JP2003232919A - Polarizing plate, method for manufacturing the same and optical element - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polarizing plate having a polarizing film produced by a coating method with high shearing stress and featuring that the polarizing film is hardly scratched but easily processed and that the film gives high yield during manufacturing and excellent productivity, to provide a method for manufacturing the polarizing plate, and to provide an optical element having an antireflection layer and an antistatic layer by using the polarizing plate having excellent processing property. <P>SOLUTION: The method for manufacturing a polarizing plate is carried out by applying a composition containing at least a photoreactive dichroic dye on at least one surface of a transparent film while adding high shearing stress in the traveling direction of the transparent film so as to form a polarizing film, then by irradiating the polarizing film with UV rays to cure and further by applying a composition for a transparent resin protective layer thereon to form a transparent resin protective layer or by laminating a transparent protective film on the polarizing film. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel polarizing plate and a method for manufacturing the same, and a novel optical element using this polarizing plate.

[0002]

2. Description of the Related Art In recent years, notebook computers have become thinner and lighter,
As the cost decreases, the demands for thinning, cost reduction, and durability of the polarizing plates used in the liquid crystal display devices used for them are increasing accordingly.

Normally, a polarizing plate is produced by laminating a polyvinyl alcohol film uniaxially and dyeing it with iodine or the like, and attaching a resin protective film to the polarizing film.
The polarizing film is fragile and damaged during production, resulting in poor yield.
Moreover, since the width and length are narrower and shorter than the protective film, the protective film is purposely cut and stuck,
It was difficult to mass-produce stable production, and the cost and productivity were inferior. There is also a problem that the above-mentioned polarizing film is thick and it is difficult to make it thinner.

Recently, in US Pat. No. 6,049,428, when a composition containing a dichroic dye is applied onto a transparent film, a shearing force is applied in a certain direction to apply the composition. A polarizing film in which a dichroic dye is oriented is disclosed. The polarizing film produced by such a method has a soft alignment surface, is easily scratched, is likely to be attached with dust, and has a large loss in the processing in the next step, and the yield is likely to decrease.

[0005]

DISCLOSURE OF THE INVENTION The present invention is to provide a novel polarizing plate, a method for producing the same, and an optical element using the same, and an object of the present invention is to obtain a high shear stress by a coating method. In the process of manufacturing a polarizing plate using a polarizing film produced by applying it to a coating composition, there is provided a polarizing plate having scratch resistance, easy processability, high yield, and excellent productivity, and a manufacturing method thereof. A second object of the present invention is to provide an optical element having an antireflection layer or an antistatic layer using the above polarizing plate.

[0006]

The present invention uses a dichroic dye having no photoreactive group or a photoreactive dichroic dye without using a stretched polyvinyl alcohol film-iodine type polarizing film. And a novel method for producing a polarizing plate.

In the method for producing a polarizing film described in the above-mentioned US Pat. No. 6,049,428, the surface of the polarizing film alignment film is easily scratched and cannot be used as it is as a polarizing plate.

According to the present invention, a protective layer or a protective film is added as early as possible to the film surface of a polarizing film produced by a special method on a transparent film as described below to obtain scratch resistance, easy workability and high processability. It is to produce a polarizing plate having high yield and excellent productivity. Further, the present invention provides an excellent polarizing plate in which the polarizing film itself is made strong and less likely to be disturbed by the polarizing film once made of a compound having a photoreactive group or the like, and the surface thereof is protected. It is a thing.

The present invention has the following constitution. (1) A polarizing film is formed by applying a composition containing a dichroic dye having no photoreactive group to at least one surface of a transparent film to be transferred while giving a high shear stress in the transfer direction of the transparent film. After forming, a transparent resin protective layer composition is applied onto the polarizing film to form a transparent resin protective layer, or a transparent protective film is laminated on the polarizing film. Production method.

(2) The polarized light as described in (1), wherein the composition containing at least a dichroic dye having no photoreactive group contains an alignment compound having no photoreactive group. Method of manufacturing a plate.

(3) A composition containing a dichroic dye having no photoreactive group and a photoreactive compound having no aligning group on at least one surface of the transparent film to be transferred in the transfer direction of the transparent film. On the other hand, after applying a high shear stress to form a polarizing film, the polarizing film is irradiated with ultraviolet rays to be cured, and a transparent resin protective layer composition is applied thereon to form a transparent resin protective layer. Alternatively, a method for producing a polarizing plate, which comprises laminating a transparent protective film on the polarizing film.

(4) The composition containing at least the dichroic dye having no photoreactive group and the photoreactive compound having no photoreactive group contains an alignment compound having no photoreactive group. (3) The method for producing a polarizing plate according to (3).

(5) A composition containing a dichroic dye having no photoreactive group and a photoreactive aligning compound on at least one surface of the transparent film to be transferred is highly sheared with respect to the transfer direction of the transparent film. After applying a stress to form a polarizing film, the polarizing film is irradiated with ultraviolet rays to be cured, and a transparent resin protective layer composition is applied thereon to form a transparent resin protective layer, or A method for producing a polarizing plate, which comprises laminating a transparent protective film on a polarizing film.

(6) The composition containing at least the dichroic dye having no photoreactive group and the photoreactive alignment compound contains an alignment compound having no photoreactive group. The method for producing a polarizing plate according to (5).

(7) A polarizing film is formed by applying a composition containing at least a photoreactive dichroic dye to at least one surface of a transparent film to be transferred while giving a high shear stress in the transfer direction of the transparent film. After that, the polarizing film is irradiated with ultraviolet rays to be cured, and a transparent resin protective layer composition is applied thereon to form a transparent resin protective layer, or a transparent protective film is laminated on the polarizing film. A method of manufacturing a polarizing plate, comprising:

(8) The method for producing a polarizing plate as described in (7), wherein the composition containing at least the photoreactive dichroic dye contains an aligning compound having no photoreactive group. .

(9) The polarized light as described in (7) or (8), wherein the composition containing at least the photoreactive dichroic dye contains a photoreactive compound having no alignment group. Method of manufacturing a plate.

(10) The composition according to any one of (7) to (9), wherein the composition containing at least the photoreactive dichroic dye contains a photoreactive alignment compound. Method for manufacturing polarizing plate.

(11) The composition containing at least the photoreactive dichroic dye contains a dichroic dye having no photoreactive group, (7) to (10) Item 1. A method for producing a polarizing plate according to item 1.

(12) The transparent resin protective layer composition contains a photoreactive compound, and after the transparent resin protective layer composition is applied, it is irradiated with ultraviolet rays (1) to (1).
The method for producing a polarizing plate according to any one of 1).

(13) Before the transparent resin protective layer is formed or before the transparent protective film is laminated, the surface of the polarizing film is surface-treated or an adhesive layer is applied (1) to 1). The method for producing a polarizing plate according to any one of (12).

(14) The method for producing a polarizing plate as described in any one of (1) to (13), characterized in that the surface on which the transparent protective film is adhered is previously treated.

(15) A transparent film is surface-treated, and then a polarizing film is formed on the surface (1)
A method for manufacturing a polarizing plate according to any one of (1) to (14).

(16) The method for producing a polarizing plate as described in any one of (13) to (15), wherein the surface treatment is corona discharge.

(17) The transparent film is a cellulose ester film (1) to (1)
The method for producing a polarizing plate according to any one of 6).

(18) The method for producing a polarizing plate as described in any one of (1) to (17), wherein the transparent protective film is a cellulose ester film.

(19) Any one of (1) to (18)
A polarizing plate manufactured by the method described in the item.

(20) An optical element having an antireflection layer on any surface of the polarizing plate described in (19) directly or through another layer.

(21) In the polarizing plate according to (19), a surface of a transparent film or a transparent protective film having an antireflection layer directly or through another layer is attached to the surface without the antireflection layer and the polarizing film. An optical element characterized by being combined.

(22) The antireflection layer applies a high-frequency voltage between the opposing electrodes under atmospheric pressure or a pressure in the vicinity thereof to bring the reaction gas introduced between the electrodes into a plasma state, and the reaction in the plasma state is performed. The optical element as described in (20) or (21), which is formed by exposing the transparent film surface to gas and performing plasma discharge treatment.

(23) The optical element according to any one of (20) to (22), wherein the other layer is a clear hard coat layer or an antiglare layer.

(24) The optical element as described in (23), wherein the clear hard coat layer composition or the antiglare layer composition has the same composition as the transparent resin protective layer composition.

(25) An optical element having an antistatic layer on at least one surface of the polarizing plate described in (19).

(26) In the polarizing plate according to (19), a surface of a transparent film or a transparent protective film having an antistatic layer, which has an antistatic layer in advance or directly through another layer, is attached to a polarizing film. An optical element characterized by being combined.

(27) The optical element as described in any one of (20) to (24), which has an antistatic layer as the outermost layer of the polarizing plate having an antireflection layer.

(28) The antistatic layer comprises an atmospheric pressure plasma discharge treatment method using a tin compound as a reaction gas, a method of applying a composition containing amorphous tin oxide, and a composition containing a crosslinked ionene polymer. The optical element according to any one of (25) to (27), which is formed by a method selected from the methods of applying an object.

The present invention will be described in detail. First, the main layer configurations of the polarizing plate and the optical element of the present invention will be briefly described below.
Here, 1) to 4) are examples of the basic configuration of the polarizing plate, and this component is represented as a = polarizing plate. See also 5)
8) is an example of the structure of an optical element using a polarizing plate,
This is represented as = optical element. Surface treatments such as a transparent film, a transparent protective film and a polarizing film surface are omitted.

1) transparent film / polarizing film / transparent resin protective layer = polarizing plate 2) transparent film / polarizing film / transparent protective film = polarizing plate 3) transparent film / polarizing film / adhesive layer / transparent resin protective layer =
Polarizing plate 4) Transparent film / polarizing film / adhesive layer / transparent protective film = polarizing plate 5) polarizing plate / antireflection layer = optical element 6) polarizing plate / clear hard coat layer or antiglare layer / antireflection layer = optical element 7) Polarizing plate / antistatic layer = optical element 8) Antistatic layer / polarizing plate / antireflection layer = optical element.

The terms used in the present invention will be described. The dichroic dye having no photoreactive group refers to a dichroic dye having no photoreactivity, which is different from the photoreactive dichroic dye described below. The photoreactive dichroic dye refers to a dichroic dye having a photoreactive group as a substituent. The alignment compound having no photoreactive group refers to an alignment compound having no photoreactivity, which is different from the photoreactive alignment compound described below. Further, the photoreactive alignment compound means an alignment compound having a photoreactive group as a substituent. Further, the photoreactive compound having no aligning group means a compound having no aligning property and having general photoreactivity, and may also be a UV-curable resin. Incidentally, when simply referring to a dichroic dye or an orientation compound,
It is used when referring to these compounds in a broad concept, and in the present invention, as described above, it is used by limiting with or not having a photoreactive group or a photoreactive group.

The basic polarizing film of the present invention comprises a transparent film to be transferred, and a composition containing at least a dichroic dye having no photoreactive group, in the direction of transfer of the transparent film. It is formed by applying high shear stress and orienting the dichroic dye having no photoreactive group. Furthermore, an alignment compound having no photoreactive group used with a dichroic dye having no photoreactive group, a photoreactive compound having no alignment group, a photoreactive alignment compound, etc. is contained in the composition. As a result, it is possible to improve the orientation degree and form a high-quality polarizing film having a stable orientation that does not easily collapse. Furthermore, orient the photoreactive dichroic dye,
Stabilizes the alignment by light irradiation, and is used with a photoreactive dichroic dye, and also has no photoreactive group, a dichroic dye that does not have a photoreactive group, and a light that does not have an alignment group. By containing a reactive compound, a photoreactive alignment compound, etc. in the composition, the degree of alignment can be improved, and a high-quality polarizing film having stable alignment that is resistant to collapse as described above can be formed.

The dichroic dye having no photoreactive group or the photoreactive dichroic dye according to the present invention has the direction of the molecular orbital of the π electron of the dye, the direction of the transition moment and the direction of the molecule. The major axis directions match as much as possible, and they have the property of being easily oriented. In the present invention, a dichroic dye having no photoreactive group or a photoreactive dichroic dye alone can be easily aligned by applying high shear stress, and an orienting compound having no photoreactive group can be used together. By exerting a high shear stress on the surface, more excellent orientation is exhibited. Also,
In the present invention, the dichroic dye having no photoreactive group or the photoreactive dichroic dye has a dichroic dye in its main chain,
Alternatively, it may be a polymer dichroic dye having a side chain.
Further, the dichroic dye in the present invention is a photoreactive dichroic dye, and after alignment, the dichroic dye is polymerized by irradiation with light, and is crosslinked to form a later external force, for example, It is less likely to be disturbed by the solvent of the composition applied on the top, and a more stable polarizing film can be formed.

The dichroic dye having no photoreactive group or the photoreactive dichroic dye useful in the present invention has various hues, and the transmittance of the polarizing film after alignment is 50% or less. Yes, the degree of polarization is 90% or more.

The dichroic dye having no photoreactive group useful in the present invention may be any dichroic dye which is generally called a dichroic dye.
Can be used without restrictions. The dichroic dyes (abbreviated as DC and numbered) having no photoreactive group useful in the present invention are exemplified below.

[0044]

[Chemical 1]

[0045]

[Chemical 2]

[0046]

[Chemical 3]

[0047]

[Chemical 4]

[0048]

[Chemical 5]

[0049]

[Chemical 6]

In the present invention, the aligning compound having no photoreactive group means that it is aligned by various alignment methods, for example, generally oriented by stretching such as a polymer film, oriented by a stretched polymer film, and rubbing. A compound that can be oriented in one direction by an operation such as orientation by (1), orientation by photo-alignment, orientation by peeling, etc. In the present invention, an orienting compound having such properties can be used without limitation. For example, a nematic liquid crystal compound, a smectic liquid crystal compound, a polymer compound that exhibits crystallinity by stretching, a polymer liquid crystal, and the like can be given. In the present invention, the technique of orienting the orienting compound is to orient the solution of the orienting compound on the transparent film by applying a high shear stress using a coating method.

Orientation compounds having no photoreactive group (numbered as OC for short) which are useful in the present invention are exemplified below.

[0052]

[Chemical 7]

[0053]

[Chemical 8]

[0054]

[Chemical 9]

[0055]

[Chemical 10]

[0056]

[Chemical 11]

In the present invention, different kinds of alignment compounds having no photoreactive group may be used in combination, which is preferable.

A transparent film is prepared from a composition containing at least a dichroic dye having no photoreactive group, or a dichroic dye having no photoreactive group and an aligning compound having no photoreactive group in the present invention. As a method for orienting a dichroic dye or the like having no photoreactive group by applying a high shear stress on it, any method can be used without limitation as long as it can be oriented. How to use, how to use doctor blade, how to use counter-rotating rolls, how to use squeeze rolls, how to rotate a roll with a very small diameter at high speed, how to drain the liquid from a very narrow slot, How to make a liquid pool on the film and squeeze it with a very fine and short comb
Further, there can be mentioned a method of using a block whose outlet is narrower than the inlet as described below, but any coating method capable of forming a high shear stress can be used without limitation.

In the present invention, the high shear stress in producing the polarizing film is 0.8 N / cm width or more, preferably 2-1.
It is preferable to apply a width of 00 N / cm. The transfer rate of the transparent film is 2 to 150 m / min, preferably 10 to 10
It is 0 m / min. It is preferable to select a coating device according to the transfer speed of the transparent film.

Means for delivering the composition to the coating device are:
In order to supply a very small capacity, it is possible to use a means for supplying with a die having a narrow slit width, a means for indirectly supplying from the die and transferring to a rotating roll and further controlling the amount with a blade or a roll, but especially There is no limit.

A composition containing no photoreactive group or containing a photoreactive dichroic dye according to the present invention, or a composition containing these dichroic dyes and no photoreactive group or containing a photoreactive alignment compound When the solvent used in the composition has a dichroic dye or a photoreactive group or a photoreactive alignment compound is a compound having a sulfonate, carboxylate or ammonium salt as a substituent For, the coating solvent used is water-based or alcohol-based,
In the case of a compound having no water-soluble group, an organic solvent type compound is used.

As the aqueous solvent, water or an organic solvent compatible with water is mixed and used. Examples of the organic solvent compatible with water include methanol, ethanol, propanol, acetone, dioxane, pyrrolidone, formamide, dimethylformamide, dimethyl sulfoxide and the like. Further, as the organic solvent-based solvent, one that can dissolve the dichroic dye is selected. For example, methylene chloride, methyl acetate, ethyl acetate, acetone, methyl ethyl ketone, furan, 1,3-dioxolane, formamide, dimethylformamide, dimethyl sulfoxide,
Fluorine-containing alcohol (eg, 2-fluoroethanol, 2,2,2-trifluoroethanol, 2,2,2
3,3,3-pentafluoropropanol etc.) and the like.

