JP2007264113A - Optical film, polarizing plate, and image display device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an optical film which is high in contrast, is free from glare and character blurring, and is good in black tightness and a polarizing plate and display device using the optical film. <P>SOLUTION: The optical film having a light diffusion layer on a transparent support body is characterized in that; the ratio I(0°)/IO of the exit light intensity I(0°) in the normal direction of the surface of the film when the transmission scattered light is the exit light intensity IO in the normal direction of the transparent support body is 30 to 100%; the ratio I(6°)/IO in the position inclined 6° in the longitudinal direction of the film from the normal direction of the film surface is 0.70 to 5.0%; and the ratio I(30°)/IO to IO of the exit light intensity I(30°) in the position inclined 30° in the longitudinal direction of the film from the normal direction of the film surface is 0.0001 to 0.007%. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

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

  In recent years, liquid crystal display devices (LCD) have increased in screen size, and for example, liquid crystal display devices having an optical film such as an antireflection film or a light diffusion sheet are increasing. For example, the antireflection film is used in various image display devices such as a liquid crystal display device (LCD), a plasma display panel (PDP), an electroluminescence display (ELD), and a cathode ray tube display device (CRT). In order to prevent a decrease in contrast due to image reflection, it is arranged on the surface of the display. Further, as the antireflection film, an antiglare antireflection film imparted with an antiglare property using light diffusibility or the like is also used.

  In addition, in the case of data broadcasting by digital high-definition broadcasting that has been carried out in recent years, the liquid crystal display device has 1) improved contrast (white brightness UP, black brightness down), 2) higher definition (reducing glare, Reduction of character blur) 3) Excellent blackening in a state where the display body is displayed in black 4) Improvement of viewing angle, etc. are required.

  Due to the occurrence of “glare”, the display quality of a high-definition display device is significantly deteriorated. This phenomenon is caused by variation in luminance generated in light reaching the user's eyes through the light diffusion sheet due to the so-called “lens effect” due to the surface projection that imparts antiglare properties becomes a minute lens.

  As a light diffusing film satisfying the improvement of glare, an antiglare antireflection film which defines scattering angle intensities I (5 °) / I (0 °) and I (20 °) / I (0 °) is disclosed. (Patent Document 1). In this document, since the refractive index difference between the refractive index of the light diffusing layer and the translucent particles contained therein is large, by increasing the internal scattering and scattering angle of the light passing through the light diffusing layer, A method for suppressing glare has been proposed.

Moreover, the anti-glare film whose scattering angle which shows the maximum value of scattered light intensity is 0.1-10 degrees is disclosed (patent document 2).
JP 2003-248101 A JP 2004-306328 A

In the invention described in Patent Document 1, although the glare reduction and the character blur can be improved, the internal scattering property is too high, so that a decrease in white luminance during white display and an increase in black luminance during black display may occur. is there.
In the invention described in Patent Document 2, it is necessary to provide antiglare properties by layer separation by spinodal decomposition, and the structure needs to be highly controlled, and mass production is expected to be very difficult.
Therefore, development of an optical film having a light diffusion layer that satisfies the above 1) to 4) improvements is desired.
The object of the present invention is to have anti-glare properties, 1) improvement of contrast, 2) higher definition (glare and character blurring reduction), 3) blackening in a state where the display body is displayed in black, 4) It is to provide an optical film that simultaneously satisfies the widening of the viewing angle. Another object of the present invention is to provide a polarizing plate and a display device using such an optical film.

As a result of intensive studies to solve the above-described problems, the present inventors have completed the present invention by adopting the following configuration.
That is, the present invention has been achieved by the following configuration.

(1)
An optical film having a light diffusing layer on a transparent support, wherein transmitted scattered light has an emitted light intensity I0 in the normal direction of the transparent support,
The ratio I (0 °) / I0 of the emitted light intensity I (0 °) in the normal direction of the film surface to I0 is 30% to 100%,
The ratio I (6 °) / I0 of the emitted light intensity I (6 °) to I0 at a position inclined by 6 ° from the normal direction of the film surface to the longitudinal direction of the film is 0.70% to 5.0%, and,
The ratio I (30 °) / I0 of the emitted light intensity I (30 °) to I0 at a position inclined by 30 ° from the normal direction of the film surface to the longitudinal direction of the film is 0.0001 to 0.007%. A featured optical film.
(2)
The ratio I (0 °) / I0 of the emitted light intensity I (0 °) in the normal direction of the surface of the film to the I0 is 40% to 95%,
The ratio I (6 °) / I0 of the emitted light intensity I (6 °) to I0 at a position inclined by 6 ° from the normal direction of the film surface to the longitudinal direction of the film is 1.0% to 4.5%. ,and,
The ratio I (30 °) / I0 of the emitted light intensity I (30 °) to I0 at a position inclined by 30 ° from the normal direction of the film surface to the longitudinal direction of the film is 0.0005 to 0.004%.
The optical film as described in (1), wherein
(3)
The optical film according to (1) or (2), wherein an internal haze of the optical film is 10 to 40%.
(4)
The arithmetic average roughness (Ra) of the light diffusion layer is 0.03 to 0.30 μm, and the average interval (Sm) of the unevenness is 40 to 200 μm. The optical film in any one.
(5)
The optical film according to any one of (1) to (4), wherein a surface haze of the optical film is 0.3 to 20%.
(6)
The optical film according to any one of (1) to (5), wherein the light diffusion layer contains an ionizing radiation curable compound, an organosilane compound, and translucent particles.
(7)
The difference between the refractive index of the light transmissive particles contained in the light diffusing layer and the refractive index of the light diffusing layer excluding the light transmissive particles is less than 0.05 as an absolute value (1) )-(6) The optical film in any one.
(8)
The optical film according to any one of (1) to (7), wherein the light diffusion layer includes a plurality of aggregated portions of translucent fine particles having a three-dimensional solid structure and has an uneven surface shape. .
(9)
The optical film according to any one of (1) to (8), wherein the light diffusing layer is at least two layers, and translucent fine particles are present in the lower layer.
(10)
The optical film according to any one of (1) to (9), which has a low refractive index layer having a lower refractive index than that of the transparent support directly or via another layer on the transparent support.
(11)
A polarizing plate having a polarizing film between two protective films, wherein at least one of the protective films is the optical film according to any one of (1) to (10). Polarizer.
(12)
An image display device having the optical film according to any one of (1) to (10) or the polarizing plate according to (11), wherein the light diffusing layer is disposed on the viewing side. An image display device.

  ADVANTAGE OF THE INVENTION According to this invention, the contrast of the display which applied the optical film of this invention is high, there is no character blur, and the optical film which can suppress a feeling of blackening and a glare feeling predominately is obtained. In addition, the display device provided with the antireflection film of the present invention and the display device provided with the polarizing plate using the optical film of the present invention have very low visibility and little reflection of external light and background. The display quality is high. Furthermore, according to the present invention, an optical film that has high contrast, no character blur, and can suppress the feeling of darkening and glare can be easily manufactured at low cost.

  In particular, in the optical film of the present invention, the improvement of the contrast is not only the dark room contrast that can be realized in a dark room at night, but also the improvement of the bright room contrast in a bright room by daylight or by a room light. .

  Hereinafter, the present invention will be described in more detail. In the present specification, when a numerical value represents a physical property value, a characteristic value, etc., the description “(numerical value 1) to (numerical value 2)” means “(numerical value 1) or more and (numerical value 2) or less”. . In the present specification, the description “(meth) acrylate” means “at least one of acrylate and methacrylate”. The same applies to “(meth) acrylic acid” and the like. Furthermore, the term “on the support” in the present invention includes both the case where the surface directly refers to the support and the case where the surface includes a layer (film) provided on the support. is there.

As described above, the optical film of the present invention is an optical film having a light diffusion layer on a transparent support, and the light diffusion layer has a specific scattering intensity.
In the conventional technology, a light diffusion film using silica particles having a low internal scattering (haze) as a light diffusion layer has a high luminance for white display and a luminance for black display when installed in a liquid crystal display device. Is a film with low contrast, so-called high contrast, but the glare and letter blur are very poor and the viewing angle does not widen.
On the other hand, a film with high internal scattering (haze) improves glare and character blur and widens the viewing angle, but lowers brightness in white display and brightness in black display, so-called contrast is low.
In conventional research, contrast, glare, text blur, and viewing angle expansion cannot be controlled independently, and it has not been possible to satisfy all of them.
The present inventors have made sincere efforts to clarify that the contrast (white luminance, black luminance), glare, character blur, and black spots correlate with the angle of transmitted scattered light (also referred to as transmitted diffused light). By determining the shape of the scattered light, they found that the contrast, glare, text blur, and viewing angle expansion were all satisfied. Originally, it is thought that the optimal diffusion angle distribution can be obtained by calculation from the light scattering profile of the cell of the liquid crystal display device and the light diffusion profile of the optical film, but the actual observation and the calculated value do not match, It was difficult to clarify the relationship between optical performance and transmitted diffused light from the viewpoint of calculation.
Films with different shapes of transmitted and scattered light were prepared and analyzed for transmission and scattering angles that correlated with contrast, glare, text blur, and viewing angle expansion. As a result, white luminance was -2 ° to 2 ° of transmitted and scattered light. The black luminance was correlated with the transmitted scattered light of 20 ° to 40 °, the glare and letter blur was 4.5 ° to 6.5 °, and the black spot was correlated with 20 ° to 40 °. Based on the results, the inventors determined the light intensity at three locations (−2 ° to 2 °, 4.5 ° to 6.5 °, and 20 ° to 40 °) of the transmitted scattered light, thereby increasing the contrast. , Found a film that satisfies all of the glare, blurred characters, and black spots. Since transmitted scattered light does not have a strong peak angle distribution profile other than 0 °, it is used as a representative value for each of the scattering intensity values of 0 °, 6 °, and 30 °.

  Specifically, when the transmitted scattered light has an outgoing light intensity I0 in the normal direction of the transparent support, the ratio I (0 °) of the outgoing light intensity I (0 °) in the normal direction of the film surface to I0. / I0 is preferably 30% to 100%, more preferably 40% to 95%, and most preferably 60% to 90%. When it is 30% to 100%, the white luminance at the time of white color development does not decrease, and the display screen is not darkened, which is preferable.

  Further, the ratio I (6 °) / I0 of the emitted light intensity I (6 °) to I0 at a position inclined by 6 ° from the normal direction of the film surface to the longitudinal direction of the film is 0.70% to 5.0%. Preferably, it is 1.0% to 4.5%, more preferably 1.2% to 4.0%. When it is 0.70 to 5.0%, glare does not occur even in a high-definition liquid crystal display device of 150 ppi (150 pixels / inch) or less, and character blurring does not occur.

  The ratio I (30 °) / I0 of the emitted light intensity I (30 °) to I0 at a position inclined by 30 ° from the normal direction of the film surface to the longitudinal direction of the film is 0.0001 to 0.007%. Preferably, it is 0.0005% to 0.004%, more preferably 0.001% to 0.003%. If it is 0.0001 to 0.007%, the black luminance in black display does not increase, and the darkness when viewing a dark scene such as a movie in an environment with particularly low illuminance is not bright, and deep black is expressed. it can.

  The ratios I (0 °) / I0, I (6 °) / I0, and I (30 °) / I0 are 30% to 100%, 0.70% to 5.0%, 0.0001 to 0.007, respectively. %, Preferably 40% to 95%, 1.0% to 4.5%, more preferably 0.0005% to 0.004%, 60% to 90%, 1.2% to 4.0% and 0.001% to 0.003% are particularly preferable.

  These physical property values are related to the surface shape and internal scattering characteristics of the optical film, and the light diffusion layer is mainly formed of translucent particles (also called translucent fine particles) and translucent resin (also called binder). <1> difference in refractive index between the light diffusing layer excluding the light transmitting fine particles and the light transmitting fine particles, <2> the particle size of the light transmitting fine particles, and <3> the amount of the light transmitting fine particles used. <4> Thickness of the light diffusing layer, <5> Coating liquid solvent composition / coating / drying conditions, <6> Hydrophobic hydrophobicity of the translucent fine particles and the translucent resin. In the present invention, in order to obtain a desired angle profile of transmitted diffused light, in particular, in order to achieve the light intensity at three positions of the angle profile of transmitted scattered light, these <1> to <6> conditions are controlled, Solved.

In controlling the angle profile of transmitted diffused light, the characteristics of the scatterers (translucent particles and transparent resin) are important in the above embodiment. In general, the characteristics of the scatterer should be determined by the combination of <1> the refractive index difference between the light diffusing layer excluding the translucent particles and the translucent particles, and <2> the particle diameter of the translucent particles. As described above, in order to increase the low-angle (4.5 ° to 6.0 °) scattering and reduce the wide-angle (20 ° to 30 °) scattering, <3> It is necessary to precisely control <1> to <3> including the amount used.
On the contrary, if the angle profile of scattered light becomes a desired value, it is not necessary to limit <1> to <3>. Further, even if non-spherical translucent particles or phase separation is used as the scatterer, a desired angle profile of transmitted diffused light can be obtained.
The explanation regarding each control factor will be given below.

  The optical film of the present invention is an optical film having a light diffusion layer on a transparent support. It is also preferable that the light diffusion layer contains translucent particles and a binder. The optical film of the present invention can be suitably used as an antireflection film by laminating a low refractive index layer directly or via another layer on the light diffusion layer of the optical film. In the present specification, a layer having physical and optical functions formed on a transparent support is referred to as a functional layer. The optical film and antireflection film of the present invention can have other functional layers as required in addition to functional layers such as a light diffusion layer and a low refractive index layer.

1. First, the various compounds that can be used in the film of the present invention will be described.

First, components used to form a binder for each layer of the film, such as an ionizing radiation curable compound, an organosilane compound used as necessary, and an initiator will be described.
The light diffusion layer in the present invention preferably contains an ionizing radiation curable compound, an organosilane compound, and translucent particles.

1- (1) Multifunctional monomer, polyfunctional oligomer The film of the present invention can be formed by a crosslinking reaction or a polymerization reaction of an ionizing radiation curable compound. That is, a coating composition containing an ionizing radiation-curable polyfunctional monomer or polyfunctional oligomer as a component for forming a binder is coated on a transparent support, and the polyfunctional monomer or polyfunctional oligomer is subjected to a crosslinking reaction or a polymerization reaction. Can be formed.
The functional group of the ionizing radiation curable polyfunctional monomer or polyfunctional oligomer is preferably a light, electron beam, or radiation polymerizable group, and among them, a photopolymerizable functional group is preferable.
Examples of the photopolymerizable functional group include unsaturated polymerizable functional groups such as a (meth) acryloyl group, a vinyl group, a styryl group, and an allyl group. Among them, a (meth) acryloyl group is preferable.
Moreover, the film of this invention can also be formed using a thermosetting compound, and may use together an ionizing radiation-curable compound and a thermosetting compound.

As a specific example of a photopolymerizable polyfunctional monomer having a photopolymerizable functional group,
(Meth) acrylic acid diesters of alkylene glycol such as neopentyl glycol acrylate, 1,6-hexanediol (meth) acrylate, propylene glycol di (meth) acrylate;
(Meth) acrylic acid diesters of polyoxyalkylene glycols such as triethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate;
(Meth) acrylic acid diesters of polyhydric alcohols such as pentaerythritol di (meth) acrylate;
(Meth) acrylic acid diesters of ethylene oxide or propylene oxide adducts such as 2,2-bis {4- (acryloxy · diethoxy) phenyl} propane and 2-bis {4- (acryloxy · polypropoxy) phenyl} propane ;
Etc.

  Furthermore, epoxy (meth) acrylates, urethane (meth) acrylates, and polyester (meth) acrylates are also preferably used as the photopolymerizable polyfunctional monomer.

  Among these, esters of polyhydric alcohol and (meth) acrylic acid are preferable. More preferably, a polyfunctional monomer having 3 or more (meth) acryloyl groups in one molecule is preferable. Specifically, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, 1,2,4-cyclohexanetetra (meth) acrylate, pentaglycerol triacrylate, pentaerythritol tetra (meth) acrylate, penta Erythritol tri (meth) acrylate, (di) pentaerythritol triacrylate, (di) pentaerythritol pentaacrylate, (di) pentaerythritol tetra (meth) acrylate, (di) pentaerythritol hexa (meth) acrylate, tripentaerythritol triacrylate , Tripentaerythritol hexatriacrylate and the like.

As the monomer binder, monomers having different refractive indexes can be used to control the refractive index of each layer. Examples of particularly high refractive index monomers include bis (4-methacryloylthiophenyl) sulfide, vinyl naphthalene, vinyl phenyl sulfide, 4-methacryloxyphenyl-4′-methoxyphenyl thioether, and the like.
Further, for example, dendrimers described in JP-A-2005-76005 and JP-A-2005-36105, and norbornene ring-containing monomers as described in JP-A-2005-60425 can also be used.

Two or more polyfunctional monomers may be used in combination.
Polymerization of these monomers having an ethylenically unsaturated group can be carried out by irradiation with ionizing radiation or heating in the presence of a photo radical initiator or a thermal radical initiator.
It is preferable to use a photopolymerization initiator for the polymerization reaction of the photopolymerizable polyfunctional monomer. As the photopolymerization initiator, a photoradical polymerization initiator and a photocationic polymerization initiator are preferable, and a photoradical polymerization initiator is particularly preferable.

1- (2) Polymer Binder In the film of the present invention, an uncrosslinked polymer or a crosslinked polymer can be applied to the binder component. The crosslinked polymer preferably has an anionic group. The polymer having a crosslinked anionic group has a structure in which the main chain of the polymer having an anionic group is crosslinked.

Examples of the polymer main chain include polyolefin (saturated hydrocarbon), polyether, polyurea, polyurethane, polyester, polyamine, polyamide and melamine resin. A polyolefin main chain, a polyether main chain and a polyurea main chain are preferable, a polyolefin main chain and a polyether main chain are more preferable, and a polyolefin main chain is most preferable.
The polyolefin main chain consists of saturated hydrocarbons. The polyolefin main chain is obtained, for example, by an addition polymerization reaction of an unsaturated polymerizable group. The polyether main chain has repeating units bonded by an ether bond (—O—). The polyether main chain is obtained, for example, by a ring-opening polymerization reaction of an epoxy group. In the polyurea main chain, repeating units are bonded by a urea bond (—NH—CO—NH—). The polyurea main chain is obtained, for example, by a condensation polymerization reaction between an isocyanate group and an amino group. In the polyurethane main chain, repeating units are bonded by a urethane bond (—NH—CO—O—). The polyurethane main chain is obtained, for example, by a polycondensation reaction between an isocyanate group and a hydroxyl group (including an N-methylol group). The polyester main chain has repeating units bonded by an ester bond (—CO—O—). The polyester main chain is obtained, for example, by a polycondensation reaction between a carboxyl group (including an acid halide group) and a hydroxyl group (including an N-methylol group). The polyamine main chain has repeating units bonded by imino bonds (—NH—). The polyamine main chain is obtained, for example, by a ring-opening polymerization reaction of an ethyleneimine group. The polyamide main chain has repeating units bonded by an amide bond (—NH—CO—). The polyamide main chain is obtained, for example, by a reaction between an isocyanate group and a carboxyl group (including an acid halide group). The melamine resin main chain is obtained, for example, by a polycondensation reaction between a triazine group (eg, melamine) and an aldehyde (eg, formaldehyde). In the melamine resin, the main chain itself has a crosslinked structure.

The anionic group is bonded directly to the main chain of the polymer or bonded to the main chain via a linking group. The anionic group is preferably bonded to the main chain as a side chain via a linking group.
Examples of the anionic group include a carboxylic acid group (carboxyl), a sulfonic acid group (sulfo), and a phosphoric acid group (phosphono), and a sulfonic acid group and a phosphoric acid group are preferable.
The anionic group may be in a salt state. The cation that forms a salt with the anionic group is preferably an alkali metal ion. Moreover, the proton of the anionic group may be dissociated.
The linking group that binds the anionic group and the polymer main chain is preferably a divalent group selected from —CO—, —O—, an alkylene group, an arylene group, and combinations thereof.

  The crosslinked structure is a structure in which two or more main chains are chemically bonded (preferably covalent bonds), but it is preferable to covalently bond three or more main chains. The crosslinked structure is preferably composed of a divalent or higher valent group selected from —CO—, —O—, —S—, a nitrogen atom, a phosphorus atom, an aliphatic residue, an aromatic residue, and combinations thereof.

  The crosslinked polymer having an anionic group is preferably a copolymer having a repeating unit having an anionic group and a repeating unit having a crosslinked structure. The proportion of the repeating unit having an anionic group in the copolymer is preferably 2 to 96% by mass, more preferably 4 to 94% by mass, and most preferably 6 to 92% by mass. The repeating unit may have two or more anionic groups. The proportion of the repeating unit having a crosslinked structure in the copolymer is preferably 4 to 98% by mass, more preferably 6 to 96% by mass, and most preferably 8 to 94% by mass.

The repeating unit of the polymer having a crosslinked anionic group may have both an anionic group and a crosslinked structure. Further, other repeating units (repeating units having neither an anionic group nor a crosslinked structure) may be contained.
Other repeating units are preferably a repeating unit having an amino group or a quaternary ammonium group and a repeating unit having a benzene ring. The amino group or the quaternary ammonium group has a function of maintaining the dispersed state of the inorganic particles, like the anionic group. The same effect can be obtained even when the amino group, quaternary ammonium group and benzene ring are contained in a repeating unit having an anionic group or a repeating unit having a crosslinked structure.
In a repeating unit having an amino group or a quaternary ammonium group, the amino group or quaternary ammonium group is directly bonded to the main chain of the polymer or bonded to the main chain through a linking group. The amino group or quaternary ammonium group is preferably bonded to the main chain as a side chain via a linking group. The amino group or quaternary ammonium group is preferably a secondary amino group, a tertiary amino group or a quaternary ammonium group, more preferably a tertiary amino group or a quaternary ammonium group. The group bonded to the nitrogen atom of the secondary amino group, tertiary amino group or quaternary ammonium group is preferably an alkyl group, preferably an alkyl group having 1 to 12 carbon atoms, Is more preferably an alkyl group of 1 to 6. The counter ion of the quaternary ammonium group is preferably a halide ion. The linking group that connects the amino group or quaternary ammonium group to the polymer main chain is a divalent group selected from -CO-, -NH-, -O-, an alkylene group, an arylene group, and combinations thereof. Preferably there is. When the polymer having a crosslinked anionic group contains a repeating unit having an amino group or a quaternary ammonium group, the ratio is preferably 0.06 to 32% by mass, and 0.08 to 30% by mass. It is more preferable that it is 0.1 to 28% by mass.

1- (3) Fluorine-containing polymer binder In the film of the present invention, a fluorine-containing polymer can be preferably used as a binder component, particularly in the low refractive index layer of the antireflection film.
Fluorinated vinyl monomers for forming a fluorinated polymer include fluoroolefins (eg, fluoroethylene, vinylidene fluoride, tetrafluoroethylene, hexafluoropropylene, etc.), (meth) acrylic acid moieties or fully fluorinated alkyl ester derivatives (For example, Biscoat 6FM (trade name, manufactured by Osaka Organic Chemical Industry Co., Ltd.) and R-2020 (trade name, manufactured by Daikin Industries, Ltd.)), complete or partially fluorinated vinyl ethers, and the like are preferable. Is a perfluoroolefin, and hexafluoropropylene is particularly preferable from the viewpoint of refractive index, solubility, transparency, availability, and the like. Increasing the composition ratio of these fluorinated vinyl monomers can lower the refractive index but lowers the film strength. In the present invention, it is preferable to introduce the fluorine-containing vinyl monomer so that the fluorine content of the fluorine-containing polymer is 20 to 60% by mass, more preferably 25 to 55% by mass, particularly preferably 30 to 50%. This is a case of mass%.

Examples of the structural unit for imparting crosslinking reactivity to the fluoropolymer include units represented by the following (A), (B), and (C).
(A): a structural unit obtained by polymerization of a monomer having a self-crosslinkable functional group in the molecule in advance such as glycidyl (meth) acrylate and glycidyl vinyl ether,
(B): a monomer having a carboxyl group, a hydroxy group, an amino group, a sulfo group, etc. (for example, (meth) acrylic acid, methylol (meth) acrylate, hydroxyalkyl (meth) acrylate, allyl acrylate, hydroxyethyl vinyl ether, hydroxybutyl vinyl ether) , Maleic acid, crotonic acid, etc.)
(C): reacting a compound having a crosslinkable functional group separately from the group that reacts with the functional group of (A) or (B) in the molecule with the structural unit of (A) or (B). Examples of the structural unit to be obtained include (for example, a structural unit that can be synthesized by a technique such as allowing acrylic acid chloride to act on a hydroxyl group).

  As the structural unit (C), a crosslinkable functional group different from the group that reacts with the functional group (A) or (B) is preferably a photopolymerizable group. Examples of the photopolymerizable group include (meth) acryloyl group, alkenyl group, cinnamoyl group, cinnamylideneacetyl group, benzalacetophenone group, styrylpyridine group, α-phenylmaleimide group, phenylazide group, sulfonylazide group, carbonyl Azide group, diazo group, o-quinonediazide group, furylacryloyl group, coumarin group, pyrone group, anthracene group, benzophenone group, stilbene group, dithiocarbamate group, xanthate group, 1,2,3-thiadiazole group, cyclopropene group, An azadioxabicyclo group etc. can be mentioned, These may be not only 1 type but 2 or more types. Of these, a (meth) acryloyl group and a cinnamoyl group are preferable, and a (meth) acryloyl group is particularly preferable.

