JP2009036818A - Antiglare film, antiglare antireflection film, polarizing plate and image display device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an antiglare film which has sufficient film strength (abrasion resistance and pencil hardness) of a surface thereof and suppresses deterioration of the film strength even after long-term use, an antiglare antireflection film, a polarizing plate and an image display device. <P>SOLUTION: A haze value of the antiglare film attributable to internal scattering of an antiglare layer in the antiglare film is 50-70% and a haze value attributable to surface scattering is 7-20%. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to an antiglare film, an antiglare antireflection film, a polarizing plate and an image display device, and more specifically, an antiglare film having an antiglare layer having a predetermined internal scattering property and surface scattering property, Antiglare antireflection film having glare layer and low refractive index layer, antiglare layer, antiglare antireflection film having low refractive index layer and high refractive index layer, or antiglare film, antiglare antireflection film The present invention relates to an image display device using a polarizing plate, an anti-glare film, and an anti-glare antireflection film.

  One of the various displays is a liquid crystal display. When pursuing ease of viewing as a display device such as wide viewing angle and high definition of a liquid crystal display, a decrease in contrast due to surface reflection on the surface of the liquid crystal display, that is, the surface of the polarizing plate cannot be ignored. In particular, in car navigation monitors and video camera monitors that are frequently used outdoors, the visibility is significantly reduced due to surface reflection.

  For this reason, anti-reflection coatings are becoming indispensable for the polarizing plates mounted on these devices. For liquid crystal displays that are frequently used outdoors, there are polarizing plates that have undergone anti-glare treatment. The actual situation is being used.

  The antiglare treatment is to blur the outline of the image reflected on the surface, thereby reducing the visibility of the reflected image and reducing the reflection of the reflected image when the display device is used. In general, the surface is roughened by an appropriate method such as sandblasting, embossing roll, chemical etching, etc., and the surface is given a fine uneven structure, the surface is given a fine uneven structure by a mold transfer method, etc., resin There are some in which fine particles are dispersed in a layer to give a fine concavo-convex structure on the surface, and the surface concavo-convex structure is designed to scatter reflected light in the visible light region.

  Among these anti-glare treatments, the method of dispersing fine particles in the resin layer is desirable because it can easily give a fine uneven structure.

  In Patent Document 1, a fine concavo-convex structure is formed on a surface by applying a dispersion liquid in which a radioactive curable resin, fine particles having an average particle size of 10 μm or less and a thixotropic agent are dispersed on a transparent film substrate and drying and curing An example in which an antiglare layer having a thickness is formed has been reported.

  Further, in Patent Document 2, the antiglare layer includes particles having a refractive index difference from that of the resin, and defines the center line average roughness (Ra) and ten-point average roughness (Rz) of the concavo-convex shape on the surface. There has been disclosed a technique that achieves both an effect of reducing reflection of a reflected image in a room and prevention of surface glare.

  However, although the above-mentioned conventional method can reduce the reflection image to some extent, the film strength tends to decrease under conditions of ozone exposure that simulates long-term use in a normal room. I understood.

  On the other hand, when an antiglare film is used for a liquid crystal display, a polarizing film is formed by adsorbing iodine or a dichroic dye to a stretched and oriented polarizing film base film, and then a protective film is formed on both surfaces thereof. Used as a protective film for film. Specifically, it is used by providing an antiglare layer on the uppermost layer of a cellulose ester film such as a triacetate film generally used as a protective film.

  As the polarizing film substrate, polyvinyl alcohol (hereinafter referred to as PVA) and a derivative film thereof are mainly used. Polarizing film is a cellulose ester such as a triacetate film with an antiglare layer to produce high-quality products more efficiently, that is, high speed, mass productivity, high yield, and low cost in the production process. Instead of laminating a film and a polarizing film, a method in which an antiglare layer is first formed on a cellulose ester film such as a triacetate film and then laminated on the polarizing film is generally performed. In addition, when laminating on a polarizing film, the cellulose ester film such as a triacetate film on which an antiglare layer is formed is subjected to alkali saponification treatment in order to improve adhesion to PVA as a polarizing film base film. . However, the above technique has insufficient surface film strength (scratch resistance, pencil hardness) after saponification treatment in the alkali bath.

  About the anti-glare film which prescribed | regulated the haze value resulting from the internal scattering of a glare-proof layer, and the surface scattering, it is disclosed by the following patent documents.

  In Patent Document 3, an antiglare film having at least an antiglare layer on a transparent support, the haze value resulting from internal scattering of the antiglare layer is 0 to 40%, and surface scattering An anti-glare film characterized in that the resulting haze value is 0.3 to 20% is disclosed.

  In patent document 4, it has a layer which has an internal scattering property on a transparent support body, and when the image clarity according to JIS-K7105 is measured with an optical comb width of 0.5 mm, it is 30.0% to 99.99. An optical film is disclosed which is 9%, has a haze value due to surface scattering of less than 3% and a haze value due to internal scattering of 15 to 40%.

  In Patent Document 5, a light diffusion layer comprising a resin film layer containing fine particles and having a fine irregular shape formed on the surface is formed on at least one surface of a transparent substrate. In the light diffusing sheet, the average particle diameter of the fine particles is 2 to 10 μm, the haze value of the light diffusing sheet is 40% or more and 60% or less, and 0.5 mm width optical in JIS-K7105 A light diffusive sheet, wherein the image clarity measured with a comb is 35 to 60.

  In Patent Document 6, in a light diffusing sheet in which a light diffusing layer composed of a resin film layer having a fine unevenness on the surface is formed on at least one surface of a transparent substrate, the following total haze values of the light diffusing sheet are as follows: The ratio of the following internal haze values (internal haze value / total haze value) is 0.5 to 0.8, the total haze value is 35% to 50%, and the internal haze is 20 to 40%. A light diffusing sheet, characterized by being.

However, the above Patent Documents 3 to 6 are all related to optical characteristics such as white blur, contrast, and glare, and are related to suppression of decrease in film strength and decrease in film strength after durability test under ozone exposure. There is no description, and there is no description or mention of any technology related to film strength.
JP-A-10-219136 JP 2000-338310 A JP 2007-45142 A JP 2007-65635 A Japanese Patent No. 3698978 Japanese Patent No. 3703133

  Accordingly, an object of the present invention is to provide an antiglare film, an antiglare antireflection film, which has sufficient surface film strength (abrasion resistance, pencil hardness) and suppresses a decrease in film strength even when used for a long period of time. The object is to provide a polarizing plate and an image display device.

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

1.
An antiglare film having at least an antiglare layer on a transparent film substrate, wherein the haze value resulting from internal scattering of the antiglare layer is 50 to 70%, and the haze value resulting from surface scattering Is an antiglare film characterized by being 7 to 20%.

2.
2. The antiglare film according to 1, wherein the haze value resulting from internal scattering of the antiglare layer is 60 to 70%.

3.
3. The antiglare film according to 1 or 2, wherein the antiglare layer contains translucent fine particles, and the translucent fine particles are fluorine-containing acrylic resin fine particles.

4).
The translucent fine particles are composed of two types having different average particle diameters, the first translucent fine particles have an average particle diameter of 0.01 to 1 μm, and the second translucent fine particles have an average particle diameter of 2 to 6 μm. And the content ratio of the first translucent fine particles and the second translucent fine particles is 1.0: 1.0 to 3.0: 1.0. 3. The antiglare film as described in 3 above.

5).
The antiglare film according to any one of 1 to 4, wherein the transparent film substrate is a cellulose ester film.

6).
6. The antiglare film according to 5, wherein the cellulose ester film contains at least one compound having an acryloyl group represented by the following general formula (Z).

(Wherein R _{31 to} R ₃₅ are the same as or different from each other, and are a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R ₃₆ is a hydrogen atom or a methyl group.)
7).
The antiglare film according to any one of 1 to 6, wherein the antiglare layer is subjected to alkali saponification treatment.

8).
A low refractive index layer containing at least one kind of hollow silica fine particles whose inside is porous or hollow is laminated on the antiglare layer of the antiglare film according to any one of 1 to 7. An antiglare antireflection film characterized by

9.
9. The antiglare antireflection film according to 8, wherein a high refractive index layer is interposed between the antiglare layer and the low refractive index layer.

10.
A polarizing plate characterized by using the antiglare film described in any one of 1 to 7 on one surface.

11.
A polarizing plate characterized by using the antiglare antireflection film according to 8 or 9 on one surface.

12
An image display device comprising the polarizing plate according to 10 or 11.

  According to the present invention, the haze value resulting from internal scattering of the antiglare layer of the antiglare film is 50 to 70%, and the haze value resulting from surface scattering is 7 to 20%. Yes. By this, by controlling the particle size, addition amount, etc. of the light-transmitting fine particles contained in the antiglare layer, it can be adjusted, the surface film strength (scratch resistance, pencil hardness) is sufficient, It is possible to provide an antiglare film, an antiglare antireflection film, a polarizing plate and an image display device in which a decrease in film strength is suppressed even when used for a long time.

  The antiglare film of the present invention has a haze caused by internal scattering (hereinafter referred to as internal haze) of 50 to 70%, more preferably 60% to 70%. Further, haze caused by surface scattering (hereinafter referred to as surface haze) is 7 to 20%, preferably 8 to 20%. By controlling the internal haze and surface haze as described above, it is possible to suppress the decrease in the film strength of the saponification treatment with an alkaline bath and to suppress the decrease in the film strength after an endurance test under ozone exposure that simulates long-term use. . That is, even if it is the above value (57% to 90%) with the total haze obtained by adding the internal haze and the surface haze, the effect of the present invention is not exhibited.

  The control of the surface haze and the internal haze can be adjusted, for example, by controlling the particle size, the addition amount, and the like of the translucent fine particles contained in the antiglare layer of the antiglare film. As a result, it is possible to obtain the effect of suppressing the decrease in the film strength after the saponification treatment with an alkaline bath and the effect of suppressing the decrease in the film strength after the durability test under ozone exposure.

The surface haze and internal haze can be measured by the following procedure.
(1) The total haze value (H) of the film is measured according to JIS-K7136.
(2) A few drops of silicone oil are added to the front and back surfaces of the antiglare layer side of the film. Two glass plates and a film were optically adhered to each other, and the haze was measured in a state where surface haze was removed, and only the silicone oil was sandwiched between two separately measured glass plates, and the measured haze was drawn. The value is calculated as the internal haze (Hi) of the film.
(3) A value obtained by subtracting the internal haze (Hi) calculated in (2) from the total haze (H) measured in (1) above is calculated as the surface haze (Hs) of the film.

  In the antiglare film of the present invention, the image clarity according to JIS-K7105 is preferably 5% to 90%, more preferably 5% to 80%, especially when measured at an optical comb width of 0.5 mm. Preferably, it is 5% to 60%. By setting the content in the above range, sufficient antiglare property, image blur, and reduction in dark room contrast can be achieved.

  Moreover, as surface uneven | corrugated shape of the anti-glare film of this invention, centerline average roughness (arithmetic mean roughness) Ra has preferable 0.03-0.35 micrometer, More preferably, it is 0.08-0.3 micrometer, Especially. Preferably, it is 0.08 to 0.22 μm. Further, the 10-point average roughness Rz is 10 times or less the centerline average roughness Ra, and the average mountain valley distance Sm is preferably 50 to 150 μm, more preferably 50 to 120 μm, and the standard deviation of the height of the protrusion from the deepest part of the unevenness. Is 0.5 μm or less, the standard deviation of the average mountain-valley distance Sm with respect to the center line is preferably 20 μm or less, and the surface with the inclination angle of 0 to 5 degrees is preferably 10% or more. By designing in this way, sufficient antiglare property and whitening can be suppressed. In particular, the centerline average roughness Ra is 0.08 μm or more, and sufficient antiglare properties can be obtained. The smaller the value is 0.3 μm or less, the more the glare and the surface of the surface when external light is reflected. It is good without suppressing problems such as whitening. Ra can be measured with an optical interference type surface roughness measuring instrument, for example, using an optical interference type surface roughness meter RST / PLUS (manufactured by WYKO).

Furthermore, the antiglare film of the present invention may be imparted with an antiglare property by the following method.
(1) A method in which a negative shape having a desired shape is formed on a roll or master, and the shape is given by embossing.
(2) A method in which a negative mold having a desired shape is formed on a roll or a master, a thermosetting resin is filled into the negative mold, and the film is peeled off from the negative mold after heat curing.
(3) A negative shape of the desired shape is formed on a roll or master, and after applying ultraviolet or electron beam curable resin to fill the recess, the transparent film substrate is covered on the intaglio via a resin solution. A method in which a cured resin and a transparent film substrate to which it is adhered are peeled off from a negative mold by irradiation with ultraviolet rays or electron beams.
(4) A solvent casting method in which a negative shape having a desired shape is formed on a casting belt and the desired shape is imparted during casting.
(5) A method in which a resin that is cured by light or heating is relief-printed on a transparent substrate and is cured by light or heating to form irregularities.
(6) A method in which a resin that is cured by light or heating is printed on the surface of the transparent film substrate by an ink jet method, and the surface of the transparent film substrate is made uneven by curing by light or heating.
(7) A method in which a resin that is cured by light or heating is printed on the surface of the transparent film substrate by an ink jet method, and is cured by light or heating to form a concavo-convex shape, and further covered with a transparent resin layer.
(8) A method of cutting the surface with a machine tool or the like.
(9) A method in which particles of various shapes such as spheres and polygons are pressed and integrated so as to be partially buried in the surface of the transparent film substrate to make the surface of the transparent film substrate uneven.
(10) A method in which particles of various shapes such as spheres and polygons are dispersed in a small amount of binder and applied to the surface of the transparent film substrate to make the surface of the transparent film substrate uneven.
(11) A method in which a binder is applied to the surface of a transparent film substrate, and particles of various shapes such as spheres and polygons are dispersed thereon to make the surface of the transparent film substrate uneven.
(12) A method of forming irregularities by pressing a mold against the surface of a transparent film substrate. Specifically, the method described in JP-A-2005-156615.

  Among the methods for forming the concavo-convex shape on the surface of the film substrate, a combination with a method for forming a negative type or an ink jet method is effective.

  In addition, the antiglare property referred to in the present invention is to reduce the visibility of the reflected image by blurring the outline of the image reflected on the surface of the film substrate, and to display an image display device such as a liquid crystal display, an organic EL display, a plasma display, etc. This prevents the reflected image from being reflected when using the projector.

Next, the antiglare layer will be described below.
(Anti-glare layer)
The antiglare layer related to the antiglare film of the present invention preferably contains translucent fine particles in order to impart antiglare properties. Next, the translucent fine particles will be described.
<Translucent fine particles>
The translucent fine particles are preferably composed of two or more kinds of fine particles from the viewpoint of easily achieving internal haze and surface haze within the scope of the present invention. As the constitution of the two or more kinds of fine particles, the first translucent fine particles (also referred to as translucent fine particles 1) having an average particle diameter of 0.01 to 1 μm or less, and the second having an average particle diameter of 2 to 6 μm. A combination with translucent fine particles (also referred to as translucent fine particles 2) is preferable from the viewpoint of achieving the object effect of the present invention.

  The average particle diameter of the translucent fine particles 1 is 0.01 to 1 μm, more preferably 0.05 μm to 1 μm. The average particle diameter of the translucent fine particles 2 is preferably 2 to 6 μm, more preferably 3 to 6 μm.

  By setting the average particle size of the first light-transmitting fine particles to 0.01 to 1 μm, it is easy to control the internal haze, suppress the decrease in the film strength of the saponification treatment with an alkali bath, and the film strength under ozone exposure conditions. The effect of suppressing the decrease is more effectively exhibited. By setting the average particle diameter of the second light-transmitting fine particles to 2 to 6 μm, the light scattering angle distribution is good, and there is no fear of causing character blur of the display. Further, since the film thickness of the antiglare layer does not increase, curling does not increase, and the material cost can be suppressed. In addition, these average particle diameters can be measured, for example with a laser diffraction type particle size distribution measuring apparatus.

  Examples of the second light-transmitting fine particles having an average particle diameter of 2 to 6 μm include acrylic particles, styrene particles or acrylic-styrene particles, melamine particles, benzoguanamine particles, and inorganic particles mainly composed of silica. Preferred examples include fluorine-containing acrylic resin fine particles, poly ((meth) acrylate) particles, cross-linked poly ((meth) acrylate) particles, polystyrene particles, cross-linked polystyrene particles, and cross-linked poly (acryl-styrene) particles. Among these, fluorine-containing acrylic resin fine particles are preferable from the viewpoint of more exerting the object effect of the present invention.

  The fluorine-containing acrylic resin fine particles are fine particles formed from, for example, a fluorine-containing acrylic acid ester or methacrylic acid ester monomer or polymer. Specific examples of the fluorine-containing acrylic ester or methacrylic ester include 1H, 1H, 3H-tetrafluoropropyl (meth) acrylate, 1H, 1H, 5H-octafluoropentyl (meth) acrylate, 1H, 1H, 7H- Dodecafluoroheptyl (meth) acrylate, 1H, 1H, 9H-hexadecafluorononyl (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3,3-pentafluoropropyl (Meth) acrylate, 2- (perfluorobutyl) ethyl (meth) acrylate, 2- (perfluorohexyl) ethyl (meth) acrylate, 2- (perfluorooctyl) ethyl (meth) acrylate, 2-perfluorodecylethyl (Meth) acrylate, 3-par Fluorobutyl-2-hydroxypropyl (meth) acrylate, 3-perfluorohexyl-2-hydroxypropyl (meth) acrylate, 3-perfluorooctyl-2-hydroxypropyl (meth) acrylate, 2- (perfluoro-3-methylbutyl) ) Ethyl (meth) acrylate, 2- (perfluoro-5-methylhexyl) ethyl (meth) acrylate, 2- (perfluoro-7-methyloctyl) ethyl (meth) acrylate, 3- (perfluoro-3-methylbutyl) 2-hydroxypropyl (meth) acrylate, 3- (perfluoro-5-methylhexyl) -2-hydroxypropyl (meth) acrylate, 3- (perfluoro-7-methyloctyl) -2-hydroxypropyl (meth) Acrylate, 1H-1- Trifluoromethyl) trifluoroethyl (meth) acrylate, 1H, 1H, 3H-hexafluorobutyl (meth) acrylate, trifluoroethyl methacrylate, tetrafluoropropyl methacrylate, perfluorooctylethyl acrylate, 2- (perfluorobutyl) ethyl In addition, among the fluorine-containing acrylic resin fine particles, fine particles made of 2- (perfluorobutyl) ethyl-α-fluoroacrylate, fluorine-containing polymethyl methacrylate fine particles, and fluorine-containing methacrylic acid are cross-linked. Fine particles copolymerized with a vinyl monomer in the presence of an agent are preferred, and fluorine-containing polymethyl methacrylate fine particles are more preferred.

  The vinyl monomer copolymerizable with fluorine-containing (meth) acrylic acid is not particularly limited as long as it has a vinyl group. Specifically, alkyl methacrylates such as methyl methacrylate and butyl methacrylate, and methyl acrylate. , Alkyl acrylates such as ethyl acrylate, and styrenes such as styrene and α-methylstyrene. These may be used alone or in combination. The crosslinking agent used in the polymerization reaction is not particularly limited, but those having two or more unsaturated groups are preferably used. For example, bifunctional dimethacrylates such as ethylene glycol dimethacrylate and polyethylene glycol dimethacrylate are used. And trimethylolpropane trimethacrylate, divinylbenzene and the like.

  The polymerization reaction for producing the fluorine-containing polymethyl methacrylate fine particles may be either random copolymerization or block copolymerization. Specifically, for example, the method described in JP-A No. 2000-169658 can also be mentioned.

  As a commercial item, commercial items, such as Negami Industries make: MF-0043, are mentioned. Note that these fluorine-containing acrylic resin fine particles may be used alone or in combination of two or more. Moreover, the state of these fluorine-containing acrylic resin fine particles may be added in any state such as powder or emulsion.

  Moreover, you may use the fluorine-containing crosslinked fine particle as described in Paragraphs 0028-0055 of Unexamined-Japanese-Patent No. 2004-83707.

  Examples of polystyrene particles include commercially available products such as those manufactured by Soken Chemicals; SX-130H, SX-200H, SX-350H), Sekisui Plastics, SBX series (SBX-6, SBX-8).

  Examples of the melamine-based particles include a product made by Nippon Shokubai: benzoguanamine / melamine / formaldehyde condensate (trade name: eposter, grade; M30, product name: eposter GP, grade; H40 to H110), and made by Nippon Shokubai: melamine / formaldehyde condensation. Commercial products such as products (trade name: eposter, grade; S12, S6, S, SC4) can be mentioned. Moreover, the core-shell type spherical composite cured melamine resin particles in which the core is made of a melamine resin and the shell is filled with silica are also exemplified. Specifically, it can be produced by the method described in JP-A-2006-171033, and commercially available products such as melamine resin / silica composite particles (trade name: Opto Beads) manufactured by Nissan Chemical Industries, Ltd. can be mentioned.

  Examples of the poly ((meth) acrylate) particles and the crosslinked poly ((meth) acrylate) particles include, for example, Soken Chemicals; MX150, MX300, Nippon Shokubai; Eposta MA, Grades; MA1002, MA1004, MA1006, MA1010, Epostor MX (Emulsion), grade: MX020W, MX030W, MX050W, MX100W, manufactured by Sekisui Plastics: MBX series (MBX-8, MBX12), and other commercial products.

  Specific examples of the crosslinked poly (acryl-styrene) particles include commercial products such as FS-201 and MG-351 manufactured by Nippon Paint. Examples of the benzoguanamine-based particles include a product manufactured by Nippon Shokubai Co., Ltd .: benzoguanamine / formaldehyde condensate (trade name: eposter, grade; L15, M05, MS, SC25).

  The second light-transmitting fine particles having an average particle diameter of 2 to 6 μm have a content of 100 mass of active energy ray-curable resin, which will be described later, from the stability of the coating liquid for forming the antiglare layer and the dispersibility of the dispersion liquid. The amount is preferably 0.01 to 500 parts by mass, more preferably 0.1 to 100 parts by mass, and particularly preferably 1 to 60 parts by mass with respect to parts.

  Examples of the first light-transmitting fine particles having an average particle diameter of 0.01 to 1 μm include acrylic particles and inorganic particles mainly composed of silica. Examples of the silica particles include product names such as Nippon Aerosil Co., Ltd., Aerosil 200, 200V, 300, Degussa, Aerosil OX50, TT600, Nippon Shokubai Co., Ltd., KEP-10, KEP-50, KEP-100 and the like. Colloidal silica may also be used. Colloidal silica is obtained by dispersing silicon dioxide in water or an organic solvent in a colloidal form, and is not particularly limited, and is spherical, acicular or beaded. Such colloidal silica is commercially available, and examples thereof include the Snowtex series of Nissan Chemical Industries, the Cataloid-S series of Catalytic Chemical Industries, and the Rebacil series of Bayer. Also, beaded colloidal silica in which primary particles of cation-modified with alumina sol or aluminum hydroxide are bonded in a bead shape by bonding the particles with divalent or higher metal ions. Examples of beaded colloidal silica include Snowtex-AK series, Snowtex-PS series, Snowtex-UP series, etc., manufactured by Nissan Chemical Industries, Ltd. Specifically, IPS-ST-L (isopropanol silica sol, particle size 40-50 nm). , Silica concentration 30%), MEK-ST-MS (methyl ethyl ketone silica sol, particle diameter 17-23 nm, silica concentration 35%), etc. MEK-ST (methyl ethyl ketone silica sol, particle diameter 10-15 nm, silica concentration 30%), MEK- ST-L (methyl ethyl ketone silica sol, particle diameter 40-50 nm, silica concentration 30%), MEK-ST-UP (methyl ethyl ketone silica sol, particle diameter 9-15 nm (chain structure), silica concentration 20%) and the like can be mentioned.

  Examples of the acrylic particles include fluorine-containing acrylic resin fine particles. For example, commercially available products such as FS-701 manufactured by Nippon Paint are listed. Examples of the acrylic particles include Nippon Paint: S-4000, and examples of the acrylic-styrene particles include Nippon Paint: S-1200, MG-251.

  Among these first light-transmitting fine particles having an average particle diameter of 0.01 to 1 μm, fluorine-containing acrylic resin fine particles are preferable from the viewpoint of more exerting the object effect of the present invention.

  The first light-transmitting fine particles having an average particle diameter of 0.01 to 1 μm have a translucent resin described later as the content because of the stability of the coating liquid for forming the antiglare layer and the dispersibility of the dispersion liquid. 0.01-500 mass parts is preferable with respect to 100 mass parts, More preferably, it is 0.1-100 mass parts.

  Moreover, the 1st translucent fine particle (translucent fine particle 1) with an average particle diameter of 0.01-1 micrometer and the 2nd translucent fine particle (translucent microparticle 2) with an average particle diameter of 2-6 micrometers The content ratio of translucent fine particles 1: translucent fine particles 2 = 1.0: 1.0 to 3.0: 1.0. By using two kinds of fine particles with different particle diameters and making the content ratio as described above, it is possible to suppress a decrease in film strength after saponification treatment with an alkaline bath or a decrease in film strength after a durability test under ozone exposure. It is preferable in that the effect is better, and is an effect that cannot be known in the prior art.

The translucent fine particles may be added in any state such as powder or emulsion. Moreover, the density of the translucent fine particles is preferably 10 to 1000 mg / m ² , more preferably 100 to 700 mg / m ² .

  For the antiglare layer, ultraviolet rays such as silicone resin powder, polystyrene resin powder, polycarbonate resin powder, polyolefin resin powder, polyester resin powder, polyamide resin powder, polyimide resin powder, or polyfluoroethylene resin powder A curable resin composition can also be added. Moreover, you may contain the microparticles | fine-particles described in Unexamined-Japanese-Patent No. 2000-241807 as needed.

  Further, the refractive index of the translucent fine particles is preferably 1.45 to 1.70, more preferably 1.45 to 1.65. The refractive index of the light-transmitting fine particles was measured by measuring the turbidity by dispersing the same amount of the light-transmitting fine particles in the solvent in which the refractive index was changed by changing the mixing ratio of two types of solvents having different refractive indexes. It can be measured by measuring the refractive index of the solvent when the turbidity is minimized with an Abbe refractometer.

  Further, the difference in refractive index between the translucent fine particles and the translucent resin described later (the refractive index of the translucent fine particles−the refractive index of the translucent resin) is 0.001 to 0.100 as an absolute value, Preferably it is 0.001-0.050, More preferably, it is 0.001-0.040, More preferably, it is 0.001-0.030, Especially preferably, it is 0.001-0.020, Optimally 0. 001 to 0.015. In order to set the refractive index within the above range, the kind and amount ratio of the light-transmitting resin and the light-transmitting fine particles may be appropriately selected. It is preferable to determine experimentally in advance how to select. If it is within the above range, problems such as film character blur, a decrease in dark room contrast, and white turbidity of the surface do not occur.

  Specifically, a combination of a curable acrylate resin having a refractive index of 1.50 to 1.53 after curing of the translucent resin and acrylic translucent fine particles is preferable, and particularly after the translucent resin is cured. Translucent fine particles (with a refractive index of 1.48 to 1.1) composed of a curable acrylate resin having a refractive index of 1.50 to 1.53, acrylic translucent fine particles, and a crosslinked poly (styrene-acrylic) copolymer. 54), a curable acrylate resin having a refractive index of 1.50 to 1.53 after curing of the translucent resin, acrylic translucent fine particles, and fluorine-containing acrylic resin fine particles (refractive index of 1.45). To 1.47) are preferred.

In addition, when the antiglare film of the present invention is used as a display film for a liquid crystal display, the antiglare layer of the antiglare film of the present invention contains a translucent resin because it is difficult to be damaged. It is preferable. Next, the translucent resin will be described.
<Translucent resin>
As a refractive index of translucent resin, it is preferable that it is 1.50 or more, More preferably, it is 1.50-1.70. In order to make the refractive index within the above range, the kind and amount ratio of the translucent resin may be appropriately selected. If the refractive index is less than 1.50, it is difficult to obtain a resin with high hardness. If the refractive index is greater than 1.70, unevenness of the film tends to be noticeable.

  The refractive index of the translucent resin can be quantitatively evaluated by directly measuring it with an Abbe refractometer or measuring a spectral reflection spectrum or a spectral ellipsometry.

  The translucent resin is preferably a binder polymer having a saturated hydrocarbon chain or a polyether chain as a main chain, and more preferably a binder polymer having a saturated hydrocarbon chain as a main chain. Particularly preferred is a resin that cures through a crosslinking reaction or the like by irradiation with active rays such as ultraviolet rays or electron beams.

  Examples of the curable resin include UV curable urethane acrylate resins, UV curable polyester acrylate resins, UV curable epoxy acrylate resins, UV curable polyol acrylate resins, and UV curable epoxy resins. A type acrylate resin is preferably used.

  The UV curable urethane acrylate resin generally includes a product obtained by reacting a polyester polyol with an isocyanate monomer or a prepolymer, and further includes 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate (hereinafter, acrylate includes methacrylate). It can be easily obtained by reacting an acrylate monomer having a hydroxyl group such as 2-hydroxypropyl acrylate. For example, those described in JP 59-151110 A can be used. For example, a mixture of 100 parts Unidic 17-806 (Dainippon Ink Co., Ltd.) and 1 part Coronate L (Nihon Polyurethane Co., Ltd.) is preferably used.

  Examples of UV curable polyester acrylate resins include those which are easily formed when 2-hydroxyethyl acrylate and 2-hydroxy acrylate monomers are generally reacted with polyester polyols. JP-A-59-151112 Those described in the publication can be used. Specific examples of the ultraviolet curable epoxy acrylate resin include an epoxy acrylate as an oligomer, a reactive diluent and a photopolymerization initiator added thereto, and reacted to form an oligomer. Those described in Japanese Patent No. 105738 can be used.

  Specific examples of UV curable polyol acrylate resins include trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, alkyl-modified dipentaerythritol pentaacrylate, etc. Can be mentioned.

  Specific examples of photopolymerization initiators for these curable resins include benzoin and its derivatives, acetophenone, benzophenone, hydroxybenzophenone, Michler's ketone, α-amyloxime ester, thioxanthone, and derivatives thereof. You may use with a photosensitizer. In addition, when using an epoxy acrylate photopolymerization initiator, a sensitizer such as n-butylamine, triethylamine, tri-n-butylphosphine can be used. The photopolymerization initiator or photosensitizer used in the curable resin composition is 0.1 to 25 parts by mass, preferably 1 to 15 parts by mass with respect to 100 parts by mass of the composition.

  As acrylate resins, methyl acrylate, ethyl acrylate, butyl acrylate, benzyl acrylate, cyclohexyl acrylate, ethylene glycol diacrylate, propylene glycol diacrylate, divinylbenzene, 1,4-cyclohexane diacrylate, 1,4-cyclohexyl dimethyl adiacrylate , Trimethylolpropane triacrylate, pentaerythritol tetraacrylic ester and the like.

  As these commercially available products, Adekaoptomer KR / BY series: KR-400, KR-410, KR-550, KR-566, KR-567, BY-320B (manufactured by Asahi Denka Co., Ltd.); 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 Co., Ltd.); Seika Beam PHC2210 (S), PHC X-9 (K-3), PHC2213, DP-10, DP-20, DP-30 , P1000, P1100, P1200, P1300, P1400, P1500, P1600, SCR900 (manufactured by Dainichi Seika Kogyo Co., Ltd.); KRM7033, KRM7 039, KRM 7130, KRM 7131, UVECRYL 29201, UVECRYL 29202 (manufactured by 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 (Dainippon Ink Chemical Co., Ltd.); 340 clear (manufactured by China Paint Co., Ltd.); Sun Rad H-601, RC-750, RC-700, RC-600, RC-500, RC-611, RC-612 (Sanyo Chemical Industries Co., Ltd.); SP-1509 , SP-1507 (Showa Polymer Co., Ltd.); RCC-15C (Grace Japan Co., Ltd.), Aronix M-6100, M-8030, M-8060 (Toagosei Co., Ltd.), NK Hard B-420 NK ester A-DOG, NK ester A-IBD-2E (manufactured by Shin-Nakamura Chemical Co., Ltd.) and the like can be appropriately selected and used. Other examples include trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, dioxane glycol acrylate, ethoxylated acrylate, alkyl-modified dipentaerythritol pentaacrylate, etc. Can be mentioned.

  Further, the antiglare layer may contain a fluorine-acrylic copolymer resin. Next, the fluorine-acrylic copolymer resin will be described.

  The fluorine-acrylic copolymer resin is a copolymer resin composed of a fluorine monomer and an acrylic monomer, and a block copolymer composed of a fluorine monomer segment and an acrylic monomer segment is particularly preferable.

  First, the fluorine monomer will be described.

  The fluorine-based monomer can be used as long as it is a known fluorine-containing monomer. Specific examples thereof include, for example, a monomer having a structure represented by the following general formulas (A) to (G). Is the body.

In the general formulas (A) to (G), R ^F is a polyfluoroalkyl group or polyfluoroalkenyl group having 3 to 21 carbon atoms, preferably a polyfluoroalkyl group or polyfluoroalkenyl group having 6 to 12 carbon atoms. It is a group. When the number of carbon atoms is 2 or less, the performance of fluorine is difficult to be exhibited. When the number of carbon atoms is 22 or more, the polymerization conversion tends to decrease because the chain becomes considerably long.

R ¹ is hydrogen or an alkyl group having 1 to 10 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms. When the number of carbon atoms exceeds 10, the polymerization conversion tends to decrease due to the long chain. R ² is an alkylene group having 1 to 10 carbon atoms, preferably an alkylene group having 1 to 4 carbon atoms. When the number of carbon atoms exceeds 10, the polymerization conversion tends to decrease due to the long chain.

R ³ is hydrogen or a methyl group.

