JP2006219632A - Applying composition, optically functioning layer, reflection-preventing film and method for producing the film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an applying composition capable of forming a uniform plane state low refractive index layer in a high speed without deteriorating the characteristics of the low refractive index layer of a reflection-preventing film, and an optically functioning layer and the reflection-preventing film by using the applying composition. <P>SOLUTION: This applying composition containing a compound capable of polymerizing with heat or an active energy beam irradiation and solvents, and capable of forming a transparent film having ≤1.50 refractive index after curing and ≤2% haze on forming a film having 100 nm thickness is characterized in that at least 2 kinds of solvents are contained, also at least 1 kind of the solvent has ≥1 mPa s viscosity, and there is ≤6 dyne/cm surface tension difference between the solvents. The optically functioning layer and reflection-preventing film formed from the applying composition are also provided. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a coating composition for an optical functional layer, an optical functional layer, a method for producing the optical functional layer, and an antireflection film optical functional layer.

  An antireflection film as an optical functional film is generally used to reflect external light in a display device such as a cathode ray tube display (CRT), a plasma display (PDP), an electroluminescence display (ELD), or a liquid crystal display (LCD). In order to prevent contrast degradation and image reflection due to the optical interference, it is arranged on the outermost surface of the display so as to reduce the reflectance by using the principle of optical interference.

  Such an antireflection film can be generally produced by forming a low refractive index layer with a film thickness of about 100 nm on the outermost layer of the film. A material having a refractive index as low as possible is desired for the low refractive index layer. In addition, since the antireflective film is used on the outermost surface of the display, the low refractive index layer, which is the outermost layer, requires not only the refractive index but also the characteristics of the film itself, such as high scratch resistance, antifouling properties and transparency. Many need to satisfy the characteristics.

  In recent years, with the trend toward thinner and larger displays, antireflection films have been required to have a uniform surface with a wider area. Conventionally, as a method of forming a low refractive index layer, a metal oxide film is formed by a chemical vapor deposition (CVD) method or a physical vapor deposition (PVD) method, particularly a vacuum vapor deposition method or a sputtering method which is a kind of physical vapor deposition method. Has been done.

  However, a method for forming a transparent thin film of metal oxide by vapor deposition or sputtering is not suitable for mass production because of low productivity, and a wet film forming method with high productivity, particularly a method of forming by a coating method has been proposed.

  In general, after applying a coating composition consisting of a diluting solvent to a base material that is continuously transported, a solvent is removed by drying and cured by heat or active energy ray irradiation. This is a method of forming a film.

  With respect to the antireflection film, an improvement in productivity is required from the viewpoint of cost reduction, and an increase in coating speed is an essential technique. However, increasing the coating speed tends to cause film thickness unevenness due to accompanying air or drying air, and it becomes difficult to maintain the surface uniformity required for the antireflection film. The surface uniformity referred to here means that variations in optical performance, such as antireflection performance, and variations in film physical properties such as scratch resistance, and variations in reflection color by visual observation are small within the entire display area of the display. Say.

  In particular, since the low refractive index layer has a very thin dry film, a solid content concentration of the coating composition is low, and generally a solution having a low viscosity is used. When the viscosity is low, there is a problem that it is easily affected by the above-mentioned drying wind, and wind unevenness is likely to occur as the coating speed increases.

  In addition, if the viscosity is low, the coating thickness is likely to fluctuate due to disturbances such as device vibration during application. In order to form a low refractive index layer uniformly at high speed by the application method, the coating composition There is preferably a method of increasing the viscosity of the product to an appropriate viscosity.

  As a method for adjusting the viscosity, it is possible to use a viscosity modifier, the kind of resin contained in the coating composition, the molecular weight, and the like. However, when a viscosity modifier is added, the content of the viscosity modifier in the dry film increases, and various properties required for the low refractive index layer described above may change greatly. Also, changing the type of resin, molecular weight, etc. may cause problems due to changes in the synthesis process, coating properties, stability of the coating composition over time, and the like. Therefore, it is preferable to adjust the viscosity of the coating composition by using a solvent having a high viscosity.

  Conventionally, as for the solvent of the coating composition, as disclosed in Patent Document 1, in order to increase the drying speed at the time of coating, the boiling point is defined and the viscosity of the coating composition is not considered. In addition, when the solvent composition is easily changed, the dissolution of the resin, the dispersion state of the inorganic fine particles, and the like are changed, making it difficult to put it into practical use.

  In order to form a low refractive index layer at high speed, the coating method is also very important. As the coating method of the antireflection film, dip coating, micro gravure, reverse roll coating, etc. have been mainly used so far.

  However, in the dip coating method, vibration of the coating liquid in the liquid receiving tank is unavoidable, and stepped unevenness is likely to occur. Further, in the reverse roll coating method and the micro gravure method, stepped unevenness is likely to occur due to roll eccentricity and deflection related to coating. Furthermore, in the microgravure method, coating amount unevenness is likely to occur due to the production accuracy of the gravure roll and the temporal change of the roll and blade due to the contact between the blade and the gravure roll.

  Further, since these coating methods are post-measuring methods, it is relatively difficult to ensure a stable film thickness. Therefore, in these coating methods, it is difficult to increase the coating speed beyond a certain speed, and although the productivity is higher than the vapor deposition method or the like, the high productivity inherent in coating cannot be fully utilized.

  On the other hand, since the die coating method of Patent Document 2 is a pre-measuring application method, it has an advantage of high film thickness stability. However, since coating is performed using a generally used die configuration, it is possible to realize only high speed comparable to the above-described various coating methods. Specifically, in a thin layer coating such as an antireflection layer, film thickness unevenness occurs in a direction perpendicular to and parallel to the transport direction of the transparent support, and it is difficult to maintain film thickness stability. .

  On the other hand, in the above-described die coating methods of Patent Documents 3 and 4, a thin layer can be applied with high accuracy by devising the configuration of the die. Therefore, by using this method, a thin layer such as an antireflection layer can be applied with high accuracy. However, depending on the type of liquid, it was difficult to apply at high speed, and sometimes it was impossible to apply itself.

In particular, as described above, when the viscosity of the coating composition is increased, the coating limit speed of the coating film when the transport speed of the base during coating is increased may cause a problem.
JP 2003-148404 A JP 7-151904 A JP 2003-200097 A JP 2003-211052 A

  The present invention has been made in view of such circumstances, and a coating composition and a manufacturing method for manufacturing an antireflection film having productivity higher than that of a vapor deposition method and other coating methods and high film thickness uniformity. The purpose is to provide. Another object of the present invention is to provide the coating composition, the optical functional layer produced by the production method, and the antireflection film.

As a result of intensive studies to solve the above problems, the present inventors have found that the above object can be achieved by adding two or more solvents having specific characteristics and using a specific coating method. The headline and the present invention have been completed.
That is, the above object of the present invention is achieved by the following coating composition, optical functional layer, antireflection film, and production method.

(1) Contains a compound polymerizable by heat or active energy ray irradiation and a solvent, has a refractive index after curing of 1.50 or less, and a haze of 2% or less when a film having a thickness of 100 nm is formed. A coating composition capable of forming a transparent film, comprising at least two kinds of solvents, wherein the viscosity of at least one kind of solvent is 1 mPa · s or more, and other solvents having a viscosity of 1 mPa · s or more The difference in surface tension from the solvent is 6 dyn / cm or less.
(2) The coating composition as described in (1) above, wherein the viscosity is 1 mPa · s to 6.5 mPa · s.
(3) The coating composition as described in (1) or (2) above, wherein the difference in boiling point between the solvent having a viscosity of 1 mPa · s or more and another solvent is 30 ° C. or less.
(4) The coating composition as described in any one of (1) to (3) above, wherein the compound polymerizable by irradiation with heat or active energy rays is a fluorine-containing compound.

(5) The coating composition as described in any one of (1) to (4) above, wherein at least one of the solvents is a ketone solvent.
(6) The film | membrane obtained by apply | coating the coating composition in any one of said (1)-(5) on a transparent base material, removing a solvent by drying, and hardening | curing by heat or active energy ray irradiation. An optical functional layer having a thickness of 200 nm or less.
(7) The optical functional layer as described in (6) above, wherein the refractive index is 1.45 or less.

(8) An antireflection film having a hard coat layer containing resin beads on a transparent support and the optical functional layer according to (6) or (7) above.
(9) A hard coat layer containing resin beads is formed by dispersing at least one kind of translucent particles having an average particle diameter of 0.5 to 8 μm in a translucent resin, the translucent particles and the translucent particles (8) The difference in refractive index with the light-sensitive resin is 0.02 to 0.30, and the light-transmitting particles are contained in an amount of 3 to 30% by mass of the total solid content of the light scattering layer (8 ) Antireflection film described in the above.
(10) Two or more kinds of residual solvents can be detected, the viscosity of at least one kind of solvent is 1 mPa · s or more, and the surface tension difference between the solvent having the viscosity of 1 mPa · s or more and other solvents is 6 dyn. / Cm or less, an antireflection film,

(11) After the land of the tip lip of the slot die is brought close to the surface of the web supported continuously by the backup roll and the coating composition is applied from the slot of the tip lip, solvent drying, if necessary And curing with ionizing radiation or heat.
(12) When the slot die having a land length in the web traveling direction of the tip lip on the web traveling direction side of the slot die of 30 μm or more and 100 μm or less is used, and the slot die is set at the coating position, the progress of the web The gap between the tip lip and the web opposite to the direction is applied using a coating apparatus installed so that the gap between the tip lip and the web on the web traveling direction side is 30 μm or more and 120 μm or less. The manufacturing method of the optical function layer as described in said (11).
(13) The method for producing an optical functional layer as described in (11) or (12) above, wherein the web conveyance speed during coating is 20 m / min or more.

As described above, the present invention is greatly characterized in that the coating composition for forming the optical functional layer contains two or more kinds of solvents having specific characteristics. Surface uniformity without point defects can be ensured by high-speed application. Two or more kinds of solvents having this specific property are particularly preferable because they have the effect of improving surface failures such as coating unevenness, drying unevenness, and point defects of the antireflection film. The effect is particularly remarkable in a coating composition having a low solid content concentration such as a low refractive index layer.
Two or more kinds of solvents having such specific characteristics can be detected by a gas chromatograph or the like as a residual solvent even in an antireflection film.

  Therefore, the antireflection film of the present invention has excellent antireflection properties and scratch resistance, and is excellent in surface shape, less unevenness, and excellent in applicability. Furthermore, it can provide stably.

  As one embodiment of the present invention, a basic configuration of an antireflection film, which is a preferred embodiment of the optical functional film of the present invention, will be described with reference to the drawings. In the present specification, the description “(numerical value 1) to (numerical value 2)” means “(numerical value 1) or more and (numerical value 2) or less”.

  The cross-sectional view schematically shown in FIG. 1 is an example of the antireflection film of the present invention. The antireflection film 1 comprises a transparent support 2, two types of functional layers (antiglare hard coat layer 3, low refractive index). The rate layer 4). As the antiglare hard coat layer 3, the mat particles 5 are dispersed in a translucent resin, and the refractive index of the material other than the mat particles 5 of the anti glare hard coat layer 3 is 1.50-2. The refractive index of the low refractive index layer 4 is preferably in the range of 1.35 to 1.49. The average particle size of at least one kind of matte particles is preferably 0.5 to 8 μm, and the difference in refractive index between the translucent particles and the translucent resin is 0.02 to 0.2. In addition, it is preferable that the translucent particles are contained in an amount of 3 to 30% by mass based on the total solid content of the light scattering layer.

  The optical functional layer in the present invention may be a hard coat layer having an antiglare property as described above, a hard coat layer having no antiglare property, a light diffusion layer, or a single layer, You may be comprised by multiple layers, for example, 2 layers-4 layers. When there is a hard coat layer having antiglare properties, the hard coat layer may not be provided as another layer. The low refractive index layer which is an optical functional layer is coated on the outermost layer.

Further, the low refractive index layer preferably satisfies the following formula (VII) from the viewpoint of reducing the reflectance.
Formula (VII) (mλ / 4) × 0.7 <n ₁ d ₁ <(mλ / 4) × 1.3
(Where m is a positive odd number, n ₁ is the refractive index of the low refractive index layer, and d ₁ is the thickness (nm) of the low refractive index layer, and λ is the wavelength. , Values in the range of 500 to 550 nm.)
In addition, satisfy | filling said numerical formula (VII) means that m (positive odd number, usually 1) which satisfy | fills numerical formula (VII) exists in the said wavelength range.

  Next, the solvent used in the coating composition for forming the optical functional layer in the antireflection film of the present invention will be described below.

  Two or more kinds of solvents used in the coating composition are designated as solvents A, B, C,. The solvent A can be arbitrarily selected. For example, a solvent having a boiling point of 100 ° C. or less (in parentheses, boiling point (° C.), surface tension (dyn / cm), viscosity (mPa · s) in this order, “° C.”, “dyn / cm”, “mPa · s” As omitted, hexane (68.7, 18.4, 0.313), heptane (98.4, 20.3, 0.418), cyclohexane (80.7, 25.3, 0.980) , Hydrocarbons such as benzene (80.1, 28.9, 0.649), dichloromethane (40.4, 28.1, 0.425), chloroform (61.2, 27.1, 0.563) , Carbon tetrachloride (76.7, 26.8, 0.965), 1,2-dichloroethane (83.5, 32.2, 0.840), trichlorethylene (87.2, 29, 0.58), etc. Of halogenated hydrocarbons, diethyl ether (34. , 17.06, 0.233), ethers such as diisopropyl ether (68.5, 17.34, 0.329), tetrahydrofuran (66, 16.5, 0.52), ethyl formate (54.2, 24.37, 0.419), methyl acetate (57.8, 24.76, 0.362), ethyl acetate (77.1, 23.9, 0.45), isopropyl acetate (89, 24.5, 0.569), ketones such as acetone (56.1, 23.7, 0.337), 2-tanone (= methyl ethyl ketone, 79.6, 24.6, 0.423), methanol ( 64.5, 22.55, 0.59), ethanol (78.3, 22.1, 1.22), 2-propanol (82.4, 20.8, 2.41), 1-propanol (97 .2, 23.8,2. 6) alcohols, such as, cyano compounds such as acetonitrile (81.6,29.1,0.375), and the like carbon disulfide (46.2,32.25,0.363).

Examples of the solvent having a boiling point exceeding 100 ° C. include octane (125.6, 21.76, 0.542), toluene (110.6, 28.53, 0.587), xylene (138, 28.31, 0.644), tetrachloroethylene (121.2, 32.32, 0.88), chlorobenzene (131.5, 33.28, 0.803), dioxane (101.3, 34.45, 1.439), Dibutyl ether (142.0, 23.40, 0.741), isobutyl acetate (118.3, 23.7, 0.697), cyclohexanone (155.7, 35.1, 2.45), 2-methyl -4-pentanone (same as MIBK, 115.9, 25.4, 0.590), 1-pentanol (117.7, 25.60, 3.31), N, N-methylformamide 149.6,36.76,0.924), dimethyl sulfoxide (189,43,2.14) and the like.
As the kind of the solvent A, ketones, aromatic hydrocarbons, esters and alcohols are preferable, and ketones are particularly preferable. Of the ketones, methyl ethyl ketone is particularly preferred.

  The solvent B needs to be determined by the difference in surface tension with the solvent A and the viscosity of the solvent. Moreover, the thing whose boiling point difference with the solvent A is 30 degrees C or less is especially preferable. When the boiling point difference is 30 ° C. or less, it is difficult to perform a two-stage drying process, ie, low-boiling solvent evaporation and high-boiling solvent drying, so that a uniform surface shape can be obtained without causing Benard cell or phase separation. It is possible and preferable.

Although the specific example of the solvent B used preferably is shown, the solvent of this invention is not limited to these.
For example, when methyl ethyl ketone (79.6, 24.6, 0.423) is selected as the solvent A, the solvent B has a surface tension of 18.6 to 30.6 dyn / cm and a viscosity of 1 mPa · s or more. It is necessary to select. Solvents B meeting these conditions are ethanol, 1-propanol, 2-propanol, 2-methyl 2-butanol (101.8, 22.8, 3.7), 1-butanol (117.7, 23.8, 2.95), 2-butanol (99.5, 22.8, 6.68), 1-pentanol (137.8, 25.6, 3.31), diacetone alcohol (167.9, 29.29). 8, 3.2). More preferably, they are ethanol, 1-propanol, 2-propanol, 2-methyl 2-butanol and 2-butanol having a boiling point difference with respect to the solvent A of 30 ° C. or less.
Further, when cyclohexanone (155.7, 35.1, 2.45) is selected as the solvent A, it is necessary to select a solvent having a surface tension of 29.1 to 41.1 as the solvent B. Examples of the solvent B that meets these conditions include cyclohexanol (161.1, 34.2, 49.8), diacetone alcohol, propylene glycol (188.2, 36.5, 56) and the like.

