JP2005004163A - Optical functional film, polarizing plate and image display device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an optically functional film exhibiting superior dispersibility for translucent fine particles in a translucent particle containing layer (an optical functional layer) and having superior adhesiveness of a resin layer. <P>SOLUTION: The optical functional film is provided with at least one layer of an optical functional layer in which at least translucent fine particles are dispersed in binder resin on a transparent substrate. As the translucent fine particles, fine particles having a particle surface of fine projected shapes are provided. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

The present invention relates to an optical functional film having a binder resin layer containing translucent fine particles on a transparent support. Specifically, optical functional films with good dispersibility of translucent fine particles and good adhesion to the binder resin and excellent film strength, that is, for image display of computers, word processors, televisions, plasma displays, organic EL displays, etc. The present invention relates to an image display element such as an antiglare film, an antireflection film and a hard coat film to be used, and a liquid crystal display element such as a polarizing plate and a touch panel using these as a protective film.
The present invention also relates to an image display device using the optical functional film or polarizing plate.

  In recent years, plastic products have been replaced with glass products in terms of processability and weight reduction, but the surface of these plastic products is easily damaged. ELD), cathode ray tube display (CRT), field emission display (FED), hard-coated film for the purpose of imparting scratch resistance to the surface of displays such as mobile phones and touch panels such as home appliances Often used by pasting. In addition, plastic films are increasingly being bonded to conventional glass products to prevent scattering, but due to insufficient hardness of the film surface, it is widely used to form a hard coat layer on the surface. It has been broken.

Conventional hard coat films are usually thin, about 3 to 15 μm, with an active energy ray polymerizable resin such as thermosetting resin or ultraviolet curable resin directly on a plastic transparent support or through a primer layer of about 1 μm. It is manufactured by forming a coating film. However, the conventional hard coat film has insufficient hardness of the hard coat layer, and because of its thin coating thickness, when a very strong external force is applied, the underlying plastic transparent support Since the body was deformed and the hard coat layer was deformed accordingly, it was not fully satisfactory. For example, in a hard coat film in which an ultraviolet curable coating is applied to the above thickness on a polyethylene terephthalate film or cellulose ester film widely used as a plastic transparent support, a pencil hardness of H to 2H is generally used. It is not at all equivalent to 9H, which is the pencil hardness of glass.
If the thickness of the hard coat layer is simply increased, the hardness of the obtained hard coat film is improved, but the hard coat layer is liable to crack and peel, and at the same time the curl of the hard coat film due to curing shrinkage is increased. is there.

  A technique for improving the hardness of the hard coat layer by adding a filler such as inorganic fine particles to the hard coat layer (publication of Japanese Patent Application Laid-Open No. 2000-214791) has been proposed. In many cases, there is a problem that the adhesion to the base material is lowered, and the hard coat layer becomes brittle and cracks are likely to occur. This is a practical problem and further improvement has been demanded.

  On the other hand, an antiglare film and an antiglare antireflection film are used in displays such as a cathode ray tube display (CRT), a plasma display (PDP), an electroluminescence display (ELD), and a liquid crystal display (LCD). In order to prevent contrast reduction and image reflection due to reflection, it has an antiglare function for diffusing light by surface protrusions, and is disposed on the outermost surface of the display.

  In recent years, the demand for high definition, that is, high image quality, has become very high along with the wide viewing angle and high speed response of liquid crystal display devices. This high definition requires the miniaturization of the liquid crystal cell size, but as the cell size decreases, the surface protrusions of the antiglare antireflection film perform a minute lens function, so-called "lens effect" When light passes through an anti-glare film or the like and reaches the user's eyes, there is a problem of “glaring”, which causes variations in luminance, and there is a problem that display quality deteriorates.

On the other hand, as described in Patent Documents 1 to 7 and the like, the antiglare layer is provided with a refractive index difference between the refractive index of the antiglare layer and the refractive index of the translucent particles contained therein. There has been proposed a method for suppressing the glare by internally scattering the light passing through the inside. However, the demand for high-definition image display in recent years has increased, and further improvements such as improvement of glare and prevention of character blurring and color mixing are desired.
Patent Document 8 discloses a technique that uses ultrafine particles that have irregularities on its surface or have a porous property to reduce diffuse reflection. However, even with this technique, a sufficient improvement in glare and characters are disclosed. The effect of preventing blur was not obtained.

Patent Documents 9 to 11 describe a technique for adjusting the refractive index or imparting physical strength (abrasion resistance) by adding inorganic particles to the low refractive index layer or the high refractive index layer. However, it is still insufficient, and further performance improvement has been demanded.
Japanese Patent Laid-Open No. 11-95012 Japanese Patent Laid-Open No. 11-305010 JP 11-326608 A JP 2000-338310 A JP 2001-154004 A JP 2000-75133 A JP 2000-227509 A Japanese Patent Laid-Open No. 5-13021 JP 59-50401 A JP-A-8-110401 JP 2001-166104 A

Accordingly, an object of the present invention is to solve various problems in various optical functional films having an optical functional layer containing translucent fine particles in a binder resin on the transparent support as described above. It is.
That is, the objective of this invention is providing the optical functional film excellent in the dispersibility of the translucent fine particle in the translucent fine particle content layer (optical functional layer), and the adhesiveness of the resin layer.
Another object of the present invention is to provide a hard coat film as an optical functional film having a large surface hardness and improved curling and brittleness, and further functions such as antireflection performance and antiglare performance. It is in providing the functional hard coat film which has.
Another object of the present invention is as an optical functional film having excellent viewing angle widening characteristics, improved glare, improved character blurring / color mixing, antiglare properties, and suitable for high-definition image display. The object is to provide an antiglare film, an antireflection film or an antiglare antireflection film.
Another object of the present invention is to provide an antiglare film, an antireflection film or an antiglare antireflection film having a further improved film hardness.
A further object of the present invention is to provide a polarizing plate, an image display device and a liquid crystal display device provided with such an optical functional film.

It has been found that the above object of the present invention can be achieved by the following constitution.
(1) In an optical functional film having at least one optical functional layer in which at least translucent fine particles are dispersed in a binder resin on a transparent support, the surface of the particles has a fine convex shape as the translucent fine particles. An optical functional film characterized by containing the fine particles.
(2) The ratio of the surface area of the particle to the surface area of the enveloping surface that is smoothly surrounded by the enveloping surface so that the translucent fine particles are in contact with the convex portion of the particle is 1.1 times or more. The optical functional film as described in (1) above.

(3) The optical functional film as described in (1) or (2) above, wherein the translucent fine particles have fine particles fixed on the surface of spherical particles (core particles).
(4) The optical functional film as described in (3) above, wherein the size of the fine particles fixed on the surface is 1/3 or less of the core particle size.
(5) The antiglare as described in (3) or (4) above, wherein the core particles of the light-transmitting fine particles are inorganic particles or organic particles, and the fine particles fixed on the surface are inorganic particles. Sex film.
(6) The antiglare film as described in (5) above, wherein the translucent fine particles are photocatalytic metal compound fine particles having fine pieces of a metal substance supported on the surface thereof.

(7) The average particle diameter of the translucent fine particles is 0.4 to 20 μm, and the optical functional layer has a hard coat property, as described in any one of (1) to (6) above Optical functional film.
(8) The average particle diameter of the translucent fine particles is 0.4 to 20 μm, and the optical functional layer has an antiglare property, and is described in any one of (1) to (7) above Optical functional film.

(9) Refractive index higher than the adjacent lower layer above the optical functional layer having the hard coat property described in (7) or above the optical functional layer having the antiglare property described in (8). An optical functional film having a low refractive index layer having a low refractive index and antireflection properties.
(10) The above (1) to (6) and (6), wherein the translucent fine particles have an average particle diameter of 0.005 to 0.1 μm, and the optical functional layer has antireflection properties. The optical functional film according to any one of 9).

(11) In the polarizing plate in which both surfaces of the polarizer are sandwiched between protective films, at least one of the protective films is the optical functional film according to any one of the above (1) to (10). Board.
(12) An image display device comprising the optical functional film according to any one of (1) to (10) or the polarizing plate according to (11).

  According to the present invention, in an optical functional film having at least one optical functional layer in which translucent fine particles are dispersed in a binder resin on a transparent support, the surface of the particles has a fine convex shape as the translucent fine particles. By using fine particles (hereinafter also referred to as “surface convex particles”), the dispersibility of the translucent fine particles in the optical functional layer and the adhesiveness of the resin layer are remarkably improved. In the functional layer, the hard coat performance is improved, that is, the hardness is improved, and the curl and brittleness are improved. In the optical functional layer having the antiglare property, the antiglare performance is improved. That is, it has been found that the viewing angle is widened and the glare is improved, and in the optical functional layer having antireflection properties, the antireflection performance and the film strength of the antireflection layer are improved. Than it is. This is because, in the optical functional layer, the surface convex particles are anchored to the binder matrix, so that the dispersibility of the fine particles is improved and the binding force with the binder is enhanced, which is effective for various performances as described above. Presumed to contribute. In the optical functional layer having both hard coat properties and antiglare properties and / or antireflection properties, any of the above performances can be effectively improved.

ADVANTAGE OF THE INVENTION According to this invention, the optical functional film excellent in the dispersibility of the translucent fine particle in the translucent fine particle content layer and the adhesiveness of the resin layer can be obtained.
Further, according to the present invention, a hard coat film having a large surface hardness and improved curling and brittleness can be obtained, and further, a functional hard coat having further functions such as antireflection performance and antiglare performance. A film can be obtained.
Furthermore, an antiglare film or an antiglare antireflection film suitable for high-definition image display, which has excellent viewing angle expansion characteristics, improved glare, and improved character blurring and color mixing, can be obtained. In addition, a liquid crystal display device and an image display device provided with a polarizing plate having excellent performance can be obtained.

Hereinafter, embodiments of the present invention will be described in more detail.
The optical functional film of the present invention has at least one optical functional layer in which at least the surface convex particles of the present invention are dispersed in a binder resin on a transparent support. It may be a layer or two or more layers, and as long as it is on a transparent support, it may be provided directly on the transparent support, or may be provided via an undercoat layer or the like, or via another optical functional layer. Or may be the outermost surface layer. Specifically, the following aspect is mentioned, for example.

(I) A mode in which the optical functional layer is a hard coat layer having hard coat properties.
As shown in the schematic cross-sectional view of FIG. 1, one preferred form of the optical functional film of the present invention is that the surface convex particles 5 are dispersed in the curable resin 4 as an optical functional layer on the transparent support 2. A hard coat film having the hard coat layer 3. The particles having a convex surface can increase the bonding strength with the curable resin, the pencil hardness of the hard coat film is 3H or higher, preferably 4H or higher, and the surface hardness can be remarkably improved. An effect of improving brittleness can be achieved. When used in the hard coat layer, the average particle size of the surface convex particles is preferably 0.4 to 20 μm.
The layer structure of the hard coat film is not limited to that shown in FIG. 1. It may be a functional hard coat film having a function such as a dirty layer, and it can be applied as a hard coat layer in other functional films to provide a polarizing film, a retardation film, and an optical compensation having excellent surface strength. An optical film such as a film can also be provided.

(ii) An embodiment in which the optical functional layer is an antiglare layer having antiglare properties.
As shown in the schematic cross-sectional view of FIG. 2, an antiglare film 11 having an antiglare layer 13 having surface convex particles 15 dispersed in a translucent binder matrix as an optical functional layer on a transparent support 12. It is. Furthermore, if necessary, as shown in FIG. 2, an antiglare antireflection film having a low refractive index layer (that is, an antireflection layer) 14 having a lower refractive index than the lower layer on the antiglare layer. Also good. By using convex surface particles as the light-transmitting fine particles of the antiglare layer, an antiglare film having a high-definition image display suitability that enlarges the viewing angle, improves glare and prevents character blurring and color mixing is obtained. be able to. When used in the antiglare layer, the average particle diameter of the surface convex particles is preferably 0.4 to 20 μm.
The layer configuration of the antiglare film is not limited to that shown in FIG. 2, and includes, for example, a configuration in which a smooth hard coat layer is provided below the antiglare layer to increase the film strength. The surface convex particles of the present invention may be further dispersed in the hard coat layer. Further, the antiglare layer itself may have a hard coat property and may also function as a hard coat layer.

(iii) An embodiment in which the optical functional layer is an antireflection layer having antireflection properties.
As shown in the schematic cross-sectional view of FIG. 2, the optical functional layer for dispersing the surface convex particles of the present invention may be a low refractive index layer 14 (antireflection layer). Alternatively, the optical functional layer of the present invention may be a high refractive index layer or a medium refractive index layer further provided between the low refractive index layer and the antiglare layer. Moreover, you may give the function as a high refractive index layer by adjusting the refractive index of an anti-glare layer.
By using particles having a convex surface for a thin low-refractive index layer, high-refractive index layer, or medium-refractive index layer, the uniformity of the film thickness is achieved by improving the liquid dispersibility and the antireflection performance is improved. In addition, film strength such as wear resistance can be improved. When used in the antireflection layer, the average particle size of the surface convex particles is preferably 0.005 to 0.1 μm.
As described above, the optical functional layer containing surface convex particles is not only used alone, but also used in both the hard coat layer and the antiglare layer, the hard coat layer (high refractive index), The structure used for both the low refractive index layer, the structure used for both the antiglare layer (high refractive index) and the low refractive index layer, the hard coat layer, the three layers of the high refractive index layer and the low refractive index layer Two or more layers, such as the structure used, can also be used. In this case, the surface convex particles to be used may be the same or different.

<Transparent support>
As the transparent support of the optical functional film of the present invention, a plastic film is preferably used. Polymers that form plastic films include cellulose esters (eg, triacetyl cellulose, diacetyl cellulose, etc.), polyamides, polycarbonates, polyesters (eg, polyethylene terephthalate, polyethylene naphthalate, etc.), polystyrene, polyolefins, polysulfones, polyether sulfones, Examples include polyarylate, polyetherimide, polymethyl methacrylate, polyether ketone, norbornene resin (Arton: trade name, manufactured by JSR), amorphous polyolefin (ZEONEX: trade name, manufactured by Nippon Zeon), and the like. Of these, triacetyl cellulose, polycarbonate, polyethylene terephthalate, and polyethylene naphthalate are preferable, and triacetyl cellulose is particularly preferable. The light transmittance of the transparent support is preferably 80% or more, more preferably 86% or more. The haze of the transparent support is preferably 2.0% or less, and more preferably 1.0% or less. The refractive index of the transparent support is preferably 1.4 to 1.7. The thickness is preferably 25 to 1000 μm. In addition, the hard coat layer of the present invention can be applied to a sheet-like or panel-like substrate other than a film.

Various additives can be added to the transparent support. For example, various additives such as a plasticizer, an ultraviolet absorber, a deterioration preventing agent, a slip agent, a peeling accelerator, an infrared absorber, and a retardation adjusting agent are contained. These addition amounts can be added within a range that does not affect the light transmittance and mechanical properties, and are preferably 0.01 to 25% by mass of the transparent support, and 0.1 to 20% by mass. More preferably.
In order to impart slipperiness, particles of an inert inorganic compound or an organic compound may be added to the transparent support. As the inorganic _{compound, SiO 2, TiO 2, BaSO} 4, CaCO 3, talc and kaolin. In addition, those described in JIII Journal of Technical Disclosure 2001-1745, page 19 (issued on March 15, 2001) can also be used.

Further, the transparent support may be subjected to surface treatment. Examples of surface treatment include chemical (acid or alkali) treatment, mechanical treatment, corona discharge treatment, flame treatment, ultraviolet irradiation treatment, high frequency treatment, glow discharge treatment, active plasma treatment, laser treatment, ozone oxidation treatment, etc. Chemical (acid or alkali) treatment, corona discharge treatment, flame treatment, ultraviolet irradiation treatment, and glow discharge treatment are preferably used.
In addition, when cellulose acetate is used as the support, the technology described in Japanese Patent Publication No. 2001-1745 (issued on March 15, 2001) can be used.