  Ar is an aryl group or a substituent such as an alkyl group having 1 to 10 carbon atoms, an ester group, a ketone group, an amino group, an amide group, an imide group, a nitro group, a hydroxyl group, a carboxylic acid group, a thiol group, or an ether group. An aryl group having

Specific examples of the general formula (A) include monomers from the following formulas (a-1) to (a-12).
F (CF ₂ ) ₆ (CH ₂ ) ₂ OCOCH═CH ₂ (a-1)
F (CF ₂ ) ₈ (CH ₂ ) ₂ OCOCH═CH ₂ (a-2)
F (CF ₂ ) ₁₀ (CH ₂ ) ₂ OCOCH═CH ₂ (a-3)
F (CF ₂ ) ₁₂ (CH ₂ ) ₂ OCOCH═CH ₂ (a-4)
_{H (CF 2) 8 CH 2} OCOCH = CH 2 ··· (a-5)
(CF ₃ ) ₂ CF (CF ₂ ) ₆ (CH ₂ ) ₂ OCOCH═CH ₂ (a-6)
(CF ₃ ) ₂ CF (CF ₂ ) ⁸ (CH ₂ ) ₂ OCOCH═CH ₂ (a-7)
_{F (CF 2) 6 (CH} 2) 2 OCOC (CH 3) = CH 2 ··· (a-8)
_{F (CF 2) 8 (CH} 2) 2 OCOC (CH 3) = CH 2 ··· (a-9)
_{F (CF 2) 10 (CH} 2) 2 OCOC (CH 3) = CH 2 ··· (a-10)
F (CF ₂ ) ₁₂ (CH ₂ ) ₂ OCOC (CH ₃ ) = CH ₂ (a-11)
_{H (CF 2) 8 CH 2} OCOC (CH 3) = CH 2 ··· (a-12)
(CF ₃ ) ₂ CF (CF ₂ ) ₆ (CH ₂ ) ₂ OCOC (CH ₃ ) = CH ₂ (a-13)
(CF ₃ ) ₂ CF (CF ₂ ) ₈ (CH ₂ ) ₂ OCOC (CH ₃ ) = CH ₂ (a-14)
Specific examples of the general formula (B) include monomers from the formula (b-1) to the formula (b-7).
F (CF ₂ ) ₈ SO ₂ N (CH ₃ ) CH ₂ CH ₂ OCOCH═CH ₂ (b-1)
F (CF ₂ ) ₈ SO ₂ N (CH ₃ ) (CH ₂ ) ₄ OCOCH═CH ₂ (b-2)
F (CF ₂ ) ₈ SO ₂ N (CH ₃ ) (CH ₂ ) ₁₀ OCOCH═CH ₂ (b-3)
F (CF ₂ ) ₈ SO ₂ N (C ₂ H ₅ ) C (C ₂ H ₅ ) HCH ₂ OCOCH═CH _2.
(B-4)
_{F (CF 2) 8 SO 2} N (CH 3) CH 2 CH 2 OCOC (CH 3) = CH 2 ··· (b-5)
_{F (CF 2) 8 SO 2} N (C 2 H 5) CH 2 CH 2 OCOC (CH 3) = CH 2 ··· (b-6)
_{F (CF 2) 8 SO 2} N (C 3 H 7) CH 2 CH 2 OCOC (CH 3) = CH 2 ··· (b-7)
Specific examples of the general formula (C) include monomers from the following formulas (c-1) to (c-4).
F (CF ₂ ) ₈ CON (C ₂ H ₅ ) CH ₂ OCOCH═CH ₂ (c-1)
F (CF ₂ ) ₈ CON (CH ₃ ) CH (CH ₃ ) CH ₂ OCOCH═CH ₂ (c-2)
_{F (CF 2) 8 CON (} CH 2 CH 2 CH 3) CH 2 CH 2 OCOC (CH 3) = CH 2
... (c-3)
F (CF ₂ ) ₈ CON (C ₂ H ₅ ) CH ₂ OCOC (CH ₃ ) = CH ₂ (c-4)
Specific examples of the general formula (D) include monomers from the following formulas (d-1) to (d-4).
_{F (CF 2) 8 CH 2} CH (OH) CH 2 OCOCH = CH 2 ··· (d-1)
(CF ₃ ) ₆ CF (CF ₂ ) ₂ CH ₂ CH (OH) CH ₂ OCOCH═CH ₂ (d-2)
_{F (CF 2) 8 CH 2} CH (OH) CH 2 OCOC (CH 3) = CH 2 ··· (d-3)
_{(CF 3) 2 CF (CF} 2) 6 CH 2 CH (OH) CH 2 OCOC (CH 3) = CH 2
... (d-4)
Specific examples of the general formula (E) include monomers of the following formula (e-1) and formula (e-2).
(CF ₃ ) ₂ CF (CH ₂ ) ₆ CH ₂ CH (OCOCH ₃ ) CH ₂ OCOCH = CH ₂
.. (e-1)
(CF ₃ ) ₂ CF (CH ₂ ) ₆ CH ₂ CH (OCOCH ₃ ) CH ₂ OCOC (CH ₃ ) =
CH ₂ (e-2)
Specific examples of the general formula (F) include monomers from the following formulas (f-1) to (f-4).

As fluorine monomers other than formulas (A) to (G), for example, F (CF ₂ ) ₆ CH ₂ OCH═CH ₂ , F (CF ₂ ) ₈ CH ₂ OCH═CH ₂ , F (CF ₂ ) ₁₀ CH ₂ OCH═CH ₂ , F (CF ₂ ) ₆ CH ₂ OCF═CF ₂ , F (CF ₂ ) ₈ CH ₂ OCF═CF ₂ , F (CF ₂ ) ₁₀ CH ₂ OCF═CF ₂ , F (CF ₂ ) ₆ CH = CH ₂ , F (CF ₂ ) ₈ CH═CH ₂ , F (CF ₂ ) ₁₀ CH═CH ₂ , F (CF ₂ ) ₆ CF = CF ₂ , F (CF ₂ ) ₈ CF = CF ₂ , Examples thereof include monomers of F (CF ₂ ) ₁₀ CF═CF ₂ , CH ₂ ═CF ₂ , and CF ₂ ═CF ₂ .

  The above fluorine monomers can be used alone or in combination of two or more. From the viewpoint of expressing the fluorine performance, the monomer of the general formula (A), the monomer of the general formula (B), and the monomer of the general formula (G) are effective.

  Among these, the formulas (a-1), (a-2), (a-3), (a-4), (a-6), (a-7), (a-8), ( The compounds described as a-9), (a-10), (a-11), (a-13), (a-14) and (g-1) are particularly effective.

  Next, the acrylic monomer will be described.

  As the acrylic monomer, long-chain alkyl (meth) acrylic acid long-chain alkyl having 12 to 20 carbon atoms is preferable. Specifically, for example, dodecyl (meth) acrylate, tridecyl (meth) acrylate, tetradecyl (meth) acrylate, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, octadecyl (meth) acrylate, ( (Meth) acrylic acid behenyl.

  Among these, hexadecyl (meth) acrylate, octadecyl (meth) acrylate, and behenyl (meth) acrylate are more preferable. In the fluorine-acrylic copolymer resin, when used in the energy active ray curable resin described above, the amount is preferably 0.05 parts by mass or more and 10 parts by mass or less with respect to the energy active ray curable resin. More preferably, they are 0.1 mass part or more and 10 mass parts or less. By using in the said range, the objective effect of this invention is exhibited better.

  The molecular weight of the fluorine-acrylic copolymer resin is 5,000 to 1,000,000 in terms of number average molecular weight, preferably 10,000 to 300,000, and more preferably 10,000 to 100,000. In the production of the fluorine-acrylic copolymer resin, polymeric peroxide was used as a polymerization initiator. It can be produced by a known production process (for example, Japanese Patent Publication No. 5-41668 and Japanese Patent Publication No. 5-59942).

  Polymeric peroxide is a compound having two or more peroxy bonds in one molecule. As the polymer peroxide, one or more of various polymer peroxides described in JP-B-5-59942 can be used.

  As a commercial item of fluorine-acrylic copolymer resin, the brand name of Nippon Oil & Fat Co., Ltd. Modiper F-200, Modiper F-600, Modiper F-2020, etc. are mentioned.

  The antiglare layer is a gravure coater, a dip coater, a reverse coater, a wire bar coater, a die coater, a coating method for forming an antiglare layer is applied using a known method such as an inkjet method, and after application, is heated and dried. It is preferable to perform UV curing treatment. The coating amount is suitably 0.1 to 40 μm, preferably 0.5 to 30 μm, as the wet film thickness. Moreover, as a dry film thickness, it is an average film thickness of 0.1-30 micrometers, Preferably it is 1-20 micrometers. Within this range, lack of hardness, deterioration of curling and brittleness, and deterioration of workability are prevented.

As the light source for the UV curing treatment, any light source that generates ultraviolet rays can be used without limitation. For example, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, or the like can be used. Irradiation conditions vary depending on each lamp, but the irradiation amount of active rays is usually 5 to 500 mJ / cm ² , preferably 5 to 150 mJ / cm ² . Moreover, when irradiating actinic radiation, it is preferable to carry out while applying tension | tensile_strength in the conveyance direction of a film, More preferably, it is performing applying tension | tensile_strength also in the width direction. The tension to be applied is preferably 30 to 300 N / m. The method for applying tension is not particularly limited, and tension may be applied in the conveying direction on the back roll, or tension may be applied in the width direction or biaxial direction by a tenter. This makes it possible to obtain a film having further excellent flatness.

  The coating composition that forms the antiglare layer may contain a solvent. Examples of the organic solvent contained in the coating composition include hydrocarbons (toluene, xylene), alcohols (methanol, ethanol, isopropanol, butanol, cyclohexanol), and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone). , Esters (methyl acetate, ethyl acetate, methyl lactate), glycol ethers, and other organic solvents may be appropriately selected or mixed for use.

As the organic solvent, propylene glycol monoalkyl ether (1 to 4 carbon atoms of the alkyl group) or propylene glycol monoalkyl ether acetate (1 to 4 carbon atoms of the alkyl group) is preferable. Moreover, as content of an organic solvent, 5-80 mass% is preferable in a coating composition.
(Other substances contained in the antiglare layer-forming coating composition)
Further, the antiglare layer preferably contains the following silicone surfactant, fluorine compound, polyoxyether compound and the like described in the low refractive index layer. These components increase productivity by imparting high-speed coating suitability while improving surface uniformity.

  Preferable examples of the fluorine-based compound include fluoroaliphatic group-containing copolymers, and specifically, the compounds and description methods described in paragraphs 0053 to 0082 of JP-A-2007-45142 can be used. In addition, the compounds and description methods described in paragraphs 0008 to 0031 of JP-A No. 2000-119354 can also be used. Since these components are added in the range of 0.01 to 5% by mass with respect to the solid content component in the coating solution, the effect of improving surface defects such as coating unevenness, drying unevenness, and point defects appears. preferable.

In addition, as the fluorine-based compound, a copolymer polymer obtained by grafting siloxane (including polysiloxane) and / or organosiloxane (including organopolysiloxane) to a fluororesin can also be preferably used. Specifically, ZX-022H, ZX-007C, ZX-049, ZX-047- manufactured by Fuji Chemical Industry Co., Ltd.
D etc. can be mentioned. These compounds may be used as a mixture.

  Examples of the polyoxyether compound include polyoxyethylene alkyl ether, polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene alkyl ether compounds such as polyoxyethylene stearyl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene Examples include polyoxyalkyl phenyl ether compounds such as ethylene octyl phenyl ether, polyoxyalkylene alkyl ethers, polyoxyethylene higher alcohol ethers, polyoxyethylene octyldodecyl ethers, and the like. Commercial products of polyoxyethylene alkyl ether include Emulgen 1108, Emulgen 1118S-70 (above, manufactured by Kao Corporation), and commercially available products of polyoxyethylene lauryl ether include Emulgen 103, Emulgen 104P, Emulgen 105, Emulgen 106, Emulgen 108, Emulgen 109P, Emulgen 120, Emulgen 123P, Emulgen 147, Emulgen 150, Emulgen 130K (above, manufactured by Kao Corporation), and polyoxyethylene cetyl ether are commercially available products of Emulgen 210P, Emulgen 220 (above, manufactured by Kao Corporation) As commercially available products of polyoxyethylene stearyl ether, Emulgen 220, Emulgen 306P (above, manufactured by Kao Corporation), and commercially available products of polyoxyalkylene alkyl ether include Examples of commercially available products of Rugen LS-106, Emulgen LS-110, Emulgen LS-114, Emulgen MS-110 (manufactured by Kao Corporation) polyoxyethylene higher alcohol ether include Emulgen 705, Emulgen 707, and Emulgen 709. .

  Among these polyoxyether compounds, a polyoxyethylene oleyl ether compound is preferable, and a compound represented by the following general formula (H).

_{C 18 H 35 -O (C 2} H 4O) nH ··· (H)
In the formula, n represents 2 to 40.

  The average addition number (n) of ethylene oxide with respect to the oleyl part is 2 to 40, preferably 2 to 10. Moreover, the compound of the said general formula (H) is obtained by making ethylene oxide and oleyl alcohol react. Specific products include Emulgen 404 [polyoxyethylene (4) oleyl ether], Emulgen 408 [polyoxyethylene (8) oleyl ether], Emulgen 409P [polyoxyethylene (9) oleyl ether], Emulgen 420 [polyoxy Ethylene (13) oleyl ether], Emulgen 430 [polyoxyethylene (30) oleyl ether] (above, manufactured by Kao Corporation), NOFBLEEAO-9905 (polyoxyethylene (5) oleyl ether) manufactured by NOF Corporation. Note that () represents the number n. The polyoxyether compounds may be used alone or in combination of two or more.

  Moreover, you may use together an acetylene glycol type compound, a nonionic surfactant, a radically polymerizable nonionic surfactant, etc.

  Nonionic surfactants include polyoxyethylene monolaurate, polyoxyethylene monostearate, polyoxyalkyl ester compounds such as polyoxyethylene monooleate, sorbitan monolaurate, sorbitan monostearate, sorbitan monooleate, etc. Sorbitan ester compounds, and the like. Examples of the acetylene glycol compounds include Surfinol 104E, Surfinol 104PA, Surfinol 420, Surfinol 440, and Dynal 604 (manufactured by Nissin Chemical Industry Co., Ltd.). Examples of the radical polymerizable nonionic surfactant include polyoxyalkylene alkyl such as “RMA-564”, “RMA-568”, “RMA-1114” [trade name, manufactured by Nippon Emulsifier Co., Ltd.]. Examples include phenyl ether (meth) acrylate polymerizable surfactants.

The antiglare layer may contain inorganic fine particles or an ionic polymer described later. Moreover, you may contain the color tone adjusting agent (dye or pigment etc.) which has a color tone adjustment function as a color correction filter with respect to various display elements. Moreover, you may make it contain an electromagnetic wave shielding agent or an infrared absorber, etc. and to have each function.
(Curing aid)
The antiglare layer may contain other functional thiol compounds as curing aids, such as 1,4-bis (3-mercaptobutyryloxy) butane, pentaerythritol tetrakis (3-mercaptobutyrate), 1, 3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione and the like can be mentioned. Moreover, as a commercial item, Showa Denko Co., Ltd. make, brand name Karenz MT series etc. are mentioned. The other functional thiol compound is preferably added in the range of 0.01 to 50 parts by mass, more preferably 0.05 to 30 parts by mass with respect to 100 parts by mass of the active energy ray-curable resin. By adding in the said range, it acts suitably as a hardening adjuvant and exists stably also in a glare-proof layer.
(Inorganic fine particles)
The antiglare layer has at least selected from titanium, zirconium, aluminum, indium, zinc, tin, and antimony, in addition to the light-transmitting fine particles, in order to improve hardness and adjust the refractive index of the layer. Inorganic fine particles mainly composed of one kind of metal oxide and having an average particle size of 10 μm or less, for example 2 μm or less, preferably 0.2 μm or less, particularly preferably 0.1 μm or less, more preferably 0.06 μm or less. You may contain. These inorganic fine particles generally have a specific gravity higher than that of organic substances and can increase the density of the coating composition, and therefore have the effect of slowing the sedimentation rate of the translucent fine particles.

  Inorganic fine particles mainly composed of an oxide of at least one metal selected from titanium, zirconium, aluminum, indium, zinc, tin, and antimony have a high refractive index, and the antiglare layer has a high refractive index. The surface reflection of the antiglare antireflection film to be described later can be sufficiently reduced. Moreover, it is preferable that at least one of the inorganic fine particles has a higher refractive index than the translucent resin.

  Of the oxides of at least one metal selected from titanium, zirconium, indium, zinc, tin, and antimony, titanium and zirconium are preferable. Further, from the viewpoint of antistatic, the above-mentioned inorganic fine particles can also be used.

  The surface of the inorganic fine particles used in the antiglare layer is preferably subjected to a silane coupling treatment or a titanium coupling treatment, and a surface treatment agent having a functional group capable of reacting with a binder species on the filler surface is preferably used. The surface treatment agent may be used by mixing in the coating composition without coupling treatment in advance.

  When using these inorganic fine particles, the addition amount is preferably 10 to 90% of the total mass of the antiglare layer, more preferably 20 to 80%, and particularly preferably 30 to 75%.

  Such inorganic fine particles have a particle size that is sufficiently smaller than the wavelength of light, so that no scattering occurs, and a dispersion in which the filler is dispersed in a binder polymer behaves as an optically uniform substance.

Moreover, the organosilane compound which can be used by the below-mentioned low refractive index layer and its derivative (s) can be used for a glare-proof layer. The addition amount of the organosilane compound and its derivative is preferably 0.001 to 50% by mass, more preferably 0.01 to 20% by mass, and still more preferably 0.3 to 18% by mass, based on the total solid content of the antiglare layer. 3 to 15% by mass is particularly preferable.
(Alkaline saponification treatment)
In order to improve the adhesion between the transparent film substrate constituting the antiglare film and the polarizing plate described later, the antiglare film of the present invention uses a cellulose ester film such as a triacetate film. In such a case, it is preferable to saponify with an alkali. In this case, the antiglare layer is also subjected to alkali saponification treatment, and surface slipperiness and film strength are likely to deteriorate. preferable. There is also a method in which an optical film protective film is applied to the antiglare layer of the antiglare film before the alkali saponification treatment, and an alkali saponification treatment is performed. Since the number of steps for combining and peeling increases, it is not preferable in terms of increase in productivity load and cost. In addition, the protective film for optical films is marketed, for example, can be purchased from Fujimori Industry Co., Ltd., Sekisui Chemical Co., Ltd., etc.

  The alkali saponification treatment is generally performed in a cycle in which an antiglare film is immersed in an alkali solution, washed with water and dried. Examples of the alkaline solution include a potassium hydroxide solution and a sodium hydroxide solution, and the prescribed concentration of hydroxide ions is preferably 0.1 to 3N, and more preferably 0.5N to 2N. Adhesiveness with the polarizing plate excellent by setting it as the said range is obtained. The alkali solution temperature is preferably in the range of 25 to 90 ° C, and more preferably 40 to 70 ° C, from the viewpoint of precipitation of the alkaline solution. In addition, various surface treatments may be performed on the antiglare layer to improve adhesion with a high refractive index layer or a low refractive index layer described later.

  Alternatively, the transparent film substrate on the back side of the antiglare layer may be bonded to the surface of a CRT, LCD, PDP, or ELD via an adhesive or adhesive.

The pencil hardness of the antiglare layer of the antiglare film of the present invention is preferably 3H to 8H from the handling property and hard coat property of the antiglare film. Especially preferably, it is 3H-6H. The pencil hardness is a pencil specified by JIS-K5400 using a test pencil specified by JIS-S6006 after the prepared antiglare film sample is conditioned for 2 hours at a temperature of 25 ° C. and a relative humidity of 60%. It is the value measured according to the hardness evaluation method.
(Back coat layer)
In the antiglare film of the present invention, a backcoat layer may be provided on the surface opposite to the side provided with the antiglare layer. The back coat layer is provided in order to correct the curl generated by providing the antiglare layer. That is, the degree of curling can be balanced by imparting the property of being rounded with the surface on which the backcoat layer is provided facing inward. The backcoat layer is preferably applied also as an antiblocking layer, and in this case, particles of an inorganic compound or an organic compound are added to the backcoat layer coating composition in order to provide an antiblocking function. Is preferred.

  As particles added to the back coat layer, examples of inorganic compounds include silicon dioxide, titanium dioxide, aluminum oxide, zirconium oxide, calcium carbonate, calcium carbonate, talc, clay, calcined kaolin, calcined calcium silicate, tin oxide, and oxidation. Mention may be made of indium, zinc oxide, ITO, hydrated calcium silicate, aluminum silicate, magnesium silicate and calcium phosphate.

  These particles include, for example, Aerosil R972, R972V, R974, R812, 200, 200V, 300, R202, OX50, TT600 (manufactured by Nippon Aerosil Co., Ltd.), Seahoster KE-P10, KE-P30, KE- P50, KE-P100, KE-P150, and KE-P250 (above, manufactured by Nippon Shokubai Co., Ltd.) are commercially available and can be used.

  Examples of organic compounds include silicone resins, fluororesins, and acrylic resins. Silicone resins are preferable, and those having a three-dimensional network structure are particularly preferable. For example, Tospearl 103, 105, 108, 120, 145, 3120, and 240 (manufactured by Toshiba Silicone Co., Ltd.) Are commercially available and can be used.

  Among these, Aerosil 200V, Aerosil R972V, Seahoster KE-P30, KE-P50, and KE-P100 are particularly preferably used because they have a large anti-blocking effect while keeping haze low. The particles contained in the backcoat layer are 0.1 to 50% by weight, preferably 0.1 to 10% by weight, based on the binder. When the back coat layer is provided, the increase in haze is preferably 1.5% or less, more preferably 0.5% or less, and particularly preferably 0.0 to 0.1%.

  The coating composition used for coating the back coat layer preferably contains a solvent. Examples of the solvent include dioxane, acetone, methyl ethyl ketone, methyl isobutyl ketone, N, N-dimethylformamide, methyl acetate, ethyl acetate, trichloroethylene, methylene chloride, ethylene chloride, tetrachloroethane, trichloroethane, chloroform, water, methanol, ethanol, Examples thereof include n-propyl alcohol, i-propyl alcohol, n-butanol, cyclohexanone, cyclohexanol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, and hydrocarbons (toluene, xylene), and are used in appropriate combinations. .

  Examples of the resin used as the binder of the backcoat layer include vinyl chloride-vinyl acetate copolymer, vinyl chloride resin, vinyl acetate resin, vinyl acetate-vinyl alcohol copolymer, partially hydrolyzed vinyl chloride-vinyl acetate copolymer. Polymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-acrylonitrile copolymer, ethylene-vinyl alcohol copolymer, chlorinated polyvinyl chloride, ethylene-vinyl chloride copolymer, ethylene-vinyl acetate copolymer, etc. Vinyl polymer or copolymer, nitrocellulose, cellulose acetate propionate (preferably acetyl group substitution degree 1.8-2.3, propionyl group substitution degree 0.1-1.0), diacetyl cellulose, cellulose Cellulose derivatives such as acetate butyrate resin, maleic acid and / or Or acrylic acid copolymer, acrylic ester copolymer, acrylonitrile-styrene copolymer, chlorinated polyethylene, acrylonitrile-chlorinated polyethylene-styrene copolymer, methyl methacrylate-butadiene-styrene copolymer, acrylic resin , Polyvinyl alcohol resin, polyvinyl acetal resin, polyvinyl butyral resin, urethane resin, polyester polyurethane resin, polyether polyurethane resin, polycarbonate polyurethane resin, polyester resin, polyether resin, polyamide resin, amino resin, styrene-butadiene resin, butadiene-acrylonitrile Examples thereof include, but are not limited to, rubber resins such as resins, silicone resins, fluorine resins, and the like.

  For example, as an acrylic resin, Acrypet MD, VH, MF, V (manufactured by Mitsubishi Rayon Co., Ltd.), Hyperl M-4003, M-4005, M-4006, M-4202, M-5000, M-5001, M -4501 (manufactured by Negami Kogyo Co., Ltd.), Dialnal BR-50, BR-52, BR-53, BR-60, BR-64, BR-73, BR-75, BR-77, BR-79, BR- 80, BR-82, BR-83, BR-85, BR-87, BR-88, BR-90, BR-93, BR-95, BR-100, BR-101, BR-102, BR-105, BR-106, BR-107, BR-108, BR-112, BR-113, BR-115, BR-116, BR-117, BR-118, etc. (Mitsubishi Rayon Co., Ltd.) acrylic Fine methacrylic monomer are commercially available various homopolymers and copolymers, etc. was prepared as a raw material, it is also possible to select a preferred mono from this appropriate.

  For example, as a resin used as a binder, it is preferable to use a blend of cellulose ester such as cellulose diacetate and cellulose acetate propionate and an acrylic resin, and using an acrylic resin particle, the refractive index of the particle and the binder By setting the difference to be less than 0 to 0.02, a highly transparent back coat layer can be obtained. The dynamic coefficient of friction of the backcoat layer is preferably 0.9 or less, particularly preferably 0.1 to 0.9.

  As a method for forming the backcoat layer, the above-described coating composition for forming the backcoat layer may be a gravure coater, a dip coater, a reverse coater, a wire bar coater, a die coater, or spray coating, ink jet coating, or the like. Although it is preferable to apply | coat to the surface of a transparent resin film with a wet film thickness of 1-100 micrometers, it is especially preferable that it is 5-30 micrometers.

  Moreover, a backcoat layer is formed by heat-drying after application | coating and carrying out the hardening process as needed. The content described in the low refractive index layer can be used for the curing treatment.

The backcoat layer can be applied in two or more steps. Further, the backcoat layer may also serve as an easy adhesion layer for improving the adhesion with the polarizer.
(Anti-glare anti-reflection film)
In the antiglare film of the present invention, an antireflection layer may be laminated on the antiglare layer in consideration of the refractive index, the film thickness, the number of layers, the layer order, etc. so that the reflectance is reduced by optical interference. . The antireflection layer is preferably composed of a high refractive index layer having a higher refractive index than the transparent film substrate, a low refractive index layer having a lower refractive index than the transparent film substrate, and the like. The antiglare layer may also serve as the high refractive index layer.

  The antiglare reflection and the low refractive index layer of the present invention contain at least one kind of hollow silica fine particles whose interior is porous or hollow as described below, thereby providing an antiglare reflection excellent in adhesion after a durability test. A prevention film can be formed. The antiglare antireflection film preferably has a high refractive index layer interposed between the antiglare layer and the low refractive index layer.

  The example of the preferable layer structure of an anti-glare antireflection film is shown below. In addition, it has shown that it has laminated | stacked here.

Backcoat layer / transparent film substrate / antiglare layer / low refractive index layer Backcoat layer / transparent film substrate / antiglare layer / high refractive index layer / low refractive index layer Antistatic layer / transparent film substrate / antiglare Layer / high refractive index layer / low refractive index layer back coat layer / transparent film substrate / antiglare layer / high refractive index layer / low refractive index layer / high refractive index layer / low refractive index layer (high refractive index layer)
Next, the high refractive index layer will be described. A high refractive index layer means a layer higher than the refractive index of a transparent film base material. A preferable refractive index of the high refractive index layer is preferably in the range of 1.5 to 2.2 when measured at 23 ° C. and a wavelength of 550 nm. The means for adjusting the refractive index of the high-refractive index layer is dominated by the type and amount of conductive particles. The refractive index of the conductive particles described below is preferably 1.60 to 2.60, and more preferably 1.65 to 2.50.

  The film thickness of the high refractive index layer is preferably 5 nm to 1 μm, more preferably 10 nm to 0.3 μm, and most preferably 30 nm to 0.2 μm from the characteristics as an optical interference layer.

  Next, conductive particles used to adjust the refractive index of the high refractive index layer will be described.

  The conductive particles are at least one conductive fine particle selected from the group consisting of antimony oxide, tin oxide, zinc oxide, tin indium oxide (ITO), tin antimonate (ATO), and zinc antimonate. .

  The average particle diameter of primary particles of these conductive particles is in the range of 10 nm to 200 nm, more preferably 20 to 150 nm, and particularly preferably 30 to 100 nm. The average particle diameter of the conductive particles can be measured from an electron micrograph taken with a scanning electron microscope (SEM) or the like. Further, it may be measured by a particle size distribution meter using a dynamic light scattering method or a static light scattering method. If the particle size is too small, aggregation tends to occur and the dispersibility deteriorates. If the particle size is too large, the haze is remarkably increased. The shape of the conductive particles is preferably a rice grain shape, a spherical shape, a cubic shape, a spindle shape, a needle shape, or an indefinite shape.

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

  The amount of the conductive fine particles used is preferably 5% by mass to 85% by mass in the high refractive index layer, more preferably 10% by mass to 80% by mass, and most preferably 20% by mass to 75% by mass. If the amount used is small, the desired refractive index and the effect of the present invention cannot be obtained.

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

  Moreover, electroconductive particle can be disperse | distributed in a medium using a disperser. Examples of the disperser include a sand grinder mill (eg, a bead mill with pins), a high-speed impeller mill, a pebble mill, a roller mill, an attritor, and a colloid mill. A sand grinder mill and a high-speed impeller mill are particularly preferred. Further, preliminary dispersion processing may be performed. Examples of the disperser used for the preliminary dispersion treatment include a ball mill, a three-roll mill, a kneader, and an extruder. It is also preferable to contain a dispersant.

  Furthermore, you may contain the electroconductive particle which has a core / shell structure. One layer of the shell may be formed around the core, or a plurality of layers may be formed in order to further improve the light resistance. The core is preferably completely covered by the shell.

  The high refractive index layer preferably contains an energy ray curable resin as a binder for the conductive particles in order to improve the film forming property and physical properties of the coating film.

  The energy ray curable resin is preferably an ultraviolet curable resin, and an alkoxylated ultraviolet curable resin having 1 to 3 carbon atoms and / or an ultraviolet curable resin having a dioxane structure is particularly preferable. Specifically, the structure of the ultraviolet curable resin contains methylene oxide, ethylene oxide, propylene oxide and / or 1,3-dioxane or 1,4-dioxane structure.

  Such UV curable resins include methoxypolyethylene glycol acrylate, methoxypolyethylene glycol methacrylate, ethoxylated phenyl acrylate, ethoxylated phenyl methacrylate, ethoxylated 2-methyl-1,3-propanediol diacrylate, and ethoxylated 2-methyl-1. , 3-propanediol dimethacrylate, ethoxylated bisphenol A diacrylate, ethoxylated propoxylated bisphenol A dimethacrylate, ethoxylated trimethylolpropane triacrylate, ethoxylated trimethylolpropane trimethacrylate, ethoxylated pentaerythritol tetraacrylate, propoxylated ditrimethylol Propane tetraacrylate, propoxylated pentaerythritol tetraacrylate , Dioxane glycol diacrylate, dioxane glycol dimethacrylate preferred.

  Further, those having one or two functional groups that cause a polymerization reaction directly by irradiation of energy rays such as ultraviolet rays or electron beams or indirectly by the action of a photopolymerization initiator are particularly preferable.

  The alkoxylated ultraviolet curable resin having 1 to 3 carbon atoms and / or the ultraviolet curable resin having a dioxane structure may be used alone or in combination. The mixing ratio at that time may be 1:99 to 99: 1 by mass ratio, more preferably 20:80 to 80:20, and still more preferably 30:70 to 70:30. Within the preferred range, the solvent resistance and adhesion after the wet heat test are improved. Further, a monomer or oligomer having two or more functional groups that cause a polymerization reaction directly by irradiation of energy rays such as ultraviolet rays or electron beams or indirectly by the action of a photopolymerization initiator can be used. Examples of the functional group include a group having an unsaturated double bond such as a (meth) acryloyloxy group, an epoxy group, and a silanol group. Among these, radically polymerizable monomers and oligomers having two or more unsaturated double bonds can be preferably used. You may combine a photoinitiator as needed. As such an ultraviolet curable resin, polyol acrylate, epoxy acrylate, urethane acrylate, polyester acrylate, or a mixture thereof is used. For example, a polyfunctional acrylate compound etc. are mentioned, It is preferable that it is a compound chosen from the group which consists of a pentaerythritol polyfunctional acrylate, a dipentaerythritol polyfunctional acrylate, a pentaerythritol polyfunctional methacrylate, and a dipentaerythritol polyfunctional methacrylate. Here, the polyfunctional acrylate compound is a compound having two or more acryloyloxy groups and / or methacryloyloxy groups in the molecule.

  Examples of the monomer of the polyfunctional acrylate compound include ethylene glycol diacrylate, diethylene glycol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, and tetramethylolmethanetriacrylate. Acrylate, tetramethylolmethane tetraacrylate, pentaglycerol triacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, glycerin triacrylate, dipentaerythritol triacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, Dipen Erythritol hexaacrylate, tris (acryloyloxyethyl) isocyanurate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, tetra Methylol methane trimethacrylate, tetramethylol methane tetramethacrylate, pentaglycerol trimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, glycerin trimethacrylate, dipentaerythritol trimethacrylate, dipentaerythritol te La methacrylate, dipentaerythritol penta methacrylate, dipentaerythritol hexa methacrylate preferred. These compounds are used alone or in admixture of two or more. Moreover, oligomers, such as a dimer and a trimer of the said monomer, may be sufficient. In order to accelerate curing, it is preferable to contain a photopolymerization initiator and an acrylic compound having two or more polymerizable unsaturated bonds in the molecule in a mass ratio of 1: 2 to 1:10. The amount of energy ray curable resin added is preferably 15% by mass or more and less than 50% by mass in the solid content in the high refractive index composition. The mixing ratio of the energy beam curable resin and the conductive particles is a solid content, preferably in the range of 1: 3 to 5: 3, more preferably 1: 1.5 to 1.6: 1, and still more preferably. 1.5: 1.2 to 1.5: 1. If it is out of this range, for example, if there are too few conductive particles, the adhesion cannot be obtained and the antistatic property is deteriorated. If there are too many conductive particles, fine particles fall off during the production of the antireflection film and adhere to the surface of the film being coated, causing an appearance failure.

