WO2008010376A1 - Anti-reflection film - Google Patents

Abstract

An anti-reflection film comprising a transparent substrate and at least a low-refractive-index layer provided on the substrate directly or through other layer, wherein the low-refractive-index layer comprises at least two silica microparticles, one of the silica microparticles is a hollow silica microparticle having a porous or hollow interior, another one of the silica microparticles is colloidal silica having an average particle diameter of not less than 1.1 times and less than 20 times that of the hollow silica microparticles, and the outermost surface of the film has an arithmetic average roughness (Ra) of not less than 40 and less than 500 nm.

Description

 Antireflection film

 Technical field

 The present invention relates to an antireflection film, and more particularly to an antireflection film having excellent visibility when used in a display device having excellent scratch resistance and low reflectance.

 Background art

 [0002] For an antireflection film used on the outermost surface of an image display device such as a liquid crystal, a technique has been proposed in which an optical interference type antireflection layer is provided to achieve low reflectance.

 [0003] As a technique for reducing the reflectance, there is a method of reducing the refractive index of the low refractive index layer on the outermost surface, and a low refractive index material or a method of reducing the refractive index by increasing the number of voids has been proposed. However, both technologies are weak in film strength and scratch resistance.

 [0004] A recently proposed technique using hollow silica-based fine particles having a porous or hollow interior (see, for example, Patent Documents 1 to 3) is capable of maintaining film strength while maintaining a decrease in refractive index due to voids. It is a technology to improve. Nevertheless, the film strength is insufficient, and there is a problem that the low refractive index layer containing 20 mass% or more of hollow silica-based fine particles decreases to a practical film strength or less. In addition, dispersions of hollow silica-based fine particles vary in pH between lots, and as a result, variations in the viscosity of the low refractive index layer coating composition occur immediately. In the meantime, alkali components such as ammonia are eluted from the inside of the hollow silica fine particles, and there is a problem that the viscosity of the low refractive index layer coating composition fluctuates (increases).

 [0005] In addition, a method of forming a metal oxide film by applying a metal alkoxide represented by titanium alkoxide or silane alkoxide on the surface of a support, drying, and heating has been performed. However, this method requires a high heating temperature of 300 ° C or higher and damages the support, and the heating temperature as described in JP-A-8-75904 is relatively high at 100 ° C. The low method required a long time for production, and both had problems.

On the other hand, as a method of forming a metal oxide film, for example, a method of forming a silica-based film as a base film of a functional film by a so-called sol-gel method (see Patent Document 4), A method of forming a refractive index layer by the same Norgel method (see Patent Document 5) is known. However, this method also had insufficient scratch resistance.

 In addition, techniques using fluorine-based resin as a binder component (see, for example, Patent Documents 6 to 8) also have a problem that the film strength is weak although the refractive index is lowered. That is, there is a trade-off between lowering the refractive index and film strength, and there is a need for improvement.

 Patent Document 1 Japanese Patent Application Laid-Open No. 2001-167637

 Patent Document 2 JP 2001--233611 A

 Patent Document 3 Japanese Unexamined Patent Application Publication No. 2002- — 79616

 Patent Document 4 Japanese Patent Laid-Open No. 11-269657

 Patent Document 5 Japanese Patent Laid-Open No. 2000-910

 Patent Document 6 Japanese Unexamined Patent Application Publication No. 2003--236970

 Patent Document 7 JP2003--240906

 Patent Document 8 JP 2003-255103 A

 Disclosure of the invention

 Problems to be solved by the invention

 [0008] The present invention has been made in view of the above problems, and an object thereof is to provide an antireflection film having excellent visibility when used in a display device having excellent scratch resistance and low reflectivity. It is in.

 Means for solving the problem

[0009] The above object of the present invention is achieved by the following constitution.

 1. In an antireflection film having at least a low refractive index layer directly or via another layer on a transparent support, the low refractive index layer contains at least two types of silica fine particles, one of which The silica fine particles are hollow silica fine particles whose inside is porous or hollow, and the other one kind of silica fine particles is colloidal silica. The average particle diameter of the colloidal silica is the average particle diameter of the hollow silica fine particles. 1.1 to less than 20 times, and the arithmetic average roughness (Ra) of the outermost surface is less than 40 to 500 nm.

2. Having a hard coat layer and a low refractive index layer on a transparent support, the surface of the hard coat layer 2. The antireflection film as described in 1 above, wherein the arithmetic average roughness (Ra) is 60 to less than 700 nm.

 3. The antireflection film as described in 1 or 2 above, wherein the surface of the transparent support has an arithmetic average roughness (Ra) of 50 to less than LOOOnm.

 4. The antireflection film as described in any one of 1 to 3 above, wherein the hard coat layer contains fluorine-containing acrylic resin fine particles.

 The invention's effect

 [0010] According to the present invention, it is possible to provide an antireflection film excellent in visibility when used in a display device having excellent scratch resistance and low reflectance.

 Brief Description of Drawings

FIG. 1 is a schematic view of an uneven surface forming apparatus using an uneven roller.

 FIG. 2 is a schematic view of an uneven surface forming apparatus in a drying apparatus.

 FIG. 3 is a schematic view showing an example of a single-frequency high-frequency voltage application type thin film forming apparatus useful for the present invention.

 4] A schematic view showing an example of a thin-film forming apparatus of a two-frequency high-frequency voltage application method useful for the present invention.

 FIG. 5 is a perspective view showing an example of the structure of a conductive metallic base material of a roll electrode and a dielectric material coated thereon.

 FIG. 6 is a perspective view showing an example of the structure of a conductive metallic base material of a rectangular tube electrode and a dielectric material coated thereon.

 Explanation of symbols

[0012] F base film

 G discharge gas

 G 'excited discharge gas

 P liquid pump

 1 die

 2 Casting belt

3, 3 'uneven roller Noc Ronore

Tenter

Film drying device

Thatch roll

 Static eliminator a Roll electrode

A, 36A Metallic base material A., 36B Dielectric

a Square tube electrode

0 Atmospheric pressure plasma treatment device 1 Atmospheric pressure plasma treatment vessel 2 Discharge space

5 Roll electrode (first electrode) 6 Square tube electrode group (second electrode) 0 Electric field application means

1 First power supply

2 Second power supply

3 First filter

4 Second filter

0 Gas supply means

1 Gas generator

2 ¼ port

3 Exhaust port

0 Electrode temperature control means 1 Piping

4, 167 Guide roll 5, 166-Pup roll 8, 169 Partition plate BEST MODE FOR CARRYING OUT THE INVENTION

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

 [0014] Conventionally, there is a technique of using hollow silica-based fine particles in the low refractive index layer in order to reduce the reflectance. To further reduce the reflectance by this method, the content of the hollow silica-based fine particles is increased. It was necessary. However, since the hollow silica fine particles are easily broken by external pressure, the surface properties, particularly the surface hardness, of the antireflection film are lowered.

 As a result of intensive studies, the present inventor has found that the antireflective film having at least a low refractive index layer on the transparent support directly or via another layer has a specific type and a specific type in the low refractive index layer. It has been found that the reflectance can be reduced by reducing the surface hardness of the antireflection film by containing silica fine particles having different particle diameters.

 [0016] Surprisingly, mixing the different types of silica fine particles has a greater effect on reducing the reflectance and not the surface hardness, rather than increasing the content of one type of hollow silica fine particles. The other layers are various functional layers such as a hard coat layer and a high refractive index layer described later.

 [0017] The mechanism by which such effects are manifested is presumed as follows. By reducing the content of hollow silica-based fine particles that reduce surface properties, especially surface hardness, and using colloidal silica that is difficult to reduce surface hardness, the surface hardness of the antireflection film is prevented from decreasing. Moreover, by including silica fine particles of different types and particle sizes, voids are formed in the dried coating film, and the refractive index is reduced. Antiglare base material (An arithmetic average roughness (Ra) of the surface of the transparent support is from 50 to less than LOOOnm, or a hard coat layer on the transparent support, and the hard coat When the anti-reflection layer is formed on the anti-glare film having an arithmetic average roughness (Ra) force of less than ½0 to 700 nm on the surface of the layer, the average particle size is larger than the average particle size of the hollow silica-based fine particles. When colloidal silica is mixed, repelling during drying is hindered, resulting in a substantially uniform film thickness and a reduced refractive index. At the same time, the anti-glare irregularities are preserved on the outermost surface of the anti-reflection film so that the anti-glare property is not impaired!

 [0018] Hereinafter, the present invention will be described in detail.

 [Low refractive index layer]

The refractive index of the low refractive index layer according to the present invention is lower than the refractive index of the transparent support that is the support. , twenty three. C, wavelength 550nm 1.30 ~: L 45 range power ^ Preferred! / ヽ.

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

 [0021] The composition for forming a low refractive index layer used in the present invention contains at least two types of silica fine particles, and one type of silica fine particles is hollow silica-based fine particles whose inside is porous or hollow. The other kind of silica fine particles is colloidal silica, and the average particle size of the colloidal silica is 1.1 to less than 20 times the average particle size of the hollow silica fine particles.

 [0022] (Hollow silica fine particles)

 The hollow silica-based fine particles (hereinafter also simply referred to as hollow fine particles) in which the inside is porous or hollow will be described.

 [0023] The hollow fine particles are: (I) composite particles composed of porous particles and a coating layer provided on the surface of the porous particles, or (II) hollow inside, and the contents are a solvent, gas Or hollow particles filled with a porous material.

 [0024] The cavity particles are particles having a cavity inside, and the cavity is surrounded by a particle wall.

 The cavity is filled with contents such as a solvent, a gas, or a porous material used at the time of preparation. The average particle size of such hollow fine particles is 5 to 200 nm, preferably 10 to 70 nm. The particle size of the hollow microparticles is preferably monodisperse with a coefficient of variation of ~ 40%. The average particle diameter can be measured from an electron micrograph taken with a scanning electron microscope (SEM) or the like. It may be measured by a particle size distribution meter using a dynamic light scattering method or a static light scattering method. The average particle diameter of the hollow fine particles to be used is appropriately selected according to the thickness of the transparent film of the low refractive index layer to be formed, and the film thickness of the transparent film is preferably 2Z3 to LZ10. These hollow fine particles are preferably used in a state of being dispersed in an appropriate medium in order to form a low refractive index layer. As the dispersion medium, water, alcohol (for example, methanol, ethanol, isopropyl alcohol), ketone (for example, methyl ethyl ketone, methyl isobutyl ketone), and ketone alcohol (for example, diacetone alcohol) are preferable.

[0025] The thickness of the coating layer of the composite particles or the thickness of the particle walls of the hollow particles is 1 to 20 nm, preferably 2 to 15 nm. For composite particles, if the coating layer thickness is less than lnm, In some cases, the coating cannot be completely covered, and the coating liquid component easily enters the inside of the composite particles, reducing the internal porosity, and the effect of lowering the refractive index may not be sufficiently obtained. The If the thickness of the coating layer exceeds 20 nm, the coating liquid component does not enter the interior, but the porosity (pore volume) of the composite particles is reduced, and the effect of lowering the refractive index is sufficiently obtained. It may disappear. In the case of hollow particles, if the particle wall thickness is less than 1 nm, the particle shape may not be maintained, and even if the thickness exceeds 20 nm, the effect of lowering the refractive index may not be sufficiently exhibited. is there.

[0026] The coating layer of the composite particles or the particle wall of the hollow particles preferably contains silica as a main component. In addition, specific components other than silica may be included. Al O, B 2 O, TiO

 2 3 2 3 2

ZrO, SnO, CeO, PO, SbO, MoO, ZnO, WO and the like. Composite grain

2 2 2 2 3 2 3 3 2 3

 Examples of the porous particles constituting the core include those made of silica, those made of silica and inorganic compounds other than silica, and those made of CaF, NaF, NaAlF, MgF, and the like. this

 2 6

 Of these, porous particles having a complex acidity of silica and an inorganic compound other than silica are particularly preferable. Inorganic compounds other than silica include Al 2 O, B 2 O, TiO, ZrO, SnO, and CeO.

 2 3 2 3 2 2 2 2

, PO, SbO, MoO, ZnO, WO, etc.

2 3 2 3 3 2 3

 . In such porous particles, silica is represented by SiO, and inorganic compounds other than silica are oxidized.

 2

 Molar ratio expressed in terms of product (MO) MO / SiO force 0.0001 ~: L 0, preferably 0

 X X 2

 It is desirable to be in the range of 001 to 0.3. The molar ratio of porous particles MO / SiO is 0.0.

 X 2

It is difficult to obtain particles less than 001, and even if obtained, particles having a small pore volume and a low refractive index cannot be obtained. Also, the molar ratio of porous particles MO / SiO force exceeds 1.0

 X 2

 If the ratio of silica is reduced, the pore volume is increased, and it may be difficult to obtain a material having a lower refractive index.

 [0027] The pore volume of such porous particles is desirably in the range of 0.1 to 1.5 ml Zg, preferably 0.2 to 1.5 ml Zg. If the pore volume is less than 0.1 mlZg, particles having a sufficiently low refractive index cannot be obtained, and if it exceeds 1.5 mlZg, the strength of the fine particles may be lowered, and the strength of the resulting film may be lowered.

[0028] The pore volume of such porous particles can be determined by a mercury intrusion method. The contents of the hollow particles include the solvent, gas, and porous material used during the preparation of the particles. Quality and so on. The solvent may contain an unreacted particle precursor used in preparing the hollow particles, the catalyst used, and the like. Examples of the porous substance include those having the compound power exemplified in the porous particles. These contents can be a single component force or a mixture of multiple components.

 [0029] As a method for producing such hollow fine particles, for example, the method for preparing composite oxide colloidal particles disclosed in Step Nos. [0010] to [0033] of JP-A-7-133105 is preferably employed. The Specifically, when the composite particles are composed of silica and an inorganic compound other than silica, the following first to third step force hollow fine particles are produced.

 [0030] Step 1: Preparation of porous particle precursor

 In the first step, the ability to individually prepare an alkaline aqueous solution of a silica raw material and an inorganic compound raw material other than silica is prepared in advance, or a mixed water solution of a silica raw material and an inorganic compound raw material other than silica is prepared in advance. According to the composite ratio of the target composite oxide, the porous particle precursor is prepared by gradually adding it to an aqueous alkali solution having a pH of 10 or more while stirring.

 [0031] As a silica raw material, an alkali metal, ammonium or an organic base silicate is used. As the alkali metal silicate, sodium silicate (water glass) or potassium silicate is used. Examples of organic bases include quaternary ammonium salts such as tetraethyl ammonium salts, and amines such as monoethanolamine, diethanolamine, and triethanolamine. For the ammonium silicate or organic base silicate, an alkaline solution in which ammonia, a quaternary ammonium hydroxide, an amine compound, or the like is added to the key acid solution. Sex solutions are also included.

[0032] Further, as a raw material for inorganic compounds other than silica, alkali-soluble inorganic compounds are used. Specifically, elemental oxoacids selected from Al, B, Ti, Zr, Sn, Ce, P, Sb, Mo, Zn, W, etc., alkali metal salts or alkaline earth metal salts of the oxoacids, ammonia -Um salt, quaternary ammonia salt. More specifically, sodium aluminate, sodium tetraborate, zirconyl ammonium carbonate, potassium antimonate, potassium stannate, sodium aluminosilicate, sodium molybdate, cerium ammonium nitrate, sodium phosphate Is appropriate. [0033] A force that changes the pH value of the mixed aqueous solution simultaneously with the addition of these aqueous solutions. There is no particular need for an operation for controlling the pH value within a predetermined range. The aqueous solution finally has a pH value determined by the type of inorganic oxide and its mixing ratio. There is no particular limitation on the addition rate of the aqueous solution at this time. Further, in the production of composite oxide particles, a dispersion of seed particles can be used as a starting material. The seed particles are not particularly limited. Inorganic oxides such as SiO, Al 2 O, TiO or ZrO or fine particles of these composite oxides

2 2 3 2 2

 Particles are used, and usually these sols can be used. Furthermore, the porous particle precursor dispersion obtained by the above production method may be used as a seed particle dispersion. When using a seed particle dispersion, adjust the pH of the seed particle dispersion to 10 or higher, and then add the aqueous solution of the compound to the seed particle dispersion while stirring into the alkaline aqueous solution. To do. In this case, it is not always necessary to control the pH of the dispersion. When seed particles are used in this way, it is easy to control the particle size of the porous particles to be prepared, and particles with uniform particle sizes can be obtained.

 [0034] The silica raw material and the inorganic compound raw material described above have high solubility on the alkali side. However, when both are mixed in this highly soluble pH range, the solubility of oxalate ions such as silicate and aluminate ions decreases, and these composites precipitate and grow into fine particles. Alternatively, the particles grow on the seed particles by precipitation. Therefore, it is not always necessary to perform pH control as in the conventional method for precipitation and growth of fine particles.

 [0035] The composite ratio of silica and inorganic compound other than silica in the first step is calculated by converting the inorganic compound to silica into an oxide (MO), and the molar ratio of MO / SiO is 0.05 to 2.0.

 X X 2

 It is desirable that it is within the range of 0.2 to 2.0. Within this range, the smaller the proportion of silica, the greater the pore volume of the porous particles. However, even if the molar ratio exceeds 2.0, the pore volume of the porous particles hardly increases. On the other hand, when the molar ratio is less than 0.05, the pore volume becomes small. When preparing hollow particles, MO / SiO

 X 2 Nore it should be within the range of 0.25-2.0! /.

[0036] Second step: removal of inorganic compounds other than silica from the porous particles

In the second step, at least a part of inorganic compounds other than silica (elements other than silicon and oxygen) is selectively removed from the porous particle precursor obtained in the first step. Specific removal As the leaving method, the inorganic compound in the porous particle precursor is dissolved and removed using mineral acid or organic acid, or is contacted with a cation exchange resin for ion exchange removal.

 [0037] The porous particle precursor obtained in the first step is a particle having a network structure in which silicon and an inorganic compound constituent element are bonded via oxygen. In this way, porous particles having a larger pore volume can be obtained by removing the inorganic compound (elements other than silicon and oxygen) from the porous particle precursor force. Further, if the amount of the porous particle precursor strength inorganic oxide (elements other than silicon and oxygen) is increased, the hollow particles can be prepared.

 [0038] Further, the porous particle precursor force can also be obtained by removing alkali metal salt of silica from the porous particle precursor dispersion obtained in the first step prior to removing inorganic compounds other than silica. It is preferable to form a silica protective film by adding a caustic acid solution containing a fluorine-substituted alkyl group-containing silane compound or a hydrolyzable organosilicon compound. The thickness of the silica protective film may be 0.5 to 15 nm. Even if a silica protective film is formed, the protective film in this step is porous and thin, so it is possible to remove the inorganic compound other than the above-described silica with the porous particle precursor force. is there.

 [0039] By forming such a silica protective film, the porous particle precursor force can be removed from inorganic compounds other than silica as described above while maintaining the particle shape. Further, when forming the silica coating layer described later, the pores of the porous particles are not blocked by the coating layer, so that the silica coating layer described later is formed without reducing the pore volume. be able to. If the amount of the inorganic compound to be removed is small, the particles will not break! /, So it is not always necessary to form a protective film.

 [0040] When preparing hollow particles, it is desirable to form this silica protective film.

 When preparing the hollow particles, the inorganic compound is removed to obtain a hollow particle precursor composed of a silica protective film, a solvent in the silica protective film, and an undissolved porous solid content. When a coating layer, which will be described later, is formed on the particle precursor, the formed coating layer becomes a particle wall to form hollow particles.

[0041] The amount of the silica source added for forming the silica protective film is preferably small as long as the particle shape can be maintained. If the amount of the silica source is too large, the silica protective film becomes too thick, so it becomes difficult to remove inorganic compounds other than the porous particle precursor force silica. Sometimes. The hydrolyzable organosilicon compound used for forming the silica protective film includes a general formula R Si (OR ') [R,: alkyl group, aryl group, bur group, acrylic group, etc.

 n 4-n

 Or an alkoxysilane represented by n = 0, 1, 2, or 3]. In particular, tetraalkoxysilanes such as fluorine-substituted tetramethoxysilane, tetraethoxysilane, and tetraisopropoxysilane are preferably used.

[0042] As an addition method, a solution obtained by adding a small amount of alkali or acid as a catalyst to a mixed solution of these alkoxysilanes, pure water, and alcohol is added to the dispersion of the porous particles to hydrolyze the alkoxysilane. The keyed acid polymer produced by decomposition is deposited on the surface of inorganic oxide particles. At this time, alkoxysilane, alcohol and catalyst may be simultaneously added to the dispersion. As the alkali catalyst, ammonia, an alkali metal hydroxide, or an amine can be used. As the acid catalyst, various inorganic acids and organic acids can be used.

 [0043] When the dispersion medium of the porous particle precursor is water alone or when the ratio of water to the organic solvent is high, it is possible to form a silica protective film using a caustic acid solution. In the case of using a key acid solution, a predetermined amount of the key acid solution is added to the dispersion, and at the same time an alkali is added to deposit the key acid solution on the surface of the porous particles. In addition, a silica protective film may be produced by using a combination of a key acid solution and the above alkoxysilane! /.

 [0044] Third step: formation of a silica coating layer

 In the third step, a hydrolyzable organosilicon compound containing a fluorine-substituted alkyl group-containing silane compound or a porous particle dispersion prepared in the second step (a hollow particle precursor dispersion in the case of hollow particles) or By adding a key acid solution or the like, the surface of the particles is coated with a hydrolyzable organosilicon compound or a polymer such as a key acid solution to form a silica coating layer.

