JP2002048913A - Retardation film, circularly polarizing plate and reflective liquid crystal display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To attain a function of a λ/4 plate all over the visible ray region and to diminish a problem of dust adhesion by improving an antistatic property. SOLUTION: A retardation film to be used is composed of a sheet of a polymer film having 100-125 nm retardation value measured at 450 nm wavelength (Re450), further having 120-160 nm retardation value measured at 590 nm wavelength (Re590) and satisfying an inequality of Re590-Re450>=2 nm and exhibits <=1012 Ω/sq. surface resistivity on at least one surface of the film.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a retardation plate having an optically anisotropic layer, a circularly polarizing plate using the retardation plate, and a reflection type liquid crystal display device. In particular, the present invention relates to a λ / 4 plate or a λ / 2 plate used in a liquid crystal display device, a λ / 4 plate used for a pickup for writing on an optical disk, or a λ / 4 plate used as an antireflection film. It relates to an effective retardation plate.

[0002]

2. Description of the Related Art A λ / 4 plate and a λ / 2 plate have many uses related to an antireflection film and a liquid crystal display device, and have already been actually used. However, λ / 4 plate or λ
Λ / 4 or λ / 2 at a specific wavelength
Most of those who achieved were. JP-A-5-27
Nos. 118 and 5-27119 disclose a retardation plate in which a birefringent film having a large retardation and a birefringent film having a small retardation are laminated so that their optical axes are orthogonal to each other. Is disclosed.
If the difference in retardation between the two films is λ / 4 or λ / 2 over the entire visible light range, the retarder theoretically has a λ / 4 plate or λ /
Functions as two plates. JP-A-10-68816 discloses a polymer film having a wavelength of λ / 2 at a specific wavelength, a polymer film made of the same material as the polymer film, and a wavelength of λ /
There is disclosed a retardation plate capable of obtaining λ / 4 in a wide wavelength region by laminating a polymer film of No. 2 with a polymer film. Japanese Patent Application Laid-Open No. Hei 10-90521 also discloses that laminating two polymer films makes it possible to obtain λ / 4 in a wide wavelength region.
Is disclosed. As the above polymer film, a stretched film of a synthetic polymer such as polycarbonate has been used.

[0003] JP-A-2000-137116 discloses that
A broadband λ / 4 plate using one polymer film is disclosed. However, when this λ / 4 plate was used in a reflection type liquid crystal display device, although the contrast was slightly improved, the effect was not sufficient. Further, there is a problem that dust easily adheres in a winding step, a cutting step, a pressure-sensitive adhesive coating step, a bonding step with a polarizing plate, and the like after the film is formed, and is seen as a defect.

[0004] The reflection type liquid crystal display device does not require a backlight and has low power consumption.
It is used as a display for portable devices such as portable game machines and mobile phones. The reflection type liquid crystal display device has a basic structure in which a reflection plate, a liquid crystal cell and a polarizing film are laminated in this order. For the display mode of the liquid crystal cell,
TN (Twisted Nematic), STN (Supper Twisted Ne)
matic), HAN (Hybrid Aligned Nematic), HPD
LC (Holographic Polymer Dispersed Liquid Crysta
Various display modes such as l) have been proposed. TN
Mode reflective liquid crystal display devices have already been put to practical use. In a transmission type liquid crystal display device, two polarizing films are indispensable, but in a reflection type liquid crystal display device, an image can be displayed with a single polarizing film by using a λ / 4 plate. If one polarizing film is reduced, light is not attenuated, and a bright image can be displayed. A reflection type liquid crystal display device having a λ / 4 plate is described in JP-A-10-186357.

[0005]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a single polymer film with λ / 4 over the entire visible light range.
Another object of the present invention is to provide a retardation plate that achieves λ / 2, improves antistatic performance, and reduces the problem of dust adhesion. Another object of the present invention is to provide a circularly polarizing plate having excellent optical performance and handleability. Still another object of the present invention is to provide a reflective liquid crystal display device with improved display quality.

[0006]

The object of the present invention is to provide a retardation plate (λ / 4 plate) of the following (1) to (5), a circularly polarizing plate of the following (6), and a following (7) to (11). ) Retardation plate (λ / 2
Plate) and the reflection type liquid crystal display device of the following (12) to (14). (1) The retardation value (Re450) measured at a wavelength of 450 nm is 100 to 125 nm, and the retardation value (Re59) measured at a wavelength of 590 nm.
0) is from 120 to 160 nm, and Re590-Re
A retardation plate comprising a single polymer film satisfying the relationship of 450 ≧ 2 nm, wherein at least one surface of the film has a surface resistivity of 10 ¹² Ω / □ or less.

(2) The retardation value (Re450) measured at a wavelength of 450 nm is from 108 to 120 nm, and the retardation value (R450) measured at a wavelength of 550 nm is
e550) is 125 to 142 nm and the wavelength is 590.
The retardation value (Re590) measured in nm is 1
30 to 152 nm, and Re590-Re
The retardation plate according to (1), which satisfies the relationship of 550 ≧ 2 nm. (3) Refractive index nx in the in-plane slow axis direction, refractive index ny in the direction perpendicular to the in-plane slow axis, and refractive index nz in the thickness direction
Satisfies the relationship of 1 ≦ (nx−nz) / (nx−ny) ≦ 2, the retardation plate according to (1). (4) The retardation plate according to (1), wherein the polymer film is a cellulose ester film. (5) The retardation according to (1), wherein the polymer film is a cellulose ester film containing a compound having at least two aromatic rings and having a molecular structure that does not hinder the conformation of the two aromatic rings. Board.