Specific methods for preparing the photopolymerizable group-containing copolymer include, but are not limited to, the following methods.
a. A method of esterifying by reacting a (meth) acrylic acid chloride with a crosslinkable functional group-containing copolymer containing a hydroxyl group,
b. A method of urethanization by reacting an isocyanate group-containing (meth) acrylic ester with a crosslinkable functional group-containing copolymer containing a hydroxyl group,
c. A method of reacting (meth) acrylic acid with a crosslinkable functional group-containing copolymer containing an epoxy group,
d. A method in which a crosslinkable functional group-containing copolymer containing a carboxyl group is reacted with a containing (meth) acrylic acid ester containing an epoxy group for esterification.
The amount of the photopolymerizable group introduced can be arbitrarily adjusted. From the viewpoints of surface stability of the coating film, reduction of surface failure when coexisting with inorganic particles, and improvement of film strength, carboxyl groups, hydroxyl groups, etc. It is also preferable to leave a certain amount.

  In the fluorine-containing polymer useful in the present invention, a repeating unit derived from the above-mentioned fluorine-containing vinyl monomer and a structural unit for imparting crosslinking reactivity such as a repeating unit having a (meth) acryloyl group in the side chain, as necessary, Copolymerize other vinyl monomers as appropriate from various viewpoints such as adhesion to substrates, polymer Tg (contributes to film hardness), solubility in solvents, transparency, slipperiness, dustproof / antifouling properties, etc. You can also. 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 total in the fluoropolymer, and in the range of 0 to 40 mol%. More preferably, it is particularly preferably in the range of 0 to 30 mol%.

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

  The fluorine-containing polymer particularly useful in the present invention is a random copolymer of perfluoroolefin and vinyl ethers or vinyl esters. In particular, it preferably has a group capable of undergoing a crosslinking reaction alone (a radical reactive group such as a (meth) acryloyl group, a ring-opening polymerizable group such as an epoxy group or an oxetanyl group). These crosslinkable group-containing polymerized units preferably occupy 5 to 70 mol% of the total polymerized units of the polymer, particularly preferably 30 to 60 mol%. Regarding preferred polymers, JP-A-2002-243907, JP-A-2002-372601, JP-A-2003-26732, JP-A-2003-222702, JP-A-2003-294911, JP-A-2003-329804, JP-A-2004. -4444 and JP, 2004-45462, A can be mentioned.

  In addition, a polysiloxane structure is preferably introduced into the fluorine-containing polymer preferably used in the present invention for the purpose of imparting antifouling properties. There is no limitation on the method of introducing the polysiloxane structure, but for example, as described in JP-A-6-93100, JP-A-11-189621, JP-A-11-228631 and JP-A-2000-313709, the initiation of silicone macroazo A method of introducing a polysiloxane block copolymer component using an agent, and a method of introducing a polysiloxane graft copolymer component using a silicone macromer as described in JP-A-2-251555 and JP-A-2-308806. preferable. Particularly preferred compounds include the polymers of Examples 1, 2, and 3 of JP-A-11-189621, and the copolymers A-2 and A-3 of JP-A-2-251555. These polysiloxane components are preferably 0.5 to 10% by mass in the polymer, and particularly preferably 1 to 5% by mass.

  The preferred molecular weight of the fluorine-containing polymer that can be preferably used in the present invention is 5000 or more, more preferably 10,000 to 500,000, and most preferably 15,000 to 200,000. By using polymers having different average molecular weights in combination, it is possible to improve the surface state of the coating film and the scratch resistance.

  As described in JP-A-10-25388 and JP-A-2000-17028, a curing agent having a polymerizable unsaturated group may be used in combination with the above polymer. Moreover, combined use with the compound which has a fluorine-containing polyfunctional polymerizable unsaturated group as described in Unexamined-Japanese-Patent No. 2002-145952 is also preferable. Examples of the compound having a polyfunctional polymerizable unsaturated group include the polyfunctional monomer. These compounds are particularly preferred because they have a large combined effect for improving scratch resistance, particularly when a compound having a polymerizable unsaturated group is used in the polymer body.

1- (4) Organosilane compound At least one of the layers constituting the film of the present invention contains at least one of a hydrolyzate of an organosilane compound and / or a partial condensate thereof in the coating solution forming the layer. It is preferable from the viewpoint of scratch resistance that it contains a kind of component, a so-called sol component (hereinafter sometimes referred to as such).
In particular, in the antireflection film, it is particularly preferable that both the low refractive index layer and the light diffusion layer contain a sol component in order to achieve both antireflection ability and scratch resistance. This sol component is condensed by a drying and heating process after coating the coating solution to form a cured product and becomes a part of the binder of these layers. Moreover, when this hardened | cured material has a polymerizable unsaturated bond, the binder which has a three-dimensional structure is formed by irradiation of actinic light.

As the organosilane compound, those represented by the following general formula 1 can be preferably used.
General formula 1: (R < ¹ >) _m- Si (X) _4-m
In the general formula 1, R ¹ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. As an alkyl group, a C1-C30 alkyl group is preferable, More preferably, it is C1-C16, Most preferably, it is a C1-C6 thing. Specific examples of the alkyl group include methyl, ethyl, propyl, isopropyl, hexyl, decyl, hexadecyl and the like. Examples of the aryl group include phenyl and naphthyl, and a phenyl group is preferable.
X 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 or an ethoxy group), a halogen atom (for example, Cl, Br, I or the like). ) And R ² COO (R ² is preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Examples include CH ₃ COO, C ₂ H ₅ COO, etc.), preferably An alkoxy group, particularly preferably a methoxy group or an ethoxy group.
m represents an integer of 1 to 3, and is preferably 1 or 2.
When R ¹ and X there are a plurality, the plurality of R ¹ and X may be different even in the same, respectively.

In General Formula 1, the substituent contained in R ¹ 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, n-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 (such as phenoxy), alkylthio group (such as methylthio, ethylthio), arylthio group (such as phenylthio), alkenyl group (such as vinyl and 1-propenyl), acyloxy group (such as acetoxy, acryloyloxy, methacryloyloxy), alkoxy Carbonyl group (methoxycarbonyl, ethoxycarbonyl, etc. , Aryloxycarbonyl groups (phenoxycarbonyl, etc.), carbamoyl groups (carbamoyl, N-methylcarbamoyl, N, N-dimethylcarbamoyl, N-methyl-N-octylcarbamoyl, etc.), acylamino groups (acetylamino, benzoylamino, acrylicamino) , Methacrylamino and the like), and these substituents may be further substituted.
R ¹ is preferably a substituted alkyl group or a substituted aryl group.
When R ¹ there are a plurality, it may be different even multiple R ¹ is the same, respectively.
Two or more compounds of the general formula 1 may be used in combination.

As the organosilane compound used in the present invention, an organosilane compound having a vinyl polymerizable substituent represented by the following general formula 2 is also preferably used. In addition, the compound of the general formula 2 can be synthesized using two kinds of the compounds of the general formula 1 as starting materials.
General formula 2

In the above general formula 2, R ₂ 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.
Y represents a single bond or * -COO-**, * -CONH-** or * -O-**, preferably a single bond, * -COO-** or * -CONH-**, * -COO-** is more preferable, and * -COO-** is particularly preferable. * Represents a position bonded to ═C (R ₂ ) —, and ** represents a position bonded to L.

  In General Formula 2, L 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 preferable, an unsubstituted alkylene group, and an alkylene group having an ether or ester linking group inside is particularly preferable. 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.

In general formula 2, l and m represent the mol% of each of the two components. l represents a number satisfying an expression of l = 100−m, and m represents a number from 0 to 50. As for m, the number of 0-40 is more preferable, and the number of 0-30 is especially preferable.
R _{3 to} R ₅ are preferably a halogen atom, a hydroxyl group, an unsubstituted alkoxy group, or an unsubstituted alkyl group. R _{3 to} R ₅ are more preferably a chlorine atom, a hydroxyl group, or an unsubstituted alkoxy group having 1 to 6 carbon atoms, more preferably a hydroxyl group or an alkoxy group having 1 to 3 carbon atoms, and particularly preferably a hydroxyl group or a methoxy group.
R ₆ represents a hydrogen atom, an alkyl group, an alkoxy group, an alkoxycarbonyl group, a cyano group, a fluorine atom, or a chlorine atom. Examples of the alkyl group include a methyl group and an ethyl group. Examples of the alkoxy group include a methoxy group, an ethoxy group, and an alkoxycarbonyl group as 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.
R ₇ has the same meaning as R ^{1 in} formula 1 above, more preferably a hydroxyl group or an unsubstituted alkyl group, still more preferably a hydroxyl group or an alkyl group having 1 to 3 carbon atoms, and particularly preferably a hydroxyl group or a methyl group.

  Although the specific example of the starting material of the compound represented by the compound of General formula 1 below is shown, it is not limited. As described above, the compound of the general formula 2 can be synthesized using two kinds of the compounds of the general formula 1 as starting materials.

  M-48 Methyltrimethoxysilane

Of these, (M-1), (M-2), and (M-25) are particularly preferable as the organosilane containing a polymerizable group.
In order to obtain the effect of the present invention, the content of the organosilane containing the vinyl polymerizable group in the hydrolyzate of organosilane and / or its partial condensate is preferably 30% by mass to 100% by mass, The mass% is more preferably 100% by mass, and more preferably 70% by mass to 95% by mass. If the content of the organosilane containing the vinyl polymerizable group is 30% by mass or more, solids are produced, the liquid is turbid, the pot life is deteriorated, and the molecular weight is difficult to control (increase in molecular weight). Or problems such as difficulty in obtaining improved performance after polymerization (for example, scratch resistance of the antireflection film) due to a low content of the polymerizable group. When synthesizing the compound represented by the general formula 2, (M-1) and (M-2) as organosilanes containing the vinyl polymerizable group, and organosilanes having no vinyl polymerizable group ( It is preferable to use one of each of M-19) to (M-21) and (M-48) in combination in the above amounts.

  In order to stabilize the performance of the coated product, at least one of the hydrolyzate of organosilane and the partial condensate thereof preferably used in the present invention preferably suppresses volatility, specifically, 1 hour at 105 ° C. The amount of volatilization per unit is preferably 5% by mass or less, more preferably 3% by mass or less, and particularly preferably 1% by mass or less.

The sol component used in the present invention is prepared by hydrolysis and / or partial condensation of the organosilane.
In the hydrolysis condensation reaction, 0.05 to 2.0 mol, preferably 0.1 to 1.0 mol of water is added to 1 mol of the hydrolyzable group (X), and the presence of the catalyst used in the present invention is present. Under stirring at 25-100 ° C.

In at least one of the hydrolyzate of organosilane and its partial condensate used in the present invention, the mass average molecular weight of either the hydrolyzate of organosilane containing a vinyl polymerizable group or its partial condensate is the molecular weight. When excluding less than 300 components, 450 to 20000 is preferable, 500 to 10,000 is more preferable, 550 to 5000 is still more preferable, and 600 to 3000 is still more preferable.
Of the components having a molecular weight of 300 or more in the hydrolyzate of organosilane and / or its partial condensate, the component having a molecular weight of more than 20000 is preferably 10% by mass or less, more preferably 5% by mass or less. More preferably, it is 3 mass% or less. If the component having a molecular weight greater than 20000 is 10% by mass or less, a cured film obtained by curing such a curable composition containing a hydrolyzate of organosilane and / or a partial condensate thereof is transparent. And adhesion to the substrate are sufficient.

Here, the mass average molecular weight and the molecular weight were measured using a solvent tetrahydrofuran (THF) and a differential refractometer detection using a GPC analyzer using columns of TSKgel GMHxL, TSKgel G4000HxL, and TSKgel G2000HxL (all trade names manufactured by Tosoh Corporation). The molecular weight expressed in terms of polystyrene is based on the molecular weight, and the content of each molecular weight component 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%.
The dispersity (mass average molecule / number average molecular weight) is preferably 3.0 to 1.1, more preferably 2.5 to 1.1, still more preferably 2.0 to 1.1, and 1.5 to 1. 1 is particularly preferred.

The ²⁹ Si-NMR analysis of the hydrolyzate and partial condensate of organosilane used in the present invention can confirm the state in which X in the general formula 1 is condensed in the form of -OSi.
At this time, when three bonds of Si are condensed in the form of -OSi (T3), when two bonds of Si are condensed in the form of -OSi (T2), one bond of Si is- When the condensation is performed in the form of OSi (T1), and the case where Si is not condensed at all (T0), the condensation rate α is expressed by the following formula (II).
Formula (II): α = (T3 × 3 + T2 × 2 + T1 × 1) / 3 / (T3 + T2 + T1 + T0)
The condensation rate α is preferably 0.2 to 0.95, more preferably 0.3 to 0.93, and particularly preferably 0.4 to 0.9.
If it is at least the lower limit, hydrolysis and condensation will proceed sufficiently, and the monomer component will not increase, so that a film with sufficient curing can be obtained. Since the hydrolyzable group remains moderately, an excellent effect can be obtained by using these without reducing the interaction between the binder polymer, the resin substrate, the inorganic fine particles and the like.

Next, the hydrolyzate and partial condensate of the organosilane compound used in the present invention will be described in detail.
The hydrolysis reaction of organosilane and the subsequent condensation reaction are generally carried out in the presence of a catalyst. Catalysts include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid; organic acids such as oxalic acid, acetic acid, butyric acid, maleic acid, citric acid, formic acid, methanesulfonic acid, toluenesulfonic acid; sodium hydroxide, potassium hydroxide, ammonia Inorganic bases such as triethylamine, pyridine, etc .; metal alkoxides such as triisopropoxyaluminum, tetrabutoxyzirconium, tetrabutyltitanate, dibutyltin dilaurate; metals such as Zr, Ti or Al as the central metal Metal chelate compounds and the like; Fluorine-containing compounds such as KF and NH4F are listed.
The said catalyst may be used independently or may use multiple types together.

The organosilane hydrolysis / condensation reaction can be carried out in the absence of a solvent or in a solvent, but an organic solvent is preferably used in order to mix the components uniformly. For example, alcohols, aromatic hydrocarbons, ethers, Ketones and esters are preferred.
The solvent preferably dissolves the organosilane and the catalyst. In addition, it is preferable in the process that an organic solvent is used as a coating liquid or a part of the coating liquid, and those that do not impair solubility or dispersibility when mixed with other materials such as a fluorine-containing polymer are preferable.

Among these, examples of the alcohols include monohydric alcohols and dihydric alcohols. Among these, monohydric alcohols are preferably saturated aliphatic alcohols having 1 to 8 carbon atoms.
Specific examples of these alcohols include methanol, ethanol, n-propyl alcohol, i-propyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, ethylene glycol, diethylene glycol, triethylene glycol, ethylene glycol. And monobutyl ether.

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, cyclohexanone, and ethylene glycol monoethyl ether include ethyl acetate, propyl acetate, butyl acetate, and propylene carbonate.
These organic solvents can be used alone or in combination of two or more. The concentration of the solid content in the hydrolysis / condensation reaction of organosilane is not particularly limited, but is usually in the range of 1% by mass to 100% by mass.

In the hydrolysis reaction, 0.05 to 2 mol, preferably 0.1 to 1 mol of water is added to 1 mol of hydrolyzable group of the organosilane, in the presence or absence of the solvent, and It is carried out by stirring at 25-100 ° C. in the presence of a catalyst.
In the present invention, (wherein, ^{R 3} represents an alkyl group having 1 to 10 carbon atoms) Formula ^R 3 OH alcohol of the general formula ^R 4 COCH ₂ COR ⁵ (formula represented by, ^{R 4} is carbon From Zr, Ti, or Al having a ligand represented by a compound represented by an alkyl group having 1 to 10 carbon atoms, R ⁵ represents an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms) It is preferable to perform hydrolysis by stirring at 25 to 100 ° C. in the presence of at least one metal chelate compound having a selected metal as a central metal.
Alternatively, when a fluorine-containing compound is used for the catalyst, the F-containing compound has the ability to completely proceed with hydrolysis and condensation, so the degree of polymerization can be determined by selecting the amount of water to be added, and any molecular weight can be set Therefore, it is preferable. That is, in order to adjust the organosilane hydrolyzate / partial condensate having an average degree of polymerization M, (M-1) mol of water may be used with respect to M mol of hydrolyzable organosilane.

Metal chelate compounds (wherein, ^{R 3} represents an alkyl group having 1 to 10 carbon atoms) Formula ^R 3 OH alcohol and ^R 4 COCH ₂ COR ⁵ (wherein represented by, ^{R 4} is C 1 -C To 10 alkyl groups, R ⁵ represents an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms), and is selected from Zr, Ti, and Al. Any metal having a metal as a central metal can be suitably used without particular limitation. Within this category, two or more metal chelate compounds may be used in combination. The metal chelate compound used in the present invention has a general formula of Zr (OR ³ ) _p1 (R ⁴ COCHCOR ⁵ ) _p2 , Ti (OR ³ ) _q1 (R ⁴ COCHCOR ⁵ ) _q2 , and Al (OR ³ ) _r1 (R ⁴ Those selected from the group of compounds represented by COCHCOR ⁵ ) _r2 are preferred, and they serve to promote the condensation reaction of the hydrolyzate and partial condensate of the organosilane compound.
R ³ and R ⁴ in the metal chelate compound may be the same or different and each is 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, sec -Butyl group, t-butyl group, n-pentyl group, phenyl group and the like. R ⁵ represents an alkyl group having 1 to 10 carbon atoms as described above, or an alkoxy group having 1 to 10 carbon atoms such as a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, and n-butoxy. Group, sec-butoxy group, t-butoxy group and the like. Moreover, p1, p2, q1, q2, r1, and r2 in the metal chelate compound represent integers determined so as to be p1 + p2 = 4, q1 + q2 = 4, and r1 + r2 = 3, respectively.

Specific examples of these metal chelate compounds include tri-n-butoxyethylacetoacetate zirconium, di-n-butoxybis (ethylacetoacetate) zirconium, n-butoxytris (ethylacetoacetate) zirconium, tetrakis (n-propylacetate). Zirconium chelate compounds such as acetate) zirconium, tetrakis (acetylacetoacetate) zirconium, tetrakis (ethylacetoacetate) zirconium; diisopropoxy bis (ethylacetoacetate) titanium, diisopropoxy bis (acetylacetate) titanium, diiso Titanium chelate compounds such as propoxy bis (acetylacetone) titanium; diisopropoxyethyl acetoacetate aluminum, diisopropyl Poxyacetylacetonate aluminum, isopropoxybis (ethylacetoacetate) aluminum, isopropoxybis (acetylacetonate) aluminum, tris (ethylacetoacetate) aluminum, tris (acetylacetonate) aluminum, monoacetylacetonate bis (ethyl) An aluminum chelate compound such as acetoacetate) aluminum.
Among these metal chelate compounds, tri-n-butoxyethyl acetoacetate zirconium, diisopropoxybis (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. When the metal chelate compound is used within the above range, the condensation reaction of the organosilane compound is fast, the durability of the coating film is good, and the hydrolyzate and partial condensate of the organosilane compound and the metal chelate compound are contained. The storage stability of the composition is good.

In addition to the composition containing the sol component and the metal chelate compound, at least one of a β-diketone compound and a β-ketoester compound is preferably added to the coating solution used in the present invention. This will be further described below.
In the present invention, at least one of a β-diketone compound and a β-ketoester compound represented by the general formula R ⁴ COCH ₂ COR ⁵ is used as a stability improver for the composition used in the present invention. It works. That is, by coordinating with a metal atom in the metal chelate compound (a compound of at least one of zirconium, titanium and aluminum compounds), condensation of hydrolyzate and partial condensate of organosilane compound by these metal chelate compounds It is considered that the action of accelerating the reaction is suppressed and the action of improving the storage stability of the resulting composition is achieved. R ⁴ and R ⁵ constituting the β- diketone compound and β- ketoester compound are the same as R ⁴ and R ⁵ constituting the metal chelate compound.

  Specific examples of the β-diketone compound and β-ketoester compound include acetylacetone, methyl acetoacetate, ethyl acetoacetate, acetoacetate-n-propyl, acetoacetate-i-propyl, acetoacetate-n-butyl, acetoacetate- sec-butyl, acetoacetate-t-butyl, 2,4-hexane-dione, 2,4-heptane-dione, 3,5-heptane-dione, 2,4-octane-dione, 2,4-nonane-dione , 5-methyl-hexane-dione and the like. Of these, ethyl acetoacetate and acetylacetone are preferred, and acetylacetone is particularly preferred. These β-diketone compounds and β-ketoester compounds can be used alone or in admixture of two or more. In the present invention, the β-diketone compound and the β-ketoester compound are preferably used in an amount of 2 mol or more, more preferably 3 to 20 mol, per 1 mol of the metal chelate compound. By making it 2 mol or more, the storage stability of the composition obtained can be improved, which is preferable.

  The content of the hydrolyzate and partial condensate of the organosilane compound is preferably small in the case of a relatively thin antireflection layer and large in the case of a thick hard coat layer or light diffusion layer. The content is preferably 0.1 to 50% by mass based on the total solid content of the composition for forming a containing layer (added layer), considering the expression of the effect, the refractive index, the shape / surface shape of the film, and the like. 30 mass% is more preferable, and 1-15 mass% is the most preferable. Within this range, after coating, it is condensed by a drying and heating step to form a cured product, and becomes a part of the binder of the antireflection layer, hard coat layer, and light diffusion layer, and the scratch resistance is improved.

1- (5) Initiator Polymerization of various polymerizable compounds, for example, monomers having an ethylenically unsaturated group, can be carried out by irradiation with ionizing radiation or heating in the presence of a photo radical initiator or a thermal radical initiator. .
In producing the film of the present invention, a photoinitiator or a thermal initiator can be used in combination.

<Photoinitiator>
Examples of photo radical polymerization initiators include acetophenones, benzoins, benzophenones, phosphine oxides, ketals, anthraquinones, thioxanthones, azo compounds, peroxides (JP-A No. 2001-139663, etc.), 2, 3 -Dialkyldione compounds, disulfide compounds, fluoroamine compounds, aromatic sulfoniums, lophine dimers, onium salts, borate salts, active esters, active halogens, inorganic complexes, coumarins and the like.
Examples of acetophenones include 2,2-dimethoxyacetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, 1-hydroxy-dimethylphenylketone, 1-hydroxy-dimethyl-p-isopropylphenylketone, 1-hydroxy Cyclohexyl phenyl ketone, 2-methyl-4-methylthio-2-morpholinopropiophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone, 4-phenoxydichloroacetophenone, 4-t- Butyl-dichloroacetophenone is included.

Examples of benzoins include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzyl dimethyl ketal, benzoin benzene sulfonate, benzoin toluene sulfonate, benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether It is.
Examples of benzophenones include benzophenone, hydroxybenzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, 2,4-dichlorobenzophenone, 4,4-dichlorobenzophenone and p-chlorobenzophenone, 4,4′-dimethylaminobenzophenone (Michler ketone), 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, and the like are included.

  Examples of the borate salt are described in Japanese Patent Nos. 2764769 and 2002-116539, and Kunz, Martin “Rad Tech'98. Proceeding April 19-22, 1998, Chicago”. And the organic borate compounds described. For example, the compounds described in JP-A-2002-116539, paragraph numbers [0022] to [0027] can be mentioned. Examples of other organic boron compounds include JP-A-6-348011, JP-A-7-128785, JP-A-7-140589, JP-A-7-306527, and JP-A-7-292014. Specific examples include organoboron transition metal coordination complexes and the like, and specific examples include ion complexes with cationic dyes.

Examples of phosphine oxides include 2,4,6-trimethylbenzoyldiphenylphosphine oxide.
Examples of active esters include 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], sulfonic acid esters, cyclic active ester compounds, and the like.
Specifically, Examples 1 to 21 described in JP-A 2000-80068 are particularly preferable.
Examples of the onium salts include aromatic diazonium salts, aromatic iodonium salts, and aromatic sulfonium salts.

Specific examples of the active halogens include Wakabayashi et al., “Bull Chem. Soc Japan” 42, 2924 (1969), US Pat. No. 3,905,815, JP-A-5-27830, M.M. P. Examples include compounds described in Hutt “Journal of Heterocyclic Chemistry”, Vol. 1 (No. 3), (1970), and in particular, oxazole compounds substituted with a trihalomethyl group: s-triazine compounds. More preferred are s-triazine derivatives in which at least one mono-, di- or trihalogen-substituted methyl group is bonded to the s-triazine ring. Specific examples include S-triazine and oxathiazole compounds, such as 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl). -4,6-bis (trichloromethyl) -s-triazine, 2- (p-styrylphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (3-Br-4-di (ethyl) Acetate) amino) phenyl) -4,6-bis (trichloromethyl) -s-triazine, 2-trihalomethyl-5- (p-methoxyphenyl) -1,3,4-oxadiazole. Specifically, p.14 to p30 in JP-A-58-15503, p6-p10 in JP-A-55-77742, and p287 in JP-B-60-27673. 1-No. 8, No. pp. 443 to p444 of JP-A-60-239736. 1-No. 17, No. 4,701,399. Compounds such as 1-19 are particularly preferred.
Examples of inorganic complexes include bis (η ⁵ -2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium.
Examples of coumarins include 3-ketocoumarin.