<Optical functional layer>
The optical functional layer of the present invention comprises a light-transmitting fine particle and a binder matrix that holds the light-transmitting fine particle, and includes surface-shaped convex particles having a specific shape as the light-transmitting fine particle. In addition to the binder resin and polymerization initiator described later, the binder matrix is a coating containing ultrafine filler added for adjusting the refractive index and increasing strength, a silane coupling agent for imparting scratch resistance, and other additives. The liquid is applied, dried and cured.
Specifically, as described above, a hard coat layer, an antiglare layer, a low refractive index layer, a high refractive index layer, a medium refractive index layer and the like can be mentioned.

<Fine particles having fine convex portions on the surface (surface convex particles)>
The specific translucent fine particles used in the present invention are fine particles (surface convex particles) having fine convex portions on the particle surface. The surface convex particle may be a particle having a fine convex shape on the surface of the particle itself, or a particle formed by fixing fine small particles (micro particles) on the surface of the particle (core particle). May be. The surface convex particles are preferably spherical, and more preferably surface convex spherical particles having fine particles fixed on the surface of the spherical core particles. The surface convex particles of the present invention, because of its specific shape, increase the binding force by increasing the interface area of the binder resin layer with the binder matrix, increase the surface hardness of the resin layer, and its anchoring effect Therefore, it is estimated that the dispersibility is improved.

  The surface convex particles of the present invention, the surface of the particles can not be represented by a smooth curve, but the enveloping surface that is smoothly surrounded by the enveloping surface so as to be in contact with the convex portion of the particle can be represented by a substantially spherical shape, The surface area of the particles is 1.1 times or more with respect to the surface area of the enveloping surface. Preferably it is 1.2 times or more, More preferably, it is 1.3 times or more.

  The surface convex particles of the present invention can be evaluated and determined by comparing the area of the enveloping surface connecting the convex portions with the area of the surface of the particles. Using AFM, the surface profile of the particles may be measured to determine the area of the actual particle relative to the reference surface, and compared with the area of the reference surface. Or it is good also by calculating | requiring the particle diameter of an encapsulated surface by SEM etc., calculating | requiring the surface area of particle | grains by means, such as a gas adsorption method, and comparing. When the area ratio of the area of the real particle to the area of the reference surface is 1.1 times or more, it is determined that the surface is convex, and the effect of the present invention can be exhibited.

Examples of the particles having a convex surface include metal oxides, metal hydroxides, hydrated metal oxides, metal sulfides, polymer particles, and composites thereof. Specifically, WO ₃ , fine TiO ₂ such as manufactured by CI Chemical Co., Ltd., hydrous titanium oxide (Ti (O) (OH) ₂ ) such as P101 manufactured by Titanium Industry Co., Ltd., Nakarai Co., Ltd. ) Hydrous zirconium oxide (ZrO ₂ .xH ₂ O), particles such as SiO ₂ , ZnO, ZnS, CuS, StTiO ₃ , StAL ₂ O ₃ , CoWO ₄ , crosslinked acrylic, polystyrene, PMMA particles, etc. It is done.

  The degree of coverage of the fine particles adhering to the surface of the core particles can be arbitrarily selected within the range where the effect of the present invention appears. Generally, the coverage is 3% or more, and the entire surface may be covered. The coverage is preferably 5 to 90%, more preferably 10 to 60%.

The surface convex particles of the present invention may be any of inorganic compounds, organic compounds, and mixtures thereof.
Examples of the organic particles include those having a glass transition point of 50 ° C. or higher selected from conventionally known synthetic resin particles and natural polymer particles. Preferably, the glass transition point is 80 ° C. or higher. Specifically, (meth) acrylic resin, olefin resin (polyethylene, polypropylene, etc.), fluorine resin, polyethylene oxide, polyether resin, polyethyleneimine, polyacrylonitrile resin, polystyrene resin, polyurethane, polyurea, polyester, Polyamide, polyimide, (meth) acrylamide resin, polycarbonate, celluloses, gelatin, starch, chitin, chitosan, and the like, more preferably resin particles such as (meth) acrylic resin, polyethylene, polypropylene, and polystyrene resin.

  In addition, inorganic particles are mainly used as the fine particles to be fixed. For example, a simple metal, a metal oxide, a hydrated metal oxide, a metal nitride, a composite thereof, and the like can be mentioned, and a simple metal and a metal oxide are preferable. As the simple metal, metallic silver is preferable.

  The surface convex particles are, for example, a method using the hetero-aggregation method described in “New Development of Fine Particle Polymer” edited by Toray Research Center Co., Ltd. or a method using a polymerization reaction from the surface of the core particle, “Design Engineering” (1987), Fumio Kitahara, Kunio Furusawa “Latest Colloid Chemistry”, p. 30 (Kodansha Scientific Co., Ltd., published in 1990) and the like, and can be easily produced using a dry mixing method using a mechano-fusion method or the like. Also, certain surface convex particles can be produced by precipitating fine particles on the surface of the core particles.

The surface convex particles of the present invention may be photoconductive metal compound particles (corresponding to core particles) carrying fine pieces (corresponding to microparticles) of a metal substance on the surface. Thereby, the particle diameters of the microparticles carried are uniform, and the particle diameters of the core particles can be made uniform. The metal compound particles having photocatalytic property on the surface of which fine pieces of metal material are supported are those that are activated by the absorption of irradiated active light and support the metal material existing in the vicinity. Specifically, TiO ₂ , RTiO ₃ (R is an alkaline earth metal atom), AB _2−x C _x D _3−x E _x O ₁₀ (A is a hydrogen atom or an alkali metal atom, B is an alkaline earth metal atom) Or a lead atom, C is a rare earth atom, D is a metal atom belonging to Group 5A element of the periodic table, E is a metal atom belonging to Group 4 element of the periodic table, and x is an arbitrary numerical value of 0 to 2.) _{SnO 2, ZrO 2, ZnO,} Bi 2 O 3, WO 3, Fe 2 O 3, Cu 2 O, V 2 O 5, MoO 3, Al 2 O 3, Cr 2 O 3, ZnS, MoS 2, FeS, _{CuS, PbS, MoSe 2, PbSe} , CuSe, SiC , etc. Ageruko Can. Further, the metal substance supported as fine pieces on the surface of the metal compound particles having photocatalytic properties is preferably one that exhibits hydrophilicity in the supported state, but the metal substance itself may be hydrophilic or hydrophobic, Any known metal material can be used. Preferred metal materials include Al, Si, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Mo, Ag, Au, Pt, Pd, Rh, In, Sn, and W. Can be mentioned. As the photoconductive metal compound particles carrying fine pieces of metal material on the surface, those described in JP-A-2001-130158 [0034] to [0056] can be used.

The surface convex particles of the present invention are preferably used after being subjected to a surface treatment. The surface treatment method includes physical surface treatment such as plasma discharge treatment and corona discharge treatment and chemical surface treatment using a coupling agent, but the use of a coupling agent is preferred. As the coupling agent, a coupling agent (eg, titanium coupling agent, silane coupling agent) including the compound of the general formula (1) described later is preferably used. A surface treatment agent having a functional group capable of reacting with the binder species on the filler surface is preferably used. When the surface convex particles are silica, a silane coupling treatment is particularly preferred.
The compound of the general formula (1) may be used as a surface treatment agent for the surface convex particles of the hard coat layer in order to perform surface treatment in advance before preparing the layer coating solution, or further added during the preparation of the layer coating solution. It may be added as an agent and contained in the layer.

  In the translucent fine particles of the present invention, two or more kinds of translucent fine particles having different particle diameters, or two or more different translucent fine particles may be used in combination. Even if there are two or more kinds of material and two or more kinds of particle sizes, there is no limitation.

In addition to the surface convex particles of the present invention, the optical functional layer of the present invention may contain conventionally known true spheres or nontransparent inorganic or organic translucent fine particles. Specific examples thereof include the particles described in JP-A-2001-281405 [0020], commercially available alumina particles, crosslinked melamine resin particles, and crosslinked benzoguanamine resin particles. The preferred particle size is 0.4 μm to 18 μm, more preferably 1 to 10 μm. In order not to increase the cost, the surface convex particles of the present invention can be used in combination.
In these known particles, the total surface area of the particles is 1.1 times or more with respect to the total surface area of the enveloping surface of the total translucent fine particles including the surface convex particles of the present invention, and the total translucent microparticles Used in less than 50% by weight. Within this range, the effects of the present invention, particularly the scratch resistance improvement effect, can be effectively expressed.

<Binder matrix>
The binder matrix is obtained by applying, drying, and curing a coating liquid containing a binder resin, a polymerization initiator, an ultrafine particle filler added for adjusting the refractive index and increasing strength, and other additives. The refractive index of the binder matrix means the refractive index of the optical functional layer that does not contain the surface convex particles of the present invention and the light-transmitting fine particles for imparting antiglare properties and internal diffusibility. Excluded layers can be created and evaluated.
The binder matrix can be designed by appropriately selecting various binder resins and other additives according to the target optical functional layer. Hereinafter, each optical functional layer will be described.

[Hard coat layer]
In the optical functional film of the present invention, the average particle diameter of the surface convex particles used for the hard coat layer is preferably 0.4 to 20 μm, more preferably 0.8 to 12 μm, and particularly preferably 1.8 to 6. 0 μm.
In addition, in the optical functional film, the preferable addition amount of the light-transmitting fine particles used in the hard coat layer is 1 to 50 vol%, more preferably 2 to 30 vol%, particularly preferably 5 to 20 vol in the hard coat layer. %.

  As particles having spherical particles as core particles and fine small particles fixed on the surface thereof, the average particle size of the core particles is suitably 0.3 to 19 μm, preferably an average particle size of 0.3 to 12 μm, More preferably, the average particle size is 0.8 to 5.9 μm. Examples of the particles having a spherical shape include particles having a ratio of the shortest diameter to the longest diameter of 0.7 to 1. The fine particles to be fixed are preferably spherical particles, and the particle diameter is 1/3 or less of the core particle diameter. Preferably it is 1/5 or less, More preferably, it is the range of 1/10-1/1000. Specifically, the average particle size of the fine particles to be fixed is suitably 0.005 to 5 μm, preferably 0.01 to 3 μm, more preferably 0.01 to 1 μm.

  The layer thickness of the hard coat layer is preferably 3 to 60 μm, more preferably 10 to 50 μm, and still more preferably 10 to 40 μm. If the film thickness is too thin, it is not possible to obtain a sufficient surface hardness, and it is impossible to contain translucent fine particles in a preferable range. On the other hand, if the film thickness is too thick, the film cannot be bent, handling becomes difficult, and poor applicability due to an increase in the viscosity of the coating solution is likely to occur.

  The haze of the hard coat layer is preferably 10% or less, more preferably 3% or less, and particularly preferably 2% or less. If it is larger than 10%, it becomes whitish and transparency may start to be lost.

(Binder resin and initiator)
As the binder resin for the hard coat layer, a known curable resin can be used, and examples thereof include a thermosetting resin and an active energy ray polymerizable resin, and an active energy ray polymerizable resin is preferable. As the thermosetting resin, it is possible to use a crosslinking reaction of a prepolymer such as a melamine resin, a urethane resin, or an epoxy resin. In addition, compounds described in JP-A-11-52103 [0012] to [0032] and [0052] to [0076] can also be preferably used.
In addition to the surface convex spherical particles and the curable resin of the present invention, the hard coat layer contains conventionally known true spheres and translucent fine particles of amorphous or organic particles, a polymerization initiator, and other additives. It may be contained.
The active energy ray polymerizable resin layer containing a crosslinked polymerizable resin can be formed by applying a coating liquid containing a polyfunctional monomer and a polymerization initiator on the transparent support and polymerizing the polyfunctional monomer. The polymerizable functional group of these monomers is preferably a radical polymerizable unsaturated double bond group or a ring-opening polymerizable cyclic ether group. Examples of the polymerizable unsaturated double bond group include an acryloyl group, a methacryloyl group, a vinyl group, and an allyl group. From the viewpoint of reactivity, an acryloyl group and a methacryloyl group are preferably used. Moreover, as a cyclic ether group, an epoxy group, an oxetane group, a tetrahydrofuryl group, an imino ether group, etc. can be mentioned, An epoxy group and an oxetane group are preferable.

  Specific examples of the polyfunctional polymerizable unsaturated double bond group-containing monomer include glycol (meth) acrylates such as ethylene glycol di (meth) acrylate and diethylene glycol di (meth) acrylate, and n-hexanediol di (meth). Acrylate, trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta ( (Meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1,4-cyclohexanediol di (meth) acrylate, 1,3,5-cyclohexanetriol tri Polyester polyols produced by the reaction of (meth) acrylate, adipic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid and glycols (ethylene glycol, polyethylene glycol, propylene glycol, etc.) and triols (glycerin, trimethylolpropane, etc.) Polyol polyacrylates such as the reaction product of oligomer and (meth) acrylate, epoxy acrylates such as the reaction product of bisphenol A and glycidyl (meth) acrylate, reaction product of hexanediol and glycidyl (meth) acrylate, condensation product of polyisocyanate and polyol Polyurethane obtained by the reaction of a polyisocyanate polyurethane oligomer composed of a hydroxyl group-containing acrylate such as hydroxyethyl (meth) acrylate And the like can be mentioned Li acrylates.

  Examples of ring-opening polymerizable cyclic ether compounds include cyclic ether derivatives such as epoxy derivatives and oxetane derivatives, cyclic imino ethers such as tetrahydrofuran derivatives and oxazoline derivatives, and particularly epoxy derivatives, oxetane derivatives and oxazoline derivatives. preferable.

  These cyclic ether compounds are preferably compounds having three or more cyclic structures as described above in the same molecule. For example, trimethylol ethane triglycidyl ether, trimethylol propane triglycidyl ether, glycerol triglycidyl ether, triglycidyl trishydroxyethyl isocyanurate, etc. as trifunctional glycidyl ether, sorbitol tetraglycidyl ether, pentaerythritol as tetrafunctional or higher glycidyl ether Examples of tri- or higher functional alicyclic epoxies such as tetraglycyl ether, polyglycidyl ether of cresol novolac resin, polyglycidyl ether of phenol novolac resin include Epolide GT-301, Epolide GT-401, EHPE (above, Daicel Chemical Industries, Ltd.) )), Trifunctional or higher oxetane such as phenol novolac resin polycyclohexyl epoxy methyl ether The OX-SQ, PNOX-1009 (manufactured by Toagosei Co.), and the like.

  A monofunctional monomer can be added to the polyfunctional monomer as necessary to adjust the surface elastic modulus, reduce cure shrinkage, and improve adhesion. Monofunctional monomers include polar groups such as alkyl esters of acrylic acid such as methyl (meth) acrylate and butyl (meth) acrylate, hydroxyethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, and glycidyl (meth) acrylate. Examples thereof include existing monomers such as acrylic acid esters, acrylamides such as (meth) acrylamide and N-methylol (meth) acrylamide, N-vinylpyrrolidone, styrene, vinyl acetate, and maleic anhydride.

  On the other hand, a compound having one or two ring-opening polymerizable groups in the same molecule can be used in combination as necessary. Preferred compounds include monofunctional or bifunctional glycidyl ethers, monofunctional or 2 Functional alicyclic epoxies, monofunctional or bifunctional oxetanes can be mentioned, and various commercially available or known compounds can be used.

  Similarly, an oligomer or polymer containing at least two polymerizable groups can be added to the polyfunctional monomer as required. Examples of the oligomer or polymer containing a radical polymerizable group include an oligomer / polymer having a polymerizable group such as a (meth) acryloyl group or an allyl group as a pendant group. ) Ester derivatives of acrylic acid, oligomers / polymers containing carboxylic acid and hydroxyl group-containing (meth) acrylic acid esters (such as hydroxyethyl (meth) acrylate) and allyl alcohol, glycidyl methacrylate ring-opening polymer, chloroethyl And polymers having an acryloyl group introduced by a dehydrochlorination reaction of the group.