  Specific examples of the photopolymerization initiator include acetophenone, benzophenone, hydroxybenzophenone, Michler's ketone, α-amyloxime ester, thioxanthone, and derivatives thereof, but are not particularly limited thereto.

  The high refractive index layer contains an organosilicon compound represented by the following general formula (α) or a hydrolyzate thereof or a polycondensate thereof in order to improve the film formability and physical properties of the coating film. Also good.

R′nSi (OR) ₄ −n (α)
In the formula, R ′ is a substituent having at least one of functional groups such as vinyl group, amino group, epoxy group, chloro group, methacryloxy group, acryloxy group, and isocyanate group, R is an alkyl group, and n is The number of substitutions.

  Specific examples of the organosilicon compound represented by the general formula (α) or a hydrolyzate or polycondensate thereof include methyltrimethoxysilane, methyltriethoxysilane, methyltrimethoxyethoxysilane, methyltriacetoxysilane, Methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, vinyltrimethoxyethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriacetoxysilane , Γ-chloropropyltrimethoxysilane, γ-chloropropyltriethoxysilane, γ-chloropropyltriacetoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, γ-glycidyl Luoxypropyltrimethoxysilane, γ-glycidyloxypropyltriethoxysilane, γ- (β-glycidyloxyethoxy) propyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3 , 4-epoxycyclohexyl) ethyltriethoxysilane, γ-acryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-mercaptopropyltri Methoxysilane, γ-mercaptopropyltriethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, and β-cyanoethyltriethoxysilane, dimethyldimethoxysilane, phenyl Methyldimethoxysilane, dimethyldiethoxysilane, phenylmethyldimethoxysilane, dimethyldiethoxysilane, phenylmethyldiethoxysilane, γ-glycidyloxypropylmethyldiethoxysilane, γ-glycidyloxypropylmethyldimethoxysilane, γ-glycidyloxypropylphenyl Diethoxysilane, γ-chloropropylmethyldiethoxysilane, dimethyldiacetoxysilane, γ-acryloyloxypropylmethyldimethoxysilane, γ-acryloyloxypropylmethyldiethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, γ-methacryloyloxy Propylmethyldiethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxy Orchids, .gamma.-aminopropyl methyl dimethoxy silane, .gamma.-aminopropyl methyl diethoxy silane, methyl vinyl dimethoxy silane, and include methyl vinyl diethoxy silane.

  Of these, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, vinyltrimethoxyethoxysilane, γ-acryloyloxypropyltrimethoxysilane, and γ-methacryloyloxypropyltrimethoxy having a double bond in the molecule. Gamma-acryloyloxypropylmethyldimethoxysilane, gamma-acryloyloxypropylmethyldiethoxysilane, gamma-methacryloyloxypropylmethyldimethoxysilane, gamma-methacryloyloxypropylmethyldisilane having a disubstituted alkyl group with respect to silane and silicon Ethoxysilane, methylvinyldimethoxysilane, and methylvinyldiethoxysilane are preferred, γ-acryloyloxypropyltrimethoxysilane, and γ-methacryloylo Xylpropyltrimethoxysilane, γ-acryloyloxypropylmethyldimethoxysilane, γ-acryloyloxypropylmethyldiethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, and γ-methacryloyloxypropylmethyldiethoxysilane are particularly preferred.

  Two or more types of organosilicon compounds represented by the above general formula (α) or a hydrolyzate thereof or a polycondensate thereof may be used in combination. In addition to the organosilicon compound or its hydrolyzate or polycondensate shown above, another organosilicon compound or its hydrolyzate or its polycondensate may be used. Other organosilicon compounds or hydrolysates thereof or polycondensates thereof may include alkyl esters of orthosilicates (eg, methyl orthosilicate, ethyl orthosilicate, n-propyl orthosilicate, i-propyl orthosilicate, orthosilicate n- Butyl, sec-butyl orthosilicate, t-butyl orthosilicate) and hydrolysates thereof.

  An organic solvent is preferably used when applying the high refractive index layer. Examples of the organic solvent include alcohols (eg, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, secondary butanol, tertiary butanol, pentanol, hexanol, cyclohexanol, benzyl alcohol, etc.), polyhydric alcohols ( For example, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, hexanediol, pentanediol, glycerin, hexanetriol, thiodiglycol, etc.), polyhydric alcohol ethers ( For example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene Glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, ethylene glycol monophenyl ether , Propylene glycol monophenyl ether, etc.), amines (for example, ethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, morpholine, N-ethylmorpholine, ethylenediamine, diethylenediamine, trie Lentetramine, tetraethylenepentamine, polyethyleneimine, pentamethyldiethylenetriamine, tetramethylpropylenediamine, etc.), amides (eg, formamide, N, N-dimethylformamide, N, N-dimethylacetamide, etc.), heterocyclics (eg, 2-pyrrolidone, N-methyl-2-pyrrolidone, cyclohexyl pyrrolidone, 2-oxazolidone, 1,3-dimethyl-2-imidazolidinone, etc.), sulfoxides (eg dimethyl sulfoxide etc.), sulfones (eg sulfolane) Etc.), urea, acetonitrile, acetone and the like, and alcohols, polyhydric alcohols, and polyhydric alcohol ethers are particularly preferable.

  Further, the high refractive index layer may contain other functional thiol compounds as curing aids, such as 1,4-bis (3-mercaptobutyryloxy) butane, pentaerythritol tetrakis (3-mercaptobutyrate). 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione and the like. Moreover, as a commercial item, Showa Denko Co., Ltd. make, brand name Karenz MT series, etc. are mentioned.

  The other functional thiol compound is preferably added in the range of 0.01 to 50 parts by mass, more preferably 0.05 to 30 parts by mass with respect to 100 parts by mass of the active energy ray-curable resin. By adding in the above range, it suitably acts as a curing aid, and also exists stably in the high refractive index layer.

The high refractive index layer is a wet film thickness of 0.1 to 100 μm on the hard coat layer surface using a gravure coater, dip coater, reverse coater, wire bar coater, die coater, spray coating, ink jet coating or the like. It is formed by applying, drying after application, and curing as necessary. The content described in the low refractive index layer described later can be used in the curing step. The dry film thickness is adjusted to the above film thickness by adjusting the solid content concentration of the coating composition.
(Low refractive index layer)
Next, the low refractive index layer will be described. In the low refractive index layer, a layer having a refractive index lower than that of the transparent film substrate is referred to as a low refractive index layer. A specific refractive index is preferably in the range of 1.30 to 1.45 at 23 ° C. and a wavelength of 550 nm. In addition, the film thickness of the low refractive index layer is preferably 5 nm to 0.5 μm, more preferably 10 nm to 0.3 μm, and further preferably 30 nm to 0.2 μm, from the characteristics as an optical interference layer.

  The difference na-nb between the refractive index (na) of the antiglare layer and the refractive index (nb) of the low refractive index layer is 0.04 or more, preferably 0.08 or more and 0.35 or less. It is more preferable that it is .17 or more and 0.35 or less, and it is more preferable that it is 0.20 or more and 0.30 or less. Within the range of this refractive index difference, the reflectance can be lowered sufficiently, reflection of the reflected image on the surface can be sufficiently prevented, the strength of the film becomes higher, and the color becomes stronger. Can be prevented.

The antiglare antireflection film has a light quantity I ⁴⁵ ° reflected in a direction inclined by 45 ° with respect to light having an amount of light I ₀ incident with an inclination of −60 ° with respect to the vertical direction from the low refractive index layer side. 5.0 ≧ −LOG ₁₀ (I ⁴⁵ ° / I ₀ ) ≧ 3.8
It is preferable to satisfy. FIG. 1 is a schematic diagram of an optical system for measuring such scattering characteristics. As shown in FIG. 1, the direction perpendicular to the surface of the antiglare antireflection film is defined as 0 °, and the counterclockwise direction is defined as minus and the clockwise direction is defined as plus. I ₀ in Equation (1) represents the amount of light is incident in the direction of -60 ° toward the low refractive index layer of the antiglare antireflection film. The amount of incident light can be adjusted with a light source.

  As the above measuring apparatus, for example, a “goniophotometer” manufactured by Murakami Color Materials Laboratory Co., Ltd. can be used.

In FIG. 1, I ₀ and I ⁴⁵ ° are measured with an anti-glare antireflection film attached to the polarizing plate in order to approximate the black display conditions of the display device. The surface opposite to the surface having the antireflection layer as the antireflection film alone may be treated with black ink and measured as a state without back surface reflection.

The larger the value of (−LOG ₁₀ (I ⁴⁵ ° / I ₀ )) in the formula (1), the smaller the scattered light in the 45 ° direction, and the white blurring when viewed from the 45 ° direction. It becomes good. As shown in the formula (1), the value of (-LOG ₁₀ (I ⁴⁵ ° / I ₀ )) is preferably 3.8 to 5.0, more preferably 4.2 to 4.7. Within this range, it is possible to prevent deterioration of white blur in the bright room and lack of antiglare property.

Further, the amount of light I ⁵⁰ ° reflected in the direction inclined 50 ° with respect to the incident light amount I0 inclined at −60 ° relative to the vertical direction, the amount of light I ⁴⁵ ° reflected in the direction inclined ⁴⁵ °, and the angle of 40 ° The amount of light reflected in the direction I ⁴⁰ °
Formula (2) 4.0 ≧ −LOG ₁₀ (I ⁵⁰ ° / I ₀ ) ≧ 3.0
Formula (3) 5.5 ≧ −LOG ₁₀ (I ⁴⁰ ° / I ₀ ) ≧ 4.5
If it satisfies, white blurring is improved in a wider viewing angle range, which is more preferable.
(Hollow silica particles)
It is preferable that the low refractive index layer contains hollow silica particles also from the characteristics of the optical interference layer such as adhesion after the durability test and lowering of the refractive index.

  Hollow silica particles (hereinafter also referred to as hollow particles) are (1) composite particles comprising porous particles and a coating layer provided on the surface of the porous particles, or (2) having cavities inside, and Cavity particles whose contents are filled with a solvent, gas or porous material.

  Note that the cavity particles are particles having a cavity inside, and the cavity is surrounded by a particle wall. The cavity is filled with contents such as a solvent, a gas, or a porous material used at the time of preparation.

  The average particle size of such hollow particles is 5 to 200 nm, preferably 10 to 70 nm. The particle size of the hollow particles is preferably monodispersed with a coefficient of variation of 1 to 40%.

  The average particle diameter of the hollow particles can be measured from an electron micrograph using a scanning electron microscope (SEM) or the like. You may measure by the particle size distribution meter etc. which utilize a dynamic light scattering method, a static light scattering method, etc.

  The average particle diameter of the hollow particles is appropriately selected according to the thickness of the transparent film of the low refractive index layer to be formed, and is 3/2 to 1/10, preferably 2/3 to 1/1 of the film thickness of the transparent film. 10 is desirable. These hollow 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), ketone alcohol (for example, diacetone alcohol), propylene monomethyl ether, propylene glycol monomethyl ether acetate and the like are preferable. .

  The thickness of the coating layer of the composite particles or the thickness of the particle walls of the hollow particles is 1 to 40 nm, preferably 1 to 20 nm, more preferably 2 to 15 nm. In the case of composite particles, if the thickness of the coating layer is less than 1 nm, the particles may not be completely covered, and the coating liquid component can easily enter the composite particles to reduce the internal porosity. However, the effect of lowering the refractive index may not be obtained sufficiently. In addition, when the thickness of the coating layer exceeds 20 nm, the coating liquid component does not enter the inside, but the porosity (pore volume) of the composite particles is lowered and the effect of lowering the refractive index cannot be sufficiently obtained. Sometimes.

  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 when the thickness exceeds 20 nm, the effect of lowering the 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 included. 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. Of these, porous particles made of a composite oxide of silica and an inorganic compound other than silica are particularly suitable.

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 and WO ₃ . 1 type or 2 or more types can be mentioned. In such porous particles, the molar ratio when the silica is represented by SiO ₂ and the inorganic compound other than silica is represented by oxide (MOx): MOx / SiO ₂ is 0.0001 to 1.0, preferably Is preferably in the range of 0.001 to 0.3.

A porous particle having a molar ratio of MOx / SiO ₂ of less than 0.0001 is difficult to obtain, and even if obtained, a pore volume is small and particles having a low refractive index cannot be obtained. Further, when the molar ratio of the porous particles: MOx / SiO ₂ exceeds 1.0, the ratio of silica decreases, so that the pore volume increases and it may be difficult to obtain a low refractive index.

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

  In addition, 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.

  Moreover, what consists of the compound illustrated by the porous particle as a porous substance is mentioned. 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 particles, for example, the method for preparing composite oxide colloidal particles disclosed in paragraphs 0010 to 0033 of JP-A-7-133105 is suitably employed. Moreover, the manufacturing method described in JP-A-2006-21938 can also be used.

Specifically, when the composite particles are composed of silica and an inorganic compound other than silica, hollow particles can be produced by carrying out the following first to third steps.
(First step: Preparation of porous particle precursor)
In the first step, an alkaline aqueous solution of a silica raw material and an inorganic compound raw material other than silica is separately prepared in advance, or a mixed aqueous solution of a silica raw material and an inorganic compound raw material other than silica is prepared in advance, According to the composite ratio of the target composite oxide, a porous particle precursor is prepared by gradually adding it to an alkaline aqueous solution having a pH of 10 or more while stirring.

  As the silica raw material, alkali metal, ammonium or organic base silicate is used. Sodium silicate (water glass) or potassium silicate is used as the alkali metal silicate. Examples of the organic base include quaternary ammonium salts such as tetraethylammonium salt, and amines such as monoethanolamine, diethanolamine, and triethanolamine. The ammonium silicate or the organic base silicate includes an alkaline solution obtained by adding ammonia, a quaternary ammonium hydroxide, an amine compound or the like to a silicic acid solution.

  In addition, alkali-soluble inorganic compounds are used as raw materials for inorganic compounds other than silica. Specifically, an oxo acid of an element selected from Al, B, Ti, Zr, Sn, Ce, P, Sb, Mo, Zn, W, etc., an alkali metal salt or alkaline earth metal salt of the oxo acid, ammonium And salts and quaternary ammonium salts. More specifically, sodium aluminate, sodium tetraborate, zirconyl ammonium carbonate, potassium antimonate, potassium stannate, sodium aluminosilicate, sodium molybdate, cerium ammonium nitrate, and sodium phosphate are suitable.

  Although the pH value of the mixed aqueous solution changes simultaneously with the addition of these aqueous solutions, an operation for controlling the pH value within a predetermined range is not particularly required. The aqueous solution finally has a pH value determined by the type of inorganic oxide and the mixing ratio thereof. There is no restriction | limiting in particular in the addition rate of the aqueous solution at this time. Further, in the production of composite oxide particles, a dispersion of seed particles can be used as a starting material.

The seed particles are not particularly limited, but inorganic oxides such as SiO ₂ , Al ₂ O ₃ , TiO ₂ , or ZrO ₂ or fine particles of these composite oxides are used, and usually these sols are used. be able to. Furthermore, the porous particle precursor dispersion obtained by the above production method may be used as a seed particle dispersion.

  When the seed particle dispersion is used, the pH of the seed particle dispersion is adjusted to 10 or more, and then an aqueous solution of the above compound is added to the alkaline aqueous solution while stirring. Also in this case, it is not always necessary to control the pH of the dispersion. When seed particles are used in this way, it is easy to control the particle size of the porous particles to be prepared, and particles with uniform particle sizes can be obtained.

  The silica raw material and the inorganic compound raw material described above have high solubility on the alkali side. However, when both are mixed in this highly soluble pH region, the solubility of oxo acid ions such as silicate ions and aluminate ions decreases, and these composites precipitate and grow into particles, or seed particles. It grows on the top and particle growth occurs. Therefore, it is not always necessary to perform pH control as in the conventional method for precipitation and growth of particles.

The composite ratio of silica and inorganic compound other than silica in the first step is that the inorganic compound relative to silica is converted to oxide (MOx), and the molar ratio of MOx / SiO ₂ is 0.05 to 2.0, preferably It is desirable to be within the range of 0.2 to 2.0. Within this range, the pore volume of the porous particles increases as the proportion of silica decreases. However, even when the molar ratio exceeds 2.0, the pore volume of the porous particles hardly increases. On the other hand, when the molar ratio is less than 0.05, the pore volume becomes small. When preparing hollow particles, the molar ratio of MOx / SiO ₂ is preferably in the range of 0.25 to 2.0.
(Second step: removal of inorganic compounds other than silica from porous particles)
In the second step, at least a part of inorganic compounds other than silica (elements other than silicon and oxygen) is selectively removed from the porous particle precursor obtained in the first step. As a specific removal method, the inorganic compound in the porous particle precursor is dissolved and removed using a mineral acid or an organic acid, or is contacted with a cation exchange resin for ion exchange removal.

  The porous particle precursor obtained in the first step is a particle having a network structure in which silicon and an inorganic compound constituent element are bonded through oxygen. By removing the inorganic compound (elements other than silicon and oxygen) from the porous particle precursor in this way, porous particles having a larger porosity and a larger pore volume can be obtained. Further, if the amount of removing the inorganic oxide (elements other than silicon and oxygen) from the porous particle precursor is increased, the hollow particles can be prepared.

  In addition, prior to removing inorganic compounds other than silica from the porous particle precursor, fluorine-substituted, obtained by dealkalizing an alkali metal salt of silica into the porous particle precursor dispersion obtained in the first step. It is preferable to form a silica protective film by adding a silicic acid solution containing an alkyl group-containing silane compound, an organic silicon compound, a hydrolyzate thereof, or a polycondensate thereof. The thickness of the silica protective film may be 0.5 to 40 nm, preferably 0.5 to 15 nm. Even if a silica protective film is formed, the protective film in this step is porous and thin, so that it is possible to remove inorganic compounds other than silica from the porous particle precursor. is there.

  By forming such a silica protective film, inorganic compounds other than silica described above can be removed from the porous particle precursor while maintaining the particle shape. Further, when forming the silica coating layer described later, the pores of the porous particles are not blocked by the coating layer, and therefore the silica coating layer described later is formed without reducing the pore volume. be able to. Note that when the amount of the inorganic compound to be removed is small, the particles are not broken, and thus it is not always necessary to form a protective film.

  Further, when preparing hollow particles, it is desirable to form this silica protective film. When preparing the hollow particles, the inorganic compound is removed to obtain a hollow particle precursor composed of a silica protective film, a solvent in the silica protective film, and an undissolved porous solid content. When a coating layer to be described later is formed on the body, the formed coating layer becomes a particle wall to form hollow particles.

  The amount of the silica source added for forming the silica protective film is preferably small as long as the particle shape can be maintained. If the amount of the silica source is too large, the silica protective film becomes too thick, and it may be difficult to remove inorganic compounds other than silica from the porous particle precursor.

  An alkoxysilane represented by the following general formula (β) can be used as the organosilicon compound or its hydrolyzate or polycondensate used for forming the silica protective film.

RnSi (OR ′) ₄ −n (β)
In the formula, R and R ′ represent a hydrocarbon group such as an alkyl group, an aryl group, a vinyl group, and an acrylic group, and n represents 0, 1, 2, or 3.

  In particular, tetraalkoxysilanes such as fluorine-substituted tetramethoxysilane, tetraethoxysilane, and tetraisopropoxysilane are preferably used.

  As a method of addition, a solution obtained by adding a small amount of alkali or acid as a catalyst to a mixed solution of these alkoxysilane, pure water, and alcohol is added to the dispersion of porous particles, and then alkoxysilane, pure water, and alcohol are added. A solution obtained by adding a small amount of alkali or acid as a catalyst to a mixed solution of the above is added to a dispersion of porous particles, and a silicic acid polymer produced by hydrolyzing alkoxysilane is deposited on the surface of inorganic oxide particles. .

  At this time, alkoxysilane, alcohol, and catalyst may be simultaneously added to the dispersion. As the alkali catalyst, ammonia, an alkali metal hydroxide, or an amine can be used. As the acid catalyst, various inorganic acids and organic acids can be used.

When the dispersion medium of the porous particle precursor is water alone or when the ratio of water to the organic solvent is high, a silica protective film can be formed using a silicic acid solution. When a silicic acid solution is used, a predetermined amount of the silicic acid solution is added to the dispersion, and at the same time an alkali is added to deposit the silicic acid solution on the surface of the porous particles. In addition, you may produce a silica protective film together using a silicic acid liquid and the said alkoxysilane.
(3rd process: Formation of a silica coating layer)
In the third step, a hydrolyzable organosilicon compound or silica containing a fluorine-substituted alkyl group-containing silane compound is added to the porous particle dispersion (in the case of hollow particles, a hollow particle precursor dispersion) prepared in the second step. By adding an acid solution or the like, the surface of the particles is coated with a hydrolyzable organosilicon compound or a polymer such as a silicic acid solution to form a silica coating layer. The silicic acid solution is an aqueous solution of a low silicic acid polymer obtained by dealkalizing an aqueous solution of an alkali metal silicate such as water glass by ion exchange treatment.

  The addition amount of the organosilicon compound or silicic acid solution used for forming the coating layer only needs to be sufficient to cover the surface of the colloidal particles, and the finally obtained silica coating layer has a thickness of 1 to 40 nm, Preferably, it is added in an amount of 1 to 20 nm in a dispersion of porous particles (in the case of hollow particles, hollow particle precursor). When the silica protective film is formed, the organosilicon compound or the silicate solution is added in such an amount that the total thickness of the silica protective film and the silica coating layer is in the range of 1 to 40 nm, preferably 1 to 20 nm. The

  Next, the dispersion liquid of the particles on which the coating layer is formed is heat-treated. By the heat treatment, in the case of porous particles, the silica coating layer covering the surface of the porous particles is densified, and a dispersion of composite particles in which the porous particles are coated with the silica coating layer is obtained. In the case of a hollow particle precursor, the formed coating layer is densified to form hollow particle walls, and a dispersion of hollow particles having cavities filled with a solvent, gas, or porous solid content is obtained.

  The heat treatment temperature at this time is not particularly limited as long as it can close the fine pores of the silica coating layer, and is preferably in the range of 80 to 300 ° C. When the heat treatment temperature is less than 80 ° C., the fine pores of the silica coating layer may not be completely closed and densified, and the treatment time may take a long time. Further, when the heat treatment temperature exceeds 300 ° C. for a long time, fine particles may be formed, and the effect of lowering the refractive index may not be obtained.

  The refractive index of the hollow silica particles thus obtained is as low as less than 1.42. Such hollow silica fine particles are presumed to have a low refractive index because the porosity inside the porous particles is maintained or the inside is hollow. From the viewpoint of stability when added to the coating composition, the hollow particles are preferably hollow particles in which a polymer having a hydrocarbon main chain is covalently bonded to the surface.

  Next, hollow fine particles in which a polymer having a hydrocarbon main chain is covalently bonded will be described. The polymer having a hydrocarbon main chain is a direct covalent bond, or a binder is interposed between the silica on the surface of the hollow silica particles and the polymer having the hydrocarbon main chain, and the silica and the binder are covalently bonded. It also refers to a covalent bond between a binder and a polymer. As the binder, a coupling agent is preferably used.

  Hollow fine particles in which a polymer having a hydrocarbon main chain is covalently bonded can be (1) capable of forming a covalent bond with the hollow silica particle surface in a state where the hollow silica particle surface is untreated or treated with a coupling agent or the like. A method in which a polymer having a functional group is reacted and the polymer is grafted on the surface of the hollow silica particles, or (2) a single amount from the surface of the hollow silica particles in a state where the surface of the hollow silica particles is untreated or treated with a coupling agent or the like. The polymer can be produced by polymerizing the body to grow a polymer chain and surface grafting. As a specific manufacturing method, the method described in JP-A-2006-257308 can be used.

  In the above production method, from the viewpoint of improving the surface modification rate, a method in which a monomer is polymerized from the surface of the hollow silica particles to grow a polymer chain and surface grafting is preferable. More preferred is a method in which hollow silica particles are surface-treated with a coupling agent containing a functional group having a polymerization initiating ability or a chain transfer ability, monomers are polymerized therefrom, polymer chains are grown, and surface grafting is performed. As a surface treatment agent (coupling agent) for introducing a functional group having polymerization initiating ability or chain transfer ability into hollow silica particles, an alkoxy metal compound (for example, titanium coupling agent, alkoxysilane compound (silane coupling agent) )) Is preferably used.

  The hollow silica particles may contain two or more kinds of hollow silica fine particles having different average particle diameters.

  Next, a coating composition for forming a low refractive index layer other than at least hollow silica particles having a porous or hollow interior will be described.

The low refractive index layer controls the surface (film surface) pH to 2 to 7, thereby suppressing the reaction in the low refractive index layer and improving the durability of the antireflection film in a high temperature and high humidity environment. This is preferable. More preferably, the surface (film surface) pH is 2-4. In order to control the surface (film surface) pH of the low refractive index layer, it is preferable to add a compound having at least one pKa value in the range of pKa2 to 7 to the composition forming the low refractive index layer. In addition, pKa is an acid dissociation constant in the following acid dissociation reaction, which is a logarithmic value of Ka, and is a numerical value represented by pKa = −log ₁₀ Ka.

HA ← → [H +] [A-]
Ka = [H +] [A −] / [HA]
As used herein, H + represents an acidic species, and A- represents a conjugate base.

  Specific compounds having at least one pKa value in the range of pKa2 to 7 include aliphatic dibasic acids, imidazoles or their derivatives. Examples of imidazole or derivatives thereof include 1-methylimidazole 2-methylimidazole, 4-methylimidazole, 4- (2-hydroxyethyl) imidazole, 4- (2-aminoethyl) imidazole, and 2- (2-hydroxyethyl) imidazole. 2-ethylimidazole 2-vinylimidazole, 4-propylimidazole, 2,4-dimethylimidazole, 2-chloroimidazole, 4,5-di (2-hydroxyethyl) imidazole, imidazole and the like.

  Examples of the aliphatic dibasic acid include formic acid, propionic acid, malonic acid, succinic acid, tartaric acid, malic acid, maleic acid, fumaric acid, glutaric acid, adipic acid, acetic acid and the like. Among these, acetic acid is preferable. .

  The aliphatic dibasic acid, imidazole or derivative thereof is preferably 0.05 to 10.0% by mass in the low refractive index layer coating composition from the viewpoint of the stability of the coating composition.

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

The solid content concentration in the coating composition for forming the low refractive index layer is preferably 1 to 4% by mass. By setting the solid content concentration to 4% by mass or less, coating unevenness is less likely to occur, and 1% by mass. By setting it as% or more, the drying load is reduced.
(Surfactant)
The coating composition for forming the low refractive index layer preferably contains a fluorine-based or silicone-based surfactant. Inclusion of the surfactant is effective for reducing coating unevenness and improving the antifouling property of the film surface.

  Fluorosurfactants include perfluoroalkyl group-containing monomers, oligomers, and polymers as the core, and include derivatives such as polyoxyethylene alkyl ether, polyoxyethylene alkyl allyl ether, and polyoxyethylene. It is done.

  Commercially available fluorine-based surfactants can also be used, for example, Surflon S-381, S-382, SC-101, SC-102, SC-103, SC-104 (Asahi Glass Co., Ltd.) Fluorade FC-430, FC-431, FC-173 (Fluorochemical-Sumitomo 3M), Ftop EF352, EF301, EF303 (Shin-Akita Kasei Co., Ltd.) 8036 (manufactured by Schwegman Co., Ltd.), BM1000, BM1100 (manufactured by BM Himmy Co., Ltd.), Megafuck F-171, F-470 (manufactured by Dainippon Ink & Chemicals, Inc.), and the like.

  The fluorine content of the fluorosurfactant is 0.05 to 2% by mass, preferably 0.1 to 1% by mass. One or two or more of the above fluorosurfactants can be used in combination.

  Next, the silicone surfactant will be described.

  Silicone surfactants can be broadly classified into straight silicone oils and modified silicone oils depending on the type of organic group bonded to the silicon atom.

Here, the straight silicone oil refers to one in which a methyl group, a phenyl group, or a hydrogen atom is bonded as a substituent. A modified silicone oil is one having components derived secondarily from straight silicone oil. On the other hand, it can be classified from the reactivity of silicone oil. These are summarized as follows.
(Silicone oil)
1. Straight silicone oil 1-1. Non-reactive silicone oil: dimethyl, methylphenyl substitution, etc.

1-2. Reactive silicone oil: methyl hydrogen substitution and the like.
2. Modified silicone oil Modified silicone oil is born by introducing various organic groups into dimethyl silicone oil.

  2-1. Non-reactive modified silicone oil: alkyl, alkyl / aralkyl, alkyl / polyether, polyether, higher fatty acid ester substitution, etc.

  The alkyl / aralkyl-modified silicone oil is a silicone oil in which a part of the methyl group of dimethyl silicone oil is substituted with a long-chain alkyl group or a phenylalkyl group.

  The polyether-modified silicone oil is a surfactant in which hydrophobic dimethyl silicone is introduced into hydrophilic polyoxyalkylene.

  The higher fatty acid-modified silicone oil is a silicone oil in which a part of the methyl group of dimethyl silicone oil is replaced with a higher fatty acid ester.

  The amino-modified silicone oil is a silicone oil having a structure in which a part of the methyl group of the silicone oil is substituted with an aminoalkyl group.

  The epoxy-modified silicone oil is a silicone oil having a structure in which a part of the methyl group of the silicone oil is substituted with an epoxy group-containing alkyl group.

  The carboxyl-modified or alcohol-modified silicone oil is a silicone oil having a structure in which a part of the methyl group of the silicone oil is substituted with a carboxyl group or a hydroxyl group-containing alkyl group.

  Of these, polyether-modified silicone oil is preferably added. The number average molecular weight of the polyether-modified silicone oil is, for example, 1,000 to 100,000, preferably 2,000 to 50,000. When the number average molecular weight is less than 1,000, the drying property of the coating film is low. Conversely, if the number average molecular weight exceeds 100,000, bleeding out to the coating surface becomes difficult.

  Specific products include L-45, L-9300, FZ-3704, FZ-3703, FZ-3720, FZ-3786, FZ-3501, FZ-3504, FZ-3508, FZ-3705, FZ-3707. , FZ-3710, FZ-3750, FZ-3760, FZ-3785, FZ-3785, Y-7499 (manufactured by Nihon Unicar Corporation) KF96L, KF96, KF96H, KF99, KF54, KF965, KF968, KF56, KF995, KF351 , KF351A, KF352, KF353, KF354, KF355, KF615, KF618, KF945, KF6004, FL100 (manufactured by Shin-Etsu Chemical Co., Ltd.), surfactant BYK series, BYK-300 / 302, BYK-306, BYK-307, BYK −310 BYK-315, BYK-320, BYK-322, BYK-323, BYK-325, BYK-330, BYK-331, BYK-333, BYK-337, BYK-340, BYK-344, BYK-370, BYK- 375, BYK-377, BYK-352, BYK-354, BYK-355 / 356, BYK-358N / 361N, BYK-357, BYK-390, BYK-392, BYK-UV3500, BYK-UV3510, BYK-UV3570, BYK-Silclean 3700 (manufactured by Big Chemie Japan Co., Ltd.), XC96-723, YF3800, XF3905, YF3057, YF3807, YF3802, YF3897 (manufactured by GE Toshiba Silicone Co., Ltd.) and the like can be mentioned.

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

  As the silicone 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 surfactants that do not have a group capable of dissociating into ions in an aqueous solution. Oxyethylene) or the like as a hydrophilic group. Hydrophilicity increases as the number of alcoholic hydroxyl groups increases and as the polyoxyalkylene chain (polyoxyethylene chain) becomes longer. When a nonionic surfactant composed of dimethylpolysiloxane as a hydrophobic group and polyoxyalkylene as a hydrophilic group is used, unevenness of the low refractive index layer and 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.

  Specific examples of the nonionic surfactant include, for example, 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, SUPERSILWET SS-2801, SS-2802, SS-2803, SS-2804, SS-2805 (manufactured by Nihon Unicar Co., Ltd.) and the like.

  Preferred structures of these nonionic surfactants comprising a hydrophobic group of dimethylpolysiloxane and a hydrophilic group of polyoxyalkylene include linear structures in which dimethylpolysiloxane structural portions and polyoxyalkylene chains are alternately and repeatedly bonded. A block copolymer is preferred. It is preferable from unevenness suppression and leveling properties when a coating composition for forming a low refractive index layer is applied. Specific examples of these include silicone surfactants ABN SILWET FZ-2203, FZ-2207, FZ-2208, and FZ-2222 (manufactured by Nihon Unicar Co., Ltd.).

  The coating composition for forming the low refractive index layer may contain a reactive modified silicone resin (also referred to as reactive modified silicone oil) described below.

  2-2. Reactive modified silicone oil: amino, epoxy, carboxyl, alcohol substitution, etc.

  The reactive modified silicone resin is a reactive type modified silicone resin in which the side chain, one end or both ends of polysiloxane is substituted with amino, epoxy, carboxyl, hydroxyl group, methacryl, mercapto, phenol or the like. As amino-modified silicone resins, specifically, KF-860, KF-861, X-22-161A, X-22-161B (above, manufactured by Shin-Etsu Chemical Co., Ltd.), FM-3311, FM-3325 (above, Chisso Corporation), epoxy-modified silicone resins such as KF-105, X-22-163A, X-22-163B, KF-101, KF-1001 (above, Shin-Etsu Chemical Co., Ltd.), polyether-modified X-22-4272, X-22-4952 as silicone resins, X-22-3701E, X-22-3710 (above, manufactured by Shin-Etsu Chemical Co., Ltd.) as carboxyl-modified silicone resins, and carbinol-modified silicone resins KF-6001, KF-6003 (Shin-Etsu Chemical Co., Ltd.), methacryl-modified silicone X-22-164C (made by Shin-Etsu Chemical Co., Ltd.) as the resin, KF-2001 (made by Shin-Etsu Chemical Co., Ltd.) as the mercapto-modified silicone resin, and X-22-1821 as the phenol-modified silicone resin (The above is manufactured by Shin-Etsu Chemical Co., Ltd.). Examples of the hydroxyl group-modified silicone resin include FM-4411, FM-4421, FM-DA21, FM-DA26 (manufactured by Chisso Corporation). In addition, X-22-170DX, X-22-2426, X-22-176F (manufactured by Shin-Etsu Chemical Co., Ltd.) and the like are also included.