These initiators may be used alone or in combination.
“Latest UV Curing Technology”, Technical Information Association, 1991, p. 159, and “UV curing system” written by Kayo Kiyomi, 1989, General Technology Center, p. Various examples are also described in 65-148 and are useful in the present invention.

  Commercially available photo radical polymerization initiators include KAYACURE (DETX-S, BP-100, BDKM, CTX, BMS, 2-EAQ, ABQ, CPTX, EPD, ITX, QTX, BTC, manufactured by Nippon Kayaku Co., Ltd. MCA, etc.), Irgacure (651, 184, 500, 819, 907, 369, 1173, 1870, 2959, 4265, 4263, etc.) manufactured by Ciba Specialty Chemicals, Ltd., Esacure (KIP100F, KB1, manufactured by Sartomer) EB3, BP, X33, KT046, KT37, KIP150, TZT) and the like and combinations thereof are preferred examples.

  It is preferable to use a photoinitiator in the range of 0.1-15 mass parts with respect to 100 mass parts of polyfunctional monomers, More preferably, it is the range of 1-10 mass parts.

<Photosensitizer>
In addition to the photopolymerization initiator, a photosensitizer may be used. Specific examples of the photosensitizer include n-butylamine, triethylamine, tri-n-butylphosphine, Michler's ketone and thioxanthone.
Further, one or more auxiliary agents such as an azide compound, a thiourea compound, and a mercapto compound may be used in combination.
Examples of commercially available photosensitizers include KAYACURE (DMBI, EPA) manufactured by Nippon Kayaku Co., Ltd.

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

  It is preferable to use a thermal initiator in the range of 0.1-15 mass parts with respect to 100 mass parts of polyfunctional monomers, More preferably, it is the range of 1-10 mass parts.

1- (6) Crosslinkable compound When the monomer or polymer binder constituting the present invention alone does not have sufficient curability, necessary curability can be imparted by blending the crosslinkable compound. .
For example, when the polymer body contains a hydroxyl group, various amino compounds are preferably used as the curing agent. The amino compound used as the crosslinkable compound is, for example, a compound containing a total of two or more of any one or both of a hydroxyalkylamino group and an alkoxyalkylamino group. Specifically, for example, a melamine compound, Examples include urea compounds, benzoguanamine compounds, glycoluril compounds, and the like.

  Melamine compounds are generally known as compounds having a skeleton in which a nitrogen atom is bonded to a triazine ring, and specific examples include melamine, alkylated melamine, methylol melamine, alkoxylated methyl melamine, and the like. However, it is preferable to have one or both of a methylol group and an alkoxylated methyl group in one molecule in total. Specifically, methylolated melamine, alkoxylated methylmelamine, or a derivative thereof obtained by reacting melamine and formaldehyde under basic conditions is preferable, and good storage stability is obtained particularly for the curable resin composition. Alkoxylated methyl melamine is preferable in that it can be obtained and good reactivity can be obtained. There are no particular restrictions on the methylolated melamine and the alkoxylated methylmelamine used as the crosslinkable compound. For example, the methylolated melamine and the alkoxylated methylmelamine can be obtained by the method described in the document “Plastic Materials Course [8] Urea Melamine Resin” (Nikkan Kogyo Shimbun). Various resinous materials can be used.

  In addition to urea, examples of the urea compound include polymethylolated urea, alkoxylated methylurea which is a derivative thereof, methylolated uron having a uron ring, and alkoxylated methyluron. And also about compounds, such as a urea derivative, the use of the various resinous materials described in said literature is possible.

1- (7) Curing Catalyst In the film of the present invention, radicals and acids generated by irradiation with ionizing radiation or heat can be used as a curing catalyst for promoting curing.

<Heat acid generator>
Specific examples of the thermal acid generator include various aliphatic sulfonic acids and salts thereof, various aliphatic carboxylic acids and salts thereof such as citric acid, acetic acid and maleic acid, and various aromatic carboxylic acids such as benzoic acid and phthalic acid. Examples thereof include acids and salts thereof, alkylbenzenesulfonic acids and ammonium salts thereof, amine salts, various metal salts, phosphoric acid and phosphoric acid esters of organic acids, and the like.
Examples of commercially available materials include catalyst 4040, catalyst 4050, catalyst 600, catalyst 602, catalyst 500, catalyst 296-9, and more made by Nippon Cytec Industries, Inc., and NACURE series 155, 1051, 5076, 4054J and its block type NACURE series 2500, 5225, X49-110, 3525, 4167 or more manufactured by King Corporation, and the like.
The use ratio of the thermal acid generator is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, with respect to 100 parts by mass of the total solid content of the composition for forming the containing layer (addition layer). Part. When the addition amount is within this range, the storage stability of the composition is good and the scratch resistance of the coating film is also good.

<Photosensitive acid generator, photoacid generator>
Furthermore, the photo-acid generator which can be used as a photoinitiator is explained in full detail.
Examples of the acid generator include a photoinitiator for photocationic polymerization, a photodecolorant for dyes, a photochromic agent, a known acid generator used in a microresist, and the like, a known compound, and a mixture thereof. Is mentioned. Examples of the acid generator include organic halogen compounds, disulfone compounds, onium compounds, and the like. Specific examples of the organic halogen compounds among these include the same as those described in <Photoinitiator>. .
Examples of the photosensitive acid generator include (1) various onium salts such as iodonium salts, sulfonium salts, phosphonium salts, diazonium salts, ammonium salts, pyridinium salts; (2) β-ketoesters, β-sulfonylsulfones and these. sulfone compounds such as α-diazo compounds; (3) sulfonic acid esters such as alkyl sulfonic acid esters, haloalkyl sulfonic acid esters, aryl sulfonic acid esters, and imino sulfonates; (4) sulfonimide compounds; and (5) diazomethane compounds. Can be mentioned.
Examples of onium salts include diazonium salts, ammonium salts, iminium salts, phosphonium salts, iodonium salts, sulfonium salts, arsonium salts, and selenonium salts. Of these, diazonium salts, iodonium salts, sulfonium salts, and iminium salts are preferable from the viewpoint of photosensitivity at the start of photopolymerization, material stability of the compound, and the like. Examples thereof include compounds described in paragraph numbers [0058] to [0059] of JP-A-2002-29162.

The use ratio of the photosensitive acid generator is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, with respect to 100 parts by mass of the total solid content of the composition for forming the containing layer (addition layer). Part.
In addition, as specific compounds and methods of use, for example, the contents described in JP-A-2005-43876 can be used.

1- (8) Translucent Particles It is preferable to use various translucent particles in the light diffusion layer of the present invention in order to impart antiglare properties (surface scattering properties) and internal scattering properties.

  The translucent particles in the light diffusion layer of the present invention are polymethyl methacrylate particles (refractive index 1.49), crosslinked poly (acryl-styrene) copolymer particles (refractive index 1.54), melamine resin particles (refractive index). 1.57), polycarbonate particles (refractive index 1.57), polystyrene particles (refractive index 1.60), crosslinked polystyrene particles (refractive index 1.61), polyvinyl chloride particles (refractive index 1.60), benzoguanamine -Melamine formaldehyde particles (refractive index 1.68), silica particles (refractive index 1.44), alumina particles (refractive index 1.63), zirconia particles, titania particles, particles having hollow or pores, etc. are used. .

Of these, crosslinked poly ((meth) acrylate) particles and crosslinked poly (acryl-styrene) particles are preferably used, and the refractive index of the binder is adjusted according to the refractive index of each light-transmitting particle selected from these particles. By adjusting, it is possible to achieve internal haze, surface haze, centerline average roughness, and scattering intensity suitable for the light diffusion layer of the optical film of the present invention.
Further, a binder (having a refractive index after curing of 1.50 to 1.53) composed mainly of a trifunctional or higher functional (meth) acrylate monomer and a crosslinked poly (meth) acrylate weight having an acrylic content of 50 to 100 mass percent. It is preferable to use a combination of translucent particles made of a combination, and in particular, a binder mainly composed of a tri- or higher functional (meth) acrylate monomer and crosslinked poly ((meth) acrylate) particles (refractive index of 1.49) The combination of is preferable.

The refractive index of the binder (translucent resin) and translucent particles in the present invention is preferably 1.45 to 1.70, more preferably 1.48 to 1.65. In order to set the refractive index within the above range, the type and amount ratio of the binder and the light-transmitting particles may be appropriately selected. How to select can be easily known experimentally in advance.
In the present invention, the difference between the translucent particles and the refractive index of the light diffusion layer excluding the translucent particles (“refractive index of the translucent particles” − “light diffusion excluding the translucent particles” The refractive index of the layer ") is preferably less than 0.05 as an absolute value, more preferably 0.001 to 0.030, still more preferably 0.005 to 0.020. When the difference between the refractive index of the light-transmitting particles in the light-diffusing layer and the light-diffusing layer excluding the light-transmitting particles is less than 0.05, the refraction angle of light by the light-transmitting particles is reduced, and the scattered light is It does not spread to a wide angle and hardly causes a decrease in contrast. In order to obtain the difference in refractive index, it is preferable to adjust the refractive index of the binder. The refractive index of the binder can be adjusted by using 1 to 90% by mass of inorganic particles described later in addition to the selection of the binder type.

  Here, the refractive index of the light diffusion layer excluding the translucent particles can be quantitatively evaluated by directly measuring with an Abbe refractometer or by measuring a spectral reflection spectrum or a spectral ellipsometry. The refractive index of the translucent particles is measured by measuring the turbidity by dispersing an equal amount of the translucent particles in the solvent in which the refractive index is changed by changing the mixing ratio of two types of solvents having different refractive indexes. It is measured by measuring the refractive index of the solvent when the turbidity is minimized with an Abbe refractometer.

  In the case of the above translucent particles, the translucent particles easily settle in the binder, and therefore an inorganic filler such as silica may be added to prevent sedimentation. As the amount of the inorganic filler added increases, it is more effective in preventing the translucent particles from settling, but adversely affects the transparency of the coating film. Accordingly, preferably, an inorganic filler having a particle size of 0.5 μm or less is contained in an amount of less than about 0.1 parts by mass with respect to 100 parts by mass of the binder-forming component so as not to impair the transparency of the coating film with respect to the binder. Good.

  The average particle diameter of the translucent particles is preferably 3 to 12 μm, more preferably 4.0 to 10.0 μm, and still more preferably 5 to 8 μm. The average particle diameter is preferably 3 μm or more from the viewpoint that the light scattering angle distribution does not spread to a wide angle and is difficult to cause blurring of characters and a decrease in contrast. On the other hand, it is not necessary to increase the thickness of the layer to be added, and 12 μm or less is preferable because it is difficult to cause problems such as curling and cost increase. Furthermore, it is preferable that the amount falls within the above range from the viewpoint that the coating amount during coating can be suppressed, drying is quick, and surface defects such as drying unevenness are unlikely to occur.

  The measuring method of the average particle diameter of the translucent particles can be any measuring method as long as it is a measuring method for measuring the average particle diameter of the particles, but preferably a transmission electron microscope (magnification of 500,000 to 2,000,000 times) The particles are observed by observing 100 particles, and the average value can be obtained as the average particle diameter.

  In the present invention, the shape of the translucent particles is not particularly limited, but in addition to true spherical particles, translucent particles having different shapes such as irregularly shaped particles (for example, non-spherical particles) may be used in combination. . In particular, when the minor axes of non-spherical particles are aligned in the normal direction of the light diffusion layer, particles having a smaller particle diameter than the true spherical particles can be used.

  The translucent particles are preferably blended so as to be contained in an amount of 5 to 40% by mass in the total solid content of the light diffusion layer. More preferably, it is 5-25 mass%, More preferably, it is 7-20 mass%. 5 mass% or more is preferable at the point of the addition effect, and 40 mass% or less is preferable at the point which image blurring, surface cloudiness, glare, etc. do not produce easily.

Moreover, the application amount of the translucent particles is preferably 30 to 2500 mg / m ² , more preferably 100 to 2400 mg / m ² , and still more preferably 600 to 2300 mg / m ² .

Compressive strength of the resin particles according to the present invention is preferably 4~10kgf / mm ^2, more preferably 4~8kgf / mm ^2, more preferably 4~6kgf / mm ^2. Within this range, there is also a contribution to increasing the film hardness, and particle breakage due to deterioration in brittleness is unlikely to occur.
The compressive strength refers to the compressive strength when the particle size (particle size) is deformed by 10%. The compressive strength when the particle size is deformed by 10% is the particle compressive strength (S10 strength). The resin particle is subjected to a compression test up to a load of 1 gf using a Shimadzu micro compression tester MCTW201. Is a value obtained by introducing the load when 10% is deformed and the particle size before compression into the following equation.
S10 strength (kgf / mm ² ) = 2.8 × load (kgf) / {(π × particle diameter (mm) × particle diameter (mm))

<Translucent particle preparation, classification method>

  Examples of the method for producing translucent particles according to the present invention include suspension polymerization, emulsion polymerization, soap-free emulsion polymerization, dispersion polymerization, seed polymerization, and the like. Good. 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.

The particle size distribution of the translucent particles is preferably monodisperse particles in terms of haze value and control of diffusibility, and uniformity of the coated surface. The CV value representing the uniformity of the particle diameter is preferably 15% or less, more preferably 13% or less, and still more preferably 10% or less. Further, 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, more preferably 0.1% or less of the total number of particles. More preferably, it is 0.01% or less. Particles having such a particle size distribution are also effective means of classification after preparation or synthesis reaction, and particles having a desired distribution can be obtained by increasing the number of classifications or increasing the degree of classification. .
It is preferable to use a method such as an air classification method, a centrifugal classification method, a sedimentation classification method, a filtration classification method, or an electrostatic classification method for classification.

1- (9) Inorganic Particles Various inorganic particles can be used in the functional layer of the film of the present invention in order to improve physical properties such as hardness, optical properties such as reflectance, and scattering properties.
As the inorganic particles, an oxide of at least one metal selected from silicon, zirconium, titanium, aluminum, indium, zinc, tin, and antimony, specific examples include ZrO ₂ , TiO ₂ , Al ₂ O ₃ , In ₂ O ₃ , ZnO, SnO ₂ , Sb ₂ O ₃ , ITO and the like can be mentioned. In addition, BaSO ₄ , CaCO ₃ , talc and kaolin are included.

  The particle diameter of the inorganic particles used in the present invention is preferably as fine as possible in the dispersion medium, and the preferred mass average diameter is 1 to 200 nm. More preferably, it is 5-150 nm, More preferably, it is 10-100 nm, Most preferably, it is 10-80 nm. A film that does not impair the transparency can be formed by refining the inorganic particles to 100 nm or less. The particle diameter of the inorganic particles can be measured by a light scattering method or an electron micrograph.

The specific surface area of the inorganic particles is preferably from 10 to 400 m ² / g, more preferably from 20 to 200 m ² / g, and most preferably from 30 to 150 m ² / g.

The inorganic particles used in the present invention are preferably added to a coating solution for a layer used as a dispersion in a dispersion medium.
As the dispersion medium for the inorganic particles, a liquid having a boiling point of 60 to 170 ° C. is preferably used. Examples of dispersion media include water, alcohol (eg, methanol, ethanol, isopropanol, butanol, benzyl alcohol), ketone (eg, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone), ester (eg, methyl acetate, ethyl acetate, Propyl acetate, butyl acetate, methyl formate, ethyl formate, propyl formate, butyl formate), aliphatic hydrocarbons (eg, hexane, cyclohexane), halogenated hydrocarbons (eg, methylene chloride, chloroform, carbon tetrachloride), aromatic Hydrocarbon (eg, benzene, toluene, xylene), amide (eg, dimethylformamide, dimethylacetamide, n-methylpyrrolidone), ether (eg, diethyl ether, dioxane, tetrahydrofuran), ether alcohol (eg, 1-methyl) Carboxymethyl-2-propanol) are included. Toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and butanol are particularly preferred.
Particularly preferred dispersion media are methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone.

  The inorganic particles are preferably dispersed using a disperser. Examples of dispersers include sand grinder mills (eg, pinned bead mills), high speed impeller mills, pebble mills, roller mills, attritors and colloid mills. A sand grinder mill and a high-speed impeller mill are particularly preferred. Further, preliminary dispersion processing may be performed. Examples of the disperser used for the preliminary dispersion treatment include a ball mill, a three-roll mill, a kneader, and an extruder.

<High refractive index particles>
For the purpose of increasing the refractive index of the functional layer provided as necessary in the film of the present invention, a composition in which inorganic particles having a high refractive index are dispersed in a monomer, an initiator, and an organically substituted silicon compound is used. A cured product is preferably used.
In this case, ZrO ₂ and TiO ₂ are particularly preferably used from the viewpoint of refractive index. ZrO ₂ is most preferable for increasing the refractive index of the light diffusion layer and the hard coat layer, and TiO ₂ fine particles are most preferable as the particles for the high refractive index layer and the medium refractive index layer.

As the TiO ₂ particles, inorganic particles mainly containing TiO ₂ containing at least one element selected from cobalt, aluminum, and zirconium are particularly preferable. The main component means a component having the largest content (mass%) among the components constituting the particles.
The particles mainly composed of TiO ₂ in the present invention preferably have a refractive index of 1.90 to 2.80, more preferably 2.10 to 2.80, and 2.20 to 2.80. Most preferably.
The mass average diameter of primary particles of TiO ₂ as a main component is preferably 1 to 200 nm, more preferably 1 to 150 nm, still more preferably 1 to 100 nm, and particularly preferably 1 to 80 nm.

The crystal structure of the particles containing TiO ₂ as the main component is preferably a rutile, rutile / anatase mixed crystal, anatase, or amorphous structure, and particularly preferably a rutile structure. The main component means a component having the largest content (mass%) among the components constituting the particles.

By containing at least one element selected from Co (cobalt), Al (aluminum), and Zr (zirconium) in particles containing TiO ₂ as a main component, the photocatalytic activity of TiO ₂ can be suppressed. The weather resistance of the inventive film can be improved.
A particularly preferable element is Co (cobalt). It is also preferable to use two or more types in combination.
The inorganic particles mainly composed of TiO ₂ of the present invention may have a core / shell structure by surface treatment as described in JP-A No. 2001-166104.

  The addition amount of the monomer and inorganic particles in the layer is preferably 1 to 45% by mass and more preferably 1 to 30% by mass with respect to the binder. Two or more kinds of inorganic particles may be used in the layer.

<Low refractive index particles>
The low refractive index layer preferably contains inorganic particles. The inorganic particles desirably have a low refractive index, and examples thereof include magnesium fluoride and silica fine particles. In particular, silica fine particles are preferable in terms of refractive index, dispersion stability, and cost.
The average particle diameter of the silica fine particles is preferably 30% to 150% of the thickness of the low refractive index layer, more preferably 35% to 80%, and still more preferably 40% to 60%. That is, when the thickness of the low refractive index layer is 100 nm, the particle diameter of the silica fine particles is preferably 30 nm to 150 nm, more preferably 35 nm to 80 nm, and still more preferably 40 nm to 60 nm.
Here, the average particle diameter of the inorganic particles is measured by a Coulter counter.

  If the particle size of the silica fine particles is too small, the effect of improving the scratch resistance is reduced. If it is too large, fine irregularities are formed on the surface of the low refractive index layer, and the appearance such as black tightening and the integrated reflectance are deteriorated. The silica fine particles may be either crystalline or amorphous, and may be monodispersed particles or aggregated particles as long as a predetermined particle size is satisfied. The shape is most preferably a spherical diameter, but there is no problem even if the shape is indefinite.

Further, at least one kind of silica fine particles having an average particle size of less than 25% of the thickness of the low refractive index layer (referred to as “small size particle size silica particles”) is used as silica fine particles having the above particle size (“large size particles”). It is preferably used in combination with “silica fine particles having a diameter”.
Since the fine silica particles having a small particle size can exist in the gaps between the fine silica particles having a large particle size, they can contribute as a retaining agent for the fine silica particles having a large particle size.
When the low refractive index layer is 100 nm, the average particle size of the silica fine particles having a small size is preferably from 1 nm to 20 nm, more preferably from 5 nm to 15 nm, and particularly preferably from 10 nm to 15 nm. Use of such silica fine particles is preferable in terms of raw material costs and a retaining agent effect.

The coating amount of the low refractive index particles is ^{preferably 1mg / m 2 ~100mg / m 2} , more preferably ^{5mg / m 2 ~80mg / m 2} , more preferably from ^{10mg / m 2 ~60mg / m 2} . If the amount is too small, the effect of improving the scratch resistance is reduced. If the amount is too large, fine irregularities are formed on the surface of the low refractive index layer, and the appearance such as black tightening and the integrated reflectance are deteriorated.

<Hollow silica particles>
For the purpose of further reducing the refractive index, it is preferable to use hollow silica fine particles.
The hollow silica fine particles preferably have a refractive index of 1.15 to 1.40, more preferably 1.17 to 1.35, and most preferably 1.17 to 1.30. The refractive index here represents the refractive index of the entire particle, and does not represent the refractive index of only the outer shell silica forming the hollow silica particles. At this time, assuming that the radius of the cavity in the particle is a and the radius of the outer shell of the particle is b, the porosity x expressed by the following formula (VIII) is (Formula VIII)
^{x = (4πa 3/3)} / (4πb 3/3) × 100
Preferably it is 10-60%, More preferably, it is 20-60%, Most preferably, it is 30-60%. If hollow silica particles are made to have a lower refractive index and a higher porosity, the thickness of the outer shell becomes thinner and the strength of the particles becomes weaker. Are preferred.

  A method for producing hollow silica is described in, for example, Japanese Patent Application Laid-Open Nos. 2001-233611 and 2002-79616. In particular, particles having cavities inside the shell and having fine pores in the shell are particularly preferred. The refractive index of these hollow silica particles can be calculated by the method described in JP-A-2002-79616.

The coating amount of the hollow silica is ^preferably from ^{1mg / m 2 ~100mg / m 2} , more preferably ^{5mg / m 2 ~80mg / m 2} , more preferably from ^{10mg / m 2 ~60mg / m 2} . If the amount is too small, the effect of lowering the refractive index and the effect of improving the scratch resistance will be reduced.
The average particle diameter of the hollow silica is preferably 30% to 150% of the thickness of the low refractive index layer, more preferably 35% to 80%, and still more preferably 40% to 60%. That is, if the thickness of the low refractive index layer is 100 nm, the particle size of the hollow silica is preferably 30 nm to 150 nm, more preferably 35 nm to 100 nm, and still more preferably 40 nm to 65 nm.
If the particle size of the silica particles is too small, the proportion of cavities will decrease and a decrease in refractive index cannot be expected. Getting worse. The silica fine particles may be either crystalline or amorphous, and monodisperse particles are preferred. The shape is most preferably a spherical diameter, but there is no problem even if the shape is indefinite.
Further, two or more kinds of hollow silica having different particle average particle sizes can be used in combination. Here, the average particle diameter of the hollow silica can be determined from an electron micrograph.
The specific surface area of the hollow silica in the present invention is preferably from 20 to 300 m ² / g, more preferably 30~120m ² / g, most preferably 40~90m ² / g. The surface area can be obtained by the BET method using nitrogen.

  In the present invention, silica particles having no voids can be used in combination with hollow silica. The preferred particle size of silica without voids is 30 nm to 150 nm, more preferably 35 nm to 100 nm, and most preferably 40 nm to 80 nm.

1- (10) Conductive Particles Various conductive particles can be used for imparting conductivity to the film of the present invention.
The conductive particles are preferably formed from a metal oxide or nitride. Examples of metal oxides or nitrides include tin oxide, indium oxide, zinc oxide and titanium nitride. Tin oxide and indium oxide are particularly preferred. The conductive inorganic particles are mainly composed of oxides or nitrides of these metals, and can further contain other elements. The main component means a component having the largest content (mass%) among the components constituting the particles. Examples of other elements include Ti, Zr, Sn, Sb, Cu, Fe, Mn, Pb, Cd, As, Cr, Hg, Zn, Al, Mg, Si, P, S, B, Nb, In, V and halogen atoms are included. In order to increase the conductivity of tin oxide and indium oxide, it is preferable to add Sb, P, B, Nb, In, V and a halogen atom. Particularly preferred are tin oxide containing Sb (ATO) and indium oxide containing Sn (ITO). The ratio of Sb in ATO is preferably 3 to 20% by mass. The ratio of Sn in ITO is preferably 5 to 20% by mass.

The average particle diameter of the primary particles of the conductive inorganic particles used for the antistatic layer is preferably 1 to 150 nm, more preferably 5 to 100 nm, and most preferably 5 to 70 nm. The average particle diameter of the conductive inorganic particles in the antistatic layer to be formed is 1 to 200 nm, preferably 5 to 150 nm, more preferably 10 to 100 nm, and more preferably 10 to 80 nm. Most preferred. The average particle diameter of the conductive inorganic particles is an average diameter weighted by the mass of the particles and can be measured by a light scattering method or an electron micrograph.
The specific surface area of the conductive inorganic particles is preferably from 10 to 400 m ² / g, more preferably from 20 to 200 m ² / g, and most preferably from 30 to 150 m ² / g.

The conductive inorganic particles may be surface treated. The surface treatment is performed using an inorganic compound or an organic compound. Examples of inorganic compounds used for the surface treatment include alumina and silica. Silica treatment is particularly preferred. Examples of organic compounds used for the surface treatment include polyols, alkanolamines, stearic acid, silane coupling agents, and titanate coupling agents. Silane coupling agents are most preferred. Two or more kinds of surface treatments may be performed in combination.
The shape of the conductive inorganic particles is preferably a rice grain shape, a spherical shape, a cubic shape, a spindle shape or an indefinite shape.

