JP2007076089A - Method for producing optical film having uneven surface and optical film having uneven surface - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing an optical film having an uneven surface in which the uneven surface is reduced in defect and which is improved in adhesion to a reflection preventing layer and the optical film having the uneven surface. <P>SOLUTION: In the method for producing the optical film having the uneven surface, an ultraviolet curable resin is irradiated with ultraviolet rays while being arranged between a film support and an uneven type roller having an uneven surface, and after the resin is polymerized/cured, the film support and the resin are peeled off from the roller. In relation to the adhesion surfaces of the roller and the resin, a gas containing no oxygen substantially is made to exist during the adhesion. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  TECHNICAL FIELD The present invention relates to a method for producing a surface irregularity-shaped optical film and a surface irregularity-shaped optical film, and more specifically, a method for producing a surface irregularity-shaped optical film and a surface having fewer irregularities and improved adhesion to an antireflection layer. The present invention relates to an uneven optical film.

  The antiglare film generally contains fine particles in the film and has antiglare properties by utilizing light scattering by the fine particles. However, the antiglare film for recent flat panel displays, particularly for large TVs. The film is required to have a low haze so as not to darken the display screen. However, if sufficient antiglare properties are to be provided, the amount of fine particles added increases, so that the haze value inevitably increases.

  For this reason, it is preferable from a haze point to use the surface uneven | corrugated film which gave antiglare property by roughening the film surface without using microparticles | fine-particles.

  An optical film manufacturing method in which an embossed member is pressed onto an optical film whose surface is plastically deformed to make the surface uneven, and then cured to produce an uneven shape on the surface. The emboss is transferred onto the hard coat. A manufacturing method (for example, refer to Patent Documents 1 to 3), a manufacturing method using an embossing roll (for example, refer to Patent Documents 4 and 5), and a manufacturing method in which the film itself has irregularities (for example, refer to Patent Documents 6 to 8) are known. .

  However, the embossing roll (member) is easily clogged with the optical film material (resin material) in the dent, and when clogged, the finished film is not uneven. In addition, if a release agent is used to prevent clogging, unevenness is produced in the production of minute irregularities. In particular, in the case of an optical film used on the outermost surface of a liquid crystal display device such as a TV, slight unevenness and defects are not allowed.

  Furthermore, as a method of forming irregularities on the film surface using an ultraviolet curable resin and an uneven roller, the ultraviolet curable resin is cured by irradiating with ultraviolet rays while pressing the uneven roller on the ultraviolet curable resin. Method (for example, see Patent Documents 9 to 11), production of UV curable resin cured by irradiating the UV curable resin with a concavo-convex type roller and peeling it from the concavo-convex type roller so that the film surface is irradiated with ultraviolet rays. There are two types of methods (for example, see Patent Document 12). However, it has been found that, in any of the production methods, the photopolymerizable resin adheres to the concavo-convex roller and causes the problem of reducing the uniformity of the antiglare film surface.

  Therefore, in order to obtain a stable surface uneven shape, Patent Document 13 discloses a method of curing by electron beam irradiation using an electron beam curable resin, and Patent Document 14 describes a method for degassing an uncured ultraviolet curable resin. The method of using after deaeration by is proposed. However, these methods are not sufficient for solving the above problem.

In addition, antiglare and antireflection films that use an uneven surface shape and an antireflection film due to optical interference have been attracting attention recently for the enlargement of TV screens, but the adhesion to the antireflection layer is good and the antireflection film is difficult to peel off. There is a need for anti-glare antireflection films.
JP 61-76328 A Japanese Patent No. 2556315 Japanese Patent No. 2604691 JP 2004-90187 A JP 2004-106015 A Japanese Patent No. 3192793 Japanese Patent Laid-Open No. 10-119067 JP 2005-156615 A Registration No. 402,025,668 JP 2001-347220 A JP 2003-321559 A Registration No. 2,604,691 JP 2004-352897 A JP 2005-138296 A

  An object of the present invention is to provide a method for producing a surface uneven-shaped optical film and a surface uneven-shaped optical film having few defects on the uneven surface and having improved adhesion to the antireflection layer.

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

(1) After irradiating ultraviolet rays in a state where the ultraviolet curable resin is interposed between the film support and the concavo-convex type roller having the concavo-convex surface and polymerizing and curing the ultraviolet curable resin, the film support and the ultraviolet curable resin are In the method for producing a surface uneven optical film peeled off from the uneven roller,
A method for producing an optical film having a concavo-convex shape, wherein a gas containing substantially no oxygen is present at the time of close contact with the close contact surface between the uneven roller and the ultraviolet curable resin.

  (2) The presence of a gas that does not substantially contain oxygen at the time of close contact with the contact surface between the uneven roller and the ultraviolet curable resin, The method for producing a concavo-convex-shaped optical film as described in (1) above, which is a method of blowing a gas substantially free of oxygen.

  (3) The method for producing a concavo-convex-shaped optical film as described in (2) above, wherein at least one portion of the portion to which the substantially oxygen-free gas is blown is the surface of the concavo-convex roller.

  (4) The ultraviolet curable resin is subjected to a pretreatment in which the substantially oxygen-free gas is blown and mixed into the ultraviolet curable resin before the close contact with the uneven roller (1) )-(3) The manufacturing method of the surface uneven | corrugated shaped optical film any one of claim | items.

  (5) The concave-convex roller is made of quartz glass having a concave-convex surface, and the concave-convex roller is hollow, and the ultraviolet light source is provided in the hollow portion. The manufacturing method of the surface uneven | corrugated shaped optical film of any one of claim | item (4) term | claim.

  (6) The method for producing a concavo-convex shape optical film according to any one of (1) to (5), wherein the gas substantially not containing oxygen is nitrogen gas.

  (7) The antireflection film containing metal oxide fine particles as a solid component in the range of 20 to 90% (mass ratio) is laminated on the surface of the surface uneven optical film (1) The manufacturing method of the surface uneven | corrugated shaped optical film of any one of Claims (6).

  (8) A concavo-convex optical film produced by the method for producing a concavo-convex optical film according to any one of (1) to (7).

  According to the present invention, it is possible to provide a method for producing a surface uneven-shaped optical film and a surface uneven-shaped optical film having few defects on the uneven surface and improved adhesion to the antireflection layer.

  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, the inventor irradiates ultraviolet rays in a state where an ultraviolet curable resin is interposed between a film support and a concavo-convex roller having a concavo-convex surface, and polymerizes and cures the ultraviolet curable resin. In addition, in the method for producing a concavo-convex-shaped optical film in which the ultraviolet curable resin is peeled from the concavo-convex roller, a gas substantially free of oxygen is present at the time of adhesion to the adhesion surface of the concavo-convex roller and the ultraviolet curable resin. It has been found that a method for producing a surface uneven-shaped optical film having a small number of defects on the uneven surface and improved adhesion to the antireflection layer can be obtained by the method for producing a surface uneven-shaped optical film.

  In other words, a space is created when the UV curable resin surface is pressed against the fine rugged surface of the concavo-convex roller, and the oxygen present in the surface or the oxygen contained in the UV curable resin contacts the concavo-convex mold when irradiated with ultraviolet rays. In contrast to the fact that the photopolymerizable resin adheres to the concavo-convex type by inhibiting the curing in the vicinity of the surface, the present invention has no oxygen in the space gas generated when the ultraviolet curable resin surface is pressed against the fine concavo-convex surface of the concavo-convex roller. For this reason, the polymerization reaction is completely performed even in the vicinity of the concavo-convex mold, and as a result, the photopolymerizable resin does not remain attached to the concavo-convex mold. For this reason, it has been found that an optical film having a very uniform surface irregularity shape can be obtained, and that the adhesion with the antireflection layer is further improved.

  Hereinafter, the present invention will be described in detail.

  The manufacturing method of the surface uneven | corrugated shaped optical film using the uneven | corrugated type roller which concerns on this invention with a figure first is illustrated. However, the present invention is not limited to this.

  FIG. 1 is a schematic view of an uneven surface forming apparatus using an uneven roller according to the present invention. An ultraviolet curable resin is coated on the film F fed from the unwinding roll 21 in a layer form with a die 22 and dried with a film drying device 23, and then an ultraviolet curable resin layer is formed with an uneven roller 24 and a back roll 25 facing it. An uneven surface is formed on the surface. At that time, a gas substantially free of oxygen is blown between the concave-convex roller 24 and the ultraviolet curable resin on the film F from the gas spray port 28, and the gas exists on the contact surface of the concave-convex roller and the ultraviolet curable resin. I will let you. Next, it is cured by irradiating with ultraviolet rays with a curing device 26 located at a position facing the concavo-convex roller and wound by a winding roll 27. At this time, it is also preferable to dispose the curing device 26 'and to completely cure by irradiating with ultraviolet rays.

  FIG. 2 is a schematic view of another preferable uneven surface forming apparatus using the uneven roller according to the present invention. According to this figure, a gas substantially free of oxygen is blown into the ultraviolet curable resin layer coating composition 31 in the preparation tank 29 from the gas blowing tube 30, and oxygen contained in the ultraviolet curable resin is converted into an inert gas. Is preferably substituted. Next, an ultraviolet curable resin layer is coated on the film F fed out from the unwinding roll 21 with the die 22 and dried with the film drying device 23, and then the adhesion surface between the ultraviolet curable resin and the concavo-convex roller through the gas blowing port 28. In addition, a gas containing substantially no oxygen is sprayed.

  Further, when the concavo-convex roller is brought into close contact, the gas is not only present on the contact surface between the concavo-convex roller and the ultraviolet curable resin as shown in FIG. It is also preferable to spray the gas in this manner. Further, it is also preferable to dispose a gas blowing port 28 ″ on the peeling side of the film. Next, as in FIG.

  The method of FIG. 3 uses a transparent hollow roller 33 that transmits ultraviolet rays, such as a quartz glass tube, as an uneven roller in the present invention, and an ultraviolet curable resin is provided by installing a curing device 26 such as a high-pressure mercury lamp inside the roll. It is a device that can be cured. The UV curable resin layer preliminarily applied to the film F is brought into close contact with the hollow roller 33 by the rubber nip roll 31, and the gas substantially free of oxygen is sprayed from the gas spray ports 28 and 28 'as in FIGS. On the other hand, the concave / convex shape is formed by the concave / convex mold formed on the circumference of the hollow roller 33, is cured by the ultraviolet ray irradiated by the curing device 26 inside the hollow roller 33, and is peeled off by the peeling roll 32.

  In the present invention, the gas that does not substantially contain oxygen is preferably an inert gas (argon, neon, nitrogen, etc.), and nitrogen gas is most preferable from the viewpoint of cost and convenience (no need for recovery). “Substantially free of oxygen” means that oxygen may be contained but the oxygen content is 1% by mass or less, and preferably no oxygen is contained. The gas supply amount is not particularly limited, but the inert gas supply amount is determined so that the oxygen concentration is 1% by mass or less, preferably the oxygen concentration is less than the measurement limit value in the vicinity of the uneven roller. It is preferable to do.

  Next, the concavo-convex roller used in the present invention will be described.

  The concavo-convex roller is a roller provided with a fine concavo-convex shape on the surface so as to act as a mold for forming concavo-convex on the film surface, but the size and shape are not limited, and plate, film, A belt-shaped or hollow mold may be used.

  As the concavo-convex roller used for forming the concavo-convex surface of the present invention, it is possible to select and apply as appropriate to fine rugged or rough rugged, concave or convex portions that are part of a pattern, mat shape, lenticular lens shape, or spherical surface. In addition, a template in which prisms for forming irregularities are regularly or randomly arranged can be used. For example, a concave portion or a convex portion made of a part of a sphere having a convex portion or a concave portion having a diameter of 5 to 100 μm and a height of 0.1 to 2 μm can be used. preferable.

  FIG. 4 shows a perspective view of an uneven roller and an example of an uneven shape in cross section. As shown in the figure, the embossing member may be formed by combining convex portions and concave portions, and the shape is not limited, and may be a combination of quadrangular pyramid shape, triangular pyramid shape, conical shape, hemispherical convex portion or concave portion. Good. Alternatively, a wave pattern or the like is preferably used. Although the specific example of the uneven | corrugated shaped pattern preferable for this invention is shown in FIG. 5, it is not limited to this, What is necessary is just to have the uneven | corrugated shaped pattern which can reproduce the uneven | corrugated shape of the ultraviolet curable resin layer mentioned later. .

  Further, a concavo-convex portion having a mesh shape may be formed by continuously using a concavo-convex roller having at least two types of concavo-convex shapes such as a first concavo-convex roller and a second concavo-convex roller as shown in FIGS. .