(6) The phase difference plate and the linear polarizing film are laminated so that the angle between the slow axis in the plane of the phase difference plate and the polarization axis of the linear polarizing film is substantially 45 °. The retardation plate is a circularly polarizing plate having a retardation value (Re450) of 100 to 125 nm measured at a wavelength of 450 nm and a retardation value (R450) measured at a wavelength of 590 nm.
e590) is from 120 to 160 nm, and R
e590-A circularly polarizing plate comprising a single polymer film satisfying the relationship of Re450 ≥ 2 nm, wherein at least one surface of the film has a surface resistivity of 10 ¹² Ω / □ or less.

(7) The retardation value (Re450) measured at a wavelength of 450 nm is 200 to 250 nm, and the retardation value (Re590) measured at a wavelength of 590 nm is 240 to 320 nm.
A retardation plate comprising a single polymer film satisfying a relationship of 90-Re450 ≧ 2 nm, wherein at least one surface of the film has a surface resistivity of 10 ¹² Ω / □ or less. (8) The retardation value (Re450) measured at a wavelength of 450 nm is from 216 to 240 nm, and the
Retardation value measured at 50 nm (Re550)
Is 250 to 284 nm, the retardation value (Re590) measured at a wavelength of 590 nm is 260 to 304 nm, and Re590-Re550
The retardation plate according to (7), which satisfies the relationship of ≧ 2 nm. (9) In-plane refractive index nx in the slow axis direction, in-plane refractive index ny in a direction perpendicular to the slow axis, and refractive index nz in the thickness direction.
Satisfies the relationship of 1 ≦ (nx−nz) / (nx−ny) ≦ 2, the retardation plate according to (7). (10) The retardation plate according to (7), wherein the polymer film is a cellulose ester film. (11) The retardation according to (7), wherein the polymer film is a cellulose ester film containing a compound having a molecular structure having at least two aromatic rings and having no steric hindrance to the conformation of the two aromatic rings. Board.

(12) A reflection type liquid crystal display device using the retardation plate according to (1). (13) A reflective liquid crystal display device using the circularly polarizing plate according to (6). (14) A reflective liquid crystal display device using the retardation plate according to (7).

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION [Retardation Plate] When a retardation plate is used as a λ / 4 plate, the retardation value (Re450) measured at a wavelength of 450 nm is 100 to 125 nm.
And the retardation value (Re590) measured at a wavelength of 590 nm is from 120 to 160 nm, and satisfies the relationship of Re590-Re450 ≧ 2 nm. More preferably, Re590-Re450 ≧ 5 nm, and most preferably, Re590-Re450 ≧ 10 nm. The retardation value (Re450) measured at a wavelength of 450 nm is 108 to 120 nm, the retardation value (Re550) measured at a wavelength of 550 nm is 125 to 142 nm, and the
Retardation value measured at 90 nm (Re590)
Is 130 to 152 nm, and Re590-
It is preferable to satisfy the relationship of Re550 ≧ 2 nm.
More preferably, Re590-Re550 ≧ 5 nm, and most preferably, Re590-Re550 ≧ 10 nm. Also, Re550−Re450 ≧ 10
nm is also preferable.

When a retardation plate is used as a λ / 2 plate, the retardation value (R
e450) is from 200 to 250 nm, and the wavelength 5
Retardation value measured at 90 nm (Re590)
Is 240 to 320 nm, and Re590-
The relationship of Re450 ≧ 4 nm is satisfied. Re590-R
e450 ≧ 10 nm, more preferably
590-Re450 ≧ 20 nm The retardation value (Re) measured at a wavelength of 450 nm is most preferable.
450) is 216 to 240 nm, and the wavelength is 550 n
The retardation value (Re550) measured in m is 25
0 to 284 nm, and the retardation value (Re590) measured at a wavelength of 590 nm is 260 to 304 n.
m, and preferably satisfy the relationship of Re590-Re550 ≧ 4 nm. Also, Re590-Re
More preferably, 550 ≧ 10 nm.
Most preferably, 90-Re550 ≧ 20 nm. Further, it is also preferable that Re550−Re450 ≧ 20 nm.

The retardation value (Re) is calculated according to the following equation. Retardation value (Re) = (nx−ny) × d where nx is the in-plane refractive index of the retardation plate in the slow axis direction (in-plane maximum refractive index); ny is the retardation The index of refraction in the direction perpendicular to the slow axis in the plane of the plate; and d is
This is the thickness (nm) of the phase difference plate.

Further, the retardation plate of the present invention preferably satisfies the following expression. 1 ≦ (nx−nz) / (nx−ny) ≦ 2 where nx is the in-plane refractive index in the plane of the retardation plate; ny is the in-plane retardation of the retardation plate Is the refractive index in the direction perpendicular to the axis; and nz is the refractive index in the thickness direction.

The thickness of one polymer film constituting the retardation plate is preferably from 5 to 1000 μm, more preferably from 10 to 500 μm,
More preferably, it is 40 to 200 μm.
Most preferably, it is from 120 to 120 μm.