  Moreover, it is particularly preferable that the compound having three or more ring-opening polymerizable groups in the same molecule contains a crosslinkable polymer containing a repeating unit represented by the following general formula (1).

In the general formula (1), R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, preferably a hydrogen atom or a methyl group. L ¹ is a single bond or a divalent linking group, preferably a single bond, —O—, an alkylene group, an arylene group, and * —COO—, * —CONH—, * —OCO linked to the main chain on the * side. -, * -NHCO-. P ¹ is a monovalent group containing a ring-opening polymerizable group, and preferred P ¹ is a monovalent group containing an imino ether ring such as an epoxy ring, an oxetane ring, a tetrahydrofuran ring, a lactone ring, a carbonate ring, or an oxazoline ring. Among these, a monovalent group including an epoxy ring, an oxetane ring and an oxazoline ring is particularly preferable.
The crosslinkable polymer containing the repeating unit represented by the general formula (1) is preferably synthesized by polymerizing a corresponding monomer. In this case, radical polymerization is the simplest and preferable as the polymerization reaction. Specific examples include polyglycidyl methacrylate, polymethyl glycidyl methacrylate, polyepoxycyclohexyl methacrylate, polymethacryloyl oxetane and the like.

  In the case of adding a monofunctional monomer, an oligomer or polymer containing at least two polymerizable unsaturated double bond groups, or a ring-opening polymerizable cyclic ether compound, the polymerizable unsaturated double bond-containing monomer is used. The amount added is preferably 50% by mass or less, and more preferably 35% by mass or less. If the ratio of the monofunctional monomer, the oligomer or polymer containing at least two polymerizable unsaturated double bond groups, or the ring-opening polymerizable cyclic ether compound is too high, the desired hardness cannot be obtained.

  Of the surface convex particles of the present invention, those having an inorganic compound on the surface and inorganic fine particles added for adjusting the refractive index have poor affinity with the active energy ray-polymerizable resin. Is easy to break, is easily broken as a film, and it is not easy to improve the scratch resistance. In order to improve the affinity between the inorganic fine particles and the active energy ray polymerizable resin, the surface of the inorganic fine particles is preferably treated with a surface modifier containing an organic segment. The surface modifier preferably forms a bond with inorganic fine particles on the one hand and has a high affinity with the active energy ray polymerizable resin on the other hand. Examples of the compound capable of forming a bond with the surface of the inorganic fine particle include metal alkoxide compounds such as silicon, aluminum, titanium, and zirconium, and anions having a phosphate ester, a phosphonate group, a sulfate ester, a sulfonate group, a carboxylic acid group, and the like. Are preferred. The active energy ray polymerizable resin is preferably chemically bonded, and a resin having a vinyl polymer group or the like introduced at the terminal is suitable. For example, when an active energy ray polymerizable resin is synthesized from a monomer having an ethylenically unsaturated group as a polymerizable group and a crosslinkable group, a polymerizable unsaturated double bond group or It preferably has a ring-opening polymerizable cyclic ether group.

Typical examples of these surface modifiers include the following.
(Unsaturated double bond group-containing coupling agent)
Metal alkoxide compounds,
H ₂ C═C (CH ₃ ) COOC ₃ H ₆ Si (OCH ₃ ) ₃ ,
H ₂ C═CHCOOC ₂ H ₄ OTi (OC ₂ H ₅ ) ₃ ,
(Anionic compound)
H ₂ C═C (CH ₃ ) COOC ₂ H ₄ OCOC ₅ H ₁₀ OPO (OH) ₂ ,
(H ₂ C═C (CH ₃ ) COOC ₂ H ₄ OCOC ₅ H ₁₀ O) ₂ POOH,
H ₂ C═C (CH ₃ ) COOC ₂ H ₄ OSO ₃ H,
H ₂ C═CHCOO (C ₅ H ₁₀ COO) ₂ H,
H ₂ C = CHCOOC ₅ H ₁₀ COOH, etc.
Glycidyl group-containing silane coupling agents having a phosphate ester, a phosphonic acid group, a sulfate ester, a sulfonic acid group, a carboxylic acid group, and the like.

  The surface modification of these fine particles is preferably performed in a solution. It is preferable to add fine particles to the solution in which the surface modifier is dissolved, and stir and disperse using an ultrasonic wave, a stirrer, a homogenizer, a dissolver, a planetary mixer, a paint shaker, and a sand grinder.

  As the solution for dissolving the surface modifier, an organic solvent having a large polarity is preferable. Specific examples include known solvents such as alcohols such as ethyl alcohol and isopropyl alcohol, ketones such as methyl ethyl ketone and methyl isobutyl ketone, and esters such as ethyl acetate and butyl acetate.

  In the present invention, when a plastic film is used as the substrate, the heat resistance of the plastic film itself is low. Therefore, when the curable resin is cured by heating, it is preferable to cure at a low temperature as much as possible. In this case, the heating temperature is 140 ° C. or lower, more preferably 100 ° C. or lower. On the other hand, curing by the action of light is preferably used because the crosslinking reaction often proceeds at a low temperature.

  When an active energy ray polymerizable resin is used for the hard coat layer, examples of the active energy rays include radiation, gamma rays, alpha rays, electron rays, ultraviolet rays, etc., but ultraviolet rays are preferred, and radicals or cations are preferred by ultraviolet rays. Particularly preferred is a method in which a polymerization initiator for generating water is added and cured by ultraviolet rays. In addition, there is a case where curing can be further advanced by heating after irradiating ultraviolet rays, which can be preferably used. A preferable heating temperature in this case is 140 ° C. or lower.

As the radical photopolymerization initiator, conventionally known compounds may be mentioned. For example, the carbonyl compounds (acetophenones, benzophenones, hydroxyacetophenones, benzoins) described in the latest UV curing technology (P.159, publisher: Kazuhiro Takasato, publisher; Technical Information Association, Inc., published in 1991) Benzoates, thioxanthones, etc.), organic halogen compounds described in JP-A-63-298339, organic boric acid compounds described in JP-A-2002-16539, JP-A-61-166544, etc. Examples include disulfones described in the publication.
Specific examples include acetophenones, benzophenones, Michler's ketone, benzoylbenzoate, benzoins, α-acyloxime esters, tetramethylthiuram monosulfide, and thioxanthone.
In addition to the photopolymerization initiator, a photosensitizer may be used. Examples of the photosensitizer include n-butylamine, triethylamine, triethanolamine, tri-n-butylphosphine, Michler's ketone thioxanthone and thioxanthone. Furthermore, a sensitization aid (such as phenylglycine) may be used.
The radical polymerization initiator is preferably used in the range of 0.1 to 15 parts by mass, more preferably in the range of 1 to 10 parts by mass with respect to 100 parts by mass of the polyfunctional monomer.

The polymer having a polyether as the main chain is preferably a polyfunctional compound cationic ring-opening polymer containing two or more cationically polymerizable groups selected from an epoxy group and an oxetane group. The ring-opening polymerization of the polyfunctional compound can be performed by irradiation with ionizing radiation and / or heating in the presence of a photoacid generator and / or a thermal acid generator.
In particular, as the cationically polymerizable group-containing compound, an alicyclic polyepoxy compound having two or more epoxy groups in one molecule is contained, and the content of the alicyclic polyepoxy compound is based on the total mass of the epoxy compound. When an epoxy compound (a mixture of epoxy compounds) of 30% by mass or more, more preferably 50% by mass or more is used, the cationic polymerization rate, thick film curability, resolution, ultraviolet transmittance, etc. are further improved, and the resin The viscosity of the composition is lowered, and film formation is performed smoothly.

  Specific examples include compounds described in JP-A-11-242101 [0084] to [0086]. As a compound containing an oxetanyl group, the number of oxetanyl groups contained in the molecule is 1 to 10, preferably 1 to 4. These compounds are preferably used in combination with an epoxy group-containing compound. Specific examples include the compounds described in JP 2000-239309 A [0024] to [0025].

  The photoacid generator is a compound that generates an acid by the action of light. Specifically, for example, “Organic Materials for Imaging” p187-198 edited by Organic Electronics Materials Research Group (Bunshin Publishing), JP-A-10-282644. Various examples are described in No. etc., and these known compounds can be used. Various onium salts such as diazonium salts, ammonium salts, phosphonium salts, iodonium salts, sulfonium salts, selenonium salts, arsonium salts, organic halides such as oxadiazole derivatives substituted with trihalomethyl groups and s-triazine derivatives, organic acids o-Nitrobenzyl ester, benzoin ester, imino ester, disulfone compound and the like can be mentioned, and onium salts are preferable, and sulfonium salts and iodonium salts are particularly preferable. Known compounds that generate a base by the action of light can also be used, and specific examples include nitrobenzyl carbamates and dinitrobenzyl carbamates.

Examples of photoacid generators that generate cations include ionic compounds such as triarylsulfonium salts and diaryliodonium salts, and nonionic compounds such as nitrobenzyl esters of sulfonic acids. Various known photoacid generators such as compounds described in “Organic Materials for Imaging” published by Bunshin Publishing Co., Ltd. (1997) can be used. Among them, a sulfonium salt or iodonium salt such as diphenyl-4-thiophenoxyphenylsulfonium hexafluoroantimonate is particularly preferable, and PF ₆ ⁻ , SbF ₆ ⁻ , AsF ₆ ⁻ , B (C ₆₎ are used as counter ions. F ₅ ) _4- ^{and the} like are preferable.

In place of, or in addition to, a monomer having two or more ethylenically unsaturated groups, a monomer having a crosslinkable functional group is used to introduce a crosslinkable functional group into the polymer, and by reaction of the crosslinkable functional group, A cross-linked structure may be introduced into the binder resin.
Examples of the crosslinkable functional group include isocyanate group, epoxy group, aziridine group, oxazoline group, formyl group, carbonyl group, hydrazine group, carboxyl group, methylol group and active methylene group. Vinylsulfonic acid, acid anhydride, cyanoacrylate derivative, melamine, etherified methylol, ester and urethane, and metal alkoxide such as tetramethoxysilane can also be used as a monomer for introducing a crosslinked structure. A functional group that exhibits crosslinkability as a result of the decomposition reaction, such as a block isocyanate group, may be used. That is, in the present invention, the crosslinkable functional group may not react immediately but may exhibit reactivity as a result of decomposition.
These binder resins having a crosslinkable functional group can form a crosslinked structure by heating after coating.

  The polymerization initiators may be used in combination with each other, or in the case of a compound that generates both radicals and cations alone. It is preferable to use a polymerization initiator in the range of 0.1-15 mass parts with respect to 100 mass parts of polyfunctional monomers, and it is still more preferable to use it in the range of 1-10 mass parts.

  The coating solution of the active energy ray polymerizable resin is polymerized with the above polyfunctional monomer in an organic solvent such as ketones such as methyl ethyl ketone and methyl isobutyl ketone, alcohols such as ethyl alcohol and isopropyl alcohol, and esters such as ethyl acetate. It is made by dissolving the initiator mainly.

(Scratch-resistant silane coupling agent)
The coating liquid of at least one of the hard coat layer and the low refractive index layer of the present invention contains a compound of the following general formula (2), applied, dried and cured to impart scratch resistance. It is preferable for this.

General formula (2)
(R ¹¹ ) m-Si (OR ¹² ) n

In the general formula (2), R ¹¹ represents a substituted or unsubstituted alkyl group or aryl group. R ¹² represents a substituted or unsubstituted alkyl group or acyl group. m represents an integer of 0 to 3. n represents an integer of 1 to 4. The sum of m and n is 4.

In the general formula (2), R ¹¹ represents a substituted or unsubstituted alkyl group or aryl group. Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, hexyl, t-butyl, sec-butyl, hexyl, decyl, hexadecyl and the like. The alkyl group preferably has 1 to 30 carbon atoms, more preferably 1 to 16 carbon atoms, and particularly preferably 1 to 6 carbon atoms. Examples of the aryl group include phenyl and naphthyl, and a phenyl group is preferable.
The substituent is not particularly limited, but halogen (fluorine, chlorine, bromine, etc.), hydroxyl group, mercapto group, carboxyl group, epoxy group, alkyl group (methyl, ethyl, i-propyl, propyl, t-butyl etc.), Aryl group (phenyl, naphthyl, etc.), aromatic heterocyclic group (furyl, pyrazolyl, pyridyl, etc.), alkoxy group (methoxy, ethoxy, i-propoxy, hexyloxy, etc.), aryloxy (phenoxy, etc.), alkylthio group (methylthio) , Ethylthio etc.), arylthio groups (phenylthio etc.), alkenyl groups (vinyl, 1-propenyl etc.), alkoxysilyl groups (trimethoxysilyl, triethoxysilyl etc.), acyloxy groups (acetoxy, acryloyloxy, methacryloyloxy etc.), Alkoxycarbonyl group Bonyl, ethoxycarbonyl, etc.), aryloxycarbonyl groups (phenoxycarbonyl, etc.), carbamoyl groups (carbamoyl, N-methylcarbamoyl, N, N-dimethylcarbamoyl, N-methyl-N-octylcarbamoyl, etc.), acylamino groups (acetylamino) Benzoylamino, acrylamino, methacrylamino and the like.

  Of these, more preferred are a hydroxyl group, a mercapto group, a carboxyl group, an epoxy group, an alkyl group, an alkoxysilyl group, an acyloxy group, and an acylamino group, and particularly preferred are an epoxy group and a polymerizable acyloxy group (acryloyloxy, methacryloyloxy). ) And a polymerizable acylamino group (acrylamino, methacrylamino). These substituents may be further substituted.

R ¹² represents a substituted or unsubstituted alkyl group or acyl group. The explanation of the alkyl group, acyl group and substituent is the same as in the case of R ¹¹ above. R ¹² is preferably an unsubstituted alkyl group or an unsubstituted acyl group, and particularly preferably an unsubstituted alkyl group.
m represents an integer of 0 to 3. n represents an integer of 1 to 4. The sum of m and n is 4. When R ¹ or the R ² there are a plurality, it may be different even multiple of R ¹ or R ² respectively the same. m is preferably 0, 1, 2 and particularly preferably 1.

  In addition to the compound of the general formula (2), the oligomer reaction product (sol) is also preferable because the strength of the hard coat layer and the low refractive index layer is further increased. Furthermore, it is also preferable to contain a coupling-reactive silyl group-containing polymer. Specific examples of these compounds include, for example, JP-A-11-52103 [0010] to [0047], JP-A-11-106704 [0013] to [0043], JP-A 2000-275403 [0015] to [0026] and the like.

  The amount of the compound of the general formula (2) is preferably 1 to 30% by mass, more preferably 3 to 20% by mass, and most preferably 5 to 10% by mass based on the total solid content of the layer containing the compound.

(Ultrafine filler)
In order to adjust the refractive index of the translucent binder matrix, apart from the above translucent fine particles, metal oxides, hydrated metal oxides, nitrides, sulfides, halides or organics having an average particle size of 0.2 μm or less An ultrafine filler made of a polymer can be added. The average particle diameter is preferably 0.1 μm or less, more preferably 0.06 μm or less. An inorganic ultrafine particle filler having a large refractive index difference from the binder resin is preferred. For example, it is preferably made of a metal oxide, a hydrous oxide, a nitride, a sulfide or a halide, and examples of the metal atom include Mg, Ca, Ba, Al, Zn, Fe, Cu, Ti, Sn, In, W, Y, Sb, Mn, Ga, V, Nb, Ta, Ag, Si, B, Bi, Mo, Ce, Cd, Be, Pb and Ni are preferable. In particular, an oxide of at least one metal atom selected from Si, Ti, Zr, AL, In, Zn, Sn, Sb, and the like can be given. The shape of these ultrafine particle fillers is not particularly limited. For example, any of spherical, plate-like, fiber-like, rod-like, indeterminate, hollow and the like, and spherical fine particles having a convex on the surface are preferably used. Spherical shape is preferable because of good dispersibility. This ultrafine filler can contribute to curling prevention and surface hardness improvement depending on the filling amount. When the hard coat layer contains an ultrafine particle filler, the refractive index of the translucent binder matrix is mainly determined by the refractive indexes of the binder resin and the inorganic ultrafine particle filler constituting the hard coat layer and the mixing ratio thereof.