The solid content concentration of the dichroic dye in the composition of the present invention is preferably 1 to 50% by mass, and 2 to 20% by mass.
Is more preferable.

The dry film thickness of the polarizing film is preferably 0.1 to 10 μm, more preferably 0.2 to 5 μm, further preferably 0.3 to 1 μm, and particularly preferably 0.3 to 0.7 μm.
Is.

The polarizing film formed on the transparent film is very weak against external force, is easily scratched in the next step, and may be redissolved in an organic solvent. It becomes something that does not exist.

The present invention can be protected or strengthened by the following methods in order to overcome the polarization disorder of the polarizing film formed as described above.

A: forming a transparent resin protective layer on the polarizing film b: laminating a transparent protective film on the polarizing film c: incorporating a photoreactive compound having no alignment group into the polarizing film d : The photoreactive alignment compound is contained in the polarizing film e: The photoreactive dichroic dye is contained in the polarizing film f: The photoreactive compound is contained in the transparent resin protective layer on the polarizing film of a Include.

Furthermore, it is also preferable to use a combination of two or more of a to f. In the present invention, as soon as the polarizing film is completed, as soon as possible, a transparent resin protective layer is coated on the polarizing film, or a transparent protective film is attached, and the polarizing film is irradiated with ultraviolet rays to form the polarizing film. It is preferable to strengthen.

Particularly, in the cases of c to e, after the coating orientation, the polarizing film itself is cured by irradiating with ultraviolet rays, so that the hardness of the surface is increased to be stable against external force and solvent, and the oriented photoreaction is caused. Fixing the polarization state of the dichroic dye having no functional group or the orientation compound having no photoreactive group, suppressing the disorder of the orientation after coating the composition, and maintaining the polarization property extremely stable. There is a feature that you can do it.

The coating of the transparent resin protective layer, the bonding of the transparent protective film, and the irradiation of ultraviolet rays are preferably carried out in the same line (in-line) as the formation of the polarizing film.

In the present invention, the composition containing no photoreactive group or a photoreactive dichroic dye or a photoreactive group-free or photoreactive aligning compound is
A resin binder may be contained, and in particular, when a photoreactive dichroic dye or a photoreactive group-free photoreactive group-free or photoreactive alignment compound is not a polymer, a resin binder is used. It is desirable to include it. The resin binder may be a water-soluble resin having no photoreactive group or having no photoreactive dichroic dye or photoreactive group, or depending on the hydrophilic property or hydrophobic property of the photoreactive alignment compound. It suffices to selectively use a hydrophilic binder and a hydrophobic binder.

In the present invention, examples of the water-soluble binder include polyvinyl alcohol, polyvinyl acetate hydrolyzate, polyvinylpyrrolidone, polyvinylimidazole hydrochloride, polyacrylamide, polymethylacrylamide, polymorpholinoacrylamide, polyacrylic acid and salts thereof. , Polyacrylic acid polyethylene glycol ester, copolymers thereof, gelatin, alginates, carboxymethyl cellulose salts and the like. Further, polymer latex may be used as a binder. The polymer latex preferably has the same components as those of the following hydrophobic binder, and partially has hydrophilic components such as 2-hydroxyacrylate and pyrrolidone therein. Is more preferable.

When the composition is an organic solvent system, the hydrophobic binder is preferably an organic solvent soluble binder, and examples thereof include polyacrylic acid esters (methyl ester, ethyl ester, propyl ester butyl ester, cyclohexyl ester, 2-ester). (Ethyl hexyl ester, alkyl ester having up to 20 carbon atoms, etc.), polymethacrylic acid ester equivalent thereto and copolymers thereof, polyvinyl chloride copolymer, butadiene copolymer, styrene copolymer, vinyl acetate copolymer You can list things etc.

It is preferable to contain a curing agent that crosslinks the binder with these resin binders. As a curing agent, a water-soluble binder protein, for example, gelatin can be preferably used as a crosslinking agent used in a photosensitive silver halide photographic light-sensitive material, and polyvinyl alcohol can be used with boric acid, Aldehyde compounds, isocyanate compounds, vinyl sulfone compounds, active ester compounds and the like can be used. Further, for the hydrophobic binder, it is preferable to use a curing agent such as an isocyanate compound having reactivity with the group to be reacted in the case of the copolymer. In the case of a hydrophobic binder, there is no particular need for a crosslinking agent, but if necessary, it is desirable that the hydrophobic binder have a reactive group or a reactive group. For example, a monomer such as 2-hydroxyethyl acrylate or glycidyl acrylate may be copolymerized with another hydrophobic monomer.

The useful photoreactive group of the photoreactive dichroic dye, the photoreactive alignment compound and the photoreactive compound having no alignment group according to the present invention include a vinyl group, an acryloyl group and a methacryloyl group. , Having a photopolymerizable group such as an isopropenyl group or an epoxy group, or having a photodimerizable group such as a chalcone group or a coumarin group, which forms a polymerized structure, a crosslinked structure or a network structure by ultraviolet irradiation. Is preferred.

In the present invention, as the photopolymerizable group, an acryloyl group, a methacryloyl group or an epoxy group is preferable from the viewpoint of polymerization rate and reactivity in the presence of a sensitizer, and a polyfunctional monomer or oligomer is more preferable.

As the photoreactive compound having an acrylic group or a methacrylic group, a photocurable acrylic urethane resin, a photocurable polyester acrylate resin, a photocurable epoxy acrylate resin, a photocurable polyol acrylate resin, etc. Can be mentioned.

The photocurable acrylic urethane resin is generally a polyester polyol, an isocyanate monomer,
Alternatively, the product obtained by reacting the prepolymer may be further added to 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate (hereinafter, acrylate is referred to as including methacrylate), and 2-hydroxypropyl acrylate. It can be easily obtained by reacting an acrylate-based monomer having a hydroxyl group (for example, JP-A-59-1).
51110).

The photocurable polyester acrylate resin can generally be easily obtained by reacting a hydroxyl group or a carboxyl group at the polyester terminal with a monomer such as 2-hydroxyethyl acrylate, glycidyl acrylate, or acrylic acid (for example, JP-A-59-151112).

The photocurable epoxy acrylate resin is
It is obtained by reacting a terminal hydroxyl group of an epoxy resin with a monomer such as acrylic acid, acrylic acid chloride or glycidyl acrylate.

Examples of the photocurable polyol acrylate resin include ethylene glycol (meth) acrylate, polyethylene glycol di (meth) acrylate, glycerin tri (meth) acrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate and pentaerythritol tetraacrylate. , Dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, alkyl-modified dipentaerythritol pentaerythritol, and the like.

A dilutable polymerizable monomer may be added to the photoreactive compound having an acrylic group or a methacrylic group. Examples thereof include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, vinyl acetate, benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate and styrene.

In the photopolymerization of the acrylic photoreactive compound used in the present invention, the photopolymerization is initiated without adding anything, but since the induction period of the polymerization is long or the initiation of the polymerization is slow, It is preferable to use a sensitizer or a photoinitiator, which can accelerate the polymerization. Known photosensitizers and photoinitiators can be used. Specific examples thereof include acetophenone, benzophenone, hydroxybenzophenone, Michler's ketone, α-amyloxime ester, tetramethyluram monosulfide, thioxanthone and derivatives thereof.

In the case of a photoreactive compound having an epoxy acrylate group, a sensitizer such as n-butylamine, triethylamine or tri-n-butylphosphine can be used. The photoreaction initiator or photosensitizer used in the photoreactive compound is sufficient to start the photoreaction with 0.1 to 15 parts by mass relative to 100 parts by mass of the photoreactive compound, and preferably, It is 1 to 10 parts by mass. This sensitizer preferably has an absorption maximum in the near-ultraviolet region to the visible light region.

A photoreactive epoxy resin as the photoreactive compound according to the present invention is also preferably used. As the light-reactive epoxy resin, an aromatic epoxy compound (polyglycidyl ether of polyhydric phenol), for example, glycidyl ether of hydrogenated bisphenol A or a reaction product of bisphenol A and epichlorohydrin, epoxy novolac resin, aliphatic epoxy resin Is a polyglycidyl ether of an aliphatic polyhydric alcohol or an alkylene oxide adduct thereof, a polyglycidyl ester of an aliphatic long-chain polybasic acid, a homopolymer or a copolymer of glycidyl acrylate or glycidyl methacrylate, and a typical example thereof is ethylene. Glycol diglycidyl ether, propylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, propylene Glycol glycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, nonapropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, glycerin triglycidyl ether,
Diglycerol triglycidyl ether, diglycerol tetraglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol triglycidyl ether, pentaerythritol tetraglycidyl ether, sorbitol polyglycidyl ether, alicyclic epoxy compounds, for example, 3,4-epoxy Cyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate, 2- (3,4-epoxycyclohexyl-5,5-spiro-3', 4'-epoxy)
Cyclohexane-meta-dioxane, bis (3,4-epoxycyclohexylmethyl) adipate, vinylcyclohexene dioxide, bis (3,4-epoxy-6)
-Methylcyclohexylmethyl) adipate, 3,4-
Epoxy-6-methylcyclohexyl-3 ', 4'-epoxy-6-methylcyclohexanecarboxylate,
Methylenebis (3,4-epoxycyclohexane) dicyclopentadiene diepoxide, di (3,4-epoxycyclohexylmethyl) ether of ethylene glycol, ethylenebis (3,4-epoxycyclohexanecarboxylate), dicyclopentadiene diepoxide, Tris Diglycidyl ether of (2-hydroxyethyl) isocyanurate, triglycidyl ether of tris (2-hydroxyethyl) isocyanurate, polyglycidyl acrylate, polyglycidyl methacrylate, copolymer of glycidyl acrylate or glycidyl methacrylate with other monomer, Poly-2-glycidyloxyethyl acrylate, poly-2-glycidyloxyethyl methacrylate, 2-glycidyloxyethyl acrylate Examples thereof include copolymers of 2-glycidyloxyethyl acrylate or 2-glycidyloxyethyl methacrylate with other monomers, bis-2,2-hydroxycyclohexylpropane diglycidyl ether, or a combination of two or more thereof. An addition polymer can be mentioned. The present invention is not limited to these compounds and includes compounds inferred from these.

The photoreactive compound epoxy resin of the present invention is
In addition to those having two or more epoxy groups in the molecule, monoepoxide can be blended and used according to desired performance.

The photoreactive epoxy resin forms a polymerized, crosslinked structure or network structure by cationic polymerization rather than radical polymerization. Unlike radical polymerization, it is a preferable photoreactive compound because it is not affected by oxygen in the reaction system.

Photoreactive epoxy resins useful in the present invention include:
A compound that releases a substance that initiates cationic polymerization upon irradiation with ultraviolet rays is polymerized with a photopolymerization initiator or a photosensitizer. Particularly preferred is the group of double salts of onium salts which release Lewis acids which undergo cationic polymerization upon irradiation. Specific examples include tetrafluoroborate (BF ₄ ⁻ ), hexafluorophosphate (PF ₄ ⁻ ), hexafluoroantimonate (SbF ₄ ⁻ ), hexafluoroarsenate (AsF ₄ ⁻ ), hexachloroantimonate (SbCl ₄ ).
₄ ^-), or the like can be mentioned.

Further, anions can also be used. Other anions include perchlorate ion (ClO
₄ ^-), trifluoromethyl sulfite ion (CF ₃ S
O ₃ ⁻ ), fluorosulfonate ion (FSO ₃ ⁻ ), toluenesulfonate ion, trinitrobenzene acid anion and the like can be mentioned.

Among these onium salts, the aromatic onium salt is preferably used as a cationic polymerization initiator.
It is particularly effective, among others, JP-A-50-151996,
Aromatic halonium salts described in JP-A-50-158680, JP-A-50-151997 and JP-A-52-3089.
No. 9, No. 59-55420, No. 55-125105, etc., Group VIA aromatic onium salts, JP-A-56.
-8428, 56-149402, 57-19.
Oxosulfoxonium salts described in Japanese Patent No. 2429, etc.,
Aromatic diazonium salts described in JP-B-49-17040 and the like, thiopyrylium salts described in US Pat. No. 4,139,655 and the like are preferable. Moreover, an aluminum complex, a photodegradable silicon compound-based polymerization initiator, and the like can be given. A photosensitizer such as benzophenone, benzoin isopropyl ether, and thioxanthone can be used in combination with the above cationic polymerization initiator.

In the composition containing a photoreactive compound having no orienting group useful in the present invention, the polymerization initiator is generally a photoreactive epoxy resin (prepolymer) 10
It is preferably added in an amount of 0.1 to 15 parts by mass, more preferably 1 to 10 parts by mass, relative to 0 parts by mass. The epoxy resin can also be used in combination with a photo-curable urethane acrylate-based resin, a photo-curable polyether acrylate-based resin, or the like. In this case, it is preferable to use a photo radical polymerization initiator and a photo cationic polymerization initiator in combination.

Among the photoreactive compounds having no orienting group useful in the present invention, compounds having a photodimerizable group include cinnamoyl group, coumarin group, chalcone group, styrylpyridinium group, alkoxystilbene group and α- A compound having a phenylmaleimide group or the like can be mentioned, and these photodimerizable groups are preferable because they have a structure in which the photodimerizable group is easily oriented and therefore they may be oriented together with the orientation compound. A photoreactive compound having a photodimerizable group and not having an aligning group (abbreviated as LR and numbered) is exemplified below.

[0093]

[Chemical 12]

Further, in the polarizing film useful in the present invention, the orientation can be stably fixed by using a dichroic dye having no photoreactive group or an orientation compound having no photoreactive group. For that purpose, it is possible to obtain a far superior polarizing film by using a photoreactive dichroic dye or a photoreactive alignment compound. As the photoreactive group, in addition to the acrylic group, methacrylic group or epoxy group of the above-mentioned polymerizable groups, cinnamoyl group, coumarin group, chalcone group, styrylpyridinium group, alkoxystilbene group, α-phenylmaleimide group, etc. Photodimerizable groups are preferred.

The dichroic dyes or orienting compounds having a polymerizable group useful in the invention are shown below. JP-A-9-28
Compounds having the structures described in 1480 and 9-281481 can also be used.

Further, since the photodimerizable group has a structure that is easily oriented, it may be oriented together with other dichroic dyes or orientation compounds. In the case of a molecule, orientation and network structure are formed, which is preferable. The photoreactive dichroic dyes (abbreviated as LDC and numbered) having a polymerizable group or a photodimerizable group useful in the present invention are exemplified below.

[0097]

[Chemical 13]

[0098]

[Chemical 14]

Photoreactive alignment compounds having a polymerizable group or a photodimerizable group useful in the present invention (abbreviated as LOC and numbered) are exemplified below.

[0100]

[Chemical 15]

[0101]

[Chemical 16]

[0102]

[Chemical 17]

[0103]

[Chemical 18]

The following symbols in DC to LOC are explained. n represents the degree of polymerization of the linear condensation polymer. n
1, n2 and n3 represent mol% in a polymer composed of an ethylenically unsaturated monomer, and n1 + n2 + n3 = 100.
Is. It is assumed that n1 has at least 30 mol%. m1, m2, and m3 represent mol% of the linear condensation polymer, and are m1 + m2 + m3 + ... = 100. (N)
Means normal (straight chain). Regarding A, a copolymerizable ethylenically unsaturated monomer is shown, and other ethylenically unsaturated monomers such as those shown below are shown, but not limited thereto.

Other ethylenically unsaturated monomer units include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, butyl acrylate, butyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, phenyl acrylate, phenyl. Methacrylate, benzyl methacrylate, phenyl methacrylate, phenethyl acrylate, phenethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate,
Acrylates or methacrylates such as glycidyl acrylate, glycidyl methacrylate, vinyl acetates such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl valerate, acrylamide, N-methyl acrylamide, N, N-dimethyl acrylamide, N-propyl acrylamide , N, N-dipropylacrylamide, N-butylacrylamide, N, N-dibutylacrylamide, benzylacrylamide and other acrylamides, styrene, p-methylstyrene, p-hydroxystyrene, p-hydroxymethylstyrene and other styrenes, Examples thereof include vinylpyrrolidone, acrylonitrile and ethylene, but are not limited thereto. Two or more kinds of these monomers may be copolymerized.

The above compound can be synthesized by a conventional synthetic method. In the present invention, the light irradiation device for irradiating the oriented polarizing film with ultraviolet rays is not particularly limited, but the light source as the light irradiation device is, 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. A lamp, a metal halide lamp, a xenon lamp, etc. can be used.