The concave / convex shape of the ultraviolet curable resin layer molded by the concave / convex type roller has a height of 0.1 μm to 2.0 μm or a depth of 0.1 to 2.0 μm based on the average level of the surface. It is preferably formed as a fine structure having 1 to 100 recesses per 100 μm ² .

Fine irregularities on the surface of the ultraviolet curable resin layer can be measured by a commercially available stylus type surface roughness measuring machine or a commercially available optical interference type surface roughness measuring machine. For example, the unevenness is measured in the range of about 4000 μm ² (55 μm × 75 μm) by an optical interference type surface roughness measuring device, and the unevenness is color-coded like contour lines from the bottom side and displayed two-dimensionally.

Here, the number of convex portions or concave portions having a height of 0.1 μm to 2.0 μm based on the average level of the surface can be counted and represented by the number per 100 μm ² area. The measurement is obtained as an average value by measuring 10 arbitrary points per 1 m ² of the antiglare low reflection film.

  Furthermore, the ultraviolet curable resin layer according to the present invention preferably has an average crest / valley spacing of fine irregularities on the surface of 1 μm to 80 μm, and more preferably 10 μm to 40 μm.

  Here, the shape of the fine concavo-convex structure can be measured by a stylus type surface roughness measuring machine or the like. For example, the fine concavo-convex structure is formed via 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. It is possible to obtain knowledge as a surface roughness curve obtained by scanning the surface with a length of 3 mm in a certain direction and measuring the movement change in the vertical direction of the measuring needle in that case. Alternatively, it can be measured by an optical interference type surface roughness measuring machine as described above.

  Here, the average peak-and-valley interval is assumed to be a reference line on which the unevenness change of the surface roughness curve can be evaluated as a protrusion based on a portion where the unevenness change in the surface roughness curve is minute (portion close to flat), Based on the intersection of the surface roughness curve passing from the bottom to the top (or from the top to the bottom) of the surface roughness curve with the average height of the convex part from the reference line as the center line, the distance between the intersections Can be defined as average.

  Moreover, it is preferable that it is a shape which becomes a glare-proof layer whose centerline average roughness (Ra) prescribed | regulated by JISB0601 is about 0.1-1 micrometer. The center line average roughness (Ra) is preferably measured by an optical interference type surface roughness measuring instrument, and can be measured, for example, using a non-contact surface fine shape measuring device WYKO NT-2000 manufactured by WYKO.

  The material of the concavo-convex roller can be metal, stainless steel, carbon steel, aluminum alloy, titanium alloy, ceramic, hard rubber, reinforced plastic, quartz, or a combination of these materials. From this point, the concavo-convex roller is preferably a metal. In particular, ease of cleaning and durability are also important, and it is preferable to use a stainless uneven roller. Further, the surface may be subjected to water repellency or water repellency treatment. As a method of forming a desired concavo-convex surface on the concavo-convex roller, it can be formed using an etching method, a sand blasting method, a mechanical processing method, a laser method, a mold, or the like.

The hollow quartz concave / convex type roller having irregularities formed on the surface illustrated in FIG. 3 can be produced by subjecting the quartz roller to sand blasting or etching with hydrogen fluoride. The quartz roll used in the present invention is made of quartz glass, and the quartz glass is also referred to as fused quartz, silica glass, fused silica, or silicon dioxide (SiO ₂ ). It is a single glass. Density 2.20 g · cm ⁻³ , softening point 1650 ° C., specific heat 0.201 cal · g ⁻¹ , coefficient of thermal expansion is 5.5 to 5.8 × 10 ⁻⁷ / ° C. ing. Refractive index n _D 1.4585, ultraviolet ray transmission ability is large. The quartz roll is produced by melting, cooling, and processing quartz, quartz, quartzite, or quartz sand. Since quartz has a high ultraviolet ray transmitting ability, it can be arranged to irradiate ultraviolet rays from the inside of the concavo-convex roller as in the present invention.

  In order to form an uneven shape on the surface of the quartz roll, it is preferable to perform the following sand plast treatment or etching treatment.

(Sand blasting)
In the sandblast treatment, it is preferable to use blast particles having an average particle size of 10 μm or less at a blast pressure (gauge pressure) of 200 kPa or less. When the average particle diameter of the blast particles exceeds 10 μm, or when the blast pressure exceeds 200 kPa, the depth of the initial fine scratches becomes too deep, which is not preferable. The particle size distribution of the blast particles is preferably as sharp as possible. When the particle size distribution is broad, the homogeneity of the obtained antiglare optical film is lowered, which is not preferable. Examples of the blast particles include Sumiko Random AA-5 (average particle size 5 μm) and Sumiko Random AA-18 (average particle size 18 μm) manufactured by Sumitomo Chemical Co., Ltd.

  Blast particles are sprayed from the tip of the spray nozzle with the force of compressed air or the like over the entire surface of the oscillating concavo-convex roller, and fine concavo-convex is formed on the entire surface of the concavo-convex roller by the blast treatment. It is formed in an eye shape. The amount of rotation and swing of the roll, the amount of blast particles sprayed, and the spraying time may be appropriately selected according to the desired uneven shape.

(Etching process)
In the etching by hydrogen fluoride treatment, the aqueous solution containing hydrogen fluoride to be used is suitably hydrofluoric acid having a concentration of about 1 to 10% by mass (aqueous solution of hydrogen fluoride), more preferably 5 to 10% by mass. Of hydrofluoric acid. When the concentration of hydrogen fluoride exceeds 10% by mass, the in-plane uniformity of the rough surface generated by etching is lowered, which is not preferable. When the concentration of hydrogen fluoride is less than 1% by mass, the etching rate is extremely slow, which is not practical. The etching temperature is preferably about 20 to 50 ° C, more preferably 30 to 40 ° C. An etching temperature lower than 20 ° C. is not preferable because a practical etching rate cannot be obtained. Further, when the etching temperature exceeds 40 ° C., the in-plane uniformity of the rough surface generated by etching is not preferable.

  In order to make the surface uneven, fine scratches may be formed by generating fine scratches on the glass surface by sandblasting and then etching with an aqueous solution containing hydrogen fluoride.

  The eccentricity of the concavo-convex roller is preferably 50 μm or less, more preferably 20 μm or less, and further preferably 0 to 5 μm.

  The diameter of the concavo-convex roller is preferably 5 to 200 cm, more preferably 10 to 100 cm, and particularly preferably 10 to 50 cm.

  In the present invention, when pressing the embossing member on the surface of the UV curable resin to be coated on the support film to process the surface of the coating layer, the embossing member is applied before or during curing after the coating layer is applied. After pressing to provide an uneven shape, it is cured by ultraviolet irradiation or heat. For this reason, it is preferable to perform the temperature at the time of uneven | corrugated formation in the range of 0-100 degreeC. It is also preferable that the uneven roller has a temperature adjusting mechanism.

  The uneven shape forming treatment speed is preferably 0.3 m / min or more and 10 m / min or less, and more preferably 0.5 m / min or more and 5 m / min or less.

  A back roll as a support member is preferably disposed at a position facing the concavo-convex roller of the present invention. The back roll is made of an elastic member, and the elastic member is preferably rubber hardness according to JIS K 6253. A plastic or rubber material of 15 to 90 °, preferably 20 to 50 ° is preferable. For example, silicone rubber is preferable, and a product having a hardness of 40 to 80 ° is obtained. By using such an elastic member, when the film support and the ultraviolet curable resin are nipped between the uneven roller and the back roll, the pressure pressing the ultraviolet curable resin layer constitutes the film and the back roll. Absorbed and dispersed by the elastic member, and the pressure dispersion can prevent the ultraviolet curable resin layer from cracking.

  When the hardness of the elastic member constituting the back roll is 90 ° or higher, the pressure dispersion does not occur, and defects due to dust or dust are not reduced on the viewing side. Moreover, defects such as cracks are likely to appear due to the pressing of the embossed member from the back surface. Further, at a low hardness of 15 ° or less, it is difficult to make unevenness following the unevenness by the embossing member, and even if the pressing (linear pressure) is increased, sufficient unevenness cannot be formed.

  The ultraviolet curable resin coating apparatus is not limited to the extrusion method shown in FIG. 1, but includes a dip coating method, an air knife coating method, a curtain coating method, a roller coating method, a rod coating method, a gravure coating method, an inkjet method, and the like. Existing application equipment can be used.

  The drying device 23 may be any drying method such as a convection drying method using hot air or a radiant drying method using radiant heat such as infrared rays. As a method for conveying the film support F in the drying device, a contact conveyance method such as roller conveyance, air, etc. Or a non-contact method of conveying while floating with gas.

  In the present invention, it is also preferable to use a static eliminator, and those described in paragraph numbers [0028] to [0032] and [0034] to [0035] of JP-A No. 2001-129839 are preferably used. It is preferable to install a static elimination bar such as SJ-B01 manufactured by Keyence Corporation in the vicinity of the embossing-forming pressing member roll in order to prevent adsorption of dust and the like due to static electricity and to form a uniform uneven surface on the web. Moreover, since the film fracture | rupture in an uneven | corrugated formation part reduces, it is used preferably.

[UV curable resin layer]
The present invention irradiates ultraviolet rays in a state in which an ultraviolet curable resin is interposed between a film support and an uneven roller having an uneven surface, polymerizes and cures the ultraviolet curable resin, and then the film support and the ultraviolet curable resin. It is characterized in that a surface irregularity-shaped optical film is produced by peeling the film from the irregularity roller.

The UV curable resin layer refers to a layer mainly composed of a resin that is cured through a crosslinking reaction or the like by UV irradiation. As the ultraviolet curable resin, a component containing a monomer having an ethylenically unsaturated double bond is preferably used, and an ultraviolet curable resin layer is formed by being cured by irradiation with ultraviolet rays. An ultraviolet curable urethane acrylate resin, an ultraviolet curable polyester acrylate resin, an ultraviolet curable epoxy acrylate resin, an ultraviolet curable polyol acrylate resin, an ultraviolet curable epoxy resin, or the like is preferably used. Of these, ultraviolet curable acrylate resins are preferred.

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

  As examples of the ultraviolet curable epoxy acrylate resin and the ultraviolet curable epoxy resin, an epoxy ultraviolet reactive compound to be used is 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. I can do it.

  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 by ultraviolet 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-based ultraviolet reactive compound is a compound capable of releasing a cationic polymerization initiator by ultraviolet irradiation, and particularly preferably has a cationic polymerization initiating ability by irradiation. It is a group of double salts that release certain Lewis acids.

  The UV-reactive compound epoxy resin forms a polymerized, crosslinked structure or network structure by cationic polymerization, not by radical polymerization. Unlike radical polymerization, it is not affected by oxygen in the reaction system, so it is a preferable ultraviolet reactive resin.

  The UV-reactive epoxy resin useful in the present invention is polymerized by a photopolymerization initiator or photosensitizer that releases a substance that initiates cationic polymerization by UV irradiation. 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)
[(R ₁ ) _a (R ₂ ) _b (R ₃ ) _c (R ₄ ) _d Z] ^{w +} [MeX _v ] ^w-
Wherein cation is onium, Z is S, Se, Te, P, As, Sb, Bi, O, halogen (eg I, Br, Cl), or N = N (diazo), R ₁ , R ₂ , R ₃ and R ₄ are organic groups which may be the same or different. a, b, c, and d are each an integer of 0 to 3, and a + b + c + d is equal to the valence of Z. Me is a metal or metalloid which is a central atom of a halide complex, and B, P, As, Sb, Fe, Sn, Bi, Al, Ca, In, Ti, Zn, Sc, V, Cr, Mn, Co, etc. X is halogen, w is the net charge of the halogenated complex ion, and v is the number of halogen atoms in the halogenated complex ion.

Specific examples of the anion [MeX _v ] ^w− of the general formula (a) include tetrafluoroborate (BF ₄ ⁻ ), tetrafluorophosphate (PF ₄ ⁻ ) and the like.

Other anions include perchlorate ion (ClO ₄ ⁻ ), trifluoromethyl sulfite ion (CF ₃ SO ₃ ⁻ ), toluene sulfonate ion, and the like.

  Among these onium salts, it is particularly effective to use an aromatic onium salt as a cationic polymerization initiator, and among them, a VIA group aromatic onium salt, an oxosulfoxonium salt, an aromatic diazonium salt, a thiopyrylium salt, and the like are preferable. . 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 ultraviolet 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 this UV-reactive compound is sufficient to initiate the photoreaction at 0.1 to 15 parts by mass with respect to 100 parts by mass of the UV-reactive compound, preferably Is 1-10 parts by mass. The sensitizer preferably has an absorption maximum from the near ultraviolet region to the visible light region.