The surface of the inorganic ultrafine filler is also preferably subjected to silane coupling treatment or titanium coupling treatment, and a surface treatment agent having a functional group capable of reacting with the binder species on the filler surface is preferably used.
The addition amount of these ultrafine particle fillers is preferably 10 to 90% by mass, more preferably 20 to 70% by mass, and particularly preferably 30 to 50% by mass with respect to the total mass of the hard coat layer. In addition, since such ultrafine particle filler has a particle size sufficiently smaller than the wavelength of light, scattering does not occur, and a composite in which the ultrafine particle filler is dispersed in a binder resin behaves as an optically uniform substance, The function of the ultrafine particle filler is different from that of the above-described translucent fine particles.

(Other additives)
These monomers having an ethylenically unsaturated group can be cured by a polymerization reaction by ionizing radiation or heat after being dissolved in a solvent, applied and dried together with various polymerization initiators and other additives.
The hard coat layer of the present invention is a fluorosurfactant (for example, a perfluoroalkylsulfonic acid amide group-containing nonionic compound, a peron Fluoroalkyl group-containing oligomers, etc.), silicone surfactants (polydimethylsiloxane compounds whose side chain or main chain ends are modified with various substituents such as oligomers such as ethylene glycol and propylene glycol) Or both can be contained in the coating composition for hard-coat layer formation. In particular, a fluorine-based surfactant is preferably used because an effect of improving surface defects such as coating unevenness, drying unevenness, and point defects of the antiglare antireflection film of the present invention appears in a smaller addition amount.

Furthermore, in order to maintain sufficient wettability of the coating composition used to form the low refractive index layer, the surface energy of the hard coat layer is adjusted by adjusting the type and amount of the surfactant used. the preferably controlled to a range of ^{25mN · m -1 ~70mN · m -1} . More preferably ^{35mN · m -1 ~70mN · m -1} .

(How to create a hard coat layer)
The production of the hard coat film of the present invention includes dipping, spinner, spray, roll coater, gravure, wire bar, extrusion, blade, etc. It can be produced by forming, drying, and irradiating with active energy rays by a known thin film forming method.

  Furthermore, for the purpose of improving the adhesion of the hard coat layer to the transparent support, one or both surfaces of the transparent support can be subjected to a surface treatment by an oxidation method, an unevenness method, or the like. Examples of the oxidation method include corona discharge treatment, glow discharge treatment, plasma treatment, chromic acid treatment (wet), flame treatment, hot air treatment, ozone / ultraviolet irradiation treatment, and the like. Furthermore, one or more undercoat layers can be provided. Examples of the material for the undercoat layer include copolymers such as vinyl chloride, vinylidene chloride, butadiene, (meth) acrylic acid ester, and vinyl ester, or water-soluble polymers such as latex, low molecular weight polyester, and gelatin.

  The hard coat layer can be a single layer, but can also be composed of two or more layers. A multilayer structure can be formed by sequentially laminating layers having different surface elastic moduli. In the case of a multilayer structure, the elastic modulus of a layer can be obtained from the average of the thickness correction of the elastic modulus of each layer.

  On these prepared hard coat layers, a thin film having functions such as an antireflection layer, an ultraviolet or infrared absorption layer, a selective wavelength absorption layer, an antistatic layer, an electromagnetic wave shielding layer or an antifouling layer may be provided. Can be provided as a functional film having high hardness. These functional thin films can be prepared by a wet method in which a solution of a known functional material is applied, or a dry method in which a vacuum film formation such as sputtering or vapor deposition is performed. These hard coat layers are used to prevent scratches on the surface of plastic sheets and films, and those with a functional thin film on the surface are displays such as LCD, PDP, EL and other FPDs (flat panel displays) and CRTs. It can be used for surface protection of materials and show windows.

{Anti-glare layer}
In the optical functional film of the present invention, the preferable average particle diameter of the surface convex particles used for the antiglare layer is 0.4 to 20 μm, more preferably 1.0 to 12 μm, and particularly preferably 1.8 to 6. 0.0 μm.

The antiglare layer is composed of translucent fine particles for imparting antiglare properties and internal scattering properties and a translucent binder matrix that holds the translucent fine particles. In addition to the binder resin and polymerization initiator described later, the translucent binder matrix is an ultrafine particle filler added for adjusting the refractive index and increasing the strength, a silane coupling agent for imparting scratch resistance, and other additions. A coating liquid containing an agent is applied, dried and cured.
The layer thickness of the antiglare layer is preferably 1 to 10 μm, more preferably 2 to 7 μm, still more preferably 3 to 5 μm. If the film thickness is too thin, the surface hardness as an antiglare film is lowered, and a harmful effect such that it becomes impossible to contain light-transmitting fine particles in a preferable range occurs. On the other hand, if the film thickness is too thick, adverse effects such as poor applicability due to an increase in the viscosity of the coating solution are likely to occur. The definition of the thickness of the antiglare layer is that there is no translucent fine particles of the antiglare layer from the most antiglare layer side portion of the lower layer component of the antiglare layer (or the support component when there is no lower layer). The vertical distance between the thinnest points is used as a reference.

  The specular average reflectance at 450 nm to 650 nm and the integrated reflectance of the antiglare film of the present invention thus formed are both preferably 2.5% or less, more preferably 2.2% or less, More preferably, it is 1.9% or less. When the reflectance is larger than 2.5%, the reflection on the screen of the fluorescent lamp in the room becomes remarkable and the visibility is deteriorated, which is not preferable.

  The surface unevenness of the antiglare film has a centerline average surface roughness (Ra) when measured at a reference length of 2.5 mm and a cutoff value of 0.8 mm defined in JIS-B-0601 (1994 edition). It is preferably 1.0 μm or less, more preferably 0.8 μm or less, further preferably 0.5 μm or less, and particularly preferably 0.2 μm or less. However, if it is less than 0.02 μm, the film transportability deteriorates, which is not preferable. Here, the center line average roughness Ra is a parameter representing the average roughness of the surface irregularities, and the larger the value, the larger the average roughness of the surface.

  The lower the haze value on the surface of the antiglare film, the smaller the blurring of the display and the clearer display can be obtained. However, if the haze value is too low, the reflection and glare called surface glare (scintillation) will occur. Shine occurs. On the other hand, if the haze value is too high, it becomes whitish (whitening; reduced black density), which is not preferable. 1. To provide an appropriate anti-glare shape on the anti-glare layer, and to provide anti-glare properties that do not cause reflection by external light, the difference in refractive index between the translucent binder matrix and the translucent fine particles is zero or The surface haze is preferably controlled to 7 to 25%, more preferably 10 to 20%.

On the other hand, in order to improve the viewing angle characteristics, the more the light emitted from the backlight is internally scattered by the anti-glare layer on the viewing side, the better the viewing angle characteristics, but if too much is scattered, Backscattering increases and front brightness decreases. Alternatively, it is not preferable because the problem is that the image sharpness deteriorates due to excessive scattering. Therefore, the difference in refractive index between the translucent binder matrix and the translucent fine particles is preferably 0.05 or more and 2.5 or less, and the internal scattering haze is preferably 30 to 80%, more preferably 35 to 70%. 40 to 60% is particularly preferable.
When the internal scattering haze and the surface haze are present, the viewing angle improvement effect is exhibited when the total haze value is 35% or more, preferably 35 to 90%, more preferably 45 to 80%, and more preferably 50 to 70%. Is particularly preferred.
As a method for controlling the internal scattering haze, there are methods such as increasing the refractive index difference between the light-transmitting binder matrix and the light-transmitting fine particles, increasing the concentration of the light-transmitting fine particles, or increasing the film thickness.
The haze value (cloudiness value) can be measured using HR-100 manufactured by Murakami Color Research Laboratory according to JIS-K-7105.

  When the antiglare antireflection film of the present invention has a haze value and an average reflectance in the above range, good antiglare antireflection properties can be obtained without causing deterioration of the transmitted image. The strength of the antiglare antireflection film is a pencil hardness of 1 kg load, and is preferably H or more, more preferably 2H or more, and particularly preferably 3H or more.

(Translucent fine particles)
When the optical functional layer of the present invention is an antiglare layer, the antiglare layer contains surface convex particles having fine convex portions on the particle surface as translucent fine particles. . Furthermore, the surface convex particles are preferably spherical fine particles having a convex shape on the surface in which fine particles are fixed on the surface of the spherical particles (core particles). By using the surface convex fine particles in the antiglare layer, the functions of imparting antiglare property and imparting internal scattering property can be effectively expressed, respectively.

  The average particle diameter of the translucent fine particles is 0.4 to 20 μm, preferably 1.0 to 12 μm, and more preferably 1.8 to 6.0 μm. Among them, the particle diameter of translucent fine particles for imparting antiglare properties (hereinafter sometimes referred to as antiglare particles or AR particles) is preferably 0.8 to 20 μm, more preferably 1.6 to 12 μm, Particularly preferably, the particle diameter is 2.4 to 6 μm, and a particle having a particle size that is approximately the same as or larger than the thickness of the antiglare layer is preferable, and is 0.8 to 2.0 times the thickness of the antiglare layer. The particle size is preferably 0.9 times to 1.4 times. The difference from the refractive index of the translucent binder matrix is preferably zero or 0.05 or less.

On the other hand, particles imparting internal scattering properties (hereinafter sometimes referred to as scattering particles or IS particles) may not only cause internal scattering but also particles imparting antiglare properties. Alternatively, particles that do not contribute to imparting antiglare property and are embedded in the layer may be used. In order to prevent the antiglare property from being increased excessively, in this case, the particle size is preferably smaller than the thickness of the antiglare layer, and the particle size is preferably 0.4 to 8.0 μm, more preferably. It is 1.0-6.0 micrometers, Most preferably, it is 1.8-4.0 micrometers.
The refractive index of the internal scattering particles (IS particles) is different from the refractive index of the translucent binder matrix of the antiglare layer, and the difference from the refractive index of the translucent binder matrix is 0.05 to 2.5. Preferably there is. If the refractive index difference is smaller than 0.05, it is not preferable because a large amount of IS particles need to be added in order to cause sufficient scattering.

  The surface convex particles of the present invention may be used in combination of two or more kinds of translucent fine particles having different particle diameters, or two or more different kinds of translucent fine particles. Even if there are two or more kinds of material and two or more kinds of particle sizes, there is no limitation. By mixing them, the viewing angle characteristics related to display quality and the reflection of external light can be optimized independently, and fine settings can be made according to the mixing ratio of translucent fine particles. Control becomes possible, and various designs can be facilitated.

The higher the monodispersity of the surface convex particles of the present invention, the less the dispersion characteristics are dispersed, and the haze design is facilitated.
The preferable addition amount of surface convex-shaped particle | grains is 30-1000 mg / m < ² > in an anti-glare layer, More preferably, it is 300-800 mg / m < ² >. Among them, the amount of AR particles is preferably 0~600mg / m ^2, the amount of IS particles, 0~800mg / m ² is preferred. When both are used in combination, the ratio of AR particles to IS particles is not particularly limited.

(Translucent binder matrix)
The translucent binder matrix is a coating, drying, and curing of a coating solution containing a binder resin and polymerization initiator, which will be described later, an ultrafine filler added for refractive index adjustment and high strength, and other additives. It is. The refractive index of the translucent binder matrix is the refractive index of the antiglare layer that does not contain translucent fine particles for imparting antiglare properties and internal scattering properties, and for imparting antiglare properties and internal scattering properties. A layer excluding the translucent fine particles can be prepared and evaluated.
The refractive index of the translucent binder matrix is preferably 1.48 to 2.00, more preferably 1.50 to 1.90, and still more preferably 1.64 to 1.80. In order to make the refractive index within the above range, it can be achieved by appropriately selecting the kind and amount ratio of the binder resin and the inorganic ultrafine particle filler which are the main constituent materials. When the refractive index is too small, the antireflection property is lowered. Furthermore, when this is too large, the color of the reflected light of the anti-glare film of the present invention becomes strong, which is not preferable.
The magnitudes of the refractive indexes of the translucent binder matrix and the translucent fine particles are not particularly limited, but in order to reduce the character blur, the refractive index of the string-proof layer is within the range of the refractive index difference described above. It is preferable to lower the rate, and in order to further reduce the reflectivity of the antiglare antireflection film, it is preferable to increase the refractive index of the antiglare layer, which is appropriately selected according to the design concept.

(Binder resin and initiator)
The binder resin used for the antiglare layer is preferably a polymer having a saturated hydrocarbon or polyether as the main chain, and more preferably a polymer having a saturated hydrocarbon as the main chain. The binder resin is preferably crosslinked. The polymer having a saturated hydrocarbon as the main chain is preferably obtained by a polymerization reaction of an ethylenically unsaturated monomer. In order to obtain a crosslinked binder resin, it is preferable to use a monomer having two or more ethylenically unsaturated groups.
In order to adjust the refractive index (in order to increase the refractive index), the monomer structure was selected from an aromatic ring, a halogen atom other than fluorine, a sulfur atom, a phosphorus atom, and a nitrogen atom. It is also preferred to include at least one atom.

  The monomer having an ethylenically unsaturated group preferably contains 2 to 10 polymerizable groups, and preferably 2 to 8 polyfunctional monomers. Specifically, polyhydric alcohol (for example, ethylene glycol, propylene glycol, butanediol, cyclohexanediol, cyclohexanedimethanol, cyclohexanetriol, pentaerythritol, trimethylolpropane, dipentaerythritol, etc.) and polymerizable unsaturated double bond Polyester compounds with group-containing organic acids ((meth) acrylic acid, crotonic acid, etc.), polyurethane polyacrylates, polyester polyacrylates, derivatives of vinylbenzene (eg, 1,4-divinylbenzene, 4-vinylbenzoic acid-2 -Acryloyl ethyl ester, 1,4-divinylcyclohexanone), vinyl sulfone (eg, divinyl sulfone), (meth) acrylamide (eg, methylenebisacrylamide) and the like. Two or more of these monomers may be used in combination. Among these, trifunctional to octafunctional acrylates or methacrylates are preferable from the viewpoint of film hardness, that is, scratch resistance.

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

Polymerization of the monomer having an ethylenically unsaturated group can be performed by irradiation with ionizing radiation and / or heating in the presence of a photo radical initiator and / or a thermal radical initiator.
Accordingly, a coating liquid containing a monomer having an ethylenically unsaturated group, a photo radical initiator and / or a thermal radical initiator, translucent fine particles, and inorganic ultrafine particle filler is prepared, and the coating liquid is placed on the transparent support. After application, it can be cured by ionizing radiation irradiation and / or polymerization reaction by heat to form an antiglare layer.
As the radical photopolymerization initiator, conventionally known compounds may be mentioned. For example, the carbonyl compounds (acetophenones, benzophenones, hydroxyacetophenones, benzoins) described in the latest UV curing technology (P.159, publisher: Kazuhiro Takasato, publisher; Technical Information Association, Inc., published in 1991) Benzoates, thioxanthones, etc.), organic halogen compounds described in JP-A-63-298339, organic boric acid compounds described in JP-A-2002-16539, JP-A-61-166544, etc. Examples include disulfones described in the publication.

In addition to the photopolymerization initiator, a photosensitizer (n-butylamine, triethylamine, tri-n-butylphosphine, Michler's ketone thioxanthone, etc.) and a sensitization aid (phenylglycine, etc.) may be used.
The radical polymerization initiator is preferably used in the range of 0.1 to 15 parts by mass, more preferably in the range of 1 to 10 parts by mass with respect to 100 parts by mass of the polyfunctional monomer.

