JP2008250276A - Anti-glare film, manufacturing method thereof, and polarizing plate and display device using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an anti-glare film which can effectively prevent reflection of external light and degradation in contrast without causing degradation in clearness of high-precision image due to reduction of pixel size or the like and can be effectively and stably formed with a desired fine rugged structure with preferable productivity, to provide a manufacturing method of the anti-glare film, and to provide a polarizing plate and the display device using the anti-glare film. <P>SOLUTION: The manufacturing method of the anti-glare film made by applying the fine rugged structure onto a transparent substrate according to an inkjet method, is characterized in that the fine rugged structure is formed of an ink composition which contains at least a polymerizable compound and a photo polymerization initiator and has a viscosity at 25°C of 10 to 500 mPa s. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to an antiglare film, a method for producing an antiglare film, a polarizing plate and a display device, and in particular, is excellent in transmission sharpness, antiglare property and bending resistance, and has a desired fine uneven structure formed with high productivity. The present invention relates to a glare film, a method for producing an antiglare film, a polarizing plate, and a display device.

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

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

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

  By providing an appropriate fine concavo-convex structure on the outermost surface of the front plate of the image display device, the above properties can be provided. For example, a method using fine particles (for example, refer to Patent Document 1), a method for embossing the surface (for example, refer to Patent Document 2), and a method for forming fine irregularities using phase separation of resin using spinodal decomposition ( For example, there are various methods such as a method for forming fine unevenness by an ink jet method (for example, see Patent Document 4).

The method for forming fine irregularities by the ink jet method can control the existence density of the uneven structure portion precisely, so it is superior in stability and productivity compared to other methods, but it is required to further improve performance and stability. It has been.
JP 59-58036 A JP-A-6-234175 JP 2005-227407 A JP 2004-151642 A

  The present invention has been made in view of the above problems, and its purpose is to effectively prevent the reflection of external light and the decrease in contrast without deteriorating the sharpness of a high-definition image due to a reduction in pixel size or the like. The present invention provides an anti-glare film in which a desired fine concavo-convex structure is formed effectively and stably with good productivity, a method for producing the anti-glare film, and a polarizing plate and a display device using the same. is there.

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

  1. In the method for producing an antiglare film in which a fine uneven structure is imparted by an inkjet method on a transparent substrate, the fine uneven structure contains at least a polymerizable compound and a photoinitiator polymer, and has a viscosity at 25 ° C. of 10 to 500 mPa. A method for producing an antiglare film, characterized by being formed of the ink composition of s.

  2. 2. The method for producing an antiglare film as described in 1 above, wherein the ink composition has a viscosity of 5 to 30 mPa · s at 60 ° C.

  3. 3. The method for producing an antiglare film as described in 1 or 2 above, wherein the ink composition is an ink composition substantially free of a solvent.

  4). 4. The method for producing an antiglare film as described in any one of 1 to 3, wherein the ink composition is ejected from an ink jet head held at 40 ° C. to 80 ° C.

  5. An antiglare film produced by the method for producing an antiglare film according to any one of 1 to 4 above.

  6). 6. A polarizing plate comprising the antiglare film described in 5 above on at least one surface.

  7. 6. A display device using the antiglare film described in 5 or the polarizing plate described in 6 above.

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

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

  Conventionally, for the purpose of improving contrast, there is a technique for forming an anti-glare film by forming a fine uneven structure on a transparent substrate by an ink jet method, but distortion occurs due to impact at the time of ink droplet landing, and each convex portion There was a problem that unevenness occurred in the height and size of the film, and the intended antiglare performance did not appear.

  As a result of intensive studies, the present inventors have found that the configuration of the present invention has excellent antiglare properties and can improve productivity.

  That is, the present invention relates to a method for producing an antiglare film, and in the method for producing an antiglare film in which a fine uneven structure is provided on a transparent substrate by an ink jet method, the fine uneven structure includes at least a polymerizable compound and light. It is characterized by being formed of an ink composition containing an initiator and having a viscosity at 25 ° C. of 10 to 500 mPa · s.

  According to the present invention, the fine concavo-convex structure that exhibits antiglare properties becomes uniform, exhibits excellent antiglare properties, and has a substantially uniform film thickness, thereby improving film strength, particularly flexibility. Furthermore, variations in production lots and between production lots are reduced, and stable productivity can be obtained.

  Hereinafter, the present invention will be described in detail. Hereinafter, in the present application, the convex portion in the fine concavo-convex structure is also referred to as a dot.

<Ink composition>
An ink composition (hereinafter also simply referred to as ink) that forms a fine relief structure according to the present invention has a viscosity at 25 ° C. of 10 to 500 mPa · s. More preferably, the viscosity is 30 to 400 mPa · s. If the viscosity at 25 ° C. of the ink composition is less than 10 mPa · s, the effect of preventing distortion of the fine uneven structure is small, while if it is more than 500 mPa · s, there is a problem in the supply of the ink liquid.

  In the present invention, it is preferable that the ink composition is 5 to 30 mPa · s at 60 ° C. in order to obtain stable light emission. More preferably, it is 5-15 mP · s.

(Polymerizable compound, photopolymerization initiator)
The ink composition of the present invention comprises at least a polymerizable compound and a photopolymerization initiator. Hereinafter, each constituent material will be described.

  The polymerizable compound is a radical polymerizable compound such as JP-A-7-159983, JP-B-7-31399, JP-A-8-224982, JP-A-10-863, JP-A-7-231444, and the like. And a photocurable material using a photopolymerizable composition described in Japanese Patent Application No. 7-231444 and a cationic polymerization type photocurable resin are known, and recently, a long wavelength region longer than visible light is known. Photo-cationic polymerization-based photocurable resins sensitized to the above are also disclosed in, for example, JP-A-6-43633 and JP-A-8-324137.

  The radical polymerizable compound is a compound having an ethylenically unsaturated bond capable of radical polymerization, and may be any compound as long as it has at least one ethylenically unsaturated bond capable of radical polymerization in the molecule. , Oligomers, polymers and the like having a chemical form. Only one kind of radically polymerizable compound may be used, or two or more kinds thereof may be used in combination at an arbitrary ratio in order to improve desired properties. A polyfunctional compound having two or more functional groups is more preferable than a monofunctional compound. More preferably, two or more polyfunctional compounds are used in combination for controlling performance such as reactivity and physical properties.

  Examples of compounds having an ethylenically unsaturated bond capable of radical polymerization include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid and their salts, esters, urethanes, amides. And radically polymerizable compounds such as various unsaturated polyesters, unsaturated polyethers, unsaturated polyamides and unsaturated urethanes. Specifically, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, butoxyethyl acrylate, carbitol acrylate, cyclohexyl acrylate, tetrahydrofurfuryl acrylate, benzyl acrylate, bis (4-acryloxypolyethoxyphenyl) propane, neopentyl glycol Diacrylate, 1,6-hexanediol diacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, pentaerythritol triacrylate, pentaerythritol Tetraacrylate, dipentaery Acrylic acid derivatives such as lithol tetraacrylate, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, oligoester acrylate, N-methylol acrylamide, diacetone acrylamide, epoxy acrylate, methyl methacrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate , Lauryl methacrylate, allyl methacrylate, glycidyl methacrylate, benzyl methacrylate, dimethylaminomethyl methacrylate, 1,6-hexanediol dimethacrylate, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, polypropylene glycol dimethacrylate, trimethylol Methacryl derivatives such as tan trimethacrylate, trimethylolpropane trimethacrylate, 2,2-bis (4-methacryloxypolyethoxyphenyl) propane, and other derivatives of allyl compounds such as allyl glycidyl ether, diallyl phthalate, triallyl trimellitate More specifically, Yamashita Junzo, “Cross-linker Handbook”, (1981 Taiseisha); Kato Kiyomi, “UV / EB Curing Handbook (Raw Materials)” (1985, Polymer Publication) ); Rad-Tech Study Group, “Application and Market of UV / EB Curing Technology”, p. 79, (1989, CMC); Eiichiro Takiyama, “Polyester Resin Handbook” (1988, Nikkan Kogyo Shimbun) Commercially available products described in the above, or radically polymerizable or crosslinkable monomers known in the industry, Ligomers and polymers can be used. The amount of the radical polymerizable compound added is preferably 1 to 97% by mass, more preferably 30 to 95% by mass.

  Examples of the radical polymerization initiator include triazine derivatives described in JP-B-59-1281, JP-B-61-9621, JP-A-60-60104, JP-A-59-1504 and JP-A-61. No. 243807, etc., Japanese Patent Publication No. 43-23684, Japanese Examined Publication No. 44-6413, Japanese Examined Publication No. 44-6413, Japanese Examined Publication No. 47-1604, etc. Diazonium compounds described in US Pat. No. 3,567,453, organic azide compounds described in US Pat. Nos. 2,848,328, 2,852,379 and 2,940,853, Ortho-quinonediazides described in JP-B Nos. 36-22062, 37-13109, 38-18015, 45-9610, etc. No. 9162, JP-A 59-14023, etc. and various onium compounds described in “Macromolecules, Vol. 10, page 1307 (1977)”, JP-A 59-142205 Azo compounds described in JP-A-1-54440, European Patent No. 109,851, European Patent No. 126,712, etc., “Journal of Imaging Science” (J. Imag. Sci.). 30, page 174 (1986), (oxo) sulfonium organoboron complexes described in Japanese Patent Application Nos. 4-56831 and 4-89535, -Titanocenes described in No. 151197, “Coordination chemistry review (Coordinantio Chemistry Review), 84, 85, 277 (1988) and transition metal complexes containing transition metals such as ruthenium described in JP-A-2-182701, described in JP-A-3-209477 Examples thereof include 2,4,5-triarylimidazole dimer, carbon tetrabromide, and organic halogen compounds described in JP-A-59-107344. These polymerization initiators are preferably contained in the range of 0.01 to 10 parts by mass with respect to 100 parts by mass of the compound having an ethylenically unsaturated bond capable of radical polymerization.