The method for determining the solvent in the case of containing three or more solvents will be described below with an example of selecting three solvents.
When methyl ethyl ketone (79.6, 24.6, 0.423) is selected as the solvent A, the solvent B and the solvent C have a surface tension of 18.6 to 30.6 dyn / cm and a viscosity of 1 mPa · s or more. It is necessary to select a solvent. Solvents B meeting these conditions are ethanol, 1-propanol, 2-propanol, 2-methyl 2-butanol (101.8, 22.8, 3.7), 1-butanol (117.7, 23.8, 2.95), 2-butanol (99.5, 22.8, 6.68), 1-pentanol (137.8, 25.6, 3.31), diacetone alcohol (167.9, 29.29). 8, 3.2). More preferably, they are ethanol, 1-propanol, 2-propanol, 2-methyl 2-butanol and 2-butanol having a boiling point difference with respect to the solvent A of 30 ° C. or less.
When ethanol (78.3, 22.1, 1.22) is selected as the solvent B, it is necessary to select a solvent having a surface tension of 16.1 to 28.1 dyn / cm as the solvent A and the solvent C. . Solvent A and Solvent C meeting these conditions are hexane, heptane, cyclohexane, dichloromethane, chloroform, carbon tetrachloride, diethyl ether, diisopropyl ether, tetrahydrofuran, ethyl formate, methyl acetate, ethyl acetate, isopropyl acetate, acetone, 2-tanone. (= Methyl ethyl ketone), methanol, 2-propanol, 1-propanol, and the like. More preferably, hexane, heptane, cyclohexane, dichloromethane, chloroform, carbon tetrachloride, diisopropyl ether, tetrahydrofuran, ethyl formate, methyl acetate, ethyl acetate, isopropyl acetate, acetone, having a boiling point difference with solvent A of 30 ° C. or less. 2-tanone (= methyl ethyl ketone), methanol, 2-propanol, 1-propanol.

  Further, the boiling point of the solvent used in the coating composition of the present invention is desirably 115 ° C. or lower. If the boiling point is too high, problems such as difficulty in drying can easily occur. As the solvent combination, methyl ethyl ketone and ethanol, methyl ethyl ketone and 1-propanol, methyl ethyl ketone and 2-propanol, methyl ethyl ketone and 2-methyl 2-butanol, and methyl ethyl ketone and 2-butanol are particularly preferable.

The viscosity of the coating composition used in the present invention is preferably from 1 to 6.5 mPa · s, particularly preferably from 1 to 3.5 mPa · s, from the viewpoint of the solid content concentration and coatability.
The solvent ratio of the coating composition used in the present invention may be any, and is preferably set so as to be in the range of the viscosity. It is preferable that the content of the ketone solvent is 10% by mass or more of the total solvent contained in the coating composition. More preferably, it is 20 mass% or more, More preferably, it is 30 mass% or more.

  The solid content concentration in the coating composition used in the present invention is preferably 1 to 20% by mass, more preferably 1 to 15% by mass, and further preferably 1 to 10% by mass or less. It is particularly preferably 1 to 7% by mass or less. When the solid content concentration is within the above range, the wet film thickness at the time of coating can be ensured in a good range, good coating properties can be obtained, and drying unevenness hardly occurs, which is preferable.

  Next, the optical functional film of the present invention, particularly the optical functional layer in the antireflection film will be described. Examples of the optical functional layer in the present invention include a low refractive index layer and an antiglare hard coat layer.

<Low refractive index layer>
The low refractive index layer used in the present invention preferably contains a fluorine-containing compound. In particular, it is preferable to construct a low refractive index layer mainly composed of a fluorine-containing compound. The low refractive index layer mainly composed of a fluorine-containing compound is usually positioned as the outermost layer of the antireflection film and also has a function as an antifouling layer. Here, “mainly containing a fluorine-containing compound” means that the mass ratio of the fluorine-containing compound is the largest among the components contained in the low refractive index layer, and the content of the fluorine-containing compound is It is preferable that it is 50 mass% or more with respect to the total mass of a low refractive index layer, and it is more preferable that 60 mass% or more is contained.

  The fluorine-containing compound of the low refractive index layer is preferably formed by a crosslinking or polymerization reaction of a fluorine-containing compound having a crosslinking or polymerizable functional group, and the crosslinking or polymerizable functional group is an ionizing radiation curable functional group. It is preferable that Hereinafter, the fluorine-containing compound contained in the low refractive index layer will be described.

(Fluorine-containing compounds)
The refractive index of the fluorine-containing compound contained in the low refractive index layer is preferably 1.35 to 1.50. More preferably, it is 1.36-1.47, More preferably, it is 1.38-1.45.
Examples of the fluorine-containing compound include a fluorine-containing polymer, a fluorine-containing silane compound, a fluorine-containing surfactant, and a fluorine-containing ether.

  Examples of the fluorine-containing polymer include those synthesized by crosslinking or polymerization reaction of ethylenically unsaturated monomers containing fluorine atoms. Examples of ethylenically unsaturated monomers containing fluorine atoms include fluoroolefins (eg, fluoroethylene, vinylidene fluoride, tetrafluoroethylene, hexafluoropropylene, perfluoro-2,2-dimethyl-1,3-dioxole), Fluorinated vinyl ethers and esters of fluorine-substituted alcohols with acrylic acid or methacrylic acid are included.

As the fluorine-containing polymer, a copolymer comprising a repeating structural unit containing a fluorine atom and a repeating structural unit not containing a fluorine atom can also be used.
The copolymer can be obtained by a polymerization reaction of an ethylenically unsaturated monomer containing a fluorine atom and an ethylenically unsaturated monomer not containing a fluorine atom.
Examples of ethylenically unsaturated monomers not containing fluorine atoms include olefins (eg, ethylene, propylene, isoprene, vinyl chloride, vinylidene chloride, etc.), acrylate esters (eg, methyl acrylate, ethyl acrylate, acrylic acid-2- Ethyl hexyl, etc.), methacrylic acid esters (eg, methyl methacrylate, ethyl methacrylate, butyl methacrylate, ethylene glycol dimethacrylate, etc.), styrene and its derivatives (eg, styrene, divinylbenzene, vinyl toluene, α-methylstyrene, etc.) , Vinyl ether (eg, methyl vinyl ether), vinyl ester (eg, vinyl acetate, vinyl propionate, vinyl cinnamate, etc.), acrylamide (eg, N-tert-butylacrylamide, N-cyclohexylacrylamide, etc.), Ruamido and acrylonitrile, and the like.

  Examples of the fluorine-containing silane compound include silane compounds containing a perfluoroalkyl group.

  Fluorine-containing surfactants are those in which part or all of the hydrocarbon hydrogen atoms constituting the hydrophobic part are replaced by fluorine atoms, and the hydrophilic part is anionic, cationic, nonionic and amphoteric. Any of these may be used.

  The fluorine-containing ether is a compound generally used as a lubricant. Examples of the fluorinated ether include perfluoropolyether.

  As the fluorine-containing compound that can be contained in the low refractive index layer, a fluorine-containing polymer into which a crosslinked or polymerized structure is introduced is particularly preferable. The fluorine-containing polymer into which a crosslinked or polymerized structure is introduced can be obtained by crosslinking or polymerizing a fluorine-containing compound having a crosslinked or polymerizable functional group.

  The fluorine-containing compound having a crosslinkable or polymerizable functional group can be obtained by introducing a crosslinkable or polymerizable functional group as a side chain into a fluorine-containing compound having no crosslinkable or polymerizable functional group. The crosslinkable or polymerizable functional group is a functional group that reacts with light (preferably ultraviolet irradiation), electron beam (EB) irradiation or heating to cause the fluorinated polymer to have a crosslinked or polymerized structure. preferable. Examples of the crosslinkable or polymerizable functional group include groups such as (meth) acryloyl, isocyanate, epoxy, aziridine, oxazoline, aldehyde, carbonyl, hydrazine, carboxyl, methylol, and active methylene. A commercially available product may be used as the fluorine-containing compound having a crosslinkable or polymerizable functional group.

  The fluorine-containing compound contained in the low refractive index layer preferably contains, as a main component, a copolymer comprising a repeating unit derived from a fluorine-containing vinyl monomer and a repeating unit having a (meth) acryloyl group in the side chain. . The component derived from the copolymer is preferably 50% by mass or more, more preferably 70% by mass or more, and particularly preferably 90% by mass or more, based on the total mass of the outermost layer. Below, the said copolymer preferable to be used for a low refractive index layer is demonstrated.

Fluorine-containing vinyl monomers include fluoroolefins (eg, fluoroethylene, vinylidene fluoride, tetrafluoroethylene, hexafluoroethylene, hexafluoropropylene, etc.), (meth) acrylic acid moieties or fully fluorinated alkyl ester derivatives (eg, biscoat) 6FM (trade name, manufactured by Osaka Organic Chemical Industry Co., Ltd.), M-2020 (trade name, manufactured by Daikin Industries, Ltd.) and the like, and fully or partially fluorinated vinyl ethers, etc. are preferable. From the viewpoints of refractive index, solubility, transparency, availability, etc., hexafluoropropylene is particularly preferred.
The fluorine-containing vinyl monomer is preferably introduced so that the fluorine content of the copolymer is 20 to 60% by mass, more preferably 25 to 55% by mass, and particularly preferably 30 to 50% by mass.

  The copolymer has a repeating unit having a (meth) acryloyl group. The method for introducing the (meth) acryloyl group is not particularly limited. For example, (i) after synthesizing a polymer having a nucleophilic group such as a hydroxyl group or an amino group, (meth) acrylic acid chloride, (meth) (Ii) a method in which acrylic acid anhydride, a mixed acid anhydride of (meth) acrylic acid and methanesulfonic acid, etc. are allowed to act, (ii) (meth) acrylic acid is added to the polymer having the nucleophilic group in the presence of a catalyst such as sulfuric acid. (Iii) a method of allowing a compound having both an isocyanate group such as methacryloyloxypropyl isocyanate and a (meth) acryloyl group to act on the polymer having the nucleophilic group, and (iv) after synthesizing a polymer having an epoxy group ( (V) a method of allowing meth) acrylic acid to act; (v) an epoxy group such as glycidyl methacrylate and (meth) acryloyl on a polymer having a carboxyl group Examples thereof include a method of allowing a compound having a group to act, and (vi) a method of dehydrochlorination after polymerizing a vinyl monomer having a 3-chloropropionic acid ester moiety. Among these, in the present invention, it is particularly preferable to introduce a (meth) acryloyl group by the method (i) or (ii) to a polymer containing a hydroxyl group.

  The repeating unit having a (meth) acryloyl group in the side chain preferably occupies 5 to 90% by mass, more preferably 30 to 70% by mass, and 40 to 60% by mass in the copolymer. It is particularly preferred.

  In addition to the repeating unit derived from the fluorine-containing vinyl monomer and the repeating unit having a (meth) acryloyl group in the side chain, the copolymer includes adhesion to a lower layer such as a transparent support, polymer Tg (for coating hardness). Other vinyl monomers can be suitably copolymerized from various viewpoints such as solubility in solvents, transparency, slipperiness, dust resistance and antifouling properties. A plurality of these vinyl monomers may be combined depending on the purpose, and are preferably introduced in the range of 0 to 65 mol% in the copolymer, more preferably 0 to 40 mol%, particularly preferably 0. ˜30 mol%.

  The vinyl monomer unit that can be used in combination is not particularly limited. For example, olefins (ethylene, propylene, isoprene, vinyl chloride, vinylidene chloride, etc.), acrylic esters (methyl acrylate, ethyl acrylate, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate), methacrylic acid esters (methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-hydroxyethyl methacrylate, etc.), styrene derivatives (styrene, p-hydroxymethyl styrene, p-methoxy styrene, etc.) ), Vinyl ethers (methyl vinyl ether, ethyl vinyl ether, cyclohexyl vinyl ether, hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, etc.), vinyl esters (vinyl acetate, vinyl propionate) , Vinyl cinnamate, etc.), unsaturated carboxylic acids (acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid, etc.), acrylamides (N, N-dimethylacrylamide, N-tert-butylacrylamide, N-cyclohexylacrylamide) Etc.), methacrylamides (N, N-dimethylmethacrylamide), acrylonitrile derivatives and the like.

  As a preferred form of a copolymer composed of a repeating unit derived from the fluorine-containing vinyl monomer used in the present invention and a repeating unit having a (meth) acryloyl group in the side chain, one represented by the following general formula (1) is exemplified. It is done.

In the general formula (1), L represents a linking group having 1 to 10 carbon atoms, more preferably a linking group having 1 to 6 carbon atoms, and particularly preferably a linking group having 2 to 4 carbon atoms. May have a branched or ring structure and may have a heteroatom selected from O, N and S.
Preferred _{examples, * - (CH 2) 2} -O - **, * - (CH 2) 2 -NH - **, * - (CH 2) 4 -O - **, * - (CH 2) ₆ −O − **, * − (CH ₂ ) ₂ −O− (CH ₂ ) ₂ −O − **, −CONH− (CH ₂ ) ₃ −O − **, * −CH ₂ CH (OH) CH ₂ —O — **, * —CH ₂ CH ₂ OCONH (CH ₂ ) ₃ —O — ** (* represents a connecting site on the polymer main chain side, and ** represents a connecting site on the (meth) acryloyl group side) And the like. m represents 0 or 1;

In general formula (1), X represents a hydrogen atom or a methyl group. From the viewpoint of curing reactivity, a hydrogen atom is preferred.
In the general formula (1), A represents a repeating unit derived from an arbitrary vinyl monomer, and is not particularly limited as long as it is a constituent component of a monomer copolymerizable with hexafluoropropylene. It can be appropriately selected from various viewpoints such as adhesion, Tg of polymer (contributing to film hardness), solubility in solvent, transparency, slipperiness, dustproof / antifouling property, and can be selected according to the purpose. You may be comprised by the some vinyl monomer.

  Preferred examples include methyl vinyl ether, ethyl vinyl ether, t-butyl vinyl ether, cyclohexyl vinyl ether, isopropyl vinyl ether, hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, glycidyl vinyl ether, vinyl ethers such as allyl vinyl ether, vinyl acetate, vinyl propionate, butyric acid. (Meth) such as vinyl esters such as vinyl, methyl (meth) acrylate, ethyl (meth) acrylate, hydroxyethyl (meth) acrylate, glycidyl methacrylate, allyl (meth) acrylate, (meth) acryloyloxypropyltrimethoxysilane Acrylates, styrene, styrene derivatives such as p-hydroxymethylstyrene, crotonic acid, maleic acid, itaconic acid Can be mentioned unsaturated carboxylic acids and derivatives thereof, more preferably ether derivatives, vinyl ester derivatives, particularly preferably a vinyl ether derivative.

  x, y, and z represent mol% of each constituent component, and represent values satisfying 30 ≦ x ≦ 60, 5 ≦ y ≦ 70, and 0 ≦ z ≦ 65. Preferably, 35 ≦ x ≦ 55, 30 ≦ y ≦ 60, and 0 ≦ z ≦ 20, and particularly preferably 40 ≦ x ≦ 55, 40 ≦ y ≦ 55, and 0 ≦ z ≦ 10.

  Furthermore, what is represented by following General formula (2) is mentioned as an especially preferable form of the said copolymer.

In general formula (2), X, x, and y are each synonymous with general formula (1), and their preferable ranges are also the same.
n represents an integer of 2 ≦ n ≦ 10, preferably 2 ≦ n ≦ 6, and particularly preferably 2 ≦ n ≦ 4.
B represents a repeating unit derived from an arbitrary vinyl monomer, and may be composed of a single composition or a plurality of compositions. As an example, what was demonstrated as an example of A in the said General formula (1) is mentioned.
z1 and z2 represent mol% of each repeating unit, and represent values satisfying 0 ≦ z1 ≦ 65 and 0 ≦ z2 ≦ 65. It is preferable that 0 ≦ z1 ≦ 30 and 0 ≦ z2 ≦ 10 respectively, and it is particularly preferable that 0 ≦ z1 ≦ 10 and 0 ≦ z2 ≦ 5.
As the copolymer represented by the general formula (2), those satisfying 40 ≦ x ≦ 60, 30 ≦ y ≦ 60, and z2 = 0 are particularly preferable.

  Preferable specific examples of the copolymer represented by the general formula (1) or the general formula (2) include those described in paragraphs [0043] to [0047] of JP-A-2004-45462. Further, the method for synthesizing the copolymer represented by the general formula (1) or the general formula (2) is also described in detail in the publication.

  In the present invention, the composition used for producing the low refractive index layer is preferably in the form of a paint, and a fluorine-containing compound is an essential constituent, and various additives and radical polymerization initiators are added as necessary. It is prepared by dissolving in an appropriate solvent. In this case, the solid content is appropriately selected depending on the use, but is preferably 0.01% by mass to 60% by mass, more preferably 0.5 to 50% by mass, and particularly preferably about 1% to 20% by mass. It is.