The irradiation conditions differ depending on the lamp, but the irradiation light amount may be about ²⁰ to 10,000 mJ / cm ² , preferably 50 to 2,000 mJ / cm 2.
^{Is 2} . It can be used by using a sensitizer having an absorption maximum in the near-ultraviolet region to the visible light region.

In the present invention, a composition containing a compound having a photoreactive group is applied / orientated, dried, and then irradiated with ultraviolet rays from a light source. The irradiation time depends on the photoreactive group. 5 seconds to 5 minutes is preferable, and 3 seconds to 2 minutes is more preferable in view of reaction efficiency and work efficiency of the compound having a photoreactive group.

When the compound having a photoreactive group used in the polarizing film according to the present invention is irradiated with ultraviolet rays, the irradiation method is not particularly limited, but the light source may be parallel to the direction in which high shear stress is applied. Linearly polarized ultraviolet light that irradiates a polarizing film with linearly polarized ultraviolet light by combining a polarizer with a
A stretch-dyed polyvinyl alcohol film can be mentioned as one mainly used. As this linearly polarized ultraviolet irradiation device, for example, JP-A-10-9068 is used.
The one disclosed in Japanese Patent Publication No. 4 can be used.
By irradiating linearly polarized ultraviolet rays, the photodimerizing compound dimerizes in that direction, and the orientation of the dichroic dye component and the orienting compound component can be more firmly fixed.

It is desirable to provide an adhesive layer for adhering the polarizing film well to the transparent film described later as a support for the polarizing film of the present invention. Further, it is desirable to provide an adhesive layer in order to further adhere a transparent protective film described later or a transparent resin protective layer described later to the polarizing film. Further, the transparent protective film may be provided with an adhesive layer and then bonded to the polarizing film. For the adhesive layer, the material of the adhesive layer may be appropriately selected from the mutual relationship among the transparent film, the polarizing film, the transparent protective film, and the transparent resin protective layer.

Examples of those used in the hydrophilic adhesive layer composition include water-soluble celluloses such as methyl cellulose, carboxymethyl cellulose sodium salt and hydroxyethyl cellulose, polyvinyl alcohol such as completely saponified polyvinyl alcohol, vinyl acetate partial hydrolyzate and polyvinyl partial acetal. Water-soluble proteins such as alcohols, gelatin, casein, and pectin, terephthalic acid / phthalic acid / sulfophthalic acid-polyethylene having a sulfone group from ethylene glycol, water-soluble vinyl resins such as polyvinylpyrrolidone, polyimidazole, and polyvinylpyrazole- COOM (M represents a hydrogen atom or a cation)
Examples thereof include polymer compounds having a group. For example, styrene / maleic anhydride copolymer or vinyl acetate /
Examples thereof include maleic anhydride copolymers, all of which are maleic anhydride partially or completely ring-opened. Further, as these polymer compounds, JP-A-6-94
Those described in Japanese Patent Nos. 915 and 7-333436 are also preferably used.

As the one used in the hydrophobic adhesive layer composition, styrene, nitrostyrene, halogenated styrene,
Styrenes such as chloromethylstyrene and alkylstyrene, vinyl ethers such as vinyl methyl ether and vinyl ethyl ether, vinyl acetate, vinyl propionate,
Vinyl esters such as vinyl butyrate, methyl acrylate,
Acrylic esters such as ethyl acrylate, propyl acrylate, butyl acrylate, hexyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, phenyl acrylate, benzyl acrylate, phenethyl acrylate and similar methacrylic acid esters , Acrylonitrile, vinyl chloride, vinylidene chloride, and the like, one polymer or two or more copolymers.

As a solvent for the adhesive composition, in an aqueous system,
Water and other organic solvents compatible with water, for example, methanol, ethanol, acetone, formamide, dimethylformamide, dimethylsulfoxide, dioxane, acetic acid and the like may be mixed and used.

As the solvent of the adhesive composition, in a hydrophobic system, acetone, methyl ethyl ketone, methanol, ethanol, propanol, butanol, methyl acetate, ethyl acetate, amyl acetate, methylene chloride, dichloroethane, dioxane, 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-2-methyl-2-propanol, 1,1,1,3,3,3-hexafluoro-2-propanol, 2,2,3,3,3-pentafluoro Examples include -1-propanol and nitroethane.

In the present invention, it is preferable that the surface of the transparent film, the transparent protective film or the polarizing film is subjected to a surface treatment before the bonding or the bonding. As surface treatment,
For example, corona discharge treatment, vacuum plasma discharge treatment, plasma discharge treatment under atmospheric pressure or a pressure in the vicinity thereof as described in JP-A-2000-072903, and the like can be mentioned. It is preferably used in the present invention because of its simplicity.

In the present invention, the same transparent film and transparent protective film can be used. As these films, any plastic film having excellent transparency, excellent smoothness, and uniform film thickness can be used, and examples thereof include a cellulose ester film, a polyester film, a polycarbonate film, a polystyrene film, and a polyolefin film. Etc. can be mentioned. As the cellulose ester film, cellulose diacetate film, cellulose acetate butyrate film, cellulose acetate propionate film, cellulose acetate phthalate film, cellulose triacetate, cellulose nitrate, etc .;
As the polyester film, polyethylene terephthalate film, polyethylene naphthalate film,
Polybutylene terephthalate film, 1,4-dimethylene cyclohexylene terephthalate film, or copolyester film of these constituent units; a polycarbonate film of bisphenol A as a polycarbonate film; a polystyrene film,
Syndiotactic polystyrene film; Polyethylene film, polypropylene film as polyolefin film; Norbornene resin film, polymethylpentene film, polyetherketone film, polyimide film, polyethersulfone film, polysulfone film, polyetherketone Examples thereof include imide film, polyamide film, fluororesin film, nylon film, polymethylmethacrylate film, acrylic film or polyarylate film, and polyvinylidene chloride film. Even for materials with a high inherent birefringence such as polycarbonate, polyarylate, polysulfone or polyethersulfone, conditions such as solution casting or melt extrusion, as well as conditions for stretching in the longitudinal and transverse directions, etc. are set appropriately. By doing so, a transparent film and a transparent protective film suitable for the present invention can be obtained. In the present invention, the film is not limited to those described above. Further, in one polarizing plate, the film materials of the transparent film and the transparent protective film may be the same or different. In the present invention, a particularly preferable transparent film and transparent protective film are cellulose ester films.

The cellulose ester film particularly useful in the present invention will be described below. First, the cellulose ester as the raw material will be described.

The raw material cellulose of the cellulose ester used in the present invention is not particularly limited, and examples thereof include cotton linter, wood pulp, kenaf and the like. The cellulose esters obtained from them can be used alone or as a mixture at an arbitrary ratio, but it is preferable to use 50% by mass or more of cotton linter.

The cellulose ester according to the present invention is mainly prepared by using an acid anhydride as an acylating agent for a cellulose raw material, an organic acid forming an acid anhydride, or an organic solvent such as methylene chloride, and a protic acid such as sulfuric acid. The reaction is carried out using a catalyst. Specifically, it can be synthesized by the method described in JP-A-10-45804.

The cellulose ester which can be used in the cellulose ester film of the present invention is not particularly limited, but the total acyl group substitution degree is from 2.40 to 2.98,
Of the acyl groups, the substitution degree of the acetyl group is preferably 1.4 or more.

The method for measuring the degree of substitution of an acyl group is ASTM-
It can be measured according to D817-96.

The cellulose ester according to the present invention is a cellulose acetate such as cellulose triacetate or cellulose diacetate, cellulose acetate propionate, cellulose acetate butyrate, or propionate in addition to acetyl group such as cellulose acetate propionate butyrate. A cellulose ester having a group or a butyrate group bonded thereto is preferable.

The number average molecular weight Mn of the cellulose ester of the present invention is preferably in the range of 70,000 to 250,000 because the resulting film has high mechanical strength and an appropriate dope viscosity. Further 80,000 to 150,000
0 is preferred. Further, the ratio Mw / of the weight average molecular weight Mw /
A cellulose ester having a Mn of 1.0 to 5.0 is preferably used, and more preferably 1.5 to 4.5.

As an organic solvent useful for dissolving a cellulose ester and forming a cellulose ester solution or dope,
Methylene chloride (methylene chloride), a chlorine-based organic solvent
It is suitable for dissolving cellulose ester, especially cellulose triacetate. Examples of the non-chlorine organic solvent include methyl acetate, ethyl acetate, amyl acetate, acetone, tetrahydrofuran, 1,3-dioxolane, 1,4-dioxane, cyclohexanone, ethyl formate and the like. When using these organic solvents for cellulose triacetate,
A melting method at room temperature can also be used, but a high temperature melting method,
By using a dissolution method such as a cooling dissolution method or a high-pressure dissolution method, it is possible to reduce the amount of insoluble matter, which is preferable. For cellulose ester other than cellulose triacetate, methylene chloride can be used, but without using methylene chloride, methyl acetate,
Ethyl acetate and acetone can be preferably used. Methyl acetate is particularly preferable. In the present invention, an organic solvent having good solubility in the above-mentioned cellulose ester is referred to as a good solvent, and also exhibits a main effect on dissolution, in which a large amount of organic solvent is the main (organic) solvent or the main ( Organic) solvent.

In addition to the above 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. These are used as a gelling solvent that makes the web gel when the dope is cast on a metal support and the solvent begins to evaporate and the ratio of alcohol increases, and makes the web tough and easy to peel from the metal support. When these proportions are small, it also has a role of promoting the dissolution of the cellulose ester of the non-chlorine organic solvent. Examples of the alcohol having 1 to 4 carbon atoms include methanol, ethanol, n-propanol, iso-propanol,
Examples thereof include n-butanol, sec-butanol and tert-butanol. Of these, ethanol is preferable because it is excellent in stability of the dope, has a relatively low boiling point, has good drying property, and has no toxicity. These organic solvents alone are not soluble in cellulose ester and are therefore called poor solvents.

In the present invention, when the above cellulose ester film is used as the transparent film having the antireflection film, the cellulose ester film contains a plasticizer,
It is preferable to contain an ultraviolet absorber, an antioxidant, fine particles (matting agent) and the like.

The plasticizer is not particularly limited, but is a phosphoric acid ester plasticizer, a phthalic acid ester plasticizer, a trimellitic acid ester plasticizer, a pyromellitic acid plasticizer,
Glycolate plasticizers, citric acid ester plasticizers, polyester plasticizers and the like can be preferably used. Triphenyl phosphate, diphenyl biphenyl phosphate, etc.
The main phthalate-based compounds are diethyl phthalate and dicyclohexyl phthalate, the main trimellitic acid-based compounds are tributyl trimellitate, and the main pyromellitic ester-based compounds are tetrabutylpyromellitate and tetra- Phenylpyromellitate and the like, glycolic acid ester-based major ones such as ethylphthalylethyl glycolate and butylphthalylbutyl glycolate, and citric acid ester-based major ones such as triethyl citrate and tri-n-butyl. Examples thereof include citrate and dicyclohexyl phthalate.

The amount of these plasticizers used is 1 to cellulose ester in view of film performance, processability and the like.
It is preferably 20% by mass.

In the present invention, the transparent film or transparent protective film preferably contains an ultraviolet absorber.

As the ultraviolet absorber, those having excellent absorption of ultraviolet rays having a wavelength of 370 nm or less and little absorption of visible light having a wavelength of 400 nm or more are preferably used from the viewpoint of good liquid crystal display property. Specific examples of the ultraviolet absorber preferably used include, for example, oxybenzophenone compounds, benzotriazole compounds, salicylate compounds, benzophenone compounds, triazine compounds, cyanoacrylate compounds, nickel complex salt compounds and the like. , But not limited to these. Further, the polymeric UV absorbers described in JP-A-6-148430 are also preferably used.

Specific examples of the benzotriazole type ultraviolet absorber useful in the present invention include 2- (2'-hydroxy-).
5'-methyl-phenyl) benzotriazole, 2-
(2'-hydroxy-3 ', 5'-di-tert-butyl-phenyl) benzotriazole, 2- (2'-hydroxy-3'-tert-butyl-5'-methyl-phenyl) benzotriazole, 2- (2'-hydroxy-
3 ', 5'-di-tert-butyl-phenyl) -5-
Chlorobenzotriazole, 2- (2'-hydroxy-
3 '-(3 ", 4", 5 ", 6" -tetrahydrophthalimidomethyl) -5'-methyl-phenyl) benzotriazole, 2,2-methylenebis (4- (1,1,3,3)
3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol), 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2H-benzotriazol-2-yl) -6- (linear and side chain dodecyl) -4-methyl-phenol << Tinuvin (TIN
UVIN) 171 >>, 2-octyl-3- [3-ter
t-Butyl-4-hydroxy-5- (chloro-2H-benzotriazol-2-yl) phenyl] propionate and 2-ethylhexyl-3- [3-tert-butyl-4-hydroxy-5- (5-chloro- 2H-benzotriazol-2-yl) phenyl] propionate mixture << TINUVIN 109 >>, 2- (2
H-benzotriazol-2yl) -4,6-bis (1
-Methyl-1-phenylethyl) phenol << Tinuvin 234 >> and the like, and commercially available tinuvin (T
INUVIN) 171, tinuvin (TINUVIN) 1
09 and TINUVIN 234 can be preferably used, and both are commercially available products manufactured by Ciba Specialty Chemicals and can be preferably used. Specific examples of benzophenone compounds include 2,4-dihydroxybenzophenone and 2,2′-
Examples thereof include, but are not limited to, dihydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone and bis (2-methoxy-4-hydroxy-5-benzoylphenylmethane). Further, for this purpose, JP-A-6-148
The polymer UV absorbers (or UV absorbing polymers) described in Japanese Patent Application No. 430 and Japanese Patent Application No. 2000-156039 can also be preferably used. As the polymeric ultraviolet absorber, PUVA-30M (manufactured by Otsuka Chemical Co., Ltd.) and the like are commercially available. General formula (1) of JP-A-6-148430
Or general formula (2) or Japanese Patent Application No. 2000-1560
The polymeric ultraviolet absorbers represented by 39 in the general formulas (3), (6) and (7) are particularly preferably used.

The fine particles added to the cellulose ester film include, as examples of inorganic compounds, silicon dioxide, titanium dioxide, aluminum oxide, zirconium oxide, calcium carbonate, calcium carbonate, talc, clay, calcined kaolin, calcined calcium silicate, Mention may be made of hydrated calcium silicate, aluminum silicate, magnesium silicate and calcium phosphate. Among them, those containing silicon are preferable because the turbidity is low and the haze of the film can be reduced, and silicon dioxide is particularly preferable. Although fine particles such as silicon dioxide are often surface-treated with an organic substance, such particles are preferable because they can reduce the haze of the film. Preferred organic substances for the surface treatment include halosilanes, alkoxysilanes, silazanes, siloxanes and the like.
The silicon dioxide fine particles can be obtained, for example, by burning a mixture of vaporized silicon tetrachloride and hydrogen at 1000 to 1200 ° C. in the air. In the present invention, the average diameter of primary particles is 20 nm or less, and the apparent specific gravity is 70 nm.
Fine particles of g / l or more are preferable, and more preferably 90
To 200 g / l, more preferably 100 to 20
It is 0 g / l. The higher the apparent specific gravity is, the higher the concentration of the dispersion liquid can be made, which is preferable because the haze and the aggregates are improved. Here, the primary average particle diameter of the fine particles is measured by observing the particles with a transmission electron microscope (magnification: 500,000 to 2,000,000 times), observing 100 particles, and averaging the average value of the average primary particles The diameter. In the present invention, the apparent specific gravity described above was calculated by the following formula by taking a certain amount of silicon dioxide fine particles in a graduated cylinder and measuring the weight at this time.

Apparent specific gravity (g / l) = mass of silicon dioxide (g) / volume of silicon dioxide (l) Examples of the fine particles of silicon dioxide preferable in the present invention include, for example, Aerosil R972 and R manufactured by Nippon Aerosil Co., Ltd.
972V, R974, R812, 200, 200V, 3
00, R202, OX50, and TT600 (all manufactured by Nippon Aerosil Co., Ltd.) are commercially available. Aerosil 200V, R972, R97
2V, R974, R202 and R812 can be preferably used. The fine particles of zirconium oxide are commercially available, for example, under the trade names of Aerosil R976 and R811 (all manufactured by Nippon Aerosil Co., Ltd.), and any of them can be used. Among these Aerosil 200
V, Aerosil R972V, and Aerosil TT600 are particularly preferable because they have a large effect of reducing the turbidity and the coefficient of friction of the cellulose ester film according to the present invention.

