JP2005298716A - Antistatic layer, antistatic hard coat film, antistatic antireflection film, polarizing plate and display device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain an antistatic layer having excellent antistatic property, no discoloration, no haze and high film strengths, to prepare an antistatic hard coat film, an antistatic antireflection film, a polarizing plate and to provide a display device. <P>SOLUTION: In the antistatic layer comprising electroconductive metal oxide particles and an ionizing radiation-curable resin, the antistatic layer comprises a polyfunctional (meth)acrylate containing at least two or more (meth)acryloyl groups in the molecule and an acrylamide derivative as the ionizing radiation-curable resin. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to an antistatic layer, an antistatic hard coat film, an antistatic antireflection film, a polarizing plate and a display device, and more specifically, an antistatic layer and an antistatic hard coat having excellent antistatic properties and strong film strength. The present invention relates to a film, an antistatic antireflection film, a polarizing plate, and a display device.

  As a means for obtaining an antistatic layer, a method using conductive metal oxide particles and an ionizing radiation curable resin is known. Since the conductive metal oxide particles do not exhibit conductivity unless the particles are in contact with each other, the antistatic property may not be obtained unless the addition amount is a certain amount or more. However, when the amount of the conductive metal oxide particles added is excessive, problems such as coloring of the antistatic layer, an increase in haze, and a decrease in film strength may occur.

  On the other hand, a hard coat film, an antireflection film, and the like are provided on the outermost surface of a display device such as a liquid crystal. However, it has been required to have antistatic properties in order to prevent dust from adhering to the screen.

  As a means for imparting antistatic properties to the hard coat film, a method of adding conductive metal oxide particles to the hard coat layer is known. Since the hard coat layer is usually about 2 to 10 μm thick, the amount of conductive metal oxide particles is large, and the antistatic property is easily developed, but there is a problem that coloring, haze, and scratch resistance are likely to deteriorate. is there.

  In addition, as a means for imparting antistatic properties to the antireflection film, a method of adding conductive metal oxide particles to the high refractive index layer or the middle refractive index layer is known. Since the layer is usually as thin as about 30 to 100 nm, there is a problem that the antistatic property does not appear and the film strength tends to be weak unless the addition ratio of the conductive metal oxide particles is increased.

Conventionally, techniques for improving the film strength of the high refractive index layer have been disclosed (see, for example, Patent Documents 1 and 2), but this is insufficient to solve the above problems, and antistatic properties and film strength are not sufficient. The development of technology that can achieve both of these is highly awaited.
JP 2000-63444 A JP 2000-143924 A

  Accordingly, an object of the present invention is to provide an antistatic layer, an antistatic hard coat film, an antistatic antireflection film, a polarizing plate, and a display device that have excellent antistatic properties, no coloring and no haze, and strong film strength. It is in.

  The above object of the present invention is achieved by the following configurations.

(Claim 1)
In an antistatic layer containing conductive metal oxide particles and an ionizing radiation curable resin, a polyfunctional (meth) acrylate having at least two (meth) acryloyl groups in the molecule and an acrylamide derivative as an ionizing radiation curable resin An antistatic layer comprising:

(Claim 2)
The antistatic layer according to claim 1, wherein the acrylamide derivative is an acrylamide derivative represented by the following general formula (I).

(In the formula, R1 and R2 may be substituted at a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, a cyclic alkyl group having 3 to 8 carbon atoms, a phenyl group, or any position. N, N-dimethylamino group, hydrochloric acid and N, N, N-trimethylamino group, hydroxy group, or R1 and R2 together form an alkylene having 2 to 8 carbon atoms, or a morpholine ring together with an oxygen atom To form.)
(Claim 3)
The antistatic layer according to claim 1 or 2, wherein the surface of the conductive metal oxide particles is modified with a silane coupling agent.

(Claim 4)
The conductive metal oxide particles are one or more metal oxide particles selected from antimony-doped tin oxide (ATO), indium tin oxide (ITO), antimony pentoxide, zinc oxide, and zirconium oxide. The antistatic layer according to any one of claims 1 to 3, wherein:

(Claim 5)
The antistatic layer according to any one of claims 1 to 4, wherein the antistatic layer or an adjacent layer thereof contains titanium oxide.

(Claim 6)
An antistatic hard coat film comprising the antistatic layer according to claim 1.

(Claim 7)
The antistatic hard coat film according to claim 6, wherein a coating width of the antistatic layer is 1.4 m or more.

(Claim 8)
An antistatic antireflection film comprising the antistatic layer according to claim 1.

(Claim 9)
The antistatic antireflection film according to claim 8, wherein the coating width of the antistatic layer is 1.4 m or more.

(Claim 10)
The antistatic antireflection film according to claim 8 or 9, wherein the low refractive index layer contains hollow fine particles.

(Claim 11)
A polarizing plate comprising the antistatic hard coat film according to claim 6.

(Claim 12)
A polarizing plate comprising the antistatic antireflection film according to claim 8.

(Claim 13)
A display device comprising the antistatic hard coat film according to claim 6.

(Claim 14)
A display device comprising the antistatic antireflection film according to claim 8.

(Claim 15)
A display device comprising the polarizing plate according to claim 11.

  According to the present invention, it is possible to provide an antistatic layer, an antistatic hard coat film, an antistatic antireflection film, a polarizing plate and a display device which are excellent in antistatic properties, do not have coloring and haze, and have strong film strength.

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

  The antistatic layer of the present invention is a polyfunctional having at least two (meth) acryloyl groups in the molecule as an ionizing radiation curable resin in an antistatic layer containing conductive metal oxide particles and an ionizing radiation curable resin. It contains (meth) acrylate and an acrylamide derivative. Furthermore, when the acrylamide derivative is the acrylamide derivative represented by the general formula (I), an antistatic layer having excellent antistatic properties, no coloring and haze, and strong film strength can be obtained. As a result, the present invention has been achieved.

  Hereinafter, the present invention will be described in detail for each element.

(Antistatic layer)
The antistatic layer of the present invention comprises a conductive metal oxide particle, a polyfunctional (meth) acrylate having at least two (meth) acryloyl groups in the molecule (hereinafter sometimes simply referred to as polyfunctional acrylate) and an acrylamide derivative. Containing. The conductive metal oxide particles exhibit antistatic properties, and the refractive index can be controlled by appropriately selecting the type and addition amount. By using a polyfunctional acrylate as a binder, the antistatic layer can have strong film strength, and by containing an acrylamide derivative, conductivity, film strength, ultraviolet light resistance, etc. can be improved. . In addition, an additive such as an acrylic resin, a methacrylic resin, a silane coupling agent, or a metal compound may be added to the antistatic layer as necessary. The antistatic layer of the present invention has excellent antistatic properties and film strength. Therefore, a hard coat layer having antistatic properties can also be obtained. In addition, since the refractive index can be controlled by appropriately selecting the type and amount of the conductive metal oxide particles, it can also be used as a high refractive index layer or a medium refractive index layer used for an antireflection film. I can do it.

(Conductive metal oxide fine particles)
The type of conductive metal oxide fine particles is not particularly limited. For example, antimony-doped tin oxide (ATO), antimony pentoxide, indium tin oxide (ITO), zirconium oxide (zirconia), zinc oxide, and the like are the main components. Can be used. These conductive metal oxide fine particles may be doped with a trace amount of atoms such as Al, In, Sn, Sb, Nb, a halogen element, and Ta. A mixture of these may also be used.

  The average particle size of the primary particles of the conductive metal oxide fine particles is preferably 5 nm to 200 nm, and more preferably 10 to 150 nm. If the particle size is too small, aggregation tends to occur and the dispersibility deteriorates. If the particle size is too large, the haze increases, which is not preferable. The shape of the inorganic fine particles is preferably a rice grain shape, a spherical shape, a cubic shape, a spindle shape, or an indefinite shape.

  When the refractive index of the conductive metal oxide fine particles is large, it can be applied to a high refractive index layer, a medium refractive index layer and the like of the antireflection film. In this case, the refractive index of the conductive metal oxide fine particles is preferably 1.80 to 2.60, and more preferably 1.85 to 2.50.

  The conductive metal oxide fine particles may be surface-treated with an organic compound. By modifying the surface of the conductive metal oxide fine particles with an organic compound, the dispersion stability in an organic solvent is improved, the control of the dispersed particle size is facilitated, and aggregation and sedimentation over time are suppressed. You can also. On the other hand, in order for the conductive metal oxide fine particles to exhibit conductivity, it is necessary for the particles to contact each other. However, if the surface modification amount is too large, contact between the particles is inhibited, and thus necessary conductivity is obtained. There are things that cannot be done. For this reason, the surface modification amount with a preferable organic compound is 0.1 mass%-5 mass% with respect to metal oxide particle, More preferably, it is 0.5 mass%-3 mass%. Examples of the organic compound used for the surface treatment include polyols, alkanolamines, stearic acid, silane coupling agents, and titanate coupling agents. Among these, the silane coupling agent mentioned later is preferable. Two or more kinds of surface treatments may be combined.

  When providing the layer containing the said electroconductive metal oxide particle, 0.05-5 micrometers is good for the thickness of the layer, Preferably it is 0.1-3 micrometers.

  The ratio of the conductive oxide to the binder used varies depending on the type of oxide, particle size, etc., but the volume ratio is preferably about 2 from the latter 2 to 1 for the former 1 and about 1 from the latter.

  The amount of the conductive metal oxide particles used in the present invention is preferably 25% by volume to 50% by volume in the antistatic layer, and more preferably 30% by volume to 45% by volume. When the amount used is small, the antistatic property is deteriorated, and when it is too large, film strength is deteriorated, haze is increased, and coloring occurs.

(Ionizing radiation curable resin)
As the ionizing radiation curable resin, a monomer or oligomer that causes a polymerization reaction directly by irradiation with ionizing radiation such as ultraviolet rays or electron beams or indirectly by the action of a photopolymerization initiator can be used. The ionizing radiation curable resin used in the present invention contains a polyfunctional acrylate and an acrylamide derivative. In addition, styrene, acrylic acid derivatives, methacrylic acid derivatives, acrylic resins, methacrylic resins, and the like may be included. It is preferable to combine a photopolymerization initiator as necessary.

The ionizing radiation used in the present invention can be used without limitation as long as it is an energy source that activates the compound by ultraviolet rays, electron beams, γ rays, etc., but ultraviolet rays and electron beams are preferable, especially easy handling and easy high energy. Ultraviolet rays are preferable in that they are obtained. As the ultraviolet light source for photopolymerizing the ultraviolet reactive compound, any light source that generates ultraviolet light can be used. For example, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, or the like can be used. The irradiation conditions vary depending on individual lamps, but the amount of light irradiated is preferably 40~2000mJ / cm ^2, more preferably 100~1500mJ / cm ^2. If the amount of irradiation light is small, curing is insufficient, and if the amount of irradiation is too large, base deformation due to heat generation occurs.

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

(Acrylamide derivatives)
When the acrylamide derivative according to the present invention is used alone, there is no antistatic property and the film strength is not as high as that of the polyfunctional acrylate. The antistatic property can be improved to help develop the conductivity of the conductive metal oxide particles, and the addition amount is reduced because good antistatic properties can be obtained even if the conductive metal oxide particles are added in a small amount. Therefore, coloring, haze, and film strength deterioration can be suppressed. Furthermore, in order to improve the reactivity of polyfunctional acrylate in the presence of oxygen, the film strength at the time of thin film can be increased. Furthermore, when a polyfunctional acrylate is irradiated with UV light for a long time using a light resistance tester or the like, the reaction proceeds and the coating film becomes hard and brittle, so that the adhesion to the substrate is deteriorated. It was also found that the light resistance can be improved.

  The acrylamide derivative used in the present invention is not particularly limited, but is preferably an acrylamide derivative represented by the general formula (I). Specific examples of the acrylamide derivative include, but are not limited to, acrylamide, N-isopropylacrylamide, N, N-dimethylacrylamide, N, N-diethylacrylamide, N, N-dimethylaminoethylacrylamide, N, N-dimethylaminopropyl acrylamide, N, N, N-trimethylaminoethyl acrylamide chloride, N, N, N-trimethylaminopropyl acrylamide chloride, N- (2-hydroxyethyl) acrylamide, acryloylmorpholine are preferably used. I can do it. In particular, N- (2-hydroxyethyl) acrylamide and acryloylmorpholine are preferable. These acrylamide derivatives may be used as a mixture.

  5-40 mass% is preferable with respect to polyfunctional acrylate, and, as for the usage-amount of the acrylamide derivative based on this invention, 10-30 mass% is more preferable. If the amount used is small, the desired effect cannot be obtained sufficiently, and if the amount used is too large, the film strength deteriorates.

(Polyfunctional acrylate compound)
The polyfunctional acrylate compound according to the present invention is a compound having two or more acryloyloxy groups or methacryloyloxy groups in the molecule.

  Examples of the monomer of the polyfunctional acrylate compound include ethylene glycol diacrylate, diethylene glycol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, and tetramethylolmethanetriacrylate. Acrylate, tetramethylolmethane tetraacrylate, pentaglycerol triacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, glycerin triacrylate, dipentaerythritol triacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, Dipen Erythritol hexaacrylate, tris (acryloyloxyethyl) isocyanurate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, tetra Methylol methane trimethacrylate, tetramethylol methane tetramethacrylate, pentaglycerol trimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, glycerin trimethacrylate, dipentaerythritol trimethacrylate, dipentaerythritol te La methacrylate, dipentaerythritol penta methacrylate, dipentaerythritol hexa methacrylate. These compounds are used alone or in admixture of two or more. Moreover, oligomers, such as a dimer and a trimer of the said monomer, may be sufficient.

  The amount of the polyfunctional acrylate compound according to the present invention is preferably 5 to 40% by mass, more preferably 10 to 30% by mass. If it exceeds 40% by mass, the film becomes brittle.

(Photopolymerization initiator)
In order to accelerate the curing of the ionizing radiation curable resin, the photopolymerization initiator is preferably contained in an amount of 5 to 30% by mass with respect to the ionizing radiation curable resin. The photopolymerization initiator is not particularly limited, and various known ones can be used. As a photoinitiator, photoinitiators, such as Irgacure-184, Irgacure-651 (made by Ciba Specialty Chemicals), Darocur-1173 (made by Merck), etc. can be used, for example. Further, a photosensitizer such as benzophenone, methyl benzoylbenzoate, p-dimethylbenzoate, thiochitosan, etc. may be used in combination.

(Acrylic resin or methacrylic resin)
An acrylic resin or a methacrylic resin may be added as a binder to the antistatic layer of the present invention.