  In the ultraviolet curable resin composition useful in the present invention, the polymerization initiator is generally preferably used in an amount of 0.1 to 15 parts by mass with respect to 100 parts by mass of the ultraviolet curable epoxy resin (prepolymer). More preferably, addition in the range of 1 part by mass to 10 parts by mass is preferable.

  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 ultraviolet radical polymerization initiator and an ultraviolet cationic polymerization initiator in combination.

  Moreover, an oxetane compound can also be used for the ultraviolet curable resin layer which concerns on this invention.

In the ultraviolet curable resin layer according to the present invention, a binder such as a known thermoplastic resin, thermosetting resin, or hydrophilic resin such as gelatin can be mixed with the above-described ultraviolet curable resin. These resins preferably have a polar group in the molecule. Examples of the polar _{group, -COOM, -OH, -NR 2,} -NR 3 X, -SO 3 M, -OSO 3 M, -PO 3 M 2, -OPO 3 M ( wherein, M represents a hydrogen atom, an alkali A metal or an ammonium group, X represents an acid forming an amine salt, R represents a hydrogen atom or an alkyl group).

As the ultraviolet light source for photopolymerizing the ultraviolet reactive compound used in the present invention, 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, or the like can also be used. Irradiation conditions vary depending on each lamp, but the irradiation light amount is preferably 20 mJ / cm ² or more, more preferably 50 mJ / cm ^{2 to} 10000 mJ / cm ² , and particularly preferably 50 mJ / cm ^{2 to} 2000 mJ / cm ^2. It is.

  Moreover, when irradiating an ultraviolet-ray, it is preferable to apply | coat tension | tensile_strength in the conveyance direction of a film, and the tension | tensile_strength to provide is preferable 30-300 N / m. The method for applying tension is not particularly limited, and tension may be applied in the transport direction on the back roll.

  In order to initiate the photopolymerization or photocrosslinking reaction of the UV curable resin used in the present invention, the UV curable resin alone is started. However, since the polymerization induction period is long or the polymerization start is delayed, the photointensification is started. It is preferable to use a sensitizer or a photoinitiator, whereby the polymerization can be accelerated.

(Photoinitiator, photosensitizer)
In the ultraviolet curable resin according to the present invention, a photoreaction initiator and a photosensitizer can be used at the time of ultraviolet irradiation.

  Specific examples include acetophenone, benzophenone, hydroxybenzophenone, Michler's ketone, α-amyloxime ester, thioxanthone, and derivatives thereof. Moreover, when using a photoreactant for the synthesis | combination of an epoxy acrylate-type resin, sensitizers, such as n-butylamine, a triethylamine, a tri-n-butylphosphine, can be used. The amount of the photoreaction initiator and / or photosensitizer contained in the ultraviolet curable resin composition excluding the solvent component that volatilizes after coating and drying is preferably 1% by mass to 10% by mass, particularly preferably. Is 2.5% by mass to 6% by mass.

  Moreover, when using an ultraviolet curable resin as an ultraviolet curable resin, you may include the ultraviolet absorber mentioned later in the ultraviolet curable resin composition to such an extent that the photocuring of the said ultraviolet curable resin is not prevented.

(Antioxidant)
In order to increase the heat resistance of the ultraviolet curable resin layer, an antioxidant that does not inhibit the photocuring reaction can be selected and used. For example, hindered phenol derivatives, thiopropionic acid derivatives, phosphite derivatives and the like can be mentioned. Specifically, for example, 4,4′-thiobis (6-tert-3-methylphenol), 4,4′-butylidenebis (6-tert-butyl-3-methylphenol), 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) mesitylene, di-octadecyl-4- Examples thereof include hydroxy-3,5-di-tert-butylbenzyl phosphate.

  Examples of the ultraviolet curable resin include Adekaoptomer KR, BY series KR-400, KR-410, KR-550, KR-566, KR-567, BY-320B (above, manufactured by 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, SCR900 )), KRM7033, KRM7039, KRM7130, KRM7131, UVECRYL29201, UVECRYL29202 (above, Daicel UC Corporation), RC-5015, RC-5016, RC-5020, RC-5031, RC-5100, RC-5102 RC-5120, RC-5122, RC-5152, RC-5171, RC-5180, RC-5181 (manufactured by Dainippon Ink & Chemicals, Inc.), Aulex No. 340 clear (manufactured by China Paint Co., Ltd.), Sun Rad H-601 (manufactured by Sanyo Chemical Industries, Ltd.), SP-1509, SP-1507 (above, Showa Polymer Co., Ltd.), RCC-15C (Grace Japan Co., Ltd.), Aronix M-6100, M-8030, M-8060 (manufactured by Toagosei Co., Ltd.), or other commercially available products can be used as appropriate.

  The coating composition containing the ultraviolet curable resin preferably has a solid content concentration of 10% by mass to 95% by mass, and an appropriate concentration is selected depending on the coating method.

(Surfactant)
The ultraviolet curable resin layer according to the present invention may contain a surfactant. As the surfactant, a silicon-based or fluorine-based surfactant is preferable.

  As the silicon-based surfactant, a nonionic surfactant having a hydrophobic group composed of dimethylpolysiloxane and a hydrophilic group composed of polyoxyalkylene is preferable.

  A nonionic surfactant is a generic term for system 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 ( Polyoxyethylene) 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 according to the present invention is characterized by having 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, the unevenness of the ultraviolet curable resin layer and the low refractive index layer and the antifouling property 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 so as to cover the surface of the silica fine particle at a plurality of locations 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.

  As the fluorine-based surfactant, a surfactant having a hydrophobic group having a perfluorocarbon chain can be used. As types, fluoroalkylcarboxylic acid, N-perfluorooctanesulfonyl glutamate disodium, sodium 3- (fluoroalkyloxy) -1-alkylsulfonate, 3- (ω-fluoroalkanoyl-N-ethylamino) -1- Sodium propanesulfonate, N- (3-perfluorooctanesulfonamido) propyl-N, N-dimethyl-N-carboxymethyleneammonium betaine, perfluoroalkylcarboxylic acid, perfluorooctanesulfonic acid diethanolamide, perfluoroalkylsulfonic acid Salt, N-propyl-N- (2-hydroxyethyl) perfluorooctanesulfonamide, perfluoroalkylsulfonamidopropyltrimethylammonium salt, perfluoroalkyl-N-ethyl Ruhonirugurishin salts, phosphoric acid bis (N- perfluorooctylsulfonyl -N- ethylamino ethyl) and the like. In the present invention, nonionic surfactants are preferred.

  These fluorosurfactants are commercially available under the trade names such as Megafac, F-Top, Surflon, Footagen, Unidyne, Florard, Zonyl and the like.

  A preferable addition amount is 0.01 to 3.0%, more preferably 0.02 to 1.0%, based on the solid content contained in the coating solution of the ultraviolet curable resin layer.

  However, other surfactants may be used in combination, and as appropriate, for example, anionic surfactants such as sulfonates, sulfates, and phosphates, and polyoxyethylene chain hydrophilic groups A nonionic surfactant such as an ether type or an ether ester type may be used in combination.

(Method for producing UV curable resin layer)
When the ultraviolet curable resin layer according to the present invention is applied, a solvent may be contained, or it may be appropriately contained and diluted as necessary. Examples of the organic solvent contained in the coating solution include hydrocarbons (toluene, xylene), alcohols (methanol, ethanol, isopropanol, butanol, cyclohexanol), ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone), It can be appropriately selected from esters (methyl acetate, ethyl acetate, methyl lactate), glycol ethers, and other organic solvents, or a mixture thereof can be used. Propylene glycol monoalkyl ether (1 to 4 carbon atoms of the alkyl group) or propylene glycol monoalkyl ether acetate ester (1 to 4 carbon atoms of the alkyl group) is 5% by mass or more, more preferably 5 to 80%. It is preferable to use the organic solvent containing at least mass%.

  As a method for applying the ultraviolet curable resin layer composition coating solution, a known method such as a gravure coater, a spinner coater, a wire bar coater, a roll coater, a reverse coater, an extrusion coater or an air doctor coater can be used. The coating amount is suitably 5 μm to 30 μm, preferably 10 μm to 20 μm in terms of wet film thickness. The dry film thickness is preferably from 0.1 to 20 μm, more preferably from 3 to 10 μm. The coating speed is preferably 10 m / min to 60 m / min.

  The ultraviolet curable resin layer composition is applied and dried, and then cured by ultraviolet irradiation. The irradiation time of the ultraviolet rays is preferably 0.5 seconds to 5 minutes, and more preferably 3 seconds to 2 minutes from the viewpoint of curing efficiency and work efficiency of the ultraviolet curable resin.

(Fine particles)
The ultraviolet curable resin layer thus obtained may contain fine particles of an inorganic compound or an organic compound in order to adjust the scratch resistance, slipperiness and refractive index, and to adjust the antiglare property.

  In the present invention, the surface uneven shape is basically formed by pressing the uneven roller. However, it is also possible to use a method of adding fine particles for the purpose of forming irregularities in an ultraviolet curable resin layer that is generally used.

  In addition, the fine particles are reflected when the antireflection layer is laminated for the purpose of preventing the occurrence of blocking in the wound state, improving the adhesion with the antireflection layer, or increasing the refractive index of the UV curable resin layer of the substrate. It can be contained in the ultraviolet curable resin layer for various purposes such as to contribute to reducing the rate, to impart an antistatic function, and to reduce charging during transportation. In this case, it is preferable to obtain the above effect by adding a small amount of fine particles and not to cause an increase in haze.

  Examples of inorganic fine particles used in the UV curable resin layer include silicon oxide, titanium oxide, aluminum oxide, tin oxide, indium oxide, ITO, zinc oxide, zirconium oxide, magnesium oxide, calcium carbonate, calcium carbonate, talc, clay, and firing. Mention may be made of kaolin, calcined calcium silicate, hydrated calcium silicate, aluminum silicate, magnesium silicate and calcium phosphate. In particular, silicon oxide, titanium oxide, aluminum oxide, zirconium oxide, magnesium oxide and the like are preferably used.

  Organic particles include polymethacrylic acid methyl acrylate resin powder, acrylic styrene resin powder, polymethyl methacrylate resin powder, silicon resin powder, polystyrene resin powder, polycarbonate resin powder, benzoguanamine resin powder, and melamine resin powder. Polyolefin resin powder, polyester resin powder, polyamide resin powder, polyimide resin powder, or polyfluorinated ethylene resin powder can be added to the ultraviolet curable resin composition. Particularly preferred are cross-linked polystyrene particles (for example, SX-130H, SX-200H, SX-350H, manufactured by Soken Chemical) and polymethyl methacrylate-based particles (for example, MX150, MX300, manufactured by Soken Chemical).

  The average particle size of these fine particle powders is preferably 0.01 to 5 μm, more preferably 0.1 to 5.0 μm, and particularly preferably 0.1 to 4.0 μm. Moreover, it is preferable to contain 2 or more types of microparticles | fine-particles from which a particle size differs. The proportion of the ultraviolet curable resin composition and the fine particles is desirably blended so as to be 0.1 to 30 parts by mass with respect to 100 parts by mass of the resin composition.

  The refractive index of the ultraviolet curable resin layer according to the present invention is preferably 1.5 to 2.0, particularly preferably 1.6 to 1.7 from the viewpoint of optical design for obtaining a low-reflective film. The refractive index of the ultraviolet curable resin layer can be adjusted depending on the refractive index and content of the fine particles to be added or the inorganic binder.

  In addition, it is particularly preferable to add a silicon compound to the ultraviolet curable resin layer composition coating solution. For example, 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 2,000 to 50,000. When the number average molecular weight is less than 1,000, the coating film is dried. On the contrary, when the number average molecular weight exceeds 100,000, it tends to be difficult to bleed out on the surface of the coating film.

  Commercially available silicon compounds include DKQ8-779 (trade name, manufactured by Dow Corning), SF3771, SF8410, SF8411, SF8419, SF8421, SF8428, SH200, SH510, SH1107, SH3749, SH3771, BX16-034, SH3746, SH3749, SH8400, SH3771M, SH3772M, SH3773M, SH3775M, BY-16-837, BY-16-839, BY-16-869, BY-16-870, BY-16-004, BY-16-891, BY-16 872, BY-16-874, BY22-008M, BY22-012M, FS-1265 (above, product names manufactured by Toray Dow Corning Silicone), KF-101, KF-100T, KF351, KF3 2, KF353, KF354, KF355, KF615, KF618, KF945, KF6004, Silicone X-22-945, X22-160AS (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), XF3940, XF3949 (trade name, manufactured by Toshiba Silicone Co., Ltd.) ), Disparon LS-009 (manufactured by Enomoto Kasei Co., Ltd.), Granol 410 (manufactured by Kyoeisha Oil Chemical Co., Ltd.), TSF4440, TSF4441, TSF4445, TSF4446, TSF4452, TSF4460 (manufactured by GE Toshiba Silicone), BYK-306, BYK- 330, BYK-307, BYK-341, BYK-344, BYK-361 (manufactured by BYK-Japan), L series, Y series, FZ series, etc. manufactured by Nippon Unicar Co., Ltd. are preferably used.

