

  Next, the thermosetting resin used for the liquid composition used for forming the ink liquid for convex structure or the transparent resin layer of the present invention will be described.

  Examples of the thermosetting resin that can be used in the present invention include unsaturated polyester resins, epoxy resins, vinyl ester resins, phenol resins, thermosetting polyimide resins, thermosetting polyamide imides, and the like.

As the unsaturated polyester resin, for example, orthophthalic acid resin, isophthalic acid resin, terephthalic acid resin, bisphenol resin, propylene glycol-maleic acid resin, dicyclopentadiene or derivatives thereof are introduced into the unsaturated polyester composition. Low styrene volatile resin with low molecular weight or added film-forming wax compound, low shrinkage with thermoplastic resin (polyvinyl acetate resin, styrene / butadiene copolymer, polystyrene, saturated polyester, etc.) Resin, unsaturated polyester brominated directly with Br ₂ , or reactive type such as copolymerization of het acid or dibromoneopentyl glycol, halides such as chlorinated paraffin, tetrabromobisphenol and antimony trioxide, phosphorus Compound combinations Additive-type flame retardant resin that uses sesame or aluminum hydroxide as an additive, toughness resin that is hybridized with polyurethane or silicone, or toughened with IPN (high strength, high elastic modulus, high elongation), etc. is there.

  Examples of the epoxy resin include glycidyl ether type epoxy resins including bisphenol A type, novolak phenol type, bisphenol F type, brominated bisphenol A type, glycidyl amine type, glycidyl ester type, cyclic aliphatic type, and heterocyclic epoxy type. Special epoxy resins containing

  As the vinyl ester resin, for example, an oligomer obtained by ring-opening addition reaction of an ordinary epoxy resin and an unsaturated monobasic acid such as methacrylic acid is dissolved in a monomer such as styrene. There are also special types such as vinyl monomers having vinyl groups at the molecular ends and side chains. Examples of vinyl ester resins of glycidyl ether type epoxy resins include bisphenol type, novolak type, brominated bisphenol type, etc., and special vinyl ester resins include vinyl ester urethane type, isocyanuric acid vinyl type, side chain vinyl ester type, etc. There is.

  The phenol resin is obtained by polycondensation using phenols and formaldehyde as raw materials, and there are a resol type and a novolac type.

  Examples of thermosetting polyimide resins include maleic acid-based polyimides such as polymaleimide amine, polyamino bismaleimide, bismaleimide / O, O'-diallyl bisphenol-A resin, bismaleimide / triazine resin, and nadic acid-modified polyimide. And acetylene-terminated polyimide.

  A part of the actinic ray curable resin described above can also be used as the thermosetting resin.

  In addition, for the ink liquid and liquid composition comprising the thermosetting resin used in the present invention, the antioxidant and the ultraviolet absorber described in the ink liquid containing the actinic ray curable resin and the liquid composition are appropriately used. May be.

  The transparent resin layer is an actinic ray curable resin, a photopolymerization initiator, a photoinitiator, a photosensitizer, a thermosetting resin, a thermoplastic resin, an ultraviolet absorber, described in detail in the above-mentioned convex structure section. A liquid composition is prepared by appropriately using fine particles, a solvent and the like, and further coated on the convex structure portion by an arbitrary coating method.

  The coating method of the transparent resin layer is not particularly limited, but the ink composition is coated by a known method such as a gravure coater, a dip coater, a reverse coater, a wire bar coater, a die coater, an ink jet method, a flexographic printing method. It is preferable to do.

  FIG. 5 is a diagram schematically showing the formation of the convex structure portion of the present invention and the covering with the transparent resin layer.

  The surface roughness (Rz) of the concavo-convex structure on the transparent resin layer surface of the present invention is preferably 0.8 to 4 μm, more preferably 1 to 3 μm. Moreover, the average center distance (Sm) of the uneven structure on the surface of the transparent resin layer is 25 to 100 μm, more preferably 25 to 75 μm. Furthermore, Rz / Sm is preferably 0.01 to 0.1, more preferably 0.02 to 0.05.

  The surface roughness (Rz) defined in the present invention is defined as a ten-point average height according to JIS B 0601 of JIS surface roughness. The difference between the average value from the highest to the fifth and the average value from the lowest to the fifth of the recesses is expressed in units of micrometers (μm).

  The average center-to-center distance (Sm) between adjacent convex portions or concave portions is the same as that defined as the average length of the contour element curve in JIS B 0601, and the vertex of the convex portion or concave portion is defined as the convex portion or the concave portion. This is the average of the distances between the centers of adjacent convex portions or concave portions as the center of the concave portion. The average distance between protrusions or recesses can be measured by a stylus type surface roughness measuring machine, for example, a fine uneven structure surface through a measuring needle having a diameter of 1 mm with a tip portion made of diamond having a conical shape with an apex angle of 55 degrees. By scanning the top in a certain direction and measuring the movement change in the vertical direction of the measuring needle in that case, it is possible to obtain knowledge as a surface roughness curve recorded, and from the result, the distance between the convex part or the concave part is obtained. The average value can be obtained by measurement. Alternatively, it can also be measured by an optical interference surface roughness measuring machine as described above.

  The surface roughness (Rz) and average center distance (Sm) are measured in the above environment after conditioning for 24 hours in a 25 ° C., 65% RH environment where the measurement samples do not overlap. Can be obtained. The non-overlapping conditions mentioned here are, for example, a method of winding with the edge portion of the sample raised, a method of stacking paper between the sample and the sample, a frame made of cardboard, etc., and fixing its four corners One of the methods. Examples of the measuring apparatus that can be used include a RSTPLUS non-contact three-dimensional micro surface shape measuring system (a typical example of an optical interference type surface roughness measuring machine) manufactured by WYKO.

  FIG. 6 is a schematic view of a fine concavo-convex structure preferable for the present invention.

  (A) is sectional drawing which coat | covered the convex structure part formed on the transparent base film with the transparent resin layer, (b) provided the cured resin layer on the transparent base film, and also a convex structure part, transparent It is sectional drawing which arranged the resin layer.

  Although the dry film thickness of the anti-glare layer of this invention says the average value of the maximum height of an anti-glare layer from a transparent base material, 3-15 micrometers is preferable, More preferably, it is 5-10 micrometers. If it is less than 3 μm, the antiglare property is insufficient, or in some cases, satisfactory hardness cannot be obtained. On the other hand, if the thickness exceeds 20 μm, the bending resistance among the film properties is remarkably deteriorated, and minute breakage is likely to occur during handling such as transport and cutting after the formation of the antiglare layer, resulting in a reduction in productivity. The dry film thickness can be measured by a conventional method using a micrometer, a microscopic observation analysis of a film slice, or the like.

  For example, when the transparent resin layer of the present invention is made of an active photocurable resin or a thermosetting resin, the dry film thickness is obtained by adjusting the ratio of the solid content of the resin and the solvent of the resin. be able to. Further, in the present invention, a transparent support and at least one cured resin layer or a smooth light diffusing layer are provided on the transparent support, and a convex structure is formed on the surface of the transparent support by an ink jet method, and then the convex structure is covered. The transparent resin layer is preferably formed as described above. At this time, the dry film thickness including the cured resin layer or the smooth light diffusion layer to the transparent resin layer is preferably 3 to 15 μm, more preferably 5 to 5 μm. 10 μm.

  The viscosity of the ink droplet forming the convex structure portion of the present invention is preferably 5 to 12 mP · s at 25 ° C., more preferably 5 to 10 mP · s. When the viscosity is less than 2 mP · s, the viscosity is too low to obtain a pattern having a desired shape, and when it exceeds 15 mP · s, the fluidity of the ink is poor and the ink output property is also unfavorable. The viscosity of the ink is not particularly limited as long as it is tested with a standard solution for viscometer calibration specified in JIS Z 8809, and a rotary, vibration or capillary type viscometer can be used. . As a viscometer, it can be measured with a Saybolt viscometer, a Redwood viscometer, etc., for example, Tokimec Co., Ltd., conical plate type E viscometer, Toki Sangyo E Type Viscometer, manufactured by Tokyo Keiki No. B type viscometer BL, FVM-80A manufactured by Yamaichi Electronics Co., Ltd., Viscoliner manufactured by Nametore Industries Co., Ltd., VISCO MATE MODEL VM-1G manufactured by Yamaichi Electronics Co., Ltd., and the like.

(Contact angle)
The contact angle (θ) between the convex structure ink of the present invention and the transparent substrate is preferably 45 to 70 ° for obtaining the effects of the present invention, and more preferably 50 to 60 °. If it is 75 ° or more and 40 ° or less, the shape of the ink droplet may not be constant. In order to adjust the surface tension of the convex structure ink, silicone oil, modified silicone oil, silicone surfactant, fluorine surfactant, fluorine resin, fluorine oligomer, fluorine modified silicone oil, fluorine silane It is preferable that the active agent such as a coupling agent is 0% by mass or more and 5% by mass or less. If the amount is too large, the convex height becomes too low, or the transparent resin layer cannot be applied on the convex structure due to the water / oil repellent effect. Since the amount of the surfactant depends on the ink composition, the solvent composition, and the surface energy of the base substrate, it is not essential to add the surfactant. The surfactant used in the present invention is described below.

  Silicone oils used in the present invention can be broadly classified into straight silicone oils and modified silicone oils depending on the type of organic groups bonded to silicon atoms. Straight silicone oil refers to those bonded with a methyl group, a phenyl group, or a hydrogen atom as a substituent. A modified silicone oil is one having a component that is secondarily derived from a straight silicone oil. On the other hand, it can be classified from the reactivity of silicone oil. These are summarized as follows.

Silicone oil Straight silicone oil 1-1. Non-reactive silicone oil: dimethyl, methylphenyl substitution, etc. 1-2. Reactive silicone oil: methyl hydrogen substitution, etc. Modified silicone oil Modified silicone oil was born by introducing various organic groups into dimethyl silicone oil 2-1. Non-reactive silicone oil: alkyl, alkyl / aralkyl, alkyl / polyether, polyether, higher fatty acid ester substitution, etc.
Alkyl / aralkyl-modified silicone oil is a silicone oil in which a part of methyl group of dimethyl silicone oil is replaced with a long-chain alkyl group or a phenylalkyl group,
Polyether-modified silicone oil is a silicone-based polymer surfactant in which hydrophilic polyoxyalkylene is introduced into hydrophobic dimethyl silicone,
Higher fatty acid-modified silicone oil is a silicone oil in which a part of methyl group of dimethyl silicone oil is replaced with higher fatty acid ester,
Amino-modified silicone oil is a silicone oil having a structure in which a part of methyl group of silicone oil is substituted with aminoalkyl group,
The epoxy-modified silicone oil is a silicone oil having a structure in which a part of the methyl group of the silicone oil is replaced with an epoxy group-containing alkyl group,
The carboxyl-modified or alcohol-modified silicone oil is a silicone oil having a structure in which a part of the methyl group of the silicone oil is substituted with a carboxyl group or a hydroxyl group-containing alkyl group 2-2. Reactive silicone oil: amino, epoxy, carboxyl, alcohol substitution, etc. Of these, polyether-modified silicone oil is preferably added. The number average molecular weight of the polyether-modified silicone oil is, for example, 1,000 to 100,000, preferably 2000 to 50,000. If the number average molecular weight is less than 1,000, the drying property of the coating film decreases, and conversely, the number average molecular weight. When it exceeds 100,000, it tends to be difficult to bleed out to the coating surface.

  As specific products, Nippon Unicar Co., Ltd. L-45, L-9300, FZ-3704, FZ-3703, FZ-3720, FZ-3786, FZ-3501, FZ-3504, FZ-3508, FZ-3705, FZ-3707, FZ-3710, FZ-3750, FZ-3760, FZ-3785, FZ-3785, Y-7499, Shin-Etsu Chemical KF96L, KF96, KF96H, KF99, KF54, KF965, KF968, KF56, KF995, KF351, KF352, KF353, KF354, KF355, KF615, KF618, KF945, KF6004, FL100, and the like.

  As the silicone surfactant used in the present invention, one obtained by substituting a part of methyl group of silicone oil with a hydrophilic group can be used. The position of substitution includes a side chain of silicone oil, both ends, one end, both end side chains, and the like. Examples of the hydrophilic group include polyether, polyglycerin, pyrrolidone, betaine, sulfate, phosphate, and quaternary salt.

  A nonionic surfactant is a generic term for surfactants that do not have a group capable of dissociating into ions in an aqueous solution. In addition to a hydrophobic group, a hydrophilic group includes a hydroxyl group of a polyhydric alcohol, a polyoxyalkylene chain (poly Oxyethylene) or the like as a hydrophilic group. The hydrophilicity becomes stronger as the number of alcoholic hydroxyl groups increases and as the polyoxyalkylene chain (polyoxyethylene chain) becomes longer. The nonionic surfactant used in the present invention preferably has dimethylpolysiloxane as a hydrophobic group.

  When a nonionic surfactant composed of a dimethylpolysiloxane having a hydrophobic group and a polyoxyalkylene having a hydrophilic group is used, unevenness of the low refractive index layer, which will be described later, and antifouling properties of the film surface are improved. It is thought that the hydrophobic group made of polymethylsiloxane is oriented on the surface and forms a film surface that is not easily soiled. This effect cannot be obtained by using other surfactants.

  Specific examples of these nonionic surfactants include, for example, Nippon Unicar Co., Ltd., silicone surfactants SILWET L-77, L-720, L-7001, L-7002, L-7604, Y-7006, FZ-2101, FZ-2104, FZ-2105, FZ-2110, FZ-2118, FZ-2120, FZ-2122, FZ-2123, FZ-2130, FZ-2154, FZ-2161, FZ-2162, FZ- 2163, FZ-2164, FZ-2166, FZ-2191 and the like.

  Moreover, SUPERSILWET SS-2801, SS-2802, SS-2803, SS-2804, SS-2805, etc. are mentioned.

  In addition, as a preferable structure of the nonionic surfactant in which the hydrophobic group is composed of dimethylpolysiloxane and the hydrophilic group is composed of polyoxyalkylene, a dimethylpolysiloxane structure portion and a polyoxyalkylene chain are alternately and repeatedly bonded. It is preferably a linear block copolymer. Since the main chain skeleton has a long chain length and a linear structure, it is excellent. This is considered to be due to the fact that one activator molecule can be adsorbed on the surface of the silica fine particle at a plurality of locations so as to cover the surface of the silica fine particle by being a block copolymer in which hydrophilic groups and hydrophobic groups are alternately repeated.

  Specific examples thereof include, for example, silicone surfactants ABN SILWET FZ-2203, FZ-2207, FZ-2208 and the like manufactured by Nippon Unicar Co., Ltd.

  Among these silicone oils or silicone surfactants, those having a polyether group are preferred.

  On the other hand, the surface of the transparent substrate is preferably modified by a known water repellent process or plasma treatment.

  The method for measuring the contact angle of the present invention is shown in FIG. An aqueous solution sample to be measured is placed in a syringe-like droplet regulator (not shown). As shown to (a), the solid sample which adjusted the surface horizontally is mounted on the sample stand which can change a position up and down, right and left, and this solid sample surface is observed with an optical mirror. The optical mirror incorporates a rotatable rotating cloth. Droplets are made at the tip of a drop adjuster placed just above the solid sample.

  Next, as shown in (b), the surface of the solid sample is raised, and the droplet is brought into contact with the surface of the solid sample. Thereafter, as shown in (c), the solid sample is lowered to the original position, the droplet is transferred from the tip of the needle to the surface of the fixed sample, and the droplet is aligned with the center of the rotating cloth.

  Then, as shown in (d), the rotary cloth is rotated to create a tangent line between the droplet and the solid sample surface, and the angle θ is read. This θ is the contact angle.