  As the acrylic or methacrylic resin, an alcohol-soluble acrylic resin or methacrylic resin having a molecular weight of 100,000 to 500,000 can be preferably used. Specifically, alkyl (meth) acrylate polymers or alkyl (meth) acrylate copolymers, for example, copolymers such as n-butyl methacrylate, isobutyl methacrylate, methyl methacrylate, ethyl methacrylate, and propyl methacrylate are preferably used. It is not limited to. Commercially available products include Dianal BR-50, BR-51, BR-52, BR-60, BR-64, BR-65, BR-70, BR-73, BR-75, BR-76, BR-77. , BR-79, BR-80, BR-82, BR-83, BR-85, BR-87, BR-88, BR-89, BR-90, BR-93, BR-95, BR-96, BR -100, BR-101, BR-102, BR-105, BR-107, BR-108, BR-112, BR-113, BR-115, BR-116, BR-117, BR-118 (above, Mitsubishi Can be used.

The acrylic resin or methacrylic resin preferably has a Tg (glass transition point) of 30 ° C. or lower. Tg is measured using a SOLIDS ANALYZER-RSAII manufactured by Rheometrics with a frequency of 100 rad / sec and a strain of 8.0 × 10 ⁻⁴ , and the temperature at which the peak value of tan δ reaches the glass transition. It can be obtained as a point (Tg).

(Layer structure)
The antistatic layer according to the present invention can be applied to a hard coat film and an antireflection film.

(Hard coat film)
Although an example of the preferable layer structure of the hard coat film concerning this invention is shown below, it is not limited to these.

Base film / antistatic property imparting hard coat layer Base film / antistatic layer / hard coat layer Antistatic layer / base film / hard coat layer Base film / hard coat layer / antistatic layer These layers are single layers However, it may consist of a plurality of layers. The antistatic property may be imparted by providing an antistatic layer, or the antistatic property may be imparted to the hard coat layer itself.

(Antistatic layer)
As the antistatic layer, the above-mentioned antistatic layer can be used.

(Antistatic property imparting hard coat layer)
When the antistatic property is imparted to the hard coat layer, the antistatic layer of the present invention can be used as the hard coat layer. When the antistatic layer of the present invention is used as a hard coat layer, the thickness of the hard coat layer is preferably in the range of 1 to 15 μm, more preferably 1 to 10 μm. When the film thickness of the hard coat layer is 1 μm or more, oxygen inhibition during ultraviolet curing is reduced, so that the film strength can be increased. Further, since the weight increases as the film thickness increases, the antistatic property can be exhibited even when the addition ratio of the conductive metal oxide particles is low. If the addition ratio of the conductive metal oxide particles can be lowered, the film strength can be improved, haze, coloring, cost, and the like can be improved. A film thickness exceeding 15 μm is not preferable because problems occur in haze, flexibility, flatness of the substrate film, and the like.

  The addition amount of the conductive metal oxide particles is not particularly limited, but is preferably 10% by mass to 50% by mass, and more preferably 15% by mass to 40% by mass.

(Hard coat layer)
A general ultraviolet curable resin can be used for a normal hard coat layer which does not impart antistatic properties.

  Although it does not specifically limit as ultraviolet curable resin, For example, Adeka optomer KR, BY series KR-400, KR-410, KR-550, KR-566, KR-567, BY-320B (above, Asahi Denka Kogyo) Co., Ltd.), Koeihard 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.), Seika Beam PHC2210 (S), PHCX-9 (K-3) ), PHC2213, DP-10, DP-20, DP-30, P1000, P1100, P1200, P1300, P1400, P1500, P1600, SCR900 , Manufactured by Dainichi Seika Kogyo Co., Ltd.), KRM7033, KRM7039, KRM7130, KRM7131, UVECRYL29201, UVECRYL29202 (above, Daicel UCB), RC-5015, RC-5016, RC-5020, RC-5031, RC-5100, RC-5102, RC-5120, RC-5122, RC-5152, RC-5171, RC-5180, RC-5181 (manufactured by Dainippon Ink & Chemicals, Inc.), Aulex No. 340 clear (manufactured by China Paint Co., Ltd.), Sun Rad H-601R (manufactured by Sanyo Chemical Industries), SP-1509, SP-1507 (above, manufactured by Showa Polymer Co., Ltd.), RCC-15C (Grace Japan Co., Ltd.), Aronix M-6100, M-8030, M-8060 (manufactured by Toagosei Co., Ltd.), or other commercially available products can be used as appropriate.

  The coating composition of the ultraviolet curable resin layer preferably has a solid content concentration of 10 to 95% by mass, and an appropriate concentration is selected depending on the coating method.

As a light source for forming a cured coating layer of an ultraviolet curable resin by a photocuring reaction, any light source that generates ultraviolet rays can be used. Specifically, the aforementioned light source can be used. The irradiation conditions vary depending on individual lamps, but the amount of light irradiated may be any degree 20~1200mJ / cm ^2, preferably from 50~1000mJ / cm ^2. From the near ultraviolet region to the visible light region, it can be used by using a sensitizer having an absorption maximum in that region.

  The film thickness of the hard coat layer can be in the range of 1 to 15 μm. This is because if the film thickness is less than 1 μm, sufficient durability and impact resistance cannot be obtained, and if the film thickness exceeds 15 μm, there is a problem in flexibility or economy. More preferably, it is 2-8 micrometers.

  In order to impart antiglare properties to the surface of the liquid crystal display panel, to prevent adhesion with other substances, and to improve scratch resistance, etc., inorganic or organic fine particles are added to the coating composition of the hard coat layer. You can also Examples of the inorganic fine particles include silicon oxide, titanium oxide, aluminum oxide, antimony oxide, tin oxide, zinc oxide, calcium carbonate, barium sulfate, talc, kaolin, and calcium sulfate. The organic fine particles include polymethacrylic acid methyl acrylate resin powder, acrylic styrene resin powder, polymethyl methacrylate resin powder, silicon resin powder, polystyrene resin powder, polycarbonate resin powder, benzoguanamine resin powder, melamine resin. Examples thereof include powder, polyolefin resin powder, polyester resin powder, polyamide resin powder, polyimide resin powder, and polyfluoroethylene resin powder. These can be used in addition to the ultraviolet curable resin composition. The average particle size of these fine particle powders is 0.01 to 10 μm, and the amount used is desirably 0.1 to 20 parts by mass with respect to 100 parts by mass of the ultraviolet curable resin composition. . In order to impart an antiglare effect, it is preferable to use 1 to 15 parts by mass of fine particles having an average particle diameter of 0.1 to 1 μm with respect to 100 parts by mass of the ultraviolet curable resin composition.

  By adding such fine particles to the ultraviolet curable resin, it is possible to form an antiglare layer having preferable irregularities having a center line average surface roughness Ra of 0.1 to 0.5 μm. Further, when such fine particles are not added to the ultraviolet curable resin composition, the hard surface having a good smooth surface with a center line average surface roughness Ra of less than 0.05 μm, more preferably less than 0.002 to 0.04 μm. A coat layer can be formed.

  In addition, as an element that performs the blocking prevention function, 0.1 to 5 parts by mass of ultrafine particles having a volume average particle size of 0.005 to 0.1 μm with the same components as described above with respect to 100 parts by mass of the resin composition Can also be used.

In the active energy ray-curable resin-containing layer used in the present invention, a binder such as a known thermoplastic resin, thermosetting resin, or hydrophilic resin such as gelatin can be mixed with the active energy ray-curable resin. . These resins preferably have polar groups in the molecule. Examples of the polar _{group, -COOM, -OH, -NR 2,} -NR 3 X, -SO 3 M, -OSO 3 M, -PO 3 M 2, -OPO 3 M ( wherein, M represents a hydrogen atom, an alkali A metal or an ammonium group, X represents an acid that forms an amine salt, R represents a hydrogen atom or an alkyl group).

  In order to increase the heat resistance of the cured layer, an antioxidant that does not inhibit the photocuring reaction can be selected and used. For example, hindered phenol derivatives, thiopropionic acid derivatives, phosphite derivatives and the like can be mentioned. Specifically, for example, 4,4′-thiobis (6-t-3-methylphenol), 4,4′-butylidenebis (6-t-butyl-3-methylphenol), 1,3,5-tris (3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate, 2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) mesitylene, di-octadecyl-4- Examples thereof include hydroxy-3,5-di-t-butylbenzyl phosphate.

(Antireflection film)
Examples of preferred layer configurations of the antireflection film (low reflection laminate) according to the present invention are shown below, but are not limited thereto.

Base film / Hard coat layer / Medium refractive index layer with antistatic property / Low refractive index layer Base film / Hard coat layer / High refractive index layer with antistatic property / Low refractive index layer Base film / Hard coat layer / Medium refractive index layer / high refractive index layer / low refractive index layer imparting antistatic property Base film / antistatic property imparting hard coat layer / low refractive index layer Base film / antistatic layer / hard coat layer / low refractive index layer Antistatic layer / Base film / Hard coat layer / Low refractive index layer Base film / Antistatic hard coat layer / Medium refractive index layer / High refractive index layer / Low refractive index layer Base film / Antistatic layer / Hard coat layer / Medium refractive index layer / High refractive index layer / Low refractive index layer Base film / Hard coat layer // Antistatic layer / Medium refractive index layer / High refractive index layer / Low refractive index layer Antistatic layer / base Material film / hard coat layer / medium refractive index layer / high refraction Layer / low refractive index layer base film / hard coat layer / antistatic property imparting high refractive index layer / low refractive index layer / high refractive index layer / low refractive index layer Antireflection film comprising the antistatic layer according to the present invention laminated Is a laminate of optical interference layers in which a high refractive index layer and a low refractive index layer are laminated in this order from the support side on at least one surface of the support (other layers may be added as described later). Then, the optical film thickness of the high-refractive index layer and the low-refractive index layer is set to λ / 4 with respect to light of wavelength λ, and an antireflection laminate is manufactured. The optical film thickness is an amount defined by the product of the refractive index n and the film thickness d of the layer. The level of the refractive index is almost determined by the metal or compound contained therein. For example, the high refractive index layer is often formed of a Ti compound, and the low refractive index layer is often formed of a compound containing Si or F. The refractive index and the film thickness can be calculated and calculated by measuring the spectral reflectance.

  As the antireflection film, a film composed of a multilayer optical interference layer, for example, a film obtained by coating a hard coat layer with a low reflection layer, and the like can be considered. The low-reflection laminate has the above-described hard coat layer on a transparent substrate as necessary, and the refractive index, film thickness, number of layers, and layers so that the reflectance is reduced by optical interference on the hard coat layer. Some are laminated in consideration of order, others are coated with a single layer. The antireflection layer is usually composed of a combination of a high refractive index layer having a higher refractive index than that of the substrate and a low refractive index layer having a lower refractive index than that of the substrate. Examples of configurations include two layers of a high refractive index layer / low refractive index layer from the base material side, and three layers having different refractive indices, a medium refractive index layer (having a higher refractive index than the base material or the hard coat layer). , A layer having a refractive index lower than that of a high refractive index layer) / a layer having a high refractive index / a layer having a low refractive index, and the like. Among them, from the viewpoint of durability, optical properties, productivity, etc., a medium refractive index layer / high refractive index layer / low refractive index layer laminated in order on a substrate having a hard coat layer, medium refractive index layer / low What laminated | stacked the refractive index layer is preferable.

  The antistatic layer of the present invention may be provided as an antistatic layer on the side opposite to the base film on which the antireflection layer is coated, or between the base film and the hard coat layer. It may be applied to the layer as an antistatic property-imparting hard coat layer, or applied to an intermediate refractive index layer, or a high refractive index layer, and an antistatic property imparting medium refractive index layer, or an antistatic property imparting high refractive index. It may be provided as a layer.

  In addition, as long as the reflectance can be reduced by optical interference, it is not particularly limited to these layer configurations. For example, an antifouling layer may be provided on the outermost layer, or an interference unevenness reducing layer may be provided between the base film and the hard coat layer.

(Medium refractive index layer, High refractive index layer)
The medium refractive index layer and the high refractive index layer are not particularly limited as long as a predetermined refractive index layer is obtained, but are preferably composed of metal oxide fine particles having a high refractive index, a binder, a solvent, and the like. In addition, you may contain an additive. The refractive index of the middle refractive index layer is preferably 1.55 to 1.75, and the refractive index of the high refractive index layer is preferably 1.75 to 1.95.

  It is also preferable to use the antistatic layer of the present invention as a middle refractive index layer or a high refractive index layer.

(Metal oxide fine particles)
Although metal oxide fine particles are not particularly limited, for example, titanium dioxide, aluminum oxide (alumina), zirconium oxide (zirconia), zinc oxide, antimony-doped tin oxide (ATO), antimony pentoxide, indium-tin oxide (ITO), Iron oxide or the like can be used as a main component. A mixture of these may also be used. When titanium dioxide is used, photocatalytic activity can be achieved by using metal oxide particles having a core / shell structure in which titanium dioxide is the core and the shell is coated with alumina, silica, zirconia, ATO, ITO, antimony pentoxide, or the like. It is preferable in terms of suppression.

  The refractive index of the metal oxide fine particles is preferably 1.80 to 2.60, more preferably 1.90 to 2.50. The average particle diameter of the primary particles of the metal oxide fine particles is 5 nm to 200 nm, more preferably 10 to 150 nm. If the particle size is too small, the metal oxide fine particles tend to aggregate and the dispersibility deteriorates. If the particle size is too large, the haze increases, which is not preferable. The shape of the inorganic fine particles is preferably a rice grain shape, a spherical shape, a cubic shape, a spindle shape, or an indefinite shape.

  The metal oxide fine particles may be surface-treated with an organic compound. Examples of the organic compound used for the surface treatment include polyols, alkanolamines, stearic acid, silane coupling agents, and titanate coupling agents. Among these, the silane coupling agent described later is most preferable. Two or more kinds of surface treatments may be combined.

  By appropriately selecting the kind and addition ratio of the metal oxide, a high refractive index layer and a medium refractive index layer having a desired refractive index can be obtained.

(Binder)
The binder is added to improve the film formability and physical properties of the coating film. As the binder, for example, the aforementioned ionizing radiation curable resin, acrylamide derivative, polyfunctional acrylate, acrylic resin or methacrylic resin can be used.

(Metal compounds, silane coupling agents)
As other additives, a metal compound, a silane coupling agent, or the like may be added. Metal compounds and silane coupling agents can also be used as binders.

  As the metal compound, a compound represented by the following formula (1) or a chelate compound thereof can be used.

Formula (1): AnMBx-n
In the formula, M represents a metal atom, A represents a hydrolyzable functional group or a hydrocarbon group having a hydrolyzable functional group, and B represents an atomic group covalently or ionically bonded to the metal atom M. x represents the valence of the metal atom M, and n represents an integer of 2 or more and x or less.