  As a cationic polymerization type radiation curable resin, an ultraviolet curable prepolymer of an epoxy type that is polymerized by cationic polymerization (mainly epoxy type), a monomer that contains two or more epoxy groups in one molecule. Mention may be made of polymers. Examples of such prepolymers include alicyclic polyepoxides, polyglycidyl esters of polybasic acids, polyglycidyl ethers of polyhydric alcohols, polyglycidyl ethers of polyoxyalkylene glycols, and polyglycidyls of aromatic polyols. Examples include ethers, hydrogenated compounds of polyglycidyl ethers of aromatic polyols, urethane polyepoxy compounds, and epoxidized polybutadienes. These prepolymers can be used alone or in a mixture of two or more.

  As an initiator of the cationic polymerization radiation curable resin, aromatic onium salts can be exemplified. Examples of the aromatic onium salt include salts of Group Va elements of the periodic table, such as phosphonium salts (for example, triphenylphenacylphosphonium hexafluorophosphate), salts of Group VIa elements, such as sulfonium salts (for example, trifluoroborate trichloride). Phenylsulfonium, triphenylsulfonium hexafluorophosphate, tris (4-thiomethoxyphenyl) hexafluorophosphate, sulfonium and triphenylsulfonium hexafluoroantimonate), and salts of Group VIIa elements such as iodonium salts (eg And diphenyliodonium chloride).

  The use of such an aromatic onium salt as a cationic polymerization initiator in the polymerization of an epoxy compound is disclosed in U.S. Pat. Nos. 4,058,401, 4,069,055, and 4,101,513. And No. 4,161,478.

  Preferable cationic polymerization initiators include sulfonium salts of Group VIa elements. Among these, from the viewpoint of storage stability of ultraviolet curable and ultraviolet curable compositions, triarylsulfonium hexafluoroantimonate is preferable. In addition, the photopolymerization initiators described in pages 39 to 56 of the photopolymer handbook (published by Photographic Society Committee, 1989), described in JP-A No. 64-13142 and JP-A No. 2-4804 Any compound can be used.

  In the present invention, (meth) acrylic monomers or prepolymers, epoxy monomers or prepolymers, urethane monomers or prepolymers are preferably used as the polymerizable compound, and the following compounds are more preferable.

  2-ethylhexyl-diglycol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxybutyl acrylate, hydroxypivalate neopentyl glycol diacrylate, 2-acryloyloxyethyl phthalate, methoxy-polyethylene glycol acrylate, tetramethylol Methane triacrylate, 2-acryloyloxyethyl-2-hydroxyethylphthalic acid, dimethylol tricyclodecane diacrylate, ethoxylated phenyl acrylate, 2-acryloyloxyethyl succinic acid, nonylphenol EO adduct acrylate, modified glycerin triacrylate Bisphenol A diglycidyl ether acrylic acid adduct, modified bisphenol A diacrylate, phenoxy-polyethylene Glycol acrylate, 2-acryloyloxyethyl hexahydrophthalic acid, bisphenol A PO adduct diacrylate, bisphenol A EO adduct diacrylate, dipentaerythritol hexaacrylate, pentaerythritol triacrylate tolylene diisocyanate urethane prepolymer, lactone Modified flexible acrylate, butoxyethyl acrylate, propylene glycol diglycidyl ether acrylic acid adduct, pentaerythritol triacrylate hexamethylene diisocyanate urethane prepolymer, 2-hydroxyethyl acrylate, methoxydipropylene glycol acrylate, ditrimethylolpropane tetraacrylate, penta Erythritol triacrylate hexamethylene di Socia sulfonates urethane prepolymer, stearyl acrylate, isoamyl acrylate, isomyristyl acrylate, isostearyl acrylate.

  These acrylate compounds have lower skin irritation and sensitization (rash) than the polymerizable compounds conventionally used in UV curable inks, can relatively reduce viscosity, and provide stable ink ejection properties. Further, the polymerization sensitivity and the adhesion to the recording medium are also good. In the present invention, the content of the compound group is 20 to 95% by mass, preferably 50 to 95%, and more preferably 70 to 95%.

  In the present invention, the monomers listed as the polymerizable compounds described above are low in sensitization even with a low molecular weight, and have high reactivity, low viscosity, and adhesion to a recording medium. Excellent.

  In order to further improve sensitivity, bleeding, and adhesion to the recording medium, it is preferable to use the above monoacrylate in combination with a polyfunctional acrylate monomer or polyfunctional acrylate oligomer having a molecular weight of 400 or more, preferably 500 or more. It is preferable in terms of improving the performance. Furthermore, it is particularly preferable to use a monofunctional, bifunctional, or trifunctional or higher polyfunctional monomer in combination. While maintaining safety, the sensitivity, bleeding, and adhesion to the recording medium can be further improved. As the oligomer, an epoxy acrylate oligomer and a urethane acrylate oligomer are particularly preferable.

  When recording on a flexible recording medium such as a PET film or PP film, the combination of a monoacrylate selected from the above compound group and a polyfunctional acrylate monomer or polyfunctional acrylate oligomer gives the film flexibility and adhesion. It is preferable because the film strength can be increased while improving the properties. As monoacrylates, stearyl acrylate, isoamyl acrylate, isomystil acrylate, and isostearyl acrylate have high sensitivity and low shrinkage to prevent curling, and are preferable in terms of prevention of bleeding, odor of printed matter, and cost reduction of irradiation apparatus. .

  Although methacrylate has better skin irritation than acrylate, sensitization is generally not different from acrylate and is not suitable because it is less sensitive than acrylate, but it has high reactivity and good sensitization. If it is, it can be used suitably.

  Among the above compounds, alkoxy acrylate has low sensitivity and causes problems such as bleeding, odor, and irradiation light source. Therefore, it is preferable to keep the amount below 70% by mass and use other acrylates in combination.

  When an electron beam, X-ray, or the like is used as irradiation light, an initiator is not necessary. However, when UV light, visible light, or infrared light is used as a radiation source, a radical polymerization initiator or initiator corresponding to each wavelength is used. Add auxiliaries and sensitizing dyes. These amounts require 1-10 parts by weight of the total composition. As the initiator system, various known compounds can be used, but the initiator system is selected from those that dissolve in the polymerizable compound. Specific examples of the initiator include xanthone or thioxanthone series, benzophenone series, quinone series, and phosphine oxide series.

  Examples of the solvent that can be used in the ink composition according to the present invention include alcohols such as methanol, ethanol, 1-propanol, 2-propanol, and butanol; ketones such as acetone, methyl ethyl ketone, and cyclohexanone; diacetone alcohol Ketone alcohols; aromatic hydrocarbons such as benzene, toluene, xylene; glycols such as ethylene glycol, propylene glycol, hexylene glycol; ethyl cellsolve, butylcellsolve, ethylcarbitol, butylcarbitol, diethylcell Glycol ethers such as sorb, diethyl carbitol, propylene glycol monomethyl ether; N-methylpyrrolidone, dimethylformamide, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate Esters such as amyl acetate; dimethyl ether, and diethyl ether, water and the like, can be used as a mixture thereof alone or in combination.

  In the ink composition according to the present invention, it is preferable that at least one kind of a solvent having a boiling point of 140 to 250 ° C. and a viscosity of 1 to 15 mPa · s at 25 ° C. is contained in an amount of 60% by mass or more. More preferably, at least one solvent having a boiling point of 180 to 230 ° C. and a viscosity of 1 to 10 mPa · s at 25 ° C. is contained in an amount of 70% by mass or more.

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

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

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

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

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

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

  By mixing solvents having different boiling points and viscosities from these solvents and appropriately changing the ratio thereof, the fine concavo-convex structure and the pattern shape can be controlled.

  It is preferable that the ink composition forming the fine concavo-convex structure of the present invention contains substantially no solvent. The term “substantially free of solvent” as used herein means that no ink is contained in the ink droplets, and also that the ink droplet contains up to 3.0% of the solvent.

  The viscosity of the ink composition is not particularly limited as long as it is tested with a standard solution for viscometer calibration specified in JIS Z 8809. Use a rotary, vibration or capillary type viscometer. I can do it. As a viscometer, it can be measured with a Saybolt viscometer, a Redwood viscometer, etc., for example, Tokimec Co., Ltd., conical plate type E type viscometer, Toki Sangyo E Type Viscometer, manufactured by Tokyo Keiki Co., Ltd. No. B type viscometer BL, FVM-80A manufactured by Yamaichi Electronics Co., Ltd., Viscoliner manufactured by Nametore Industries Co., Ltd., VISCO MATE MODEL VM-1G manufactured by Yamaichi Electronics Co., Ltd., and the like.

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

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

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

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

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

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

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

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

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

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

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

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

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

  The method for measuring the contact angle described above is shown in FIG. An aqueous solution sample to be measured is placed in a syringe-like droplet regulator (not shown). As shown in (a), a solid sample whose surface is horizontally adjusted is placed on a sample stage (not shown) whose position can be changed vertically and horizontally, and the surface of the solid sample is observed with an optical mirror. The optical mirror incorporates a rotatable rotating cloth. Droplets are made at the tip of a drop adjuster placed just above the solid sample.

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

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

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

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

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

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

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

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

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

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

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

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

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

  4, (a) in FIG. 4 is a method (line) in which the inkjet head 30 is arranged in the width direction of the transparent substrate film 10 and a fine uneven structure is formed on the surface of the transparent substrate film 10 while being conveyed. FIG. 4B shows a method (flat head method) in which the inkjet head 30 moves in the sub-scanning direction and forms a fine uneven structure on the surface thereof. FIG. 4C shows an inkjet method. The head 30 is a method (capstan method) for forming a fine concavo-convex structure on the surface of the transparent substrate film 10 while scanning in the width direction, and any method can be used in the present invention. From the viewpoint of productivity, the line head method is preferable. In addition, it is preferable to attach the actinic ray irradiation part used when using the above-mentioned actinic ray curable resin as an ink like 29 of (a)-(c) of FIG.