The above-described surfactants may be used in combination with other surfactants. Also, for example, anionic surfactants such as sulfonate, sulfate, phosphate, etc. You may use together with nonionic surfactants, such as an ether type | mold and ether ester type | mold which have oxyethylene chain | strand hydrophilic group. The addition amount of the surfactant described above is 0.05 to 3.0% by mass in the low refractive index layer coating composition, not only to improve the water repellency, oil repellency and antifouling property of the coating film. From the standpoint of exerting an effect on the scratch resistance of the surface.
(Other substances contained in the coating composition for forming a low refractive index layer)
The coating composition for forming the low refractive index layer can contain other silica particles. Here, although it does not specifically limit as another silica particle, Colloidal silica etc. are mentioned. Specific examples of colloidal silica are those in which silicon dioxide is dispersed in water or an organic solvent in a colloidal form, and are not particularly limited, but are spherical, acicular or beaded.

  The average particle size of the colloidal silica is preferably in the range of 50 to 300 nm, and is preferably monodispersed with a coefficient of variation of 1 to 40%. The average particle diameter can be measured from an electron micrograph taken with a scanning electron microscope (SEM) or the like. You may measure by the particle size distribution meter etc. which utilize a dynamic light scattering method, a static light scattering method, etc.

  Colloidal silica is commercially available, and examples thereof include the Snowtex series of Nissan Chemical Industries, the Cataloid-S series of Catalytic Chemical Industry, and the Lebasil series of Bayer. Further, bead-like colloidal silica in which primary particles of colloidal silica or silica cation-modified with alumina sol or aluminum hydroxide are bonded to each other with metal ions having a valence of 2 or more and connected in a bead shape is also preferably used. There are beaded colloidal silicas such as SNOWTEX-AK series, SNOWTEX-PS series, SNOWTEX-UP series of Nissan Chemical Industries, Ltd. Specifically, IPS-ST-L (isopropanol dispersion, particle diameter 40-50 nm, Silica concentration 30%), MEK-ST-MS (methyl ethyl ketone dispersion, particle diameter 17-23 nm, silica concentration 35%) and the like. When colloidal silica is contained in the low refractive index layer-forming coating composition, it is preferably 10 to 60% by mass, more preferably 30 to 60% by mass, based on the solid content in the low refractive index layer, from the viewpoint of film strength. .

  Moreover, it is preferable that 5-80 mass% binder is included in the coating composition for low refractive index layer formation with respect to solid content in a low refractive index layer. The binder has a function of adhering particles such as hollow silica particles and maintaining the structure of the low refractive index layer including voids. The usage-amount of a binder is adjusted so that the intensity | strength of a low-refractive-index layer can be maintained, without filling a space | gap.

  In addition, other inorganic fine particles may be contained, and examples thereof include MgF2, specifically, MFS-10P (isopropyl alcohol-dispersed magnesium fluoride sol, particle system 100 nm), NF-10P manufactured by Nissan Chemical Industries, Ltd. Etc.

  Examples of binders include alkoxy metal compounds and hydrolysates or polycondensates thereof, and also polyvinyl alcohol, polyoxyethylene, polymethyl methacrylate, polymethyl acrylate, diacetyl cellulose, triacetyl cellulose, nitrocellulose, polyester, and alkyd resins. , Fluoroacrylate, fluorine-containing polymer and the like. Examples of the fluoropolymer include fluoroolefins (eg, fluoroethylene, vinylidene fluoride, tetrafluoroethylene, perfluorooctylethylene, hexafluoropropylene, perfluoro-2,2-dimethyl-1,3-dioxole, etc.) (meta ) A part of acrylic acid or a fully fluorinated alkyl ester derivative (for example, Biscoat 6FM (manufactured by Osaka Organic Chemical) or M-2020 (manufactured by Daikin)), a fully or partially fluorinated vinyl ether or the like. Among these, perfluoroolefins are preferable, and hexafluoropropylene is particularly preferable from the viewpoint of refractive index, solubility, transparency, availability, and the like.

  As the alkoxy metal compound, the organosilicon compound described in the above-mentioned section of the high refractive index layer, its hydrolyzate or its polycondensate is particularly preferable because of its excellent properties as a binder for the hollow silica particles.

  The low refractive index layer can contain a compound represented by the following general formula (γ) or a chelate compound thereof, and can improve physical properties such as hardness.

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

  Examples of the hydrolyzable functional group A include halogens such as alkoxyl groups and chloro atoms, ester groups and amide groups.

  The metal compound belonging to the general formula (γ) includes an alkoxide having two or more alkoxyl groups directly bonded to a metal atom, or a chelate compound thereof. Preferable metal compounds include titanium alkoxide, zirconium alkoxide, aluminum alkoxide or chelate compounds thereof.

Preferred chelating agents for forming a chelate compound by coordination to a free metal compound include alkanolamines such as diethanolamine and triethanolamine, glycols such as ethylene glycol, diethylene glycol and propylene glycol, acetylacetone and acetoacetic acid. Examples thereof include ethyl and the like having a molecular weight of 10,000 or less. By using these chelating agents, it is possible to form a chelate compound that is stable against water contamination and is excellent in the effect of reinforcing the coating film. The addition amount of the chelate compound is preferably adjusted so that it is 0.3 to 5% by mass in the low refractive index layer. If it is less than 0.3% by mass, the scratch resistance is insufficient, and if it exceeds 5% by mass, the light resistance tends to deteriorate.
<Fluoropolymer>
The low refractive index layer has a thermosetting and / or photocuring composition mainly comprising a fluorine-containing compound containing fluorine atoms in a range of 35 to 80% by mass and containing a crosslinkable or polymerizable functional group. You may contain a thing.

  As the fluorine-containing compound, it is preferable to use a fluorine-containing polymer having a low refractive index or a fluorine-containing sol-gel material. The fluorine-containing polymer or fluorine-containing sol-gel is a material that has a dynamic friction coefficient of 0.03 to 0.30 on the surface of the low refractive index layer formed by crosslinking by heat or ionizing radiation and a contact angle of 85 to 120 ° with water. Is preferred. Hereinafter, the fluorine-containing polymer will be described in more detail.

  The fluorine-containing polymer is preferably a fluorine-containing polymer containing a fluorine atom in a range of 35 to 80% by mass and containing a crosslinkable or polymerizable functional group. For example, a perfluoroalkyl group-containing silane compound [for example, (Heptadecafluoro-1,1,2,2-tetrahydrodecyl) triethoxysilane] hydrofluorinated copolymer having fluorine monomer units and crosslinking reactive units as constituent units Coalescence is mentioned. In the case of a fluorinated copolymer, the main chain preferably consists of only carbon atoms. That is, it is preferable that the main chain skeleton does not have an oxygen atom or a nitrogen atom. Specific examples of the fluorine-containing monomer unit include, for example, fluoroolefins (for example, fluoroethylene, vinylidene fluoride, tetrafluoroethylene, perfluorooctylethylene, hexafluoropropylene, perfluoro-2,2-dimethyl-1,3-dioxole. Etc.), partially (meth) acrylic acid or fully fluorinated alkyl ester derivatives (for example, Biscoat 6FM (manufactured by Osaka Organic Chemical), M-2020 (manufactured by Daikin), etc.), fully or partially fluorinated vinyl ethers, etc. However, perfluoroolefins are preferred, and hexafluoropropylene is particularly preferred from the viewpoints of refractive index, solubility, transparency, availability, and the like.

  As the crosslinking reactive unit, a structural unit obtained by polymerization of a monomer having a self-crosslinking functional group in the molecule in advance such as glycidyl (meth) acrylate or glycidyl vinyl ether; carboxyl group, hydroxy group, amino group, sulfo group, etc. A structural unit obtained by polymerization of a monomer having (for example, (meth) acrylic acid, methylol (meth) acrylate, hydroxyalkyl (meth) acrylate, allyl acrylate, hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, maleic acid, crotonic acid, etc.) Examples thereof include a structural unit in which a crosslinking reactive group such as a (meth) acryloyl group is introduced by a polymer reaction (for example, it can be introduced by a technique such as allowing acrylic acid chloride to act on a hydroxy group).

  In addition to the fluorine-containing monomer unit and the cross-linking reactive unit, from the viewpoint of solubility in a solvent, film transparency, and the like, a monomer that does not contain a fluorine atom is appropriately copolymerized to introduce another polymerization unit. You can also. There are no particular limitations on the monomer units that can be used in combination, such as olefins [ethylene, propylene, isoprene, vinyl chloride, vinylidene chloride, etc.], acrylic esters [methyl acrylate, methyl acrylate, ethyl acrylate, acrylic acid 2 -Ethylhexyl], methacrylates (methyl methacrylate, ethyl methacrylate, butyl methacrylate, ethylene glycol dimethacrylate, etc.), styrene derivatives (styrene, divinylbenzene, vinyl toluene, α-methylstyrene, etc.), vinyl ethers [methyl Vinyl ether, ethyl vinyl ether, cyclohexyl vinyl ether, etc.], vinyl esters [vinyl acetate, vinyl propionate, vinyl cinnamate, etc.], acrylamides [N-tertbutylacrylamide, N-silane] B hexyl acrylamide], methacrylamides, and acrylonitrile derivatives.

  As described in JP-A-10-25388 and JP-A-10-147739, a curing agent may be appropriately used in combination with the fluorine-containing polymer.

  Preferable fluorine-containing polymer is a random copolymer of perfluoroolefin and vinyl ethers or vinyl esters. In particular, it preferably has a group capable of undergoing crosslinking reaction alone (radical reactive group such as (meth) acryloyl group, ring-opening polymerizable group such as epoxy group and oxetanyl group).

  These cross-linking reactive group-containing polymer units preferably occupy 5 to 70 mol%, particularly preferably 30 to 60 mol% of the total polymer units of the polymer.

  Preferred examples of the fluoropolymer include the compounds described in paragraphs 0099 to 0106 of JP-A-2007-45142, and those described in paragraphs 0035 to 0047 of JP-A-2004-45462. It can be synthesized by the method described in 1.

  The low refractive index layer is a gravure coater, a dip coater, a reverse coater, a wire bar coater, a die coater, a known method such as an inkjet method, and the above coating composition for forming the low refractive index layer is applied, and after coating, It can be formed by heat drying and curing treatment as necessary.

  The coating amount is suitably 0.05 to 100 μm, preferably 0.1 to 50 μm, as the wet film thickness. Further, the solid content concentration of the coating composition is adjusted so that the dry film thickness becomes the film pressure.

Moreover, after forming a low refractive index layer, you may include the process of heat-processing at the temperature of 50-160 degreeC. The period of the heat treatment may be appropriately determined depending on the set temperature. For example, if it is 50 ° C., it is preferably a period of 3 days or more and less than 30 days, and if it is 160 ° C., a range of 10 minutes or more and 1 day or less is preferable. . Examples of the curing method include a method of thermosetting by heating, a method of curing by irradiation with light such as ultraviolet rays, and the like. In the case of thermosetting, the heating temperature is preferably 50 to 300 ° C, preferably 60 to 250 ° C, more preferably 80 to 150 ° C. When curing by light irradiation, the wavelength range of light is not particularly limited, but light having a wavelength in the ultraviolet region is preferably used. Specifically, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, or the like can be used. Irradiation conditions vary depending on each lamp, but the irradiation amount of active rays is usually 5 to 500 mJ / cm ² , preferably 5 to 200 mJ / cm ² , and particularly preferably 20 to 150 mJ / cm ² .

  Moreover, when each of the above-mentioned layers is formed by coating, the transparent film substrate is unwound in a roll form with a width of 1.4 to 4 m, applied, and dried and cured. It is preferably wound up in a roll. In addition, in the antireflection film, after the antireflection layer is laminated, the antireflection film may be manufactured by a manufacturing method in which a heat treatment is performed at 50 to 160 ° C. in a state of being wound in a roll shape. From the standpoint of efficiency and stability. The heat treatment period may be appropriately determined depending on the set temperature. For example, if it is 50 ° C., it is preferably a period of 3 days or more and less than 30 days, and if it is 160 ° C., a range of 10 minutes or more and 1 day or less is preferable. . Usually, it is preferably set at a relatively low temperature so that the heat treatment effect at the outside of the winding, the center of the winding, and the core is not biased, and is preferably performed at around 50 to 60 ° C. for about 7 days.

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

When winding the antiglare film and the antiglare antireflection film into a roll, the wound core is not particularly limited as long as it is a cylindrical core, but is preferably a hollow plastic core, and as a plastic material, A heat-resistant plastic that can withstand the heat treatment temperature is preferable, and examples thereof include resins such as phenol resin, xylene resin, melamine resin, polyester resin, and epoxy resin. A thermosetting resin reinforced with a filler such as glass fiber is preferable. The number of windings on these winding cores is preferably 100 windings or more, more preferably 500 windings or more, and the winding thickness is preferably 5 cm or more.
(Reflectivity of antiglare antireflection film)
The reflectance of the antireflection film described above can be measured with a spectrophotometer. At that time, after the surface on the measurement side of the sample is roughened, the light absorption treatment is performed using a black spray, and then the reflected light in the visible light region (400 to 700 nm) is measured. The lower the reflectivity, the better. However, the average value in the visible light wavelength is preferably 2.5% or less, and the minimum reflectivity is preferably 1.5% or less. It is preferable to have a flat reflection spectrum in the visible light wavelength region.

  In addition, the reflection hue on the surface of the display device that has been subjected to the antireflection treatment is often colored red or blue because the reflectance in the short wavelength region and the long wavelength region is high in the visible light region due to the design of the antireflection film. The color tone of the reflected light varies depending on the application, and when used on the outermost surface of a flat-screen television or the like, a neutral color tone is preferred.

In this case, the generally preferred reflection hue range is the XYZ color system (CIE 1931 color system),
0.17 ≦ x ≦ 0.27,
0.07 ≦ y ≦ 0.17.

  The film thicknesses of the high refractive index layer and the low refractive index layer can be obtained by calculation according to a conventional method in consideration of the reflectance and the color of reflected light based on the refractive index of each layer.

The minimum of the reflectance within the tint of reflected light is the a ^* value from -2 to 2, the b ^* values -3~3,380nm~780nm in CIE1976L ^* a ^* b ^* color space under a C light source A ratio between the value and the maximum value of 0.5 to 0.99 is preferable because the color of the reflected light becomes neutral. Further, when the b ^* value of the transmitted light under the C light source is 0 to 3, the yellow color of white display when applied to a display device is reduced, which is more preferable.
(surface treatment)
You may surface-treat before apply | coating each above-mentioned layer. Examples of the surface treatment method include a cleaning method, an alkali treatment method, a flame plasma treatment method, a high frequency discharge plasma method, an electron beam method, an ion beam method, a sputtering method, an acid treatment, a corona treatment method, and an atmospheric pressure glow discharge plasma method. It is done.

  The corona treatment is a treatment performed by applying a high voltage of 1 kV or more between the electrodes at atmospheric pressure and discharging it, using an apparatus commercially available from Kasuga Electric Co., Ltd. or Toyo Electric Co., Ltd. Can be done. The intensity of the corona discharge treatment depends on the distance between the electrodes, the output per unit area, and the generator frequency.

As one electrode (A electrode) of the corona treatment apparatus, a commercially available one can be used, but the material can be selected from aluminum, stainless steel and the like. The other is an electrode (B electrode) for holding a plastic film, and is a roll electrode installed at a certain distance from the A electrode so that the corona treatment is carried out stably and uniformly. A commercially available one can also be used, and the material is preferably a roll made of aluminum, stainless steel, or a metal thereof and lined with ceramic, silicon, EPT rubber, hyperon rubber, or the like. It is done. The frequency used for the corona treatment is a frequency of 20 kHz or more and 100 kHz or less, and a frequency of 30 kHz to 60 kHz is preferable. When the frequency decreases, the uniformity of the corona treatment deteriorates, and unevenness of the corona treatment occurs. In addition, when the frequency is increased, there is no particular problem when performing high-output corona treatment, but when performing low-output corona treatment, it is difficult to perform stable processing, resulting in uneven processing. Occurs. The output of the corona treatment is 1 to 5 W · min. / M ² but ² to 4 W · min. An output of / m ² is preferred. The distance between the electrode and the film is 5 mm or more and 50 mm or less, preferably 10 mm or more and 35 mm or less. When the gap is opened, a higher voltage is required to maintain a constant output, and unevenness is likely to occur. On the other hand, if the gap is too narrow, the applied voltage becomes too low and unevenness is likely to occur. Further, when the film is conveyed and continuously processed, the film comes into contact with the electrodes and scratches are generated.

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

The alkali concentration of the alkaline aqueous solution, for example, sodium hydroxide concentration is preferably 0.1 to 25% by mass, and more preferably 0.5 to 15% by mass. The alkali treatment temperature is usually 10 to 80 ° C, preferably 20 to 60 ° C. The alkali treatment time is 5 seconds to 5 minutes, preferably 30 seconds to 3 minutes. The film after the alkali treatment is preferably neutralized with acidic water and then thoroughly washed with water.
(Transparent film substrate)
The transparent film substrate (also referred to as a transparent resin film) used in the present invention will be described.

As the transparent film substrate, preferable requirements include ease of production, good adhesion to the antiglare layer, optical isotropy, and optical transparency.
The term “transparent” as used herein means that the visible light transmittance is 60% or more, preferably 80% or more, and particularly preferably 90% or more.

  Although it will not specifically limit if it has said property, For example, cellulose ester films, such as a cellulose diacetate film, a cellulose triacetate film, a cellulose acetate propionate film, a cellulose acetate butyrate film, a polyester film, a polycarbonate Film, polyarylate film, polysulfone (including polyethersulfone) film, polyester film such as polyethylene terephthalate and polyethylene naphthalate, polyethylene film, polypropylene film, cellophane, polyvinylidene chloride film, polyvinyl alcohol film, ethylene vinyl alcohol Film, syndiotactic polystyrene film, cycloolefin polymer fill (Arton (manufactured by JSR)), ZEONEX, ZEONOR (manufactured by Nippon Zeon), polyvinyl acetal, polymethylpentene film, polyetherketone film, polyetherketoneimide film, polyamide film, fluororesin film, nylon film, A polymethyl methacrylate film, an acrylic film, a glass plate, etc. can be mentioned. Among these, a cellulose ester film, a polycarbonate film, a polysulfone (including polyether sulfone) film, and a cycloolefin polymer film are preferable. In the present invention, in particular, a cellulose ester film (for example, Konica Minoltack, product name KC8UX, KC4UX, KC5UX, KC8UCR3, KC8UCR4, KC8UCR5, KC8UY, KC4UY, KC4UE, KC12UR (above, manufactured by Konica Minolta Opto Co., Ltd.) are preferably used from the viewpoints of cost, transparency, adhesion and the like.

  These films may be films produced by melt casting film formation or films produced by solution casting film formation.

  As the transparent film substrate, it is preferable to use a cellulose ester film (hereinafter also referred to as a cellulose ester film). As the cellulose ester, cellulose acetate, cellulose acetate butyrate, and cellulose acetate propionate are preferable. Among them, cellulose acetate butyrate, cellulose acetate phthalate, and cellulose acetate propionate are preferably used.

  In particular, when the substitution degree of the acetyl group is X and the substitution degree of the propionyl group or butyryl group is Y, it is preferable to use a cellulose ester film in which X and Y are in the following ranges.

2.3 ≦ X + Y ≦ 3.0 0.1 ≦ Y ≦ 2.0
In particular, it is preferable that 2.5 ≦ X + Y ≦ 2.9 3 ≦ Y ≦ 1.2.

  Hereinafter, the cellulose ester film which is a preferable transparent resin film will be described in detail.

The cellulose ester film preferably has a free volume radius of 0.250 to 0.310 nm determined by the positron annihilation lifetime method in order to obtain an antireflection film with little substrate deformation due to heat treatment and excellent flatness. Furthermore, it is more preferable that it is a cellulose-ester film whose total free volume parameter is 1.0-2.0.

In addition, the said free volume represents the space | gap part which is not occupied by the molecular chain of a transparent resin film. This can be measured using the positron annihilation lifetime method. Specifically, by measuring the time from the incidence of positrons to the sample until annihilation, non-destructively observing information on the vacancies, the size of free volumes, the number concentration, etc. from the annihilation lifetime Can be sought.
(Measurement of free volume radius and total free volume parameters by positron annihilation lifetime method)
The positron annihilation lifetime and relative intensity were measured under the following measurement conditions.

(Measurement condition)
Positron beam source: 22 NaCl (strength 1.85 MBq)
Gamma ray detector: Plastic scintillator + photomultiplier tube Time resolution: 290ps
Measurement temperature: 23 ° C
Total count: 1 million counts Sample size: 20 mm x 15 mm
Twenty pieces of sample sections cut to 20 mm × 15 mm were stacked to a thickness of about 2 mm. The sample was vacuum dried for 24 hours before measurement.

Irradiation area: About 10mmφ
Time per channel: 23.3ps / ch
In accordance with the above measurement conditions, positron annihilation lifetime measurement is performed, and three-component analysis is performed by the nonlinear least square method, and τ1, τ2, and τ3 are determined from those having a small annihilation lifetime, and the corresponding intensities are I1, I2, I3 ( I1 + I2 + I3 = 100%).

  From the average annihilation lifetime τ3 having the longest lifetime, the free volume radius R3 (nm) was determined using the following formula. τ3 corresponds to positron annihilation in the vacancies, and it is considered that the larger the τ3, the larger the vacancy size.

τ3 = (1/2) [1- {R3 / (R3 + 0.166)}
+ (1 / 2π) sin {2πR3 / (R3 + 0.166)}]-1
Here, 0.166 (nm) corresponds to the thickness of the electron layer leached from the hole wall.

  Further, the total free volume parameter Vp was determined by the following equation.

V3 = {(4/3) π (R3) ³ } (nm ³ )
Vp = I3 (%) × V3 (nm ³ )
Here, since I3 (%) corresponds to the relative number concentration of vacancies, Vp corresponds to the relative amount of vacancies.

  The above measurement was repeated twice, and the average value was obtained.

  The positron annihilation lifetime method is described in, for example, MATERIAL STAGE vol. 4, no. 5 2004 p21-25, Toray Research Center THE TRC NEWS No. 80 (Jul. 2002) p20-22, “Bunseki” (1988, pp.11-20), “Evaluation of free volume of polymer by positron annihilation method” is published. it can.

  The free volume radius in the cellulose ester film is 0.250 to 0.315 nm, preferably 0.250 to 0.310 nm, and a more preferable range is 0.285 to 0.305 nm. The free volume radius is less than 0.250 nm. When the free volume radius is 0.250 to 0.315 nm, the base material deformation with respect to the heat treatment is small, and an antireflection film excellent in flatness can be obtained.

  The raw material of the cellulose ester forming the cellulose ester film is not particularly limited, and examples thereof include cotton linter, wood pulp (derived from coniferous tree, derived from broadleaf tree), kenaf and the like. Moreover, the cellulose ester obtained from them can be mixed and used in arbitrary ratios, respectively. When the acylating agent is an acid anhydride (acetic anhydride, propionic anhydride, butyric anhydride), these cellulose esters use an organic solvent such as acetic acid or an organic solvent such as methylene chloride, and It can be obtained by reacting with a cellulose raw material using a protic catalyst.

Acylating agent, acid chloride _{(CH 3 COCl, C 2 H} 5 COCl, C 3 H 7 COCl) in the case of the reaction is carried out using a basic compound such as an amine as a catalyst. Specifically, it can be synthesized with reference to the method described in JP-A-10-45804.

  The cellulose ester is obtained by mixing and reacting the amount of the acylating agent according to the degree of substitution. In the cellulose ester, these acylating agents react with the hydroxyl group of the cellulose molecule. Cellulose molecules are composed of many glucose units linked together, and the glucose unit has three hydroxyl groups. The number of acyl groups derived from these three hydroxyl groups is called the degree of substitution (mol%). For example, cellulose triacetate has acetyl groups bonded to all three hydroxyl groups of the glucose unit (actually 2.6 to 3.0).

  The measuring method of the substitution degree of an acyl group can be measured according to the rule of ASTM-D817-96.

  The number average molecular weight of the cellulose ester is preferably from 50,000 to 250,000 because the mechanical strength when molded is high and an appropriate dope viscosity is obtained, and more preferably from 80,000 to 150,000.

  Cellulose ester film is a solution in which a cellulose ester solution (dope), commonly referred to as a solution casting film forming method, is pressed onto a casting support of an endless metal belt or rotating metal drum, for example. It is manufactured by casting a dope from a die and forming a film.

  As the organic solvent used for preparing these dopes, it is preferable that the cellulose ester can be dissolved and has an appropriate boiling point. For example, methylene chloride, methyl acetate, ethyl acetate, amyl acetate, methyl acetoacetate, acetone, tetrahydrofuran 1,3-dioxolane, 1,4-dioxane, cyclohexanone, ethyl formate, 2,2,2-trifluoroethanol, 2,2,3,3-tetrafluoro-1-propanol, 1,3-difluoro-2 -Propanol, 1,1,1,3,3,3-hexafluoro-2-methyl-2-propanol, 1,1,1,3,3,3-hexafluoro-2-propanol, 2,2,3 , 3,3-pentafluoro-1-propanol, nitroethane, 1,3-dimethyl-2-imidazolidinone, etc. Can, organic halogen compounds such as methylene chloride, dioxolane derivatives, methyl acetate, ethyl acetate, acetone, methyl acetoacetate, and the like are preferable organic solvents (i.e., good solvent), and as.

  Moreover, as shown in the following film forming process, it is used from the viewpoint of preventing foaming in the web when the solvent is dried from the web (dope film) formed on the casting support in the solvent evaporation process. The boiling point of the organic solvent is preferably 30 to 80 ° C. For example, the good solvent described above has a boiling point of methylene chloride (boiling point 40.4 ° C), methyl acetate (boiling point 56.32 ° C), acetone (boiling point 56.56 ° C). 3 ° C.), ethyl acetate (boiling point 76.82 ° C.) and the like.

  Among the above good solvents, methylene chloride or methyl acetate having excellent solubility is preferably used.

  In addition to the organic solvent, it is preferable to contain 0.1 to 40% by mass of an alcohol having 1 to 4 carbon atoms. It is particularly preferable that the alcohol is contained at 5 to 30% by mass.

  After casting the above dope onto the casting support, the solvent starts to evaporate and the alcohol ratio increases and the web (dope film) gels, making the web strong and peeling from the casting support. When it is used as a gelling solvent for facilitating or the ratio of these is small, it also has a role of promoting the dissolution of the cellulose ester of the non-chlorine organic solvent. Examples of the alcohol having 1 to 4 carbon atoms include methanol, ethanol, n-propanol, iso-propanol, n-butanol, sec-butanol, tert-butanol and the like.

  Of these solvents, ethanol is preferred because it has good dope stability, relatively low boiling point, good drying properties, and no toxicity. It is preferable to use a solvent containing 5 to 30% by mass of ethanol with respect to 70 to 95% by mass of methylene chloride. Methyl acetate can be used in place of methylene chloride. At this time, the dope may be prepared by a cooling dissolution method.

  The cellulose ester film preferably contains the following plasticizer. Examples of plasticizers include phosphate ester plasticizers, polyhydric alcohol ester plasticizers, phthalate ester plasticizers, trimellitic ester plasticizers, pyromellitic acid plasticizers, glycolate plasticizers, Citric acid ester plasticizers, polyester plasticizers, fatty acid ester plasticizers, polycarboxylic acid ester plasticizers, and the like can be preferably used.

  Among these, polyhydric alcohol ester plasticizers, phthalate ester plasticizers, citrate ester plasticizers, fatty acid ester plasticizers, glycolate plasticizers, polycarboxylic acid ester plasticizers, and the like are preferable. In particular, it is preferable to use a polyhydric alcohol ester plasticizer, which is preferable because the pencil hardness of the hard coat layer can be stably obtained as 4H or more.

  The polyhydric alcohol ester plasticizer is a plasticizer composed of an ester of a divalent or higher aliphatic polyhydric alcohol and a monocarboxylic acid, and preferably has an aromatic ring or a cycloalkyl ring in the molecule. Preferably it is a 2-20 valent aliphatic polyhydric alcohol ester.

  The polyhydric alcohol preferably used in the present invention is represented by the following general formula (ω).

R1- (OH) n (ω)
In the formula, R1 represents an n-valent organic group, n represents a positive integer of 2 or more, and an OH group represents an alcoholic and / or phenolic hydroxyl group.

  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, galactitol, mannitol, 3-methylpentane- Examples include 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 are 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. The number of carbon atoms is more preferably 1-20, and particularly preferably 1-10. 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-hexanoic 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 1 to 3 alkoxy groups such as an alkyl group, a methoxy group or an ethoxy group are introduced into the benzene ring of benzoic acid such as benzoic acid or toluic acid, biphenylcarboxylic acid, Examples thereof include aromatic monocarboxylic acids having two or more benzene rings such as naphthalenecarboxylic acid and tetralincarboxylic acid, or derivatives thereof. Benzoic acid is particularly preferable.

  The molecular weight of the polyhydric alcohol ester is not particularly limited, but is preferably 300 to 1500, and more preferably 350 to 750. A higher molecular weight is preferred because it is less likely to volatilize, and a smaller one is preferred 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, or a part of the OH groups may be left as they are.

  Below, the specific compound of a polyhydric alcohol ester is illustrated.

  The glycolate plasticizer is not particularly limited, but alkylphthalylalkyl glycolates can be preferably used. Examples of alkyl phthalyl alkyl glycolates include methyl phthalyl methyl glycolate, ethyl phthalyl ethyl glycolate, propyl phthalyl propyl glycolate, butyl phthalyl butyl glycolate, octyl phthalyl octyl glycolate, methyl phthalyl ethyl Glycolate, ethyl phthalyl methyl glycolate, ethyl phthalyl propyl glycolate, methyl phthalyl butyl glycolate, ethyl phthalyl butyl glycolate, butyl phthalyl methyl glycolate, butyl phthalyl ethyl glycolate, propyl phthalyl butyl glycol Butyl phthalyl propyl glycolate, methyl phthalyl octyl glycolate, ethyl phthalyl octyl glycolate, octyl phthalyl methyl glycolate, octyl phthalate Ethyl glycolate, and the like.

  Examples of the phthalate ester plasticizer include diethyl phthalate, dimethoxyethyl phthalate, dimethyl phthalate, dioctyl phthalate, dibutyl phthalate, di-2-ethylhexyl phthalate, dioctyl phthalate, dicyclohexyl phthalate, and dicyclohexyl terephthalate.

  Examples of the citrate plasticizer include acetyl trimethyl citrate, acetyl triethyl citrate, and acetyl tributyl citrate.

  Examples of fatty acid ester plasticizers include butyl oleate, methylacetyl ricinoleate, and dibutyl sebacate.

  Polycarboxylic acid ester plasticizers can also be preferably used. Specifically, it is preferable to add a polyvalent carboxylic acid ester described in paragraph Nos. 0015 to 0020 of JP-A No. 2002-265639 as one of plasticizers.

  In addition, phosphate plasticizers can also be used as other plasticizers, such as triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, octyl diphenyl phosphate, diphenyl biphenyl phosphate, trioctyl phosphate, tributyl phosphate, etc. It is done.

In addition, it is also preferable to contain an acrylic polymer described in JP-A-2003-12859.
<Acrylic polymer>
It is preferable that a cellulose-ester film contains the acrylic polymer whose weight average molecular weight which shows negative orientation birefringence with respect to a extending | stretching direction is 500-30000.

  By controlling the composition of the polymer so that the weight average molecular weight of the polymer is 500 or more and 30000 or less, the compatibility between the cellulose ester and the polymer can be improved.

  In particular, for an acrylic polymer, an acrylic polymer having an aromatic ring in the side chain, or an acrylic polymer having a cyclohexyl group in the side chain, if the weight average molecular weight is preferably 500 or more and 10,000 or less, in addition to the above, The transparency of the cellulose ester film is excellent, the moisture permeability is extremely low, and it exhibits excellent performance as an antireflection film.

  Since the polymer has a weight average molecular weight of 500 or more and 30000 or less, it is considered to be between the oligomer and the low molecular weight polymer. In order to synthesize such a polymer, it is difficult to control the molecular weight in normal polymerization, and it is desirable to use a method that can align the molecular weight as much as possible by a method that does not increase the molecular weight too much.

  Such polymerization methods include a method using a peroxide polymerization initiator such as cumene peroxide and t-butyl hydroperoxide, a method using a polymerization initiator in a larger amount than normal polymerization, and a mercapto compound in addition to the polymerization initiator. And a method using a chain transfer agent such as carbon tetrachloride, a method using a polymerization terminator such as benzoquinone and dinitrobenzene in addition to the polymerization initiator, and JP 2000-128911 A or 2000-344823 And a method of bulk polymerization using a compound having one thiol group and a secondary hydroxyl group, or a polymerization catalyst in which the compound and an organometallic compound are used in combination. However, the method described in the publication is particularly preferable.

  The acrylic polymer refers to a homopolymer or copolymer of acrylic acid or alkyl methacrylate that does not have a monomer unit having an aromatic ring or a cyclohexyl group. An acrylic polymer having an aromatic ring in the side chain is an acrylic polymer that always contains an acrylic acid or methacrylic acid ester monomer unit having an aromatic ring.