 [0045] The hydrolyzable organosilicon compound used for forming the silica coating layer includes the general formula R Si (OR ') [R,: alkyl group, aryl group, bur group, acrylic group as described above.

 n 4-n

 A hydrocarbon group such as a group, and alkoxysilanes represented by n = 0, 1, 2 or 3] can be used. In particular, tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, and tetraisopropoxysilane are preferably used.

[0046] As an addition method, a mixed solution of these alkoxysilanes, pure water, and alcohol Touch

 A solution obtained by adding a small amount of alkali or acid as a medium to the above-described dispersion of porous particles (cavity particle precursor in the case of hollow particles) and hydrolyzing alkoxysilane is used to form a porous polymer. It is deposited on the surface of the particles (in the case of hollow particles, the hollow particle precursor). At this time, alkoxysilane, alcohol, and catalyst may be simultaneously added to the dispersion. As the alkali catalyst, ammonia, an alkali metal hydroxide or an amine can be used. As the acid catalyst, various inorganic acids and organic acids can be used.

 [0047] In the case where the dispersion medium of porous particles (in the case of hollow particles, the hollow particle precursor) is water alone or a mixed solvent with an organic solvent, and the ratio of water to the organic solvent is high! May form a coating layer using a caustic acid solution. The key acid solution is an aqueous solution of a low-polymerization product of key acid obtained by dealkalizing an aqueous solution of an alkali metal silicate such as water glass by ion exchange treatment.

 [0048] The caustic acid solution is added to the dispersion of porous particles (in the case of hollow particles, hollow particle precursors), and at the same time, alkali is added to lower the key acid low polymer to the porous particles (in the case of hollow particles). Cavity is deposited on the particle precursor surface. A caustic acid solution may be used in combination with the above alkoxysilane for forming a coating layer. The addition amount of the organosilicon compound or the caustic acid solution used for forming the coating layer is sufficient if the surface of the colloidal particles can be sufficiently covered. It is added in an amount of 20 nm in a dispersion of porous particles (in the case of hollow particles, hollow particle precursor). When the silica protective film is formed, the organosilicon compound or the caustic acid solution is added in such an amount that the total thickness force of the silica protective film and the silica coating layer is in the range of 20 nm to 20 nm.

 [0049] Next, the dispersion liquid of the particles on which the coating layer is formed is heat-treated. By the heat treatment, in the case of porous particles, the silica coating layer covering the surface of the porous particles is densified, and a dispersion of composite particles in which the porous particles are coated with the silica coating layer is obtained. In the case of a hollow particle precursor, the formed coating layer is densified to become hollow particle walls, and a dispersion of hollow particles having cavities filled with a solvent, gas, or porous solid content is obtained.

[0050] The heat treatment temperature at this time is not particularly limited as long as it can close the fine pores of the silica coating layer. A range of 80 to 300 ° C is preferable. When the heat treatment temperature is less than 80 ° C, the fine pores of the silica coating layer may not be completely closed and densified, and the treatment time may take a long time. In addition, when the heat treatment temperature exceeds 300 ° C for a long time, fine particles may be formed, and the effect of low refractive index may not be obtained.

 [0051] The refractive index of the inorganic fine particles thus obtained is as low as less than 1.42. Such an inorganic fine particle is presumed to have a low refractive index because the inside of the porous particle is hollow and the inside of the force is hollow.

 [0052] The content of the hollow fine particles having a porous or hollow interior in the low refractive index layer is preferably 10 to 40% by mass. In order to obtain the effect of lowering the refractive index, 15% by mass or more is preferable. If it exceeds 40% by mass, the binder component decreases and the film strength becomes insufficient. Especially preferably, it is 20-40 mass%.

 [0053] (Colloidal silica)

 The colloidal silica used in the present invention is a colloidal dispersion of water and organic solvent in a colloidal form, and is spherical, acicular or beaded. The average particle size of the colloidal silica needs to be 1.1 to less than 20 times the average particle size of the hollow fine particles, and preferably 1.5 to 5.0 times. Therefore, the average particle diameter of colloidal silica is preferably in the range of 50 to 300 nm. The particle size of colloidal silica is preferably monodispersed with a coefficient of variation of 1 to 40%. The average particle diameter can also be measured by photographic power of an electron microscope using a scanning electron microscope (SEM) or the like. It may be measured by a particle size distribution meter using a dynamic light scattering method or a static light scattering method. However, the same measurement method must be used to determine the ratio between the average particle size of colloidal silica and the average particle size of hollow particles! /.

[0054] Such colloidal silica used in the present invention is commercially available. For example, a snow tex series manufactured by Nissan Chemical Industries, a cataloid S series manufactured by Catalytic Co., Ltd., a rebacil series manufactured by Bayer, etc. Can be mentioned. Further, colloidal silica cation-modified with alumina sol or aluminum hydroxide, or bead-like colloidal silica in which primary particles of silica are connected in a bead-like manner by connecting particles with metal ions having a valence of 2 or more is also preferably used. There are rosary colloidal silicas, such as the Snowtex AK series, Snowtex-PS series, and Snowtex UP series from Nissan Chemical Industries. [0055] The content of colloidal silica in the low refractive index layer is preferably 30 to 60 mass% with respect to the solid content in the low refractive index layer. In order to obtain the effect of lowering the refractive index, 30% by mass or more is preferable. If it exceeds 40% by mass, the binder component decreases and the film strength becomes insufficient.

 [0056] The content ratio between the hollow fine particles and the colloidal silica in the low refractive index layer is selected from the viewpoint of the reflectance reduction effect and the surface hardness, but is preferably in the range of 1: 0.1 to 10: 1: 0.8. ~ 5 is more preferred

[0057] (Binder)

 The low refractive index layer preferably contains 5 to 80% by mass of binder as a whole. The binder 1 has a function of adhering silica fine particles and maintaining the structure of a low refractive index layer including voids. The amount of the binder used is adjusted so that the strength of the low refractive index layer can be maintained without filling the voids. Examples of the binder include an organosilicon compound represented by the following general formula (1), a hydrolyzate thereof, or a polycondensate thereof.

 [0058] General formula (1) Si (OR)

 Four

 In the formula, R is an alkyl group, preferably an alkyl group having 1 to 4 carbon atoms. As specific compound compounds, tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane and the like are preferably used.

[0059] Further, the low refractive index layer may contain a silane coupling agent as a binder! Examples of silane coupling agents include methyltrimethoxysilane, methyltriethoxysilane, methyltrimethoxyethoxysilane, methyltriacetoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, butyltrimethoxysilane. , Butyltrioxysilane, vinyltriacetoxysilane, vinyltrimethoxyethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriacetoxysilane, γ-black propyltrimethoxysilane, γ-black propyltriethoxysilane , Γ-chloropropyl propyltriacetoxysilane, 3, 3, 3-trifluoropropyltrimethoxysilane, γ-glycidyl β-glycidinole oxyethoxy) propinoretrimethoxysila , 13 (3, 4 Eposhishishiku port hexyl) E trimethoxysilane, j8 (3, 4-epoxycyclohexyl) Echiruto triethoxysilane, _Y - Atari Roy Ruo trimethoxysilane, _Y - methacryloyl Luoxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, Ν- β- (aminoethyl) γ— Examples include aminopropyltrimethoxysilane and j8-cyanethyltriethoxysilane.

[0060] In addition, examples of silane coupling agents having a disubstituted alkyl group with respect to silicon include dimethylenoresimethoxysilane, pheninolemethinoresimethoxymethoxysilane, dimethylenolegetoxysilane, and phenenolemethinolegetoxy. Silane, _{グ リ} -Glycidinore _{xyloxypropenolemethino} lesoxy silane _Lufenyl oxyoxy silane, γ-chloropropyl methoxy silane, dimethyl diacetoxy silane, γ-Ataryl oxypropyl methyl dimethoxy silane, γ- attayloxy propyl methyl Getoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, γ-methacryloyloxypropylmethyljetoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ mercaptopropylmethyljetoxy Run-, .gamma. § amino propyl methyl dimethoxy silane, .gamma. § amino propyl methyl jet Kishishi run, Mechirubi - dimethoxysilane and Mechirubi - Rougier butoxy silane.

[0061] Of these, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, vinyltrimethoxyethoxysilane, γ-atarylloyoxypropyltrimethoxysilane and γ-methacryloyloxy having a double bond in the molecule. Propyltrimethoxysilane, which has a disubstituted alkyl group with respect to silicon, γ-Ataryloxypropyl propylmethyldimethoxysilane, γ Ataryloxypropylmethyl jetoxysilane, oral pyrmethylmethoxysilane, methylbiphenyl two dimethoxysilane and Mechirubi two Rujeto Kishishiran is preferred instrument y- Atari Roy Ruo trimethoxysilane and γ- methacryloyloxy Ruo _{trimethoxysilane,} Ί - Atari Roy Ruo carboxypropyl methyl dimethacrylate Toki Silane, .gamma. Atari Roy Ruo carboxypropyl methyl jet silane, .gamma. methacrylonitrile I Ruo propyl methyl dimethoxy silane and .gamma.-methacryloyloxy Ruo propyl methylol Rougier butoxy silane is particularly preferred.

[0062] Two or more types of coupling agents may be used in combination. Silane coupling agent shown above In addition to the above, other silane coupling agents may be used. Other silane coupling agents include alkyl esters of orthokeys (eg, methyl orthokeate, ethyl orthokete, n-propyl orthokeate, i-propyl orthokeate, n-butyl orthokeate, sec-butyl orthokeate, orthokeate t -Butyl) and hydrolysates thereof.

[0063] Other binders for the low refractive index layer include, for example, polybutyl alcohol, polyoxyethylene, polymethyl methacrylate, polymethyl acrylate, diacetyl cellulose, triacetyl cellulose, nitrocellulose, polyester, alkyd Fats are listed.

 [0064] (Solvent)

 The low refractive index layer coating composition according to the present invention preferably contains an organic solvent. Specific examples of organic solvents include alcohols (eg, methanol, ethanol, isopropanol, butanol, benzyl alcohol), ketones (eg, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone), esters ( Examples: methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl formate, ethyl formate, propyl formate, butyl formate), aliphatic hydrocarbons (eg, hexane, cyclohexane), halogenated hydrocarbons (eg , Methylene chloride, chloroform, carbon tetrachloride), aromatic hydrocarbons (eg, benzene, toluene, xylene), amides (eg, dimethylformamide, dimethylacetamide, n-methylpyrrolidone), ethers (eg, , Jetyl ether, Dioxane, Tetrahydrate mouth furan), Ether alcohol Example, 1-methoxy - 2-propanol) and the like. Of these, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and butanol are particularly preferable.

 [0065] The solid content concentration in the low refractive index layer coating composition is preferably 1 to 4% by mass, and when the solid content concentration is 4% by mass or less, uneven coating is less likely to occur. By making it 1% by mass or more, the drying load is reduced.

[0066] (Fluorine-based or silicone surfactant)

The low refractive index layer preferably contains a fluorine type or silicone type surfactant. Inclusion of the surfactant is effective for reducing coating unevenness and improving the antifouling property of the film surface. [0067] Fluorosurfactants include monomers, oligomers, and polymers containing perfluoroalkyl groups as the core, and are polyoxyethylene alkyl ether, polyoxyethylene alkylaryl ether, polyoxyethylene. And the like.

 [0068] Commercially available fluorosurfactants can also be used. For example, Surflon "S-381", "S-382", "SC-101", "SC-102", "SC-103", " SC-104 (all manufactured by Asahi Glass Co., Ltd.), FLORARD “FC-430”, “FC-431”, “FC-173” (all fluorochemicals—manufactured by Sumitomo 3EM), F-top “EF352”, “ "EF301", "EF303" (both manufactured by Shin-Akita Kasei Co., Ltd.), Schweggo Fureer "8035", "8036" (both manufactured by Schwegman), ": B M1000", "BM1100" (all BM 'Himmy'), MegaFuck "F-171", "F-470" (all manufactured by Dainippon Ink & Chemicals, Inc.), and the like.

 [0069] The fluorine content of the fluorosurfactant in the present invention is 0.05 to 2% by mass, and preferably 0.1 to 1% by mass. One or more of the above fluorosurfactants can be used in combination, and can be used in combination with other surfactants.

 [0070] Silicone oil or silicone surfactant! Explain that.

 [0071] Silicone oils used in the present invention can be broadly classified into straight silicone oils and modified silicone oils, depending on the type of organic group bonded to the silicon atom. Straight silicone oil refers to those bonded with a methyl group, a phenol group, or a hydrogen atom as a substituent. A modified silicone oil is one that has components derived secondarily from straight silicone oil. On the other hand, it can be classified from the reactivity of silicone oil. These are summarized as follows.

 [0072] Silicone oil

 1.Straight silicone talent

 1— 1. Non-reactive silicone oil: dimethyl, methylphenol substitution, etc.

 1-2. Reactive silicone oil: methyl hydrogen substitution, etc.

 2. Modified silicone oil

 Modified silicone oil is born by introducing various organic groups into dimethyl silicone oil.

2- 1. Non-reactive silicone oil: alkyl, alkyl Z aralkyl, alkyl Z poly Rie Itel, polyether, higher fatty acid ester substitution, etc.

 Alkyl / aralkyl-modified silicone oil is a silicone oil in which a part of methyl group of dimethyl silicone oil is replaced with a long-chain alkyl group or a phenyl alkyl group.

 Polyether-modified silicone oil is a silicone-based polymeric surfactant in which hydrophilic polyoxyalkylene is introduced into hydrophobic dimethyl silicone,

 Higher fatty acid-modified silicone oil is a silicone oil in which a part of methyl group of dimethyl silicone oil is replaced with higher fatty acid ester,

 The amino-modified silicone oil is a silicone oil having a structure in which a part of the methyl group of the silicone oil is replaced with an aminoalkyl group.

 Epoxy-modified silicone oil is a silicone oil having a structure in which a part of methyl group of silicone oil is replaced with an epoxy group-containing alkyl group,

 A carboxyl-modified or alcohol-modified silicone oil is a silicone oil having a structure in which a part of the methyl group of the silicone oil is replaced with a carboxyl group or a hydroxyl group-containing alkyl group.

 2- 2. Reactive silicone oil: Amide-containing epoxy, carboxyl, alcohol substitution, etc.

 Of these, polyether-modified silicone oil is preferably added. The number average molecular weight of the polyether-modified silicone oil is, for example, 1,000-100,000, preferably 2,000-50,000, and if the number average molecular weight is less than 1,000, the drying property of the coating film On the contrary, when the number average molecular weight exceeds 100,000, it tends to be difficult to bleed out to the coating surface.

Specific products include L45, L9300, FZ-3704, FZ-3703, FZ-3720, FZ-3786, FZ-3501, FZ-3504, FZ-3508, FZ from Nippon Car Co., Ltd. — 3 705, FZ— 3707, FZ— 3710, FZ— 3750, FZ— 3760, FZ— 3785, FZ-3785, Y—7499, Shinetsu Yi Gaksha KF96L, KF96, KF96H, KF99, KF54, KF965, K F968, KF56, KF995, KF351, KF352, KF353, KF354, KF355, KF615, KF618, KF945, KF6004, FL100 etc. [0074] The silicone surfactant used in the present invention is a surfactant obtained by substituting a part of the methyl group of the silicone oil with a hydrophilic group. Substitution positions include silicone oil side chains, both ends, one end, both end side chains, and the like. Examples of hydrophilic groups include polyether, polyglycerin, pyrrolidone, betaine, sulfate, phosphate, and quaternary salt.

 [0075] The silicone surfactant is preferably a nonionic surfactant in which the hydrophobic group is dimethylpolysiloxane and the hydrophilic group is also composed of a polyoxyalkylene force.

 [0076] A nonionic surfactant is a generic term for surfactants that do not have a group capable of dissociating into ions in an aqueous solution. However, in addition to a hydrophobic group, a hydroxyl group of a polyhydric alcohol can be used as a hydrophilic group. It has a reoxyalkylene chain (polyoxyethylene) or the like as a hydrophilic group. The hydrophilicity becomes stronger as the number of alcoholic hydroxyl groups increases and as the polyoxyalkylene chain (polyoxyethylene chain) becomes longer. The nonionic surfactant according to the present invention is characterized by having dimethylpolysiloxane as a hydrophobic group.

 [0077] When a nonionic surfactant having a hydrophobic group as dimethylpolysiloxane and a hydrophilic group as polyoxyalkylene force is used, unevenness of the low refractive index layer and antifouling property of the film surface are improved. It is thought that the hydrophobic group that also has polymethylsiloxane force is oriented on the surface and forms a film surface that is not easily soiled. This effect cannot be obtained by using other surfactants.

 [0078] Specific examples of these nonionic surfactants include, for example, silicone surfactants manufactured by Nippon Car Co., Ltd. SILWET L-77, L-720, L-7001, L-7002, L- 7604, Y — 7006, FZ— 2101, FZ— 2104, FZ— 2105, FZ— 2110, FZ— 2118, FZ— 2 120, FZ— 2122, FZ— 2123, FZ— 2130, FZ— 2154, FZ— 2161 FZ-2162, FZ-2163, FZ-2164, FZ-2166, FZ-2191 and the like.

 [0079] Further, SUPERSILWET SS-2801, SS-2802, SS-2803, SS-2804, SS-2805 and the like can be mentioned.

[0080] These nonionic surfactants are preferably composed of dimethylpolysiloxane having a hydrophobic group and polyoxyalkylene having a hydrophilic group. The structure includes a dimethylpolysiloxane structure portion and a polyoxyalkylene. A linear block copolymer in which chains are alternately and repeatedly bonded is preferable. It is excellent because it has a linear structure with a long chain length of the main chain skeleton. By being a block copolymer with repeating hydrophilic groups and hydrophobic groups alternately This is probably because one activator molecule can be adsorbed on the surface of silica fine particles so as to cover it at multiple locations.

 Specific examples of these include, for example, silicone surfactant A BN SILWET FZ-2203, FZ-2207, FZ-2208, FZ-2222, etc., manufactured by Nippon Car Co., Ltd.

[0082] Among these silicone oils or silicone surfactants, those having a polyether group are preferred.

 [0083] In addition, BYK series, BYK-3007302, BY-306, BYK-307, BYK-310, BYK-315, BYK-320, BYK-322, BYK-323, BYK manufactured by BYK Japan — 325, BYK—330, BYK—331, BYK—333, BYK—337, BYK—340, BYK—344, BYK—370, BYK—375, BYK—377, BYK—352, BYK—354, BYK-355 / 356, BYK- 358N / 361N, BYK—357, BYK—390, BYK—392, BYK—UV3500, BYK—UV3510, BYK—UV3570, BYK Silclean3700, GE Silicone Dimethyl Silicone Series, XC96—7 23, YF3800, XF3905, YF3057, YF3807, YF3802, YF3897 can be preferably used.

 [0084] Other surfactants may be used in combination. For example, sulfonate-based, sulfate ester-based, phosphate ester salt-based surfactants, and polyoxyethylene A nonionic surfactant such as an ether type or ether ester type having a chain hydrophilic group may be used in combination.

 [0085] In the present invention, these silicone oils or silicone surfactants are preferably used in the low refractive index layer and the layer adjacent to the low refractive index layer, specifically, the hard coat layer and the high refractive index layer. . In the case where the low refractive index layer is the outermost surface layer of the antireflection film, it is effective for improving the scratch resistance of the surface by the force by increasing the water repellency, oil repellency and antifouling property of the coating film. The content in the low refractive index layer coating solution is preferably 0.05 to 2.0% by mass. If it is less than 5% by mass, the crack resistance effect is insufficient, and if it exceeds 2.0% by mass, uneven coating may occur.

[0086] (Acid) In the present invention, by adding an acid to the low refractive index layer coating composition, alkaline components such as ammonia are eluted from the inside of the hollow fine particles, and the coating composition of the low refractive index layer is applied after the coating solution is prepared and applied. It is also possible to prevent the viscosity of the product from increasing.

 [0087] Examples of the acid to be added include known inorganic acids and organic acids. In the present invention, organic acids are preferable. Examples of the organic acid include acetic acid, formic acid, propionic acid, and among these, acetic acid is preferable. The addition amount of the organic acid is an amount corresponding to an alkali component such as ammonia from the inside of the hollow fine particles, and an acid, for example, acetic acid, for example, 5 to LOO mass% is added to the solid content in the hollow fine particle dispersion. Depending on the concentration of the hollow fine particle dispersion, it is usually preferable to add the acid in the range of 0.5 to 30% by mass of the hollow fine particle dispersion.

 [0088] [High refractive index layer]

 Various functional layers can be provided between the transparent support and the low refractive index layer. A typical example of such a high refractive index layer will be described.

 [0089] (Metal oxide fine particles of high refractive index layer)

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

[0090] The average primary particle size of these metal oxide fine particles is preferably 10 to 200 nm, more preferably 10 to 150 nm. The average particle diameter of the metal oxide fine particles can be measured with an electron microscope photographic force using a scanning electron microscope (SEM) or the like. It may be measured by a particle size distribution meter using the dynamic light scattering method or the static light scattering method. If the particle size is too small, aggregation tends to occur and the dispersibility deteriorates. If the particle size is too large, the haze is remarkably increased. The shape of the metal oxide fine particles may be rice grain, sphere, cube, spindle, needle or It is preferable to have an indefinite shape.