The polymer having a polyether as the main chain is preferably a polyfunctional compound cationic ring-opening polymer containing two or more cationically polymerizable groups selected from an epoxy group and an oxetane group. The ring-opening polymerization of the polyfunctional compound can be performed by irradiation with ionizing radiation and / or heating in the presence of a photoacid generator and / or a thermal acid generator.
In particular, as the cationically polymerizable group-containing compound, an alicyclic polyepoxy compound having two or more epoxy groups in one molecule is contained, and the content of the alicyclic polyepoxy compound is based on the total mass of the epoxy compound. When an epoxy compound (a mixture of epoxy compounds) of 30% by mass or more, more preferably 50% by mass or more is used, the cationic polymerization rate, thick film curability, resolution, ultraviolet transmittance, etc. are further improved, and the resin The viscosity of the composition is lowered, and film formation is performed smoothly.

Specific examples include compounds described in paragraph numbers [0084] to [0086] in the specification of JP-A No. 11-242101.
As a compound containing an oxetanyl group, the number of oxetanyl groups contained in the molecule is 1 to 10, preferably 1 to 4. These compounds are preferably used in combination with an epoxy group-containing compound. Specific examples include the compounds described in paragraphs [0024] to [0025] in JP-A 2000-239309. Accordingly, a coating liquid containing a polyfunctional compound containing two or more cationically polymerizable groups selected from epoxy groups and oxetane groups, a photoacid generator and / or a thermal acid generator, translucent fine particles and inorganic ultrafine particle fillers The coating solution is applied on a transparent support and then cured by irradiation with ionizing radiation and / or a polymerization reaction by heat to form an antiglare layer.

  The photoacid generator is a compound that generates an acid by the action of light. Specifically, for example, “Organic Materials for Imaging” p187-198 edited by Organic Electronics Materials Research Group (Bunshin Publishing), JP-A-10-282644. Various examples are described in No. Gazette and the like, and these known compounds can be used. Various onium salts such as diazonium salts, ammonium salts, phosphonium salts, iodonium salts, sulfonium salts, selenonium salts, and arsonium salts, organic halides such as oxadiazole derivatives and S-triazine derivatives substituted with trihalomethyl groups, and organic acids o-Nitrobenzyl ester, benzoin ester, imino ester, disulfone compound and the like can be mentioned, and onium salts are preferable, and sulfonium salts and iodonium salts are particularly preferable. Known compounds that generate a base by the action of light can also be used, and specific examples include nitrobenzyl carbamates and dinitrobenzyl carbamates.

In place of, or in addition to, a monomer having two or more ethylenically unsaturated groups, a monomer having a crosslinkable functional group is used to introduce a crosslinkable functional group into the polymer, and by reaction of the crosslinkable functional group, A cross-linked structure may be introduced into the binder resin.
Examples of the crosslinkable functional group include isocyanate group, epoxy group, aziridine group, oxazoline group, formyl group, carbonyl group, hydrazine group, carboxyl group, methylol group and active methylene group. Vinylsulfonic acid, acid anhydride, cyanoacrylate derivative, melamine, etherified methylol, ester and urethane, and metal alkoxide such as tetramethoxysilane can also be used as a monomer for introducing a crosslinked structure. A functional group that exhibits crosslinkability as a result of the decomposition reaction, such as a block isocyanate group, may be used. That is, in the present invention, the crosslinkable functional group may not react immediately but may exhibit reactivity as a result of decomposition.
These binder resins having a crosslinkable functional group can form a crosslinked structure by heating after coating.

It is preferable that the antiglare layer of the present invention further contains the silane coupling agent of the above general formula (2) because scratch resistance is imparted.
The appropriate amount of the compound of the general formula (2) is preferably 1 to 30% by mass, more preferably 3 to 20% by mass, and most preferably 5 to 10% by mass based on the total solid content of the layer containing the compound. .

(Ultrafine filler)
In order to adjust the refractive index of the translucent binder matrix, apart from the above translucent fine particles, metal oxides, hydrous metal oxides, nitrides, sulfides or halides having an average particle size of 0.2 μm or less and organic At least one ultrafine filler selected from polymers can be added. The average particle diameter is preferably 0.1 μm or less, more preferably 0.06 μm or less. An inorganic ultrafine particle filler having a large refractive index difference from the binder resin is preferred. For example, it is preferably made of a metal oxide, a hydrous oxide, a nitride, a sulfide or a halide, and examples of the metal atom include Mg, Ca, Ba, Al, Zn, Fe, Cu, Ti, Sn, In, W, Y, Sb, Mn, Ga, V, Nb, Ta, Ag, Si, B, Bi, Mo, Ce, Cd, Be, Pb and Ni are preferable. In particular, an oxide of at least one metal atom selected from Si, Ti, Zr, AL, In, Zn, Sn, Sb, and the like can be given. The shape of these ultrafine particle fillers is not particularly limited, and for example, any of spherical shape, plate shape, fiber shape, rod shape, irregular shape, hollow shape, and spherical shape fine particles having a convex shape on the surface is preferably used. . Of these, spherical ones are preferable in terms of good dispersibility. This ultrafine filler can contribute to curling prevention and surface hardness improvement depending on the filling amount. When the antiglare layer contains an ultrafine particle filler, the refractive index of the translucent binder matrix is mainly determined by the refractive index of each of the binder resin and the inorganic ultrafine particle filler constituting the antiglare layer and the mixing ratio thereof. .

The surface of the inorganic ultrafine filler is also preferably subjected to silane coupling treatment or titanium coupling treatment, and a surface treatment agent having a functional group capable of reacting with the binder species on the filler surface is preferably used.
The addition amount of these ultrafine particle fillers is preferably 10 to 90% by mass, more preferably 20 to 70% by mass, and particularly preferably 30 to 50% by mass with respect to the total mass of the antiglare layer. . In addition, since such ultrafine particle filler has a particle size sufficiently smaller than the wavelength of light, scattering does not occur, and a composite in which the ultrafine particle filler is dispersed in a binder resin behaves as an optically uniform substance, The function of the ultrafine particle filler is different from that of the above-described translucent fine particles.

(Other additives)
These monomers having an ethylenically unsaturated group and monomers having a crosslinkable functional group must be dissolved in a solvent together with various polymerization initiators and other additives, coated and dried, and then cured by a polymerization reaction by ionizing radiation or heat. Can do.
The antiglare layer of the present invention is a fluorine-based surfactant (for example, a perfluoroalkylsulfonic acid amide group-containing nonionic compound, in order to further ensure surface uniformity such as coating unevenness, drying unevenness, point defect, etc. Perfluoroalkyl group-containing oligomers, etc.), silicone surfactants (polydimethylsiloxane compounds whose side chain or main chain ends are modified with various substituents such as oligomers such as ethylene glycol and propylene glycol) Or both of them can be contained in the coating composition for forming the antiglare layer. In particular, a fluorine-based surfactant is preferably used because an effect of improving surface defects such as coating unevenness, drying unevenness, and point defects of the antiglare antireflection film of the present invention appears in a smaller addition amount.

Furthermore, in order to maintain sufficient wettability of the coating composition used to form the low refractive index layer, the surface of the antiglare layer is adjusted by adjusting the type and amount of the surfactant used. preferably, to control the energy in the range of ^{25mN · m -1 ~70mN · m -1} . More preferably ^{35mN · m -1 ~70mN · m -1} .

(Anti-glare layer coating solution solvent)
The solvent of the coating solution for forming the antiglare layer is a lower layer (transparent support) in order to achieve the antiglare property and the compatibility between the lower layer (transparent support) and the antiglare layer. And at least one solvent that does not dissolve the lower layer (transparent support). For example, when a triacetyl cellulose support is used as the transparent support, at least one of the solvents that do not dissolve triacetyl cellulose has a higher boiling point than at least one of the solvents that dissolve triacetyl cellulose. preferable. More preferably, the boiling point temperature difference between the solvent having the highest boiling point among the solvents not dissolving the triacetyl cellulose support and the solvent having the highest boiling point among the solvents dissolving the triacetyl cellulose support is 30 ° C. or more. And most preferably 50 degrees or more.

As a solvent for dissolving triacetyl cellulose, ethers having 3 to 12 carbon atoms: specifically, dibutyl ether, dimethoxymethane, dimethoxyethane, diethoxyethane, propylene oxide, 1,4-dioxane, 1,3 -Ketones having 3 to 12 carbon atoms such as dioxolane, 1,3,5-trioxane, tetrahydrofuran, anisole and phenetole: specifically, acetone, methyl ethyl ketone, diethyl ketone, dipropyl ketone, diisobutyl ketone, cyclopentanone , Cyclohexanone, methylcyclohexanone, methylcyclohexanone and the like, and esters having 3 to 12 carbon atoms: specifically, ethyl formate, propyl formate, n-pentyl formate, methyl acetate, ethyl acetate, methyl propionate, propion brewing ethyl , Acetic acid -Organic solvent having two or more functional groups such as pentyl and γ-butyrolactone: specifically, methyl 2-methoxyacetate, methyl 2-ethoxyacetate, ethyl 2-ethoxyacetate, ethyl 2-ethoxypropionate, Examples include 2-methoxyethanol, 2-propoxyethanol, 2-butoxyethanol, 1,2-diacetoxyacetone, acetylacetone, diacetone alcohol, methyl acetoacetate, and ethyl acetoacetate.
These can be used individually by 1 type or in combination of 2 or more types.

As solvents that do not dissolve triacetyl cellulose, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, tert-butanol, 1-pentanol, 2-methyl-2-butanol, cyclohexanol, acetic acid Examples include isobutyl, methyl isobutyl ketone, 2-octanone, 2-pentanone, 2-hexanone, 2-heptanone, 3-pentanone, 3-heptanone and 4-heptanone.
These can be used individually by 1 type or in combination of 2 or more types.

  The mass ratio (A / B) of the total amount (A) of the solvent that dissolves triacetyl cellulose and the total amount (B) of the solvent that does not dissolve triacetyl cellulose is preferably 5/95 to 50/50, more preferably 10 /. It is 90-40 / 60, More preferably, it is 15 / 85-30 / 70.

(How to create an antiglare layer)
The antiglare antireflection film of the present invention can be formed by the following method, and the antiglare layer is one of them, but is not limited to this method.
First, a coating solution containing components for forming each layer is prepared. Next, the coating liquid for forming the antiglare layer is reverse gravure method (classified as gravure coating method, micro gravure coating method, etc.), dip coating method, air knife coating method, curtain coating method, roller coating The coating is applied onto a transparent support by a method, a wire bar coating method and an extrusion coating method (see US Pat. No. 2,681,294), and is heated and dried. A micro gravure coating method is particularly preferred. Thereafter, the monomer for forming the antiglare layer is polymerized and cured by light irradiation or heating. Thereby, an anti-glare layer is formed.

(Low refractive index layer)
The low refractive index layer of the present invention has a kinetic friction coefficient of 0.03 to 0.15 as a low refractive index binder, a fluorine-containing polymer that is crosslinked by heat or ionizing radiation having a contact angle of 90 to 120 degrees with water, and an improvement in film strength. It is characterized by using a surface convex ultrafine particle filler for improving low reflectance performance.

In the optical functional film of the present invention, the refractive index of the low refractive index layer is preferably from 1.38 to 1.49, more preferably from 1.38 to 1.44.
Furthermore, the low refractive index layer preferably satisfies the following formula (I) in order to achieve a low reflectance.

m · λ / 4 × 0.7 <n ₁ d ₁ <m · λ / 4 × 1.3 Formula (I)

In the formula (I), m is a positive odd number, n ₁ is the refractive index of the low refractive index layer, and d ₁ is the layer thickness (nm) of the low refractive index layer. Further, λ is a wavelength, which is a value in the range of 500 to 550 nm.
In addition, satisfy | filling said numerical formula (I) means that m (positive odd number, usually 1) which satisfy | fills numerical formula (I) exists in the said wavelength range.

As a crosslinkable fluorine-containing polymer used for the low refractive index layer, a condensation product of a perfluoroalkyl group-containing silane compound (for example, (heptadecafluoro-1,1,2,2-tetradecyl) triethoxysilane), fluorine-containing Examples thereof include a fluorine-containing polymer having a monomer and a monomer for imparting a crosslinkable group as structural units.
Specific examples of the fluorine-containing monomer unit include, for example, fluoroolefins, (meth) acrylic acid partial or fully fluorinated alkyl ester derivatives, fully or partially fluorinated vinyl ethers, and the like. And the compounds described in paragraph [0040] of JP-A No. 2001-281405.
As a monomer for imparting a crosslinkable group, in addition to a (meth) acrylate monomer having a crosslinkable functional group in the molecule in advance such as glycidyl methacrylate, it has a carboxyl group, a hydroxyl group, an amino group, a sulfonic acid group, etc. ) Acrylate monomers (for example, (meth) acrylic acid, methylol (meth) acrylate, hydroxyalkyl (meth) acrylate, allyl acrylate, etc.). It is known from Japanese Patent Application Laid-Open Nos. 10-25388 and 10-147739 that the latter can introduce a crosslinked structure after copolymerization.

  Further, not only a polymer having the above-mentioned fluorine-containing monomer as a structural unit but also a copolymer with a monomer not containing a fluorine atom may be used. There are no particular limitations on the monomer units that can be used in combination. For example, olefins, (meth) acrylic acid esters, styrene derivatives, vinyl ethers (such as methyl vinyl ether), vinyl esters, (meth) acrylamides, and acrylonitrile derivatives. Etc.

The average particle diameter of the surface convex ultrafine particle filler (L) used in the low refractive index layer of the present invention is preferably 0.001 to 0.2 μm, more preferably 0.005 to 0.1 μm. . The particle diameter of the filler is preferably as uniform (monodispersed) as possible.
Since the surface convex ultrafine particle filler (L) of the present invention is excellent in binding force with a low refractive index binder, it can increase the film strength of the low refractive index layer and also has excellent coating solution stability. The layer thickness can be made uniform, and the reflectance can be lowered.
The surface convex ultrafine particle filler (L) preferably has a low refractive index, and may be a surface convex organic ultrafine particle filler (L) or a surface convex inorganic ultrafine particle filler (L). The surface convex inorganic ultrafine particle filler (L) is preferable from the viewpoint of improving the film strength.
The addition amount of the ultrafine filler (L) is preferably 5 to 70% by mass of the total mass of the low refractive index layer, more preferably 10 to 50% by mass, and particularly preferably 15 to 30% by mass.
The surface convex inorganic ultrafine particle filler (L) is preferably amorphous. Examples of the surface convex inorganic ultrafine particle filler (L) include compounds similar to the inorganic particles for the antiglare layer, and Mg, Ca, B and Si are particularly preferable as the metal atom. An inorganic compound containing two kinds of metals may be used. Particularly preferred inorganic compounds include silicon dioxide and magnesium fluoride.
A part of the surface convex ultrafine particle filler (L) of the present invention can be replaced with an ultrafine particle filler having no surface convex shape. The ratio of the surface convex ultrafine particle filler (L) at that time is in the range of 50 to 100%, which is preferable because the cost can be reduced without reducing the surface convex ultrafine particle filler (L) effect.
The surface convex inorganic ultrafine particle filler (L) is preferably used after being subjected to a surface treatment. As the surface treatment method, the above-described surface treatment method and procedure for the convex surface particles in the hard coat layer can be used.

  Furthermore, the low refractive index layer may contain the compound represented by the general formula (2) for the purpose of imparting scratch resistance. It is preferable to contain the compound represented by the general formula (2) in at least one of the antiglare layer and the low refractive index layer of the present invention.

The solvent composition of the coating solution used for forming the low refractive index layer may be either alone or mixed. When mixing, the solvent having a boiling point of 100 degrees or less is preferably 50 to 100%, more Preferably it is 80 to 100%, more preferably 90 to 100%. When the solvent having a boiling point of 100 ° C. or less is 50% or less, the drying speed becomes very slow, the coating surface condition is deteriorated, and the coating film thickness is also uneven.
As a preferable solvent, the solvents described in JP-A-2002-148404, [0031] to [0032] can be used. In particular, selection from solvents having different boiling points among ketones and esters is preferable, and ketones are particularly preferable.