  The acrylic polymer having a cyclohexyl group in the side chain is an acrylic polymer containing an acrylic acid or methacrylic acid ester monomer unit having a cyclohexyl group.

  Examples of the acrylate monomer having no aromatic ring and cyclohexyl group include, for example, methyl acrylate, ethyl acrylate, propyl acrylate (i-, n-), butyl acrylate (n-, i-, s-, t-), pentyl acrylate (n-, i-, s-), hexyl acrylate (n-, i-), heptyl acrylate (n-, i-), octyl acrylate (n-, i-) , Nonyl acrylate (n-, i-), myristyl acrylate (n-, i-), acrylic acid (2-ethylhexyl), acrylic acid (ε-caprolactone), acrylic acid (2-hydroxyethyl), acrylic acid (2-hydroxypropyl), acrylic acid (3-hydroxypropyl), acrylic acid (4-hydroxybutyl), acrylic acid (2-hydroxybutyl), acrylic acid 2-methoxy-ethyl), acrylic acid (2-ethoxyethyl), or the acrylic acid ester may include those obtained by changing the methacrylic acid ester.

  The acrylic polymer is a homopolymer or copolymer of the above-mentioned monomers, but the acrylic acid methyl ester monomer unit preferably has 30% by mass or more, and the methacrylic acid methyl ester monomer unit has 40% by mass or more. preferable. In particular, a homopolymer of methyl acrylate or methyl methacrylate is preferred.

  Examples of acrylic acid or methacrylic acid ester monomers having an aromatic ring include phenyl acrylate, phenyl methacrylate, acrylic acid (2 or 4-chlorophenyl), methacrylic acid (2 or 4-chlorophenyl), and acrylic acid (2 or 3 Or 4-ethoxycarbonylphenyl), methacrylic acid (2 or 3 or 4-ethoxycarbonylphenyl), acrylic acid (o or m or p-tolyl), methacrylic acid (o or m or p-tolyl), benzyl acrylate, Benzyl methacrylate, phenethyl acrylate, phenethyl methacrylate, acrylic acid (2-naphthyl) and the like can be mentioned, but benzyl acrylate, benzyl methacrylate, phenethyl acrylate, and phenethyl methacrylate are preferably used. That.

  Among acrylic polymers having an aromatic ring in the side chain, the acrylic acid or methacrylic acid ester monomer unit having an aromatic ring has 20 to 40% by mass, and the acrylic acid or methacrylic acid methyl ester monomer unit is 50 to 80% by mass. % Is preferable. The polymer preferably has 2 to 20% by mass of acrylic acid or methacrylic acid ester monomer units having a hydroxyl group.

  Examples of the acrylate monomer having a cyclohexyl group include cyclohexyl acrylate, cyclohexyl methacrylate, acrylic acid (4-methylcyclohexyl), methacrylic acid (4-methylcyclohexyl), acrylic acid (4-ethylcyclohexyl), and methacrylic acid. (4-ethylcyclohexyl) and the like can be mentioned, but cyclohexyl acrylate and cyclohexyl methacrylate can be preferably used.

  In the acrylic polymer having a cyclohexyl group in the side chain, the acrylic acid or methacrylic acid ester monomer unit having a cyclohexyl group has 20 to 40% by mass and preferably 50 to 80% by mass. Moreover, it is preferable to have 2-20 mass% of acrylic acid or methacrylic acid ester monomer units having a hydroxyl group in the polymer.

  A polymer obtained by polymerizing the above ethylenically unsaturated monomer, an acrylic polymer, an acrylic polymer having an aromatic ring in the side chain, and an acrylic polymer having a cyclohexyl group in the side chain are all excellent in compatibility with the cellulose resin.

  In the case of an acrylic acid or methacrylic acid ester monomer having these hydroxyl groups, it is not a homopolymer but a structural unit of a copolymer. In this case, it is preferable that the acrylic acid or methacrylic acid ester monomer unit having a hydroxyl group is contained in the acrylic polymer in an amount of 2 to 20% by mass.

  A polymer having a hydroxyl group in the side chain can also be preferably used. The monomer unit having a hydroxyl group is the same as the monomer described above, but acrylic acid or methacrylic acid ester is preferable. For example, acrylic acid (2-hydroxyethyl), acrylic acid (2-hydroxypropyl), acrylic acid (3 -Hydroxypropyl), acrylic acid (4-hydroxybutyl), acrylic acid (2-hydroxybutyl), acrylic acid-p-hydroxymethylphenyl, acrylic acid-p- (2-hydroxyethyl) phenyl, or these acrylic acids. The thing replaced by methacrylic acid can be mentioned, Preferably, it is 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate. The acrylic acid ester or methacrylic acid ester monomer unit having a hydroxyl group in the polymer is preferably contained in the polymer in an amount of 2 to 20% by mass, more preferably 2 to 10% by mass.

  A polymer containing 2 to 20% by mass of the above-mentioned monomer unit having a hydroxyl group, of course, is excellent in compatibility with cellulose ester, retention, dimensional stability, low moisture permeability, and polarized light. It is particularly excellent in adhesiveness with a polarizer as a plate protective film, and has the effect of improving the durability of the polarizing plate.

  The method of having a hydroxyl group at at least one terminal of the main chain of the acrylic polymer is not particularly limited as long as it has a hydroxyl group at the terminal of the main chain, but azobis (2-hydroxyethylbutyrate) A method using a radical polymerization initiator having such a hydroxyl group, a method using a chain transfer agent having a hydroxyl group such as 2-mercaptoethanol, a method using a polymerization terminator having a hydroxyl group, and terminating a hydroxyl group by living ion polymerization. And a method comprising a compound having one thiol group and a secondary hydroxyl group as described in Japanese Patent Application Laid-Open No. 2000-344823, or a combination of the compound and an organometallic compound. It can be obtained by a bulk polymerization method using a catalyst, and the method described in the publication is particularly preferable.

  The polymer produced by the method related to the description in this publication is commercially available as Act Flow Series manufactured by Soken Chemical Co., Ltd., and can be preferably used. The polymer having a hydroxyl group at the terminal and / or the polymer having a hydroxyl group in a side chain has an effect of remarkably improving compatibility and transparency.

  Furthermore, a polymer using styrene as an ethylenically unsaturated monomer exhibiting negative orientation birefringence with respect to the stretching direction is preferable in order to develop negative refraction. Examples of styrenes include styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, isopropyl styrene, chloromethyl styrene, methoxy styrene, acetoxy styrene, chloro styrene, dichloro styrene, bromo styrene, and vinyl benzoic acid methyl ester. Although it is mentioned, it is not a thing limited to these.

  It may be copolymerized with the exemplified monomers listed as the unsaturated ethylenic monomer, or may be used by being dissolved in a cellulose ester using two or more kinds of the above polymers for the purpose of controlling birefringence.

In addition, the cellulose ester film contains an ethylenically unsaturated monomer Xa having no aromatic ring and a hydrophilic group in the molecule and an ethylenically unsaturated monomer Xb having no aromatic ring in the molecule and having a hydrophilic group. Polymer Y having a weight average molecular weight of 5,000 to 30,000 obtained by polymerization, and more preferably a polymer Y having a weight average molecular weight of 500 to 3,000 obtained by polymerizing an ethylenically unsaturated monomer Ya having no aromatic ring It is preferable to contain.
(Polymer X, Polymer Y)
The polymer X used in the present invention includes an ethylenically unsaturated monomer Xa having no aromatic ring and a hydrophilic group in the molecule, and an ethylenically unsaturated monomer Xb having no aromatic ring in the molecule and having a hydrophilic group. Is a polymer having a weight average molecular weight of 5,000 or more and 30,000 or less obtained by copolymerization.

  Preferably, Xa is an acrylic or methacrylic monomer that does not have an aromatic ring and a hydrophilic group in the molecule, and Xb is an acrylic or methacrylic monomer that does not have an aromatic ring in the molecule and has a hydrophilic group.

  The polymer X is represented by the following general formula (Q).

-(Xa) m- (Xb) n- (Xc) p- (Q)
More preferably, it is a polymer represented by the following general formula (R).

_{- [CH 2 -C (-R 1} ) (- CO 2 R 2)] m- [CH 2 -C (-R 3)
_{(-CO 2 R 4 -OH) -} ] n- [Xc] p- ··· (R)
(In the formula, R ₁ and R ₃ represent H or CH _3. R ₂ represents an alkyl group having 1 to 12 carbon atoms or a cycloalkyl group. R ₄ represents —CH ₂ —, —C ₂ H ₄ —. Or -C ₃ H _6- , Xc represents a monomer unit polymerizable to Xa and Xb, m, n and p represent molar composition ratios, provided that m ≠ 0, n ≠ 0, k ≠ 0, m + n + p = 100.)
Although the monomer as a monomer unit which comprises the acrylic polymer X is mentioned below, it is not limited to this.

  In the acrylic polymer X, the hydrophilic group means a group having a hydroxyl group or an ethylene oxide chain.

  The ethylenically unsaturated monomer Xa having no aromatic ring and no hydrophilic group in the molecule includes, for example, methyl acrylate, ethyl acrylate, propyl acrylate (i-, n-), butyl acrylate (n-, i-, s-, t-), pentyl acrylate (n-, i-, s-), hexyl acrylate (n-, i-), heptyl acrylate (n-, i-), octyl acrylate (n-, i-), nonyl acrylate (n-, i-), myristyl acrylate (n-, i-), acrylic acid (2-ethylhexyl), acrylic acid (ε-caprolactone), etc., or the above acrylate ester What changed to the methacrylic acid ester can be mentioned.

  Among these, methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, and propyl methacrylate (i-, n-) are preferable.

  The ethylenically unsaturated monomer Xb having no aromatic ring in the molecule and having a hydrophilic group is preferably acrylic acid or methacrylic acid ester as a monomer unit having a hydroxyl group. For example, acrylic acid (2-hydroxyethyl), acrylic Examples include acid (2-hydroxypropyl), acrylic acid (3-hydroxypropyl), acrylic acid (4-hydroxybutyl), acrylic acid (2-hydroxybutyl), or those obtained by replacing these acrylic acids with methacrylic acid. Preferred are acrylic acid (2-hydroxyethyl), methacrylic acid (2-hydroxyethyl), acrylic acid (2-hydroxypropyl), and acrylic acid (3-hydroxypropyl).

  Xc is not particularly limited as long as it is an ethylenically unsaturated monomer other than Xa and Xb and copolymerizable, but preferably has no aromatic ring.

  The molar composition ratio of Xa, Xb, and Xc = m: n is preferably in the range of 99: 1 to 65:35, and more preferably in the range of 95: 5 to 75:25. P of Xc is 0-10.

  Xc may be a plurality of monomer units.

  When the molar composition ratio of Xa is large, compatibility with the cellulose ester is improved, but the film thickness direction retardation (Rt) value is increased. When the molar composition ratio of Xb is large, the compatibility is deteriorated, but the effect of reducing the thickness direction retardation (Rt) is high. Further, if the molar composition ratio of Xb exceeds the above range, haze tends to occur during film formation. It is preferable to optimize these and determine the molar composition ratio of Xa and Xb.

  As for the molecular weight of the polymer X, the weight average molecular weight is from 5,000 to 30,000, and more preferably from 8,000 to 25,000.

  By setting the weight average molecular weight to 5,000 or more, it is preferable because the cellulose ester film has advantages such as less dimensional change under high temperature and high humidity and less curling as a polarizing plate protective film. When the weight average molecular weight is 30000 or less, the compatibility with the cellulose ester is further improved, and bleeding out under high temperature and high humidity, and further haze generation immediately after film formation is suppressed.

  The weight average molecular weight of the polymer X can be adjusted by a known molecular weight adjusting method. Examples of such a molecular weight adjusting method include a method of adding a chain transfer agent such as carbon tetrachloride, lauryl mercaptan, octyl thioglycolate, and the like. The polymerization temperature is usually room temperature to 130 ° C., preferably 50 ° C. to 100 ° C., and this temperature or the polymerization reaction time can be adjusted.

  Next, the polymer Y is a polymer having a weight average molecular weight of 500 or more and 3000 or less obtained by polymerizing an ethylenically unsaturated monomer Ya having no aromatic ring.

  Here, when the weight average molecular weight of the polymer Y is 500 or more, the residual monomer of the polymer decreases, which is preferable. Moreover, it is preferable to make the weight average molecular weight of the polymer Y 3000 or less in order to maintain the fall performance of the thickness direction retardation (Rt) value. Ya is preferably an acrylic or methacrylic monomer having no aromatic ring.

  The polymer Y is represented by the following general formula (S).

-(Ya) k- (Yb) q- (S)
More preferably, it is a polymer represented by the following general formula (T).

_{- [CH 2 -C (-R 5} ) (- CO 2 R 6)] k- [Yb] q- ·· (T)
(In the formula, R ₅ represents H or CH _3. R ₆ represents an alkyl group or a cycloalkyl group having 1 to 12 carbon atoms. Yb represents a monomer unit copolymerizable with Ya. q represents a molar composition ratio, where k ≠ 0 and k + q = 100.
Yb is not particularly limited as long as it is an ethylenically unsaturated monomer copolymerizable with Ya. Yb may be plural. k + q = 100, q is preferably 0-30.

  The ethylenically unsaturated monomer Ya constituting the polymer Y obtained by polymerizing an ethylenically unsaturated monomer having no aromatic ring is, for example, methyl acrylate, ethyl acrylate, propyl acrylate (i- , N-), butyl acrylate (n-, i-, s-, t-), pentyl acrylate (n-, i-, s-), hexyl acrylate (n-, i-), heptyl acrylate (N-, i-), octyl acrylate (n-, i-), nonyl acrylate (n-, i-), myristyl acrylate (n-, i-), cyclohexyl acrylate, acrylic acid (2- Ethyl hexyl), acrylic acid (ε-caprolactone), acrylic acid (2-hydroxyethyl), acrylic acid (2-hydroxypropyl), acrylic acid (3-hydroxypropiyl) ), Acrylic acid (4-hydroxybutyl), acrylic acid (2-hydroxybutyl), methacrylic acid ester, the above acrylic acid ester changed to methacrylic acid ester; unsaturated acid such as acrylic acid, methacrylic acid, Mention may be made of maleic anhydride, crotonic acid, itaconic acid and the like.

  Yb is not particularly limited as long as it is an ethylenically unsaturated monomer copolymerizable with Ya. Examples of vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl valerate, vinyl pivalate, and vinyl caproate. Vinyl caprate, vinyl laurate, vinyl myristate, vinyl palmitate, vinyl stearate, vinyl cyclohexanecarboxylate, vinyl octylate, vinyl methacrylate, vinyl crotonate, vinyl sorbate, vinyl cinnamate and the like are preferred. Yb may be plural.

  In order to synthesize the polymer X and the polymer Y, it is difficult to control the molecular weight in normal polymerization, and it is desirable to use a method that can make the molecular weights as uniform as possible without increasing the molecular weight.

  Polymerization methods of polymer X and polymer Y include a method using a peroxide polymerization initiator such as cumene peroxide and t-butyl hydroperoxide, a method using a polymerization initiator in a larger amount than normal polymerization, and a polymerization start. A method using a chain transfer agent such as a mercapto compound or carbon tetrachloride in addition to the agent, a method using a polymerization terminator such as benzoquinone or dinitrobenzene in addition to the polymerization initiator, and JP 2000-128911 A or Examples thereof include a method of bulk polymerization using a compound having one thiol group and a secondary hydroxyl group described in JP-A-2000-344823, or a polymerization catalyst in which the compound and an organometallic compound are used in combination. .

  The polymer Y is preferably a polymerization method using a compound having a thiol group and a secondary hydroxyl group in the molecule as a chain transfer agent. In this case, the terminal of the polymer Y has a hydroxyl group and a thioether resulting from the polymerization catalyst and the chain transfer agent. By this terminal residue, the compatibility between the polymer Y and the cellulose ester can be adjusted. The hydroxyl value of the polymer X and the polymer Y is preferably 30 to 150 [mg KOH / g]. Here, the measurement of a hydroxyl value is based on JIS-K0070 (1992). This hydroxyl value is defined as the number of mg of potassium hydroxide required to neutralize acetic acid bonded to a hydroxyl group when 1 g of a sample is acetylated. Specifically, a sample xg (about 1 g) is precisely weighed in a flask, and 20 ml of an acetylating reagent (a solution obtained by adding pyridine to 20 ml of acetic anhydride to 400 ml) is accurately added thereto. An air cooling tube is attached to the mouth of the flask and heated in a glycerin bath at 95-100 ° C. After 1 hour and 30 minutes, the mixture is cooled, 1 ml of purified water is added from an air condenser, and acetic anhydride is decomposed into acetic acid. Next, titration is performed with a 0.5 mol / L potassium hydroxide ethanol solution using a potentiometric titrator, and the inflection point of the obtained titration curve is set as the end point. Further, as a blank test, titration is performed without a sample, and an inflection point of the titration curve is obtained. The hydroxyl value is calculated by the following formula.

Hydroxyl value = {(BC) × f × 28.05 / x} + D
(In the formula, B is the amount of 0.5 mol / L potassium hydroxide ethanol solution (ml) used for the blank test, and C is the amount of 0.5 mol / L potassium hydroxide ethanol solution used for titration ( ml), f is a factor of 0.5 mol / L potassium hydroxide ethanol solution, D is acid value, and 28.05 is 1/2 of 1 mol amount of potassium hydroxide 56.11)
The content of the polymer X and the polymer Y in the cellulose ester film is preferably in the range satisfying the following formulas (i) and (ii). When the content of the polymer X is xg (mass% = the mass of the polymer X / the mass of the cellulose ester × 100) and the content of the polymer Y is yg (mass%),
Formula (i) 5 ≦ xg + yg ≦ 35 (mass%)
Formula (ii) 0.05 ≦ yg / (xg + yg) ≦ 0.4
A preferable range of the formula (i) is 10 to 25% by mass.

  In addition, the weight average molecular weight Mw of a polymer can be measured using gel permeation chromatography.

  The measurement conditions are as follows.

Solvent: Methylene chloride Column: Shodex K806, K805, K803G
(Used by connecting three Showa Denko Co., Ltd.)
Column temperature: 25 ° C
Sample concentration: 0.1% by mass
Detector: RI Model 504 (manufactured by GL Sciences)
Pump: L6000 (manufactured by Hitachi, Ltd.)
Flow rate: 1.0ml / min
Positive curve: Standard polystyrene STK standard polystyrene (manufactured by Tosoh Corporation) Mw = 1,000,000-500 calibration curves with 13 samples were used. Thirteen samples are used at approximately equal intervals.

  If the total amount of the polymer X and the polymer Y is 5% by mass or more, the polymer X and the polymer Y sufficiently act to reduce the thickness direction retardation (Rt) value. Moreover, if it is 35 mass% or less as a total amount, adhesiveness with polarizer PVA is favorable.

  The polymer X and the polymer Y can be directly added and dissolved as a material constituting the dope solution described later, or can be added to the dope solution after being previously dissolved in an organic solvent for dissolving the cellulose ester.

  The total content of the plasticizer in the cellulose ester film is preferably 5 to 20% by mass, more preferably 6 to 16% by mass, and particularly preferably 8 to 13% by mass with respect to the total solid content. The contents of the two kinds of plasticizers are each at least 1% by mass, preferably 2% by mass or more.

The polyhydric alcohol ester plasticizer is preferably contained in an amount of 1 to 15% by mass, particularly preferably 3 to 11% by mass. When the content of the polyhydric alcohol ester plasticizer is small, deterioration of planarity is recognized, and when the content is too large, bleeding out tends to occur. The mass ratio of the polyhydric alcohol ester plasticizer and the other plasticizer is preferably in the range of 1: 4 to 4: 1, and more preferably 1: 3 to 3: 1. If the amount of the plasticizer added is too large or too small, the film is liable to be deformed, which is not preferable.
(Solution casting film forming method)
The cellulose ester film is produced by a solution casting method, in which a cellulose ester and an additive are dissolved in a solvent to prepare a dope, a dope is cast on a belt-shaped or drum-shaped metal support, It is performed by a step of drying the stretched dope as a web, a step of peeling from the metal support, a step of stretching or maintaining the width, a step of further drying, and a step of winding the finished film.

First, the process for preparing the dope will be described. The concentration of cellulose ester in the dope is preferably higher because the drying load after casting on the metal support can be reduced, but if the concentration of cellulose ester is too high, the load during filtration increases and the filtration accuracy Becomes worse. As a concentration that makes these compatible, 10 to 35% by mass is preferable,
More preferably, it is 15-25 mass%.

  The solvent used in the dope may be used alone or in combination of two or more, but it is preferable to use a mixture of a good solvent and a poor solvent of cellulose ester in terms of production efficiency, and there are many good solvents. This is preferable from the viewpoint of the solubility of the cellulose ester. The preferable range of the mixing ratio of the good solvent and the poor solvent is 70 to 98% by mass for the good solvent and 2 to 30% by mass for the poor solvent. With a good solvent and a poor solvent, what dissolve | melts the cellulose ester to be used independently is defined as a good solvent, and what poorly swells or does not melt | dissolve is defined as a poor solvent. Therefore, depending on the acyl group substitution degree of the cellulose ester, the good solvent and the poor solvent change. For example, when acetone is used as the solvent, the cellulose ester acetate ester (acetyl group substitution degree 2.4) and cellulose acetate propionate are good. As a solvent, cellulose acetate (acetyl group substitution degree 2.8) is a poor solvent.

  The good solvent is not particularly limited, and examples thereof include organic halogen compounds such as methylene chloride, dioxolanes, acetone, methyl acetate, and methyl acetoacetate. Particularly preferred is methylene chloride or methyl acetate.

  Moreover, although a poor solvent is not specifically limited, For example, methanol, ethanol, n-butanol, cyclohexane, cyclohexanone etc. are used preferably. Moreover, it is preferable that 0.01-2 mass% of water contains in dope.

  A general method can be used as a dissolution method of the cellulose ester when preparing the dope described above. When heating and pressurization are combined, it is possible to heat above the boiling point at normal pressure. It is preferable to stir and dissolve while heating at a temperature that is equal to or higher than the boiling point of the solvent at normal pressure and does not boil under pressure, in order to prevent the formation of massive undissolved material called gel or mamako. Moreover, after mixing a cellulose ester with a poor solvent and making it wet or swell, the method of adding a good solvent and melt | dissolving is also used preferably.

  The pressurization may be performed by a method of injecting an inert gas such as nitrogen gas or a method of increasing the vapor pressure of the solvent by heating. Heating is preferably performed from the outside. For example, a jacket type is preferable because temperature control is easy.

  The heating temperature with the addition of the solvent is preferably higher from the viewpoint of the solubility of the cellulose ester, but if the heating temperature is too high, the required pressure increases and the productivity deteriorates. A preferable heating temperature is 45 to 120 ° C, more preferably 60 to 110 ° C, and still more preferably 70 ° C to 105 ° C. The pressure is adjusted so that the solvent does not boil at the set temperature.

  Alternatively, a cooling dissolution method is also preferably used, whereby the cellulose ester can be dissolved in a solvent such as methyl acetate.

  Next, this cellulose ester solution is filtered using a suitable filter medium such as filter paper. As the filter medium, in order to remove insoluble matters and the like, it is preferable that the absolute filtration accuracy is small. However, if the absolute filtration accuracy is too small, there is a problem that the filter medium is likely to be clogged. For this reason, a filter medium with an absolute filtration accuracy of 0.008 mm or less is preferable, a filter medium with 0.001 to 0.008 mm is more preferable, and a filter medium with 0.003 to 0.006 mm is more preferable.

  The material of the filter medium is not particularly limited, and a normal filter medium can be used. However, a plastic filter medium such as polypropylene or Teflon (registered trademark), or a metal filter medium such as stainless steel may cause fibers to fall off. Less preferred. It is preferable to remove and reduce impurities, particularly bright spot foreign matter, contained in the raw material cellulose ester by filtration.

Bright spot foreign matter is when two polarizing plates are placed in a crossed Nicol state, a cellulose ester film is placed between them, light is applied from the side of one polarizing plate, and observed from the side of the other polarizing plate. It is a point (foreign matter) where light from the opposite side appears to leak, and the number of bright spots having a diameter of 0.01 mm or more is preferably 200 / cm ² or less. More preferably, it is 100 pieces / cm < ² > or less, More preferably, it is 50 pieces / cm < ² > or less, More preferably, it is 0-10 pieces / cm < ² > or less. Further, it is preferable that the number of bright spots of 0.01 mm or less is small.

  The dope can be filtered by a normal method, but the method of filtering while heating at a temperature not lower than the boiling point at normal pressure of the solvent and at which the solvent does not boil under pressure is the filtration pressure before and after filtration. The increase in the difference (referred to as differential pressure) is small and preferable. A preferred temperature is 45 to 120 ° C, more preferably 45 to 70 ° C, and even more preferably 45 to 55 ° C.

  A smaller filtration pressure is preferred. The filtration pressure is preferably 1.6 MPa or less, more preferably 1.2 MPa or less, and further preferably 1.0 MPa or less.

  Next, dope casting will be described.

  The metal support in the casting (casting) step preferably has a mirror-finished surface. As the metal support, a stainless steel belt or a drum whose surface is plated with a casting is preferably used.

  The cast width can be 1 to 4 m. The surface temperature of the metal support in the casting step is set to −50 ° C. to a temperature at which the solvent boils and does not foam. A higher temperature is preferred because the web can be dried faster, but if it is too high, the web may foam or the flatness may deteriorate. A preferable support temperature is appropriately determined at 0 to 100 ° C, and more preferably 5 to 30 ° C. Alternatively, it is also a preferable method that the web is gelled by cooling and peeled from the drum in a state containing a large amount of residual solvent.

  The method for controlling the temperature of the metal support is not particularly limited, and there are a method of blowing hot air or cold air, and a method of contacting hot water with the back side of the metal support. It is preferable to use warm water because heat transfer is performed efficiently, so that the time until the temperature of the metal support becomes constant is short. When using warm air, considering the temperature drop of the web due to the latent heat of vaporization of the solvent, while using warm air above the boiling point of the solvent and preventing foaming, there are cases where wind at a temperature higher than the target temperature is used. is there. In particular, it is preferable to perform drying efficiently by changing the temperature of the support and the temperature of the drying air during the period from casting to peeling.

  In order for the cellulose ester film to exhibit good flatness, the residual solvent amount when peeling the web from the metal support is preferably 10 to 150% by mass, more preferably 20 to 40% by mass or 60 to 130% by mass. Especially preferably, it is 20-30 mass% or 70-120 mass%.

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

Residual solvent amount (% by mass) = {(MN) / N} × 100
Here, M is the mass of a sample taken at any time during or after the production of the web or film, and N is the mass after heating M at 115 ° C. for 1 hour.

  Further, in the drying step of the cellulose ester film, the web is peeled off from the metal support, and further dried, and the residual solvent amount is preferably 1% by mass or less, more preferably 0.1% by mass or less, Especially preferably, it is 0-0.01 mass% or less.

  In the film drying process, generally, a roll drying method (a method in which a plurality of rolls arranged on the upper and lower sides are alternately passed through and dried) or a method of drying while transporting the web by a tenter method is adopted.

  In order to produce a cellulose ester film for an antiglare film and an antiglare antireflection film, the web is stretched in the transport direction where the amount of residual solvent of the web immediately after peeling from the metal support is large, and both ends of the web are It is particularly preferable to perform stretching in the width direction by a tenter method gripped by a clip or the like. A preferable draw ratio in both the machine direction and the transverse direction is 1.01 to 1.3 times, and more preferably 1.05 to 1.15 times. It is preferable that the area is 1.12 to 1.44 times, and preferably 1.15 to 1.32 times due to longitudinal and lateral stretching. This can be determined by the draw ratio in the longitudinal direction × the draw ratio in the transverse direction. If one of the stretching ratios in the longitudinal direction and the transverse direction is less than 1.01, the flatness is likely to deteriorate due to ultraviolet irradiation when forming the antiglare layer.

  In order to stretch in the machine direction immediately after peeling, it is preferable to stretch by peeling tension and subsequent transport tension. For example, it is preferable to peel at a peeling tension of 210 N / m or more, and particularly preferably 220 to 300 N / m. The means for drying the web is not particularly limited, and can be generally performed with hot air, infrared rays, a heating roll, microwave, or the like, but it is preferably performed with hot air in terms of simplicity.

  The drying temperature in the web drying step is preferably increased stepwise from 30 to 200 ° C, and more preferably stepwise increased from 50 to 180 ° C in order to improve dimensional stability.

  Although the film thickness of a cellulose-ester film is not specifically limited, 10-200 micrometers is used preferably. In particular, it was difficult to obtain an antireflection film excellent in flatness and scratch resistance with a thin film of 10 to 70 μm, but a thin antireflection film excellent in flatness and scratch resistance was obtained and produced. Since it is excellent also in the property, it is especially preferable that the film thickness of a cellulose-ester film is 10-70 micrometers. More preferably, it is 20-60 micrometers. Most preferably, it is 35-60 micrometers. Moreover, the cellulose ester film made into the multilayer structure by the co-casting method can also be used preferably. Even when the cellulose ester has a multilayer structure, it has a layer containing an ultraviolet absorber and a plasticizer, and it may be a core layer, a skin layer, or both.

The centerline average roughness (Ra) of the surface on which the antiglare layer of the cellulose ester film is provided can be 0.001 to 1 μm.
(Melt casting method)
The cellulose ester film is also preferably formed by a melt casting film forming method.

  The molding method by melt casting that is heated and melted without using the solvent (for example, methylene chloride, etc.) used in the solution casting film forming method, more specifically, melt extrusion molding method, press molding method, inflation method, injection It can be classified into molding method, blow molding method, stretch molding method and the like. Among these, in order to obtain a cellulose ester film excellent in mechanical strength, surface accuracy and the like, the melt extrusion method is excellent.

  A mixture of cellulose ester and additives is dried with hot air or vacuum, then melt extruded, extruded into a film from a T-die, and brought into close contact with a cooling drum by an electrostatic application method, etc., and cooled and solidified to obtain an unstretched film . The temperature of the cooling drum is preferably maintained at 90 to 150 ° C.

  The cellulose ester and other additives such as a stabilizer added as necessary are preferably mixed before melting, and more preferably mixed before heating. Mixing may be performed by a mixer or the like, or may be performed in the cellulose ester preparation process. When a mixer is used, a general mixer such as a V-type mixer, a conical screw type mixer, a horizontal cylindrical type mixer, a Henschel mixer, or a ribbon mixer can be used.

  After the film constituent materials are mixed as described above, the mixture may be directly melted and formed into a film using an extruder, but once the film constituent materials are pelletized, the pellets are extruded. The film may be melted to form a film. In addition, when the film constituent material includes a plurality of materials having different melting points, a so-called braided semi-melt is once produced at a temperature at which only a material having a low melting point is melted, and the semi-melt is put into an extruder. It is also possible to form a film. If the film component contains a material that is easily pyrolyzed, in order to reduce the number of times of melting, a method of directly forming a film without producing pellets, or after making a paste-like semi-molten material as described above A method of forming a film is preferred.

  As the extruder, various commercially available extruders can be used, but a melt-kneading extruder is preferable, and a single-screw extruder or a twin-screw extruder may be used. When forming a film directly without producing pellets from film constituent materials, it is preferable to use a twin-screw extruder because an appropriate degree of kneading is necessary, but even with a single-screw extruder, the screw shape is a Maddock type. By changing to a kneading type screw such as unimelt or dull mage, moderate kneading can be obtained, so that it can be used. When a pellet or braided semi-melt is once used as a film constituent material, it can be used in either a single screw extruder or a twin screw extruder.

  In the extruder and in the cooling step after extrusion, it is preferable to reduce the oxygen concentration by replacing with an inert gas such as nitrogen gas or reducing the pressure.

  The melting temperature of the film constituent material in the extruder varies depending on the viscosity and discharge amount of the film constituent material, the thickness of the sheet to be manufactured, etc., but generally, with respect to the glass transition temperature (Tg) of the film, Tg or more and Tg + 100 ° C. or less, preferably Tg + 10 ° C. or more and Tg + 90 ° C. or less. Specifically, the temperature during melt extrusion is preferably 150 to 300 ° C, and particularly preferably 180 to 270 ° C. Furthermore, it is preferable that it is the range of 200-250 degreeC. The melt viscosity at the time of extrusion is 10 to 100,000 poise, preferably 100 to 10,000 poise.

  Further, the residence time of the film constituting material in the extruder is preferably shorter, and is within 5 minutes, preferably within 3 minutes, more preferably within 2 minutes. Although the residence time depends on the type of the extruder 1 and the extrusion conditions, it can be shortened by adjusting the material supply amount, L / D, screw rotation speed, screw groove depth, etc. It is.

  Extruded into a film by the above extruder, brought into close contact with a cooling drum by an electrostatic application method or the like, cooled and solidified to obtain an unstretched film. The temperature of the cooling drum is preferably maintained at 90 to 150 ° C.

  The cellulose ester film is particularly preferably a film stretched in the width direction or the film forming direction.

  The unstretched film peeled off from the cooling drum is heated within a range of Tg + 100 ° C. from the glass transition temperature (Tg) of the cellulose ester via a plurality of roll groups and / or a heating device such as an infrared heater. In addition, it is preferable to perform single-stage or multistage longitudinal stretching.

  Next, the cellulose ester film stretched in the longitudinal direction obtained as described above is preferably stretched in the transverse direction and then heat-treated.

  It is preferable to perform heat processing within the range of glass transition temperature (Tg) -20 degreeC-extending | stretching temperature, normally conveying for 0.5 to 300 second.