Two or more kinds of conductive particles may be used in combination in a specific functional layer of the film of the present invention or in different layers in the film.
The proportion of the conductive inorganic particles in the antistatic layer is preferably 20 to 90% by mass, preferably 25 to 85% by mass, and more preferably 30 to 80% by mass.

  The conductive inorganic particles can be used for forming an antistatic layer in the form of a dispersion.

1- (11) Surface treatment agent The inorganic particles used in the present invention are plasma in order to stabilize dispersion in a dispersion or coating solution, or to increase affinity and binding properties with a binder component. A physical surface treatment such as a discharge treatment or a corona discharge treatment, or a chemical surface treatment with a surfactant or a coupling agent may be performed.

The surface treatment can be performed using a surface treatment agent of an inorganic compound or an organic compound. Examples of inorganic compounds used for the surface treatment include inorganic compounds containing cobalt (CoO ₂ , Co ₂ O ₃ , Co ₃ O _4, etc.) and inorganic compounds containing aluminum (Al ₂ O ₃ , Al (OH) ₃ Etc.), inorganic compounds containing zirconium (ZrO ₂ , Zr (OH) ₄ etc.), inorganic compounds containing silicon (SiO ₂ etc.), inorganic compounds containing iron (Fe ₂ O ₃ etc.), etc. .
An inorganic compound containing cobalt, an inorganic compound containing aluminum, and an inorganic compound containing zirconium are particularly preferable, and an inorganic compound containing cobalt, Al (OH) ₃ , and Zr (OH) ₄ are most preferable.
Examples of organic compounds used for the surface treatment include polyols, alkanolamines, stearic acid, silane coupling agents, and titanate coupling agents. Silane coupling agents are most preferred. In particular, the surface treatment is preferably performed with at least one of a silane coupling agent (organosilane compound), a partial hydrolyzate thereof, and a condensate thereof.

Examples of titanate coupling agents include metal alkoxides such as tetramethoxy titanium, tetraethoxy titanium, and throat tetraisopropoxy titanium, and preneact (KR-TTS, KR-46B, KR-55, KR-41B, etc .; Ajinomoto Co., Inc. ))).
Examples of the organic compound used for the surface treatment include polyols, alkanolamines, and other organic compounds having an anionic group, and particularly preferable are organic compounds having a carboxyl group, a sulfonic acid group, or a phosphoric acid group. is there. Stearic acid, lauric acid, oleic acid, linoleic acid, linolenic acid and the like can be preferably used.
The organic compound used for the surface treatment preferably further has a crosslinked or polymerizable functional group. Crosslinkable or polymerizable functional groups include ethylenically unsaturated groups (for example, (meth) acrylic groups, allyl groups, styryl groups, vinyloxy groups, etc.) that can undergo addition reactions and polymerization reactions with radical species, cationic polymerizable groups (Epoxy groups, oxatanyl groups, vinyloxy groups, etc.), polycondensation reactive groups (hydrolyzable silyl groups, etc., N-methylol groups) and the like can be mentioned, and groups having an ethylenically unsaturated group are preferred.

  Two or more kinds of these surface treatments can be used in combination, and it is particularly preferable to use an inorganic compound containing aluminum and an inorganic compound containing zirconium.

When the inorganic particles are silica, the use of a coupling agent is particularly preferred. As the coupling agent, an alkoxy metal compound (eg, titanium coupling agent, silane coupling agent) is preferably used. Of these, silane coupling treatment is particularly effective.
The above coupling agent is used as a surface treatment agent for the inorganic particles of the low refractive index layer in advance for surface treatment prior to the preparation of the layer coating solution, and is further added as an additive during the preparation of the layer coating solution. It is preferable to make it contain in a layer.
The silica fine particles are preferably dispersed in the medium in advance before the surface treatment in order to reduce the load of the surface treatment.
Specific examples of the surface treatment agent and the surface treatment catalyst that can be preferably used in the present invention include organosilane compounds and catalysts described in WO 2004/017105.
The amount of the surface treatment agent used relative to the inorganic particles is preferably in the range of 10 to 150 parts by mass, more preferably in the range of 15 to 120 parts by mass, with respect to 100 parts by mass of the inorganic fine particles. Most preferably. Two or more surface treatment agents may be used in combination.

1- (12) Dispersant Various dispersants can be used for dispersing the particles used in the present invention.
The dispersant preferably further contains a crosslinkable or polymerizable functional group. Crosslinkable or polymerizable functional groups include ethylenically unsaturated groups (for example, (meth) acryloyl groups, allyl groups, styryl groups, vinyloxy groups, etc.) that can undergo addition reactions and polymerization reactions with radical species, and cationic polymerizable groups (epoxies). Groups, oxatanyl groups, vinyloxy groups, etc.), polycondensation reactive groups (hydrolyzable silyl groups, etc., N-methylol groups) and the like, and functional groups having an ethylenically unsaturated group are preferred.

It is preferable to use a dispersant having an anionic group for the dispersion of inorganic particles, particularly the dispersion of inorganic particles mainly composed of TiO ₂ , more preferably an anionic group and a cross-linkable or polymerizable functional group, It is particularly preferable that the dispersant has the cross-linked or polymerizable functional group in the side chain.

  As the anionic group, a group having an acidic proton such as a carboxyl group, a sulfonic acid group (sulfo), a phosphoric acid group (phosphono), a sulfonamide group, or a salt thereof is effective, and in particular, a carboxyl group, a sulfonic acid group, A phosphoric acid group or a salt thereof is preferable, and a carboxyl group and a phosphoric acid group are particularly preferable. The number of anionic groups contained in the dispersing agent per molecule may be plural, but is preferably 2 or more on average, more preferably 5 or more, Particularly preferred is 10 or more. Moreover, the anionic group contained in a dispersing agent may contain multiple types in 1 molecule.

In the dispersant having an anionic group in the side chain, the composition of the anionic group-containing repeating unit is in the range of 10 ^{−4 to} 100 mol%, preferably 1 to 50 mol%, particularly preferably 5 in the total repeating units. ˜20 mol%.

  The dispersant preferably further contains a crosslinkable or polymerizable functional group. Crosslinkable or polymerizable functional groups include ethylenically unsaturated groups (for example, (meth) acryloyl groups, allyl groups, styryl groups, vinyloxy groups, etc.) that can undergo addition reactions and polymerization reactions with radical species, and cationic polymerizable groups (epoxies). Groups, oxatanyl groups, vinyloxy groups, etc.), polycondensation reactive groups (hydrolyzable silyl groups, etc., N-methylol groups) and the like, and functional groups having an ethylenically unsaturated group are preferred.

  The average number of cross-linkable or polymerizable functional groups contained in the dispersant per molecule is preferably 2 or more, more preferably 5 or more, and particularly preferably 10 or more. Moreover, the crosslinking or polymerizable functional group contained in the dispersant may contain a plurality of types in one molecule.

In the preferred dispersant for use in the present invention, examples of the repeating unit having an ethylenically unsaturated group in the side chain include poly-1,2-butadiene and poly-1,2-isoprene structures or (meth) acrylic acid. An ester or amide repeating unit to which a specific residue (the R group of —COOR or —CONHR) is bonded can be used. Examples of the specific residue (R _{^{group), - (CH 2) n}} -CR 21 = CR 22 R 23, - (CH 2 O) n -CH 2 CR 21 = CR 22 R 23, - (CH _{2 CH 2 O) n -CH 2} CR 21 = CR 22 R 23, - (CH 2) n -NH-CO-O-CH 2 CR 21 = CR 22 R 23, - (CH 2) n -O-CO —CR ²¹ ═CR ²² R ²³ and — (CH ₂ CH ₂ O) ₂ —X (R ^{21 to} R ²³ are each a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group, or an alkoxy group. R ²¹ and R ²² or R ²³ may be bonded to each other to form a ring, n is an integer of 1 to 10, and X is a dicyclopentadienyl residue. There are). Specific examples of R of the ester residue include —CH ₂ CH═CH ₂ (corresponding to an allyl (meth) acrylate polymer described in JP-A No. 64-17047), —CH ₂ CH ₂ O—CH ₂ CH. _{= CH 2, -CH 2 CH 2} OCOCH = CH 2, -CH 2 CH 2 OCOC (CH 3) = CH 2, -CH 2 C (CH 3) = CH 2, -CH 2 CH = CH-C 6 H ₅ , —CH ₂ CH ₂ OCOCH═CH—C ₆ H ₅ , —CH ₂ CH ₂ —NHCOO—CH ₂ CH═CH ₂ and —CH ₂ CH ₂ O—X (X is a dicyclopentadienyl residue) Is included. Specific examples of R of the amide residue include —CH ₂ CH═CH ₂ , —CH ₂ CH ₂ —Y (Y is a 1-cyclohexenyl residue) and —CH ₂ CH ₂ —OCO—CH═CH ₂ , _{-CH 2 CH 2 -OCO-C (} CH 3) = CH 2 are included.

  In the dispersant having an ethylenically unsaturated group, a free radical (a polymerization initiation radical or a growth radical of a polymerization process of a polymerizable compound) is added to the unsaturated bond group, and the polymer compound is directly or between molecules. Addition polymerization is carried out through the polymerization chain, and a crosslink is formed between the molecules to cure. Alternatively, atoms in the molecule (for example, hydrogen atoms on carbon atoms adjacent to the unsaturated bond group) are extracted by free radicals to form polymer radicals that are bonded together to form a bridge between the molecules. Harden.

  The weight average molecular weight (Mw) of the dispersant having an anionic group and a crosslinkable or polymerizable functional group and having the crosslinkable or polymerizable functional group in the side chain is not particularly limited, but is preferably 1000 or more. . The more preferable mass average molecular weight (Mw) of the dispersant is 2000 to 1000000, more preferably 5000 to 200000, and particularly preferably 10000 to 100000.

  The cross-linkable or polymerizable functional group-containing unit may constitute all repeating units other than the anionic group-containing repeating unit, preferably 5 to 50 mol% of the total cross-linking or repeating unit, particularly Preferably it is 5-30 mol%.

  The dispersant may be a copolymer with an appropriate monomer other than a monomer having a crosslinking or polymerizable functional group or an anionic group. Although it does not specifically limit regarding a copolymerization component, It selects from various viewpoints, such as dispersion stability, compatibility with another monomer component, and the intensity | strength of a formed film. Preferable examples include methyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, styrene and the like.

  The form of the dispersant is not particularly limited, but is preferably a block copolymer or a random copolymer, and particularly preferably a random copolymer from the viewpoint of cost and ease of synthesis.

  The amount of the dispersant used relative to the inorganic particles is preferably in the range of 1 to 50 parts by mass, more preferably in the range of 5 to 30 parts by mass, and 5 to 20 parts by mass with respect to 100 parts by mass of the inorganic fine particles. Most preferably. Two or more dispersants may be used in combination.

  Specific examples of the dispersant preferably used in the present invention are shown below, but the dispersant used in the present invention is not limited thereto. Unless otherwise specified, it represents a random copolymer.

1- (13) Antifouling agent For the purpose of imparting antifouling properties, water resistance, chemical resistance, slipping properties and the like to the film of the present invention, particularly the uppermost layer of the film, known silicone type or fluorine type It is preferable to add an antifouling agent, a slip agent and the like as appropriate.
When these additives are added, it is preferably added in the range of 0.01 to 20% by mass of the total solid content of the low refractive index layer, more preferably in the range of 0.05 to 10% by mass. Particularly preferred is 0.1 to 5% by mass.

  Preferable examples of the silicone compound include those having a substituent at the terminal and / or side chain of a compound chain containing a plurality of dimethylsilyloxy units as repeating units. The compound chain containing dimethylsilyloxy as a repeating unit may contain a structural unit other than dimethylsilyloxy. The substituents may be the same or different, and a plurality of substituents are preferable. Examples of preferred substituents include acryloyl group, methacryloyl group, vinyl group, aryl group, cinnamoyl group, epoxy group, oxetanyl group, hydroxyl group, fluoroalkyl group, polyoxyalkylene group, carboxyl group, amino group and the like. It is done. Although there is no restriction | limiting in particular in molecular weight, It is preferable that it is 100,000 or less, It is more preferable that it is 50,000 or less, It is especially preferable that it is 3000-30000, It is most preferable that it is 10,000-20000. Although there is no restriction | limiting in particular in silicone atom content of a silicone type compound, it is preferable that it is 18.0 mass% or more, it is especially preferable that it is 25.0-37.8 mass%, and 30.0-37.0. Most preferably, it is mass%. Examples of preferable silicone-based compounds are X-22-174DX, X-22-2426, X-22-164B, X22-164C, X-22-170DX, X-22-176D, X, manufactured by Shin-Etsu Chemical Co., Ltd. -22-1821 (named above), Chisso Corporation, FM-0725, FM-7725, FM-4421, FM-5521, FM6621, FM-1121, Gelest DMS-U22, RMS-033, RMS- 083, UMS-182, DMS-H21, DMS-H31, HMS-301, FMS121, FMS123, FMS131, FMS141, FMS221 (and above are trade names) and the like, but are not limited thereto.

As the fluorine compound, a compound having a fluoroalkyl group is preferable. The fluoroalkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and a straight chain (for example, —CF ₂ CF ₃ , —CH ₂ (CF ₂ ) ₄ H, —CH ₂ (CF ₂ ) ₈ CF ₃ , —CH ₂ CH ₂ (CF ₂ ) ₄ H, etc.), even branched structures (eg, CH (CF ₃ ) ₂ , CH ₂ CF (CF ₃ ) ₂ , CH (CH ₃ ) CF ₂ CF ₃ , CH (CH ₃ ) (CF ₂ ) ₅ CF ₂ H, etc.), alicyclic structures (preferably 5-membered or 6-membered rings such as perfluorocyclohexyl group, perfluorocyclopentyl, etc. Group or an alkyl group substituted with these, and may have an ether bond (for example, CH ₂ OCH ₂ CF ₂ CF ₃ , CH ₂ CH ₂ OCH ₂ C ₄ F ₈ H, CH ₂ CH _{2 CH 2 CH 2 C 8 F 17} , CH 2 CH 2 OCF 2 CF 2 OCF 2 CF 2 H , etc.). A plurality of the fluoroalkyl groups may be contained in the same molecule.

  It is preferable that the fluorine-based compound further has a substituent that contributes to bond formation or compatibility with the low refractive index layer film. The substituents may be the same or different, and a plurality of substituents are preferable. Examples of preferred substituents include acryloyl group, methacryloyl group, vinyl group, aryl group, cinnamoyl group, epoxy group, oxetanyl group, hydroxyl group, polyoxyalkylene group, carboxyl group, amino group and the like. The fluorine-based compound may be a polymer or an oligomer with a compound not containing a fluorine atom, and the molecular weight is not particularly limited. Although there is no restriction | limiting in particular in fluorine atom content of a fluorine-type compound, It is preferable that it is 20 mass% or more, It is especially preferable that it is 30-70 mass%, It is most preferable that it is 40-70 mass%. Examples of preferred fluorine-based compounds include Daikin Chemical Industries, Ltd., R-2020, M-2020, R-3833, M-3833 (named above), Dainippon Ink Co., Ltd., Megafac F-171. , F-172, F-179A, and defender MCF-300 (named above), but are not limited thereto.

  For the purpose of imparting properties such as dust resistance and antistatic properties, a known cationic surfactant or a dustproof agent such as a polyoxyalkylene compound, an antistatic agent, or the like can be appropriately added. These dustproofing agent and antistatic agent may contain the structural unit as a part of the function in the above-mentioned silicone compound or fluorine compound. When these are added as additives, it is preferably added in the range of 0.01 to 20% by mass of the total solid content of the low refractive index layer, more preferably in the range of 0.05 to 10% by mass. Particularly preferred is 0.1 to 5% by mass. Examples of preferred compounds include, but are not limited to, Dainippon Ink Co., Ltd., MegaFace F-150 (trade name), Toray Dow Corning Co., Ltd., SH-3748 (trade name), and the like. Do not mean.

1- (14) Surfactant For the film of the present invention, in order to ensure surface uniformity such as coating unevenness, drying unevenness, point defect, etc., any one of fluorine-based and silicone-based surfactants, or Both of them are preferably contained in the coating composition for forming the light diffusion layer. In particular, a fluorine-based surfactant can be preferably used because an effect of improving surface defects such as coating unevenness, drying unevenness, and point defects appears at a smaller addition amount. Productivity can be improved by giving high-speed coating suitability while improving surface uniformity.

  Preferable examples of the fluorosurfactant include a fluoroaliphatic group-containing copolymer (sometimes abbreviated as “fluorine polymer”), and the fluoropolymer includes the following monomer (i): An acrylic resin, a methacrylic resin, and a vinyl copolymerizable therewith, including a corresponding repeating unit or a repeating unit corresponding to the monomer (i) and a repeating unit corresponding to the monomer (ii) below A copolymer with a monomer is useful.

(I) Fluoroaliphatic group-containing monomer represented by the following general formula A

In the general formula A, R ¹¹ represents a hydrogen atom or a methyl group, X represents an oxygen atom, a sulfur atom or —N (R ¹² ) —, m is an integer of 1 to 6 and n is an integer of 2 to 4. To express. R ¹² represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, specifically a methyl group, an ethyl group, a propyl group or a butyl group, preferably a hydrogen atom or a methyl group. X is preferably an oxygen atom.

(Ii) Monomer represented by the following general formula (b) copolymerizable with the above (i)

In the general formula (b), R ¹³ represents a hydrogen atom or a methyl group, Y represents an oxygen atom, a sulfur atom or —N (R ¹⁵ ) —, R ¹⁵ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, specifically Specifically, it represents a methyl group, an ethyl group, a propyl group, or a butyl group, preferably a hydrogen atom or a methyl group. Y is an oxygen atom, -N (H) -, and -N (CH ₃₎ - are preferred.
R ¹⁴ represents a linear, branched or cyclic alkyl group having 4 to 20 carbon atoms which may have a substituent. Examples of the substituent for the alkyl group represented by R ¹⁴ include a hydroxyl group, an alkylcarbonyl group, an arylcarbonyl group, a carboxyl group, an alkyl ether group, an aryl ether group, a halogen atom such as a fluorine atom, a chlorine atom, and a bromine atom, a nitro group, and a cyano group. , Amino groups and the like, but not limited thereto. Examples of the linear, branched or cyclic alkyl group having 4 to 20 carbon atoms include a butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group and undecyl group which may be linear or branched. , Dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, octadecyl group, eicosanyl group, etc., and monocyclic cycloalkyl groups such as cyclohexyl group, cycloheptyl group and bicycloheptyl group, bicyclodecyl group, tricycloundecyl group, A polycyclic cycloalkyl group such as a tetracyclododecyl group, an adamantyl group, a norbornyl group, a tetracyclodecyl group, or the like is preferably used.

  The amount of the fluoroaliphatic group-containing monomer represented by the general formula A used in the fluorine-based polymer used in the present invention is 10 mol% or more based on each monomer of the fluorine-based polymer, preferably It is 15-70 mol%, More preferably, it is the range of 20-60 mol%.

The preferred weight average molecular weight of the fluoropolymer used in the present invention is preferably 3000 to 100,000, more preferably 5,000 to 80,000.
Furthermore, the preferable addition amount of the fluoropolymer used in the present invention is in the range of 0.001 to 5 parts by mass, more preferably in the range of 0.005 to 3 parts by mass with respect to 100 parts by mass of the coating solution. More preferably, it is the range of 0.01-1 mass part. If the addition amount of the fluorine-based polymer is 0.001 part by mass or more, the effect of adding the fluorine-based polymer is sufficiently obtained, and if it is 5 parts by mass or less, the coating film cannot be sufficiently dried or the coating is not performed. There is no problem that the film performance (for example, reflectance, scratch resistance) is adversely affected.

  Examples of the specific structure of the fluorine-based polymer derived from the repeating unit corresponding to the fluoroaliphatic group-containing monomer represented by the general formula (i) are shown below, but not limited thereto. In addition, the number in a formula shows the molar ratio of each monomer component. Mw represents a mass average molecular weight.

1- (15) Thickener

The film of the present invention may use a thickener to adjust the viscosity of the coating solution.
The term “thickener” as used herein means that the viscosity of the liquid increases when it is added, and the amount by which the viscosity of the coating liquid increases when added is preferably 0.05 to 50 cP (0. 05 to 50 mPa · s), more preferably 0.10 to 20 cP (0.10 to 20 mPa · s), and most preferably 0.10 to 10 cP (0.10 to 10 mPa · s).

Examples of such thickeners include, but are not limited to:
Poly-ε-caprolactone poly-ε-caprolactone diol poly-ε-caprolactone triol polyvinyl acetate poly (ethylene adipate)
Poly (1,4-butylene adipate)
Poly (1,4-butylene glutarate)
Poly (1,4-butylene succinate)
Poly (1,4-butylene terephthalate)
polyethylene terephthalate)
Poly (2-methyl-1,3-propylene adipate)
Poly (2-methyl-1,3-propylene glutarate)
Poly (neopentyl glycol adipate)
Poly (neopentyl glycol sebacate)
Poly (1,3-propylene adipate)
Poly (1,3-propylene glutarate)
Polyvinyl butyral Polyvinyl formal Polyvinyl acetal Polyvinyl propanal Polyvinyl hexanal Polyvinyl pyrrolidone Polyacrylic acid ester Polymethacrylic acid ester Cellulose acetate Cellulose propionate Cellulose acetate butyrate

  Other known viscosity modifiers such as smectite, tetrasilica mica, bentonite, silica, montmorillonite and sodium polyacrylate, JP-A-10-219136, ethyl cellulose, polyacrylic acid, and organic clay described in JP-A-8-325491. Or a thixotropic agent can be used.

1- (16) Coating solvent As a solvent used in the coating composition for forming each layer of the film of the present invention, each component can be dissolved or dispersed, and a uniform surface is formed in the coating process and the drying process. Various solvents selected from the viewpoints of being easy, ensuring liquid storage stability, having an appropriate saturated vapor pressure, and the like can be used.
Two or more kinds of solvents can be mixed and used. In particular, from the viewpoint of drying load, it is preferable that a solvent having a boiling point of 100 ° C. or lower at normal pressure and room temperature as a main component and a small amount of solvent having a boiling point of 100 ° C. or higher for adjusting the drying speed.

  Examples of the solvent having a boiling point of 100 ° C. or lower include hydrocarbons such as hexane (boiling point 68.7 ° C.), heptane (98.4 ° C.), cyclohexane (80.7 ° C.), benzene (80.1 ° C.), Halogenated carbonization such as dichloromethane (39.8 ° C), chloroform (61.2 ° C), carbon tetrachloride (76.8 ° C), 1,2-dichloroethane (83.5 ° C), trichloroethylene (87.2 ° C) Hydrogens, diethyl ether (34.6 ° C), diisopropyl ether (68.5 ° C), dipropyl ether (90.5 ° C), ethers such as tetrahydrofuran (66 ° C), ethyl formate (54.2 ° C), Esters such as methyl acetate (57.8 ° C.), ethyl acetate (77.1 ° C.), isopropyl acetate (89 ° C.), acetone (56.1 ° C.), 2-butanone (methyl ether) Ketones such as Luketone, 79.6 ° C, methanol (64.5 ° C), ethanol (78.3 ° C), 2-propanol (82.4 ° C), 1-propanol (97.2 ° C), etc. Alcohols, cyano compounds such as acetonitrile (81.6 ° C.), propionitrile (97.4 ° C.), carbon disulfide (46.2 ° C.), and the like. Of these, ketones and esters are preferable, and ketones are particularly preferable. Among the ketones, 2-butanone is particularly preferable.

  Examples of the solvent having a boiling point of 100 ° C. or more include, for example, octane (125.7 ° C.), toluene (110.6 ° C.), xylene (138 ° C.), tetrachloroethylene (121.2 ° C.), and chlorobenzene (131.7 ° C.). , Dioxane (101.3 ° C), dibutyl ether (142.4 ° C), isobutyl acetate (118 ° C), cyclohexanone (155.7 ° C), 2-methyl-4-pentanone (same as MIBK, 115.9 ° C) 1-butanol (117.7 ° C.), N, N-dimethylformamide (153 ° C.), N, N-dimethylacetamide (166 ° C.), dimethyl sulfoxide (189 ° C.) and the like. Cyclohexanone and 2-methyl-4-pentanone are preferable.

1- (17) Others In addition to the above-described components, the film of the present invention includes a resin, a coupling agent, a coloring inhibitor, a coloring agent (pigment, dye), an antifoaming agent, a leveling agent, a flame retardant, and an ultraviolet absorber. , Infrared absorbers, adhesion-imparting agents, polymerization inhibitors, antioxidants, surface modifiers, and the like can also be added.