  Examples of the hydrolyzable functional group A include halogens such as alkoxyl groups and chloro atoms, ester groups and amide groups. The metal compound belonging to the above formula (1) includes an alkoxide having two or more alkoxyl groups bonded directly to a metal atom, or a chelate compound thereof. Preferable metal compounds include titanium alkoxides, zirconium alkoxides, silicon alkoxides or chelate compounds thereof from the viewpoints of the reinforcing effect of refractive index and coating film strength, ease of handling, material cost, and the like. Titanium alkoxide has a high reaction rate and a high refractive index and is easy to handle. However, since it has a photocatalytic action, its light resistance deteriorates when added in a large amount. Zirconium alkoxide has a high refractive index but tends to become cloudy, so care must be taken in dew point management during coating. Silicon alkoxide has a slow reaction rate and a low refractive index, but is easy to handle and has excellent light resistance. Since the silane coupling agent can react with both the inorganic fine particles and the organic polymer, a tough coating film can be formed. Moreover, since titanium alkoxide has the effect of accelerating the reaction of the ultraviolet curable resin and metal alkoxide, the physical properties of the coating film can be improved by adding a small amount.

  Examples of the titanium alkoxide include tetramethoxy titanium, tetraethoxy titanium, tetra-iso-propoxy titanium, tetra-n-propoxy titanium, tetra-n-butoxy titanium, tetra-sec-butoxy titanium, tetra-tert-butoxy titanium, and the like. Is mentioned.

  Examples of the zirconium alkoxide include tetramethoxy zirconium, tetraethoxy zirconium, tetra-iso-propoxy zirconium, tetra-n-propoxy zirconium, tetra-n-butoxy zirconium, tetra-sec-butoxy zirconium, tetra-tert-butoxy zirconium and the like. Is mentioned.

  The silicon alkoxide and the silane coupling agent are compounds represented by the following formula (2).

Formula (2): RmSi (OR ′) n
In the formula, R is an alkyl group (preferably an alkyl group having 1 to 10 carbon atoms), or a reaction such as a vinyl group, a (meth) acryloyl group, an epoxy group, an amide group, a sulfonyl group, a hydroxyl group, a carboxyl group, or an alkoxyl group. R ′ represents an alkyl group (preferably an alkyl group having 1 to 10 carbon atoms), and m + n is 4.

  Specifically, tetramethoxysilane, tetraethoxysilane, tetra-iso-propoxysilane, tetra-n-propoxysilane, tetra-n-butoxysilane, tetra-sec-butoxysilane, tetra-tert-butoxysilane, tetrapenta Ethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltributoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, hexyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane , Γ-glycidoxypropyltrimethoxysilane, 3- (2-aminoethylaminopropyl) trimethoxysilane and the like.

  Preferred chelating agents for forming a chelate compound by coordination with a free metal compound include alkanolamines such as diethanolamine and triethanolamine, glycols such as ethylene glycol, diethylene glycol and propylene glycol, acetylacetone and acetoacetic acid. Examples thereof include ethyl and the like having a molecular weight of 10,000 or less. By using these chelating agents, it is possible to form a chelate compound that is stable against moisture mixing and is excellent in the effect of reinforcing the coating film.

  The addition amount of the metal compound is preferably less than 5% by mass in terms of metal oxide in the medium refractive index composition, and less than 20% by mass in terms of metal oxide in the high refractive index composition. Is preferred.

(Coating liquid for forming low refractive index layer)
The low refractive index layer used in the present invention contains silicon alkoxide as a matrix precursor, and may contain the following inorganic fine particles, silane coupling agent, curing agent and the like as necessary.

(Matrix precursor)
As the matrix precursor, a hydrolyzate of an alkoxysilicon compound and a condensate formed by a subsequent condensation reaction are generally used. The low refractive index layer is preferably mainly composed of a SiO ₂ sol prepared by adjusting an alkoxysilicon compound represented by the following general formula (1) and / or (2) or a hydrolyzate thereof.

General formula (1) R1-Si (OR2) ₃
General formula (2) Si (OR2) ₄
(Wherein R1 represents a methyl group, an ethyl group, a vinyl group, or an organic group containing an acryloyl group, a methacryloyl group, an amino group or an epoxy group, and R2 represents a methyl group or an ethyl group)
Hydrolysis of the silicon alkoxide and silane coupling agent is performed by dissolving the silicon alkoxide and silane coupling agent in a suitable solvent. Examples of the solvent to be used include ketones such as methyl ethyl ketone, alcohols such as methanol, ethanol and isopropyl alcohol butanol, esters such as ethyl acetate, and mixtures thereof.

  To the solution obtained by dissolving the silicon alkoxide or silane coupling agent in a solvent, an amount of water slightly larger than the amount required for hydrolysis is added, and the temperature is 15 to 35 ° C., preferably 20 to 30 ° C. for 1 to 48 hours. The stirring is preferably performed for 3 to 36 hours.

  In the hydrolysis, a catalyst is preferably used. As such a catalyst, an acid such as hydrochloric acid, nitric acid, sulfuric acid or acetic acid is preferably used. These acids are used in an aqueous solution of about 0.001N to 20.0N, preferably about 0.005 to 5.0N. The water in the catalyst aqueous solution can be water for hydrolysis.

  The alkoxy silicon compound is hydrolyzed for a predetermined time, the prepared alkoxy silicon hydrolyzed solution is diluted with a solvent, and other necessary additives are mixed to prepare a coating solution for a low refractive index layer. The low refractive index layer can be formed on the base material by applying and drying on a base material such as a film.

(Alkoxy silicon compound)
In the present invention, the alkoxysilicon compound (hereinafter also referred to as alkoxysilane) used for the preparation of the coating solution for the low refractive index layer is preferably represented by the following general formula.

Formula R4-nSi (OR ') n
In the general formula, R ′ represents an alkyl group, R represents a hydrogen atom or a monovalent substituent, and n represents 3 or 4.

  Examples of the alkyl group represented by R ′ include groups such as a methyl group, an ethyl group, a propyl group, and a butyl group, which may have a substituent, and the substituent exhibits properties as an alkoxysilane. If it is, there is no restriction | limiting in particular, For example, although it may be substituted by the halogen atom, the alkoxy group, etc., More preferably, it is an unsubstituted alkyl group, and especially a methyl group and an ethyl group are preferable.

  The monovalent substituent represented by R is not particularly limited, and examples thereof include an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, an aromatic heterocyclic group, and a silyl group. Of these, an alkyl group, a cycloalkyl group, and an alkenyl group are preferable. These may be further substituted. Examples of the substituent for R include a halogen atom such as a fluorine atom and a chlorine atom, an amino group, an epoxy group, a mercapto group, a hydroxyl group, and an acetoxy group.

Specific preferred examples of the alkoxysilane represented by the general formula include tetramethoxysilane, tetraethoxysilane (TEOS), tetra n-propoxy silane, tetraisopropoxy silane, tetra n-butoxy silane, tetra t- Butoxysilane, tetrakis (methoxyethoxy) silane, tetrakis (methoxypropoxy) silane,
Further, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-butyltrimethoxysilane, i-butyltrimethoxysilane, n-hexyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropyltrimethoxysilane, 3 -Mercaptopropyltrimethoxysilane, acetoxytriethoxysilane, (heptadecafluoro-1,1,2,2-tetrahydrodecyl) trimethoxysilane, (3,3,3-trifluoropropyl) trimethoxysilane, (3, 3, - trifluoropropyl) trimethoxysilane, pentafluorophenyl phenylpropyl trimethoxysilane, further, vinyltrimethoxysilane, vinyltriethoxysilane, phenyltrimethoxysilane, vinyltrimethoxysilane, and vinyltriethoxysilane and the like.

  Alternatively, quantified silicon compounds such as silicate 40, silicate 45, silicate 48, and M silicate 51 manufactured by Tama Chemical, in which these compounds are partially condensed may be used.

  Since the alkoxysilane has a silicon alkoxide group that can be hydrolyzed and polycondensed, these alkoxysilanes are crosslinked by hydrolysis and condensation to form a network structure of the polymer compound. A layer containing uniform silicon oxide is formed on the base material by applying it on the base material and drying it as a refractive index layer coating solution.

  The hydrolysis reaction can be carried out by a known method and dissolved in the presence of a predetermined amount of water and a hydrophilic organic solvent such as methanol, ethanol or acetonitrile so that the hydrophobic alkoxysilane and water can be easily mixed. -After mixing, a hydrolysis catalyst is added to hydrolyze and condense the alkoxysilane. Usually, by carrying out hydrolysis and condensation reaction at 10 ° C. to 100 ° C., a liquid silicate oligomer having two or more hydroxyl groups is generated, and a hydrolyzed solution is formed. The degree of hydrolysis can be appropriately adjusted depending on the amount of water used.

  In the present invention, as a solvent to be added to alkoxysilane together with water, methanol and ethanol are preferable because they are inexpensive and the properties of the resulting film are excellent and the hardness is good. Although isopropanol, n-butanol, isobutanol, octanol, and the like can be used, the hardness of the obtained film tends to be low. The amount of the solvent is 50 to 400 parts by mass, preferably 100 to 250 parts by mass with respect to 100 parts by mass of the tetraalkoxysilane before hydrolysis.

  In this way, a hydrolyzed solution is prepared, diluted with a solvent, and if necessary, an additive is added and mixed with components necessary to form a low refractive index layer coating solution. A coating solution is used.

(Hydrolysis catalyst)
Examples of the hydrolysis catalyst include acids, alkalis, organic metals, metal alkoxides, etc. In the present invention, inorganic acids or organic acids such as sulfuric acid, hydrochloric acid, nitric acid, hypochlorous acid, and boric acid are preferable. In particular, carboxylic acids such as nitric acid and acetic acid, polyacrylic acid, benzenesulfonic acid, paratoluenesulfonic acid, methylsulfonic acid and the like are preferable, and among these, nitric acid, acetic acid, citric acid, tartaric acid and the like are preferably used. In addition to the citric acid and tartaric acid, levulinic acid, formic acid, propionic acid, malic acid, succinic acid, methyl succinic acid, fumaric acid, oxaloacetic acid, pyruvic acid, 2-oxoglutaric acid, glycolic acid, D-glyceric acid, D- Gluconic acid, malonic acid, maleic acid, oxalic acid, isocitric acid, lactic acid and the like are also preferably used.

  Of these, those which volatilize the acid during drying and do not remain in the film are preferred, and those having a low boiling point are preferred. Therefore, acetic acid and nitric acid are particularly preferable.

  The added amount is 0.001 to 10 parts by mass, preferably 0.005 to 5 parts by mass with respect to 100 parts by mass of the alkoxysilicon compound (for example, tetraalkoxysilane) to be used. In addition, the amount of water added may be equal to or greater than the amount that the partial hydrolyzate can theoretically hydrolyze to 100%, and an amount equivalent to 100 to 300%, preferably an amount equivalent to 100 to 200% is added.

  When the alkoxysilane is hydrolyzed, the following inorganic fine particles are preferably mixed.

  The hydrolysis solution is allowed to stand for a predetermined time after the start of hydrolysis, and used after the progress of hydrolysis reaches a predetermined level. The standing time is a time during which the above-described crosslinking by hydrolysis and condensation proceeds sufficiently to obtain desired film characteristics. Specifically, depending on the type of acid catalyst used, for example, acetic acid is preferably 15 hours or more at room temperature, and nitric acid is preferably 2 hours or more. The aging temperature affects the aging time. Generally, the aging proceeds quickly at high temperatures, but when heated to 100 ° C. or higher, gelation occurs, so heating at 20 to 60 ° C. and keeping the temperature are appropriate.

  In this way, the following inorganic fine particles and additives are added to the silicate oligomer solution formed by hydrolysis and condensation, and the necessary dilution is performed to prepare a low refractive index layer coating solution. By applying and drying, a layer containing an excellent silicon oxide film as a low refractive index layer can be formed.

  In the present invention, in addition to the above alkoxysilane, for example, a modified product modified with a silane compound (monomer, oligomer, polymer) having a functional group such as an epoxy group, an amino group, an isocyanate group, or a carboxyl group. It may be used alone or in combination.

(Inorganic fine particles)
The low refractive index layer preferably contains hollow fine particles as inorganic fine particles.

  The hollow fine particles referred to here are (1) composite particles composed of porous particles and a coating layer provided on the surface of the porous particles, or (2) hollow inside, and the contents are a solvent, gas or Cavity particles filled with a porous material. In addition, the coating liquid for low refractive index layers should just contain either (1) composite particle | grains or (2) cavity particle | grains, and may contain both.

  The hollow particles are particles having cavities inside, and the cavities are surrounded by particle walls. The cavity is filled with contents such as a solvent, a gas, or a porous material used at the time of preparation. It is desirable that the average particle size of such inorganic fine particles is in the range of 5 to 300 nm, preferably 10 to 200 nm. The inorganic fine particles used are appropriately selected according to the thickness of the transparent film to be formed, and may be in the range of 2/3 to 1/10 of the film thickness of the formed transparent film such as a low refractive index layer. desirable. These inorganic 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.

  The thickness of the coating layer of the composite particles or the thickness of the particle walls of the hollow particles is desirably in the range of 1 to 20 nm, preferably 2 to 15 nm. In the case of composite particles, when the thickness of the coating layer is less than 1 nm, the particles may not be completely covered, and it is easy to use silicate monomers and oligomers with a low polymerization degree, which are coating liquid components described later. In some cases, the inside of the composite particle enters the inside and the porosity of the inside is reduced, so that the effect of the low refractive index cannot be sufficiently obtained. When the thickness of the coating layer exceeds 20 nm, the silicic acid monomer and oligomer do not enter the inside, but the porosity (pore volume) of the composite particles is lowered and the effect of low refractive index is sufficiently obtained. It may not be possible. 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 low refractive index may not be sufficiently exhibited. is there.

