JP2006184493A - Optical functional film and its manufacturing method, and polarizing plate and image display device using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an optical functional film which is excellent in optical performance such as an antiglare property and a light diffusion effect and which has a satisfactory coating surface shape and further to provide a polarizing plate and an image display device subjected to antiglaring treatment and light diffusion treatment by using the optical functional film. <P>SOLUTION: The optical functional film has at least one optical functional layer (A) containing resin particles of 1 to 8μm average grain size and a binder matrix on a transparent supporting body. The optical functional layer (A) is formed by a method of applying a coating solution comprising the resin particles of 1 to 8μm average grain size, a matrix forming binder and an organic solvent onto the transparent supporting body. Amount of the resin particles precipitated after the coating solution is left standing at 25°C for 24 hours is ≤30 mass% to total amount of the resin particles in the coating solution and a gel fraction of the resin particle is 70 to 95 mass%. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to an optical functional film and a method for producing the same, and a polarizing plate and an image display device using the optical functional film.

  In recent years, liquid crystal display devices (LCDs) have been increased in screen size, and liquid crystal display devices provided with optical functional films are increasing. For example, antireflection films, which are one type of optical functional film, are various image display devices such as liquid crystal display devices (LCD), plasma display panels (PDP), electroluminescence displays (ELD), and cathode ray tube display devices (CRT). In order to prevent a decrease in contrast due to reflection of external light or reflection of an image, it is arranged on the surface of the display.

  An optical functional layer may be installed as one means for imparting antireflection ability to the antireflection film. By containing fine particles in this layer, antiglare property can be exhibited as one of the effects. The antiglare property greatly depends on the surface shape of the antireflection film, and the fine particles contained in the optical functional layer increase the surface unevenness, thereby scattering the reflected light and reducing the reflection of the image.

  In the process of producing such an antireflection film, the resin particles contained in the optical functional layer settle in the liquid feeding system in the vicinity of the coating part during coating, and the amount of coated particles varies and is prevented. There was a problem that dazzling was reduced or a surface failure was caused by sedimentation aggregates. Moreover, in order to avoid these, if the frequency of cleaning in a liquid feeding system is increased, manufacturing cost will increase and it has been a big subject from before.

  As a technology related to this, a technology for containing a thixotropic agent in a light diffusion layer has been proposed (Patent Document 1), but it is difficult to achieve both anti-glare properties and a good coated surface, and a better countermeasure. Was desired.

  On the other hand, in a liquid crystal display device, a polarizing plate is an indispensable optical material, and generally has a structure in which a polarizing film is protected by two protective films. If these protective films can be provided with an antiglare function, a light diffusing effect, and other optical functions, a significant cost reduction and a thin display device can be achieved.

The protective film used for the polarizing plate needs to have sufficient adhesion to be bonded to the polarizing film. As a technique for improving the adhesion to the polarizing film, it is common practice to saponify the protective film and hydrophilize the surface of the protective film.
JP 2000-56104 A

  An object of the present invention is to stably provide an optical functional film excellent in antiglare property, light diffusion effect and other optical performances, and having a good coated surface. Another object of the present invention is to provide a polarizing plate and an image display device that have been subjected to an antiglare treatment or a light diffusion treatment using such an optical functional film.

  The above problems have been achieved by an optical functional film, a polarizing plate, and an image display device having the following configuration.

<1> On an optical functional film having at least one optical functional layer (A) containing resin particles having an average particle diameter of 1 to 8 μm and a binder matrix on a transparent support,
The optical functional layer (A) is a layer formed by a method of applying a coating liquid containing resin particles having an average particle diameter of 1 to 8 μm, a matrix-forming binder and an organic solvent on a transparent support, The amount of resin particles that settle after the coating solution is allowed to stand at 25 ° C. for 24 hours is 30% by mass or less with respect to the total amount of resin particles in the coating solution, and the gel fraction of the resin particles is 70 to 70%. An optical functional film, characterized by being 95% by mass.
<2> The above <1, wherein the resin particles are crosslinked with a bifunctional or higher functional crosslinkable monomer, and the content of the crosslinkable monomer is 2 to 10 mol% with respect to the total monomers for forming the resin particles. > Optical functional film.
<3> The optical functional film according to <1> or <2>, wherein the difference between the density of the organic solvent contained in the coating liquid and the density of the resin particles is 0.20 g / cm ³ or less.
<4> The difference between the I / O value of the organic solvent contained in the coating liquid and the I / O value of the resin particles is 0.4 or less, and the I / O value of the organic solvent is greater than 0 <1 >-<3> The optical function film in any one of.
<5> The refractive index of the binder matrix is 1.45 to 1.90, and the refractive index difference between the binder matrix and the resin particles is 0 to 0.30. Optical function film.
<6> The film thickness of the optical functional layer (A) is 3 to 10 μm, and the average particle diameter of the resin particles contained in the optical functional layer (A) is equal to the film thickness of the optical functional layer (A). The optical functional film according to any one of <1> to <5>, in a range of 30 to 100%.
<7> The optical functional layer (A) or an optical functional layer (B) other than the optical functional layer (A) and the optical functional layer (A) is provided on the transparent support, and any one of the layers has the following general properties. Optical function film in any one of said <1>-<6> containing the organosilane compound represented by Formula (1), and its derivative (s).
Formula _{^{(1) :( R 10) s}} -Si (Z) 4-s
(In the formula, R ¹⁰ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. Z represents a hydroxyl group or a hydrolyzable group. S represents an integer of 1 to 3)
<8> The optical functional layer (B) is a low refractive index layer, and the low refractive index layer is formed by a crosslinking reaction or a polymerization reaction of a fluorine-containing compound represented by the following general formula (2). The optical functional film according to any one of <1> to <7>.
General formula (2):

(In the formula, L ²¹ represents a linking group having 1 to 10 carbon atoms, m1 represents 0 or 1, X represents a hydrogen atom or a methyl group, A represents a polymerization unit of any vinyl monomer, and It may be a polymer unit or may be composed of a plurality of polymer units, where x, y and z represent the mol% of each constituent polymer unit, 30 ≦ x ≦ 60, 5 ≦ y ≦ 70, 0 ≦ z. Represents a value satisfying ≦ 65.)
<9> The optical functional film according to <8>, wherein the low refractive index layer further contains hollow silica fine particles.
<10> The optical functional layer (A) according to any one of the above <1> to <9> or the optical functional layer (B) according to any one of the above <7> to <9>, wherein the coating liquid is die-coated. A method for producing an optical functional film, wherein the optical functional film is formed by coating by a method.
<11> A coating liquid for forming an optical functional layer containing resin particles having an average particle diameter of 1 to 8 μm, a matrix-forming binder and an organic solvent, wherein the resin particles form all of the resin particles. It is formed by crosslinking with a bifunctional or higher monomer blended at a ratio of 2 to 10 mol% with respect to the monomer, and the amount of resin particles settled on the bottom after the coating solution is allowed to stand for 24 hours. A coating solution for forming an optical functional layer, wherein the coating amount is 30% by mass or less with respect to the total amount of resin in the solution, and the gel fraction of resin particles is 70% by mass to 95% by mass.
<12> The optical functional film according to any one of <1> to <9> or the optical functional film produced by the method according to <10> is at least one of two protective films of a polarizing film. A polarizing plate characterized by being used in the above.
<13> The optical functional film according to any one of <1> to <9>, the optical functional film produced by the method according to <10>, or the polarizing plate according to <12>. An image display device arranged on a display surface.
<14> The image display device according to <13>, wherein the image display device is a TN, STN, IPS, VA, or OCB mode transmissive, reflective, or transflective liquid crystal display device.

  The optical functional film of the present invention is excellent in antiglare property, light diffusing effect and other optical performances, has a good coated surface shape, and can be provided stably. The polarizing plate and the image display device of the present invention in which the antiglare treatment and the light diffusion treatment are performed using such an optical functional film can obtain a high quality image excellent in visibility.

  In this specification, when a numerical value represents a physical property value, a characteristic value, or the like, the description “(numerical value I) to (numerical value II)” means “(numerical value I) to (numerical value II)”. The description “(meth) acryloyl” means “at least one of acryloyl and methacryloyl”. The same applies to “(meth) acrylate”, “(meth) acrylic acid” and the like.

Hereinafter, the present invention will be described in more detail.
The optical functional film of the present invention is an optical functional film having at least one optical functional layer (A) containing a resin particle having an average particle diameter of 1 to 8 μm and a binder matrix, and the optical functional layer (A) is It is a layer formed by a method in which a coating liquid containing resin particles having an average particle diameter of 1 to 8 μm, a matrix-forming binder and an organic solvent is coated on a transparent support, and the coating liquid is heated at 25 ° C. for 24 hours. The amount of resin particles that settle after standing is 30% by mass or less based on the total amount of resin particles in the coating solution.

<Optical function film>
[Optical function layer (A)]
The optical functional layer (A) according to the present invention is a layer that affects optical performance, and is a method of applying a coating liquid containing resin particles having an average particle diameter of 1 to 8 μm, a binder for forming a matrix, and an organic solvent. All of the optical functional layers formed and thereby including the resin particles in the optical functional layer are included. Examples of such an optical functional layer (A) include a high refractive index layer, an antiglare layer, an antiglare antireflection layer, a light diffusion layer, and an optically anisotropic layer. Moreover, the anti-glare hard coat layer which gave the anti-glare property to the hard-coat layer mentioned later is also contained in an optical function layer (A).

  The optical functional layer (A) is, for example, a translucent polymer formed by curing monomers with ionizing radiation or the like as a main matrix-forming binder, and the translucent resin particles having the above specific particle diameter in the binder, preferably It is formed containing a polymer compound, and if necessary, an additive for increasing the film strength and an inorganic fine particle filler for adjusting the refractive index.

  The thickness of the optical functional layer (A) is usually about 0.5 to 30 μm, preferably 1 to 15 μm, and more preferably 3 to 10 μm. When the thickness is within this range, there are no defects such as curl, haze value, and high cost, and the adjustment of antiglare property and light diffusion effect is easy.

In the optical functional layer (A) according to the present invention, the difference between the density of the organic solvent contained in the coating liquid for forming the optical functional layer and the density of the resin particles is generally 0.30 g / cm ³ or less. Preferably, it is formed of a coating solution using a solvent of 0.20 g / cm ³ or less, more preferably 0.10 g / cm ³ or less.
The density of the resin particles here refers to the density in a non-swelled state. When the resin particles are formed of a plurality of monomers, the density of the homopolymer of each monomer is used, and the value obtained by weighted averaging according to the monomer composition of the resin particles is used as the resin particle density. Moreover, when using multiple types of organic solvents, the weighted average value according to the solvent composition is used.
If the density difference between the density of the organic solvent and the density of the resin particles is not more than the above upper limit value, the particle sedimentation speed or the particle floating speed becomes too fast, which causes a problem such as a process trouble.

  Furthermore, in the optical functional layer (A) according to the present invention, the difference between the I / O value of the resin particles contained in the coating liquid for forming the layer and the I / O value of the organic solvent is generally 0. From the viewpoint of dispersion stability of the particles, it is preferably 5 or less, preferably 0.4 or less, more preferably 0.3 or less, and the I / O value of the organic solvent is more than 0.

The I / O value was determined by the method described in Satoshi Fujita “Organicity: Organic Concept by Inorganic Value”, Yoshio Koda “Organic Conceptual Diagram” Sankyo Publishing (1984), etc. ) / Organic (O) ”value. The I / O value is used as a means for predicting various physicochemical properties of organic compounds. Organicity can be obtained by comparing the number of carbons, and inorganicity can be obtained by comparing the boiling points of hydrocarbons having the same number of carbons. For example, one (—CH ₂ —) (actually C) is determined to have an organic value of 20, and the inorganic property is determined to have an inorganic value of 100 from the influence of hydroxyl groups (—OH) on the boiling point. . What calculated | required the value of the other substituent (inorganic group) on the basis of the inorganic value 100 of this (-OH) is shown as "inorganic group table".

  In the case of copolymer resin particles, the I / O value of the resin particles was obtained by multiplying the molar ratio of each composition by the respective I / O values and adding them to average the I / O values of the entire particles. Similarly, when a plurality of organic solvents were mixed, the I / O values of the whole solvent were averaged according to each molar ratio.

[Main binder]
The main matrix-forming binder for forming the optical functional layer (A) (hereinafter also simply referred to as a binder) is a light-transmitting polymer having a saturated hydrocarbon chain or a polyether chain as the main chain after curing with ionizing radiation or the like. The polymer having a saturated hydrocarbon chain as the main chain is more preferable. 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 at least one selected from an aromatic ring, a halogen atom other than fluorine, a sulfur atom, a phosphorus atom, and a nitrogen atom.

As the monomer having two or more ethylenically unsaturated groups used in the binder polymer for forming the optical functional layer (A), an ester of a polyhydric alcohol and (meth) acrylic acid {for example, ethylene glycol diester (Meth) acrylate, 1,4-cyclohexanediacrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, dipentaerythritol Tetra (meta)
Acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, pentaerythritol hexa (meth) acrylate, 1,2,3-chlorohexane tetramethacrylate, polyurethane polyacrylate, polyester polyacrylate}, vinylbenzene And derivatives thereof (eg, 1,4-divinylbenzene, 4-vinylbenzoic acid-2-acryloylethyl ester, 1,4-divinylcyclohexanone), vinyl sulfone (eg, divinyl sulfone), (meth) acrylamide (eg, methylene) Bisacrylamide) and the like.

  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 photoradical polymerization initiator or a thermal radical polymerization initiator. Accordingly, a coating liquid containing a monomer having an ethylenically unsaturated group, a photo radical polymerization initiator or a thermal radical polymerization initiator, and resin particles, and if necessary, an inorganic filler, and other additives is prepared, and the coating liquid Is coated on a transparent support and then cured by a polymerization reaction with ionizing radiation or heat to form an optical functional 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 2.00, more preferably 1.45 to 1.90, still more preferably 1.48 to 1.85, and particularly preferably as the whole matrix. Is 1.51-1.80. The refractive index of the binder is a value measured by removing resin particles from the component of the optical functional layer (A).

  The binder of the optical functional layer (A) is preferably added in a range of 20 to 95% by mass with respect to the solid content of the coating solution of the layer.

  As radical photopolymerization initiators, acetophenones, benzoins, benzophenones, phosphine oxides, ketals, anthraquinones, thioxanthones, azo compounds, peroxides, 2,3-alkyldione compounds, disulfide compounds And 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 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 also described in “Latest UV Curing Technology” (p.159, publisher: Kazuhiro Takasato, publisher; Technical Information Association, Inc., published in 1991), which is useful for the present invention.
Preferable examples of commercially available photocleavable photoradical polymerization initiators include “Irgacure (651, 184, 907)” manufactured by Ciba Specialty Chemicals.