 [0091] The refractive index of the high refractive index layer is specifically higher than the refractive index of the transparent support, which is the support, and is in the range of 1.50-1.90 when measured at 23 ° C and wavelength of 550 nm. It is preferable. The means for adjusting the refractive index of the high refractive index layer is dominated by the type and amount of metal oxide fine particles, so that the refractive index of the metal oxide fine particles is preferably 1.80-2.60.

 [0092] The metal oxide fine particles may be surface-treated with an organic compound. By modifying the surface of the metal oxide fine particles with an organic compound, the dispersion stability in an organic solvent is improved, the dispersion particle size can be easily controlled, and aggregation and sedimentation over time can be suppressed. it can. For this reason, the surface modification amount with a preferable organic compound is 0.1 to 5% by mass, more preferably 0.5 to 3% by mass with respect to the metal oxide particles. Examples of organic compounds used for the surface treatment include polyols, alkanolamines, stearic acid, silane coupling agents and titanate coupling agents. Of these, the silane coupling agents described below are preferred. Two or more kinds of surface treatments may be combined.

 [0093] The thickness of the high refractive index layer containing the metal oxide fine particles is 5ηπ! Preferably ~ 1 μm, ΙΟηπ! It is more preferable that it is ~ 0.2 / z m 30ηπ! Most preferred is ~ 0.1 m.

 [0094] The ratio of the metal oxide fine particles to be used and a binder such as ionizing radiation curable resin, which will be described later, depends on the type of metal oxide fine particles, the particle size, etc., but the volume ratio of the former 1% versus the latter 2 Therefore, the latter 1 is preferable to the former 2.

 [0095] The amount of the metal oxide fine particles used in the present invention is preferably 5 to 85% by mass, more preferably 10 to 80% by mass, and more preferably 20 to 75% by mass in the high refractive index layer. Further preferred. If the amount used is small, the desired refractive index and the effect of the present invention cannot be obtained, and if it is too large, the film strength is deteriorated.

[0096] The metal oxide fine particles are supplied to a coating solution for forming a high refractive index layer in a dispersion state dispersed in a medium. As a dispersion medium for metal oxide particles, it is preferable to use a liquid having a boiling point of 60 to 170 ° C. Specific examples of the dispersion solvent include water, alcohol (eg, methanol, ethanol, isopropanol, butanol, benzyl alcohol), ketone (eg, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone), Ketone alcohol (eg, diacetone alcohol), ester (eg, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl formate, ethyl formate, propyl formate, butyrate formate), aliphatic hydrocarbon (eg, Xylene, cyclohexane), halogenated hydrocarbons (eg, methyl chloride, chloroform, carbon tetrachloride), aromatic hydrocarbons (eg, benzene, toluene, xylene), amides (eg, dimethylformamide, Examples thereof include dimethylacetamide, n-methylbicycloidone), ether (eg, jetyl ether, dioxane, tetrahydride furan), and ether alcohol (eg, 1-methoxy-2-propanol). Of these, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and butanol are particularly preferable.

 [0097] The metal oxide fine particles can be dispersed in the medium using a disperser. Examples of the dispersing machine include a sand grinder mill (eg, a bead mill with a pin), a high-speed impeller mill, a pebble mill, a roller mill, an attritor, and a colloid mill. A sand grinder mill and a high-speed impeller mill are particularly preferred. In addition, preliminary dispersion processing may be performed. Examples of the disperser used for the preliminary dispersion treatment include a ball mill, a three-roll mill, a kneader, and an etastruder.

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

[0099] The core is titanium oxide (rutile type, anatase type, amorphous type, etc.), zirconium oxide

, Dumbbell, cerium oxide, indium oxide doped with tin, tin oxide doped with antimony, and the like can be used.

 [0100] The shell preferably contains an inorganic compound other than titanium oxide as a main component and also forms a metal oxide or sulfide force. For example, inorganic materials mainly composed of silicon dioxide (silica), aluminum oxide (alumina), zirconium oxide, dumbbell, tin oxide, antimony oxide, indium oxide, iron oxide, zinc oxide zinc, etc. A compound is used. Of these, alumina, silica and zirconium (acid zirconium) are preferable. A mixture of these may also be used.

[0101] The coating amount of the shell to the core is 2 to 50% by mass in average coating amount. Preferably It is 3-40 mass%, More preferably, it is 4-25 mass%. When the coating amount of the shell is large, the refractive index of the fine particles is lowered, and when the coating amount is too small, the light resistance is deteriorated. Two or more kinds of inorganic fine particles may be used in combination.

 [0102] Titanium oxide titanium used as a core can be prepared by a liquid phase method or a gas phase method. Examples of methods for forming the shell around the core include, for example, U.S. Pat. No. 3,410,708, JP-B 58-47061, U.S. Pat. No. 2,885,366, and 3,437,502. No. 1, British Patent No. 1,134,249, U.S. Pat.No. 3,383,231, British Patent No. 2,629,953, No. 1,365,999, etc. be able to.

 [0103] (Ionizing radiation curable resin)

 Ionizing radiation curable resin is added as a binder for fine metal oxide particles to improve the film formability and physical properties of the coating. Ionizing radiation curable resins include monomers or oligomers that have two or more functional groups that cause polymerization reaction either directly by irradiation with ionizing radiation such as ultraviolet rays or electron beams, or indirectly by the action of a photopolymerization initiator. You can use V. Examples of the functional group include a group having an unsaturated double bond such as a (meth) ataryloxy group, an epoxy group, and a silanol group. Of these, radically polymerizable monomers and oligomers having two or more unsaturated double bonds can be preferably used. You may combine a photoinitiator as needed. Examples of such ionizing radiation curable resins include polyfunctional attareito toy compounds, such as pentaerythritol polyfunctional attalylate, dipentaerythritol polyfunctional attalylate, pentaerythritol polyfunctional metatalylate, and dipentaylate. It is preferable that the compound is selected from the group power consisting of erythritol polyfunctional metatalylate. Here, the polyfunctional ate relato toy compound is a compound having two or more allyloyloxy groups and Z or methacryloxy groups in the molecule.

[0104] Examples of the monomer of the polyfunctional talaritoy compound include ethylene glycol diatalylate, diethylene glycol diatalylate, 1,6-hexanediol diatalylate, neopentyl glycol diatalylate, Methylolpropane tritalylate, trimethylolethane tritalylate, tetramethylol methane tritalylate, tetramethylol methane tetratalylate, pentaglycerol tritalylate, pentaerythritol diatali Rate, Pentaerythritol Triatalylate, Pentaerythritol Tetratallate, Glycerin Triatalylate, Dipentaerythritol Triatalylate, Dipentaerythritol Tetraatalylate, Dipentaerythritol Pentatalate, Dipentaerythritol Toxaatalylate, Tris (Ataryllooxychetyl) isocyanurate, ethylene glycol dimetatalylate, diethylene glycol dimetatalylate, 1, 6 hexanediol dimetatalylate, neopentyl glycol dimetatalylate, trimethylolpropane trimetatalylate, trimethylolethanetri Methacrylate, tetramethylol methane trimethacrylate, tetramethylol methane tetramethacrylate, pentaglycol Roll Trimetatalylate, Pentaerythritol Dimetatalylate, Pentaerythritol Trimetatalylate, Pentaerythritol Tetrametatalylate, Glycerin Trimetatalylate, Dipentaerythritol Trimetatalylate, Dipentaerythritol Tetrametatalylate, Dipentaerythritol Pentamethacrylate Preferred examples include rate and dipentaerythritol hexametatalylate. These compounds may be used alone or in combination of two or more. Further, it may be an oligomer such as a dimer or trimer of the above monomer.

 [0105] The addition amount of the ionizing radiation curable resin is preferably 15% by mass or more and less than 50% by mass in the solid content in the high refractive index composition.

 [0106] In order to accelerate the curing of the ionizing radiation curable resin, the mass ratio of the photopolymerization initiator and the acrylic compound having two or more polymerizable unsaturated bonds in the molecule is from 3: 7 to 1: 9. It is preferably contained.

[0107] Specific examples of the photopolymerization initiator include acetophenone, benzophenone, hydroxybenzophenone, Michler's ketone, _a amioxime ester, thixanthone, and derivatives thereof, and particularly limited thereto. It is not something.

 [0108] (Solvent)

 Examples of the organic solvent used for coating the high refractive index layer include alcohols (for example, methanol, ethanol, propanol, isopropanol, butanol).

, Isobutanol, secondary butanol, tertiary butanol, pentanol, hexanol, cyclohexanol, benzyl alcohol, etc.), polyhydric alcohols (eg, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene) Glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, hexanediol, pentanediol, glycerin, hexanetriol, thiodiglycol, etc.), polyhydric alcohol ethers (for example, ethylene glycol mono-monomono-methylolate) Tenole, Ethylene glycol monoethyl enoate ethere, Ethylene glycol monobutyl ether, Diethylene glycol monomethyl ether, Diethylene glycol monomethyl ether, Diethylene glycol monobutyl ether, Propylene glycol monomethino enoate ethere, Propylene glycol nole monobutenoate ethere, Ethylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether, triethylene glycol Tylene glycol monoethanolino ester, ethylene glycol monophenol enoate, propylene glycol monophenol ether, etc., amines (eg ethanolamine, diethanolamine, triethanolamine, N-methyl ester) Tananolamine, N-ethyldiethanolamine, morpholine, N-ethylmorpholine, ethylenediamine, jetylenediamine, triethylenetetramine, tetraethylenepentamine, polyethyleneimine, pentamethyljetylenetriamine, tetramethylpropylenediamine, etc. ), Amides (eg, formamide, N, N dimethylformamide, N, N dimethylacetamide, etc.), heterocyclics (eg, 2-pyrrolidone, N-methyl 2-pyrrolidone, cyclohexyl pyrrolidone, 2— Oxazo Don, 1,3 dimethyl-2 imidazolidinone, etc.), sulfoxides (eg, dimethyl sulfoxide, etc.), sulfones (eg, sulfolane, etc.), urea, acetonitrile, acetone, etc. Preferred are monohydric alcohols and polyhydric alcohol ethers.

 [Hard coat layer]

 In the antireflection film of the present invention, it is preferable to provide a hard coat layer between the transparent support and an antireflection layer such as a high refractive index layer or a low refractive index layer. The hard coat layer is preferably an activated energy line cured resin layer.

[0110] The active energy ray-cured resin layer is a layer mainly composed of resin that is cured through a bridge reaction or the like by irradiation with active rays such as ultraviolet rays and electron beams. Active energy ray curing As the resin, a component containing a monomer having an ethylenically unsaturated double bond is preferably used V, which is cured by irradiation with an active ray such as an ultraviolet ray or an electron beam to activate active energy. A lug-line cured resin layer is formed. Typical examples of the active energy ray curable resin include ultraviolet ray curable resins and electron beam curable resins. Preferred are those that are cured by ultraviolet irradiation.

[0111] Examples of the ultraviolet curable resin include an ultraviolet curable urethane acrylate resin, an ultraviolet curable polyester acrylate resin, an ultraviolet curable epoxy acrylate resin, and an ultraviolet curable polyol acrylate. A system resin or an ultraviolet curable epoxy resin is preferably used. Of these, ultraviolet curable attalylate resin is preferable.

 [0112] In general, UV-curable acrylic urethane-based resins are obtained by reacting isocyanate monomers or prepolymers with polyester polyols in addition to 2-hydroxy cetyl acrylate, 2-hydroxy ethynole methacrylate. (Hereinafter, only acrylate is included in the acrylate as including methacrylate), and it can be easily obtained by reacting an acrylate monomer having a hydroxyl group such as 2-hydroxypropyl acrylate. For example, those described in JP-A-59-151110 can be used.

 [0113] For example, a mixture of 100 parts of Dudick 17-806 (Dainippon Ink Chemical Co., Ltd.) and 1 part of Coronate L (Nippon Polyurethane Co., Ltd.) is preferably used.

 [0114] Examples of UV-curable polyester acrylate-based resins generally include those that are easily formed when 2-hydroxyethyl acrylate or 2-hydroxy acrylate monomers are reacted with polyester polyol. And those described in JP-A-59-151112 can be used.

 [0115] As a specific example of the ultraviolet curable epoxy acrylate resin, an epoxy acrylate is used as an oligomer, and a reactive diluent and a photopolymerization initiator are added to the oligomer and reacted to form an oligomer. And those described in JP-A-1-105738 can be used.

[0116] Specific examples of the UV curable polyol atarylate-based resin include trimethylolpronone tritalylate, ditrimethylolpropane tetratalylate, pentaerythritol triarylate, pentaerythritol tetratalate, dipentaerythritol hexatalylate , Alkyl-modified dipentaerythritol pentaatrate, etc. wear.

 [0117] Specific examples of the photopolymerization initiators for these ultraviolet curable resin include benzoin and its derivatives, acetophenone, benzophenone, hydroxybenzophenone, Michler's keton, a amioxime ester, thixanthone, and the like. Derivatives can be mentioned. You may use with a photosensitizer. The photopolymerization initiator can also be used as a photosensitizer. Further, when using an epoxy acrylate-based photopolymerization initiator, a sensitizer such as n-butylamine, triethylamine, tri-n-butylphosphine or the like can be used. The photopolymerization initiator or photosensitizer used in the ultraviolet curable resin composition is 0.1 to 15 parts by weight, preferably 1 to 10 parts by weight, based on 100 parts by weight of the composition.

 [0118] As the resin monomer, for example, a monomer having an unsaturated double bond, such as methyl acrylate, ethyl acrylate, butyl acrylate, benzyl acrylate, cyclohexyl acrylate, vinyl acetate, styrene, etc. The following general monomers can be mentioned. In addition, as monomers having two or more unsaturated double bonds, ethylene glycol ditalylate, propylene glycol ditalylate, dibutenebenzene, 1,4-cyclohexane diatalylate, 1,4-cyclohexyldimethyl asialate Examples thereof include the above-mentioned rates, the above-mentioned trimethylol-type pantriatalylate, and pentaerythritol tetraacrylic ester.

[0119] Commercially available UV curable resins that can be used in the present invention include Adeka Obtomer KR 'BY series: KR-400, KR-410, KR-550, KR-566, KR-567, BY-320B (Asahi Denka) KOIHARD A—101—KK, A—101—WS, C—302, C—401—N, C—501, M—101, M—102, T—102, D—102, NS—101, FT 102Q8, MAG—1—P20, AG—106, M—101—C (manufactured by Guangei Chemical Co., Ltd.); SE force beam PHC2210 (S) ゝ PHC X—9 (K—3), PHC2213 , DP-10, DP-20, DP-30, P1000, P1100, P1200, P1300, P1400, P1500, P1600, SCR90 0 (manufactured by Dainichi Seiki Kogyo Co., Ltd.); KRM7033, KRM7039, KRM7130, KRM7131, U VECRYL29201, UVECRYL29202 (Daicel, UCB Co., Ltd.); RC—50 15, RC—5016, RC—5020, RC—5031, RC—5100, RC—5102, RC-512 0, RC—5122, RC- 51 52, RC—5171, RC—5180, RC—5181 (Dainippon Ink Chemical Co., Ltd.); Orex No. 340 Clear (manufactured by China Paint Co., Ltd.); Sunrad H—601, RC—750, RC — 700, RC-600, RC—500, RC—611, RC—612 (Sanyo Kosei Kogyo Co., Ltd.); SP—150 9, SP—1507 (Showa Polymer Co., Ltd.); RCC— 15C (Grace 'Japan Co., Ltd.), Aronix M-6100, M-8030, M-8060 (Toagosei Co., Ltd.); NK Node B-420, B-500 (Shin Nakamura) Gaku Kogyo Co., Ltd.) can be selected as appropriate.

[0120] In addition, specific examples of compounds include trimethylolpropane tritalylate, ditrimethylolpropane tetratalylate, pentaerythritol tritalate, pentaerythritol tetratalylate, dipentaerythritol hexatalylate, Examples thereof include alkyl-modified dipentaerythritol pentaatalylate.

 [0121] The cured resin layer thus obtained contains fine particles of an inorganic compound or an organic compound in order to adjust the scratch resistance, slipperiness and refractive index, and to provide the antireflection film with antiglare properties. But you can.

 [0122] Inorganic fine particles used in the hard coat layer include silicon oxide, titanium oxide, nickel oxide, tin oxide, indium oxide, ITO, zinc oxide, zirconium oxide, magnesium oxide, calcium carbonate Calcium carbonate, talc, clay, calcined kaolin, calcined calcium silicate, hydrated calcium silicate, aluminum silicate, magnesium silicate and calcium phosphate. In particular, silicon oxide, titanium oxide, acid aluminum, acid zirconium, acid magnesium and the like are preferably used.

 [0123] Further, as the organic particles, polymethacrylic acid methyl acrylate resin powder, acrylic styrene resin powder, polymethylmethacrylate resin powder, silicone resin powder, polystyrene resin powder, polycarbonate Fatty powder, benzoguanamine-based resin powder, melamine-based resin powder, polyolefin-based resin powder, polyester-based resin powder, polyamide-based resin powder, polyimide-based resin powder, or polyfluorinated-ethylene resin powder It can be added to the ultraviolet curable resin composition. Particularly preferred are cross-linked polystyrene particles (for example, SX-130H, SX-200H, SX-350Η manufactured by Soken Chemical Co., Ltd.) and polymethyl methacrylate-based particles (for example, MX150, MX300 manufactured by Soken Chemical).

[0124] The average particle size of these fine particle powders is preferably 0.01 to 5 µm, and preferably 0.1 to 5.0 µm. m, and more preferably 0.1 to 4.0 m. It is also preferable to contain two or more kinds of fine particles having different particle diameters. It is desirable that the ratio of the ultraviolet curable resin composition to the fine particles is 0.1 to 30 parts by mass with respect to 100 parts by mass of the resin composition.

 [0125] These hard coat layers can be applied by a known method such as a gravure coater, a dip coater, a reverse coater, a fiber coater, a die coater, or an ink jet method. After coating, heat-dry and perform UV curing.

[0126] As a light source for curing an ultraviolet curable resin by a photocuring reaction to form a cured film layer, any light source that generates ultraviolet light can be used without any limitation. For example, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, or the like can be used. Irradiation conditions differ depending on each lamp, but the irradiation amount of active rays is usually 5 to 500 mj / cm ² , preferably 5 to 150 mj / cm ² , and particularly preferably 20 to: LOOmj / cm ² . .

 [0127] Further, when irradiating actinic radiation, it is preferable to apply tension in the film transport direction, and more preferably to apply tension in the width direction. The tension to be applied is preferably 30 to 300 NZm. The method of applying tension is not particularly limited, and tension may be applied in the width direction or biaxial direction by a tenter that may apply tension in the transport direction on the back roll. This makes it possible to obtain a film with further excellent flatness.

[0128] The hard coat layer coating solution may contain a solvent or may be appropriately contained and diluted as necessary. Examples of the organic solvent contained in the coating solution include hydrocarbons (toluene, xylene), alcohols (methanol, ethanol, isopropanol, butanol, cyclohexanol), ketones (acetone, methylethyl). It can be appropriately selected from ketones, methyl isobutyl ketone), esters (methyl acetate, ethyl acetate, methyl lactate), glycol ethers, and other organic solvents, or a mixture thereof can be used. Propylene glycol monoalkyl ether (1 to 4 carbon atoms in the alkyl group) or propylene glycol monoalkyl ether acetate ester (1 to 4 carbon atoms in the alkyl group) is 5% by mass or more, more preferably 5 to 80%. Containing more than mass% It is preferable to use the above organic solvent.

[0129] (Anti-glare property)

 The antireflection film of the present invention is preferably antiglare. The anti-glare property reduces the visibility of the reflected image by blurring the outline of the image reflected on the surface, and reflects the reflected image when using an image display device such as a liquid crystal display, organic EL display, or plasma display. It is intended not to worry about the complexity. By providing appropriate unevenness on the surface, such a property can be imparted.

 [0130] As a method for forming such irregularities, processing to a transparent support, processing to a hard coat layer, processing to an antireflection film after applying an antireflection layer, and the like can be selected. In the processing to the anti-reflection film, the convex and concave portions may break through the anti-reflection layer or deform the anti-reflection layer to impair the anti-reflection effect. Therefore, in the present invention, the processing to the transparent support, the hard coat layer Is preferred.

 [0131] Examples of the concavo-convex shape referred to in the present invention include structures selected from right cones, oblique cones, pyramids, oblique pyramids, wedge shapes, convex polygons, hemispheres, and the like, and structures having partial shapes thereof. The hemispherical shape may be an ellipsoidal shape that does not necessarily need to be a true spherical shape, or a more deformed convex curved shape. Also included are prism shapes, lenticular lens shapes, and Fresnel lens shapes in which the ridges of the concavo-convex shape extend linearly. The ridgeline force The slope to the valley line may be flat, curved, or a combination of both.

 [0132] The hard coat layer is preferably an antiglare hard coat layer having an arithmetic average roughness (Ra) force of ½0 to 7 OOnm, preferably 80 to 400nm, as defined in JIS B 0601: 2001. If Ra is less than 60nm, the anti-glare effect is weak. If it exceeds 700nm, the impression is too rough. The arithmetic average roughness (Ra) is preferably measured using an optical interference type surface roughness meter RSTZPLUS (manufactured by WYKO).

 [0133] Examples of a method for forming an uneven shape on the surface of the hard coat layer and the transparent support described later include the following methods.