  These components enhance the applicability to the substrate and the lower layer. When added to the outermost surface layer of the laminate, it not only improves the water repellency, oil repellency and antifouling properties of the coating film, but also exhibits an effect on the scratch resistance of the surface. These components are preferably added in a range of 0.01 to 3% by mass with respect to the solid component in the coating solution.

  The ultraviolet curable resin layer of the present invention may contain conductive metal oxide fine particles. The conductive metal oxide fine particles are preferably metal oxide fine particles selected from Zr, Sn, Sb, As, Zn, Nb, In, and Al. Specifically, aluminum oxide, tin oxide, and indium oxide. , ITO (indium tin oxide), zinc oxide, and aluminum silicate. In particular, ITO or the like is preferably used.

  Further, the ultraviolet curable resin layer may have a multilayer structure of two or more layers, and one of the layers may be, for example, a so-called antistatic layer containing the conductive fine particles or an ionic polymer. In addition, a color tone adjusting agent having a color tone adjusting function may be included as a color correction filter for various display elements, or an electromagnetic wave blocking agent or an infrared absorber may be included to have each function. You can also.

[Film support]
As a support (base film) generally used for optical films, cellulose ester film, polyester film, polycarbonate film, polyarylate film, polysulfone (including polyethersulfone) film, polyethylene terephthalate, polyester film such as polyethylene naphthalate , Polyethylene film, polypropylene film, cellophane, cellulose diacetate film, cellulose acetate butyrate film, polyvinylidene chloride film, polyvinyl alcohol film, ethylene vinyl alcohol film, syndiotactic polystyrene film, polycarbonate film, norbornene resin film, polymethyl Pentene film, polyetherketone film, Examples thereof include polyether ketone imide film, polyamide film, fluororesin film, nylon film, cycloolefin polymer film, polymethyl methacrylate film, and acrylic film. A cellulose ester film is preferred because it has good adhesion to the layer, is optically isotropic, and is optically transparent. Among the cellulose ester films, a cellulose triacetate film and a cellulose acetate propionate film are preferable from the viewpoint of production, cost, transparency, isotropic properties, adhesiveness, and the like. Specifically, for example, Konica Minoltak KC8UX2M, KC4UX2M, KC4UY, KC8UT, KC5UN, KC12UR, KC8UCR-3, KC8UCR-4 (above, manufactured by Konica Minolta Opto Co., Ltd.) is preferably used.

(Cellulose ester film)
The cellulose ester used in the present invention is preferably a lower fatty acid ester of cellulose. The lower fatty acid in the lower fatty acid ester of cellulose means a fatty acid having 6 or less carbon atoms. For example, cellulose acetate, cellulose propionate, cellulose butyrate and the like, and JP-A Nos. 10-45804 and 8-231761 , Mixed fatty acid esters such as cellulose acetate propionate and cellulose acetate butyrate as described in US Pat. No. 2,319,052 can be used. Among the above descriptions, the lower fatty acid esters of cellulose particularly preferably used are cellulose triacetate and cellulose acetate propionate. These cellulose esters can be used alone or in combination.

  If the molecular weight of the cellulose ester is too small, the tear strength decreases. However, if the molecular weight is excessively increased, the viscosity of the cellulose ester solution becomes too high, resulting in a decrease in productivity. The molecular weight of the cellulose ester is preferably 70000-200000, more preferably 100,000-200000 in terms of number average molecular weight (Mn).

  In the case of cellulose triacetate, those having an average degree of acetylation (bound acetic acid amount) of 54.0 to 62.5% are preferably used, and more preferably an average degree of acetylation of 58.0 to 62.5%. Cellulose triacetate. When the average degree of acetylation is small, the dimensional change is large, and the polarization degree of the polarizing plate is lowered. When the average degree of acetylation is large, the solubility in a solvent is lowered and the productivity is lowered.

  Preferred cellulose esters other than cellulose triacetate have an acyl group having 2 to 4 carbon atoms as a substituent, and when the substitution degree of acetyl group is X and the substitution degree of propionyl group or butyryl group is Y, the following formula ( It is a cellulose ester containing the cellulose ester which satisfy | fills I) and (II) simultaneously.

Formula (I) 2.6 ≦ X + Y ≦ 3.0
Formula (II) 0 ≦ X ≦ 2.5
Among these, cellulose acetate propionate is particularly preferably used, and it is particularly preferable that 1.9 ≦ X ≦ 2.5 and 0.1 ≦ Y ≦ 0.9. The portion that is not substituted with an acyl group usually exists as a hydroxyl group. These can be synthesized by known methods.

  As the cellulose ester, a cellulose ester synthesized using cotton linter, wood pulp, kenaf or the like as a raw material can be used alone or in combination. In particular, it is preferable to use a cellulose ester synthesized from cotton linter (hereinafter sometimes simply referred to as linter) alone or in combination.

  The cellulose ester film used in the present invention may be either produced by a solution casting method or produced by a melt casting method, but is preferably at least stretched in the width direction, and in particular, solution casting. When the amount of residual solvent after peeling is 3 to 40% by mass in the process, it is preferably stretched 1.01 to 1.5 times in the width direction. More preferably, biaxial stretching is performed in the width direction and the longitudinal direction, and when the amount of the residual solvent is 3 to 40% by mass, the film is stretched by 1.01 to 1.5 times in the width direction and the longitudinal direction, respectively. It is desirable that By carrying out like this, the antireflection film excellent in visibility can be obtained.

  The draw ratio at this time is preferably 1.01 to 1.5 times, and more preferably 1.03 to 1.45 times.

  In the present invention, it is preferable to use a long film, and the long film specifically refers to a film of about 100 to 5000 m. Further, the width of the film is preferably 1.3 m or more, more preferably 1.3 to 4 m, and more preferably 1.3 to 2 m.

  The cellulose ester film used in the present invention is preferably a transparent support having a light transmittance of 90% or more, more preferably 93% or more.

The cellulose ester film support used in the present invention preferably has a thickness of 10 to 100 μm, and its moisture permeability is 200 g / m ² · 24 hours or less at 25 ° C. and 90 ± 2% RH. More preferably, it is 10 to 180 g / m ² · 24 hours or less, and particularly preferably 160 g / m ² · 24 hours or less.

  In particular, it is preferable that the film thickness is 10 to 60 μm and the moisture permeability is within the above range.

  Here, the moisture permeability of a support body can measure the moisture permeability of each sample according to the method of JISZ0208.

(Plasticizer)
The cellulose ester film preferably contains the following plasticizer. Examples of plasticizers include phosphate ester plasticizers, phthalate ester plasticizers, trimellitic acid ester plasticizers, pyromellitic acid plasticizers, glycolate plasticizers, citrate ester plasticizers, and polyesters. A plasticizer, a polyhydric alcohol ester plasticizer, and the like can be preferably used.

  For phosphate plasticizers, triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, octyl diphenyl phosphate, diphenylbiphenyl phosphate, trioctyl phosphate, tributyl phosphate, etc. For phthalate ester plasticizers, diethyl phthalate, dimethoxy For trimellitic acid plasticizers such as ethyl phthalate, dimethyl phthalate, dioctyl phthalate, dibutyl phthalate, di-2-ethylhexyl phthalate, butyl benzyl phthalate, diphenyl phthalate, dicyclohexyl phthalate, tributyl trimellitate, triphenyl trimellitate, triethyl For pyromellitic acid ester plasticizers such as trimellitate, tetrabutylpyromellitate, In the case of glycolate plasticizers such as lupyromelitate and tetraethylpyromellitate, triacetin, tributyrin, ethylphthalylethyl glycolate, methylphthalylethyl glycolate, butylphthalylbutyl glycolate, etc. 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.

  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.

  The polyhydric alcohol ester plasticizer comprises an ester of a divalent or higher aliphatic polyhydric alcohol and a monocarboxylic acid. Examples of preferred polyhydric alcohols include the following, but the present invention is not limited to these. Adonitol, arabitol, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,2-propanediol, 1,3-propanediol, dipropylene glycol, tripropylene glycol, 1,2-butanediol, 1,3-butanediol 1,4-butanediol, dibutylene glycol, 1,2,4-butanetriol, 1,5-pentanediol, 1,6-hexanediol, hexanetriol, 2-n-butyl-2-ethyl-1,3- Examples thereof include propanediol, galactitol, mannitol, 3-methylpentane-1,3,5-triol, pinacol, sorbitol, trimethylolpropane, trimethylolethane, xylitol and the like. In particular, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, sorbitol, trimethylolpropane, and xylitol are preferable. There is no restriction | limiting in particular as monocarboxylic acid used for polyhydric alcohol ester, Well-known aliphatic monocarboxylic acid, alicyclic monocarboxylic acid, aromatic monocarboxylic acid, etc. can be used. Use of an alicyclic monocarboxylic acid or aromatic monocarboxylic acid is preferred in terms of improving moisture permeability and retention. Examples of preferred monocarboxylic acids include the following, but the present invention is not limited thereto. As the aliphatic monocarboxylic acid, a fatty acid having a straight chain or a side chain having 1 to 32 carbon atoms can be preferably used. It is more preferable that it is C1-C20, and it is especially preferable that it is C1-C10. When acetic acid is contained, the compatibility with the cellulose ester is increased, and it is also preferable to use a mixture of acetic acid and another monocarboxylic acid. Preferred aliphatic monocarboxylic acids include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, 2-ethyl-hexanecarboxylic acid, undecylic acid, lauric acid, tridecylic acid, Saturated fatty acids such as myristic acid, pentadecylic acid, palmitic acid, heptadecylic acid, stearic acid, nonadecanoic acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, heptacosanoic acid, montanic acid, melicic acid, laccelic acid, undecylenic acid, olein Examples thereof include unsaturated fatty acids such as acid, sorbic acid, linoleic acid, linolenic acid, and arachidonic acid. Examples of preferred alicyclic monocarboxylic acids include cyclopentane carboxylic acid, cyclohexane carboxylic acid, cyclooctane carboxylic acid, or derivatives thereof. Examples of preferred aromatic monocarboxylic acids include those in which an alkyl group is introduced into the benzene ring of benzoic acid such as benzoic acid and toluic acid, and two or more benzene rings such as biphenylcarboxylic acid, naphthalenecarboxylic acid, and tetralincarboxylic acid. And aromatic monocarboxylic acids possessed by them, or derivatives thereof. Particularly preferred is benzoic acid. Although there is no restriction | limiting in particular in the molecular weight of a polyhydric alcohol ester, It is preferable that it is the range of molecular weight 300-1500, and it is further more preferable that it is the range of 350-750. The larger one is preferable in terms of improvement in retention, and the smaller one is preferable in terms of moisture permeability and compatibility with cellulose ester.

  The carboxylic acid used for the polyhydric alcohol ester may be one kind or a mixture of two or more kinds. Moreover, all the OH groups in the polyhydric alcohol may be esterified with carboxylic acid, or a part of the OH groups may be left as they are.

  These plasticizers are preferably used alone or in combination.

  The amount of these plasticizers used is preferably from 1 to 20% by weight, particularly preferably from 3 to 13% by weight, based on the cellulose ester, in terms of film performance, processability and the like.

(UV absorber)
In the present invention, an ultraviolet absorber is preferably used for the support.

  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. For example, but not limited to.

  As the benzotriazole ultraviolet absorber, a compound represented by the following general formula (A) is preferably used.

In the formula, R ₁ , R ₂ , R ₃ , R ₄ and R ₅ may be the same or different, and are a hydrogen atom, halogen atom, nitro group, hydroxyl group, alkyl group, alkenyl group, aryl group, alkoxyl group, acyloxy Represents a group, aryloxy group, alkylthio group, arylthio group, mono- or dialkylamino group, acylamino group or 5- to 6-membered heterocyclic group, and R ₄ and R ₅ are closed to form a 5- to 6-membered carbocyclic ring May be.

  Moreover, these groups described above may have an arbitrary substituent.

  Although the specific example of the ultraviolet absorber used for this invention is given to the following, this invention is not limited to these.