1- (18) Support The support of the film of the present invention is not particularly limited, such as a transparent resin film, a transparent resin plate, a transparent resin sheet, and transparent glass. Transparent resin films include cellulose acylate films (for example, cellulose triacetate film (refractive index 1.48), cellulose diacetate film, cellulose acetate butyrate film, cellulose acetate propionate film), polyethylene terephthalate film, polyethersulfone. Films, polyacrylic resin films, polyurethane resin films, polyester films, polycarbonate films, polysulfone films, polyether films, polymethylpentene films, polyetherketone films, (meth) acrylonitrile films, and the like can be used.
Although the thickness of a support body can use the thing of about 25 micrometers-1000 micrometers normally, Preferably it is 25 micrometers-250 micrometers, and it is more preferable that it is 30 micrometers-90 micrometers.
Any width of the support can be used, but from the viewpoint of handling, yield, and productivity, a width of 100 to 5000 mm is usually used, preferably 800 to 3000 mm, and preferably 1000 to 2000 mm. More preferably.
The surface of the support is preferably smooth, and the average roughness Ra is preferably 1 μm or less, preferably 0.0001 to 0.5 μm, and 0.001 to 0.1 μm. Is more preferable.

<Cellulose acylate film>
As the support, among the above-mentioned various films, a cellulose acylate film having high transparency, optically low birefringence, easy production and generally used as a protective film for a polarizing plate is preferable.
For the cellulose acylate film, various improvement techniques are known for the purpose of improving mechanical properties, transparency, flatness and the like. It can be used for the film of the invention.

In the present invention, among the cellulose acylate films, a cellulose triacetate film is particularly preferable, and it is preferable to use cellulose acetate having an acetylation degree of 59.0 to 61.5% for the cellulose acylate film. The degree of acetylation means the amount of bound acetic acid per unit mass of cellulose. The degree of acetylation follows the measurement and calculation of the degree of acetylation in ASTM: D-817-91 (test method for cellulose acetate and the like).
The viscosity average degree of polymerization (DP) of cellulose acylate is preferably 250 or more, and more preferably 290 or more.
In addition, the cellulose acylate used in the present invention has a Mw / Mn (Mw is mass average molecular weight, Mn is number average molecular weight) value by gel permeation chromatography close to 1.0, in other words, a molecular weight distribution. Narrow is preferred. The specific value of Mw / Mn is preferably 1.0 to 1.7, more preferably 1.3 to 1.65, and most preferably 1.4 to 1.6. preferable.

In general, the hydroxyl groups at 2, 3, and 6 positions of cellulose acylate are not evenly distributed by 1/3 of the total substitution degree, and the substitution degree of the 6-position hydroxyl group tends to be small. In the present invention, it is preferable that the substitution degree of the 6-position hydroxyl group of cellulose acylate is larger than that of the 2- and 3-positions.
The hydroxyl group at the 6-position with respect to the total degree of substitution is preferably substituted with an acyl group of 32% or more, more preferably 33% or more, and particularly preferably 34% or more. Furthermore, the substitution degree of the 6-position acyl group of cellulose acylate is preferably 0.88 or more. The 6-position hydroxyl group may be substituted with a propionyl group, butyroyl group, valeroyl group, benzoyl group, acryloyl group or the like, which is an acyl group having 3 or more carbon atoms, in addition to the acetyl group. The degree of substitution at each position can be determined by NMR.
In the present invention, as cellulose acylate, paragraphs [0043] to [0044] [Example] [Synthesis Example 1], paragraphs [0048] to [0049] [Synthesis Example 2], paragraph [ [0051] Cellulose acetate obtained by the method described in [0052] [Synthesis Example 3] can be used.

<Polyethylene terephthalate film>
In the present invention, the polyethylene terephthalate film is also preferably used because it is excellent in transparency, mechanical strength, flatness, chemical resistance and moisture resistance, and is inexpensive.
In order to further improve the adhesion strength between the transparent plastic film and the light diffusion layer provided thereon, the transparent plastic film is more preferably subjected to an easy adhesion treatment.
Examples of commercially available PET films with an easily adhesive layer for optics include Toyobo Co., Ltd. Cosmo Shine A4100 and A4300.

2. Layers constituting film The film of the present invention can be obtained by mixing and coating the above-mentioned various compounds. As described above, the optical film of the present invention is an optical film having a light diffusion layer on a transparent support. The light diffusion layer preferably contains translucent particles and a binder. Moreover, the optical film of the present invention is suitable for use as an antireflection film by having a low refractive index layer directly or via another layer in the light diffusion layer of the optical film. The optical film of the present invention can have other functional layers as required in addition to functional layers such as a light diffusion layer and a low refractive index layer. Next, it describes about the layer which comprises the film of this invention.

2- (1) Hard Coat Layer The film of the present invention is preferably provided with a hard coat layer on one surface of the transparent support in order to impart the physical strength of the film. As will be described later in “2- (2) Light Diffusion Layer” and “3. Layer Structure of Film”, it is preferable that the light diffusion layer also has a hard coat property, and the light diffusion layer also serves as the hard coat layer. It is. When a hard coat layer is provided separately from the light diffusion layer, the position of the hard coat layer may be on the transparent support side or on the opposite side of the light diffusion layer from the transparent support side. The hard coat layer may be composed of two or more layers.

  Moreover, it is also preferable that the optical film of the present invention has at least two light diffusion layers, and the light-transmitting particles are present in the lower layer. For this purpose, it is preferable to laminate a hard coat layer on the light diffusion layer. In such a configuration, the surface unevenness of the light diffusion layer is smoothed to form smooth unevenness, thereby reducing the frequency of the peaks and increasing the interval between the unevenness (increasing the Sm value), and reducing the height of the peaks. (Ra value can be lowered).

From the viewpoint of imparting sufficient durability and impact resistance to the film, the thickness of the hard coat layer is preferably about 0.5 μm to 50 μm, more preferably 1 μm to 20 μm, and more preferably Preferably they are 2 micrometers-10 micrometers, Most preferably, they are 3 micrometers-7 micrometers.
Further, the strength 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.
Furthermore, in the Taber test according to JIS K5400, the smaller the wear amount of the test piece before and after the test, the better.

The hard coat layer is preferably formed by a crosslinking reaction or a polymerization reaction of an ionizing radiation curable compound. For example, it may be formed by coating a coating composition containing an ionizing radiation-curable polyfunctional monomer or polyfunctional oligomer on a transparent support and subjecting the polyfunctional monomer or polyfunctional oligomer to a crosslinking reaction or a polymerization reaction. it can.
The functional group of the ionizing radiation curable polyfunctional monomer or polyfunctional oligomer is preferably a light, electron beam, or radiation polymerizable group, and among them, a photopolymerizable functional group is preferable.
Examples of the photopolymerizable functional group include unsaturated polymerizable functional groups such as a (meth) acryloyl group, a vinyl group, a styryl group, and an allyl group. Among them, a (meth) acryloyl group is preferable.

For the purpose of controlling the refractive index of the hard coat layer, a high refractive index monomer, inorganic particles, or both can be added to the binder of the hard coat layer. In addition to the effect of controlling the refractive index, the inorganic particles also have the effect of suppressing cure shrinkage due to the crosslinking reaction. In the present invention, a polymer formed by polymerizing the polyfunctional monomer and / or the high refractive index monomer after the hard coat layer is formed, and the inorganic particles dispersed therein are referred to as a binder.
Also, when it is difficult to see the pattern, color unevenness, brightness unevenness, glare, etc. of the liquid crystal panel due to internal scattering of the hard coat layer, or to add the function of expanding the viewing angle by scattering, the internal haze value (from the total haze value) The value obtained by subtracting the surface haze value) is preferably 0% to 60%, more preferably 10% to 40%, and most preferably 20% to 30%.
The film of the present invention can freely set surface haze and internal haze according to the purpose.

2- (2) Light Diffusing Layer As described above, the optical film of the present invention is an optical film having a light diffusing layer on a transparent support, and has a specific scattering intensity as described above. A scattered light profile is measured about the created light-scattering film using a commercially available automatic variable angle photometer (GP-5 type, manufactured by Murakami Color Research Laboratory Co., Ltd.).
In order to increase the accuracy of the measurement, each film is measured three times at another position separated by 1 cm or more and averaged. In addition, in order to correct for instrumental differences and day-to-day differences, an antireflection film “CV film CV02” manufactured by Fuji Photo Film Co., Ltd. as a light scattering film, and a 80 μm-thick film of Fuji Photo Film Co., Ltd. as a transparent support. The acetylcellulose film “TD80U” was measured, and the ratio I (0 °) / I0 was 51.5% to 55.5%, I (6 °) / I0 was 1.51% to 1.59% and I (30 °) / I0 is adjusted to be 0.0071% to 0.0084%.

Adjustment of the haze value is also important for improving the viewing angle characteristics, glare, and character blur. When it is difficult to see the pattern, color unevenness, brightness unevenness, glare, etc. of the liquid crystal panel due to the internal scattering of the light diffusion layer, or to add the function of expanding the viewing angle by the scattering, the internal haze value (from the total haze value to the surface haze value) The value obtained by subtracting the value is preferably 0% to 60%, more preferably 10% to 40%, particularly preferably 15% to 35%, and most preferably 20% to 30%. As a method for increasing the internal scattering haze, there are methods such as increasing the particle concentration, increasing the film thickness, and further increasing the refractive index of the particles. In addition to the internal scattering haze, when providing surface haze with surface irregularities from the viewpoint of antiglare properties, it is preferably 0.3% to 20% in order to achieve both antiglare properties and blackening, It is more preferably 0.3% to 10%, and still more preferably 0.3% to 1.5%.
Moreover, the film of this invention can set a surface haze and an internal haze freely according to the objective.

  The arithmetic average roughness (Ra) of the light diffusion layer is preferably 0.03 to 0.30 μm and more preferably 0.05 to 0.12 μm in order to achieve both antiglare properties and blackening. 40-200 micrometers is preferable, as for the average space | interval (Sm) of an unevenness | corrugation, 50-170 micrometers is more preferable, and 60-150 micrometers is still more preferable.

The light diffusion layer contributes to the film with antiglare properties due to surface scattering, and preferably contributes to the film with a hard coat property for improving the scratch resistance of the film, that is, the light diffusion layer is a hard coat layer. It is also a preferred embodiment that serves as both.
The antireflection film of the present invention is constituted by providing a low refractive index layer on the light diffusion layer of the optical film. More preferably, an intermediate refractive index layer and a high refractive index layer are provided between a hard coat layer provided according to necessity and a low refractive index layer. The refractive index of the light diffusion layer in the present invention is preferably in the range of 1.48 to 2.00, more preferably 1.52 to 1, from the optical design for obtaining an antireflection film. .90, more preferably 1.55 to 1.80. The above range is preferable from the viewpoints of antireflection properties and the color of reflected light.

As a method of forming the antiglare property, a method of laminating and forming a mat-shaped shaping film having fine irregularities on the surface as described in JP-A-6-16851, as described in JP-A-2000-206317 A method of forming by curing shrinkage of an ionizing radiation curable resin due to a difference in the amount of ionizing radiation applied, and by reducing the mass ratio of a good solvent to a light transmitting resin by drying as described in JP-A No. 2000-338310. A method of solidifying the light-sensitive fine particles and the translucent resin while gelling to form unevenness on the coating film surface, a method of imparting surface unevenness by external pressure as described in JP-A-2000-275404, etc. These known methods can be used.
The light diffusing layer of the present invention comprises a light diffusing layer forming composition, preferably a binder forming component capable of imparting hard coat properties to the coating composition, translucent particles for imparting antiglare properties, and When a light diffusing layer is formed containing a solvent, there are a plurality of convex portions formed by the translucent particles themselves or agglomerated portions of particles having a three-dimensional structure, and surface irregularities are formed. It is preferable.

As the translucent particles, those described in the section 1- (8) Translucent particles can be used.
Specific examples of the translucent particles (mat particles) include resin particles such as acrylic particles, crosslinked acrylic particles, polystyrene particles, crosslinked styrene particles, melamine resin particles, and benzoguanamine resin particles. Of these, crosslinked styrene particles, crosslinked poly (acryl-styrene) copolymer particles, and crosslinked acrylic particles are preferred.

  The average film thickness of the light diffusion layer is preferably 2 to 30 μm, more preferably 4 to 20 μm, and still more preferably 6 to 16 μm. If it is too thin, the hard coat property will be insufficient, and if it is too thick, curling and brittleness may be deteriorated and the workability may be lowered. In order to control the surface shape of the light diffusion layer, the average film thickness is preferably 0.5 to 5 times the translucent particle diameter.

(Also referred to as matte particles.) The light-transmitting particles, matting particles of a light diffusing layer formed is preferably 30~2500mg / ^{m 2,} more preferably 100~2300mg / ^{m 2,} more preferably 600 to It is contained in the light diffusion layer so as to be 2300 mg / m ² . If it is 30-2500 mg / m < ² >, since internal scattering does not become high, the raise of the black luminance in black display or the fall of the white luminance in white display does not arise, and it is preferable.

  Moreover, as shown in the section of 1- (4) organosilane compound, the light diffusion layer preferably contains an organosilane compound.

  The strength of the light diffusion layer is preferably 2H or more, more preferably 3H or more, and most preferably 4H or more in the pencil hardness test.

2- (3) High Refractive Index Layer, Medium Refractive Index Layer The film of the present invention can be provided with a high refractive index layer and a medium refractive index layer to enhance antireflection properties.
In the following specification, the high refractive index layer and the medium refractive index layer may be collectively referred to as a high refractive index layer. In the present invention, “high”, “medium”, and “low” in the high refractive index layer, the medium refractive index layer, and the low refractive index layer represent the relative refractive index relationship between the layers. In terms of the relationship with the transparent support, the refractive index preferably satisfies the relationship of transparent support> low refractive index layer, high refractive index layer> transparent support.
In the present specification, the high refractive index layer, the middle refractive index layer, and the low refractive index layer may be collectively referred to as an antireflection layer.

  In order to construct an antireflection film by constructing a low refractive index layer on a high refractive index layer, the refractive index of the high refractive index layer is preferably 1.55 to 2.40, more preferably 1.60 to 2.20, more preferably 1.65 to 2.10, and most preferably 1.80 to 2.00.

  When an antireflective film is prepared by coating a medium refractive index layer, a high refractive index layer, and a low refractive index layer in order from the support, the refractive index of the high refractive index layer is 1.65 to 2.40. Preferably, it is 1.70-2.20. The refractive index of the middle refractive index layer is adjusted to be a value between the refractive index of the low refractive index layer and the refractive index of the high refractive index layer. The refractive index of the middle refractive index layer is preferably 1.55-1.80.

As the inorganic particles used in the high refractive index layer and the medium refractive index layer, as described above in 1- (9), inorganic particles containing TiO ₂ as a main component are preferable, and the inorganic particles are in a dispersion state and have a high refractive index. Used to form layers and medium refractive index layers.
In the dispersion of the inorganic particles, the inorganic particles are dispersed in a dispersion medium in the presence of a dispersant.

  The high refractive index layer and medium refractive index layer used in the present invention are preferably used in a dispersion liquid in which inorganic particles are dispersed in a dispersion medium, preferably a binder precursor necessary for matrix formation (for example, the ionizing radiation curable composition described above). Polyfunctional monomer, polyfunctional oligomer, etc.), photopolymerization initiator, etc. are added to form a coating composition for forming a high refractive index layer and a medium refractive index layer, and a high refractive index layer and a medium refractive index layer are formed on a transparent support. It is preferable that the coating composition is applied and cured by a crosslinking reaction or a polymerization reaction of an ionizing radiation curable compound (for example, a polyfunctional monomer or a polyfunctional oligomer).

Furthermore, it is preferable to cause the binder component of the high refractive index layer and the medium refractive index layer to undergo a crosslinking reaction or a polymerization reaction with the dispersant at the same time as or after the coating of the layer.
The binder of the high refractive index layer and the medium refractive index layer produced in this way is, for example, the above-mentioned preferred dispersant and ionizing radiation curable polyfunctional monomer or polyfunctional oligomer are crosslinked or polymerized to form a binder. The anionic group of the dispersant is incorporated. Furthermore, the binder of the high refractive index layer and the medium refractive index layer has a function in which the anionic group maintains the dispersion state of the inorganic particles, and the crosslinked or polymerized structure imparts a film forming ability to the binder and contains inorganic particles. To improve the physical strength, chemical resistance and weather resistance of the high refractive index layer and medium refractive index layer.

  The binder forming component of the high refractive index layer is preferably added so as to be 5 to 80 parts by mass in 100 parts by mass of the solid content of the coating composition of the layer.

The content of the inorganic particles in the high refractive index layer is preferably 10 to 90% by mass, more preferably 15 to 80% by mass, and particularly preferably 15 to 75% by mass with respect to the mass of the high refractive index layer. . Two or more inorganic particles may be used in combination in the high refractive index layer.
When the low refractive index layer is provided on the high refractive index layer, the refractive index of the high refractive index layer is preferably higher than the refractive index of the transparent support.
The high refractive index layer contains an ionizing radiation curable compound containing an aromatic ring, an ionizing radiation curable compound containing a halogenated element other than fluorine (for example, Br, I, Cl, etc.), and atoms such as S, N, P, etc. A binder obtained by a crosslinking or polymerization reaction such as an ionizing radiation curable compound can also be preferably used.

  The film thickness of the high refractive index layer can be appropriately designed depending on the application. The high refractive index layer can also be used as an interference unevenness preventing layer described later. In this case, the thickness is preferably 30 to 200 nm, more preferably 50 to 170 nm, and particularly preferably 60 to 150 nm.

The haze of the high refractive index layer is preferably as low as possible. It is preferably 5% or less, more preferably 3% or less, and particularly preferably 1% or less.
The high refractive index layer is preferably constructed by coating a light diffusion layer on the transparent support and directly or through another layer thereon.

2- (4) Low Refractive Index Layer As described above, the antireflective film of the present invention is an antireflective film having a low refractive index layer on the light diffusion layer of the optical film. The reflectance of the film of the present invention can be reduced.

The refractive index of the low refractive index layer is preferably 1.20 to 1.46, more preferably 1.25 to 1.46, and particularly preferably 1.30 to 1.46.
The thickness of the low refractive index layer is preferably 50 to 200 nm, and more preferably 70 to 100 nm. The haze of the low refractive index layer is preferably 3% or less, more preferably 2% or less, and most preferably 1% or less. The specific strength of the low refractive index layer is preferably H or higher, more preferably 2H or higher, and most preferably 3H or higher in a pencil hardness test under a 500 g load.
Moreover, in order to improve the antifouling performance of the antireflection film, it is preferable that the contact angle of water with respect to the surface is 90 degrees or more. More preferably, it is 95 degrees or more, and particularly preferably 100 degrees or more.

  In the low refractive index layer, a binder is used for dispersing and fixing the fine particles of the present invention. As the binder forming component, the binder described in 1- (1) above can be used, but the refractive index of the binder itself is low, the fluorine-containing polymer described in 1- (3), or the fluorine-containing sol-gel material. It is preferable to use it. As the fluorine-containing polymer or fluorine-containing sol-gel, a material that crosslinks by heat or ionizing radiation and has a dynamic friction coefficient of 0.03 to 0.30 on the surface of the formed low refractive index layer is preferable.

  The composition for forming a low refractive index layer comprises 1- (3) the fluorine-containing polymer described above, 1- (9) the inorganic particles described above, and 1- (4) the organosilane compound described above. Is preferred.

2- (5) Antistatic Layer, Conductive Layer In the present invention, it is preferable to provide an antistatic layer in terms of preventing static electricity on the film surface. The antistatic layer can be formed by, for example, applying a conductive coating solution containing conductive fine particles and a reactive curable resin, or depositing or sputtering a metal or metal oxide that forms a transparent film. Conventionally known methods such as a method of forming a conductive thin film can be listed. The conductive layer can be formed directly on the support or via a primer layer that strengthens adhesion to the support. Further, the antistatic layer can be used as a part of the antireflection film. In this case, when used in a layer close to the outermost layer, sufficient antistatic properties can be obtained even if the film is thin.

The thickness of the antistatic layer is preferably from 0.01 to 10 μm, more preferably from 0.03 to 7 μm, and even more preferably from 0.05 to 5 μm. The surface resistance of the antistatic layer is ^preferably from ¹⁰ 5 ~10 ¹² Ω / ^sq, more preferably from 10 5 ~10 ⁹ Ω / ^sq, most be 10 5 ~10 ⁸ Ω / sq preferable. The surface resistance of the antistatic layer can be measured by a four probe method.

The antistatic layer is preferably substantially transparent. Specifically, the haze of the antistatic layer is preferably 10% or less, more preferably 5% or less, further preferably 3% or less, and most preferably 1% or less. . The transmittance of light having a wavelength of 550 nm is preferably 50% or more, more preferably 60% or more, further preferably 65% or more, and most preferably 70% or more.
The antistatic layer used in the present invention preferably has excellent strength, and the specific antistatic layer has a pencil hardness of 1 kg, preferably H or higher, and preferably 2H or higher. More preferably, it is more preferably 3H or more, and most preferably 4H or more.

2- (6) Antifouling layer An antifouling layer can be provided on the outermost surface of the present invention. The antifouling layer lowers the surface energy of the antireflection layer and makes it difficult to attach hydrophilic or lipophilic stains.
The antifouling layer can be formed using a fluorine-containing polymer or an antifouling agent.
The thickness of the antifouling layer is preferably 2 to 100 nm, and more preferably 5 to 30 nm.

2- (7) Interference unevenness (rainbow unevenness) prevention layer When there is a substantial refractive index difference (refractive index difference of 0.03 or more) between the transparent support and the hard coat layer, or between the transparent support and the light diffusion layer, Reflected light is generated at the interface of the transparent support / hard coat layer or the transparent support / light diffusion layer. This reflected light interferes with the reflected light on the surface of the antireflection layer, and may cause interference unevenness due to fine film thickness unevenness of the hard coat layer and the light diffusion layer. In order to prevent such interference unevenness, for example, an interference unevenness prevention in which an intermediate refractive index n _P is provided between the transparent support and the hard coat layer or the light diffusion layer, and the film thickness d _P satisfies the following formula: Layers can also be provided.

Formula (III)
d _P = (2N−1) × λ / (4n _P )
Where λ is the wavelength of visible light and any value in the range of 450 to 650 nm, and N is a natural number.

  Moreover, when bonding an antireflection film to an image display etc., an adhesive layer (or adhesive layer) may be laminated | stacked on the side which has not laminated | stacked the antireflection layer of a transparent support body. In such an embodiment, when there is a substantial refractive index difference (0.03 or more) between the transparent support and the pressure-sensitive adhesive layer (or adhesive layer), the transparent support / pressure-sensitive adhesive layer (or adhesive layer) ) Reflected light, and this reflected light interferes with the reflected light on the surface of the antireflection layer and causes interference unevenness due to uneven film thickness of the support, hard coat layer, and light interference layer in the same manner as described above. There is. For the purpose of preventing such interference unevenness, an interference unevenness preventing layer similar to the above can be provided on the side of the transparent support on which the antireflection layer is not laminated.

  Such an interference non-uniformity prevention layer is described in detail in Japanese Patent Application Laid-Open No. 2004-345333, and the interference non-uniformity prevention layer introduced here can also be used in the present invention.

2- (8) Easy-Adhesion Layer An easy-adhesion layer can be applied to the film of the present invention. The easy adhesion layer refers to, for example, a layer imparting a function of facilitating adhesion between the protective film for polarizing plate and the adjacent layer, or the hard coat layer and the support, and the light diffusion layer and the support.
Examples of the easy adhesion treatment include a treatment of providing an easy adhesion layer on a transparent plastic film with an easy adhesive composed of polyester, acrylic acid ester, polyurethane, polyethyleneimine, silane coupling agent and the like.
Examples of the easy-adhesion layer preferably used in the present technology include a layer containing a polymer compound having a -COOM (M represents a hydrogen atom or a cation) group, and a more preferable embodiment is a film substrate. A layer containing a polymer compound having a —COOM group is provided on the side, and a layer containing a hydrophilic polymer compound as a main component is provided on the polarizing film side adjacent to the layer. Examples of the polymer compound having -COOM group herein include styrene-maleic acid copolymer having -COOM group, vinyl acetate-maleic acid copolymer having -COOM group, and vinyl acetate-maleic acid-maleic anhydride. For example, it is preferable to use a vinyl acetate-maleic acid copolymer having a —COOM group. These polymer compounds are used alone or in combination of two or more, and the preferred mass average molecular weight is preferably about 500 to 500,000. Particularly preferred examples of the polymer compound having a —COOM group include those described in JP-A-6-094915 and JP-A-7-333436.

The hydrophilic polymer compound is preferably a hydrophilic cellulose derivative (eg, methyl cellulose, carboxymethyl cellulose, hydroxy cellulose, etc.), a polyvinyl alcohol derivative (eg, polyvinyl alcohol, vinyl acetate-vinyl alcohol copolymer, polyvinyl acetal, polyvinyl formal). , Polyvinyl benzal, etc.), natural polymer compounds (eg, gelatin, casein, gum arabic, etc.), hydrophilic polyester derivatives (eg, partially sulfonated polyethylene terephthalate), hydrophilic polyvinyl derivatives (eg, poly -N-vinylpyrrolidone, polyacrylamide, polyvinylindazole, polyvinylpyrazole and the like), and may be used alone or in combination of two or more.
The thickness of the easy adhesion layer is preferably in the range of 0.05 to 1.0 μm. If it is thinner than 0.05 μm, it is difficult to obtain sufficient adhesiveness, and if it is thicker than 1.0 μm, the effect of adhesiveness is saturated.