(1) A method of forming a negative shape of the desired shape on a roll or master and giving the shape by embossing. (2) A method in which a negative mold having a desired shape is formed on a roll or master, a thermosetting resin is filled into the negative mold, and is peeled off from the negative mold after heat curing.

 (3) Form a negative shape of the desired shape on the roll or master, apply ultraviolet ray or electron beam curable resin, fill the recesses, and then coat the transparent support on the intaglio via a resin solution A method in which ultraviolet ray or electron beam is irradiated as it is, and the cured resin and the transparent support to which it is adhered are peeled off with a negative force.

 (4) A solvent casting method in which a negative shape having a desired shape is formed on a casting belt, and a desired shape is imparted during casting.

 (5) A method of forming relief by curing letterpress on a transparent substrate with a resin cured by light or heating, and curing by light or heating.

 (6) A method in which a resin that is cured by light or heating is printed on the surface of the transparent support by an ink jet method, and is cured by light or heating to make the surface of the transparent support uneven.

 (7) A method of cutting the surface with a machine tool or the like.

 (8) A method in which particles of various shapes such as spheres and polygons are pressed and integrated so as to be partially buried in the surface of the transparent support to make the surface of the transparent support uneven.

 (9) A method in which particles of various shapes such as spheres and polygons dispersed in a small amount of binder are applied to the surface of the transparent support to make the surface of the transparent support uneven.

 (10) A method in which a binder is applied to the surface of a transparent support, and particles of various shapes such as spheres and polygons are dispersed thereon to make the surface of the transparent support uneven.

 [0134] In order to make the hard coat layer antiglare, there is a method of adding the fine particles to the coating solution.

[0135] In the present invention, as the antiglare fine particles, for example, fluorine-containing acrylic resin particles are preferable in addition to the inorganic fine particles or the organic fine particles.

 The fluorine-containing acrylic resin fine particles are fine particles formed from, for example, a fluorine-containing acrylic ester or methacrylic ester monomer or polymer. Specific examples of fluorine-containing acrylic ester or methacrylic ester include 1H

, 1H, 3H—Tetrafluoropropyl (meth) atalylate, 1H, 1H, 5H—Octafluoro oral pentyl (meth) atarylate, 1H, 1H, 7H—Dodecafluoro oral heptyl (meth) acrylate, 1H, 1H, 9H—Hexadecafluoronol (meth) atarylate, 2, 2, 2—Triflu Oloethyl (meth) acrylate, 2, 2, 3, 3, 3 pentafluoropropyl (meth) acrylate, 2- (perfluorobutyl) ethyl (meth) acrylate, 2- (perfluor mouth) Xylyl) ethyl (meth) acrylate, 2- (perfluorooctyl) ethyl) (meth) arylate, 2 perfluorodecylethyl (meth) acrylate, 3 perfluorobutyl 2 hydroxyl Propyl (meth) acrylate, 3-perfluohexyl 2-hydroxypropyl (meth) acrylate, 3-perfluorooctyl 2-hydroxypropyl (meth) acrylate, 2- (perfluoro-3-methylbutyl) ethyl ( (Meth) Atarylate, 2- (Perfluorool 5-methylhexyl) ethyl (meth) acrylate, 2- (Perfluoro-7-methyloctyl) ethyl (meth) atalyte Relate, 3 (perfluoro-3-methylbutyl-2-hydroxypropyl (meth) acrylate, 3- (perfluoro-5-methylhexyl)-2-hydroxypropyl (meth) acrylate, 3- (perfluoro-7-methyloctyl) 2— Hydroxypropyl (meth) acrylate, 1H—1— (trifluoromethyl) trifluoroethyl (meth) acrylate, 1H, 1H, 3H Hexafluorobutyl (meth) acrylate, trifluoroethyl methacrylate , Tetrafluoropropyl metatalylate, perfluorooctyl acetyl acrylate, 2- (perfluorobutyl) ethyl fluor acrylate.

 [0136] Among the fluorine-containing acrylic resin fine particles, 2- (perfluorobutyl) ethyl

 -Fine particles composed of a-fluoroatalylate, fluorine-containing polymethylmethacrylate fine particles, and fine particles obtained by copolymerizing fluorine-containing methacrylic acid with a vinyl monomer in the presence of a crosslinking agent are preferred. Fluorine-containing polymethyl methacrylate fine particles are preferred.

 [0137] The vinyl monomer copolymerizable with fluorine-containing (meth) acrylic acid is not particularly limited as long as it has a vinyl group, and more specifically, alkyl methacrylates such as methyl methacrylate and butyl methacrylate. Examples include esters, alkyl acrylates such as methyl acrylate and ethyl acrylate, and styrenes such as styrene and a-methyl styrene. These may be used alone or in combination.

The cross-linking agent used in the polymerization reaction is not particularly limited, but it is preferable to use one having two or more unsaturated groups. For example, ethylene glycol dimetatalylate, polyethylene glycol dimetatalylate 2 Functional dimetatalylate and trimethylol Examples thereof include propane trimetatalylate, dibutene benzene and the like.

 [0138] In the present invention, the polymerization reaction for producing the fluorine-containing polymethylmethacrylate fine particles may be any of random copolymerization and block copolymerization.

 Specifically, for example, the method described in JP-A-2000-169658 can also be mentioned, and examples of commercially available products include commercially available products such as FS-701 manufactured by Nippon Paint and MF-0043 manufactured by Negami Kogyo. Can be mentioned.

 Note that these fluorine-containing acrylic resin fine particles may be used alone or in combination of two or more. The state of these fluorine-containing acrylic resin particles is

, Powder or emulsion, etc. may be used in any state.

 The average particle size of the fluorine-containing acrylic resin fine particle powder is preferably 0.01 to 5 111.

1 to 5. O / z m, more preferably 0.1 to 4.0 m.

 Further, it is preferable to contain two or more kinds of fine particles having different particle diameters. The proportion of the ultraviolet curable resin composition and the fine particles is desirably blended so as to be 0.1 to 30 parts by mass with respect to 100 parts by mass of the resin composition.

 [0139] Further, it is also preferable that the hard coat layer contains the fluorine-based or silicone-based surfactant. These improve the applicability to the lower layer. These components are preferably added in the range of 0.01 to 3% by mass with respect to the solid component in the coating solution. Specific examples of the silicone surfactant include BYK series surfactants manufactured by Big Chemie Japan Co., Ltd. described in the low refractive index layer.

 [0140] Further, the hard coat layer has a multilayer structure of two or more layers, and one of the layers may be a so-called antistatic layer containing, for example, conductive fine particles or an ionic polymer. As a color correction filter for various display elements, a color tone adjusting agent having a color tone adjusting function may be included, and an electromagnetic wave blocking agent or an infrared absorber may be included to have each function. U like to be.

 [0141] As a coating method of the hard coat layer coating solution, the above-described methods can be used. The coating amount is suitably from 0.1 to 30 111 as the wet film thickness, and preferably from 0.5 to 15 / ζ πι. The dry film thickness is 0.1 to 15 m, preferably 1 to 8 μm.

[0142] The hard coat layer is irradiated with actinic radiation that is necessary to be irradiated with ultraviolet rays after coating and drying. The irradiation time for obtaining the amount is preferably from about 0.1 second to about 1 minute, and the viewpoint of the curing efficiency or work efficiency of the ultraviolet curable resin is preferably 0.1 to LO seconds.

[0143] Further, it is preferable illuminance of the active ray irradiation unit is 50~150mWZm ^2.

 [0144] [Backcoat layer]

 In the antireflection film of the present invention, it is preferable to provide a backcoat layer on the surface opposite to the side on which the active energy ray-cured resin layer of the cellulose ester film serving as the transparent support is provided. The knock coat layer is provided in order to correct curling caused by the provision of an active energy ray-cured resin layer or other layers. In other words, the degree of curling can be balanced by imparting the property of being rounded with the surface provided with the knock coat layer inside. The knock coat layer is preferably applied also as an anti-blocking layer. In this case, it is preferable that fine particles are added to the knock coat layer coating composition in order to provide an anti-blocking function.

 [0145] As fine particles added to the knock coat layer, examples of inorganic compounds include silicon dioxide, titanium dioxide, aluminum oxide, zirconium oxide, calcium carbonate, calcium carbonate, talc, clay, calcined kaolin, calcined calcium silicate, Mention may be made of tin oxide, indium oxide, zinc oxide, ITO, hydrated calcium silicate, aluminum silicate, magnesium silicate and calcium phosphate. Fine particles containing silicon are preferred in that haze is low, and silicon dioxide is particularly preferred.

 [0146] These fine particles are sold under the trade names of, for example, Aerosil R972, R972V, R974, R812, 200, 20 OV, 300, R202, 0X50, TT600 (manufactured by Enomoto Aerosil Co., Ltd.). And can be used. The fine particles of zirconium oxide are commercially available under the trade names of Aerosil R976 and R811 (manufactured by Nippon Aerosil Co., Ltd.), and can be used. Examples of polymers include silicone resin, fluorine resin and acrylic resin. Silicone resin is preferred, especially those having a three-dimensional network structure S Preferred, if it is arranged, Tosuno Kunore 103, 105, 108, 120, 145, 3120 and 240 (and above) It is commercially available under the trade name of Toshiba Silicone Co., Ltd. and can be used.

[0147] Among them, Aerosil 200V, Aerosil R972V kept haze low, It is particularly preferably used because of its great anti-blocking effect. In the antireflection film used in the present invention, the dynamic friction coefficient on the back side of the active energy ray-cured resin layer is preferably 0.9 or less, particularly 0.1 to 0.9.

[0148] fine particles contained in the knock coat layer is preferably 0.1 to 50 mass _^0/0 preferably from 0.1 to 10 weight _^0/0 of the binder. When a knock coat layer is provided, the increase in haze is preferably 1% or less, more preferably 0.5% or less, and particularly preferably 0.0 to 0.1%.

 [0149] Specifically, the knock coat layer is formed by applying a composition containing a solvent for dissolving or swelling a cellulose ester film. The solvent to be used may include a solvent to be dissolved and a mixture of Z or a solvent to be swollen in addition to a non-dissolved soot solvent. These may be appropriately selected depending on the curl degree of the transparent resin film and the type of resin. The composition and the coating amount mixed at a ratio of 5 are used.

 [0150] In the case of strengthening the curl prevention function! / が, it is effective to increase the mixing ratio of the solvent that dissolves the solvent composition to be used and Z or the solvent that swells, and to reduce the ratio of the solvent that does not dissolve . This mixing ratio is preferably (solvent to be dissolved and Z or solvent to be swollen) :( solvent not to be dissolved) = 10: 0 to 1: 9. Examples of the solvent for dissolving or swelling the transparent resin film contained in such a mixed composition include dioxane, acetone, methyl ethyl ketone, N, N-dimethylformamide, methyl acetate, ethyl acetate, Examples include trichlorethylene, methylene chloride, ethylene chloride, tetrachloroethane, trichloroethane, and black form. Examples of the solvent that does not dissolve include methanol, ethanol, n-propyl alcohol, i-propyl alcohol, n-butanol, cyclohexanol, and hydrocarbons (toluene, xylene).

[0151] These coated yarns and composites are coated on the surface of the transparent resin film using a gravure coater, dip coater, reverse coater, wire bar coater, die coater, spray coating, ink jet coating or the like. ~: It is preferable to apply with LOO m, but it is particularly preferably 5 to 30 µm. Examples of the resin used as a binder for the back coat layer include a salty vinyl-vinyl acetate copolymer, vinyl chloride resin, vinyl acetate resin, vinyl acetate and vinyl alcohol copolymer, and partial hydrolysis. PVC RU-acetate butyl copolymer, butyl chloride monochloride / vinylidene chloride copolymer, bulure chloride chloro-tolyl copolymer, ethylene vinyl alcohol copolymer, chlorinated poly salt vinyl, ethylene vinyl chloride monochloride copolymer Polymer, vinyl-based polymer or copolymer such as ethylene vinyl acetate copolymer, nitrocellulose, cellulose acetate propionate (preferably acetyl group substitution degree 1.8 to 2.3, propionol group substitution degree 0.1 to 1.0), cellulose derivatives such as diacetyl cellulose, cellulose acetate butyrate resin, maleic acid and Z or acrylic acid copolymers, acrylic acid ester copolymers, atta-tri-tri- Styrene copolymer, chlorinated polyethylene, acrylonitrile-chlorinated polyethylene styrene copolymer, methyl methacrylate-butadiene styrene Copolymer, Acrylic resin, Polybulassetal resin, Polybutylbutyral resin, Polyester polyurethane resin, Polyether polyurethane resin, Polycarbonate polyurethane resin, Polyester resin, Polyether resin, Polyamide resin Forces that can include rubber-based resins such as fats, amino-based resins, styrene-butadiene-based resins, and butadiene-acrylonitrile-based resins, silicone-based resins, and fluorine-based resins are not limited to these. For example, for acrylic resin, Ataripet MD, VH, MF IV (Mitsubishi Rayon Co., Ltd.), Hyperl M-400 3, M-4005, M-4006, M-4202, M-5000, M-5001, M-4501 (manufactured by Negami Kogyo Co., Ltd.), Dialnal BR-50, BR-52, BR-53, BR-60, BR-64, BR-73, BR-75, BR-77, BR — 79, BR—80, BR—82, BR—83, BR—85, BR—87, BR—88, BR—90, BR—93, BR—95, BR—100, BR—101, BR—102 , BR-105, BR-106, BR-107, BR-108, BR-112, BR-113, BR-115, BR-116, BR-117, BR-118, etc. (manufactured by Mitsubishi Rayon Co., Ltd.) Various homopolymers and copolymers produced from acrylic and methacrylic monomers as raw materials are on the market, and this medium strength is also preferred, and mono can also be selected as appropriate.

[0152] A cellulose-based resin layer such as diacetyl cellulose and cellulose acetate propionate is particularly preferable.

[0153] The order of coating the backcoat layer may be before or after coating the active energy ray-cured resin layer of the cellulose ester film. However, if the backcoat layer also serves as an anti-blocking layer, coat it first. It is desirable to do. Or back coat in two or more times A layer can also be applied.

 [0154] The surfactant BYK series manufactured by Big Chemie Japan Co., Ltd. described in the low refractive index layer and the dimethyl silicone series manufactured by GE Toshiba Silicone can be preferably used for an antireflection layer other than the low refractive index layer. .

 [Transparent support]

 Next, the transparent support that can be used in the present invention will be described.

 [0156] The transparent support used in the present invention is easy to manufacture, has good adhesion to an actinic radiation curable resin layer, is optically isotropic, and is optically transparent. It is preferred that it be!

 [0157] The term "transparent" as used in the present invention means a visible light transmittance of 60% or more, preferably 80% or more, particularly preferably 90% or more.

[0158] Having the above properties! / If there is no particular limitation, for example, cellulose ester film, polyester film, polycarbonate film, polyarylate film, polysulfone (including polyethersulfone) ) Film, polyester film such as polyethylene terephthalate, polyethylene naphthalate, etc., polyethylene film, polypropylene phenol, cellophane, cenorelose diacetate phenol, cenorelose triacetate, cenorelose acetate propionate, finolem, cenorelose acetate butyrate Rate film, polyvinylidene chloride film, polybulal alcohol film, ethylene bulcolol film, syndiotactic polystyrene film, polycarbonate Film, cycloolefin polymer film (Arton (manufactured by JSR), ZEONEX, ZENOOR (manufactured by ZEON CORPORATION)), polymethylpentene film, polyetherketone film, polyetherketoneimide film, polyamide film, fluorine Examples thereof include a resin film, nylon film, polymethyl methacrylate film, acrylic film, and glass plate. Of these, cellulose triacetate film, polycarbonate film, and polysulfone (including polyethersulfone) are preferred in the present invention. In particular, cellulose ester films (for example, co-minol tuck, product names KC8UX2MW, KC4U X2MW, KC8UY ゝ KC4UY ゝ KC5UN ゝ KC12UR, KC8UCR—3, KC8UCR—4, KC8UCR—5 (manufactured by Konica Minoltaput Co., Ltd.)), manufacturing, cost, transparency, isotropic Viewpoints such as property and adhesiveness are preferably used. These films may be films produced by melt casting film production or films produced by solution casting film production.

 [0159] (Cellulose ester)

 In the present invention, it is preferable to use a cellulose ester film as the transparent support. Among the cellulose esters, cellulose acetate butyrate, cellulose acetate phthalate, and cellulose acetate propionate are preferably used, among which cellulose acetate, cellulose acetate butyrate, and cellulose acetate propionate are preferred.

 [0160] In particular, when the substitution degree of the acetyl group is X and the substitution degree of the propiol group or butyryl group is Y, X and Y are on the transparent support having a mixed fatty acid ester of cellulose in the following range. A low reflection laminate provided with an actinic radiation curable resin layer and an antireflection layer is preferably used.

 [0161] 2. 3≤X + Y≤3.0

 0. 1≤Υ≤1.2

 In particular, 2.5 ≤ Χ + Υ ≤ 2. 9

 It is preferable that 0. 3≤Υ≤1.2.

 [0162] When a cellulose ester is used as the transparent support used in the present invention, the cellulose used as the raw material for the cell mouth ester is not particularly limited. Can be mentioned. Moreover, the cellulose ester obtained from them can be mixed and used in arbitrary ratios, respectively. When the acylating agent is an acid anhydride (acetic anhydride, propionic anhydride, butyric anhydride), these cellulose esters use an organic solvent such as acetic acid-like organic acid methylene chloride, etc. It can be obtained by reacting with a cellulose raw material using such a protic catalyst.

 [0163] The acylating agent is acid chloride (CH COCl

 3, C H COCl)

 2 5, C H COC1

 3 7

 The reaction is carried out using a basic compound such as ammine as a medium. Specifically,

It can be synthesized with reference to the method described in 10-45804. In addition, the cellulose ester used in the present invention is mixed with the amount of the acylating agent according to the degree of substitution. In the cellulose ester, these acylating agents react with the hydroxyl groups of cellulose molecules. Cellulose molecules are composed of many glucose units linked together, and the glucose unit has three hydroxyl groups. The number of substituted acyl groups at these three hydroxyl groups is called the degree of substitution (mol%). For example, cellulose triacetate has a acetyl group bonded to all three hydroxyl groups of a dalcos unit (actually 2.6 to 3.0).

[0164] Examples of the cellulose ester used in the present invention include cellulose acetate propionate, cellulose acetate butyrate or cellulose acetate propionate but also a cetyl group to which a propionate group or a butyrate group is bonded. A mixed fatty acid ester of roulose is particularly preferably used. The petityl group forming the petitate may be linear or branched.

[0165] Cellulose acetate propionate containing a propionate group as a substituent has excellent water resistance and is useful as a film for liquid crystal image display devices.

[0166] The method for measuring the degree of substitution of the acyl group can be carried out in accordance with ASTM-D817-96.

 [0167] The number average molecular weight of the cellulose ester is preferably 70000 to 250,000, more preferably 80,000 to 150,000, which has a high mechanical strength when molded and has an appropriate dope viscosity.

 [0168] These cellulose ester films are, for example, an endless metal belt for infinitely transferring a cell mouth ester solution (dope) called a solution casting film forming method, or a casting support for a rotating metal drum. It is preferable that the dope is cast on a body by casting from a pressure die to form a film.

[0169] (Organic solvent)

As the organic solvent used for preparing these dopes, it is preferable that the cellulose ester can be dissolved and has an appropriate boiling point, for example, methylene chloride, methyl acetate, ethyl acetate, amyl acetate, methyl acetate acetate, acetone. , Tetrahydrofuran, 1,3-dioxolan, 1,4-dioxane, cyclohexanone, ethyl formate, 2, 2,2-trifluoroethane, 2, 2, 3, 3-tetrafluoro-1-propanol, 1, 3-difluoro-2-propanol, 1, 1, 1, 3, 3, 3-hexafluoro-2-methyl-2-propanol, 1, 1, 1, 3, 3, 3 Hexafnoreolol 2 Prono Norole, 2, 2, 3, 3, 3 Pentafunole Olho 1 Propanol, Nitroethane, 1,3 Dimethyl-2 Imidazolidinone, etc. Organic halogen compounds such as methylene chloride, dioxolane derivatives, methyl acetate, ethyl acetate, acetone, methyl acetoacetate and the like are preferable organic solvents (that is, good solvents).

 [0170] Further, as shown in the following film forming process, the web (dope film) force formed on the casting support in the solvent evaporation process is a view that prevents foaming in the web when the solvent is dried. In view of the above, the boiling point of the organic solvent used is preferably 30 to 80 ° C.For example, the boiling point of the good solvent described above is methylene chloride (boiling point 40.4 ° C), methyl acetate (boiling point 56. 32 ° C), acetone (boiling point 56.3 ° C), ethyl acetate (boiling point 76.82 ° C), and the like.

 [0171] Among the good solvents described above, methylene chloride or methyl acetate having excellent solubility is preferably used.

 [0172] In addition to the organic solvent, it is preferable to contain 0.1 to 40% by mass of an alcohol having 1 to 4 carbon atoms. It is particularly preferable that the alcohol is contained at 5 to 30% by mass. After casting the dope described above onto a casting support, the solvent begins to evaporate and the alcohol ratio increases, the web (dope film) gels, making the web strong and peeling from the casting support. It is used as a gelling solvent that makes it easy to perform, and when these ratios are small, it also plays a role in promoting the dissolution of cellulose esters of non-chlorine organic solvents.

 [0173] Examples of the alcohol having 1 to 4 carbon atoms include methanol, ethanol, n-propanol, isopropanol, n-butanol, sec butanol, tert-butanol and the like.