UV-1: 2- (2'-hydroxy-5'-methylphenyl) benzotriazole UV-2: 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) benzotriazole UV-3 : 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) benzotriazole UV-4: 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl)- 5-Chlorobenzotriazole UV-5: 2- (2'-hydroxy-3 '-(3 ", 4", 5 ", 6" -tetrahydrophthalimidomethyl) -5'-methylphenyl) benzotriazole UV-6: 2,2-methylenebis (4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol)
UV-7: 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole UV-8: 2- (2H-benzotriazol-2-yl) -6 (Linear and side chain dodecyl) -4-methylphenol (TINUVIN171, manufactured by Ciba Specialty Chemicals)
UV-9: Octyl-3- [3-tert-butyl-4-hydroxy-5- (chloro-2H-benzotriazol-2-yl) phenyl] propionate and 2-ethylhexyl-3- [3-tert-butyl- Mixture of 4-hydroxy-5- (5-chloro-2H-benzotriazol-2-yl) phenyl] propionate (TINUVIN109, manufactured by Ciba Specialty Chemicals)
As the benzophenone-based ultraviolet absorber, a compound represented by the following general formula (B) is preferably used.

In the formula, Y represents a hydrogen atom, a halogen atom or an alkyl group, an alkenyl group, an alkoxyl group, and a phenyl group, and these alkyl group, alkenyl group, and phenyl group may have a substituent. A represents a hydrogen atom, an alkyl group, an alkenyl group, a phenyl group, a cycloalkyl group, an alkylcarbonyl group, an alkylsulfonyl group or a —CO (NH) _n-1 —D group, and D represents an alkyl group, an alkenyl group or a substituent. Represents a phenyl group which may have m and n represent 1 or 2.

  In the above, the alkyl group represents, for example, a linear or branched aliphatic group having up to 24 carbon atoms, the alkoxyl group represents, for example, an alkoxyl group having up to 18 carbon atoms, and the alkenyl group has, for example, carbon number An alkenyl group up to 16 represents an allyl group, a 2-butenyl group, or the like. In addition, as substituents to alkyl groups, alkenyl groups, and phenyl groups, halogen atoms such as chlorine atoms, bromine atoms, fluorine atoms, etc., hydroxyl groups, phenyl groups (this phenyl group is substituted with alkyl groups or halogen atoms, etc.) May be used).

  Specific examples of the benzophenone compound represented by the general formula (B) are shown below, but the present invention is not limited thereto.

UV-10: 2,4-dihydroxybenzophenone UV-11: 2,2'-dihydroxy-4-methoxybenzophenone UV-12: 2-hydroxy-4-methoxy-5-sulfobenzophenone UV-13: Bis (2-methoxy -4-hydroxy-5-benzoylphenylmethane)
As the above-mentioned ultraviolet absorbers preferably used in the present invention, benzotriazole-based ultraviolet absorbers and benzophenone-based ultraviolet absorbers that are highly transparent and excellent in preventing deterioration of polarizing plates and liquid crystals are preferable, and unnecessary coloring A benzotriazole-based ultraviolet absorber with a lower content is particularly preferably used.

  In addition, an ultraviolet absorber having a distribution coefficient of 9.2 or more described in Japanese Patent Application No. 11-295209 is excellent in surface quality of the support and excellent in coatability when used in the support. In particular, it is preferable to use an ultraviolet absorber having a distribution coefficient of 10.1 or more.

  Further, the polymer ultraviolet absorber (or ultraviolet ray) described in the general formula (1) or general formula (2) of JP-A-6-148430 and the general formulas (3), (6), and (7) of Japanese Patent Application No. 2000-156039. Absorbable polymers) are also preferably used. As a polymer ultraviolet absorber, PUVA-30M (manufactured by Otsuka Chemical Co., Ltd.) and the like are commercially available.

(Fine particles)
In the present invention, the cellulose ester film preferably contains fine particles. Examples of the fine particles include silicon dioxide, titanium dioxide, aluminum oxide, zirconium oxide, calcium carbonate, kaolin, talc, calcined calcium silicate, and hydration. It is preferable to contain inorganic fine particles such as calcium silicate, aluminum silicate, magnesium silicate, calcium phosphate, and crosslinked polymer fine particles. Of these, silicon dioxide is preferable because it can reduce the haze of the film. The average particle size of the secondary particles of the fine particles is in the range of 0.01 to 1.0 μm, and the content is preferably 0.005 to 0.3% by mass with respect to the cellulose ester. In many cases, fine particles such as silicon dioxide are surface-treated with an organic substance, but such particles are preferable because they can reduce the haze of the film. Preferred organic substances for the surface treatment include halosilanes, alkoxysilanes (particularly alkoxysilanes having a methyl group), silazane, siloxane and the like. The larger the average particle size of the fine particles, the greater the mat effect, and on the contrary, the smaller the average particle size, the better the transparency. Therefore, the average particle size of the preferred primary particles is 5 to 50 nm, more preferably 7 to 16 nm. It is. These fine particles are usually present as aggregates in the cellulose ester film, and it is preferable to form irregularities of 0.01 to 1.0 μm on the surface of the cellulose ester film. Examples of the fine particles of silicon dioxide include Aerosil (Aerosil) 200, 200V, 300, R972, R972V, R974, R202, R812, OX50, TT600 manufactured by Aerosil Co., preferably AEROSIL (Aerosil) 200V, R972, R972V, R974, R202, and R812. Two or more kinds of these fine particles may be used in combination. When using 2 or more types together, it can mix and use in arbitrary ratios. In this case, fine particles having different average particle sizes and materials, for example, AEROSIL (Aerosil) 200V and R972V can be used in a mass ratio of 0.1: 99.9 to 99.9: 0.1. In the present invention, the fine particles may be dispersed together with cellulose ester, other additives, and an organic solvent at the time of preparing the dope, but in a sufficiently dispersed state like a fine particle dispersion separately from the cellulose ester solution. It is preferable to prepare the dope. In order to disperse the fine particles, it is preferably preliminarily dispersed in an organic solvent and then finely dispersed by a disperser (high pressure disperser) having a high shearing force. After that, it is preferable to disperse in a larger amount of organic solvent, merge with the cellulose ester solution, and mix with an in-line mixer to obtain a dope. In this case, an ultraviolet absorbent may be added to the fine particle dispersion to form an ultraviolet absorbent liquid.

  The deterioration inhibitor, the ultraviolet absorber and / or the fine particles may be added together with the cellulose ester and the solvent during the preparation of the cellulose ester solution, or may be added during or after the solution preparation.

(Organic solvent)
The organic solvent useful for forming the dope used in the present invention is a cellulose ester, a compound having at least two aromatic rings, and at least two aromatic rings having a planar structure, and other additives at the same time. Any material that can be dissolved can be used without limitation. For example, as the chlorinated organic solvent, methylene chloride, as the non-chlorinated organic solvent, methyl acetate, ethyl acetate, amyl acetate, acetone, tetrahydrofuran, 1,3-dioxolane, 1,4-dioxane, cyclohexanone, ethyl formate, 2,2,2-trifluoroethanol, 2,2,3,3-hexafluoro-1-propanol, 1,3-difluoro-2-propanol, 1,1,1,3,3,3-hexafluoro- Examples include 2-methyl-2-propanol, 1,1,1,3,3,3-hexafluoro-2-propanol, 2,2,3,3,3-pentafluoro-1-propanol, and nitroethane. Methylene chloride, methyl acetate, ethyl acetate and acetone can be preferably used. Particularly preferred is methyl acetate.

  The dope preferably contains 1 to 40% by mass of an alcohol having 1 to 4 carbon atoms in addition to the organic solvent. When the proportion of alcohol in the dope increases, the web gels, facilitating peeling from the metal support, and when the proportion of alcohol is small, the role of promoting dissolution of cellulose esters in non-chlorine organic solvent systems There is also. Examples of the alcohol having 1 to 4 carbon atoms include methanol, ethanol, n-propanol, iso-propanol, n-butanol, sec-butanol, and tert-butanol. Ethanol is preferred because of the stability, boiling point of these inner dopes, relatively good drying, and no toxicity.

  The concentration of the cellulose ester in the dope is preferably adjusted to 15 to 40% by mass, and the dope viscosity is preferably adjusted to a range of 10 to 50 Pa · s in order to obtain good film surface quality.

(Antireflection layer)
In the present invention, an antireflection film containing metal oxide fine particles as a solid component in the range of 20 to 90% (mass ratio) is provided on the surface of the surface uneven optical film to provide an antiglare antireflection film. Is preferred.

  The antireflection layer used in the present invention will be described.

  For the low refractive index layer used in the present invention, an antireflection film is produced by setting the optical film thickness of the low refractive index layer to λ / 4 with respect to light of wavelength λ. The optical film thickness is an amount defined by the product of the refractive index n and the film thickness d of the layer. The level of the refractive index is largely determined by the metal or compound contained therein, for example, Ti is high, Si is low, F-containing compounds are further low, and the refractive index is set by such a combination. The refractive index and the film thickness can be calculated and calculated by measuring the spectral reflectance.

  The antireflection film which is one of the optical films of the present invention preferably includes a multilayer refractive index layer including a low refractive index layer. An ultraviolet curable resin layer is provided on a transparent cellulose ester film support, and can be laminated in consideration of the refractive index, the film thickness, the number of layers, the layer order, and the like so that the reflectance is reduced by optical interference. The antireflection layer is composed of a combination of a high refractive index layer having a higher refractive index than that of the support and a low refractive index layer having a lower refractive index than that of the support, and particularly preferably from three or more refractive index layers. An antireflection layer comprising three layers having different refractive indexes from the support side, a medium refractive index layer (a layer having a higher refractive index than that of the support or the UV curable resin layer and a lower refractive index than that of the high refractive index layer) ) / High refractive index layer / low refractive index layer are preferably laminated in this order.

  Alternatively, an antireflection layer having a layer structure of four or more layers in which two or more high refractive index layers and two or more low refractive index layers are alternately laminated is also preferably used.

  Examples of preferred layer configurations of the antireflection film according to the present invention are shown below. Here, / indicates that the layers are arranged in layers.

Back coat layer / support / UV curable resin layer / low refractive index layer Back coat layer / support / UV curable resin layer / medium refractive index layer / low refractive index layer Back coat layer / support / UV curable resin layer / high Refractive index layer / Low refractive index layer Back coat layer / Support / UV curable resin layer / Medium refractive index layer / High refractive index layer / Low refractive index layer Back coat layer / Support / Antistatic layer / UV curable resin layer / Medium refractive index layer / High refractive index layer / Low refractive index layer Antistatic layer / Support / UV curable resin layer / Medium refractive index layer / High refractive index layer / Low refractive index layer Back coat layer / Support / UV curable resin Layer / High Refractive Index Layer / Low Refractive Index Layer / High Refractive Index Layer / Low Refractive Index Layer An antifouling layer is further provided on the outermost low refractive index layer so that dirt and fingerprints can be easily wiped off. You can also. As the antifouling layer, fluorine-containing organic compounds are preferably used.

As long as the reflectance can be reduced by optical interference, it is not limited to these layer configurations. The antistatic layer is preferably a layer containing conductive polymer fine particles (for example, crosslinked cation fine particles) or metal oxide fine particles (for example, SnO ₂ , ITO, etc.), and can be provided by coating. Alternatively, a metal oxide layer (ZnO ₂ , SnO ₂ , ITO, or the like) can be provided by atmospheric pressure plasma treatment, plasma CVD, or the like.

<Low refractive index layer>
In the low refractive index layer used in the present invention, the following hollow silica fine particles are preferably used.

(Hollow silica fine particles)
The hollow fine particles are: (I) a composite particle comprising a porous particle and a coating layer provided on the surface of the porous particle, or (II) a cavity inside, and the content is a solvent, gas or porous substance It is a hollow particle filled with. 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 diameter of such hollow spherical fine particles is in the range of 5 to 300 nm, preferably 10 to 200 nm. The hollow spherical fine particles used are appropriately selected according to the thickness of the transparent film to be formed, and are in the range of 2/3 to 1/10 of the film thickness of the transparent film such as the low refractive index layer to be formed. Is desirable. These hollow spherical 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 composite particles enter the inside of the composite particle, the internal porosity is reduced, and the low refractive index effect cannot be obtained sufficiently. 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, when 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 MO _X / SiO ₂ when the silica is expressed by SiO ₂ and the inorganic compound other than silica is expressed in terms of oxide (MO _X ) is 0.0001 to 1.0, Preferably it is in the range of 0.001 to 0.3. It is difficult to obtain a porous particle having a molar ratio MO _X / 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. In addition, when the molar ratio MO _X / SiO _{2 of} the porous particles exceeds 1.0, the ratio of silica decreases, so that the pore volume increases and it is difficult to obtain a material having a lower refractive index. is there.

  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 spherical fine particles, for example, the method for preparing complex oxide colloidal particles disclosed in paragraphs [0010] to [0033] of JP-A-7-133105 is suitably employed.

  The refractive index of the hollow fine particles thus obtained is low because the inside is hollow, and the refractive index of the low refractive index layer used in the present invention using the hollow fine particle is 1.30 to 1.50. It is preferable that it is 1.35-1.44.