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

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

  The fine concavo-convex structure has a convex major axis of 1 to 40 μm, more preferably 15 to 30 μm, and a convex height of 0.5 to 10 μm, preferably 1 to 10 μm, more preferably 2 to 8 μm. It is preferable to have a size and a height, and the arrangement of the protrusions is preferably a random arrangement by a method such as FM screening. Here, the diameter of the convex portion represents the diameter when the convex portion is circular, and the diameter converted into the same area when the convex portion is triangular, quadrangular, polygonal, or indefinite. The height of a convex part means the difference of the height of the highest part of a dot from a base film surface.

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

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

(Transparent resin layer)
In the method for producing an antiglare film of the present invention, it is preferable that after forming a fine uneven structure on a transparent substrate by an ink jet method, a transparent resin layer is formed so as to cover the fine uneven structure.

  The liquid composition of the transparent resin layer is preferably an actinic ray curable resin, a thermoplastic resin, a thermosetting resin, a metal alkoxide, or a hydrolyzate thereof.

  The actinic ray curable resin preferably used for the liquid composition of the transparent resin layer will be described.

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

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

  UV curable acrylic urethane resins generally include 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate (hereinafter referred to as acrylates) in products obtained by reacting polyester polyols with isocyanate monomers or prepolymers. It can be easily obtained by reacting an acrylate monomer having a hydroxyl group such as 2-hydroxypropyl acrylate. For example, a mixture of 100 parts Unidic 17-806 (Dainippon Ink Co., Ltd.) and 1 part Coronate L (Nihon Polyurethane Co., Ltd.) described in JP-A-59-151110 is preferably used. .

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

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

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

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

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

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

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

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

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

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

  A typical example of such a compound is a compound represented by the following general formula (2).

General formula (2)
[(R1) a (R2) b (R3) c (R4) dZ] w ⁺ [MeXv] w ⁻
Wherein cation is onium, Z is S, Se, Te, P, As, Sb, Bi, O, halogen (eg, I, Br, Cl), or N = N (diazo), R1, R2, R3 and R4 are organic groups which may be the same or different. a, b, c, and d are each an integer of 0 to 3, and a + b + c + d is equal to the valence of Z. Me is a metal or metalloid which is a central atom of a halide complex, and B, P, As, Sb, Fe, Sn, Bi, Al, Ca, In, Ti, Zn, Sc, V, Cr, Mn, Co, etc. X is halogen, w is the net charge of the halogenated complex ion, and v is the number of halogen atoms in the halogenated complex ion.

Specific examples of the anion [MeXv] w ⁻ of the general formula (2) include tetrafluoroborate (BF ₄ ⁻ ), tetrafluorophosphate (PF ₄ ⁻ ), tetrafluoroantimonate (SbF ₄ ⁻ ), and tetrafluoro. Examples include arsenate (AsF ₄ ⁻ ) and tetrachloroantimonate (SbCl ₄ ⁻ ).

Other anions include perchlorate ion (ClO ₄ ⁻ ), trifluoromethyl sulfite ion (CF ₃ SO ₃ ⁻ ), fluorosulfonate ion (FSO ₃ ⁻ ), toluenesulfonate ion, and trinitrobenzene acid anion. An ion etc. can be mentioned.

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

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

  In the liquid composition containing the actinic ray curable resin useful in the present invention, the photopolymerization initiator is generally 0.1 parts by mass with respect to 100 parts by mass of the actinic ray curable epoxy resin (prepolymer). Use of -15 mass parts is preferable, More preferably, addition of the range of 1 mass part-10 mass parts is preferable.

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

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

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

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

  Further, when an ultraviolet curable resin is used as the actinic ray curable resin, an ultraviolet absorber may be included in the ultraviolet curable resin composition to the extent that does not hinder the photocuring of the ultraviolet curable resin. As the ultraviolet absorber, those excellent in the ability to absorb ultraviolet rays having a wavelength of 370 nm or less and having little absorption of visible light having a wavelength of 400 nm or more are preferably used from the viewpoint of good liquid crystal display properties.

  Specific examples of ultraviolet absorbers preferably used in the present invention include, for example, oxybenzophenone compounds, benzotriazole compounds, salicylic acid ester compounds, benzophenone compounds, cyanoacrylate compounds, triazine compounds, nickel complex compounds, and the like. However, it is not limited to these.

  Subsequently, the thermosetting resin used for the liquid composition used for transparent resin layer formation is demonstrated.

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

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

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

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

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

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

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

  In addition, you may use suitably the antioxidant and ultraviolet absorber which were described in the liquid composition containing actinic-light curable resin for the liquid composition which consists of a thermosetting resin used for this invention.

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

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

  FIG. 5 is a diagram schematically showing the formation of the fine concavo-convex structure of the present invention and the coating with a transparent resin layer.

The arithmetic average surface roughness (Ra) of the concavo-convex structure on the surface of the transparent resin layer used in the present invention is preferably 0.01 to 10 μm, more preferably 0.05 to 1 μm, still more preferably 0.1 to 0.1 μm. 0.5 μm. The average center distance (Sm) of the concavo-convex structure on the surface of the transparent resin layer is 10 to 200 μm, more preferably 20 to 100 μm, and still more preferably 25 to 75 μm. Furthermore, the following Rz / Sm is preferably 0.01 to 0.1, and more preferably 0.02 to 0.05. Furthermore, it is preferable to have 5 to 25 surface shape portions of the convex portions or concave portions per 0.01 mm ² .

  The arithmetic average roughness (Ra) is defined by JIS B 0601 and represents a value obtained by the following formula expressed in micrometers (μm).

  The surface roughness (Rz) is defined as a ten-point average height according to JIS B 0601 of JIS surface roughness, and is the fifth highest from the convex portion in the portion extracted from the sectional curve by the reference length. The difference between the average value up to and the average value from the lowest to the fifth concave portion is expressed in micrometer units (μm).

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

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

  FIG. 6 is a schematic view of a fine uneven structure preferable for the present invention.

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

  As for the dry film thickness of the transparent resin layer used for this invention, 3-15 micrometers is preferable, More preferably, it is 5-10 micrometers. If the thickness exceeds 20 μm, the bending resistance among the film properties is remarkably deteriorated, and minute folds are likely to occur during handling such as transport and cutting after the formation of the transparent resin layer, resulting in a decrease in productivity.

  For example, when the transparent resin layer used in the present invention is composed of an active photocurable resin or a thermosetting resin, the dry film thickness is adjusted to a desired dry film thickness by adjusting the ratio of the resin solid content and the resin solvent. Can be obtained. Further, in the present invention, as will be described later, a cured resin layer or a smooth light diffusion layer is provided on a transparent support, and a fine concavo-convex structure is formed on the surface by an ink jet method and then the fine concavo-convex structure is covered. It is preferable that a transparent resin layer is formed, but at this time, the dry film thickness including the cured resin layer or the smooth light diffusion layer to the transparent resin layer is preferably 3 to 15 μm, more preferably 5 to 10 μm. is there.

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

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

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

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

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

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

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

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

  As the polyester plasticizer, a copolymer of a dibasic acid and a glycol such as an aliphatic dibasic acid, an alicyclic dibasic acid, or an aromatic dibasic acid can be used. The aliphatic dibasic acid is not particularly limited, and adipic acid, sebacic acid, phthalic acid, terephthalic acid, 1,4-cyclohexyl dicarboxylic acid, and the like can be used. As glycol, ethylene glycol, diethylene glycol, 1,3-propylene glycol, 1,2-propylene glycol, 1,4-butylene glycol, 1,3-butylene glycol, 1,2-butylene glycol and the like can be used. These dibasic acids and glycols may be used alone or in combination of two or more.

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

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

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

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

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

  Examples of the solvent for coating the curable resin layer or the smooth light diffusing layer used in the present invention include hydrocarbons, alcohols, ketones, esters, glycol ethers, and other solvents. It can select suitably or can be mixed and used. Preferably, a solvent containing 5% by mass or more, more preferably 5% by mass to 80% by mass or more of propylene glycol mono (C 1-4) alkyl ether or propylene glycol mono (C 1-4) alkyl ether ester. Used.

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

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

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

  In the present invention, it is preferable to form a transparent resin layer so as to cover the fine concavo-convex structure after forming the fine concavo-convex structure and then plasma-treating the surface. The plasma treatment is particularly preferably atmospheric plasma treatment, and a rare gas such as helium or argon or a discharge gas such as nitrogen or air and, if necessary, oxygen, hydrogen, nitrogen, carbon monoxide, carbon dioxide, carbon dioxide, A reaction gas containing one or more of nitrogen oxide, nitrogen dioxide, water vapor, methane, tetrafluoromethane, and the like can be used. In Japanese Patent Application Laid-Open No. 2000-356714, the surface of the cured resin layer can be subjected to plasma treatment with reference to a specific plasma treatment method.

  The transparent resin layer used in the present invention is produced by coating by a general thin film uniform coating method such as a micro gravure method, an extrusion coating method, a wire bar method, a flexographic printing method, and an ink jet method. The transparent resin layer is applied on the fine concavo-convex structure described above, covers the fine concavo-convex structure, and smoothes the concavo-convex structure so that the anti-glare property can be expressed by a preferable surface shape.

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

In the present invention, it is also preferable that both the fine concavo-convex structure and the transparent resin layer contain an antistatic agent such as conductive fine particles such as SnO ₂ , ITO and ZnO, and crosslinked cationic polymer particles. In the present invention, it is preferable to add an antistatic agent to the transparent resin layer.

  In the present invention, it is also preferable that the fine concavo-convex structure and the transparent resin layer contain the fine particles. For example, inorganic fine particles or organic fine particles can be added.

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

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

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

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

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

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

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

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

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

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

  Moreover, in this invention, in order to advance the hardening reaction of actinic light efficiently, a base film etc. can also be heated. The heating method is not particularly limited, but it is preferable to use a heat plate, a heat roll, a thermal head, or a method of spraying hot air on the landed ink surface.