 [0174] Of these solvents, ethanol is preferable because of the stability of the dope, the boiling point of which is relatively low, the drying property, the non-toxicity and the like. It is preferable to use a solvent containing 5 to 30% by mass of ethanol with respect to 70 to 95% by mass of methylene chloride. Methyl acetate can be used in place of methyl chloride. At this time, the dope may be prepared by a cooling dissolution method.

[0175] (Plasticizer) When a cellulose ester film is used for the antireflection film of the present invention, it preferably contains a plasticizer as described below. Examples of the plasticizer include phosphate ester plasticizers, phthalate ester plasticizers, trimellitic acid ester plasticizers, pyromellitic acid plasticizers, glycolate plasticizers, and citrate ester plasticizers. Polyester plasticizers can be preferably used.

 [0176] Phosphate ester plasticizers include triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, octyl diphenyl phosphate, diphenyl-norbiphenyl phosphate, trioctyl phosphate, tributyl phosphate, etc. Plasticizers such as jetyl phthalate, dimethoxyethyl phthalate, dimethyl phthalate, dioctyl phthalate, dibutyl phthalate, di-2-ethyl hexyl phthalate, butyl benzyl phthalate, diphenyl phthalate, dicyclohexyl phthalate, etc. Examples of acid plasticizers include tributyl trimellitate, tributyl trimellitate, triethyl trimellitate, etc., and pyromellitic acid ester plasticizers such as tetrabutyl pyromellitate and tetraphenol. -Glycolate plasticizers such as lupyromelitate and tetraethylpyromellitate include triacetin, tributylline, ethylphthalyl ethyl dallicolate, methyl phthalyl ethyl dallicolate, butyl phthalyl butyl dallicolate, etc. As the agent, triethyl citrate, tri-n-butyl citrate, acetyl acetyl citrate, acetyl butyl n-butyl citrate, acetyl acetyl n- (2-ethyl hexyl) citrate and the like can be preferably used. Examples of other carboxylic acid esters include trimethylol propane tribenzoate, butyl oleate, methyl acetyl ricinoleate, dibutyl sebacate, and various trimellitic acid esters.

[0177] As the polyester plasticizer, a copolymer of a dibasic acid such as an aliphatic dibasic acid, an alicyclic dibasic acid, an aromatic dibasic acid, and the like, and dalicol can be used. The aliphatic dibasic acid is not particularly limited, and adipic acid, sebacic acid, phthalic acid, terephthalic acid, 1,4-cyclohexyldicarboxylic acid and the like can be used. As glycols, ethylene glycol, diethylene glycol, 1,3-propylene glycol, 1,2-propylene glycol, 1,4-butylene glycol, 1,3-butylene glycol, 1,2-butylene glycol and the like can be used. . These dibasic acids and glycols are each simple. You can use it alone! Or you can use a mixture of two or more.

[0178] The amount of these plasticizers used is preferably from 1 to 20% by mass, more preferably from 3 to 13% by mass, based on the cellulose ester, in terms of film performance, processability and the like.

[0179] (UV absorber)

 For the long film for the low reflection laminate of the present invention, an ultraviolet absorber is preferably used.

 [0180] As the ultraviolet absorber, those excellent in the ability to absorb ultraviolet rays having a wavelength of 370 nm or less and having little absorption of visible light having a wavelength of 400 nm or more are preferably used from the viewpoint of good liquid crystal display properties.

 [0181] Specific examples of the ultraviolet absorber preferably used in the present invention include, for example, oxybenzophenone compounds, benzotriazole compounds, salicylate compounds, benzophenone compounds, cyanoacrylate compounds, nickel complex salts, and the like. Forces including compounds, etc. The present invention is not limited to these.

 [0182] Examples of benzotriazole-based ultraviolet absorbers include the following ultraviolet absorbers as specific examples. The present invention is not limited to these.

 [0183] UV— 1: 2— (2 ′ —hydroxy 1 5 ′ —methyl phenol) benzotriazole

 UV— 2: 2— (2 ′ —Hydroxy—3 ′, 5 ′ —Di-tert-butylphenol) benzotriazole

 UV— 3: 2— (2 ′ —hydroxy 1 3 ′ — tert-butyl 5 ′ —methyl phenol) benzotriazolene

 UV— 4: 2— (2 ′ —hydroxy— 3 ′, 5 ′ —di- tert-butylphenol) — 5 black mouth benzotriazolole

 UV— 5: 2— (2 ′ —Hydroxy 1 ′ 3 ′ — (3 “, 5 et al” —Tetrahyphthalimidomethyl) 5 ′ —Methylphenol) benzotriazole

 UV-6: 2,2-Methylenebis (4- (1, 1, 3, 3-tetramethylbutyl) -6- (2H-benzotriazole-2-yl) phenol)

UV— 7: 2— (2 ′ —hydroxy 1 3 ′ — tert-butyl 5 ′ —methyl phenol) 1 5 UV— 8: 2— (2H benzotriazole-2-yl) -6- (linear and side chain dodecyl)

— 4—Methylphenol (TINUVIN171, manufactured by Ciba)

 UV—9: Octyl- 3 -— [3-tert-butyl 4-hydroxy-5- (black mouth 2H benzotriazole 2-yl) phenyl] propionate and 2-ethylhexyl 3 -— [3

—Tert-Butyl 4 Hydroxy 1-5— (5 Black 1H 2 Benzotriazole 2-Fil) Fel] propionate mixture (TINUVIN109, Ciba)

 Further, the following specific examples of the benzophenone-based ultraviolet absorber are shown, but the present invention is not limited thereto.

[0184] UV-10: 2, 4-Dihydroxybenzophenone

 UV-11: 2, 2'-dihydroxy-4-methoxybenzophenone

 UV—12: 2 Hydroxy 4-methoxy-1-sulfobenzophenone

 UV-13: Bis (2-methoxy-4-hydroxy-5-benzoylmethane) UV absorbers preferably used in the present invention include benzotriazole-based UV rays that are highly transparent and have excellent effects of preventing deterioration of liquid crystals. Benzotriazole-based ultraviolet absorbers are particularly preferably used because they have less unwanted coloration, which is preferred by absorbers and benzophenone-based ultraviolet absorbers.

[0185] Further, the ultraviolet absorber having a distribution coefficient of 9.2 or more described in JP-A-2001-187825 improves the surface quality of a long film and is excellent in coatability. It is particularly preferable to use an ultraviolet absorber having a distribution coefficient of 1 or more.

[0186] Further, the general formula (1) or the general formula (2) described in JP-A-6-148430, Japanese Patent Application No. 2000-

Polymer ultraviolet absorbers (or ultraviolet absorbing polymers) described in general formulas (2), (6) and (7) of No. 156039 are also preferably used. As polymer UV absorber, PUVA-30M

(Otsuka Chemical Co., Ltd.) is commercially available.

[0187] (Fine particles)

 Further, in order to impart slipperiness to the cellulose ester film used in the present invention, fine particles similar to those described in the coating layer containing actinic ray curable resin described later can be used.

[0188] As fine particles, examples of inorganic compounds include silicon dioxide, titanium dioxide, aluminum oxide. Mention may be made of yuum, zirconium oxide, calcium carbonate, calcium carbonate, talc, clay, calcining power, calcined calcium silicate, hydrated calcium silicate, aluminum silicate, magnesium silicate and calcium phosphate. Fine particles containing silicon are preferred in terms of low turbidity, and silicon dioxide is particularly preferred.

 [0189] The average primary particle diameter of the fine particles is preferably 5 to 50 nm, and more preferably 7 to 20 nm. These are preferably contained mainly as secondary aggregates having a particle size of 0.05 to 0.3 μm. The content of these fine particles in the cellulose ester film is preferably 0.05 to 1% by mass, more preferably 0.1 to 0.5% by mass. In the case of a cellulose ester film having a multi-layer structure formed by a co-casting method, it is preferable that the added amount of fine particles is contained on the surface.

 [0190] The fine particles of silicon dioxide are sold under the trade names of Aerosil R972, R972V, R974, R812, 200, 200V, 300, R202, 0X50, TT600 (above made by Enomoto Aerosil Co., Ltd.), for example. Can be used.

 [0191] The fine particles of zirconium oxide are commercially available under the trade names of Aerosil R976 and R811 (manufactured by Nippon Aerosil Co., Ltd.) and can be used.

 [0192] Examples of the polymer include silicone resin, fluorine resin, and acrylic resin. Silicone resin is preferred, especially those having a three-dimensional network structure.For example, Tosnor 103, 105, 108, 120, 145, 3120 and 240 (above Toshiba Silicone ( It is commercially available under the trade name of “Made by Co., Ltd.” and can be used.

 Among these, Aerosil 200V and Aerosil R972V are particularly preferably used because they have a large effect of reducing the friction coefficient while keeping the turbidity of the cellulose ester film low. In the cellulose ester film used in the present invention, the dynamic friction coefficient on the back side of the active energy ray-cured resin layer is preferably 1.0 or less.

 [0194] (Method for producing cellulose ester film)

 Next, the manufacturing method of a cellulose-ester film is demonstrated.

[0195] The cellulose ester film is produced by dissolving a cellulose ester and an additive in a solvent to prepare a dope, casting a dope on a belt-shaped or drum-shaped metal support, casting a dope. The process of drying as a web, peeling from the metal support It is carried out by the following steps: stretching, maintaining the width, further drying, and scraping the finished film.

 [0196] The step of preparing the dope will be described. The concentration of cellulose ester in the dope is preferably higher because the drying load after casting on a metal support can be reduced. However, if the concentration of cellulose ester is too high, the load during filtration increases and the filtration is performed. The accuracy becomes worse. The concentration that achieves both of these is preferably 10 to 35% by mass, more preferably 15 to 25% by mass.

 [0197] Solvents used in the dope may be used singly or in combination of two or more. However, it is preferable from the viewpoint of production efficiency to use a mixture of good and poor cellulose ester solvents. Good Solvents are preferred! The preferred is the solubility of cellulose ester. The preferable range of the mixing ratio of the good solvent and the poor solvent is 70 to 98% by mass for the good solvent and 2 to 30% by mass for the poor solvent. The good solvent and the poor solvent are defined as a good solvent if the cellulose ester used alone is dissolved, and a poor solvent is a solvent that swells alone or does not dissolve. Therefore, depending on the degree of acyl substitution of the cellulose ester, the good solvent and poor solvent change. For example, when acetone is used as the solvent, the cellulose ester acetate (acetylation degree 2.4), cellulose acetate propionate It becomes a good solvent, and it is a poor solvent for cellulose acetate (acetylene substitution degree 2.8).

 [0198] The good solvent used in the present invention is not particularly limited, and examples thereof include organic halogen compounds such as methylene chloride, dioxolanes, acetone, methyl acetate, and methyl acetate acetate. Particularly preferred is methylene chloride or methyl acetate.

 [0199] The poor solvent used in the present invention is not particularly limited, but for example, methanol, ethanol, n-butanol, cyclohexane, cyclohexanone and the like are preferably used. The dope preferably contains 0.01 to 2% by mass of water.

[0200] As a method for dissolving the cellulose ester in preparing the dope described above, a general method can be used. When heating and pressurization are combined, it can be heated above the boiling point at normal pressure. The boiling point of the solvent exceeds the normal pressure and the solvent does not boil under pressure! It is preferable to stir and dissolve while heating at a temperature in the range, in order to prevent the formation of massive undissolved substances called gels and mamaco. Also, the cellulose ester is mixed with a poor solvent to wet or A method in which a good solvent is further added and dissolved after swelling is also preferably used.

 [0201] The pressurization may be performed by a method of injecting an inert gas such as nitrogen gas or a method of increasing the vapor pressure of the solvent by heating. Heating is preferably performed by an external force. For example, a jacket type is preferable because temperature control is easy.

 [0202] The heating temperature with the addition of a solvent is preferably higher from the viewpoint of the solubility of the cellulose ester, but if the heating temperature is too high, the required pressure increases and the productivity deteriorates. A preferable heating temperature is 45 to 120 ° C, more preferably 60 to 110 ° C force S, and further preferably 70 to 105 ° C force S. The pressure is adjusted so that the solvent does not boil at the set temperature.

 [0203] Alternatively, a cooling dissolution method is also preferably used, whereby the cellulose ester can be dissolved in a solvent such as methyl acetate.

 [0204] Next, the cellulose ester solution is filtered using a suitable filter medium such as filter paper.

 As a filter medium, the absolute filtration accuracy is low in order to remove insoluble matters and the like is preferable. However, if the absolute filtration accuracy is too small, there is a problem that the filter medium is likely to be clogged. For this reason, a filter medium with an absolute filtration accuracy of 0.008 mm or less is preferable. 0.001 to 0.008 mm of the filter medium S is preferable, 0.003 to 0.006 mm of the filter medium is more preferable!

 [0205] The filter medium may be a normal filter medium with no particular restrictions. However, a plastic filter medium such as polypropylene or Teflon (registered trademark), or a metal filter medium such as stainless steel may be used. It is preferable because there is no dropout. It is preferable to remove and reduce impurities, particularly bright spot foreign matter, contained in the raw material cellulose ester by filtration.

[0206] A bright spot foreign material is a film in which two polarizing plates are placed in a cross-cold state, a cellulose ester film is placed between them, and the side force of one polarizing plate is also exposed to light. and it means a point visible light leaks from the opposite side (foreign matter) when observed from is preferably bright points diameter is the 0. Olmm more is 200 or ZCM ² below. More preferably 100 Z cm ² or less, more preferably 50 or Zm ² or less, more preferably 0 to 10 or Z cm ² or less. Also, it is preferable that the number of bright spots of 0. Olmm or less is small.

[0207] The dope can be filtered by a normal method, but the method of filtering while heating at a temperature within a range where the solvent is not boiling under pressure above the boiling point at normal pressure of the solvent is It is preferable that the difference in filtration pressure before and after filtration (referred to as differential pressure) is small. Preferred temperature is 45 ~ 120 ° C It is more preferable that it is 45-55 degreeC which 45-70 degreeC is more preferable.

[0208] A smaller filtration pressure is preferable. The filtration pressure is preferably 1.6 MPa or less. 1. It is more preferably 2 MPa or less. 1. More preferably, it is OMPa or less.

[0209] Here, casting of the dope will be described.

 [0210] The metal support in the casting process is preferably a mirror-finished surface. As the metal support, a stainless steel belt or a drum whose surface is finished with a porcelain is preferably used. The cast width can be l ~ 4m. The surface temperature of the metal support in the casting process is set to 50 ° C to below the temperature at which the solvent does not boil and foam. A higher temperature is preferable because the web can be dried faster, but if it is too high, the web may foam or flatness may deteriorate. A preferable metal support temperature is appropriately determined at 0 to 100 ° C, and more preferably 5 to 30 ° C. Alternatively, it is also preferable to make the web gel by cooling and peel the drum force in a state containing a large amount of residual solvent. The method for controlling the temperature of the metal support is not particularly limited, but there are a method in which hot air or cold air is blown or a method in which hot water is brought into contact with the back side of the metal support. It is preferable to use hot water because heat transfer is performed efficiently, so that the time until the temperature of the metal support becomes constant is short. When using hot air, considering the temperature drop of the web due to the latent heat of vaporization of the solvent, use hot air that is higher than the target temperature while using hot air above the boiling point of the solvent and preventing foaming. There is. In particular, it is preferable to efficiently dry by changing the temperature of the metal support and the temperature of the drying air during the period from casting to peeling.

 [0211] In order for the cellulose ester film to exhibit good planarity, the amount of residual solvent when peeling the web from the metal support is preferably 10 to 150% by mass, more preferably 20 to 40% by mass or 60 to 130% by mass, particularly preferably 20 to 30% by mass or 70 to 120% by mass.

 [0212] In the present invention, the amount of residual solvent is defined by the following formula.

 [0213] Residual solvent amount (mass%) = {(M-N) / N} X 100

M is the mass of the sample collected during or after the production of the tube or film, and N is the mass after heating M at 115 ° C for 1 hour. [0214] Further, in the drying step of the cellulose ester film, it is preferable and more preferable that the web is peeled off from the metal support and further dried to make the residual solvent amount 1% by mass or less. The content is not more than mass%, particularly preferably 0 to 0.01 mass%.

 [0215] In the film drying process, generally, a roll drying method (a method in which a plurality of rolls arranged above and below are alternately passed through a web to dry) or a tenter method is used while drying a web.

 [0216] In order to produce a cellulose ester film for an antireflective film of the present invention, the web is stretched in the conveying direction immediately after peeling from the metal support where the residual solvent amount is large, and both ends of the web are clipped or the like. It is particularly preferable to perform stretching in the width direction by a tenter method of gripping with. The preferred draw ratio in both the machine direction and the transverse direction is 1.05 to L 3 times, and 1.05 to L 15 times is more preferred. It is preferable that the area is 1.12-1.44 times due to longitudinal and transverse stretching. 1.15-1.32 times is preferable. This can be determined by the draw ratio in the machine direction X and the draw ratio in the transverse direction. If the difference between the draw ratios in the machine direction and the transverse direction is less than 1.05, flatness deterioration due to ultraviolet irradiation when forming the active energy ray-cured resin layer is unfavorable. Further, even if the draw ratio exceeds 1.3 times, the flatness deteriorates and haze increases, which is preferable.

 [0217] In order to stretch in the machine direction immediately after peeling, it is preferable to stretch by peeling tension and subsequent transport tension. For example, it is preferable to peel at a peeling tension of 210 NZm or more, and particularly preferably 220 to 300 NZm.

 [0218] The means for drying the web is not particularly limited. In general, it can be carried out with hot air, infrared rays, heated rolls, microphone mouth waves, etc. It is preferably carried out with hot air in terms of simplicity.

 [0219] The drying temperature in the web drying step is preferably 30 to 150 ° C, and is preferably increased stepwise. More preferably, the drying is performed in the range of 50 to 140 ° C in order to improve dimensional stability.

[0220] The thickness of the cellulose ester film is not particularly limited, but is preferably 10 to 200 µm. In particular, it was difficult to obtain an antireflection film excellent in flatness and hardness with a thin film of 10 to 70 m. According to the present invention, a thin antireflection film excellent in flatness and hardness was obtained. Moreover, since it is excellent also in productivity, it is especially preferable that the film thickness of a cellulose ester film is 10-70 micrometers. More preferably 20 ~ 60 m. Most preferably, it is 35-60 / ζ πι. A cellulose ester film having a multilayer structure by a co-casting method can also be preferably used. Even when the cellulose ester has a multilayer structure, it has a layer containing an ultraviolet absorber and a plasticizer, and it may be a core layer, a skin layer, or both.

 [0221] The antireflection film of the present invention preferably has a width of 1.4 to 5 m. The surface of the cellulose ester film (transparent support), particularly the surface on which the low refractive index layer is provided, should have an arithmetic average roughness (Ra) of 50 to less than LOOOnm, preferably 80 to 600 nm. preferable. If Ra is less than 50nm, the anti-glare effect is weak. If it exceeds lOOOnm, the impression is too rough. Arithmetic mean roughness (Ra) is preferably measured with an optical interference type surface roughness measuring instrument as in the case of the hard coat layer. For example, an optical interference type surface roughness meter RS T / PLUS (manufactured by WYKO) ).

 [0222] The method for forming an irregular shape having an arithmetic average roughness (Ra) of 50 to less than LOOOnm on the surface of the transparent support has been described in the section of antiglare property. An embossing method that is preferably used as a method for forming an uneven shape on the surface of the transparent support will be described below.

 [0223] First, in the film forming process of the transparent support, a method of forming irregularities on the front or back surface by pressing the concave-convex roller as a saddle on the film surface will be described with reference to the drawings. The figure shows an example, and the present invention is not limited to these.

 [0224] Examples of the saddle type include a concave-convex roller having irregularities on the surface, but a plate-like, film-like, or belt-like saddle type may also be used.

 [0225] FIG. 1 is a schematic view of an uneven surface forming apparatus using an uneven roller. A resin solution prepared in advance is cast from a die 1 onto a casting belt 2 to form a web (a film containing a residual solvent after casting a dope on a metal support is called a web). After the peeling, the concavo-convex surface is formed on the web by the concavo-convex roller 3 for forming the concavo-convex surface and the back roll 4 facing it. Next, in the same manner, a concave / convex surface forming roller having a concave / convex surface having a concave / convex shape on the opposite surface of the web and a back roll 4 are used to form a concave / convex surface on the back surface of the web. The film is dried by a film drying device 6 and wound by a winding roll 7.

[0226] Further, the uneven surface can be formed either after the tenter 5 in FIG. 1 or in the drying device 6 in FIG. In the figure, which can be performed after the drying is finished, a pair of concavo-convex rollers and a back roll are arranged on the front side and the back side to form the concavo-convex shape. You may go.

 FIG. 2 shows a schematic diagram of the uneven surface forming apparatus in the drying apparatus. In this case, the amount of residual solvent is significantly lower than in the case of Fig. 1, but the temperature of the transparent support surface can be set to a desired temperature by controlling the heating conditions with the drying device, so that the uneven shape can be accurately formed. There is an advantage that can be achieved.

 [0228] After returning the film to room temperature, it is also possible to use an uneven surface forming apparatus using an uneven roller on another line, but in this case, if the residual solvent or temperature is low, the uneven surface forming stability is improved. Lack. In addition, there is a risk of foreign matter adhering to the ruggedness before the concavo-convex processing by the concavo-convex roller, and as shown in FIGS. Is also easy to form.