  The coating solution for a low refractive index layer of the present invention is prepared by diluting the low refractive index layer component according to the present invention with the solvent having the above composition. The concentration of the coating solution is preferably adjusted appropriately in consideration of the viscosity of the coating solution, the specific gravity of the low refractive index layer material, etc., but is preferably 0.1 to 20% by mass, more preferably 1 to 10% by mass. is there.

  The low refractive index layer is formed by applying a low refractive index layer coating solution on the antiglare layer and irradiating or heating it to form the low refractive index layer. In this way, the antiglare antireflection film of the present invention having a low refractive index layer having a uniform thickness along the surface irregularities can be obtained on the antiglare layer having the surface irregularities.

[Medium refractive index layer and high refractive index layer]
In order to further improve the antireflection performance, a middle refractive index layer and a high refractive index layer described in JP-A No. 2000-47004 can be provided below the low reflectance layer.

  As an organic material for forming a layer having a higher refractive index than the above low refractive index layer, a thermoplastic film (eg, polystyrene, polystyrene copolymer, polycarbonate, aromatic ring other than polystyrene, heterocyclic ring, alicyclic ring) A polymer having a group or a polymer having a halogen group other than fluorine); a composition having a low thermal refractive index layer (eg, a film composition using a melamine film, a phenol film, or an epoxy film as a curing agent); urethane forming property Compositions (eg, combinations of alicyclic or aromatic isocyanates and polyols); and radical polymerizable compositions (modified films capable of radical curing by introducing double bonds into the above compounds (polymers, etc.)) Or a composition containing a prepolymer). A material having high film-forming properties is preferred. For the layer having a higher refractive index, inorganic fine particles dispersed in an organic material can also be used. As the organic material to be used above, those having a refractive index lower than that in the case where the organic fine particles are used alone because inorganic fine particles generally have a high refractive index can be used. As such materials, in addition to the above-mentioned organic materials, acrylic copolymers, vinyl copolymers, polyesters, alkyd coatings, fibrous polymers, urethane coatings, various curing agents that cure these, and curability Examples thereof include various organic materials that are transparent and stably disperse inorganic fine particles, such as a composition having a functional group.

  Further organically substituted silicon-based compounds can be included therein. These silicon compounds are compounds represented by the following general formula (3), or hydrolysis products thereof.

General formula (3) R ^a pR ^b q SiZ _(4-pq)

Here, R ^a and R ^b each represents an alkyl group, an alkenyl group, an allyl group, or a hydrocarbon group substituted with halogen, epoxy, amino, mercapto, methacryloyl or cyano, and Z represents an alkoxyl group or an alkoxyalkoxyl group. Represents a hydrolyzable group selected from a halogen atom to an acyloxy group, and p and q are 0, 1 or 2 respectively under the condition that p + q is 1 or 2.

  Preferable inorganic compounds of inorganic fine particles dispersed in these include oxides of metal elements such as aluminum, titanium, zirconium and antimony. These compounds are commercially available in particulate form, ie as a colloidal dispersion in powder or water and / or other solvents. These are further mixed and dispersed in the above organic material or organosilicon compound.

As a material for forming a layer having a higher refractive index than the above, an inorganic material (eg, alkoxide of various elements, salt of organic acid, coordination property) which can be dispersed in a solvent with a film-forming property or itself is liquid. And coordination compounds (eg, chelate compounds) and inorganic polymers bonded to the compound.
In addition to those mentioned above, various alkyl silicates or hydrolysates thereof, particularly finely divided silica, particularly silica gel dispersed in a colloidal form, can be used as those having a relatively low refractive index but can be used in combination with the above-mentioned compounds. .

  The refractive index of the high refractive index layer is generally 1.70 to 2.20. The thickness of the high refractive index layer is preferably 5 nm to 10 μm, more preferably 10 nm to 1 μm, and most preferably 30 nm to 0.5 μm. The haze of the high refractive index layer is preferably 5% or less, more preferably 3% or less, and most preferably 1% or less. The specific strength of the high refractive index layer is preferably H or more, more preferably 2H or more, and most preferably 3H or more, with a pencil hardness of 1 kg.

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 1.50 to 1.70.
It is particularly preferable that inorganic fine particles and a polymer are used for the high refractive index layer, and the middle refractive index layer is formed by adjusting the refractive index to be lower than that of the high refractive index layer. The haze of the medium refractive index layer is preferably 3% or less.

[Other functional layers]
The optical functional film of the present invention further includes an antifouling layer, a sliding layer, a moisture proof layer, an antistatic layer, an electromagnetic wave shielding layer, an infrared absorbing layer, an ultraviolet absorbing layer, a selective wavelength absorbing layer, a polarized light separating layer, an undercoat layer, Functional thin layers such as an easy-adhesion layer and a protective layer can be provided and provided as an optical functional film. In particular, the technique described in Japanese Patent Publication No. 2001-1745, page 32 to page 45 (issued on March 15, 2001) can be preferably used. These functional thin layers can be produced by a wet method in which a solution of a known functional material is applied, or a dry method such as sputtering or vacuum deposition.

<Use of optical functional film>
The optical functional film of the present invention includes various liquid crystal display devices (LCD), cathode ray tube display devices (CRT), plasma display panels (PDP), electroluminescence displays (ELD), and field emission displays (FED). It can be used as a display element for an image display device, a display such as a mobile phone, a touch panel such as a home appliance, and the like.

As a specific example, the image by reflection of external light is obtained by sticking the transparent support side of the antiglare film of the present invention to the image display surface of the image display device on the outermost surface of an image display device such as CRT or PDP or a touch panel. It is possible to obtain an image display device which is excellent in anti-glare property without reflection of light and has improved glare, character blur and color mixing. Furthermore, by using an optical functional film having the hard coat layer, the antireflection layer and the like of the present invention, an image display device having excellent functionality can be obtained.
As another specific example, the present invention can be applied to, for example, a polarizing plate used in a liquid crystal display device. That is, when used as a viewing side protective film of the outermost layer of a polarizer (polarizing film) of a polarizing plate, a polarizing plate having a hard coat property excellent in pencil hardness and scratch resistance, and no reflection of an image due to reflection of external light It is possible to obtain a polarizing plate that has excellent antiglare properties, improved glare, further improves character blurring and color mixing, and has excellent antireflection properties without deterioration of contrast due to external light reflection. In addition, as compared with the case where an optical functional film is pasted on a conventional polarizing plate, one protective film used for the polarizing plate can be reduced, the cost can be reduced, and the polarizing plate can be made thin and light, which is preferable.
In addition, as a preferred embodiment of the polarizing plate of the present invention, an anti-glare reflection of the present invention is provided as an optically anisotropic layer comprising a liquid crystalline compound on one protective film of a polarizer and the other viewing side protective film. The thing using a prevention film can be mentioned. Thereby, the liquid crystal cell of a liquid crystal display device can be optically compensated, and the viewing angle characteristic of a liquid crystal display device can be improved markedly by using together with the anti-glare film of this invention.

  The optical functional film of the present invention, when used as one side of the surface protective film of the polarizing film, is TN (Twisted Nematic), STN (Super Twisted Nematic), VA (Vertically Aligned), IPS (In-Plane Switching), FLC (FLC). Ferroelectric Liquid Crystal), AFLC (Anti-ferroelectric Liquid Crystal), OCB (Optically Compensatory Bend), HAN (Hybrid Aligned Nematic), GH (Guest-Host), ASM (Axially Symmetric Aligned Microcell), etc. It can be preferably used for a reflective or transflective liquid crystal display device. In particular, for a liquid crystal display device in TN mode or IPS mode, it is described in JP-A-2001-100043.

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

[Polarizer]
The polarizing plate with an optical functional film of the present invention is formed by using the optical functional film as at least one of two protective films sandwiching a polarizing film. By using the antiglare antireflection film of the present invention on the outermost surface as an optical functional film, reflection of outside light is prevented, and a polarizing plate having high definition suitability can be obtained. A polarizing plate excellent in antifouling property can be obtained by providing an antifouling layer to the conductive film. By using the hard coat film of the present invention on the outermost surface of the polarizing plate, a polarizing plate having excellent scratch resistance can be obtained. Moreover, it can be set as the polarizing plate excellent in antireflection property by using the antireflection film of this invention for the outermost surface of a polarizing plate.
Since the optical functional film also serves as a protective film in the polarizing plate of the present invention, the manufacturing cost can be reduced, and the weight and resources can be saved.

When the optical functional film of the present invention is used in a liquid crystal display device, it is preferably disposed on the outermost surface of the display by providing an adhesive layer on one side and attaching it to a polarizing plate. When the transparent support of the optical functional film is triacetyl cellulose, since triacetyl cellulose is used as a protective film for protecting the polarizing film of the polarizing plate, the optical functional film of the present invention can be used as it is for the protective film. it can.
The slow axis of the protective film (for example, cellulose acetate film) and the transmission axis of the polarizer are arranged so as to be substantially parallel or inclined according to the liquid crystal mode of the liquid crystal display device.

  In the polarizing plate with an optical functional film of the present invention, an optical functional layer is formed on the transparent support of the optical functional film, and then surface treatment is performed on the opposite transparent support surface, and the polarizing film is bonded. Can be obtained. A known method can be used for the surface treatment. An example is alkali saponification. The alkali saponification treatment is performed by a method of immersing at least once in an alkali solution or a method of saponifying only the back surface of the film by applying an alkali solution to the surface-treated surface, heating, washing and / or neutralizing. It can be carried out.

[Polarizing film]
Any polarizing film can be applied as the polarizing film, and examples thereof include an iodine-based polarizing film, a dye-based polarizing film using a dichroic dye, and a polyene-based polarizing film. The iodine-based polarizing film and the dye-based polarizing film can be generally produced using a polyvinyl alcohol film. In addition, the polarizing film can be produced either by a conventional production method or by oblique stretching.

[Other films constituting polarizing plate]
In the polarizing plate of the present invention, it has been stated that an antiglare antireflection film can be used as one of the protective films that can be disposed on both sides of the polarizing film. An optical compensation film composed of an optical anisotropic layer in which the orientation of the discotic liquid crystal is fixed can be used.

[Liquid crystalline compounds]
The liquid crystal compound used in the present invention may be a rod-like liquid crystal or a discotic liquid crystal, and they may be a polymer liquid crystal, a low-molecular liquid crystal, or a liquid crystal compound in which a low-molecular liquid crystal is cross-linked and no longer exhibits liquid crystallinity. Can do.
As rod-shaped liquid crystals, azomethines, azoxys, cyanobiphenyls, cyanophenyl esters, benzoic acid esters, cyclohexanecarboxylic acid phenyl esters, cyanophenylcyclohexanes, cyano-substituted phenylpyrimidines, alkoxy-substituted phenylpyrimidines, phenyl Dioxanes, tolanes and alkenylcyclohexylbenzonitriles are preferably used. The rod-like liquid crystallinity includes a metal complex. A liquid crystal polymer containing rod-like liquid crystalline molecules in the repeating unit can also be used as the rod-like liquid crystal. In other words, the rod-like liquid crystal may be bonded to a (liquid crystal) polymer.
For rod-shaped liquid crystals, quarterly review of chemical review, Volume 22, Liquid Crystal Chemistry (1994), Chapter 4, Chapter 7 and Chapter 11 of the Chemical Society of Japan, Liquid Crystal Device Handbook, 142th Committee of the Japan Society for the Promotion of Science Chapters and Japanese Patent Application Laid-Open No. 2000-304932.

  Most preferred as the liquid crystalline compound of the present invention is a discotic liquid crystal. Examples of the discotic liquid crystal of the present invention include C.I. Destrade et al., Mol. Cryst. 71, 111 (1981), benzene derivatives described in C.I. Destrode et al. (Mol. Cryst. 122, p. 141 (1985), hysics lett, A, p. 78, p. 82 (1990)). Kohne et al. (Angew. Chem. 96, 70 (1984)) and cyclohexane derivatives described in J. M.M. Lehn et al. (J. Chem. Commun., 1794 (1985)), J. Chem. Examples include azacrown-type and phenylacetylene-type macrocycles described in a research report of Zhang et al. (J. Am. Chem. Soc. 116, 2655 (1994)). The discotic liquid crystal generally has a structure in which these are used as a mother nucleus at the center of a molecule, and a linear alkyl group, an alkoxy group, a substituted benzoyloxy group, etc. are radially substituted as the linear chain. Show. However, the molecule itself is not limited to the above description as long as the molecule itself has negative uniaxiality and can give a certain orientation. Further, in the present invention, it is not necessary that the final product is formed from a discotic compound, for example, the low molecular discotic liquid crystal has a group that reacts with heat, light, or the like. As a result, it may be polymerized or cross-linked by reaction with heat, light or the like, resulting in high molecular weight and loss of liquid crystallinity. Preferred examples of the discotic liquid crystal are described in JP-A-8-50206.

[Optically anisotropic layer]
The optically anisotropic layer of the present invention is a layer made of a compound having a discotic structural unit, and the angle of the surface of the discotic structural unit with respect to the transparent support surface changes in the depth direction of the optically anisotropic layer. It is preferable.

  The tilt angle of the surface of the discotic structural unit generally increases or decreases in the depth direction of the optical anisotropic layer and with an increase in the distance from the bottom surface of the optical anisotropic layer. The tilt angle preferably increases with increasing distance. Further, the change in the inclination angle includes continuous increase, continuous decrease, intermittent increase, intermittent decrease, change including continuous increase and continuous decrease, and intermittent change including increase and decrease. it can. The intermittent change includes a region where the inclination angle does not change in the middle of the thickness direction. Even if the inclination angle includes a region that does not change, it is preferable that the inclination angle increases or decreases as a whole. Further, it is preferable that the inclination angle increases as a whole, and it is particularly preferable that the inclination angle changes continuously.

  The optically anisotropic layer is generally formed by applying a solution obtained by dissolving a discotic compound and other compounds in a solvent onto an alignment film, drying it, and then heating it to a discotic nematic phase formation temperature, and then aligning it (discotic nematic). Obtained by maintaining the phase) and cooling. Alternatively, the optically anisotropic layer is formed by applying a solution obtained by dissolving a discotic compound and another compound (for example, a polymerizable monomer, a photopolymerization initiator) in a solvent onto the alignment film, drying, and then discotic nematic. It is obtained by heating to the phase formation temperature, followed by polymerization (by irradiation with UV light, etc.) and further cooling. The discotic nematic liquid crystal phase-solid phase transition temperature of the discotic liquid crystalline compound used in the present invention is preferably 70 to 300 degrees, and particularly preferably 70 to 170 degrees.

  For example, the inclination angle of the discotic unit on the support side can be generally adjusted by selecting a discotic compound or a material for the alignment film, or by selecting a rubbing treatment method. The inclination angle of the discotic unit on the surface side (air side) is generally selected from the discotic compound or other compounds (eg, plasticizer, surfactant, polymerizable monomer and polymer) used together with the discotic compound. Can be adjusted. Furthermore, the degree of change in the tilt angle can be adjusted by the above selection.

  As the plasticizer, surfactant and polymerizable monomer, any compound is used as long as it has compatibility with the discotic compound and can change the tilt angle of the liquid crystalline discotic compound or does not inhibit the alignment. Can also be used. Among these, polymerizable monomers (eg, compounds having a vinyl group, a vinyloxy group, an acryloyl group, and a methacryloyl group) are preferable. The above compound is generally used in an amount of 1 to 50% by mass (preferably 5 to 30% by mass) based on the discotic compound. Furthermore, a polyfunctional acrylate is mentioned as an example of a preferable polymerizable monomer. The number of functional groups is preferably 3 or more, and more preferably 4 or more. Most preferred is a hexafunctional monomer. A preferred example of the hexafunctional monomer is dipentaerythritol hexaacrylate. It is also possible to use a mixture of these polyfunctional monomers having different numbers of functional groups.