The coating layer of the composite particles or the particle wall of the hollow particles is preferably composed mainly of silica. The coating layer of the composite particle or the particle wall of the hollow particle may contain a component other than silica, specifically, Al ₂ O ₃ , B ₂ O ₃ , TiO ₂ , ZrO ₂ , SnO _2. CeO ₂ , P ₂ O ₃ , Sb ₂ O ₃ , MoO ₃ , ZnO ₂ , WO _{3 and the} like. Examples of the porous particles constituting the composite particles include those made of silica, those made of silica and an inorganic compound other than silica, and those made of CaF ₂ , NaF, NaAlF ₆ , MgF, and the like. Of these, porous particles made of a composite oxide of silica and an inorganic compound other than silica are particularly suitable. Examples of inorganic compounds other than silica include Al ₂ O ₃ , B ₂ O ₃ , TiO ₂ , ZrO ₂ , SnO ₂ , CeO ₂ , P ₂ O ₃ , Sb ₂ O ₃ , MoO ₃ , ZnO ₂ , WO _{3 and the} like. 1 type or 2 types or more can be mentioned. In such porous particles, the molar ratio MOX / SiO ₂ when the silica is represented by SiO ₂ and the inorganic compound other than silica is represented by oxide (MOX) is 0.0001 to 1.0, preferably It is desirable to be in the range of 0.001 to 0.3. It is difficult to obtain porous particles having a molar ratio MOX / SiO ₂ of less than 0.0001, and even if obtained, those having a lower refractive index are not obtained. On the other hand, if the molar ratio MOX / SiO _{2 of} the porous particles exceeds 1.0, the ratio of silica decreases, so that particles having a small pore volume and a low refractive index may not be obtained.

  The pore volume of such porous particles is desirably in the range of 0.1 to 1.5 ml / g, preferably 0.2 to 1.5 ml / g. If the pore volume is less than 0.1 ml / g, particles having a sufficiently reduced refractive index cannot be obtained. If the pore volume exceeds 1.5 ml / g, the strength of the fine particles is lowered, and the strength of the resulting coating may be lowered. is there.

  Incidentally, the pore volume of such porous particles can be determined by a mercury intrusion method. Examples of the contents of the hollow particles include a solvent, a gas, and a porous substance used at the time of preparing the particles. The solvent may contain an unreacted particle precursor used in preparing the hollow particles, the catalyst used, and the like. Moreover, what consists of the compound illustrated by the said porous particle as a porous substance is mentioned. These contents may be composed of a single component or may be a mixture of a plurality of components.

  As a method for producing such inorganic fine particles, for example, the method for preparing composite oxide colloidal particles disclosed in paragraphs [0010] to [0033] of JP-A-7-133105 is suitably employed. Specifically, when the composite particles are composed of silica and an inorganic compound other than silica, the inorganic compound particles are produced from the following first to third steps.

First Step: Preparation of Porous Particle Precursor In the first step, an alkali aqueous solution of a silica raw material and an inorganic compound raw material other than silica is separately prepared in advance, or a silica raw material and an inorganic compound raw material other than silica are prepared in advance. A mixed aqueous solution is prepared, and this aqueous solution is gradually added to an aqueous alkaline solution having a pH of 10 or more while stirring according to the composite ratio of the target composite oxide to prepare a porous particle precursor.

  As the silica raw material, alkali metal, ammonium or organic base silicate is used. Sodium silicate (water glass) or potassium silicate is used as the alkali metal silicate. Examples of the organic base include quaternary ammonium salts such as tetraethylammonium salt, and amines such as monoethanolamine, diethanolamine, and triethanolamine. The ammonium silicate or the organic base silicate includes an alkaline solution obtained by adding ammonia, a quaternary ammonium hydroxide, an amine compound or the like to a silicic acid solution.

  In addition, alkali-soluble inorganic compounds are used as raw materials for inorganic compounds other than silica. Specifically, an oxo acid of an element selected from Al, B, Ti, Zr, Sn, Ce, P, Sb, Mo, Zn, W, etc., an alkali metal salt or alkaline earth metal salt of the oxo acid, ammonium Salts and quaternary ammonium salts. More specifically, sodium aluminate, sodium tetraborate, zirconyl ammonium carbonate, potassium antimonate, potassium stannate, sodium aluminosilicate, sodium molybdate, cerium ammonium nitrate, and sodium phosphate are suitable.

Although the pH value of the mixed aqueous solution changes simultaneously with the addition of these aqueous solutions, an operation for controlling the pH value within a predetermined range is not particularly required. The aqueous solution finally has a pH value determined by the type of inorganic oxide and the mixing ratio thereof. There is no restriction | limiting in particular in 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, but inorganic oxides such as SiO ₂ , Al ₂ O ₃ , TiO ₂ or ZrO ₂ or fine particles of these composite oxides are used. Usually, these sols are used. I can do it. Furthermore, the porous particle precursor dispersion obtained by the above production method may be used as a seed particle dispersion. When the seed particle dispersion is used, the pH of the seed particle dispersion is adjusted to 10 or more, and then the aqueous solution of the compound is added to the above-described alkaline aqueous solution while stirring. Also in this case, it is not always necessary to control the pH of the dispersion. In this way, when seed particles are used, it is easy to control the particle size of the porous particles to be prepared, and particles having a uniform particle size can be obtained.

  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 region, the solubility of oxo acid ions such as silicate ions and aluminate ions decreases, and these composites precipitate and grow into fine particles, or seed particles. Particle deposition occurs on the top. Therefore, it is not always necessary to perform pH control as in the conventional method for precipitation and growth of fine particles.

The composite ratio of silica and inorganic compound other than silica in the first step is that the inorganic compound relative to silica is converted to oxide (MOx), and the molar ratio of MOx / SiO ₂ is 0.05 to 2.0, preferably It is desirable to be within the range of 0.2 to 2.0. Within this range, the pore volume of the porous particles increases as the proportion of silica decreases. However, even when 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, the molar ratio of MOx / SiO ₂ is preferably in the range of 0.25 to 2.0.

Second step: Removal of inorganic compound other than silica from porous particles In the second step, inorganic compounds other than silica (elements other than silicon and oxygen) are obtained from the porous particle precursor obtained in the first step. At least a portion is selectively removed. As a specific removal method, the inorganic compound in the porous particle precursor is dissolved and removed using a mineral acid or an organic acid, or is contacted with a cation exchange resin for ion exchange removal.

  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. By removing the inorganic compound (elements other than silicon and oxygen) from the porous particle precursor in this way, porous particles having a larger porosity and a larger pore volume can be obtained. Further, if the amount of removing the inorganic oxide (elements other than silicon and oxygen) from the porous particle precursor is increased, the hollow particles can be prepared.

  In addition, prior to removing inorganic compounds other than silica from the porous particle precursor, a silicic acid solution obtained by removing the alkali metal salt of silica from the porous particle precursor dispersion obtained in the first step. Alternatively, it is preferable to form a silica protective film by adding a hydrolyzable organosilicon compound. The thickness of the silica protective film may be 0.5 to 15 nm. Even if the silica protective film is formed, the protective film in this step is porous and thin, so that it is possible to remove inorganic compounds other than silica described above from the porous particle precursor.

  By forming such a silica protective film, inorganic compounds other than silica described above can be removed from the porous particle precursor 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, and therefore the silica coating layer described later is formed without reducing the pore volume. I can do it. Note that when the amount of the inorganic compound to be removed is small, the particles are not broken, and thus it is not always necessary to form a protective film.

  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 to be described later is formed on the precursor, the formed coating layer becomes a particle wall to form hollow particles.

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, and it may be difficult to remove inorganic compounds other than silica from the porous particle precursor. The hydrolyzable organic silicon compound used for the silica protective film formed of the general formula _{R n Si (OR ') 4} -n [R, R': an alkyl group, an aryl group, a vinyl group, such as acrylic group An alkoxysilane represented by a hydrocarbon group, n = 0, 1, 2, or 3] can be used. In particular, tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, and tetraisopropoxysilane are preferably used.

  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 alkoxysilane, pure water, and alcohol is added to the dispersion of the porous particles, and the alkoxysilane is hydrolyzed. The produced silicic acid polymer is deposited on the surface of the 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.

  When the dispersion medium of the porous particle precursor is water alone or when the ratio of water to the organic solvent is high, a silica protective film can be formed using a silicic acid solution. When a silicic acid solution is used, a predetermined amount of the silicic acid solution is added to the dispersion, and at the same time an alkali is added to deposit the silicic acid solution on the surface of the porous particles. In addition, you may produce a silica protective film together using a silicic acid liquid and the said alkoxysilane.

Third Step: Formation of Silica Coating Layer In the third step, a hydrolyzable organosilicon compound or silicic acid solution is added to the porous particle dispersion prepared in the second step (in the case of hollow particles, a hollow particle precursor dispersion). Etc. is added to coat the surface of the particles with a polymer such as a hydrolyzable organosilicon compound or silicic acid solution to form a silica coating layer.

The hydrolyzable organic silicon compound used for the silica coating layer formed, the above-mentioned such general formula _{R n Si (OR ') 4} -n [R, R': an alkyl group, an aryl group, a vinyl group, A hydrocarbon group such as an acryl group or an alkoxysilane represented by n = 0, 1, 2, or 3] can be used. In particular, tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, and tetraisopropoxysilane are preferably used.

  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 alkoxysilane, pure water, and alcohol is used as a dispersion of the porous particles (in the case of hollow particles, a hollow particle precursor). In addition, the silicic acid polymer produced by hydrolyzing alkoxysilane is deposited on the surface of the porous particles (in the case of hollow particles, hollow particle precursors). 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.

  When 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 mixed solvent has a high ratio of water to the organic solvent, a silicate solution You may form a coating layer using. The silicic acid solution is an aqueous solution of a low silicic acid polymer obtained by dealkalizing an aqueous solution of an alkali metal silicate such as water glass by ion exchange treatment.

  The silicic 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 make the low-silicic acid polymer into porous particles (in the case of hollow particles, hollow particle precursors). ) Deposit on the surface. A silicic acid solution may be used in combination with the alkoxysilane for forming a coating layer. The addition amount of the organosilicon compound or silicic acid solution used for forming the coating layer only needs to be sufficient to cover the surface of the colloidal particles, and the finally obtained silica coating layer has a thickness of 1 to 20 nm. In such an amount, it is added in a dispersion of porous particles (in the case of hollow particles, hollow particle precursor) in a dispersion. When the silica protective film is formed, the organosilicon compound or the silicate solution is added in such an amount that the total thickness of the silica protective film and the silica coating layer is in the range of 1 to 20 nm.

  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 form hollow particle walls, and a dispersion of hollow particles having cavities filled with a solvent, gas, or porous solid content is obtained.

  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, and is preferably in the range of 80 to 300 ° C. 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. Further, 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.

  The refractive index of the inorganic fine particles thus obtained is as low as less than 1.44. Such inorganic fine particles are presumed to have a low refractive index because the porosity inside the porous particles is maintained or the inside is hollow.

(Additive)
The low refractive index layer coating solution may contain additives such as a silane coupling agent and a curing agent as necessary.
The silane coupling agent is a compound represented by the following formula (2).

Formula (2): RmSi (OR ′) n
In the formula, R is an alkyl group (preferably an alkyl group having 1 to 10 carbon atoms), or a reaction such as a vinyl group, a (meth) acryloyl group, an epoxy group, an amide group, a sulfonyl group, a hydroxyl group, a carboxyl group, or an alkoxyl group. R ′ represents an alkyl group (preferably an alkyl group having 1 to 10 carbon atoms), and m + n is 4.

  Specific examples include vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, and 3- (2-aminoethylaminopropyl) trimethoxysilane.

  Examples of the curing agent include organic acid metal salts such as sodium acetate and lithium acetate, and sodium acetate is particularly preferable. The amount of addition to the silicon alkoxysilane hydrolysis solution is preferably in the range of about 0.1 to 1 part by mass with respect to 100 parts by mass of the solid content present in the hydrolysis solution.

  Moreover, it is preferable to add various surface leveling agents, surfactants, low surface tension substances such as silicone oil to the coating solution for each layer of the present invention. Specific silicon oils include the compounds in Table 1.

  These components enhance the applicability to the substrate and the lower layer. When added to the outermost surface layer of the laminate, it not only improves the water repellency, oil repellency and antifouling properties of the coating film, but also exhibits an effect on the scratch resistance of the surface. When these components are added in an excessive amount, they cause repelling during coating. Therefore, it is preferable to add them in a range of 0.01 to 3% by mass with respect to the solid component in the coating solution.

(solvent)
Solvents used in the coating solution for coating the low refractive index layer are alcohols such as methanol, ethanol, 1-propanol, 2-propanol and butanol; ketones such as acetone, methyl ethyl ketone and cyclohexanone; benzene, toluene, Aromatic hydrocarbons such as xylene; glycols such as ethylene glycol, propylene glycol, hexylene glycol; ethyl cellosolve, butyl cellosolve, ethyl carbitol, butyl carbitol, diethyl cellosolve, diethyl carbitol, propylene glycol monomethyl Examples include glycol ethers such as ether; N-methylpyrrolidone, dimethylformamide, methyl lactate, ethyl lactate, water, and the like, and these can be used alone or in combination of two or more.

(Application method)
Coating methods such as antistatic layer, low refractive index layer, medium refractive index layer, high refractive index layer, hard coat layer coating solution include dipping, spin coating, knife coating, bar coating, air doctor coating, blade coating, squeeze A known coating method such as coating, reverse roll coating, gravure roll coating, curtain coating, spray coating, die coating or the like or a known inkjet method can be used, and a coating method capable of continuous coating or thin film coating is preferably used. The coating amount is suitably 0.1 to 30 μm, preferably 0.5 to 15 μm in terms of wet film thickness. The coating speed is preferably 10 to 60 m / min.

  When the composition of the present invention is applied to a substrate, the thickness of the layer, coating uniformity, and the like can be controlled by adjusting the solid content concentration and the coating amount in the coating solution. Moreover, in order to improve the applicability | paintability of a composition, you may add a trace amount surfactant etc. in a coating liquid.

(Base film)
As a base film used for the antireflection film (low reflection laminate) of the present invention, it is easy to produce, a hard coat layer or an antireflection layer is easily adhered, and is optically isotropic. In particular, it is preferably optically transparent. Any of these may be used, for example, cellulose ester film, polyester film, polycarbonate film, polyarylate film, polysulfone (including polyethersulfone) film, polyethylene terephthalate, polyethylene naphthalate. Polyester film, polyethylene film, polypropylene film, cellophane, cellulose diacetate film, cellulose acetate butyrate film, polyvinylidene chloride film, polyvinyl alcohol film, ethylene vinyl alcohol film, syndiotactic polystyrene film, polycarbonate film, norbornene resin Film, polymethylpentene film, polyetherketone film, Polyether ketone imide film, a polyamide film, a fluororesin film, a nylon film, a cycloolefin polymer film, polymethyl methacrylate film, or an acrylic film or the like can be mentioned, but is not limited thereto. Of these, cellulose triacetate films (for example, Konica Katak KC8UX2M, KC4UX2M, KC4UY, KC5UN (manufactured by Konica Minolta Opto, Inc.)), polycarbonate films, polysulfones (including polyethersulfone), and cycloolefin polymer films are preferred. In the present invention, a cellulose triacetate film, a cellulose acetate propionate film, or a cycloolefin polymer film is particularly preferable from the viewpoint of production, cost, transparency, isotropic properties, adhesiveness, and the like.