The low refractive index layer is made up of fillers (for example, inorganic fine particles and organic fine particles), slip agents (polysiloxane compounds such as dimethyl silicone), organosilane compounds and derivatives thereof, binders, surfactants, etc. Additives can be included. In particular, it is preferable to add a filler (for example, inorganic fine particles and organic fine particles) and a slipping agent (polysiloxane compound such as dimethyl silicone).
Hereinafter, preferred fillers, slip agents and the like used for the low refractive index layer will be described.

(Preferable filler for low refractive index layer)
It is preferable to add a filler (for example, inorganic fine particles or organic fine particles) in terms of improving the physical strength (such as scratch resistance) of the low refractive index layer. As the filler added to the low refractive index layer, inorganic fine particles are preferable. Among them, silicon dioxide (silica) having a low refractive index, hollow silica, silica having pores, fluorine-containing particles (magnesium fluoride, calcium fluoride, fluorine). Barium fluoride) and the like are preferable. Particularly preferred are silicon dioxide (silica) and hollow silica.

  The mass average particle diameter of the primary particles of the filler is preferably 1 nm to 150 nm, more preferably 1 nm to 100 nm, and most preferably 1 nm to 80 nm. It is preferable that the filler is more finely dispersed in the low refractive index layer. The shape of the filler is preferably a rice grain shape, a spherical shape, a cubic shape, a spindle shape, a short fiber shape, a ring shape, or an indefinite shape, and has a structure having hollow, fine pores or fine voids as a particle structure. Is more preferable. Particularly preferable shapes are a spherical shape and an indefinite shape. The filler may be crystalline or amorphous.

  The filler is used in plasma dispersion or corona discharge treatment in order to stabilize dispersion in the dispersion or paint, or to increase the affinity and binding properties with the components of the low refractive index layer. Physical surface treatment, chemical surface treatment with a surfactant, a coupling agent, or the like may be performed. A surface treatment with a coupling agent is particularly preferred. As the coupling agent, an alkoxy compound (eg, titanate coupling agent, silane coupling agent) is preferably used. In particular, silane coupling agent treatment is effective.

As for the surface treatment of the filler, it is preferable to carry out the surface treatment in advance before preparing the paint for the low refractive index layer, but in the case of surface treatment with a coupling agent, a coupling agent is added to the paint at the time of preparation of the paint. It is also preferable to carry out the addition.
The filler is preferably dispersed in advance in a medium (such as a solvent).

  The addition amount of the filler is 5% by mass to 70% by mass with respect to the total mass of the low refractive index layer from the viewpoint of improving the physical strength (such as scratch resistance) and preventing the low refractive index layer from becoming clouded. More preferably, it is 10 mass%-50 mass%, Most preferably, it is 20 mass%-40 mass%.

  The average particle diameter of the filler is preferably 20% to 100%, more preferably 30% to 80%, and particularly preferably 30% to 50% with respect to the film thickness of the low refractive index layer.

  When the filler added to the low refractive index layer is silicon dioxide fine particles, it is particularly preferable to use hollow silicon dioxide fine particles. The hollow silicon dioxide fine particles preferably have a refractive index of 1.17 to 1.45, more preferably 1.17 to 1.40, and still more preferably 1.17 to 1.37. Here, the refractive index of the hollow silicon dioxide fine particles represents the refractive index of the entire particles, and does not represent the refractive index of only the outer shell silicon dioxide forming the hollow silicon dioxide fine particles. The refractive index of the low refractive index layer can be lowered by using hollow silicon dioxide fine particles.

When the radius of the cavity in the particle is a and the radius of the particle outer shell is b, the porosity x is expressed by the following formula (1).
Equation ^{(1) x = (4πa 3} /3) / (4πb 3/3) × 100

  The porosity x is preferably 10 to 60%, more preferably 20 to 60%, and most preferably 30 to 60%.

  It is also preferable to use two or more fillers in combination. Further, particles having different average particle diameters can be used in combination.

(Preferable slip agent for low refractive index layer)
The slip agent is preferably added from the viewpoint of improving the physical strength (such as scratch resistance) and antifouling property of the low refractive index layer.
Examples of the slip agent include fluorine-containing ether compounds (perfluoropolyether and derivatives thereof), polysiloxane compounds (dimethylpolysiloxane and derivatives thereof), and the like. Polysiloxane compounds are preferred.

Preferable examples of the polysiloxane compound include those having a substituent at at least one of a terminal and a side chain of a compound containing a plurality of dimethylsilyloxy units as repeating units.
The compound containing a dimethylsilyloxy unit as a repeating unit may contain a structural unit (substituent) other than the dimethylsilyloxy unit. The substituents may be the same or different, and a plurality of substituents are preferable.

  Examples of preferred substituents include groups containing (meth) acryloyl group, vinyl group, aryl group, cinnamoyl group, epoxy group, oxetanyl group, hydroxyl group, fluoroalkyl group, polyoxyalkylene group, carboxyl group, amino group and the like. It is done.

  The molecular weight of the slip agent is not particularly limited, but is preferably 100,000 or less, particularly preferably 50,000 or less, and most preferably 3,000 to 30,000. Although there is no restriction | limiting in particular in Si atom content of a siloxane compound, it is preferable that it is 5 mass% or more, it is especially preferable that it is 10-60 mass%, and it is most preferable that it is 15-50 mass%.

  Particularly preferred slipping agents are polysiloxane compounds having a crosslinkable or polymerizable functional group represented by the following general formula (A) and derivatives thereof (for example, a polysiloxane compound represented by the general formula (A) Or a reaction product of a polysiloxane compound represented by the general formula (A) and a compound having a crosslinkable or polymerizable functional group other than the polysiloxane compound).

In general formula (A), R ^{1 to} R ⁴ each independently represent a substituent having 1 to 20 carbon atoms, and when there are a plurality of each group, they may be the same or different from each other, R ¹ , R ³ and R ⁴ represent a cross-linkable or polymerizable functional group.
p represents an integer satisfying 1 ≦ p ≦ 4. q represents an integer satisfying 10 ≦ q ≦ 500, r represents an integer satisfying 0 ≦ r ≦ 500, and the polysiloxane portion surrounded by {} is a block copolymer even if it is a random copolymer. There may be.

  The low refractive index layer of the present invention may contain a cured product containing at least one of a polysiloxane compound having a crosslinking or polymerizable functional group represented by the general formula (A) and a derivative thereof and a fluorine-containing compound. preferable.

  The content of at least one of the polysiloxane compound and the derivative thereof is preferably 0.1 to 30% by mass, more preferably 0.5 to 15% by mass, and particularly preferably 1 to 1% by mass with respect to the fluorine-containing compound. 10% by mass.

  Preferred cross-linkable or polymerizable functional groups of the polysiloxane compound and derivatives thereof are functional groups capable of forming a bond by cross-linking or polymerizing with other constituent components (fluorine-containing compound, binder, etc.) of the outermost layer. For example, a group having an active hydrogen atom (for example, a hydroxyl group, a carboxyl group, an amino group, a carbamoyl group, a mercapto group, a β-ketoester group, a hydrosilyl group, a silanol group, etc.), a group capable of cationic polymerization (epoxy group, An oxetanyl group, an oxazolyl group, a vinyl group, a vinyloxy group, etc.), a group having an unsaturated double bond that can be crosslinked or polymerized by a radical species (a (meth) acryloyl group, an allyl group, etc.), a hydrolyzable silyl group (for example, Alkoxysilyl group, acyloxysilyl group, etc.), acid anhydride, isocyanate group, nucleophile Group capable of being (active halogen atom, a sulfonic acid ester, etc.) and the like.

  These crosslinkable or polymerizable functional groups are appropriately selected according to the constituent components of the low refractive index layer. Preferably, it is an ionizing radiation curable functional group.

  The crosslinkable or polymerizable functional group of the general formula (A) preferably crosslinks or undergoes a polymerization reaction with the crosslinkable or polymerizable functional group of the fluorine-containing compound, and the particularly preferred functional group is cationic ring-opening polymerization reactivity. Groups (especially epoxy groups, oxetanyl groups, etc.) and radical polymerization reactive groups (particularly (meth) acryloyl groups).

The substituent represented by R ^{2 in the} general formula (A) is a substituted or unsubstituted organic group having 1 to 20 carbon atoms, preferably an alkyl group having 1 to 10 carbon atoms (for example, a methyl group, an ethyl group, a hexyl group). Etc.), a fluorinated alkyl group (trifluoromethyl group, pentafluoroethyl group, etc.) or an aryl group having 6 to 20 carbon atoms (for example, a phenyl group, a naphthyl group, etc.), more preferably an alkyl having 1 to 5 carbon atoms. Group, a fluorinated alkyl group or a phenyl group, particularly preferably a methyl group. These may be further substituted with these groups.
In the case where R ¹ , R ³ and R ^{4 in the} general formula (A) are not cross-linked or polymerizable functional groups, they can be the above organic groups.

  p represents an integer satisfying 1 ≦ p ≦ 4. q represents an integer satisfying 10 ≦ q ≦ 500, preferably 50 ≦ q ≦ 400, and particularly preferably 100 ≦ q ≦ 300. r represents an integer satisfying 0 ≦ r ≦ 500, preferably 0 ≦ r ≦ q, and particularly preferably 0 ≦ r ≦ 0.5q.

The polysiloxane structure of the compound represented by the general formula (A) is a homopolymer in which the repeating unit (—OSi (R ² ) ₂ —) is composed of only a single substituent (R ² ). Alternatively, it may be a random copolymer constituted by a combination of repeating units having different substituents, or may be a block copolymer.

The compound represented by the general formula (A) preferably has a mass average molecular weight of 10 ³ to 10 ⁶ , more preferably 5 × 10 ^{3 to} 5 × 10 ⁵ , and particularly preferably 10 ⁴ to 10 ^5. It is.

  The polysiloxane compound represented by the general formula (A) is commercially available, for example, KF-100T, X-22-169AS, KF-102, X-22-3701IE, X-22-164B, X-22 -164C, X-22-5002, X-22-173B, X-22-174D, X-22-167B, X-22-161AS, X-22-174DX, X-22-2426, X-22-170DX , X-22-176D, X-22-1821 (manufactured by Shin-Etsu Chemical Co., Ltd.), AK-5, AK-30, AK-32 (manufactured by Toa Gosei Chemical Co., Ltd.), Silaplane FM-0275, FM -0721, FM-0725, FM-7725, DMS-U22, RMS-033, RMS-083, UMS-182 (manufactured by Chisso Corporation) and the like can also be used. Moreover, it can also produce by introduce | transducing a crosslinking or polymerizable functional group into the hydroxyl group, amino group, mercapto group, etc. which a commercially available polysiloxane compound contains.

  Specific examples of preferable polysiloxane compounds represented by the general formula (A) include those described in JP-A 2003-329804 [0041] to [0045]. It is not limited.

  The addition amount of at least one of the polysiloxane compound represented by the general formula (A) and the derivative thereof is preferably 0.05 to 30% by mass, more preferably 0%, based on the total solid content of the outermost layer. 0.1 to 20% by mass, more preferably 0.5 to 15% by mass, and particularly preferably 1 to 10% by mass.

(Production method of low refractive index layer)
The low refractive index layer is prepared by applying a paint in which at least one of the above-mentioned fluorine-containing compound and, if necessary, the above-mentioned filler, the above-mentioned polysiloxane compound and its derivative is dissolved or dispersed in a solvent. Is preferred.

In the case of a fluorine-containing compound having a crosslinkable or polymerizable functional group, it is preferable to produce a low refractive index layer by crosslinking or polymerizing the fluorine-containing compound simultaneously with or after the application of the low refractive index layer.
If the fluorine-containing compound has a functional group that crosslinks or polymerizes with a radical, it is preferable to perform a crosslinking or polymerization reaction using a radical polymerization initiator, particularly a photoradical polymerization initiator. Moreover, if it has a functional group which crosslinks or polymerizes with a cation, it is preferable to carry out a crosslinking or polymerization reaction using a cationic polymerization initiator, particularly a photocationic polymerization initiator.

  As the radical polymerization initiator, those that generate radicals by the action of heat or those that generate radicals by the action of light are preferable. Particularly preferred are radical photopolymerization initiators.

As the compound that initiates radical polymerization by the action of heat, organic or inorganic peroxides, organic azo, diazo compounds, and the like can be used.
Specifically, benzoyl peroxide, halogen benzoyl peroxide, lauroyl peroxide, acetyl peroxide, dibutyl peroxide, cumene hydroperoxide, butyl hydroperoxide as organic peroxides, hydrogen peroxide, peroxides as inorganic peroxides. Ammonium sulfate, potassium persulfate, etc., 2-azo-bis-isobutyronitrile, 2-azo-bis-propionitrile, 2-azo-bis-cyclohexanedinitrile, etc. as diazo compounds, diazoaminobenzene, p -Nitrobenzenediazonium etc. can be mentioned.

In the case of using a compound that initiates radical polymerization by the action of light, for example, it can be cured by irradiation with light according to the compound to be used such as ultraviolet rays to produce a low refractive index layer.
Examples of photo radical polymerization initiators include acetophenones, benzoins, benzophenones, phosphine oxides, ketals, anthraquinones, thioxanthones, azo compounds, peroxides, 2,3-dialkyldione compounds, disulfides There are compounds, fluoroamine compounds and aromatic sulfoniums. Examples of acetophenones include 2,2-diethoxyacetophenone, p-dimethylacetophenone, 1-hydroxydimethylphenyl ketone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-4-methylthio-2-morpholinopropiophenone and 2 -Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone is included. Examples of benzoins include benzoin benzene sulfonate, benzoin toluene sulfonate, benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether. Examples of the benzophenones include benzophenone, 2,4-dichlorobenzophenone, 4,4-dichlorobenzophenone and p-chlorobenzophenone. Examples of phosphine oxides include 2,4,6-trimethylbenzoyldiphenylphosphine oxide.
In particular, photocleavable photoradical polymerization initiators are preferred. The photocleavable photoradical polymerization initiator is described in “Latest UV Curing Technology” by Kazuhiro Takashiro (Technical Information Association, Inc., page 159, 1991).
Preferable examples of commercially available photocleavable photoradical polymerization initiators include Irgacure (651, 184, 907) manufactured by Ciba Specialty Chemicals.

  It is preferable to use a photoinitiator in the range of 0.1-15 mass parts with respect to 100 mass parts of fluorine-containing compounds, More preferably, it is the range of 1-10 mass parts. Furthermore, a photosensitizer can be preferably used in combination with these photopolymerization initiators, and examples thereof include n-butylamine, triethylamine, tri-n-butylphosphine, Michler's ketone and thioxanthone. Commercially available photosensitizers can also be preferably used.

The binder is preferably added in terms of improving the physical strength (such as scratch resistance) of the low refractive index layer and the adhesion between the outermost layer and the adjacent layer.
If the fluorine-containing compound is a compound having a crosslinkable or polymerizable functional group, the binder is preferably a binder having a functional group that crosslinks or polymerizes with the fluorine containing compound.
In particular, if the fluorine-containing compound is a compound having a photocrosslinkable or photopolymerizable functional group, the binder is preferably a polyfunctional monomer having a photocrosslinkable or photopolymerizable functional group. Specific examples of the photopolymerizable polyfunctional monomer having a photopolymerizable functional group include those described for the antistatic layer. Two or more polyfunctional monomers may be used in combination.
The fluorine-containing compound used for the low refractive index layer of the present invention is preferably a fluorine-containing compound having a crosslinkable or polymerizable functional group. Examples of the compound that can be used in combination with the fluorine-containing compound include a polysiloxane compound represented by the general formula (A) and a derivative thereof, and a binder that crosslinks or polymerizes the fluorine-containing compound having the crosslinkable or polymerizable functional group. Etc. A plurality of compounds used in combination with the fluorine-containing compound may be used in combination.

The low-refractive index layer is formed by dissolving or dispersing a fluorine-containing compound and other constituents of the outermost layer at the same time as or after application, and then performing light irradiation, electron beam irradiation, heat treatment, etc. It is preferable to carry out a polymerization reaction.
In the case of ultraviolet irradiation, ultraviolet rays emitted from light such as an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a xenon arc, a metal halide lamp, and the like can be used.

The production of the low refractive index layer is preferably carried out in an atmosphere having an oxygen concentration of 4% by volume or less, particularly when the outermost layer is formed by the crosslinking or polymerization reaction of an ionizing radiation curable compound.
By producing the low refractive index layer in an atmosphere having an oxygen concentration of 4% by volume or less, the physical strength (scratch resistance, etc.), chemical resistance and weather resistance of the low refractive index layer, and the outermost and outermost layers Adhesion between adjacent layers can be improved.
Preferably, it is produced by a crosslinking reaction or a polymerization reaction of an ionizing radiation curable compound in an atmosphere having an oxygen concentration of 3% by volume or less, more preferably an oxygen concentration of 2% by volume or less, particularly preferably an oxygen concentration. Is 1% by volume or less, most preferably 0.5% by volume or less.
As a method for reducing the oxygen concentration to 4% by volume or less, it is preferable to replace the atmosphere (nitrogen concentration of about 79% by volume, oxygen concentration of about 21% by volume) with another gas, particularly preferably replacement with nitrogen (nitrogen purge). It is to be.