Cellulose ester film 1 m ² as a transparent film or transparent protective film in the present invention
The amount of fine particles added per unit is preferably 0.01 to 1.0 g, more preferably 0.03 to 0.3 g, and 0.08 to
0.16 g is more preferred.

A method for forming a cellulose ester film according to the present invention will be described. The cellulose ester film is produced by a conventional solution casting film forming method. An example is shown below.

A good solvent for cellulose ester (flake-like) is added to an organic solvent mainly composed of a solvent by pressurizing at a temperature not lower than the boiling point of the main solvent to dissolve the cellulose ester, polymer and additives with stirring to form a dope. A dope is formed by mixing the cellulose ester solution with a polymer solution or an additive solution. The concentration of cellulose ester in the dope is preferably 10 to 35% by mass. An additive is added to the dope during or after the dissolution to dissolve and disperse it, and the dope is filtered through a filter medium, defoamed, and sent to the next step by a liquid sending pump. A casting position on a metal support such as an endless metal belt, for example, a stainless steel belt, or a rotating metal drum, which feeds the dope to a pressure die through a liquid feed pump (for example, a pressure-type metering gear pump) and transfers it indefinitely. In the second step, the dope is cast from the pressure die slit. It is preferable to use a pressure die that can adjust the slit shape of the die of the die and can easily make the film thickness uniform. The pressure die includes a coat hanger die and a T die, and any of them is preferably used. The surface of the metal support is a mirror surface. In order to increase the film formation speed, two or more pressure dies may be provided on the metal support, and the dope amount may be divided to form multiple layers. A web (hereinafter referred to as a dope film after casting the dope on the metal support is referred to as a web) is heated on the metal support to evaporate the solvent until the web can be peeled from the metal support. To evaporate the solvent, there are a method of blowing air from the web side and / or a method of transferring heat from the back surface of the metal support by a liquid, a method of transferring heat from the front and back sides by radiant heat, and the like. Is preferable because of good drying efficiency. A method of combining them is also preferable. In the case of rear surface liquid heat transfer, it is preferable to heat at a temperature not higher than the boiling point of the main solvent of the organic solvent used for the dope or the organic solvent having the lowest boiling point. The solvent-evaporated web on the metal support is peeled off at the peeling position. If the residual solvent amount of the web at the time of peeling (the following formula) is too large, it is difficult to peel, or conversely if you peel it after drying it sufficiently on the metal support, part of the web may peel off in the middle . Drying of the web on the metal support can be peeled in the range of 5 to 150 mass% depending on the strength and weakness of the conditions, the length of the metal support, etc., but when peeling at a time when the residual solvent amount is larger, the web If is too soft, the flatness is deteriorated at the time of peeling, and cracks and vertical lines due to peeling tension are likely to occur, and the amount of residual solvent at the time of peeling can be determined in consideration of economic speed and quality. Therefore, in the present invention, the temperature at the peeling position on the metal support is 10 to 40 ° C., preferably 15 to 30 ° C., and the residual solvent amount of the web at the peeling position is 10 to 120% by mass. Is preferred. In the present invention, the amount of residual solvent can be represented by the following formula.

Amount of residual solvent (% by mass) = {(M−N) / N} × 100 Here, M is the mass of the web at an arbitrary time point, and N is the one when M is dried at 110 ° C. for 3 hours. Is the mass of.

After the peeling, the web is dried by using a drying device that alternately conveys the web through a plurality of rolls arranged in the drying device and / or a tenter device that conveys the web by clipping both ends of the web. As described above, in the present invention, the width direction between the clips is 1.02 to 1.02.
As a method of stretching 1.50 times, it is preferable to stretch using a tenter device. Dry both sides of the web with hot air. Generally, the drying temperature is 40 to 250 throughout
It is preferable that the temperature is in the range of ° C.

The retardation film obtained by such stretching is preferably used as the transparent film and / or the transparent protective film according to the present invention.

The cellulose ester film as the transparent film and / or the transparent protective film according to the present invention may be alkali-saponified, and then bonded to polarized light. The saponified cellulose ester film has about 6
It can be obtained by immersing in a 2 mol / l NaOH aqueous solution at 0 ° C. for about 90 seconds, then washing with normal temperature water and drying at about 80 ° C.

The transparent resin protective layer coated on the polarizing film, which is useful in the present invention, will be described below. In the transparent resin protective layer composition, the description is given in the section of the photoreactive compound of the polarizing film. It is preferable to contain a photoreactive compound having an acryl group, a methacryloyl group or an epoxy group, a sensitizer solvent and the like. Since the above description is given here, it is omitted. As a method for applying the transparent resin protective layer composition, known methods such as a gravure coater, a spinner coater, a wire bar coater, a roll coater, a reverse coater, an extrusion coater and an air doctor coater can be used. The coating amount is 0.1 to 30μ in terms of wet film thickness.
m is suitable, and preferably 0.5 to 15 μm. The coating speed is preferably 10 to 60 m / min. After the transparent resin protective layer composition is applied and dried, it is irradiated with ultraviolet rays from a light source, and the irradiation time is preferably 0.5 seconds to 5 minutes. From the curing efficiency and work efficiency of the ultraviolet curable resin, it is 3 seconds to 2 minutes. Minutes are more preferred. Examples of commercially available photoreactive compounds that can be used here are shown below. For example, as an ultraviolet curable resin, ADEKA OPTOMER KR / BY series: KR-
400, KR-410, KR-550, KR-566,
KR-567, BY-320B (above, Asahi Denka Kogyo Co., Ltd.), or Koei Hard A-101-KK,
A-101-WS, C-302, C-401-N, C-
501, M-101, M-102, T-102, D-1
02, NS-101, FT-102Q8, MAG-1-
P20, AG-106, M-101-C (all manufactured by Koei Chemical Industry Co., Ltd.), or Seika Beam PHC22
10 (S), PHC X-9 (K-3), PHC221
3, DP-10, DP-20, DP-30, P100
0, P1100, P1200, P1300, P140
0, P1500, P1600, SCR900 (above, manufactured by Dainichiseika Kogyo Co., Ltd.), or KRM7033, K
RM7039, KRM7130, KRM7131, UV
ECRYL29201, UVECRYL29202 (above, Daicel UCB), or RC
-5015, RC-5016, RC-5020, RC-
5031, RC-5100, RC-5102, RC-5
120, RC-5122, RC-5152, RC-51
71, RC-5180, RC-5181 (above, manufactured by Dainippon Ink and Chemicals, Inc.) or Aurex N
o. 340 Kuriya (Chugoku Paint Co., Ltd.), Sunrad H-601 (Sanyo Kasei Co., Ltd.), SP-1509, SP-1507 (Showa High Polymer Co., Ltd.), or RCC-15C (Grace Japan Co., Ltd.) Company made), Aronix M-6100, M-80
30, M-8060 (above, manufactured by Toagosei Co., Ltd.) or other commercially available ones can be appropriately selected and used.

As an optical element of the present invention, a polarizing plate having an antireflection layer is provided by providing an antireflection layer directly or on another layer (preferably a hard coat layer or an antiglare layer) on the polarizing plate of the present invention. Plates can be formed.

Here, the hard coat layer or the antiglare layer will be described. The main component of the coating composition for the hard coat layer or the antiglare layer is the same as the above-mentioned photoreactive compound of the polarizing film or the transparent resin protective layer. . Regarding the hard coat layer and the antiglare layer, Example 1 of Japanese Patent Application No. 2001-237684
An ultraviolet curable resin layer as described in 1. can be used.

In the present invention, a clear hard coat layer or an antiglare layer is not laminated on the transparent resin protective layer,
The clear hard coat layer or the antiglare layer may be coated instead of the transparent resin protective layer.

Inorganic or organic fine particles are preferably added to the hard coat layer or antiglare layer of the present invention to prevent blocking and to enhance scratch resistance. For example, examples of the inorganic fine particles include silicon oxide, titanium oxide, aluminum oxide, tin oxide, zinc oxide, calcium carbonate, barium sulfate, talc, kaolin, calcium sulfate, and the like.
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 powder, polyolefin resin powder, Polyester resin powder, polyamide resin powder,
Examples thereof include polyimide resin powder and polyfluorinated ethylene resin powder, which can be added to the ultraviolet curable resin composition. The average particle size of these fine particle powders is preferably 0.005 μm to 1 μm.
It is particularly preferable that the thickness is 0.1 μm.

The ratio with respect to the fine particle powder in the hard coat layer or antiglare layer composition is 100% by weight of the ultraviolet curable resin composition 100.
It is desirable that the amount be 0.1 to 10 parts by mass with respect to parts by mass.

The layer formed by curing the ultraviolet curable resin thus formed is a clear hard coat layer having a center line average roughness Ra of 1 to 50 nm, but Ra is 0.1 to 1 μm.
It may be an antiglare layer having a thickness of about m. In the present invention, a metal oxide layer can be formed on these layers by plasma discharge treatment. It is preferable because the plasma treatment can be performed uniformly on the antiglare layer having a center line average roughness (Ra) defined by JIS B 0601 of 0.1 to 0.5 μm.

In the present invention, the clear hard coat layer or antiglare layer may contain a dye having an absorption wavelength of 500 to 600 nm. There is no particular limitation as long as it is a dye having an absorption wavelength in the range of 500 to 600 nm, but any dye may be used as long as it is soluble in the organic solvent used for the clear hard coat layer or antiglare layer composition. As the dye useful in the present invention, an azo dye, a polymethine dye and a quinone dye having an absorption wavelength of 500 to 600 nm are preferable. In the present invention, two or more kinds of these dyes may be mixed and used. Light having a wavelength in the range of 500 to 600 nm is a wavelength range in which the human eye has a relatively high visibility, and reflected light gives glare to the viewer, so by using a dye having an absorption wavelength in this region, An easily viewable image display device can be provided. Further, the presence of an antireflection layer or an antiglare layer provided thereon can provide a more observable one.

The optical element having an antireflection layer on the polarizing plate of the present invention is a transparent resin protective layer, a transparent protective film or a transparent film on a polarizing film (hereinafter, in the present invention, a transparent resin protective layer, a transparent protective film, A transparent film may be collectively referred to as a substrate), and a metal compound thin film is laminated on the transparent film. Further, on the above base material,
It is preferable to provide an antireflection layer on the hard coat layer or the antiglare layer.

The optical element of the present invention comprises a method of forming a thin film on a transparent protective film or a transparent film substrate after forming a polarizing plate, and a thin film of an antireflection layer on the surface of the transparent protective film or transparent film in advance. After forming a polarizing film according to the present invention on the opposite surface of the antireflection layer of the transparent film having this antireflection layer, or a polarizing film is formed on the transparent film, on which It may be produced by a method of pasting a transparent protective film having an antireflection layer in advance.

In the present invention, the method for forming the antireflection layer is not particularly limited, and for example, a composition containing a metal compound for the antireflection layer and an ultraviolet curable resin is applied on the surface of the base material of the polarizing plate. , Drying, and further irradiating with ultraviolet rays to form an antireflection layer, for example, the method described in JP-A No. 11-246692 or vacuum plasma, sputtering, plasma discharge treatment using a compound gas for the antireflection layer. It is possible to use the method according to the above. In the present invention, it is particularly preferable to form the antireflection layer by the atmospheric pressure plasma discharge treatment method. The atmospheric pressure plasma discharge treatment method is a method in which a high frequency voltage is applied between opposing electrodes at atmospheric pressure or a pressure in the vicinity thereof to generate plasma, and a rare gas and a reactive gas introduced between the opposing electrodes are contained. In this method, an antireflection layer for forming a functional thin film according to the composition of the reaction gas is formed by exposing the substrate to the reaction gas in the plasma state with the reaction gas to be formed into a plasma state.

In the present invention, the atmospheric pressure or a pressure in the vicinity thereof means a pressure of 20 to 200 kPa, but in order to obtain the effect described in the present invention preferably 90 to 110 kPa.
Pa, particularly 93 to 104 kPa is preferable.

The atmospheric pressure plasma discharge treatment method useful in the present invention is described in Japanese Patent Application Nos. 2001-127649 and 2001-17.
5475, 2001-131663, 2001-2
By the discharge treatment apparatus having a counter electrode described in 37684 and 2001-377091, the gap between the counter electrodes is set to atmospheric pressure or a pressure in the vicinity thereof, and at least a metal compound gas (reactive gas) and a noble gas are present therein. Is a method of forming a thin film of a metal compound on a base material that is continuously transferred to a plasma discharge treatment chamber by introducing a reaction gas containing the metal oxide. For example, when laminating three-layer thin films, the structure shown in FIG.
3 and the device described in FIG. 3 of 2001-377091, respectively.
4 layers are arranged and 3 layers of medium refractive index layer / high refractive index layer / low refractive index layer are laminated (4 layers when the antifouling layer is provided as the uppermost layer) on the substrate which is being transferred to be continuous. Can be treated as
This continuous lamination process is suitable for producing the optical element of the present invention because of stable quality and improvement in productivity. In addition, without laminating, each layer may be treated, wound after treatment, and sequentially treated to be laminated.

The antireflection layer used in the optical element of the present invention is
The high refractive index layer, the medium refractive index layer, and the low refractive index layer can be obtained by appropriately combining and laminating them, but it is preferable to laminate these three layers, and particularly from the base material side, the medium refractive index layer / high refractive index layer. / It is preferable to stack the low refractive index layers in this order.

An apparatus for forming the antireflection layer of the invention will be described. FIG. 1 is a schematic view of an example of an atmospheric pressure plasma discharge treatment apparatus useful in the present invention. FIG. 1 comprises a plasma discharge treatment device 30, a gas filling means 50, a voltage applying means 40, and an electrode temperature adjusting means 60. The base material F is unwound from an unillustrated original roll and conveyed, or is conveyed from the previous step and is guided by the guide roll 6
The nip roll 65 cuts off air and the like entrained in the base material via the nip roll 65, and is wound while being in contact with the roll rotating electrode 25 as an earth electrode, and between the square tubular fixed electrode group 36 as an applying electrode. After being transferred, it passes through the nip roll 66 and the guide roll 67 and is wound by a winder (not shown) or transferred to the next step. The reaction gas is the gas filling means 50 and the reaction gas G generated by the gas generator 51.
Is controlled into the plasma discharge processing container 31 of the discharge processing chamber 32 through the air supply port 52, the inside of the plasma discharge processing container 31 is filled with the reaction gas G, and the processing exhaust gas G ′ is discharged from the exhaust port 53. To do so. Next, the voltage applying means 40
Then, a voltage is applied to the rectangular cylindrical fixed electrode group 36 by the high frequency power source 41, and the roll rotating electrode 25 is grounded to generate discharge plasma. The roll rotating electrode 25 and the prismatic fixed electrode group 36 are heated or cooled by the electrode temperature adjusting means 60 to feed the medium to the electrodes. The temperature of the medium whose temperature has been adjusted by the electrode temperature adjusting means 60 is adjusted by the liquid feed pump P through the pipe 61 from the inside of the roll rotating electrode 25 and the prismatic fixed electrode group 36. During plasma discharge treatment, the physical properties and composition of the thin film obtained may change depending on the temperature of the base material, and it is preferable to appropriately control this. An insulating material such as distilled water or oil is preferably used as the medium. During the plasma discharge treatment, it is desired to control the temperature inside the rotary electrode using a roll so that the temperature unevenness of the base material in the width direction or the longitudinal direction is not generated as much as possible. Incidentally, 68 and 69 are plasma discharge processing containers 31.
And the partition that separates the outside world.

The electrode according to the present invention is composed of a metal base material and a dielectric material coated thereon. FIG. 2 is a perspective view showing an example of the roll rotating electrode in the present invention.
In FIG. 2, the roll rotating electrode 25a is configured such that a metal base material 25A having metal conductivity is sprayed with ceramics and then covered with a dielectric 25B that is sealed with an inorganic substance. The dielectric may be a lining.

FIG. 3 is a perspective view showing an example of a rectangular tube type electrode. In FIG. 1, the prismatic electrode 36a is the same as the roll rotating electrode 25a, or a combination of a metal base material 36A having metal conductivity and ceramics sprayed and then covered with a dielectric material 36B sealed with an inorganic substance. It consists of The dielectric may be a lining. The fixed electrode may be cylindrical. The prismatic electrode 36a as a fixed electrode is preferable because it has the effect of widening the discharge range as compared with the cylindrical electrode.

In the present invention, an electrode (with a dielectric)
Regarding the surface roughness of, the maximum height (Rmax) of the surface roughness defined by JIS B 0601 on at least the side of the electrode in contact with the base material is adjusted to be 10 μm or less. It is preferable from the viewpoint of obtaining the effect described above, but more preferably the maximum height of surface roughness (Rma).
x) is 8 μm or less, particularly preferably 7 μm or less.