  The heat-treated film is usually cooled to a glass transition temperature (Tg) or lower, and clip holding portions at both ends of the film are cut and wound. Further, the cooling is preferably performed by gradually cooling from the final heat treatment temperature to the glass transition temperature (Tg) at a cooling rate of 100 ° C. or less per second.

  The means for cooling is not particularly limited, and can be performed by a conventionally known means. In particular, it is preferable to perform these treatments while sequentially cooling in a plurality of temperature ranges from the viewpoint of improving the dimensional stability of the film. The cooling rate is a value obtained by (T1−Tg) / t, where T1 is the final heat treatment temperature and t is the time until the film reaches Tg from the final heat treatment temperature.

  An ultraviolet absorber is preferably used for the cellulose ester film.

  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 the ultraviolet absorber include, for example, oxybenzophenone compounds, benzotriazole compounds, salicylic acid ester compounds, benzophenone compounds, cyanoacrylate compounds, triazine compounds, nickel complex compounds, and the like. It is not limited to.

  Specific examples of the benzotriazole-based ultraviolet absorber include the following ultraviolet absorbers, but are not limited thereto.

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)
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 (TINUVIN 109, manufactured by Ciba)
Moreover, although the following specific example is shown as a benzophenone series ultraviolet absorber, it is not limited to these.

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 UV absorber preferably used, a benzotriazole UV absorber and a benzophenone UV absorber that are highly transparent and excellent in preventing the deterioration of the polarizing plate and the liquid crystal are preferable, and the benzotriazole type with less unnecessary coloring. A UV absorber is particularly preferably used. As commercial products, TINUVIN 326, TINUVIN 109, TINUVIN 171, TINUVIN 900, TINUVIN 928, TINUVIN 928, TINUVIN 360 (all of which are Ciba Specialty Chemicals) Product), LA31 (manufactured by Asahi Denka Co., Ltd.), Sumisorb 250 (manufactured by Sumitomo Chemical Co., Ltd.), and RUVA-100 (manufactured by Otsuka Chemical).

  Moreover, the ultraviolet absorber whose distribution coefficient described in Unexamined-Japanese-Patent No. 2001-187825 is 9.2 or more improves the surface quality of a long film, and is excellent also in applicability | paintability. In particular, it is preferable to use an ultraviolet absorber having a distribution coefficient of 10.1 or more.

  In addition, fine particles can be used to impart slipperiness to the cellulose ester film.

  As fine particles, examples of inorganic compounds include silicon dioxide, titanium dioxide, aluminum oxide, zirconium oxide, calcium carbonate, calcium carbonate, talc, clay, calcined kaolin, calcined calcium silicate, hydrated calcium silicate, aluminum silicate And magnesium silicate and calcium phosphate.

  Fine particles containing silicon are preferable in terms of low turbidity, and silicon dioxide is particularly preferable.

  The average primary particle diameter of the fine particles is preferably 5 to 50 nm, and more preferably 7 to 20 nm. These are preferably contained mainly as secondary aggregates having a particle size of 0.05 to 0.3 μm. The content is preferably 0.05 to 1% by mass, particularly preferably 0.1 to 0.5% by mass.

  Silicon dioxide fine particles are commercially available under the trade names of, for example, Aerosil R972, R972V, R974, R812, 200, 200V, 300, R202, OX50, TT600 (manufactured by Nippon Aerosil Co., Ltd.), and these fine particles are used. can do.

  Zirconium oxide fine particles are commercially available, for example, under the trade names Aerosil R976 and R811 (manufactured by Nippon Aerosil Co., Ltd.), and can be used.

  Polymer particles can also be used as the fine particles, and examples of the polymer include silicone resins, fluororesins, and acrylic resins. Silicone resins are preferable, and those having a three-dimensional network structure are particularly preferable. For example, Tospearl 103, 105, 108, 120, 145, 3120, and 240 (manufactured by Toshiba Silicone Co., Ltd.) Are commercially available and can be used.

  Among these, Aerosil 200V and Aerosil R972V are particularly preferably used because they have a large effect of reducing the friction coefficient while keeping turbidity low.

  Moreover, it is preferable to contain the deterioration inhibitor demonstrated below in a cellulose-ester film.

Next, the deterioration preventing agent will be described.
(Deterioration inhibitor)
A deterioration inhibitor is a material that suppresses decomposition of a polymer by heat, oxygen, moisture, acid, or the like by a chemical action. In the case of the melt casting method, the transparent substrate film used in the present invention is formed at a high temperature of 200 ° C. or more. It is preferable to make it contain in material.

  It is represented by coloring and molecular weight reduction, including decomposition reactions that have not been elucidated, such as preventing oxidation of film-forming materials, capturing acid generated by decomposition, and suppressing or prohibiting decomposition reactions caused by radical species due to light or heat. Degradation inhibitors are used to suppress the generation of volatile components due to deterioration and material decomposition.

  Examples of the degradation inhibitor include, but are not limited to, an antioxidant, a hindered amine light stabilizer, an acid scavenger, and a metal deactivator. These are described in JP-A-3-199201, JP-A-5-1907073, JP-A-5-194789, JP-A-5-271471, JP-A-6-107854, and the like. Among these, it is preferable to contain an antioxidant as a deterioration preventing agent in the film-forming material, and from the viewpoint of the objective effect of the present invention, it is preferable to contain an antioxidant represented by the above general formula (Z). . At least one or more kinds of deterioration preventing agents in the film forming material can be selected, and the amount added from the transparency of the film is the addition of the deterioration preventing agent with respect to 100% by mass of the transparent substrate resin forming the transparent substrate film. The amount is preferably 0.01% by mass or more and 10% by mass or less, more preferably 0.1% by mass or more and 5.0% by mass or less, and further preferably 0.2% by mass or more and 2.0% by mass. It is as follows.

  The film-forming material can be stored by dividing the constituent material into one or a plurality of types of pellets for the purpose of avoiding material alteration and hygroscopicity. Pelletization may improve the mixing or compatibility of the melt during heating, or may ensure the optical uniformity of the resulting film.

  In the present invention, by adding a compound having an acryloyl group represented by the following general formula (Z) to a transparent film substrate such as a cellulose ester film, antiglare is formed on the transparent film substrate such as a cellulose ester film. An antiglare film or an antiglare antireflection film is prepared by providing a layer or an antireflection layer, and it is preferable from the viewpoint of preventing the deterioration of these films and easily exhibiting the object effects of the present invention. Hereinafter, the compound having an acryloyl group represented by the general formula (Z) will be described.

  General formula (Z)

R _{31 to} R ₃₅ in the compound having an acrylate group or a methacrylate group represented by the general formula (Z) and a phenolic hydroxyl group in the same molecule are the same or different, a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, Preferably it is a 1-5 alkyl group. The alkyl group is selected in consideration of the effect as a stabilizer and the ease of production. Specific examples of the alkyl group represented by R _{31 to} R ₃₅ include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, tert-butyl group, 1, A 1-dimethylpropyl group may be mentioned. In particular, as R31 and R32, bulky alkyl groups such as isopropyl group, sec-butyl group, tert-butyl group, and 1,1-dimethylpropyl group are sterically hindered, which has a stabilizing effect and ease of production. Also preferred above. Of these, a tert-butyl group and a 1,1-dimethylpropyl group are preferable. As R33 and R34, from the viewpoint of ease of production, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, tert-butyl group, 1,1 -A dimethylpropyl group is used, but a tert-butyl group and a 1,1-dimethylpropyl group are preferable in consideration of a formation reaction of a quinoid structure with hydrogen abstraction. R35 is preferably an alkyl group that is less likely to be sterically hindered, such as a methyl group, an ethyl group, a propyl group, or an n-butyl group, from the viewpoint of production. R ₃₆ is a hydrogen atom or a methyl group. Specific examples of the compound represented by formula (Z) are shown below, but are not limited thereto.

  Moreover, it is marketed as a brand name "Sumilyzer GS" "Sumilyzer GM" (made by Sumitomo Chemical Co., Ltd.).

It is preferable that the compound which has acryloyl group represented by general formula (Z) is used in 0.01-5 mass parts with respect to 100 mass parts of cellulose esters. Moreover, 0.1-3 mass parts is preferable and, as for content in a composition, the range of 0.5-1 mass part is especially preferable.
(Antioxidant)
It is also preferable that the cellulose ester film contains an antioxidant described below. Any antioxidant can be used without limitation as long as it is a compound that suppresses deterioration of the film-forming material due to oxygen.

Among them, phenolic antioxidants, phosphorus antioxidants, sulfur antioxidants, alkyl radical scavengers, peroxide decomposers, oxygen scavengers and the like can be mentioned. Among these, phenolic antioxidants, phosphorus antioxidants, and alkyl radical scavengers are preferable, but it is more preferable to use a combination of two of a phenolic antioxidant and a phosphorus antioxidant, and phenolic antioxidants. It is most preferable to use a combination of three of an agent, a phosphorus-based antioxidant, and an alkyl radical scavenger. By blending these antioxidants, it is possible to prevent coloration or strength reduction of the molded product due to heat during heat molding or deterioration due to thermal oxidation without lowering transparency, heat resistance and the like. These antioxidants can be used alone or in combination of two or more, and the blending amount is preferably 0.01% by mass or more and 10% by mass or less, more preferably the mass of the cellulose ester. Preferably they are 0.1 mass% or more and 5.0 mass% or less, More preferably, they are 0.2 mass% or more and 2.0 mass% or less.
(Phenolic antioxidant)
Phenol-based antioxidants are known compounds. In addition to alkyl group-substituted phenols such as para-t-butylphenol and para- (1,1,3,3-tetramethylbutyl) phenol, for example, US Pat. Examples include 2,6-dialkylphenol derivative compounds, so-called hindered phenol compounds, described in columns 12 to 14 of the specification of 839,405. Among these, hindered phenol compounds are preferable.

Specific examples of the hindered phenol phenol compound include n-octadecyl 3- (3,5-di-t-butyl-4-hydroxyphenyl) -propionate, n-octadecyl 3- (3,5-di-t- Butyl-4-hydroxyphenyl) -acetate, n-octadecyl 3,5-di-t-butyl-4-hydroxybenzoate, n-hexyl 3,5-di-t-butyl-4-hydroxyphenylbenzoate, n-dodecyl 3,5-di-t-butyl-4-hydroxyphenylbenzoate, neo-dodecyl 3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, dodecyl β (3,5-di-t- Butyl-4-hydroxyphenyl) propionate, ethyl α- (4-hydroxy-3,5-di-t-butylphenyl) isobuty Rate, octadecyl α- (4-hydroxy-3,5-di-t-butylphenyl) isobutyrate, octadecyl α- (4-hydroxy-3,5-di-t-butyl-4-hydroxyphenyl) propionate, 2- (N-octylthio) ethyl 3,5-di-t-butyl-4-hydroxy-benzoate, 2- (n-octylthio) ethyl 3,5-di-t-butyl-4-hydroxy-phenyl acetate, 2- ( n-octadecylthio) ethyl 3,5-di-t-butyl-4-hydroxyphenyl acetate, 2- (n-octadecylthio) ethyl 3,5-di-t-butyl-4-hydroxy-benzoate, 2- ( 2-hydroxyethylthio) ethyl 3,5-di-t-butyl-4-hydroxybenzoate, diethyl glycol bis- (3,5-di -T-butyl-4-hydroxy-phenyl) propionate, 2- (n-octadecylthio) ethyl 3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, stearamide N, N-bis- [ Ethylene 3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], n-butylimino N, N-bis- [ethylene 3- (3,5-di-t-butyl-4-hydroxyphenyl) ) Propionate], 2- (2-stearoyloxyethylthio) ethyl 3,5-di-t-butyl-4-hydroxybenzoate, 2- (2-stearoyloxyethylthio) ethyl 7- (3-methyl-5- t-butyl-4-hydroxyphenyl) heptanoate, 1,2-propylene glycol bis- [3- (3,5-di-t-butyl- -Hydroxyphenyl) propionate], ethylene glycol bis- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], neopentylglycol bis- [3- (3,5-di-t- Butyl-4-hydroxyphenyl) propionate], ethylene glycol bis- (3,5-di-t-butyl-4-hydroxyphenyl acetate), glycerin-1-n-octadecanoate-2,3-bis- ( 3,5-di-t-butyl-4-hydroxyphenyl acetate), pentaerythritol-tetrakis- [3- (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionate], 1,1 , 1-Trimethylolethane-tris- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propione ), Sorbitol hexa- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2-hydroxyethyl 7- (3-methyl-5-tbutyl-4-hydroxyphenyl) propionate 2-stearoyloxyethyl 7- (3-methyl-5-t-butyl-4-hydroxyphenyl) heptanoate, 1,6-n-hexanediol-bis [(3 ', 5'-di-t-butyl- 4-hydroxyphenyl) propionate], pentaerythritol-tetrakis (3,5-di-t-butyl-4-hydroxyhydrocinnamate). The above types of phenolic compounds are commercially available from Ciba Specialty Chemicals under the trade names “IRGANOX1076” and “IRGANOX1010”, for example.
(Phosphorus antioxidant)
Examples of phosphorus antioxidants include phosphite compounds and phosphonite compounds. Specific examples of the phosphite compound include triphenyl phosphite, diphenylisodecyl phosphite, phenyl diisodecyl phosphite, tris (nonylphenyl) phosphite, tris (dinonylphenyl) phosphite, tris (2,4-di -T-butylphenyl) phosphite, tris (2,4-di-t-butyl-5-methylphenyl) phosphite, 10- (3,5-di-t-butyl-4-hydroxybenzyl) -9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 6- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propoxy] -2,4,8,10- Mono such as tetra-t-butyldibenz [d, f] [1.3.2] dioxaphosphine, tridecyl phosphite Sphite compounds; 4,4'-butylidene-bis (3-methyl-6-tert-butylphenyl-di-tridecyl phosphite), 4,4'-isopropylidene-bis (phenyl-di-alkyl (C12- And diphosphite compounds such as C15) phosphite). The above type of phosphite compounds are, for example, Sumitomo Chemical Co., Ltd., “Sumilizer GP”, Asahi Denka Kogyo Co., Ltd. “ADK STAB PEP-24G”, “ADK STAB PEP-36”, “ADK STAB 3010”, “ It is marketed under the brand names of “ADK STAB HP-10” and “ADK STAB 2112”.

  Specific examples of the phosphonite compound include dimethyl-phenylphosphonite, di-t-butyl-phenylphosphonite, diphenyl-phenylphosphonite, di- (4-pentyl-phenyl) -phenylphosphonite, di- (2- t-butyl-phenyl) -phenylphosphonite, di- (2-methyl-3-pentyl-phenyl) -phenylphosphonite, di- (2-methyl-4-octyl-phenyl) -phenylphosphonite, di- ( 3-butyl-4-methyl-phenyl) -phenylphosphonite, di- (3-hexyl-4-ethyl-phenyl) -phenylphosphonite, di- (2,4,6-trimethylphenyl) -phenylphosphonite, Di- (2,3-dimethyl-4-ethyl-phenyl) -phenylphosphonite, di- (2,6-diethi -3-butylphenyl) -phenylphosphonite, di- (2,3-dipropyl-5-butylphenyl) -phenylphosphonite, di- (2,4,6-tri-t-butylphenyl) -phenylphosphonite Bis (2,4-di-t-butyl-5-methylphenyl) biphenyl-4-yl-phosphonite, bis (2,4-di-t-butyl-5-methylphenyl) -4 '-(bis ( 2,4-di-tert-butyl-5-methylphenoxy) phosphino) biphenyl-4-yl-phosphonite, tetrakis (2,4-di-tert-butyl-phenyl) -4,4'-biphenylenediphosphonite, Tetrakis (2,5-di-t-butyl-phenyl) -4,4'-biphenylenediphosphonite, tetrakis (3,5-di-t-butyl-phenyl) -4,4'-bif Nylene diphosphonite, tetrakis (2,3,4-trimethylphenyl) -4,4'-biphenylene diphosphonite, tetrakis (2,3-dimethyl-5-ethyl-phenyl) -4,4'-biphenylene diphospho Knight, tetrakis (2,3-dimethyl-4-propylphenyl) -4,4'-biphenylene diphosphonite, tetrakis (2,3-dimethyl-5-t-butylphenyl) -4,4'-biphenylene diphospho Knight, tetrakis (2,5-dimethyl-4-t-butylphenyl) -4,4'-biphenylene diphosphonite, tetrakis (2,3-diethyl-5-methylphenyl) -4,4'-biphenylene diphospho Knight, tetrakis (2,6-diethyl-4-methylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,4,5-triethylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,6-diethyl-4-propylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2, 5-diethyl-6-butylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,3-diethyl-5-t-butylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2, 5-diethyl-6-tert-butylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,3-dipropyl-5-methylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2, 6-dipropyl-4-methylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,6-dipropyl-5- Tilphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,3-dipropyl-6-butylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,6-dipropyl-5-butylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,3-dibutyl-4-methylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,5-dibutyl-3-methylphenyl) -4 , 4'-biphenylenediphosphonite, tetrakis (2,6-dibutyl-4-methylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,4-di-t-butyl-3-methylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,4-di-t-butyl-5-methylphenyl) -4 4'-biphenylenediphosphonite, tetrakis (2,4-di-t-butyl-6-methylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,5-di-t-butyl-3- Methylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,5-di-t-butyl-4-methylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,5-di-) t-butyl-6-methylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,6-di-t-butyl-3-methylphenyl) -4,4'-biphenylenediphosphonite, tetrakis ( 2,6-di-t-butyl-4-methylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,6-di-t-butyl-5-methylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,3-dibutyl-4-ethylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,4-dibutyl-3-ethylphenyl) -4 , 4'-biphenylenediphosphonite, tetrakis (2,5-dibutyl-4-ethylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,4-di-t-butyl-3-ethylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,4-di-t-butyl-5-ethylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,4-di-t-butyl) -6-ethylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,5-di-t-butyl-3-ethylphenyl) -4,4'- Phenylenediphosphonite, tetrakis (2,5-di-t-butyl-4-ethylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,5-di-t-butyl-6-ethylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,6-di-t-butyl-3-ethylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,6-di-t-butyl) -4-ethylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,6-di-t-butyl-5-ethylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,3 , 4-tributylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,4,6-tri-t-butylphenyl) -4,4'-biphenylene Phosphonite, and the like.

  The phosphorus compound of the above type is commercially available, for example, from Ciba Specialty Chemicals Co., Ltd. under the trade name “IRGAFOSP-EPQ” and from Sakai Chemical Industry Co., Ltd. as “GSY-P101”.

As the phosphorus antioxidant, phosphonite compounds are preferable, and among them, 4,4′-biphenylene diphosphonite such as tetrakis (2,4-di-t-butyl-phenyl) -4,4′-biphenylene diphosphonite. Compounds are preferred, and particularly preferred is tetrakis (2,4-di-t-butyl-5-methylphenyl) -4,4'-biphenylenediphosphonite.
(Alkyl radical scavenger)
The cellulose ester film preferably contains an alkyl radical scavenger described below. The term “alkyl radical scavenger” as used herein means a compound that has a group with which an alkyl radical can react rapidly and gives a stable product in which no subsequent reaction occurs after the reaction with the alkyl radical.
(Hindered amine light stabilizer)
Cellulose ester films have hindered amine light stabilizers (degradation inhibitors for film-forming materials during heat melting, and as degradation inhibitors for external light exposed as a polarizer protective film after production and light from the backlight of liquid crystal displays) It is preferred to add a HALS) compound. Examples of the hindered amine light stabilizer are described in US Pat. No. 4,619,956, columns 5-11 and US Pat. No. 4,839,405, columns 3-5. 2,2,6,6-tetraalkylpiperidine compounds, or acid addition salts thereof or complexes of these with metal compounds.

  Specific examples of the hindered amine light stabilizer include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (2,2,6,6-tetramethyl-4-piperidyl) succinate, bis ( 1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (N-octoxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (N-benzyloxy-2, 2,6,6-tetramethyl-4-piperidyl) sebacate, bis (N-cyclohexyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6) -Pentamethyl-4-piperidyl) 2- (3,5-di-t-butyl-4-hydroxybenzyl) -2-butylmalonate, bis (1-acryloyl-2,2,6,6- Tramethyl-4-piperidyl) 2,2-bis (3,5-di-tert-butyl-4-hydroxybenzyl) -2-butylmalonate, bis (1,2,2,6,6-pentamethyl-4- Piperidyl) decanedioate, 2,2,6,6-tetramethyl-4-piperidyl methacrylate, 4- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] -1- [ 2- (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy) ethyl] -2,2,6,6-tetramethylpiperidine, 2-methyl-2- (2,2, 6,6-tetramethyl-4-piperidyl) amino-N- (2,2,6,6-tetramethyl-4-piperidyl) propionamide, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) 1,2,3,4-butane tetracarboxylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) 1,2,3,4-butane tetracarboxylate, and the like.

  Further, it may be a polymer type compound. As specific examples, N, N ′, N ″, N ″ ′-tetrakis- [4,6-bis- [butyl- (N-methyl-2,2,6, 6-tetramethylpiperidin-4-yl) amino] -triazin-2-yl] -4,7-diazadecane-1,10-diamine, dibutylamine and 1,3,5-triazine-N, N′-bis ( 2,2,6,6-tetramethyl-4-piperidyl) -1,6-hexamethylenediamine and N- (2,2,6,6-tetramethyl-4-piperidyl) butylamine polycondensate, di Polycondensate of butylamine, 1,3,5-triazine and N, N′-bis (2,2,6,6-tetramethyl-4-piperidyl) butylamine, poly [{(1,1,3,3 -Tetramethylbutyl) amino-1,3,5-tri Gin-2,4-diyl} {(2,2,6,6-tetramethyl-4-piperidyl) imino} hexamethylene {(2,2,6,6-tetramethyl-4-piperidyl) imino}], Weight of 1,6-hexanediamine-N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) and morpholine-2,4,6-trichloro-1,3,5-triazine Condensate, poly [(6-morpholino-s-triazine-2,4-diyl) [(2,2,6,6-tetramethyl-4-piperidyl) imino] -hexamethylene [(2,2,6, 6-tetramethyl-4-piperidyl) imino]] and other high molecular weight HALS in which a plurality of piperidine rings are bonded via a triazine skeleton; dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl-1 -Piperidine Etano 1,2,3,4-butanetetracarboxylic acid, 1,2,2,6,6-pentamethyl-4-piperidinol and 3,9-bis (2-hydroxy-1,1-dimethyl) (Ethyl) -2,4,8,10-tetraoxaspiro [5,5] undecane and the like, and the like are exemplified by compounds in which a piperidine ring is bonded through an ester bond, but the present invention is not limited thereto. It is not a thing.

  Among these, polycondensates of dibutylamine, 1,3,5-triazine and N, N′-bis (2,2,6,6-tetramethyl-4-piperidyl) butylamine, poly [{(1, 1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl} {(2,2,6,6-tetramethyl-4-piperidyl) imino} hexamethylene {(2 , 2,6,6-tetramethyl-4-piperidyl) imino}], a polymer of dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol, etc. Those having a molecular weight (Mn) of 2,000 to 5,000 are preferred.

Hindered amine compounds of the above type are commercially available, for example, from Ciba Specialty Chemicals under the trade names “TINUVIN 144” and “TINUVIN 770” and from Asahi Denka Kogyo Co., Ltd. under the name “ADK STAB LA-52”. The hindered amine light stabilizer is preferably added in an amount of 0.1 to 10% by mass, more preferably 0.2 to 5% by mass, and further 0.5 to 2% by mass based on the mass of the cellulose ester. It is preferable to do. Two or more of these may be used in combination. In addition, the cellulose ester film may contain a compound represented by the following structural formula, and is manufactured under the name HP-136 from Ciba Specialty Chemicals.
(Acid scavenger)
It is preferable that an acid scavenger is contained in the cellulose ester film because it suppresses decomposition by an acid in a high temperature environment. The acid scavenger can be used without limitation as long as it is a compound that reacts with an acid to inactivate the acid, and among them, an epoxy as described in US Pat. Compounds having a group are preferred.

  Epoxy compounds as such acid scavengers are known in the art and are derived by condensation of various polyglycol diglycidyl ethers, particularly about 8 to 40 moles of ethylene oxide per mole of polyglycol. Glycol, diglycidyl ether of glycerol, etc., metal epoxy compounds (such as those conventionally used in and with vinyl chloride polymer compositions), epoxidized ether condensation products, diphenols of bisphenol A Glycidyl ether (ie, 4,4′-dihydroxydiphenyldimethylmethane), epoxidized unsaturated fatty acid ester (especially an ester of an alkyl of about 4 to 2 carbon atoms of a fatty acid of 2 to 22 carbon atoms (for example, Butyl epoxy stearate Epoxidized vegetable oils and other unsaturated natural oils, which may be represented and exemplified by compositions of various epoxidized long chain fatty acid triglycerides and the like (eg, epoxidized soybean oil, epoxidized linseed oil, etc.) As epoxidized natural glycerides or unsaturated fatty acids, which generally contain from 12 to 22 carbon atoms). Moreover, EPON 815C and other epoxidized ether oligomer condensation products can also be preferably used as commercially available epoxy group-containing epoxide resin compounds.

  In addition to the above, acid scavengers that can be used include oxetane compounds, oxazoline compounds, alkaline earth metal organic acid salts and acetylacetonate complexes, and paragraphs 0068 to 0105 in JP-A-5-194788. What is listed is included.

  The acid scavenger is preferably added in an amount of 0.1 to 10% by mass, more preferably 0.2 to 5% by mass, and more preferably 0.5 to 0.5%, based on the mass of the cellulose ester used in the present invention. It is preferable to add 2% by mass. Two or more of these may be used in combination.

In addition, although an acid scavenger may be called an acid scavenger, an acid scavenger, an acid catcher, etc., it can be used without the difference by these names.
(Metal deactivator)
It is also preferred that the cellulose ester film contains a metal deactivator. A metal deactivator means a metal ion deactivating compound that acts as an initiator or a catalyst in an oxidation reaction, and examples thereof include hydrazide compounds, oxalic acid diamide compounds, triazole compounds, and the like. N'-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyl] hydrazine, 2-hydroxyethyl oxalic acid diamide, 2-hydroxy-N- (1H-1,2,4- And triazol-3-yl) benzamide and N- (5-tert-butyl-2-ethoxyphenyl) -N '-(2-ethylphenyl) oxalic acid amide.

The metal deactivator is preferably added in an amount of 0.0002 to 2% by mass, more preferably 0.0005 to 2% by mass, and more preferably 0.001 to 100% by mass of the resin of the transparent base film. It is preferable to add ~ 1 mass%. Two or more of these may be used in combination.
(Other additives)
For the cellulose ester film, as other additives, for example, dyes, pigments, phosphors, dichroic dyes, retardation control agents, refractive index regulators, gas permeation inhibitors, antibacterial agents, biodegradability imparting agents, etc. May be added.

And, as a method of incorporating these additives into the cellulose ester film, the respective materials are mixed as solid or liquid, heated and melted and kneaded to obtain a uniform melt, and then cast into a cellulose ester film. Even in the method of forming a film, all materials may be dissolved in advance using a solvent or the like to obtain a uniform solution, and then the solvent may be removed and contained in a mixture of an additive and a cellulose ester film.
(Polarizer)
A polarizing plate using the antiglare film or the antiglare antireflection film of the present invention will be described.

  The polarizing plate can be produced by a general method. The back side of the antiglare film of the present invention is subjected to alkali saponification treatment, and a completely saponified polyvinyl alcohol aqueous solution is applied to at least one surface of a polarizing film prepared by immersing and stretching the treated antiglare film in an iodine solution. It is preferable to use and bond together.

  With respect to the antiglare film or the antiglare antireflection film of the present invention, the polarizing plate protective film used on the other surface has an in-plane retardation (Ro) of 20 to 70 nm and a thickness direction retardation (Rt). Is an optical compensation film (retardation film) having a retardation of 100 to 400 nm.

  The retardation values Ro and Rt can be measured using an automatic birefringence meter. For example, using KOBRA-21ADH (manufactured by Oji Scientific Instruments Co., Ltd.), the wavelength can be obtained at 590 nm in an environment of a temperature of 23 ° C. and a humidity of 55% RH.

  These can be prepared, for example, by the methods described in JP-A No. 2002-71957 and Japanese Patent Application No. 2002-155395. Alternatively, it is preferable to use a polarizing plate protective film that also serves as an optical compensation film having an optically anisotropic layer formed by aligning a liquid crystal compound such as a discotic liquid crystal. For example, the optically anisotropic layer can be formed by the method described in JP-A-2003-98348. Alternatively, an unoriented film having an in-plane retardation (Ro) of 0 to 5 nm and a thickness direction retardation (Rt) of -20 to +20 nm is also preferably used.

  By using in combination with the antiglare film or antiglare antireflection film of the present invention, a polarizing plate having excellent flatness and a stable viewing angle expansion effect can be obtained.

  As a polarizing plate protective film used on the back side, as a commercially available cellulose ester film, KC8UX2MW, KC4UX, KC5UX, KC4UY, KC8UY, KC12UR, KC4UEW, KC8UCR-3, KC8UCR-4, KC8UCR-5, KC4FR-1, KC4F-1, -2 (manufactured by Konica Minolta Opto Co., Ltd.) and the like are preferably used.

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 ones in which iodine is dyed on a system film and ones in which a dichroic dye is dyed, but it is not limited to this. As the polarizing film, a polyvinyl alcohol aqueous solution is formed and dyed by uniaxial stretching or dyed, or uniaxially stretched after dyeing, and then preferably subjected to a durability treatment with a boron compound. A polarizing film having a thickness of 5 to 30 μm, preferably 8 to 15 μm is preferably used. On the surface of the polarizing film, one side of the antireflection film of the present invention is bonded to form a polarizing plate. It is preferably bonded with an aqueous adhesive mainly composed of completely saponified polyvinyl alcohol or the like.
(Display device)
By incorporating the antiglare film or the antiglare antireflection film surface of the present invention on the viewing surface side of the display device, the display device of the present invention excellent in various visibility can be produced.

  The antiglare film or the antiglare antireflection film of the present invention is incorporated in a polarizing plate, and is a reflection type, transmission type, transflective LCD or TN type, STN type, OCB type, HAN type, VA type (PVA Type, MVA type), IPS type, and other various drive system LCDs. In addition, the antiglare film of the present invention has significantly less color unevenness in the reflected light of the antiglare layer, low reflectance, excellent flatness, plasma display, field emission display, organic EL display, inorganic EL display, It is also preferably used for various display devices such as electronic paper. In particular, the anti-glare film or anti-glare antireflection film of the present invention is processed as a front plate filter of a plasma display, and the mounted plasma display is a display device having excellent visibility without light interference unevenness. . In addition, even a 30-inch or larger plasma display device having a large screen has less color unevenness and wavy unevenness, and has an effect that eyes are not tired even during long-time viewing.

Examples of the present invention will be described below, but the present invention is not limited thereto.
Example 1
(Example 1-1)
-Production of transparent film substrate 1 (cellulose ester film 1) (preparation of dope solution)
The following materials were sequentially put into a sealed container, the temperature in the container was raised from 20 ° C. to 80 ° C., and the mixture was stirred for 3 hours while maintaining the temperature at 80 ° C. to completely dissolve the cellulose ester. The silicon oxide fine particles were added dispersed in a solution of a solvent to be added in advance and a small amount of cellulose ester. This dope was filtered using a filter paper (Azumi filter paper No. 244 manufactured by Azumi Filter Paper Co., Ltd.) to obtain a dope solution A.

(Preparation of dope solution A)
Cellulose triacetate (acetyl group substitution degree 2.9) 100 parts by mass Trimethylolpropane tribenzoate 5 parts by mass Ethylphthalylethyl glycolate 5 parts by mass Fine particles of silicon oxide 0.1 part by mass (Aerosil R972V, manufactured by Nippon Aerosil Co., Ltd.)
Tinuvin 109 (manufactured by Ciba Specialty Chemicals) 1 part by weight Tinuvin 171 (manufactured by Ciba Specialty Chemicals) 1 part by weight Methylene chloride 400 parts by weight Ethanol 40 parts by weight Butanol 5 parts by weight The above materials are mixed to form a dope solution A was prepared, and the obtained dope A was passed through a casting die kept at a temperature of 35 ° C. onto a support having a temperature of 35 ° C. made of a stainless steel endless belt to form a web. .

  Next, the web was dried on the support, and the web was peeled from the support with a peeling roll when the residual solvent amount of the web reached 80% by mass.

Next, the web is transported while being dried with a drying air of 90 ° C. in a transport and drying process using a plurality of rolls arranged on the top and bottom, subsequently gripping both end portions of the web with a tenter, and then before stretching in the width direction at 130 ° C. The film was stretched so as to be 1 time. After stretching with a tenter, the web was dried with a drying air of 135 ° C. in a transport drying process using a plurality of rolls arranged vertically. After heat-treating for 15 minutes in an atmosphere with an atmosphere substitution rate of 15 (times / hour) in the drying process, the film was cooled to room temperature and wound up, with a width of 1.5 m, a film thickness of 80 μm, a length of 4000 m, and a refractive index of 1.49. A long cellulose ester film 1 was produced. The draw ratio in the web conveyance direction immediately after peeling calculated from the rotational speed of the stainless steel band support and the operating speed of the tenter was 1.1 times.
-Preparation of anti-glare film 1 Anti-glare film 1 was produced to the cellulose ester film 1 produced above by the following procedure.
(Preparation of antiglare film)
On the produced cellulose ester film 1, the following antiglare layer composition 1 was treated with an ultrasonic homogenizer for 30 minutes, filtered with a polypropylene filter having a pore size of 30 μm, applied with an extrusion coater, and dried at 80 ° C. Thereafter, while purging with nitrogen so that the oxygen concentration becomes 1.0% by volume or less, using an ultraviolet lamp, the illuminance of the irradiated part is 100 mW / cm ² , and the irradiation amount is 0.15 J / cm ^2. Curing was performed to form an antiglare layer having a dry film thickness of 6.5 μm. Next, the following back coat layer composition 1 was applied to the surface opposite to the surface on which the antiglare layer was applied with a coater so as to have a wet film thickness of 10 μm, dried at 50 ° C., and antiglare film 1 Was made.