  The film thickness of the low refractive index layer is preferably 30 to 200 nm, more preferably 50 to 150 nm, and particularly preferably 60 to 120 nm. When the low refractive index layer is used as an antifouling layer, the film thickness is preferably 3 to 50 nm, more preferably 5 to 35 nm, and particularly preferably 7 to 25 nm.

  The low refractive index layer preferably has a surface dynamic friction coefficient of 0.25 or less in order to improve the physical strength of the antireflection film. The dynamic friction coefficient described here refers to a dynamic friction coefficient between a surface and a stainless steel hard sphere having a diameter of 5 mm when a load of 0.98 N is applied to a stainless steel hard sphere having a diameter of 5 mm and the surface is moved at a speed of 60 cm / min. Preferably it is 0.17 or less, Most preferably, it is 0.15 or less.

Further, in order to improve the antifouling performance of the antireflection film, it is preferable that the contact angle of the surface with respect to water is 90 ° or more. More preferably, it is 95 ° or more, and particularly preferably 100 ° or more.
Further, the contact angle of the surface of the low refractive index layer with water is preferably not changed before and after the saponification treatment, which will be described later. It is.

  The haze when a film having a thickness of 100 nm is formed as the low refractive index layer is preferably as low as possible. It is preferably 2% or less, more preferably 1.5% or less, and particularly preferably 1% or less.

  The strength of the low refractive index layer is preferably H or more, more preferably 2H or more, and most preferably 3H or more in a pencil hardness test according to JIS K5400. Further, in the Taber test according to JIS K5400, the smaller the wear amount of the test piece before and after the test, the better.

  In addition to the above components (fluorine-containing compounds, polymerization initiators, photosensitizers, fillers, slip agents, binders, etc.), the low refractive index layer contains surfactants, antistatic agents, coupling agents, and thickeners. Agents, anti-coloring agents, coloring agents (pigments, dyes), antifoaming agents, leveling agents, flame retardants, ultraviolet absorbers, infrared absorbers, adhesion promoters, polymerization inhibitors, antioxidants, surface modifiers, etc. Can also be added.

The refractive index of the low refractive index layer is preferably 1.20 to 1.50. More preferably, it is 1.25-1.50, More preferably 1.30-1.50, Most preferably 1.35-1.49.
The low refractive index layer is composed of an organosilane compound represented by the following general formula (a) and a derivative thereof (hydrolyzate and a crosslinked silicon compound formed by condensation of the hydrolyzate). It is also preferable to contain the compound chosen from these.

<Anti-glare hard coat layer>
Anti-glare hard coat layer is mainly composed of translucent polymer formed by curing monomers with ionizing radiation, translucent particles, and high refractive index or low refractive index, preventing cross-linking shrinkage. It is formed from a fine inorganic filler and a polymer compound for increasing the strength.
The thickness of the antiglare hard coat layer is usually about 0.5 μm to 30 μm, preferably 1 μm to 15 μm, and more preferably 1.2 μm to 10 μm. When the thickness is in the above range, there are no defects such as curling, haze value, and high cost, and the adjustment of antiglare property and light diffusion effect is easy.

(Main binder)
The main binder for forming the antiglare hard coat layer is preferably a translucent polymer having a saturated hydrocarbon chain or a polyether chain as the main chain after curing such as ionizing radiation, and the saturated hydrocarbon chain as the main chain. More preferably, it is a polymer. The cured main binder polymer preferably has a crosslinked structure.
As the binder polymer having a saturated hydrocarbon chain as a main chain after curing, a polymer of an ethylenically unsaturated monomer (binder precursor) is preferable. As the binder polymer having a saturated hydrocarbon chain as the main chain and having a crosslinked structure, a (co) polymer of monomers having two or more ethylenically unsaturated groups is preferable.
In order to obtain a high refractive index, the monomer structure preferably contains an aromatic ring or at least one atom selected from a halogen atom other than fluorine, a sulfur atom, a phosphorus atom, and a nitrogen atom.

As a monomer having two or more ethylenically unsaturated groups for forming an antiglare hard coat layer, an ester of a polyhydric alcohol and (meth) acrylic acid (eg, ethylene glycol di (meth) acrylate, 1,4-cyclohexanediacrylate, pentaerythritol tetra (meth) acrylate), pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, dipentaerythritol tetra (meth) Acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, pentaerythritol hexa (meth) acrylate, 1,2,3-chlorohexane tetramethacrylate, polyurea Polyacrylate, polyester polyacrylate), vinylbenzene and derivatives thereof (eg, 1,4-vinylbenzene, 4-vinylbenzoic acid-2-acryloylethyl ester, 1,4-vinylcyclohexanone), vinyl sulfone (eg, divinyl) Sulfone), acrylamide (eg, methylenebisacrylamide) and methacrylamide.
Furthermore, resins having two or more ethylenically unsaturated groups, such as relatively low molecular weight polyester resins, polyether resins, acrylic resins, epoxy resins, urethane resins, alkyd resins, spiroacetal resins, polybutadiene resins, polythiol polyene resins And oligomers or prepolymers such as polyfunctional compounds such as polyhydric alcohols. Two or more of these monomers may be used in combination, and the resin having two or more ethylenically unsaturated groups is preferably contained in an amount of 10 to 70% based on the total amount of the binder.

  Specific examples of the high refractive index monomer include bis (4-methacryloylthiophenyl) sulfide, vinyl naphthalene, vinyl phenyl sulfide, 4-methacryloxyphenyl-4′-methoxyphenyl thioether, and the like. Two or more of these monomers may be used in combination.

Polymerization of the monomer having an ethylenically unsaturated group can be performed by irradiation with ionizing radiation or heating in the presence of a photo radical initiator or a thermal radical initiator.
Accordingly, a cured composition containing a monomer having an ethylenically unsaturated group, a photo radical initiator or a thermal radical initiator, mat particles and an inorganic filler, and other additives is prepared, and the cured composition is placed on a transparent support. After coating, the film is cured by ionizing radiation or a polymerization reaction by heat to form an antireflection film. It is also preferable to perform ionizing radiation curing and thermal curing together.
The refractive index of the binder is preferably 1.40 to 2.10, more preferably 1.45 to 2.00, and still more preferably 1.50 to 2.00. In addition, the refractive index of a binder is the value measured by remove | excluding translucent particle | grains from the component of the light-diffusion layer.
The binder of the antiglare hard coat layer is preferably added in the range of 20 to 95% by mass with respect to the solid content of the coating composition of the layer.

As radical photopolymerization initiators, acetophenones, benzoins, benzophenones, phosphine oxides, ketals, anthraquinones, thioxanthones, azo compounds, peroxides, 2,3-alkyldione compounds, disulfide compounds , Fluoroamine compounds and aromatic sulfoniums. Examples of acetophenones include 2,2-ethoxyacetophenone, p-methylacetophenone, 1-hydroxydimethylphenyl ketone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-4-methylthio-2-morpholinopropiophenone and 2- Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone is included. Examples of benzoins include benzoin benzene sulfonate, benzoin toluene sulfonate, benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether. Examples of the benzophenones include benzophenone, 2,4-chlorobenzophenone, 4,4-dichlorobenzophenone and p-chlorobenzophenone. Examples of phosphine oxides include 2,4,6-trimethylbenzoyldiphenylphosphine oxide.
Various examples are described in the latest UV curing technology (P.159, issuer; Kazuhiro Takasagi, publisher; Technical Information Association, Inc., published in 1991), which is useful for the present invention.
Commercially available radical photopolymerization initiators can also be preferably used, and examples include the initiators described in the section of the low refractive index layer.
It is preferable to use a photoinitiator in the range of 0.1-15 mass parts with respect to 100 mass parts of polyfunctional monomers, More preferably, it is the range of 1-10 mass parts.
In addition to the photopolymerization initiator, a photosensitizer may be used. Specific examples of the photosensitizer include n-butylamine, triethylamine, tri-n-butylphosphine, Michler's ketone and thioxanthone.

As the thermal radical initiator, organic or inorganic peroxides, organic azo, diazo compounds, and the like can be used.
Specifically, benzoyl peroxide, halogen benzoyl peroxide, lauroyl peroxide, acetyl peroxide, dibutyl peroxide, cumene hydroperoxide, butyl hydroperoxide as organic peroxides, hydrogen peroxide, peroxides as inorganic peroxides. Diazo compounds such as ammonium sulfate, potassium persulfate and the like, 2,2′-azobis (isobutyronitrile), 2,2′-azobis (propionitrile), 1,1′-azobis (cyclohexanecarbonitrile), etc. And diazoaminobenzene, p-nitrobenzenediazonium and the like.

The polymer having a polyether as the main chain is preferably a ring-opening polymer of a polyfunctional epoxy compound. The ring-opening polymerization of the polyfunctional epoxy compound can be performed by irradiation with ionizing radiation or heating in the presence of a photoacid generator or a thermal acid generator.
Therefore, a coating solution containing a polyfunctional epoxy compound, a photoacid generator or a thermal acid generator, translucent particles and an inorganic filler is prepared, and the coating solution is applied onto a transparent support and then polymerized by ionizing radiation or heat. It can be cured by reaction to form an antireflection film.

Instead of or in addition to a monomer having two or more ethylenically unsaturated groups, a monomer having a crosslinkable functional group is used to introduce a crosslinkable functional group into the polymer, and by reaction of this crosslinkable functional group, A crosslinked structure may be introduced into the binder polymer.
Examples of the crosslinkable functional group include isocyanate group, epoxy group, aziridine group, oxazoline group, aldehyde group, carbonyl group, hydrazine group, carboxyl group, methylol group and active methylene group. Vinylsulfonic acid, acid anhydrides, cyanoacrylate derivatives, melamine, etherified methylol, esters and urethanes, and metal alkoxides such as tetramethoxysilane can also be used as monomers for introducing a crosslinked structure. A functional group that exhibits crosslinkability as a result of the decomposition reaction, such as a block isocyanate group, may be used. That is, in the present invention, the crosslinkable functional group may not react immediately but may exhibit reactivity as a result of decomposition.
These binder polymers having a crosslinkable functional group can form a crosslinked structure by heating after coating.
The binder of the antiglare hard coat layer is preferably added in an amount of 20 to 95% by mass based on the solid content of the coating composition of the layer.

(Translucent particles)
The antiglare hard coat layer has a particle size larger than that of the fine inorganic filler particles described later and has an average particle size of 0.5 μm to 10 μm, preferably 0.5 μm to 8 μm, such as inorganic compound particles or Resin particles are contained. This is because the external light reflected on the display surface is scattered and weakened, or the viewing angle of the liquid crystal display device (especially the downward viewing angle) is enlarged, so that the contrast decreases, black / white inversion or hue changes even if the viewing angle in the viewing direction changes. Used to make it difficult to occur. When the average particle size is in the above range, an antiglare effect is exhibited, and a rough feeling does not occur.
The difference in refractive index between the translucent particles and the translucent resin is preferably 0.02 to 0.30 from the viewpoint of preventing the film from becoming clouded and obtaining a sufficient light diffusion effect. Particularly preferred is 0.02 to 0.20.

From the same viewpoint, the preferable range of the addition amount of the translucent particles to the translucent resin is determined. The preferable in-layer content of the translucent particles is 3% by mass to 40% by mass in the total solid content of the antiglare hard coat layer, and particularly preferably 5% by mass to 25% by mass.
The coating amount of the translucent particles is preferably 10 mg / m ^{2 to} 10,000 mg / m ² , more preferably 50 mg / m ^{2 to} 4000 mg / m ² , and most preferably in terms of the amount of particles in the formed antiglare hard coat layer. It is contained in the diffusion layer so as to ^{100mg / m 2 ~1500mg / m 2} .
The relationship between the particle diameter of the translucent particles and the film thickness of the layer to be contained is preferably 20% to 100% of the film thickness of the layer containing the average particle diameter of the translucent particles, and preferably 30% to 80%. % Is more preferable, and 35% to 70% is most preferable. When the average particle size is within this range, the screen is excellent in blackening and the antiglare property is also excellent.
The particle size distribution of the particles is measured by a Coulter counter method, and the measured distribution is converted into a particle number distribution. The average particle size is calculated from the obtained particle distribution.

  The translucent particles may be used in combination of two or more different translucent particles. When two or more kinds of translucent particles are used, the translucent particles having the highest refractive index and the translucent particles having the lowest refractive index are used to effectively exert the refractive index control by mixing a plurality of types of particles. The difference in refractive index with the active particles is preferably 0.02 or more and 0.10 or less, and particularly preferably 0.03 or more and 0.07 or less. It is also possible to impart antiglare properties with translucent particles having a larger particle size and to impart other optical characteristics with translucent particles having a smaller particle size. For example, when an antireflection film is attached to a high-definition display of 133 ppi or higher, it is required that there is no problem in optical performance called glare. Glare is derived from the fact that the unevenness of the film surface (which contributes to antiglare properties) causes the pixels to be enlarged or reduced and loses brightness uniformity, but is smaller than the light-transmitting particles that impart antiglare properties. The diameter can be greatly improved by using translucent particles different from the refractive index of the translucent resin.

Specific examples of the translucent particles include particles of inorganic compounds such as silica particles, hollow silica particles, alumina particles, and TiO ₂ particles; polymethyl methacrylate particles, crosslinked polymethyl methacrylate particles, crosslinked methyl methacrylate- Preferred examples include resin particles such as styrene copolymer particles, polystyrene particles, crosslinked polystyrene particles, melamine resin particles, benzoguanamine resin particles, polycarbonate particles, and polyvinyl chloride particles. Among these, crosslinked styrene particles, crosslinked polymethyl methacrylate particles, crosslinked methyl methacrylate-styrene copolymer particles, and silica particles are preferable.

  As the shape of the translucent particle, either a true sphere or an indeterminate shape can be used, but monodisperse particles are preferable from the viewpoint of controllability of haze value and diffusibility, and uniformity of the coated surface. For example, when a particle having a particle size of 20% or more than the average particle size is defined as a coarse particle, the proportion of the coarse particle is preferably 1% or less of the total number of particles, more preferably 0.1% or less. Yes, more preferably 0.01% or less. Particles having such a particle size distribution are obtained by classification after a normal synthesis reaction, and particles having a more preferable distribution can be obtained by increasing the number of classifications or increasing the degree of classification.

The antiglare hard coat layer has at least one selected from titanium, zirconium, aluminum, indium, zinc, tin, and antimony in addition to the above light-transmitting particles in order to increase the refractive index of the layer. It is preferable to contain a fine inorganic filler made of a metal oxide and having an average primary particle diameter of 0.2 μm or less, preferably 0.1 μm or less, more preferably 0.06 μm or less.
Conversely, in an antiglare hard coat layer using light-transmitting particles having a high refractive index, the refractive index of the binder must be lowered in order to increase the difference in refractive index from the light-transmitting particles. For this purpose, it is also preferable to use silica fine particles and hollow silica fine particles. The preferred particle size is the same as that of the high refractive index fine inorganic filler.

Specific examples of the fine inorganic filler used for the antiglare hard coat layer include TiO ₂ , ZrO ₂ , Al ₂ O ₃ , In ₂ O ₃ , ZnO, SnO ₂ , Sb ₂ O ₃ , ITO and SiO _2. Can be mentioned. TiO ₂ and ZrO ₂ are particularly preferable from the viewpoint of increasing the refractive index. The surface of the inorganic filler is preferably subjected to a silane coupling treatment or a titanium coupling treatment, and a surface treatment agent having a functional group capable of reacting with a binder species on the filler surface is preferably used.
The addition amount of these fine inorganic fillers is preferably 10 to 90% of the total mass of the antiglare hard coat layer, more preferably 20 to 80%, and particularly preferably 30 to 75%.
The fine inorganic filler does not scatter because the particle size is sufficiently shorter than the wavelength of light, and the dispersion in which the filler is dispersed in the binder polymer has the property of an optically uniform substance.

  The bulk refractive index of the mixture of binder and inorganic filler in the antiglare hard coat layer of the present invention is preferably 1.48 to 2.00, more preferably 1.50 to 1.80. In order to make the refractive index within the above range, the kind and amount ratio of the binder and the inorganic filler may be appropriately selected. How to select can be easily known experimentally in advance.

  Resin, dispersant, surfactant, antistatic agent, silane coupling agent, thickener, anti-coloring agent, coloring agent (pigment, dye), antifoaming agent, leveling agent, flame retardant, UV Absorbers, adhesion promoters, polymerization inhibitors, antioxidants, surface modifiers, and the like can also be added.