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

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

  FIG. 7 is a schematic diagram showing an example of a flow for producing an antiglare film formed of a transparent resin layer so as to cover a fine uneven structure after forming the fine uneven structure on a transparent substrate by an ink jet method. . Specifically, after coating a curable resin layer or a smooth light diffusing layer on a transparent substrate by a coating method, a transparent resin layer is formed so as to cover the fine concavo-convex structure after forming a fine concavo-convex structure by an inkjet method. An example of a flow for producing an antiglare film by providing a plurality of antireflection layers on the antiglare layer formed with a coating method is shown.

  In FIG. 7, the transparent base material 102 fed out from the laminating roll 101 is conveyed, and a curable resin layer or a smooth light diffusing layer is applied by the first coater 103 of the extrusion method at the first coater station A. To do. At this time, the curable resin layer or the smooth light diffusing layer may be a single layer structure or a layer composed of a plurality of layers combined with each other. The transparent substrate 102 on which the curable resin layer or the smooth light diffusion layer is applied is then dried in the drying zone 105A. Drying is performed from both surfaces of the transparent substrate 102 by warm air with controlled temperature and humidity. After drying, when an actinic ray curable resin is used as a binder in the curable resin layer or the smooth light diffusing layer, the actinic ray irradiating unit 106A is irradiated with actinic rays such as ultraviolet rays to be cured. In addition, the amount of irradiation and irradiation conditions can be controlled to achieve a half-cure state, or it can be directly conveyed to the inkjet emitting unit 109 without being cured.

  Subsequently, although it conveys to the 2nd coater station B which provides a fine uneven structure using an inkjet system, it is preferable that a curable resin layer is a half-cure state. Alternatively, the surface treatment may be performed by the plasma processing unit 107 before the fine uneven structure is formed. An ink supply tank 108 is connected to the ink jet emitting portion 109, and ink liquid is supplied therefrom. The ink jet emitting unit 109 has a plurality of ink jet nozzles as shown in FIG. 3B arranged in a staggered manner, preferably in multiple stages, across the entire width of the transparent substrate, and the ink droplets are made of a curable resin layer or a smooth type. The light is emitted onto the light diffusion layer to form a fine relief structure on the surface. In addition, when ejecting two or more types of ink droplets, each ink droplet may be ejected from two or more rows of inkjet nozzles, or randomly from any inkjet nozzle. It may be emitted. Further, a plurality of ink jet emitting portions may be arranged, and different ink droplets may be emitted from each ink emitting portion. In the present invention, since fine droplets of 0.1 to 100 pl and in some cases 0.1 to 10 pl are emitted, the flying property of the ink droplets is easily affected by the airflow of the outside air. It is preferable that the entire coater station B is covered with a partition wall or the like to perform windproof treatment. In addition, in order to fly extremely fine droplets of 1 pl or less with high accuracy, a voltage is applied between the ink jet emitting unit 109 and the transparent base material 102 or the back roll 104B to give an electric charge to the ink droplets to electrically inject the ink liquid. A method of assisting droplet flight stability is also preferred.

  In the present invention, it is preferable to heat the ink jet head in order to stabilize the flight of the ink composition. The heating temperature cannot be generally specified depending on the type of the ink composition to be used, but is preferably in a temperature range that does not affect the thermal deformation of the inkjet head, preferably 40 to 80 ° C., particularly 45 to 45 ° C. 75 ° C. is preferred.

  In order to prevent deformation of the landed ink droplets, it is also preferable to use a method in which the transparent substrate is cooled to quickly reduce the flow of the ink droplets after landing. The temperature of the transparent substrate relative to the ink droplet temperature at the time of ejection is preferably −5 to −50 ° C., more preferably −10 to −40 ° C., and particularly preferably −15 to −30 ° C.

  Alternatively, it is possible to volatilize the solvent contained during the flight from when the ink droplets are ejected until they land, and to land with the amount of the solvent contained in the ink droplets decreasing, thereby forming a finer uneven structure. Preferred above. Therefore, a method of increasing the temperature of the ink flying space or controlling the atmospheric pressure to 1 atm or lower, for example, 20 to 100 kPa is also preferable. It is also preferable to lower the atmospheric solvent concentration in the ink flying space, and it is 50% or less, more preferably 1 to 30% of the saturation concentration.

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

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

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

  The transparent substrate 102 provided with the fine concavo-convex structure is then transported to the third coater station C on which the transparent resin layer covering the fine concavo-convex structure is coated. Before the fine concavo-convex structure is coated with the transparent resin layer, Surface treatment is preferably performed by the plasma processing unit 107.

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

  The transparent base material 102 provided with the antiglare layer having a fine concavo-convex structure is then provided with a low refractive index layer in the fourth coater station D, or a fifth coater station when a plurality of antireflection layers and antifouling layers are provided. The sixth coater station (not shown) performs coating, drying, and curing processes in the same manner as the first coater station A to produce an antiglare film, and is then wound by a winding roll 113.

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

  In FIG. 7, the coating method is exemplified as the method for forming the antireflection layer, but the antireflection layer or the antifouling layer may be formed by a known atmospheric pressure plasma treatment method instead of the coating method.

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

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

  Although it will not specifically limit if it has said property, For example, cellulose ester 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, polycarbonate film, nor Runen resin film, a polymethylpentene film, a polyether ketone film, polyether ketone imide film, a polyamide film, a fluororesin film, a nylon film, polymethyl methacrylate film, acrylic film or a glass plate or the like. Among these, a polycarbonate film, a polyester film, a norbornene resin film, and a cellulose ester film are preferable.

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

  In the present invention, it is particularly preferable to use a cellulose ester film.

  The cellulose used as the raw material for the cellulose ester is not particularly limited, and examples thereof include cotton linters, wood pulp (derived from conifers and hardwoods), 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 is obtained by reacting with a cellulose raw material using a protic catalyst.

When the acylating agent is acid chloride (CH ₃ COCl, C ₂ H ₅ COCl, C ₃ H ₇ COCl), 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. In addition, the cellulose ester used in the present invention is obtained by mixing and reacting the amount of the acylating agent in accordance with the degree of substitution. In the cellulose ester, these acylating agents react with hydroxyl groups of cellulose molecules. 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 cellulose ester used in the present invention is preferably cellulose acetate, cellulose acetate butyrate, or cellulose acetate propionate. Among them, cellulose acetate butyrate, cellulose acetate phthalate, or cellulose acetate propionate is preferably used.

  Among them, cellulose acetate propionate containing a propionate group as a substituent is excellent in water resistance and is preferable as a protective film for a polarizing plate.

  In particular, when the substitution degree of the acetyl group is X and the substitution degree of the propionyl group is Y, cellulose acetate propionate in which X and Y are in the following ranges is preferable.

2.0 ≦ X + Y ≦ 2.9
0.1 ≦ Y ≦ 1.8
In particular, 2.2 ≦ X + Y ≦ 2.8
It is preferable that 0.3 ≦ Y ≦ 1.2.

  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.

  Moreover, the thing of 50000-350,000 is used by a weight average molecular weight (Mw). More preferable is 60000-300000, and 80000-250,000 is particularly preferable.

  The average molecular weight and molecular weight distribution of the cellulose ester can be measured by a known method using gel permeation chromatography. Using this, the number average molecular weight and the weight average molecular weight are measured.

  The measurement conditions are as follows.

<Gel permeation chromatography: molecular weight measurement by GPC>
The method for measuring the number average molecular weight by GPC was diluted with tetrahydrofuran so that the sample solid content concentration was 0.1%. Since the particles were included, the particles were removed using a filter, and the measurement was performed at a column temperature of 25 ° C. under the following conditions.

Column: Tosoh Corporation TSKgelG5000HXL-TSKgelG2000H XL
Eluent: THF (tetrahydrofuran)
Pump: L6000 (manufactured by Hitachi, Ltd.)
Flow rate: 1.0 ml / min
Detection: RI Model 504 (manufactured by GL Sciences)
Sample concentration: 0.8%
Standard sample / calibration curve: Standard polystyrene STK standard polystyrene (manufactured by Tosoh Corp.) Mw = 100000-500 calibration curves with 13 samples are used. It is preferable that the 13 samples are substantially equally spaced.

  The transparent substrate of the present invention 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.

  The polyhydric alcohol ester plasticizer is a plasticizer comprising an ester of a dihydric 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 (3).

Formula (3) R ₁ — (OH) _n
However, R ₁ represents an n-valent organic group, n represents a positive integer of 2 or more, and the 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, and xylitol. In particular, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, sorbitol, trimethylolpropane, and xylitol are preferable.

  There is no restriction | limiting in particular as monocarboxylic acid used for polyhydric alcohol ester, Well-known aliphatic monocarboxylic acid, alicyclic monocarboxylic acid, aromatic monocarboxylic acid, etc. can be used. Use of an alicyclic monocarboxylic acid or aromatic monocarboxylic acid is preferred in terms of improving moisture permeability and retention.

  Examples of preferred monocarboxylic acids include the following, but the present invention is not limited thereto.

  As the aliphatic monocarboxylic acid, a fatty acid having a straight chain or a side chain having 1 to 32 carbon atoms can be preferably used. 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 preferable alicyclic monocarboxylic acids include cyclopentanecarboxylic acid, cyclohexanecarboxylic acid, cyclooctanecarboxylic acid, and 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 the polyvalent carboxylic acid ester described in paragraphs [0015] to [0020] of JP-A No. 2002-265639 as one of the plasticizers.

  In addition, phosphate plasticizers can 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>
The transparent base material of the present invention preferably contains an acrylic polymer having a negative average birefringence in the stretching direction and having a weight average molecular weight of 500 or more and 30000 or less, and the acrylic polymer has an aromatic ring as a side chain. An acrylic polymer having a cyclohexyl group in the side chain is preferable.

  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 transparent substrate is excellent, the moisture permeability is extremely low, and excellent performance as a transparent substrate is exhibited.