  The radical photopolymerization initiator is preferably used in the range of 0.1 to 15 parts by mass, more preferably in the range of 1 to 10 parts by mass with respect to 100 parts by mass of the polyfunctional monomer.

  In addition to the photo radical polymerization initiator, a photo sensitizer may be used. Specific examples of the photosensitizer include n-butylamine, triethylamine, tri-n-butylphosphine, Michler's ketone and thioxanthone.

  As the thermal radical polymerization 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 2,2′-azobis (isobutyronitrile), 2,2′-azobis (propionitrile), 1,1′-azobis (cyclohexanecarbonitrile) as azo compounds such as ammonium sulfate and potassium persulfate 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.
Accordingly, a coating liquid containing a polyfunctional epoxy compound, a photoacid generator or a thermal acid generator, resin particles, and inorganic fillers as necessary is prepared, and the coating liquid is applied on a transparent support and then ionizing radiation. Alternatively, it can be cured by a polymerization reaction with heat to form an optical functional 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 this crosslinkable functional group reacts. A crosslinked structure may be introduced into the binder polymer.

Examples of the crosslinkable functional group include an isocyanate group, an epoxy group, an aziridine group, an oxazoline group, an aldehyde group, a carbonyl group, a hydrazine group, a carboxyl group, a methylol group, and an active methylene group. In addition, vinylsulfonic acid, acid anhydride, cyanoacrylate derivative, melamine, etherified methylol, ester, urethane, and metal alkoxide such as tetramethoxysilane can also be used as a monomer 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 be immediately reactive but may be reactive as a result of decomposition.
These binder polymers having a crosslinkable functional group can form a crosslinked structure by heating after coating.

  The optical functional layer (A) according to the present invention may contain a polymer compound. By adding a polymer compound, the viscosity adjustment of the coating solution related to the dispersion stability (cohesiveness) of the resin particles can be performed more preferentially. Furthermore, the polarity of the solidified product during the drying process can be controlled. It is preferable because the aggregation behavior of the resin particles can be changed and drying unevenness in the drying process can be reduced.

  The polymer compound has already formed a polymer when added to the coating solution. Examples of the polymer compound include cellulose esters (for example, cellulose triacetate, cellulose diacetate, cellulose propionate, cellulose acetate Pionate, cellulose acetate butyrate, cellulose nitrate, etc.), urethane acrylates, polyester acrylates, (meth) acrylic acid esters (for example, methyl methacrylate / (meth) methyl acrylate copolymer, methyl methacrylate / (Meth) ethyl acrylate copolymer, methyl methacrylate / (meth) butyl acrylate copolymer, methyl methacrylate / styrene copolymer, methyl methacrylate / (meth) acrylic acid copolymer, polymethyl methacrylate Etc.), poly Resins such as styrene are preferably used.

  The polymer compound is preferably 3% by mass to 40% by mass, more preferably based on the total binder contained in the layer containing the polymer compound, from the viewpoint of expressing the effect of increasing the viscosity of the coating liquid and maintaining the film strength of the containing layer. Is preferably contained in the range of 5% by mass to 30% by mass, more preferably 8% by mass to 25% by mass. If the content rate is equal to or higher than the lower limit value, the effect of increasing the viscosity of the coating solution is exhibited. If the content rate is equal to or lower than the upper limit value, problems such as a decrease in film strength of the content layer do not occur.

  Further, the molecular weight of the polymer compound is preferably from 30,000 to 400,000 in terms of mass average, more preferably from 50,000 to 300,000, and even more preferably from 50,000 to 200,000. When the molecular weight is within this range, the effect of increasing the viscosity of the coating composition is sufficiently exhibited, the dissolution time is short, and there are few insolubles.

  The optical functional layer (A) is preferably formed by applying the coating solution to a support, and then carrying out light irradiation, electron beam irradiation, heat treatment or the like to cause crosslinking or 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, etc. can be used.

  Curing with ultraviolet rays is preferably performed by nitrogen purge or the like with an oxygen concentration of 4% by volume or less, more preferably 2% by volume or less, and most preferably 0.5% by volume or less.

[Resin particles]
The optical functional layer (A) contains resin particles having a particle size larger than that of the fine inorganic filler particles described later and having an average particle size of 1 to 8 μm, preferably 1.5 to 6 μm. 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 and the black-and-white reversal occurs even if the viewing angle changes. Or, it is used for the purpose of making the hue change less likely to occur. When the average particle size is within the above range, an antiglare effect is easily exhibited and a rough feeling does not occur.

  The refractive index difference between the resin particles and the translucent resin as the binder is 0 to 0.30 from the viewpoint that the film does not become cloudy and obtains a light diffusion effect depending on the type of the optical functional layer. , 0. It is especially preferable that it is -0.20.

  A preferable range of the addition amount of the resin particles to the translucent resin is determined from the same viewpoint as described above. The preferable content rate of the resin particle in an optical function layer (A) is 3-40 mass% in the total solid of an optical function layer (A), and it is especially preferable that it is 5-25 mass%.

The application amount of the resin particles is preferably 10 mg / m ^{2 to} 10000 mg / m ² , more preferably 50 mg / m ^{2 to} 4000 mg / m ² in consideration of the amount of particles contained in the optical functional layer (A) to be formed. m ^2, and most preferably in the range of ^{100mg / m 2 ~1500mg / m 2} .

  Regarding the relationship between the particle diameter of the resin particles and the film thickness of the optical functional layer (A) containing the resin particles, the average particle diameter of the resin particles is generally 20 to 110% of the film thickness of the optical functional layer (A). However, it is preferable that it is 30 to 100%, and 35 to 80% is further more 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 resin particles may be used in combination of two or more different resin particles. When two or more types of resin particles are used, in order to effectively exert the refractive index control by mixing a plurality of types of particles, the resin particles having the highest refractive index and the resin particles having the lowest refractive index are used. The difference in refractive index is preferably 0.02 or more and 0.10 or less, and particularly preferably 0.03 or more and 0.07 or less. Further, the antiglare property may be imparted with resin particles having a large particle size, and another optical characteristic may be imparted with resin particles having a small particle size. For example, it is possible to improve unevenness in luminance due to unevenness (contributing to antiglare property) on the film surface called glare, which is particularly problematic in an antireflection film for high-definition displays of 133 ppi or higher.

  The optical functional layer (A) according to the present invention is formed by applying a coating liquid containing the resin particles on a transparent support. It is required that the resin particles contained in the coating solution are difficult to settle in the liquid feeding system and the coater during coating.

  The coating solution of the optical function layer (A) is the total amount of resin particles in the coating solution after the coating solution is allowed to stand at 25 ° C. without stirring for 24 hours and settled on the bottom of the storage container. It is necessary that it is 30 mass% or less with respect to 15 mass% or less. When the amount of precipitated resin particles is within the above range, a good coated surface-like optical functional layer (A) can be obtained. This eliminates the need for a great improvement on the apparatus for improving the coated surface state, thereby reducing the cost.

The standing evaluation of the coating solution for 24 hours may be performed whenever the resin particles are uniformly dispersed after the preparation of the coating solution is completed. Even after the resin particles once settled to the bottom by storage, if the particles are uniformly redispersed in the coating solution by stirring, the resin particles can be used for evaluation of sedimentation properties.
The evaluation of sedimentation can be easily performed, for example, by the following method.

(Evaluation of sedimentation)
In a 50 mL transparent glass bottle with a sealed stopper, 30 g of a coating solution containing a known amount of resin particles is accurately weighed and sealed, and then left in a thermostatic bath at 25 ° C. for 24 hours. After a lapse of time, the supernatant of the coating solution is emptied into another container by very careful decantation. The end point of the supernatant liquid separation is the time when some of the settled resin particles begin to be mixed into the supernatant liquid of another container. Thereafter, the washing step of the precipitated resin particles with a small amount of acetone is allowed to stand, and the acetone washing step of waiting for separation into a supernatant and precipitated resin particles and discarding the supernatant is repeated three times in total. Thereafter, the remaining resin particles are dried and weighed to determine the ratio of the amount of precipitated resin particles to the total amount of resin particles contained in a known 30 g coating solution before standing.

  Further, the so-called apparent density including the particle swelling of the resin particles in the coating liquid of the optical functional layer (A) is required to be as close as possible to the density of the coating solvent, and the preferable true density of the resin particles and the coating liquid solvent. The difference is as described above.

The crosslinking rate of the resin particles is preferably as low as possible within a range in which the particles can maintain resistance to dissolution. The crosslinking rate of the resin particles according to the present invention can be based on the content of the crosslinkable monomer with respect to the total monomers that contribute to particle formation. The content of the crosslinkable monomer is 2 to 10 mol%, preferably 2 to 8 mol%, more preferably 3 to 7 mol%, to prevent particle dissolution resistance and prevent particle settling in the coating solution. It is preferable from the viewpoint of compatibility.

Further, the gel fraction of the resin particles according to the present invention needs to be 70 to 95% by mass, and preferably 80 to 92% by mass. When the gel fraction of the resin particles is within the above range, the surface unevenness after coating and curing is sufficient, and the particles in the coating solution are difficult to settle.
The gel fraction described here was determined by the following method.

(Measurement of gel fraction)
After a certain amount of particle powder is heated and stirred in methyl ethyl ketone for a certain period of time, the particles are separated by a filtration method, and the liquid after filtration is dried to obtain the residue mass. From this value, methyl ethyl ketone is obtained with respect to the original mass. Calculate the ratio of the solid content that remains without eluting.

  Specific examples of the resin particles according to the present invention include, for example, crosslinked polymethyl methacrylate particles, crosslinked methyl methacrylate-styrene copolymer particles, crosslinked polystyrene particles, crosslinked methyl methacrylate-methyl acrylate copolymer particles, and crosslinked acrylate-styrene. Resin particles such as copolymer particle particles are preferred. Of these, crosslinked styrene particles, crosslinked polymethyl methacrylate particles, crosslinked methyl methacrylate-styrene copolymer particles, and the like are preferable.

  As a crosslinkable monomer, for example, divinylbenzene, ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, etc. A monomer having a polymerizable group is preferably used.

  The method for producing the resin particles according to the present invention may be produced by any method such as suspension polymerization, emulsion polymerization, soap-free emulsion polymerization, dispersion polymerization, and seed polymerization. These production methods are described in, for example, “Experimental Methods for Polymer Synthesis” (Takayuki Otsu and Masaaki Kinoshita, Chemical Dojinsha), pages 130 and 146 to 147, “Synthetic Polymers”, Vol. 246-290, 3rd volume, p. 1 to 108, etc., and Japanese Patent Nos. 2543503, 3508304, 2746275, 3521560, 3580320, and Japanese Patent Laid-Open No. 10-1561. Reference can be made to methods described in JP-A No. 7-2908, JP-A No. 5-297506, JP-A No. 2002-145919, and the like.

For example, in emulsion polymerization and suspension polymerization, a method in which a monomer is refined in an aqueous medium and polymerized is an example. As dispersion-stabilizing surfactants, anionic surfactants such as dodecylbenzenesulfonate, dodecylsulfate, laurylsulfate, dialkylsulfosuccinate; nonionics such as polyoxyethylene nonylphenyl ether and polyethylene glycol monostearate Surfactant etc. can be mentioned. Further, examples of the dispersion stabilizer include polymers and oligomers such as polyvinyl alcohol, sodium polyacrylate, hydrolyzate of styrene-maleic anhydride copolymer, sodium alginate, and a water-soluble cellulose derivative. In addition, in a method of performing an addition polymerization reaction initiated with an oil-soluble polymerization initiator using water as a dispersion medium in the presence of inorganic salts and / or dispersion stabilizers, examples of water-soluble salts include sodium chloride, potassium chloride, and calcium chloride. Magnesium sulfate or the like can also be used. Examples of the polymerization initiator include azobis compounds {azobisisobutyronitrile, azobis (cyclohexane-1-carbonitrile)}, peroxides (benzoyl peroxide, t-butyl peroxide, etc.) and the like.
Furthermore, a so-called multi-stage polymerization method is also preferred, in which a micropolymer is prepared in advance and the particles are impregnated to thicken the particles.

  As the shape of the resin particles, either a true sphere or an indefinite shape can be used. The particle size distribution is preferably monodisperse particles because of the haze value, controllability of 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.

[Inorganic filler]
The optical functional layer (A) has an oxide of at least one metal selected from titanium, zirconium, aluminum, indium, zinc, tin, and antimony in addition to the above particles in order to increase the refractive index of the layer. It is also preferable to contain a fine inorganic filler having an average particle size of primary particles of generally 0.2 μm or less, preferably 0.1 μm or less, more preferably 0.06 μm or less.

  Conversely, in the optical functional layer (A) using resin particles having a high refractive index, it is also preferable to lower the refractive index of the binder in order to increase the refractive index difference from the particles. For this purpose, silica fine particles, hollow silica fine particles and the like can be used as the inorganic filler. The preferred particle size is the same as that of the above high refractive index fine inorganic filler.

Specific examples of the fine inorganic filler used for the optical functional layer (A) include TiO ₂ , ZrO ₂ , Al ₂ O ₃ , In ₂ O ₃ , ZnO, SnO ₂ , Sb ₂ O ₃ , ITO (doped with Sn Indium oxide), SiO _{2 and the} like. 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% by mass, more preferably 20 to 80% by mass, and particularly preferably 30 to 75% by mass with respect to the total mass of the optical functional layer (A). It is.

  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.

[Organosilane compound]
Next, an organosilane compound that can be particularly preferably used for each layer of the optical functional film according to the present invention, particularly the optical functional layer (A) will be described.
From the viewpoint 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, in the present invention, at least one of the optical functional layers on the transparent support is treated with organo It is preferable to add at least one compound selected from silane compounds and derivatives thereof.

As the organosilane compound and derivatives thereof, compounds represented by the following general formula (1) 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, a polymerizable acyloxy group {( Meth) acryloyl, etc.}, an organosilane compound containing a polymerizable acylamino group (acrylamino, methacrylamino, etc.).
Formula _{^{(1) :( R 10) s}} -Si (Z) 4-s

In general formula (1), 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, s-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 (preferably an alkoxy group having 1 to 5 carbon atoms, such as 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 (for example, CH ₃ COO, C ₂ H ₅ COO, etc.) is preferable, an alkoxy group is preferable, and a methoxy group or ethoxy is particularly preferable. It is a group.
s represents an integer of 1 to 3. 1 or 2 is preferable, and 1 is particularly preferable.
When R ¹⁰ or Z is presence of a plurality, the plurality of R ¹⁰ or Z may be different from each other.