<Other components>
(Antistatic layer)
The antiglare antireflection film of the present invention preferably uses an antistatic layer in order to prevent dust (dust etc.) from adhering to the surface. The dust resistance is expressed by lowering the surface resistance value of the surface. The surface resistance value is preferably 1 × 10 ¹³ Ω / □ or less, more preferably 1 × 10 ¹² Ω / □ or less, and further preferably 1 × 10 ¹⁰ Ω / □ or less.
The antistatic layer is preferably provided between the antiglare hard coat layer and the low refractive index layer, or between the transparent support and the antiglare hard coat layer.

  When the antistatic layer is formed by coating, an antistatic layer may be formed by incorporating a conductive material (electroconductive particles, electron conductive organic compounds, etc.) in a binder (binder, etc.). preferable. In particular, an electron conductive type conductive material is preferable in that it is less susceptible to environmental changes and has stable conductive performance, so that it exhibits good conductive performance even in a low humidity environment.

Preferred conductive materials used for the antistatic layer include tin oxide, antimony-doped tin oxide (ATO), indium oxide, tin-doped indium oxide (ITO), zinc oxide, and aluminum-doped zinc oxide. Can be mentioned.
The mass average particle size of the primary particles of the conductive material is preferably 1 to 200 nm, more preferably 1 to 100 nm. Specific surface of the conductive material is preferably 10 to 400 m ² / g, further preferably 20 to 200 m ² / g.

  In dispersing the conductive material, it is preferable to disperse in the dispersion medium in the presence of a dispersant. For the dispersion, for example, a dispersant having an anionic group having an acidic proton such as a carboxyl group, a sulfonic acid group (sulfo group), a phosphoric acid group (phosphono group), or a sulfonamide group can be used. Examples of the dispersant having an anionic polar group include phosphanol (PE-510, PE-610, LB-400, EC-6103, RE-410, etc .; manufactured by Toho Chemical Industry Co., Ltd.), Disperbyk (-110, − 111, -116, -140, -161, -162, -163, -164, -164, -170, -171, etc .; manufactured by Big Chemie Japan). The dispersant preferably further contains a crosslinkable or polymerizable functional group.

As the dispersion medium, a liquid having a boiling point of 60 to 170 ° C. is preferably used.
Among these, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, butanol, propanol, and cellosolves (for example, propylene glycol monomethyl ether) are preferable, and methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone are particularly preferable.

The conductive material is preferably dispersed using a media-type disperser such as a sand grinder mill (eg, a bead mill with pins), a dyno mill, a high-speed impeller mill, an Eiger mill, a pebble mill, a roller mill, an attritor and a colloid mill, or a paint shaker. .
The conductive material is preferably as fine as possible in the dispersion medium, and the mass average particle diameter is preferably 1 to 200 nm.

As the binder precursor of the antistatic layer, ionizing radiation curable polyfunctional monomers and polyfunctional oligomers such as (meth) acryloyl group, vinyl group, styryl group and allyl group described in the light diffusion layer and the like are preferable.
The antistatic layer is preferably formed by crosslinking or polymerization reaction of an ionizing radiation curable compound in an atmosphere of 4% by volume or less.

The film thickness of the antistatic layer can be appropriately designed depending on the application, and when the antistatic layer is formed with priority given to transparency, the film thickness is preferably 1 μm or less, more preferably 500 nm or less, still more preferably Is 200 nm or less, particularly preferably 150 nm or less.
Moreover, when an antistatic layer is hard-coated and serves also as a hard-coat layer, 1-10 micrometers is preferable, More preferably, it is 2-7 micrometers, Most preferably, it is 3-5 micrometers.

  In the antistatic layer, in addition to the above components (conductive material, polymerization initiator, photosensitizer, binder, etc.), resin, surfactant, coupling agent, thickener, anti-coloring agent, coloring agent (pigment) Dyes), antifoaming agents, leveling agents, flame retardants, ultraviolet absorbers, infrared absorbers, adhesion-imparting agents, polymerization inhibitors, antioxidants, surface modifiers, and the like.

(Transparent support)
The transparent support is preferably a plastic film. As the plastic film, cellulose ester (eg, triacetyl cellulose, diacetyl cellulose, propionyl cellulose, butyryl cellulose, acetyl propionyl cellulose, nitrocellulose), polyamide, polycarbonate, polyester (eg, polyethylene terephthalate, polyethylene naphthalate, poly-1, 4-cyclohexanedimethylene terephthalate, polyethylene-1,2-diphenoxyethane-4,4′-dicarboxylate, polybutylene terephthalate), polystyrene (eg, syndiotactic polystyrene), polyolefin (eg, polypropylene, polyethylene, poly Methylpentene), polysulfone, polyethersulfone, polyarylate, polyetherimide, polymethylmethacrylate And polyether ketones. Triacetyl cellulose, polycarbonate, polyethylene terephthalate and polyethylene naphthalate are preferred, and triacetyl cellulose is particularly preferred when used in a liquid crystal display device.

  When the transparent support is a triacetyl cellulose film, a triacetyl cellulose dope prepared by dissolving triacetyl cellulose in a solvent is prepared by a single layer casting method or a multi-layer co-casting method. A cellulose film is preferred.

In particular, from the viewpoint of environmental conservation, a triacetyl cellulose film prepared using a triacetyl cellulose dope prepared by dissolving triacetyl cellulose in a solvent substantially free of dichloromethane by a low temperature dissolution method or a high temperature dissolution method is preferable. .
The triacetylcellulose film preferably used in the present invention is exemplified in the Japan Society for Invention and Innovation (public technical number 2001-1745).

The film thickness of the transparent support is not particularly limited, but the film thickness is preferably 1 to 300 μm, preferably 30 to 150 μm, particularly preferably 40 to 120 μm, and most preferably 40 to 100 μm.
The light transmittance of the transparent support is preferably 80% or more, and more preferably 86% or more.
The haze of the transparent support is preferably low. It is preferably 2.0% or less, and more preferably 1.0% or less.
The refractive index of the transparent support is preferably 1.40 to 1.70.

An infrared absorbent or an ultraviolet absorbent may be added to the transparent support. The addition amount of the infrared absorber is preferably 0.01 to 20% by mass of the transparent support, and more preferably 0.05 to 10% by mass.
In addition, an inert inorganic compound particle may be added to the transparent support as a slipping agent. Examples of the inorganic _{compound, SiO 2, TiO 2, BaSO} 4, CaCO 3, talc and kaolin.

  A surface treatment may be performed on the transparent support. Examples of the surface treatment include chemical treatment, mechanical treatment, corona discharge treatment, flame treatment, ultraviolet irradiation treatment, high frequency treatment, glow discharge treatment, active plasma treatment, laser treatment, mixed acid treatment and ozone oxidation treatment. Glow discharge treatment, ultraviolet irradiation treatment, corona discharge treatment and flame treatment are preferred, and glow discharge treatment and corona discharge treatment are particularly preferred.

(Organosilane compound)
The organosilane compound that can be particularly preferably used for each layer of the antiglare antireflection film according to the present invention will be described.
Any layer on the transparent support containing at least one compound selected from organosilane compounds and derivatives thereof in terms of improving the physical strength of the film (such as scratch resistance) and the adhesion between the film and the layer adjacent to the film. It is preferable to add to.

  As the organosilane compound and derivatives thereof, compounds represented by the following general formula (a) and derivatives thereof can be used. Preferred are organosilane compounds containing a hydroxyl group, a mercapto group, a carboxyl group, an epoxy group, an alkyl group, an alkoxysilyl group, an acyloxy group, and an acylamino group, and particularly preferred are an epoxy group and a polymerizable acyloxy group (( (Meth) acryloyl, etc.) and a polymerizable acylamino group (acrylamino, methacrylamino, etc.).

Formula _{^{(a) :( R 10) S}} -Si (Z) 4-S

In general formula (a), R ¹⁰ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, t-butyl, sec-butyl, hexyl, decyl, hexadecyl and the like. The alkyl group preferably has 1 to 30 carbon atoms, more preferably 1 to 16 carbon atoms, and particularly preferably 1 to 6 carbon atoms. Examples of the aryl group include phenyl and naphthyl, and a phenyl group is preferable.
Z represents a hydroxyl group or a hydrolyzable group. For example, an alkoxy group (an alkoxy group having 1 to 5 carbon atoms is preferable. Examples thereof include a methoxy group and an ethoxy group), a halogen atom (for example, Cl, Br, I and the like), and R ¹² COO (R ¹² is a hydrogen atom or An alkyl group having 1 to 5 carbon atoms is preferred, and examples thereof include CH ₃ COO, C ₂ H ₅ COO, etc., preferably an alkoxy group, particularly preferably a methoxy group or an ethoxy group. It is.
s represents an integer of 1 to 3. 1 or 2 is preferable, and 1 is particularly preferable.
When R ¹⁰ or Z there is a plurality, the plurality of R ¹⁰ or Z may be different.

The substituent contained in R ¹⁰ is not particularly limited, but a halogen atom (fluorine, chlorine, bromine, etc.), hydroxyl group, mercapto group, carboxyl group, epoxy group, alkyl group (methyl, ethyl, i-propyl, propyl, t-butyl etc.), aryl groups (phenyl, naphthyl etc.), aromatic heterocyclic groups (furyl, pyrazolyl, pyridyl etc.), alkoxy groups (methoxy, ethoxy, i-propoxy, hexyloxy etc.), aryloxy groups (phenoxy) Etc.), alkylthio groups (such as methylthio and ethylthio), arylthio groups (such as phenylthio), alkenyl groups (such as vinyl and 1-propenyl), alkoxysilyl groups (such as trimethoxysilyl and triethoxysilyl), acyloxy groups (acetoxy, acryloyl) Oxy, methacryloyloxy, etc.), alkoxycal Nyl group (methoxycarbonyl, ethoxycarbonyl, etc.), aryloxycarbonyl group (phenoxycarbonyl, etc.), carbamoyl group (carbamoyl, N-methylcarbamoyl, N, N-dimethylcarbamoyl, N-methyl-N-octylcarbamoyl, etc.), acylamino Groups (acetylamino, benzoylamino, acrylamino, methacrylamino and the like) and the like, and these substituents may be further substituted with these substituents.

  Of these, more preferred are a hydroxyl group, a mercapto group, a carboxyl group, an epoxy group, an alkyl group, an alkoxysilyl group, an acyloxy group, and an acylamino group. In particular, a crosslinked or polymerizable functional group is preferable, and an epoxy group, a polymerizable acyloxy group ((meth) acryloyl), and a polymerizable acylamino group (acrylamino, methacrylamino) are preferable. These substituents may be further substituted with the above-described substituents.

When there are a plurality of R ^{10 s} , at least one is preferably a substituted alkyl group or a substituted aryl group. Among the organosilane compounds represented by the general formula (a) and derivatives thereof, at least one selected from the organosilane compounds having a vinyl polymerizable substituent represented by the following general formula (b) and derivatives thereof Compounds are preferred.

In the general formula (b), R ¹¹ represents a hydrogen atom, a methyl group, a methoxy group, an alkoxycarbonyl group, a cyano group, a fluorine atom, or a chlorine atom. Examples of the alkoxycarbonyl group include a methoxycarbonyl group and an ethoxycarbonyl group. A hydrogen atom, a methyl group, a methoxy group, a methoxycarbonyl group, a cyano group, a fluorine atom and a chlorine atom are preferred, a hydrogen atom, a methyl group, a methoxycarbonyl group, a fluorine atom and a chlorine atom are more preferred, and a hydrogen atom and a methyl group Is particularly preferred.
Y represents a single bond, * -COO-**, * -CONH-**, * -O-**, or * -NH-CO-NH-**, and represents a single bond, * -COO-**, * -CONH-** is preferred, single bond, * -COO-** is more preferred, and * -COO-** is particularly preferred. Here, * represents a position bonded to ═C (R ¹¹ ) —, and ** represents a position bonded to L ¹ .

L ¹ represents a divalent linking chain. Specifically, a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, a substituted or unsubstituted alkylene group having a linking group (for example, ether, ester, amide, etc.) inside, and a linking group inside. A substituted or unsubstituted arylene group, a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, and an alkylene group having a linking group therein are preferred. An unsubstituted alkylene group and an unsubstituted arylene group Further, an alkylene group having an ether or ester linking group inside is more preferred, an unsubstituted alkylene group, and an alkylene group having an ether or ester linking group inside is particularly preferred. Examples of the substituent include a halogen, a hydroxyl group, a mercapto group, a carboxyl group, an epoxy group, an alkyl group, and an aryl group, and these substituents may be further substituted.

t represents 0 or 1; t is preferably 0.
R ¹⁰ has the same meaning as R ^{10 in} formula (a), preferably a substituted or unsubstituted alkyl group or an unsubstituted aryl group, and more preferably an unsubstituted alkyl group or an unsubstituted aryl group.
Z has the same meaning as in formula (a), preferably a halogen atom, a hydroxyl group or an unsubstituted alkoxy group, more preferably a chlorine atom, a hydroxyl group or an unsubstituted alkoxy group having 1 to 6 carbon atoms, a hydroxyl group or a carbon number of 1 -3 alkoxy groups are more preferred, and methoxy groups are particularly preferred. When a plurality of Z are present, the plurality of Z may be the same or different.

Two or more kinds of the compounds represented by the general formula (a) and the general formula (b) and their derivatives may be used in combination.
Although the specific example of the organosilane compound represented by general formula (a) and general formula (b) below is shown, this invention is not limited to these.

  Of these, (M-1), (M-2), and (M-5) are particularly preferable.

In the present invention, the derivative of the organosilane compound represented by the general formula (a) and the general formula (b) is a hydrolyzate of the organosilane compound represented by the general formula (a) and the general formula (b), It means a partial condensate. Hereinafter, preferred derivatives (hydrolyzate and partial condensate) of the organosilane compound used in the present invention will be described.
The hydrolysis reaction and condensation reaction of the organosilane compound are generally performed in the presence of a catalyst. Catalysts include inorganic acids such as hydrochloric acid, sulfuric acid and nitric acid; organic acids such as oxalic acid, acetic acid, formic acid, methanesulfonic acid and toluenesulfonic acid; inorganic bases such as sodium hydroxide, potassium hydroxide and ammonia; triethylamine, Examples thereof include organic bases such as pyridine; metal alkoxides such as triisopropoxyaluminum and tetrabutoxyzirconium; metal chelate compounds having a metal such as Zr, Ti or Al as a central metal. Among inorganic acids, hydrochloric acid, sulfuric acid, and organic acids preferably have an acid dissociation constant (pKa value (25 ° C.)) of 4.5 or less in water, and an acid dissociation constant in hydrochloric acid, sulfuric acid, or water of 3.0 or less. More preferred is an organic acid, hydrochloric acid, sulfuric acid, an organic acid having an acid dissociation constant of 2.5 or less in water is more preferred, an organic acid having an acid dissociation constant in water of 2.5 or less is more preferred, and methanesulfonic acid Further, oxalic acid, phthalic acid, and malonic acid are more preferable, and oxalic acid is particularly preferable.

The organosilane hydrolysis / condensation reaction can be carried out in the absence of a solvent or in a solvent, but an organic solvent is preferably used in order to mix the components uniformly. For example, alcohols, aromatic hydrocarbons, ethers, Ketones and esters are preferred.
The solvent preferably dissolves the organosilane and the catalyst. Moreover, it is preferable to use an organic solvent as a paint or a part of the paint, and it is preferable that the solvent does not impair the solubility or dispersibility when mixed with other materials.

Among these, as alcohol, monohydric alcohol or dihydric alcohol can be mentioned, for example, As C1-C8, a C1-C8 saturated aliphatic alcohol is preferable.
Specific examples of these alcohols include methanol, ethanol, n-propyl alcohol, i-propyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, ethylene glycol, diethylene glycol, triethylene glycol, ethylene glycol. Examples thereof include monobutyl ether and ethylene glycol monoethyl ether acetate.

Specific examples of aromatic hydrocarbons include benzene, toluene, xylene and the like. Specific examples of ethers include tetrahydrofuran and dioxane. Specific examples of ketones include acetone, methyl ethyl ketone, methyl isobutyl ketone, Specific examples of esters such as diisobutyl ketone include ethyl acetate, propyl acetate, butyl acetate, and propylene carbonate.
These organic solvents can be used alone or in combination of two or more. The concentration of the solid content in the reaction is not particularly limited, but is usually in the range of 1% to 90%, preferably in the range of 20% to 70%.