[Polymer] The polymer of the polymer film is preferably a cellulose ester, more preferably a lower fatty acid ester of cellulose. The lower fatty acid means a fatty acid having 6 or less carbon atoms. The number of carbon atoms is preferably 2 (cellulose acetate), 3 (cellulose propionate) or 4 (cellulose butyrate). Cellulose acetate is particularly preferred. Mixed fatty acid esters such as cellulose acetate propionate and cellulose acetate butyrate may be used. The average acetylation degree (acetylation degree) of cellulose acetate is preferably 45.0 to 62.5%, more preferably 55.0 to 61.0%, and more preferably 56.0 to 60.5%. % Is most preferred.

[Retardation increasing agent] In order to adjust the retardation value at each wavelength, a retardation increasing agent can be added to the polymer film.
The retardation increasing agent is preferably used in an amount of 0.05 to 20 parts by weight, more preferably 0.1 to 10 parts by weight, and more preferably 0.2 to 10 parts by weight, based on 100 parts by weight of the polymer. It is more preferably used in the range of from 5 to 5 parts by weight, and most preferably used in the range of from 0.5 to 2 parts by weight. Two or more retardation increasing agents may be used in combination. The retardation increasing agent preferably has a maximum absorption in a wavelength region of 250 to 400 nm. It is preferable that the retardation increasing agent has substantially no absorption in the visible region.

As the retardation increasing agent, a compound having at least two aromatic rings is preferably used. In the present specification, the “aromatic ring” includes an aromatic hetero ring in addition to an aromatic hydrocarbon ring. The aromatic hydrocarbon ring is particularly preferably a 6-membered ring (that is, a benzene ring). Aromatic heterocycles are generally unsaturated heterocycles. The aromatic hetero ring is preferably a 5-, 6-, or 7-membered ring, more preferably a 5- or 6-membered ring. Aromatic heterocycles generally have the most double bonds. As the hetero atom, a nitrogen atom, an oxygen atom and a sulfur atom are preferable, and a nitrogen atom is particularly preferable. Examples of the aromatic hetero ring include a furan ring, a thiophene ring, a pyrrole ring, an oxazole ring, an isoxazole ring, a thiazole ring, an isothiazole ring, an imidazole ring, a pyrazole ring, a furazane ring, a triazole ring, a pyran ring, and a pyridine ring. , Pyridazine ring, pyrimidine ring, pyrazine ring and 1,3,5-triazine ring. As the aromatic ring, a benzene ring, a furan ring, a thiophene ring, a pyrrole ring, an oxazole ring, a thiazole ring, an imidazole ring, a triazole ring, a pyridine ring, a pyrimidine ring, a pyrazine ring and a 1,3,5-triazine ring are preferable.

The number of aromatic rings possessed by the retardation increasing agent is preferably from 2 to 20, preferably from 2 to 12.
Is more preferably, 2 to 8 is more preferable, and 2 to 6 is most preferable. The bonding relationship between two aromatic rings can be classified into (a) a case where a condensed ring is formed, (b) a case where they are directly connected by a single bond, and (c) a case where they are bonded via a linking group. , A spiro bond cannot be formed). The connection relationship is (a)-
Any of (c) may be used.

Examples of the condensed ring of (a) (condensed ring of two or more aromatic rings) include an indene ring, a naphthalene ring, an azulene ring, a fluorene ring, a phenanthrene ring, an anthracene ring, an acenaphthylene ring, a biphenylene ring, Naphthacene ring, pyrene ring, indole ring, isoindole ring, benzofuran ring, benzothiophene ring, indolizine ring, benzoxazole ring, benzothiazole ring, benzimidazole ring, benzotriazole ring, purine ring, indazole ring, chromene ring, quinoline Ring, isoquinoline ring,
A quinolidine ring, a quinazoline ring, a cinnoline ring, a quinoxaline ring, a phthalazine ring, a pteridine ring, a carbazole ring, an acridine ring, a phenanthridine ring, a xanthene ring, a phenazine ring, a phenothiazine ring, a phenoxatiin ring, a phenoxazine ring and a thianthrene ring; included. Preferred are a naphthalene ring, an azulene ring, an indole ring, a benzoxazole ring, a benzothiazole ring, a benzimidazole ring, a benzotriazole ring and a quinoline ring. The single bond in (b) is preferably a bond between carbon atoms of two aromatic rings. Two aromatic rings may be linked by two or more single bonds to form an aliphatic ring or a non-aromatic heterocyclic ring between the two aromatic rings.

The connecting group (c) is also preferably bonded to carbon atoms of two aromatic rings. The linking group is an alkylene group, alkenylene group, alkynylene group, -CO-, -O
-, -NH-, -S- or a combination thereof is preferred. Examples of the linking group consisting of a combination are shown below. Note that the left and right relationships in the following examples of the linking group may be reversed. c1: -CO-O-c2: -CO-NH-c3: -alkylene-O-c4: -NH-CO-NH-c5: -NH-CO-O-c6: -O-CO-O-c7: -O-alkylene-O-c8: -CO-alkenylene-c9: -CO-alkenylene-NH-c10: -CO-alkenylene-O-c11: -alkylene-CO-O-alkylene-O-CO
-Alkylene-c12: -O-alkylene-CO-O-alkylene-O-
CO-alkylene-O-c13: -O-CO-alkylene-CO-O-c14: -NH-CO-alkenylene- c15: -O-CO-alkenylene-