  Since there is an individual error in this reading method, the contact angle reading method shown in (e) to (g) is performed based on the assumption that the droplet is a part of a circle.

  First, as shown in (e), the rotation cross is set at 45 °, and the sample stage is adjusted so that the cross is in contact with both sides of the droplet symmetrically. Next, as shown in (f), the sample stage is raised and the center of the cloth is aligned with the top of the droplet. Then, as shown in (g), the apex of the droplet, the solid sample, and the contact point of the droplet are connected, and the extension angle is measured. The angle becomes the half value θ / 2 of the contact angle θ. The contact angle of the present invention was measured using DropMaster (manufactured by Kyowa Interface Science Co., Ltd.).

  Examples of the solvent that can be used in the ink liquid or the liquid composition according to the present invention include alcohols such as methanol, ethanol, 1-propanol, 2-propanol, and butanol; ketones such as acetone, methyl ethyl ketone, and cyclohexanone; Ketone alcohols such as diacetone alcohol; aromatic hydrocarbons such as benzene, toluene and xylene; glycols such as ethylene glycol, propylene glycol and hexylene glycol; ethyl cellosolve, butylcellosolve, ethylcarbitol, butylcarbi Glycol ethers such as Tol, Diethyl Cellosolve, Diethyl Carbitol, Propylene Glycol Monomethyl Ether; N-methylpyrrolidone, dimethylformamide, methyl lactate, ethyl lactate, methyl acetate Le, ethyl acetate, esters such as amyl acetate; dimethyl ether, and diethyl ether, water and the like, can be used as a mixture thereof alone or in combination.

  In the ink composition according to the present invention, it is preferable that at least one kind of a solvent having a boiling point of 140 to 250 ° C. and a viscosity of 1 to 15 mPa · s at 25 ° C. is contained in an amount of 60% by mass or more. More preferably, at least one solvent having a boiling point of 180 to 230 ° C. and a viscosity of 1 to 10 mPa · s at 25 ° C. is contained in an amount of 70% by mass or more. The reason for this is that the solvent contained in the convex structure part and the ink composition for forming a transparent resin layer is preferably volatilized and dried as quickly as the desired pattern shape is maintained after transfer printing or landing. However, if it exceeds the above range, the adhesion with the base is inferior, further uneven drying occurs between the formed convex structure pattern, the subsequent transparent resin layer is not uniformly coated, the antiglare film This is because deterioration of physical properties, non-uniformity in optical performance between production lots, and in production lots is likely to occur.

The boiling point in the present invention is a boiling point at 1 atm, that is, a pressure of 1.013 × 10 5 N / m ² . For the measurement of the boiling point, a known technique can be applied, and in the case of a simple substance, values described in documents such as a chemical handbook can also be referred to.

Among the solvents satisfying the above boiling point and viscosity, compounds represented by the following general formula (1) are more preferably used.
Formula _{(1) R 1 -O- (C} x H 2x -O) n-R 2
R _1, R _2: a hydrogen atom, an aryl group, an alkyl group having 1 to 6 carbon atoms, an alkoxyalkyl group, an alkylcarbonyl group. The hydrocarbon chain may be linear or branched. However, at least one of R ₁ and R ₂ is a substituent other than a hydrogen atom.

n: an integer of 1 to 3 x: an integer of 2 to 4 More preferably, x = 2 or 3, and R ₂ is an acetyl group.

  Specific examples of the solvent preferably used in the ink of the present invention include the following solvents, but are not limited thereto.

  Furthermore, specific examples of the compound represented by the general formula (1) include the following solvents, but the present invention is not particularly limited thereto.

  In addition to the above, ethylene glycol monoisopropyl ether, ethylene glycol mono-t-butyl ether, diethylene glycol monopropyl ether, diethylene glycol monoisopropyl ether, diethylene glycol mono-t-butyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol mono Isopropyl ether, propylene glycol monobutyl ether, propylene glycol mono-t-butyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoisopropyl ether, dipropylene glycol monobutyl ether, ethylene glycol monoisopropyl ether Tate, ethylene glycol mono-t-butyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monoisopropyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monoisopropyl ether acetate, propylene Glycol monobutyl ether acetate, propylene glycol mono-t-butyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoisopropyl ether, ethylene glycol monomethoxymethyl ether, Ethylene glycol monoethyl ether acetate (alias: 2- (ethoxyethoxy) ethyl acetate), triethylene glycol dimethyl ether, diethylene glycol diacetate, propylene glycol diacetate (alias: 1,2-diacetoxypropane), dipropylene glycol dimethyl ether, di Propylene glycol monomethyl ether acetate and the like are also preferably used.

  A convex structure part and a pattern shape can also be controlled by mixing the solvent from which a boiling point and a viscosity differ among these solvents and changing the ratio suitably.

  The viscosity of each solvent can be measured using Viscomate VM-1G (manufactured by Yamaichi Electronics Co., Ltd.).

  In the antiglare film of the present invention, a convex structure can be formed directly on a transparent substrate by an ink jet method, but more preferably, one or more curable resin layers or a smooth type formed by a coating method. After forming the light diffusion layer, it is preferable to form a convex structure portion on the surface of the curable resin layer or the smooth light diffusion layer. The dry film thickness of these layers is preferably from 0.1 to 10 μm, more preferably from 0.1 to 5 μm.

  For the curable resin layer or the smooth light diffusing layer, the same thermosetting resin or actinic radiation curable resin as that used in the convex structure ink composition and the transparent resin layer can be preferably used. In particular, an ultraviolet curable resin is preferable. Further, when forming a curable resin layer or a smooth light diffusing layer, in addition to each of the above resins, the same light diffusing agent, photoreaction initiator, photosensitizer, oxidation agent as described in the ink composition are used. An inhibitor, an ultraviolet absorber, an antistatic agent, inorganic fine particles, organic fine particles and the like can be appropriately added.

  In the present invention, the curable resin layer or the smooth light diffusing layer may be composed of a plurality of layers, but the outermost layer of the curable resin layer or the smooth light diffusing layer for landing ink droplets. However, it preferably contains a plasticizer.

  It is preferable that a plasticizer contains 0.1-10 mass%. For example, it is preferable to add a plasticizer in advance to the coating composition for the curable resin layer or the smooth light diffusing layer. A plasticizer can be applied or adhered to the surface. These improve the adhesion of the ink droplets after curing.

  Examples of the plasticizer that can be used in the curable resin layer or the smooth light diffusing layer include a phosphate ester plasticizer, a phthalate ester plasticizer, a trimellitic ester plasticizer, and a pyromellitic acid plasticizer. Agents, glycolate plasticizers, citrate ester plasticizers, polyester plasticizers, and the like can be preferably used.

  Examples of phosphate ester plasticizers include triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, octyl diphenyl phosphate, diphenyl biphenyl phosphate, trioctyl phosphate, and tributyl phosphate. For trimellitic plasticizers such as phthalate, dimethoxyethyl phthalate, dimethyl phthalate, dioctyl phthalate, dibutyl phthalate, di-2-ethylhexyl phthalate, butyl benzyl phthalate, diphenyl phthalate, dicyclohexyl phthalate, For pyromellitic acid ester plasticizers such as tate and triethyl trimellitate, tetrabutyl pyromellitate For glycolate plasticizers such as tetraphenylpyromellitate and tetraethylpyromellitate, triacetin, tributyrin, ethylphthalylethyl glycolate, methylphthalylethyl glycolate, butylphthalylbutyl glycolate, etc. As the agent, 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. Trimethylolpropane tribenzoate and the like can also be preferably used.

  As the polyester plasticizer, a copolymer of a dibasic acid and a glycol such as an aliphatic dibasic acid, an alicyclic dibasic acid, or an aromatic dibasic acid can be used. 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 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.

  In particular, cellulose esters having additives such as epoxy compounds, rosin compounds, phenol novolac type epoxy resins, cresol novolac type epoxy resins, ketone resins, and toluenesulfonamide resins described in JP-A No. 2002-146044 are also preferably used. .

  As the above compounds, KE-604 and KE-610 are commercially available from Arakawa Chemical Industries, Ltd. with acid values of 237 and 170, respectively. Similarly, KE-100 and KE-356 are commercially available from Arakawa Chemical Industries, Ltd. as an esterified product of a mixture of abietic acid, dehydroabietic acid, and parastrinic acid, with acid values of 8 and 0, respectively. A mixture of abietic acid, dehydroabietic acid, and parastrinic acid is commercially available from Harima Kasei Co., Ltd. under G-7 and Hartle RX with acid values of 167 and 168, respectively.

  Moreover, as an epoxy resin, Araldide EPN1179 and Araldide AER260 are commercially available from Asahi Ciba.

  As a ketone resin, Hilac 110 and Hilac 110H are commercially available from Hitachi Chemical Co., Ltd.

  As para-toluenesulfonamide resin, as a topler, it is commercially available from Fujiamide Chemical Co., Ltd.

  The solvent for coating the curable resin layer or the smooth light diffusing layer according to the present invention is suitably selected from, for example, hydrocarbons, alcohols, ketones, esters, glycol ethers, and other solvents. Can be selected or mixed. Preferably, a solvent containing 5% by mass or more, more preferably 5% by mass to 80% by mass or more of propylene glycol mono (C 1-4) alkyl ether or propylene glycol mono (C 1-4) alkyl ether ester. Used.

  Gravure coater, spinner coater, wire bar coater, roll coater, reverse coater, extrusion can be applied as a method of applying a curable resin layer or a smooth light diffusing layer composition coating solution having the above-described composition onto a transparent substrate. A known method such as a coater or an air doctor coater can be used. The coating amount is suitably 5 μm to 30 μm, preferably 10 μm to 20 μm in terms of wet film thickness. The coating speed is preferably 10 m / min to 60 m / min. Moreover, as a dry film thickness, 0.1-10 micrometers is preferable.

  The curable resin layer composition or the smooth light diffusing layer is coated and dried, and then cured by irradiation with actinic rays such as ultraviolet rays and electron beams, or by heat treatment, in the same manner as ink curing. However, the irradiation time of the actinic ray is preferably from 0.1 second to 5 minutes, and more preferably from 0.1 to 10 seconds from the viewpoint of curing efficiency and work efficiency of the ultraviolet curable resin.

  In the present invention, the curable resin layer or smooth light diffusing layer applied on the transparent substrate by the above method is in an uncured state, or at any time after complete curing, by an inkjet method, The ink droplets that form the convex structure may be landed and subsequently covered with a transparent resin layer. Preferably, however, after the curable resin layer or the smooth light diffusion layer is cured, the ink droplets are ejected by an inkjet method. It is preferable to form the convex structure by landing. When the curable resin layer or the smooth light diffusing layer is half-cured (semi-cured state), ink droplets are landed to form a convex structure and subsequently covered with a transparent resin layer. It is preferable because it is easy to form and is excellent in productivity. Further, the adhesion between the convex structure portion or the transparent resin layer and the curable resin layer or the surface of the smooth light diffusing layer can be improved.

  In the present invention, after forming the convex structure portion, it is preferable to form a transparent resin layer so as to cover the convex structure portion after the surface is subjected to plasma treatment. And a rare gas such as helium or argon or a discharge gas such as nitrogen or air and oxygen, hydrogen, nitrogen, carbon monoxide, carbon dioxide, nitrogen monoxide, nitrogen dioxide, water vapor, methane, 4 A reaction gas containing at least one kind of methane fluoride or the like can be used. In Japanese Patent Application Laid-Open No. 2000-356714, the surface of the cured resin layer can be subjected to plasma treatment with reference to a specific plasma treatment method.

  The transparent resin layer of the present invention is produced by coating by a general thin film uniform coating method such as a micro gravure method, an extrusion coating method, a wire bar method, a flexographic printing method, or an ink jet method. The transparent resin layer is coated on the above-described convex structure portion, covers the convex structure portion, and smoothes the irregularities formed only by the convex structure portion, thereby obtaining a preferable surface shape, thereby providing an antiglare property. Can be expressed. 50% or more of the resin contained in the transparent resin layer is preferably the same as the resin used for the convex structure portion, and this can improve the adhesion between the convex structure portion and the transparent resin layer.

  Examples of the solvent that can be used in the transparent resin layer of the present invention include alcohols such as methanol, ethanol, 1-propanol, 2-propanol, and butanol; ketones such as acetone, methyl ethyl ketone, and cyclohexanone; N-methylpyrrolidone, Amides such as dimethylformamide and dimethylacetamide; ketone alcohols such as diacetone alcohol; aromatic hydrocarbons such as benzene, toluene and xylene; polyalkylene glycols such as polyethylene glycol and polypropylene glycol; ethylene glycol, propylene glycol, 2-6 alkylene groups such as butylene glycol, triethylene glycol, 1,2,6-hexanetriol, thiodiglycol, hexylene glycol, diethylene glycol Alkylene glycols containing elemental atoms; glycol ethers such as ethyl cellosolve, butyl cellosolve, ethyl carbitol, butyl carbitol, diethyl cellosolve, diethyl carbitol, propylene glycol monomethyl ether; cellosolve acetate, diethylene glycol monoethyl ether Examples include glycol esters such as acetate; esters such as methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, and amyl acetate; ethers such as dimethyl ether and diethyl ether, and water. These may be used alone or in combination of two or more. Can be used. Further, those having an ether bond in the molecule are particularly preferred, and glycol ethers are also preferably used.

  Specific examples of glycol ethers include, but are not limited to, the following solvents. Propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, diethylene glycol dimethyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether Ac, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether Ac, ethylene glycol Examples thereof include diethyl ether, and Ac represents acetate.

  The transparent resin layer of the present invention is the same silicone oil, modified silicone oil, silicone surfactant, fluorine surfactant, fluorine resin, fluorine oligomer, fluorine modified silicone oil as described for the convex structure ink. It is preferable to contain 0.1% by mass or more and 5% by mass or less of an activator such as a fluorine-based silane coupling agent. If the amount is too large, the transparent resin layer cannot be applied on the convex structure due to the water / oil repellent effect, which is not preferable. Further, since the amount of the surfactant depends on the ink composition, the solvent composition, and the surface energy of the base substrate, it is not essential to add the surfactant.

In the present invention, convex portions, the transparent resin layer together SnO _2, ITO, it is also preferred to incorporate conductive particles and crosslinking antistatic agents such as cationic polymers particles such as ZnO. In the present invention, it is preferable to add an antistatic agent to the transparent resin layer.

  In the present invention, it is also preferable to contain the fine particles in both the convex structure portion and the transparent resin layer. For example, inorganic fine particles or organic fine particles can be added.

  Examples of inorganic fine particles include silicon-containing compounds, silicon dioxide, aluminum oxide, zirconium oxide, calcium carbonate, talc, clay, calcined kaolin, calcined calcium silicate, hydrated calcium silicate, aluminum silicate, magnesium silicate and Calcium phosphate and the like are preferable, and an inorganic compound containing silicon and zirconium oxide are more preferable, and silicon dioxide is particularly preferably used. These include particles having a shape such as a spherical shape, a flat plate shape, and an amorphous shape.

  As the silicon dioxide fine particles, for example, commercially available products such as Aerosil R972, R972V, R974, R812, 200, 200V, 300, R202, OX50, TT600 (manufactured by Nippon Aerosil Co., Ltd.) can be used.

  As the fine particles of zirconium oxide, for example, commercially available products such as Aerosil R976 and R811 (manufactured by Nippon Aerosil Co., Ltd.) can be used.

  The organic fine particles include polymethacrylate methyl acrylate resin fine particles, acrylic styrene resin fine particles, polymethyl methacrylate resin fine particles, silicon resin fine particles, polystyrene resin fine particles, polycarbonate resin fine particles, benzoguanamine resin fine particles, and melamine resin. Examples thereof include fine particles, polyolefin resin fine particles, polyester resin fine particles, polyamide resin fine particles, polyimide resin fine particles, and polyfluoroethylene resin fine particles.