Antiglare layer coating composition 1
After mixing 80 parts by mass of cyclohexanone and 100 parts by mass of methyl ethyl ketone and crosslinked poly (acryl-styrene) particles having an average particle size of 3.0 μm (copolymerization composition ratio = 50/50), 35.0 parts by mass, And stirred for 10 minutes. Next, 80.0 parts by mass of silica particles (trade name; KEP-10, average particle size 140 nm, manufactured by Nippon Shokubai Co., Ltd.) and 80.0 parts by mass were mixed with this dispersion, and further stirred with an air disperser for 10 minutes to disperse the fine particles. A liquid was obtained. The following materials were mixed and stirred in this fine particle dispersion to prepare antiglare layer coating composition 1.

Pentaerythritol triacrylate 20.0 parts by weight Pentaerythritol tetraacrylate 40.0 parts by weight Dipentaerythritol hexaacrylate 30.0 parts by weight Dipentaerythritol pentaacrylate 30.0 parts by weight Irgacure 184 5.0 parts by weight (Ciba Specialty (Chemicals)
Irgacure 907 8.0 parts by mass (Ciba Specialty Chemicals)
Silicone surfactant (trade name: BYK-3510, manufactured by Big Chemie Japan)
1.2 parts by mass Silane coupling agent (trade name: KBM-5103, manufactured by Shin-Etsu Chemical Co., Ltd.)
8.0 parts by weight Emulgen 408 (polyoxyethylene (8) oleyl ether, manufactured by Kao Corporation)
1.0 part by mass ZX-047-D (mixed solution of 45% by mass fluorine-siloxane graft polymer and 55% by mass butyl acetate, manufactured by Fuji Kasei Kogyo Co., Ltd.) 0.8 part by mass Backcoat layer coating composition 1
Diacetyl cellulose 0.6 parts by mass Acetone 35 parts by mass Methyl ethyl ketone 35 parts by mass Methanol 35 parts by mass 2% methanol dispersion of silica particles 16 parts by mass (KE-P50, manufactured by Nippon Shokubai Co., Ltd.)
(Example 1-2)
-Preparation of anti-glare film 2 In the anti-glare film of Example 1-1 produced above, the same applies except that the anti-glare layer coating composition 1 is changed to the anti-glare layer coating composition 2 adjusted below. An antiglare film 2 was produced.

Antiglare layer coating composition 2
After 80 parts by mass of cyclohexanone and 100 parts by mass of methyl ethyl ketone and 40.0 parts by mass of crosslinked poly ((meth) acrylate) particles having an average particle size of 3.5 μm were mixed, the mixture was stirred with an air disperser for 10 minutes. Next, 80.0 parts by mass of silica particles (trade name; KEP-10, average particle size 140 nm, manufactured by Nippon Shokubai Co., Ltd.) and 80.0 parts by mass were mixed with this dispersion, and further stirred with an air disperser for 10 minutes to disperse the fine particles. A liquid was obtained. The following materials were mixed and stirred in this fine particle dispersion to obtain an antiglare layer coating composition 2.

Pentaerythritol triacrylate 20.0 parts by weight Pentaerythritol tetraacrylate 40.0 parts by weight Dipentaerythritol hexaacrylate 30.0 parts by weight Dipentaerythritol pentaacrylate 30.0 parts by weight Irgacure 184 5.0 parts by weight (Ciba Specialty (Chemicals)
Irgacure 907 8.0 parts by mass (Ciba Specialty Chemicals)
Silicone surfactant (trade name: BYK-3510, manufactured by Big Chemie Japan)
1.2 parts by mass Silane coupling agent (trade name: KBM-5103, manufactured by Shin-Etsu Chemical Co., Ltd.)
8.0 parts by weight Emulgen 408 (polyoxyethylene (8) oleyl ether, manufactured by Kao Corporation)
1.0 part by mass ZX-047-D (45% by mass fluorine-siloxane graft polymer, mixed solution of 55% by mass butyl acetate, manufactured by Fuji Kasei Kogyo Co., Ltd.) 0.8 part by mass (Example 1-3)
-Preparation of anti-glare film 3 In the anti-glare film of Example 1-1 produced above, the same applies except that the anti-glare layer coating composition 1 is changed to the anti-glare layer coating composition 3 adjusted below. An antiglare film 3 was produced.

Antiglare layer coating composition 3
After mixing 80 parts by mass of cyclohexanone and 100 parts by mass of methyl ethyl ketone and 30.0 parts by mass of crosslinked polystyrene particles having an average particle size of 3.0 μm, the mixture was stirred for 10 minutes with an air disper. Next, 80.0 parts by mass of silica particles (trade name; KEP-10, average particle size 140 nm, manufactured by Nippon Shokubai Co., Ltd.) and 80.0 parts by mass were mixed with this dispersion, and further stirred with an air disperser for 10 minutes to disperse the fine particles. A liquid was obtained. The following materials were mixed and stirred in this fine particle dispersion to obtain an antiglare layer coating composition 3.

Pentaerythritol triacrylate 20.0 parts by weight Pentaerythritol tetraacrylate 40.0 parts by weight Dipentaerythritol hexaacrylate 30.0 parts by weight Dipentaerythritol pentaacrylate 30.0 parts by weight Irgacure 184 5.0 parts by weight (Ciba Specialty (Chemicals)
Irgacure 907 8.0 parts by mass (Ciba Specialty Chemicals)
Silicone surfactant (trade name: BYK-3510, manufactured by Big Chemie Japan)
1.2 parts by mass Silane coupling agent (trade name: KBM-5103, manufactured by Shin-Etsu Chemical Co., Ltd.)
8.0 parts by weight Emulgen 408 (polyoxyethylene (8) oleyl ether, manufactured by Kao Corporation)
1.0 part by mass ZX-047-D (45% by mass fluorine-siloxane graft polymer, mixed solution of 55% by mass butyl acetate, manufactured by Fuji Kasei Kogyo Co., Ltd.) 0.8 part by mass (Example 1-4)
-Preparation of anti-glare film 4 In the anti-glare film of Example 1-1 produced above, the same applies except that the anti-glare layer coating composition 1 is changed to the anti-glare layer coating composition 4 adjusted below. An antiglare film 4 was produced.

Antiglare layer coating composition 4
After mixing 80 parts by mass of cyclohexanone and 100 parts by mass of methyl ethyl ketone and crosslinked poly (acryl-styrene) particles having an average particle size of 3.5 μm (copolymerization composition ratio = 50/50), 35.0 parts by mass, an air disper was used. Stir for 10 minutes. Next, silica particles (trade name: KEP-50, average particle size 500 nm, manufactured by Nippon Shokubai Co., Ltd.) and 70.0 parts by mass were mixed with this dispersion, and then further stirred for 10 minutes with an air disperser to disperse the fine particles. A liquid was obtained. The following materials were mixed and stirred in this fine particle dispersion to obtain an antiglare layer coating composition 4.

Pentaerythritol triacrylate 20.0 parts by weight Pentaerythritol tetraacrylate 40.0 parts by weight Dipentaerythritol hexaacrylate 30.0 parts by weight Dipentaerythritol pentaacrylate 30.0 parts by weight Irgacure 184 5.0 parts by weight (Ciba Specialty (Chemicals)
Irgacure 907 8.0 parts by mass (Ciba Specialty Chemicals)
Silicone surfactant (trade name: BYK-3510, manufactured by Big Chemie Japan)
1.2 parts by mass Silane coupling agent (trade name: KBM-5103, manufactured by Shin-Etsu Chemical Co., Ltd.)
8.0 parts by mass Emulgen 408 (polyoxyethylene (8) oleyl ether, manufactured by Kao Corporation)
1.0 part by mass ZX-047-D (45% by mass fluorine-siloxane graft polymer, mixed solution of 55% by mass butyl acetate, manufactured by Fuji Kasei Kogyo Co., Ltd.) 0.8 part by mass (Example 1-5)
-Preparation of anti-glare film 5 In the anti-glare film of Example 1-1 produced above, the same applies except that the anti-glare layer coating composition 1 is changed to the anti-glare layer coating composition 5 adjusted below. An antiglare film 5 was produced.

Antiglare layer coating composition 5
After mixing 80 parts by mass of cyclohexanone and 100 parts by mass of methyl ethyl ketone and crosslinked poly (acryl-styrene) particles having an average particle size of 3.5 μm (copolymerization composition ratio = 50/50), 35.0 parts by mass, an air disper was used. Stir for 10 minutes. Next, silica particles (trade name: KEP-100, average particle size: 1 μm, manufactured by Nippon Shokubai Co., Ltd.) and 50.0 parts by mass are mixed with this dispersion, and the mixture is further stirred with an air disperser for 10 minutes to disperse the fine particles. A liquid was obtained. The following materials were mixed and stirred in this fine particle dispersion to obtain an antiglare layer coating composition 5.

Pentaerythritol triacrylate 20.0 parts by weight Pentaerythritol tetraacrylate 40.0 parts by weight Dipentaerythritol hexaacrylate 30.0 parts by weight Dipentaerythritol pentaacrylate 30.0 parts by weight Irgacure 184 5.0 parts by weight (Ciba Specialty (Chemicals)
Irgacure 907 8.0 parts by mass (Ciba Specialty Chemicals)
Silicone surfactant (trade name: BYK-3510, manufactured by Big Chemie Japan)
1.2 parts by mass Silane coupling agent (trade name: KBM-5103, manufactured by Shin-Etsu Chemical Co., Ltd.)
8.0 parts by weight Emulgen 408 (polyoxyethylene (8) oleyl ether, manufactured by Kao Corporation)
1.0 part by mass ZX-047-D (45% by mass fluorine-siloxane graft polymer, mixed solution of 55% by mass butyl acetate, manufactured by Fuji Kasei Kogyo Co., Ltd.) 0.8 part by mass (Example 1-6)
-Preparation of anti-glare film 6 In the anti-glare film of Example 1-1 produced above, the same applies except that the anti-glare layer coating composition 1 is changed to the anti-glare layer coating composition 6 adjusted below. An antiglare film 6 was produced.

Antiglare layer coating composition 6
After 80 parts by mass of cyclohexanone and 100 parts by mass of methyl ethyl ketone and 40.0 parts by mass of crosslinked poly ((meth) acrylate) particles having an average particle size of 3.5 μm were mixed, the mixture was stirred with an air disperser for 10 minutes. Next, silica particles (trade name: KEP-100, average particle size: 1 μm, manufactured by Nippon Shokubai Co., Ltd.) and 50.0 parts by mass are mixed with this dispersion, and the mixture is further stirred with an air disperser for 10 minutes to disperse the fine particles. A liquid was obtained. The following materials were mixed and stirred in this fine particle dispersion to obtain an antiglare layer coating composition 6.

Pentaerythritol triacrylate 20.0 parts by weight Pentaerythritol tetraacrylate 40.0 parts by weight Dipentaerythritol hexaacrylate 30.0 parts by weight Dipentaerythritol pentaacrylate 30.0 parts by weight Irgacure 184 5.0 parts by weight (Ciba Specialty (Chemicals)
Irgacure 907 8.0 parts by mass (Ciba Specialty Chemicals)
Silicone surfactant (trade name: BYK-3510, manufactured by Big Chemie Japan)
1.2 parts by mass Silane coupling agent (trade name: KBM-5103, manufactured by Shin-Etsu Chemical Co., Ltd.)
8.0 parts by weight Emulgen 408 (polyoxyethylene (8) oleyl ether, manufactured by Kao Corporation)
1.0 part by mass ZX-047-D (45% by mass fluorine-siloxane graft polymer, mixed solution of 55% by mass butyl acetate, manufactured by Fuji Kasei Kogyo Co., Ltd.) 0.8 part by mass (Example 1-7)
-Preparation of anti-glare film 7 In the anti-glare film of Example 1-1 produced above, the same applies except that the anti-glare layer coating composition 1 is changed to the anti-glare layer coating composition 7 adjusted below. Thus, an antiglare film 7 was produced.

Antiglare layer coating composition 7
After mixing 80 parts by mass of cyclohexanone and 100 parts by mass of methyl ethyl ketone and 58.0 parts by mass of crosslinked polystyrene particles having an average particle size of 4.5 μm, the mixture was stirred with an air disper for 10 minutes to obtain a fine particle dispersion. The following materials were mixed and stirred in this fine particle dispersion to obtain an antiglare layer coating composition 7.

Pentaerythritol triacrylate 20.0 parts by weight Pentaerythritol tetraacrylate 40.0 parts by weight Dipentaerythritol hexaacrylate 30.0 parts by weight Dipentaerythritol pentaacrylate 30.0 parts by weight Irgacure 184 5.0 parts by weight (Ciba Specialty (Chemicals)
Irgacure 907 8.0 parts by mass (Ciba Specialty Chemicals)
Silicone surfactant (trade name: BYK-3510, manufactured by Big Chemie Japan)
1.2 parts by mass Silane coupling agent (trade name: KBM-5103, manufactured by Shin-Etsu Chemical Co., Ltd.)
8.0 parts by weight Emulgen 408 (polyoxyethylene (8) oleyl ether, manufactured by Kao Corporation)
1.0 part by mass ZX-047-D (45% by mass fluorine-siloxane graft polymer, mixed solution of 55% by mass butyl acetate, manufactured by Fuji Chemical Industry Co., Ltd.) 0.8 part by mass (Example 1-8)
-Preparation of anti-glare film 8 In the anti-glare film of Example 1-1 produced above, the same applies except that the anti-glare layer coating composition 1 is changed to the anti-glare layer coating composition 9 adjusted below. Thus, an antiglare film 8 was produced.

Antiglare layer coating composition 8
After mixing 80 parts by mass of cyclohexanone and 100 parts by mass of methyl ethyl ketone and 65.0 parts by mass of melamine resin / silica composite particles having an average particle size of 3.5 μm (trade name: Opt Beads, 3500M), the mixture was stirred with an air disper for 10 minutes. A fine particle dispersion was obtained. The following materials were mixed and stirred in this fine particle dispersion to obtain an antiglare layer coating composition 8.

Pentaerythritol triacrylate 20.0 parts by weight Pentaerythritol tetraacrylate 40.0 parts by weight Dipentaerythritol hexaacrylate 30.0 parts by weight Dipentaerythritol pentaacrylate 30.0 parts by weight Irgacure 184 5.0 parts by weight (Ciba Specialty (Chemicals)
Irgacure 907 8.0 parts by mass (Ciba Specialty Chemicals)
Silicone surfactant (trade name: BYK-3510, manufactured by Big Chemie Japan)
1.2 parts by mass Silane coupling agent (trade name: KBM-5103, manufactured by Shin-Etsu Chemical Co., Ltd.)
8.0 parts by weight Emulgen 408 (polyoxyethylene (8) oleyl ether, manufactured by Kao Corporation)
1.0 part by mass ZX-047-D (45% by mass fluorine-siloxane graft polymer, mixed solution of 55% by mass butyl acetate, manufactured by Fuji Kasei Kogyo Co., Ltd.) 0.8 part by mass (Example 1-9)
-Preparation of antiglare film 9 In the antiglare film of Example 1-1 produced above, the same applies except that the antiglare layer coating composition 1 was changed to the antiglare layer coating composition 9 adjusted as follows. Thus, an antiglare film 9 was produced.

Antiglare layer coating composition 9
After mixing 80 parts by mass of cyclohexanone and 100 parts by mass of methyl ethyl ketone and 30.0 parts by mass of melamine resin / silica composite particles having an average particle size of 3.5 μm (trade name: Opt Beads, 3500M), the mixture was stirred with an air disper for 10 minutes. A fine particle dispersion was obtained. Next, silica particles (trade name; KEP-50, average particle size 500 nm, manufactured by Nippon Shokubai Co., Ltd.) and 55.0 parts by mass were mixed into this dispersion, and then stirred with an air disperser for 10 minutes to disperse the fine particles. A liquid was obtained. The following materials were mixed and stirred in this fine particle dispersion to obtain an antiglare layer coating composition 9.

Pentaerythritol triacrylate 20.0 parts by weight Pentaerythritol tetraacrylate 40.0 parts by weight Dipentaerythritol hexaacrylate 30.0 parts by weight Dipentaerythritol pentaacrylate 30.0 parts by weight Irgacure 184 5.0 parts by weight (Ciba Specialty (Chemicals)
Irgacure 907 8.0 parts by mass (Ciba Specialty Chemicals)
Silicone surfactant (trade name: BYK-3510, manufactured by Big Chemie Japan)
1.2 parts by mass Silane coupling agent (trade name: KBM-5103, manufactured by Shin-Etsu Chemical Co., Ltd.)
8.0 parts by weight Emulgen 408 (polyoxyethylene (8) oleyl ether, manufactured by Kao Corporation)
1.0 part by mass ZX-047-D (45% by mass fluorine-siloxane graft polymer, mixed solution of 55% by mass butyl acetate, manufactured by Fuji Chemical Industry Co., Ltd.) 0.8 part by mass (Example 1-10)
-Preparation of anti-glare film 10 In the anti-glare film of Example 1-1 produced above, the same applies except that the anti-glare layer coating composition 1 is changed to the anti-glare layer coating composition 10 adjusted below. An antiglare film 10 was produced.

Antiglare layer coating composition 10
After mixing 80 parts by mass of cyclohexanone and 100 parts by mass of methyl ethyl ketone and crosslinked poly (acryl-styrene) particles having an average particle size of 4.5 μm (copolymerization composition ratio = 50/50), 25.0 parts by mass, using an air disper The mixture was stirred for 10 minutes to obtain a fine particle dispersion. Next, silica particles (trade name: KEP-50, average particle size 500 nm, manufactured by Nippon Shokubai Co., Ltd.) and 70.0 parts by mass were mixed with this dispersion, and then further stirred for 10 minutes with an air disperser to disperse the fine particles. A liquid was obtained. The following materials were mixed and stirred in this fine particle dispersion to obtain an antiglare layer coating composition 10.

Pentaerythritol triacrylate 20.0 parts by weight Pentaerythritol tetraacrylate 40.0 parts by weight Dipentaerythritol hexaacrylate 30.0 parts by weight Dipentaerythritol pentaacrylate 30.0 parts by weight Irgacure 184 5.0 parts by weight (Ciba Specialty (Chemicals)
Irgacure 907 8.0 parts by mass (Ciba Specialty Chemicals)
Silicone surfactant (trade name: BYK-3510, manufactured by Big Chemie Japan)
1.2 parts by mass Silane coupling agent (trade name: KBM-5103, manufactured by Shin-Etsu Chemical Co., Ltd.)
8.0 parts by weight Emulgen 408 (polyoxyethylene (8) oleyl ether, manufactured by Kao Corporation)
1.0 part by mass ZX-047-D (45% by mass fluorine-siloxane graft polymer, mixed solution of 55% by mass butyl acetate, manufactured by Fuji Chemical Industry Co., Ltd.) 0.8 part by mass (Example 1-11)
-Preparation of anti-glare film 11 In the anti-glare film of Example 1-1 produced above, the same applies except that the anti-glare layer coating composition 1 is changed to the anti-glare layer coating composition 11 adjusted below. An antiglare film 11 was produced.

Antiglare layer coating composition 11
After mixing 80 parts by mass of cyclohexanone and 100 parts by mass of methyl ethyl ketone with an average particle size of 5.5 μm crosslinked poly (acryl-styrene) particles (copolymerization composition ratio = 50/50) and 30.0 parts by mass, using an air disperser The mixture was stirred for 10 minutes to obtain a fine particle dispersion. Next, silica particles (trade name: KEP-50, average particle size 500 nm, manufactured by Nippon Shokubai Co., Ltd.) and 70.0 parts by mass were mixed with this dispersion, and then further stirred for 10 minutes with an air disperser to disperse the fine particles. A liquid was obtained. The following materials were mixed and stirred in this fine particle dispersion to obtain an antiglare layer coating composition 11.

Pentaerythritol triacrylate 20.0 parts by weight Pentaerythritol tetraacrylate 40.0 parts by weight Dipentaerythritol hexaacrylate 30.0 parts by weight Dipentaerythritol pentaacrylate 30.0 parts by weight Irgacure 184 5.0 parts by weight (Ciba Specialty (Chemicals)
Irgacure 907 8.0 parts by mass (Ciba Specialty Chemicals)
Silicone surfactant (trade name: BYK-3510, manufactured by Big Chemie Japan)
1.2 parts by mass Silane coupling agent (trade name: KBM-5103, manufactured by Shin-Etsu Chemical Co., Ltd.)
8.0 parts by weight Emulgen 408 (polyoxyethylene (8) oleyl ether, manufactured by Kao Corporation)
1.0 part by mass ZX-047-D (45% by mass fluorine-siloxane graft polymer, mixed solution of 55% by mass butyl acetate, manufactured by Fuji Kasei Kogyo Co., Ltd.) 0.8 part by mass (Example 1-12)
-Preparation of anti-glare film 12 In the anti-glare film of Example 1-1 produced above, the same applies except that the anti-glare layer coating composition 1 is changed to the anti-glare layer coating composition 12 adjusted below. An antiglare film 12 was produced.

Antiglare layer coating composition 12
After mixing 80 parts by mass of cyclohexanone and 100 parts by mass of methyl ethyl ketone and 30.0 parts by mass of crosslinked polystyrene particles having an average particle size of 5.5 μm, the mixture was stirred with an air disperser for 10 minutes to obtain a fine particle dispersion. Next, silica particles (trade name: KEP-50, average particle size 500 nm, manufactured by Nippon Shokubai Co., Ltd.) and 70.0 parts by mass were mixed with this dispersion, and then further stirred for 10 minutes with an air disperser to disperse the fine particles. A liquid was obtained. The following materials were mixed and stirred in this fine particle dispersion to obtain an antiglare layer coating composition 12.

Pentaerythritol triacrylate 20.0 parts by weight Pentaerythritol tetraacrylate 40.0 parts by weight Dipentaerythritol hexaacrylate 30.0 parts by weight Dipentaerythritol pentaacrylate 30.0 parts by weight Irgacure 184 5.0 parts by weight (Ciba Specialty (Chemicals)
Irgacure 907 8.0 parts by mass (Ciba Specialty Chemicals)
Silicone surfactant (trade name: BYK-3510, manufactured by Big Chemie Japan)
1.2 parts by mass Silane coupling agent (trade name: KBM-5103, manufactured by Shin-Etsu Chemical Co., Ltd.)
8.0 parts by weight Emulgen 408 (polyoxyethylene (8) oleyl ether, manufactured by Kao Corporation)
1.0 part by mass ZX-047-D (45% by mass fluorine-siloxane graft polymer, mixed solution of 55% by mass butyl acetate, manufactured by Fuji Kasei Kogyo Co., Ltd.) 0.8 part by mass (Example 1-13)
-Preparation of anti-glare film 13 In the anti-glare film of Example 1-1 produced above, the same applies except that the anti-glare layer coating composition 1 was changed to the anti-glare layer coating composition 13 prepared below. An antiglare film 13 was produced.

Antiglare layer coating composition 13
After mixing 80 parts by mass of cyclohexanone and 100 parts by mass of methyl ethyl ketone and crosslinked poly (acryl-styrene) particles having an average particle size of 3.5 μm (copolymerization composition ratio = 50/50), 30.0 parts by mass, using an air disper Stir for 10 minutes. Next, 85.0 parts by mass of cross-linked poly (acryl-styrene) particles (trade name: MG-251, average particle size 450 nm, manufactured by Nippon Paint Co., Ltd.) were mixed with this dispersion, and then further mixed with an air disperser for 10 minutes. Stirring to obtain a fine particle dispersion. The following materials were mixed and stirred in this fine particle dispersion to obtain an antiglare layer coating composition 13.

Pentaerythritol triacrylate 20.0 parts by weight Pentaerythritol tetraacrylate 40.0 parts by weight Dipentaerythritol hexaacrylate 30.0 parts by weight Dipentaerythritol pentaacrylate 30.0 parts by weight Irgacure 184 5.0 parts by weight (Ciba Specialty (Chemicals)
Irgacure 907 8.0 parts by mass (Ciba Specialty Chemicals)
Silicone surfactant (trade name: BYK-3510, manufactured by Big Chemie Japan)
1.2 parts by mass Silane coupling agent (trade name: KBM-5103, manufactured by Shin-Etsu Chemical Co., Ltd.)
8.0 parts by weight Emulgen 408 (polyoxyethylene (8) oleyl ether, manufactured by Kao Corporation)
1.0 part by mass ZX-047-D (45% by mass fluorine-siloxane graft polymer, mixed solution of 55% by mass butyl acetate, manufactured by Fuji Kasei Kogyo Co., Ltd.) 0.8 part by mass (Comparative Example 1-1)
-Preparation of anti-glare film 14 In the anti-glare film of Example 1-1 produced above, the same applies except that the anti-glare layer coating composition 1 is changed to the anti-glare layer coating composition 14 adjusted below. An antiglare film 14 was produced.

Antiglare layer coating composition 14
After mixing 80 parts by mass of cyclohexanone and 100 parts by mass of methyl ethyl ketone and 45.0 parts by mass of crosslinked poly ((meth) acrylate) particles having an average particle size of 3.5 μm, the mixture is further stirred for 10 minutes with an air disperser, and a fine particle dispersion Got. The following materials were mixed and stirred in this fine particle dispersion to obtain an antiglare layer coating composition 14.

Pentaerythritol triacrylate 20.0 parts by weight Pentaerythritol tetraacrylate 40.0 parts by weight Dipentaerythritol hexaacrylate 30.0 parts by weight Dipentaerythritol pentaacrylate 30.0 parts by weight Irgacure 184 5.0 parts by weight (Ciba Specialty (Chemicals)
Irgacure 907 8.0 parts by mass (Ciba Specialty Chemicals)
Silicone surfactant (trade name: BYK-3510, manufactured by Big Chemie Japan)
1.2 parts by mass Silane coupling agent (trade name: KBM-5103, manufactured by Shin-Etsu Chemical Co., Ltd.)
8.0 parts by weight Emulgen 408 (polyoxyethylene (8) oleyl ether, manufactured by Kao Corporation)
1.0 part by mass ZX-047-D (45% by mass fluorine-siloxane graft polymer, mixed solution of 55% by mass butyl acetate, manufactured by Fuji Kasei Kogyo Co., Ltd.) 0.8 part by mass (Comparative Example 1-2)
-Preparation of anti-glare film 15 In the anti-glare film of Example 1-1 produced above, the same applies except that the anti-glare layer coating composition 1 is changed to the anti-glare layer coating composition 15 adjusted below. An antiglare film 15 was produced.

Antiglare layer coating composition 15
After mixing 80 parts by mass of cyclohexanone and 100 parts by mass of methyl ethyl ketone and crosslinked poly (acryl-styrene) particles having an average particle size of 3.5 μm (copolymerization composition ratio = 50/50), 45.0 parts by mass, the mixture was further added to the air disperser. For 10 minutes to obtain a fine particle dispersion. The following materials were mixed and stirred in this fine particle dispersion to obtain an antiglare layer coating composition 15.

Pentaerythritol triacrylate 20.0 parts by weight Pentaerythritol tetraacrylate 40.0 parts by weight Dipentaerythritol hexaacrylate 30.0 parts by weight Dipentaerythritol pentaacrylate 30.0 parts by weight Irgacure 184 5.0 parts by weight (Ciba Specialty (Chemicals)
Irgacure 907 8.0 parts by mass (Ciba Specialty Chemicals)
Silicone surfactant (trade name: BYK-3510, manufactured by Big Chemie Japan)
1.2 parts by mass Silane coupling agent (trade name: KBM-5103, manufactured by Shin-Etsu Chemical Co., Ltd.)
8.0 parts by weight Emulgen 408 (polyoxyethylene (8) oleyl ether, manufactured by Kao Corporation)
1.0 part by mass ZX-047-D (45% by mass fluorine-siloxane graft polymer, mixed solution of 55% by mass butyl acetate, manufactured by Fuji Kasei Kogyo Co., Ltd.) 0.8 part by mass (Comparative Example 1-3)
-Preparation of anti-glare film 16 In the anti-glare film of Example 1-1 produced above, the anti-glare layer coating composition 1 was changed to the anti-glare layer coating composition 16 adjusted as follows. An antiglare film 16 was produced.

Antiglare layer coating composition 16
After mixing 80 parts by mass of cyclohexanone and 100 parts by mass of methyl ethyl ketone and crosslinked poly (acryl-styrene) particles having an average particle size of 3.5 μm (copolymerization composition ratio = 50/50), 30.0 parts by mass, using an air disper The mixture was stirred for 10 minutes to obtain a fine particle dispersion. Next, silica particles (trade name: KEP-100, average particle size 1 μm, manufactured by Nippon Shokubai Co., Ltd.) and 110.0 parts by mass were mixed with this dispersion, and then further stirred for 10 minutes with an air disperser to disperse the fine particles. A liquid was obtained. The following materials were mixed and stirred in this fine particle dispersion to obtain an antiglare layer coating composition 16.

Pentaerythritol triacrylate 20.0 parts by weight Pentaerythritol tetraacrylate 40.0 parts by weight Dipentaerythritol hexaacrylate 30.0 parts by weight Dipentaerythritol pentaacrylate 30.0 parts by weight Irgacure 184 5.0 parts by weight (Ciba Specialty (Chemicals)
Irgacure 907 8.0 parts by mass (Ciba Specialty Chemicals)
Silicone surfactant (trade name: BYK-3510, manufactured by Big Chemie Japan)
1.2 parts by mass Silane coupling agent (trade name: KBM-5103, manufactured by Shin-Etsu Chemical Co., Ltd.)
8.0 parts by weight Emulgen 408 (polyoxyethylene (8) oleyl ether, manufactured by Kao Corporation)
1.0 part by mass ZX-047-D (45% by mass fluorine-siloxane graft polymer, mixed solution of 55% by mass butyl acetate, manufactured by Fuji Kasei Kogyo Co., Ltd.) 0.8 part by mass (Comparative Example 1-4)
-Preparation of anti-glare film 17 In the anti-glare film of Example 1-1 produced above, the same applies except that the anti-glare layer coating composition 1 is changed to the anti-glare layer coating composition 17 adjusted below. An antiglare film 17 was produced.

Antiglare layer coating composition 17
After mixing 80 parts by mass of cyclohexanone and 100 parts by mass of methyl ethyl ketone and crosslinked poly (acryl-styrene) particles having an average particle size of 3.5 μm (copolymerization composition ratio = 50/50), 30.0 parts by mass, using an air disper The mixture was stirred for 10 minutes to obtain a fine particle dispersion. Next, silica particles (trade name: KEP-100, average particle size 100 nm, manufactured by Nippon Shokubai Co., Ltd.) and 125.0 parts by mass were mixed with this dispersion, and then stirred for 10 minutes with an air disperser to disperse the fine particles. A liquid was obtained. The following materials were mixed and stirred in this fine particle dispersion to obtain an antiglare layer coating composition 17.

Pentaerythritol triacrylate 20.0 parts by weight Pentaerythritol tetraacrylate 40.0 parts by weight Dipentaerythritol hexaacrylate 30.0 parts by weight Dipentaerythritol pentaacrylate 30.0 parts by weight Irgacure 184 5.0 parts by weight (Ciba Specialty (Chemicals)
Irgacure 907 8.0 parts by mass (Ciba Specialty Chemicals)
Silicone surfactant (trade name: BYK-3510, manufactured by Big Chemie Japan)
1.2 parts by mass Silane coupling agent (trade name: KBM-5103, manufactured by Shin-Etsu Chemical Co., Ltd.)
8.0 parts by weight Emulgen 408 (polyoxyethylene (8) oleyl ether, manufactured by Kao Corporation)
1.0 part by mass ZX-047-D (45% by mass fluorine-siloxane graft polymer, mixed solution of 55% by mass butyl acetate, manufactured by Fuji Kasei Kogyo Co., Ltd.) 0.8 part by mass (Comparative Example 1-5)
-Preparation of anti-glare film 18 In the anti-glare film of Example 1-1 produced above, the same applies except that the anti-glare layer coating composition 1 is changed to the anti-glare layer coating composition 18 adjusted below. An antiglare film 18 was produced.

Antiglare layer coating composition 18
After mixing 80 parts by mass of cyclohexanone and 100 parts by mass of methyl ethyl ketone with silica particles (trade name: KEP-100, average particle size 100 nm, manufactured by Nippon Shokubai Co., Ltd.) and 155.0 parts by mass, the mixture is further stirred with an air disperser for 10 minutes. As a result, a fine particle dispersion was obtained. The following materials were mixed and stirred in this fine particle dispersion to obtain an antiglare layer coating composition 18.

Pentaerythritol triacrylate 20.0 parts by weight Pentaerythritol tetraacrylate 40.0 parts by weight Dipentaerythritol hexaacrylate 30.0 parts by weight Dipentaerythritol pentaacrylate 30.0 parts by weight Irgacure 184 5.0 parts by weight (Ciba Specialty (Chemicals)
Irgacure 907 8.0 parts by mass (Ciba Specialty Chemicals)
Silicone surfactant (trade name: BYK-3510, manufactured by Big Chemie Japan)
1.2 parts by mass Silane coupling agent (trade name: KBM-5103, manufactured by Shin-Etsu Chemical Co., Ltd.)
8.0 parts by weight Emulgen 408 (polyoxyethylene (8) oleyl ether, manufactured by Kao Corporation)
1.0 part by mass ZX-047-D (45% by mass fluorine-siloxane graft polymer, mixed solution of 55% by mass butyl acetate, manufactured by Fuji Kasei Kogyo Co., Ltd.) 0.8 part by mass (Comparative Example 1-6)
-Preparation of the anti-glare film 19 In the anti-glare film of Example 1-1 produced above, the anti-glare layer coating composition 1 was changed to the anti-glare layer coating composition 19 adjusted as follows. An antiglare film 19 was produced.