The aromatic ring and the linking group may have a substituent. Examples of the substituent include a halogen atom (F, C
l, Br, I), hydroxyl, carboxyl, cyano, amino, nitro, sulfo, carbamoyl, sulfamoyl, ureido, alkyl, alkenyl, alkynyl, aliphatic acyl, aliphatic acyloxy, alkoxy, alkoxycarbonyl , Alkoxycarbonylamino group, alkylthio group, alkylsulfonyl group, aliphatic amide group, aliphatic sulfonamide group, aliphatic substituted amino group, aliphatic substituted carbamoyl group, aliphatic substituted sulfamoyl group, aliphatic substituted ureido group and non-aromatic Group heterocyclic groups.

The alkyl group preferably has 1 to 8 carbon atoms. A chain alkyl group is preferable to a cyclic alkyl group, and a linear alkyl group is particularly preferable.
The alkyl group may further have a substituent (eg, hydroxy, carboxy, alkoxy group, alkyl-substituted amino group). Examples of alkyl groups (including substituted alkyl groups) include methyl, ethyl, n-butyl, n-hexyl,
-Hydroxyethyl, 4-carboxybutyl, 2-methoxyethyl and 2-diethylaminoethyl. The alkenyl group preferably has 2 to 8 carbon atoms. A chain alkenyl group is preferable to a cyclic alkenyl group, and a linear alkenyl group is particularly preferable.
The alkenyl group may further have a substituent. Examples of the alkenyl group include vinyl, allyl and 1-hexenyl. The alkynyl group preferably has 2 to 8 carbon atoms. A chain alkynyl group is preferable to a cyclic alkynyl group, and a linear alkynyl group is particularly preferable. The alkynyl group may further have a substituent. Examples of the alkynyl group include ethynyl, 1-butynyl and 1-hexynyl.

The number of carbon atoms of the aliphatic acyl group is 1 to 1
It is preferably 0. Examples of the aliphatic acyl group include acetyl, propanoyl and butanoyl. The aliphatic acyloxy group preferably has 1 to 10 carbon atoms. Examples of the aliphatic acyloxy group include acetoxy. The alkoxy group preferably has 1 to 8 carbon atoms. The alkoxy group may further have a substituent (eg, an alkoxy group). Examples of alkoxy groups (including substituted alkoxy groups) include methoxy, ethoxy, butoxy and methoxyethoxy. The alkoxycarbonyl group preferably has 2 to 10 carbon atoms. Examples of the alkoxycarbonyl group include methoxycarbonyl and ethoxycarbonyl. The alkoxycarbonylamino group preferably has 2 to 10 carbon atoms. Examples of the alkoxycarbonylamino group include methoxycarbonylamino and ethoxycarbonylamino.

The number of carbon atoms of the alkylthio group is 1 to 1
It is preferably 2. Examples of the alkylthio group include methylthio, ethylthio and octylthio.
The alkylsulfonyl group preferably has 1 to 8 carbon atoms. Examples of the alkylsulfonyl group include methanesulfonyl and ethanesulfonyl. The aliphatic amide group preferably has 1 to 10 carbon atoms. Examples of the aliphatic amide group include acetamide. The aliphatic sulfonamide group preferably has 1 to 8 carbon atoms. Examples of the aliphatic sulfonamide group include methanesulfonamide, butanesulfonamide and n-octanesulfonamide. The aliphatic substituted amino group preferably has 1 to 10 carbon atoms. Examples of the aliphatic substituted amino group include dimethylamino, diethylamino and 2-carboxyethylamino. The aliphatic substituted carbamoyl group preferably has 2 to 10 carbon atoms. Examples of the aliphatic substituted carbamoyl group include methylcarbamoyl and diethylcarbamoyl. The aliphatic substituted sulfamoyl group preferably has 1 to 8 carbon atoms. Examples of the aliphatic substituted sulfamoyl group include methylsulfamoyl and diethylsulfamoyl. The aliphatic substituted ureido group preferably has 2 to 10 carbon atoms. Examples of the aliphatic substituted ureido group include methyl ureide. Examples of the non-aromatic heterocyclic group include piperidino and morpholino. The molecular weight of the retardation increasing agent is preferably from 300 to 800.

[Infrared absorber] In order to adjust the retardation value at each wavelength, an infrared absorber can be added to the polymer film. The infrared absorber is preferably used in an amount of 0.01 to 5 parts by weight, more preferably 0.02 to 2 parts by weight, and more preferably 0.05 to 5 parts by weight, based on 100 parts by weight of the polymer. It is more preferably used in the range of 1 part by weight, and most preferably used in the range of 0.1 to 0.5 part by weight.
Two or more infrared absorbers may be used in combination. The infrared absorber preferably has a maximum absorption in a wavelength range of 750 to 1100 nm, and more preferably has a maximum absorption in a wavelength range of 800 to 1000 nm. It is preferred that the infrared absorber has substantially no absorption in the visible region.