(Cellulose ester film)
The cellulose ester used in the present invention is preferably a lower fatty acid ester of cellulose. The lower fatty acid in the lower fatty acid ester of cellulose means a fatty acid having 6 or less carbon atoms. For example, cellulose acetate, cellulose propionate, cellulose butyrate and the like, and JP-A Nos. 10-45804 and 08-231761 Further, mixed fatty acid esters such as cellulose acetate propionate and cellulose acetate butyrate as described in US Pat. No. 2,319,052 can be used. Among the above descriptions, the lower fatty acid esters of cellulose particularly preferably used are cellulose triacetate and cellulose acetate propionate. These cellulose esters can be used alone or in combination.

  If the molecular weight of the cellulose ester is too small, the tear strength decreases. However, if the molecular weight is excessively increased, the viscosity of the cellulose ester solution becomes too high, resulting in a decrease in productivity. The molecular weight of the cellulose ester is preferably 70000-200000 in terms of number average molecular weight (Mn), more preferably 100,000-200000.

  In the case of cellulose triacetate, those having an average degree of acetylation (bound acetic acid amount) of 54.0 to 62.5% are preferably used, and more preferably an average degree of acetylation of 58.0 to 62.5%. Cellulose triacetate. When the average degree of acetylation is small, the dimensional change is large, and the polarization degree of the polarizing plate is lowered. When the average degree of acetylation is large, the solubility in a solvent is lowered and the productivity is lowered.

  Preferred cellulose esters other than cellulose triacetate have an acyl group having 2 to 4 carbon atoms as a substituent, and when the substitution degree of acetyl group is X and the substitution degree of propionyl group or butyryl group is Y, the following formula ( It is a cellulose ester containing the cellulose ester which satisfy | fills I) and (II) simultaneously.

Formula (I) 2.6 ≦ X + Y ≦ 3.0
Formula (II) 0 ≦ X ≦ 2.5
Of these, cellulose acetate propionate is preferably used, and it is particularly preferable that 1.9 ≦ X ≦ 2.5 and 0.1 ≦ Y ≦ 0.9. The portion that is not substituted with an acyl group is usually present as a hydroxyl group. These can be synthesized by known methods.

  As the cellulose ester, cellulose ester synthesized using cotton linter, wood pulp, kenaf or the like as a raw material can be used alone or in combination. In particular, it is preferable to use a cellulose ester synthesized from a cotton linter (hereinafter sometimes simply referred to as linter) alone or in combination.

  The cellulose ester film used in the present invention is preferably stretched at least in the width direction, and is 1.01 to 1.1 in the width direction, particularly when the amount of residual dissolution is 3 to 40% by mass in the solution casting step. It is preferable that the film is stretched 5 times. More preferably, it is biaxially stretched in the width direction and the lengthwise direction, and when the amount of residual dissolution is 3 to 40% by mass, it is stretched by 1.01 to 1.5 times in the width direction and the lengthwise direction, respectively. It is desirable that By carrying out like this, the antireflection film excellent in visibility can be obtained. Furthermore, by performing biaxial stretching and knurling, it is possible to remarkably improve the deterioration of the winding shape during storage in the form of a roll of a long low-reflection film.

  The draw ratio at this time is preferably 1.01 to 1.5 times, and more preferably 1.03 to 1.45 times.

  The cellulose ester film according to the present invention is preferably a transparent support having a light transmittance of 90% or more, more preferably 93% or more.

The cellulose ester film support according to the present invention preferably has a thickness of 10 to 100 μm, and the moisture permeability is preferably 200 g / m ² · 24 hours or less at 25 ° C. and 90 ± 2% RH. More preferably, it is 10 to 180 g / m ² · 24 hours or less, and particularly preferably 160 g / m ² · 24 hours or less.

  In particular, it is preferable that the film thickness is 10 to 60 μm and the moisture permeability is within the above range.

  Here, the moisture permeability of the support was measured according to the method described in JIS Z 0208.

(Plasticizer)
When a cellulose ester film is used for the support used in the present invention, the following plasticizer is preferably contained. Examples of plasticizers include phosphate ester plasticizers, phthalate ester plasticizers, trimellitic acid ester plasticizers, pyromellitic acid plasticizers, glycolate plasticizers, citrate ester plasticizers, and polyesters. A plasticizer, a polyhydric alcohol ester plasticizer, and the like can be preferably used.

  For phosphate plasticizers, triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, octyl diphenyl phosphate, diphenylbiphenyl phosphate, trioctyl phosphate, tributyl phosphate, etc. For phthalate ester plasticizers, diethyl phthalate, dimethoxy For trimellitic acid plasticizers such as ethyl phthalate, dimethyl phthalate, dioctyl phthalate, dibutyl phthalate, di-2-ethylhexyl phthalate, butyl benzyl phthalate, diphenyl phthalate, dicyclohexyl phthalate, tributyl trimellitate, triphenyl trimellitate, triethyl For pyromellitic acid ester plasticizers such as trimellitate, tetrabutylpyromellitate, In the case of glycolate plasticizers such as lupyromelitate and tetraethylpyromellitate, triacetin, tributyrin, ethylphthalylethyl glycolate, methylphthalylethyl glycolate, butylphthalylbutyl glycolate, etc. Citrate, tri-n-butyl citrate, acetyl triethyl citrate, acetyl tri-n-butyl citrate, acetyl tri-n- (2-ethylhexyl) citrate and the like can be preferably used. Examples of other carboxylic acid esters include butyl oleate, methylacetyl ricinoleate, dibutyl sebacate, and various trimellitic acid esters.

  As the polyester plasticizer, a copolymer of a dibasic acid such as an aliphatic dibasic acid, an alicyclic dibasic acid, or an aromatic dibasic acid and a glycol can be used. The aliphatic dibasic acid is not particularly limited, and adipic acid, sebacic acid, phthalic acid, terephthalic acid, 1,4-cyclohexyl dicarboxylic acid and the like can be used. As the glycol, 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 may be used alone or in combination of two or more.

  The polyhydric alcohol ester plasticizer comprises an ester of a divalent or higher aliphatic polyhydric alcohol and a monocarboxylic acid. Examples of preferred polyhydric alcohols include the following, but the present invention is not limited to these. Adonitol, arabitol, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,2-propanediol, 1,3-propanediol, dipropylene glycol, tripropylene glycol, 1,2-butanediol, 1,3-butanediol 1,4-butanediol, dibutylene glycol, 1,2,4-butanetriol, 1,5-pentanediol, 1,6-hexanediol, hexanetriol, 2-n-butyl-2-ethyl-1,3- Propanediol, galactitol, mannitol, 3-methylpentane-1,3,5-triol, pinacol, sorbitol, trimethylolpropane, trimethylolethane, xylitol, and the like can be raised. In particular, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, sorbitol, trimethylolpropane, and xylitol are preferable. There is no restriction | limiting in particular as monocarboxylic acid used for polyhydric alcohol ester, Well-known aliphatic monocarboxylic acid, alicyclic monocarboxylic acid, aromatic monocarboxylic acid, etc. can be used. Use of an alicyclic monocarboxylic acid or aromatic monocarboxylic acid is preferred in terms of improving moisture permeability and retention. Examples of the preferred monocarboxylic acid include the following, but the present invention is not limited to this. As the aliphatic monocarboxylic acid, a fatty acid having a straight chain or a side chain having 1 to 32 carbon atoms can be preferably used. It is more preferable that it is C1-C20, and it is especially preferable that it is C1-C10. When acetic acid is contained, the compatibility with the cellulose ester is increased, and it is also preferable to use a mixture of acetic acid and another monocarboxylic acid. Preferred aliphatic monocarboxylic acids include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, 2-ethyl-hexanecarboxylic acid, undecylic acid, lauric acid, tridecylic acid, Saturated fatty acids such as myristic acid, pentadecylic acid, palmitic acid, heptadecylic acid, stearic acid, nonadecanoic acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, heptacosanoic acid, montanic acid, melicic acid, laccelic acid, undecylenic acid, olein Unsaturated fatty acids such as acid, sorbic acid, linoleic acid, linolenic acid and arachidonic acid can be raised. Examples of preferable alicyclic monocarboxylic acids include cyclopentanecarboxylic acid, cyclohexanecarboxylic acid, cyclooctanecarboxylic acid, and derivatives thereof. Examples of preferred aromatic monocarboxylic acids include those in which an alkyl group is introduced into the benzene ring of benzoic acid such as benzoic acid and toluic acid, and two or more benzene rings such as biphenyl carboxylic acid, naphthalene carboxylic acid, and tetralin carboxylic acid. Aromatic monocarboxylic acids or derivatives thereof can be raised. Particularly preferred is benzoic acid. The molecular weight of the polyhydric alcohol ester is not particularly limited, but is preferably in the range of 300 to 1500, and more preferably in the range of 350 to 750. The larger one is preferable in terms of improvement in retention, and the smaller one is preferable in terms of moisture permeability and compatibility with cellulose ester.

  The carboxylic acid used in the polyhydric alcohol ester of the present invention may be one kind or a mixture of two or more kinds. Further, all of the OH groups in the polyhydric alcohol may be esterified with carboxylic acid, or a part of the OH groups may be left as they are.

  These plasticizers are preferably used alone or in combination.

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

(UV absorber)
The ultraviolet absorber according to the support used in the present invention will be described. For the support of the low reflection laminate, an ultraviolet absorber is preferably used.

  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.

  Specific examples of ultraviolet absorbers preferably used in the present invention include, for example, oxybenzophenone compounds, benzotriazole compounds, salicylic acid ester compounds, benzophenone compounds, cyanoacrylate compounds, nickel complex compounds, and the like. It is not limited to these.

  As the benzotriazole ultraviolet absorber, a compound represented by the following general formula (A) is preferably used.

In the formula, R ₁ , R ₂ , R ₃ , R ₄ and R ₅ may be the same or different, and are a hydrogen atom, halogen atom, nitro group, hydroxyl group, alkyl group, alkenyl group, aryl group, alkoxyl group, acyloxy Represents a group, aryloxy group, alkylthio group, arylthio group, mono- or dialkylamino group, acylamino group or 5- to 6-membered heterocyclic group, and R ₄ and R ₅ are closed to form a 5- to 6-membered carbocyclic ring May be.

  Moreover, these groups described above may have an arbitrary substituent.

  Although the specific example of the ultraviolet absorber used for this invention is given to the following, this invention is not limited to these.

UV-1: 2- (2'-hydroxy-5'-methylphenyl) benzotriazole UV-2: 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) benzotriazole UV-3 : 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) benzotriazole UV-4: 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl)- 5-Chlorobenzotriazole UV-5: 2- (2'-hydroxy-3 '-(3 ", 4", 5 ", 6" -tetrahydrophthalimidomethyl) -5'-methylphenyl) benzotriazole UV-6: 2,2-methylenebis (4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol)
UV-7: 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole UV-8: 2- (2H-benzotriazol-2-yl) -6 (Linear and side chain dodecyl) -4-methylphenol (TINUVIN171, manufactured by Ciba Specialty Chemicals)
UV-9: Octyl-3- [3-tert-butyl-4-hydroxy-5- (chloro-2H-benzotriazol-2-yl) phenyl] propionate and 2-ethylhexyl-3- [3-tert-butyl- Mixture of 4-hydroxy-5- (5-chloro-2H-benzotriazol-2-yl) phenyl] propionate (TINUVIN109, manufactured by Ciba Specialty Chemicals)
As the benzophenone-based ultraviolet absorber, a compound represented by the following general formula (B) is preferably used.

In the formula, Y represents a hydrogen atom, a halogen atom or an alkyl group, an alkenyl group, an alkoxyl group, and a phenyl group, and these alkyl group, alkenyl group, and phenyl group may have a substituent. A represents a hydrogen atom, an alkyl group, an alkenyl group, a phenyl group, a cycloalkyl group, an alkylcarbonyl group, an alkylsulfonyl group or a —CO (NH) _n-1 —D group, and D represents an alkyl group, an alkenyl group or a substituent. Represents a phenyl group which may have m and n represent 1 or 2.

  In the above, the alkyl group represents, for example, a linear or branched aliphatic group having up to 24 carbon atoms, the alkoxyl group represents, for example, an alkoxyl group having up to 18 carbon atoms, and the alkenyl group has, for example, carbon number An alkenyl group up to 16 represents an allyl group, a 2-butenyl group, or the like. In addition, as substituents to alkyl groups, alkenyl groups, and phenyl groups, halogen atoms such as chlorine atoms, bromine atoms, fluorine atoms, etc., hydroxyl groups, phenyl groups (this phenyl group is substituted with alkyl groups or halogen atoms, etc.) May be used).

  Specific examples of the benzophenone compound represented by the general formula (B) are shown below, but the present invention is not limited thereto.

UV-10: 2,4-dihydroxybenzophenone UV-11: 2,2'-dihydroxy-4-methoxybenzophenone UV-12: 2-hydroxy-4-methoxy-5-sulfobenzophenone UV-13: Bis (2-methoxy -4-hydroxy-5-benzoylphenylmethane)
As the above-mentioned ultraviolet absorbers preferably used in the present invention, benzotriazole-based ultraviolet absorbers and benzophenone-based ultraviolet absorbers that are highly transparent and excellent in preventing deterioration of polarizing plates and liquid crystals are preferable, and unnecessary coloring A benzotriazole-based ultraviolet absorber with a lower content is particularly preferably used.

  In addition, an ultraviolet absorber having a distribution coefficient of 9.2 or more described in Japanese Patent Application No. 11-295209 is excellent in surface quality of the support and excellent in coatability when used in the support. In particular, it is preferable to use an ultraviolet absorber having a distribution coefficient of 10.1 or more.

  Further, the polymer ultraviolet absorber (or ultraviolet ray) described in the general formula (1) or general formula (2) of JP-A-6-148430 and the general formulas (3), (6), and (7) of Japanese Patent Application No. 2000-156039. Absorbable polymers) are also preferably used. As a polymer ultraviolet absorber, PUVA-30M (manufactured by Otsuka Chemical Co., Ltd.) and the like are commercially available.