0.3 to 2 mol, preferably 0.5 to 1 mol of water is added to 1 mol of the hydrolyzable group of the organosilane compound, in the presence or absence of the above solvent, and in the presence of a catalyst. And by stirring at 25 to 100 ° C.
In the present invention, (wherein, R ¹³ represents an alkyl group having 1 to 10 carbon atoms) Formula R ¹³ OH alcohol of the general formula R ¹⁴ COCH ₂ COR ¹⁵ (wherein represented by, R ¹⁴ is the number of carbon atoms 1 to 10 alkyl groups, R ¹⁵ represents an alkyl group having 1 to 10 carbon atoms or a compound represented by an alkoxy group having 1 to 10 carbon atoms), and is selected from Zr, Ti and Al. It is preferable to perform the hydrolysis by stirring at 25 to 100 ° C. in the presence of at least one metal chelate compound having a metal as a central metal.

The metal chelate compound includes an alcohol represented by a general formula R ¹³ OH (wherein R ¹³ represents an alkyl group having 1 to 10 carbon atoms) and a general formula R ¹⁴ COCH ₂ COR ¹⁵ (wherein R ¹⁴ is carbon. From Zr, Ti, and Al having a ligand represented by a compound represented by an alkyl group having 1 to 10 carbon atoms, R ¹⁵ represents an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms) Any metal having a selected metal as a central metal can be suitably used without particular limitation. Two or more metal chelate compounds may be used in combination. The metal chelate compound used in the present invention has the general formula Zr (OR ¹³ ) _p1 (R ¹⁴ COCHCOR ¹⁵ ) _p2 , Ti (OR ¹³ ) _q1 (R ¹⁴ COCHCOR ¹⁵ ) _q2 , and Al (OR ¹³ ) _r1 (R ¹⁴ Those selected from the group of compounds represented by COCHCOR ¹⁵ ) _r2 are preferred, and serve to promote the condensation reaction of the hydrolyzate and partial condensate of the organosilane compound.

R ¹³ and R ¹⁴ in the metal chelate compound may be the same or different, and an alkyl group having 1 to 10 carbon atoms, specifically, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, and sec-butyl group, t-butyl group, n-pentyl group, phenyl group and the like. R ¹⁵ represents an alkyl group having 1 to 10 carbon atoms as described above, or an alkoxy group having 1 to 10 carbon atoms such as a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, and n-butoxy. Group, sec-butoxy group, t-butoxy group and the like. Moreover, p1, p2, q1, q2, r1, and r2 in the metal chelate compound represent integers determined so as to be p1 + p2 = 4, q1 + q2 = 4, and r1 + r2 = 3, respectively.

Specific examples of these metal chelate compounds include tri-n-butoxyethylacetoacetate zirconium, di-n-butoxybis (ethylacetoacetate) zirconium, n-butoxytris (ethylacetoacetate) zirconium, tetrakis (n-propylacetate). Zirconium chelate compounds such as acetate) zirconium, tetrakis (acetylacetoacetate) zirconium, tetrakis (ethylacetoacetate) zirconium; diisopropoxy bis (ethylacetoacetate) titanium, diisopropoxy bis (acetylacetate) titanium, diiso Titanium chelate compounds such as propoxy bis (acetylacetone) titanium; diisopropoxyethyl acetoacetate aluminum, diisopropyl Poxyacetylacetonate aluminum, isopropoxybis (ethylacetoacetate) aluminum, isopropoxybis (acetylacetonate) aluminum, tris (ethylacetoacetate) aluminum, tris (acetylacetonate) aluminum, monoacetylacetonate bis (ethyl) An aluminum chelate compound such as acetoacetate) aluminum.
Among these metal chelate compounds, tri-n-butoxyethyl acetoacetate zirconium, diisopropoxy bis (acetylacetonate) titanium, diisopropoxyethyl acetoacetate aluminum, and tris (ethyl acetoacetate) aluminum are preferable. . These metal chelate compounds can be used individually by 1 type or in mixture of 2 or more types. Moreover, the partial hydrolyzate of these metal chelate compounds can also be used.

  The metal chelate compound is preferably used in a proportion of 0.01 to 50% by mass, more preferably 0.1 to 50% by mass, and still more preferably 0.5 to 10% by mass with respect to the organosilane compound. If the metal chelate compound is within the above range, the condensation reaction of the organosilane compound is fast, the coating film has excellent durability, and at least one of the hydrolyzate and partial condensate of the organosilane compound and the metal chelate compound are contained. The storage stability of the resulting composition is also excellent and preferable.

  A composition containing at least one compound selected from the above organosilane compounds and derivatives thereof (hydrolysates, partial condensates), a metal chelate compound added as necessary, and the like are added to a β-diketone compound and β- It is preferable to add at least one of keto ester compounds.

In the present invention, at least one of a β-diketone compound and a β-ketoester compound represented by the general formula R ¹⁴ COCH ₂ COR ¹⁵ is preferably used and acts as a stability improver for the composition. That is, by coordinating to metal atoms in the metal chelate compounds (zirconium, titanium and aluminum compounds), condensation reactions of organosilane compounds derivatives (hydrolysates, partial condensates, etc.) by these metal chelate compounds It is thought that the effect | action which accelerates | stimulates is suppressed, and the effect | action which improves the storage stability of the obtained composition is made | formed. R ¹⁴ and R ¹⁵ constitute a β- diketone compound and β- ketoester compound are the same as R ¹⁴ and R ¹⁵ constituting the metal chelate compound.

  Specific examples of the β-diketone compound and β-ketoester compound include acetylacetone, methyl acetoacetate, ethyl acetoacetate, acetoacetate-n-propyl, acetoacetate-i-propyl, acetoacetate-n-butyl, acetoacetate- sec-butyl, acetoacetate-t-butyl, 2,4-hexane-dione, 2,4-heptane-dione, 3,5-heptane-dione, 2,4-octane-dione, 2,4-nonane-dione , 5-methyl-hexane-dione and the like. Of these, ethyl acetoacetate and acetylacetone are preferred, and acetylacetone is particularly preferred. These β-diketone compounds and β-ketoester compounds may be used alone or in combination of two or more. In the present invention, the compound selected from the β-diketone compound and the β-ketoester compound is preferably used in an amount of 2 mol or more, more preferably 3 to 20 mol, relative to 1 mol of the metal chelate compound, and the storage stability of the resulting composition. Will improve.

  The addition amount of at least one compound selected from the above organosilane compounds and derivatives thereof is appropriately adjusted depending on the layer to be added. The addition amount is preferably 0.1 to 50% by mass, more preferably 1 to 30% by mass, further preferably 3 to 25% by mass, and particularly preferably 5 to 20% by mass with respect to the total solid content of the layer. It is.

At least one compound selected from an organosilane compound and a derivative thereof can crosslink or undergo a polymerization reaction with other components of the layer containing them, which can significantly improve the physical strength (such as scratch resistance) of the film. This is preferable because it becomes possible. For this reason, it is preferable that the organosilane compound has a functional group that crosslinks or polymerizes, or a compound having a functional group that crosslinks or polymerizes with the organosilane compound in an inorganic fine particle or a binder.
For example, at least one compound selected from an organosilane compound having an ionizing radiation curable crosslinking or polymerizable functional group and a derivative thereof further has an ionizing radiation curable crosslinking or polymerizable functional group in the film. A cured product is formed by crosslinking or polymerization reaction with other compounds.

  Preferred layers for adding the organosilane compound are antistatic layer, hard coat layer, antiglare hard coat layer, light diffusion layer, high refractive index layer, low refractive index layer, and outermost layer, more preferably A hard coat layer, an antiglare hard coat layer, a light diffusion layer, a low refractive index layer, and an outermost layer, particularly preferably an outermost layer and a layer adjacent to the outermost layer.

  When each layer of the antireflection film is prepared by a coating method, it is preferable to add a surface conditioner to the coating material used for preparing the layer. Hereinafter, the surface conditioner will be described.

(Surface improver)
In order to improve surface defects (coating unevenness, drying unevenness, point defects, etc.), the paint used to make any layer on the transparent support has at least one of fluorine-based and silicone-based surfaces. It is preferable to add a state improver.

The surface improver preferably changes the surface tension of the paint by 1 mN / m or more. Here, the surface tension of the paint changes by 1 mN / m or more when the surface tension of the paint after the addition of the surface conditioner is added, including the concentration process during coating / drying. It means that it changes by 1 mN / m or more as compared with the surface tension of the paint.
Preferably, it is a surface improver that has the effect of lowering the surface tension of the paint by 1 mN / m or more, more preferably a surface improver that lowers by 2 mN / m or more, and particularly preferably a surface improver that lowers by 3 mN / m or more.

Preferable examples of the fluorine-based surface improving agent include compounds containing a fluoroaliphatic group (abbreviated as “fluorine surface improving agent”). In particular, an acrylic resin, a methacrylic resin, and a vinyl monomer copolymerizable with the repeating unit corresponding to the monomer of the following general formula (i) and the repeating unit corresponding to the monomer of the following general formula (ii) And a copolymer are preferred.
Such monomers include Polymer Handbook 2nd ed. , J .; Brandrup, Wiley Interscience (1975) Chapter 2, Pages 1-483 are preferably used.
For example, a compound having one addition polymerizable unsaturated bond selected from acrylic acid, methacrylic acid, acrylic esters, methacrylic esters, acrylamides, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, etc. I can give you.

In the general formula (i), R ²¹ represents a hydrogen atom, a halogen atom or a methyl group, more preferably a hydrogen atom or a methyl group. X ² represents an oxygen atom, a sulfur atom or —N (R ²² ) —, more preferably an oxygen atom or —N (R ²² ) —, and particularly preferably an oxygen atom. R ²² represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, particularly preferably a hydrogen atom or a methyl group. a represents an integer of 1 to 6, more preferably 1 to 3, and particularly preferably 1. b represents an integer of 1 to 18, more preferably 4 to 12, and particularly preferably 6 to 8.
Two or more types of fluoroaliphatic group-containing monomers represented by the general formula (i) may be contained in the fluorine-based surface improver as a constituent component.

In the general formula (ii), R ²³ represents a hydrogen atom, a halogen atom or a methyl group, more preferably a hydrogen atom or a methyl group. Y ² represents an oxygen atom, a sulfur atom or —N (R ²⁵ ) —, more preferably an oxygen atom or —N (R ²⁵ ) —, and particularly preferably an oxygen atom. R ²⁵ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, particularly preferably a hydrogen atom or a methyl group.
R ²⁴ represents a hydrogen atom, a substituted or unsubstituted linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, an alkyl group containing a poly (alkyleneoxy) group, or a substituted or unsubstituted aromatic group (for example, A phenyl group or a naphthyl group). A linear, branched or cyclic alkyl group having 1 to 12 carbon atoms or an aromatic group having 6 to 18 carbon atoms in total is more preferable, and a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms is still more preferable. The poly (alkyleneoxy) group will be described below.

Poly (alkyleneoxy) group, - (OR) - a group in which a repeating unit, R represents an alkylene group having 2 to 4 carbon atoms, such as _{-CH 2 CH 2 -, - CH} 2 CH 2 CH _2- , -CH (CH ₃ ) CH _2- , and -CH (CH ₃ ) CH (CH ₃ )-.
The oxyalkylene units (the -OR-) in the poly (oxyalkylene) group may be the same as in poly (oxypropylene), and two or more different oxyalkylenes are randomly distributed. May be a linear or branched oxypropylene or oxyethylene unit, or a linear or branched block of oxypropylene units or a block of oxyethylene units It may be.

The poly (oxyalkylene) chain may also include those linked by one or more chain bonds (for example, —CONH—Ph—NHCO—, —S—, etc .: Ph represents a phenylene group). If the chain bond has a valence of 3 or more, this provides a means for obtaining branched oxyalkylene units. When this copolymer is used in the present invention, the molecular weight of the poly (oxyalkylene) group is suitably from 250 to 3,000.
Poly (oxyalkylene) acrylates and methacrylates are commercially available hydroxypoly (oxyalkylene) materials, such as “Pluronic” (Pluronic (Asahi Denka Kogyo Co., Ltd.), Adeka Polyether (Asahi Denka Kogyo Co., Ltd.) "Carbowax" [Carbowax (Glico Product)], "Triton" (Toriton (Rohm and Haas)) and PEG (Daiichi Kogyo Seiyaku Co., Ltd.) It can be produced by reacting with acrylic acid, methacrylic acid, acrylic chloride, methacrylic chloride or acrylic acid anhydride by a known method. Separately, poly (oxyalkylene) diacrylate produced by a known method can also be used.

  In the fluorine-based surface improver used in the present invention, the amount of the fluoroaliphatic group-containing monomer represented by the general formula (i) with respect to the total amount of monomers used for forming the fluorine-based surface improver is 50 mol% or more. It is preferable that there is, more preferably 70 to 100 mol%, particularly preferably in the range of 80 to 100 mol%.

The preferred mass average molecular weight of the fluorine-based surface improver used in the present invention is 3000 to 100,000, more preferably 6,000 to 80,000, and still more preferably 8,000 to 60,000.
Here, the mass average molecular weight is expressed in terms of polystyrene by GTH analyzer using TSKgel GMHxL, TSKgel G4000HxL, and TSKgel G2000HxL (both trade names manufactured by Tosoh Corporation) by solvent THF and differential refractometer detection. The content is the area% of the peak in the molecular weight range when the peak area of a component having a molecular weight of 300 or more is defined as 100%.

  Furthermore, the preferable addition amount of the fluorine-type surface improving agent used by this invention is the range of 0.001-5 mass% with respect to the coating material of the layer to add, Preferably it is the range of 0.005-3 mass%. More preferably, it is the range of 0.01-1 mass%.

  Hereinafter, although the example of the specific structure of the fluorine-type surface improvement agent by this invention is shown, this invention is not limited to these. In addition, the number in a formula shows the molar ratio of each monomer component. Mw represents a mass average molecular weight.

  Surface improvers include ketone solvents (acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), ester solvents (ethyl acetate, butyl acetate, etc.), ethers (tetrahydrofuran, 1,4-dioxane, etc.), aromatic carbonization It is preferably used for a paint containing a hydrogen solvent (toluene, xylene, etc.), and a ketone solvent is particularly preferable. Among the ketone solvents, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone are preferable.

  A planarity improving agent may worsen the adhesiveness of the interface of a layer. Accordingly, it is preferable to elute the surface improver present on the surface of the layer into the coating material forming the adjacent layer of the layer so that the surface improver does not remain in the vicinity of the interface between the layers. Therefore, it is preferable to contain a solvent that dissolves the surface improver in the paint of the adjacent layer. As such a solvent, the above ketone solvents are preferable.

  In the coating of the layer formed on the transparent support, it is particularly preferable to add a surface improver to the hard coat layer, the antiglare hard coat layer, the antistatic layer, the high refractive index layer, or the low refractive index layer. A paint for forming a hard coat layer and an antiglare hard coat layer is particularly preferred.

<Formation of optical functional layer>
The optical functional layer is applied by a dip coating method, an air knife coating method, a curtain coating method, a roller coating method, a die coating method, a wire bar coating method, a gravure coating method or an extrusion coating method (described in US Pat. No. 2,681,294). However, it is preferable to apply by a die coating method, and it is more preferable to apply using a new die coater described later. Two or more layers may be applied simultaneously. The method of simultaneous application is described in US Pat. Nos. 2,761,791, 2,941,898, 3,508,947, and 3,526,528 and Yuji Harasaki, Coating Engineering, page 253, Asakura Shoten (1973).

In the optical functional film of the present invention, it is also desired that there are few bright spot defects. The bright spot defect in the present invention is a defect that can be seen by reflection on the coating film, and can be detected by an operation such as black coating on the back surface of the optical functional film after coating. The bright spot defects that can be visually observed are generally 50 μm or more. When there are many bright spot defects, the yield at the time of manufacture falls, and a large-area antireflection film cannot be manufactured.
In the optical functional film of the present invention, the number of bright spot defects is 20 or less per square meter, preferably 10 or less, more preferably 5 or less, and particularly preferably 1 or less.

In order to continuously produce the optical functional film of the present invention, a process of continuously feeding a roll-shaped support film, a process of applying and drying a coating liquid, a process of curing a coating film, and a support having a cured layer A step of winding the body film is performed.
The film support is continuously sent from the roll-shaped film support to the clean room, and the static electricity charged on the film support is removed by the electrostatic charge-off device in the clean room, and then the film support adheres on the film support. Remove the foreign material that has been removed with a dust remover. Subsequently, the coating solution is applied onto the film support in the application section installed in the clean room, and the applied film support is sent to the drying chamber and dried.
The film support having the dried coating layer is sent from the drying chamber to the radiation curing chamber, irradiated with radiation, and the monomer contained in the coating layer is polymerized and cured. Furthermore, the film support having a layer cured by radiation can be sent to the thermosetting section and heated to complete the curing. The film support having a layer that has been cured is wound into a roll.