It is preferable to use an infrared absorbing dye or an infrared absorbing pigment as the infrared absorbing agent, and it is particularly preferable to use an infrared absorbing dye. The infrared absorbing dye includes an organic compound and an inorganic compound. It is preferable to use an infrared absorbing dye which is an organic compound. Organic infrared absorbing dyes include cyanine compounds, metal chelate compounds, aminium compounds, diimonium compounds, quinone compounds, squarylium compounds and methine compounds. For the infrared absorbing dye, coloring material, 61 [4] 2
15-226 (1988), and Chemical Industry, 43-5.
3 (1986, May).

When examining the types of dyes from the viewpoint of infrared absorption function or absorption spectrum, infrared absorption dyes developed in the technical field of silver halide photographic materials are excellent. Infrared absorbing dyes developed in the technical field of silver halide photographic light-sensitive materials include dihydroperimidine squarylium dyes (described in US Pat. No. 5,380,635 and Japanese Patent Application No. 8-189817) and cyanine dyes (JP-A No. No. 62-123454, No. 3-138640, No. 3
-21542, 3-226736, 5-31
Nos. 3305 and 6-43583, Japanese Patent Application No. 7-435.
269097 and EP 0430244), pyrylium dyes (JP-A-3-13864).
Nos. 0 and 3-21542) and diimmonium dyes (JP-A-3-138640 and JP-A-3-2115).
No. 42), pyrazolopyridone dyes (described in JP-A-2-282244), indoaniline dyes (described in JP-A-5-323500 and JP-A-5-323501), polymethine dyes (described in JP-A-3-26765). Nos. 4,190,343 and EP 37796.
No. 1), oxonol dyes (JP-A-3-93)
No. 46), anthraquinone dyes (Japanese Unexamined Patent Publication No.
13654), a naphthalocyanine dye (described in US Pat. No. 5,099,899) and a naphtholactam dye (described in European Patent 568,267).

[Production of polymer film] It is preferable to produce a polymer film by a solvent casting method. In the solvent casting method, a film is manufactured using a solution (dope) in which a polymer is dissolved in an organic solvent. The organic solvent is an ether having 3 to 12 carbon atoms,
It is preferable to include a solvent selected from ketones having 3 to 12 carbon atoms, esters having 3 to 12 carbon atoms, and halogenated hydrocarbons having 1 to 6 carbon atoms. Ethers, ketones and esters may have a cyclic structure. A compound having two or more functional groups of ether, ketone and ester (that is, -O-, -CO- and -COO-) can also be used as the organic solvent. The organic solvent may have another functional group such as an alcoholic hydroxyl group. In the case of an organic solvent having two or more types of functional groups, the number of carbon atoms may be within the specified range of the compound having any one of the functional groups.

Examples of the ethers having 3 to 12 carbon atoms include diisopropyl ether, dimethoxymethane, dimethoxyethane, 1,4-dioxane, 1,3-dioxolan, tetrahydrofuran, anisole and phenetole. Examples of the ketones having 3 to 12 carbon atoms include acetone, methyl ethyl ketone, diethyl ketone, diisobutyl ketone, cyclohexanone and methylcyclohexanone. Examples of the esters having 3 to 12 carbon atoms include ethyl formate, propyl formate, pentyl formate, methyl acetate, ethyl acetate and pentyl acetate. Examples of the organic solvent having two or more types of functional groups include
Includes 2-ethoxyethyl acetate, 2-methoxyethanol and 2-butoxyethanol. The number of carbon atoms of the halogenated hydrocarbon is preferably 1 or 2, and most preferably 1. The halogen of the halogenated hydrocarbon is preferably chlorine. The proportion of halogen atoms substituted by halogen atoms in halogenated hydrocarbons is preferably 25 to 75 mol%, and preferably 3 to 75 mol%.
The content is more preferably 0 to 70 mol%, still more preferably 35 to 65 mol%, and 40 to 60 mol%.
Most preferably, it is mol%. Methylene chloride is a typical halogenated hydrocarbon. Two or more organic solvents may be used as a mixture.

The polymer solution can be prepared by a general method. The general method means that the treatment is performed at a temperature of 0 ° C. or higher (normal temperature or high temperature). The solution can be prepared using a dope preparation method and apparatus in a usual solvent casting method. In the case of a general method, it is preferable to use a halogenated hydrocarbon (particularly, methylene chloride) as the organic solvent. The amount of the polymer is adjusted so that the obtained solution contains 10 to 40% by weight. More preferably, the amount of polymer is from 10 to 30% by weight. In the organic solvent (main solvent), any additives described below may be added.
The solution can be prepared by stirring the polymer and the organic solvent at room temperature (0 to 40 ° C.). The highly concentrated solution may be stirred under pressure and heating conditions. Specifically, the polymer and the organic solvent are placed in a pressurized container and hermetically sealed, and the mixture is stirred while being heated under pressure to a temperature not lower than the boiling point of the solvent at normal temperature and in a range where the solvent does not boil. The heating temperature is usually 40 ° C. or higher, preferably 60 to 2
It is 00 ° C, more preferably 80 to 110 ° C.