  When the fine particles are contained, the average particle diameter is preferably 5 to 300 nm, more preferably 20 to 100 nm. You may contain 2 or more types of microparticles | fine-particles from which a particle size and refractive index differ. Moreover, it is preferable that content is 5-50 mass% with respect to a convex structure part or a transparent resin layer.

  In the present invention, when the convex structure portion or the transparent resin layer contains an actinic ray curable resin, the actinic ray irradiation method includes landing the ink on the transparent substrate, evaporating the solvent and the like, and then irradiating the actinic ray. It is preferable to do. The timing of irradiation can be determined in consideration of the pattern shape to be formed. For example, when the ink is solvent-free, irradiation is performed after 2 minutes after landing, and when the ink contains a solvent, the solvent in the ink Immediately after the volatilization is completed, irradiation can be performed after 2 minutes.

  The term “immediately after the ink is landed on the transparent substrate” or after the solvent in the ink has been volatilized, specifically refers to a period of 5 seconds after the ink has landed. Irradiation with actinic light may be performed to such an extent that the fluidity of the ink is lowered and a desired pattern shape can be formed, and may be in a half-cured state. In this case, it can be cured completely by irradiating an active light source separately installed on the downstream side. In the present invention, it is preferable to use an actinic radiation curable resin for forming the convex structure and forming the transparent resin layer.

The actinic ray that can be used in the present invention can be used without limitation as long as it is a light source that activates the actinic ray curable resin formed in a pattern with ultraviolet rays, electron beams, γ rays, etc. Electron beams are preferable, and ultraviolet rays are particularly preferable in that they are easy to handle and high energy can be easily obtained. As the ultraviolet light source for photopolymerizing the ultraviolet reactive compound, any light source that generates ultraviolet light can be used. For example, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, or the like can be used. An ArF excimer laser, a KrF excimer laser, an excimer lamp, synchrotron radiation, or the like can also be used. Irradiation conditions vary depending on each lamp, but the amount of irradiation light is preferably 1 mJ / cm ² or more, more preferably 20 mJ / cm ^{2 to} 10000 mJ / cm ² , and particularly preferably 50 mJ / cm ^{2 to} 2000 mJ / cm ^2. It is.

  Moreover, an electron beam can be used similarly. As an electron beam, 50 to 1000 keV, preferably 100 to 100, emitted from various electron beam accelerators such as a cockroft Walton type, a bandegraph type, a resonance transformation type, an insulated core transformer type, a linear type, a dynamitron type, and a high frequency type. An electron beam having an energy of 300 keV can be given.

  In the present invention, the oxygen concentration in the atmosphere upon irradiation with actinic rays is preferably 10% or less, particularly preferably 1% or less. In order to obtain this atmosphere, it is effective to introduce nitrogen gas or the like.

  Moreover, in this invention, in order to advance the hardening reaction of actinic light efficiently, a base film etc. can also be heated. The heating method is not particularly limited, but it is preferable to use a heat plate, a heat roll, a thermal head, or a method of spraying hot air on the landed ink surface. Moreover, you may heat continuously by using the back roll used on the opposite side across the base film of a flexographic printing part as a heat roll.

  The heating temperature cannot be generally specified depending on the type of actinic ray curable resin to be used, but is preferably in a temperature range that does not affect the base film such as thermal deformation, and is preferably 30 to 200 ° C. Furthermore, 50-120 degreeC is preferable, Most preferably, it is 70-100 degreeC.

  Subsequently, the manufacturing method of the anti-glare film of this invention is demonstrated.

  FIG. 8 is a schematic diagram showing an example of a flow for producing an antiglare film formed with a transparent resin layer so as to cover a convex structure portion after forming the convex structure portion on a transparent substrate by an ink jet method. . Specifically, after a curable resin layer or a smooth light diffusing layer is coated on a transparent substrate by a coating method, a transparent resin layer is formed so as to cover the convex structure portion after forming the convex structure portion by an inkjet method. An example of a flow for producing an antiglare film by providing a plurality of antireflection layers on the antiglare layer formed with a coating method is shown.

  In FIG. 8, the transparent base material 102 fed out from the laminating roll 101 is conveyed, and a curable resin layer or a smooth light diffusion layer is applied by the first coater 103 of the extrusion method at the first coater station A. To do. At this time, the curable resin layer or the smooth light diffusing layer may be a single layer structure or a layer composed of a plurality of layers combined with each other. The transparent substrate 102 on which the curable resin layer or the smooth light diffusion layer is applied is then dried in the drying zone 105A. Drying is performed from both surfaces of the transparent substrate 102 by warm air with controlled temperature and humidity. After drying, when an actinic ray curable resin is used as a binder in the curable resin layer or the smooth light diffusing layer, the actinic ray irradiating unit 106A is irradiated with actinic rays such as ultraviolet rays to be cured. In addition, the amount of irradiation and irradiation conditions can be controlled to achieve a half-cure state, or it can be directly conveyed to the inkjet emitting unit 109 without being cured.

  Subsequently, although it conveys to the 2nd coater station B which provides a convex structure part using an inkjet system, it is preferable that a curable resin layer is a half-cure state. Alternatively, the surface treatment may be performed by the plasma processing unit 107 before forming the convex structure portion. An ink supply tank 108 is connected to the ink jet emitting portion 109, and ink liquid is supplied therefrom. The ink jet emitting unit 109 has a plurality of ink jet nozzles as shown in FIG. 3B arranged in a staggered manner, preferably in multiple stages, across the entire width of the transparent substrate, and the ink droplets are made of a curable resin layer or a smooth type. The light is emitted onto the light diffusion layer, and a convex structure is formed on the surface. In addition, when ejecting two or more types of ink droplets, each ink droplet may be ejected from two or more rows of inkjet nozzles, or randomly from any inkjet nozzle. It may be emitted. Further, a plurality of ink jet emitting portions may be arranged, and different ink droplets may be emitted from each ink emitting portion. In the present invention, since fine droplets of 0.1 to 100 pl and in some cases 0.1 to 10 pl are emitted, the flying property of the ink droplets is easily affected by the airflow of the outside air. It is preferable that the entire coater station B is covered with a partition wall or the like to perform windproof treatment. In addition, in order to fly extremely fine droplets of 1 pl or less with high accuracy, a voltage is applied between the ink jet emitting unit 109 and the transparent base material 102 or the back roll 104B to give an electric charge to the ink droplets to electrically inject the ink liquid. A method of assisting droplet flight stability is also preferred. In order to prevent deformation of the landed ink droplets, it is also preferable to use a method in which the transparent substrate is cooled to quickly reduce the flow of the ink droplets after landing. Or, after the ink droplets are ejected, the solvent contained during the flight until landing is volatilized, and landing with the amount of solvent contained in the ink droplets reduced makes it possible to form a finer convex structure. This is preferable. Therefore, a method of increasing the temperature of the ink flying space or controlling the atmospheric pressure to 1 atm or lower, for example, 20 to 100 kPa is also preferable. It is also preferable to lower the atmospheric solvent concentration in the ink flying space, and it is 50% or less, more preferably 1 to 30% of the saturation concentration.

  Ink droplets that have landed on the surface of the curable resin layer or the smooth light diffusing layer, when an actinic ray curable resin is used, are generated by the actinic ray irradiation unit 106B disposed immediately after the inkjet emitting unit 109. Then, it is cured by irradiation with actinic rays such as ultraviolet rays. Further, when the ink droplet uses a thermosetting resin, the ink droplet is heated and cured by the heating unit 110, for example, a heat plate. A method of heating the back roll 104B as a heat roll is also preferable.

  In the second coater station B, the actinic ray irradiation unit 106B and the inkjet emission unit 109 are arranged at an appropriate interval so that the irradiation light of the actinic ray irradiation unit 106B does not directly affect the inkjet nozzle of the inkjet emission unit 109. Alternatively, it is preferable to install a light shielding wall or the like between the actinic ray irradiation unit 106B and the inkjet emission unit 109. Further, in order to prevent the heat of the heating unit 110 from directly affecting the ink jet nozzles of the ink jet emitting unit 109, the ink jet emitting unit 109 is covered with a heat insulating cover, or as shown in FIG. It is preferable to arrange on the back side of the material 102 so as not to affect the ink jet emitting portion 109.

  The transparent substrate 102 that has been cured to such an extent that the convex structure formed by the landed ink droplets can be maintained is evaporated after the unnecessary organic solvent or the like is evaporated in the drying zone 105B. Then, it may be irradiated with actinic rays to complete curing, or may be in a half-cured state, but is preferably in a half-cured state.

  The transparent base material 102 provided with the convex structure portion is then transported to the third coater station C where the transparent resin layer covering the convex structure portion is coated, but before the convex structure portion is covered with the transparent resin layer. Surface treatment is preferably performed by the plasma processing unit 107.

  The transparent substrate 102 on which the transparent resin layer is applied is then dried in the drying zone 105C. Drying is performed from both surfaces of the transparent substrate 102 by warm air with controlled temperature and humidity. Further, the actinic ray irradiation unit 106D irradiates actinic rays to complete the curing.

  The transparent base material 102 provided with the antiglare layer having the convex structure is then applied to the fourth coater station D, or the fifth coater station and the sixth coater station (non-coated layer) when a plurality of antireflection layers and antifouling layers are provided. In the same manner as in the first coater station A, the coating, drying and curing processes are performed to produce an antiglare film, which is then wound up by a winding roll 113.

  The transparent substrate 102 may be appropriately wound up by a winding roll after coating, drying, and curing treatment at each coater station.

  In FIG. 8, the coating method is exemplified as the method for forming the antireflection layer, but the antireflection layer or the antifouling layer may be formed by a known atmospheric pressure plasma treatment method instead of the coating method.

<Transparent substrate>
The transparent substrate used in the present invention is easy to manufacture, has good adhesion to the actinic ray curable resin layer, is optically isotropic, is optically transparent, etc. Is preferable, and a transparent film is preferable.

  The term “transparent” as used in the present invention means that the visible light transmittance is 60% or more, preferably 80% or more, and particularly preferably 90% or more.

  Although it will not specifically limit if it has said property, For example, cellulose ester-type films, such as a cellulose diacetate film, a cellulose triacetate film, a cellulose acetate propionate film, a cellulose acetate butyrate film, a polyester-type film, a polycarbonate Film, polyarylate film, polysulfone (including polyethersulfone) film, polyester film such as polyethylene terephthalate and polyethylene naphthalate, polyethylene film, polypropylene film, cellophane, polyvinylidene chloride film, polyvinyl alcohol film, ethylene vinyl alcohol Film, syndiotactic polystyrene film, polycarbonate film, nor Runen resin film, a polymethylpentene film, a polyether ketone film, polyether ketone imide film, a polyamide film, a fluororesin film, a nylon film, polymethyl methacrylate film, acrylic film or a glass plate or the like. Among these, a polycarbonate film, a polyester film, a norbornene resin film, and a cellulose ester film are preferable.

  The norbornene-based resin film preferably used in the present invention is an amorphous polyolefin film having a norbornene structure, such as APO manufactured by Mitsui Petrochemical Co., Ltd., ZEONEX manufactured by Nippon Zeon Co., Ltd., manufactured by JSR Co., Ltd. ARTON etc.

  In the present invention, it is particularly preferable to use a cellulose ester film. As the cellulose ester, cellulose acetate, cellulose acetate butyrate, and cellulose acetate propionate are preferable. Among them, cellulose acetate butyrate, cellulose acetate phthalate, and cellulose acetate propionate are preferably used. Examples of commercially available cellulose ester films include Konica Minoltak KC8UX, KC4UX, KC5UX, KC8UCR3, KC8UCR4, KC8UCR5, KC8UY, KC4UY, KC12UR, KC4FR (manufactured by Konica Minolta Opto Co., Ltd. It is preferably used from the viewpoints of transparency and adhesion. These films may be films produced by melt casting film formation or films produced by solution casting film formation.

《Anti-glare anti-reflection film》
In the present invention, it is preferable to provide an antiglare antireflection film by providing the following low refractive index layer on the surface having the fine concavo-convex structure of the antiglare film having the convex structure portion and the transparent resin layer.

  In particular, in the present invention, the low refractive index layer is preferably coated with a low refractive index layer coating solution containing hollow silica-based fine particles having an outer shell layer and porous or hollow inside.

<Low refractive index layer>
The refractive index of the low refractive index layer according to the present invention is preferably lower than the refractive index of the substrate film as the support, and is preferably in the range of 1.30 to 1.45 at 23 ° C. and a wavelength of 550 nm.

  The film thickness of the low refractive index layer is preferably 5 nm to 0.5 μm, more preferably 10 nm to 0.3 μm, and most preferably 30 nm to 0.2 μm.

  The composition for forming a low refractive index layer used in the present invention comprises (a) an organosilicon compound represented by the following general formula (2) or a hydrolyzate thereof or a polycondensate thereof, and (b) an outer shell layer. It is preferable that hollow silica-based fine particles having a porous or hollow interior constitute the composition.

General formula (2) Si (OR) ₄
(In the formula, R is an alkyl group, preferably an alkyl group having 1 to 4 carbon atoms.)
In addition, a silane coupling agent, a curing agent, and the like may be added as necessary.

[Hollow silica fine particles]
First, hollow silica-based fine particles having the outer shell layer represented by (b) and having a porous or hollow interior will be described.

  The hollow silica-based fine particles are (I) composite particles comprising porous particles and a coating layer provided on the surface of the porous particles, or (II) having cavities inside, and the contents are solvent, gas or porous It is a hollow particle filled with a porous material. The low refractive index layer may contain either (I) composite particles or (II) hollow particles, or may contain both.

  The hollow particles are particles having cavities inside, and the cavities are surrounded by particle walls. The cavity is filled with contents such as a solvent, a gas, or a porous material used at the time of preparation. It is desirable that the average particle size of such hollow fine particles is in the range of 5 to 300 nm, preferably 10 to 200 nm. The hollow fine particles to be used are appropriately selected according to the thickness of the transparent coating to be formed, and may be in the range of 2/3 to 1/10 of the thickness of the transparent coating such as the low refractive index layer to be formed. desirable. These hollow fine particles are preferably used in a state of being dispersed in an appropriate medium in order to form a low refractive index layer. As the dispersion medium, water, alcohol (for example, methanol, ethanol, isopropyl alcohol), ketone (for example, methyl ethyl ketone, methyl isobutyl ketone), and ketone alcohol (for example, diacetone alcohol) are preferable.

  The thickness of the coating layer of the composite particles or the thickness of the particle walls of the hollow particles is desirably in the range of 1 to 20 nm, preferably 2 to 15 nm. In the case of composite particles, when the thickness of the coating layer is less than 1 nm, the particles may not be completely covered, and it is easy to use silicate monomers and oligomers with a low polymerization degree, which are coating liquid components described later. In some cases, the inside of the composite particle enters the inside and the porosity of the inside is reduced, so that the effect of the low refractive index cannot be sufficiently obtained. When the thickness of the coating layer exceeds 20 nm, the silicic acid monomer and oligomer do not enter the inside, but the porosity (pore volume) of the composite particles is lowered and the effect of low refractive index is sufficiently obtained. It may not be possible. In the case of hollow particles, if the particle wall thickness is less than 1 nm, the particle shape may not be maintained, and even if the thickness exceeds 20 nm, the effect of low refractive index may not be sufficiently exhibited. is there.