The voltage applying means 40 uses a high frequency power source 41,
A voltage is applied to the metal base material having the metal conductivity of each electrode. The high frequency power source for applying a voltage to the counter electrode for forming the antireflection layer according to the present invention is not particularly limited, but is preferably a relatively high power source. Further, the formation of the antifouling layer does not need to have the high power as described above. As a high frequency power source that can be used for forming the antireflection layer and the antifouling layer, a high frequency power source (50k
Hz), high frequency power supply manufactured by HEIDEN R & D Co., Ltd. (continuous mode used, 100 kHz), high frequency power supply manufactured by Pearl Industry (200
kHz), high frequency power supply (800 kHz) made by Pearl Industry,
High frequency power supply made by Pearl Industry (2MHz), high frequency power supply made by JEOL (13.56MHz), high frequency power supply made by Pearl Industry (27MHz), high frequency power supply made by Pearl Industry (150MH)
z) and the like can be preferably used.

The plasma discharge processing container 31 may be a metallic container insulated with Pyrex (R) glass or plastic. For example, a polyimide resin or the like may be attached to the inner surface of a frame made of aluminum or stainless steel, and the metal frame may be sprayed with ceramics to have an insulating property.

The atmospheric pressure plasma discharge treatment method or conditions according to the present invention will be described. In the present invention, the atmospheric pressure or the pressure in the vicinity thereof means 20 to 200 kPa.
In order to obtain the effect described in the present invention, 90 to 110 kPa, particularly 93 to 104 kPa is preferable.

The frequency of the high-frequency electric field applied between the counter electrodes when forming the antireflection layer according to the present invention is not particularly limited, but the frequency between the counter electrodes should be in the range of 150 MHz to more than 100 kHz. It is preferable to apply a high frequency electric field having the electric field. In particular, the higher the frequency, the higher the thin film formation rate. 100kH between opposing electrodes
Electric power of 1 W / cm ² or more is supplied at a high frequency voltage exceeding z to excite the reaction gas and generate plasma. By applying such a high-power electric field, a dense and highly functional thin film with high film thickness uniformity can be obtained with high production efficiency. In the present invention, the frequency of the high frequency voltage applied between the opposed electrodes is preferably 150 MHz or less. The frequency of the high frequency voltage is preferably 200 kHz or higher, more preferably 800 kHz.
That is all. The power supplied between the opposing electrodes is preferably 1.2 W / cm ² or more, preferably 50 W.
/ Cm ² or less, more preferably 30 W / cm ² or less. The voltage application area (/ cm ² ) at the counter electrode
Refers to the area in the range where discharge occurs. The high-frequency voltage applied between the opposing electrodes may be an intermittent pulse wave or a continuous sine wave, but in order to obtain the effect of the present invention high, it should be a continuous sine wave. Is preferred.

In the present invention, the distance between the electrodes is defined by the thickness of the dielectric material provided on the metal base material of the electrodes, the magnitude of the applied voltage,
It is determined in consideration of the purpose of using plasma. The shortest distance between the dielectric and the electrode when the dielectric is installed on one of the electrodes, and the distance between the dielectrics when the dielectric is installed on both of the electrodes, from the viewpoint of uniform discharge in both cases. Is preferably 0.5 to 20 mm, more preferably 0.5 to 5 mm, still more preferably 0.5 to 3 mm, and particularly preferably 1 mm ± 0.5 mm.

When plasma discharge treatment is carried out in a reaction gas atmosphere under atmospheric pressure or a pressure in the vicinity thereof according to the present invention, before the treatment, the surface of the base material is preliminarily destaticized, and dust is further removed. It is preferable because the uniformity of treatment is further improved. As the charge removing means and the dust removing means after the charge removing processing, the same means as those used in the above-mentioned apparatus can be adopted. Although not shown, as the static elimination means, in addition to a normal blower type or contact type, a static eliminator in which a plurality of positive / negative ion-eliminating electrodes and an ion-suction electrode are placed so as to sandwich the substrate and a positive / negative The high-density static elimination system (Japanese Patent Application Laid-Open No. 7-263173) provided with the DC static eliminator of No. 2 can be mentioned and can be preferably used. Further, the charge amount of the base material at this time is preferably ± 500 V or less. Further, as the dust removing means after the static elimination processing, a non-contact type jet type decompression type dust removing device (Japanese Patent Laid-Open No. 7-6
No. 0211) and the like can be mentioned and can be preferably used, but the invention is not limited thereto.

The reaction gas filling the discharge processing chamber between the opposing electrodes of the atmospheric pressure plasma discharge processing apparatus according to the present invention, that is, the reaction gas forming the antireflection layer will be described.

The reaction gas used in the present invention is preferably a mixed gas containing a rare gas and a reactive gas.

As the rare gas, an element belonging to Group 18 of the periodic table,
Specific examples thereof include helium, neon, argon, krypton, xenon, and radon, but in order to obtain the effects described in the present invention, helium and argon are preferably used, and particularly relatively inexpensive argon. Gas is preferred.

In the present invention, the mixing ratio of the rare gas in the reaction gas is preferably 90.0 to 99.9% by volume.

The reactive gas is a gas used for forming a thin film, and there are a compound for directly forming a thin film and a gas for auxiliary use such as hydrogen gas, oxygen gas, nitrogen gas and carbon dioxide gas.

As the reaction gas for forming the antireflection layer of the optical element of the present invention, any compound capable of obtaining an appropriate refractive index can be used without limitation. In the present invention, the reaction for forming the high refractive index layer is used. As a reactive gas for forming a medium refractive index layer, a titanium compound is mainly used as a reactive gas, and as a reactive gas for forming a medium refractive index layer, a tin compound or a mixture of a titanium compound and a silicon compound (or a layer formed of a titanium compound for forming a high refractive index and a low refractive index are used). A layer formed of a silicon compound forming the refractive index layer may be laminated), and a silicon compound is mainly used as the reactive gas for forming the low refractive index layer,
A fluorine compound or a mixture of a silicon compound and a fluorine compound can be preferably used. Two or more kinds of these compounds may be mixed and used as a reactive gas for forming any layer in order to adjust the refractive index.

Titanium compounds used in the reactive gas for forming a high refractive index layer useful in the present invention include organic titanium compounds, titanium hydrogen compounds and titanium halides. Examples of the organic titanium compounds include triethyl titanium. ,
Trimethyl titanium, triisopropyl titanium, tributyl titanium, tetraethyl titanium, tetraisopropyl titanium, tetrabutyl titanium, triethoxy titanium, trimethoxy titanium, triisopropoxy titanium, tributoxy titanium, tetraethoxy titanium, tetraisopropoxy titanium, methyldimethoxy titanium , Ethyltriethoxytitanium, methyltriisopropoxytitanium, tetradimethylaminotitanium, dimethyltitanium diacetoacetonate, ethyltitanium triacetoacetonate, etc., as titanium hydrogen compounds, monotitanium hydrogen compounds, dititanium hydrogen compounds, etc., titanium halides. Examples thereof include trichlorotitanium and tetrachlorotitanium, and any of them can be preferably used in the present invention. Further, two or more kinds of these reactive gases can be mixed and used at the same time.

Examples of the tin compound used in the reactive gas for forming the medium refractive index layer useful in the present invention include organic tin compounds, tin hydrogen compounds, tin halides, and the like.
For example, tetraethyl tin, tetramethyl tin, diacetate di-
n-butyltin, tetrabutyltin, tetraoctyltin, tetraethoxytin, methyltriethoxytin, diethyldiethoxytin, triisopropylethoxytin, diethyltin,
Dimethyltin, diisopropyltin, dibutyltin, diethoxytin, dimethoxytin, diisopropoxytin, dibutoxytin, tin dibutyrate, tin diacetoacetonate, ethyltin acetoacetonate, ethoxytin acetoacetonate, dimethyltin diacetoacetonate Etc. Examples of tin halides such as tin-hydrogen compounds include tin dichloride, tin tetrachloride and the like, and any of them can be preferably used in the present invention. Further, two or more kinds of these reactive gases may be mixed and used at the same time. The tin oxide layer thus formed has a surface resistivity of 10 ¹¹ Ω / c.
Since it can be reduced to m ² or less, it is also useful as an antistatic layer.

Examples of the silicon compound used in the reactive gas for forming the low refractive index layer useful in the present invention include organic silicon compounds, silicon hydride compounds, silicon halide compounds, and the like. For example, tetraethylsilane, tetramethylsilane, tetraisopropylsilane, tetrabutylsilane, tetraethoxysilane, tetraisopropoxysilane, tetrabutoxysilane, dimethyldimethoxysilane, diethyldiethoxysilane, diethylsilanediacetacetonate, methyltrimethoxysilane. , Methyltriethoxysilane, ethyltriethoxysilane and the like, silicon hydrogen compounds such as tetrahydrogenated silane and hexahydrogenated disilane, and silicon halide compounds such as tetrachlorosilane, methyltrichlorosilane and diethyldisilane. And the like can be mentioned Roroshiran,
Both can be preferably used in the present invention. Further, the above-mentioned fluorine compound can be used. Two or more of these reactive gases can be mixed and used at the same time. Further, for fine adjustment of the refractive index, two or more kinds of these tin compounds, titanium compounds and silicon compounds may be appropriately mixed and used at the same time.

The above-mentioned organotin compound, organotitanium compound or organosilicon compound is preferably a metal hydrogen compound or a metal alkoxide from the viewpoint of handling, and it is free from corrosiveness, generation of harmful gas, and little stain in the process. From
Metal alkoxides are preferably used. Further, in order to introduce the above-mentioned organotin compound, organotitanium compound or organosilicon compound between the electrodes, which is the discharge space, both may be in a gas, liquid or solid state at normal temperature and pressure. In the case of gas, it can be directly introduced into the discharge space,
In the case of a liquid or solid, it is used after being vaporized by means such as heating, decompression, and ultrasonic irradiation. When an organic tin compound, an organic titanium compound, or an organic silicon compound is vaporized by heating and used, a metal alkoxide, such as metal tetraethoxide or metal tetraisopropoxide, which is liquid at room temperature and has a boiling point of 200 ° C. or lower is an antireflection film. It is preferably used for the formation of The metal alkoxide may be diluted with a solvent before use, and in this case, it may be vaporized into a rare gas by a vaporizer or the like and used as a reaction gas. As the vaporizer, for example, a vaporizer manufactured by Lintec Co., Ltd. can be used. Organic solvents that can be used at this time include methanol, ethanol, isopropanol, butanol, and n-.
Hexane and the like and mixed solvents thereof can be used.

With respect to the reactive gas, from the viewpoint of forming a uniform thin film on the transparent film by the discharge plasma treatment,
The content rate in the reaction gas is preferably 0.01 to 10% by volume, and more preferably 0.01 to 1% by volume.

The medium refractive index layer can also be obtained by appropriately mixing the above silicon compound, the above titanium compound or the above tin compound in accordance with the target refractive index.

In the present invention, hereinafter, a metal oxide layer containing tin oxide, a metal oxide layer containing titanium oxide, and a metal oxide layer containing silicon oxide will be described in this order.
It may be abbreviated as a tin oxide layer, a titanium oxide layer, and a silicon oxide layer. Further, in the present invention, the metal oxide layer containing tin oxide means a metal oxide layer mainly containing tin oxide in the metal oxide layer, and mainly refers to the metal oxide layer 8
It means to contain 0 mass% or more. The same applies to the metal oxide layer containing titanium oxide and the metal oxide layer containing silicon oxide.

In the present invention, an excellent antireflection layer could be formed by providing a tin oxide layer having a refractive index of 1.60 to 1.90 as the medium refractive index layer as the medium refractive index layer. This tin oxide medium refractive index layer has a refractive index of 2.00
~ 2.35 titanium oxide layer and refractive index 1.40 ~ 1.
48 by laminating with a silicon oxide layer, preferably by depositing a titanium oxide layer on the tin oxide layer, and further laminating a silicon oxide layer thereon, the reflectance in the visible light wavelength region becomes almost zero. It was possible to obtain an efficient antireflection film. As a preferred example, the tin oxide layer has a refractive index of 1.70 and a thickness of 67 nm, the titanium oxide layer has a refractive index of 2.14 and a thickness of 110 nm, and the silicon oxide layer has a refractive index of 1.44. In addition, a combination having a film thickness of 87 nm can be mentioned. Each layer is an amorphous metal oxide layer.

On the above-mentioned antireflection layer, Japanese Patent Application No.
The antifouling layer containing a fluorine compound, a mixture of a fluorine compound and a silicon compound or a compound having both a fluorine atom and a silicon atom as described in 1-286722 may be provided by an atmospheric pressure plasma discharge treatment method. Also,
The antifouling layer may be provided by coating.

An antistatic layer is preferably provided on the base material of the polarizing plate of the present invention. This is preferable in order to eliminate static electricity when the polarizing plate is further incorporated into the image display device, and this will prevent dust and the like from adhering, which will greatly contribute to improvement in yield and productivity.

The substance forming the antistatic layer useful for the optical element according to the present invention can be used without particular limitation as long as it is a conductive material having low humidity and conductivity. In particular, in the present invention, an organic tin compound for forming a tin oxide thin film by atmospheric pressure plasma discharge treatment, metal oxide fine particles for forming a conductive layer by coating, and cationic crosslinkable ionene type polymer fine particles are used as optical elements. It is preferably used.

One of the preferable methods for forming the antistatic layer in the present invention is to use the reaction gas containing the tin compound gas and the rare gas used for forming the medium refractive index layer, and to perform the above atmospheric pressure plasma discharge. Similar to the treatment, it is a method of forming a medium refractive index layer thin film on the transparent film, transparent protective film, transparent resin protective layer or antireflection layer by atmospheric pressure plasma discharge treatment. As the tin compound, compounds such as those described above for the medium refractive index layer can be used, and an organic tin compound is particularly preferable. When the antireflection film is formed as the optical element of the present invention, it is not necessary to form a further tin oxide film because the antireflection layer having conductivity is formed without newly forming the tin oxide thin film.

Second Preferred Antistatic Layer in the Invention
In the method of forming, the coating liquid containing the amorphous tin oxide fine particles is applied on the transparent film, the transparent protective film or the transparent resin protective layer. Amorphous tin oxide fine particles and a method for forming an antistatic layer are described in, for example, JP-A-10-59720 and JP-A-2000-128.
532, 2000-128533, 2001-06
7938 and 2001-072421, Japanese Patent Application 2001
The thing described in 319299 can be used. For example, the raw material of amorphous tin oxide is a hydrolyzable tin compound, and this is hydrolyzed and hydrolyzed to prepare amorphous tin oxide. While the aqueous dispersion containing the hydrolyzed amorphous tin oxide is separated or washed with water, the pH is about 4 due to chlorine ions remaining due to adsorption or the like on the amorphous tin oxide in a slurry form. The pH is adjusted using an alkaline aqueous solution such as ammonia, and the composition is prepared together with a binder, a surfactant, water and / or an organic solvent.

In the present invention, amorphous means a state of a substance different from crystalline. As used herein, the term “crystalline” refers to a long array of atoms, as described in Electrical and Electronic Engineering, Volume 72, Crystal Evaluation (Itsuji, Inuzuka Nao, Corona, 1982), page 4. It is characterized by distance order and the melting point of the solid phase of the substance. For example, it is known that high-purity, colorless and transparent crystalline tin oxide has a tetragonal rutile structure, a refractive index of 1.9968, and a high resistance of 10 ⁶ Ωcm or more at room temperature. Has been. The melting point is 1127 ° C., and crystalline tin oxide is thermally stable up to this temperature. On the other hand, in general, amorphous tin oxide is a substance that does not exhibit the above properties, and there is no long-range order in the arrangement of the atoms, and the temperature range where the substance changes below the melting point of crystalline tin oxide is It is the existing tin oxide.

The structure of tin oxide can be identified by X-ray diffraction, and the crystallite size was described in the new edition of Karity X-ray diffraction (Translated by Gentaro Matsumura, Agne Co., 1977). You can know the approximate value of long-range order. For example, the interplanar spacing of the (110) plane of tin oxide is approximately 0.33 nm, and in the case of crystalline tin oxide, it is several 1
There must be 0 or more repeating units, and it can be discriminated from the fact that a value of 10 and several nm can be observed by performing crystallite measurement. Therefore, 10n in crystallite measurement
If it is less than m, it can no longer be said that there is long-range order,
It can be considered amorphous. If it is less than 5 nm, there are no repeating units and crystals do not exist.
Whether it is amorphous or crystalline is easily clarified by conducting a thermal analysis of the solid, and even if the influence of the measurement conditions and the influence of the sample size are taken into consideration, there is a thermal change below 1000 ° C. If it occurs, it is hard to call it a crystal. Thermal mass spectrometry is easily observable due to thermal changes.
If the mass reduction at the starting mass is 0.1 mass% or more in the temperature range up to 500 ° C., which is much lower than the melting point of crystalline tin oxide, it is no longer single crystal tin oxide.