  The above process may be performed every time each layer is formed, or a plurality of coating units-drying chambers-radiation curing units-thermosetting chambers may be provided to form each layer continuously. In view of the above, it is preferable to continuously form each layer. An example of the configuration of an apparatus for continuously applying each layer is shown in FIG. The apparatus has a necessary number of film forming units 100, 200, 300, 400 installed between Step 1 for continuously feeding a roll-shaped support film and Step 2 for winding the roll-shaped support film. Is. The apparatus shown in FIG. 2 is an example of a configuration in which four layers are continuously applied without winding up, but it is of course possible to change the number of film forming units according to the layer configuration. The film forming unit 100 includes a process 101 for applying a coating liquid, a process 102 for drying a coating film, and a process 103 for curing the coating film. The film forming units 200, 300, and 400 are similarly configured.

  For example, in the case of a three-layer thin film interference type antireflection film having different refractive indexes, a roll-shaped support film coated with the hard coat layer is continuously formed using an apparatus having three film forming units. It is more preferable to wind up after sequentially coating the delivery layer, the middle refractive index layer, the high refractive index layer, and the low refractive index layer with each film forming unit. Using the apparatus shown in Fig. 4, a roll-shaped support film is continuously fed out, and a hard coat layer, a medium refractive index layer, a high refractive index layer, and a low refractive index layer are sequentially coated on each film forming unit and wound up. More preferred.

  In order to produce an antireflection film with few bright spot defects in the present invention, improvement of dispersibility of particles and fine particles dispersed in the layer, and microfiltration operation of the coating liquid can be mentioned. At the same time, each layer forming the antireflection layer is subjected to a dusting process on the film before the coating process in the coating unit and the drying process performed in the drying chamber are performed in a clean air atmosphere and before the coating is performed. It is preferable that dust is sufficiently removed. The air cleanliness of the coating process and the drying process is desirably class 100 (353 particles (0.5 μm or more) / (cubic meter) or less) of class 100 or more based on the standard of air cleanliness in US Federal Standard 209E. Preferably it is Class 10 or higher, more preferably Class 1 (35.5 particles / (cubic meter) or lower, 0.5 μm or more) or more. Moreover, it is more preferable that the degree of air cleanliness is high also in the feeding and winding parts other than the coating-drying process.

  As a dust removal method used in the dust removal step as a pre-process for coating, a method of pressing a nonwoven fabric, a blade or the like against the film surface described in JP-A-59-150571, or JP-A-10-309553 Highly clean air is blown at a high speed to peel off the deposit from the film surface, and suction is performed by a suction port close to the surface. Ultrasonic-vibrated compressed air described in JP-A-7-333613 is sprayed to deposit. And a dry dust removal method such as a method of peeling and suctioning (manufactured by Shinkosha, New Ultra Cleaner, etc.).

  In addition, a method of introducing a film into a cleaning tank and peeling off deposits with an ultrasonic vibrator, supplying a cleaning liquid to the film described in Japanese Patent Publication No. 49-13020, and then blowing and sucking high-speed air As described in JP-A-2001-38306, a wet dust removal method such as a method in which a web is continuously rubbed with a roll wetted with a liquid and then the liquid is sprayed onto the rubbed surface for cleaning. be able to. Among such dust removal methods, a method using ultrasonic dust removal or a method using wet dust removal is particularly preferable in terms of dust removal effect.

  In addition, it is particularly preferable to remove static electricity on the film support before performing such a dust removal step from the viewpoint of increasing dust removal efficiency and suppressing adhesion of dust. As such a static elimination method, a corona discharge ionizer, a light irradiation ionizer such as UV or soft X-ray, or the like can be used. The charged voltage of the film support before and after dust removal and coating is desirably 1000 V or less, preferably 300 V or less, and particularly preferably 100 V or less.

[filtration]
The coating solution used for coating is preferably filtered before coating. As a filter for filtration, it is preferable to use a filter having a pore diameter as small as possible within a range in which components in the coating solution are not removed. For filtration, a filter having an absolute filtration accuracy of 0.1 to 10 μm is used, and a filter having an absolute filtration accuracy of 0.1 to 5 μm is preferably used. The thickness of the filter is preferably 0.1 to 10 mm, and more preferably 0.2 to 2 mm. In that case, the filtration pressure is preferably 15 kg / cm ² or less, more preferably 10 kg / cm ² or less, and further preferably 2 kg / cm ² or less.
The filtration filter member is not particularly limited as long as it does not affect the coating solution. Specifically, the same thing as the filtration member of the wet dispersion of an inorganic compound mentioned above is mentioned.
It is also preferable to ultrasonically disperse the filtered coating solution immediately before coating to assist defoaming and dispersion holding of the dispersion.

In the present invention, the method for curing each layer of the antireflection film is preferably formed by a crosslinking reaction or a polymerization reaction at the same time as or after application of the coating composition by light irradiation, electron beam irradiation or heating. .
When each layer of the antireflection film is formed by a crosslinking reaction or a polymerization reaction of an ionizing radiation curable compound, the crosslinking reaction or the polymerization reaction is preferably performed in an atmosphere having an oxygen concentration of 10% by volume or less. By forming in an atmosphere having an oxygen concentration of 10% by volume or less, an outermost layer excellent in physical strength and chemical resistance can be obtained.
The oxygen concentration is preferably 5% by volume or less, more preferably 1% by volume or less, particularly preferably the oxygen concentration is 0.5% by volume or less, and most preferably 0.1% by volume or less.

  As a method of reducing the oxygen concentration to 10% by volume or less, it is preferable to replace the atmosphere (nitrogen concentration of about 79% by volume, oxygen concentration of about 21% by volume) with another gas, particularly preferably replacement with nitrogen (nitrogen purge). It is to be.

The light source for light irradiation may be any one in the ultraviolet light region or near infrared light. Ultraviolet, high pressure, medium pressure and low pressure mercury lamps, chemical lamps, carbon arc lamps, metal halide lamps may be used as ultraviolet light sources. Xenon lamps, sunlight, etc. Various available laser light sources having a wavelength of 350 to 420 nm may be irradiated as a multi-beam. Further, examples of the near-infrared light source include a halogen lamp, a xenon lamp, and a high-pressure sodium lamp.
When a near infrared light source is used, it may be used in combination with an ultraviolet light source, or light may be irradiated from the substrate surface side opposite to the coating surface side. Film curing in the depth direction in the coating layer proceeds without delay with the vicinity of the surface, and a cured film having a uniform cured state is obtained.

Irradiation intensity of ultraviolet irradiation is preferably about 0.1~1000mW / cm ^2, irradiation amount on the coating film surface is preferably 10~1000mJ / cm ^2. Further, the temperature distribution of the coating film in the light irradiation step is preferably as uniform as possible, preferably within ± 3 ° C., and more preferably controlled within ± 1.5 ° C. In this range, the polymerization reaction in the in-plane and in-layer depth directions of the coating film proceeds uniformly, which is preferable.

[Configuration of die coater]
FIG. 3 is a sectional view of a coater using a slot die embodying the present invention. The coater 10 applies the coating liquid 14 from the slot die 13 to the bead 14a on the web W that is continuously supported by the backup roll 11, thereby forming the coating film 14b on the web WW.

  Inside the slot die 13, a pocket 15 and a slot 16 are formed. The pocket 15 has a curved section and a straight section, and may be substantially circular as shown in FIG. 3, for example, or semicircular. The pocket 15 is a liquid storage space for the coating liquid extended in the width direction of the slot die 13 with its cross-sectional shape, and the length of the effective extension is generally equal to or slightly longer than the coating width. The supply of the coating liquid 14 to the pocket 15 is performed from the side surface of the slot die 13 or from the center of the surface opposite to the slot opening 16a. The pocket 15 is provided with a stopper that prevents the coating liquid 14 from leaking out.

  The slot 16 is a flow path of the coating liquid 14 from the pocket 15 to the web W, and has a cross-sectional shape in the width direction of the slot die 13 similarly to the pocket 15, and the opening 16a located on the web side is generally Using a width regulating plate (not shown), the width is adjusted to be approximately the same as the coating width. The angle between the slot tip of the slot 16 and the tangent in the web running direction of the backup roll 11 is preferably 30 ° or more and 90 ° or less.

  The tip lip 17 of the slot die 13 where the opening 16a of the slot 16 is located is tapered, and the tip is a flat part 18 called a land. In the land 18, the upstream side in the traveling direction of the web W with respect to the slot 16 is referred to as an upstream lip land 18 a and the downstream side is referred to as a downstream lip land 18 b.

4A and 4B show the cross-sectional shape of the slot die 13 in comparison with the conventional one. FIG. 4A shows the slot die 13 used in the present invention, and FIG. 4B shows the conventional slot die 30. In the conventional slot die 30, the distance between the upstream lip land 31a and the web W of the downstream lip land 31b is equal. Reference numeral 32 denotes a pocket, and 33 denotes a slot. On the other hand, in the slot die 13 of the present invention, the downstream side lip land length I _LO is shortened, so that application with a wet film thickness of 20 μm or less can be performed with high accuracy.

The land length I _UP of the upstream lip land 18a is not particularly limited, but is preferably used in the range of 500 μm to 1 mm. The land length I _LO of the downstream lip land 18b is not less than 30 μm and not more than 100 μm, preferably not less than 30 μm and not more than 80 μm, more preferably not less than 30 μm and not more than 60 μm. When the land length I _LO of the downstream lip is shorter than 30 μm, the edge or land of the tip lip is likely to be chipped, streaks are likely to occur in the coating film, and as a result, coating becomes impossible. In addition, it becomes difficult to set the position of the wetting line on the downstream side, and there is a problem that the coating liquid tends to spread on the downstream side. It has been conventionally known that this spreading of the coating liquid on the downstream side means non-uniform wetting lines and leads to a problem of causing a defective shape such as a streak on the coating surface. On the other hand, when the land length I _LO of the downstream lip is longer than 100 μm, the bead itself cannot be formed, so that it is impossible to apply the thin layer.

  Further, the downstream lip land 18b has an overbite shape closer to the web W than the upstream lip land 18a. Therefore, the degree of decompression can be lowered, and a bead suitable for thin film coating can be formed. The difference in distance between the downstream side lip land 18b and the web W of the upstream side lip land 18a (hereinafter referred to as overbit length LO) is preferably 30 μm or more and 120 μm or less, more preferably 30 μm or more and 100 μm or less, and most preferably 30 μm. It is 80 μm or less. When the slot die 13 has an overbite shape, the gap GL between the tip lip 17 and the web W indicates the gap between the downstream lip land 18b and the web W.

FIG. 5 is a perspective view showing a slot die and its periphery in a coating process in which the present invention is implemented. On the opposite side of the web W in the direction of travel, the decompression chamber 40 is installed at a position where it does not come into contact with the bead 14a so that sufficient decompression adjustment can be performed. The decompression chamber 40 is provided with a back plate 40a and a side plate 40b for maintaining its operating efficiency, and there are gaps G _B , G between the back plate 40a and the web W and between the side plate 40b and the web W, respectively. _S exists. 6 and 7 are cross-sectional views showing the decompression chamber 40 and the web W that are close to each other. The side plate and the back plate may be integrated with the chamber body as shown in FIG. 6, or may be structured such that the gap is appropriately changed as shown in FIG. In any structure, portions that are actually opened between the back plate 40a and the web W and between the side plate 40b and the web W are defined as gaps G _B and G _S , respectively. The gap G _B between the back plate 40a and the web W of the decompression chamber 40, when the vacuum chamber 40 is installed beneath the web W and the slot die 13 as shown in FIG. 5, the uppermost end of the back plate 40a to the web W Indicates the gap.

It is preferable that the gap GB between the back plate 40a and the web W be set larger than the gap _GL between the tip lip 17 of the slot die 13 and the web W, so that the vicinity of the bead due to the eccentricity of the backup roll 11 can be obtained. A change in the degree of decompression can be suppressed. For example, when the gap G _L between the end lip 17 and the web W2 of the slot die 13 is 30μm or more 100μm or less, the gap G _B between the back plate 40a and the web W is preferably 100μm or 500μm or less.

[Material and accuracy]
The longer the length of the tip lip on the traveling direction side of the web in the web traveling direction, the more disadvantageous it is for bead formation.If this length varies between arbitrary locations in the slot die width direction, It becomes unstable. Therefore, it is preferable that the fluctuation width in the slot die width direction is within 20 μm.

  Further, if the material of the tip end lip of the slot die is made of a material such as stainless steel, the length of the slot die tip lip in the web running direction is 30 μm to 100 μm as described above. Even within this range, the accuracy of the tip lip cannot be satisfied. Therefore, in order to maintain high processing accuracy, it is important to use a cemented carbide material as described in Japanese Patent No. 2817053. Specifically, at least the tip lip of the slot die is preferably made of a cemented carbide formed by bonding carbide crystals having an average particle size of 5 μm or less. Cemented carbides include carbide crystal particles such as tungsten carbide (hereinafter referred to as WC) bonded by a bonding metal such as cobalt, and other bonding metals include titanium, tantalum, niobium, and mixed metals thereof. Can also be used. The average particle size of the WC crystal is more preferably 3 μm or less.

  In order to realize high-precision coating, the length of the land on the web traveling direction side of the tip lip and the variation in the slot die width direction of the gap with the web are also important factors. It is desirable to achieve a combination of these two factors, that is, straightness within a range in which the fluctuation range of the gap can be suppressed to some extent. Preferably, the straightness of the tip lip and the backup roll is set so that the fluctuation width of the gap in the slot die width direction is 5 μm or less.

[Application speed]
By achieving the accuracy of the backup roll and the tip lip as described above, the coating method of the present invention has high film thickness stability during high-speed coating. Furthermore, since the coating method of the present invention is a pre-measuring method, it is easy to ensure a stable film thickness even during high-speed coating. The coating method of the present invention can be applied at high speed and with good film thickness stability to a coating solution having a low coating amount such as the antireflection film of the present invention. Although coating is possible with other coating methods, the dip coating method inevitably causes vibration of the coating liquid in the liquid receiving tank, and stepped unevenness is likely to occur. In the reverse roll coating method and the micro gravure method, stepped unevenness is likely to occur due to roll eccentricity and deflection related to coating. Also, in the microgravure method, uneven coating amount tends to occur due to the manufacturing accuracy of the gravure roll and the change of the roll and the blade due to the contact between the blade and the gravure roll. In addition, since these coating methods are post-measuring methods, it is difficult to ensure a stable film thickness. From the viewpoint of productivity, it is preferable to apply at 25 m / min or more by using the production method of the present invention.

(Physical performance of antiglare antireflection film)
The antireflection film according to the present invention preferably has a coefficient of dynamic friction on the surface having the coated outermost layer of 0.25 or less in order to improve physical strength (such as scratch resistance). The coefficient of dynamic friction is such that when a load of 0.98 N is applied to a stainless steel hard sphere having a diameter of 5 mm and the surface having the outermost layer is moved at a speed of 60 cm / min, the surface having the outermost layer and the stainless steel hard sphere having a diameter of 5 mm The coefficient of dynamic friction between Preferably it is 0.17 or less, Most preferably, it is 0.15 or less.
Further, the antireflection film preferably has a contact angle with water of 80 ° or more on the surface having the outermost layer in order to improve the antifouling performance. More preferably, it is 90 ° or more, and particularly preferably 100 ° or more.
Furthermore, the haze of the antireflection film according to the present invention is preferably 0.5 to 60%, more preferably 1 to 50%, and most preferably 1 to 40%.
Furthermore, the reflectance of the antireflection film according to the present invention is preferably as low as possible, preferably 3.0% or less, more preferably 2.5% or less, still more preferably 2.0% or less, and particularly preferably 1.5%. % Or less.

  In order to describe the present invention in detail, examples will be described below, but the present invention is not limited thereto. Unless otherwise specified, “part” and “%” are based on mass.

(Preparation of sol solution a)
In a reactor equipped with a stirrer and a reflux condenser, 120 parts of methyl ethyl ketone, 100 parts of acryloyloxypropyltrimethoxysilane (KBM-5103, manufactured by Shin-Etsu Chemical Co., Ltd.), diisopropoxyaluminum ethyl acetoacetate (Kelope EP- 12, 3 parts of Hope Pharmaceutical Co., Ltd.) were added and mixed, 30 parts of ion-exchanged water was added and reacted at 60 ° C. for 4 hours, and then cooled to room temperature to obtain sol solution a. The mass average molecular weight was 1600, and among the components higher than the oligomer component, the component having a molecular weight of 1000 to 20000 was 100%. Further, from the gas chromatography analysis, the raw material acryloyloxypropyltrimethoxysilane did not remain at all.

(Preparation of sol liquid b)
After cooling to room temperature after the reaction, a sol liquid b was obtained in the same manner as in the sol composition a except that 6 parts of acetylacetone was added.
The present invention will be described in more detail based on examples, but the present invention is not limited thereto.