The coating layer of the composite particles or the particle wall of the hollow particles is preferably composed mainly of silica. In addition, components other than silica may be contained. Specifically, Al ₂ O ₃ , B ₂ O ₃ , TiO ₂ , ZrO ₂ , SnO ₂ , CeO ₂ , P ₂ O ₃ , Sb ₂ O ₃ , MoO ₃ , ZnO ₂ , WO _{3 and the} like. Examples of the porous particles constituting the composite particles include those made of silica, those made of silica and an inorganic compound other than silica, and those made of CaF ₂ , NaF, NaAlF ₆ , MgF, and the like. Among these, porous particles made of a composite oxide of silica and an inorganic compound other than silica are particularly preferable. Examples of inorganic compounds other than silica include Al ₂ O ₃ , B ₂ O ₃ , TiO ₂ , ZrO ₂ , SnO ₂ , CeO ₂ , P ₂ O ₃ , Sb ₂ O ₃ , MoO ₃ , ZnO ₂ , WO _{3 and the} like. 1 type or 2 types or more can be mentioned. In such porous particles, the molar ratio MOX / SiO ₂ when the silica is represented by SiO ₂ and the inorganic compound other than silica is represented by oxide (MOX) is 0.0001 to 1.0, preferably It is desirable to be in the range of 0.001 to 0.3. It is difficult to obtain a porous particle having a molar ratio MOX / SiO ₂ of less than 0.0001. Even if it is obtained, particles having a small pore volume and a low refractive index cannot be obtained. Further, when the molar ratio MOX / SiO _{2 of} the porous particles exceeds 1.0, the ratio of silica decreases, so that the pore volume increases and it may be difficult to obtain a low refractive index. .

  The pore volume of such porous particles is desirably in the range of 0.1 to 1.5 ml / g, preferably 0.2 to 1.5 ml / g. If the pore volume is less than 0.1 ml / g, particles having a sufficiently reduced refractive index cannot be obtained. If the pore volume exceeds 1.5 ml / g, the strength of the fine particles is lowered, and the strength of the resulting coating may be lowered. is there.

  Incidentally, the pore volume of such porous particles can be determined by a mercury intrusion method. Examples of the contents of the hollow particles include a solvent, a gas, and a porous substance used at the time of preparing the particles. The solvent may contain an unreacted particle precursor used when preparing the hollow particles, the catalyst used, and the like. Examples of the porous substance include those composed of the compounds exemplified for the porous particles. These contents may be composed of a single component or may be a mixture of a plurality of components.

  As a method for producing such hollow fine particles, for example, the method for preparing composite oxide colloidal particles disclosed in paragraphs [0010] to [0033] of JP-A-7-133105 is suitably employed.

[Organic silicon compound]
In the organosilicon compound represented by the general formula (2), R represents an alkyl group having 1 to 4 carbon atoms.

  Specifically, tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane and the like are preferably used.

  As a method of adding to the low refractive index layer, a solution obtained by adding a small amount of alkali or acid as a catalyst to a mixed solution of these tetraalkoxysilane, pure water, and alcohol is added to the dispersion of the hollow silica fine particles. The silicic acid polymer produced by hydrolyzing tetraalkoxysilane is deposited on the surface of the hollow silica fine particles. At this time, tetraalkoxysilane, alcohol, and catalyst may be simultaneously added to the dispersion. As the alkali catalyst, ammonia, an alkali metal hydroxide, or an amine can be used. As the acid catalyst, various inorganic acids and organic acids can be used.

  In the present invention, the low refractive index layer may contain a fluorine-substituted alkyl group-containing silane compound represented by the following general formula (3).

  The fluorine-substituted alkyl group-containing silane compound represented by the general formula (3) will be described.

In the formula, R ^{1 to} R ⁶ are alkyl groups having 1 to 16 carbon atoms, preferably 1 to 4 carbon atoms, halogenated alkyl groups having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, 6 to 12 carbon atoms, preferably 6 carbon atoms. 10 to 10 aryl groups, 7 to 14 carbon atoms, preferably 7 to 12 alkylaryl groups, arylalkyl groups, 2 to 8 carbon atoms, preferably 2 to 6 alkenyl groups, or 1 to 6 carbon atoms, preferably 1 to 3 alkoxy groups, a hydrogen atom or a halogen atom.

Rf represents-(CaHbFc)-, a is an integer of 1 to 12, b + c is 2a, b is an integer of 0 to 24, and c is an integer of 0 to 24. Such Rf is preferably a group having a fluoroalkylene group and an alkylene group. Specifically, as such a fluorine-containing silicone compound, (MeO) ₃ SiC ₂ H ₄ C ₂ F ₄ C ₂ H ₄ Si (MeO) ₃ , (MeO) ₃ SiC ₂ H ₄ C ₄ F ₈ C ₂ H ₄ Si (MeO) ₃ , (MeO) ₃ SiC ₂ H ₄ C ₆ F ₁₂ C ₂ H ₄ Si (MeO) ₃ , (H ₅ C ₂ O) ₃ SiC ₂ H ₄ C ₄ F ₈ C ₂ H Examples include methoxydisilane compounds represented by ₄ Si (OC ₂ H ₅ ) ₃ , (H ₅ C ₂ O) ₃ SiC ₂ H ₄ C ₆ F ₁₂ C ₂ H ₄ Si (OC ₂ H ₅ ) ₃ , and the like.

If the fluorine-containing alkyl group-containing silane compound is included as a binder, the transparent film itself is hydrophobic, so the transparent film is not sufficiently densified and is porous or cracked. Even if it has a void or a void, entry into the transparent film by chemicals such as moisture, acid and alkali is suppressed. Furthermore, fine particles such as metals contained in the conductive layer which is the substrate surface or the lower layer do not react with chemicals such as moisture, acid and alkali. For this reason, such a transparent film has excellent chemical resistance.

  In addition, when a fluorine-substituted alkyl group-containing silane compound is included as a binder, not only the hydrophobic property but also the slipperiness (low contact resistance) is obtained, and thus a transparent film having excellent scratch strength can be obtained. Can do. Furthermore, when the binder contains a fluorine-substituted alkyl group-containing silane compound having such a structural unit, when the conductive layer is formed in the lower layer, the shrinkage of the binder is equal to or close to that of the conductive layer. Since it is a thing, the transparent film excellent in adhesiveness with the conductive layer can be formed. Furthermore, when the transparent film is heat-treated, the conductive layer is not peeled off due to the difference in shrinkage rate, and a portion having no electrical contact is not generated in the transparent conductive layer. For this reason, sufficient electroconductivity can be maintained as a whole film.

  A transparent film containing a fluorine-substituted alkyl group-containing silane compound and hollow silica-based fine particles having the outer shell layer and being porous or hollow inside has high scratch strength and is evaluated by eraser strength or nail strength. The film strength is high, the pencil hardness is high, and a transparent film excellent in strength can be formed.

  The low refractive index layer according to the present invention may contain a silane coupling agent. Silane coupling agents include methyltrimethoxysilane, methyltriethoxysilane, methyltrimethoxyethoxysilane, methyltriacetoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, vinyltrimethoxysilane. Ethoxysilane, vinyltriacetoxysilane, vinyltrimethoxyethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriacetoxysilane, γ-chloropropyltrimethoxysilane, γ-chloropropyltriethoxysilane, γ-chloropropyltri Acetoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, γ-glycidyloxypropyltrimethoxysilane, γ-glycidyloxypropyltri Ethoxysilane, γ- (β-glycidyloxyethoxy) propyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, γ- Acryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, N- Examples include β- (aminoethyl) -γ-aminopropyltrimethoxysilane and β-cyanoethyltriethoxysilane.

  Examples of silane coupling agents having a disubstituted alkyl group with respect to silicon include dimethyldimethoxysilane, phenylmethyldimethoxysilane, dimethyldiethoxysilane, phenylmethyldiethoxysilane, and γ-glycidyloxypropylmethyldiethoxysilane. Γ-glycidyloxypropylmethyldimethoxysilane, γ-glycidyloxypropylphenyldiethoxysilane, γ-chloropropylmethyldiethoxysilane, dimethyldiacetoxysilane, γ-acryloyloxypropylmethyldimethoxysilane, γ-acryloyloxypropylmethyldi Ethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, γ-methacryloyloxypropylmethyldiethoxysilane, γ-mercaptopropylmethyldimeth Shishiran, .gamma.-mercaptopropyl methyl diethoxy silane, .gamma.-aminopropyl methyl dimethoxy silane, .gamma.-aminopropyl methyl diethoxy silane, methyl vinyl dimethoxy silane, and methyl vinyl diethoxy silane.

  Among these, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, vinyltrimethoxyethoxysilane, γ-acryloyloxypropyltrimethoxysilane and γ-methacryloyloxypropyltrimethoxysilane having a double bond in the molecule. Γ-acryloyloxypropylmethyldimethoxysilane, γ-acryloyloxypropylmethyldiethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, and γ-methacryloyloxypropylmethyldiethoxy having a disubstituted alkyl group with respect to silicon Silane, methylvinyldimethoxysilane and methylvinyldiethoxysilane are preferred, and γ-acryloyloxypropyltrimethoxysilane and γ-methacryloyloxyp Particularly preferred are propyltrimethoxysilane, γ-acryloyloxypropylmethyldimethoxysilane, γ-acryloyloxypropylmethyldiethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane and γ-methacryloyloxypropylmethyldiethoxysilane.

  Two or more coupling agents may be used in combination. In addition to the silane coupling agents shown above, other silane coupling agents may be used. Other silane coupling agents include alkyl esters of orthosilicate (eg, methyl orthosilicate, ethyl orthosilicate, n-propyl orthosilicate, i-propyl orthosilicate, n-butyl orthosilicate, sec-butyl orthosilicate, orthosilicate). Acid t-butyl) and its hydrolyzate.

  Examples of the polymer used as the other binder of the low refractive index layer include polyvinyl alcohol, polyoxyethylene, polymethyl methacrylate, polymethyl acrylate, diacetyl cellulose, triacetyl cellulose, nitrocellulose, polyester, and alkyd resin.

  The low refractive index layer preferably contains 5 to 80% by mass of binder as a whole. The binder has a function of adhering the hollow silica fine particles and maintaining the structure of the low refractive index layer including voids. The usage-amount of a binder is adjusted so that the intensity | strength of a low refractive index layer can be maintained, without filling a space | gap.

(solvent)
The low refractive index layer according to the present invention preferably contains an organic solvent. Specific examples of organic solvents include alcohols (eg, methanol, ethanol, isopropanol, butanol, benzyl alcohol), ketones (eg, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone), esters (eg, methyl acetate, ethyl acetate). , Propyl acetate, butyl acetate, methyl formate, ethyl formate, propyl formate, butyl formate), aliphatic hydrocarbons (eg, hexane, cyclohexane), halogenated hydrocarbons (eg, methylene chloride, chloroform, carbon tetrachloride), aromatic Group hydrocarbon (eg, benzene, toluene, xylene), amide (eg, dimethylformamide, dimethylacetamide, n-methylpyrrolidone), ether (eg, diethyl ether, dioxane, tetrahydrofuran), ether alcohol (eg, 1-methoxy-2-propanol). Of these, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and butanol are particularly preferable.

  The content of the organic solvent is preferably 1 to 4% by mass of the solid content concentration in the low refractive index layer coating composition. The organic solvent is preferably 1% by mass or more in order to prevent coating unevenness and achieve a uniform film thickness, and if it exceeds 4% by mass, the drying load increases, which is not preferable because the size of the drying apparatus is increased and the time is increased.

<High refractive index layer>
In the present invention, in order to further improve the antireflection property, a plurality of the following high refractive index layers can be provided below the low refractive index layer.

  The high refractive index layer preferable for the present invention preferably contains (c) metal oxide fine particles having an average particle diameter of 10 to 200 nm, (d) a metal compound, and (e) an actinic ray curable resin.

(Metal oxide fine particles)
The high refractive index layer of the present invention preferably contains metal oxide fine particles. The kind of metal oxide fine particles is not particularly limited, and Ti, Zr, Sn, Sb, Cu, Fe, Mn, Pb, Cd, As, Cr, Hg, Zn, Al, Mg, Si, P and S A metal oxide having at least one element selected from the above can be used, and these metal oxide fine particles are doped with a trace amount of atoms such as Al, In, Sn, Sb, Nb, a halogen element, and Ta. May be. A mixture of these may also be used. In the present invention, at least one metal oxide fine particle selected from among zirconium oxide, antimony oxide, tin oxide, zinc oxide, indium-tin oxide (ITO), antimony-doped tin oxide (ATO), and zinc antimonate is used. It is preferably used as a main component, and particularly preferably indium tin oxide (ITO).

  The average particle diameter of the primary particles of these metal oxide fine particles is in the range of 10 nm to 200 nm, particularly preferably 10 to 150 nm. The average particle diameter of the metal oxide fine particles may be measured from an electron micrograph by a scanning electron microscope (SEM) or the like, or measured by a particle size distribution meter using a dynamic light scattering method or a static light scattering method. May be. If the particle size is too small, aggregation tends to occur and the dispersibility deteriorates. If the particle size is too large, the haze is remarkably increased. The shape of the metal oxide fine particles is preferably a rice grain shape, a spherical shape, a cubic shape, a spindle shape, a needle shape, or an indefinite shape.

  Specifically, the refractive index of the high refractive index layer is higher than the refractive index of the base film as a support, and is preferably in the range of 1.50 to 1.90 when measured at 23 ° C. and a wavelength of 550 nm. The means for adjusting the refractive index of the high refractive index layer is that the kind and addition amount of the metal oxide fine particles are dominant, so that the refractive index of the metal oxide fine particles is preferably 1.80 to 2.60, More preferably, it is 1.85 to 2.50.

  The metal oxide fine particles may be surface-treated with an organic compound. By modifying the surface of the metal oxide fine particles with an organic compound, the dispersion stability in an organic solvent is improved, the dispersion particle size can be easily controlled, and aggregation and sedimentation over time can be suppressed. . For this reason, the surface modification amount with a preferable organic compound is 0.1 mass%-5 mass% with respect to metal oxide particle, More preferably, it is 0.5 mass%-3 mass%. Examples of the organic compound used for the surface treatment include polyols, alkanolamines, stearic acid, silane coupling agents, and titanate coupling agents. Among these, the silane coupling agent mentioned later is preferable. Two or more kinds of surface treatments may be combined.

  The thickness of the high refractive index layer containing the metal oxide fine particles is preferably 5 nm to 1 μm, more preferably 10 nm to 0.2 μm, and most preferably 30 nm to 0.1 μm.

  The ratio of the metal oxide fine particles to be used and a binder such as actinic ray curable resin, which will be described later, varies depending on the kind of metal oxide fine particles, the particle size, etc. The latter one is preferable.

  The amount of the metal oxide fine particles used in the present invention is preferably 5% by mass to 85% by mass in the high refractive index layer, more preferably 10% by mass to 80% by mass, and most preferably 20% to 75% by mass. preferable. If the amount used is small, the desired refractive index and the effect of the present invention cannot be obtained, and if it is too large, the film strength deteriorates.

  The metal oxide fine particles are supplied to a coating solution for forming a high refractive index layer in a dispersion state dispersed in a medium. As a dispersion medium for metal oxide particles, it is preferable to use a liquid having a boiling point of 60 to 170 ° C. Specific examples of the dispersion solvent include water, alcohol (eg, methanol, ethanol, isopropanol, butanol, benzyl alcohol), ketone (eg, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone), ketone alcohol (eg, diacetone alcohol). , Esters (eg, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl formate, ethyl formate, propyl formate, butyl formate), aliphatic hydrocarbons (eg, hexane, cyclohexane), halogenated hydrocarbons (eg, methylene) Chloride, chloroform, carbon tetrachloride), aromatic hydrocarbons (eg, benzene, toluene, xylene), amides (eg, dimethylformamide, dimethylacetamide, n-methylpyrrolidone), ethers (eg, diethyl ether, dioxane, Tiger hydrofuran), ether alcohols (e.g., 1-methoxy-2-propanol). Of these, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and butanol are particularly preferable.