Antiglare layer coating composition 19
After mixing 80 parts by mass of cyclohexanone and 100 parts by mass of methyl ethyl ketone and 170.0 parts by mass of crosslinked poly (acryl-styrene) particles (trade name: MG-251, average particle size 450 nm, manufactured by Nippon Paint Co., Ltd.), air disperser is further added. For 10 minutes to obtain a fine particle dispersion. The following materials were mixed and stirred in this fine particle dispersion to obtain an antiglare layer coating composition 19.

Pentaerythritol triacrylate 20.0 parts by weight Pentaerythritol tetraacrylate 40.0 parts by weight Dipentaerythritol hexaacrylate 30.0 parts by weight Dipentaerythritol pentaacrylate 30.0 parts by weight Irgacure 184 5.0 parts by weight (Ciba Specialty (Chemicals)
Irgacure 907 8.0 parts by mass (Ciba Specialty Chemicals)
Silicone surfactant (trade name: BYK-3510, manufactured by Big Chemie Japan)
1.2 parts by mass Silane coupling agent (trade name: KBM-5103, manufactured by Shin-Etsu Chemical Co., Ltd.)
8.0 parts by weight Emulgen 408 (polyoxyethylene (8) oleyl ether, manufactured by Kao Corporation)
1.0 part by mass ZX-047-D (45% by mass fluorine-siloxane graft polymer, mixed solution of 55% by mass butyl acetate, manufactured by Fuji Kasei Kogyo Co., Ltd.) 0.8 part by mass (Comparative Example 1-7)
-Preparation of anti-glare film 20 In the anti-glare film of Example 1-1 produced above, the same applies except that the anti-glare layer coating composition 1 is changed to the anti-glare layer coating composition 20 adjusted below. An antiglare film 20 was produced.

Antiglare layer coating composition 20
After mixing 80 parts by mass of cyclohexanone, 100 parts by mass of methyl ethyl ketone, 6.5 μm poly ((meth) acrylate) particles having an average particle diameter of 60.0 parts by mass, the mixture is stirred for 10 minutes with an air disper to obtain a fine particle dispersion. It was. The following materials were mixed and stirred in this fine particle dispersion to obtain an antiglare layer coating composition 20.

Pentaerythritol triacrylate 20.0 parts by weight Pentaerythritol tetraacrylate 40.0 parts by weight Dipentaerythritol hexaacrylate 30.0 parts by weight Dipentaerythritol pentaacrylate 30.0 parts by weight Irgacure 184 5.0 parts by weight (Ciba Specialty (Chemicals)
Irgacure 907 8.0 parts by mass (Ciba Specialty Chemicals)
Silicone surfactant (trade name: BYK-3510, manufactured by Big Chemie Japan)
1.2 parts by mass Silane coupling agent (trade name: KBM-5103, manufactured by Shin-Etsu Chemical Co., Ltd.)
8.0 parts by weight Emulgen 408 (polyoxyethylene (8) oleyl ether, manufactured by Kao Corporation)
1.0 part by mass ZX-047-D (45% by mass fluorine-siloxane graft polymer, mixed solution of 55% by mass butyl acetate, manufactured by Fuji Kasei Kogyo Co., Ltd.) 0.8 part by mass (Comparative Example 1-8)
-Preparation of anti-glare film 21 In the anti-glare film of Example 1-1 produced above, the same applies except that the anti-glare layer coating composition 1 is changed to the anti-glare layer coating composition 21 adjusted below. An antiglare film 21 was produced.

Antiglare layer coating composition 21
After mixing 80 parts by mass of cyclohexanone, 100 parts by mass of methyl ethyl ketone, 6.5 μm-crosslinked poly (acryl-styrene) particles (copolymerization composition ratio = 50/50), 58.0 parts by mass with an air disperser. The mixture was stirred for 10 minutes to obtain a fine particle dispersion. The following materials were mixed and stirred in this fine particle dispersion to obtain an antiglare layer coating composition 21.

Pentaerythritol triacrylate 20.0 parts by weight Pentaerythritol tetraacrylate 40.0 parts by weight Dipentaerythritol hexaacrylate 30.0 parts by weight Dipentaerythritol pentaacrylate 30.0 parts by weight Irgacure 184 5.0 parts by weight (Ciba Specialty (Chemicals)
Irgacure 907 8.0 parts by mass (Ciba Specialty Chemicals)
Silicone surfactant (trade name: BYK-3510, manufactured by Big Chemie Japan)
1.2 parts by mass Silane coupling agent (trade name: KBM-5103, manufactured by Shin-Etsu Chemical Co., Ltd.)
8.0 parts by weight Emulgen 408 (polyoxyethylene (8) oleyl ether, manufactured by Kao Corporation)
1.0 part by mass ZX-047-D (45% by mass fluorine-siloxane graft polymer, mixed solution of 55% by mass butyl acetate, manufactured by Fuji Kasei Kogyo Co., Ltd.) 0.8 part by mass (evaluation of antiglare film)
The following items were evaluated about the obtained film. The results are shown in Table 1.
(1) Haze Total haze (H), internal haze (Hi), and surface haze (Hs) of the obtained film were measured by the following measurements.

  1. The total haze value (H) of the film obtained according to JIS-K7136 is measured.

  2. A few drops of silicone oil are added to the front and back surfaces of the antiglare layer side of the obtained film, and two glass plates (micro slide glass product number S 9111, manufactured by MATSUNAMI) with a thickness of 1 mm are used to be sandwiched from the front and back. Two glass plates and the obtained film were optically adhered, and the haze was measured with the surface haze removed, and the haze was measured by sandwiching only silicone oil between two separately measured glass plates. The value obtained by subtracting was calculated as the internal haze (Hi) of the film.

  3. The value obtained by subtracting the internal haze (Hi) calculated in 2 above from the total haze (H) measured in 1 above was calculated as the surface haze (Hs) of the film.

In addition, the haze value as used in the field of this invention means the total haze (H) obtained by the said method.
(2) Film strength evaluation / alkali saponification treatment The antiglare films of Examples 1 to 11 and Comparative Examples 1 to 8 prepared above were cut in A4 size, and 2 mol / L potassium hydroxide solution at 60 ° C. for 4 minutes. It was immersed, then washed with water and dried to produce an anti-glare film that had been subjected to alkali saponification treatment. Next, with the antiglare layer of the saponified antiglare film as the surface, the film was irradiated with light for 120 hours using a weather resistance tester (eye super UV tester, manufactured by Iwasaki Electric Co., Ltd.). Subsequently, these samples were conditioned for 2 hours under the conditions of a temperature of 25 ° C. and a relative humidity of 60%, and then tested for the following scratch resistance and pencil hardness to evaluate the film strength of the antiglare film.
-Scratch resistance A load of 500 g / cm < ² > was applied on steel wool (SW) of product number # 0000 manufactured by Nippon Steel Wool Co., Ltd., and the antiglare layer surface was reciprocated 20 times. The number of scratches generated per 1 cm width after 20 reciprocations was measured to evaluate the scratch resistance. The number of scratches is preferably 5 / cm width or less from the practical viewpoint. Particularly preferably, it is 1 / cm width or less. The obtained results are shown in Table 1 below. In addition, the apparatus which reciprocated steel wool used the Shinto Kagaku Co., Ltd. friction abrasion tester (Tribo station TYPE: 32, moving speed 1000mm / min.).
・ Pencil hardness Using the test pencil specified by JIS-S6006, according to the pencil hardness evaluation method specified by JIS-K5400, the surface of the antiglare layer was repeatedly scratched and scratched with a pencil of each hardness using a 1 kg weight. The hardness of up to 1 was measured. The higher the number is, the higher the hardness is, and the hardness is 3H or more, which is practically preferable.
(3) Evaluation of ozone exposure durability test The anti-glare films not subjected to the alkali saponification treatment of Examples 1 to 11 and Comparative Examples 1 to 8 were cut into A4 size, and the environment was ozone 10 ppm, 30 ° C., 60% RH. The sample was stored for 500 hours below to prepare an ozone exposure durability test sample. Next, the membrane strength of the ozone exposure durability test sample was also evaluated by the above test method. The obtained results are shown in Tables 1 and 2.

As apparent from the results of Tables 1 and 2, the haze value (internal haze) due to internal scattering of the antiglare layer is 50 to 70%, and the haze value (surface haze) due to surface scattering is 7 to 70%. It turns out that the anti-glare film of the Example of this invention which is 20% has the outstanding film | membrane intensity | strength. Of these, those having an internal haze of 60 to 70% are found to have particularly excellent film strength (scratch resistance). The antiglare layer contains two kinds of light-transmitting fine particles having different average particle diameters, and the average particle diameter of the first light-transmitting fine particles is 0.01 to 1 μm. It contains translucent fine particles having an average particle diameter of 2 to 6 μm, and the content ratio of the first translucent fine particles to the second translucent fine particles is 1.0: 1.0 to 3.0. : 1.0 indicates that the film has excellent film strength.
(Example 2)
(Example 2-1)
-Preparation of anti-glare film 22 In the anti-glare film of Example 1-4 produced above, an average particle size of 3.5 μm crosslinked poly (acryl-styrene) particles (copolymerization composition ratio = 50/50) was manufactured by Negami Kogyo. An anti-glare film 22 was produced in the same manner except that it was changed to fluorine-containing polymethyl methacrylate fine particles (trade name: MF-0043) having an average particle size of 3.5 μm.
(Example 2-2)
-Preparation of anti-glare film 23 In the anti-glare film of Example 1-5 produced above, an average particle size of 3.5 μm crosslinked poly (acryl-styrene) particles (copolymerization composition ratio = 50/50) Changed to fluorine-containing polymethyl methacrylate fine particles (trade name: MF-0043) having an average particle size of 3.5 μm, and silica particles (trade name: KEP-50, average particle size: 500 nm, manufactured by Nippon Shokubai Co., Ltd.) An antiglare film 23 was produced in the same manner except that the fluorine-containing polymethyl methacrylate fine particles having an average particle size of 550 nm (trade name: F-191, manufactured by Nippon Paint Co., Ltd.) were used.

  The antiglare films 22 and 23 of Examples 2-1 and 2-2 produced above and the antiglare film 4 produced in Example 1-4 were cut in A4 size, and a 3 mol / L potassium hydroxide solution was obtained. Was immersed in the film at 60 ° C. for 2 minutes to produce an anti-glare film that had been subjected to alkali saponification treatment. Next, these saponified anti-glare films were stored in an environment of ozone 10 ppm, 30 ° C., 60% RH for 850 hours to prepare a durability test sample. Next, these manufactured durability test samples were evaluated for film strength using the test method described above. The obtained results are shown in Table 3.

As is clear from the results of Table 3, in the more severe durability test, the antiglare layer has particularly excellent film strength by containing the fluorine-containing acrylic resin fine particles among the translucent fine particles. I understand.
(Example 3)
(Example 3-1)
-Preparation of the anti-glare film 24 In preparation of the anti-glare film of Example 1-4, except having changed the transparent film base material 1 into the transparent film base material 2, the anti-glare film 22 is produced. The durability test was performed under the same conditions as in Example 2. The film strength of the sample subjected to the durability test was evaluated by the test method described above. The obtained results are shown in Table 3.
-Production of transparent film substrate 2 (cellulose ester film 2) (Preparation of dope solution)
The following materials were sequentially put into a sealed container, the temperature in the container was raised from 20 ° C. to 80 ° C., and the mixture was stirred for 3 hours while maintaining the temperature at 80 ° C. to completely dissolve the cellulose ester. . The silicon oxide fine particles were added dispersed in a solution of a solvent to be added in advance and a small amount of cellulose ester. This dope was filtered using a filter paper (Azumi filter paper No. 244, manufactured by Azumi Filter Paper Co., Ltd.) to obtain a dope solution B.

(Preparation of dope solution B)
Cellulose triacetate (acetyl group substitution degree 2.9) 100 parts by mass Trimethylolpropane tribenzoate 5 parts by mass Ethylphthalylethyl glycolate 5 parts by mass Fine particles of silicon oxide 0.1 part by mass (Aerosil R972V, manufactured by Nippon Aerosil Co., Ltd.)
Tinuvin 109 (manufactured by Ciba Specialty Chemicals) 1 part by weight Tinuvin 171 (manufactured by Ciba Specialty Chemicals) 1 part by weight Methylene chloride 400 parts by weight Ethanol 40 parts by weight Butanol 5 parts by weight Sumilyzer GS (manufactured by Sumitomo Chemical Co., Ltd.) 0.25 parts by mass Sumilizer GM (manufactured by Sumitomo Chemical Co., Ltd.) 0.25 parts by mass The above materials were mixed to prepare a dope solution B, and the resulting dope solution B was kept at a temperature of 35 ° C. The web was cast on a support made of stainless steel endless belt and having a temperature of 35 ° C.

  Next, the web was dried on the support, and the web was peeled from the support with a peeling roll when the residual solvent amount of the web reached 80% by mass.

  Next, the web is transported while being dried with a drying air of 90 ° C. in a transport and drying process using a plurality of rolls arranged on the upper and lower sides. Subsequently, both ends of the web are gripped with a tenter, and then the web 1 is stretched in the width direction at 130 ° C. The film was stretched so as to be 1 time. After stretching with a tenter, the web was dried with a drying air of 135 ° C. in a transport drying process using a plurality of rolls arranged vertically. After heat-treating for 15 minutes in an atmosphere with an atmosphere substitution rate of 15 (times / hour) in the drying process, the film was cooled to room temperature and wound up. A long cellulose ester film 2 was produced. The draw ratio in the web conveyance direction immediately after peeling calculated from the rotational speed of the stainless steel band support and the operating speed of the tenter was 1.1 times. The surface roughness (Ra) of the film was 6 nm as measured using an optical interference surface roughness meter (RST / PLUS, manufactured by WYKO).

As can be seen from the results in Table 4, in a more severe durability test, the transparent film substrate 2 contains a compound having an acryloyl group represented by the general formula (Z), thereby exhibiting superior film strength. To do.
Example 4
-Production of antiglare antireflection films 1 and 2 Antiglare antireflection films 1 and 2 were produced using the antiglare films produced in Example 1-5 and Comparative Example 1-1.
<Atmospheric pressure plasma treatment>
First, on the surface of the antiglare layer of the antiglare film produced in Example 1-5 and Comparative Example 1-1, an atmospheric pressure plasma processing apparatus was used, the electrode gap was set to 0.5 mm, and the following discharge gas was discharged into the discharge space. Was discharged at 100 kHz, and surface treatment was performed by atmospheric pressure plasma treatment.
(Discharge gas)
Nitrogen gas 80.0% by volume
Oxygen gas 20.0% by volume
<Formation of high refractive index layer>
In coating a high refractive index layer on the surface of the antiglare layer of each antiglare film treated with atmospheric pressure plasma, a particle dispersion A was prepared, and then a coating composition for a high refractive index layer was prepared.
(Preparation of particle dispersion A)
Methanol-dispersed antimony double oxide colloid (zinc antimonate sol, solid content 60%, trade name: Celnax CX-Z610M-F2, manufactured by Nissan Chemical Industries, Ltd.) 6.0 kg and gradually stirring 12.0 kg of isopropyl alcohol To prepare a fine particle dispersion A.
(Coating composition for high refractive index layer)
PGME (propylene glycol monomethyl ether) 40 parts by mass Isopropyl alcohol 25 parts by mass Methyl ethyl ketone 25 parts by mass Pentaerythritol triacrylate 0.9 parts by mass Pentaerythritol tetraacrylate 1.0 part by mass Urethane acrylate 0.6 parts by mass (trade name: U- 4HA, manufactured by Shin-Nakamura Chemical Co., Ltd.)
Fine particle dispersion A 20 parts by mass 1-hydroxy-cyclohexyl-phenyl-ketone 0.4 parts by mass (Irgacure 184, manufactured by Ciba Specialty Chemicals)
2-Methyl-1- [4- (methylthio) phenyl] -2-monoforinopropan-1-one (Irgacure 907, manufactured by Ciba Specialty Chemicals) 0.2 parts by mass FZ-2207 0.4 parts by mass (10% propylene glycol monomethyl ether solution, manufactured by Nihon Unicar)
The anti-glare layer surface of each anti-glare film treated with atmospheric pressure plasma is die-coated with the coating composition for high refractive index layer and dried at a temperature of 70 ° C., and then the oxygen concentration is 1.0% by volume or less. A high refractive index layer was provided so that the film thickness after curing was 120 nm by irradiating ultraviolet rays of 0.18 J / cm ² with a high-pressure mercury lamp while purging with an atmosphere of nitrogen. The refractive index of the high refractive index layer was 1.60.
<Formation of low refractive index layer>
In forming a low refractive index layer on each antiglare film surface coated with the above high refractive index layer, first, an isopropyl alcohol dispersion of hollow silica fine particles 1 and a tetraethoxysilane hydrolyzate A were prepared. Then, the coating composition 1 for low refractive index layers was prepared.
(Preparation of isopropyl alcohol dispersion of hollow silica fine particles 1)
Step (a): A mixture of 100 g of silica sol having an average particle diameter of 5 nm and a SiO ₂ concentration of 20% by mass and 1900 g of pure water was heated to 80 ° C. The pH of this reaction mother liquor was 10.5, and 9000 g of 0.98 mass% sodium silicate aqueous solution as SiO ₂ and 9000 g of 1.02 mass% sodium aluminate aqueous solution as Al ₂ O ₃ were added to the mother liquor. Added simultaneously. Meanwhile, the temperature of the reaction solution was kept at 80 ° C. The pH of the reaction solution rose to 12.5 immediately after the addition and hardly changed thereafter. After completion of the addition, the reaction solution was cooled to room temperature and washed with an ultrafiltration membrane to prepare a SiO ₂ .Al ₂ O ₃ core particle dispersion having a solid content concentration of 20% by mass.

Step (b): Obtained by adding 1700 g of pure water to 500 g of this core particle dispersion and heating to 98 ° C., and maintaining the temperature while dealkalizing the sodium silicate aqueous solution with a cation exchange resin. Further, 3000 g of a silicic acid solution (SiO ₂ concentration: 3.5% by mass) was added to obtain a dispersion of core particles in which a first silica coating layer was formed.

Step (c): Next, 1125 g of pure water was added to 500 g of the core particle dispersion formed with the first silica coating layer washed with an ultrafiltration membrane to a solid content concentration of 13% by mass, and concentrated hydrochloric acid (35. 5%) was added dropwise to adjust the pH 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 (d): A mixture of 1500 g of the above porous particle dispersion, 500 g of pure water, 1,750 g of ethanol, and 626 g of 28% aqueous ammonia is heated to a temperature of 35 ° C., and then ethyl silicate ( It was added SiO ₂ 28 wt%) 104 g, the surface of the porous particles forming the first silica coating layer, coated with hydrolyzed polycondensate of ethyl silicate, to form a second silica coating layer. Next, a dispersion of hollow silica fine particles 1 having a solid content concentration of 20% by mass was prepared by replacing the solvent with isopropyl alcohol using an ultrafiltration membrane.

The thickness of the first silica coating layer of the hollow silica fine particles was 3 nm, the average particle size was 45 nm, MOx / SiO ₂ (molar ratio) was 0.0017, and the refractive index was 1.28. Here, the average particle diameter and the coefficient of variation of the particle diameter were measured by a dynamic light scattering method.
(Preparation of tetraethoxysilane hydrolyzate A)
After mixing 230 g of tetraethoxysilane (trade name: KBE04, manufactured by Shin-Etsu Chemical Co., Ltd.) and 440 g of ethanol and adding 120 g of a 2% aqueous acetic acid solution thereto, the mixture is stirred for 28 hours at room temperature (25 ° C.). Silane hydrolyzate A was prepared.
(Coating composition 1 for low refractive index layer)
Propylene glycol monomethyl ether 430 parts by mass Isopropyl alcohol 430 parts by mass Tetraethoxysilane hydrolyzate A (solid content 21% conversion) 120 parts by mass γ-methacryloxypropyltrimethoxysilane 3.0 parts by mass (trade name: KBM503, Shin-Etsu) (Made by Chemical Industries)
40 parts by mass of isopropyl alcohol dispersion of hollow silica fine particles 1 (average particle size 45 nm, particle size variation coefficient 30%)
20 parts by mass of isopropyl alcohol-dispersed spherical colloidal silica (solid content 20%, average particle size 45 nm, particle size variation coefficient 30%, commercially available product)
Aluminum ethyl acetoacetate / diisopropylate 3.0 parts by mass (manufactured by Kawaken Fine Chemical Co., Ltd.)
3.0 parts by mass of FZ-2207 (10% propylene glycol monomethyl ether solution, manufactured by Nihon Unicar Company)
On the surface of each antiglare film coated with a high refractive index layer, the low refractive index layer coating composition 1 is die-coated, dried at a temperature of 80 ° C., and then in an atmosphere having an oxygen concentration of 1.0% by volume or less. While purging with nitrogen, ultraviolet rays of 0.15 J / cm ² were irradiated with a high-pressure mercury lamp to provide a low refractive index layer so that the film thickness was 86 nm, and antiglare antireflection films 1 and 2 were produced. did. The refractive index of the low refractive index layer was 1.38. In addition, about the refractive index, it calculated | required from the measurement result of the spectral reflectance of a spectrophotometer.
<Evaluation of antiglare antireflection film>
The anti-glare antireflection films 1 and 2 of Example 4-1 and Comparative Example 4-1 were subjected to ozone exposure durability test evaluation in the same manner as in Example 1, and the following adhesion evaluation and Example 1 were performed. The film strength was evaluated in the same manner as described above. The results obtained are shown in Table 4.
(Adhesion evaluation)
The durability test samples of the antiglare antireflection films 1 and 2 were conditioned for 2 hours under the conditions of a temperature of 25 ° C. and a relative humidity of 60%. Next, on the surface of each sample having the antiglare and antireflection layer, cut in 11 vertical and 11 horizontal grids with a cutter knife, and engrave 100 square squares in total. Polyester The adhesion test on the adhesive tape (product number 31B, manufactured by Nitto Denko Corporation) was repeated three times at the same place. The presence or absence of peeling was visually observed, and the following four-stage evaluation was performed.

◎: No peeling was observed at the 100th mesh ○: Peeling was within the second mesh at the 100th mesh △: Peeling at the 100th mesh, 3rd to 10th mesh ×: Peeling at the 100th mesh, More than eleventh square

As is apparent from the results in Table 5, the antiglare antireflection film 1 of Example 4-1 of the present invention has better adhesion and film than the antiglare antireflection film 2 of Comparative Example 4-1. It can be seen that the strength is excellent. In addition, the anti-glare antireflection film 1 of Example 4-1 had excellent antireflection performance (low reflectance).
(Example 5)
-Preparation of anti-glare anti-reflection films 3 and 4 Anti-glare anti-reflection films 3 and 4 are prepared using the anti-glare films prepared in Example 1-5 and Comparative Example 1-1. 4 is that a low refractive index layer is directly provided on the antiglare film surface.
<Formation of low refractive index layer>
In forming the low refractive index layer on the antiglare layer surface of the antiglare film, after preparing the fluorinated polymer 1 and the sol solution I, the coating composition 1 for the low refractive index layer was prepared.
(Preparation of fluoropolymer 1)
In an autoclave with a stirrer made of stainless steel having an internal volume of 100 ml, 40 ml of ethyl acetate, 14.7 g of hydroxyethyl vinyl ether and 0.55 g of dilauroyl peroxide were charged, and the reaction system was degassed and replaced with nitrogen gas. Furthermore, 25 g of hexafluoropropylene (HFP) was introduced into the autoclave and the temperature was raised to 65 ° C. The pressure when the temperature in the autoclave reached 65 ° C. was 5.4 kg / cm ² . The temperature was maintained and the reaction was continued for 8 hours. When the pressure reached 3.2 kg / cm ² , the heating was stopped and the mixture was allowed to cool. When the internal temperature decreased to room temperature, unreacted monomers were driven out, the autoclave was opened, and the reaction solution was taken out. The obtained reaction solution was put into a large excess of hexane, and the solvent was removed by decantation to take out the precipitated polymer. Further, this polymer was dissolved in a small amount of ethyl acetate and reprecipitated twice from hexane to completely remove the residual monomer. After drying, 28 g of polymer was obtained. Next, 20 g of the polymer was dissolved in 100 ml of N, N-dimethylacetamide, and 11.4 g of acrylic acid chloride was added dropwise under ice cooling, followed by stirring at room temperature for 10 hours. Ethyl acetate was added to the reaction solution, washed with water, the organic layer was extracted and concentrated, and the resulting polymer was reprecipitated with hexane to obtain 19 g of fluorinated polymer 1.
(Preparation of sol solution I)
In a reactor equipped with a stirrer and a reflux condenser, 120 parts by mass of methyl ethyl ketone, 100 parts by mass of acryloyloxypropyltrimethoxysilane (KBM-5103, manufactured by Shin-Etsu Chemical Co., Ltd.), 3 parts by mass of diisopropoxyaluminum ethyl acetoacetate After adding and mixing, 30 parts by mass of ion-exchanged water was added and reacted at a temperature of 60 ° C. for 4 hours, and then cooled to room temperature to obtain a sol solution I.

The mass average molecular weight of the reaction product in the sol solution I was 1600, and among the components higher than the oligomer component, the component having a molecular weight of 1000 to 20000 was 100% by mass. Further, from the gas chromatography analysis, the raw material acryloyloxypropyltrimethoxysilane did not remain at all.
(Preparation of coating composition 2 for low refractive index layer)
Methyl ethyl ketone 200 parts by mass Cyclohexanone 150 parts by mass Fluoropolymer 1 30 parts by mass Methacrylate group-containing silicone resin 3 parts by mass (trade name, RMS-033, manufactured by Gelest Co., Ltd.)
Photoradical generator (trade name, Irgacure 907) 3 parts by mass A mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.) 7 parts by mass Sol solution I (27 as solid content after solvent volatilization) 45 parts by mass Hollow silica fine particles 1 Isopropyl alcohol dispersion 100 parts by mass Of the coating composition 2 for low refractive index layer, with respect to methyl ethyl ketone and cyclohexanone, the fluoropolymer 1 prepared above, a methacrylate group-containing silicone resin, After the photoradical generator, a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, was added and dissolved in the above ratio, the sol solution I and the hollow silica fine particle 1 isopropyl alcohol dispersion prepared in Example 5 were used. It was added at a serial rate of.

  Next, it diluted with methyl ethyl ketone so that the solid content concentration of the whole coating composition might be 7 mass%, and the coating composition 2 for low refractive index layers was prepared.

The anti-glare layer surface of each anti-glare film is 0.15 J while purging with nitrogen so that the oxygen concentration becomes 1.0 vol% or less by die coating the above coating composition 2 for low refractive index layer. An anti-glare antireflection film of Example 5-1 and Comparative Example 5-1 was prepared by irradiating UV / cm ² with a high-pressure mercury lamp so as to have a film thickness of 86 nm and providing a low refractive index layer. Was made. The refractive index of the low refractive index layer was 1.44. About refractive index, it calculated | required from the measurement result of the spectral reflectance of a spectrophotometer.
<Evaluation of antiglare antireflection film>
About the anti-glare antireflection film of Example 5-1 and Comparative Example 5-1, an ozone exposure endurance test sample was prepared in the same manner as in Example 1, and in the same manner as in Example 4, adhesion was observed. The film strength was evaluated. The obtained results are shown in Table 6.

As is clear from the results in Table 6, the antiglare antireflection film 3 of Example 5-1 of the present invention has better adhesion and film than the antiglare antireflection film 4 of Comparative Example 5-1. It can be seen that the strength is excellent. In addition, the anti-glare antireflection film 3 of Example 5-1 had excellent antireflection performance (low reflectance).
(Example 6)
-Production of Polarizing Film To produce a liquid crystal display panel, first, a polarizing film was produced. That is, a 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 consisting 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 of 68 ° C. consisting of 6 g of potassium iodide, 7.5 g of boric acid and 100 g of water. This was washed with water and dried to obtain a polarizing film.
-Preparation of polarizing plate Next, the anti-glare film produced in Examples 1-1 to 1-13 and Comparative Examples 1-1 to 1-8 according to the following steps 1 to 5 on one surface of the polarizing film. The polarizing plate is prepared by laminating the anti-glare layer on the outside and laminating a commercially available cellulose ester film Konica Minolta Tac (manufactured by Konica Minolta Opto Co., Ltd.) having a retardation on the other back surface of the polarizing film. did.

  Step 1: Dipped in a 1 mol / L sodium hydroxide solution at 50 ° C. for 60 seconds, then washed with water and dried to obtain an antiglare film and a cellulose ester film having a saponified side to be bonded to a polarizing film.

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

  Step 3: The excess adhesive adhered to the polarizing film in Step 2 was gently wiped off, and this polarizing film was placed on the cellulose ester film treated in Step 1, and further treated in Step 1 on the polarizing film. The antiglare film was laminated and arranged in this order so that the antiglare layer was on the outside.

Step 4: an antiglare film laminated in step 3 and the polarizing cellulose ester film, pressure 20-30 N / cm ^2, the conveyance speed was pasted at approximately 2m / min.

Step 5: The antiglare film, the polarizing film and the cellulose ester film prepared in Step 4 were dried for 2 minutes in a dryer at 80 ° C. to prepare a polarizing plate.
-Production of liquid crystal display panel Next, 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) is carefully peeled off, and the produced polarizing plate is used here. The liquid crystal display panels, Examples 6-1 to 6-13, and Comparative Examples 6-1 to 6-8 were prepared by bonding, and the screenability (visibility) of the obtained liquid crystal display panels was obtained. Evaluated.
<Evaluation>
〔Visibility〕
The liquid crystal panels of Examples 6-1 to 6-13 and Comparative Examples 6-1 to 6-8 obtained as described above were placed on a ceiling portion of a height of 2 m from the floor. FLR40S · D / MX (made by Matsushita Electric Industrial Co., Ltd.) 40W × 2 were used as one set, and 10 sets were arranged at 1.5 m intervals. At this time, when the evaluator is in front of the display surface of the liquid crystal panel, the fluorescent lamp is arranged so that the fluorescent lamp comes to the ceiling from the evaluator's overhead to the rear. The liquid crystal panel was tilted by 25 ° from the vertical direction with respect to the desk, and a fluorescent lamp was reflected so that the visibility of the screen (visibility) was evaluated as follows.

A: I don't mind from the reflection of the nearest fluorescent lamp, and I can clearly read characters with a font size of 8 or less. B: The reflection of the nearby fluorescent lamp is a little worrisome, but I don't care about the distance. Can manage to read characters with a font size of 8 or less. C: It is difficult to read characters with a font size of 8 or less. Worrying, the portion of the reflection cannot read characters with a font size of 8 or less. As a result of the evaluation, both the antiglare film of the embodiment of the present invention and the liquid crystal panel using the polarizing plate are B It was the above evaluation result, and visibility was better than the liquid crystal panel using the comparative anti-glare film and polarizing plate.
(Example 7)
-Production of polarizing plate and liquid crystal display panel Using the antiglare antireflection film produced in Examples 4-1 and 5-1 and Comparative Examples 4-1 and 5-1, the same as in Example 6 above. Then, after producing the polarizing plate, the liquid crystal display panels of Examples 7-1 and 7-2 and Comparative Examples 7-1 and 7-2 were produced, and the screenability of the obtained liquid crystal display panels was easy to see. (Visibility) was evaluated in the same manner as in Example 6.

  As a result of the evaluation, the antiglare antireflection film and the liquid crystal panel using the polarizing plate of the examples of the present invention are all B or more evaluation results, and the comparative antiglare antireflection film and the polarizing plate are used. Visibility was better than the liquid crystal panel.

It is the schematic of the apparatus which measures the amount of reflected light in the 40-50 degree direction when it injects from the -60 degree direction of an anti-glare antireflection film.

Explanation of symbols

  1 Anti-glare anti-reflection film

Claims (12)

An antiglare film having at least an antiglare layer on a transparent film substrate, wherein the haze value resulting from internal scattering of the antiglare layer is 50 to 70%, and the haze value resulting from surface scattering Is an antiglare film characterized by being 7 to 20%. The anti-glare film according to claim 1, wherein a haze value resulting from internal scattering of the anti-glare layer is 60 to 70%. The antiglare film according to claim 1 or 2, wherein the antiglare layer contains translucent fine particles, and the translucent fine particles are fluorine-containing acrylic resin fine particles. The translucent fine particles are composed of two types having different average particle diameters. The first translucent fine particles have an average particle diameter of 0.01 to 1 μm, and the second translucent fine particles have an average particle diameter of 2 to 6 μm. And the content ratio of the first translucent fine particles and the second translucent fine particles is 1.0: 1.0 to 3.0: 1.0. The antiglare film according to claim 3, wherein the antiglare film is present. The antiglare film according to any one of claims 1 to 4, wherein the transparent film substrate is a cellulose ester film. 6. The antiglare film according to claim 5, wherein the cellulose ester film contains at least one compound having an acryloyl group represented by the following general formula (Z).

(Wherein R _{31 to} R ₃₅ are the same as or different from each other, and are a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R ₃₆ is a hydrogen atom or a methyl group.) The antiglare film according to any one of claims 1 to 6, wherein the antiglare property is subjected to alkali saponification treatment. A low refractive index layer containing at least one kind of hollow silica fine particles whose inside is porous or hollow is laminated on the antiglare layer of the antiglare film according to any one of claims 1 to 7. An antiglare antireflection film characterized by comprising: The antiglare antireflection film according to claim 8, wherein a high refractive index layer is interposed between the antiglare layer and the low refractive index layer. A polarizing plate, wherein the antiglare film according to claim 1 is used on one surface. A polarizing plate comprising the antiglare antireflection film according to claim 8 on one surface. An image display device comprising the polarizing plate according to claim 10.

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