 [0229] The concave-convex type roller used for forming the concave-convex surface can be selected and applied to those with fine irregularities and rough ones, and is a pattern, matte shape, lenticular lens shape, concave portion or convex portion consisting of a part of a spherical surface. In addition, it is possible to use a material in which embosses for forming prism-like irregularities are regularly or randomly arranged. For example, the diameter of the convex part or the concave part is 5 to: LO O ^ m, and the concave part or convex part is a partial force of a sphere having a height of 0.1 to 2 m. May be combined.

 [0230] The material of the concavo-convex roller and the back roll may be metal, stainless steel, carbon steel, aluminum alloy, titanium alloy, ceramic, hard rubber, reinforced plastic, or a combination of these, but the strength and processing Point of ease of handling The concave-convex roller is preferably a metal. In particular, ease of cleaning and durability are also important, and it is preferable to use a stainless uneven roller. Particularly preferably, the surface-side uneven shape is formed of a metal material or a ceramic material for the viewing side, and the surface uneven-shape is formed of a rubber material for the back side. By using concavo-convex rollers of different materials, concavo-convex shapes with slightly different concavo-convex shapes (shapes of peaks, valleys, ridge lines, etc.) can be formed, and glare can be effectively prevented.

[0231] Further, the surface may be subjected to water repellency or water repellency. As a method of forming a desired concavo-convex surface on the concavo-convex roller, etching, sand blasting, mechanically It can be formed using a processing method or a mold. As the knock roll, hard rubber or metal is preferably used.

 [0232] The surface temperature T1 of the concavo-convex roller is T2 + 10 ° C to T2 + 55 ° C with respect to the thermal deformation temperature T2 of the resin used, preferably 2 +30 to 2 + 50 I like it. The heat distortion temperature T2 is a value measured according to ASTM D-648.

 [0233] When the surface temperature T1 of the concavo-convex roller is lower than the thermal deformation temperature T2, it becomes difficult to form a fine concavo-convex shape. If the surface temperature T1 exceeds 55 ° C than the heat distortion temperature T2, the flatness of the resulting film tends to deteriorate. The surface temperature T1 of the concavo-convex roller can be controlled by setting the temperature of the concavo-convex roller itself, the ambient temperature, the film temperature for forming the concavo-convex, the amount of residual solvent in the film, and the concavo-convex formation speed. The temperature of the concavo-convex roller itself can be controlled by circulating a temperature-controlled gas or liquid medium in the concavo-convex roller. For example, it is selected in accordance with the type of resin and the uneven shape to be formed in the range of 40 to 300 ° C, preferably 50 to 250 ° C. At that time, it is preferable to prevent the residual solvent in the film from foaming. Even if the surface of the concavo-convex roller is at a temperature equal to or higher than the boiling point of the residual solvent, foaming can be prevented if the concavo-convex formation speed is high. it can. For example, irregularities can be formed at a speed of lOmZmin or more.

 [0234] It is preferable to set the temperature of the knock roll to a temperature lower than that of the concave-convex roller, which is preferably controlled in the same manner.

 [0235] The roll pressure at the time of forming the unevenness is appropriately determined from a linear pressure of 5 to 500 NZcm, more preferably from 30 to 500 NZcm in consideration of the type of thermoplastic resin, the shape of the unevenness to be formed, temperature, etc. The

[0236] When the width of the cellulose ester film becomes wider, the illuminance unevenness of the irradiated light during UV curing cannot be ignored, not only the flatness is deteriorated, but also the hardness is uneven, and an antireflection layer is formed thereon. In this case, there is a problem that the uneven reflection becomes remarkable. Since the antireflection film of the present invention has a small amount and sufficient hardness can be obtained with the irradiation amount, even if there is unevenness of the irradiation amount in the width direction of the irradiated light, the unevenness of the hardness in the width direction is less likely to occur. Since an excellent antireflection film is obtained, a wide cellulose ester film is markedly effective! In particular, a width of 1.4 to 4 m is preferably used, and particularly preferably 1.4 to 3 m. Four If it exceeds m, conveyance becomes difficult.

[0237] (Antireflection layer)

 In the present invention, the method of providing an antireflection layer such as a low refractive index layer is not particularly limited, but it is preferably formed by coating.

[0238] In the present invention, an antireflection layer is produced by sequentially coating other functional layers on the cellulose ester film provided with a hard coat layer, using the above-described low refractive index layer composition. Is preferred.

[0239] Preferred configurations of the antireflection film are shown below, but are not limited thereto.

 Here, the no-coat layer means the above-mentioned active energy ray-cured resin layer.

[0241] Transparent support Z hard coat layer Z low refractive index layer

 Transparent support Z Hard coat layer Z High refractive index layer Z Low refractive index layer

 Transparent support Z Antistatic layer Z Hard coat layer Z High refractive index layer Z Low refractive index layer Transparent support Z Antiglare hard coat layer Z High refractive index layer Z Low refractive index layer

 Transparent support Z Antistatic layer Z Antiglare hard coat layer Z High refractive index layer Z Low refractive index layer The arithmetic average roughness (Ra) of the outermost surface of the antireflection film is 40 to less than 500 nm, preferably 60 to 300 nm. It is preferable to make it anti-glare.

 [0242] As a method of forming such unevenness on the outermost surface of the antireflection film, there is a method of forming unevenness on the antireflection film after applying the antireflection layer as described above. Since the convex portion may break through the antireflection layer or deform the antireflection layer to impair the antireflection effect, in the present invention, processing to a transparent support and processing to a hard coat layer are preferred. Unevenness is also formed on the outermost surface of the antireflection film by processing to a transparent support and processing to a hard coat layer.

 [0243] The arithmetic average roughness (Ra) of the outermost surface of the antireflection film can be measured using, for example, an optical interference type surface roughness meter RSTZPLUS (manufactured by WYKO) in the same manner as the hard coat layer.

[0244] In any case, the back coat layer described above is preferably provided on the surface of the transparent support opposite to the side on which the low refractive index layer is applied. [0245] In the present invention, after the hard coat layer is formed, the surface of the hard coat layer is subjected to a surface treatment, and the low refractive index layer according to the present invention is formed on the surface of the hard coat layer subjected to the surface treatment. Is preferred.

 [0246] The reflectance of the antireflection film according to the present invention can be measured with a spectrophotometer. At that time, after roughening the back side of the measurement side of the sample, use a black spray to perform light absorption treatment, and then measure the reflected light in the visible light region (400 to 700 nm). The lower the reflectance, the better. However, the average reflectance at wavelengths in the visible light region is preferably 1.5% or less, and the minimum reflectance is preferably 0.8% or less. Further, it is preferable that the reflection spectrum has a flat shape over the wavelength range of visible light.

 [0247] The reflection hue on the surface of the polarizing plate subjected to the antireflection treatment is colored red or blue because the reflectance in the short wavelength region and the long wavelength region is high in the visible light region due to the design of the antireflection film. In many cases, however, the color of the reflected light varies depending on the application, and when used on the outermost surface of an FPD TV or the like, a neutral color tone is required. In this case, the generally preferred reflection hue range is 0.17≤x≤0.27 and 0.007≤y≤0.17 on the XYZ color system (CIE1931 color system).

 [0248] The film thickness of the low refractive index layer is obtained by calculation according to a conventional method in consideration of the reflectance and the color of reflected light based on the refractive index of the layer.

 [0249] The surface treatment of the hard coat layer is performed by a cleaning method, an alkali treatment method, a flame plasma treatment method, a high-frequency discharge plasma method, an electron beam method, an ion beam method, a sputtering method, an acid treatment, a corona treatment method, or an atmospheric pressure plasma method. The alkali treatment method, the corona treatment method, and the atmospheric pressure plasma method are preferable, and the atmospheric pressure plasma method is particularly preferable.

 [0250] (Corona treatment method)

Corona treatment is a treatment performed by applying a high voltage of lkV or higher between electrodes at atmospheric pressure and discharging it, and it is commercially available from Kasuga Electric Co., Ltd. and Toyo Electric Co., Ltd. This can be done using a device. The intensity of the corona discharge treatment depends on the distance between the electrodes, the output per unit area, and the generator frequency. One electrode (A electrode) of the corona treatment device can be a commercially available force Material such as aluminum or stainless steel can be selected. The other is an electrode (B electrode) for holding a plastic film. The roll electrode is disposed at a certain distance from the A electrode so that the na treatment is performed stably and uniformly. The ones that are usually sold on the market can also be used, and the material is a roll made of aluminum, stainless steel, or a metal thereof, and a roll that is lined with ceramic, silicone, EPT rubber, high ballon rubber, or the like. Preferably used. The frequency used for the corona treatment used in the present invention is a frequency of 20 to: LOO kHz, and preferably a frequency of 30 to 60 kHz. When the frequency is lowered, the uniformity of the corona treatment is deteriorated and unevenness of the corona treatment occurs. In addition, when the frequency is increased, there is no particular problem when performing high-power corona processing, but when performing low-power corona processing, it becomes difficult to perform stable processing. Processing unevenness occurs. Output of corona treatment, l~5wmin. Zm ² a is force 2～4Wmin. Output Zm ² is preferred. The distance between the electrode and the film is a force of 5 to 50 mm, preferably 10 to 35 mm. When the gap opens, a higher voltage is required to maintain a constant output, and unevenness is likely to occur. If the gap is too narrow, the applied voltage becomes too low and unevenness is likely to occur. Furthermore, when the film is conveyed and continuously processed, the film comes into contact with the electrodes and scratches are generated.

 [0251] (Alkaline treatment method)

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

 [0252] As the alkaline aqueous solution, an aqueous sodium hydroxide solution, an aqueous potassium hydroxide solution, an aqueous ammonia solution or the like can be used, and among them, an aqueous sodium hydroxide solution is preferable.

[0253] The alkali concentration of the alkali aqueous solution, for example Mizusani匕sodium concentration is preferably 0.1 to 25 mass%, 0.5 to 15 weight _^0/0 is more preferable.

 [0254] The alkali treatment temperature is usually 10 to 80 ° C, preferably 20 to 60 ° C.

 [0255] The alkali treatment time is 5 seconds to 5 minutes, preferably 30 seconds to 3 minutes. It is preferable to neutralize the alkali-treated film with acid water and then wash it thoroughly with water.

 [0256] (Atmospheric pressure plasma method)

In the present invention, a discharge is formed by applying a high-frequency voltage having a frequency of 5 OkHz to 150 MHz between opposing electrodes under atmospheric pressure or a pressure near the atmospheric pressure, and the discharge is formed. It is preferable to form the antireflection layer by coating after bringing the excitation gas into contact with the transparent support or the surface of the film having the hard coat layer on the transparent support.

[0257] The frequency is preferably 50 kHz to 27 MHz! /.

 [0258] It is preferable that the opposing electrode is composed of a first electrode and a second electrode, and the frequency of the high-frequency voltage applied to any one of the electrodes is 50 kHz to 150 MHz. Moreover, it is preferable that the frequency of the high-frequency voltage applied to the first electrode is 1 to 200 kHz, and the frequency of the high-frequency voltage applied to the second electrode is 800 kHz to 150 MHz.

 [0259] Hereinafter, the plasma discharge treatment performed at or near atmospheric pressure is also simply referred to as the atmospheric pressure plasma method.

 [0260] That is, the present invention provides a transparent support or a film having a hard coat layer on the transparent support, between the counter electrodes constituted by the first electrode and the second electrode under atmospheric pressure or a pressure in the vicinity thereof. A high frequency voltage having a voltage component of the first frequency ω is applied to the first electrode, and the second electrode is applied to the second electrode.

 1

 Second frequency ω

 A high frequency voltage having a voltage component of 2 is applied to form a discharge, and the surface of the transparent support is brought into contact with the excitation gas formed by the discharge, and then an antireflection layer is formed thereon.

 As the atmospheric pressure plasma method applicable to the present invention, JP-A-11-133205, JP-A-2000-185362, JP-A-11-61406, JP-A-2000-147209, 2000- You can refer to the technology disclosed in 121804

[0262] The atmospheric pressure plasma method used in the present invention will be described.

[0263] First, an atmospheric pressure plasma method and apparatus useful for the present invention will be described.

[0264] In the present invention, a gas is supplied to the discharge space (between the counter electrodes) under atmospheric pressure or a pressure in the vicinity thereof, a high frequency voltage is applied to the discharge space, and the gas is excited into a plasma state. A transparent support or the surface of a film having a hard coat layer on the transparent support is exposed to an excited plasma state gas. The high frequency voltage applied to the discharge space formed between the counter electrodes may be a high frequency of one frequency, or may be a high frequency of two or more frequencies.

In the present invention, the atmospheric pressure plasma treatment is performed under atmospheric pressure or a pressure in the vicinity thereof. However, the atmospheric pressure or the pressure in the vicinity thereof is about 20 to 110 kPa, and 93 to 104 kPa is preferable in order to obtain the good effects described in the present invention.

 [0266] In the present invention, the gas supplied between the counter electrodes (discharge space) is at least an excitation gas excited by a high-frequency voltage, or an excitation gas excited by a high-frequency voltage and its energy to receive a plasma state or Including the gas in an excited state. The high frequency referred to in the present invention means one having a frequency of at least 0.5 kHz.

 [0267] When plasma discharge treatment is performed with a high frequency voltage of one frequency (sometimes referred to as a one-frequency high-frequency voltage application method), or when plasma discharge treatment is performed with a high-frequency voltage of two frequencies (a two-frequency high-frequency voltage application method) The same electrode can be used, and the device itself is not significantly different. The difference is that there are two high-frequency power supplies and an associated filter, and that the electrode force high-frequency voltage of both counter electrodes is applied.

 [0268] In the case of the one-frequency high-frequency voltage application method useful in the present invention, one of the counter electrodes is a ground electrode, and the other is an application electrode, and a high-frequency power source is connected to the application electrode. The ground electrode is grounded.

The thin film forming apparatus (atmospheric pressure plasma processing apparatus) of each of the 1-frequency high-frequency voltage application method and the 2-frequency high-frequency voltage application method will be described with reference to the drawings.

[0270] FIG. 3 is a schematic diagram showing an example of a single-frequency high-frequency voltage application type thin film forming apparatus useful for the present invention.

[0271] A counter electrode is formed by an application electrode (square tube electrode) 136 for applying a high-frequency voltage inside the plasma discharge vessel 130 and a roll-type ground electrode 135 around which the base film F is wound. ing. Any number of the application electrodes 136 may be arranged. The gas G is supplied from the gas supply port 152 of the plasma discharge container 10, passes through the mesh for uniformizing the gas G, passes between the application electrode 136 and along the inner wall of the application electrode and the plasma discharge vessel 131, The discharge space 13 is filled with gas G. A high-frequency voltage is applied to the application electrode 136 by the high-frequency power source 21, and the base film F is exposed to the gas G excited in the discharge space 132. The frequency of the applied high frequency voltage is preferably 50 kHz or more. More preferably, it is in the range of 50 kHz to 15 OMHz. [0272] The effect of the present invention cannot be obtained at less than 50 kHz. Also, if the frequency exceeds 150 MHz, it is difficult to form a discharge and complicated equipment is required. Also, the generation of potential distribution causes non-uniform processing, making it unsuitable for large-area processing, and is suitable for the present invention. It is not considered.

 [0273] While the base film F is exposed to the excited gas G, the electrode is heated or cooled via the pipe from the electrode temperature adjusting means 160. An insulating material such as distilled water or oil is preferably used as the temperature control medium. During the plasma discharge treatment, it is desirable to uniformly adjust the temperature inside the electrode so that the temperature unevenness of the substrate in the width direction or the longitudinal direction does not occur as much as possible.

 [0274] In the present invention, the base film F is the transparent support film, that is, the base film, a film obtained by applying a hard coat layer on the base film, or a high film thereon. It may be a film coated with a refractive index layer and Z or a medium refractive index layer.

 FIG. 4 is a schematic diagram showing another example of a two-frequency high-frequency voltage application type thin film forming apparatus useful for the present invention. In the same manner as in FIG. 3, the base film F is subjected to plasma discharge treatment between the opposing electrodes (discharge space) 132 between the roll electrode (first electrode) 135 and the square tube electrode group (second electrode) 136. It is.

 [0276] The discharge space (between the counter electrodes) 132 between the roll electrode (first electrode) 135 and the square tube electrode group (second electrode) 136 is the first electrode in the roll electrode (first electrode) 135. From electrode 141 at frequency ω

 One high-frequency voltage V, and the rectangular tube electrode group (second electrode) 136 from the second power source 142

 1

 A high frequency voltage V is applied at several ω.

 twenty two

[0277] Between the roll electrode (first electrode) 135 and the first power supply 141, the first filter 143 is arranged so that the current from the first power supply 141 flows toward the roll electrode (first electrode) 135. The first filter is designed to make it difficult for the current from the first power source 141 to pass through and to easily pass the current from the second power source 142. In addition, the gap between the rectangular tube electrode group (second electrode) 136 and the second power source 142 is such that a second filter 144 is installed so that a current of the second power source flows toward the second electrode. The second filter 144 is designed to make it difficult for the current from the second power source 142 to pass through and to easily pass the current from the first power source 141! Here, the phrase “difficult to pass” preferably means that only 20% or less, more preferably 10% or less, of the current passes. On the contrary, being easy to pass is preferably 80% or more of the current, more preferably More than 90% is recommended.

 [0278] In the present invention, any filter having the above properties can be used without limitation.

 For example, as the first filter, a capacitor of several tens to several tens of thousands of pF or a coil of about several H can be used depending on the frequency of the second power source. The second filter can be used as a filter by using a coil of 10 H or higher according to the frequency of the first power supply and grounding it through these coils or capacitors.

 [0279] In the present invention, the roll electrode 135 may be the second electrode, and the rectangular tube electrode group 136 may be the first electrode. In any case, the first power source is connected to the first electrode, and the second power source is connected to the second electrode. In addition, the first power supply can apply a higher frequency voltage (V> V) than the second power supply.

 It only needs to have the ability to 1 2. The frequency should have the ability to satisfy ω <ω.

 1 2

 Yes.

 The gas G generated by the gas supply device 151 of the gas supply means 150 is introduced into the plasma discharge treatment vessel 131 through the supply port 152 while controlling the flow rate. The inside of the discharge space 132 and the plasma discharge treatment vessel 131 is filled with gas G.

 [0281] The base film F shown in the figure, the original winding force, the force that is unwound and conveyed, or the material film that is conveyed from the previous step, passes through the guide roll 164, and the substrate is made by the roll 165 Shut off the air entrained by the film, roll it while it is in contact with the roll electrode 135, and transfer it to and from the rectangular tube electrode group 136. Roll electrode (first electrode) 135 and the rectangular tube electrode A voltage is also applied to both the group (second electrode) 136 and a discharge plasma is generated between the counter electrodes (discharge space) 132. The base film F is exposed to the plasma state gas while being wound while being in contact with the roll electrode 135. The base film F passes through the -roll roll 166 and the guide roll 1 67, and is transferred to the next process by the winding force not shown.

 [0282] Discharged treated exhaust gas G 'is discharged from the exhaust port 153.

[0283] During the exposure to the plasma gas, the temperature was adjusted by the electrode temperature adjusting means 160 in order to heat or cool the roll electrode (first electrode) 135 and the rectangular tube electrode group (second electrode) 136. The medium is sent to both electrodes via pipe 161 with a liquid feed pump Ρ, and the temperature is adjusted from the inside of the electrode. Reference numerals 165 and 166 denote partition plates that partition the plasma discharge processing vessel 131 from the outside. [0284] In the present invention, the applied high-frequency voltage may be an intermittent pulse wave or a continuous sine wave, but is not limited to an applied voltage waveform. In order to form a strong thin film, a sine wave is preferable.

 In the present invention, the frequency of the high frequency voltage applied to the first electrode is preferably 1 to 200 kHz, and the frequency of the high frequency voltage applied to the second electrode is preferably 800 kHz or more.

[0286] The power density at that time is preferably 1 to 50 W / cm ² (where the denominator cm ² is the area where discharge occurs! /), More preferably 1.2 to 30 WZcm ² It is.

[0287] High-frequency power supplies useful for the present invention include 100 kHz * (manufactured by HEIDEN Laboratory), 200 kHz

800 kHz, 2 MHz, 13.56 MHz, 27 MHz, and 150 MHz (all manufactured by Nord Kogyo). The asterisk indicates the HEIDEN Institute impulse high-frequency power supply (100 kHz in continuous mode).

In the present invention, it is necessary to employ an electrode capable of maintaining a uniform glow discharge state described below by applying such a voltage to a plasma discharge processing apparatus.

FIG. 5 is a perspective view showing an example of the structure of the conductive metallic base material of the roll electrode shown in the figure and the dielectric material coated thereon.

In FIG. 5, a roll electrode 35a is formed by covering a conductive metallic base material 35A and a dielectric 35B thereon. The inside is a hollow jacket for temperature control.

 FIG. 6 is a perspective view showing an example of the structure of the conductive metallic base material of the rectangular tube type electrode shown in FIGS. 3 and 4 and the dielectric material covered thereon.

[0292] In Fig. 6, a rectangular tube electrode 36a has a coating of a dielectric 36B similar to Fig. 5 on a conductive metallic base material 36A, and the structure of the electrode is a metallic pipe. It becomes a jacket that allows temperature adjustment during discharge.

[0293] Note that the number of rectangular tube-type electrodes is set in plural along a circumference larger than the circumference of the roll electrode, and the discharge area of the electrodes is a full-square tube facing the roll electrode 35. It is expressed as the sum of the area of the type electrode surface.