Any polymer can be used as the polymer as long as it is compatible with the discotic compound and can change the tilt angle of the liquid crystalline discotic compound. Examples of polymers include cellulose esters. Preferred examples of the cellulose ester include cellulose acetate, cellulose acetate propionate, hydroxypropyl cellulose, and cellulose acetate butyrate. The polymer is generally 0.1 to 10% by mass (preferably 0.1 to 8% by mass, particularly 0.1 to 5% by mass) based on the discotic compound so as not to inhibit the alignment of the liquid crystalline discotic compound. ).
The optical compensation sheet of the present invention is an optical compensation sheet comprising a cellulose acetate film, an alignment film provided thereon, and a discotic liquid crystal formed on the alignment film, the rubbing comprising a polymer having the alignment film crosslinked. Processed membrane.

  Examples of the present invention will be described below, but the present invention is not limited thereto.

Example 1
By the method shown below, fine particles having protrusions on the surface, in which fine particles were fixed on the surface of the core particles, were prepared.

<Creation of surface convex particles 1>
70 parts by mass of polymethyl methacrylate particles having an average particle diameter of 12 μm and 30 parts by mass of silica (AEROSIL, manufactured by Nippon Aerosil Co., Ltd.) having an average particle diameter of 0.02 μm, combined by a dry agglomeration stirring method for 15 minutes with a hybridizer. Made it.

<Creation of surface convex particles 2>
Add 100 parts by mass of silica particles (Silicia, manufactured by Fuji Silysia) with an average particle size of 4 μm, 200 parts by mass of methanol, and 30 parts by mass of 3-aminopropyltrimethoxysilane (manufactured by Chisso Corporation), and stir for 1 hour to obtain silica particles. The surface was coupled. The supernatant was removed, 200 parts by mass of colloidal silica (Snowtex C, manufactured by Nissan Chemical Co., Ltd.) with an average particle size of 0.02 μm was added, stirred for 2 hours, allowed to stand for 1 hour, the supernatant was removed, and vacuum was removed. By drying, surface convex silica particles having an average particle diameter of 4.1 μm, on which silica particles having an average particle diameter of 0.02 μm were adsorbed, were obtained.

<Creation of surface convex particles 3>
100 parts by mass of silica particles having an average particle diameter of 4 μm, 200 parts by mass of methanol, and 20 parts by mass of 3-aminopropyltrimethoxysilane (manufactured by Chisso Corporation) were added, and the silica particles were subjected to coupling treatment by stirring for 1 hour. The supernatant was removed, 70 parts by mass of alumina sol (alumina sol 520, manufactured by Nissan Chemical Co., Ltd.) with an average particle size of 0.02 μm was added, stirred for 2 hours, allowed to stand for 30 minutes, and then the supernatant was removed and vacuum dried. Thus, silica particles having surface convexities with an average particle size of 4 μm, on which alumina particles with an average particle size of 0.02 μm were adsorbed, were obtained.

<Creation of surface convex particles 4>
Add 100 parts by mass of titanium oxide particles having an average particle size of 0.6 μm (rutile type, manufactured by Wako Pure Chemical Industries, Ltd.), 200 parts by mass of methanol, and 20 parts by mass of 3-aminopropyltrimethoxysilane (manufactured by Chisso Corporation). The titanium oxide surface was subjected to coupling treatment by stirring for 1 hour. The supernatant was removed, 80 parts by mass of colloidal silica particles (Snowtex, manufactured by Nissan Chemical Co., Ltd.) having an average particle size of 0.2 μm were added, stirred for 2 hours, allowed to stand for 1 hour, and then the supernatant was removed, followed by vacuum. After drying, titanium oxide particles having surface convexities with an average particle size of 0.9 μm, on which silica particles with an average particle size of 0.2 μm were adsorbed, were obtained.

<Creation of surface convex particles 5>
Add 100 parts by mass of zinc oxide particles having an average particle size of 0.6 μm (manufactured by Sakai Chemical Industry Co., Ltd.), 200 parts by mass of methanol, and 20 parts by mass of 3-aminopropyltrimethoxysilane (manufactured by Chisso Corporation) for 1 hour. The titanium oxide surface was coupled by stirring. The supernatant was removed, 80 parts by mass of colloidal silica (Snowtex, manufactured by Nissan Chemical Co., Ltd.) with an average particle size of 0.2 μm was added, stirred for 2 hours, allowed to stand for 1 hour, then the supernatant was removed and vacuum dried Thus, zinc oxide particles having surface convexities with an average particle diameter of 0.8 μm, on which silica particles with an average particle diameter of 0.2 μm were adsorbed, were obtained.

<Creation of surface convex particles 6>
80 parts by mass of crosslinked acrylic particles having an average particle size of 3.5 μm (MX-150, manufactured by Soken Chemical Co., Ltd.) and 20 parts by mass of titanium oxide having an average particle size of 0.03 μm (STO1, manufactured by Ishihara Sangyo Co., Ltd.) The composite was formed by a dry agglomeration stirring method in which treatment was performed at 20000 rpm for 15 minutes with a hybridizer.

<Creation of surface convex particles 7>
100 parts by weight of titanium oxide powder (Wako Pure Chemical Industries, Ltd., rutile type, average particle size 0.4 μ) is mixed with 600 parts by weight of 0.2N aqueous silver nitrate solution and stirred with a 100 W high pressure mercury lamp using a Pyrex filter. For 15 minutes. Thereafter, the particles were filtered, washed with pure water, and dried to obtain titanium oxide-silver composite particles having surface protrusions with an average particle size of 0.47 μm, on which metal silver was deposited on the particle surfaces.

<Creation of surface convex particles 8>
100 parts by mass of zinc oxide powder (manufactured by Sakai Chemical Co., Ltd., average particle size 0.35 μ) was mixed with 800 parts by mass of 0.2N aqueous silver nitrate solution, and irradiated for 20 minutes through a Pyrex filter with a 100 W high-pressure mercury lamp while stirring. did. Thereafter, the particles were filtered, washed with pure water, and dried to obtain zinc oxide-silver composite particles having surface protrusions having an average particle diameter of 0.39 μm, on which metal silver was deposited.

<Particle H1 having no surface protrusion>
Polymethylmethacrylate particles having an average particle diameter of 12 μm used for the production of the surface convex particles 1 were used.

<Particle H2 not having convex surface>
Silica particles having an average particle diameter of 4 μm used for the production of the surface convex particles 2 were used.

<Preparation of PET base with primer layer>
Latex (LX407C5, Nippon Zeon Co., Ltd.) made of styrene-butadiene copolymer with a refractive index of 1.55 and a glass transition temperature of 37 ° C. treated on both sides of PET (biaxially stretched polyethylene terephthalate film, refractive index of 1.64) with a thickness of 125 μm. Co., Ltd.) and tin oxide / antimony oxide composite oxide (FS-10D, manufactured by Ishihara Sangyo Co., Ltd.) are mixed so that the film thickness after drying is 0.1 μm, applied to one side, and a primer layer is applied. Formed.

<Preparation of hard coat layer coating solution (H-1)>
Glycidyl methacrylate is dissolved in methyl ethyl ketone, reacted for 1 hour 30 minutes at 75 ° C. while dropwise adding a thermal polymerization initiator, the resulting reaction solution is dropped into hexane, the precipitate is dried under reduced pressure, and polyglycidyl methacrylate (polystyrene). The converted molecular weight was 8,000). In a solution obtained by dissolving 30 parts by mass of this polyglycidyl methacrylate in 50 parts by mass of methyl ethyl ketone, 160 parts by mass of trimethylolpropane triacrylate (Biscoat # 295; manufactured by Osaka Organic Chemical Industry Co., Ltd.) and a photo radical polymerization initiator (Irgacure 184, Ciba Geigy Co., Ltd.) 3 parts by mass and photocationic polymerization initiator (Lordsil 2074, Rhodia Co., Ltd.) 7 parts by mass dissolved in 50 parts by mass of methyl isobutyl ketone were mixed with stirring to prepare a hard coat layer coating solution. did.

<Preparation of hard coat layer coating liquids (H-4) to (H-13)>
Hard coat layer coating solutions (H-4) to (H-11) were prepared by adding particles having surface protrusions in the amount shown in Table 1 to the hard coat layer coating solution (H-1). Moreover, the comparison particle | grains were added by the same operation and the hard-coat layer coating liquid (H-12)-(H-13) was prepared.

<Preparation of hard coat film>
On the prepared PET film with a primer layer, the hard coat layer coating solution is applied by an extrusion method so as to have the thickness after curing described in Table 1, dried, and irradiated with ultraviolet rays to cure the hard coat layer. Hard coat films (HF-1) to (HF-13) were produced.

  The obtained hard coat film was evaluated by the following method. The evaluation results are shown in Table 2.

(Pencil hardness test)
The hardness of the pencil scratch test is as follows. The prepared hard coat film was conditioned at a temperature of 25 ° C. and a relative humidity of 60% for 2 hours, and then a test pencil specified by JIS-S-6006 was used. According to the pencil hardness evaluation method specified by 5400, this is the value of the hardness of a pencil in which no scratches are observed at a load of 9.8 N.

(Adhesion test)
Using a cutter on the surface of the hard coat, scratches were made at intervals of 1 mm × 1 mm, and cellophane (registered trademark No. 405; manufactured by Nichiban Co., Ltd.) was applied to 100 squares, and after 30 seconds, the cellophane was peeled off and peeled off. The number of squares with missing edges was observed.

(Crackability test)
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. did. The case where cracking does not occur even with a curvature of 40 mm in diameter is indicated as “◯”, the case where cracking occurs at a curvature of 40 to 60 mm is indicated as “Δ”, and the case where cracking occurs at 60 mm is indicated as “x”.

(Evaluation of curl)
The curl radius of curvature of the prepared hard coat film was rated as ◯, less than 0.2 m, 0.1 m or more, and less than 0.1 m as x.

From the results shown in Table 2, the following is clear.
The hard coat film prepared using the surface convex particles of the present invention as additive particles in the hard coat layer has higher pencil hardness than the hard coat film containing no additive particles or the hard coat film added with fine particles having no surface convex. It turns out that it is excellent. Moreover, it is also excellent in adhesion, and it can be seen that it has good performance in the cracking test and curl evaluation.

Example 2
[Application of hard coat film to antireflection film]
<Preparation of antireflection layer>
(1) Preparation of high refractive index layer coating solution (a-1) 30.0 parts by mass of titanium dioxide fine particles (TTO-55B, manufactured by Ishihara Sangyo Co., Ltd.), anionic monomer (PM-21, Nippon Kayaku Co., Ltd.) )) 3.8 parts by mass, 1.0% by mass of a cationic monomer (DMAEA, manufactured by Kojin Co., Ltd.) and 65.2 parts by mass of cyclohexanone were dispersed by a sand grinder mill, and titanium dioxide having a mass average diameter of 55 nm. A dispersion was prepared. The titanium dioxide dispersion and dipentaerythritol hexaacrylate (DPHA, manufactured by Nippon Kayaku Co., Ltd.), photopolymerization initiator (Irgacure 907, manufactured by Ciba Geigy), photosensitizer (Kayacure DETX, Nippon Kayaku Co., Ltd.) The volume ratio of the total amount of monomers (the total amount of dipentaerythritol hexaacrylate, anionic monomer and cationic monomer) to titanium dioxide is 80/20, the photopolymerization initiator and the photosensitizer The refractive index of the high refractive index layer was added to methyl ethyl ketone so that the mass ratio was 4/1, and the mass ratio of the total amount of photopolymerization initiator and photosensitizer to the total amount of monomers was 5/100. Was adjusted to 1.81.

(2) Preparation of low refractive index layer coating liquid (a-2) 60 parts by mass of pentaerythritol tetraacrylate (PETA, Nippon Kayaku Co., Ltd.), 5 parts by mass of a photopolymerization initiator (Irgacure 907, manufactured by Ciba Geigy) , 2 parts by mass of photosensitizer (Kayacure DETX, manufactured by Nippon Kayaku Co., Ltd.), MegaFac 531A (C ₈ F ₁₇ SO ₂ N (C ₃ H ₇ ) CH ₂ CH ₂ OCOCH═CH ₂ , Dainippon Ink (Chemical Industry Co., Ltd.) 10 parts by mass, 100 parts by mass of methyl ethyl ketone, and the following silicon dioxide fine particle dispersion were added, mixed and stirred to prepare a coating solution for the low refractive index layer.

  The silicon dioxide fine particle dispersion was composed of 30.0 parts by mass of silicon dioxide fine particles (Aerosil 200, manufactured by Nippon Aerosil Co., Ltd.), 4.5 parts by mass of a carboxylic acid group-containing monomer (Aronix M-5300 manufactured by Toagosei Co., Ltd.) 65.5 parts by mass of cyclohexanone was dispersed and adjusted by a sand grinder mill.

  On the hard coat film, as described in Table 3, the coating liquid was adjusted, applied, and irradiated with ultraviolet rays so as to have the layer thickness and refractive index value of each layer, to prepare an antireflection hard coat film. The properties of these antireflection hard coat films are shown in Table 3. Application of the coating solution and ultraviolet irradiation were performed in the same manner as the formation of the hard coat layer.

  The surface reflectance shown in Table 3 was measured as follows.

(Measurement of surface reflectance)
A sample was prepared by rubbing the back surface with sandpaper and applying black magic so that reflection on the back surface did not occur. Using a spectrophotometer (manufactured by JASCO Corporation), incident light in the wavelength region of 450 to 650 nm 5 The surface reflectance of regular reflection at ° was determined.

  As shown in Table 3, it was confirmed that the antireflection film using the hard coat film of the present invention has extremely good antireflection performance.

Example 3
[Application of antireflection film to PDP front panel]
The antireflection film on the surface of the front plate of the plasma display (PDP-433HD-U, manufactured by Pioneer) is peeled off, and the antireflection hard coat film (HBF-4) shown in Table 7 is an acrylic adhesive having a refractive index of 1.52. We pasted together. As a result of observation in a room using a three-wavelength fluorescent lamp (National Panac Fluorescent Lamp FL40SS / EX-D / 37) as indoor lighting, it was found that the plasma display was very good in visibility. It was confirmed that the obtained antireflection hard coat film was suitable for a PDP front plate as an image display device.

Example 4
By the method shown below, fine particles having a convex shape on the surface (surface convex particles) in which fine particles were fixed on the surface of the core particles were prepared.

<Creation of surface convex particles 11>
Combined by dry agglomeration stirring method in which 70% by weight of polymethylmethacrylate particles with an average particle size of 4 μm and 30% by weight of silica (AEROSIL MOX170, manufactured by Nippon Aerosil Co., Ltd.) with an average particle size of 0.01 μm are treated with a hybridizer at 16000 rpm for 5 minutes. Made it.

<Creation of surface convex particles 12>
100 g of silica particles having an average particle diameter of 2 μm (Silicia, manufactured by Fuji Silysia), 200 g of methanol, and 20 g of 3-aminopropyltrimethoxysilane (manufactured by Chisso Corporation) were added, and the surface was subjected to coupling treatment by stirring for 1 hour. Thereafter, the supernatant was removed. Next, 100 g of colloidal silica (Snowtex C, manufactured by Nissan Chemical Co., Ltd.) having an average particle size of 0.02 μm was added, stirred for 2 hours, allowed to stand for 10 minutes, the supernatant was removed, vacuum dried, Surface convex silica particles having an average particle diameter of 2 μm on which silica particles having an average particle diameter of 0.02 μm were adsorbed were obtained.

<Creation of surface convex particles 13>
Using silica particles having an average particle diameter of 4 μm instead of silica particles having an average particle diameter of 2 μm, the surface of the convex particles 12 is formed, and the silica particles having an average particle diameter of 0.02 μm are adsorbed on the surface. Silica particles having a convex surface were obtained.