(Fine particles)
In the present invention, the cellulose ester film preferably contains fine particles. Examples of the fine particles include silicon dioxide, titanium dioxide, aluminum oxide, zirconium oxide, calcium carbonate, kaolin, talc, calcined calcium silicate, and hydration. It is preferable to contain inorganic fine particles such as calcium silicate, aluminum silicate, magnesium silicate, calcium phosphate, and crosslinked polymer fine particles. Of these, silicon dioxide is preferable because it can reduce the haze of the film. The average particle size of the secondary particles of the fine particles is in the range of 0.01 to 1.0 μm, and the content is preferably 0.005 to 0.3% by mass with respect to the cellulose ester. In many cases, fine particles such as silicon dioxide are surface-treated with an organic material, but such a material is preferable because the haze of the film can be reduced. Preferred organic substances for the surface treatment include halosilanes, alkoxysilanes (particularly alkoxysilanes having a methyl group), silazane, siloxane and the like. The larger the average particle size of the fine particles, the greater the mat effect, and on the contrary, the smaller the average particle size, the better the transparency. Therefore, the average particle size of the preferred primary particles is 5 to 50 nm, more preferably 7 to 16 nm. It is. These fine particles are usually present as aggregates in the cellulose ester film, and it is preferable to form irregularities of 0.01 to 1.0 μm on the surface of the cellulose ester film. Examples of the fine particles of silicon dioxide include Aerosil 200, 200V, 300, R972, R972V, R974, R202, R812, OX50, TT600, etc. manufactured by Aerosil, preferably AEROSIL (Aerosil) 200V, R972, R972V, R974, R202, and R812. Two or more kinds of these fine particles may be used in combination. When using 2 or more types together, it can mix and use in arbitrary ratios. In this case, fine particles having different average particle sizes and materials, for example, AEROSIL (Aerosil) 200V and R972V can be used in a mass ratio of 0.1: 99.9 to 99.9 to 0.1. In the present invention, the fine particles may be dispersed together with cellulose ester, other additives, and an organic solvent at the time of preparing the dope, but in a sufficiently dispersed state like a fine particle dispersion separately from the cellulose ester solution. It is preferable to prepare the dope. In order to disperse the fine particles, it is preferably preliminarily dispersed in an organic solvent and then finely dispersed by a disperser (high pressure disperser) having a high shearing force. After that, it is preferable to disperse in a larger amount of organic solvent, merge with the cellulose ester solution, and mix with an in-line mixer to obtain a dope. In this case, an ultraviolet absorbent may be added to the fine particle dispersion to form an ultraviolet absorbent liquid.

  The deterioration inhibitor, the ultraviolet absorber and / or the fine particles may be added together with the cellulose ester and the solvent during the preparation of the cellulose ester solution, or may be added during or after the solution preparation.

(Organic solvent)
Organic solvents useful for forming the dope according to the present invention simultaneously dissolve cellulose ester, compounds having at least two aromatic rings, and at least two aromatic rings having a planar structure, and other additives. If it does, it can be used without limitation. For example, as the chlorinated organic solvent, methylene chloride, as the non-chlorinated organic solvent, methyl acetate, ethyl acetate, amyl acetate, acetone, tetrahydrofuran, 1,3-dioxolane, 1,4-dioxane, cyclohexanone, ethyl formate, 2,2,2-trifluoroethanol, 2,2,3,3-hexafluoro-1-propanol, 1,3-difluoro-2-propanol, 1,1,1,3,3,3-hexafluoro- Examples include 2-methyl-2-propanol, 1,1,1,3,3,3-hexafluoro-2-propanol, 2,2,3,3,3-pentafluoro-1-propanol, and nitroethane. Methylene chloride, methyl acetate, ethyl acetate and acetone can be preferably used. Particularly preferred is methyl acetate.

  In addition to the organic solvent, the dope according to the present invention preferably contains 1 to 40% by mass of an alcohol having 1 to 4 carbon atoms. When the proportion of alcohol in the dope increases, the web gels, facilitating peeling from the metal support, and when the proportion of alcohol is small, the role of promoting dissolution of cellulose esters in non-chlorine organic solvent systems There is also. Examples of the alcohol having 1 to 4 carbon atoms include methanol, ethanol, n-propanol, iso-propanol, n-butanol, sec-butanol, and tert-butanol. Ethanol is preferred because of the stability of these dopes, the relatively low boiling point, good drying properties, and no toxicity.

  The concentration of the cellulose ester in the dope is preferably adjusted to 15 to 40% by mass, and the dope viscosity is preferably adjusted to a range of 100 to 500 poise (P) in order to obtain good film surface quality.

(Cycloolefin polymer film)
Next, the cycloolefin polymer film used in the present invention will be described.

  The cycloolefin polymer used in the present invention is composed of a polymer resin containing an alicyclic structure.

  A preferred cycloolefin polymer is a resin obtained by polymerizing or copolymerizing a cyclic olefin. Examples of the cyclic olefin include norbornene, dicyclopentadiene, tetracyclododecene, ethyltetracyclododecene, ethylidenetetracyclododecene, tetracyclo [7.4.0.110, 13.02,7] trideca-2,4. Unsaturated hydrocarbons of polycyclic structures such as 6,11-tetraene and derivatives thereof; cyclobutene, cyclopentene, cyclohexene, 3,4-dimethylcyclopentene, 3-methylcyclohexene, 2- (2-methylbutyl) -1-cyclohexene, cyclo Examples thereof include monocyclic unsaturated hydrocarbons such as octene, 3a, 5,6,7a-tetrahydro-4,7-methano-1H-indene, cycloheptene, cyclopentadiene, cyclohexadiene, and derivatives thereof. These cyclic olefins may have a polar group as a substituent. Examples of the polar group include a hydroxyl group, a carboxyl group, an alkoxyl group, an epoxy group, a glycidyl group, an oxycarbonyl group, a carbonyl group, an amino group, an ester group, and a carboxylic acid anhydride group. Or a carboxylic anhydride group is preferred.

  Preferred cycloolefin polymers may be those obtained by addition copolymerization of monomers other than cyclic olefins. Addition copolymerizable monomers include ethylene, propylene, 1-butene, 1-pentene and other ethylene or α-olefins; 1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl- Examples include dienes such as 1,4-hexadiene and 1,7-octadiene.

The cyclic olefin is obtained by an addition polymerization reaction or a metathesis ring-opening polymerization reaction. The polymerization is carried out in the presence of a catalyst. Examples of the addition polymerization catalyst include a polymerization catalyst composed of a vanadium compound and an organoaluminum compound. As a catalyst for ring-opening polymerization, a polymerization catalyst comprising a metal halide such as ruthenium, rhodium, palladium, osmium, iridium, platinum, nitrate or acetylacetone compound and a reducing agent; or titanium, vanadium, zirconium, tungsten, molybdenum Examples thereof include a polymerization catalyst comprising a metal halide such as acetylacetone compound and an organoaluminum compound. The polymerization temperature, pressure and the like are not particularly limited, but the polymerization is usually carried out at a polymerization temperature of -50 ° C to 100 ° C and a polymerization pressure of 0 to 490 N / cm ² .

  The cycloolefin polymer used in the present invention is preferably a polymer obtained by polymerizing or copolymerizing a cyclic olefin, followed by a hydrogenation reaction to change the unsaturated bond in the molecule to a saturated bond. The hydrogenation reaction is performed by blowing hydrogen in the presence of a known hydrogenation catalyst. Hydrogenation catalysts include cobalt acetate / triethylaluminum, nickel acetylacetonate / triisobutylaluminum, transition metal compounds such as titanocene dichloride / n-butyllithium, zirconocene dichloride / sec-butyllithium, tetrabutoxytitanate / dimethylmagnesium / alkyl Homogeneous catalyst consisting of a combination of metal compounds; heterogeneous metal catalyst such as nickel, palladium, platinum; nickel / silica, nickel / diatomaceous earth, nickel / alumina, palladium / carbon, palladium / silica, palladium / diatomaceous earth And a heterogeneous solid-supported catalyst in which a metal catalyst such as palladium / alumina is supported on a carrier.

  Or the following norbornene-type polymer is also mentioned as a cycloolefin polymer. The norbornene-based polymer preferably has a norbornene skeleton as a repeating unit. Specific examples thereof include JP-A-62-252406, JP-A-62-2252407, and JP-A-2-133413. JP, JP 63-145324, JP 63-264626, JP 1-224017, JP 57-8815, JP 5-39403, JP 5-43663 JP-A-5-43834, JP-A-5-70655, JP-A-5-279554, JP-A-6-206985, JP-A-7-62028, JP-A-8-176411, Although what was described in Unexamined-Japanese-Patent No. 9-241484 etc. can use preferably, it is not limited to these. Moreover, these may be used individually by 1 type and may use 2 or more types together.

  In the present invention, among the norbornene-based polymers, those having a repeating unit represented by any of the following structural formulas (I) to (IV) are preferable.

  In the structural formulas (I) to (IV), A, B, C and D each independently represent a hydrogen atom or a monovalent organic group.

  Among the norbornene-based polymers, a polymer obtained by metathesis polymerization of at least one compound represented by the following structural formula (V) or (VI) and an unsaturated cyclic compound copolymerizable therewith. A hydrogenated polymer obtained by hydrogenating is also preferred.

  In the structural formula, A, B, C and D each independently represent a hydrogen atom or a monovalent organic group.

  Here, A, B, C and D are not particularly limited, but preferably an organic group may be linked through a hydrogen atom, a halogen atom, a monovalent organic group, or at least a divalent linking group. These may be the same or different. A or B and C or D may form a monocyclic or polycyclic structure. Here, the at least divalent linking group includes a hetero atom typified by an oxygen atom, a sulfur atom, and a nitrogen atom, and examples thereof include ethers, esters, carbonyls, urethanes, amides, and thioethers. It is not limited. Further, the organic group may be further substituted via the linking group.

  Examples of other monomers copolymerizable with the norbornene-based monomer include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, C2-C20 alpha olefins, such as 1-hexadecene, 1-octadecene, 1-eicocene, and derivatives thereof; cyclobutene, cyclopentene, cyclohexene, cyclooctene, 3a, 5,6,7a-tetrahydro-4,7 -Cycloolefins such as methano-1H-indene, and derivatives thereof; non 1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 1,7-octadiene, etc. Conjugated dienes; and the like are used. Among these, an α-olefin, particularly ethylene is preferable.

  These other monomers copolymerizable with the norbornene-based monomer can be used alone or in combination of two or more. In the case of addition copolymerization of a norbornene monomer and another monomer copolymerizable therewith, the ratio of the structural unit derived from the norbornene monomer and the structural unit derived from the other monomer copolymerizable in the addition copolymer However, it is appropriately selected so that the mass ratio is usually 30:70 to 99: 1, preferably 50:50 to 97: 3, more preferably 70:30 to 95: 5.

  When the unsaturated bond remaining in the molecular chain of the synthesized polymer is saturated by a hydrogenation reaction, the hydrogenation rate is 90% or more, preferably 95% or more, particularly from the viewpoint of light resistance deterioration, weather resistance deterioration, etc. Preferably it is 99% or more.

  In addition, examples of the cycloolefin polymer used in the present invention include thermoplastic saturated norbornene resins described in paragraph Nos. [0014] to [0019] of JP-A-5-2108, and paragraph Nos. [0015] of JP-A-2001-277430. ] To [0031] thermoplastic norbornene polymers, JP 2003-14901 paragraph numbers [0008] to [0045] thermoplastic norbornene resins, JP 2003-139950 paragraph numbers [0014] to [0028] Norbornene-based resin composition, paragraph Nos. [0029] to [0037] described in JP-A No. 2003-161832, paragraph Nos. [0027] to [0036] described in JP-A No. 2003-195268 Norbornene resin, Japanese Patent Application Laid-Open No. 2003-211589 Paragraph Nos. [0009] to [0023] alicyclic structure-containing polymer resin, norbornene polymer resin or vinyl alicyclic hydrocarbon heavy as described in JP-A-2003-212588, paragraph Nos. [0008] to [0024] Examples include coalesced resins.

  The molecular weight of the cycloolefin polymer used in the present invention is appropriately selected according to the purpose of use, and was measured by a gel permeation chromatography method of a cyclohexane solution (or a toluene solution when the polymer resin does not dissolve). When the polyisoprene or polystyrene-equivalent weight average molecular weight is usually in the range of 5,000 to 500,000, preferably 8,000 to 200,000, more preferably 10,000 to 100,000, the mechanical strength and molding processability of the molded body are high. Balanced and suitable.

  Moreover, when a low-volatile antioxidant is blended at a ratio of 0.01 to 5 parts by mass with respect to 100 parts by mass of the cycloolefin polymer, it can effectively prevent the polymer from being decomposed or colored during the molding process. I can do it.

  As the antioxidant, an antioxidant having a vapor pressure at 20 ° C. of 10 −5 Pa or less, particularly preferably 10 −8 Pa or less is desirable. Antioxidants having a vapor pressure higher than 10-5 Pa cause foaming during extrusion molding, and the antioxidants volatilize from the surface of the molded product when exposed to high temperatures.

  Examples of the antioxidant that can be used in the present invention include the following, and one or several of these may be used in combination.

  Hinted phenolic 2,6-di-t-butyl-4-methylphenol, 2,6-di-t-butylphenol, 4-hydroxymethyl-2,6-di-t-butylphenol, 2,6-di- t-butyl-α-methoxy-p-dimethyl-phenol, 2,4-di-t-amylphenol, t-butyl-m-cresol, 4-t-butylphenol, styrenated phenol, 3-t-butyl-4 -Hydroxyanisole, 2,4-dimethyl-6-tert-butylphenol, octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 3,5-di-tert-butyl-4- Hydroxybenzyl phosphonate-diethyl ester, 4,4'-bisphenol, 4,4'-bis- (2,6-di-tert-butylphenol), 2 2'-methylene-bis- (4-methyl-6-tert-butylphenol), 2,2'-methylene-bis- (4-methyl-6-α-methylcyclohexylphenol), 4,4'-methylene-bis -(2-methyl-6-tert-butylphenol), 4,4'-methylene-bis- (2,6-di-tert-butylphenol), 1,1'-methylene-bis- (2,6-di-) t-butylnaphthol), 4,4'-butylidene-bis- (2,6-di-t-butyl-meta-cresol), 2,2'-thio-bis- (4-methyl-6-t-butylphenol) ), Di-o-cresol sulfide, 2,2′-thio-bis- (2-methyl-6-tert-butylphenol), 4,4′-thio-bis (3-methyl-6-tert-butylphenol), 4,4'-thio-bis- (2,3 Di-sec-amylphenol), 1,1'-thio-bis- (2-naphthol), 3,5-di-t-butyl-4-hydroxybenzyl ether, 1,6-hexanediol-bis- [3 -(3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino)- 1,3,5-triazine, 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,2-thiobis (4-methyl-6- t-butylphenol), N, N′-hexamethylenebis (3,5-di-t-butyl-4-hydroxy-hydrocinnamamide), bis (3,5-di-t-butyl-4-hydroxybenzyl) Phosphon Ethyl) calcium, 1,3,5-trimethyl-2,4,6-tris- (3,5-di-t-butyl-4-hydroxybenzyl) benzene, triethylene glycol-bis [3- (3-t -Butyl-5-methyl-4-hydroxyphenyl) propionate], 1,3,5-trimethyl-2,4,6, -tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, tris -(3,5-di-tert-butyl-4-hydroxybenzyl) -isocyanurate, pentaerythrityl-tetrakis [3- (3,5-di-tert-butyl-4-hydroxygenyl) propionate] and the like.