[0294] The rectangular tube electrode 36a shown in Fig. 6 may be a cylindrical electrode, but the rectangular tube electrode is a cylindrical electrode. Since it has the effect of extending the discharge range (discharge area) compared to the pole, it is preferably used in the present invention.

 [0295] In Figs. 3 and 4, the roll electrode 35a and the rectangular tube electrode 36a are encapsulated with inorganic compounds after spraying ceramics as dielectrics 35B and 36B on conductive metallic base materials 35A and 36A, respectively. The material is sealed using a pore material. The ceramic dielectric only needs to be covered by about 1 mm with a single wall. As a ceramic material used for thermal spraying, alumina or silicon nitride is preferably used. Among these, alumina is particularly preferred because it is easy to process. In addition, the dielectric layer may be a lining-processed dielectric provided with an inorganic material by glass lining.

 [0296] The conductive metallic base materials 35A and 36A include metals such as titanium or titanium alloys, silver, platinum, stainless steel, aluminum and iron, composite materials of iron and ceramics, or aluminum and ceramics. Forces that can mention composite materials Titanium or a titanium alloy is particularly preferred for the reasons described below.

 [0297] The distance between the two electrodes (electrode gap) is determined in consideration of the thickness of the dielectric provided on the conductive metal base material, the magnitude of the applied voltage, the purpose of using the plasma, etc. However, the shortest distance between the dielectric surface when the dielectric is provided on one of the electrodes and the surface of the conductive metallic base material, and the distance between the dielectric surfaces when the dielectric is provided on both electrodes In any case, the viewpoint power for performing uniform discharge is preferably 0.1 to 20 mm, and more preferably 0.5 to 2 mm.

 [0298] The plasma discharge treatment vessel 10 or 31 is preferably a treatment vessel made of Pyrex (registered trademark) glass or the like, but may be made of metal as long as it can be insulated from the electrodes. For example, it is also possible to achieve insulation by spraying ceramics on the metal frame, which may be affixed with polyimide resin or the like on the inner surface of an aluminum or stainless steel frame. In Fig. 6, it is preferable to cover both sides of the parallel electrodes (up to near the substrate surface) with the material of the above-mentioned material.

 [0299] The conductive metal base material and dielectric useful in the present invention will be described in detail.

[0300] The electrodes used in such a high-power atmospheric pressure plasma method are structurally and performance-friendly. It must be able to withstand harsh conditions. Such an electrode is preferably a metal base material coated with a dielectric.

[0301] In the dielectric-coated electrode used in the present invention, one of the characteristics that is suitable between various metallic base materials and dielectrics is preferred. the difference in the linear thermal expansion coefficient is of the combination of the following 10 X 10- ⁶ Z ° C. Preferably below 8 X 10- ⁶ Z ° C, more preferably not more than 5 X 10- ⁶ Z ° C, more preferably not more than 2 X 10- ⁶ Z ° C. The linear thermal expansion coefficient is a well-known physical property value of a material.

 [0302] A combination of a conductive metallic base material and a dielectric whose difference in linear thermal expansion coefficient is within this range is as follows:

 Metal matrix Dielectric

 (1) Pure titanium or titanium alloy ceramic spray coating

 (2) Pure titanium or titanium alloy glass lining

 (3) Stainless steel Ceramic spray coating

 (4) Stainless steel glass lining

 (5) Ceramics and iron composite material Ceramic spray coating

 (6) Composite materials of ceramics and iron Glass lining

 (7) Composite material of ceramics and aluminum Ceramic spray coating

 (8) Composite material of ceramics and aluminum Glass lining

 Etc. From the viewpoint of the difference in linear thermal expansion coefficient, (1) or (2) and (5) to (8) are preferred, and (1) is particularly preferred.

 [0303] In the present invention, titanium or a titanium alloy is particularly useful as the metallic base material from the above characteristics. By using titanium or titanium alloy as the metal base material, by using the above dielectric material, it can withstand long-term use under harsh conditions where there is no deterioration of the electrode in use, especially cracking, peeling, or falling off. be able to.

[0304] The metallic base material of the electrode useful in the present invention is a titanium alloy or titanium containing 70 mass% or more of titanium. In the present invention, if the titanium content in the titanium alloy or titanium is 70% by mass or more, it can be used without problems, but preferably contains 80% by mass or more of titanium. Titanium alloys or titanium useful in the present invention are: Those commonly used as industrial pure titanium, corrosion-resistant titanium, high-strength titanium and the like can be used. Examples of pure titanium for industrial use include TIA, TIB, TIC, TID, etc., all of which contain very few iron atoms, carbon atoms, nitrogen atoms, oxygen atoms, hydrogen atoms, etc. The content is 99% by mass or more. As the corrosion-resistant titanium alloy, T15PB can be preferably used, and it contains lead in addition to the above-mentioned atoms, and the titanium content is 98% by mass or more. Further, as the titanium alloy, T64, Τ325, Τ525, 等 3, etc. containing aluminum and other vanadium and tin in addition to the above-mentioned atoms excluding lead can be preferably used. As a quantity, it contains 85% by mass or more. These titanium alloys or titanium have a coefficient of thermal expansion smaller than that of stainless steel, such as AISI316, by about 1Z2, and can be combined with a titanium alloy or a dielectric described later on titanium as a metallic base material. Can withstand use at high temperatures for long periods of time.

 [0305] On the other hand, as the required characteristics of the dielectric, specifically, an inorganic compound having a relative dielectric constant of 6 to 45 is preferable. Also, as such a dielectric, alumina, silicon nitride, and the like are preferable. And glass lining materials such as silicate glass and borate glass. Of these, those sprayed with ceramics described later and those provided with glass lining are preferred. In particular, a dielectric with thermal spraying of alumina is preferred.

 [0306] Alternatively, as one of the specifications that can withstand high power as described above, the dielectric porosity is 10 volume% or less, preferably 8 volume% or less, and preferably exceeds 0 volume%. 5% by volume or less. The porosity of the dielectric can be measured by the BET adsorption method or mercury porosimeter. In the examples described later, the porosity is measured using a piece of dielectric covered with a metallic base material by a mercury porosimeter manufactured by Shimadzu Corporation. Dielectric force High durability is achieved by having a low porosity. Examples of the dielectric having such voids and a low void ratio include a high-density, high-adhesion ceramic sprayed coating by the atmospheric plasma spraying method described later. In order to further reduce the porosity, it is preferable to perform a sealing treatment.

[0307] In the above-mentioned atmospheric plasma spraying method, fine powders such as ceramics, wires, etc. are put into a plasma heat source and sprayed onto the metal base material to be coated as fine particles in a molten or semi-molten state. This is a technique for forming a film. A plasma heat source is a high-temperature plasma gas in which a molecular gas is heated to a high temperature, dissociated into atoms, and further given energy to release electrons. Compared with conventional arc spraying or flame spraying, which has a higher plasma gas spraying speed, the sprayed material collides with the metallic base material at a higher speed, so a high-density coating with higher adhesion strength can be obtained. For details, reference can be made to a thermal spraying method for forming a heat shielding film on a high-temperature exposed member described in JP-A-2000-301655. By this method, the porosity of the dielectric (ceramic sprayed film) to be coated can be obtained.

[0308] Another preferable specification that can withstand high power is that the thickness of the dielectric is 0.5 to 3 mm. This film thickness variation is desirably 5% or less, preferably 3% or less, and more preferably 1% or less.

[0309] In order to further reduce the porosity of the dielectric, as described above, the thermal spray film such as ceramics is applied.

Further, it is preferable to perform a sealing treatment with an inorganic compound. Of these, metal oxides are preferred as the inorganic compound, and those containing silicon oxide (SiO 2) as the main component are particularly preferred.

 [0310] The inorganic compound for sealing treatment is preferably formed by curing by a sol-gel reaction. In the case where the inorganic compound for sealing treatment contains a metal oxide as a main component, a metal alkoxide or the like is applied as a sealing liquid on the ceramic sprayed film and cured by sol-gel reaction. When the inorganic compound is mainly composed of silica, it is preferable to use alkoxysilane as the sealing liquid.

 [0311] Here, it is preferable to use energy treatment to promote the sol-gel reaction. Examples of the energy treatment include thermal curing (preferably 200 ° C. or less) and ultraviolet irradiation. Further, as a method of sealing treatment, when the sealing liquid is diluted, and coating and curing are repeated several times in succession, the inorganic quality is improved more and a dense electrode without deterioration can be obtained.

[0312] In the case of performing a sealing treatment that cures by a sol-gel reaction after coating a ceramic sprayed coating using a metal alkoxide or the like of a dielectric-coated electrode as a sealing liquid, the content of the metal oxide after curing is 60 It is preferable to be at least mol%! /. When alkoxysilane is used as the metal alkoxide of the sealing liquid, the cured SiO 2 (X is 2 or less) content is preferably 60 mol% or more. The SiO content after curing is determined by XPS. It is measured by analyzing.

 [0313] In the present invention, the maximum height (Rmax) of the surface roughness specified in JIS B 0601: 2001 on at least the side of the electrode in contact with the base material is adjusted to be 10 m or less. The viewpoint power for obtaining the effects described in the present invention is preferable, but more preferably, the maximum value of surface roughness is not more than ^ / zm, and particularly preferably 7 m or less. By such a method of polishing the dielectric surface of the dielectric-coated electrode, the thickness of the dielectric and the gap between the electrodes can be kept constant, the discharge state can be stabilized, and further, the heat can be reduced. Distortion and cracking due to differences and residual stresses can be eliminated, and durability can be greatly improved with high accuracy. The polishing finish on the dielectric surface is preferably performed at least on the dielectric that is in contact with the substrate. Further, the arithmetic average roughness (Ra) defined in JIS B 0601: 2001 is preferably 0.5 μm or less, and more preferably 0.1 μm or less.

 [0314] The dielectric coated electrode used in the present invention! On the other hand, another preferred specification that can withstand high power is that the heat-resistant temperature is 100 ° C or higher. More preferably, it is 120 ° C or higher, particularly preferably 150 ° C or higher. The upper limit is 500 ° C. The heat-resistant temperature refers to the highest temperature that can withstand normal discharge without breakdown. For such heat-resistant temperatures, the above ceramic spraying and the dielectric provided with layered glass linings with different amounts of bubbles mixed can be applied, or the range of difference in linear thermal expansion coefficient between the metallic base material and dielectric below. This can be achieved by appropriately combining means for appropriately selecting the materials.

 [0315] In the present invention, it is necessary to employ an electrode capable of maintaining a uniform glow discharge state by applying such a voltage in a plasma discharge treatment apparatus.

[0316] In the present invention, the power applied between the opposing electrodes supplies a power density of 1 to 50 WZcm ^{2 to} the second electrode, excites the discharge gas to generate plasma, and converts the energy into a thin film forming gas. To form a thin film. Preferably is 1. 2~30WZcm ^2.

[0317] Here, regarding the method of applying the high-frequency power supply, either a continuous sine wave continuous oscillation mode called continuous mode or an intermittent oscillation mode called ON / OFF intermittently called pulse mode may be adopted. At least on the second electrode side, the continuous sine wave is preferred because a finer and better quality film can be obtained. [0318] The discharge condition is that a high frequency voltage is applied to the discharge space between the opposing first electrode and second electrode, and the high frequency voltage is derived from the voltage component of the first frequency ω and the first frequency ω. Second high

 1 1

 It is preferable to have at least a component obtained by superimposing a voltage component of frequency ω.

 2

 [0319] The high frequency voltage is higher than the voltage component of the first frequency ω and the first frequency ω.

 1 1 The component with the voltage component of the second frequency ω superimposed, and its waveform is

 2 1 A sine wave with a higher frequency ω superimposed on a sine wave

 twenty one

 It becomes. Even if it is a double pulse wave that is not limited to a waveform with superimposed sine waves, it does not matter if one is a sine wave and the other is a pulse wave. Further, it may have a third voltage component. However, in the present invention, as in the case of the one-frequency high-frequency voltage application method, a continuous sine wave at least on the second electrode side can provide a denser and better film.

 [0320] In the present invention, the discharge start voltage refers to the lowest voltage that can cause discharge in the discharge space (electrode configuration, etc.) and reaction conditions (gas conditions, etc.) actually used. The The discharge start voltage varies slightly depending on the type of gas supplied to the discharge space, the dielectric type of the electrode, etc., but may be considered to be substantially the same as the discharge start voltage of the discharge gas alone.

 [0321] By applying a high-frequency voltage as described above between the counter electrodes (discharge space), it is presumed that discharge can be caused and high-density plasma can be generated.

 [0322] In the present invention, a specific method of applying a high-frequency voltage to the discharge space is to apply a first high-frequency voltage having a frequency ω and a voltage V to the first electrode constituting the counter electrode.

 1 1

 A second high-frequency voltage of frequency ω and voltage V is connected to the second electrode.

 twenty two

 A thin film forming apparatus (atmospheric pressure plasma processing apparatus) to which a second power source for applying the voltage is connected is used.

[0323] The application of a high-frequency voltage from such two high-frequency power sources means that the first frequency ω side

 1 is necessary to start discharge of a discharge gas having a high discharge starting voltage, and the second frequency ω side is necessary to increase the plasma density and form a dense and high-quality thin film.

 2

 It ’s important to say that!

[0324] In the present invention, a high frequency voltage of about 1 to 200 kHz is applied from the first electrode using the first power supply, and a high frequency voltage of about 800 kHz to 15 MHz is applied from the second electrode using the second power supply. It is preferable to apply. In this case, the applied high frequency voltage of l ~ 200kHz A discharge gas having a high discharge start voltage is excited to generate plasma.

 [0325] Furthermore, it is preferable that the first power source has the capability of applying a higher high-frequency voltage than the second power source.

 [0326] Further, as another discharge condition in the present invention, a high frequency voltage is applied between the first electrode and the second electrode facing each other, and the high frequency voltage is applied to the first high frequency voltage V and the second high voltage. High frequency

 1

 When the voltage V is superimposed and the discharge start voltage is IV,

 2

 V≥IV> V

 1 2

 Or V> IV≥V

 1 2

 Meet. More preferably,

 V> IV> V

 1 2

 Is to satisfy.

 [0327] The definition of the high frequency and the discharge start voltage and the specific method of applying the high frequency voltage between the counter electrodes (discharge space) are the same as those described above.

 [0328] Here, the high-frequency voltage (applied voltage) and the discharge start voltage are those measured by the following methods.

 [0329] Measuring method of high frequency voltage V and V (unit: kV / mm):

 1 2

 Install a high-frequency probe (P6015A) for each electrode, connect the high-frequency probe to an oscilloscope (Tektronix, TDS3012B), and measure the voltage.

[0330] Measuring method of discharge start voltage IV (unit: kV / mm):

 The discharge gas is supplied between the electrodes, the voltage between the electrodes is increased, and the voltage at which discharge starts is defined as the discharge start voltage IV. The measuring instrument is the same as the above high-frequency voltage measurement.

[0331] By adopting a discharge condition in which a high voltage is applied, even a discharge gas having a high discharge start voltage such as nitrogen gas can start the discharge gas and maintain a high-density and stable plasma state.

 [0332] When the discharge gas is nitrogen gas by the above measurement, the discharge start voltage IV is about 3.7 kV Zmm. Therefore, in the above relationship, the first high-frequency voltage is V≥3.7k

 1

By applying it as VZmm, the nitrogen gas can be excited and put into a plasma state. [0333] As the discharge gas, there are noble gases such as nitrogen, helium, and argon, air, hydrogen, oxygen, etc., and these may be used alone as a discharge gas or mixed and used. The use of nitrogen gas is particularly preferred because it can provide higher discharge gas economy than the use of rare gases such as helium or argon.

 [0334] The high-frequency power source installed in the atmospheric pressure plasma processing apparatus is the same as described above, but it is divided into the first power source (high-frequency power source) and the second power source (high-frequency power source) as follows. .

 [0335] As the first power supply,

 High frequency power supply symbol Manufacturer Frequency

 A1 Shinko Electric 3kHz

 A2 Shinko Electric 5kHz

 A3 Kasuga Electric 15kHz

 A4 Shinko Electric 50kHz

 A5 HEIDEN Laboratory 100kHz *

 A6 Pearl Industry 200kHz

 The asterisk is the HEIDEN Institute impulse high-frequency power supply (100 kHz in continuous mode).

 High frequency power supply symbol Manufacturer Frequency

 B1 par industrial 800kHz

 B2 pulse industry 2MHz

 B3 Pal Industry 13. 56MHz

 B4 Pulse Industry 27MHz

 B5 Pulse Industrial 150MHz

 And the like, and any of them can be preferably used.

[0337] At least one electrode force of the counter electrode is preferably provided with a gas supply means for supplying a discharge gas between the counter electrodes. Furthermore, it is preferable to have an electrode temperature control means for controlling the temperature of the electrode. [0338] Further, although the metal base material and the dielectric are not shown in the electrodes of Figs. 6 and 7, the same dielectric is coated on the metal base material of the electrode as in Figs. That's ugly.

 [0339] The high-frequency voltage applied between the counter electrodes may be an intermittent pulse wave or a continuous sine wave. However, in order to obtain a high effect of the present invention, a continuous sine wave may be used. A wave is preferred.

 [0340] In the present invention, the distance between the electrodes is determined in consideration of the thickness of the dielectric provided on the metal base material of the electrodes, the magnitude of the applied voltage, and the like. When the dielectric is placed on one of the electrodes, the shortest distance between the dielectric and the electrode, and when the dielectric is placed on both of the electrodes, the distance between the dielectric and the dielectric is uniform. The viewpoint power is preferably 0.5 to 20 mm, more preferably 0.5 to 5 mm, still more preferably 0.5 to 3 mm, and particularly preferably lmm ± 0.5 mm.

 [0341] Each layer of the antireflection layer is formed on a transparent support by a dip coating method, an air knife coating method, a curtain coating method, a roller coating method, a wire bar coating method, a gravure coating method, a microgravure coating method or an etch. It can be formed by coating using a rouge coating method. Upon coating, it is preferable that the transparent support is rolled up in a roll shape with a width of 1.4 to 4 m, and is applied in the above-mentioned manner, applied and dried / cured, and then wound into a roll. .

 [0342] Furthermore, the antireflection film of the present invention is produced by a production method in which an antireflection layer or the like is laminated on a transparent support and then heat-treated at 50 to 160 ° C in a state of being wound in a roll. It is preferable to do. The duration of the heat treatment may be determined appropriately according to the set temperature.For example, if it is 50 ° C, it is preferably 3 days or more and less than 30 days, if it is 160 ° C, it is 10 minutes or more and 1 day or less. The range of is preferable. Usually, it is preferable to set it at a relatively low temperature so that the heat treatment effect at the outside of the heel, the center of the heel, and the core is not biased.

 [0343] In order to perform heat treatment stably, it is necessary to perform in a place where the temperature and humidity can be adjusted, and it is preferable to perform in a heat treatment room such as a clean room without dust.

[0344] The winding core for winding the antireflection film into a roll is not particularly limited as long as it is a cylindrical core, but is preferably a hollow plastic core, which is a plastic material. For example, a heat-resistant plastic that can withstand the heat treatment temperature is preferable, and examples thereof include resins such as phenol resin, xylene resin, melamine resin, polyester resin, and epoxy resin. Thermosetting resin reinforced with fillers such as glass fiber is preferred.

[0345] The winding number of these winding cores is preferably 100 windings or more, more preferably 500 windings or more, and the winding thickness more preferably 5 cm or more.

[0346] When the heat treatment is performed in a state where the long antireflection film is wound in this manner, the rotation preferably rotating the roll has a speed of 1 rotation or less per minute. It may be continuous or intermittent rotation as desired. Further, it is preferable to perform the roll rewinding once or more during the heating period.

[0347] In order to rotate the long antireflection film wound around the core during the heat treatment, it is preferable to provide a dedicated turntable in the heat treatment chamber.

[0348] In the case of intermittent rotation, it is preferable that the stopping time is within 10 hours. It is preferable that the stop position is uniform in the circumferential direction. The stopping time is 10 minutes. It is more preferable to be within the range. Most preferred is continuous rotation.

[0349] The rotation speed in continuous rotation is preferably set to 10 hours or less for one rotation, and if it is fast, it is burdensome to the apparatus, so the range of 15 minutes to 2 hours is practically preferable. Good.

 [0350] In the case of a dedicated carriage having a rotation function, it is preferable that the optical film roll can be rotated during movement and storage. In this case, it is preferable to prevent black bands that occur when the storage period is long. As the rotation works effectively.

 [Polarizer]

 A polarizing plate using the antireflection film of the present invention will be described.

[0352] The polarizing plate can be produced by a general method. The back surface side of the antireflection film of the present invention is subjected to an alkali hatching treatment, and the treated antireflection film is immersed and stretched in an iodine solution. It is preferable to use an aqueous solution. The antireflection film may be used on the other surface, or another polarizing plate protective film may be used. With respect to the antireflection film of the present invention, the polarizing plate protective film used on the other surface is an in-plane retardation Ro of 590η. It is preferably an optical compensation film (retardation film) having a retardation of 20 to 70 nm and Rt of 100 to 400 nm. These can be prepared, for example, by the methods described in JP-A No. 2002-71957 and Japanese Patent Application No. 2002-155395. Alternatively, it is preferable to use a polarizing plate protective film that also serves as an optical compensation film having an optically anisotropic layer formed by aligning a liquid crystal compound such as a discotic liquid crystal. For example, the optically anisotropic layer can be formed by the method described in JP-A-2003-98348. By using in combination with the antireflection film of the present invention, a polarizing plate having excellent flatness and a stable viewing angle expansion effect can be obtained.