  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 of using a chain transfer agent such as carbon tetrachloride, a method of using a polymerization terminator such as benzoquinone and dinitrobenzene in addition to the polymerization initiator, and further, Japanese Patent Application Laid-Open No. 2000-128911 or 2000-344823. Examples thereof include a compound having one thiol group and a secondary hydroxyl group, or a bulk polymerization method using a polymerization catalyst in which the compound and an organometallic compound are used in combination. Although used, the method described in the publication is particularly preferable.

  Although the monomer as a monomer unit which comprises the polymer useful for this invention is mentioned below, it is not limited to this.

  The ethylenically unsaturated monomer unit constituting the polymer obtained by polymerizing the ethylenically unsaturated monomer is as a vinyl ester, for example, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl valerate, vinyl pivalate, caproic acid. Vinyl, vinyl caprate, vinyl laurate, vinyl myristate, vinyl palmitate, vinyl stearate, vinyl cyclohexanecarboxylate, vinyl octylate, vinyl methacrylate, vinyl crotonate, vinyl sorbate, vinyl benzoate, vinyl cinnamate Etc .; As acrylate ester, 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 Cyclohexyl acid, acrylic acid (2-ethylhexyl), benzyl acrylate, phenethyl acrylate, 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-p-hydroxymethylphenyl, acrylic acid-p- (2-hydroxyethyl) phenyl, etc .; The above acrylic acid ester is changed to methacrylic acid ester; Examples thereof include acrylic acid, methacrylic acid, maleic anhydride, crotonic acid, itaconic acid and the like. The polymer composed of the above monomers may be a copolymer or a homopolymer, and is preferably a vinyl ester homopolymer, a vinyl ester copolymer, or a copolymer of vinyl ester and acrylic acid or methacrylic acid ester.

  In the present invention, the acrylic polymer refers to a homopolymer or copolymer of acrylic acid or methacrylic acid alkyl ester having no 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.

  In the present invention, 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 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. A compound having one thiol group and a secondary hydroxyl group as described in JP-A No. 2000-128911 or 2000-344823, or polymerization using the compound and an organometallic compound in combination 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. In the present invention, 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 significantly improving the compatibility and transparency of the polymer.

  Furthermore, a polymer using styrene as an ethylenically unsaturated monomer exhibiting negative orientation birefringence with respect to the stretching direction is preferred 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.

  Further, the transparent substrate of the present invention comprises 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. And a polymer X having a weight average molecular weight of 5,000 to 30,000, and more preferably a weight average molecular weight of 500 to 3,000 obtained by polymerizing an ethylenically unsaturated monomer Ya having no aromatic ring. The polymer Y is preferably contained.

(Polymer X, Polymer Y)
The polymer X used in the present invention comprises 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 and having a hydrophilic group in the molecule. It is a polymer having a weight average molecular weight of 5,000 to 30,000 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 used in the present invention is represented by the following general formula (X).

Formula (X)
-(Xa) m- (Xb) n- (Xc) p-
More preferably, it is a polymer represented by the following general formula (X-1).

Formula (X-1)
_{- [CH 2 -C (-R1)} (- CO 2 R2)] m- [CH 2 -C (-R3) (- CO 2 R4-OH) -] n- [Xc] p-
(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- represents X. X represents a monomer unit that can be polymerized to Xa and Xb. M, n, and p represent molar composition ratios, where m ≠ 0, n ≠ 0, and m + n + p = 100.)
Although the monomer as a monomer unit which comprises the polymer X used for this invention is mentioned below, it is not limited to this.

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

  Examples of the ethylenically unsaturated monomer Xa having no aromatic ring and no hydrophilic group in the molecule include methyl acrylate, ethyl acrylate, propyl acrylate (i-, n-), and 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-ethoxyethyl) ) Or the like, or those obtained by replacing the acrylic ester with a methacrylic ester. 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), List acrylic acid (2-hydroxypropyl), acrylic acid (3-hydroxypropyl), acrylic acid (4-hydroxybutyl), acrylic acid (2-hydroxybutyl), or those in which these acrylic acids are replaced by methacrylic acid. Acrylic acid (2-hydroxyethyl) and methacrylic acid (2-hydroxyethyl), acrylic acid (2-hydroxypropyl), and acrylic acid (3-hydroxypropyl) are preferable.

  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 m: n of Xa, Xb and Xc is preferably in the range of 99: 1 to 65:35, 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, the compatibility with the cellulose ester is improved, but the retardation value Rt in the film thickness direction is increased. When the molar composition ratio of Xb is large, the compatibility is deteriorated, but the effect of reducing Rt is high. Further, if the molar composition ratio of Xb exceeds the above range, haze tends to occur during film formation, and 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, more preferably from 8,000 to 25,000.

  By setting the weight average molecular weight to 5,000 or more, it is preferable to obtain advantages such as little dimensional change of the transparent substrate 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 used in the present invention 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.

  The measuring method of a weight average molecular weight can be based on the following method.

(Weight average molecular weight measurement method)
The weight average molecular weight Mw was measured using gel permeation chromatography.

  The measurement conditions are as follows.

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

  The polymer Y used in the present invention 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.

  A weight average molecular weight of 500 or more is preferable because the residual monomer of the polymer is reduced. Moreover, it is preferable to set it as 3000 or less in order to maintain the retardation value Rt fall performance of a film thickness direction.

  Ya is preferably an acrylic or methacrylic monomer having no aromatic ring.

  The polymer Y used in the present invention is represented by the following general formula (Y).

General formula (Y)
-(Ya) k- (Yb) q-
More preferably, it is a polymer represented by the following general formula (Y-1).

General formula (Y-1)
_{- [CH 2 -C (-R5)} (- CO 2 R6)] k- [Yb] q-
(Wherein, R5 is, .Yb .R6 representing H or CH ₃ is representing an alkyl group or a cycloalkyl group having 1 to 12 carbon atoms, .k and q represents the Ya and copolymerizable monomer units, This represents the 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, for example, acrylic acid, methacrylic acid And 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 polymers X and 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. 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 of using a chain transfer agent such as carbon tetrachloride, a method of using a polymerization terminator such as benzoquinone and dinitrobenzene in addition to the polymerization initiator, and further, Japanese Patent Application Laid-Open No. 2000-128911 or 2000-344823. Examples thereof include a compound having one thiol group and a secondary hydroxyl group, or a bulk polymerization method using a polymerization catalyst in which the compound and an organometallic compound are used in combination. In particular, a polymerization method using a compound having a thiol group and a secondary hydroxyl group in the molecule as a chain transfer agent. It is preferred.

  In this case, the terminal of the polymer X and 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 polymers X and Y and the cellulose ester can be adjusted.

  The hydroxyl values of the polymers X and Y are preferably 30 to 150 [mg KOH / g].

(Measurement method of hydroxyl value)
This measurement conforms to JIS K 0070 (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, 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
(Wherein B is the amount of 0.5 mol / L potassium hydroxide ethanol solution used in the blank test (ml), and C is the amount of 0.5 mol / L potassium hydroxide ethanol solution used in the titration (ml). F is a factor of 0.5 mol / L potassium hydroxide ethanol solution, D is an acid value, and 28.05 is 1/2 of 1 mol amount of potassium hydroxide 56.11)
The above-mentioned polymer X and polymer Y are both excellent in compatibility with cellulose ester, excellent in productivity without evaporation and volatilization, good retention as a protective film for polarizing plates, low moisture permeability, and dimensional stability. Are better.

The content of the polymer X and the polymer Y in the transparent substrate is preferably in a 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.

  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 retardation value Rt. 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 liquid described later, or can be added to the dope liquid after being previously dissolved in an organic solvent for dissolving the cellulose ester.

  The total content of the plasticizer in the transparent substrate 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. If the amount is too small, deterioration of flatness is recognized, and if it is too large, bleeding out tends to occur. The mass ratio between the polyhydric alcohol ester plasticizer and the other plasticizer is preferably in the range of 1: 4 to 4: 1, 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.

  For the transparent substrate of the present invention, an ultraviolet absorber is preferably used.

  As the ultraviolet absorber, those excellent in the ability to absorb ultraviolet rays having a wavelength of 370 nm or less and having little absorption of visible light having a wavelength of 400 nm or more are preferably used from the viewpoint of good liquid crystal display properties.

  Specific examples of ultraviolet absorbers preferably used in the present invention include, for example, oxybenzophenone compounds, benzotriazole compounds, salicylic acid ester compounds, benzophenone compounds, cyanoacrylate compounds, triazine compounds, nickel complex compounds, and the like. However, it is not limited to these.

  Specific examples of the benzotriazole-based ultraviolet absorbers include the following ultraviolet absorbers, but the present invention is 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, this invention 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 ultraviolet absorber preferably used in the present invention, a benzotriazole-based ultraviolet absorber and a benzophenone-based ultraviolet absorber that are highly transparent and excellent in preventing the deterioration of the polarizing plate and the liquid crystal are preferable, and unnecessary coloring is less. A benzotriazole-based ultraviolet absorber is particularly preferably used.

  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.

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

  Moreover, in order to provide slipperiness | lubricity to the transparent base material of this invention, microparticles | fine-particles can be used.

  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 of these fine particles in the transparent substrate is preferably 0.05 to 1% by mass, particularly preferably 0.1 to 0.5% by mass. In the case of a film having a multilayer structure formed by a co-casting method, it is preferable that the surface contains this amount of fine particles.

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

  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.) It is marketed by name 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 the turbidity of the transparent substrate low. In the transparent base material of this invention, it is preferable that the dynamic friction coefficient on the opposite side to a hard-coat layer is 1.0 or less.

  It is also preferable to use a commercially available cellulose ester film as the transparent substrate of the present invention. Etc.) are preferably used from the viewpoints of production, 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.

(Solution casting method)
Film formation by a solution casting method of a transparent substrate is a step of preparing a dope by dissolving the cellulose ester and the above various additives in a solvent, a step of casting the dope on a belt-shaped or drum-shaped metal support It is performed by a step of drying the cast 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 up the finished film.