  Aminophenols normal butyl-p-aminophenol, normal butyroyl-p-aminophenol, normal peragonoyl-p-aminophenol, normal lauroyl-p-aminophenol, normal stearoyl-p-aminophenol, 2,6- Di-t-butyl-α-dimethyl, amino-p-cresol and the like.

  Hydroquinone hydroquinone, 2,5-di-t-butyl hydroquinone, 2,5-di-t-amyl hydroquinone, hydroquinone methyl ether, hydroquinone monobenzyl ether, and the like.

  Phosphite triphosphite, tris (3,4-di-t-butylphenyl) phosphite, tris (nonylphenyl) phosphite, tetrakis (2,4-di-t-butylphenyl) -4,4'-biphenylene Phosphanite, 2-ethylhexyl octyl phosphite, etc.

  Others such as 2-mercaptobenzothiazole zinc salt, dicatechol borate-di-o-tolylguanidine salt, nickel-dimethyldithiocarbamate, nickel-pentamethylene dithiocarbanate, mercaptobenzimidazole, 2-mercaptobenzimidazole zinc salt.

  The cycloolefin polymer film may contain an additive that can be generally blended into a plastic film, if necessary. Examples of such additives include heat stabilizers, light stabilizers, ultraviolet absorbers, antistatic agents, lubricants, plasticizers, and fillers, and the content thereof is within a range that does not impair the purpose of the present invention. You can choose.

<Melt casting method>
There is no particular limitation on the method for forming the cycloolefin polymer film, and either a heat-melt molding method or a solution casting method can be used. The heat-melt molding method can be further classified into an extrusion molding method, a press molding method, an inflation molding method, an injection molding method, a blow molding method, a stretch molding method, etc. Among these methods, mechanical strength, surface accuracy are included. In order to obtain an excellent film, an extrusion molding method, an inflation molding method, and a press molding method are preferable, and an extrusion molding method is most preferable. The molding conditions are appropriately selected depending on the purpose of use and the molding method. In the case of the hot melt molding method, the cylinder temperature is usually in the range of 150 to 400 ° C, preferably 200 to 350 ° C, more preferably 230 to 330 ° C. Is set as appropriate. If the resin temperature is too low, fluidity will deteriorate, causing shrinkage and distortion in the film. If the resin temperature is too high, voids and silver streaks will occur due to thermal decomposition of the resin, and the film will turn yellow. Defects may occur. The thickness of the film is usually in the range of 5 to 300 μm, preferably 10 to 200 μm, more preferably 20 to 100 μm. When the thickness is too thin, handling at the time of lamination becomes difficult, and when it is too thick, the drying time after the lamination becomes long and the productivity is lowered.

  The wetting tension of the surface of the cycloolefin polymer film is preferably 40 mN / m or more, more preferably 50 mN / m or more, and further preferably 55 mN / m or more. When the surface wetting tension is in the above range, the adhesive strength between the film and the polarizing film is improved. In order to adjust the surface wetting tension, for example, corona discharge treatment, ozone spraying, ultraviolet irradiation, flame treatment, chemical treatment, and other known surface treatments can be performed.

  The sheet before stretching needs to have a thickness of about 50 to 500 μm, and the thickness unevenness is preferably as small as possible. The entire surface is within ± 8%, preferably within ± 6%, more preferably within ± 4%. is there.

  In order to make the said cycloolefin polymer film into the base film of this invention, it is obtained by extending | stretching a sheet | seat at least uniaxially like a cellulose-ester film. In addition, it may be substantially uniaxial stretching, for example, biaxial stretching in which uniaxial stretching is performed in order to orient the molecules after stretching in a range that does not affect the molecular orientation. For stretching, it is preferable to use the tenter device or the like.

  The draw ratio is 1.3 to 10 times, preferably 1.5 to 8 times.

  Stretching is usually performed in a temperature range of Tg to Tg + 50 ° C., preferably Tg to Tg + 40 ° C. of the resin constituting the sheet.

(Back side)
In the present invention, the back surface of the antireflection film (low reflection laminate) provided with the optical interference layer including the low refractive index layer according to the present invention has 1 to 500 protrusions having a height of 0.1 to 10 μm. It is preferable to have 0.01 mm ² . Preferably from 10 to 400 pieces /0.01mm ^2, more preferably from 15 to 300 pieces /0.01mm ^2. This not only prevents the occurrence of blocking even if winding in the form of a roll once during coating of each optical interference layer, but also significantly reduces coating unevenness when coating the next optical interference layer. I can do it. Although the cause of coating unevenness is not completely clarified, it is presumed that as one of the causes, peeling electrification at the time of feeding a film wound up in a roll shape to the coating process is related. By adding fine particles to the base film, it is possible to have 1 to 500 protrusions / 0.01 mm ² with a height of 0.1 to 10 μm on the back surface. At this time, the base film can be formed into a multilayer structure, and fine particles can be included only in the surface layer.

  The fine particles to be added may be organic compounds or inorganic compounds, such as silicon dioxide, titanium dioxide, aluminum oxide, zirconium oxide, calcium carbonate, kaolin, talc, calcined calcium silicate, hydrated calcium silicate, silicic acid. It is preferable to contain inorganic fine particles such as aluminum, magnesium silicate, calcium phosphate, and crosslinked polymer fine particles. Of these, silicon dioxide is preferable because it can reduce the haze of the film. The average particle size of the secondary particles of the fine particles is 0.1 to 10 μm, and the content is preferably 0.04 to 0.3% by mass with respect to the cellulose ester of the base material. In many cases, fine particles such as silicon dioxide are surface-treated with an organic substance, but this is preferable because the haze of the film can be reduced. Preferred organic substances for the surface treatment include halosilanes, alkoxysilanes (particularly alkoxysilanes having a methyl group), silazane, siloxane and the like. The larger the average particle size of the fine particles, the greater the mat effect, and on the contrary, the smaller the average particle size is, the better the transparency. It is. Examples of the fine particles of silicon dioxide include AEROSIL (Aerosil) 200, 200V, 300, R972, R972V, R974, R202, R812, OX50, TT600, etc. manufactured by Aerosil Co., preferably AEROSIL (Aerosil) 200V, R972, R972V, R974, R202, and R812. Two or more kinds of these fine particles may be used in combination. When using 2 or more types together, it can mix and use in arbitrary ratios. In this case, fine particles having different average particle sizes and materials, for example, AEROSIL (Aerosil) 200V and R972V can be used in a mass ratio of 0.1: 99.9 to 99.9: 0.1.

  In the present invention, the fine particles may be dispersed together with cellulose ester, other additives and an organic solvent at the time of preparing the dope. However, the dope may be dispersed in a sufficiently dispersed state like a fine particle dispersion separately from the cellulose ester solution. Is preferably prepared. In order to disperse the fine particles, it is preferably preliminarily dispersed in an organic solvent and then finely dispersed by a disperser (high pressure disperser) having a high shearing force. After that, it is preferable to disperse in a larger amount of organic solvent, merge with the cellulose ester solution, and mix with an in-line mixer to obtain a dope. In this case, an ultraviolet absorbent may be added to the fine particle dispersion to form an ultraviolet absorbent liquid.

Moreover, by providing a layer containing fine particles on the back surface side of the optical interference layer, a low reflective laminate having 1 to 500 protrusions with a height of 0.1 to 10 μm / 0.01 mm ² on the back surface is provided. I can do it.

(Deflection plate)
When a hard coat film or an antireflection film is used as the protective film for a polarizing plate on the outermost surface of the liquid crystal display device, at least one surface of the polarizing film is bonded to the hard coat film or the antireflection film of the present invention to form a polarizing plate. It is preferable to produce it.

  Here, the polarizing film refers to an element that transmits only light having a plane of polarization in a certain direction, but in the present invention, there are one in which a polyvinyl film is dyed with iodine and one in which a dichroic dye is dyed. These are formed by forming a polyvinyl alcohol aqueous solution into a film and uniaxially stretching it to dye it. However, after dyeing and uniaxially stretching, those subjected to a durability treatment with a boron compound are preferably used. A polarizing plate is formed by laminating the hard coat film or antireflection film of the present invention as a protective film for a polarizing plate on at least one surface of the polarizing film thus prepared. When using as a polarizing plate protective film in order to produce a polarizing plate by laminating a polarizing film with a 5% aqueous solution of completely saponified polyvinyl alcohol as an adhesive, the hard coat film according to the present invention or The antireflection film is required to have alkali resistance.

(Display device)
By incorporating the polarizing plate of the present invention into a display device, the display device of the present invention having various visibility can be manufactured. The hard coat film or antireflection film of the present invention can be used in various types of driving such as reflective, transmissive, transflective LCD or TN, STN, OCB, HAN, VA (PVA, MVA), and IPS. It is preferably used in the LCD of the type. The hard coat film or antireflection film of the present invention is excellent in flatness and is preferably used for various display devices such as a plasma display, a field emission display, an organic EL display, an inorganic EL display, and electronic paper. In particular, a large-screen display device having a screen of 30 or more types, particularly 30 to 54 types, has no white spots at the periphery of the screen, and the effect is maintained for a long period of time. In particular, the MVA liquid crystal display device has a remarkable effect. Is recognized. In addition, there was little color unevenness, glare and wavy unevenness, and the eyes were not tired even during long viewing.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated in detail, this invention is not limited to these. Unless otherwise specified, “%” in the examples represents “mass%”.

Example 1
An antireflection film was produced according to the following method.

  A cellulose acetate film (Konica Minolta Opto KC8UX, thickness 80 μm, width 1.45 m) was used as a transparent substrate. The following hard coat layer composition 1 was applied to one surface of this cellulose acetate film, dried at 80 ° C. for 30 seconds, and then cured by irradiation with a high pressure mercury lamp of 80 W / cm for 4 seconds from a distance of 12 cm to obtain a hard coat layer. 1 was provided. The hard coat layer 1 had a thickness of 6.0 μm and a coating width of 1.4 m.

<< Preparation of hard coat layer >>
<Hard coat layer composition 1>
Dipentaerythritol hexaacrylate monomer 600g
Dipentaerythritol hexaacrylate dimer 200g
Dipentaerythritol hexaacrylate trimer 200g
Irgacure 184 (Ciba Specialty Chemicals Co., Ltd.) 20g
Silicone surfactant 10g
Methyl ethyl ketone 500g
Ethyl acetate 500g
Isopropyl alcohol 500g
Next, an antireflection film 101 was prepared by coating an antireflection layer in the order of the conductive middle refractive index layer, the high refractive index layer, and the low refractive index layer.

<< Preparation of antireflection layer: medium refractive index layer >>
On the hard coat layer, the following medium refractive index layer composition 1 was applied by an extrusion coater, dried at 100 ° C. for 30 seconds, and then irradiated with an 80 W / cm high-pressure mercury lamp from a distance of 12 cm for 4 seconds. A refractive index layer 1 was provided. The middle refractive index layer 1 had a thickness of 95 nm and a coating width of 1.4 m.

<Medium refractive index layer composition 1>
LCOM V-2504 (manufactured by Catalyst Kasei Kogyo Co., Ltd., ITO sol, solid content 20%)
100g
Dipentaerythritol hexaacrylate 5.12 g
Acryloyl morpholine (manufactured by Kojin Co., Ltd.) 1.28 g
Irgacure 184 (Ciba Specialty Chemicals Co., Ltd.) 1.6g
Tetrabutoxy titanium 4.0g
10% FZ-2207 (Nihon Unicar Co., Ltd., propylene glycol monomethyl ether solution) 3.0 g
Isopropyl alcohol 530g
90g of methyl ethyl ketone
265 g of propylene glycol monomethyl ether
<Preparation of antireflection layer: high refractive index layer>
On the medium refractive index layer, the following high refractive index layer composition 1 was applied with an extrusion coater, dried at 100 ° C. for 30 seconds, and then irradiated with an 80 W / cm high-pressure mercury lamp from a distance of 12 cm for 4 seconds, A high refractive index layer 1 was provided. The thickness of the high refractive index layer 1 was 50 nm and the coating width was 1.4 m.

<High refractive index layer composition 1>
RTSDNB (Ci Kasei Kogyo Co., Ltd., titanium oxide fine particle dispersion, solid content 15%)
60g
γ-methacryloxypropyl trimethoxysilane (KBM503 manufactured by Shin-Etsu Chemical Co., Ltd.)
2g
Tetrabutoxy titanium 5g
10% FZ-2207 (Nihon Unicar Co., Ltd., propylene glycol monomethyl ether solution) 3 g
Isopropyl alcohol 560g
90g of methyl ethyl ketone
280 g of propylene glycol monomethyl ether
<< Preparation of antireflection layer: low refractive index layer >>
On the high refractive index layer, the following low refractive index layer composition 1 was applied with an extrusion coater, dried at 100 ° C. for 30 seconds, and then irradiated with an 80 W / cm high-pressure mercury lamp from a distance of 12 cm for 4 seconds, A low refractive index layer 1 was provided. The thickness of the low refractive index layer 1 was 100 nm and the coating width was 1.4 m.

<Preparation of hydrolyzate A>
172 g of tetraethoxysilane and 700 g of ethanol were mixed, and 129 g of 0.4% nitric acid aqueous solution was added thereto to prepare a hydrolyzate A.

  Furthermore, it prepared by advancing a hydrolysis reaction by agitating the hydrolysis liquid A for 5 hours at room temperature (25 degreeC).

(Low refractive index layer composition 1)
The following low refractive index layer composition 1 was prepared using the produced hydrolyzed liquid A.

Propylene glycol monomethyl ether 366 parts by mass Isopropyl alcohol 366 parts by mass Hydrolyzed liquid A (hydrolysis time 5 hours) 232 parts by mass ELCOM P special product 4 (manufactured by Catalytic Chemical Industry, hollow silica dispersion, solid content 20%)
29 parts by mass γ-methacryloxypropyltrimethoxysilane (KBM503 manufactured by Shin-Etsu Chemical Co., Ltd.)
2.1 parts by mass 10% FZ-2207 (manufactured by Nippon Unicar Co., Ltd., propylene glycol monomethyl ether solution) 1.9 parts by mass The amounts of dipentaerythritol and acryloylmorpholine in the medium refractive index layer composition are shown in Table 2. The antireflection films 102 to 110 and 115 to 117 were produced in the same manner as the antireflection film 101 except that the thickness was changed as described above. Also, the V-2504 ATO, to prepare a ZrO ₂ (Al-doped) The antireflection film 111 is changed to. Moreover, the acryloyl morpholine was changed into the hydroxyethyl acrylamide and N, N- dimethylaminopropyl acrylamide, and the antireflection films 113 and 114 were produced. The antireflection film 118 is a sample to which no conductive metal oxide particles are added. In addition, the addition amount of Table 2 is the mass% with respect to solid content in a coating liquid.