[0353] As the polarizing plate protective film used on the back side, commercially available cellulose ester films include KC8UX2MW, KC4UX, KC5UX, KC4UY ゝ KC8UY ゝ KC12UR, KC8UCR-3, KC8UCR-4, KC8UCR-5 (co-caminoltopto) Etc.) are preferably used.

 [0354] The polarizing film, which is the main component of the polarizing plate, is an element that passes only light having a plane of polarization in a certain direction. A typical polarizing film that is currently known is a polyvinyl alcohol polarizing film. However, this is not limited to this, although there are a polyburoalcohol-based film dyed with iodine and a dichroic dye dyed. For the polarizing film, a polyvinyl alcohol aqueous solution is formed, and the film is uniaxially stretched and dyed, and after being dyed, the film is uniaxially stretched and is preferably subjected to a durability treatment with a boron compound. A polarizing film having a thickness of 5 to 30 111, preferably 8 to 15 m is preferably used. On the surface of the polarizing film, one side of the antireflection film of the present invention is bonded to form a polarizing plate. Bonding is preferably performed using a water-based adhesive mainly composed of completely acid-polybutyl alcohol or the like.

[0355] [Image display device]

By incorporating the antireflection film surface of the polarizing plate using the antireflection film of the present invention into the viewing surface side of the image display device, various image display devices with excellent visibility can be produced. The antireflection film of the present invention can be applied to various types of drive systems such as reflective, transmissive, transflective LCD, TN, STN, OCB, HAN, VA (PVA, MVA), and IPS. It is preferably used in LCDs. In addition, the antireflection film of the present invention is reflective. The prevention layer has very little color unevenness in the reflected light, and the reflectance is low, and it has excellent flatness. It is also used in various display devices such as plasma display, field emission display, organic EL display, inorganic EL display, and electronic paper. Preferably used. In particular, an image display device with a large screen of 30-inch or larger has the effect of preventing eyestrain even during long-time viewing with less color unevenness and wavy unevenness.

 Example

 [0356] Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited thereto. Unless otherwise specified, “%” in the examples represents “mass%”.

[0357] Example 1

 <Preparation of antireflection film 1>

 <Preparation of transparent support>

 A transparent support with a transparent cellulose triacetate film (film thickness 80 m, width 1330 mm) was produced as follows.

[0358] (Dope composition)

 Cellulose triacetate (average degree of acetylation 61.0%) 100 parts by weight Triphenol-norephosphate 8 parts by weight

 2- [5 Black mouth (2H) -Benzotriazole- 2 yl] -4-methyl-6 (tert-butyl) phenol 1 part by mass

 2-[(2H) monobenzotriazole 2 yl] —4,6 di-t-pentylphenol

 1 part by mass

 430 parts by mass of methylene chloride

 90 parts by mass of methanol

 The above composition was put into a closed container, kept at 80 ° C. under pressure, and completely dissolved while stirring to obtain a dope composition.

[0359] Next, this dope composition was filtered, cooled and kept at 33 ° C, and evenly cast on a stainless steel band. After the solvent was evaporated until peeling became possible, the dope composition was peeled off from the stainless steel band. The film was dried while being conveyed by a number of rolls to obtain a transparent support having a thickness of 80 m.

[0360] The surface facing the stainless steel band is the b-side, and the other side is the a-side. Hard The b side was used to form the coat layer.

[0361] <Formation of hard coat layer>

Thick film thickness after curing by applying the following hard coat layer coating solution to the prepared transparent support with a coating width of 1.4m, drying at 80 ° C, and then irradiating with 120mjZcm ² ultraviolet light with a high-pressure mercury lamp

 A hard coat layer was provided so as to have a force / zm.

[0362] (Hard coat layer coating solution)

 45 parts by mass of acetone

 Ethyl acetate 45 parts by mass

 PGME (propylene glycol monomethyl ether) 10 parts by mass Pentaerythritol tritalylate 30 parts by mass

 45 parts by mass of pentaerythritol tetraatalylate

 Urethane acrylate (trade name U-4HA, Shin-Nakamura Chemical Co., Ltd.) 25 parts by mass

1-hydroxy-cyclohexyl-phenyl monoketone (Irgacure 184, manufactured by Special Chemicals) 5 parts by mass

 2-Methyl 1- [4 (Methylthio) phenol] -2-monoforino 1-one (Irgaki Your 907, Chinoku's Specialty Chemicals) 3 parts by mass

 BYK-331 (Silicone surfactant, manufactured by Big Chemie Japan Co., Ltd.)

 0.5 parts by mass

 Fluorine-containing polymethylmetatalylate fine particles (Negami Kogyo Co., Ltd.), average particle size 3.5 m 20 parts by mass

 <Formation of back coat layer>

 On the opposite side of the surface on which the hard coat layer was applied, the following back coat layer coating solution was die-coated so as to have a wet film thickness of 14 m, dried at 85 ° C. and wound to provide a knock coat layer.

 [0363] (Coating liquid for back coat layer)

 30 parts by mass of acetone

Ethyl acetate 45 parts by mass Cole 10 parts by weight Diacetino Resenellose 0.6 parts by weight

 Ultrafine silica 2% acetone dispersion (Aerosil 200V manufactured by Nippon Aerosil Co., Ltd.)

 0.2 parts by mass

 <Atmospheric pressure plasma treatment>

 The following atmospheric pressure plasma treatment was performed on the surface of the hard coat layer using the atmospheric pressure plasma treatment apparatus described in Fig. 7 of Japanese Patent Application No. 2005-351829.

[0364] The electrode gap was set to 0.5 mm, the following discharge gas was supplied to the discharge space, and the frequency was 13.5 MHz, the applied voltage Vp = 9.5 kV, and the output density 1 using a high-frequency power source manufactured by Shinko Electric Co., Ltd. Surface treatment was performed by forming a discharge as 5 WZcm ² .

[0365] (Discharge gas)

 Nitrogen gas 80.0% by volume

 Oxygen gas 20. 0% by volume

 <Formation of high refractive index layer>

The surface of the hard coat layer is die-coated with the following high refractive index layer coating solution, dried at 80 ° C, and then irradiated with 120mjZcm ² of UV light with a high-pressure mercury lamp so that the film thickness after curing becomes lOnm. A high refractive index layer was provided. The refractive index of the high refractive index layer was 1.60.

[0366] (High refractive index layer coating solution)

 PGME (propylene glycol monomethyl ether) 40 parts by mass Isopropyl alcohol 25 parts by mass

 Methyl ethyl ketone 25 parts by mass

 Pentaerythritol triatalylate 0.9 parts by mass

 Pentaerythritol tetraatalylate 1.0 parts by mass

 Urethane acrylate (trade name: U-4HA, manufactured by Shin-Nakamura Co., Ltd.) 0.6 parts by mass Particle dispersion A (below) 20 parts by mass

 1-hydroxy-cyclohexyl-phenyl monoketone (Irgacure 184, manufactured by Special Chemicals) 0.4 parts by weight

2 Methyl 1— [4 (methylthio) phenol]-2-monoforinopropane 1-one ( Irgacure 907, manufactured by Chinoku 'Specialty' Chemicals Co., Ltd.) 0.2 parts by mass FZ-2207 (10% propylene glycol monomethyl ether solution, manufactured by Nippon Car Co., Ltd.) 0.4 parts by mass

 (Preparation of particle dispersion A)

 Methanol-dispersed antimony double acid colloid (solid content 60%, manufactured by Nissan Chemical Industries, Ltd., zinc antimonate sol, trade name: Celnax CX—Z610M—F2) 6.0 kg of isopropyl alcohol The mixture was gradually added with stirring to prepare a particle dispersion A.

<Formation of low refractive index layer>

In the high refractive index layer, and die coating a low refractive index layer coating solution having the following, after drying at 80 ° C, Tei屈folding as the film thickness is irradiated with a high pressure mercury lamp UV 120MjZcm ² is 92nm An antireflection film 1 was prepared by providing a rate layer. The refractive index of the low refractive index layer was 1.38.

 [0368] The refractive index of the refractive index layer was determined from the measurement result of the spectral reflectance of the spectrophotometer. The spectrophotometer is U-4000 type (manufactured by Hitachi, Ltd.). After the surface on the measurement side of the sample is roughened, it is light-absorbed with black spray to prevent reflection of light on the back side. Then, the reflectance in the visible light region (400 to 700 nm) was measured under the condition of regular reflection at 5 degrees.

[0369] (Low refractive index layer coating solution)

 Propylene glycol monomethyl ether 430 parts by mass Isopropyl alcohol 430 parts by mass

 Tetraethoxysilane hydrolyzate A (following, solid content 21% conversion) 120 parts by mass γ-methacryloxypropyltrimethoxysilane (trade name: ΚΒΜ503, manufactured by Shin-Etsu Chemical Co., Ltd.) 3.0 parts by mass

 Isopropyl alcohol-dispersed hollow silica-based fine particles 1 (below, solid content 20%, average particle size 45 nm, particle size variation coefficient 30%) 40 parts by mass

 Aluminum ethyl acetate acetate diisopropylate (by Kawaken Fine Chemical Co., Ltd.)

ALCH) 3.0 parts by mass

FZ-2207 (10% propylene glycol monomethyl ether solution, manufactured by Nippon Car Company) 3.0 parts by mass (Preparation of tetraethoxysilane hydrolyzate A)

 230 g of tetraethoxysilane (trade name: KBE04, manufactured by Shin-Etsu Chemical Co., Ltd.) and 440 g of ethanol are added, 120 g of 2% aqueous acetic acid solution is added thereto, and the mixture is stirred at room temperature (25 ° C) for 28 hours. Thus, tetraethoxysilane hydrolyzate A was prepared.

[0370] (Preparation of isopropyl alcohol-dispersed hollow silica fine particles 1)

The average particle diameter of 5 nm, a mixture of silica sol 100g of pure water 1900g of SiO concentration of 20 mass _^0/0 8

 2

 Warmed to 0 ° C. The pH of this reaction mother liquor is 10.5, and 0.98 mass as SiO in the mother liquor.

 2

% Of sodium aluminate 1.02 mass _^0/0 as Kei aqueous sodium 9000g and AI O

 twenty three

 9000 g of aqueous solution was added simultaneously. Meanwhile, the temperature of the reaction solution was kept at 80 ° C. The pH of the reaction solution rose to 12.5 immediately after the addition, and after that, almost unchanged. After completion of the addition, the reaction solution is cooled to room temperature, washed with an ultrafiltration membrane, and a solid content of 20% by mass of SiO 2

 2

1 A hemorrhoid particle dispersion was prepared. (Process (a))

 twenty three

 1700 g of pure water was added to 500 g of this core particle dispersion and heated to 98 ° C, and while maintaining this temperature, a sodium silicate aqueous solution obtained by dealkalizing with a cation exchange resin ( (SiO concentration 3.5 mass%) Core particles with the addition of 3000 g to form the first silica coating layer

 2

 A dispersion of the child was obtained. (Process (b))

 Next, 1125 g of pure water was added to 500 g of the core particle dispersion formed with the first silica coating layer having a solid content concentration of 13% by washing with an ultrafiltration membrane, and further concentrated hydrochloric acid (35.5%) was added dropwise. The pH was adjusted to 0.1 and dealumination was performed. Next, the aluminum salt dissolved in the ultrafiltration membrane was separated while adding 10 L of pH 3 hydrochloric acid aqueous solution and 5 L of pure water, and SiO · Α1 し た which removed some of the components of the core particles that formed the first silica coating layer. Porous particle dispersion

 2 2 3

 Prepared (step (c)). A mixture of 1500 g of the above porous particle dispersion, 500 g of pure water, 1,750 g of ethanol and 626 g of 28% ammonia water is heated to 35 ° C, and then 104 g of ethyl silicate (SiO 28 mass%) is added. The surface of the porous particles on which the first silica coating layer is formed.

2

 A second silica coating layer was formed by coating with a hydrolyzed polycondensate of ethyl silicate. Next, a dispersion of hollow silica-based fine particles i having a solid content concentration of 20% by mass was prepared by replacing the solvent with isopropyl alcohol using an ultrafiltration membrane.

[0371] The thickness of the first silica coating layer of these hollow silica-based fine particles is 3 nm, the average particle size is 45 nm, M Ox / SiO 2 (molar ratio) was 0.0019, and the refractive index was 1.28. Where the average particle size and grain

2

 The variation coefficient of the diameter was measured by a dynamic light scattering method.

 [0372] <Preparation of antireflection film 2>

 For the production of the antireflection film 1, the amount of isopropyl alcohol-dispersed hollow silica fine particles 1 in the coating solution for the low refractive index layer was changed to 120 parts by mass, and the antireflection film 2 was produced in the same manner. .

[0373] <Preparation of antireflection film 3>

 In the production of the antireflection film 1, the following was further added to the coating solution for the low refractive index layer, and the others were similarly produced.

[0374] Isopropyl alcohol-dispersed spherical colloidal silica 1 (solid content 20%, average particle size 20 nm, particle size variation coefficient 30%, commercially available product) 80 parts by mass

 <Preparation of antireflection film 4>

 In the production of the antireflection film 1, the following was further added to the coating solution for the low refractive index layer, and the antireflection film 4 was produced in the same manner as the others.

[0375] Isopropyl alcohol-dispersed spherical colloidal silica 2 (solid content 20%, average particle size 45 nm, particle size variation coefficient 30%, commercially available product) 80 parts by mass

 << Preparation of antireflection film 5 >>

 In the production of the antireflection film 1, the following was further added to the coating solution for the low refractive index layer, and the antireflection film 5 was produced in the same manner as the others.

[0376] Isopropyl alcohol-dispersed spherical colloidal silica 3 (solid content 20%, average particle size 90 nm, particle size variation coefficient 30%, commercially available product) 20 parts by mass

 <Preparation of antireflection film 6>

 For the production of the antireflection film 5, the amount of isopropyl alcohol-dispersed spherical colloidal silica 3 in the coating solution for the low refractive index layer was changed to 80 parts by mass, and the antireflection film 6 was produced in the same manner.

[0377] <Preparation of antireflection film 7>

For the production of the anti-reflection film 5, the amount of isopropyl alcohol-dispersed spherical colloidal silica 3 in the coating solution for the low refractive index layer was changed to 140 parts by mass, and the others were similarly anti-reflective. Film 7 was produced.

[0378] <Preparation of antireflection film 8>

 In the production of the antireflection film 1, the following was further added to the coating solution for the low refractive index layer, and an antireflection film 8 was produced in the same manner as the others.

[0379] Isopropyl alcohol-dispersed spherical colloidal silica 4 (solid content 20%, average particle size 200ηm, particle size variation coefficient 30%, commercially available product) 80 parts by mass

 << Preparation of antireflection film 9 >>

 In the production of the antireflection film 1, the following was further added to the coating solution for the low refractive index layer, and an antireflection film 9 was produced in the same manner as the others.

[0380] Isopropyl alcohol-dispersed spherical colloidal silica 5 (solid content 20%, average particle size 9500 nm, particle size variation coefficient 30%, commercially available product) 80 parts by mass

 << Preparation of antireflection film 10 >>

 In the preparation of the antireflection film 6, the isopropyl alcohol-dispersed hollow silica-based fine particles 1 and the isopropyl alcohol-dispersed spherical colloidal silica 3 in the coating solution for the low refractive index layer were changed to the following, and the others were similarly treated. 9 was produced.

[0381] Isopropyl alcohol-dispersed hollow silica-based fine particles 2 (prepared by adjusting the production conditions of the above-mentioned isopropyl alcohol-dispersed hollow silica-based fine particles 1 with a solid content of 20%, an average particle size of 45 nm, a particle size variation coefficient of 10%) 40 Part by mass Isopropyl alcohol-dispersed spherical colloidal silica 6 (solid content 20%, average particle size 90 nm, particle size variation coefficient 10%, commercially available product) 80 parts by mass

 <Preparation of antireflection film 11>

 In the production of the antireflection film 6, the following was further added to the coating solution for the low refractive index layer, and the antireflection film 11 was produced in the same manner as the others.

[0382] Isopropyl alcohol-dispersed acicular colloidal silica 7 (solid content 20%, average particle size 90 nm, particle size variation coefficient 50%, commercially available product) 40 parts by mass

 <Preparation of antireflection film 12>

Antireflection film 12 was prepared in the same manner as in the preparation of antireflection film 6, except that the hard coating layer coating solution PMMA fine particles were removed. [0383] <Evaluation of antireflection film>

 The produced antireflection film was evaluated for reflectivity and scratch resistance as follows.

 [0384] (Reflectance)

 In order to prevent backside reflection, the sample was attached to a black acrylic board with a baseless double-sided tape, and the reflectance was measured with a SPECTROPHOTOMETER CM-2500d manufactured by Minolta.

[0385] (Abrasion)

Under the environment of the sample [This _{^{23 0 C, 55 0/0}} RH, multiplied by the scan Ticino Lek over Norre (SW) [load of this 250g / cm ² of # 0000, the number of scratches per lcm width at the time of the 10 round-trip Was measured. Note that the number of scratches is measured at the highest number of scratches in the portion where the load is applied. If it is 10 Zcm or less, there is no practical problem, but 5 Zcm or less is preferable. 3 Zcm or less is more preferable.

 [0386] The results of the evaluation are shown in Table 1.

[0387] [Table 1]

[0388] From the table, it can be seen that the reflectance and scratch resistance of the sample of the present invention are improved. It can be seen that the amount of colloidal silica is large and the preferred particle size is large, which is preferred.

[0389] Example 2

 << Preparation of antireflection film 13 >>

In the production of the antireflection film 6 of Example 1, the antireflection film 13 was produced in the same manner except that the hard coat layer surface was not subjected to the atmospheric pressure plasma treatment. [0390] <Preparation of antireflection film 14>

 In the production of the antireflection film 6 of Example 1, the antireflection film 14 was produced in the same manner except that the PMMA fine particles in the hard coat layer coating solution were changed to those having an average particle diameter of 2 m.

 [0391] <Preparation of antireflection film 15>

 In the production of the antireflection film 12 of Example 1, the hard coat layer coating solution was die-coated, temporarily dried at 50 ° C., and then the surface of the hard coat layer was embossed with a roll having protrusions. Anti-reflection film 15 was produced in the same manner except that the film was dried at ° C.

[0392] <Preparation of antireflection film 16>

 In the production of the antireflection film 12 of Example 1, the dope composition was cast on a stainless steel band, and after the solvent was evaporated, it was peeled off from the stainless steel band. The anti-reflection film 16 was produced in the same manner except that it was embossed with the attached roll.

[0393] <Evaluation of antireflection film>

 About the produced antireflection film, together with the antireflection films 6 and 12 produced in Example 1, it is reflected as an arithmetic average roughness and a visibility indicator when used in a display device as follows. Sharpness and transmission image clarity were evaluated.

[0394] (Arithmetic mean roughness)

 In accordance with JIS B 0601: 2001, using optical interference type surface roughness meter RSTZPLUS (manufactured by WYKO), each surface of transparent support (b surface), hard coat layer and antireflection film 1.2mm X O Arithmetic mean roughness was determined for an area of 9 mm.

[0395] (Reflection, sharpness)

 Each sample was affixed to the monitor with a substrate-less double-sided tape, and 30 people performed image evaluation and sharpness sensory evaluation to determine the average score. Ten points are the best, with little reflections or high sharpness. One point is the worst. Five or more points are acceptable levels.

[0396] (Transparency mapping)

The transmission image quality at a comb width of 2.5 mm was measured with an ICM-IDP image clarity measuring instrument from Suga Test Instruments Co., Ltd. Transmission image clarity is a parameter that correlates with sharpness. [0397] The results of the evaluation are shown in Table 2.

[0398] [Table 2]

 [0399] From the table, the antireflection films 6 and 13 to 16 corresponding to any one of claims 2 to 4 correspond to claim 1 but any of claims 2 to 4 Compared to the antireflection film 12 that does not fall under any of the above items, there is less reflection on the screen and it is good. It can be seen that the antireflection film 13 that was not present is somewhat inferior. Further, the antireflection film 12 that falls within the first claim but does not fall within the second claim is considerably inferior. The antireflection film 16 corresponding to claim 4 is as good as the antireflection film 12 in sharpness and transmission image clarity.

Claims

The scope of the claims

 [1] In an antireflection film having at least a low refractive index layer on a transparent support directly or via another layer, the low refractive index layer contains at least two types of silica fine particles, and one of them Silica fine particles are hollow silica-based fine particles whose inside is porous or hollow, and the other one type of silica fine particles is colloidal silica, and the average particle size of the colloidal silica is the average particle size of the hollow silica-based fine particles. 1. An antireflection film characterized by being 1 to less than 20 times and having an arithmetic average roughness (Ra) of an outermost surface of less than 40 to 500 nm.

 [2] The hard coat layer and the low refractive index layer are provided on the transparent support, and the arithmetic average roughness (Ra) of the surface of the hard coat layer is less than 60 to 700 nm. The antireflection film as described in Item 1.

 [3] The antireflection film according to claim 1 or 2, wherein the surface of the transparent support has an arithmetic average roughness (Ra) of 50 to less than LOOOnm.

 [4] The antireflection film as described in any one of [1] to [3], wherein the hard coat layer contains fluorine-containing acrylic resin fine particles.