The substituent contained in R ¹⁰ is not particularly limited, but is 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 (methylthio, ethylthio, etc.), arylthio groups (phenylthio, etc.), alkenyl groups (vinyl, 1-propenyl, etc.), alkoxysilyl groups (trimethoxysilyl, triethoxysilyl, etc.), acyloxy groups (acetoxy, Acryloyloxy, methacryloyloxy, etc.), alkoxyca Bonyl 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 of them is preferably a substituted alkyl group or a substituted aryl group. Among the organosilane compounds represented by the general formula (1) and derivatives thereof, at least one selected from the organosilane compounds having a vinyl polymerizable substituent represented by the following general formula (1-1) and derivatives thereof Certain compounds are preferred.
General formula (1-1):

In General Formula (1-1), 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 preferable, a hydrogen atom, a methyl group, a methoxycarbonyl group, a fluorine atom, and a chlorine atom are more preferable, and a hydrogen atom and a methyl group Is particularly preferred.

L ¹¹ represents a single bond, * -COO-**, * -CONH-**, * -O-**, or * -NH-CO-NH-**, 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 ¹² .

L ¹² 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, an alkylene group having a linking group therein is preferred, an unsubstituted alkylene group, 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 in formula (1), 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 is synonymous with General formula (1), A halogen atom, a hydroxyl group, and an unsubstituted alkoxy group are preferable, A chlorine atom, a hydroxyl group, and an unsubstituted C1-C6 alkoxy group are more preferable, A hydroxyl group and carbon number 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 of the compounds represented by general formula (1), general formula (1-1), and derivatives thereof may be used in combination.
Although the specific example of the organosilane compound represented by General formula (1) and General formula (1-1) 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 derivatives of the organosilane compound represented by the general formula (1) and the general formula (1-1) are those of the organosilane compound represented by the general formula (1) and the general formula (1-1). It means hydrolyzate, partial condensate and the like. 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. Of 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 of 3.0 or less in hydrochloric acid, sulfuric acid, or water. 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 hydrolysis / condensation reaction of the organosilane can be carried out without a solvent or in a solvent, but it is preferable to use an organic solvent in order to mix the components uniformly. For example, alcohols, aromatic hydrocarbons, ethers , Ketones, esters and the like are preferred.

  Among these, as alcohols, a monohydric alcohol or a dihydric alcohol can be mentioned, for example, As a monohydric alcohol, 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, t-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 also be used individually by 1 type or in mixture of 2 or more types. The concentration of the solid content in the reaction is not particularly limited, but is usually in the range of 1 to 90% by mass, and preferably in the range of 20 to 70% by mass.

  Hydrolysis of the organosilane compound is carried out by adding 0.3 to 2 mol, preferably 0.5 to 1 mol of water to 1 mol of the hydrolyzable group of the organosilane compound in the presence or absence of the above solvent. It is carried out by stirring at 25-100 ° C. in the presence and in the presence of a catalyst.

(Metal chelate compound)
The hydrolysis of the organosilane compound in the present invention is carried out by using an alcohol represented by the 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 ( In the formula, R ¹⁴ represents an alkyl group having 1 to 10 carbon atoms, and R ¹⁵ represents an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms). It is preferable to carry out by stirring at 25 to 100 ° C. in the presence of at least one metal chelate compound having a metal selected from Zr, Ti and Al as a central metal.

  The metal chelate compound can be suitably used without particular limitation as long as it has the above configuration. 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, s −
A butyl group, a t-butyl group, an n-pentyl group, a 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, s-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 (acetylacetonato) 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. The condensation reaction rate and the durability of the coating film are preferred.

  The coating liquid used for forming each layer of the optical functional film according to the present invention, particularly the optical functional layer (A), is at least one selected from the above organosilane compounds and derivatives thereof (hydrolysates, partial condensates). It is preferable to add a β-diketone compound and / or a β-ketoester compound together with a seed compound and a metal chelate compound added as necessary.

The above β-diketone compound and β-ketoester compound are represented by the general formula R ¹⁴ COCH ₂ COR ¹⁵ , and at least one of them is preferably used in the present invention. It 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- s-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-methylhexane-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 resulting composition has storage stability. improves.

  The addition amount of at least one compound selected from the organosilane compound 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.

  The organosilane compound can be preferably used in the optical functional layer (A) described above, but in addition, the optical functional layer (B) described below, for example, a low refractive index layer, an outermost layer, a layer other than the optical functional layer, For example, it can be suitably used for an antistatic layer or a hard coat layer.

[Optical function layer (B)]
The optical functional film of the present invention can have an optical functional layer (B) other than the optical functional layer (A) as necessary together with the optical functional layer (A) described above.
As a suitable aspect of the optical function layer (B) in this invention, a low refractive index layer can be mentioned, for example.

[Low refractive index layer]
The low refractive index layer preferably contains a fluorine-containing compound, and it is particularly preferable to construct a low refractive index layer mainly composed of the fluorine-containing compound. The low refractive index layer mainly composed of a fluorine-containing compound is usually positioned as the outermost layer of an antireflection film which is a preferred embodiment of the optical functional film, and also has a function as an antifouling layer. Here, “mainly comprising 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 Further, it is preferably 50% by mass or more, more preferably 60% by mass or more, based on the total mass of the low refractive index layer.

  The fluorine-containing compound of the low refractive index layer is preferably formed by a crosslinking reaction or polymerization reaction of a fluorine-containing compound having a crosslinkable or polymerizable functional group by heating or ionizing radiation curing. The fluorine-containing compound may be a commercially available product and is not particularly limited, but a preferable composition is described below.

(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 (e.g., 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.

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 the ethylenically unsaturated monomer containing no fluorine atom include olefin, acrylic ester, methacrylic ester, styrene and derivatives thereof, vinyl ether, vinyl ester, acrylamide, N-cyclohexyl acrylamide, etc.), methacrylamide and acrylonitrile.

  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 of 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.

  A fluorine-containing compound having a crosslinkable or polymerizable functional group is 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. Can do. 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. Furthermore, you may have groups, such as hydroxy, amino, and sulfo. Commercial products may be used for these compounds.

  The fluorine-containing compound of 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.

  Examples of the fluorine-containing vinyl monomer include fluoroolefins (for example, fluoroethylene, vinylidene fluoride, tetrafluoroethylene, hexafluoroethylene, hexafluoropropylene, etc.), a part of (meth) acrylic acid or fully fluorinated alkyl ester derivatives {for example, “ Biscoat 6FM "(trade name), manufactured by Osaka Organic Chemical Industry Co., Ltd.}," M-2020 "(trade name) manufactured by Daikin Industries, Ltd., etc.}, complete or partially fluorinated vinyl ethers, and the like are preferable. Is a perfluoroolefin, and hexafluoropropylene is particularly preferred from the viewpoint of refractive index, solubility, transparency, availability, and the like.

  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 may have a repeating unit having a (meth) acryloyl 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, other vinyl monomers can be appropriately copolymerized with the copolymer. 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, acrylic esters, methacrylic esters, styrene derivatives, vinyl ethers, vinyl esters, unsaturated carboxylic acids, acrylamides, methacrylamides, acrylonitrile. Derivatives and the like can be mentioned.

What is represented by the following general formula (2) is a preferred form of 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, used in the present invention. Can be mentioned.
General formula (2):

In the general formula (2), L ²¹ 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. It may have a chain, branch, 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 linking site on the polymer main chain side, and ** represents a linking site on the (meth) acryloyl group side. } And the like. m1 represents 0 or 1.

  In general formula (2), X represents a hydrogen atom or a methyl group. From the viewpoint of curing reactivity, a hydrogen atom is more preferable.

  In the general formula (2), 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 esters such as vinyl acetate, vinyl propionate, vinyl butyrate, methyl (meth) acrylate, ethyl (meth) acrylate, hydroxyethyl (meth) acrylate, glycidyl methacrylate, allyl (meth) acrylate (Meth) acrylates such as (meth) acryloyloxypropyltrimethoxysilane, styrene derivatives such as styrene and p-hydroxymethylstyrene, unsaturated carboxylic acids such as crotonic acid, maleic acid and itaconic acid, and derivatives thereof More preferred are vinyl ether derivatives and vinyl ester derivatives, and particularly preferred are vinyl ether derivatives.

  In general formula (2), x, y, and z represent mol% of each structural 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. However, x + y + z = 100.

Furthermore, what is represented by general formula (2-1) is mentioned as an especially preferable form of the said copolymer.
General formula (2-1):

In general formula (2-1), X, x, and y are synonymous with general formula (2), respectively, and their preferable ranges are also the same.
m2 represents an integer of 2 ≦ m2 ≦ 10, preferably 2 ≦ m2 ≦ 6, and particularly preferably 2 ≦ m2 ≦ 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 (2) is applicable.

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 more preferably 0 ≦ z1 ≦ 10 and 0 ≦ z2 ≦ 5.
As the copolymer represented by the general formula (2-1), those satisfying 40 ≦ x ≦ 60, 30 ≦ y ≦ 60, and z2 = 0 are particularly preferable.
However, x + y + z1 + z2 = 100.

  As preferred specific examples and synthesis methods of the copolymer represented by the general formula (2) or the general formula (2-1), those described in paragraphs [0043] to [0047] of JP-A No. 2004-45462 may be used. Can be mentioned.

  In addition, a polysiloxane structure may be introduced into the fluorine-containing compound for the purpose of imparting antifouling properties. The introduction is preferably block copolymerization or graft copolymerization. A polysiloxane component is 0.5-10 mass% in a compound, Preferably it is 1-5 mass%.

  In the present invention, the concentration of the fluorine-containing compound in the coating solution is appropriately selected depending on the use, but is preferably 0.01 to 60% by mass, more preferably 0.5 to 50% by mass, and particularly preferably 1 to It is about 20% by mass.

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.

(Preferred filler)
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. These may be subjected to chemical surface treatment.

  The addition amount of the filler is preferably from 5 to 70% by mass, more preferably from 10 to 50% by mass, particularly preferably from the viewpoint of physical strength, avoidance of cloudiness, and the like based on the total mass of the low refractive index layer. 20 to 40% by 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.
Two or more kinds of fillers may be used in combination.

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 particle, and thereby the refractive index of the low refractive index layer can be lowered.

For hollow silicon dioxide fine particles, the void ratio θ is expressed by the following formula (1), where r _{i is} the radius of the cavity in the particle and r _o is the radius of the particle outer shell.
Formula (1): θ = (r _i / r _o ) ³ × 100

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

(Preferable slip agent)
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 (meth) acryloyl groups, vinyl groups, aryl groups, cinnamoyl groups, epoxy groups, oxetanyl groups, hydroxyl groups, fluoroalkyl groups, polyoxyalkylene groups, carboxyl groups, amino groups, and the like. Can be mentioned.

  Although there is no restriction | limiting in particular in the molecular weight of a slip agent, It is preferable that it is 100,000 or less, It is especially preferable that it is 50,000 or less, It is most preferable that it is 3000-30000.

  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 (3) and derivatives thereof {for example, a polysiloxane compound represented by the general formula (3) Or a reaction product of a polysiloxane compound and a compound having a crosslinkable or polymerizable functional group other than the polysiloxane compound represented by the general formula (3)}.
General formula (3):

In the general formula (3), R ³¹ ~R ³⁴ each independently represent a substituent having 1 to 20 carbon atoms, they if each group is more or different be the same as each other, R ³¹ , R ³³ or R ³⁴ represents a crosslinked 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 suitably used in the present invention is a cured product containing a polysiloxane compound having a crosslinkable or polymerizable functional group represented by the general formula (3) and a derivative thereof and a fluorine-containing compound. It is preferable to contain.

  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.

  The preferred crosslinkable or polymerizable functional group of the polysiloxane compound and its derivative may form a bond by crosslinking reaction or polymerization reaction with other constituent components (fluorine-containing compound, binder, etc.) of the outermost layer. Any functional group can be used, 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), a group capable of cationic polymerization. (Epoxy groups, oxetanyl groups, oxazolyl groups, vinyl groups, vinyloxy groups, etc.), groups having unsaturated double bonds that can be cross-linked or polymerized by radical species ((meth) acryloyl groups, allyl groups, etc.), hydrolyzable For silyl groups (eg alkoxysilyl groups, acyloxysilyl groups, etc.), acid anhydrides, isocyanate groups, nucleophiles Group capable of being (active halogen atom, a sulfonic acid ester) substituted I, 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.

  Further, the crosslinkable or polymerizable functional group of the general formula (3) preferably undergoes a crosslinking reaction or a polymerization reaction with the crosslinkable or polymerizable functional group of the fluorine-containing compound, and the particularly preferable functional group is a cation. A ring-opening polymerization reactive group (particularly an epoxy group, an oxetanyl group, etc.) and a radical polymerization reactive group {particularly a (meth) acryloyl group}.

The substituent represented by R ^{32 in the} general formula (3) 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.), fluorinated alkyl groups (trifluoromethyl group, pentafluoroethyl group, etc.) or aryl groups having 6 to 20 carbon atoms (for example, phenyl group, naphthyl group, etc.), more preferably alkyl having 1 to 5 carbon atoms. Group, a fluorinated alkyl group or a phenyl group, particularly preferably a methyl group. These groups may be further substituted with these groups.

When R ³¹ , R ³³ or R ^{34 in the} general formula (3) is not a crosslinkable or polymerizable functional group, it can be the organic group.

  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 (3) is a homopolymer in which the repeating unit [—OSi (R ³² ) ₂ —] is composed of only a single substituent (R ³² ). Alternatively, it may be a random copolymer or a block copolymer constituted by a combination of repeating units having different substituents.

The compound represented by the general formula (3) 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 . is there.

  The polysiloxane compound represented by the general formula (3) 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 "{Since, Shin-Etsu Chemical "AK-5", "AK-30", "AK-32" {above, manufactured by Toa Gosei Chemical Co., Ltd.}; "Silaplane FM-0275", "Silaplane FM-0721" ”,“ Silaplane FM-0725 ” , "Silaplane FM-7725", "Silaplane DMS-U22", "Silaplane RMS-033", "Silaplane RMS-083", "Silaplane UMS-182" {above, manufactured by Chisso Corporation}, etc. Can also be used. Moreover, it can also produce by introduce | transducing a crosslinkable or polymeric 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 (3) include those described in [0041] to [0045] of JP-A No. 2003-329804, It is not limited to these.

  The addition amount of at least one of the polysiloxane compound represented by the general formula (3) and derivatives 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.

(Low refractive index layer and its formation method)
The low refractive index layer is prepared by applying a coating solution in which at least one of the fluorine-containing compound and, if necessary, the filler, the polysiloxane compound and a derivative thereof is dissolved or dispersed in a solvent. It is preferable to do.