2- (9) Anti-curl Layer The film of the present invention can be subjected to anti-curl processing. The anti-curl processing is to impart a function of rounding with the surface to which the curl is applied. By applying this processing, the surface of the transparent resin film is prevented from curling inward when it is subjected to some degree or type of surface processing on each of the two surfaces of the transparent resin film. It works to do. The curl prevention process is performed on the surface opposite to the surface to be curled on the inner side of the transparent resin film. An example of the anti-curl process is a process of providing an anti-curl layer.
The anti-curl layer is provided on the side opposite to the side having the light diffusion layer or anti-reflection layer of the substrate, or an easy-adhesion layer may be coated on one side of the transparent resin film, for example. The mode which coats is mentioned.

  Specific examples of the anti-curl processing include solvent coating, and a method of applying a solvent and a transparent resin layer such as cellulose triacetate, cellulose diacetate, and cellulose acetate propionate. The method using a solvent is specifically performed by applying a composition containing a solvent for dissolving or swelling a cellulose acylate film used as a protective film for a polarizing plate. Accordingly, the coating solution for the layer having a function of preventing curling preferably contains a ketone-based or ester-based organic solvent. Examples of preferred ketone-based organic solvents include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl lactate, acetyl acetone, diacetone alcohol, isophorone, ethyl-n-butyl ketone, diisopropyl ketone, diethyl ketone, di-n-propyl ketone, Examples thereof include methylcyclohexanone, methyl-n-butyl ketone, methyl-n-propyl ketone, methyl-n-hexyl ketone, methyl-n-heptyl ketone, etc. Examples of preferable ester organic solvents include methyl acetate, ethyl acetate, acetic acid Examples include butyl, methyl lactate, and ethyl lactate. However, as a solvent to be used, in addition to a solvent mixture to be dissolved and / or a solvent to be swollen, it may further contain a solvent that does not dissolve, and a composition in which these are mixed at an appropriate ratio depending on the degree of curl of the transparent resin film and the type of resin. This is done using the product and the coating amount. In addition, the anti-curl function is exhibited even if transparent hard processing or antistatic processing is applied.

2- (10) Water Absorbing Layer A water absorbent can be used in the film of the present invention. The water absorbent can be selected from compounds having a water absorption function, mainly alkaline earth metals. Examples thereof include BaO, SrO, CaO, and MgO. Further, it can be selected from metal elements such as Ti, Mg, Ba, and Ca. The particle size of these absorbent particles is preferably 100 nm or less, and more preferably 50 nm or less.
The layer containing these water absorbents may be prepared by using a vacuum deposition method or the like, or nanoparticles may be prepared by various methods. The thickness of the layer is preferably 1 to 100 nm, and more preferably 1 to 10 nm. The layer containing a water absorbent may be added between the support and the functional layer, between the uppermost layer of the functional layer and the functional layer.

2- (11) Primer Layer / Inorganic Thin Film Layer In the film of the present invention, gas barrier properties can be enhanced by installing a known primer layer or inorganic thin film layer between the support and the laminate. .
As the primer layer, for example, an acrylic resin, an epoxy resin, a urethane resin, a silicone resin or the like can be used. In the present invention, an organic-inorganic hybrid layer is used as the primer layer, an inorganic vapor deposition layer or a sol-gel is used as the inorganic thin film layer. A dense inorganic coating thin film by the method is preferred. As an inorganic vapor deposition layer, vapor deposition layers, such as a silica, a zirconia, an alumina, are preferable. The inorganic vapor deposition layer can be formed by a vacuum vapor deposition method, a sputtering method, or the like.

3. Layer structure of film About the film of this invention, a well-known layer structure can be used using the above layers. For example, the following are typical examples.
a. Support / light diffusion layer (configuration of only essential layers in the optical film of the present invention)
b. Support / Light Diffusing Layer / Low Refractive Index Layer (FIG. 1) (Configuration of Essential Layer in Antireflection Film of the Present Invention)
c. Support / light diffusion layer / high refractive index layer / low refractive index layer (FIG. 2)
d. Support / Light Diffusing Layer / Medium Refractive Index Layer / High Refractive Index Layer / Low Refractive Index Layer (FIG. 3)

As shown in b (FIG. 1), a light diffusing layer is applied on a support, and a low refractive index layer is laminated, so that it can be suitably used as an antireflection film. By forming the low refractive index layer 4 with a film thickness of about ¼ of the wavelength of light on the light diffusion layer, the low refractive index layer can reduce surface reflection by the principle of thin film interference.
Moreover, even if a high-refractive-index layer and a low-refractive-index layer are laminated | stacked after apply | coating a light-diffusion layer on a support body like c (FIG. 2), it can use suitably as an antireflection film. Further, by installing a layer structure in the order of a support, a light diffusion layer, a medium refractive index layer, a high refractive index layer, and a low refractive index layer as shown in d (FIG. 3), the reflectance is 1% or less. can do.

  In the structures a to d described above, the light diffusion layer (2) has antiglare properties, and may be one layer or two or more layers. The antiglare property may be formed by dispersion of matte particles as shown in FIGS. 1 to 4 or may be formed by surface shaping by a method such as embossing as shown in FIG. The light diffusion layer formed by the dispersion of the matte particles contains a binder and translucent particles dispersed in the binder. As shown in FIG. 4, the light diffusion layer (2) may be provided on the hard coat layer (6), and conversely, by providing the hard coat layer (6) on the light diffusion layer (2), The hard coat layer may have a function of adjusting the surface unevenness of the light diffusion layer. The light diffusion layer having antiglare properties preferably has both antiglare properties and hard coat properties. You may be comprised by multiple layers, for example, 2 layers-4 layers.

In addition, interference unevenness (rainbow unevenness) prevention layer, antistatic layer (reduction of surface resistance value from the display side, etc.) may be provided between the transparent support and the surface side layer or the outermost layer. If there is a dust on the surface, there is a problem), another hard coat layer (when only one hard coat layer or light diffusion layer is insufficient in hardness, for example, the embodiment shown in FIG. 4), gas Examples thereof include a barrier layer, a water absorbing layer (moisture-proof layer), an adhesion improving layer, an antifouling layer (contamination preventing layer), and the like.
The refractive index of each layer constituting the antireflection film in the present invention preferably satisfies the following relationship.
Refractive index of light diffusion layer> Refractive index of transparent support> Refractive index of low refractive index layer

4). Manufacturing Method The film of the present invention can be formed by the following method, but is not limited to this method.
4- (1) Adjustment of coating solution

<Preparation>
First, a coating solution containing components for forming each layer is prepared. In that case, the raise of the moisture content in a coating liquid can be suppressed by suppressing the volatilization amount of a solvent to the minimum. The moisture content in the coating solution is preferably 5% or less, more preferably 2% or less. The suppression of the volatilization amount of the solvent is achieved by improving the sealing property at the time of stirring after putting each material into the tank, minimizing the air contact area of the coating liquid at the time of liquid transfer operation, and the like. Moreover, you may provide the means to reduce the moisture content in a coating liquid during application | coating, or before and behind that.

<Physical properties of coating solution>
For coating liquids having a dry film thickness of preferably 200 nm or less, such as a low refractive index layer, medium refractive index layer, high refractive index layer, and antifouling layer, the upper limit speed that can be applied is greatly affected by the liquid properties. It is necessary to control the liquid properties at the moment of application, particularly the viscosity and surface tension.
The viscosity is preferably 2.0 [mPa · sec] or less, more preferably 1.5 [mPa · sec] or less, and most preferably 1.0 [mPa · sec] or less. Since there are some coating solutions whose viscosity changes depending on the shear rate, the above value indicates the viscosity at the shear rate at the moment of coating. When a thixotropic agent is added to the coating solution and the coating solution is subjected to high shear, the viscosity is low, and when the coating solution is hardly sheared, if the viscosity is high, unevenness during drying is less likely to occur.
Moreover, although it is not a liquid physical property, the quantity of the coating liquid apply | coated to a transparent support body also affects the upper limit speed | rate which can be apply | coated. The amount of the coating solution applied to the transparent support is preferably 2.0 to 5.0 [cm ³ / m ² ]. Increasing the amount of the coating liquid applied to the transparent support is preferable because the upper limit of the application rate can be increased, but if the amount of the coating liquid applied to the transparent support is increased too much, the load on drying increases. It is preferable to determine the optimal amount of coating liquid to be applied to the transparent support depending on the liquid formulation and process conditions.
The surface tension is preferably in the range of 15 to 36 [mN / m]. It is preferable to reduce the surface tension by adding a leveling agent or the like because unevenness during drying is suppressed. On the other hand, if the surface tension is too low, the upper limit speed at which coating can be performed is reduced. Therefore, a range of 17 [mN / m] to 32 [mN / m] is more preferable, and 19 [mN / m] to 26 [mN / m]. mN / m] is more preferable.
In the light diffusion layer containing translucent particles, it is preferable to adjust the coating liquid to a viscosity of 4 cp (4 mPa · s) or more, and to a viscosity of 6 cp (6 mPa · s) or more from the viewpoint of preventing sedimentation of the particles. More preferably.

<Filtration>
The coating solution used for coating is preferably filtered before coating. As the filter for filtration, it is preferable to use a filter having a pore diameter as small as possible within the range in which the components in the coating solution are not removed. Usually, a filter having an absolute filtration accuracy of 0.1 to 50 μm is used for filtration, and a filter having an absolute filtration accuracy of 0.1 to 40 μm is preferably used. The thickness of the filter is preferably 0.1 to 10 mm, and more preferably 0.2 to 2 mm. In that case, the filtration pressure is preferably 1.5 MPa or less, more preferably 1.0 MPa or less, and further preferably 0.2 MPa or less.
The filtration filter member is not particularly limited as long as it does not affect the coating solution.
It is also preferable to ultrasonically disperse the filtered coating solution immediately before coating to assist defoaming and dispersion holding of the dispersion.

4- (2) Treatment before coating The support used in the present invention is preferably subjected to a surface treatment before coating other layers. Specific examples include corona discharge treatment, glow discharge treatment, flame treatment, acid treatment, alkali treatment, and ultraviolet irradiation treatment. In addition, as described in JP-A-7-333433, it is preferable to provide an undercoat layer.

Furthermore, as a dust removing method used in the dust removing step as a pre-process for application, a method of pressing a nonwoven fabric, a blade or the like on the film surface described in JP-A-59-150571, JP-A-10-309553 A method of blowing the air with high cleanliness described at a high speed to peel off the deposits from the film surface and sucking it with a suction port close to it, blowing compressed air that is ultrasonically vibrated as described in JP-A-7-333613 Examples thereof include a dry dust removing method such as a method for peeling and sucking adhered substances (manufactured by Shinkosha, New Ultra Cleaner, etc.).
In addition, a method of introducing a film into a cleaning tank and peeling off deposits with an ultrasonic vibrator, supplying a cleaning liquid to the film described in Japanese Patent Publication No. 49-13020, and then blowing and sucking high-speed air As described in JP-A-2001-38306, a wet dust removal method such as a method in which a web is continuously rubbed with a roll wetted with liquid and then the liquid is sprayed onto the rubbed surface for cleaning. Can do. Among such dust removal methods, a method using ultrasonic dust removal or a method using wet dust removal is particularly preferable in terms of dust removal effect.
In addition, it is particularly preferable to remove static electricity on the film support before performing such a dust removal step from the viewpoint of increasing dust removal efficiency and suppressing adhesion of dust. As such a static elimination method, a corona discharge ionizer, a light irradiation ionizer such as UV or soft X-ray, or the like can be used. The charged voltage of the film support before and after dust removal and coating is desirably 1000 V or less, preferably 300 V or less, and particularly preferably 100 V or less.

When a cellulose acylate film is used as the support, it is preferable that the temperature of the cellulose acylate film in these treatments is Tg or less, specifically 150 ° C. or less, from the viewpoint of maintaining the flatness of the film.
When the cellulose acylate film is adhered to the polarizing film as in the case of using the film of the present invention as a protective film for a polarizing plate, from the viewpoint of adhesiveness to the polarizing film, acid treatment or alkali treatment, that is, cellulose acylate. It is particularly preferred to carry out a saponification treatment on the rate.
From the viewpoint of adhesiveness and the like, the surface energy of the cellulose acylate film is preferably 55 mN / m or more, more preferably 60 mN / m or more and 75 mN / m or less, and it can be adjusted by the surface treatment. .

4- (3) Coating Each layer of the film of the present invention can be formed by the following coating method, but is not limited to this method.
Dip coating method, air knife coating method, curtain coating method, roller coating method, wire bar coating method, gravure coating method and extrusion coating method (die coating method) (see US Pat. No. 2,681,294, WO 2005/123274), micro Known methods such as a gravure coating method are used, and among them, a micro gravure coating method and a die coating method are preferable.

  The micro gravure coating method used in the present invention is a gravure roll having a diameter of about 10 to 100 mm, preferably about 20 to 50 mm and engraved with a gravure pattern on the entire circumference, below the support and in the transport direction of the support. The gravure roll is rotated in reverse with respect to the gravure roll, the excess coating liquid is scraped off from the surface of the gravure roll by a doctor blade, and a fixed amount of the coating liquid is removed from the support in a position where the upper surface of the support is in a free state. The coating method is characterized in that the coating liquid is transferred onto the lower surface for coating. A roll-shaped transparent support is continuously unwound, and at least one layer of at least one of a light diffusion layer or a low-refractive index layer containing a fluorine-containing olefin polymer is formed on one side of the unwound support. It can be applied by a gravure coating method.

  As coating conditions by the micro gravure coating method, the number of gravure patterns imprinted on the gravure roll is preferably 50 to 800 lines / inch, more preferably 100 to 300 lines / inch, and the depth of the gravure pattern is 1 to 600 μm. Is preferable, 5 to 200 μm is more preferable, the rotation speed of the gravure roll is preferably 3 to 800 rpm, more preferably 5 to 200 rpm, and the conveyance speed of the support is 0.5 to 100 m / min. It is preferably 1 to 50 m / min.

In order to supply the film of the present invention with high productivity, an extrusion method (die coating method) is preferably used.
Since the die coating method is a pre-measuring method, it is easy to secure a stable film thickness. With respect to a coating solution of a low coating amount, the coating method can be applied at high speed with good film thickness stability. Although application is possible by other application methods, the dip coating method inevitably causes vibration of the application liquid in the liquid receiving tank, and stepped unevenness is likely to occur. In the reverse roll coating method, stepped unevenness is likely to occur due to eccentricity and deflection of the roll related to coating. Moreover, since these coating methods are post-measuring methods, it is difficult to ensure a stable film thickness. From the viewpoint of productivity, it is preferable to apply the die coating method at 25 m / min or more.

  In particular, when a hard coat layer is applied on the light diffusing layer, the light diffusing layer can be applied by a single application by applying the coating method described in JP-A-2002-86050 and JP-A-2003-260400. And a hard coat layer can be coated at the same time.

4- (4) <Drying>
The film of the present invention is preferably applied on a support directly or via another layer and then conveyed by a web to a heated zone to dry the solvent.
Various knowledges can be used as a method for drying the solvent. Specific examples include JP-A Nos. 2001-286817, 2001-314798, 2003-126768, 2003-315505, and 2004-34002.
The temperature of the drying zone is preferably 25 ° C. to 140 ° C., the first half of the drying zone is preferably a relatively low temperature, and the latter half is preferably a relatively high temperature. However, it is preferably below the temperature at which components other than the solvent contained in the coating composition of each layer start to volatilize. For example, some of the commercially available photo radical generators used in combination with ultraviolet curable resins volatilize around several tens of percent within a few minutes in warm air at 120 ° C. Some acrylate monomers and the like undergo volatilization in warm air at 100 ° C. In such a case, it is preferable that it is below the temperature at which components other than the solvent contained in the coating composition of each layer start to volatilize as described above.

Moreover, the dry wind after apply | coating the coating composition of each layer on a support body has the wind speed of the coating-film surface of 0.1-2 m / sec while the solid content concentration of the said coating composition is 1-50%. It is preferable to be in the range in order to prevent drying unevenness.
Moreover, after apply | coating the coating composition of each layer on a support body, the temperature difference of the conveyance roll which contacts the surface opposite to the coating surface of a support body in a drying zone, and a support body is 0 to 20 degreeC or less. Then, the drying nonuniformity by the heat transfer nonuniformity on a conveyance roll can be prevented, and it is preferable.

4- (5) Curing After drying the solvent, the film of the present invention can be passed through a zone in which each coating film is cured by ionizing radiation and / or heat on the web to cure the coating film.

The ionizing radiation species in the present invention is not particularly limited, and is appropriately selected from ultraviolet rays, electron beams, near ultraviolet rays, visible light, near infrared rays, infrared rays, X-rays and the like according to the type of curable composition forming the film. Although it can be selected, ultraviolet rays and electron beams are preferred, and ultraviolet rays are particularly preferred because they are easy to handle and high energy can be easily obtained.
As the ultraviolet light source for photopolymerizing the ultraviolet reactive compound, any light source that generates ultraviolet light can be used. For example, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, or the like can be used. An ArF excimer laser, a KrF excimer laser, an excimer lamp, synchrotron radiation, or the like can also be used. Among these, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a xenon arc, and a metal halide lamp can be preferably used.

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

Irradiation conditions vary depending on each lamp, but the amount of irradiation light is preferably 10 mJ / cm ² or more, more preferably 50 mJ / cm ^{2 to} 10000 mJ / cm ² , and particularly preferably 50 mJ / cm ^{2 to} 2000 mJ / cm ^2. It is. At that time, the irradiation distribution in the width direction of the web is preferably 50 to 100%, more preferably 80 to 100%, including both ends with respect to the central maximum irradiation.

In the present invention, at least one layer laminated on the support is irradiated with ionizing radiation and heated to a film surface temperature of 60 ° C. or more for 0.5 seconds or more from the start of irradiation with ionizing radiation, with an oxygen concentration of 10 volumes. It is preferable to cure by the step of irradiating ionizing radiation in an atmosphere of less than or equal to%.
It is also preferable to heat in an atmosphere having an oxygen concentration of 3% by volume or less simultaneously and / or continuously with ionizing radiation irradiation.
In particular, it is preferable that the low refractive index layer which is the outermost layer and has a small film thickness is cured by this method. The curing reaction is accelerated by heat, and a film having excellent physical strength and chemical resistance can be formed.

  The time for irradiating with ionizing radiation is preferably 0.7 seconds or longer and 60 seconds or shorter, more preferably 0.7 seconds or longer and 10 seconds or shorter from the viewpoints of completion of the curing reaction, a necessary amount of inert gas, and the like.

  The oxygen concentration is preferably formed by a crosslinking reaction or polymerization reaction of an ionizing radiation curable compound in an atmosphere of 10% by volume or less, more preferably an oxygen concentration of 4% by volume or less, and particularly preferably an oxygen concentration of 2% by volume. Hereinafter, it is most preferably 1% by volume or less.

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

By supplying inert gas to the ionizing radiation irradiation chamber and making it slightly blown out to the web entrance side of the irradiation chamber, it is possible to effectively reduce the oxygen concentration in the reaction chamber by eliminating the carry air accompanying the web transfer, It is possible to efficiently reduce the substantial oxygen concentration on the pole surface where the inhibition of curing by oxygen is large. The direction of the inert gas flow on the web entrance side of the irradiation chamber can be controlled by adjusting the balance between the supply and exhaust of the irradiation chamber.
Direct blowing of an inert gas onto the web surface is also preferably used as a method for removing the carried air.

  Further, by providing a front chamber in front of the reaction chamber and excluding oxygen on the web surface in advance, the curing can proceed more efficiently. Further, the side surface constituting the web entrance side of the ionizing radiation reaction chamber or the front chamber is preferably 0.2 to 15 mm in gap with the web surface in order to use the inert gas efficiently, more preferably, 0.1%. The thickness is preferably 2 to 10 mm, and most preferably 0.2 to 5 mm. However, in order to continuously manufacture the web, it is necessary to join and connect the webs, and a method of sticking with a joining tape or the like is widely used for joining. For this reason, if the gap between the entrance surface of the ionizing radiation reaction chamber or the front chamber and the web is too narrow, there arises a problem that the joining member such as the joining tape is caught. For this reason, in order to narrow the gap, it is preferable to make at least a part of the entrance surface of the ionizing radiation reaction chamber or the front chamber movable, and to widen the gap by the junction thickness when the junction enters. In order to realize this, the entrance surface of the ionizing radiation reaction chamber or the front chamber is made movable in the forward and backward direction, and when the joint passes, the gap is moved back and forth to widen the gap, It is possible to move the chamber entrance surface vertically with respect to the web surface and move up and down to widen the gap as the joint passes.

  In curing, the film surface is preferably heated at 60 ° C. or higher and 170 ° C. or lower. Below 60 ° C., there is little curing by heating, and at 170 ° C. or higher, problems such as deformation of the substrate occur. Furthermore, this preferable temperature is 60 degreeC-100 degreeC. The film surface refers to the film surface temperature of the layer to be cured. The time for the film to reach the temperature is preferably 0.1 second or more and 300 seconds or less from the start of UV irradiation, and more preferably 10 seconds or less. If the time for maintaining the temperature of the film surface in the above temperature range is too short, the reaction of the curable composition that forms the film cannot be accelerated, and conversely, if it is too long, the optical performance of the film deteriorates and the equipment is large. Manufacturing problems such as

  There is no particular limitation on the heating method, but a method of heating a roll to contact the film, a method of spraying heated nitrogen, irradiation with far infrared rays or infrared rays is preferable. A method of heating a rotating metal roll described in Japanese Patent No. 2523574 by flowing a medium such as hot water, steam or oil can also be used. As a heating means, a dielectric heating roll or the like may be used.

  The ultraviolet irradiation may be performed every time one layer is provided for each of a plurality of constituent layers, or may be performed after lamination. Or you may irradiate combining these. From the viewpoint of productivity, it is preferable to irradiate ultraviolet rays after laminating multiple layers.

In the present invention, at least one layer laminated on the support can be cured by multiple times of ionizing radiation. In this case, it is preferable that at least two ionizing radiations are performed in a continuous reaction chamber in which the oxygen concentration does not exceed 3% by volume. By performing multiple times of ionizing radiation irradiation in the same low oxygen concentration reaction chamber, the reaction time required for curing can be effectively ensured.
In particular, when the production rate is increased for high productivity, irradiation with ionizing radiation multiple times is preferable in order to ensure the energy of ionizing radiation necessary for the curing reaction.

  Further, when the curing rate (100-residual functional group content) is a certain value of less than 100%, the lower layer has a curing rate of the upper layer when a layer is provided thereon and cured by ionizing radiation and / or heat. When the height is higher than before, the adhesion between the lower layer and the upper layer is improved, which is preferable.

4- (6) Handling In order to continuously produce the film of the present invention, a process of continuously feeding a roll-shaped support film, a process of applying / drying a coating liquid, a process of curing a coating film, and curing It is preferable that the process of winding up the support film which has a layer is performed.
The film support is continuously sent out from the roll-shaped film support to the clean room. In the clean room, the static electricity charged on the film support is removed by an electrostatic charge-off device, and then the film support adheres on the film support. Remove the foreign material that has been removed with a dust remover. Subsequently, the coating liquid is applied onto the film support in the application section installed in the clean room, and the applied film support is sent to the drying chamber and dried.
The film support having the dried coating layer is fed from the drying chamber to the curing chamber, and the monomer contained in the coating layer is polymerized and cured. Further, the film support having the cured layer is sent to the curing unit to complete the curing, and the film support having the layer having been completely cured is wound up into a roll shape.

The above steps may be performed every time each layer is formed, or a plurality of coating parts-drying chambers-curing parts may be provided to continuously form each layer. In particular, when a hard coat layer is sequentially coated on the light diffusing layer, it is preferable to perform a method in which a plurality of coating portions-drying chambers-curing portions are provided.
In order to create the film of the present invention, as described above, the coating step in the coating unit and the drying step performed in the drying chamber are performed in a highly clean air atmosphere simultaneously with the microfiltration operation of the coating solution, and It is preferable that dust and dust on the film are sufficiently removed before application. The air cleanliness of the coating process and the drying process is desirably class 10 (353 particles / 0.5 m or more / (cubic meter) or less) based on the standard of air cleanliness in the US Federal Standard 209E. Preferably it is class 1 (35.5 particles / (cubic meter) or less) having a particle size of 0.5 μm or more. Moreover, it is more preferable that the degree of air cleanliness is high also in the feeding and winding parts other than the coating-drying process.

4- (7) Saponification treatment When producing a polarizing plate using the film of the present invention as at least one of two surface protective films of a polarizing film, the surface on the side to be bonded to the polarizing film is hydrophilized. Thus, it is preferable to improve the adhesion on the bonding surface.

a. Method of immersing in alkaline solution This is a method of saponifying all surfaces that are reactive with alkali on the entire surface of the film by immersing the film in an alkaline solution under appropriate conditions, and no special equipment is required. From the viewpoint of cost. The alkaline liquid is preferably 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 30-75 degreeC, Most preferably, it is 40-60 degreeC.
The combination of the saponification conditions is preferably a combination of relatively mild conditions, but can be set according to the material and composition of the film and the target contact angle.
After being immersed in the alkaline solution, it is preferable to sufficiently wash with water or neutralize the alkaline component by immersing in a dilute acid so that the alkaline component does not remain in the film.