  The metal oxide fine particles can be dispersed in the medium using a disperser. Examples of the disperser include a sand grinder mill (eg, a bead mill with pins), a high-speed impeller mill, a pebble mill, a roller mill, an attritor, and a colloid mill. A sand grinder mill and a high-speed impeller mill are particularly preferred. Further, preliminary dispersion processing may be performed. Examples of the disperser used for the preliminary dispersion treatment include a ball mill, a three-roll mill, a kneader, and an extruder.

  In the present invention, metal oxide fine particles having a core / shell structure may be further contained. One layer of the shell may be formed around the core, or a plurality of layers may be formed in order to further improve the light resistance. The core is preferably completely covered by the shell.

  For the core, titanium oxide (rutile type, anatase type, amorphous type, etc.), zirconium oxide, zinc oxide, cerium oxide, indium oxide doped with tin, tin oxide doped with antimony, etc. can be used. Titanium may be the main component.

  The shell is preferably formed of a metal oxide or sulfide containing an inorganic compound other than titanium oxide as a main component. For example, an inorganic compound mainly composed of silicon dioxide (silica), aluminum oxide (alumina) zirconium oxide, zinc oxide, tin oxide, antimony oxide, indium oxide, iron oxide, zinc sulfide, or the like is used. Of these, alumina, silica, and zirconia (zirconium oxide) are preferable. A mixture of these may also be used.

  The coating amount of the shell with respect to the core is 2 to 50% by mass as an average coating amount. Preferably it is 3-40 mass%, More preferably, it is 4-25 mass%. When the coating amount of the shell is large, the refractive index of the fine particles is lowered, and when the coating amount is too small, the light resistance is deteriorated. Two or more kinds of metal oxide fine particles may be used in combination.

  The titanium oxide used as a core can use what was produced by the liquid phase method or the gaseous-phase method. As a method for forming the shell around the core, for example, U.S. Pat. No. 3,410,708, JP-B-58-47061, U.S. Pat. No. 2,885,366, and U.S. Pat. No. 1, British Patent No. 1,134,249, US Pat. No. 3,383,231, British Patent No. 2,629,953, No. 1,365,999, etc. Can do.

[Metal compounds]
As the metal compound used in the present invention, a compound represented by the following general formula (4) or a chelate compound thereof can be used.

General formula (4) AnMBx-n
In the formula, M represents a metal atom, A represents a hydrolyzable functional group or a hydrocarbon group having a hydrolyzable functional group, and B represents an atomic group covalently or ionically bonded to the metal atom M. x represents the valence of the metal atom M, and n represents an integer of 2 or more and x or less.

  Examples of the hydrolyzable functional group A include halogens such as alkoxyl groups and chloro atoms, ester groups and amide groups. The metal compound belonging to the above formula (4) includes an alkoxide having two or more alkoxyl groups bonded directly to a metal atom, or a chelate compound thereof. Preferable metal compounds include titanium alkoxide, zirconium alkoxide, or chelate compounds thereof. Titanium alkoxide has a high reaction rate and a high refractive index and is easy to handle. However, since it has a photocatalytic action, its light resistance deteriorates when added in a large amount. Zirconium alkoxide has a high refractive index but tends to become cloudy, so care must be taken in dew point management during coating. Moreover, since titanium alkoxide has the effect of promoting the reaction between the ultraviolet curable resin and the metal alkoxide, the physical properties of the coating film can be improved even by adding a small amount.

  Examples of the titanium alkoxide include tetramethoxy titanium, tetraethoxy titanium, tetra-iso-propoxy titanium, tetra-n-propoxy titanium, tetra-n-butoxy titanium, tetra-sec-butoxy titanium, tetra-tert-butoxy titanium, and the like. Is mentioned.

  Examples of the zirconium alkoxide include tetramethoxy zirconium, tetraethoxy zirconium, tetra-iso-propoxy zirconium, tetra-n-propoxy zirconium, tetra-n-butoxy zirconium, tetra-sec-butoxy zirconium, tetra-tert-butoxy zirconium and the like. Is mentioned.

  Preferred chelating agents for forming a chelate compound by coordination with a free metal compound include alkanolamines such as diethanolamine and triethanolamine, glycols such as ethylene glycol, diethylene glycol and propylene glycol, acetylacetone and acetoacetic acid. Examples thereof include ethyl and the like having a molecular weight of 10,000 or less. By using these chelating agents, it is possible to form a chelate compound that is stable against water mixing and is excellent in the effect of reinforcing the coating film.

  The addition amount of the metal compound is preferably adjusted so that the content of the metal oxide derived from the metal compound contained in the high refractive index layer is 0.3 to 5% by mass. If it is less than 0.3% by mass, the scratch resistance is insufficient, and if it exceeds 5% by mass, the light resistance tends to deteriorate.

(Actinic ray curable resin)
The actinic ray curable resin is added as a binder for the metal oxide fine particles in order to improve the film formability and physical properties of the coating film. As the actinic ray curable resin, a monomer or oligomer having two or more functional groups that undergo a polymerization reaction directly by irradiation with actinic rays such as ultraviolet rays or electron beams or indirectly by the action of a photopolymerization initiator. Can be used. Examples of the functional group include a group having an unsaturated double bond such as a (meth) acryloyloxy group, an epoxy group, and a silanol group. Among these, radically polymerizable monomers and oligomers having two or more unsaturated double bonds can be preferably used. You may combine a photoinitiator as needed. Examples of such actinic ray curable resins include polyfunctional acrylate compounds and the like, and the group consisting of pentaerythritol polyfunctional acrylate, dipentaerythritol polyfunctional acrylate, pentaerythritol polyfunctional methacrylate, and dipentaerythritol polyfunctional methacrylate. It is preferable that it is a compound chosen from these. Here, the polyfunctional acrylate compound is a compound having two or more acryloyloxy groups and / or methacryloyloxy groups in the molecule.

  Examples of the monomer of the polyfunctional acrylate compound include ethylene glycol diacrylate, diethylene glycol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, and tetramethylolmethanetriacrylate. Acrylate, tetramethylol methane tetraacrylate, pentaglycerol triacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, glycerin triacrylate, dipentaerythritol triacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, Dipen Erythritol hexaacrylate, tris (acryloyloxyethyl) isocyanurate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, tetra Methylol methane trimethacrylate, tetramethylol methane tetramethacrylate, pentaglycerol trimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, glycerol trimethacrylate, dipentaerythritol trimethacrylate, dipentaerythritol te La methacrylate, dipentaerythritol penta methacrylate, dipentaerythritol hexa methacrylate preferred. These compounds are used alone or in admixture of two or more. Moreover, oligomers, such as a dimer and a trimer of the said monomer, may be sufficient.

  The addition amount of the actinic ray curable resin is preferably less than 50% by mass in the solid content in the high refractive index composition.

  In order to accelerate the curing of the actinic radiation curable resin according to the present invention, the photopolymerization initiator and the acrylic compound having two or more polymerizable unsaturated bonds in the molecule are in a mass ratio of 3: 7 to 1: 9. It is preferable to contain.

  Specific examples of the photopolymerization initiator include acetophenone, benzophenone, hydroxybenzophenone, Michler's ketone, α-amyloxime ester, thioxanthone, and derivatives thereof.

(solvent)
Examples of the organic solvent used for coating the high refractive index layer of the present invention include alcohols (for example, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, secondary butanol, tertiary butanol, pentanol, hexanol). , Cyclohexanol, benzyl alcohol, etc.), polyhydric alcohols (for example, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, hexanediol, pentanediol, glycerin, hexane Triol, thiodiglycol, etc.), polyhydric alcohol ethers (for example, ethylene glycol monomethyl ether) Ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether, triethylene glycol Monoethyl ether, ethylene glycol monophenyl ether, propylene glycol monophenyl ether, etc.), amines (for example, ethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, morpholine, N-ethylmorpholine) , Ethylenediamine, diethylenediamine, triethylenetetramine, tetraethylenepentamine, polyethyleneimine, pentamethyldiethylenetriamine, tetramethylpropylenediamine, etc.), amides (eg, formamide, N, N-dimethylformamide, N, N-dimethylacetamide) Etc.), heterocyclic rings (for example, 2-pyrrolidone, N-methyl-2-pyrrolidone, cyclohexyl pyrrolidone, 2-oxazolidone, 1,3-dimethyl-2-imidazolidinone, etc.), sulfoxides (for example, dimethyl sulfoxide, etc.) ), Sulfones (for example, sulfolane, etc.), urea, acetonitrile, acetone and the like, and alcohols, polyhydric alcohols, and polyhydric alcohol ethers are particularly preferable.

(Anti-fouling layer)
The antiglare film or antiglare antireflection film of the present invention preferably has an antifouling layer on the outermost layer.

  The antifouling layer preferable for the present invention preferably contains a fluorine-containing silane compound in the antifouling layer forming composition, and is prepared by coating a silane compound solution having a fluoroalkyl group or a fluoroalkyl ether group. In particular, the fluorine-containing silane compound is preferably silazane or alkoxysilane.

  In addition, among the silane compounds having the fluoroalkyl group or the fluoroalkyl ether group, the fluoroalkyl group in the silane compound is bonded to Si atoms at a ratio of 1 or less to one Si atom, and the remaining Is preferably a silane compound which is a hydrolyzable group or a siloxane bond group.

  The hydrolyzable group here is, for example, a group such as an alkoxy group, and becomes a hydroxyl group by hydrolysis, whereby the silane compound forms a polycondensate.

  For example, the silane compound is usually reacted with water (in the presence of an acid catalyst if necessary) in the range of room temperature to 100 ° C. while distilling off by-produced alcohol. As a result, the alkoxysilane is (partially) hydrolyzed to cause a partial condensation reaction, and can be obtained as a hydrolyzate having a hydroxyl group. The degree of hydrolysis and condensation can be adjusted as appropriate depending on the amount of water to be reacted. However, in the present invention, water is not positively added to the silane compound solution used for the antifouling treatment. It is preferable to dilute and use the solid content concentration of the solution in order to cause a hydrolysis reaction with moisture in the air during drying.

  Preferably, in the composition for forming an antifouling layer, the silane compound having a fluoroalkyl group is represented by the following general formula (5), and the concentration of the silane compound is diluted to 0.01 to 5% by mass. Use antifouling treatment.

Formula _{(5) CF 3 (CF 2} ) m (CH 2) n-Si- (ORa) 3
Here, m is an integer of 1-10. n is an integer of 0-10. Ra represents the same or different alkyl group.

  In the compound represented by the general formula (5), Ra has 3 or less carbon atoms and is preferably an alkyl group consisting of only carbon and hydrogen, for example, a group such as methyl, ethyl, isopropyl and the like.

Examples of the silane compound having a fluoroalkyl group or fluoroalkyl ether group preferably used in the present invention include CF ₃ (CH ₂ ) ₂ Si (OCH ₃ ) ₃ , CF ₃ (CH ₂ ) ₂ Si (OC ₂ H ₅ ). ₃ , CF ₃ (CH ₂ ) ₂ Si (OC ₃ H ₇ ) ₃ , CF ₃ (CH ₂ ) ₂ Si (OC ₄ H ₉ ) ₃ , CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ Si (OCH ₃ ) ₃ , CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ Si (OC ₂ H ₅ ) ₃ , CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ Si (OC ₃ H ₇ ) ₃ , CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (OCH ₃ ) ₃ , CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (OC ₂ H ₅ ) ₃ , CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (OC _{3 H 7) 3, CF 3} (CF 2) 7 (CH 2) 2 Si (OCH 3) (OC 3 H 7) 2, CF 3 (CF 2) 7 _{CH 2) 2 Si (OCH 3} ) 2 OC 3 H 7, CF 3 (CF 2) 7 (CH 2) 2 SiCH 3 (OCH 3) 2, CF 3 (CF 2) 7 (CH 2) 2 SiCH 3 ( OC ₂ H ₅ ) ₂ , CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ SiCH ₃ (OC ₃ H ₇ ) ₂ , (CF ₃ ) ₂ CF (CF ₂ ) ₈ (CH ₂ ) ₂ Si (OCH ₃ ) ₃ , C ₇ F ₁₅ CONH (CH ₂ ) ₃ Si (OC ₂ H ₅ ) ₃ , C ₈ F ₁₇ SO ₂ NH (CH ₂ ) ₃ Si (OC ₂ H ₅ ) ₃ , C ₈ F ₁₇ (CH ₂ ) ₂ OCONH (CH ₂ ) ₃ Si (OCH ₃ ) ₃ , CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (CH ₃ ) (OCH ₃ ) ₂ , CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (CH ₃ ) (OC ₂ H ₅ ) ₂ , CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (CH ₃ ) (OC ₃ H ₇ ) ₂ , CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (C ₂ H ₅ ) (OCH ₃ ) ₂ , CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (C ₂ H ₅ ) (OC ₃ H ₇ ) ₂ , CF ₃ (CH ₂ ) ₂ Si (CH ₃ ) (OCH ₃ ) ₂ , CF ₃ (CH ₂ ) ₂ Si (CH ₃ ) (OC ₂ H ₅ ) ₂ , CF ₃ (CH ₂ ) ₂ Si (CH ₃ ) (OC ₃ H ₇ ) ₂ , CF ₃ (CF ₂ ) ₅ ( _{CH 2) 2 Si (CH 3} ) (OCH 3) 2, CF 3 (CF 2) 5 (CH 2) 2 Si (CH 3) (OC 3 H 7) 2, CF 3 (CF 2) 2 O (CF _{2) 3 (CH 2) 2} Si (OC 3 H 7), C 7 F 15 CH 2 O (CH 2) 3 Si (OC 2 H 5) 3, C 8 F 17 SO 2 O (CH 2) 3 Si Examples include (OC ₂ H ₅ ) ₃ , C ₈ F ₁₇ (CH ₂ ) ₂ OCHO (CH ₂ ) ₃ Si (OCH ₃ ) ₃ , but not limited thereto.

  Examples of the fluorine-based silane compound include KP801M and X-24-9146 manufactured by Shin-Etsu Chemical Co., Ltd., GE Toshiba Silicones Co., Ltd. XC98-A5382, XC98-B2472, Daikin Industries Co., Ltd. As the compound for surface treatment, perfluoroalkylsilazane, perfluoroalkylsilane, or perfluoropolyether group-containing silane compound, particularly perfluoroalkyltrialkoxysilane, perfluoropolyethertrialkoxysilane, Examples include perfluoropolyether ditrialkoxysilane.

  When these silane compounds are used, they are diluted to 0.01 to 10% by mass, preferably 0.03 to 5% by mass, more preferably 0.05 to 2% by mass with an organic solvent not containing fluorine. It is preferable to use in.

  In the present invention, an organic solvent containing no fluorine is preferably used to prepare the silane compound solution, and the following may be mentioned.

  As a solvent of the coating composition for the antifouling layer used in the present invention, propylene glycol mono (C1-C4) alkyl ether and / or propylene glycol mono (C1-C4) alkyl ether ester, propylene glycol mono (C1-C4). Specific examples of the alkyl ether include propylene glycol monomethyl ether (PGME), propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol monoisopropyl ether, propylene glycol monobutyl ether and the like. The propylene glycol mono (C1 to C4) alkyl ether ester includes propylene glycol monoalkyl ether acetate, specifically, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate and the like. Propylene glycol mono (C1-C4) alkyl ether and / or propylene glycol mono (C1-C4) alkyl ether ester, etc., alcohols such as methanol, ethanol, propanol, n-butanol, 2-butanol, t-butanol, cyclohexanol , Ketones such as methyl ethyl ketone, methyl isobutyl ketone and acetone, esters such as ethyl acetate, methyl acetate, ethyl lactate, isopropyl acetate, amyl acetate and ethyl butyrate, hydrocarbons such as benzene, toluene and xylene, dioxane, N, N-dimethylformamide and other solvents. Alternatively, these solvents are used by being appropriately mixed. The solvent to be mixed is not particularly limited to these.