  Preferred solvents include ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), esters (ethyl acetate, butyl acetate, etc.), ethers (tetrahydrofuran, 1,4-dioxane, etc.), alcohols (methanol, ethanol, etc.) Isopropyl alcohol, butanol, ethylene glycol, etc.), aromatic hydrocarbons (toluene, xylene, etc.), water and the like.

Particularly preferred solvents are ketones, aromatic hydrocarbons and esters, and most preferred solvents are ketones. Of the ketones, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone are particularly preferable. As a solvent, it is preferable that content of a ketone solvent is 10 mass% or more of all the solvents contained in a coating liquid. Preferably it is 30 mass% or more, More preferably, it is 60 mass% or more.
Two or more kinds of solvents can be used in combination.

  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.

  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. As these polymerization initiators, those described in the section of the optical functional layer (A) can be used, and it is preferable to perform thermosetting or radical photocuring after coating in the same manner as the optical functional layer (A). 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 binder, other than the fluorine-containing compound, for example, a polymer compound containing no fluorine, monomers having a polymerizable group, and the like may be used.

  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 optical functional film. More preferably, it is 0.17 or less, Especially preferably, it is 0.15 or less.
The dynamic friction coefficient described here refers to a dynamic friction coefficient between a surface and a stainless hard sphere having a diameter of 5 mm when a load of 0.98 N is applied to a stainless hard sphere having a diameter of 5 mm and the surface is moved at a speed of 60 cm / min.

In order to improve the antifouling performance of the optical functional film, it is preferable that the contact angle of the film surface with water is 90 ° or more. More preferably, it is 95 ° or more, and particularly preferably 100 ° or more.
Furthermore, it is desirable that the contact angle of the surface of the low refractive index layer with water does not change before and after the saponification treatment described later, and the amount of change before and after the saponification treatment is preferably within 10 °, particularly preferably 5 °. Is within.

The lower the haze of the low refractive index layer, the better. The haze is preferably 3% or less,
More preferably, it is 2% or less, and particularly preferably 1% or less.

  The surface hardness 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 K-5400. Moreover, in the Taber test according to JIS K-5400, the smaller the amount of wear 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 1.55. More preferably, it is 1.30-1.50, More preferably, it is 1.35-1.48, Most preferably, it is 1.37-1.45.

  The low refractive index layer is composed of the organosilane compound represented by the general formula (1) 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.

[Layers other than optical functional layers]
The optical functional film of the present invention can have a layer other than the optical functional layer, if necessary, together with the optical functional layer (A) and the optical functional layer (B) described above.

[Antistatic layer]
The optical functional 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 optical functional layer (A) and the low refractive index layer, or between the transparent support and the optical functional layer (A).

  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.

  Preferable conductive materials used for the antistatic layer include tin oxide, antimony-doped tin oxide (ATO), indium oxide, ITO, zinc oxide, and aluminum-doped zinc oxide.

The mass average particle diameter 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 Co., Ltd.}, “Disperbyk ( -110, -111, -116, -140, -161, -162, -163, -164, -170, -171, etc.) "{manufactured by Big Chemie Japan Co., Ltd.}. The dispersant preferably further contains a crosslinkable or polymerizable functional group.

It is preferable to use a liquid having a boiling point of 60 to 170 ° C. as the dispersion medium.
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 dispersing machine such as a sand grinder mill (for example, a bead mill with a pin), a dyno mill, a high-speed impeller mill, an Eiger mill, a pebble mill, a roller mill, an attritor and a colloid mill, and 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 of the present invention, ionizing radiation curable polyfunctional monomers such as (meth) acryloyl group, vinyl group, styryl group, allyl group and the like described in the optical functional layer (A) Oligomers are preferred.

  The antistatic layer is preferably formed by crosslinking or polymerizing an ionizing radiation curable compound in an atmosphere of 4% by volume or less using the same polymerization initiator as that of the optical functional layer (A).

The film thickness of the antistatic layer can be appropriately designed depending on the application. When the antistatic layer is formed with priority on transparency, the film thickness is preferably 1 μm or less, more preferably 500 nm or less, Preferably it is 200 nm or less, Most preferably, it is 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.

[Hard coat layer]
In order to impart physical strength to the optical functional film of the present invention, it is also preferable to provide a hard coat layer between the transparent support and the outermost layer such as a low refractive index layer.
The hard coat layer is preferably formed by a crosslinking or polymerization reaction of an ionizing radiation curable compound. For example, by applying an ionizing radiation curable polyfunctional monomer such as a (meth) acryloyl group, vinyl group, styryl group, allyl group or the like and a coating solution containing a polyfunctional oligomer on a transparent support and crosslinking or polymerizing it. Can be formed.

  Specific examples of the photopolymerizable polyfunctional monomer having a photopolymerizable functional group include those exemplified in the optical functional layer (A), and it is preferable to perform polymerization using a photopolymerization initiator and a photosensitizer. . The photopolymerization reaction is preferably performed by ultraviolet irradiation after the hard coat layer is applied and dried.

  The film thickness of the hard coat layer is preferably 1 to 10 μm, more preferably 2 to 7 μm, and particularly preferably 3 to 5 μm.

  The surface hardness of the hard coat 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 K-5400. Moreover, in the Taber test according to JIS K-5400, the smaller the amount of wear of the test piece before and after the test, the better.

  Hard coat layer includes resin, dispersant, surfactant, antistatic agent, silane coupling agent, thickener, anti-coloring agent, coloring agent (pigment, dye), antifoaming agent, leveling agent, flame retardant, Ultraviolet absorbers, adhesion promoters, polymerization inhibitors, antioxidants, surface modifiers, and the like can also be added. Alternatively, for the purpose of increasing the hardness of the hard coat layer, suppressing curing shrinkage, controlling the refractive index, etc., the fineness of 0.2 μm or less used in the optical functional layer (A) described above in the section of [Inorganic filler] An inorganic filler can be added.

  Further, as described above in the section of the optical functional layer (A), the resin particles having the average particle diameter of 1 to 8 μm are contained to form an optical functional layer (A) such as an antiglare or scattering hard coat layer. This is preferable because it can provide an anti-glare function and a viewing angle expansion function of a liquid crystal display device.

(Transparent support)
The transparent support is preferably a plastic film. As the plastic film, cellulose ester (for example, triacetyl cellulose, diacetyl cellulose, propionyl cellulose, butyryl cellulose, acetyl propionyl cellulose, nitrocellulose), polyamide, polycarbonate, polyester (for example, 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, Polymethylpentene), polysulfone, polyethersulfone, polyarylate, polyetherimide, polyester Limethyl methacrylate and polyether ketone are included. Triacetyl cellulose, polycarbonate, polyethylene terephthalate and polyethylene naphthalate are preferred.

Further, by including a retardation reducing compound, Re _λ and Rth _λ defined by the following formulas (2) and (3) can satisfy the following formulas (4) and (5). A film may be used.
Equation _{(2): Re λ = (} n x -n y) × d
Formula (3): Rth _λ = {(n _x + _ny ) / 2−n _z } × d
Formula (4): 0 ≦ Re ₆₃₀ ≦ 10 and | Rth ₆₃₀ | ≦ 25
Formula (5): | Re ₄₀₀ −Re ₇₀₀ | ≦ 10 and | Rth ₄₀₀ −Rth ₇₀₀ | ≦ 35

[In the formula, Re _λ is a front retardation value (unit: nm) at a wavelength _λ nm, and Rth _λ is a retardation value (unit: nm) in a film thickness direction at a wavelength _λ nm. The n _x is a refractive index in a slow axis direction in the film plane, n _y is a refractive index in a fast axis direction in the film plane, n _z is a refractive index in the thickness direction of the film, d is It is the thickness of the film. ]

  When using an optical functional film for a liquid crystal display device, it is preferable to use triacetyl cellulose among these transparent supports.

  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 casting method. An acetylcellulose 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. preferable.

  The triacetyl cellulose 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 absorber or an ultraviolet absorber 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.

  The transparent support may be subjected to a surface treatment. 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.

[Method of forming optical functional film]
In the present invention, each layer constituting the optical functional film is preferably prepared by a coating method. When formed by coating, each layer is formed by dip coating, air knife coating, curtain coating, roller coating, wire bar coating, gravure coating, micro gravure coating or extrusion coating (US Pat. No. 2,681, 294 specification) or a die coating method (described in JP2003-20097, 2003-211052, 2003-236434, 2003-260400, 2003-260402, etc.). it can. Two or more layers may be applied simultaneously. Regarding the method of simultaneous application, U.S. Pat. Nos. 2,761,791, 2,941,898, 3,508,947, 3,526,528, and Yuji Harasaki, “ Coating Engineering ", page 253, Asakura Shoten (1973). Wire bar coating, gravure coating, micro gravure coating and die coating are preferred. In particular, the micro gravure coating method and the die coating method are preferable, and the die coating method is most preferable.

  The micro gravure coating method is a gravure roll having a diameter of about 10 to 100 mm, preferably about 20 to 50 mm, and having a gravure pattern engraved on the entire circumference, below the support and in the transport direction of the support In addition, the coating method is characterized in that the coating is reversely rotated, the excess coating solution is scraped off from the surface of the gravure roll by a doctor blade, and a fixed amount of coating solution is transferred to the support.

  In the micro gravure coating method, the number of gravure patterns engraved on the gravure roll is preferably 50 to 800 lines / inch, more preferably 100 to 300 lines / inch. The depth of the gravure pattern is preferably 1 to 600 μm, more preferably 5 to 200 μm. The rotation speed of the gravure roll is preferably 3 to 800 rpm, more preferably 5 to 200 rpm. It is preferable that the conveyance speed of a support body is 0.5-100 m / min, More preferably, it is 1-50 m / min.

  In the die coating method, a coating film is formed on a web by coating the web continuously running supported by a backup roller from a slot die in which pockets are formed. By appropriately adjusting the distance between the tip of the slot die and the web on the upstream side and the downstream side of the slot member with respect to the web traveling direction, it is possible to accurately apply a wet film thickness of several tens of μm or less.

  When producing each layer of the optical functional film by a coating method, it is preferable to add a surface conditioner to the coating solution used to produce the layer. Hereinafter, the surface conditioner will be described.

[Surface improver]
The coating liquid used for producing any layer on the transparent support of the present invention includes fluorine-based and silicone-based coatings in order to further improve surface defects (coating irregularities, drying irregularities, point defects, etc.). It is preferable to add at least one of the surface conditioner.

The surface improver preferably changes the surface tension of the coating solution by 1 mN / m or more. Here, when the surface tension of the coating liquid changes by 1 mN / m or more, the surface tension of the coating liquid 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 coating liquid that has not been applied.
Preferably, it is a surface conditioner that has the effect of lowering the surface tension of the coating solution by 1 mN / m or more, more preferably a surface conditioner that lowers by 2 mN / m or more, and particularly preferably a surface conditioner 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 (4) and the repeating unit corresponding to the monomer of the following general formula (5) And a copolymer are preferred.

  Such monomers include "Polymer Handbook 2nd ed." Brandrup, “Wiley lnterscience (1975) Chapter 2”, p. It is preferable to use those described in 1-483.

  Specifically, for example, an addition polymerizable unsaturated bond selected from acrylic acid, methacrylic acid, acrylic esters, methacrylic esters, acrylamides, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, etc. is 1 The compound which has an individual can be mentioned.

  General formula (4):

In the general formula (4), R ⁴¹ represents a hydrogen atom, a halogen atom or a methyl group, and more preferably a hydrogen atom or a methyl group. L ⁴¹ represents an oxygen atom, a sulfur atom or —N (R ⁴² ) —, more preferably an oxygen atom or —N (R ⁴² ) —, and particularly preferably an oxygen atom. R ⁴² is 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 kinds of fluoroaliphatic group-containing monomers represented by the general formula (4) may be contained in the fluorine-based surface improver as a constituent component.

General formula (5)

In the general formula (5), R ⁵¹ represents a hydrogen atom, a halogen atom or a methyl group, more preferably a hydrogen atom or a methyl group. L ⁵¹ represents an oxygen atom, a sulfur atom or —N (R ⁵³ ) —, more preferably an oxygen atom or —N (R ⁵³ ) —, and particularly preferably an oxygen atom. R ⁵³ 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 ⁵² 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- , -CH (CH ₃ ) CH (CH ₃ )-.

  The oxyalkylene units in the poly (oxyalkylene) group (the -OR-) 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 may be present as a linear or branched block of oxypropylene units or a block of oxyethylene units It may be.

  The poly (oxyalkylene) chain may 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 hydroxy poly (oxyalkylene) materials such as “Pluronic” (manufactured by Asahi Denka Kogyo Co., Ltd.), “
"Adeka Polyether" {manufactured by Asahi Denka Kogyo Co., Ltd.}, "Carbowax" (manufactured by Dow Chemical Company), "Toriton" (manufactured by Rohm and Haas) and "PEGG" What is sold as {manufactured by Daiichi Kogyo Seiyaku Co., Ltd.} 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 (4) with respect to the total monomer amount used for forming the fluorine-based surface improver is 50 mol% or more. More preferably, it is 70-100 mol%, Most preferably, it is the range of 80-100 mol%.

  The preferred mass average molecular weight of the fluorine-based surface improver used in the present invention is preferably 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 was determined using a GPC analyzer using columns of “TSK _gel GMH _xL ”, “TSK _gel G4000H _xL , TSK _gel G2000H _xL {(trade name), both manufactured by Tosoh Corp.}” The molecular weight is expressed in terms of polystyrene by THF and differential refractometer detection, and the content is the area% of the peak in the molecular weight range when the peak area of the component having a molecular weight of 300 or more is defined as 100%.

  Furthermore, the preferable addition amount of the fluorine-type surface conditioner used by this invention is the range of 0.001-5 mass% with respect to the coating liquid of the layer to add, Preferably it is 0.005-3 mass%. It is a range, 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.

  The surface conditioner of the present invention includes ketone solvents (acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), ester solvents (ethyl acetate, butyl acetate, etc.), ethers (tetrahydrofuran, 1,4-dioxane, etc.), It is preferable to use it for a coating solution containing an aromatic hydrocarbon solvent (toluene, xylene, etc.). In particular, a ketone solvent is preferable. Among the ketone solvents, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone are preferable.

  In particular, a coating solution containing a ketone solvent in an amount of 10% by mass or more of the total solvent is preferable. Preferably it is 30 mass% or more, More preferably, it is 60 mass% or more.

The solvent of the coating solution may contain a solvent other than the ketone solvent. For example, water, alcohol (eg, methanol, ethanol, isopropanol, butanol, benzyl alcohol), ester (eg, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl formate, ethyl formate, propyl formate, butyl formate), fat Group hydrocarbons (eg hexane, cyclohexane), halogenated hydrocarbons (eg methylene chloride, chloroform, carbon tetrachloride), aromatic hydrocarbons (eg benzene, toluene, xylene), amides (
For example, dimethylformamide, dimethylacetamide, n-methylpyrrolidone), ether (for example, diethyl ether, dioxane, tetrahydrofuran), ether alcohol (for example, 1-methoxy-2-propanol) and the like can be mentioned.