By saponification treatment, the surface opposite to the surface having the coating layer 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 adhesiveness with the adhesive layer mainly composed of polyvinyl alcohol.
In the saponification treatment, the lower the contact angle with respect to the surface of the transparent support opposite to the side having the coating layer, the better from the viewpoint of adhesion to the polarizing film, while the dipping method simultaneously has the coating layer. Since it is damaged by alkali from the surface to the inside, it is important to set the minimum reaction conditions. When the contact angle to water of the transparent support on the opposite surface is used as an index of damage to each layer due to alkali, particularly when the transparent support is triacetylcellulose, preferably 10 to 50 degrees, more preferably Is 30 to 50 degrees, more preferably 40 to 50 degrees. If it is 50 degrees or more, there is a problem in the adhesion to the polarizing film, which is not preferable. On the other hand, if it is less than 10 degrees, the film suffers too much damage, which impairs physical strength and is not preferable.

b. Method of applying alkaline solution As a means of avoiding damage to each film in the above-mentioned immersion method, an alkali solution is applied, heated, washed with water, and dried only on the surface opposite to the surface having the coating layer under appropriate conditions. A liquid coating method is preferably used. The application in this case means that an alkaline solution or the like is brought into contact only with the surface to be saponified, and in addition to the application, it may be carried out by spraying or contacting a belt containing the solution. Including. By adopting these methods, a separate facility and process for applying an alkaline solution are required, which is inferior to the dipping method of a from the viewpoint of cost. On the other hand, since the alkali solution contacts only the surface to be saponified, the opposite surface can have a layer using a material that is weak against the alkali solution. For example, vapor deposition films and sol-gel films have various effects such as corrosion, dissolution, and peeling due to alkali solution, so it is not desirable to use the immersion method. Is possible.

  In both of the saponification methods a and b, since each layer can be formed after being unwound from a roll-shaped support, it may be performed by a series of operations in addition to the film manufacturing process. Furthermore, the polarizing plate can be produced more efficiently than the same operation with a single wafer by continuously performing the pasting step with the polarizing plate made of the unwound support.

c. Method of saponification by protecting with a laminate film As in the case of b above, when the coating layer is insufficient in resistance to an alkaline solution, the laminate film is bonded to the surface on which the final layer is formed after forming the final layer. Then, only the triacetyl cellulose surface opposite to the surface on which the final layer is formed is hydrophilized by dipping in an alkaline solution, and then the laminate film can be peeled off. Even in this method, the hydrophilic treatment necessary for the polarizing plate protective film can be applied only to the surface opposite to the surface on which the final layer of the triacetyl cellulose film is formed without damaging the coating layer. Compared with the method b, there is an advantage that a laminating film is generated as waste, but a device for applying a special alkaline solution is unnecessary.

d. Method of immersing in alkaline solution after forming up to middle layer Although resistant to alkaline solution up to lower layer, but insufficient resistance to alkaline solution of upper layer, dip into alkaline solution after forming up to lower layer to make both sides hydrophilic The upper layer can also be formed after processing. Although the manufacturing process is complicated, for example, in an antireflection film composed of a light diffusion layer and a low refractive index layer, when it has a hydrophilic group, there is an advantage that the interlayer adhesion between the light diffusion layer and the low refractive index layer is improved. is there.

e. Method of forming a coating layer on a pre-saponified triacetyl cellulose film Saponification of the triacetyl cellulose film by immersing it in an alkaline solution in advance, and forming a coating layer directly on one side or via another layer May be. In the case of saponification by dipping in an alkaline solution, the interlayer adhesion with the triacetyl cellulose surface hydrophilized by saponification may deteriorate. In such a case, after saponification, only the surface on which the coating layer is to be formed is treated by corona discharge, glow discharge or the like to remove the hydrophilic surface and then form the coating layer. Further, when the coating layer has a hydrophilic group, the interlayer adhesion may be good.

4- (8) Production of Polarizing Film The film of the present invention can be used as a polarizing film and a protective film disposed on one side or both sides thereof, and can be used as a polarizing plate.
As one protective film, the film of the present invention may be used, and the other protective film may be a normal cellulose acetate film, but is produced by the above-mentioned solution casting method and at a stretch ratio of 10 to 100%. It is preferable to use a cellulose acetate film stretched in the width direction in the form of a roll film.

Examples of the polarizing film include an iodine polarizing film, a dye polarizing film using a dichroic dye, and a polyene polarizing film. The iodine polarizing film and the dye polarizing film are generally produced using a polyvinyl alcohol film.
It is preferable to arrange so that the slow axis of the transparent support of the antireflection film or the cellulose acetate film and the transmission axis of the polarizing film are substantially parallel.

The moisture permeability of the protective film is important for the productivity of the polarizing plate. The polarizing film and the protective film are preferably bonded with a water-based adhesive, and the adhesive solvent is dried by diffusing in the protective film. The higher the moisture permeability of the protective film, the faster the drying and the higher the productivity. However, if the protective film is too high, moisture will enter the polarizing film depending on the usage environment (high humidity) of the liquid crystal display device. Polarization ability decreases.
The moisture permeability of the protective film is determined by the thickness, free volume, hydrophilicity / hydrophobicity, etc. of the transparent support or polymer film (and polymerizable liquid crystal compound).
When using the film of the present invention as a protective film of a polarizing plate, the moisture permeability is preferably from 100~1000g ^/ m 2 · 24hrs, and more preferably a 300~700g ^/ m 2 · 24hrs.
In the case of film formation, the thickness of the transparent support can be adjusted by lip flow rate and line speed, or stretching and compression. Since the moisture permeability varies depending on the main material to be used, it is possible to make a preferable range by adjusting the thickness.
In the case of film formation, the free volume of the transparent support can be adjusted by the drying temperature and time.
Also in this case, moisture permeability varies depending on the main material to be used, so that a preferable range can be obtained by adjusting the free volume.
The hydrophilicity / hydrophobicity of the transparent support can be adjusted by an additive. The moisture permeability can be increased by adding a hydrophilic additive to the free volume, and conversely, the moisture permeability can be lowered by adding a hydrophobic additive.
By independently controlling the moisture permeability, the polarizing plate can be produced at low cost with high productivity.

As the polarizing film, a known polarizing film or a polarizing film cut out from a long polarizing film whose absorption axis is neither parallel nor perpendicular to the longitudinal direction may be used. A long polarizing film whose absorption axis is neither parallel nor perpendicular to the longitudinal direction is produced by the following method.
That is, a polarizing film stretched by applying tension while holding both ends of a continuously supplied polymer film by a holding means, stretched at least 1.1 to 20.0 times in the film width direction, The progress of the film is such that the difference between the moving speeds in the longitudinal direction of the holding device is within 3%, and the angle formed by the film moving direction at the exit of the step of holding both ends of the film and the substantial stretching direction of the film is inclined by 20 to 70 °. The film can be produced by a stretching method in which the direction is bent while holding both ends of the film. In particular, those inclined by 45 ° are preferably used from the viewpoint of productivity.

The method for stretching the polymer film is described in detail in paragraphs 0020 to 0030 of JP-A-2002-86554.
Of the two protective films in the polarizing plate, the protective film other than the optical film and the antireflection film is preferably an optical compensation film having an optical compensation layer comprising an optically anisotropic layer. The optical compensation film (retardation film) can improve the viewing angle characteristics of the liquid crystal display screen.
A known film can be used as the optical compensation film, but the optical compensation film described in JP-A-2001-100042 is preferable in terms of widening the viewing angle.

5). Form of use of the present invention The film and polarizing plate of the present invention are used in 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). It is done. The optical filter according to the present invention can be used on a known display such as a plasma display panel (PDP) or a cathode ray tube display (CRT). At this time, it is preferable that the light diffusion layer is disposed on the viewing side in the optical film, and the low refractive index layer is disposed on the viewing side in the antireflection film. The same applies to a polarizing plate having an optical film and an antireflection film.

5- (1) Liquid Crystal Display Device The film and polarizing plate of the present invention can be advantageously used for an image display device such as a liquid crystal display device, and is preferably used for the outermost layer of the display.
The liquid crystal display device has a liquid crystal cell and two polarizing plates arranged on both sides thereof, and the liquid crystal cell carries a liquid crystal between two electrode substrates. Furthermore, one optically anisotropic layer may be disposed between the liquid crystal cell and one polarizing plate, or two optically anisotropic layers may be disposed between the liquid crystal cell and both polarizing plates.

  The liquid crystal cell is preferably in TN mode, VA mode, OCB mode, IPS mode or ECB mode.

<TN mode>
In the TN mode liquid crystal cell, rod-like liquid crystal molecules are substantially horizontally aligned when no voltage is applied, and are twisted and aligned at 60 to 120 °.
The TN mode liquid crystal cell is most frequently used as a color TFT liquid crystal display device, and is described in many documents.

<VA mode>
In a VA mode liquid crystal cell, rod-like liquid crystalline molecules are aligned substantially vertically when no voltage is applied.
The VA mode liquid crystal cell includes (1) a narrowly defined VA mode liquid crystal cell in which rod-like liquid crystalline molecules are aligned substantially vertically when no voltage is applied, and substantially horizontally when a voltage is applied (Japanese Patent Laid-Open No. Hei 2-). 176625) (2) Liquid crystal cell (SID97, Digest of Tech. Papers (Proceedings) 28 (1997) 845 in which the VA mode is converted into a multi-domain (for MVA mode) in order to enlarge the viewing angle. ), (3) A liquid crystal cell in a mode (n-ASM mode) in which rod-like liquid crystalline molecules are substantially vertically aligned when no voltage is applied and twisted multi-domain alignment is applied when a voltage is applied (Preliminary collections 58-59 of the Japan Liquid Crystal Society) (1998)) and (4) SURVAVAL mode liquid crystal cells (announced at LCD International 98).

<OCB mode>
The OCB mode liquid crystal cell is a bend alignment mode liquid crystal cell in which rod-like liquid crystalline molecules are aligned in substantially opposite directions (symmetrically) at the upper and lower portions of the liquid crystal cell. US Pat. No. 4,583,825, No. 5,410,422. Since the rod-like liquid crystal molecules are symmetrically aligned at the upper and lower portions of the liquid crystal cell, the bend alignment mode liquid crystal cell has a self-optical compensation function. Therefore, this liquid crystal mode is called an OCB (Optically Compensatory Bend) liquid crystal mode. The bend alignment mode liquid crystal display device has an advantage of high response speed.

<IPS mode>
The IPS mode liquid crystal cell is a type in which a nematic liquid crystal is switched by applying a lateral electric field. IDRC (Asia Display '95), p. 577-580 and p. 707-710.

<ECB mode>
In the ECB mode liquid crystal cell, rod-like liquid crystalline molecules are substantially horizontally aligned when no voltage is applied. The ECB mode is one of the liquid crystal display modes having the simplest structure, and is described in detail in, for example, Japanese Patent Application Laid-Open No. 5-203946.

5- (2) Display other than liquid crystal display device <PDP>
A plasma display panel (PDP) is generally composed of a gas, a glass substrate, an electrode, an electrode lead material, a thick film printing material, and a phosphor. Two glass substrates are a front glass substrate and a rear glass substrate. An electrode and an insulating layer are formed on the two glass substrates. A phosphor layer is further formed on the rear glass substrate. Two glass substrates are assembled and gas is sealed between them.
Plasma display panels (PDP) are already commercially available. The plasma display panel is described in JP-A-5-205643 and JP-A-9-306366.

The front plate may be disposed on the front surface of the plasma display panel. The front plate preferably has sufficient strength to protect the plasma display panel. The front plate can be used with a gap from the plasma display panel, or can be used by directly pasting the front plate to the plasma display body.
In an image display device such as a plasma display panel, an optical filter using the film of the present invention can be directly attached to the display surface. When a front plate is provided in front of the display, an optical filter using the film of the present invention can be attached to the front side (outside) or back side (display side) of the front plate.

<Touch panel>
The film of the present invention can be applied to touch panels described in JP-A-5-127822 and JP-A-2002-48913.

<Organic EL device>
The film of the present invention can be used as a substrate (base film) such as an organic EL element or a protective film.
When the film of the present invention is used for an organic EL device or the like, JP-A-11-335661, JP-A-11-335368, JP-A-2001-192651, JP-A-2001-192652, JP-A-2001-192653, JP-A-2001-335776, JP-A-2001-247859, JP-A-2001-181616, JP-A-2001-181617, JP-A-2002-181816, JP-A-2002-181617, JP-A-2002-056776, etc. The contents described in each publication can be applied. Moreover, it is preferable to use together with the content of each gazette of Unexamined-Japanese-Patent No. 2001-148291, Unexamined-Japanese-Patent No. 2001-221916, and Unexamined-Japanese-Patent No. 2001-231443.

6). Various characteristic values Various measurement methods related to the present invention and preferable characteristic values are shown below.
6- (1) Reflectance Specular reflectance and color are measured by attaching an adapter “ARV-474” to a spectrophotometer “V-5502 [manufactured by JASCO Corporation], and a wavelength region of 380 to 780 nm. , The specular reflectance at an exit angle of −5 ° at an incident angle of 5 ° is measured, the average reflectance at 450 to 650 nm is calculated, and the antireflection property can be evaluated.

6- (2) color antireflection performance polarizing plate of the present invention, the CIE standard illuminant _{D 65,} with respect to the incident angle of 5 ° incident light at 780nm region from the wavelength 380 nm, of the specularly reflected light color, That is, the color tone can be evaluated by obtaining the L ^* , a ^* , and b ^* values of the CIE 1976 L ^* a ^* b ^* color space.
The L ^* , a ^* , and b ^* values are preferably in the ranges of 3 ≦ L ^* ≦ 20, −7 ≦ a ^* ≦ 7, and −10 ≦ b ^* ≦ 10, respectively. By setting it within this range, the color of reflected light from red purple to blue purple, which has been a problem with conventional polarizing plates, is reduced, and further 3 ≦ L ^* ≦ 10, 0 ≦ a ^* ≦ 5, and − 7 ≦ b ^* ≦ 0 is greatly reduced, and when applied to a liquid crystal display device, when applied to a liquid crystal display device, such as indoor fluorescent lamps, a slight brightness of bright external light is reflected. Neutral, don't mind. Specifically, if a ^* ≦ 7, the reddish color will not be too strong, and if a ^* ≧ −7, the cyan color will not be too strong. If b ^* ≧ −7, the bluish color does not become too strong, and if b ^* ≦ 0, the yellowish color does not become too strong.

Furthermore, the color uniformity of the reflected light is determined according to the following formula (21) from a ^* b ^* on the L ^* a ^* b ^* chromaticity diagram obtained from the reflection spectrum of the reflected light from 380 nm to 680 nm. It can be obtained as the rate of change in taste.

Here, a ^* _max and a ^* _min are the maximum value and minimum value of the a ^* value, respectively; b ^* _max and b ^* _min are the maximum value and minimum value of the b ^* value, respectively; a ^* _av and b ^* _av Are average values of a ^* value and b ^* value, respectively. The color change rate is preferably 30% or less, more preferably 20% or less, and most preferably 8% or less.

The film of the present invention preferably has a Delta] E _w is 15 or less is the change in color before and after the weather resistance test, more preferably 10 or less, and most preferably 5 or less. In this range, it is possible to achieve both low reflection and reduction of the color of the reflected light. For example, when applied to the outermost surface of an image display device, there is a slight amount of high-brightness external light such as an indoor fluorescent lamp. The color tone when it is reflected is neutral, and the quality of the displayed image is good, which is preferable.

The color change ΔE _w can be obtained according to the following formula (22).

Formula (22): ΔE _w = [(ΔL _w ) ² + (Δa _w ) ² + (Δb _w ) ² ] ^1/2

Here, ΔL _w , Δa _w , and Δb _w are change amounts of the L ^* value, the a ^* value, and the b ^* value before and after the weather resistance test.

6- (3) Transmission Image Sharpness The transmission image definition was measured according to JIS-K7105 using an optical comb having a slit width of 0.5 mm using a image clarity measuring instrument (ICM-2D type) manufactured by Suga Test Instruments Co., Ltd. Can be measured.

  The transmission image definition of the film of the present invention is preferably 60% or more. The transmitted image clarity is generally an index indicating the degree of blurring of an image reflected through a film, and the larger this value, the clearer and better the image viewed through the film. The transmitted image definition is preferably 70% or more, and more preferably 80% or more.

6- (4) Surface Roughness Centerline average roughness (also called arithmetic average roughness) (Ra) and uneven spacing average (Sm) can be measured according to JIS-B0601.

6- (5) Haze The haze of the film of the present invention is the haze value defined in JIS-K7105. Based on the measurement method defined in JIS-K7361-1, manufactured by Nippon Denshoku Industries Co., Ltd. A value automatically measured as haze = (diffused light / total transmitted light) × 100 (%) measured using a turbidimeter “NDH-1001DP” was used.
The internal haze of the optical film of the present invention is preferably 0 to 60%, more preferably 10 to 40%, further preferably 15 to 35%, and most preferably 20% to 30%.
The surface haze is preferably 0.3 to 20%, more preferably 0.3 to 10%, and further preferably 0.3% to 1.5%.

6- (6) Hardness <Pencil hardness>
The strength of the film of the present invention can be evaluated by a pencil hardness test according to JIS-K5400.
The pencil hardness is preferably H or higher, more preferably 2H or higher, and most preferably 3H or higher.

<Surface elastic modulus>
The surface elastic modulus in the present invention is a value determined using a micro surface hardness tester (manufactured by Fisher Instruments: Fisherscope H100VP-HCU). Specifically, using a diamond pyramid indenter (tip-to-face angle: 136 °), the indentation depth is measured under an appropriate test load within a range where the indentation depth does not exceed 1 μm. This is the elastic modulus obtained from the change in load and displacement over time.
Further, the surface hardness can be obtained as a universal hardness by using the above-mentioned micro surface hardness tester. The universal hardness is a value obtained by measuring the indentation depth of a quadrangular pyramid indenter under a test load and dividing the test load by the surface area of the indent calculated from the geometric shape of the indent generated by the test load. It is known that there is a positive correlation between the surface elastic modulus and the universal hardness.

In this specification, the universal hardness is a universal hardness (N) determined by the following measurement procedure using a microhardness meter H100 manufactured by Fischer Instruments Co., Ltd. with respect to the crosslinkable polymer film having a thickness of about 20 to 30 μm cured and formed on a glass plate. / Mm ² ).
Appropriate bar coater is selected so that the film thickness after curing of a coating solution with a solid content of about 25% containing the necessary catalyst, crosslinking agent, polymerization initiator, etc. in addition to the crosslinkable polymer is about 20-30 μm. TOSHINRIKO. CO. Made of LTD (26 mm × 76 mm × 1.2 mm) coated on a polished glass slide plate. In the case where the crosslinkable polymer is thermosetting, a thermosetting condition for sufficiently curing the film is obtained in advance (for example, 125 ° C. for 10 minutes), and when the crosslinkable polymer is ionizing radiation curable, the film is similarly formed. The curing conditions for sufficient curing are obtained in advance (as an example, the oxygen concentration is 12 ppm, the UV irradiation amount is 750 mJ / cm ² ). Recess area for each film F when the load is continuously increased from 0 to 4 mN for each film, and the conical diamond indenter is pushed in with the maximum 1/10 film thickness not affected by the glass plate hardness of the substrate. Universal hardness is calculated from N = 6 measurement average value of F / A determined from A (mm ² ).
The surface hardness can be determined by nanoindentation described in JP-A No. 2004-354828. In this case, the hardness is preferably 2 GPa to 4 GPa, and the nanoindentation elastic modulus is preferably 10 GPa to 30 GPa.

6- (7) Antifouling test <Magic wiping property>
The film is fixed on the glass surface with an adhesive, and a circle with a diameter of 5 mm is written three times with a pen tip (thin) of black magic “Mckey extra fine (product name: made by ZEBRA)” at 25 ° C. and 60 RH%. After 5 seconds, wipe it back and forth 20 times with a load that dents the bundle of Bencot (Brand name, Asahi Kasei Co., Ltd.) folded into 10 sheets. The writing and wiping are repeated under the above conditions until after the magic does not disappear by wiping, and the antifouling property can be evaluated by the number of times of wiping.
The number of times until it no longer disappears is preferably 5 times or more, and more preferably 10 times or more.

  For Black Magic, Magic Ink No. 700 (M700-T1 black) Using an ultra-fine sample, draw a circle with a diameter of 1 cm on the sample, paint it for 24 hours, rub it with Bencott (Asahi Kasei Co., Ltd.), and evaluate whether the magic can be wiped off. .

6- (8) Surface Tension The surface tension measured and evaluated in the present invention is the surface tension meter (Kyowa Interface Science, KYOWA CBVP SURFACE TENSIOMETER A3) under the environment at a temperature of 25 ° C. ).

6- (9) Contact angle Using a contact angle meter [“CA-X” type contact angle meter, manufactured by Kyowa Interface Science Co., Ltd.], using pure water as a liquid in a dry state (20 ° C./65% RH) Then, a droplet having a diameter of 1.0 mm was formed on the needle tip, and this was brought into contact with the surface of the film to form a droplet on the film. The angle formed between the tangent to the liquid surface and the film surface at the point where the film and the liquid are in contact with each other is defined as the contact angle.

6- (10) Surface free energy The surface energy can be determined by the contact angle method, the wet heat method, and the adsorption method as described in “Basics and Applications of Wetting”, Realize, Inc., 1989.12.10. . In the case of the film of the present invention, it is preferable to use a contact angle method.
Specifically, two types of solutions having known surface energies are dropped on the film, and at the intersection between the droplet surface and the film surface, the droplet is formed at the angle formed by the tangent line drawn on the droplet and the film surface. The included angle is defined as the contact angle, and the surface energy of the film can be calculated by calculation.

The surface free energy (γs ^v : unit, mN / m) of the film of the present invention is D.I. K. Owens: J.M. Appl. Polym. Sci. , 13, 1741 (1969), the following simultaneous equations a from the contact angles θ _H2O and θ _{CH2I2 of} pure water H ₂ O and methylene iodide CH ₂ I ₂ obtained experimentally on the antireflection film. represents the surface tension of the antireflection film to be defined by the value represented by the sum of the gamma] s ^d and gamma] s ^h determined from the ^{b γs v (= γs d +} γs h). The gamma] s ^v is small, the more high repellency of the surface with a low surface free energy, generally excellent antifouling property.
a. 1 + cos θ _H2O =
_{^{2√γs d (√γ H2O d / γ}} H2O v) + 2√γs h (√γ H2O h / γ H2O v)
b. 1 + cos θ _CH2I2 =
_{^{2√γs d (√γ CH2I2 d / γ}} CH2I2 v) + 2√γs h (√γ CH2I2 h / γ CH2I2 v)
γ _{H 2 O} ^d = 21.8, γ _{H 2 O} ^h = 51.0, γ _{H 2 O} ^v = 72.8,
γ _CH2I2 ^d = 49.5, _γCH2I2 ^h = 1.3, _γCH2I2 ^v = 50.8
In the contact angle measurement, after the film was conditioned for 1 hour or more at 25 ° C. and 60%, 2 μl of the droplet was formed into a film using an automatic contact angle meter CA-V150 manufactured by Kyowa Interface Science Co., Ltd. The contact angle was determined 30 seconds after dropping.

  The surface free energy of the film of the present invention is preferably 25 mN / m or less, and particularly preferably 20 mN / m or less.

6- (11) Curl The curl is measured by using the curl measurement template of Method A in “Measuring Method of Curling of Photographic Film” of JIS-K7619-1988.
The measurement conditions are 25 ° C., relative humidity 60%, and humidity control time 10 hours.
The film according to the present invention preferably has a value when curl is expressed by the following formula (23) in the range of minus 15 to plus 15, more preferably in the range of minus 12 to plus 12. Is minus 10 to plus 10. In this case, the measurement direction of the curl in the sample is measured in the conveyance direction of the base material in the case of application in a web form.
Formula (23): Curl = 1 / R R is the radius of curvature (m)
This is an important characteristic for preventing cracks and film peeling during film production, processing, and market handling. It is preferable that the curl value is in the above range and the curl is small.
Here, “curl plus” means a curl in which the coating side of the film is inside the curve, and “minus” means a curl in which the coating side is outside the curve.

  In the film according to the present invention, the absolute value of the difference between the curl values when the relative humidity is changed to 80% and 10% based on the curl measurement method is preferably 24 to 0, and preferably 15 to 0. Is more preferable, and 8 to 0 is most preferable. This is a property related to handling, peeling and cracking when films are attached under various humidity.

6- (12) Adhesion Evaluation The adhesion between the layers of the film or between the support and the coating layer can be evaluated by the following method.
Nitto Denko Co., Ltd. Polyester adhesive tape with 11 squares and 11 horizontal cuts at 1 mm intervals and a total of 100 squares on the surface of the coated layer. (NO.31B) is pressure-bonded, and the test for peeling off after leaving for 24 hours is repeated three times at the same place, and the presence or absence of peeling is visually observed.

  Of 100 squares, peeling is preferably within 10 mm, and more preferably within 2 mm.

6- (13) Brittleness test (crack resistance)
Crack resistance is an important characteristic for preventing crack defects by handling such as film application, processing, cutting, adhesive application, and application to various objects.
A film sample is cut into 35 mm x 140 mm, left to stand for 2 hours at a temperature of 25 ° C and a relative humidity of 60%, and then the curvature diameter at which cracks start to occur when rolled into a cylinder is measured to evaluate surface cracks. can do.

  The crack resistance of the film of the present invention is preferably 50 mm or less, more preferably 40 mm or less, and most preferably 30 mm or less, when the film is rolled with the coating layer side facing outward. About the crack of an edge part, it is preferable that there is no crack or the length of a crack is less than 1 mm on average.