  Particularly preferred solvents are one or more organic solvents selected from ethanol, isopropyl alcohol, propylene glycol, and propylene glycol monomethyl ether.

  Among these solvents, those having a boiling point of less than 100 ° C. (low boiling solvent) such as methanol, ethanol and isopropyl alcohol, and boiling points of 100 ° C. or more such as propylene glycol monomethyl ether and n-butyl alcohol. (Boiling point solvent) is preferably used in combination, and in particular, those having a boiling point of 60 to 98 ° C. and those having a boiling point of 100 to 160 ° C. are preferably used in combination. The ratio of the low boiling point solvent and the high boiling point solvent when used in combination is preferably 98.0% by mass or more and the high boiling point solvent is 0.5 to 2% by mass in the composition.

  In the antifouling layer forming composition used in the present invention, it is preferable to add an acid to adjust the pH to 5.0 or less. Since the acid promotes hydrolysis of the silane compound and acts as a catalyst for the polycondensation reaction, the polycondensation film of the silane compound can be easily formed on the surface of the substrate, and the antifouling property can be enhanced. The pH is preferably in the range of 1.5 to 5.0. If the pH is 1.5 or less, the acidity of the solution is too strong, and the container or the piping may be damaged. If the pH is 5 or more, the reaction does not proceed easily. Preferably it is the range of pH2.0-4.0.

  In the present invention, it is preferable not to positively add water to the silane compound solution used for the antifouling treatment, but to cause a hydrolysis reaction with moisture in the air mainly after drying after preparation. Therefore, it is used when the solid content concentration of the solution is diluted. If too much water is added to the treatment liquid, the pot life is shortened accordingly.

  In the present invention, sulfuric acid, hydrochloric acid, nitric acid, hypochlorous acid, boric acid, hydrofluoric acid, preferably an inorganic acid such as hydrochloric acid and nitric acid, an organic acid having a sulfo group (also referred to as a sulfonic acid group) or a carboxyl group, For example, acetic acid, polyacrylic acid, benzenesulfonic acid, p-toluenesulfonic acid, methylsulfonic acid and the like are used. The organic acid is more preferably a compound having a hydroxyl group and a carboxyl group in one molecule. For example, a hydroxydicarboxylic acid such as citric acid or tartaric acid is used. The organic acid is more preferably a water-soluble acid. For example, in addition to the citric acid and tartaric acid, levulinic acid, formic acid, propionic acid, malic acid, succinic acid, methyl succinic acid, fumaric acid, oxaloacetic acid, pyruvin. Acid, 2-oxoglutaric acid, glycolic acid, D-glyceric acid, D-gluconic acid, malonic acid, maleic acid, oxalic acid, isocitric acid, lactic acid and the like are preferably used. Also, benzoic acid, hydroxybenzoic acid, atorvaic acid and the like can be used as appropriate.

  The addition amount is 0.1 to 10 parts by mass, preferably 0.2 to 5 parts by mass with respect to 100 parts by mass of the partial hydrolyzate of the silane compound. Further, the amount of water added is not limited as long as the partial hydrolyzate can theoretically be hydrolyzed by 100%, and an amount equivalent to 100% to 300%, preferably an amount equivalent to 100% to 200% is added. Good.

  By using a fluorine-containing silane compound, it is not only preferable in terms of lowering the refractive index of the antifouling layer and imparting water and oil repellency, but also has an effect of being highly scratch resistant and particularly excellent in blocking between films. .

(Formation of antireflection layer)
In the present invention, the method for providing the antireflection layer is not particularly limited, but it is preferably formed by coating.

  In the present invention, an antireflection layer is formed by a step of forming a concavo-convex structure with a convex structure portion and a transparent resin layer on a base film and sequentially coating with the above high refractive index layer composition and low refractive index layer composition. It is preferable to manufacture. It is also preferable to coat the antifouling layer.

  Although the structure of a preferable anti-glare antireflection film is shown below, it is not limited to these. Here, the antiglare layer of the present invention means a layer comprising the convex structure portion and the transparent resin layer according to the present invention.

Base film / Anti-glare layer of the present invention / Low refractive index layer Base film / Anti-glare layer of the present invention / High refractive index layer / Low refractive index layer Base film / Antistatic layer / Anti-glare layer of the present invention / Low refractive index layer Base film / Antistatic layer / Anti-glare layer of the present invention / High refractive index layer / Low refractive index layer Base film / Anti-glare layer of the present invention / Low refractive index layer / Anti-fouling layer Base film / Anti-glare layer of the present invention / High refractive index layer / Low refractive index layer / Anti-fouling layer Substrate film / Antistatic layer / Anti-glare layer / Low refractive index layer / Anti-fouling layer Substrate film / Antistatic Layer / antiglare layer of the present invention / high refractive index layer / low refractive index layer / antifouling layer In the present invention, after the antiglare layer of the present invention is formed, the surface of the antiglare layer of the present invention is subjected to surface treatment, It is preferable to form the low refractive index layer (and high refractive index layer) according to the present invention on the surface of the antiglare layer of the present invention that has been subjected to the surface treatment. It is also preferable to subject the low refractive index layer to a surface treatment before providing the antifouling layer.

Examples of the surface treatment include cleaning methods, alkali treatment methods, flame plasma treatment methods, high frequency discharge plasma methods, electron beam methods, ion beam methods, sputtering methods, acid treatments, corona treatment methods, atmospheric pressure glow discharge plasma methods, and the like. An alkali treatment method and a corona treatment method are preferable, and an alkali treatment method can be used particularly preferably. The corona treatment is a treatment performed by applying a high voltage of 1 kV or more between the electrodes under atmospheric pressure and discharging it. An apparatus commercially available from Kasuga Electric Co., Ltd. or Toyo Electric Co., Ltd. Can be used. The intensity of the corona discharge treatment depends on the distance between the electrodes, the output per unit area, and the generator frequency. As one electrode (A electrode) of the corona treatment apparatus, a commercially available one can be used, but the material can be selected from aluminum, stainless steel and the like. The other is an electrode (B electrode) for holding a plastic film, and is a roll electrode installed at a certain distance from the A electrode so that the corona treatment is carried out stably and uniformly. A commercially available one can also be used, and the material is preferably a roll made of aluminum, stainless steel, or a metal thereof, and a roll lined with ceramics, silicon, EPT rubber, hyperon rubber, or the like. It is done. The frequency used for the corona treatment used in the present invention is a frequency of 20 kHz to 100 kHz, and a frequency of 30 kHz to 60 kHz is preferable. When the frequency is lowered, the uniformity of the corona treatment is deteriorated and unevenness of the corona treatment occurs. In addition, when the frequency is increased, there is no particular problem when performing high-output corona treatment, but when performing low-output corona treatment, it is difficult to perform stable processing, resulting in uneven processing. Occurs. The output of the corona treatment is 1 to 5 w · min. / M ² but ² to 4 w · min. An output of / m ² is preferred. The distance between the electrode and the film is 5 mm or more and 50 mm or less, preferably 10 mm or more and 35 mm or less. When the gap is opened, a higher voltage is required to maintain a constant output, and unevenness is likely to occur. If the gap is too narrow, the applied voltage becomes too low and unevenness is likely to occur. Furthermore, when the film is transported and continuously processed, the film comes into contact with the electrodes and scratches are generated.

  The alkali treatment method is not particularly limited as long as it is a method in which a film coated with a hard coat layer is immersed in an alkaline aqueous solution.

  As the aqueous alkali solution, an aqueous sodium hydroxide solution, an aqueous potassium hydroxide solution, an aqueous ammonia solution or the like can be used, and an aqueous sodium hydroxide solution is particularly preferable.

  The alkali concentration of the aqueous alkali solution, for example, sodium hydroxide concentration is preferably 0.1 to 25% by mass, and more preferably 0.5 to 15% by mass.

  The alkali treatment temperature is usually 10 to 80 ° C, preferably 20 to 60 ° C.

  The alkali treatment time is 5 seconds to 5 minutes, preferably 30 seconds to 3 minutes. The film after the alkali treatment is preferably neutralized with acidic water and then thoroughly washed with water.

  Each layer of the antireflection layer is formed on the convex structure and the transparent resin layer by dip coating, air knife coating, curtain coating, roller coating, wire bar coating, gravure coating, micro gravure coating, and extrusion. It can be formed by coating using a coating method. At the time of application, the base film is preferably wound up in a roll shape after being unwound from a state wound in a roll shape with a width of 1.4 to 4 m, performing the above-described application, drying and curing treatment. .

  Furthermore, the anti-glare antireflection film using the anti-glare film of the present invention is laminated at 50 to 150 ° C. and 1 to 30 in a rolled state after the antireflection layer is laminated on the base film. It can manufacture by the manufacturing method which heat-processes in the range of a day. The period of the heat treatment may be appropriately determined depending on the set temperature. For example, if it is 50 ° C, it is preferably a period of 3 days or more and less than 30 days, and if it is 150 ° C, a range of 1 to 3 days is preferable. Usually, it is preferable to set it at a relatively low temperature so that the heat treatment effect on the outside of the winding, the center of the winding, and the core is not biased, and it is preferable to carry out at around 50 to 80 ° C. for about 3 to 7 days.

  In order to stably perform the heat treatment, it is necessary to perform in a place where the temperature and humidity can be adjusted, and it is preferable to perform in a heat treatment chamber such as a clean room without dust.

  When winding an antiglare film coated with a functional thin film such as the antireflection layer or antifouling layer into a roll, the wound core may be of any material, whether it is a cylindrical core. However, it is preferably a hollow plastic core, and the plastic material may be any heat-resistant plastic that can withstand the heat treatment temperature. For example, phenol resin, xylene resin, melamine resin, polyester Resins such as resins and epoxy resins are listed. A thermosetting resin reinforced with a filler such as glass fiber is preferable.

  The number of windings on these winding cores is preferably 100 windings or more, more preferably 500 windings or more, and the winding thickness is preferably 5 cm or more.

  In this way, when the heat treatment is performed in a state where the functional thin film is coated on the long base film and the roll wound around the plastic core is wound, it is preferable to rotate the roll, The rotation is preferably performed at a speed of 1 rotation or less per minute, and may be continuous or intermittent. Moreover, it is preferable to perform rewinding of the roll once or more during the heating period.

  In order to rotate the long antiglare film roll wound around the core during the heat treatment, it is preferable to provide a dedicated turntable in the heat treatment chamber.

  In the case of intermittent rotation, the stop time is preferably within 10 hours, the stop position is preferably made uniform in the circumferential direction, and the stop time is within 10 minutes. More preferred. Most preferred is continuous rotation.

  As for the rotation speed in continuous rotation, the time required for one rotation is preferably 10 hours or less, and if it is early, it becomes a burden on the apparatus, so the range of 15 minutes to 2 hours is substantially preferable.

  In the case of a dedicated carriage having a rotation function, it is preferable that the optical film roll can be rotated during movement and storage. In this case, rotation is effective as a countermeasure against black bands that occur when the storage period is long. Function.

(Polarizer)
The polarizing plate can be produced by a general method. Using a fully saponified polyvinyl alcohol aqueous solution on at least one surface of a polarizing film prepared by subjecting the back side of the antiglare film and the antiglare antireflection film of the present invention to alkali saponification treatment and immersion drawing in an iodine solution It is preferable to stick them together. The film may be used on the other surface, or another polarizing plate protective film may be used. Commercially available cellulose ester films (for example, Konica Minoltak KC8UX, KC4UX, KC5UX, KC8UCR3, KC8UCR4, KC8UCR5, KC8UY, KC4UY, KC12UR, KC4FR, and the above manufactured by Konica Minolta Opto Co., Ltd. are also preferably used). In contrast to the antiglare film and the antiglare antireflection film of the present invention, the polarizing plate protective film used on the other surface has an in-plane retardation Ro of 590 nm, 30 to 300 nm, and Rt of 70 to 400 nm. It is preferable to have a phase difference. These can be produced, for example, by the methods described in JP-A-2002-71957 and Japanese Patent Application No. 2002-155395. Alternatively, it is preferable to use a polarizing plate protective film that also serves as an optical compensation film having an optically anisotropic layer formed by aligning a liquid crystal compound such as a discotic liquid crystal. For example, the optically anisotropic layer can be formed by the method described in JP-A-2003-98348. By using in combination with the antiglare film and the antiglare antireflection film of the present invention, a polarizing plate having excellent flatness and a stable viewing angle widening effect can be obtained.

  A polarizing film, which is a main component of a polarizing plate, is an element that transmits only light having a plane of polarization in a certain direction. A typical polarizing film currently known is a polyvinyl alcohol polarizing film, which is a polyvinyl alcohol film. There are one in which iodine is dyed on a system film and one in which dichroic dye is dyed. As the polarizing film, a polyvinyl alcohol aqueous solution is formed and dyed by uniaxially stretching or dyed, or uniaxially stretched after dyeing, and then preferably subjected to a durability treatment with a boron compound. On the surface of the polarizing film, one side of the antiglare film and the antiglare antireflection film of the present invention is bonded to form a polarizing plate. It is preferably bonded with an aqueous adhesive mainly composed of completely saponified polyvinyl alcohol or the like.

(Display device)
By incorporating the polarizing plate of the present invention into a display device, the display device of the present invention having various visibility can be manufactured. The antiglare film and antiglare antireflection film of the present invention are reflective, transmissive, transflective LCD or TN, STN, OCB, HAN, VA (PVA, MVA), IPS. It is preferably used in LCDs of various drive systems such as. Further, the antiglare film and the antiglare antireflection film of the present invention are excellent in flatness and are preferably used for various display devices such as a plasma display, a field emission display, an organic EL display, an inorganic EL display, and electronic paper. In particular, in a large-screen display device having a screen of 30 or more types, particularly 30 to 54 types, there is no white spot at the periphery of the screen, and the effect is maintained for a long period of time. MVA liquid crystal display device, IPS liquid crystal display A noticeable effect is observed in the device. In particular, there was little color unevenness, glare and wavy unevenness, which is the object of the present invention.
[Example]
EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

Example 1
[Production of Cellulose Ester Film 1]
<Synthesis of Polymer X>
In a glass flask equipped with a stirrer, two dropping funnels, a gas introduction tube and a thermometer, 40 g of a monomer Xa and Xb mixed solution of the types and ratios (molar composition ratio) described in Table 3, and 2 g of mercaptopropionic acid as a chain transfer agent And 30 g of toluene were charged, and the temperature was raised to 90 ° C. Thereafter, 60 g of a mixture of monomers Xa and Xb having the types and ratios (molar composition ratios) shown in Table 3 was dropped from one dropping funnel over 3 hours, and at the same time, azobis dissolved in 14 g of toluene from the other funnel. 0.4 g of isobutyronitrile was added dropwise over 3 hours. Thereafter, 0.6 g of azobisisobutyronitrile dissolved in 56 g of toluene was added dropwise over 2 hours, and the reaction was further continued for 2 hours to obtain polymer X. The obtained polymer X was solid at room temperature. The weight average molecular weight of the polymer X is shown in Table 3 by the following measurement method.

  In Table 3, MMA and HEA are abbreviations for the following compounds, respectively.

MMA: methyl methacrylate HEA: 2-hydroxyethyl acrylate (weight average molecular weight measurement)
The weight average molecular weight was measured using gel permeation chromatography.

  The measurement conditions are as follows.