The components may be roughly mixed in advance and then placed in a container. Moreover, you may put in a container sequentially. The container must be configured to be able to stir. The container can be pressurized by injecting an inert gas such as nitrogen gas. Further, an increase in the vapor pressure of the solvent due to heating may be used.
Alternatively, each component may be added under pressure after the container is sealed. When heating, it is preferable to heat from outside the container. For example, a jacket-type heating device can be used. Alternatively, a plate heater may be provided outside the container, and the entire container may be heated by circulating the liquid through piping. It is preferable to provide a stirring blade inside the container and stir using the stirring blade. The stirring blade preferably has a length reaching the vicinity of the container wall. At the end of the stirring blade, a scraping blade is preferably provided to renew the liquid film on the container wall. Instruments such as a pressure gauge and a thermometer may be installed in the container. Dissolve each component in the solvent in the container.
The prepared dope is taken out of the vessel after cooling, or is taken out and then cooled using a heat exchanger or the like.

A solution can be prepared by a cooling dissolution method. In the cooling dissolution method, the polymer can be dissolved even in an organic solvent that is difficult to dissolve by a normal dissolution method. In addition, even if it is a solvent which can dissolve a polymer by a usual dissolution method, the cooling dissolution method has an effect that a uniform solution can be obtained quickly. In the cooling dissolution method, first, a polymer is gradually added to an organic solvent with stirring at room temperature. The amount of polymer is between 10 and 4 in this mixture.
It is preferable to adjust so as to contain 0% by weight. More preferably, the amount of polymer is from 10 to 30% by weight. Further, an optional additive described below may be added to the mixture.

Next, the mixture is heated to -100 to -10 ° C (preferably -80 to -10 ° C, more preferably -50 to -10 ° C).
To -20 ° C, most preferably -50 to -30 ° C). The cooling can be performed, for example, in a dry ice / methanol bath (−75 ° C.) or a cooled diethylene glycol solution (−30 to −20 ° C.). Upon such cooling, the mixture of polymer and organic solvent solidifies. The cooling rate is preferably 4 ° C./min or more, and 8 ° C./min.
Minutes or more, and most preferably 12 ° C./minute or more. The higher the cooling rate, the better, but the theoretical upper limit is 10,000 ° C./sec.
0 ° C./sec is a technical upper limit, and 100 ° C./sec is a practical upper limit. The cooling rate is a value obtained by dividing the difference between the temperature at which the cooling is started and the final cooling temperature by the time from when the cooling is started to when the temperature reaches the final cooling temperature.

Further, the temperature is raised to 0 to 200 ° C. (preferably 0 to 150 ° C., more preferably 0 to 120 ° C.,
Upon heating to (most preferably 0 to 50 ° C.), the polymer dissolves in the organic solvent. The temperature may be raised only by leaving it at room temperature or may be heated in a warm bath. Heating rate is 4
C./min or more, more preferably 8 ° C./min or more, and most preferably 12 ° C./min or more. The heating rate is preferably as fast as possible.
00 ° C / sec is the theoretical upper limit, 1000 ° C / sec is the technical upper limit, and 100 ° C / sec is the practical upper limit. Note that the heating rate is a value obtained by dividing the difference between the temperature at which heating is started and the final heating temperature by the time from when the heating is started until the final heating temperature is reached. . As described above, a uniform solution is obtained. If the dissolution is insufficient, the operation of cooling and heating may be repeated.
Whether or not the dissolution is sufficient can be determined only by visually observing the appearance of the solution.

In the cooling dissolution method, it is desirable to use a closed container in order to avoid water contamination due to dew condensation during cooling. Also, in the cooling and heating operation, pressurization during cooling,
By reducing the pressure during the heating, the dissolution time can be shortened. In order to perform pressurization and decompression, it is desirable to use a pressure-resistant container. According to the differential scanning calorimetry (DSC), a 20% by weight solution of cellulose acetate (acetylation degree: 60.9%, viscosity average polymerization degree: 299) dissolved in methyl acetate by a cooling dissolution method was 3%.
A pseudo phase transition point between the sol state and the gel state exists near 3 ° C., and below this temperature, the gel state becomes uniform. Therefore,
This solution must be stored at a temperature equal to or higher than the quasi phase transition temperature, preferably at a temperature of about 10 ° C. plus the gel phase transition temperature. However, the pseudo phase transition temperature varies depending on the average acetylation degree of cellulose acetate, the average degree of viscosity polymerization, the solution concentration, and the organic solvent used.

From the prepared polymer solution (dope), a polymer film is produced by a solvent casting method. The dope is cast on a drum or band and the solvent is evaporated to form a film. The concentration of the dope before casting is preferably adjusted so that the solid content is 18 to 35%. It is preferable that the surface of the drum or the band is finished in a mirror state. The casting and drying methods in the solvent casting method are described in US Pat.
No. 36310, No. 2367603, No. 2492078
Nos. 2492977, 2492978, 26
No. 07704, No. 2739069, No. 2739070
Nos., British Patent Nos. 640731 and 736892, Japanese Patent Publication Nos. 45-4554 and 49-5614,
JP-A-60-176834 and JP-A-60-203430
And JP-A-62-115035. The dope is preferably cast on a drum or band having a surface temperature of 10 ° C. or less. It is preferable to dry the film by blowing it for 2 seconds or more. The obtained film is peeled off from the drum or band, and further heated at 100 to 160 ° C.
It is also possible to evaporate the residual solvent by drying with a high-temperature air having a temperature which is sequentially changed up to the above. The above method is described in Tokuhei 5-178.
No. 44 discloses this. According to this method, the time from casting to stripping can be reduced. In order to carry out this method, it is necessary that the dope gels at the surface temperature of the drum or band during casting. The solution (dope) prepared according to the present invention satisfies this condition. The thickness of the film to be manufactured is 40 to 12
The thickness is preferably 0 μm, more preferably 70 to 100 μm.