  The content (mass) of the hollow silica fine particles having an outer shell layer and porous or hollow inside in the low refractive index layer coating solution is preferably 10 to 80% by mass, more preferably 20 to 60% by mass. It is.

(Tetraalkoxysilane compound or its hydrolyzate)
The low refractive index layer used in the present invention preferably contains a tetraalkoxysilane compound or a hydrolyzate thereof as a sol-gel material.

  As a material for the low refractive index layer used in the present invention, it is also preferable to use a silicon oxide having an organic group in addition to the inorganic silicon oxide. These are generally called sol-gel materials, but metal alcoholates, organoalkoxy metal compounds and hydrolysates thereof can be used. In particular, alkoxysilane, organoalkoxysilane and its hydrolyzate are preferable. Examples of these include tetraalkoxysilane (tetramethoxysilane, tetraethoxysilane, etc.), alkyltrialkoxysilane (methyltrimethoxysilane, ethyltrimethoxysilane, etc.), aryltrialkoxysilane (phenyltrimethoxysilane, etc.), dialkyl. Examples thereof include dialkoxysilane and diaryl dialkoxysilane.

  The low refractive index layer used in the present invention preferably contains the silicon oxide and the following silane coupling agent.

  Specific examples of the silane coupling agent include methyltrimethoxysilane, methyltriethoxysilane, methyltrimethoxyethoxysilane, methyltriacetoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane. Examples include methoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, vinyltrimethoxyethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, and phenyltriacetoxysilane.

  Examples of the silane coupling agent having a disubstituted alkyl group with respect to silicon include dimethyldimethoxysilane, phenylmethyldimethoxysilane, dimethyldiethoxysilane, and phenylmethyldiethoxysilane.

  Specific examples of the silane coupling agent include: Shin-Etsu Chemical Co., Ltd. KBM-303, KBM-403, KBM-402, KBM-403, KBM-1403, KBM-502, KBM-503, KBE-502, KBE- 503, KBM-603, KBE-603, KBM-903, KBE-903, KBE-9103, KBM-802, KBM-803 and the like.

  These silane coupling agents are preferably hydrolyzed with a necessary amount of water in advance. When the silane coupling agent is hydrolyzed, the above-described silicon oxide particles and the surface of the silicon oxide having an organic group easily react, and a stronger film is formed. Moreover, you may add the hydrolyzed silane coupling agent in a coating liquid previously.

  The low refractive index layer can also contain a polymer in an amount of 5-50% by weight. The polymer has a function of adhering fine particles and maintaining the structure of a low refractive index layer including voids. The amount of the polymer used is adjusted so that the strength of the low refractive index layer can be maintained without filling the voids. The amount of the polymer is preferably 10 to 30% by mass of the total amount of the low refractive index layer. In order to adhere the fine particles with the polymer, (1) the polymer is bonded to the surface treatment agent of the fine particles, (2) the fine particles are used as a core, and a polymer shell is formed around the fine particles. It is preferable to use a polymer as the binder.

  The binder polymer is preferably a polymer having a saturated hydrocarbon or polyether as the main chain, and more preferably a polymer having a saturated hydrocarbon as the main chain. The binder polymer is preferably crosslinked. The polymer having a saturated hydrocarbon as the main chain is preferably obtained by a polymerization reaction of an ethylenically unsaturated monomer. In order to obtain a crosslinked binder polymer, it is preferable to use a monomer having two or more ethylenically unsaturated groups. Examples of monomers having two or more ethylenically unsaturated groups include esters of polyhydric alcohols and (meth) acrylic acid (for example, ethylene glycol di (meth) acrylate, 1,4-dichlorohexane diacrylate, pentaerythritol). Tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, Pentaerythritol hexa (meth) acrylate, 1,2,3-cyclohexanetetramethacrylate, polyurethane polyacrylate, polyester polyacrylate), vinylbenzene and its derivatives For example, 1,4-divinylbenzene, 4-vinylbenzoic acid-2-acryloyl ethyl ester, 1,4-divinylcyclohexanone), vinyl sulfone (eg, divinyl sulfone), acrylamide (eg, methylene bisacrylamide) and methacrylamide Can be mentioned.

  Further, the low refractive index layer used in the present invention may be a low refractive index layer formed by crosslinking a fluorine-containing resin that is crosslinked by heat or ionizing radiation (hereinafter also referred to as “fluorine-containing resin before crosslinking”). .

  Preferred examples of the fluorine-containing resin before crosslinking include a fluorine-containing copolymer formed from a fluorine-containing vinyl monomer and a monomer for imparting a crosslinkable group. Specific examples of the fluorine-containing vinyl monomer unit include, for example, fluoroolefins (for example, fluoroethylene, vinylidene fluoride, tetrafluoroethylene, hexafluoroethylene, hexafluoropropylene, perfluoro-2,2-dimethyl-1,3 -Dioxoles, etc.), (meth) acrylic acid partial or fully fluorinated alkyl ester derivatives (for example, Biscoat 6FM (produced by Osaka Organic Chemicals) or M-2020 (produced by Daikin)), fully or partially fluorinated vinyl ethers, etc. Is mentioned. As monomers for imparting a crosslinkable group, glycidyl methacrylate, vinyltrimethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, vinyl glycidyl ether, and other vinyl monomers having a crosslinkable functional group in advance in the molecule. , Vinyl monomers having a carboxyl group, hydroxyl group, amino group, sulfonic acid group, etc. (for example, (meth) acrylic acid, methylol (meth) acrylate, hydroxyalkyl (meth) acrylate, allyl acrylate, hydroxyalkyl vinyl ether, hydroxyalkyl allyl) Ether, etc.). The latter can introduce a crosslinked structure after copolymerization by adding a compound that reacts with a functional group in the polymer and one or more reactive groups. No. 147739. Examples of the crosslinkable group include acryloyl, methacryloyl, isocyanate, epoxy, aziridine, oxazoline, aldehyde, carbonyl, hydrazine, carboxyl, methylol, and active methylene group. When the fluorine-containing copolymer is cross-linked by heating by a cross-linking group that reacts by heating, or a combination of an ethylenically unsaturated group and a thermal radical generator or an epoxy group and a thermal acid generator, the thermosetting type In the case of crosslinking by irradiation with light (preferably ultraviolet rays, electron beams, etc.) by a combination of an ethylenically unsaturated group and a photo radical generator, or an epoxy group and a photo acid generator, etc., it is an ionizing radiation curable type. .

  The proportion of each of the above monomers used to form the fluorinated copolymer before crosslinking is preferably 20 to 70 mol%, more preferably 40 to 70 mol%, more preferably 40 to 70 mol% of the fluorinated vinyl monomer. The amount of the monomer is preferably 1 to 20 mol%, more preferably 5 to 20 mol%, and the other monomer used in combination is preferably 10 to 70 mol%, more preferably 10 to 50 mol%.

  The low refractive index layer used in the present invention is applied by dip coating, air knife coating, curtain coating, roller coating, wire bar coating, gravure coating or extrusion coating (US Pat. No. 2,681,294). Can be formed. Two or more layers may be applied simultaneously. For the method of simultaneous application, US Pat. Nos. 2,761,791, 2,941,898, 3,508,947, 3,526,528 and Yuji Harasaki, Coating Engineering, page 253, It is described in Asakura Shoten (1973).

  The film thickness of the low refractive index layer used in the present invention is preferably 50 to 200 nm, and more preferably 60 to 150 nm.

<High refractive index layer and medium refractive index layer>
In the present invention, it is preferable to provide a high refractive index layer between the concave-convex ultraviolet curable resin permeable layer and the low refractive index layer in order to reduce the reflectance. In addition, it is more preferable to provide a middle refractive index layer between the uneven ultraviolet curable resin permeable layer and the high refractive index layer in order to reduce the reflectance. The refractive index of the high refractive index layer is preferably 1.55 to 2.30, and more preferably 1.57 to 2.20. The refractive index of the medium refractive index layer is adjusted to be an intermediate value between the refractive index of the transparent support and the refractive index of the high refractive index layer. The refractive index of the middle refractive index layer is preferably 1.55 to 1.80. The thickness of the high refractive index layer and the medium refractive index layer 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 haze of the high refractive index layer and the medium refractive index layer is preferably 5% or less, more preferably 3% or less, and most preferably 1% or less. The strength of the high refractive index layer and the medium refractive index layer is preferably H or higher, more preferably 2H or higher, and most preferably 3H or higher, with a pencil hardness of 1 kg.

  The middle refractive index layer is formed by applying a coating solution containing a monomer, oligomer or hydrolyzate of an organic titanium compound represented by the following general formula (1) and drying it. A 2.5 layer is preferred.

General formula (1) Ti (OR ₁ ) ₄
In the formula, R ₁ is preferably an aliphatic hydrocarbon group having 1 to 8 carbon atoms, preferably an aliphatic hydrocarbon group having 1 to 4 carbon atoms. Moreover, the monomer, oligomer, or hydrolyzate thereof of an organic titanium compound reacts like -Ti-O-Ti- when an alkoxide group is hydrolyzed to form a crosslinked structure, thereby forming a cured layer.

Examples of the monomer or oligomer of the organic titanium compound used in the present invention include Ti (OCH ₃ ) ₄ , Ti (OC ₂ H ₅ ) ₄ , Ti (On-C ₃ H ₇ ) ₄ , Ti (O-i- _{C 3 H 7) 4, Ti} (O-n-C 4 H 9) 4, Ti (O-n-C 3 H 7) 4 2-10 mer, Ti (O-i-C 3 H 7) Preferred examples include ₄ to 10 mer of ₄ and 2 to 10 mer of Ti (On-C ₄ H ₉ ) ₄ . These may be used alone or in combination of two or more. Of these _{Ti (O-n-C 3} H 7) 4, Ti (O-i-C 3 H 7) 4, Ti (O-n-C 4 H 9) 4, Ti (O-n-C 3 H 7 ) ₄ to 10-mer and Ti (On-C ₄ H ₉ ) ₄ to 10-mer are particularly preferable.

  It is desirable that the monomer, oligomer or hydrolyzate thereof of the organic titanium compound occupy 50.0% by mass to 98.0% by mass in the solid content contained in the coating liquid. The solid content ratio is more preferably 50% by mass to 90% by mass, and further preferably 55% by mass to 90% by mass. In addition, it is also preferable to add to the coating composition a polymer of an organic titanium compound (a product obtained by crosslinking the organic titanium compound in advance by hydrolysis) or titanium oxide fine particles.

  The high refractive index layer and medium refractive index layer preferably used in the present invention preferably contain metal oxide fine particles in the range of 20 to 90% (mass ratio) as a solid component, and further contain a binder polymer.

  The high refractive index layer and medium refractive index layer preferably contain metal oxide particles as fine particles, and further contain a binder polymer.

  When the organic titanium compound hydrolyzed / polymerized by the coating liquid preparation method and the metal oxide particles are combined, the metal oxide particles and the hydrolyzed / polymerized organic titanium compound are firmly bonded, and the hardness and uniform film of the particles It is possible to obtain a strong coating film having both flexibility.

The metal oxide particles used for the high refractive index layer and the medium refractive index layer preferably have a refractive index of 1.80 to 2.80, and more preferably 1.90 to 2.80. The weight average diameter of the primary particles of the metal oxide particles is preferably 1 to 150 nm, more preferably 1 to 100 nm, and most preferably 1 to 80 nm. The weight average diameter of the metal oxide particles in the layer is preferably 1 to 200 nm, more preferably 5 to 150 nm, still more preferably 10 to 100 nm, and more preferably 10 to 80 nm. Most preferred. The average particle diameter of the metal oxide particles is measured by a light scattering method if it is 20-30 nm or more, and by an electron micrograph if it is 20-30 nm or less. The specific surface area of metal oxide particles, as measured values by the BET method is preferably from 10 to 400 m ² / g, more preferably from 20 to 200 m ² / g, with 30 to 150 m ² / g Most preferably it is.

  Examples of the metal oxide particles include at least one selected from Ti, Zr, Sn, Sb, Cu, Fe, Mn, Pb, Cd, As, Cr, Hg, Zn, Al, Mg, Si, P, and S. Specific examples of the metal oxide include titanium dioxide (eg, rutile, rutile / anatase mixed crystal, anatase, amorphous structure), tin oxide, indium oxide, zinc oxide, and zirconium oxide. Of these, titanium oxide, tin oxide, and indium oxide are particularly preferable. The metal oxide particles are mainly composed of oxides of these metals and can further contain other elements. The main component means a component having the largest content (mass%) among the components constituting the particles. Examples of other elements include Ti, Zr, Sn, Sb, Cu, Fe, Mn, Pb, Cd, As, Cr, Hg, Zn, Al, Mg, Si, P, and S.