Solvent: Methylene chloride Column: Shodex K806, K805, K803G (Used by connecting three Showa Denko Co., Ltd.)
Column temperature: 25 ° C
Sample concentration: 0.1% by mass
Detector: RI Model 504 (manufactured by GL Sciences)
Pump: L6000 (manufactured by Hitachi, Ltd.)
Flow rate: 1.0ml / min
Calibration curve: Standard polystyrene STK standard polystyrene (manufactured by Tosoh Corp.) Mw = 100000-500 calibration curves with 13 samples were used. Thirteen samples are used at approximately equal intervals.

<Synthesis of polymer Y>
Bulk polymerization was performed by the polymerization method described in JP-A No. 2000-128911. That is, the following methyl acrylate (MA) as monomer Ya was introduced into a flask equipped with a stirrer, nitrogen gas inlet tube, thermometer, inlet, and reflux condenser, and nitrogen gas was introduced to replace the inside of the flask with nitrogen gas. The following thioglycerol was added with stirring. After the addition of thioglycerol, the temperature of the contents was appropriately changed and polymerization was performed for 4 hours. The contents were returned to room temperature, and 20 parts by mass of a 5% by weight benzoquinone tetrahydrofuran solution was added thereto to stop the polymerization. The contents were transferred to an evaporator, and tetrahydrofuran, residual monomer and residual thioglycerol were removed under reduced pressure at 80 ° C. to obtain polymer Y shown in Table 3. The obtained polymer Y was liquid at room temperature. The weight average molecular weight of the polymer Y is shown in Table 3 by the above measurement method.

Methyl acrylate 100 parts by weight Thioglycerol 5 parts by weight

<Dope composition>
(Silicon dioxide dispersion)
Aerosil 972V (manufactured by Nippon Aerosil Co., Ltd.) 12 parts by mass (average diameter of primary particles 16 nm, apparent specific gravity 90 g / liter)
88 parts by mass of ethanol or more was stirred and mixed with a dissolver for 30 minutes, and then dispersed with Manton Gorin. The liquid turbidity after dispersion was 200 ppm. 88 parts by mass of methylene chloride was added to the silicon dioxide dispersion while stirring, and the mixture was stirred and mixed with a dissolver for 30 minutes to prepare a silicon dioxide dispersion dilution.

(Dope additive)
Methylene chloride 50 parts by weight Polymer X 12 parts by weight Polymer Y 7 parts by weight Silicon dioxide dispersion diluent 10 parts by weight Tinuvin 109 (manufactured by Ciba Specialty Chemicals) 1.2 parts by weight Tinuvin 171 (Ciba Specialty Chemicals) Manufactured) 0.8 parts by mass The methylene chloride, the polymer X, and the polymer Y were completely dissolved while stirring, and then a silicon dioxide dispersion was added and mixed by stirring to prepare a dope additive solution.

(Preparation of main dope solution)
Cellulose ester (cellulose triacetate synthesized from linter cotton, acetyl group substitution degree 2.92) 100 parts by weight Methylene chloride 380 parts by weight Ethanol 30 parts by weight Dope additive liquid The above preparation parts by weight are charged into a sealed container, and heated. While stirring, it completely dissolved, and Azumi Filter Paper No. 24 was used to prepare a main dope solution.

  The main dope solution was filtered with Finemet NF manufactured by Nippon Seisen Co., Ltd., and uniformly cast on a stainless steel band support at a temperature of 22 ° C. and a width of 2 m using a belt casting apparatus. With the stainless steel band support, the solvent was evaporated until the residual solvent amount became 105%, and the film was peeled from the stainless steel band support with a peeling tension of 162 N / m. The peeled cellulose ester web was evaporated at 35 ° C., slit to 1.6 m width, and then dried at a drying temperature of 135 ° C. while stretching 1.1 times in the width direction with a tenter. At this time, the residual solvent amount when starting stretching with a tenter was 10%. After stretching with a tenter and releasing the width retention by releasing the width tension at 130 ° C., the drying is finished while conveying the drying zone of 120 ° C. and 130 ° C. with a number of rolls, and slitting to a width of 1.5 m, Both ends of the film were subjected to a knurling process having a width of 10 mm and a height of 7 μm, and wound on a core having an inner diameter of 6 inches with an initial tension of 220 N / m and a final tension of 110 N / m, whereby a cellulose ester film 1 was obtained. The draw ratio in the MD direction calculated from the rotational speed of the stainless steel band support and the operating speed of the tenter was 1.1 times. The residual solvent amount of the cellulose ester film 1 was less than 0.1%, respectively, and the film thickness was 40 μm.

[Preparation of antiglare film 1 by adding fine particles]
On the surface of the cellulose ester film 1 (B surface side; surface in contact with a support mirror surface such as a stainless steel band used in the casting film forming method; support side), the following coating solution 1 for hard coat layer has a pore diameter of 20 μm. A hard coat layer coating solution is prepared by filtration through a polypropylene filter, and this is applied using a micro gravure coater, dried at 90 ° C., and then irradiated with an ultraviolet lamp with an illuminance of 0.1 W / cm ^2. Thus, the coating layer was cured with an irradiation dose of 0.1 J / cm ² to form an anti-glare hard coat layer having a thickness of 5 μm, thereby producing an anti-glare film 1. It was 1.1 micrometers as a result of measuring the average surface roughness (Rz) about the formed unevenness | corrugation using the optical interference type surface roughness measuring machine by WYKO. Further, the average center distance of the convex portions was 77 μm.

(Hard coat layer coating solution 1)
The following materials were stirred and mixed to obtain hard coat layer coating solution 1.

Acrylic monomer: KAYARAD DPHA (dipentaerythritol hexaacrylate, manufactured by Nippon Kayaku Co., Ltd.) 200 parts by mass Photopolymerization initiator (Irgacure 184 (manufactured by Ciba Specialty Chemicals))
25 parts by weight Propylene glycol monomethyl ether 110 parts by weight Ethyl acetate 110 parts by weight Synthetic silica fine particles Average particle size 1.8 μm 40 parts by weight Surfactant (silicone surfactant; FZ2207 (manufactured by Nippon Unicar)) 10% by weight propylene glycol monomethyl ether Solution) 0.6 parts by mass in solid content [Preparation of antiglare film 2 by embossing]
In the production of the cellulose ester film 1, a roll provided with a mold after the stretching treatment by a tenter (after forming the unevenness, the height of the convex part is 1 μm, the convex part size (long side) is 10 μm, and the distance between the convex parts is 50 μm. A B-side of the film (the side in contact with the stainless steel band support is the B-side, with the film containing the solvent sandwiched between the concavo-convex forming part consisting of a fine roll and the back roll, and the opposite side is the A side. In the same manner, except that a hot roll provided with a mold on the side is pressed, a back roll is placed on the A side, and irregularities are formed on the B side by passing between both rolls. An embossed cellulose ester film 2 was produced. In addition, the static elimination wire was installed in the uneven | corrugated formation vicinity vicinity, and charging of the film was suppressed.

On the surface of the embossed cellulose ester film 2 (B side; surface in contact with a mirror surface of a support such as a stainless steel band used in the casting film forming method; support side), the following coating liquid 2 for hard coat layer Is filtered through a polypropylene filter having a pore size of 20 μm to prepare a hard coat layer coating solution, which is applied using a micro gravure coater, dried at 90 ° C., and then irradiated with an ultraviolet lamp with an illuminance of 0.1 W. / in cm ^2, thereby curing the coated layer to irradiation dose as 0.1 J / cm ^2, to prepare an antiglare film 2 to form an antiglare hard coat layer having a thickness of 5 [mu] m.

  It was 1.2 micrometers as a result of measuring the average surface roughness (Rz) about the formed unevenness | corrugation using the optical interference type surface roughness measuring machine by WYKO. The average center distance of the convex portions was 65 μm.

(Hard coat layer coating solution 2)
Acrylic monomer: KAYARAD DPHA (dipentaerythritol hexaacrylate, manufactured by Nippon Kayaku Co., Ltd.) 60 parts by mass Trimethylolpropane triacrylate 40 parts by mass Photopolymerization initiator (Irgacure 184 (manufactured by Ciba Specialty Chemicals))
4 parts by mass Ethyl acetate 50 parts by mass Propylene glycol monomethyl ether 50 parts by mass Silicon compound 0.5 parts by mass (BYK-307 (manufactured by Big Chemie Japan))
[Preparation of antiglare films 3 to 31]
(Preparation of the first layer)
The following cured resin layer coating composition 1 is applied to the surface of the cellulose ester film 1 (B surface side; surface in contact with a mirror surface of a support such as a stainless steel band used in the casting film forming method) with a slit die. Then, the temperature and speed of the hot air are gradually increased and finally dried at 85 ° C., followed by ultraviolet irradiation with an irradiation intensity of 115 mJ / cm ² from the actinic ray irradiation part to form a cured resin layer. First layers of Samples 3 and 7 to 31 were prepared. The dry film thickness by the following composition was 5 micrometers.

In the present invention, the dry film thickness was varied by adjusting the solid content and the solvent amount. No. No. 18 was formed in a half cure state. 16 was prepared with an actinic ray irradiation dose of 80 mJ / cm ² .

(Solid content)
Acrylic monomer: KAYARAD DPHA (dipentaerythritol hexaacrylate, manufactured by Nippon Kayaku Co., Ltd.) 70 parts by mass Trimethylolpropane triacrylate 30 parts by mass Photopolymerization initiator (Irgacure 184 (manufactured by Ciba Specialty Chemicals))
4 parts by mass (solvent)
Propylene glycol monomethyl ether 75 parts by weight Methyl ethyl ketone 25 parts by weight (Preparation of antiglare film having convex structure part by ink jet method)
On the surface of the cellulose ester film 1 (B surface side; surface in contact with a support mirror surface such as a stainless steel band used in the casting film forming method; support side) and the first layer, the following convex structure coating solution 1 ~ 5 is ejected as ink droplets by ink jet method at 2-16 pl, 0.2 seconds after drying, cured with actinic ray irradiation part with UV illuminance of 0.1 W / cm ² and irradiation dose of 100 mJ / cm ² The convex structure portions described in Tables 4 and 5 were formed. The number of convex structures was adjusted by the thinning rate when ejecting ink liquid. No. No. 18 was formed in a half cure state. 16 was prepared by changing the irradiation amount to 80 mJ / cm ² .

  As the inkjet emitting device, a line head method (FIG. 4A) was used, and 10 inkjet heads having 256 nozzles having a nozzle diameter of 3.5 μm were prepared. An ink jet head having the structure shown in FIG. 3 was used. The ink supply system is composed of an ink supply tank, a filter, a piezo-type ink jet head, and piping. The ink supply tank to the ink jet head section is insulated and heated (40 ° C.), and the emission temperature is 40 ° C. The driving frequency was 20 kHz.

  Further, when the viscosity of the ink liquid (the following convex structure portion coating liquid) is less than 5 mPa · s, the followability of the discharge is reduced, and when it exceeds 12 mPa · s, the discharge stability becomes poor. The viscosity was adjusted to the stated value. Adjustment was performed by appropriately changing the solid content, the solvent amount, and the solvent type.

  The transparent resin layer coating liquid 6 described below was applied to the convex structure thus prepared by changing the film thickness by a reduced pressure extrusion method, and antiglare films 3 to 31 shown in Tables 4 and 5 were produced. No. 21 is No. 21. After the convex structure was formed, the surface of the film was treated with plasma discharge at a high frequency voltage of 100 KHz under atmospheric pressure in a nitrogen atmosphere containing 1% oxygen, and the following coating solution 6 for transparent resin layer was applied. did.

(Convex structure coating solution 1)
Acrylic monomer: KAYARAD DPHA (dipentaerythritol hexaacrylate, manufactured by Nippon Kayaku Co., Ltd.) 70 parts by mass Trimethylolpropane triacrylate 30 parts by mass Photopolymerization initiator (Irgacure 184 (manufactured by Ciba Specialty Chemicals))
4 parts by mass Propylene glycol monoethyl ether 70 parts by mass Diethylene glycol monobutyl ether acetate 30 parts by mass The above composition was mixed and stirred to prepare a convex structure part coating liquid 1.

(Convex structure coating solution 2)
Acrylic monomer: KAYARAD DPHA (dipentaerythritol hexaacrylate, manufactured by Nippon Kayaku Co., Ltd.) 70 parts by mass Trimethylolpropane triacrylate 30 parts by mass Photopolymerization initiator (Irgacure 184 (manufactured by Ciba Specialty Chemicals))
4 parts by mass Silicon compound (BYK-307 (by Big Chemie Japan)) 0.1 part by mass Propylene glycol monomethyl ether 20 parts by mass Diethylene glycol monobutyl ether acetate 80 parts by mass The above composition is mixed and stirred, and convex structure part coating liquid 2 Was prepared.

(Convex structure coating solution 3)
Acrylic monomer: KAYARAD DPHA (dipentaerythritol hexaacrylate, manufactured by Nippon Kayaku Co., Ltd.) 70 parts by mass Trimethylolpropane triacrylate 30 parts by mass Photopolymerization initiator (Irgacure 184 (manufactured by Ciba Specialty Chemicals))
4 parts by mass Propylene glycol monomethyl ether 20 parts by mass Diethylene glycol monobutyl ether acetate 80 parts by mass The above composition was mixed and stirred to prepare a convex structure part coating liquid 3.

(Convex structure coating solution 4)
Acrylic monomer: KAYARAD DPHA (dipentaerythritol hexaacrylate, manufactured by Nippon Kayaku Co., Ltd.) 70 parts by mass Trimethylolpropane triacrylate 30 parts by mass Photopolymerization initiator (Irgacure 184 (manufactured by Ciba Specialty Chemicals))
4 parts by mass Propylene glycol monomethyl ether 40 parts by mass Diethylene glycol monobutyl ether acetate 60 parts by mass The above composition was mixed and stirred to prepare convex structure part coating liquid 4.

(Convex structure coating solution 5)
Acrylic monomer: KAYARAD DPHA (dipentaerythritol hexaacrylate, manufactured by Nippon Kayaku Co., Ltd.) 70 parts by mass Trimethylolpropane triacrylate 30 parts by mass Photopolymerization initiator (Irgacure 184 (manufactured by Ciba Specialty Chemicals))
4 parts by mass Propylene glycol monomethyl ether 20 parts by mass Dipropylene glycol monomethyl ether 80 parts by mass The above composition was mixed and stirred to prepare a convex structure part coating solution 5.

(Transparent resin layer coating solution 6)
Acrylic monomer: KAYARAD DPHA (dipentaerythritol hexaacrylate, manufactured by Nippon Kayaku Co., Ltd.) 100 parts by mass Trimethylolpropane triacrylate 40 parts by mass Photopolymerization initiator (Irgacure 184 (manufactured by Ciba Specialty Chemicals))
6 parts by mass Propylene glycol monomethyl ether 50 parts by mass Methyl ethyl ketone 50 parts by mass The above composition was mixed and stirred to prepare transparent resin layer coating solution 6.

  The dry film thickness was adjusted by changing only the solid content and the solvent amount.

<Measurement / Evaluation>
(Measurement of convex structure part diameter, convex structure part height, number of convex structure parts, Rz, Sm)
The convex structure part diameter, the convex structure part height, and the number of convex structure parts (per 0.01 mm ² ) were measured using an optical interference type surface roughness measuring machine (manufactured by WYKO) using a film sample before applying the transparent resin layer ( Using a Veeco Metrology Group Wyko NT3300), the range of about 4000 μm ² (55 μm × 75 μm) is measured two-dimensionally, and the convex part is color-coded as a contour line from the bottom side, and the film surface is used as a reference. The height of the convex part and the convex part diameter, which is the major axis of the convex structure part, were measured. The number of convex structure portions was determined by converting the number of obtained convex structure portions per 0.01 mm ² . These measurements were obtained as an average value by measuring arbitrary 10 points of the corresponding part of the base film.