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

[Physical performance of optical functional film]
In order to improve physical strength (such as scratch resistance), the optical functional film according to the present invention preferably has a dynamic friction coefficient of 0.25 or less on the surface having the coated outermost layer. 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 More preferably, it is 0.17 or less, Especially preferably, it is 0.15 or less.

  The optical functional film preferably has a contact angle with water of 90 ° or more on the surface having the outermost layer in order to improve the antifouling performance. More preferably, it is 95 ° or more, and particularly preferably 100 ° or more.

Furthermore, the haze of the optical functional 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 optical functional 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.

[Protective film for polarizing plate]
The optical functional film of the present invention can be used as a protective film for a polarizing film (protective film for polarizing plate). In this case, it is preferable that the contact angle with water on the surface of the transparent support opposite to the side having the outermost layer, that is, the surface to be bonded to the polarizing film, is 40 ° or less. More preferably, it is 30 ° or less, and particularly preferably 25 ° or less. Setting the contact angle to 40 ° or less is effective in improving the adhesion with a polarizing film containing polyvinyl alcohol as a main component. This contact angle can be adjusted by the following saponification treatment conditions.

  When the optical functional film of the present invention is used as a protective film for a polarizing plate, it is particularly preferable to use a triacetyl cellulose film as the transparent support.

The following two methods are mentioned as a method of producing the protective film for polarizing plates in this invention.
(1) On one surface of a saponified transparent support, each of the above layers (for example, an antistatic layer, a hard coat layer, an antiglare layer that is an optical functional layer, a low refractive index layer, a high refractive index layer, A method of coating the outermost layer.
(2) After coating each of the above layers (for example, antistatic layer, hard coat layer, antiglare layer, low refractive index layer, outermost layer, etc.) on one surface of the transparent support, the side to be bonded to the polarizing film Saponification treatment method.

In the method (1), when only one surface of the transparent support is saponified, each layer is coated on the side not saponified. When both surfaces of the transparent support are saponified, the surface of the saponified transparent support on the side where each layer is applied is surface-treated by a technique such as corona discharge treatment, glow discharge treatment, flame treatment, etc. It is preferable to coat each layer.

  In the above method (2), it is preferable to immerse the entire optical functional film in a saponification solution. In this case, the surface of the optical functional film having the respective layers can be protected with a protective film and immersed in a saponification solution, and the surface of the transparent support to be bonded to the polarizing film can be saponified.

  Furthermore, a saponification treatment liquid can be applied to the surface of the transparent support to be bonded to the polarizing film of the optical functional film, and the saponification process can be performed on the side to be bonded to the polarizing film.

  The saponification treatment is carried out after the optical functional layer is provided on the protective film, whereby the cost can be further reduced. In particular, the method (2) is preferable in that the protective film for polarizing plate can be produced at a low cost.

  The protective film for polarizing plate has the anti-glare performance and other optical performance (such as low reflection performance), physical performance (such as scratch resistance), antifouling performance (such as stain resistance), and dustproof performance. It is preferable to satisfy the performance described in the functional film.

Accordingly, the surface resistance value of the surface having the outermost layer is preferably 1 × 10 ¹³ Ω / □ or less, more preferably 1 × 10 ¹² Ω / □ or less, and more preferably 1 × 10 ¹⁰ Ω / □. More preferably, it is as follows.
The coefficient of dynamic friction on the surface having the outermost layer is preferably 0.25 or less. Preferably it is 0.17 or less, Most preferably, it is 0.15 or less.
Further, the contact angle with respect to water on the surface having the outermost layer is preferably 90 ° or more. More preferably, it is 95 ° or more, and particularly preferably 100 ° or more.

[Saponification]
The saponification treatment is preferably carried out by a known method, for example, by immersing the transparent support or the optical functional film in an alkali solution for an appropriate time.

  The alkaline liquid is preferably a potassium hydroxide aqueous solution and / or a sodium hydroxide aqueous solution. A preferred concentration is 0.5 to 3 mol / L, particularly preferably 1 to 2 mol / L. The liquid temperature of a preferable alkali liquid is 30-70 degreeC, Most preferably, it is 40-60 degreeC.

  After being immersed in the alkaline solution, it is preferable that the film is sufficiently washed with water so that the alkali component does not remain in the film, or is immersed in a dilute acid to neutralize the alkali component.

  By saponification treatment, the surface of the transparent support is hydrophilized. The protective film for polarizing plate is used by adhering the hydrophilic surface of the transparent support to the polarizing film.

  The hydrophilized surface is effective for improving the adhesion with a polarizing film containing polyvinyl alcohol as a main component.

  The saponification treatment is preferably carried out so that the contact angle with water on the surface of the transparent support opposite to the side having the antiglare layer or the low refractive index layer is 40 ° or less. More preferably, it is 30 ° or less, particularly preferably 25 ° or less.

<Polarizing plate>
The polarizing plate of this invention has the optical function film of this invention in at least one of the protective film (protective film for polarizing plates) of a polarizing film. As described above, the polarizing plate protective film has a water contact angle of 40 ° or less on the surface of the transparent support opposite to the side having the outermost layer, that is, the surface to be bonded to the polarizing film. preferable.

  By using the optical functional film of the present invention as a protective film for a polarizing plate, a polarizing plate having an antiglare function can be produced, and a significant cost reduction and a thin display device can be achieved.

  Further, the polarizing plate using the optical functional film of the present invention as one of the two protective films and the optical compensation film described below as the other further improves the contrast in the bright room of the liquid crystal display device, It is preferable because the left and right viewing angles can be greatly widened.

[Optical compensation film]
The optical compensation film (retardation film) can improve the viewing angle characteristics of the liquid crystal display screen.

  As the optical compensation film, a known film can be used, but in terms of widening the viewing angle, an optically anisotropic layer made of a compound having a discotic structural unit described in JP-A-2001-100042 is disclosed. An optical compensation film characterized in that the angle formed by the discotic compound and the film surface changes in the depth direction of the optically anisotropic layer is preferable. That is, the orientation state of the compound having a discotic structural unit is preferably, for example, a hybrid orientation, a bent orientation, a twist orientation, a homogeneous orientation, a homeotropic orientation, or the like, and particularly preferably a hybrid orientation. It is preferable that the angle generally increases with an increase in the distance from the support surface side of the optical compensation film in the optically anisotropic layer when viewed in the entire layer.

  When the optical compensation film is used as a protective film for the polarizing film, the surface on the side to be bonded to the polarizing film is preferably saponified, and is preferably performed according to the saponifying process.

Also, an embodiment in which the optically anisotropic layer further contains a cellulose ester, an embodiment in which an alignment layer is formed between the optically anisotropic layer and the transparent support of the optical compensation film, and the optically anisotropic layer The transparent support of the optical compensation film has an optically negative uniaxial property and an optical axis in the normal direction of the surface of the transparent support, and further satisfies the condition represented by the following formula (6): It is also preferable that it is an aspect.
Formula (6): 20 ≦ {(n _x + _ny ) / 2−n _z } × d ≦ 400

Wherein, n _x is the slow axis direction of the refractive index in the plane (the maximum in-plane refractive index), n _y is a refractive index in a direction perpendicular to the in-plane slow axis, n _z is perpendicular to the plane The refractive index in the direction. D is the thickness (nm) of the optically anisotropic layer.

<Image display device>
The optical functional film can be applied to an image display device such as a liquid crystal display device (LCD), a plasma display panel (PDP), an electroluminescence display (ELD), or a cathode ray tube display device (CRT). The optical functional film of the present invention has its transparent support side adhered to the image display surface of the image display device.

Optical functional film and polarizing plate used in the present invention are twisted nematic (TN), super twisted nematic (STN), vertical alignment (VA), in-plane switching (IPS), optically compensated bend cell (OCB). It can be preferably used for a transmissive, reflective, or semi-transmissive liquid crystal display device of the mode.
In particular, for a TN mode or IPS mode liquid crystal display device, as described in JP-A-2001-100043, etc., a polarizing plate having the optical compensation film and the optical functional film as protective films is used. Thus, viewing angle characteristics and anti-glare characteristics can be greatly improved.

Further, by using in combination with a commercially available brightness enhancement film {polarized light separation film having a polarization selective layer, such as “D-BEF” manufactured by Sumitomo 3M Co., Ltd.}, a transmissive or transflective liquid crystal display In the device, a display device with higher visibility can be obtained.
Furthermore, by combining with a λ / 4 plate, it can be used to reduce reflected light from the surface and inside as a polarizing plate for reflective liquid crystal or a surface protective plate for organic EL display.

  In order to describe the present invention in detail, examples will be described below, but the present invention is not limited thereto.

Synthesis Example 1 {Synthesis of Polymer Compound (K-1)}
A reactor equipped with a stirrer and a reflux condenser was charged with 300 parts by mass of water, and 0.6 parts by mass of polyvinyl alcohol was added thereto and dissolved. Next, a mixed solution of 81.6 parts by mass of methyl methacrylate and 15.9 parts by mass of methyl acrylate in which 2 parts by mass of azobisisobutyronitrile was dissolved was added thereto. The mixture was stirred with a disper for 5 minutes, and then allowed to react in a nitrogen atmosphere at 75 ° C. for 4 hours with weak stirring.
After completion of the reaction, the obtained reaction mixture was dehydrated weakly with a centrifuge, and the product was washed with water and dried to obtain a polymer compound (K-1).

Synthesis Example 2 {Synthesis of Perfluoroolefin Copolymer (PF-1)}
A stainless steel autoclave with a stirrer was charged with 40 parts by mass of ethyl acetate, 14.7 parts by mass of hydroxyethyl vinyl ether, and 0.55 parts by mass of dilauroyl peroxide, and the system was degassed and replaced with nitrogen gas. Further, 25 parts by mass of hexafluoropropylene (HFP) was introduced into the autoclave and the temperature was raised to 65 ° C. The pressure when the temperature in the autoclave reached 65 ° C. was 5.4 kg / cm ² (529 kPa). The reaction was continued for 8 hours while maintaining the temperature, and when the pressure reached 3.2 kg / cm ² (314 kPa), the heating was stopped and the mixture was allowed to cool. When the internal temperature dropped to room temperature, unreacted monomers were driven out, the autoclave was opened, and the reaction solution was taken out.

  The obtained reaction solution was poured into a large excess of hexane, and the polymer was precipitated by removing the solvent by decantation. Further, this polymer was dissolved in a small amount of ethyl acetate and reprecipitated twice from hexane to completely remove the residual monomer. After drying, 28 parts by mass of the polymer product was obtained.

Next, 20 parts by mass of the polymer product was dissolved in 100 parts by mass of N, N-dimethylacetamide, and 11.4 parts by mass of acrylic acid chloride was added dropwise under ice cooling, followed by stirring at room temperature for 10 hours. Ethyl acetate was added to the reaction solution and washed with water. The organic layer was extracted and concentrated, and the resulting polymer was reprecipitated with hexane to obtain 19 parts by mass of a perfluoroolefin copolymer (PF-1) having the following structure. Obtained. The obtained perfluoroolefin copolymer had a refractive index of 1.421.
The perfluoroolefin copolymer PF-1 was dissolved in methyl ethyl ketone to obtain a solution having a solid content concentration of 30%.

Synthesis Example 3 {Preparation of organosilane compound (OS) solution)
In a reactor equipped with a stirrer and a reflux condenser, 120 parts by mass of methyl ethyl ketone, 100 parts by mass of 3-acryloxypropyltrimethoxysilane “KBM-5103” (manufactured by Shin-Etsu Chemical Co., Ltd.), diisopropoxyaluminum ethyl acetoacetate After adding 3 parts by mass and mixing, 30 parts by mass of ion-exchanged water was added and reacted at 60 ° C. for 4 hours. The solution was cooled to room temperature to obtain a solution of an organosilane compound (OS). 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, when analyzed by gas chromatography, the raw material 3-acryloxypropyltrimethoxysilane hardly remained.

Synthesis Example 4-1 {Preparation of Resin Particle (J-1)}
A reactor equipped with a stirrer and a reflux condenser is charged with 600 parts by mass of water, and 0.7 parts by mass of polyvinyl alcohol (PVA) and 3.0 parts by mass of sodium dodecylbenzenesulfonate (ABS) are added thereto and dissolved. did. Next, a mixed liquid of 101.7 parts by mass of styrene (St), 2.9 parts by mass of divinylbenzene (DVB), and 2.0 parts by mass of benzoyl peroxide (BPO) was added thereto and stirred. This mixture was dispersed and homogenized at 10,000 rpm for 20 minutes using a homogenizer. Next, stirring was continued at 75 ° C. for 4 hours while blowing nitrogen gas. Thereafter, it was lightly dehydrated by centrifugation, and the product was washed with water and dried. The obtained crosslinked polystyrene-based resin particles (J-1) had an average particle size of 3.6 μm and a refractive index of 1.60.

  The gel fraction obtained by adding 10 parts by mass of the resin particles (J-1) to 190 parts by mass of methyl ethyl ketone, stirring for 3 hours while heating at 60 ° C., and filtering the particles was 72% by mass.

Synthesis Example 4-2 {Preparation of Resin Particle (J-2)}
In Synthesis Example 4-1, in place of using St 101.7 parts by mass and DVB 2.9 parts by mass, except that St 100.3 parts by mass and DVB 4.6 parts by mass were used, the same as Synthesis Example 4-1. And resin particles (J-2) were prepared. The average particle diameter of the obtained particles was 3.6 μm, the refractive index was 1.60, and the gel fraction was 78% by mass.

Synthesis Example 4-3 {Preparation of resin particles (J-3)}
In Synthesis Example 4-1, in place of using St 101.7 parts by mass and DVB 2.9 parts by mass, except that St 98.7 parts by mass and DVB 6.5 parts by mass were used, the same as Synthesis Example 4-1. And resin particles (J-3) were prepared. The average particle diameter of the obtained particles was 3.5 μm, the refractive index was 1.60, and the gel fraction was 83% by mass.

Synthesis Example 4-4 {Preparation of resin particles (J-4)}
In Synthesis Example 4-1, instead of using St 101.7 parts by mass and DVB 2.9 parts by mass, St 95.7 parts by weight and DVB 10.4 parts by mass were used as in Synthesis Example 4-1. And resin particles (J-4) were prepared. The average particle diameter of the obtained particles was 3.6 μm, the refractive index was 1.60, and the gel fraction was 88% by mass.