  The metal oxide particles are preferably surface-treated. The surface treatment can be performed using an inorganic compound or an organic compound. Examples of inorganic compounds used for the surface treatment include alumina, silica, zirconium oxide and iron oxide. Of these, alumina and silica are preferable. Examples of the organic compound used for the surface treatment include polyols, alkanolamines, stearic acid, silane coupling agents, and titanate coupling agents. Of these, a silane coupling agent is most preferable.

  The ratio of the metal oxide particles in the high refractive index layer and the medium refractive index layer is preferably 5 to 95% by volume, more preferably 20 to 90% by volume, and still more preferably 40 to 85% by volume. is there.

  The metal oxide particles are supplied to a coating solution for forming a high refractive index layer and a medium 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), ester (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 metal oxide particles can be dispersed in the medium using a disperser. Examples of the disperser include a sand grinder mill (for example, 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.

  The high refractive index layer and the medium refractive index layer preferably use a polymer having a crosslinked structure (hereinafter also referred to as a crosslinked polymer) as a binder polymer. Examples of the crosslinked polymer include polymers having a saturated hydrocarbon chain such as polyolefin, and crosslinked products such as polyether, polyurea, polyurethane, polyester, polyamine, polyamide and melamine resin. Among them, a crosslinked product of polyolefin, polyether and polyurethane is preferred, a crosslinked product of polyolefin and polyether is more preferred, and a crosslinked product of polyolefin is most preferred.

  The monomer used for the binder polymer is most preferably a monomer having two or more ethylenically unsaturated groups. Examples of the monomer include an ester of a polyhydric alcohol and (meth) acrylic acid (eg, ethylene glycol di ( (Meth) acrylate, 1,4-dichlorohexanediacrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, dipentaerythritol Tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, pentaerythritol hexa (meth) acrylate, 1,2,3-cyclohexanetetramethacrylate, polyurethane polyacrylate Polyester, polyacrylate), vinylbenzene and its derivatives (eg, 1,4-divinylbenzene, 4-vinylbenzoic acid-2-acryloylethyl ester, 1,4-divinylcyclohexanone), vinylsulfone (eg, divinylsulfone) ), Acrylamide (eg, methylenebisacrylamide), methacrylamide and the like. Commercially available monomers may be used as the monomer having an anionic group and the monomer having an amino group or a quaternary ammonium group. As a commercially available monomer having a commercially available anionic group, KAYAMAPMPM-21, PM-2 (manufactured by Nippon Kayaku Co., Ltd.), Antox MS-60, MS-2N, MS-NH4 (manufactured by Nippon Emulsifier Co., Ltd.) , Aronix M-5000, M-6000, M-8000 series (manufactured by Toagosei Chemical Industry Co., Ltd.), Biscote # 2000 series (manufactured by Osaka Organic Chemical Industry Co., Ltd.), New Frontier GX-8289 (Daiichi Kogyo Seiyaku) NK ester CB-1, A-SA (manufactured by Shin-Nakamura Chemical Co., Ltd.), AR-100, MR-100, MR-200 (manufactured by Eighth Chemical Industry Co., Ltd.), and the like. It is done. Examples of commercially available monomers having a commercially available amino group or quaternary ammonium group include DMAA (manufactured by Osaka Organic Chemical Industry Co., Ltd.), DMAEA, DMAPAA (manufactured by Kojin Co., Ltd.), and Bremer QA (Nippon Yushi Co., Ltd.). ) And New Frontier C-1615 (Daiichi Kogyo Seiyaku Co., Ltd.).

  For the polymerization reaction of the polymer, a photopolymerization reaction or a thermal polymerization reaction can be used. A photopolymerization reaction is particularly preferable. A polymerization initiator is preferably used for the polymerization reaction. For example, the thermal polymerization initiator used in order to form the binder polymer of an ultraviolet curable resin layer, and a photoinitiator are mentioned.

  A commercially available polymerization initiator may be used as the polymerization initiator. In addition to the polymerization initiator, a polymerization accelerator may be used. The addition amount of the polymerization initiator and the polymerization accelerator is preferably in the range of 0.2 to 10% by mass of the total amount of monomers.

  In addition to the above-mentioned components (metal oxide particles, polymer, dispersion medium, polymerization initiator, polymerization accelerator), each layer of the antireflection layer or its coating solution is a polymerization inhibitor, leveling agent, thickener, anti-coloring agent. An agent, an ultraviolet absorber, a silane coupling agent, an antistatic agent or an adhesion promoter may be added.

  In order to accelerate the hydrolysis or curing of the composition containing the metal alkoxide after the coating of the medium to high refractive index layer and the low refractive index layer, it is preferable to irradiate active energy rays. More preferably, the active energy ray is irradiated every time each layer is coated.

The active energy ray is an ultraviolet ray, an electron beam, a γ ray or the like, and can be used without limitation as long as it is an energy source that activates the compound. However, the ultraviolet ray and the electron beam are preferable, and handling is particularly simple and high energy can be easily obtained. In this respect, ultraviolet rays are preferable. 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 individual lamps, irradiation dose is preferably ^{20mJ / cm 2 ~10000mJ / cm 2} , more preferably from ^{100mJ / cm 2 ~2000mJ / cm 2} , particularly preferably 400 mJ / cm ² ~ 2000 mJ / cm ² .

〔Polarizer〕
The polarizing plate used in the present invention can be produced by a general method. The back side of the antiglare antireflection film according to the present invention is subjected to alkali saponification treatment, and is bonded to at least one surface of a polarizing film prepared by immersing and stretching in an iodine solution using a completely saponified polyvinyl alcohol aqueous solution. Is preferred. 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, KC8UY, KC4UY, KC12UR, and above, manufactured by Konica Minolta Opto Co., Ltd.) are preferably used. With respect to the antiglare antireflection film according to the present invention, the polarizing plate protective film used on the other surface has an in-plane retardation Ro of 590 nm, a phase difference of 20 to 70 nm, and Rt of 100 to 400 nm. It is preferable. These can be produced by, for example, the methods described in JP-A-2002-71957 and 2003-170492. 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 antireflection film according to the present invention, a polarizing plate having excellent flatness and a stable viewing angle expansion effect can be obtained.

  The polarizing film, which is the main component of the polarizing plate, is an element that transmits only light having a polarization plane in a certain direction. A typical polarizing film known at present 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 antireflection film according to 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.

  A conventional polarizing plate using an antiglare antireflection film is inferior in flatness, and when a reflection image is seen, a fine wavy unevenness is recognized, and the endurance test under conditions of 60 ° C. and 90% RH shows a wavy shape. On the other hand, the polarizing plate using the antiglare antireflection film according to the present invention was excellent in flatness. Further, even in the durability test under the conditions of 60 ° C. and 90% RH, the wavy unevenness did not increase.

(Image display device)
By incorporating the polarizing plate of the present invention into an image display device, various image display devices with excellent visibility can be produced. The anti-glare antireflection film according to the present invention is of various types such as reflective, transmissive, transflective LCD or TN, STN, OCB, HAN, VA (PVA, MVA), IPS, etc. It is preferably used in the LCD of the type. Further, the antiglare antireflection film according to the present invention is excellent in flatness and is 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 size of 30 or more, especially 30 to 54, there is no white spot at the periphery of the screen, and the effect is maintained for a long time. In particular, the MVA image display device has a remarkable effect. Is recognized. In addition, there was little color unevenness, glare and wavy unevenness, and the eyes were not tired even during long-time viewing.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. Unless otherwise specified, “%” in the examples represents “mass%”.

Example 1
[Preparation of surface uneven optical film 1]
(Preparation of cellulose triacetate film 1)
A transparent cellulose triacetate film 1 was produced using the following dope composition 1 as described below.

<Dope composition 1>
Cellulose triacetate (average degree of acetylation 62.0%) 100 parts by mass Plasticizer (trimethylolpropane tribenzoate) 5 parts by mass Plasticizer (ethylphthalylethyl glycolate) 5 parts by mass UV absorber (2- [5-chloro (2H) -benzotriazol-2-yl] -4-methyl-6- (t-butyl) phenol) 1 part by mass UV absorber (2-[(2H) -benzotriazol-2-yl] -4,6 -Di-t-pentylphenol) 1 part by weight Fine particles (Aerosil R972V, manufactured by Nippon Aerosil Co., Ltd.) 0.3 part by weight Methylene chloride 430 parts by weight Ethanol 90 parts by weight The dope composition was obtained by keeping it at 80 ° C. and completely dissolving it with stirring.

  Next, this dope composition was filtered, cooled, kept at 33 ° C., and uniformly cast on a stainless steel band. On the stainless steel band, the solvent was evaporated until the residual solvent amount reached 80%, and then peeled off from the stainless steel band. The peeled cellulose triacetate film web was evaporated at 50 ° C, the solvent was slit to 1.7m width, and then stretched 1.1 times at 120 ° C in the TD direction (direction perpendicular to the film transport direction) with a tenter. did. The residual solvent amount when starting stretching with a tenter was 20%. Furthermore, after carrying out a high temperature process until the amount of residual solvents becomes 0.1%, conveying a heating zone with many rolls, it slits to 1.5m width, winds by giving a knurling process to both ends of a film, and a film thickness of 80 micrometers A cellulose triacetate film 1 was obtained.

(Coating of UV curable resin layer 1)
The following UV curable resin layer coating solution 1 was applied onto the cellulose triacetate film 1 with a die coater so that the dry film thickness was 10 μm, and then dried until the residual solvent amount of the UV curable resin layer was 2% or less. .

<Ultraviolet curing resin layer coating solution 1>
The following materials were stirred and mixed to obtain an ultraviolet curable resin layer coating solution 1.

Acrylic monomer: KAYARAD DPHA (dipentaerythritol hexaacrylate) 226 parts by mass Irgacure 184 (manufactured by Ciba Specialty Chemicals) 25 parts by mass FZ-2222 (manufactured by Nippon Unicar, 10% propylene glycol monomethyl ether solution) 1 part by mass propylene glycol monomethyl ether 101 Part by mass Ethyl acetate 101 part by mass (formation of irregular shape)
Next, the uneven surface was pressed against the film surface in a plastically deformed state by the following uneven roller to make the film surface uneven. Subsequently, the film surface was irradiated with ultraviolet rays and cured.

<Uneven roller 1>
Concavity and convexity roller 1: quartz glass hollow roller shown in FIG. 3 Groove depth 1 μm, pitch 3 μm on the roller surface, the cross-sectional shape of the groove is FIG. 5A, diameter 300 mm, width 1.4 m
The surface irregularities of the quartz glass hollow roller were produced as follows.

  While rotating and swinging the quartz glass roll, sandblast treatment was performed with a monodispersed alumina crystal “Sumicorundum AA-5” (average particle size 5 μm) manufactured by Sumitomo Chemical Co., Ltd. The blast pressure was 50 kPa and the blast time was 120 seconds. The quartz roll thus sandblasted is ultrasonically cleaned and dried, then dipped in 10% by mass of hydrofluoric acid at 40 ° C. for 1200 seconds, then thoroughly washed with pure water and dried to form a quartz glass cavity. An uneven roller was produced.

Ultraviolet irradiation light source, irradiation conditions: high pressure mercury lamp (HN-64NL manufactured by Nihon Batteries Co., Ltd.), 500 mJ / cm ² , irradiation for 15 seconds Arrangement: see FIG.
The measurement of the refractive index of the antireflection layer and the particle size of the metal oxide fine particles is as follows.

(Refractive index)
The refractive index of each refractive index layer was calculated | required from the measurement result of the spectral reflectance of the spectrophotometer about the sample which coated each layer on the hard coat film produced below. The spectrophotometer uses U-4000 type (manufactured by Hitachi, Ltd.), and after roughening the back side of the measurement side of the sample, light absorption treatment is performed with black spray to prevent reflection of light on the back side. The reflectance in the visible light region (400 nm to 700 nm) was measured under the condition of regular reflection at 5 degrees.

(Particle size of metal oxide fine particles)
As for the particle diameter of the metal oxide fine particles used, 100 fine particles were observed with an electron microscope (SEM), the diameter of a circle circumscribing each fine particle was taken as the particle diameter, and the average value was taken as the particle diameter.

(Medium, low refractive index layer coating)
The following medium refractive index layer coating solution 1 and low refractive index layer coating solution 1 were applied on the ultraviolet curable resin layer of the above film, irradiated with ultraviolet rays, and dried to produce a surface uneven optical film 1.

<Medium refractive index layer coating solution 1>
The following materials were stirred and mixed to obtain a medium refractive index layer coating solution 1.