(Preparation of coating solution A for antiglare hard coat layer)
50 g of a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate (PET-30, manufactured by Nippon Kayaku Co., Ltd.) was diluted with 38.5 g of toluene. Further, 2 g of a polymerization initiator (Irgacure 184, manufactured by Ciba Specialty Chemicals Co., Ltd.) was added and mixed and stirred. The refractive index of the coating film obtained by applying this solution and curing with ultraviolet rays was 1.51.
Further, a 30% toluene dispersion of polystyrene particles having an average particle size of 3.5 μm (refractive index 1.61, SX-350, manufactured by Soken Chemical Co., Ltd.) dispersed in this solution for 20 minutes at 10,000 rpm with a Polytron disperser is 1 13.3 g of 30% toluene dispersion of acrylic styrene particles (refractive index 1.55, manufactured by Soken Chemical Co., Ltd.) having an average particle size of 3.5 μm was added. Finally, a silane coupling agent (KBM- 5103, manufactured by Shin-Etsu Chemical Co., Ltd.) was added to obtain a finished solution.
The mixture solution was filtered through a polypropylene filter having a pore size of 30 μm to prepare a coating solution A for an antiglare hard coat layer.

(Preparation of coating solution B for antiglare hard coat layer)
Commercially available zirconia-containing UV curable hard coat liquid (Desolite Z7404, manufactured by JSR Corporation, solid content concentration of about 61%, ZrO2 average particle size of 20 nm, solid content of ZrO2 content of about 70%, polymerizable monomer, polymerization initiator 285 g), 85 g of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA, manufactured by Nippon Kayaku Co., Ltd.), and further diluted with 60 g of methyl isobutyl ketone and 17 g of methyl ethyl ketone. Furthermore, 28 g of a silane coupling agent (KBM-5103, manufactured by Shin-Etsu Chemical Co., Ltd.) was mixed and stirred. The refractive index of the coating film obtained by applying this solution and curing with ultraviolet rays was 1.61.

Further, a 30% methyl isobutyl ketone dispersion of classified strengthened crosslinked PMMA particles (refractive index: 1.49, MXS-300, manufactured by Soken Chemical Co., Ltd.) having an average particle size of 3.0 μm was added to this solution at 10,000 rpm with a Polytron disperser. 35 g of a dispersion dispersed for 20 minutes was added, and then a 30% methyl ethyl ketone dispersion of silica particles having an average particle diameter of 1.5 μm (refractive index 1.46, Seahosta KE-P150, manufactured by Nippon Shokubai Co., Ltd.) 90 g of a dispersion dispersed at 10,000 rpm for 30 minutes was added to obtain a finished solution.
The mixture solution was filtered through a polypropylene filter having a pore size of 30 μm to prepare a coating solution B for the light diffusion layer.

(Adjustment of coating solution A for low refractive index layer)
Thermally crosslinkable fluorine-containing polymer having a refractive index of 1.42 (JN7228, solid content concentration 6%, manufactured by JSR Corporation) 13 g, colloidal silica dispersion MEK-ST-L (silica, average particle size 45 nm, solid content concentration 30) %, Manufactured by Nissan Chemical Co., Ltd.) and 0.6 g of sol solution a were added, and then methyl ethyl ketone and 0.6 g of cyclohexano were added to adjust the solid content concentration to 2.3 mass%. The ratio of methyl ethyl ketone and cyclohexanone in the coating solution was 94: 6. After stirring, the mixture was filtered through a polypropylene filter having a pore size of 1 μm to prepare a coating solution A for low refractive index layer.

(Preparation of hollow silica dispersion)
Hollow silica fine particle sol (particle size of about 40 to 50 nm, shell thickness of 6 to 8 nm, refractive index of 1.31, solid content concentration of 20%, main solvent isopropyl alcohol, particles according to Preparation Example 4 of JP 2002-79616 A 500 parts with acryloyloxypropyltrimethoxysilane (KBM-5103, manufactured by Shin-Etsu Chemical Co., Ltd.), and diisopropoxyaluminum ethyl acetoacetate (Kerope EP-12, Hope Pharmaceutical ( 9 parts) of ion-exchanged water was added after adding 1.5 parts and mixing. After reacting at 60 ° C. for 8 hours, the mixture was cooled to room temperature, and 1.8 parts of acetylacetone was added. While adding cyclohexanone to 500 g of this dispersion so that the silica content was almost constant, solvent substitution was performed by distillation under reduced pressure at a pressure of 20 kPa. There was no generation of foreign matter in the dispersion, and the viscosity when the solid content concentration was adjusted to 20% by mass with cyclohexanone was 5 mPa · s at 25 ° C. When the residual amount of isopropyl alcohol in the obtained dispersion A-1 was analyzed by gas chromatography, it was 1.5%.

(Preparation of coating solution B for low refractive index layer)
In the preparation of the coating liquid A for the low refractive index layer, the low refractive index layer was prepared in the same manner as the coating liquid A including the addition amount except that 1.95 g of the hollow silica dispersion was used instead of the colloidal silica dispersion. Coating solution B was prepared.

(Preparation of coating solution for low refractive index layer with viscosity modifier)
The solvents of the low refractive index coating liquids A and B were prepared with the solvent types and ratios shown in Table 1.

[Example 1: Preparation and Evaluation of Invention Samples 1 to 13 and Comparative Samples 1 to 5 of Antireflection Film] (1) Application of Functional Layer Application of Antiglare Hard Coat Layer

(Die coater configuration)

The slot die 13 has an upstream lip land length I _UP of 0.5 mm, a downstream lip land length I _LO of 50 μm, a length of the opening of the slot 16 in the web running direction of 150 μm, and a length of the slot 16 of 50 mm. I used something. The gap between the upstream lip land 18a and the web WW is 50 μm longer than the gap between the downstream lip land 18b and the web WW (hereinafter referred to as an overbite length of 50 μm), and the gap between the downstream lip land 18b and the web WW. GL was set to 60 μm. Further, the gap GS between the side plate 40b and the web WW of the decompression chamber 40 and the gap GB between the back plate 40a and the web WW were both set to 200 μm.

(Film preparation method)
An 80 μm-thick triacetyl cellulose film (TD80U: trade name, manufactured by Fuji Photo Film Co., Ltd.) is unwound in a roll form, and the coating solution for the antiglare hard coat layer has a dry film thickness shown in Table 1. It was applied at a coating speed of 25 m / min using the die coater. The degree of vacuum in the vacuum chamber was 0.8 kPa. After solvent drying at 110 ° C. for 10 seconds, 50 ° C. for 20 seconds, and under nitrogen purge (oxygen concentration of 200 ppm or less), UV irradiation (half cure) is performed so that the integrated light amount becomes 55 mJ, photocuring, An antiglare layer was formed and wound up.

(Coating method A for low refractive index layer)
The triacetyl cellulose film provided with the antiglare hard coat layer was unwound again, and the low refractive index layer coating solution was applied at a coating speed of 25 m / min using the die coater. The gap GL between the downstream lip land 18b and the web W was changed to 50 μm, and the degree of vacuum in the vacuum chamber was 0.8 kPa. After drying at 120 ° C. for 70 seconds and further drying at 110 ° C. for 10 minutes and thermosetting, UV irradiation (full cure) is performed under a nitrogen purge (oxygen concentration of 100 ppm or less) so that the integrated light amount becomes 120 mJ. Then, it was photocured to form an antireflection film coated with a low refractive index layer and wound up.
In the above, the coating and drying steps are performed in an air atmosphere with an air cleanliness of 30 particles / (cubic meter) or less as particles of 0.5 μm or more, and the cleanliness described in JP-A-10-309553 is just before the coating. High air was blown at a high speed to separate the deposits from the film surface, and coating was performed while removing dust by a method of sucking with a suction port close to the film. The charged voltage of the base before dust removal was 200 V or less. Said application | coating was performed by each process of sending-out-dust removal-application-dry- (UV or heat) hardening-winding up for every layer.

(Coating method B for low refractive index layer)
An antiglare layer was formed by the same method as the coating method A for the low refractive index layer except that the overbite length was changed to 0 μm.

(Coating method C for low refractive index layer)
An antiglare layer was prepared by the same method as the coating method A for the low refractive index layer except that the coating was performed by bar coating.

(Saponification treatment of antireflection film)
The antireflection film was subjected to the following treatment.
A 1.5 mol / l aqueous sodium hydroxide solution was prepared and kept at 55 ° C. A 0.01 mol / l dilute sulfuric acid aqueous solution was prepared and kept at 35 ° C. The prepared antireflection film was immersed in the aqueous sodium hydroxide solution for 2 minutes, and then immersed in water to sufficiently wash away the aqueous sodium hydroxide solution. Subsequently, after being immersed in the above-mentioned dilute sulfuric acid aqueous solution for 1 minute, it was immersed in water to sufficiently wash away the dilute sulfuric acid aqueous solution. Finally, the sample was thoroughly dried at 120 ° C.
In this manner, saponified antireflection films (present invention samples 1 to 13 and comparative samples 1 to 5) were produced.

(Evaluation of antireflection film)
About these obtained antireflection film samples, the following items were evaluated. The results are shown in Table 1.

(1) Average reflectance Using a spectrophotometer (manufactured by JASCO Corporation), the spectral reflectance at an incident angle of 5 ° was measured in a wavelength region of 380 to 780 nm. For the result, an integrating sphere average reflectance in a wavelength region of 450 to 650 nm was used.

(2) Steel wool scratch resistance evaluation A rubbing test was performed using a rubbing tester under the following conditions.
Evaluation environmental conditions: 25 ° C., 60% RH.
Rub material: Steel wool (manufactured by Nippon Steel Wool Co., Ltd., Gelade No. 0000) was wound around the rubbing tip (1 cm × 1 cm) of a tester that was in contact with the sample, and the band was fixed so as not to move.
Movement distance (one way): 13 cm, rubbing speed: 13 cm / sec, load: 500 g / cm 2, tip contact area: 1 cm × 1 cm, rubbing frequency: 10 reciprocations.

Oily black ink was applied to the back side of the rubbed sample and visually observed with reflected light, and scratches on the rubbed portion were evaluated according to the following criteria.
○: No scratches are visible, or slightly weak scratches are observed when viewed very carefully.
○ △: Weak scratches are visible.
Δ: Moderate scratches are visible.
X: There are scratches that can be seen at first glance.

(3) Viscosity The viscosity was measured with a vibration viscometer (CJV-5000 manufactured by A & D Co., Ltd.) at a liquid temperature of 25 ° C. ± 1 °.
(4) Surface uniformity (visually)
The surface opposite to the coated surface was painted black, and a fluorescent lamp was irradiated from the surface side, and surface irregularities such as coating unevenness and drying unevenness were evaluated by reflection visual inspection.
×: Strong unevenness is visible △: Unevenness is visible ○: Unevenness is visible if you look closely ◎: No unevenness

(5) Planar (Butt, cloudy)
The surface opposite to the coated surface was painted black, irradiated with a fluorescent lamp from the surface side, and the occurrence of foreign matter was evaluated by reflection visual inspection.
×: Conspicuous and cloudy are conspicuous △: Conspicuous and cloudy when viewed closely ○: Conspicuous and opaque are not conspicuous (6) Planar (optical microscope)
The surface state was observed with an optical microscope at a magnification of × 400, and the change in the surface state before and after the addition of the viscosity modifier was evaluated.
×: Significant change (phase separation)
(Triangle | delta): Although it has changed a little, the film | membrane is formed uniformly.
Y: No change

According to the present invention, an antireflection film having excellent surface uniformity and high productivity can be obtained.
Note that the haze value of the sample in which the coating solution for low refractive index of the present invention was applied in a single layer to a thickness of 100 nm was 1% or less.

In the inventive samples 1 to 12, when the diluent solvent used in the antiglare hard coat layer coating solution A is a solvent composition of toluene / cyclohexanone = 85/15 and toluene / cyclohexanone = 70/30 instead of toluene, the ratio of cyclohexanone As the thickness increased, the interfacial adhesion of the support / antiglare hard coat layer was strengthened, and the scratch resistance was improved.
Moreover, in this invention samples 1-12, when the sol liquid b was used instead of the sol liquid a of the organosilane used for the low refractive index layer coating liquid, the temporal stability of the coating liquid was improved, and continuous coating was not performed. The aptitude increased.
Moreover, in this invention samples 1-12, instead of the heat-crosslinkable fluorine-containing polymer used for the coating solution for the low refractive index layer, a heat-crosslinkable fluorine-containing polymer having a refractive index of 1.44 (JTA113, solid content concentration 6%) , Manufactured by JSR Co., Ltd.), the scratch resistance was remarkably improved.
In addition, 80 μm thick triacetyl cellulose film kneaded with 0.23% by mass of 2- (2′hydroxy-3′-t-butyl-5′-methylphenyl) -5-chlorobenzotriazole instead of TD80U Were used to make similar films with similar results.

It is a cross-sectional schematic diagram which shows the layer structure of an anti-glare antireflection film. It is a structural example of the apparatus which performs application | coating of each structural layer of an optical functional film continuously. It is a schematic sectional drawing which shows the coater using a slot die. (A) is a schematic sectional drawing which shows the slot die of this invention. (B) is a schematic sectional view showing a conventional slot die. It is a perspective view which shows the slot die and its peripheral part of an application | coating process. It is a schematic sectional drawing which shows the pressure reduction chamber and web which adjoin. It is a schematic sectional drawing which shows the pressure reduction chamber and web which adjoin.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Antireflection film 2 Transparent support 3 Anti-glare hard coat layer 4 Low refractive index layer 5 Fine particle 10 Coater 11 Backup roll 13 Slot die 14a Bead 14b Coating film 15 Pocket 16 Slot 16a Opening part 17 Tip lip 18 Flat part (land )
18a upstream lip land 18b downstream lip land 30 conventional slot die 31a upstream lip land 31b downstream lip land 32 pocket 33 slot 40 decompression chamber 40a back plate 40b side plate 40c screw
100, 200, 300, 400 Film forming unit
101, 201, 301, 401 Step 102, 202, 302, 402 for applying the coating solution Step 103, 203, 303, 403 for drying the coating solution 110 Step for curing the coating solution 110 Continuous feeding step 120 for the roll-shaped support Continuous body winding process W Web I _UP upstream lip land length I _LO downstream lip land length GL Downstream lip land and web gap GS Side plate and web gap GB Back plate and web gap

Claims (13)

  A transparent film containing a compound polymerizable by irradiation with heat or active energy rays and a solvent, having a refractive index after curing of 1.50 or less, and a haze of 2% or less when a film having a thickness of 100 nm is formed A coating composition containing at least two kinds of solvents, wherein at least one kind of solvent has a viscosity of 1 mPa · s or more, and a solvent having a viscosity of 1 mPa · s or more and another solvent; The surface tension difference of each is 6 dyn / cm or less, The coating composition characterized by the above-mentioned.   The coating composition according to claim 1, wherein the viscosity is 1 mPa · s to 6.5 mPa · s.   The coating composition according to claim 1 or 2, wherein the difference in boiling point between the solvent having a viscosity of 1 mPa · s or more and another solvent is 30 ° C or less.   The coating composition according to any one of claims 1 to 3, wherein the compound polymerizable by irradiation with heat or active energy rays is a fluorine-containing compound.   The coating composition according to claim 1, wherein at least one of the solvents is a ketone solvent.   An optical function having a film thickness of 200 nm or less obtained by applying the coating composition according to any one of claims 1 to 5 on a transparent substrate, removing the solvent by drying, and curing by heat or active energy ray irradiation. layer.   A refractive index is 1.45 or less, The optical function layer of Claim 6 characterized by the above-mentioned.   An antireflection film comprising a hard coat layer containing resin beads on a transparent support, and the optical functional layer according to claim 6 or 7 thereon.   A hard coat layer containing resin beads is formed by dispersing at least one kind of translucent particles having an average particle diameter of 0.5 to 8 μm in the translucent resin, the translucent particles, the translucent resin, The difference in the refractive index is 0.02 to 0.30, and the translucent particles are contained in an amount of 3 to 30% by mass of the total solid content of the light scattering layer. Antireflection film.   Two or more kinds of residual solvents can be detected, the viscosity of at least one kind of solvent is 1 mPa · s or more, and the difference in surface tension between the solvent having the viscosity of 1 mPa · s or more and other solvents is 6 dyn / cm or less. An antireflective film characterized by being   The land of the tip lip of the slot die is brought close to the surface of the web supported continuously by the backup roll, and the coating composition is applied from the slot of the tip lip, followed by solvent drying and ionizing radiation as necessary. The method for producing an optical functional layer according to claim 6, wherein the optical functional layer is cured by heat.   When a slot die having a land length in a web traveling direction of a tip lip on the web traveling direction side of the slot die is set to 30 μm or more and 100 μm or less and the slot die is set at a coating position, what is the traveling direction of the web? The gap between the tip lip on the opposite side and the web is applied using a coating apparatus installed so that the gap between the tip lip on the web traveling direction side and the web is larger by 30 μm or more and 120 μm or less. Item 12. A method for producing an optical functional layer according to Item 11.   The method for producing an optical functional layer according to claim 11 or 12, wherein the web conveyance speed during coating is 20 m / min or more.

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