Since the amorphous tin oxide used in the present invention is not treated at a high temperature of 200 ° C. or higher in the manufacturing process, it satisfies the above conditions and is obviously amorphous.

In the present invention, the aqueous dispersion containing amorphous tin oxide means an aqueous dispersion containing at least amorphous tin oxide and contains a small amount of other metal compounds and organic compounds. May be.

The raw material of tin oxide is a hydrolyzable tin compound, which is hydrolyzed to prepare amorphous tin oxide. The tin compound is a compound containing an oxo anion such as K ₂ SnO ₃ .3H ₂ O, a water-soluble halide such as SnCl ₄ , SnCl ₄ .5H ₂ O, RSnR _4-m・ R ' _4-mn.・ X
_4-mnp (where R is an alkyl group or a group having an aromatic ring, _R'is an alkyloxy group, an ether group having an aromatic ring, an aliphatic carbooxy group or a group having a β-ketone ring, and X is a halogen atom) , M is 0, 1, 2,
3, n is 0, 1, 2, 3 and p is 0, 1, 2), for example, (C ₂ H ₅ ) ₄ Sn,
(CH ₃ ) ₃ SnOC ₂ H ₅ , (C ₄ H ₉ ) ₂ Sn (OCOC _{2
H 5) 2, (C 2} H 5) 2 SnCl 2, (CH 3) 3 SnCl ·
Organotin compounds such as C ₅ H ₅ N, Sn (SO ₄ ) ₂ .2H ₂ O
Examples thereof include compounds containing an oxo salt.

The steps of producing an aqueous dispersion containing amorphous tin oxide include a step of subjecting a hydrolyzable tin compound to a hydrolysis treatment, a step of washing the hydrolyzate with water, and a step of washing during or after washing with water.
Although the main step of adjusting and dispersing H is three steps, the washing step and the pH adjusting step may be performed at the same time. Also,
The step of forcibly mechanically dispersing may be performed after the water washing step or the pH adjusting step. Further, the present invention does not limit the subdivision of each step.

A water-soluble polymer may be added to the aqueous dispersion containing the amorphous tin oxide of the present invention. Examples of the water-soluble polymer include polyvinyl alcohol, polyacrylamide, acrylamide / sodium sulfo-2,2 dimethylethyl acrylamide copolymer, sodium polyacrylate and copolymers with other monomers, sodium polymethacrylate, poly-p-chloroammonium. Examples thereof include copolymers with methylstyrene and other monomers, polyvinylpyrrolidone, and the like, but are not limited thereto.

The solid content in the aqueous dispersion containing amorphous tin oxide of the present invention is adjusted so that the residue obtained by heating 1 g of the aqueous dispersion in a crucible at 800 ° C. for 1 hour becomes 30 to 200 mg. Is preferred. Here, in the present invention, the solid content means that most of the aqueous dispersion contains amorphous tin oxide, but there may be a small amount of other metal compounds. It refers to all that remains. However, substantially amorphous tin oxide occupies most of the solid content.

When the aqueous dispersion containing amorphous tin oxide of the present invention is thin, it may be concentrated. Concentration is preferably performed using an ultrafiltration membrane so as not to deteriorate the dispersibility of amorphous tin oxide.

Further, in order to make the particles in the above slurry be in an appropriately dispersed state or to facilitate pH adjustment,
Ultrasonic dispersion or mechanical dispersion may be performed. In particular, aggregated particles can be crushed and the dispersibility can be improved. In addition, a mechanical dispersion method may be used in order to make the particle sizes uniform. As the mechanical dispersion method in the present invention, a media mill, a colloid mill, a high-speed shear stirring,
Those by high-pressure impact dispersion or the like are preferable. Specific examples of the medium mill include a ball mill, an attritor, a sand mill and a bead mill. Specific examples of the colloid mill include a colloid mill, a stone mill, a caddy mill and a homogenizer. Specific examples of the device for high-speed shear stirring include those known as high speed dispersers, high speed impellers, and dissolvers as trade names.

Third Antistatic Layer Preferred in the Invention
The method of forming (1) uses crosslinked ionene polymer fine particles. Using the crosslinked ionene polymer based on the general formulas (1) to (15) described in JP-A-07-028194, the dispersion composition is prepared into a transparent film, a transparent protective film, a transparent resin protective layer or an antireflection coating. It can be formed by coating on the layer. Examples of the crosslinked ionene units of the crosslinked ionene polymer are shown below.

[0195]

[Chemical 19]

[0196]

[Chemical 20]

[0197]

[Chemical 21]

The above-mentioned crosslinked ionene unit may be a homocrosslinked polymer or a copolymer with another monomer, and the structure of the crosslinked ionene polymer according to the present invention always has a crosslinked structure. Have Here, n represents the degree of condensation of ionene, and n = 1 to 500, preferably 2 to
About 100 is preferable. Further, n1, n2 and n3 represent mol% of each unit in the crosslinked ionene polymer. n1 has at least 30 mol%. A and B represent other ethylenically unsaturated monomer units. In a polymer without B, A is the following ethylenically unsaturated monomer, and when B is present, A is a non-crosslinkable group. It is an ethylenically unsaturated monomer, and B represents a crosslinkable ethylenically unsaturated monomer. Other these ethylenically unsaturated monomers include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, butyl acrylate, butyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, phenyl acrylate, phenyl methacrylate, Acrylates or methacrylates such as benzyl methacrylate, phenyl methacrylate, phenethyl acrylate, phenethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, glycidyl acrylate, glycidyl methacrylate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl valerate. Vinyl esters such as De, N- methyl acrylamide, N, N- dimethylacrylamide, N
-Propylacrylamide, N, N-dipropylacrylamide, N-butylacrylamide, N, N-dibutylacrylamide, benzylacrylamide and other acrylamides, styrene, p-methylstyrene, p-hydroxystyrene, p-hydroxymethylstyrene, etc. Styrenes, ethylene glycol diacrylate, ethylene glycol dimethacrylate, propylene glycol diacrylate, propylene glycol dimethacrylate, 1,4-dimethylcyclohexylene diacrylate, 1,4-dimethylcyclohexylene dimethacrylate, divinylbenzene, trimethylolpropane tri Acrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethyl Acrylate, polyfunctional monomers such as pentaerythritol tetraacrylate, vinyl pyrrolidone, acrylonitrile, it can be mentioned ethylene, and the like. Two or more kinds of these monomers may be copolymerized. In the crosslinkable ionene monomer, n is 1 to 300, preferably 1 to 100. The content of the crosslinkable ionene monomer unit is preferably 10 to 100 mol% of all the monomers in the polymer.

In the present invention, in the case of the non-crosslinkable ionene monomer unit, the non-crosslinkable ionene monomer is necessarily copolymerized with the polyfunctional monomer unit and / or the crosslinkable ionene monomer unit. It is essential to use it as a partner and make it a crosslinkable polymer. The above-mentioned other monofunctional monomers may be appropriately copolymerized. The content of the non-crosslinkable ionene monomer is preferably about 10 to 60 mol%.

Each of the above antistatic layers has a temperature of 25 ° C. and 20% R
It has a surface resistivity value of 10 ¹² Ω / □ or less in the low humidity state of H, and can be preferably applied to the transparent film, the transparent resin protective layer, or the transparent protective film according to the present invention.

[0201]

EXAMPLES The embodiments of the present invention will be specifically described below with reference to examples, but the present invention is not limited thereto.

[Measurement / Evaluation] <Scratch> The scratch resistance was evaluated by measuring the pencil hardness of the alignment film surface, the transparent resin protective layer surface, or the transparent protective film surface by a test method according to JIS K5400.

<Yield in the process of producing a polarizing plate> In the process of producing a polarizing plate, scratches, easiness of production, occurrence of cracks and breakage troubles were checked, and the product finish of the original cellulose ester film was checked. The yield% (ratio of the polarizing plate area) was also checked, and the following evaluation was performed.

[0204] A: Yield is 98% or more B: Yield 90-97% C: Yield 75-89% D: Yield 65-74% E: Yield 50-64% F: Yield 49% or less.

<Yield in Manufacturing Process of Optical Element> A: Yield is 98% or more B: Yield 90-97% C: Yield 75-89% D: Yield 65-74% E: Yield 50-64% F: Yield 49% or less.

<Polarization Degree> When the transmittances of two polarizing plates of the same kind in the parallel position and the orthogonal position are P ₀ and P ₉₀ , respectively,
The degree of polarization V is expressed as follows.

V = {(P ₀ −P ₉₀ ) / (P ₀ + P ₉₀ )} ^1/2 <Parallel transmittance and orthogonal transmittance> The above P ₀ was expressed as parallel transmittance.

<Average Spectral Reflectance> The average spectral reflectance of the above optical elements is spectrophotometer U-4000 type (manufactured by Hitachi Ltd.).
Was used to measure the reflectance under the condition of regular reflection at 5 degrees. The measurement is performed by roughening the back surface of the observation side, then performing light absorption processing using a black spray, preventing reflection of light on the back surface of the film, and measuring the reflectance to 450 nm.
The average spectral reflectance at a wavelength of ˜650 nm was determined.

<Measurement of surface specific resistance value>
After conditioning the humidity for 24 hours under the condition of 20 ° C. and 20% RH, the surface specific resistance of the antistatic layer surface was measured at an applied voltage of 100 V by using a teraohm meter VE-30 manufactured by Kawaguchi Electric Co., Ltd. under the same condition, and log (Ω / □).

Example 1 [Production of Cellulose Ester Film (Transparent Film and Transparent Protective Film)] <Preparation of Dope A and B> Aerosil 200V in the following dope composition was added to a part of ethanol to be added in advance, and high pressure was applied. A dispersion liquid was obtained which was sufficiently dispersed with a disperser, Manton-Gaulin. The rest of the following composition and the above-mentioned dispersion liquid were put into a closed container, pressurized and kept at 80 ° C. and completely dissolved while stirring. After cooling to a casting temperature (30 ° C.), the mixture was allowed to stand and defoamed, and then Azumi Filter Paper Co., Ltd.
Azumi filter paper No. Each dope was obtained by filtration using 244.

[0211]   << Dope A composition >>   Cellulose triacetate (acetyl group substitution degree 2.87) 85 kg   Methylene chloride 290L   Ethanol 25L   Aerosil 200V 0.12kg   Tinuvin 171 0.5 kg   Tinuvin 109 0.5 kg   Tinuvin 326 0.3 kg   Dicyclohexyl phthalate 10kg   << Dope B composition >>   Cellulose acetate propionate   (Acetyl group substitution degree 1.9, propionyl group substitution degree 0.7) 85 kg   Ethyl acetate 290L   Ethanol 25L   Aerosil 200V 0.12kg   Tinuvin 171 0.5 kg   Tinuvin 109 0.5 kg   Tinuvin 326 0.3 kg   Triphenyl phosphate 8kg   2 kg of ethylphthalylethyl glycolate.

<< Preparation of Cellulose Ester Films 1 and 2 >> Using two solution casting film forming apparatuses, the dopes A and B whose temperature was adjusted to 30 ° C. were introduced into separate dies, and the dope was passed through the respective die slits. Width A and B evenly 172 on each endless stainless steel belt
It was cast in a width of cm. The casting portion of the endless stainless steel belt having a width of 180 cm was heated from the back surface with hot water at 35 ° C. for the dope A and 45 ° C. for the dope B. After the casting, the dope films A and B on the endless stainless steel belt (hereinafter referred to as webs A and B on the stainless steel belt) are dried by applying warm air at 44 ° C. and 55 ° C., After 90 seconds from casting, the amount of residual solvent for peeling was set to 80% by mass, and each was peeled off, and dried while being conveyed by a large number of rolls. The temperature of the endless stainless belt at the peeling part is 11
℃ was made. The peeled web was conveyed through the first drying zone set at 50 ° C. for 1 minute, and then the second drying zone was set to 85 ° C. by using a tenter dryer, and the width was 1.06 times in the width direction. Stretching was carried out and it was conveyed for 30 seconds. Grip the clips of the tenter device and cut off both ends.
It is transported in the third drying zone set at 20 ° C for 20 minutes to be dried, and finally both edges are cut off and the width is 1300 m.
Cellulose ester film 1 was obtained using dope A and cellulose ester film 2 was obtained using dope B, each having a length of m, a length of 2000 m and a film thickness of 80 μm. The amount of residual solvent when the film was wound was less than 0.01%. Cellulose ester films 1 and 2 are used as a transparent film and a transparent protective film, cellulose ester film 1 is used as transparent film 1 and transparent protective film 1, and cellulose ester film 2 is used as transparent film 2 and transparent protective film 2. did. When the web is dried on a stainless steel belt, the surface in contact with the belt is referred to as surface B, and the surface on the air side is referred to as surface A.

[Preparation of Polarizing Plates 1 to 16] <Preparation of Polarizing Plate 1> The transparent film has a width of 1300 mm, a length of 2000 m, a film thickness of 80 μm, and a transfer speed of 10 m / min. After applying shear stress using the coating apparatus shown and drying at 100 to 130 ° C. to form a polarizing film 1, the following transparent resin protective layer coating composition is applied on the polarizing film 1 in a wet film thickness. It was coated with a gravure coater so as to have a thickness of 13 μm, then dried in a drying section set at 85 ° C., and then was irradiated with ultraviolet rays at an irradiation intensity of 115 mJ / cm ² to form a transparent resin protective layer to prepare a polarizing plate 1. did.

[0214]   << Polarizing Film Composition 1 >>   DC-6 20 parts by mass   p-Nonylphenoxy polyethylene oxide (degree of polymerization 12) 2 parts by mass   Polyvinyl alcohol (saponification degree 92.5 mol%) 10 parts by mass   Boric acid 1 part by mass   Pure water 67.5 parts by mass   << Transparent resin protective layer coating composition >>   Dipentaerythritol hexaacrylate monomer 24 parts by mass   Dipentaerythritol hexaacrylate dimer 8 parts by mass   Dipentaerythritol hexaacrylate trimer or more components                                                             7 parts by mass   2 parts by weight of dimethoxybenzophenone   Propylene glycol monomethyl ether 29 parts by mass   Methyl ethyl ketone 30 parts by mass.

<Preparation of Polarizing Plate 2> The transparent film 1 transported at 15 m / min was subjected to corona discharge with an intensity of 8 W / cm ² · min, and then the following polarizing film composition 2 was applied on the polarizing plate 1. Apply a shear stress by the coating device used and apply
After drying at ˜120 ° C. to form the polarizing film 2, a corona discharge is applied thereon with a strength of 8 W / cm ² · min, and the following adhesive composition is further applied onto it so that the wet film thickness is 15 μm. Apply the transparent protective film 1 immediately after coating 70
The film was passed through a nip roll heated to 0 ° C., subsequently heated at 80 ° C., cooled, and wound up to prepare a polarizing plate 2.

[0216]   <Polarizing film composition 2>   DC-4 15 parts by mass   OC-10 10 parts by mass   p-Nonylphenoxy polyethylene oxide (degree of polymerization 12) 1 part by mass   Gelatin 9 parts by mass   1 part by mass of the following carbodiimide type curing agent   Pure water 59 parts by mass   5 parts by mass of methanol

[0217]

[Chemical formula 22]

[0218]   << Adhesive composition >>   Polyvinyl butyral (butyral substitution degree 50 mol%) 20 parts by mass   30 parts by mass of dioxane   50 parts by mass of ethanol.

<Preparation of Polarizing Plate 3> The transparent film 2 transported at 15 m / min was subjected to corona discharge with an intensity of 8 W / cm ² · min, and then the following polarizing film composition 3 was applied on the polarizing plate 1. Apply a shear stress by the coating device used to coat 80
The surface dried at ~ 120 ° C is irradiated with ultraviolet rays of 300 mJ / cm ² using a high pressure mercury lamp (80 W) to cure the surface,
After forming the polarizing film 3, apply corona discharge on it at 8 W / c
m ² · minute strength, and further, the adhesive composition is coated thereon so that the wet film thickness is 15 μm, and the transparent protective film 2 is immediately stuck and passed through a nip roll heated to 70 ° C. It was heated at 80 ° C., cooled and wound up to prepare a polarizing plate 3.