Conductive zinc antimonate fine particle dispersion (Celnax CX-Z610M-F2, manufactured by Nissan Chemical Industries, solvent MeOH, solid content 60%) 200 parts by mass Dipentaerythritol hexaacrylate (matrix) 50 parts by mass Irgacure 184 (photopolymerization started) Agent) 3 parts by mass γ-methacryloxypropylmethoxysilane (KBM503 manufactured by Shin-Etsu Chemical Co., Ltd.)
8 parts by mass Poly-n-butyl methacrylate (matrix) 5 parts by mass Propylene glycol monomethyl ether (PGME) 720 parts by mass Isopropyl alcohol 1470 parts by mass Methyl ethyl ketone (MEK) 250 parts by mass The thickness of the medium refractive index layer is 78 nm, and the refractive index is 1.62.

<Low refractive index layer coating solution 1>
The following materials were stirred and mixed to obtain a low refractive index layer coating solution 1.

The following tetraethoxysilane hydrolyzate A 59.5 parts by mass The following hollow silica-based fine particle dispersion 35 parts by mass γ-methacryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM503)
5 parts by mass FZ-2222 (Nihon Unicar, 10% propylene glycol monomethyl ether solution) 0.5 parts by mass Isopropyl alcohol 500 parts by mass Propylene glycol monomethyl ether (PGME) 300 parts by mass Methyl ethyl ketone (MEK) 100 parts by mass Low refraction The refractive index layer had a thickness of 95 nm and a refractive index of 1.37.

<Preparation of tetraethoxysilane hydrolyzate A>
Tetraethoxysilane hydrolyzate A was prepared by mixing 58 g of tetraethoxysilane and 114 g of ethanol and adding 60 g of an acetic acid aqueous solution (1%) thereto, followed by stirring at 25 ° C. for 1 hour.

<Preparation of hollow silica-based fine particle dispersion>
A mixture of 100 g of silica sol having an average particle diameter of 5 nm and a SiO ₂ concentration of 20% 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% sodium silicate aqueous solution as SiO ₂ and 9000 g of 1.02% sodium aluminate aqueous solution as Al ₂ O ₃ were simultaneously added to the mother liquor. 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 with a solid content concentration of 20%. (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 3.5%) was added to form a first silica coating layer was obtained. (Process (b))
Next, 1125 g of pure water was added to 500 g of the core particle dispersion formed with the first silica coating layer having a solid content of 13% by washing with an ultrafiltration membrane, and concentrated hydrochloric acid (35.5%) was 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 porous particle dispersion, 500 g of pure water, 1,750 g of ethanol, and 626 g of 28% ammonia water was heated to 35 ° C., and 104 g of ethyl silicate (SiO ₂ 28%) was added. The surface of the porous particles on which the 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 dispersion with a solid content concentration of 20% was prepared by replacing the solvent with ethanol using an ultrafiltration membrane.

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.

[Preparation of surface uneven optical film 2]
In the production of the optical film 1, nitrogen gas was blown into the UV curable resin layer coating solution for 15 minutes, and nitrogen gas was further contacted between the UV curable resin layer and the concavo-convex roller through the gas spray ports 28 and 28 'shown in FIG. The surface uneven | corrugated shaped optical film 2 was produced similarly except having sprayed on the surface and the roller surface.

[Preparation of surface uneven optical film 3]
In the production of the optical film 2, an optical film 3 having an uneven surface was produced in the same manner except that nitrogen gas was not blown into the UV curable resin layer coating solution.

[Preparation of surface uneven optical film 4]
In the production of the cellulose triacetate film 1, the cellulose triacetate film 2 was produced in the same manner except that the ultraviolet absorber was removed, and in the production of the optical film 2 using the same, the following uneven roller and conditions for forming the irregularities were used. Except for the above, a surface uneven optical film 4 was produced in the same manner (formation of uneven shape)
The uneven surface was pressed by the following uneven roller to make the film surface uneven. Subsequently, the film surface was irradiated with ultraviolet rays and cured.

<Uneven roller 2>
Concavity and convexity type roller 2: groove depth 1.5 μm, pitch 5 μm, groove cross-sectional shape as shown in FIG. 5A, diameter 100 mm, width 1.4 m, iron material surface amorphous chrome plating (see FIG. 4 for roller shape)
Ultraviolet irradiation light source, irradiation conditions: high-pressure mercury lamp (HN-64NL manufactured by Nippon Battery Co., Ltd.), 500 mJ / cm ² , irradiation for 15 seconds Arrangement: see FIG. 2 Atmosphere in the vicinity of the concavo-convex roller 2: gas blowing ports 28, 28 ′, 28 "Natural gas is sprayed by [Preparation of surface uneven optical film 5]
In the production of the optical film 4, the surface uneven optical film 5 was produced in the same manner except that nitrogen gas was not blown into the ultraviolet curable resin layer coating solution.

[Preparation of surface uneven optical film 6]
In production of the optical film 5, the ultraviolet curable resin layer coating solution 1 was changed to the following electron beam curable resin coating solution.

<Electron beam curable resin layer coating solution 1>
Dicyclopentadienyl acrylate (M-203 manufactured by Toagosei Co., Ltd.) 58 parts by mass Bis [4- (acryloyloxyethoxy) phenyl] sulfide (TO-2066 manufactured by Toagosei Co., Ltd.) 42 parts by mass 1-hydroxy -Cyclohexyl-phenyl-ketone (manufactured by Ciba Specialty Chemicals, Irgacure 184) 0.5 parts by mass was melt-mixed at 80 ° C. to obtain a coating resin.

  Subsequently, the coating liquid was coated on the surface of the cellulose triacetate film 2 so as to have a dry film thickness of 10 μm using a die coater. The gap between the lips is 500 μm, the clearance between the lip and the substrate is 30 μm, and the liquid temperature is 50 ° C.

  Furthermore, instead of the high-pressure mercury lamp, Min-EB manufactured by Ushio Electric Co., Ltd. was used as an electron beam irradiation device. The acceleration voltage was 55 kV and the irradiation dose was 100 kGy.

Except for these conditions, the surface uneven optical film 6 is the same as the production of the optical film 5.
Was made.

[Evaluation of optical film]
The following evaluation was performed about the obtained surface uneven | corrugated shaped optical films 1-6. Table 1 shows the configuration and evaluation results of the optical film.

(village)
The surface is visually observed for the optical film (before applying the medium refractive index layer coating solution 1 and the low refractive index layer coating solution 1) at the start of production and at the time of 1000 m production after forming an uneven shape. It was evaluated with.

A: Almost no irregularity is observed on the film surface. O: Some irregularity is observed on the film surface, but there is no problem in practical use. X: Many irregularities are observed on the film surface (SW resistance)
A sample was subjected to a load of 200 g / cm ^{2 on} # 0000 steel wool (SW) in an environment of 23 ° C. and 55% RH, and the number of scratches per 1 cm width was measured after 10 reciprocations. In addition, the number of scratches is measured at a place where the number of scratches is the largest among the portions where the load is applied. If it is 10 / cm or less, there is no practical problem, but 5 / cm or less is preferable, and 3 / cm or less is more preferable.

  As is clear from Table 1, it can be seen that the optical films 2 to 5 of the present invention have less unevenness and excellent SW resistance with respect to the optical films 1 and 6 of the comparative examples. In particular, the optical films 2 and 4 of the present invention in which nitrogen was blown into the ultraviolet curable resin coating solution were particularly excellent in unevenness and SW resistance.

  Moreover, even if the optical film of this invention was manufactured continuously, the adhesion of cellulose triacetate was not observed on the concavo-convex roller.

Example 2
According to the following method, the surface uneven-shaped optical films 1, 2, and 4 produced in Example 1, and Konica Minolta Tack KC8UCR-5 (made by Konica Minolta Opto Co., Ltd.), each of which is a retardation film, are each polarizing plate. A polarizing plate was produced using it as a protective film.

(A) Production of Polarizing Film A long polyvinyl alcohol film having a thickness of 120 μm was uniaxially stretched (temperature: 110 ° C., stretch ratio: 5 times). This was immersed in an aqueous solution composed of 0.075 g of iodine, 5 g of potassium iodide, and 100 g of water for 60 seconds, and then immersed in an aqueous solution at 68 ° C. composed 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 long polarizing film.

(B) Production of Polarizing Plate Next, according to the following Steps 1 to 5, the polarizing film and the polarizing plate protective film were bonded together to produce a polarizing plate.

  Step 1: KC8UCR-5 was immersed in a 2 mol / L sodium hydroxide solution at 60 ° C. for 90 seconds, then washed with water and dried. The surface provided with the antireflection layer of the surface uneven optical film was previously protected by attaching a peelable protective film (made of PET).

  Process 2: The above-mentioned polarizing film was immersed for 1 to 2 seconds in the polyvinyl alcohol adhesive tank of 2 mass% of solid content.

  Step 3: Excess adhesive adhered to the polarizing film in Step 2 was lightly removed, and it was sandwiched between KC8UCR-5 subjected to alkali treatment in Step 1 and a surface uneven-shaped optical film, and laminated.

Process 4: It bonded together at the speed | rate of about 2 m / min with the pressure of 20-30 N / cm < ² > with two rotating rolls. At this time, care was taken to prevent bubbles from entering.

  Step 5: The sample prepared in Step 4 in a dryer at 80 ° C. was dried for 2 minutes to prepare a polarizing plate.

  Carefully peel off the polarizing plate on the outermost surface of a commercially available liquid crystal display panel (NEC color liquid crystal display MultiSync LCD1525J: model name LA-1529HM). A sticking image display device was prepared so as to be on the side.

  As a result of the evaluation, the image display device using the surface uneven optical films 2 and 4 of the present invention is superior in antiglare property, and has visibility, color tone, and display as compared with the comparative example using the surface uneven optical film 1 of the comparative example. Both sexes were good.

It is the schematic of the uneven | corrugated surface forming apparatus using the uneven | corrugated roller which concerns on this invention. It is the schematic of another preferable uneven surface forming apparatus using the uneven | corrugated roller which concerns on this invention. It is the schematic of another preferable uneven surface forming apparatus using the uneven | corrugated roller which concerns on this invention. It is an example of the uneven | corrugated shape of a perspective view and a cross section of an uneven | corrugated type | mold roller. It is a specific example of an uneven | corrugated shaped pattern preferable for this invention. It is a schematic diagram of a 1st uneven | corrugated roller and a 2nd uneven | corrugated roller. It is a schematic diagram of a 1st uneven | corrugated roller and a 2nd uneven | corrugated roller.

Explanation of symbols

F film 21 Unwinding roll 22 Die 23 Film drying device 24 Concave roller 25 Back roll 26, 26 'Curing device 27 Winding roll 28, 28', 28 "Gas blowing port 29 Preparation tank 30 Gas blowing tube 31 UV curable resin Layer coating liquid 32 Nip roll 33 Peeling roll 34 Hollow roller

Claims (8)

The ultraviolet curable resin is irradiated between the film support and the concavo-convex type roller having the concavo-convex surface, irradiated with ultraviolet rays, and after the ultraviolet curable resin is polymerized and cured, the film support and the ultraviolet curable resin are converted into the concavo-convex mold. In the method of manufacturing the surface uneven optical film peeled off from the roller,
A method for producing an optical film having a concavo-convex shape, wherein a gas containing substantially no oxygen is present at the time of close contact with the close contact surface between the uneven roller and the ultraviolet curable resin. The presence of a gas that does not substantially contain oxygen at the time of close contact with the contact surface between the uneven roller and the UV curable resin, The method for producing an optical film having a concavo-convex shape according to claim 1, wherein the method comprises spraying a gas not containing oxygen. The method for producing a surface uneven-shaped optical film according to claim 2, wherein at least one portion of the portion to which the gas containing substantially no oxygen is blown is the surface of the uneven roller. The ultraviolet curable resin is subjected to a pretreatment in which the substantially oxygen-free gas is blown and mixed into the ultraviolet curable resin before the adhesion to the concave-convex roller. The manufacturing method of the surface uneven | corrugated shaped optical film of any one of Claims 1. 5. The uneven roller according to claim 1, wherein the uneven roller is made of quartz glass having an uneven surface, the uneven roller is a cavity, and the ultraviolet light source is provided in the cavity. The manufacturing method of the surface uneven | corrugated shaped optical film of any one of Claims 1. The method for producing a surface uneven optical film according to any one of claims 1 to 5, wherein the gas that does not substantially contain oxygen is nitrogen gas. The antireflection film containing metal oxide fine particles as a solid component in a range of 20 to 90% (mass ratio) is laminated on the surface of the surface uneven optical film. The manufacturing method of the surface uneven | corrugated shaped optical film of [1]. A surface irregularity-shaped optical film produced by the method for producing a surface irregularity-shaped optical film according to any one of claims 1 to 7.

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