[Plasticizer] A plasticizer can be added to the polymer film in order to improve mechanical properties or to increase the drying speed. As a plasticizer,
Phosphate or carboxylate esters are used. Examples of phosphate esters include triphenyl phosphate (TPP) and tricresyl phosphate (TCC).
P) is included. Representative carboxylic esters include phthalic esters and citric esters. Examples of phthalate esters include dimethyl phthalate (DM
P), diethyl phthalate (DEP), dibutyl phthalate (DBP), dioctyl phthalate (DOP), diphenyl phthalate (DPP) and diethylhexyl phthalate (DEHP). Examples of citrate esters include O-acetyl triethyl citrate (OACT
E) and tributyl O-acetylcitrate (OACT
B) is included. Examples of other carboxylic esters include butyl oleate, methylacetyl ricinoleate,
It includes dibutyl sebacate and various trimellitate esters. Phthalate ester plasticizers (DMP, DE
P, DBP, DOP, DPP, DEHP) are preferably used. DEP and DPP are particularly preferred. The amount of the plasticizer added is preferably 0.1 to 25% by weight, more preferably 1 to 20% by weight, and most preferably 3 to 15% by weight of the amount of the polymer.

[Deterioration inhibitor] The polymer film may be added with a degradation inhibitor (eg, antioxidant, peroxide decomposer, radical inhibitor, metal deactivator, acid scavenger, amine). Good. Regarding the deterioration inhibitor, see JP-A-3-1992
No. 01, 5-1907073, 5-194789
And JP-A-5-271471 and JP-A-6-107854. The amount of the deterioration inhibitor added is preferably 0.01 to 1% by weight, more preferably 0.01 to 0.2% by weight of the solution (dope) to be prepared. If the amount is less than 0.01% by weight, the effect of the deterioration inhibitor is hardly recognized. 1% by weight
Exceeding the limit may cause bleed-out (bleeding-out) of the deterioration inhibitor to the film surface. Particularly preferred examples of the deterioration inhibitor include butylated hydroxytoluene (BHT) and tribenzylamine (TBA).

[Stretching Treatment] The polymer film is further subjected to a stretching treatment to obtain a refractive index (refractive index n in the in-plane slow axis direction).
It is preferable to adjust x, the refractive index ny in the direction perpendicular to the in-plane slow axis, and the refractive index nz in the thickness direction. When the intrinsic birefringence is positive, the refractive index increases in the direction in which the polymer chains are oriented. When such a polymer having a positive intrinsic birefringence is stretched, the refractive index usually becomes nx> ny ≧ nz. This is because the x-component of the polymer chain oriented in the in-plane direction is increased by stretching, and the z-component is minimized. Thus, 1 ≦ (nx−nz) / (nx−
ny) can be satisfied. Further, (nx
In order to satisfy the relationship of −nz) / (nx−ny) ≦ 2, the refractive index may be adjusted by controlling the stretching ratio of uniaxial stretching or by performing unbalanced biaxial stretching.
Specifically, uniaxial stretching or unbalanced biaxial stretching is performed so that the maximum stretching ratio SA and the stretching ratio SB in the direction perpendicular to the stretching direction satisfy the relationship of 1 <SA / SB ≦ 3. What is necessary is just to implement. The stretching ratio is a relative value when the length before stretching is set to 1. SB may be a value less than 1 (in other words, contract). If the relationship of the above expression is satisfied, SB may be a value less than 1. Further, the stretching ratio is such that the front retardation is λ /
4 or λ / 2. The stretching process may be a simultaneous process or a sequential process.

[Circularly Polarizing Plate] The λ / 4 plate and the polarizing film are
A circularly polarizing plate is obtained by laminating such that the angle between the in-plane slow axis of the four plates and the polarizing axis of the polarizing film is substantially 45 °.
Substantially 45 ° means 40 to 50 °. The angle between the in-plane slow axis of the λ / 4 plate and the polarization axis of the polarizing film is preferably 41 to 49 °, more preferably 42 to 48 °, and 43 to 47 °. Is more preferable, and most preferably 44 to 46 °. The polarizing film includes an iodine-based polarizing film, a dye-based polarizing film using a dichroic dye, and a polyene-based polarizing film. The iodine-based polarizing film and the dye-based polarizing film are generally manufactured using a polyvinyl alcohol-based film. The polarization axis of the polarizing film corresponds to a direction perpendicular to the stretching direction of the film. It is preferable to provide a transparent protective film on the surface of the polarizing film opposite to the λ / 4 plate. It is preferable to provide an anti-reflection layer as the outermost layer.

[Transparent Conductive Film] The surface resistivity of the polymer film for antistatic purposes is preferably 10 ¹² Ω / □ or less, more preferably 10 ¹¹ Ω / □ or less, and more preferably 10 ¹⁰ Ω / □. □ It is particularly preferred that it is not more than.
It is sufficient that at least one surface of the polymer film has the above surface resistivity.