Synthesis Example 4-5 {Preparation of resin particles (J-5)}
In Synthesis Example 4-1, in place of using St 101.7 parts by mass and DVB 2.9 parts by mass, except that St 92.1 parts by mass and DVB 14.8 parts by mass were used, the same as Synthesis Example 4-1. And resin particles (J-5) were prepared. The average particle diameter of the obtained particles was 3.7 μm, the refractive index was 1.60, and the gel fraction was 94% by mass.

Synthesis Example 4-6 {Preparation of resin particles (J-6)}
In the synthesis example 4-1, instead of using St 101.7 parts by mass and DVB 2.9 parts by mass, St 68.5 parts by mass, DVB 5.2 parts by mass and methyl methacrylate (MM
A) Resin particles (J-6) were prepared in the same manner as in Synthesis Example 4-1, except that 30.0 parts by mass were used. The average particle diameter of the obtained particles was 3.7 μm, the refractive index was 1.57, and the gel fraction was 81% by mass.

Synthesis Example 4-7 {Preparation of resin particles (J-7)}
In the synthesis example 4-1, instead of using St 101.7 parts by mass and DVB 2.9 parts by mass, synthesis was performed except that St 48.0 parts by mass, DVB 5.2 parts by mass and MMA 50.0 parts by mass were used. Resin particles (J-7) were prepared in the same manner as in Example 4-1. The average particle diameter of the obtained particles was 3.6 μm, the refractive index was 1.54, and the gel fraction was 80% by mass.

Synthesis Example 4-8 {Preparation of resin particles (J-8)}
In the synthesis example 4-1, instead of using St 101.7 parts by mass and DVB 2.9 parts by mass, synthesis was performed except that St 27.0 parts by mass, DVB 5.2 parts by mass and MMA 70.0 parts by mass were used. Resin particles (J-8) were prepared in the same manner as in Example 4-1. The average particle diameter of the obtained particles was 3.5 μm, the refractive index was 1.52, and the gel fraction was 81% by mass.

Synthesis Example 4-9 {Preparation of resin particles (J-9)}
In Synthesis Example 4-1, in place of using St 101.7 parts by mass and DVB 2.9 parts by mass, except that St 99.8 parts by mass and DVB 5.2 parts by mass were used, the same as Synthesis Example 4-1. And resin particles (J-9) were prepared. The average particle diameter of the obtained particles was 3.5 μm, the refractive index was 1.60, and the gel fraction was 81% by mass.

Synthesis Example 4-10 {Preparation of Comparative Resin Particles (RJ-1)}
In Synthesis Example 4-1, in place of using St 101.7 parts by mass and DVB 2.9 parts by mass, except that St 102.5 parts by mass and DVB 1.7 parts by mass were used, the same as Synthesis Example 4-1. Comparative resin particles (RJ-1) were prepared. The average particle diameter of the obtained particles was 3.6 μm, the refractive index was 1.60, and the gel fraction was 67% by mass.

Synthesis Example 4-11 {Preparation of Comparative Resin Particles (RJ-2)}
In Synthesis Example 4-1, instead of using St 101.7 parts by mass and DVB 2.9 parts by mass, the same as Synthesis Example 4-1, except that St 90.0 parts by mass and DVB 17.5 parts by mass were used. Comparative resin particles (RJ-2) were prepared. The average particle size of the obtained particles was 3.5 μm, the refractive index was 1.60, and the gel fraction was 98% by mass.

Synthesis Example 4-12 {Preparation of Resin Particle (J-10)}
A reactor similar to that used in Synthesis Example 4-1 was charged with 600 parts by mass of water, and this was added to PVA.
0.7 parts by mass and 2.7 parts by mass of ABS were added and dissolved. Next, a mixed solution of 96.0 parts by mass of MMA, 8.0 parts by mass of ethylene glycol dimethacrylate (EDMA), and 2.0 parts by mass of BPO was added thereto and stirred. This mixed solution was dispersed and homogenized at 9000 rpm for 15 minutes using a homogenizer. Next, stirring was continued at 75 ° C. for 4 hours while blowing nitrogen gas. Thereafter, it was dehydrated lightly by centrifugation, and the product was washed with water and dried. The obtained crosslinked MMA resin particles (J-10) had an average particle size of 3.3 μm and a refractive index of 1.50.
The gel fraction obtained by treating this resin particle (J-10) by the same method as in the above (J-1) was 89% by mass.

Synthesis Example 4-13 {Preparation of Resin Particle (J-11)}
In the above Synthesis Example 4-12, resin particles (J-) were prepared in the same manner as in Synthesis Example 4-12 except that the amount of ABS was changed to 3.4 parts by mass and the rotation speed of homogenizer dispersion was changed to 14000 rpm for 30 minutes. 11) was prepared. The average particle diameter of the obtained resin particles (J-11) is 1.5 μm.
m, the refractive index was 1.50, and the gel fraction was 90% by mass.

Synthesis Example 4-14 {Preparation of resin particles (J-12)}
In Synthesis Example 4-12, instead of using 96.0 parts by mass of MMA and 8.0 parts by mass of EDMA, the procedure was the same as in Synthesis Example 4-12 except that 98.7 parts by mass of MMA and 2.6 parts by mass of EDMA were used. Thus, crosslinked MMA resin particles (J-12) were prepared. The obtained crosslinked polymethyl methacrylate resin particles (J-12) had an average particle size of 3.3 μm, a refractive index of 1.50 and a gel fraction of 72% by mass.

Synthesis Example 4-15 {Preparation of resin particles (J-13)}
In Synthesis Example 4-13, instead of using 96.0 parts by mass of MMA and 8.0 parts by mass of EDMA, the procedure was the same as in Synthesis Example 4-13, except that 98.7 parts by mass of MMA and 2.6 parts by mass of EDMA were used. Resin particles (J-13) were prepared. The obtained resin particles (J-13) had an average particle size of 1.5 μm, a refractive index of 1.50, and a gel fraction of 71% by mass.

Synthesis Example 4-16 {Preparation of Comparative Resin Particles (RJ-3)}
In Synthesis Example 4-12, instead of using 96.0 parts by mass of MMA and 8.0 parts by mass of EDMA, the procedure was the same as in Synthesis Example 4-12, except that 88.0 parts by mass of MMA and 24.0 parts by mass of EDMA were used. Comparative resin particles (RJ-3) were prepared. The average particle size of the comparative resin particles (RJ-3) obtained was 3.3 μm, the refractive index was 1.50, and the gel fraction was 97% by mass.

Synthesis Example 4-17 {Preparation of Comparative Resin Particles (RJ-4)}
In Synthesis Example 4-13, instead of using 96.0 parts by mass of MMA and 8.0 parts by mass of EDMA, the procedure was the same as in Synthesis Example 4-13, except that 88.0 parts by mass of MMA and 24.0 parts by mass of EDMA were used. Comparative resin particles (RJ-4) were prepared. The average particle diameter of the comparative resin particles (RJ-4) obtained was 1.5 μm, the refractive index was 1.50, and the gel fraction was 97% by mass.

Synthesis Example 4-18 {Preparation of Resin Particle (J-14)}
Resin particles (J-14) were prepared in the same manner as in Synthesis Example 4-1, except that the dispersion using a homogenizer was performed at 6000 rpm for 20 minutes in Synthesis Example 4-1. The average particle diameter of the obtained particles was 5.0 μm, and the refractive index was 1.60.

  About each resin particle obtained by the synthesis examples 4-1 to 4-18, the composition of the copolymer which comprises them, and the gel fraction of these resin particles are put together in Table 3, and are shown.

Formulation Example 1-1 {Preparation of coating liquid (AL-1) for forming optical functional layer (A)}
A container equipped with a stirrer was charged with 47.0 parts by mass of a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate “Kayarad PET-30” {manufactured by Nippon Kayaku Co., Ltd.}, and the polymerization initiator “Irgacure” 184 "{manufactured by Ciba Specialty Chemicals Co., Ltd.} 2.0 parts by mass, 0.75 parts by mass of the fluorine-based surface improver (F-12) shown in Table 1 above, and organosilane compound" KBM-5103 " {Shin-Etsu Chemical Co., Ltd.} 10.0 parts by mass, 15.0 parts by mass of a 20% by weight toluene solution of the polymer compound (K-1) produced in Synthesis Example 1 and 23.5 parts by mass of toluene are added. And stirred. After applying this solution, the refractive index of the coating film obtained by ultraviolet curing was 1.51.

Further, 25.5 parts by mass of the resin particles (J-1) produced in Synthesis Example 4-1 were dispersed at 10,000 rpm with a Polytron disperser to give a 30% by mass toluene dispersion. And stirred. It filtered with the polypropylene filter with a hole diameter of 30 micrometers, and prepared the coating liquid (AL-1) for optical function layer (A) formation.

Formulation Examples 1-2 to 1-11 {Coating liquids (AL-2) to (AL-9), (RAL-1) (comparison), (RAL-2) (comparison) for forming the optical functional layer (A) Preparation}
In the above blending example 1-1, the resin particles (J-1) are blended examples except that the resin particles (J-1) are changed to any one of (J-2) to (J-9), (RJ-1) and (RJ-2). In the same manner as in 1-1, (A) coating liquids (AL-2) to (AL-9), (RAL-1) (comparison), and (RAL-2) (comparison) for optical function layer formation were prepared. . In each coating solution, resin particles were used as a single product.

  Table 4 shows the types of resin particles used in each coating solution, the types of dispersion media, the types of organosilane compounds, the I / O values of resin particles and dispersion media and their differences, and the densities of resin particles and dispersion media and their differences. Show.

Formulation Example 1-12 {Preparation of coating solution for forming optical functional layer (A) (AL-10)}
In the above Formulation Example 1-1, the resin particles (J-1) are changed to (J-9), and the organosilane compound “KBM-5103” {manufactured by Shin-Etsu Chemical Co., Ltd.} (KBM) 10.0 parts by mass Was changed to 12.7 parts by mass of a 30% solution of the organosilane compound (OS) produced in Synthesis Example 3 in the same manner as in Formulation Example 1-1, except that the coating solution for forming the optical functional layer (A) ( AL-10) was prepared. Type of resin particles, type of dispersion medium, type of organosilane compound, I / O value of resin particles and dispersion medium and their difference, and density of resin particles and dispersion medium used in the obtained coating liquid (AL-10) Table 4 shows the differences.

Formulation Example 1-13 {Preparation of coating solution for forming optical functional layer (A) (AL-11)}
In the above Formulation Example 1-1, the resin particles (J-1) are changed to (J-9), and the portion using toluene (pure toluene, the solvent of the polymer compound and the resin particle dispersion medium added in preparation of the coating solution) A coating solution (AL-11) for forming an optical functional layer (A) was prepared in the same manner as in Formulation Example 1-1 except that all of toluene was changed to methyl isobutyl ketone (MIBK). Type of resin particles, type of dispersion medium, type of organosilane compound, I / O value of resin particles and dispersion medium and their difference, and density of resin particles and dispersion medium used in the obtained coating liquid (AL-11) Table 4 shows the differences.

Formulation Example 1-14 {Preparation of coating liquid (AL-12) for forming optical functional layer (A)}
In the above Formulation Example 1-1, the optical functional layer (A) forming coating solution (AL-12) was prepared in the same manner as Formulation Example 1-1 except that all the portions using toluene were changed to ethyl acetate (EAc). Prepared. Type of resin particles, type of dispersion medium, type of organosilane compound, I / O value of resin particles and dispersion medium and their difference, and density of resin particles and dispersion medium used in the obtained coating liquid (AL-12) Table 4 shows the differences.

Formulation Example 1-15 {Preparation of coating solution for forming optical functional layer (A) (AL-13)}
In the above Formulation Example 1-1, the coating solution for forming the optical functional layer (A) (AL-13) was prepared in the same manner as the coating solution B-1, except that all the portions using toluene were changed to cyclohexanone (CHN). did. Type of resin particles, type of dispersion medium, type of organosilane compound, I / O value of resin particles and dispersion medium and their difference, and density of resin particles and dispersion medium used in the obtained coating liquid (AL-13) Table 4 shows the differences.

Formulation Example 1-16 {Preparation of coating liquid for forming optical functional layer (A) (AL-14)}
A coating liquid (AL-14) for forming an optical functional layer (A) was prepared in the same manner as in the coating liquid B-1, except that all the portions using toluene were changed to xylene in the above formulation example 1-1. Type of resin particles, type of dispersion medium, type of organosilane compound, I / O value of resin particles and dispersion medium and their difference, and density of resin particles and dispersion medium used in the obtained coating liquid (AL-14) Table 4 shows the differences.

Formulation Example 1-17 {Preparation of coating liquid for forming optical functional layer (A) (AL-15)}
In the above Formulation Example 1-11, an optical functional layer was prepared in the same manner as Formulation Example 1-11 except that the pure solvent added in the preparation of the coating liquid and the solvent of the resin particle dispersion medium were changed from MIBK to 1-butanol (BuOH). (A) A forming coating solution (AL-15) was prepared. Resin particle type, dispersion medium type, organosilane compound type, I / O value of resin particle and dispersion medium and their difference, and density of resin particle and dispersion medium used in the obtained coating liquid (AL-15) Table 4 shows the differences.

Formulation Example 1-18 {Preparation of coating liquid for forming optical functional layer (A) (AL-16)}
A container equipped with a stirrer was filled with 285.0 parts by mass of a transparent high refractive index hard coat material “Desolite Z7404” {manufactured by JSR Corporation) containing fine zirconium oxide particles, and dipentaerythritol pentaacrylate and dipenta were added thereto. Mixture of erythritol hexaacrylate "DPHA" {manufactured by Nippon Kayaku Co., Ltd.} 85.0 parts by mass, organosilane compound "KBM-5103" {manufactured by Shin-Etsu Chemical Co., Ltd.} 28.0 parts by mass, MIBK 60.0 parts by mass And 17.0 parts by mass of methyl ethyl ketone (MEK) were added and stirred. The refractive index of the coating film obtained by applying this solution and curing with ultraviolet rays was 1.61.

  Furthermore, the resin particles (J-10) produced in Synthesis Example 4-12 were dispersed in this solution at 10,000 rpm with a Polytron disperser to give a 30% by mass MIBK dispersion, 35.0 parts by mass, and 90.0 parts by mass of the resin particles (J-11) produced in Synthesis Example 4-13, which was dispersed at 10,000 rpm with a Polytron disperser to give a 30% by mass MIBK dispersion, was added and stirred. It filtered with the polypropylene filter with a hole diameter of 30 micrometers, and prepared the coating liquid (AL-16) for optical function layer (A) formation.

  Type of resin particles, type of dispersion medium, type of organosilane compound, I / O value of resin particles and dispersion medium and their difference, and density of resin particles and dispersion medium used in the obtained coating liquid (AL-16) Table 4 shows the differences.