  The surface roughness (Rz) and the average center-to-center distance (Sm) are measured according to JIS B 0601 using an optical interference type surface roughness measuring machine manufactured by WYKO, using the sample after forming the transparent resin layer. It was measured by.

(Anti-glare effect)
In an office with a window, each film was spread on a desk, and fluorescent lighting on the ceiling and reflection of external light on the film were evaluated as follows.

5: The outline of the fluorescent lamp and the external light are blurred and I don't care about the reflection at all 4: Between 5 and 3 3: The outline of the fluorescent lamp and the reflection of the external light are slightly recognized 2: 3: 1 Middle of 1: The outline of the fluorescent lamp and the external light are understood and the reflection is worrisome (glare)
About the produced film, the glare was determined visually.

5: I don't know the glare at all. 4: I can understand the glare very slightly. 3: I can understand the slight glare. 2: Between 3 and 1. 1: I'm worried about the glare.
Based on the image line brightness measurement method described in JIS K 7105 6.6, the total of values measured with an optical comb (0.125 mm, 0.5 mm, 1.0 mm, 2.0 mm) is evaluated as sharpness. did.

  The measuring machine used was an IMAGE CLARITY METER ICM-1T Suga Test Instruments Co., Ltd. product.

5: 301 or more 4: 251-300
3: 201-250
2: 151-200
1: 150 or less (evaluation of bending resistance)
Each anti-glare film was bent 180 degrees with a bending tester (using a mandrel 3 mm) so that the anti-glare layer side would face outward, then the surface was visually observed, and bending resistance was evaluated according to the following criteria. Went.

○: No change on the antiglare layer coating surface side △: Fine cracks are observed on the antiglare layer coating surface surface ×: Many cracks are observed on the antiglare layer coating surface surface It is impossible.

  The above evaluation results are shown in Table 6.

  The antiglare film 1 imparted with a fine concavo-convex structure by addition of fine particles is inferior in glare and sharpness because of dispersion in fine particle dispersibility. The antiglare film 2 imparted with a fine concavo-convex structure by embossing is inferior in sharpness. Further, the height and size of the fine concavo-convex structure differed between the head and the tail of the antiglare film 2, and when the mold was observed, clogging was caused by the film dissolved in a part of the mold.

  It can be seen that the antiglare films 4 to 13, 16 to 21, 24, 25, and 27 of the present invention are excellent in bending resistance in addition to the antiglare effect, glare, and sharpness.

  Further, when the contact angle was 30 ° or less, the dots spread too much, and when the contact angle was 80 ° or more, the dots were difficult to adhere to the substrate, and the dots were bonded to each other, and neither of them could form a stable convex portion.

Example 2
The antiglare film sample of Example 1 was selected and the adhesion was compared.

(Evaluation of adhesion)
A cross-cut test based on JIS K 5400 was performed. Specifically, using the sample at the stage where the antiglare layer of the obtained antiglare film was formed, 11 cuts were made vertically and horizontally at intervals of 1 mm, and 100 1 mm square grids were made, A cellophane adhesive tape was affixed on this, peeled off quickly at 90 °, the number of grids remaining without peeling was counted, and rank evaluation as shown below was performed.

A: 100
○: 95-99
Δ: 90-94
X: 70 or less x is impractical.

  The results are shown in Table 7.

  It can be seen that the antiglare film of the present invention is excellent in adhesion. Among them, No. 1 in which the first layer and the convex structure were formed in a half-cured state. No. 18 and No. 18 subjected to surface treatment by plasma discharge under atmospheric pressure. No. 21 was found to be more effective due to adhesion.

Example 3
The following low refractive index layers were coated on the transparent resin layers of the antiglare films 1 to 31 produced in Example 1.

[Preparation of antireflection layer: low refractive index layer]
The following low refractive index layer coating composition 1 is applied by an extrusion coater, dried at 100 ° C. for 1 minute, cured by irradiation with ultraviolet rays of 0.1 J / cm ² , and further thermally cured at 120 ° C. for 5 minutes. A low refractive index layer was provided so as to have a thickness of 95 nm, and antiglare antireflection films 1 to 31 were produced. The refractive index of this low refractive index layer was 1.37.

  Moreover, about the produced anti-glare antireflection film, a spectral reflectance at an incident angle of 5 ° was measured in a wavelength region of 380 to 780 nm using a spectrophotometer (manufactured by JASCO Corporation). Since the antireflection performance is better as the reflectance is smaller in a wide wavelength region, the minimum reflectance at 450 to 650 nm is obtained from the measurement result. In the measurement, the back surface on the observation side was roughened, and then light absorption processing was performed using a black spray to prevent reflection of light on the back surface of the film, and the reflectance was measured. As a result of the measurement, all of the antiglare antireflection films had a reflectance of 0.7 to 1.2 and showed good results.

(Preparation of low refractive index layer coating composition 1)
<Preparation of tetraethoxysilane hydrolyzate A>
Hydrolyzate A was prepared by mixing 289 g of tetraethoxysilane and 553 g of ethanol, adding 157 g of 0.15% aqueous acetic acid solution thereto, and stirring in a water bath at 25 ° C. for 30 hours.

Tetraethoxysilane hydrolyzate A 110 parts by mass Hollow silica-based fine particle (P-2 below) dispersion 30 parts by mass KBM503 (silane coupling agent, manufactured by Shin-Etsu Chemical Co., Ltd.) 4 parts by mass Linear dimethyl silicone-EO block copolymer (FZ-2207, manufactured by Nippon Unicar Co., Ltd.) 10% propylene glycol monomethyl ether solution 3 parts by mass Propylene glycol monomethyl ether 400 parts by mass Isopropyl alcohol 400 parts by mass <Preparation of hollow silica-based fine particle P-2 dispersion>
A mixture of 100 g of silica sol having an average particle diameter of 5 nm and a SiO ₂ concentration of 20% by mass and 1900 g of pure water was heated to 80 ° C. The pH of this reaction mother liquor was 10.5, and 9000 g of 0.98 mass% sodium silicate aqueous solution as SiO ₂ and 9000 g of 1.02 mass% sodium aluminate aqueous solution as Al ₂ O ₃ were simultaneously added to the mother liquor. did. Meanwhile, the temperature of the reaction solution was kept at 80 ° C. The pH of the reaction solution rose to 12.5 immediately after the addition and hardly changed thereafter. After completion of the addition, the reaction solution was cooled to room temperature and washed with an ultrafiltration membrane to prepare a SiO ₂ .Al ₂ O ₃ core particle dispersion having a solid content concentration of 20% by mass. (Process (a))
1700 g of pure water is added to 500 g of this core particle dispersion and heated to 98 ° C., and while maintaining this temperature, a silicic acid solution (SiO ₂₎ obtained by dealkalizing a sodium silicate aqueous solution with a cation exchange resin. A dispersion of core particles in which 3000 g (concentration of 3.5% by mass) was added to form a first silica coating layer was obtained. (Process (b))
Next, 1125 g of pure water is added to 500 g of the core particle dispersion liquid that has been washed with an ultrafiltration membrane to form a first silica coating layer having a solid concentration of 13% by mass, and concentrated hydrochloric acid (35.5%) is further added dropwise. The pH was adjusted to 1.0 and dealumination was performed. Next, the aluminum salt dissolved in the ultrafiltration membrane was separated while adding 10 L of hydrochloric acid aqueous solution of pH 3 and 5 L of pure water, and SiO ₂ · Al from which some of the constituent components of the core particles forming the first silica coating layer were removed. A dispersion of ₂ O ₃ porous particles was prepared (step (c)). A mixture of 1500 g of the above porous particle dispersion, 500 g of pure water, 1,750 g of ethanol, and 626 g of 28% ammonia water is heated to 35 ° C., and then 104 g of ethyl silicate (SiO ₂ 28 mass%) is added. The surface of the porous particles on which the first silica coating layer was formed was coated with a hydrolyzed polycondensate of ethyl silicate to form a second silica coating layer. Next, a hollow silica-based fine particle (P-2) dispersion having a solid content concentration of 20% by mass, in which the solvent was replaced with ethanol using an ultrafiltration membrane, was prepared.

The thickness of the first silica coating layer of the hollow silica-based fine particles was 3 nm, the average particle size was 47 nm, MOx / SiO ₂ (molar ratio) was 0.0017, and the refractive index was 1.28. Here, the average particle diameter was measured by a dynamic light scattering method.

  Subsequently, a polarizing plate was prepared using each of the antiglare antireflection films 1 to 31.

a) Production of Polarizing Film A polyvinyl alcohol film having a thickness of 120 μm was uniaxially stretched (temperature: 110 ° C., stretch ratio: 5 times). This was immersed for 60 seconds in an aqueous solution consisting of 0.075 g of iodine, 5 g of potassium iodide, and 100 g of water, and then immersed in an aqueous solution of 68 ° C. consisting of 6 g of potassium iodide, 7.5 g of boric acid, and 100 g of water. This was washed with water and dried to obtain a polarizing film.

b) Preparation of Polarizing Plate A polarizing plate is bonded to the antiglare antireflection films 1 to 31 and a cellulose ester film KC8UCR-5 (manufactured by Konica Minolta Opto) on the back side in accordance with the following steps 1 to 5. Was made. The polarizing plate protective film on the back side was a cellulose ester film having a retardation, and retardation values were Ro = 43 nm and Rt = 132 nm.

  Process 1: Immerse in a 1 mol / L sodium hydroxide solution at 50 ° C. for 60 seconds, then wash with water and dry to obtain an antiglare antireflection film and a cellulose ester film in which the side to be bonded to the polarizing film is saponified. It was.

  Step 2: The polarizing film was immersed in a polyvinyl alcohol adhesive tank having a solid content of 2% by mass for 1 to 2 seconds.

  Step 3: Gently wipe off the excess adhesive adhering to the polarizing film in Step 2, and place it on the antiglare antireflection film and cellulose ester film treated in Step 1, and further the antireflection layer on the outside Laminated and arranged as follows.

Step 4: The antiglare antireflection film, the polarizing film, and the cellulose ester film sample laminated in Step 3 were bonded at a pressure of 20 to 30 N / cm ² and a conveyance speed of about 2 m / min.

  Step 5: A sample obtained by bonding the polarizing film, the cellulose ester film, and the antiglare antireflection films 1 to 31 prepared in Step 4 in a dryer at 80 ° C. is dried for 2 minutes to produce polarizing plates 1 to 31. did.

<Production of liquid crystal display device>
A liquid crystal panel was produced as follows, and the characteristics as a liquid crystal display device were evaluated.

  The polarizing plate on the surface of the commercially available 32-inch liquid crystal television (MVA type cell) previously bonded was peeled off, and the prepared polarizing plates 1 to 31 were bonded to the glass surface of the liquid crystal cell, respectively.

  At that time, the direction of bonding of the polarizing plate is such that the surface of the cellulose ester film having a retardation is on the liquid crystal cell side, and the absorption axis is in the same direction as the polarizing plate previously bonded. The liquid crystal display devices 1 to 31 were produced respectively.

<Evaluation>
The obtained liquid crystal display devices 1 to 31 are used in the environment as shown in FIG. 9 to observe the anti-glare effect, glare, and the blackness when the following visibility and moving images are displayed. Visual evaluation was made according to the criteria. In addition, 10 40W fluorescent lamps (FLR40S-EX-D / M manufactured by Matsushita Electric) were installed on the ceiling. Moreover, it evaluated in the state which external light inserts from a window.

(Visibility and black spots when displaying video)
As described above, a moving image of a TV program was displayed on the same display in an environment where artificial lighting by a fluorescent lamp and external light from a window were inserted from the ceiling, and a comparative experiment was performed. A moving image was observed at a position 1 m away from the front of the display, and sensory evaluation was performed.

5: I don't mind the reflection of the fluorescent lamp at the top of the screen, and the center of the screen looks black even when there is external light. Middle 3: Slight reflection of fluorescent light at the top of the screen is observed, and the center of the screen is slightly tired after observation if there is external light 2: Intermediate between 1: 3 and 1: 1: Fluorescence at the top of the screen The reflection of the light is observed, the center of the screen lacks black spots due to the influence of external light, and eyes are tired when viewed. The composition of the antiglare antireflection film / liquid crystal display device and the evaluation results are shown in Table 8 below. Shown in

  From the above table, the antiglare antireflection film of the present invention and the polarizing plates / liquid crystal display devices 4 to 13, 16 to 21, 24, 25, and 27 using the antiglare effect and glare are the same as in Example 1. In addition, even in an environment where artificial light and external light from the window are inserted, it is understood that black is excellent.

Claims (13)

An anti-glare film having a fine uneven structure on a transparent substrate, wherein the anti-glare layer has a convex diameter of 15 to 40 μm, a convex height of 2 to 10 μm, and the convex structure The antiglare layer has a surface roughness (Rz) of 0.8 to 4 μm and an average center-to-center distance (Sm) of the protrusions or recesses of the antiglare layer. 25 to 100 μm, Rz / Sm is 0.01 to 0.1, and further the surface shape portion of the convex portion or concave portion is 5 to 0.01 mm ^2.
An antiglare film characterized by having 25 pieces. 2. The antiglare film according to claim 1, wherein the convex structure is formed by an ink jet method. The antiglare film according to claim 1 or 2, wherein a dry film thickness of the antiglare layer formed of the convex structure portion and the transparent resin layer is 3 to 15 µm. The convex structure is made of an actinic ray curable resin or a thermosetting resin, and the viscosity of the convex structure forming ink containing the resin is 5 to 12 mPa · s. Item 4. The antiglare film according to any one of Items 1 to 3. The antiglare film according to claim 4, wherein a contact angle (θ) between the ink liquid for forming the convex structure portion and the transparent substrate is 45 to 70 °. 5. The method according to claim 4, wherein the convex structure forming ink liquid contains 60% by mass or more of at least one solvent having a boiling point of 140 to 250 ° C. and a viscosity of 1 to 15 mPa · s. 6. An antiglare film according to item 5. The antiglare film according to claim 6, wherein the solvent is a compound represented by the following general formula (1).
Formula _{(1) R 1 -O- (C} x H 2x -O) n-R 2
In the formula, R ₁ and R ₂ are a hydrogen atom, an aryl group, an alkyl group having 1 to 6 carbon atoms, an alkoxyalkyl group, or an alkylcarbonyl group. The hydrocarbon chain may be linear or branched. However, at least one of R ₁ and R ₂ is a substituent other than a hydrogen atom.
n: an integer from 1 to 3 x: an integer from 2 to 4 The antiglare film according to any one of claims 1 to 7, further comprising an antireflection layer or an antifouling layer formed on the antiglare layer. The transparent substrate has a transparent support and at least one cured resin layer or smooth light diffusing layer thereon, and a convex structure is formed on the surface by an inkjet method, and then the convex structure is covered. Thus, the transparent resin layer is formed, and the dry film thickness to the transparent resin layer except this transparent support body is 3-15 micrometers, The manufacturing method of the anti-glare film characterized by the above-mentioned. A convex resin is formed on the surface of the cured resin layer or light diffusing layer in a half-cured state by an inkjet method, and then a transparent resin layer is formed so as to cover the convex structure. A method for producing an antiglare film according to claim 9. The antiglare property according to claim 9 or 10, wherein after forming the convex structure portion, a transparent resin layer is formed so as to cover a surface of the convex structure portion by plasma treatment. A method for producing a film. A polarizing plate using the antiglare film according to any one of claims 1 to 8. A display device comprising the antiglare film according to any one of claims 1 to 8 or the polarizing plate according to claim 12.