<< Polarizing Film Composition 3 >> DC-12 15 parts by mass DC-13 15 parts by mass F-177 (surfactant, manufactured by Dainippon Ink and Chemicals, Inc.) 1 part by mass Dipentaerythritol hexaacrylate monomer 10 parts by mass Dipentaerythritol hexaacrylate dimer 3 parts by mass Dipentaerythritol hexaacrylate trimer 3 parts by mass or more 3 parts by mass Dimethoxybenzophenone 0.5 parts by mass Dimethylacetamide 10 parts by mass Ethyl pentafluoropropionate 10 parts by mass Methyl ethyl ketone 32.5 Parts by mass The mixture of dipentaerythritol hexaacrylate will be abbreviated as DPEHA in Table 1 below.

<Preparation of Polarizing Plate 4> The transparent film 1 transported at 15 m / min was subjected to corona discharge with an intensity of 8 W / cm ² · min, and then the following polarizing film composition 4 was applied on the polarizing plate 1. Apply a shear stress by the coating device used to coat 80
The surface dried at ~ 120 ° C is irradiated with ultraviolet rays of 300 mJ / cm ² using a high pressure mercury lamp (80 W) to cure the surface,
After forming the polarizing film 4, apply corona discharge on it at 8W / c
m ² · minute strength, and further, the adhesive composition is coated thereon to have a wet film thickness of 15 μm, and immediately the transparent protective film 1 is attached and passed through a nip roll heated to 70 ° C. It was heated at 80 ° C., cooled and wound up to prepare a polarizing plate 4.

[0222]   <Polarizing film composition 4>   DC-2 8 parts by mass   DC-10 8 parts by mass   LR-10 (A: 4'-methylpyridinium-4-methylstyrene chloride) De, n1: n2 = 80: 20) 34 parts by mass   OC-18 4 parts by mass   Propylene glycol monomethyl ether 10 parts by mass   36 parts by mass of ethanol.

<Preparation of Polarizing Plate 5> The transparent film 1 transported at 15 m / min was subjected to corona discharge with an intensity of 8 W / cm ² · min, and then the following polarizing film composition 5 was applied on the polarizing plate 1. Apply a shear stress by the coating device used to coat 80
The surface dried at ~ 120 ° C is irradiated with ultraviolet rays of 300 mJ / cm ² using a high pressure mercury lamp (80 W) to cure the surface,
After forming the polarizing film 5, apply corona discharge on it at 8W / c
m ² · minute strength, further coated with the adhesive composition to have a wet film thickness of 15 μm, immediately attach the transparent protective film 1 and pass through a nip roll heated to 70 ° C., It was heated at 80 ° C., cooled, and wound up to prepare a polarizing plate 5.

[0224]   <Polarizing film composition 5>   DC-11 7 parts by mass   LOC-21 7 parts by mass   F-177 (surfactant, Dainippon Ink and Chemicals, Inc.) 1 part by mass   Dipentaerythritol hexaacrylate monomer 20 parts by mass   Dipentaerythritol hexaacrylate dimer 7 parts by mass   Dipentaerythritol hexaacrylate trimer or more components                                                             7 parts by mass   Dimethoxybenzophenone 0.5 parts by mass   Propylene glycol methyl ether acetate 10 parts by mass   Methyl ethyl ketone 40.5 parts by mass.

<Preparation of Polarizing Plate 6> The transparent film 1 transported at 13 m / min was subjected to corona discharge with a strength of 8 W / cm ² · min, and then the following polarizing film composition 6 was applied on the polarizing plate 1. Apply a shear stress by the coating device used to coat 80
The surface dried at ~ 120 ° C is irradiated with ultraviolet rays of 300 mJ / cm ² using a high pressure mercury lamp (80 W) to cure the surface,
After forming the polarizing film 6, apply corona discharge on it at 8 W / c
m ² · minute strength, further coated with the adhesive composition to have a wet film thickness of 15 μm, immediately attach the transparent protective film 1 and pass through a nip roll heated to 70 ° C., It was heated at 80 ° C., cooled and wound up to prepare a polarizing plate 6.

[0226]   <Polarizing film composition 6>   DC-6 7 parts by mass   OC-19 10 parts by mass   LOC-28 10 parts by mass   p-Nonylphenoxy polyethylene oxide (degree of polymerization 12) 2 parts by mass   Ethylene glycol monomethyl ether 5 parts by mass   66 parts by mass of pure water.

<Production of Polarizing Plate 7> Corona discharge was applied to the transparent film 2 transported at 17 m / min with a strength of 8 W / cm ² · min, and then the following polarizing film composition 7 was applied on the polarizing plate 1. Apply a shear stress by the coating device used to coat 80
The surface dried at ~ 120 ° C is irradiated with ultraviolet rays of 300 mJ / cm ² using a high pressure mercury lamp (80 W) to cure the surface,
After forming the polarizing film 7, apply corona discharge 8W / c on it.
m ² · minute strength, and further, the adhesive composition is coated thereon so that the wet film thickness is 15 μm, and the transparent protective film 2 is immediately stuck and passed through a nip roll heated to 70 ° C. It was heated at 80 ° C., cooled, and wound up to prepare a polarizing plate 7.

[0228]   <Polarizing film composition 7>   LDC-6 20 parts by mass   F-177 (surfactant, Dainippon Ink and Chemicals, Inc.) 1 part by mass   Polyvinyl acetal (Acetalization degree 70 mol%) 15 parts by mass   Trifluoroboron 1 part by mass   Thioxanthone 3 parts by mass   Dimethylformamide 2 parts by mass   Methyl ethyl ketone 68 parts by mass.

<Preparation of Polarizing Plate 8> The transparent film 1 transported at 15 m / min was subjected to corona discharge with a strength of 8 W / cm ² · min, and then the following polarizing film composition 8 was applied on the polarizing plate 1. Apply a shear stress by the coating device used to coat 80
The surface dried at ~ 120 ° C is irradiated with ultraviolet rays of 300 mJ / cm ² using a high pressure mercury lamp (80 W) to cure the surface,
After the polarizing film 8 was formed, the transparent resin protective layer coating composition was applied onto the polarizing film 8 by a gravure coater so that the wet film thickness was 13 μm, and then dried in a drying section set to 85 ° C. Then, it was irradiated with ultraviolet rays at an irradiation intensity of 115 mJ / cm ² to form a transparent resin protective layer, and a polarizing plate 8 was produced.

<< Polarizing Film Composition 8 >> LDC-8 20 parts by mass OC-18 10 parts by mass F-177 (surfactant, Dainippon Ink and Chemicals, Inc.) 1 part by mass Polyvinyl butyral (degree of butyralization 50 mol%) 5 parts by mass Parts thioxanthone 2 parts by mass ethylene glycol monomethyl ether 10 parts by mass ethanol 52 parts by mass <Preparation of polarizing plate 9> After corona discharge was applied to the transparent film 2 transported at 12 m / min at a strength of 8 W / cm ² · min,
The following polarizing film composition 9 was applied with shear stress by a coating device used in the polarizing plate 1 and applied to the surface dried at 80 to 120 ° C. using a high pressure mercury lamp (80 W) to emit 300 mJ / cm of ultraviolet rays. ^After irradiating and curing to form a polarizing film 9, a corona discharge is applied on the polarizing film 9 with a strength of 8 W / cm ² · min, and the above adhesive composition is further applied thereon to a wet film thickness of 15 μm. , And immediately attach the transparent protective film 2 and pass it through a nip roll heated to 70 ° C.
Continue heating at 80 ° C., cool and wind up, polarizing plate 9
Was produced.

[0231]   <Polarizing film composition 9>   LDC-10 20 parts by mass   LR-6 (A = methyl methacrylate, n1: n2 = 50: 50)                                                           10 parts by mass   F-177 (surfactant, Dainippon Ink and Chemicals, Inc.) 1 part by mass   Polymethylmethacrylate 5 parts by mass   Thioxanthone 1 part by mass   Methyl ethyl ketone 10 parts by mass   Cyclohexanone 10 parts by mass   Methylene chloride 43 parts by mass.

<Production of Polarizing Plate 10> The transparent film 1 transported at 18 m / min was subjected to corona discharge at a strength of 8 W / cm ² · min, and then the following polarizing film composition 10 was applied on the polarizing plate 1. A high-pressure mercury lamp (80
W) is used to irradiate the film with ultraviolet rays to cure it to 300 mJ / cm ² to form a polarizing film 10, and then corona discharge is applied thereon with a strength of 8 W / cm ² · min, and the adhesive composition The product is applied to have a wet film thickness of 15 μm, the transparent protective film 1 is immediately pasted onto the nip roll heated to 70 ° C., the product is subsequently heated at 80 ° C., and the film is cooled and wound to form a polarizing plate 10. did.

[0233]   << Polarizing film composition 10 >>   LDC-5 20 parts by mass   LOC-20 20 parts by mass   Propane-2,2-bis (p-phenonyl glycidyl ether) 5 parts by mass   F-177 (surfactant, Dainippon Ink and Chemicals, Inc.) 1 part by mass   Thioxanthone 1 part by mass   Dimethylformamide 10 parts by mass   Cyclohexanone 10 parts by mass   Methylene chloride 43 parts by mass.

Propane-2,2-bis (p-phenonyl glycidyl ether) was added to PB in Table 1 below.
It is abbreviated as PG.

<Preparation of Polarizing Plate 11> The transparent film 2 transported at 15 m / min was subjected to corona discharge with an intensity of 8 W / cm ² · min, and then the following polarizing film composition 11 was applied on the polarizing plate 1. A high pressure mercury lamp (80
W) to 300 mJ / cm ^{2 of} ultraviolet light for curing to form the polarizing film 11, and then corona discharge is applied thereon with a strength of 8 W / cm ² · min. The product is applied so as to have a wet film thickness of 15 μm, the transparent protective film 2 is immediately attached, and the product is passed through a nip roll heated to 70 ° C., followed by heating at 80 ° C. and winding after cooling to prepare a polarizing plate 11. did.

[0236]   << Polarizing film composition 11 >>   LDC-11 (A: N-acryloyloxyethylpyrrolidone, n1: n2: n3 = 30: 30: 40) 10 parts by mass   OC-42 (A: N-acryloyloxyethylpyrrolidone, n1: n2 = 7) 0:30) 10 parts by mass   LR-9 (A: N-acryloyloxyethylpyrrolidone, n1: n2 = 60 : 40) 5 parts by mass   F-177 (surfactant, Dainippon Ink and Chemicals, Inc.) 1 part by mass   p, p'-tetramethyldiaminobenzophenone (Michler's ketone)                                                             2 parts by mass   F-177 (surfactant, Dainippon Ink and Chemicals, Inc.) 1 part by mass   20 parts by mass of pyrrolidone   Dimethylformamide 13 parts by mass   37 parts by mass of 2,2,3,3,3-pentafluoropropyl acetate.

<Production of Polarizing Plate 12> The transparent film 1 transported at 15 m / min was subjected to corona discharge at a strength of 8 W / cm ² · min, and then the following polarizing film composition 12 was applied to the polarizing plate 1. A high pressure mercury lamp (80
W) is used to irradiate the film with ultraviolet rays to cure it to 300 mJ / cm ² to form a polarizing film 12, which is then subjected to corona discharge with a strength of 8 W / cm ² · min, and the adhesive composition The product is applied to have a wet film thickness of 15 μm, the transparent protective film 1 is immediately pasted on the product, passed through a nip roll heated to 70 ° C., subsequently heated at 80 ° C., and after winding, rolled up, a polarizing plate 12 is prepared. did.

[0238]   << Polarizing film composition 12 >>   LDC-12 10 parts by mass   OC-46 (A: 2-methoxyethyl acrylate,               n1: n2 = 50: 50) 10 parts by mass   LOC-3 10 parts by mass   F-177 (surfactant, Dainippon Ink and Chemicals, Inc.) 1 part by mass   Dimethylformamide 20 parts by mass   Methyl acetate 30 parts by mass   19 parts by mass of ethylene glycol acetate methyl ether.

<Preparation of Polarizing Plate 13> The transparent film 1 transported at 14 m / min was subjected to corona discharge with an intensity of 8 W / cm ² · min, and then the following polarizing film composition 13 was applied on the polarizing plate 1. A high-pressure mercury lamp (80
W) is used to irradiate the film with ultraviolet rays to cure it to 300 mJ / cm ² to form a polarizing film 13, which is then subjected to corona discharge with a strength of 8 W / cm ² · min, and the adhesive composition The product is applied to have a wet film thickness of 15 μm, the transparent protective film 1 is immediately applied, and the product is passed through a nip roll heated to 70 ° C., followed by heating at 80 ° C. and winding after cooling to prepare a polarizing plate 13. did.

[0240]   << Polarizing Film Composition 13 >>   LDC-13 (A: 2-triethylammonium ethyl acrylate bromide Id, n1: n2: n3 = 50: 25: 25) 10 parts by mass   DC-2 10 parts by mass   LR-11 (A: 2-triethylammonium ethyl acrylate bromide De, n1: n2 = 50: 50) 5 parts by mass   Triethylbenzylammonium bromide 1 part by mass   40 parts by mass of ethanol   Monomethyl ethylene glycol 5 parts by mass   29 parts by mass of 2,2,3,3,3-pentafluoropropanol.

<Production of Polarizing Plate 14 (Comparative Example)> Polarizing plate 14 was prepared in the same manner as in polarizing plate 1 except that the transparent resin protective layer coating composition was not applied.

<Production of Polarizing Plate 15 (Comparative Example)> Polarizing plate 15 was prepared in the same manner as in polarizing plate 2 except that the transparent protective film was not attached.

<Production of Polarizing Plate 16 (Comparative Example)> Length 20
A polyvinyl alcohol film having a width of 0 m, a width of 600 mm and a thickness of 120 μm is immersed in 100 parts by mass of an aqueous solution containing 1 part by mass of iodine and 4 parts by mass of boric acid, and stretched 4 times at 50 ° C. to form a polarizing film (polarizer). It was On both sides of this polarizing film, the following alkali saponification-treated transparent film (length 250 m, width 650
mm, 80 μm thick cellulose ester film 1)
A 5% aqueous solution of completely saponified polyvinyl alcohol was used as an adhesive to bond the sheets to prepare a polarizing plate 16.

<< Alkali saponification-treated transparent film >> Transparent film 1 was immersed in an aqueous sodium hydroxide solution having a concentration of 2 mol / l for 2 minutes at 60 ° C., washed with water, and then at 100 ° C. for 1 minute.
It was dried for 0 minutes to obtain an alkali saponification-treated transparent film.

With respect to the above polarizing plates 1 to 16, scratches,
The yield, the degree of polarization V, and the parallel transmittance in the process for producing a polarizing plate were evaluated, and the results are shown in Table 1.

In Table 1, dichroic dyes and alignment compounds having no photoreactive group are simply dichroic dyes (D
C) and the orienting compound (OC).

[0247]

[Table 1]

(Results) A polarizing plate obtained by forming a polarizing film by the method of the present invention and then immediately providing a transparent protective film or a transparent resin protective layer on the polarizing film is a polarizing film which protects the polarizing film and is not scratched. The yield in the process of producing was also good. On the other hand, in the case of Comparative Example in which the protective film or protective layer was not provided, it was difficult to handle after forming the polarizing film, and the yield was very low. In addition, the polyvinyl alcohol-iodine type polarizing film has a good degree of polarization and transmittance, but the yield is low due to the difficulty of handling the polarizing film.

In addition, in the method of the present invention, when the polarizing film uses only the dichroic dye having no photoreactivity,
It was found that the one using the photoreactive compound, the photoreactive dichroic compound or the photoalignment compound has an excellent degree of polarization and an excellent transmittance, and a more excellent polarizing plate can be obtained.

Example 2 [Production of Optical Elements 1 to 16 Having Antireflection Layer] An antireflection layer was provided on each of the above polarizing plates 1 to 16 to prepare an optical element 1.
~ 16 were produced.

First, the following back coat layer was coated on the transparent film surface of each of the polarizing plates 1 to 13. In addition, the polarizing plates 1 to 13
Polarizing plates 2, 3, 4, 5, 6, 7, 9, 10, 11, 1 having a transparent protective film on the opposite side of the back coat layer of
Regarding Nos. 2 and 13, the following clear hard coat layer was applied on the transparent protective film, and further on the clear hard coat layer, a medium refractive index layer, a high refractive index layer, a low refractive index layer and an antifouling layer were formed in this order. Optical elements 2, 3, 4, 5 having an antireflection layer laminated by the atmospheric plasma discharge treatment method as described below.
6, 7, 9, 10, 11, 12, 13 were made, and
Regarding 1 and 8 having a transparent resin protective layer, an antireflection layer was laminated on the transparent resin protective layer in the same manner as above to prepare optical elements 1 and 8 having an antireflection layer. Regarding the polarizing plates 14 and 15, after providing a back layer on a transparent film, an antireflection layer similar to the above was directly provided on the polarizing film to obtain optical elements 14 and 15. Polarizer 16
For, the backing layer was laminated on one surface of the transparent film on both sides of the polyvinyl alcohol-iodine polarizing film, and the antireflection layer was laminated on the other surface in the same manner as above to prepare the optical element 16. However, the width of the optical elements 1 to 15 is 1100.
The optical element 11 is manufactured with a size of mm and a length of 1000 m.
Is an optical element with a width of 600 mm and a length of 200 m,
Using an atmospheric pressure plasma discharge treatment device with a width of 650 mm,
It was made.