  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. However, if the concentration of cellulose ester is too high, the load during filtration increases and the filtration accuracy increases. Becomes worse. The concentration for achieving both of these is preferably 10 to 35% by mass, and more preferably 15 to 25% by 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, cellulose acetate ester (acetyl group substitution degree 2.4), cellulose acetate propionate is a good solvent. Thus, cellulose acetate (acetyl group substitution degree 2.8) is a poor solvent.

  Although the good solvent used for this invention is not specifically limited, Organic halogen compounds, such as a methylene chloride, dioxolanes, acetone, methyl acetate, methyl acetoacetate, etc. are mentioned. Particularly preferred is methylene chloride or methyl acetate.

  Moreover, although the poor solvent used for this invention 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 that the solvent does not boil under pressure, in order to prevent the generation of massive undissolved materials called gels and mamacos. 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 a 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.

  The prepared cellulose ester solution is filtered using a suitable filter medium such as filter paper. As the filter medium, it is preferable that the absolute filtration accuracy is small in order to remove insoluble matters and the like. 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.

  There are no particular restrictions on the material of the filter medium, and ordinary filter media can be used. However, plastic filter media such as polypropylene and Teflon (registered trademark), and metal filter media such as stainless steel do not drop off fibers. preferable. 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 Nicols state, a transparent base material is placed between them, light is applied from one polarizing plate side, and observed from the other polarizing plate side. 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 / m < 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 of the solvent at normal pressure and in a range where 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.

  Here, the 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 preferable 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, there may be cases where wind at a temperature higher than the target temperature is used while preventing foaming. . 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 transparent substrate 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 amount of residual solvent is defined by the following formula.

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

  In the drying step of the transparent substrate, the web is peeled 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.

  The transparent base material of the present invention is stretched in the conveying direction where the amount of residual solvent of the web immediately after peeling from the metal support is large, and is further stretched in the width direction by a tenter method that grips both ends of the web with clips or the like Is preferred. 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 transverse stretching. This can be determined by the draw ratio in the longitudinal direction × the draw ratio in the transverse direction. A film with good flatness can be obtained if either of the draw ratios in the machine direction or the transverse direction is 1.01 or more.

  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 transparent base material is not specifically limited, 10-200 micrometers is used preferably. In particular, the film thickness is particularly preferably 10 to 100 μm. More preferably, it is 20-60 micrometers. Most preferably, it is 35-60 micrometers. Moreover, the transparent base material made into the multilayer structure by the co-casting method can be used preferably.

  The transparent base material of the present invention has a width of 1 m or more and preferably has a width of 1.4 to 4 m. Especially preferably, it is 1.4-3 m. If it exceeds 4 m, conveyance becomes difficult. Moreover, it is preferable that the centerline average roughness (Ra) of the transparent base material surface is 0.001-1 micrometer.

  The transparent substrate of the present invention is useful as a polarizing plate protective film, and is an optically isotropic protective film that suppresses the development of retardation due to birefringence as much as possible, and for widening the viewing angle having a desired retardation. The provided retardation film can be used as a transparent substrate.

  As the protective film, the in-plane retardation Ro represented by the following formula in an environment of 23 ° C. and 55% RH is 0 ≦ Ro ≦ 50 nm, and the retardation Rt in the thickness direction is −400 nm ≦ Rt ≦ 400 nm. Preferably there is. The retardation film preferably has an in-plane retardation Ro of 20 ≦ Ro ≦ 70 nm and a thickness direction retardation Rt of 70 ≦ Rt ≦ 400 nm. Furthermore, Rt is preferably 100 to 400 nm, and more preferably 100 to 200 nm. In particular, Rt / Ro is preferably 1.5 to 6.0.

  The angle θ (°) between the transverse direction of Ro, Rt or the long film and the slow axis can be measured using an automatic birefringence meter. Using an automatic birefringence meter KOBRA-21ADH (manufactured by Oji Scientific Instruments Co., Ltd.), the birefringence measurement at 590 nm of the transparent substrate is performed in an environment of 23 ° C. and 55% RH, and the refractive indexes nx, ny , Nz, and calculate Ro and Rt according to the following formula.

Ro = (nx−ny) × d
Rt = {(nx + ny) / 2−nz} × d
(In the formula, the refractive index in the slow axis direction in the film plane is nx, the refractive index in the direction perpendicular to the slow axis in the plane is ny, the refractive index in the thickness direction is nz, and d is the film thickness (nm). Represents.)
The adjustment of the retardation can be controlled by the type of cellulose ester, the degree of acyl group substitution, the type and content of additives, the film thickness, the stretching operation, and the like.

<Anti-glare anti-reflection film>
The present invention can provide an antiglare antireflection film by providing the following low refractive index layer on the surface having the fine uneven structure or the fine uneven structure of the antiglare film having the fine uneven structure and the transparent resin layer.

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

(Low refractive index layer)
The refractive index of the low refractive index layer used in the present invention is lower than the refractive index of the base film as a support, and is preferably in the range of 1.30 to 1.45 when measured at 23 ° C. and a wavelength of 550 nm.

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

  The composition for forming a low refractive index layer used in the present invention comprises (a) an organosilicon compound represented by the following general formula (4) or a hydrolyzate thereof or a polycondensate thereof, and (b) an outer shell layer. It is preferable that hollow silica-based fine particles having a porous or hollow interior constitute the composition.

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

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

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

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

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

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

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

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

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

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

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

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

  In the present invention, the low refractive index layer may contain a fluorine-substituted alkyl group-containing silane compound represented by the following general formula (5).

  The fluorine-substituted alkyl group-containing silane compound represented by the general formula (5) will be described.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

(Metal compound)
As the metal compound used in the present invention, a compound represented by the following general formula (6) or a chelate compound thereof can be used.

General formula (6) AnMBx-n
In the formula, M represents a metal atom, A represents a hydrolyzable functional group or a hydrocarbon group having a hydrolyzable functional group, and B represents an atomic group covalently or ionically bonded to the metal atom M. x represents the valence of the metal atom M, and n represents an integer of 2 or more and x or less.

  Examples of the hydrolyzable functional group A include halogens such as alkoxyl groups and chloro atoms, ester groups and amide groups. The metal compound belonging to the general formula (6) includes an alkoxide having two or more alkoxyl groups bonded directly to a metal atom, or a chelate compound thereof. Preferable metal compounds include titanium alkoxide, zirconium alkoxide, or chelate compounds thereof. Titanium alkoxide has a high reaction rate and a high refractive index and is easy to handle. However, since it has a photocatalytic action, its light resistance deteriorates when added in a large amount. Zirconium alkoxide has a high refractive index but tends to become cloudy, so care must be taken in dew point management during coating. Moreover, since titanium alkoxide has the effect of promoting the reaction between the ultraviolet curable resin and the metal alkoxide, the physical properties of the coating film can be improved even by adding a small amount.

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

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

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

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

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

  Examples of the monomer of the polyfunctional acrylate compound include ethylene glycol diacrylate, diethylene glycol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, and tetramethylolmethanetriacrylate. Acrylate, 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.

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

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

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

(solvent)
Examples of the organic solvent used for coating the high refractive index layer used in the present invention include alcohols (for example, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, secondary butanol, tertiary butanol, pentanol). , Hexanol, cyclohexanol, benzyl alcohol, etc.), polyhydric alcohols (eg, 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 mono Chill 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 (eg, ethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, morpholine, N-ethylene) Lumorpholine, ethylenediamine, diethylenediamine, triethylenetetramine, tetraethylenepentamine, polyethyleneimine, pentamethyldiethylenetriamine, tetramethylpropylenediamine, etc.), amides (eg, formamide, N, N-dimethylformamide, N, N-dimethylacetamide) Etc.), heterocyclic rings (for example, 2-pyrrolidone, N-methyl-2-pyrrolidone, cyclohexyl pyrrolidone, 2-oxazolidone, 1,3-dimethyl-2-imidazolidinone, etc.), sulfoxides (for example, dimethyl sulfoxide, etc.) ), Sulfones (for example, sulfolane, etc.), urea, acetonitrile, acetone and the like, and alcohols, polyhydric alcohols, and polyhydric alcohol ethers are particularly preferable.

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

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

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

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

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

  Preferably, in the composition for forming an antifouling layer, the silane compound having a fluoroalkyl group is represented by the following general formula (7), and the concentration of the silane compound is diluted to 0.01 to 5% by mass. Use antifouling treatment.

Formula _{(7) CF 3 (CF 2} ) m (CH 2) n-Si- (ORa) 3
Here, m is an integer of 1-10. n is an integer of 0-10. Ra represents the same or different alkyl group.

  In the compound represented by the general formula (7), Ra has 3 or less carbon atoms and is preferably an alkyl group consisting of only carbon and hydrogen, for example, a group such as methyl, ethyl, isopropyl and the like.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

(Polarizer)
The polarizing plate can be produced by a general method. A fully saponified polyvinyl alcohol aqueous solution is applied to at least one surface of a polarizing film prepared by subjecting the back side of the antiglare film or the antiglare antireflection film of the present invention to an alkali saponification treatment and immersion drawing in an iodine solution. It is preferable to use and bond together. The film may be used on the other surface, or another polarizing plate protective film may be used. Commercially available cellulose ester films (for example, Konica Minoltak KC8UX, KC4UX, KC5UX, KC8UCR3, KC8UCR4, KC8UCR5, KC8UY, KC4UY, KC12UR, KC4FR, and the above manufactured by Konica Minolta Opto Co., Ltd. are also preferably used). In contrast to the antiglare film 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 590 nm, 30 to 300 nm, and Rt of 70 to 400 nm. It preferably has a phase difference. 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. 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.

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

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

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

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

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

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

  The measurement conditions are as follows.

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

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

Methyl acrylate 100 parts by weight Thioglycerol 5 parts by weight

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

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

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

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

[Preparation of antiglare film 1]
(Preparation of the first layer)
The following cured resin layer coating composition 1 is applied to the surface of the cellulose ester film 1 (B surface side; surface in contact with a mirror surface of a support such as a stainless steel band used in the casting film forming method) with a slit die. Then, the temperature and speed of the hot air were gradually increased and finally dried at 85 ° C., followed by irradiation with ultraviolet rays at an irradiation intensity of 115 mJ / cm ² from the actinic ray irradiation part to form a cured resin layer, thereby producing a first layer. . The dry film thickness by the following composition was 5 micrometers.