Formulation Example 1-19 {Preparation of coating liquid for forming optical functional layer (A) (AL-17)}
In the blending example 1-18, the resin particles (J-10) were replaced with the resin particles (J-12) in an equal amount, and the resin particles (J-11) were replaced with the resin particles (J-13) in an equal amount. Were carried out in the same manner as in Formulation Example 1-18 to prepare a coating solution (AL-17) for forming an optical functional layer (A).
Type of resin particles, type of dispersion medium, type of organosilane compound, I / O value of resin particles and dispersion medium and their difference, and density of resin particles and dispersion medium used in the obtained coating liquid (AL-17) Table 4 shows the differences.

Formulation Example 1-20 {Preparation of coating liquid for forming optical functional layer (A) (RAL-3)}
In the blending example 1-18, the resin particle (J-10) was replaced with an equal amount of resin particles (RJ-3), and the resin particle (J-11) was replaced with an equal amount of resin particles (RJ-4). Were carried out in the same manner as in Formulation Example 1-18 to prepare a comparative coating solution (RAL-3) for forming an optical functional layer (A).
Types of resin particles, types of dispersion media, types of organosilane compounds, I / O values of resin particles and dispersion media and their differences, and density of resin particles and dispersion media used in the obtained coating liquid (RAL-3) Table 4 shows the differences.

Formulation Example 1-21 {Preparation of Coating Solution for Forming Optical Functional Layer (A) (AL-18)}
In the above Formulation Example 1-1, except that the resin particles (J-1) are changed to (J-14), the same as Formulation Example 1-1, (A) coating liquid for forming an optical functional layer (AL- 18) was prepared. In each coating solution, resin particles were used as a single product.
Type of resin particles, type of dispersion medium, type of organosilane compound, I / O value of resin particles and dispersion medium and their difference, and density of resin particles and dispersion medium used in the obtained coating liquid (AL-18) Table 4 shows the differences.

[Evaluation of sedimentation property of coating solution for forming optical functional layer (A)]
Resins of optical functional layer (A) forming coating solutions (AL-1) to (AL-18) and (RAL-1) to (RAL-3) prepared in the above formulation examples 1-1 to 1-21 The sedimentation property of the particles was evaluated as follows according to the above method.

  30 g of the coating solution was put in a 50 mL transparent glass bottle with a sealed stopper, and left standing in a thermostatic bath at 25 ° C. for 24 hours, and then elapsed. The supernatant of the coating solution is separated by a decantation method, and the remaining precipitated resin particles are washed with acetone three times, dried, weighed, and resin particles contained in a known 30 g coating solution before standing. The ratio of the amount of precipitated resin particles to the total amount was determined.

  Table 4 shows the results of evaluating the particle sedimentation amount of the coating liquids (AL-1) to (AL-18) and (RAL-1) to (RAL-3) for forming the optical functional layer (A).

Formulation Example 2-1 {Preparation of Low Refractive Index Layer Coating Liquid (LL-1)}
A container equipped with a stirrer was charged with 13.0 parts by mass of a heat-crosslinkable fluorine-containing polymer “JN7228A” {solid content concentration 6% by mass, manufactured by JSR Co., Ltd.} having a refractive index of 1.42. MEK dispersion “MEK-ST-L” {average particle size 45 nm, solid content concentration 30% by mass, manufactured by Nissan Chemical Industries, Ltd.} 1.3 parts by mass, organosilane compound (OS) prepared in Synthesis Example 3 0.6 parts by mass of the solution, 5.0 parts by mass of methyl ethyl ketone and 0.6 parts by mass of cyclohexanone were added and stirred. The solution was filtered through a polypropylene filter having a pore diameter of 1 μm to prepare a coating solution for forming a low refractive index layer (LL-1). The refractive index of the coating film by this coating solution was 1.42.

Formulation Example 2-2 {Preparation of Low Refractive Index Layer Coating Liquid (LL-2)}
A container equipped with a stirrer was charged with 15.0 parts by mass of a heat-crosslinkable fluorine-containing polymer “JN7228A” {solid content concentration 6% by mass, manufactured by JSR Co., Ltd.} having a refractive index of 1.42. MEK dispersion “MEK-ST” {average particle size 15 nm, solid content concentration 30% by mass, manufactured by Nissan Chemical Industries, Ltd.} 0.6 parts by mass, silica fine particle MEK dispersion “MEK-ST-L” {average Particle size 45 nm, solid content concentration 30% by mass, manufactured by Nissan Chemical Industries, Ltd.} 0.8 part by mass, organosilane compound (OS) solution 0.4 part by mass produced in Synthesis Example 3, and methyl ethyl ketone 3.0 Part by mass and 0.6 part by mass of cyclohexanone were added and stirred. The mixture was filtered through a polypropylene filter having a pore diameter of 1 μm to prepare a coating solution for forming a low refractive index layer (LL-2). The refractive index of the coating film by this coating solution was 1.42.

Formulation Example 2-3 {Preparation of coating liquid for forming a low refractive index layer (LL-3)}
(Preparation of MEK dispersion of hollow silica fine particles)
In a container equipped with a stirrer, hollow silica fine particle sol {Isopropyl alcohol silica sol, manufactured by Catalyst Kasei Kogyo Co., Ltd., average particle diameter 60 nm, shell thickness 10 nm, silica concentration 20% by mass, silica particle refractive index 1.31, Fabricated by changing the size according to Preparation Example 4 of 2002-79616} filled with 500 parts by mass, 30 parts by mass of acryloyloxypropyltrimethoxysilane {manufactured by Shin-Etsu Chemical Co., Ltd.}, and diisopropoxyaluminum ethyl After adding 1.5 parts by mass of acetate “Kelope EP-12” (manufactured by Hope Pharmaceutical Co., Ltd.) and mixing, 9 parts by mass of ion-exchanged water was added. After making it react at 60 degreeC for 8 hours, it cooled to room temperature and added 1.8 mass parts of acetylacetone. While adding methyl ethyl ketone so that the content of silica was almost constant in 500 g of this dispersion, solvent substitution by vacuum distillation was performed at a pressure of 20 kPa. No foreign matter was generated in the dispersion, and the viscosity when the solid content was adjusted to 20% by mass with methyl ethyl ketone was 5 mPa · s at 25 ° C. When the residual amount of isopropyl alcohol in the obtained dispersion was analyzed by gas chromatography, it was 1.5% by mass.

(Preparation of coating liquid LL-3 for forming a low refractive index layer)
A container equipped with a stirrer is filled with 13.0 parts by mass of a thermally crosslinkable fluorine-containing polymer “JN7228A” {solid content concentration 6% by mass, manufactured by JSR Corporation) having a refractive index of 1.42, and the above hollow MEK dispersion of silica fine particles (refractive index 1.31, average particle size 60 nm, solid content concentration 20% by mass) 1.95 parts by mass, organosilane compound (OS) solution 0.6 parts by mass produced in Synthesis Example 3 And 4.35 parts by mass of methyl ethyl ketone and 0.6 parts by mass of cyclohexanone were added and stirred. The solution was filtered through a polypropylene filter having a pore size of 1 μm to prepare a coating solution for forming a low refractive index layer (LL-3). The refractive index of the coating film by this coating solution was 1.40.

Formulation Example 2-4 {Preparation of Coating Solution for Forming Low Refractive Index Layer (LL-4)}
A container equipped with a stirrer is charged with 100 parts by mass of trifluoropropyltrimethoxysilane, 200 parts by mass of tridecafluorooctyltrimethoxysilane, 1700 parts by mass of tetraethoxysilane, 200 parts by mass of isobutanol and 6 parts by mass of aluminum acetylacetonate. Stir with. Next, 500 parts by mass of 0.25 mol / L acetic acid water was added dropwise little by little. After completion of dropping, the mixture was stirred at room temperature for 3 hours. Thereafter, 600 parts by mass of diacetone alcohol was added, and the mixture was filtered through a polypropylene filter having a pore size of 1 μm to prepare a coating solution for low refractive index layer (LL-4). The refractive index of the coating film by this coating solution was 1.44.

Formulation Example 2-5 {Preparation of low refractive index layer-forming coating solution (LL-5)}
A container equipped with a stirrer is charged with 10.5 parts by mass of a solution (solid content concentration 30% by mass) of the perfluoroolefin copolymer (PF-1) produced in Synthesis Example 2 above, and methyl ethyl ketone of silica fine particles is filled therein. Dispersion liquid “MEK-ST-L” {average particle size 45 nm, solid content concentration 30% by mass, manufactured by Nissan Chemical Industries, Ltd.} 4.5 parts by mass, polysiloxane compound “X-22-164C” having an acryloyl group {Manufactured by Shin-Etsu Chemical Co., Ltd.} 0.15 parts by mass, photopolymerization initiator “Irgacure 907” {manufactured by Ciba Specialty Chemicals Co., Ltd.} 0.23 parts by mass, organosilane compound produced in Synthesis Example 3 (OS) Solution 2.0 parts by mass, methyl ethyl ketone 81.2 parts by mass and cyclohexanone 2.8 parts by mass were added and stirred. The solution was filtered through a polypropylene filter having a pore size of 1 μm to prepare a coating solution for forming a low refractive index layer (LL-5). The refractive index of the coating film by this coating solution was 1.44.

Formulation Example 2-6 {Preparation of coating solution for forming low refractive index layer (LL-6)}
A container equipped with a stirrer is charged with 10.5 parts by mass of a solution (solid content concentration of 30% by mass) of the perfluoroolefin copolymer (PF-1) produced in Synthesis Example 2 above, and this is combined with Formulation Example 2 above. MEK dispersion of hollow silica fine particles (refractive index 1.31, average particle size 60 nm, solid content concentration 20% by mass) prepared in 3-3, 6.75 parts by mass, polysiloxane compound having an acryloyl group “X-22— 164C "{manufactured by Shin-Etsu Chemical Co., Ltd.} 0.15 parts by mass, photopolymerization initiator" Irgacure 907 "{manufactured by Ciba Specialty Chemicals Co., Ltd.} 0.23 parts by mass, organo prepared in Synthesis Example 3 2.0 parts by mass of a silane compound (OS) solution, 81.2 parts by mass of methyl ethyl ketone, and 2.8 parts by mass of cyclohexanone were added and stirred. The solution is filtered through a polypropylene filter having a pore size of 1 μm to form a low refractive index layer forming coating solution (LL-6
) Was prepared. The refractive index of the coating film by this coating solution was 1.41.

[Evaluation of sedimentation property of resin particles of coating solution for forming optical functional layer (A)]
About the said optical function layer coating liquid (AL-2), (AL-8), (AL-9), and (RAL-2) (comparison), 5 hours of continuous coating was implemented by the slot die coating system. The slot die coater was disassembled after coating in each coating solution, and the amount of resin particles settled on the bottom of the coater was subjected to sensory evaluation. The results are shown below.
Coating solution (AL-2): No sediment was observed.
Coating solution (AL-8): A small amount of sediment was observed but was acceptable.
Coating solution (AL-9): Almost no precipitation was observed.
Coating solution (RAL-2) (comparative): Sedimentation was unacceptable.

Production Example 1
{Preparation of antistatic layer forming coating solution (ASL)}
For forming an antistatic layer, a liquid prepared by adding 20 parts by mass of methyl ethyl ketone to 100 parts by mass of a commercially available transparent antistatic coating “Pertron C-4456S-7” (solid content: 45%, manufactured by Nippon Pernox Co., Ltd.) Used as a coating solution (ASL). “Pertron C-4456S-7” is a transparent antistatic coating material containing conductive fine particles ATO dispersed using a dispersant. The refractive index after curing of the coating film with this paint was 1.57.

(Preparation of antistatic film)
On the triacetyl cellulose film “TAC-TD80U” {manufactured by Fuji Photo Film Co., Ltd.) having a thickness of 80 μm and a width of 1340 mm, an antistatic layer coating solution (ASL) is applied by a slot die coating method at a transport speed of 25 m / min. It apply | coated on the conditions of. After drying at 100 ° C. for 150 seconds, using a 240 W / cm air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) with nitrogen purge (oxygen concentration 0.5% or less), irradiation is 400 mW / cm ² . A sample of a film (antistatic film) having an antistatic layer (AS) was prepared by irradiating an ultraviolet ray with an amount of 500 mJ / cm ² to cure the coating layer.

Examples 1-1 to 1-25 and Comparative Examples 1-1 to 1-3
On the triacetyl cellulose film “TAC-TD80U” {manufactured by Fuji Photo Film Co., Ltd.} having a film thickness of 80 μm and a width of 1340 mm, or on the antistatic film produced as described above, the formulation examples 1-1 to 1- A slot die coating method using any one of the coating liquids (AL-1) to (AL-18) for forming the optical functional layer (A) prepared in 21 and the coating liquids for comparison (RAL-1) to (RAL-3). Then, the coating was performed under the condition of a conveyance speed of 25 m / min. After drying at 60 ° C. for 150 seconds, using a 160 W / cm air-cooled metal halide lamp {manufactured by Eye Graphics Co., Ltd.) with nitrogen purge (oxygen concentration of 0.5% or less), irradiation is 400 mW / cm ² , irradiation The coating layer was cured by irradiating with an ultraviolet ray having an amount of 250 mJ / cm ² .

  Next, on the optical functional layer (A), any one of the coating liquids (LL-1) to (LL-6) for forming a low refractive index layer is applied by a slot die coating method at a conveying speed of 25 m / min. Applied. The drying and curing conditions for each coating solution for forming a low refractive index layer were as follows. Thus, film samples (101) to (124), (201) to (203) and (301) having the optical functional layer (A) and the low refractive index layer were produced.

Low refractive index layer forming coating solutions (LL-1) to (LL-3): After drying at 120 ° C. for 150 seconds and further drying at 140 ° C. for 8 minutes, nitrogen purge (oxygen concentration 0.5% by volume) The coating layer is cured by irradiating ultraviolet rays with an illuminance of 400 mW / cm ² and an irradiation amount of 900 mJ / cm ² using a 240 W / cm air-cooled metal halide lamp {manufactured by Eye Graphics Co., Ltd.} Refractive index layers (outermost layers) (L-1) to (L-3) were formed.

  Low refractive index layer forming coating solution (LL-4): After drying at 120 ° C. for 150 seconds, heat treatment is further performed at 140 ° C. for 20 minutes to cure the coating layer, and the low refractive index layer (outermost layer) (L-4) Formed.