6- (14) Dust Removability The film of the present invention can be attached to a monitor, dust (futon, textile waste) can be sprinkled on the monitor surface, the dust can be wiped off with a cleaning cloth, and the dust removability can be evaluated.
It is preferable to remove completely by wiping 6 times, and it is more preferable to remove dust completely by wiping within 3 times.

6- (15) Performance of liquid crystal display device Hereinafter, a method for evaluating characteristics and a preferable situation when the film of the present invention is used on a display device will be described.
The polarizing plate on the viewing side provided in the liquid crystal display device is peeled off. Instead, the film or polarizing plate of the present invention is applied to the polarizing plate on which the coated surface is on the viewing side and the transmission axis of the polarizing plate is attached to the product. Paste through adhesive to match. In a 500 lux bright room, the liquid crystal display device is displayed in black, and the following various characteristics can be evaluated visually from various viewing angles.

<Evaluation of image unevenness and color>
Using the prepared liquid crystal display device, unevenness, streaks, and color change during black display (L1) are visually evaluated by a plurality of observers.
It is preferable that 10 or less people can recognize unevenness, streaks, left and right color change, color change due to temperature and humidity, and white blur, and more preferably no one can recognize it.
In addition, reflection of external light is performed using a fluorescent lamp, and a change in reflection can be relatively evaluated visually.

<Light leakage of black display>
The light leakage rate of black display in the azimuth direction 45 ° and polar angle direction 70 ° from the front of the liquid crystal display device is measured. The light leakage rate is preferably 0.4% or less, and more preferably 0.1% or less.

<Evaluation of glare>
In the present invention, “glare” is not the presence or absence of glare of lighting such as an electric light, which is discussed in terms of antiglare properties, but R, G, B for the human eye due to the enlargement of pixels due to the lens effect caused by the film. Says that it is glaring and visible. The evaluation is performed by attaching an antiglare antireflection film to the display and visually evaluating the liquid crystal display device. It is preferable that 10 people can evaluate and recognize the glare is 3 or less, more preferably 1 person cannot recognize.

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

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

(Preparation of sol liquid b)
After the reaction, the mixture was cooled to room temperature, and then a sol solution b was obtained in the same manner as the sol composition a except that 6 parts of acetylacetone was added.

(Synthesis of fluororesin-containing polymer (FP-132))
To a reactor equipped with a stirrer and a reflux condenser, 39.93 g of 1H, 1H, 7H-dodecafluoroheptyl acrylate, 1.1 g of dimethyl 2,2′-azobisisobutyrate and 30 g of 2-butanone were added, and a nitrogen atmosphere was added. For 6 hours at 78 ° C. to complete the reaction. The weight average molecular weight was 1.5 × 10 ⁴ .
Fluoro resin-containing copolymer (FP-132)

───────────────────────────────────
Composition of coating liquid A for light diffusion layer ───────────────────────────────────
PET-30 46.0g
Irgacure 184 1.7g
MX-600 (30%) 23.0 g
FP-132 0.06g
KBM-5103 6.0g
MiBK (methyl isobutyl ketone) 14.0 g
MEK (methyl ethyl ketone) 10.0 g
───────────────────────────────────

───────────────────────────────────
Composition of coating liquid B for light diffusion layer ───────────────────────────────────
PET-30 50.3g
Irgacure 184 1.7g
MX-600 (30%) 10.0 g
FP-132 0.06g
KBM-5103 6.0g
MiBK 21.0g
MEK 10.0g
───────────────────────────────────

───────────────────────────────────
Composition of coating solution C for light diffusion layer ───────────────────────────────────
PET-30 49.0g
Irgacure 184 1.7g
MX-800 (30%) 15.3 g
FP-132 0.06g
KBM-5103 6.0g
MiBK 18.0g
MEK 10.0g
───────────────────────────────────

───────────────────────────────────
Composition of coating liquid D for light diffusion layer ───────────────────────────────────
PET-30 40.0g
Irgacure 184 1.7g
MX-600 (30%) 48.0g
FP-132 0.06g
KBM-5103 6.0g
MEK 10.0g
───────────────────────────────────

───────────────────────────────────
Composition of coating liquid E for light diffusion layer ───────────────────────────────────
Desolite Z7404 5.0g
DPHA 44.0g
Irgacure 184 1.7g
MX-800 (30%) 15.3 g
FP-132 0.06g
KBM-5103 6.0g
MiBK 18.0g
MEK 10.0g
───────────────────────────────────

───────────────────────────────────
Composition of coating solution F for light diffusion layer ───────────────────────────────────
PET-30 40.0g
DPHA 6.0g
Irgacure 184 2.0g
MX-800 (30%) 28.6g
FP-132 0.06g
KBM-5103 6.0g
MiBK 9.0g
MEK 10.0g
───────────────────────────────────

───────────────────────────────────
Composition of coating liquid G for light diffusion layer ───────────────────────────────────
PET-30 50.0g
Irgacure 184 2.0g
SX-350 (30%) 2.7 g
Cross-linked acrylic-styrene particles (30%) 12.3 g
FP-132 0.06g
KBM-5103 10.0g
Toluene 38.5g
───────────────────────────────────

───────────────────────────────────
Composition of coating liquid H for light diffusion layer ───────────────────────────────────
PET-30 55.0g
Irgacure 184 1.7g
MXS-300 (30%) 6.2g
FP-132 0.06g
KBM-5103 3.0g
MiBK 25.0g
MEK 10.0g
───────────────────────────────────

───────────────────────────────────
Composition of coating liquid I for light diffusion layer ───────────────────────────────────
PET-30 45.0g
Irgacure 184 1.7g
MX-600 (30%) 28.6g
FP-132 0.06g
KBM-5103 6.0g
MiBK 9.0g
MEK 10.0g
───────────────────────────────────

───────────────────────────────────
Composition of coating liquid J for hard coat layer ───────────────────────────────────
PET-30 47.5g
DPHA 2.5g
Irgacure 184 2.0g
FP-132 0.06g
MiBK 58.5g
MEK 5.0g
───────────────────────────────────

───────────────────────────────────
Composition of coating liquid K for light diffusion layer ───────────────────────────────────
PET-30 40.0g
Irgacure 184 1.7g
MXS-300 (30%) 48.0g
FP-132 0.06g
KBM-5103 6.0g
MEK 10.0g
───────────────────────────────────

  Each of the above compositions was filtered through a polypropylene filter having a pore diameter of 30 μm to prepare a coating solution for the light diffusion layer and the hard coat layer.

───────────────────────────────────
Composition of coating solution E-1 for low refractive index layer ───────────────────────────────────
DPHA 3.3g
Hollow silica (18.2%) 40.0g
RMS-033 0.7g
Irgacure 907 0.2g
Sol liquid a 6.2g
MEK 299.6g
───────────────────────────────────

───────────────────────────────────
Preparation of coating solution E-2 for low refractive index layer ───────────────────────────────────
OPSTAR JN7228A (6%) 13.0g
MEK-ST (30%) 1.3g
MEK-ST-L (30%) 1.3g
Sol liquid a 0.6g
MEK 5.0g
Cyclohexanone 0.6g
───────────────────────────────────

  Each of the above compositions was stirred and then filtered through a polypropylene filter having a pore size of 1 μm to prepare a coating solution for a low refractive index layer.

The compounds used are shown below.
KBM-5103:
Silane coupling agent [Shin-Etsu Chemical Co., Ltd.]

PET-30:
A mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate [manufactured by Nippon Kayaku Co., Ltd.]
Irgacure 184:
Polymerization initiator [Ciba Specialty Chemicals Co., Ltd.]
SX-350:
Cross-linked polystyrene particles having an average particle size of 3.5 μm [refractive index of 1.61, manufactured by Soken Chemical Co., Ltd., 30% toluene dispersion, used after dispersion for 20 minutes at 10,000 rpm in a polytron disperser]
Cross-linked acrylic-styrene particles:
Average particle size 3.5 μm [refractive index 1.55, manufactured by Soken Chemical Co., Ltd., 30% toluene dispersion, used after dispersion for 20 minutes at 10,000 rpm in a polytron disperser]
FP-132:
Fluororesin-containing copolymer synthesized as described above

Desolite Z7404:
ZrO ₂ fine particle-containing hard coat agent [refractive index 1.62, solid content concentration: 60% by mass, zirconium oxide fine particle content: 70% by mass (relative to solid content), average particle size of zirconium oxide fine particles: about 20 nm, solvent composition: MIBK / MEK = 9/1, manufactured by JSR Corporation]
DPHA:
Mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate [refractive index 1.52, manufactured by Nippon Kayaku Co., Ltd.]
MXS-300:
PMMA particles having an average particle size of 3 μm [refractive index: 1.49, manufactured by Soken Chemical Co., Ltd., 30% MIBK dispersion, used after dispersion at 10,000 rpm for 20 minutes in a Polytron disperser]
MX-600:
PMMA particles having an average particle size of 6 μm [refractive index: 1.49, manufactured by Soken Chemical Co., Ltd., 30% MIBK dispersion, used after dispersion at 10,000 rpm for 20 minutes in a Polytron disperser]
MX-800:
PMMA particles having an average particle size of 8 μm [refractive index: 1.49, manufactured by Soken Chemical Co., Ltd., 30% MIBK dispersion, used after dispersion for 20 minutes at 10,000 rpm in a Polytron disperser]
MX-1000:
PMMA particles having an average particle diameter of 10 μm [refractive index: 1.49, manufactured by Soken Chemical Co., Ltd., 30% MIBK dispersion, used after dispersion at 10,000 rpm for 20 minutes in a Polytron disperser]
MBX-5:
Average particle size 5 μm PMMA particles [refractive index 1.49, manufactured by Sekisui Plastics Co., Ltd., 30% MIBK dispersion, used after dispersion for 20 minutes at 10,000 rpm in a Polytron disperser]

OPSTAR JN7228A: Thermally crosslinkable fluorine-containing polymer [refractive index 1.42, solid content concentration 6%, manufactured by JSR Corporation]
MEK-ST:
Colloidal silica dispersion [average particle size 10-20 nm, solid content 30%, manufactured by Nissan Chemical Co., Ltd.]
MEK-ST-L:
Colloidal silica dispersion [MEK-ST particle size difference, average particle size 45 nm, solid content concentration 30%, manufactured by Nissan Chemical Co., Ltd.]
Hollow silica: Hollow silica fine particle dispersion prepared as follows

(Preparation of hollow silica fine particle dispersion)
Hollow silica fine particle sol (isopropyl alcohol silica sol, CS60-IPA manufactured by Catalytic Chemical Industry Co., Ltd., average particle diameter 60 nm, shell thickness 10 nm, silica concentration 20%, silica particle refractive index 1.31) in 500 parts, acryloyloxypropyl After 30 parts of trimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-5103) and 1.5 parts of diisopropoxyaluminum ethyl acetate were added and mixed, 9 parts 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 parts of acetylacetone, and obtained the hollow silica dispersion liquid. The resulting hollow silica dispersion had a solid content concentration of 18% by mass and a refractive index after solvent drying of 1.31.

X-22-164C:
Reactive silicone (manufactured by Shin-Etsu Chemical Co., Ltd.)
RMS-033:
Reactive silicone (manufactured by Gelest Co., Ltd.)
Irgacure 907:
Photopolymerization initiator (Ciba Specialty Chemicals Co., Ltd.)
Irgacure 651
Photopolymerization initiator [Ciba Specialty Chemicals Co., Ltd.]

[Example 1: Preparation and evaluation of optical film]
(1) Coating of functional layer: hard coat layer or light diffusion layer Triacetyl cellulose film (TD80U: Fuji Photo Film Co., Ltd.) having a thickness of 80 μm is unrolled in the form of a roll, and each functional layer described in Table 1 The coating solution for (hard coat layer or light diffusing layer) is applied under conditions of a conveyance speed of 10 m / min using a micro gravure roll having a diameter of 135 lines / inch and a gravure pattern having a depth of 60 μm and a doctor blade. After drying at 60 ° C. for 150 seconds, using an air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) under a nitrogen purge, UV light with an illuminance of 400 mW / cm ² and an irradiation amount of 250 mJ / cm ² The coated layer was cured by irradiation to form a functional layer of the light diffusing layer and wound up. Rums 1-6 and 8-11 were prepared.
For the optical film 7, a triacetyl cellulose film (TD80U: Fuji Photo Film Co., Ltd.) having a thickness of 80 μm was unwound in a roll form, and the light diffusion layer was used by using the Giesser of Example 1 described in JP-A-2003-260400. Was supplied from slot 23 and the hard coat layer was supplied from slot 24, applied at a transfer speed of 30 m / min, dried at 60 ° C. for 150 seconds, and further air-cooled metal halide lamp (eye graphics with 160 W / cm under nitrogen purge). (Co., Ltd.) was used to irradiate ultraviolet rays having an illuminance of 400 mW / cm ² and an irradiation amount of 250 mJ / cm ² to cure the coating layer, and a functional layer was formed and wound up.
The refractive index excluding particles of the light diffusion layer and hard coat coating liquids A to D and F to K was 1.52, and the refractive index of the film excluding the particles of the light diffusion layer coating liquid E was 1.54. It was.

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

(1) Anti-glare property The entire back side of the coated surface of the obtained film is painted with black magic ink, and a bare fluorescent lamp (8000 cd / m ² ) without louver is projected from an angle of 5 degrees, from a direction of −5 degrees. The degree of blurring of the reflected image when observed was evaluated according to the following criteria.
A: Not reflected so much that the outline of the fluorescent lamp is completely unknown.
○: The outline of the fluorescent lamp is slightly observed, but hardly reflected.
Δ: Fluorescent light is blurred but slightly reflected.
X: The outline of the fluorescent light is clearly visible or dazzling.

(2) Haze The following measurements measured the total haze (H), internal haze (Hi), and surface haze (Hs) of the obtained film.
1. The total haze value (H) of the film obtained according to JIS-K7136 is measured.
2. A few drops of silicone oil were added to the surface and the back surface of the low refractive index layer side of the obtained film, and sandwiched from the front and back using two 1 mm thick glass plates (micro slide glass product number S 9111, manufactured by MATSANAMI), Two glass plates and the obtained film were optically adhered to each other, and the haze was measured in a state where surface haze was removed, and measurement was performed by sandwiching only silicone oil between two separately measured glass plates. The value obtained by subtracting haze was calculated as the internal haze (Hi) of the film.
3. The value obtained by subtracting the internal haze (Hi) calculated in 2 above from the total haze (H) measured in 1 above was calculated as the surface haze (Hs) of the film.
In the present specification, the term “haze” or “haze value” means the total haze (H) obtained by the above method unless otherwise specified.

(3) Arithmetic average roughness (Ra), average interval of unevenness (Sm)
The film surface was measured using a micromap machine (manufactured by RYOKA SYSTEM).

(4) Transmission and scattering properties The obtained film was measured using an automatic variable angle photometer (GP-5 type) manufactured by Murakami Color Research Laboratory. Each film was measured three times at another position separated by 1 cm or more, averaged, and emitted light intensities of 0 °, 6 °, and 30 ° from the normal direction on the back side of the film were I (0 °) and I (6 °, respectively). ), I (30 °). In addition, Fuji Photo Film Co., Ltd. 80 μm thick triacetyl cellulose film was measured in the same manner, and the emitted light intensity at 0 ° from the normal direction on the back side of the film was I0, and I (0 °) / I0, I ( 6 °) / I0 and I (30 °) / I0.

(Saponification of optical film)
After film formation, the sample was subjected to the following treatment. A 1.5 mol / L aqueous sodium hydroxide solution was prepared and kept at 55 ° C. A 0.01 mol / L dilute sulfuric acid aqueous solution was prepared and kept at 35 ° C. The prepared antireflection film was immersed in the aqueous sodium hydroxide solution for 2 minutes, and then immersed in water to sufficiently wash away the aqueous sodium hydroxide solution. Subsequently, after being immersed in the above-mentioned dilute sulfuric acid aqueous solution for 1 minute, it was immersed in water to sufficiently wash away the dilute sulfuric acid aqueous solution. Finally, the sample was thoroughly dried at 120 ° C.

  An 80 μm-thick triacetylcellulose film (TD80U, manufactured by Fuji Photo Film Co., Ltd.), which was immersed in a 1.5 mol / L, 55 ° C. NaOH aqueous solution for 2 minutes and then neutralized and washed with water, and a sample of the present invention ( A polarizing plate was prepared by adhering iodine to polyvinyl alcohol and adhering and protecting both sides of the polarizing film prepared by stretching. The polarizing plate thus produced was replaced with a polarizing plate on the viewing side of a high-vision liquid crystal television LC-20AX5 manufactured by Sharp Corporation so that the side having the light diffusion layer was the outermost surface. About the obtained display apparatus, the following items were evaluated. The results are shown in Table 2.

(6) Contrast The produced optical film was mounted on a liquid crystal television, and the contrast ratio was measured from white luminance and black luminance using a measuring device (“EZ-Contrast 160D” manufactured by ELDIM).

(7) Blackening property The feeling of blackening was sensorially evaluated about the liquid crystal display device which has arrange | positioned the polarizing plate which stuck the optical film on the visual recognition side surface on the transparent support side. The evaluation method is a method in which multiple displays are arranged in parallel and compared at the same time. From the front, the blackness when the power is turned off and the blackness (black image) when the power is turned on are compared for each film, and evaluated according to the following criteria. did. It was expressed by the standard that the stronger the blackness, the stronger the tightness of the screen.
A: Strong blackness and the screen appears to be strong.
○: Black is faintly gray and the screen appears slightly distorted.
Δ: Black but grayish, and the screen is not tight.
×: The color is quite gray and the screen is not tight.
(8) Evaluation of Glare The produced optical film was mounted on a liquid crystal television, and the degree of glare (luminance variation caused by the lens effect of the surface protrusion of the optical film) was visually evaluated according to the following criteria.
No glare is seen: ◎
Almost no glare seen: ○
There is an unpleasant glare: ×

(9) Character blur evaluation The produced optical film is mounted on a liquid crystal television, and the characters of “rose” are displayed on a white background with 25-point characters of “Rose” in a 10-point size Mincho style. The degree of blur of the outline of characters (image blur) when compared with the case where the same display was performed using a polarizing plate having no antiglare property was evaluated according to the following criteria.
Almost no character blur is seen: ◎
There is no problem with slightly blurred characters: ○
There is character blur: ×
(10) Reflection The degree of blurring of the reflected image when the produced optical film is mounted on a liquid crystal television, a fluorescent lamp (8000 cd / m ² ) is projected from an angle of 45 degrees, and observed from a direction of −45 degrees. Was evaluated according to the following criteria.
A: Not reflected so much that the outline of the fluorescent lamp is completely unknown.
○: The outline of the fluorescent lamp is slightly observed, but hardly reflected.
Δ: The fluorescent lamp is blurred, but it is reflected slightly, but there is no actual harm.
X: The outline of the fluorescent light is clearly visible or dazzling.

(11) Oblique direction viewing angle The produced optical film is mounted on a liquid crystal television, and using a measuring device ("EZ-Contrast 160D" ELDIM), the polar angle direction of 45 ° from the front of the liquid crystal television Then, the contrast ratio was measured, and the angle at which the contrast ratio was 20 or less was measured.

From the results shown in Table 2, the following is clear.
Examples Samples 1 to 7 of the present invention have high white luminance, low black luminance, good blackness, no problem with glare and character blur, and the performance is improved as an optical film as a whole. Further, since the viewing angle in the oblique direction is 69 ° or more, there is no problem.
On the other hand, among Comparative Samples 8 to 11, those with I (0 °) / I0 of less than 30% have low white luminance, and those with I (6 °) / I0 of less than 0.70% have poor glare. When (30 °) / I0 is greater than 0.007%, blackening occurs, black luminance and character blur become a problem, and the display device has poor visibility.

[Example 2]
(Coating of low refractive index layer)
Each of the triacetylcellulose films coated with the hard coat layer and / or the light diffusion layer is unwound again to form a low refractive index layer coating solution E-1 having a number of lines of 200 lines / inch and a depth of 30 μm. Using a microgravure roll having a diameter of 50 mm and a doctor blade, the coating was carried out under the condition of a conveyance speed of 20 m / min, dried at 120 ° C. for 75 seconds, further dried for 10 minutes, and then air-cooled at 240 W / cm under a nitrogen purge. Using a metal halide lamp (manufactured by Eye Graphics Co., Ltd.), an ultraviolet ray having an illuminance of 400 mW / cm ² and an irradiation amount of 240 mJ / cm ² was irradiated to form a low refractive index layer having a thickness of 100 nm and wound up.
In the same manner as in Example 1, saponification treatment and polarizing plate processing were performed and attached to a liquid crystal television.
The example with the low refractive index layer of Example 2 was better than Example 1 and the black spots were improved by one rank. Further, even when external light of 1000 cd / m ² is incident, the present inventions 1 to 7 coated with the low refractive index layer have a contrast higher than the comparative examples 8 to 11 coated with the low refractive index layer. A high-quality liquid crystal display device with high glare and no character blur was obtained.

[Example 3]
When E-2 was used instead of the coating solution E-1 for the low refractive index layer, the magic wiping property was further improved. Further, when the sol solution b is used in place of the organosilane sol solution a used for the low refractive index layer coating solutions E-1 and E-2, the stability of the coating solution with the passage of time is improved. The aptitude increased.

[Example 4]
When the sample of the present invention of Example 2 was bonded to a glass plate on the surface of an organic EL display device via an adhesive, reflection on the glass surface was suppressed, and a display device with high visibility was obtained.

[Example 5]
Using the sample of the present invention of Example 2, a polarizing plate with a single-sided antireflection film was prepared, and a λ / 4 plate was bonded to the opposite side of the polarizing plate on the side having the antireflection film, with the antireflection layer side closest to the antireflection layer side. When attached to the glass plate on the surface of the organic EL display device so as to be on the surface, the surface reflection and the reflection from the inside of the surface glass were cut, and a display with extremely high visibility was obtained.

It is a schematic sectional drawing which shows typically preferable embodiment of the film of this invention. It is a schematic sectional drawing which shows typically preferable embodiment of the film of this invention. It is a schematic sectional drawing which shows typically preferable embodiment of the film of this invention. It is a schematic sectional drawing which shows typically preferable embodiment of the film of this invention. It is a schematic sectional drawing which shows typically preferable embodiment of the film of this invention. It is the schematic for demonstrating the measuring method of the intensity | strength of the transmission scattered light in a light-scattering sheet.

Explanation of symbols

(1) Support (2) Light diffusion layer (3) Medium refractive index layer (4) High refractive index layer (5) Low refractive index layer (6) Hard coat layer 12 samples (optical film)
20 Light source 21 Detector θ3 Angle from normal direction

Claims (12)

An optical film having a light diffusing layer on a transparent support, wherein transmitted scattered light has an emitted light intensity I0 in the normal direction of the transparent support,
The ratio I (0 °) / I0 of the emitted light intensity I (0 °) in the normal direction of the film surface to I0 is 30% to 100%,
The ratio I (6 °) / I0 of the emitted light intensity I (6 °) to I0 at a position inclined by 6 ° from the normal direction of the film surface to the longitudinal direction of the film is 0.70% to 5.0%, and,
The ratio I (30 °) / I0 of the emitted light intensity I (30 °) to I0 at a position inclined by 30 ° from the normal direction of the film surface to the longitudinal direction of the film is 0.0001 to 0.007%. A featured optical film. The ratio I (0 °) / I0 of the emitted light intensity I (0 °) in the normal direction of the surface of the film to the I0 is 40% to 95%,
The ratio I (6 °) / I0 of the emitted light intensity I (6 °) to I0 at a position inclined by 6 ° from the normal direction of the film surface to the longitudinal direction of the film is 1.0% to 4.5%. ,and,
The ratio I (30 °) / I0 of the emitted light intensity I (30 °) to I0 at a position inclined by 30 ° from the normal direction of the film surface to the longitudinal direction of the film is 0.0005 to 0.004%.
The optical film according to claim 1, wherein:   The optical film according to claim 1 or 2, wherein an internal haze of the optical film is 10 to 40%.   4. The arithmetic average roughness (Ra) of the light diffusion layer is 0.03 to 0.30 μm, and the average interval (Sm) of the unevenness is 40 to 200 μm. The optical film described in 1.   The optical film according to claim 1, wherein a surface haze of the optical film is 0.3 to 20%.   The optical film according to claim 1, wherein the light diffusion layer contains an ionizing radiation curable compound, an organosilane compound, and translucent particles.   The difference between the refractive index of the light transmissive particles contained in the light diffusing layer and the refractive index of the light diffusing layer excluding the light transmissive particles is less than 0.05 as an absolute value. The optical film in any one of 1-6.   The optical film according to any one of claims 1 to 7, wherein the light diffusion layer contains a plurality of aggregated portions of translucent fine particles having a three-dimensional solid structure and has an uneven surface shape.   The optical film according to claim 1, wherein the light diffusion layer is at least two layers, and the light-transmitting fine particles are present in the lower layer.   10. The optical film according to claim 1, further comprising a low refractive index layer having a lower refractive index than that of the transparent support directly or via another layer on the transparent support.   A polarizing plate having a polarizing film between two protective films, wherein at least one of the protective films is the optical film according to claim 1. .   It is an image display apparatus which has the optical film in any one of Claims 1-10, or the polarizing plate of Claim 11, Comprising: It arrange | positions so that the said light-diffusion layer may become a visual recognition side, It is characterized by the above-mentioned. Image display device.

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