  The surface specific resistance, scratch resistance, and ultraviolet light resistance of the obtained antireflection film were measured according to the following methods. The results are shown in Table 2.

<Evaluation>
The produced antireflection film was evaluated by the following method.

(Surface resistivity)
The sample was conditioned for 24 hours in an environment of 23 ° C. and 55% RH, and then the surface specific resistance of both surfaces was measured at an applied voltage of 100 V using a Terra Ohm Meter VE-30 manufactured by Kawaguchi Electric Co., Ltd. If it is 1 × 10 ¹² (Ω / □) or less, there is no practical problem, but it is preferably 1 × 10 ¹¹ (Ω / □) or less, and more preferably 1 × 10 ¹⁰ (Ω / □) or less. preferable.

(Scratch resistance)
The sample is placed on the sample under a load of 200 g / cm ^{2 on} # 0000 steel wool (SW) in an environment of 23 ° C. and 55% RH, and it can be obtained per 10 cm width when the load is applied and reciprocated 10 times. The number of wounds was measured. Note that the number of scratches is measured at a place where the number of scratches is the largest among the portions to which a load is applied. If it is 10 / cm or less, there is no practical problem, but 5 / cm or less is preferable, and 3 / cm or less is more preferable.

(UV light resistance)
UV irradiation was performed using an ultraviolet auto fade meter (U48AU, manufactured by Suga Test Instruments Co., Ltd.). A sample was taken out every 48 hours, an adhesion test was performed, and an irradiation time at which peeling started was measured. The adhesion was performed according to the cross-cut adhesion test method of JIS-K5400. If there is no peeling in 96 hours, there is no practical problem.

  The antireflection films 101 to 105 and 111 to 117 containing conductive metal oxide particles, ionizing radiation curable resin and acrylamide derivative, which are the constitution of the present invention, have excellent surface specific resistance, scratch resistance, and ultraviolet light resistance. In particular, when an acrylamide derivative is contained, it has been found that these characteristics can be achieved at extremely high levels.

  Moreover, the antireflection film of the present invention had no problem in coloring and haze.

Example 2
A hard coat film was obtained according to the following method.

  A cellulose acetate film (Konica Minolta Opto KC8UX, thickness 80 μm) was used as a transparent substrate. The following hard coat layer composition 2 was applied to one surface of this cellulose acetate film, dried at 80 ° C. for 30 seconds, and then cured by irradiation with a 80 W / cm high-pressure mercury lamp from a distance of 12 cm for 4 seconds to obtain a hard coat film. 201 was obtained. The thickness of the hard coat layer was 6.0 μm and the coating width was 1.4 m.

<Hard coat layer composition 2>
Acrylic monomer (KAYARAD DPHA (dipentaerythritol hexaacrylate, Nippon Kayaku)) 180 parts by mass Acryloyl morpholine (manufactured by Kojin Co., Ltd.) 46 parts by mass Photoinitiator (Irgacure 184, manufactured by Ciba Specialty Chemicals)
25 parts by mass of conductive fine particles (ELCOM V2504, ITO sol, solid content 20%, manufactured by Catalyst Chemical)
540 parts by mass Leveling agent (FZ2207, Nippon Unicar, 10% propylene glycol monomethyl ether solution) 7 parts by mass Propylene glycol monomethyl ether 101 parts by mass Ethyl acetate 101 parts by mass of dipentaerythritol and acryloylmorpholine in the hard coat layer composition Hard coat films 202 to 213 were produced in the same manner as the hard coat film 201 except that the amount was changed as shown in Table 3. The hard coat film 214 is a sample to which no conductive metal oxide particles are added. In addition, the addition amount of Table 3 is the mass% with respect to solid content in a coating liquid.

<Evaluation>
The surface resistivity and scratch resistance of the obtained hard coat film were measured according to the above methods. The results are shown in Table 3.

  The hard coat films 201 to 205 and 211 to 213 containing the conductive metal oxide particles, ionizing radiation curable resin, and acrylamide derivative, which are the constitution of the present invention, have excellent surface specific resistance, scratch resistance, and ultraviolet light resistance. It was also found that the effect of Example 1 can be reproduced as a hard coat film.

  Moreover, the hard coat film of the present invention had no problem in coloring and haze.

Example 3
The same coating composition as in Examples 1 and 2 except that the cellulose acetate film used in Examples 1 and 2 (KC8UX manufactured by Konica Minolta Opto Co., Ltd., thickness 80 μm) was replaced with the following cycloolefin polymer film. The thing was apply | coated and the antireflection film and the hard coat film were produced.

<Production of cycloolefin polymer film>
A cycloolefin polymer film stretched in the width direction was prepared as follows.

<Manufacture of cycloolefin polymer film>
In a nitrogen atmosphere, 500 parts of dehydrated cyclohexane, 1.2 parts of 1-hexene, 0.15 part of dibutyl ether, and 0.30 part of triisobutylaluminum were mixed in a reactor at room temperature, and then kept at 45 ° C. 20 parts of tricyclo [4.3.0.12,5] deca-3,7-diene (dicyclopentadiene, hereinafter abbreviated as DCP), 1,4-methano-1,4,4a, 9a-tetrahydrofluorene ( Hereinafter, a norbornene-based monomer comprising 140 parts of MTF) and 40 parts of 8-methyl-tetracyclo [4.4.0.12, 5.17,10] -dodec-3-ene (hereinafter abbreviated as MTD). The mixture and 40 parts of tungsten hexachloride (0.7% toluene solution) were continuously added over 2 hours for polymerization. To the polymerization solution, 1.06 part of butyl glycidyl ether and 0.52 part of isopropyl alcohol were added to deactivate the polymerization catalyst and stop the polymerization reaction.

  Next, 270 parts of cyclohexane is added to 100 parts of the reaction solution containing the obtained ring-opening polymer, and further 5 parts of a nickel-alumina catalyst (manufactured by JGC Chemical Co., Ltd.) is added as a hydrogenation catalyst, and the pressure is increased to 5 MPa with hydrogen. The mixture was heated to 200 ° C. while being pressurized and stirred, and then reacted for 4 hours to obtain a reaction solution containing 20% of a DCP / MTF / MTD ring-opening polymer hydrogenated polymer. After removing the hydrogenation catalyst by filtration, a soft polymer (manufactured by Kuraray; Septon 2002) and an antioxidant (manufactured by Ciba Specialty Chemicals; Irganox 1010) are added and dissolved in the resulting solution. (Both 0.1 parts per 100 parts polymer). Next, cyclohexane and other volatile components, which are solvents, are removed from the solution using a cylindrical concentration dryer (manufactured by Hitachi, Ltd.), the hydrogenated polymer is extruded in a strand form from an extruder in a molten state, and pellets after cooling. And recovered. When the copolymerization ratio of each norbornene monomer in the polymer was calculated from the composition of residual norbornenes in the solution after polymerization (by gas chromatography method), it was almost charged at DCP / MTF / MTD = 10/70/20. It was equal to the composition. This hydrogenated ring-opened polymer had a weight average molecular weight (Mw) of 31,000, a molecular weight distribution (Mw / Mn) of 2.5, a hydrogenation rate of 99.9%, and a Tg of 134 ° C.

  The obtained pellets of the ring-opened polymer hydrogenated product were dried at 70 ° C. for 2 hours using a hot air dryer in which air was circulated to remove moisture. Next, the pellets were subjected to a short shaft extruder having a coat hanger type T die having a lip width of 1400 mm (manufactured by Mitsubishi Heavy Industries, Ltd .: screw diameter 90 mm, T die lip material is tungsten carbide, peel strength 44N from molten resin). The resulting product was melt extruded to produce a cycloolefin polymer film having a thickness of 80 μm. Extrusion molding was performed in a clean room of class 10,000 or less under molding conditions of a molten resin temperature of 240 ° C. and a T die temperature of 240 ° C. In the middle of the drying process, the obtained film was stretched 1.50 times in the width direction at a stretching temperature of 155 ° C. using a tenter device to obtain a cycloolefin polymer film.

  About the antireflection film and the hard coat film produced in the same manner as in Examples 1 and 2 using the obtained cycloolefin polymer film, the surface specific resistance, scratch resistance, and ultraviolet light resistance in the same manner as in Examples 1 and 2. As a result, the film of the present invention reproduced excellent surface specific resistance, scratch resistance, and ultraviolet light resistance.

Example 4
The following polarizing plate was produced using the antireflection film and hard coat film obtained in Examples 1, 2, and 3.

[Preparation of polarizing plate]
A polyvinyl alcohol film having a thickness of 120 μm was uniaxially stretched (temperature: 110 ° C., stretch ratio: 5 times). This was immersed in an aqueous solution composed of 0.075 g of iodine, 5 g of potassium iodide and 100 g of water for 60 seconds, and then immersed in an aqueous solution of 68 ° C. composed of 6 g of potassium iodide, 7.5 g of boric acid and 100 g of water. This was washed with water and dried to obtain a polarizing film.

  Subsequently, according to the following processes 1-5, the polarizing film, the said antireflection film or hard coat film, and the cellulose ester film (optical compensation film) of the back side were bonded together, and the polarizing plate was produced. As the polarizing plate protective film on the back surface side, a cellulose ester film having a retardation (measured at 590 nm, in-plane retardation Ro = 43 nm, retardation in the thickness direction Rt = 135 nm) was used as a polarizing plate.

  Step 1: Soaked in a 2 mol / L sodium hydroxide solution at 60 ° C. for 90 seconds, then washed with water and dried to obtain a saponified cellulose ester film bonded to the polarizer.

  On the other hand, the surface on the antireflection layer side of the antireflection film was subjected to the above saponification treatment while applying a peelable polyethylene film and protecting it from alkali.

  Step 2: The polarizing film was immersed in a polyvinyl alcohol adhesive tank having a solid content of 2% by mass for 1 to 2 seconds.

  Step 3: Gently wipe off excess adhesive adhered to the polarizing film in Step 2 and place it on the cellulose ester film treated in Step 1 so that the antireflection film or hard coat film is on the outside Laminated and placed.

Step 4: Excess adhesive and air bubbles were removed from the end of the laminate of the antireflection film or hard coat film laminated in Step 3 with a hand roller, the polarizing film, and the cellulose ester film sample, and bonded together. The pressure of the hand roller was 20 to 30 N / cm ² and the roller speed was about 2 m / min.

  Step 5: A polarizing plate prepared in Step 4 in a drier at 80 ° C., a sample obtained by bonding the cellulose ester film and the antireflection film or the hard coat film was dried for 2 minutes to prepare a polarizing plate.

  Since the antireflection film and the hard coat film of the present invention have excellent surface resistivity and scratch resistance, they have excellent polarizing plate processing suitability without the adhesion of dust and scratches during the production of the polarizing plate. I found out.

[Production of liquid crystal display device]
A liquid crystal panel for viewing angle measurement was produced as follows, and the characteristics as a liquid crystal display device were evaluated.

  The both-sided polarizing plates of the Fujitsu 15-type display VL-150SD were peeled off, and the prepared polarizing plates were each bonded to the glass surface of the liquid crystal cell.

  At that time, the direction of bonding of the polarizing plate is the same direction as that of the polarizing plate bonded in advance so that the surface of the cellulose ester film (optical compensation film) on the back side is on the liquid crystal cell side. The liquid crystal display device was manufactured by making the absorption axis face the surface.

  When the following items were evaluated for the obtained liquid crystal display device, the one using the antireflection film or the hard coat film of the present invention was excellent in flatness, whereas the polarizing plate of the comparative example was finely wavy. Unevenness was observed, and the eyes were easily tired. Moreover, it turned out that the liquid crystal display device of this invention is excellent also in reflective color nonuniformity. Furthermore, since the film of the present invention has excellent ultraviolet light resistance as a surface film of a liquid crystal display device, the durability of the display device was also excellent.

(Visibility evaluation)
Each liquid crystal display device thus obtained was allowed to stand for 100 hours at 60 ° C. and 90% RH, then returned to 23 ° C. and 55% RH, and the surface wavy unevenness was visually evaluated.

(Evaluation of reflection color unevenness)
About each liquid crystal display device, the screen was set as black display and the reflection unevenness of the surface was evaluated visually.

Claims (15)

In an antistatic layer containing conductive metal oxide particles and an ionizing radiation curable resin, a polyfunctional (meth) acrylate having at least two (meth) acryloyl groups in the molecule and an acrylamide derivative as an ionizing radiation curable resin An antistatic layer comprising: The antistatic layer according to claim 1, wherein the acrylamide derivative is an acrylamide derivative represented by the following general formula (I).

(In the formula, R1 and R2 may be substituted at a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, a cyclic alkyl group having 3 to 8 carbon atoms, a phenyl group, or any position. N, N-dimethylamino group, hydrochloric acid and N, N, N-trimethylamino group, hydroxy group, or R1 and R2 together form an alkylene having 2 to 8 carbon atoms, or a morpholine ring together with an oxygen atom To form.) The antistatic layer according to claim 1 or 2, wherein the surface of the conductive metal oxide particles is modified with a silane coupling agent. The conductive metal oxide particles are one or more metal oxide particles selected from antimony-doped tin oxide (ATO), indium tin oxide (ITO), antimony pentoxide, zinc oxide, and zirconium oxide. The antistatic layer according to any one of claims 1 to 3, wherein: The antistatic layer according to any one of claims 1 to 4, wherein the antistatic layer or an adjacent layer thereof contains titanium oxide. An antistatic hard coat film comprising the antistatic layer according to claim 1. The antistatic hard coat film according to claim 6, wherein a coating width of the antistatic layer is 1.4 m or more. An antistatic antireflection film comprising the antistatic layer according to claim 1. The antistatic antireflection film according to claim 8, wherein the coating width of the antistatic layer is 1.4 m or more. The antistatic antireflection film according to claim 8 or 9, wherein the low refractive index layer contains hollow fine particles. A polarizing plate comprising the antistatic hard coat film according to claim 6. A polarizing plate comprising the antistatic antireflection film according to claim 8. A display device comprising the antistatic hard coat film according to claim 6. A display device comprising the antistatic antireflection film according to claim 8. A display device comprising the polarizing plate according to claim 11.