Low refractive index layer forming coating solutions (LL-5) and (LL-6): After drying at 90 ° C. for 30 seconds, a nitrogen-purged (oxygen concentration of 0.5% or less) 240 W / cm air-cooled metal halide lamp ( Using an iGraphics Co., Ltd.), an ultraviolet ray having an illuminance of 600 mW / cm ² and an irradiation amount of 600 mJ / cm ² is applied to cure the coating layer, and the low refractive index layer (outermost layer) (L-5) and ( L-6) was formed.

  The coating combinations of the antistatic layer, the optical functional layer, and the low refractive index layer of the optical functional film sample according to the present invention are as described in Table 5.

  In the said Table 5, the film thickness of each layer shows the film thickness after drying, UV irradiation, or heat processing of each coating layer.

[Evaluation of optical functional film]
The following items were evaluated for each obtained optical functional film sample. The results are shown in Table 6.

(1) Evaluation of surface resistance The surface resistance of the optical functional film sample on the side having the low refractive index layer (outermost layer) was measured using a super insulation resistance / microammeter “TR8601” {manufactured by Advantest Co., Ltd.}. , 25 ° C. and 60% RH.

(2) Evaluation of dust removability The optical functional film sample was attached to a monitor, and dust (futon, fiber waste from clothes) was sprinkled on the monitor surface. The dust was wiped off with a cleaning cloth, the dust removal property was examined, and the following three grades were evaluated.
○: Dust completely removed.
Δ: Some dust remained (within tolerance).
×: Dust remains considerably.

(3) Evaluation of anti-glare property An exposed fluorescent lamp (8000 cd / cm ² ) without a louver was projected on the produced optical functional film sample, and the degree of blur of the reflected image was evaluated according to the following criteria.
A: The outline of the fluorescent lamp is hardly understood.
○: The outline of the fluorescent lamp is slightly understood.
Δ: The periphery of the fluorescent lamp looks whitish, but the outline can be identified (within an allowable range).
X: Fluorescent lamp is hardly blurred.

(4) Evaluation of average reflectance Using a spectrophotometer “V-550” {manufactured by JASCO Corp.}, spectral reflectance at an incident angle of 5 ° using an integrating sphere in a wavelength range of 380 to 780 nm. Was measured. In the evaluation of the spectral reflectance, an average reflectance of 450 to 650 nm was used.

(5) Evaluation of coated surface shape The optical functional film sample was cut 30 cm in the coating direction with the entire coating width, placed on the black cloth with the coating layer facing upward, and the surface shape was visually observed under an incandescent lamp. Evaluation based on the criteria.
A: No point defect or streak defect is observed.
○: If you look carefully, weak spot defects and streaky defects are partially seen.
Δ: Some weak point defects or streak defects are observed.
Δ ×: weak point defects and streak-like defects are seen in full width.
×: Strong point defects and streak-like defects can be seen in the full width.

  From the results of Tables 4 and 6, the amount of resin particles settled is 30% by mass or less and the gel fraction is in the range of 70 to 95% by mass for forming an optical functional layer according to the present invention. Optical functional films of Examples 1-1 to 1-22, and 1-25 (samples 101 to 122 and 301) prepared using coating solutions (AL-1) to (AL-15) and (AL-18) ) Is excellent in anti-glare properties, and further exhibits both anti-glare properties and good coated surface properties, and is excellent in anti-reflection enhancement. On the other hand, the optical functional film of Comparative Example 1-1 (sample 123) produced using a coating liquid (RAL-1) containing comparative resin particles (RJ-1) whose gel fraction is too low. Although the coated surface was good, the antiglare property was not exhibited after coating. Moreover, the optical function film (sample 124) of Comparative Example 1-2 produced using the coating liquid (RAL-2) containing the comparative resin particles (RJ-2) having a gel fraction that is too high, The amount of settled particles was large, and many point defects and streaks due to agglomerates were generated in the film sample after coating, and it was impossible to achieve both coating surface shape and antiglare property.

Furthermore, when the optical functional film (sample 124) of Comparative Example 1-2 was magnified and photographed with an optical microscope and the number of resin particles was counted, it was compared with the optical functional film (Sample 111) of Example 1-11 of the present invention. The number of particles was 18% less.
Thus, it is clear that the above-described effect is due to the effect of the present invention by optimally selecting the physical properties of the resin particles and the coating solvent.

Example 11
[Evaluation of image display device]
The optical functional films of Examples 1-1 to 1-25 (samples 101 to 122, 201 to 202, and 301) are transmissive and reflective in the image display device (TN, STN, IPS, VA, or OCB mode). Alternatively, the display device is mounted on a display surface of a transflective liquid crystal display device and a plasma display panel (PDP), an electroluminescence display (ELD), or a cathode tube display device (CRT). The image display devices using the optical functional films of Samples 101 to 122 and 301 of the present invention are all excellent in antiglare property, antireflection property, dustproof property, scratch resistance, and antifouling property. The image display apparatus used had wide viewing angles in the vertical and horizontal directions due to the light diffusion effect, and had good visibility.
In addition, there was no occurrence of glare failure in the image display device when the area of the cut surface was not more than 100 μm ² and the pixel size was 100 ppi (100 pixels / inch: 100 pixels per inch length). .

Example 12
[Preparation of protective film for polarizing plate]
A saponification solution was prepared by keeping a 1.5 mol / L sodium hydroxide aqueous solution at 50 ° C. Furthermore, a 0.005 mol / L dilute sulfuric acid aqueous solution was prepared.

In the optical functional films (Samples 101 to 122) of Examples 1-1 to 1-22, the surface of the transparent support opposite to the side having the low refractive index layer (outermost layer) was used with the saponification solution. Saponification treatment was performed. The aqueous sodium hydroxide solution on the surface of the saponified transparent support was thoroughly washed with water, then washed with the above dilute sulfuric acid aqueous solution, and further the dilute sulfuric acid aqueous solution was thoroughly washed with water.
And dried thoroughly.
When the contact angle to water of the surface of the transparent support on the saponified side of the optical functional film was evaluated, it was 40 ° or less. Thus, the protective film for polarizing plates was produced.

[Preparation of polarizing plate]
On one surface of the polarizing film described in Japanese Patent Application Laid-Open No. 2002-86554, an optical material of the present invention produced as described above using a 3% by mass aqueous solution of PVA {"PVA-117H"} manufactured by Kuraray Co., Ltd. as an adhesive. The transparent support (triacetylcellulose) surface of the functional film (protective film for polarizing plate) subjected to saponification treatment was bonded. Further, on the other surface of the polarizing film, a saponified triacetylcellulose film {"Fujitack" manufactured by Fuji Photo Film Co., Ltd., retardation value 3.0 nm} was used in the same manner as above. And pasted together. Thus, the polarizing plate of this invention was produced.

[Evaluation of image display device]
The polarizing plate of the present invention thus produced was mounted on a TN, STN, IPS, VA, OCB mode transmissive, reflective, or transflective liquid crystal display device. Thus, all the liquid crystal display devices equipped with the polarizing plate of the present invention were excellent in antiglare property and excellent in antireflection property, dustproof property, scratch resistance and antifouling property.

  In addition, the same result was obtained also in the polarizing plate produced using the well-known polarizing film and using the optical function film (protective film for polarizing plates) of this invention similarly to the above.

Example 13
[Preparation of polarizing plate]
The surface of the optical compensation film “Wide View Film SA 12B” {manufactured by Fuji Photo Film Co., Ltd.) opposite to the side having the optically anisotropic layer was saponified under the same conditions as in Example 12.

  Next, a saponification treatment of the optical functional film (protective film for polarizing plate) produced in Example 12 on one surface of the same polarizing film as used in Example 12 in the same manner as in Example 12. The polarizing plate of the present invention was prepared by bonding the surface of the optical compensation film to the other surface and bonding the surface of the optical compensation film subjected to the saponification treatment to the other surface.

[Evaluation of image display device]
The polarizing plate of the present invention thus produced was mounted on a TN, STN, IPS, VA, OCB mode transmissive, reflective, or transflective liquid crystal display device. Thus, the liquid crystal display device equipped with the polarizing plate of the present invention is superior in anti-glare property and contrast in a bright room than the liquid crystal display device equipped with the polarizing plate not using the optical compensation film. Excellent, wide viewing angle, top / bottom / left / right, and excellent antireflection, dustproof, scratch resistance and antifouling properties.
In particular, due to the light scattering effect of the resin particles, the viewing angle in the downward direction is remarkably widened, and the yellowness in the horizontal direction is improved.

  It should be noted that the same results were obtained with polarizing plates prepared in the same manner as described above, using various known polarizing films, and using the optical functional film of the present invention (protective film for polarizing plate) and single-sided saponified optical compensation film. was gotten.

Examples 14-1 to 14-2 Comparative Example 14-1
[Preparation of polarizing plate]
Optical functional films prepared in Examples 1-23-24 and Comparative Example 1-3 (Samples 201-2)
03) was subjected to a saponification treatment in the same manner as in Example 12. Similarly, the surface of the optical compensation film “Wide View Film SA 12B” {manufactured by Fuji Photo Film Co., Ltd.) opposite to the side having the optical anisotropic layer was saponified under the same conditions as in Example 12. .

  Next, in the same manner as in Example 12, on one surface of the polarizing film similar to that used in Example 12, the optical functional film (samples 201 to 203) (protective film for polarizing plate) The surface on the saponified side was bonded, and the surface on the saponified side of the optical compensation film was bonded to the other surface to produce a polarizing plate.

[Evaluation of image display device]
A TN, STN, IPS, VA, OCB mode transmission type, reflection type, or transflective type liquid crystal having the optical functional film {samples 201 to 202} produced in this manner and equipped with an optical compensation film. Due to the light diffusing effect, the display device had better contrast in a bright room than the liquid crystal display device using 203 (Comparative Example), wide viewing angles in the vertical and horizontal directions, and good visibility. In particular, the liquid crystal display device to which the sample 201 of the present invention was applied had a significantly wider viewing angle in the lower direction than the device to which the sample 202 was applied, and the yellowness in the left-right direction was improved.

Example 15
[Evaluation of image display device]
When the optical functional films of Examples 1-1 to 1-25 (samples 101 to 122, 201 to 202, and 301) were mounted on an organic EL display device, the samples 101 to 122 and 301 were excellent in antiglare properties. It was excellent in antireflection, dustproof, scratch resistance, and antifouling properties, and the samples 201 and 202 had a wide viewing angle in the vertical and horizontal directions due to the light diffusion effect and good visibility.

Example 16
[Preparation of polarizing plate and evaluation of image display device]
A polarizing plate protective film produced in Example 12 on one side of the polarizing film and a polarizing plate having a λ / 4 plate on the other side were produced in the same manner as in Example 13. When the obtained polarizing plate was mounted on an organic EL display device, the antiglare property was high, and reflection of light from the glass surface on which the polarizing plate was attached was cut, and a display device with extremely high visibility was obtained.

Claims (14)

In the optical functional film having at least one optical functional layer (A) containing resin particles having an average particle diameter of 1 to 8 μm and a binder matrix on the transparent support,
The optical functional layer (A) is a layer formed by a method of applying a coating liquid containing resin particles having an average particle diameter of 1 to 8 μm, a matrix-forming binder and an organic solvent on a transparent support, The amount of resin particles that settle after the coating solution is allowed to stand at 25 ° C. for 24 hours is 30% by mass or less with respect to the total amount of resin particles in the coating solution, and the gel fraction of the resin particles is 70 to 70%. An optical functional film, characterized by being 95% by mass.   The resin particles are crosslinked with a bifunctional or higher functional crosslinkable monomer, and the content of the crosslinkable monomer is 2 to 10 mol% with respect to the total monomers for forming the resin particles. Optical functional film. The optical functional film according to claim 1 or 2, wherein the difference between the density of the organic solvent contained in the coating liquid and the density of the resin particles is 0.20 g / cm ³ or less.   The difference between the I / O value of the organic solvent contained in the coating liquid and the I / O value of the resin particles is 0.4 or less, and the I / O value of the organic solvent is greater than 0. The optical function film in any one.   The optical function film according to any one of claims 1 to 4, wherein the refractive index of the binder matrix is 1.45 to 1.90, and the refractive index difference between the binder matrix and the resin particles is 0 to 0.30.   The film thickness of the optical functional layer (A) is 3 to 10 μm, and the average particle diameter of the resin particles contained in the optical functional layer (A) is 30 with respect to the film thickness of the optical functional layer (A). The optical functional film according to claim 1, which is in a range of ˜100%. An optical functional layer (A) or an optical functional layer (B) other than the optical functional layer (A) and the optical functional layer (A) is provided on the transparent support, and any one of the layers has the following general formula (1) The optical functional film in any one of Claims 1-6 containing at least 1 sort (s) of the organosilane compound represented by this, and its derivative (s).
Formula _{^{(1) :( R 10) s}} -Si (Z) 4-s
(In the formula, R ¹⁰ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. Z represents a hydroxyl group or a hydrolyzable group. S represents an integer of 1 to 3) The optical functional layer (B) is a low refractive index layer, and the low refractive index layer is formed by a crosslinking reaction or a polymerization reaction of a fluorine-containing compound represented by the following general formula (2). 8. The optical functional film according to any one of 7.
General formula (2):

(In the formula, L ²¹ represents a linking group having 1 to 10 carbon atoms, m1 represents 0 or 1, X represents a hydrogen atom or a methyl group, A represents a polymerization unit of any vinyl monomer, and It may be a polymer unit or may be composed of a plurality of polymer units, where x, y and z represent the mol% of each constituent polymer unit, 30 ≦ x ≦ 60, 5 ≦ y ≦ 70, 0 ≦ z. Represents a value satisfying ≦ 65.)   The optical functional film according to claim 8, wherein the low refractive index layer further contains hollow silica fine particles. The optical functional layer (A) according to any one of claims 1 to 9 or the optical functional layer (B) according to any one of claims 7 to 9 is formed by applying a coating liquid by a die coating method. A method for producing an optical functional film.   A coating liquid for forming an optical functional layer containing resin particles having an average particle diameter of 1 to 8 μm, a matrix-forming binder and an organic solvent, wherein the resin particles are based on all monomers forming the resin particles. The amount of resin particles settled on the bottom after the coating solution is allowed to stand for 24 hours is determined by the coating solution. A coating solution for forming an optical functional layer, which is 30% by mass or less with respect to the total amount of resin in the resin, and the gel fraction of the resin particles is 70% by mass to 95% by mass.   The optical functional film according to claim 1 or the optical functional film produced by the method according to claim 10 is used for at least one of the two protective films of the polarizing film. A characteristic polarizing plate.   The optical functional film according to claim 1, the optical functional film produced by the method according to claim 10, or the polarizing plate according to claim 12 is disposed on the image display surface. An image display device characterized by the above.   14. The image display device according to claim 13, wherein the image display device is a TN, STN, IPS, VA, or OCB mode transmissive, reflective, or transflective liquid crystal display device.