(Solid content)
Acrylic monomer: KAYARAD DPHA (dipentaerythritol hexaacrylate, manufactured by Nippon Kayaku Co., Ltd.) 70 parts by mass Trimethylolpropane triacrylate 30 parts by mass Photopolymerization initiator (Irgacure 184 (manufactured by Ciba Specialty Chemicals))
4 parts by mass (solvent)
Propylene glycol monomethyl ether 75 parts by weight Methyl ethyl ketone 25 parts by weight On the first layer, the following fine concavo-convex structure-forming coating solution 1 is ejected as ink droplets by an ink jet method at 2 to 16 pl and activated 0.2 seconds after drying. Curing was carried out at an ultraviolet ray illuminance of 0.1 W / cm ² and an irradiation amount of 100 mJ / cm ² from the light irradiation part, thereby forming a convex part.

  As the inkjet emitting device, a line head method (FIG. 4A) was used, and 10 inkjet heads having 256 nozzles having a nozzle diameter of 3.5 μm were prepared. An ink jet head having the structure shown in FIG. 3 was used. The ink supply system is composed of an ink supply tank, a filter, a piezo-type ink jet head, and piping. The ink supply tank to the ink jet head section is insulated and heated (25 ° C.), and the emission temperature is 25 ° C. The driving frequency was 20 kHz. Temperature sensors were provided in the vicinity of the front chamber ink tank and the nozzle of the piezo head, respectively, and temperature control was performed so that the nozzle portion was always 25 ° C. ± 2 ° C.

After the convex portion is formed, the surface of the film is subjected to surface treatment by plasma discharge at a high frequency voltage of 100 kHz under atmospheric pressure of nitrogen atmosphere containing 1% oxygen, and then the transparent resin layer coating solution 1 is dried by a reduced pressure extrusion method. The film was applied to a thickness of 7 μm and cured at an ultraviolet illuminance of 0.2 W / cm ² and an irradiation amount of 150 mJ / cm ² , thereby producing an antiglare film 1.

  It was 127 nm as a result of measuring arithmetic mean surface roughness Ra about the formed anti-glare film using the optical interference type surface roughness measuring machine by WYKO. The average center distance of the convex portions was 28 μm.

(Fine uneven structure forming coating solution 1)
KAYARAD DPHA (dipentaerythritol hexaacrylate, Nippon Kayaku) 20 parts by mass TEMPTA (trimethylolpropane triacrylate, manufactured by Daicel Cytec Co., Ltd.) 20 parts by mass Photopolymerization initiator (Irgacure 184 (Ciba Specialty Chemicals) ))
1 part by weight Photopolymerization initiator (Irgacure 907 (Ciba Specialty Chemicals Co., Ltd.))
1 part by mass Ethylene glycol monobutyl ether acetate 40 parts by mass Diethylene glycol monoethyl ether 12 parts by mass Propylene glycol monomethyl ether 6 parts by mass The above composition was mixed and stirred to prepare a coating solution 1 for forming a fine uneven structure.

  In addition, the viscosity of the coating liquid 1 for forming a fine uneven structure was 5.1 mPa · s at 25 ° C. and 1.7 mPa · s at 60 ° C.

(Transparent resin layer coating solution 1)
Acrylic monomer: KAYARAD DPHA (dipentaerythritol hexaacrylate, manufactured by Nippon Kayaku Co., Ltd.) 100 parts by mass Trimethylolpropane triacrylate 40 parts by mass Photopolymerization initiator (Irgacure 184 (manufactured by Ciba Specialty Chemicals))
6 parts by mass Propylene glycol monomethyl ether 50 parts by mass Methyl ethyl ketone 50 parts by mass The above composition was mixed and stirred to prepare a transparent resin layer coating solution 1.

[Preparation of antiglare films 2 to 16]
Antiglare films 2 to 16 were produced in the same manner as antiglare film 1 except that the following fine concavo-convex structure forming coating solutions 2 to 12 were used and the emission temperature was controlled as shown in Table 4.

(Fine relief structure forming coating solution 2)
KAYARAD DPHA (dipentaerythritol hexaacrylate, manufactured by Nippon Kayaku Co., Ltd.) 58 parts by mass PETAK (pentaerythritol tetraacrylate, manufactured by Daicel Cytec Co., Ltd.) 25 parts by mass Photopolymerization initiator (Irgacure 184 (manufactured by Ciba Specialty Chemicals Co., Ltd.)) )
2 parts by mass Photopolymerization initiator (Irgacure 907 (Ciba Specialty Chemicals Co., Ltd.))
2 parts by mass Ethylene glycol monobutyl ether acetate 9 parts by mass Diethylene glycol monoethyl ether 3 parts by mass Propylene glycol monomethyl ether 1 part by mass The above composition was mixed and stirred to prepare a coating solution 2 for forming a fine uneven structure.

  The viscosity of the fine concavo-convex structure forming coating solution 2 was 620 mPa · s at 25 ° C. and 53 mPa · s at 60 ° C.

(Fine relief structure forming coating solution 3)
KAYARAD DPHA (dipentaerythritol hexaacrylate, Nippon Kayaku Co., Ltd.) 35 parts by mass TEMPTA (trimethylolpropane triacrylate, manufactured by Daicel Cytec Co., Ltd.) 35 parts by mass Photopolymerization initiator (Irgacure 184 (Ciba Specialty Chemicals Co., Ltd.) ))
1.7 parts by mass Photopolymerization initiator (Irgacure 907 (Ciba Specialty Chemicals Co., Ltd.))
1.7 parts by mass Ethylene glycol monobutyl ether acetate 20 parts by mass Diethylene glycol monoethyl ether 6 parts by mass Propylene glycol monomethyl ether 3 parts by mass The above composition was mixed and stirred to prepare coating solution 3 for forming a fine uneven structure.

  The viscosity of the fine concavo-convex structure forming coating solution 3 was 15 mPa · s at 25 ° C. and 7.3 mPa · s at 60 ° C.

(Fine relief structure forming coating solution 4)
KAYARAD DPHA (dipentaerythritol hexaacrylate, Nippon Kayaku Co., Ltd.) 62 parts by mass TEMPTA (trimethylolpropane triacrylate, manufactured by Daicel Cytec Co., Ltd.) 15 parts by mass Photopolymerization initiator (Irgacure 184 (Ciba Specialty Chemicals Co., Ltd.) ))
2 parts by mass Photopolymerization initiator (Irgacure 907 (Ciba Specialty Chemicals Co., Ltd.))
2 parts by mass Ethylene glycol monobutyl ether acetate 13 parts by mass Diethylene glycol monoethyl ether 4 parts by mass Propylene glycol monomethyl ether 2 parts by mass The above composition was mixed and stirred to prepare a coating solution 4 for forming a fine uneven structure.

  In addition, the viscosity of this fine concavo-convex structure forming coating solution 4 was 31 mPa · s at 25 ° C. and 4.6 mPa · s at 60 ° C.

(Fine relief forming liquid 5)
KAYARAD DPHA (dipentaerythritol hexaacrylate, manufactured by Nippon Kayaku Co., Ltd.) 24 parts by mass TEMPTA (trimethylolpropane triacrylate, manufactured by Daicel Cytec Co., Ltd.) 12 parts by mass EBECRYL 220 (urethane acrylate, manufactured by Daicel Cytec Co., Ltd.)
24 parts by mass of photopolymerization initiator (Irgacure 184 (manufactured by Ciba Specialty Chemicals))
1 part by weight Photopolymerization initiator (Irgacure 907 (Ciba Specialty Chemicals Co., Ltd.))
1 part by mass Ethylene glycol monobutyl ether acetate 27 parts by mass Diethylene glycol monoethyl ether 8 parts by mass Propylene glycol monomethyl ether 4 parts by mass The above composition was mixed and stirred to prepare a fine uneven structure forming coating solution 5.

  In addition, the viscosity of the coating liquid 5 for forming a fine concavo-convex structure was 35 mPa · s at 25 ° C. and 17 mPa · s at 60 ° C.

(Fine concavo-convex structure forming coating solution 6)
KAYARAD DPHA (dipentaerythritol hexaacrylate, Nippon Kayaku) 35 parts by mass PETAK (pentaerythritol tetraacrylate, manufactured by Daicel Cytec Co., Ltd.) 35 parts by mass Photopolymerization initiator (Irgacure 184 (manufactured by Ciba Specialty Chemicals)) )
2 parts by mass Photopolymerization initiator (Irgacure 907 (Ciba Specialty Chemicals Co., Ltd.))
2 parts by mass Ethylene glycol monobutyl ether acetate 19 parts by mass Diethylene glycol monoethyl ether 5 parts by mass Propylene glycol monomethyl ether 2 parts by mass The above composition was mixed and stirred to prepare a fine uneven structure forming coating solution 6.

  The viscosity of the coating liquid 6 for forming a fine concavo-convex structure was 32 mPa · s at 25 ° C. and 9.3 mPa · s at 60 ° C.

(Fine concavo-convex structure forming coating solution 7)
KAYARAD DPHA (dipentaerythritol hexaacrylate, manufactured by Nippon Kayaku Co., Ltd.) 36 parts by mass PETAK (pentaerythritol tetraacrylate, manufactured by Daicel Cytec Co., Ltd.) 12 parts by mass EBECRYL220 (urethane acrylate, manufactured by Daicel Cytec Co., Ltd.)
12 parts by mass Photopolymerization initiator (Irgacure 184 (manufactured by Ciba Specialty Chemicals))
1.5 parts by mass of photopolymerization initiator (Irgacure 907 (Ciba Specialty Chemicals))
1.5 parts by mass Ethylene glycol monobutyl ether acetate 27 parts by mass Diethylene glycol monoethyl ether 8 parts by mass Propylene glycol monomethyl ether 4 parts by mass The above composition was mixed and stirred to prepare a fine uneven structure forming coating solution 7.