<Creation of surface convex particles 14>
100 g of silica particles having an average particle diameter of 2 μm, 200 g of methanol, and 20 g of 3-aminopropyltrimethoxysilane (manufactured by Chisso Corporation) were added and the surface was subjected to coupling treatment by stirring for 1 hour. Thereafter, the supernatant was removed. Next, 100 g of alumina sol (alumina sol 520, manufactured by Nissan Chemical Co., Ltd.) having an average particle size of 0.02 μm was added, stirred for 2 hours, allowed to stand for 10 minutes, the supernatant was removed, vacuum dried, and average particles on the surface. Silica particles having a convex surface with an average particle diameter of 2 μm on which alumina particles having a diameter of 0.02 μm were adsorbed were obtained.

<Creation of surface convex particles 15>
100 g of titanium oxide particles having an average particle diameter of 0.6 μm (rutile type, manufactured by Wako Pure Chemical Industries, Ltd.), 200 g of methanol, and 20 g of 3-aminopropyltrimethoxysilane (manufactured by Chisso Corporation) were added and stirred for 1 hour to surface. Were coupled. Thereafter, the supernatant was removed. Next, 100 g of colloidal silica particles (Snowtex, manufactured by Nissan Chemical Co., Ltd.) having an average particle diameter of 0.2 μm are added, stirred for 2 hours, allowed to stand for 10 minutes, and then the supernatant is removed and vacuum dried. Surface uneven titanium oxide particles having an average particle size of 0.9 μm on which silica particles having an average particle size of 0.2 μm were adsorbed were obtained.

<Creation of surface convex particles 16>
100 g of zinc oxide particles having an average particle diameter of 0.6 μm (manufactured by Sakai Chemical Industry Co., Ltd.) and 200 g of distilled water are added with 100 g of colloidal silica (Snowtex C, manufactured by Nissan Chemical Industries, Ltd.) having an average particle diameter of 0.02 μm. The mixture was stirred for 2 hours and allowed to stand for 10 minutes, and then the supernatant liquid was removed and vacuum-dried to obtain surface uneven zinc oxide particles having an average particle size of 0.6 μm with silica particles having an average particle size of 0.02 μm adsorbed on the surface. .

<Creation of surface convex particles 17>
To 100 g of styrene latex with an average particle size of 1.6 μm and 100 g of distilled water, add 100 g of colloidal silica (Snowtex C, manufactured by Nissan Chemical Co., Ltd.) with an average particle size of 0.02 μm, and stir for 2 hours. Styrene particles having a convex surface shape with an average particle diameter of 1.6 μm on which silica particles with a diameter of 0.02 μm were adsorbed were obtained.

<Creation of surface convex particles 18>
To 100 g of styrene latex having an average particle size of 6 μm and 100 g of distilled water, 100 g of colloidal silica (Snowtex C, manufactured by Nissan Chemical Co., Ltd.) having an average particle size of 0.02 μm is added and stirred for 2 hours. Styrene particles having a convex surface shape with an average particle diameter of 6 μm adsorbed with 0.02 μm silica particles were obtained.

<Creation of surface convex particles 19>
70% by mass of crosslinked acrylic particles having an average particle diameter of 1.5 μm (MX-150, manufactured by Soken Chemical Co., Ltd.) and 30% by mass of titanium oxide having an average particle diameter of 0.03 μm (STO1, manufactured by Ishihara Sangyo Co., Ltd.) They were combined by a dry agglomeration stirring method in which treatment was performed at 16000 rpm for 5 minutes with a hybridizer.

<Preparation of coating solution for antiglare layer>
An anti-glare layer coating solution (BG-11) was prepared according to the following formulation and stirred to prepare.

{Anti-glare layer coating solution (BG-11) formulation}
Desolite Z7526 (manufactured by JSR Co., Ltd., refractive index 1.51, containing silica ultrafine particle dispersion hard coat liquid (translucent resin)) 100 parts by mass Surface convex particles 11 (refractive index 1.49) 24 parts by mass Surface Convex particles 12 (refractive index 1.44) 6 parts by weight KBM-5103 (manufactured by Shin-Etsu Chemical Co., Ltd., refractive index 1.42, γ-acryloxypropyltrimethoxysilane) 1 part by weight methyl ethyl ketone 32 parts by weight methyl isobutyl 128 parts by weight of ketone

<Coating of antiglare layer, production of light diffusion film>
On the triacetyl cellulose film (manufactured by Fuji Photo Film Co., Ltd., TD-80U), the antiglare layer coating solution (BG-11) is applied so that the coating amount of the surface convex particles 11 is 2 g / m ^2. After coating and solvent drying, the coating layer is cured by irradiating with UV light with an illuminance of 400 mW / cm ² and an irradiation amount of 600 mJ / cm ² using a 180 W / cm air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.). A light diffusion film (A-101) was produced. The antiglare layer dry film thickness of this film was 4.5 μm. The refractive index of the translucent binder was 1.51.

<Preparation of coating solution for low refractive index layer>
The raw materials were prepared according to the following formulation, stirred, and then filtered through a polypropylene filter having a pore size of 1 μm to prepare a coating solution for low refractive index layer (TK-11).

{Formulation of coating liquid for low refractive index layer (TK-11)}
JN-7228 (manufactured by JSR, thermally crosslinkable fluoropolymer, refractive index 1.42, solid content concentration 6% by mass) 100 parts by mass MEK-ST (manufactured by Nissan Chemical Co., Ltd., average particle size 10-20 nm, solid content Concentration 30% by mass, SiO ₂ sol methyl ethyl ketone dispersion) 10 parts by mass Methyl ethyl ketone 35 parts by mass Cyclohexanone 5 parts by mass The following silane coupling sol solution 20 parts by mass

(Preparation of silane coupling sol solution)
After adding 120 parts of methyl ethyl ketone, 100 parts of acryloyloxypropyltrimethoxysilane (KBM5103 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.)) and 4 parts of diisopropoxyaluminum ethyl acetoacetate to a reactor equipped with a stirrer and a reflux condenser. Then, 30 parts of ion-exchanged water was added and reacted at 65 ° C. for 4 hours, followed by cooling to room temperature to obtain a silane coupling sol liquid, having a mass average molecular weight of 1600, and the molecular weight of the components higher than the oligomer component. The component of 1000 to 20000 was 100%, and the raw material acryloyloxypropyltrimethoxysilane did not remain at all from gas chromatography analysis.

  On the anti-glare layer of the light diffusing film (A-101), the above-mentioned coating solution for low refractive index layer (TK-11) is applied using a bar coater, dried at 80 ° C., and further 10 ° C. at 120 ° C. The film was thermally crosslinked for minutes to form a low refractive index layer having a thickness of 0.1 μm, and an antiglare antireflection film (A-101) was produced.

  The surface convex particles are changed as shown in Table 4 to prepare an antiglare layer coating solution in the same manner as the antiglare layer coating solution (BG-11), and the light diffusion film (A-101) and the antiglare layer A light diffusion film and antiglare antireflection films (A-102) to (A-109) were prepared in the same manner as the antiglare antireflection film (A-101).

<Evaluation of antiglare antireflection film>
The following evaluation was performed about the obtained anti-glare antireflection film. The results are shown in Table 5.

(1) Specular reflectivity A spectrophotometer V-550 (manufactured by JASCO Corporation) is equipped with an adapter ARV-474, and in the wavelength region of 380 to 780 nm, the mirror surface has an output angle of -5 degrees at an incident angle of 5 °. The reflectance was measured, the average reflectance of 450 to 650 nm was calculated, and the antireflection property was evaluated.

<Preparation of viewing side polarizing plate>
A polarizing film was prepared by adsorbing iodine to a stretched polyvinyl alcohol film.
The produced antiglare antireflection film (A-101) is subjected to saponification treatment, and the transparent support (triacetylcellulose) of the antiglare antireflection film (A-101) is polarized using a polyvinyl alcohol-based adhesive. It was affixed on one side of the polarizing film so as to be on the film side. The optical compensation film (KH-101) was attached to the opposite side of the polarizing film using a polyvinyl alcohol-based adhesive so that the cellulose acetate film was on the polarizing film side. The transmission axis of the polarizing film and the slow axis of the optical compensation film (KH-101) were arranged in parallel. In this way, an antiglare and antireflection polarizing plate (BHHA-101) was produced.

  The optical compensation film (KH-101) was produced by the method described in paragraphs [0064] to [0076] of JP-A-2002-55230.

  In the same manner as the antiglare antireflection polarizing plate (BHHA-101) was produced, the antiglare antireflection polarizing plate (A-109) was used using the antiglare antireflection films (A-102). BHHA-102) to (BHHA-109) were prepared.

<Preparation of backlight-side polarizing plate>
A polarizing film was prepared by adsorbing iodine to a stretched polyvinyl alcohol film. A commercially available triacetylcellulose film (Fuji Photo Film, Fujitac TD80) was saponified and attached to one side of the polarizing film using a polyvinyl alcohol-based adhesive. Further, the optical compensation film (KH-101) was subjected to saponification treatment and attached to the opposite side using a polyvinyl alcohol adhesive so that the cellulose acetate film was on the polarizing film side. In this way, a backlight side polarizing plate was produced.

<Production of liquid crystal display device>
A pair of polarizing plates provided in a liquid crystal display device (6E-A3, manufactured by Sharp Corporation) using a TN type liquid crystal cell is peeled off, and polarizing plates (BHHA-101) to (BHHA-109) are used instead. Each optical compensation film was affixed to the viewer side via an adhesive so that the liquid crystal cell side would be on the liquid crystal cell side. On the backlight side, a backlight side polarizing plate was attached via an adhesive so that the optical compensation film was on the liquid crystal cell side. The transmission axis of the polarizing plate on the viewer side and the transmission axis of the polarizing plate on the backlight side were arranged to be in the O mode.

<Evaluation of liquid crystal display device>
About the produced liquid crystal display device, the following items were evaluated. The results are shown in Table 5.

(2) Evaluation of antiglare property The produced antiglare antireflection film was mounted on a 15-inch UXGA notebook PC manufactured by DELL Co., Ltd., and a bare fluorescent light (8000 cd / m ² ) without a louver was projected. The degree of blurring of the reflected image was visually evaluated according to the following criteria.

I do not know the outline of the fluorescent lamp at all: ◎
I do not know the outline of the fluorescent lamp well: ○
Slightly understand the outline of the fluorescent lamp: △
Fluorescent lamp clearly understood: ×

(3) Evaluation of glare The produced antiglare antireflection film was mounted on a 15-inch UXGA notebook PC manufactured by DELL Co., Ltd., and glare (brightness variation caused by the lens effect of surface protrusions of the antiglare antireflection film) Was visually evaluated according to the following criteria.

No glare is seen: ◎
Almost no glare seen: ○
There is slight glare: △
There is an unpleasant glare: ×

(4) Viewing angle Using a measuring device (EZ-Contrast 160D, manufactured by ELDIM), the viewing angle was measured in 8 stages from black display (L1) to white display (L8).
The viewing angle was determined in a range where the contrast ratio was 10 or more and no gradation inversion occurred. Black-side gradation inversion was determined by inversion between L1 and L2.

(5) Character blur evaluation The produced anti-glare antireflection film was mounted on a 15-inch UXGA notebook PC manufactured by DEL Co., Ltd., and the degree of character blur was evaluated according to the following criteria.

No character blur is seen: ◎
Almost no character blur is seen: ○
Slight character blurring: △
There is character blur: ×

From the results of Table 5, the following was found.
A display device with a polarizing plate using an antiglare antireflection film prepared by using fine particles having a convex shape on the surface of the present invention as translucent fine particles of the antiglare layer has excellent antireflection properties, In addition to its wide viewing angle, it was confirmed that it was extremely excellent in the difficulty of reflecting outside light (anti-glare property), and it was also excellent in glare and letter blurring.

Example 5
<Creation of surface convex particles 20>
To 100 g of crosslinked polystyrene particles having an average particle diameter of 16 μm and 100 g of distilled water, 100 g of colloidal silica (Snowtex, manufactured by Nissan Chemical Industries, Ltd.) having an average particle diameter of 0.2 μm is added and stirred for 2 hours. Cross-linked polystyrene particles having a convex surface with an average particle diameter of 16.2 μm on which silica particles of 2 μm were adsorbed were obtained.

<Creation of surface convex particles 21>
200 g of titanium oxide powder (Wako Pure Chemical Industries, Ltd., rutile type, average particle size 0.42 μm) was mixed in 600 g of 0.1 N aqueous silver nitrate solution and irradiated with a 100 w high-pressure mercury lamp through a Pyrex filter for 3 minutes while stirring. did. Thereafter, the particles are filtered, washed with 1 liter of water, and dried to deposit metal silver having an average particle size of 0.02 μm on the particle surface to obtain titanium oxide particles having a convex surface shape with an average particle size of 0.45 μm. It was.

<Creation of surface convex particles 22>
200 g of zinc oxide powder (manufactured by Sakai Chemical Co., Ltd., average particle size 0.38 μm) was mixed in 600 g of a 0.1 N silver nitrate aqueous solution, and irradiated with a 100 w high pressure mercury lamp through a Pyrex filter for 2 minutes while stirring. Thereafter, the particles are filtered, washed with 1 liter of water, and dried to deposit metal silver having an average particle size of 0.02 μm on the particle surface, thereby obtaining zinc oxide particles having a convex surface shape having an average particle size of 0.42 μm. It was.

  The antiglare layer coating liquid was prepared in the same manner as in Example 4 by changing the thickness of the antiglare layer and the fine particles having convex shapes on the surface as shown in Table 6, and the antiglare antireflection film (B-101) was prepared. ) To (B-105) were prepared and evaluated in the same manner as in Example 4. The results are shown in Table 7.

  A display device to which a polarizing plate using an anti-glare antireflection film prepared by using the convex particles of the present invention as a light-transmitting fine particle of an anti-glare layer is excellent in anti-reflection and its viewing angle is Although it was not widely applicable to the present invention described in Example 4, it was confirmed that the external light was difficult to be reflected (antiglare property) and no glare or character blur was observed.

It is a cross-sectional schematic diagram which shows the basic composition of the optical functional film of this invention. It is a cross-sectional schematic diagram which shows the basic composition of an anti-glare film.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Hard coat film 2 Transparent support 3 Hard coat layer 4 Curable resin 5 Surface convex particle 11 Anti-glare film 12 Transparent support 13 Anti-glare layer 14 Low refractive index layer 15 Translucent fine particle (anti-glare particle) )
16 Translucent fine particles (internal scattering particles)

Claims (10)

  In an optical functional film having at least one optical functional layer in which at least translucent fine particles are dispersed in a binder resin on a transparent support, fine particles having a fine convex shape on the particle surface are used as the translucent fine particles. An optical functional film characterized by containing.   The ratio of the surface area of the translucent fine particles to the surface area of the enveloping surface smoothly surrounded by the enveloping surface so that the translucent fine particles are in contact with the convex portions of the particles is 1.1 times or more. The optical functional film according to claim 1.   3. The optical functional film according to claim 1, wherein the translucent fine particles are obtained by fixing fine particles on the surface of spherical particles (core particles).   4. The optical functional film according to claim 3, wherein the size of the fine particles fixed on the surface is 1/3 or less of the core particle size.   The optical functional film according to any one of claims 1 to 4, wherein the translucent fine particles have an average particle size of 0.4 to 20 µm, and the optical functional layer has a hard coat property.   The optical functional film according to any one of claims 1 to 5, wherein the translucent fine particles have an average particle size of 0.4 to 20 µm, and the optical functional layer has an antiglare property.   A low refractive index layer having a lower refractive index than an adjacent layer on the optical functional layer having hard coat properties according to claim 5 or on the optical functional layer having antiglare properties according to claim 6. An optical functional film characterized by having antireflection properties.   The average particle diameter of the translucent fine particles is 0.005 to 0.1 μm, and the optical functional layer has antireflection properties, any one of claims 1 to 4 and claim 7 An optical functional film according to claim 1.   The polarizing plate which clamped both surfaces of the polarizer with the protective film, At least one of a protective film is the optical functional film in any one of Claims 1-8, The polarizing plate characterized by the above-mentioned.   An image display device comprising the optical functional film according to claim 1 or the polarizing plate according to claim 9.

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