<Coating of Backcoat Layer> The following backcoat layer coating composition was coated on a transparent film of a polarizing plate with a gravure coater so that a wet film thickness was 14 μm, and dried at a drying temperature of 85 ° C. A coat layer (sometimes abbreviated as BC layer) was applied.

<< Backcoat Layer Coating Composition >> Acetone 30 parts by mass Ethyl acetate 45 parts by mass Isopropyl alcohol 10 parts by mass Cellulose diacetate 0.5 parts by mass Aerosil 200V 0.1 parts by mass <Clear hard coat layer (CHC layer) Coating> Here, the same composition as the transparent resin protective layer composition described above was used as the clear hard coat layer coating composition. The clear hard coat layer coating composition was applied by a gravure coater so that the wet film thickness was 13 μm, and then dried in a drying section set at 85 ° C., followed by ultraviolet irradiation at an irradiation intensity of 115 mJ / cm ² and drying. Center line average surface roughness (R
a) A 12 nm clear hard coat layer was provided. However,
No CHC layer was provided for polarizing plates 1 and 8 coated with a transparent resin protective layer, and for Comparative Examples 14 to 16.

<Formation of Antireflection Layer by Atmospheric Pressure Plasma Discharge Treatment> For the roll electrode, a stainless steel jacket roll base material having a temperature adjusting function was used. Alumina was coated to 1 mm by ceramic spraying on this, and a solution of tetramethoxysilane diluted with ethyl acetate was applied and dried, and then cured by ultraviolet irradiation to perform sealing treatment and Rm.
A roll electrode having a dielectric of ax1 μm was manufactured and grounded. As the application electrode, a hollow stainless steel pipe was coated with the same dielectric material as above under the same conditions to form an opposing electrode group, and the first plasma discharge treatment device was used for the medium refractive index layer and the second electrode. Was used for the high refractive index layer, and the third was used for the low refractive index layer so as to obtain the required film thicknesses. Further, the first, second and third plasma discharge processing devices were powered by a JEOL high frequency power source, with a continuous frequency of 13.56 MHz and 15 W / c.
m ² of electric power was supplied. However, the roll electrode was rotated using a drive in synchronization with the transport speed. Polarizer CH
On the C layer or the transparent resin protective layer, put an electrode gap of 1.0
mm, the pressure of the reaction gas was 103 kPa, and atmospheric pressure plasma discharge treatment was performed using the following reaction gas to prepare optical elements 1 to 16 having an antireflection layer.

The composition of the reaction gas used for the plasma discharge treatment is described below. << Reactive Gas for Forming Tin Oxide Layer (Medium Refractive Index Layer) >> Inert Gas (Argon) 98.7% by Volume Reactive Gas (Oxygen Gas) 1% by Volume Reactive Gas (Tetrabutyltin Vapor) 0.3% by Volume << Reaction Gas for Forming Titanium Oxide Layer (High Refractive Index Layer) >> Inert gas (argon) 98.7% by volume Reactive gas (oxygen gas) 1% by volume Reactive gas (tetraisopropoxytitanium vapor) 0.3% by volume << Reaction Gas for Forming Silicon Oxide Layer (Low Refractive Index Layer) >> Inert Gas (Argon) 98.7% by Volume Reactive Gas (Oxygen Gas) 1% by Volume Reactive Gas (Tetraethoxysilane Vapor) 0.3% by Volume Continuous atmospheric pressure plasma treatment was performed, and a tin oxide layer (refractive index 1.7, film thickness 67 nm) and a titanium oxide layer (refractive index 2.
14, film thickness 110 nm), silicon oxide layer (refractive index 1.4
4 and a film thickness of 87 nm) were provided.

Optical Element 1 Having Produced Antireflection Layer
For No. 16, the yield in the optical element production process (the yield in the antireflection layer production process), the polarization degree V, the parallel transmittance, and the average spectral reflectance were evaluated, and the results are shown in Table 2.

[0257]

[Table 2]

(Results) The yield of the optical element having the antireflection layer of the present invention was good, but the transparent protective film or the transparent resin protective layer of Comparative Example or PVA was not used.
The system had a low yield at the time of production.

Example 3 [Production of Optical Elements 17 to 36 Having Antistatic Layer] Optical elements 1 and 2 having an antireflection layer produced in Example 2
Used in Example 2 on transparent films of 4, 6, 7, 10, 13, 13, 14, 15 and 16 and polarizing plates 1, 2, 4, 6, 7, 10, 13, 14, 15 and 16. BC
A layer was applied, and the following antistatic layer was further formed thereon to prepare optical elements 17 to 36 having an antistatic layer.

<Antistatic Layer 1, Formation of Antistatic Layer by Atmospheric Pressure Plasma Discharge Treatment> On the exposed transparent film surface opposite to the surface of the antireflection layer, the medium refractive index layer of Example 2 was formed. An optical element having a tin oxide thin film was prepared by atmospheric pressure plasma discharge treatment using the conditions used for formation and tetrabutyltin vapor as a reactive gas.

<Formation of Antistatic Layer 2, Amorphous Tin Oxide Layer><Preparation of Amorphous Tin Oxide Aqueous Dispersion> Dropping funnel, thermometer,
Pure water 200 in a 300 liter reaction kettle equipped with a stir bar.
Add liter and put anhydrous stannic chloride (SnC) in the dropping funnel.
I ₄ ) 5.4 kg was added. While stirring the inside of the flask with a stir bar, first add anhydrous stannic chloride 4.8 from the dropping funnel.
kg was dropped and the mixture was stirred for 5 minutes. After that, 0.5 kg of anhydrous stannic chloride was dropped and stirred for 5 minutes, and then the remaining anhydrous stannic chloride was dropped. After the dropping of all the stannic chloride was completed, the dropping funnel was removed and replaced with a U-shaped bent tube. The tip of the tube was immersed in an aqueous solution of sodium carbonate. Then, the kettle was heated with steam, and the inside of the kettle was maintained at 85 ° C. The inside of the flask became cloudy as it approached 85 ° C. While intermittently stirring the inside of the kettle, it was kept warm for 1 hour and cooled with water, and when the internal temperature reached 60 ° C, the hydrolyzed contents in the flask were poured into 1000 liters of pure water at 40 ° C. . After waiting for the slurry to spontaneously settle in a slurry state, the supernatant was discarded when the bulkiness of the slurry became 1/3 in water. In this, 6
00 liters of 40 ° C. pure water was added, and the mixture was further added and allowed to settle, and decantation was repeated 17 times. During the 17th decantation, an aqueous solution of sodium hydroxide 1 mol / L was poured so that the pH became 6.8. 1
After the 7th decantation, SEP-
Amorphous tin oxide was concentrated using 1013 ultrafiltration membrane (manufactured by Asahi Kasei Co., Ltd.) until the solid content of the amorphous tin oxide (solid content after heating and drying at 800 ° C. for 1 hour) was 10% by mass. An aqueous dispersion was prepared.

The following amorphous tin oxide coating solution is applied to the transparent film surface.
The coating amount after drying is 0.12 / m ²So that
Coat using a strung coater, and 2 at 140 ℃
Dry for minutes.

[0263]   << Amorphous tin oxide coating liquid >>   Amorphous tin oxide (amount of amorphous tin oxide in aqueous dispersion) 592 g   Polymer latex (butyl acrylate / styrene / glycidyl acrylate     Rate: (mass ratio) 30/20/50) (solid content 30 mass%) 83 g   Sodium dodecylbenzene sulfonate 0.5g   Hexamethylene-1,6-bis (ethylene urea) 0.5 g Make up to 1000 ml with distilled water.

<Formation of Antistatic Layer 3, Crosslinkable Ionene Polymer Antistatic Layer> The following crosslinkable ionene polymer antistatic processing liquid was applied on the transparent film surface at a rate of 18 ml / m ² , followed by drying. On the antistatic layer, the following protective layer liquid composition was dried and then coated and dried to a mass per square meter to prepare an optical element, which was provided for measurement of the surface specific resistance.

<< Crosslinkable Ionene Polymer Antistatic Processing Liquid >> P-1 8 parts by mass Acetone: methanol (55:45 by mass ratio) mixed solvent 450 parts by mass Cellulose diacetate 8 parts by mass << Protective Layer Liquid Composition >> Cellulose Diacetate 100 mg / m ² Stearic acid 50 mg / m ² Silica matting agent 50 mg / m ² or more, the polarizing plate prepared in Example 1, and an antistatic layer in which an antistatic layer is provided in the optical element having an antireflection layer. For optical elements 17 to 36, the results of evaluation of optical element production process yield (yield of antistatic layer production step), polarization degree V, parallel transmittance, average spectral reflectance and surface specific resistance are shown in Table 3. It was shown to.

[0266]

[Table 3]

(Results) An optical element having a polarizing plate or a polarizing plate having an antireflection layer provided with an antistatic layer could be easily obtained in a good yield by the method of the present invention, but those of the comparative examples were collected. The rate was equally bad. The surface resistivity of the one having the antireflection layer is small, and it is considered that this is influenced by tin oxide of the medium refractive index layer.

[0268]

INDUSTRIAL APPLICABILITY The present invention can provide a polarizing plate excellent in quality, yield and productivity by a simple method of forming a polarizing film by applying a high shear stress depending on the coating method. Furthermore, it is possible to provide a high-quality and high-productivity optical element having an antireflection layer or an antistatic layer using this polarizing plate.

[Brief description of drawings]

FIG. 1 is a schematic view of an example of an atmospheric pressure plasma discharge treatment apparatus useful in the present invention.

FIG. 2 is a perspective view showing an example of a roll rotating electrode according to the present invention.

FIG. 3 is a perspective view showing an example of a rectangular tube type electrode.

[Explanation of symbols]

25 roll rotating electrode 25A, 36A Metal base material 25B, 36B dielectric 30 Plasma discharge treatment device 31 Plasma discharge treatment vessel 32 processing unit 36 square tube fixed electrode 40 voltage applying means 50 Gas filling means 51 gas generator 52 Air inlet 53 Exhaust port 60 Electrode temperature control means 64, 67 Guide roll 65, 66 nip roll 68, 69 Partition plate CF base material G reaction gas G'treatment exhaust gas P liquid feed pump

   ─────────────────────────────────────────────────── ─── Continued front page    F term (reference) 2H049 BA02 BA26 BB17 BB63 BB65                       BB67 BC02 BC22                 2H091 FA08X FA08Z FA37X GA16                       GA17 LA02                 4F006 AA02 AB03 AB24 AB55 AB62                       BA01 BA02 CA05 DA04 EA03

Claims (28)

[Claims] 1. A polarizing film prepared by applying a composition containing a dichroic dye having no photoreactive group to at least one surface of a transparent film to be transferred while applying a high shear stress to the transparent film in the transfer direction. After forming a film, a transparent resin protective layer composition is applied onto the polarizing film to form a transparent resin protective layer, or a transparent protective film is laminated on the polarizing film. Method of manufacturing a plate. 2. The polarizing plate according to claim 1, wherein the composition containing at least the dichroic dye having no photoreactive group contains an aligning compound having no photoreactive group. Manufacturing method. 3. A composition containing a dichroic dye having no photoreactive group and a photoreactive compound having no orienting group on at least one surface of the transparent film to be transferred, in the direction of transfer of the transparent film. After applying a high shear stress to form a polarizing film, the polarizing film is irradiated with ultraviolet rays to be cured, and then a transparent resin protective layer composition is applied to form a transparent resin protective layer. Or a method for manufacturing a polarizing plate, which comprises laminating a transparent protective film on the polarizing film. 4. A composition containing at least a dichroic dye having no photoreactive group and a photoreactive compound having no alignment group contains an alignment compound having no photoreactive group. The method for manufacturing a polarizing plate according to claim 3, wherein the polarizing plate is manufactured. 5. A composition containing a dichroic dye having no photoreactive group and a photoreactive alignment compound on at least one surface of a transparent film to be transferred has a high shear stress in the transfer direction of the transparent film. Is applied to form a polarizing film, and then the polarizing film is irradiated with ultraviolet rays to be cured, and a transparent resin protective layer composition is applied thereon to form a transparent resin protective layer. A method for producing a polarizing plate, which comprises laminating a transparent protective film on a film. 6. The composition containing at least the dichroic dye having no photoreactive group and the photoreactive alignment compound contains an alignment compound having no photoreactive group. Item 6. A method for producing a polarizing plate according to item 5. 7. A polarizing film is formed by applying a composition containing at least a photoreactive dichroic dye to at least one surface of a transparent film to be transferred while applying a high shear stress in the direction of transfer of the transparent film. After that, the polarizing film is irradiated with ultraviolet rays to be cured, and a transparent resin protective layer composition is applied thereon to form a transparent resin protective layer, or a transparent protective film is laminated on the polarizing film. A method for manufacturing a polarizing plate, comprising: 8. The method for producing a polarizing plate according to claim 7, wherein the composition containing at least the photoreactive dichroic dye contains an alignment compound having no photoreactive group. 9. The production of a polarizing plate according to claim 7, wherein the composition containing at least the photoreactive dichroic dye contains a photoreactive compound having no alignment group. Method. 10. The polarizing plate according to claim 7, wherein the composition containing at least the photoreactive dichroic dye contains a photoreactive alignment compound. Production method. 11. The composition according to claim 7, wherein the composition containing at least the photoreactive dichroic dye contains a dichroic dye having no photoreactive group. A method for producing the polarizing plate described above. 12. The transparent resin protective layer composition contains a photoreactive compound, and after the transparent resin protective layer composition is applied, the composition is irradiated with ultraviolet rays. A method for producing a polarizing plate according to item. 13. The surface of the polarizing film is surface-treated or an adhesive layer is applied before the transparent resin protective layer is formed or before the transparent protective film is attached. A method for manufacturing a polarizing plate according to any one of 1. 14. The method for producing a polarizing plate according to claim 1, wherein the surface to which the transparent protective film is attached is previously surface-treated. 15. The transparent film is surface-treated and then a polarizing film is formed on the surface thereof.
4. The method for manufacturing a polarizing plate according to any one of 4 above. 16. The method of manufacturing a polarizing plate according to claim 13, wherein the surface treatment is corona discharge. 17. The method for producing a polarizing plate according to claim 1, wherein the transparent film is a cellulose ester film. 18. The method for producing a polarizing plate according to claim 1, wherein the transparent protective film is a cellulose ester film. 19. A polarizing plate manufactured by the method according to any one of claims 1 to 18. 20. An optical element having an antireflection layer on any surface of the polarizing plate according to claim 19 either directly or through another layer. 21. The polarizing plate according to claim 19, wherein a surface of a transparent film or a transparent protective film having an antireflection layer in advance, directly or through another layer, is attached to the surface without the antireflection layer and the polarizing film. An optical element characterized by being a thing. 22. The antireflection layer applies a high-frequency voltage between opposing electrodes under atmospheric pressure or a pressure in the vicinity thereof to make a reaction gas introduced between the electrodes into a plasma state, and the reaction gas in the plasma state 22. The optical element according to claim 20, which is formed by exposing the transparent film surface to a plasma discharge treatment. 23. The other layer is a clear hard coat layer or an antiglare layer.
The optical element according to any one of 1. 24. The optical element according to claim 23, wherein the clear hard coat layer composition or the antiglare layer composition has the same composition as the transparent resin protective layer composition. 25. An optical element having an antistatic layer on at least one surface of the polarizing plate according to claim 19. 26. The polarizing plate according to claim 19, wherein a surface of a transparent film or a transparent protective film having an antistatic layer directly or through another layer, which has no antistatic layer, is bonded to a polarizing film. An optical element characterized by being a thing. 27. An antistatic layer is provided as the outermost layer of a polarizing plate having an antireflection layer.
4. The optical element according to any one of 4 above. 28. An antistatic layer comprising an atmospheric pressure plasma discharge treatment method using a tin compound as a reaction gas, a method of applying a composition containing amorphous tin oxide, and a composition containing a crosslinked ionene polymer. The coating material is formed by a method selected from the coating methods of
The optical element according to any one of 5 to 27.