  In addition, the viscosity of the coating liquid 7 for forming a fine concavo-convex structure was 35 mPa · s at 25 ° C. and 8.1 mPa · s at 60 ° C.

(Fine concavo-convex structure forming coating solution 8)
Lauryl acrylate (monofunctional) 13 parts by mass Stearyl acrylate (monofunctional) 8 parts by mass Tetraethylene glycol diacrylate (bifunctional) 36 parts by mass Ethylene oxide-modified trimethylolpropane triacrylate (manufactured by Kyoeisha Chemical Co., Ltd., TMP-3EO-A) 24 Mass parts Photopolymerization initiator (Irgacure 907 (Ciba Specialty Chemicals Co., Ltd.))
5 parts by mass Photopolymerization initiator (diethylthioxanthone) 1 part by mass Diethylene glycol monoethyl ether 3 parts by mass Ethylene glycol monobutyl ether acetate 10 parts by mass The above composition was mixed and stirred to prepare a fine uneven structure forming coating solution 8.

  The viscosity of the fine concavo-convex structure forming coating solution 8 was 54 mPa · s at 25 ° C. and 8.0 mPa · s at 60 ° C.

(Fine concavo-convex structure forming coating solution 9)
Lauryl acrylate (monofunctional) 14 parts by mass Stearyl acrylate (monofunctional) 10 parts by mass Tetraethylene glycol diacrylate (bifunctional) 45 parts by mass Ethylene oxide-modified trimethylolpropane triacrylate (manufactured by Kyoeisha Chemical Co., Ltd., TMP-3EO-A) 25 Mass parts Photopolymerization initiator (Irgacure 907 (Ciba Specialty Chemicals Co., Ltd.))
5 parts by mass Photopolymerization initiator (diethylthioxanthone) 1 part by mass The above composition was mixed and stirred to prepare a fine uneven structure forming coating solution 9.

  In addition, the viscosity of the coating liquid 9 for forming a fine uneven structure was 76 mPa · s at 25 ° C. and 9.7 mPa · s at 60 ° C.

(Fine concavo-convex structure forming coating solution 10)
Lauryl acrylate (monofunctional) 14 parts by mass Ethoxydiethylene glycol acrylate (monofunctional) 10 parts by mass Tetraethylene glycol diacrylate (bifunctional) 45 parts by mass Caprolactam-modified dipentaerythritol hexaacrylate (hexafunctional)
25 parts by mass of photopolymerization initiator (Irgacure 907 (manufactured by Ciba Specialty Chemicals))
5 parts by mass Photopolymerization initiator (diethylthioxanthone) 1 part by mass The above composition was mixed and stirred to prepare a fine uneven structure forming coating solution 10.

  The viscosity of the coating solution 10 for forming a fine uneven structure was 80 mPa · s at 25 ° C. and 15 mPa · s at 60 ° C.

(Fine uneven structure forming coating solution 11)
Isobornyl acrylate (monofunctional) 14 parts by mass Ethoxydiethylene glycol acrylate (monofunctional) 10 parts by mass Tetraethylene glycol diacrylate (bifunctional) 45 parts by mass Glycerin propoxytriacrylate (trifunctional) (manufactured by Daicel UCB, OTA480) 25 parts by mass Part photopolymerization initiator (Irgacure 819 (Ciba Specialty Chemicals Co., Ltd.))
5 parts by weight Photopolymerization initiator (Irgacure 184 (Ciba Specialty Chemicals Co., Ltd.))
2 mass parts The said composition was mixed and stirred and the fine uneven | corrugated structure formation coating liquid 11 was prepared.

  In addition, the viscosity of the coating liquid 11 for forming a fine uneven structure was 51 mPa · s at 25 ° C. and 6.1 mPa · s at 60 ° C.

(Fine concavo-convex structure forming coating solution 12)
Lauryl acrylate (monofunctional) 6 parts by mass Ethoxydiethylene glycol acrylate (monofunctional) 9 parts by mass Tetraethylene glycol diacrylate (bifunctional) 15 parts by mass KAYARAD DPHA (dipentaerythritol hexaacrylate, Nippon Kayaku) 49 parts by mass Caprolactam modification Dipentaerythritol hexaacrylate (hexafunctional)
15 parts by mass of photopolymerization initiator (Irgacure 184 (manufactured by Ciba Specialty Chemicals))
3 parts by mass Photopolymerization initiator (Irgacure 907 (Ciba Specialty Chemicals Co., Ltd.))
3 mass parts The said composition was mixed and stirred and the fine uneven | corrugated structure formation coating liquid 12 was prepared.

  The viscosity of the convex coating solution 1 was 476 mPa · s at 25 ° C. and 41 mPa · s at 60 ° C.

[Preparation of antiglare films 17 to 18]
The same method as the anti-glare film 1 except that the fine concavo-convex structure forming coating liquids 9 and 11 are used, the emission temperature is controlled as shown in Table 4, and the first layer (cured resin layer coating composition 1) is not coated. Thus, antiglare films 17 to 18 were produced.

  The following measurements and evaluations were performed using the antiglare films 1 to 18 produced above.

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

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

5: Glitter is not known at all 4: Slight glare is known 3: Slight glare is observed 2: Between 3 and 1 1: Glitter is quite worrisome (Partial unevenness evaluation of anti-glare film)
The produced anti-glare film is cut into A4 size (297 × 210 mm), and a 1 mm thick black acrylic plate (acrylic resin plate manufactured by Nitto Resin Co., Ltd.) is bonded to the surface where the anti-glare layer is not formed. Then, the reflection on the back surface was eliminated, and the partial unevenness of the antiglare layer was visually determined according to the following criteria.

5: There is no partial unevenness 4: There is almost no partial unevenness 3: Partial unevenness is faintly confirmed 2: There is partial unevenness, but there is no practical problem 1: Partial unevenness is clearly visible Table 4 shows the measurement results Show.

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

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

  The composition of the antiglare film and the evaluation results are shown in Table 4 below.

  As is apparent from Table 4, the composition of the present invention can provide an antiglare film having excellent antiglare effect, glare, partial unevenness of antiglare effect, and adhesion. Moreover, the optical performance which was excellent irrespective of the state of the base | substrate which forms a convex part can be obtained, and the stable anti-glare film can be obtained.

Example 2
The following low refractive index layers were coated on the transparent resin layers of the antiglare films 1 to 18 produced in Example 1.

[Preparation of antireflection layer: low refractive index layer]
The following low refractive index layer coating composition 1 is applied by an extrusion coater, dried at 100 ° C. for 1 minute, cured by irradiation with ultraviolet rays of 0.1 J / cm ² , and further thermally cured at 120 ° C. for 5 minutes. A low refractive index layer was provided so as to have a thickness of 95 nm, and antiglare and antireflection films 1 to 18 were produced. The refractive index of this low refractive index layer was 1.37.

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

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

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

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

  Subsequently, a polarizing plate was produced using each antiglare antireflection film 1-18.

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

b) Preparation of Polarizing Plate A polarizing plate is bonded to the antiglare antireflection film 1 to 18 and the cellulose ester film KC8UCR-5 (manufactured by Konica Minolta Opto) on the back side in accordance with the following steps 1 to 5. Was made. The polarizing plate protective film on the back side was a cellulose ester film having a retardation, and retardation values were Ro = 43 nm and Rt = 132 nm.

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

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

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

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

  Process 5: A sample obtained by bonding the polarizing film, the cellulose ester film, and the antiglare antireflection films 1 to 18 produced in Process 4 in a dryer at 80 ° C. is dried for 2 minutes to produce polarizing plates 1 to 18. did.

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

  The polarizing plate of the surface previously bonded of the commercially available 32-inch liquid crystal television (MVA type cell) was peeled off, and the produced polarizing plates 1 to 18 were each bonded to the glass surface of the liquid crystal cell.

  At that time, the direction of bonding of the polarizing plate is such that the surface of the cellulose ester film having a retardation is on the liquid crystal cell side, and the absorption axis is in the same direction as the polarizing plate previously bonded. It carried out so that it might face, and produced the liquid crystal display devices 1-18, respectively.

<Evaluation>
The obtained liquid crystal display devices 1 to 18 were observed in an environment as shown in FIG. 8, and the anti-glare effect, glare, and the blackness when displaying the following visibility and moving images were respectively shown below. Visual evaluation was made according to the criteria. In addition, 10 40W fluorescent lamps (FLR40S-EX-D / M manufactured by Matsushita Electric) were installed on the ceiling. Moreover, it evaluated in the state which external light inserts from a window.

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

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

  From the above table, the anti-glare antireflection film of the present invention and the polarizing plate / liquid crystal display devices 3 to 18 using the anti-glare film have the same anti-glare effect and glare as in Example 1, and further from artificial lighting and windows. It can be seen that it is excellent in blacking even in an environment where external light is inserted.

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

Explanation of symbols

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

Claims (7)

In the method for producing an antiglare film in which a fine uneven structure is imparted by an inkjet method on a transparent substrate, the fine uneven structure contains at least a polymerizable compound and a photoinitiator polymer, and has a viscosity at 25 ° C. of 10 to 500 mPa. A method for producing an antiglare film, characterized by being formed of the ink composition of s. The method for producing an antiglare film according to claim 1, wherein the ink composition has a viscosity of 5 to 30 mPa · s at 60 ° C. The method for producing an antiglare film according to claim 1 or 2, wherein the ink composition is an ink composition substantially free of a solvent. The method for producing an antiglare film according to any one of claims 1 to 3, wherein the ink composition is ejected from an inkjet head held at 40 ° C to 80 ° C. An anti-glare film produced by the method for producing an anti-glare film according to claim 1. A polarizing plate comprising the antiglare film according to claim 5 on at least one surface. A display device comprising the antiglare film according to claim 5 or the polarizing plate according to claim 6.

Images