In order to set the surface resistivity of the polymer film to the above value, a transparent conductive film may be provided using a surfactant or a dispersion of conductive fine particles, or the whole or a part of the polymer film may be provided. Although conductivity may be imparted to the substrate, it is more preferable to provide a transparent conductive film. The transparent conductive film may be provided by coating,
It may be provided by co-casting at the time of film casting. Further, a transparent conductive film may be formed by a vacuum film forming method such as sputtering, vacuum evaporation, or ion plating. A transparent conductive film may be provided on one side of the film, or may be provided on both sides. Also, these methods can be used in combination.

Surfactants used as the transparent conductive film include nonionic and ionic (anions, cations,
Betaine) can be used. Further, a fluorine-based surfactant is also preferably used as a coating agent in an organic solvent or as an antistatic agent.

Preferred nonionic surfactants include:
Polyoxyethylene, polyoxypropylene, polyoxybutylene, a surfactant having a nonionic hydrophilic group of polyglycidyl and sorbitan, specifically, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene Ethylene-polyoxypropylene glycol, polyhydric alcohol fatty acid partial ester, polyoxyethylene polyhydric alcohol fatty acid partial ester, polyoxyethylene fatty acid ester, polyglycerin fatty acid ester, fatty acid diethanolamide, triethanolamine fatty acid partial ester can be exemplified. .

The anionic surfactants include carboxylate, sulfate, sulfonate and phosphate ester salts. Representative examples are fatty acid salt, alkylbenzene sulfonate, alkylnaphthalene sulfonate,
Alkyl sulfonate, α-olefin sulfonate, dialkyl sulfosuccinate, α-sulfonated fatty acid salt, N-methyl-N-oleyltaurine, petroleum sulfonate, alkyl sulfate, sulfated oil, polyoxyethylene alkyl Ether sulfate, polyoxyethylene alkyl phenyl ether sulfate, polyoxyethylene styrenated phenyl ether sulfate, alkyl phosphate, polyoxyethylene alkyl ether phosphate,
And naphthalene sulfonate formaldehyde condensate.

As the cationic surfactant, an amine salt,
Examples thereof include quaternary ammonium salts, pyridum salts and the like, and primary to tertiary fatty amine salts, quaternary ammonium salts (tetraalkylammonium salts, trialkylbenzylammonium salts, alkylpyridium salts, alkylimidazolium salts and the like) ).

Examples of the amphoteric surfactant include carboxybetaine and sulfobetaine, such as N-trialkyl-N-carboxymethylammonium betaine and N-trialkyl-N-sulfoalkyleneammonium betaine.

These surfactants are described in Application of Surfactants (Koshobo, Takao Karimei, published on September 1, 1980). In the present invention, a preferred surfactant is not particularly limited in its use amount, and any surfactant may be used as long as desired surfactant properties can be obtained. The amount of the surfactant to be applied is preferably 0.02 to 1000 mg, preferably 0.05 to 200 mg per 1 m ² .

Specific examples of the surfactant will be described below. Here, -C ₆ H _4- represents a phenylene group. _{WA-1: C 12 H 25} (OCH 2 CH 2) 10 OH WA-2: C 9 H 19 -C 6 H 4 - (OCH 2 CH 2) 12
OH WA-3: poly (degree of polymerization 20) oxyethylene sorbitan monolaurate WA-4: sodium dodecylbenzenesulfonate WA-5: sodium tri (isopropyl) naphthalene sulfonate WA-6: sodium dodecyl sulfate WA-7: α -Sulfasuccinic acid di (2-ethylhexyl) ester sodium salt WA-8: Cetyltrimethylammonium chloride WA-9: C ₁₁ H ₂₃ CONHCH ₂ CH ₂ N ⁺ (C
H _{3) 2} -CH ₂ COO ^-

WA-10: C ₈ F ₁₇ SO ₂ N (C
_{3 H 7) (CH 2 CH} 2 O) 16 H WA-11: C 8 F 17 SO 2 N (C 3 H 7) CH 2 CO
_{OK WA-12: C 7 F} 15 COONH4 WA-13: C 8 F 17 SO 3 K WA-14: C 8 F 17 SO 2 N (C 3 H 7) (CH 2 CH 2 O) 4 (CH 2) ₄ SO ₃ Na WA-15: C ₈ F ₁₇ SO ₂ N (C ₃ H ₇ )-(CH ₂ ) ₃ -N (+) (CH ₃ ) ₃ .I
(-) WA-16: C 8 F 17 SO 2 N (C 3 H 7) CH 2 CH 2 CH 2 -N (+) (CH 3) 2 -CH
₂ COO (-) WA-17: C ₈ F ₁₇ CH ₂ CH ₂ O (CH ₂ CH ₂ O) ₁₆ H WA-18: C ₈ F ₁₇ CH ₂ CH ₂ O (CH ₂ ) ₃ -N (+) (CH ₃ ) ₃ · I (-) WA-19: H (CF ₂ ) ₈ CH ₂ CH ₂ OCOCH ₂ CH (SO ₃ ) COOCH ₂ CH ₂ CH ₂
CH ₂ (CF) ₈ H WA-20: H (CF ₂ ) ₆ CH ₂ CH ₂ O (CH ₂ CH ₂ O) ₁₆ H WA-21: H (CF ₂ ) ₈ CH ₂ CH ₂ O (CH ₂ ) ₃ -N (+) (CH ₃ ) ₃ · I (-) WA-22: H (CF ₂ ) ₈ CH ₂ CH ₂ OCOCH ₂ CH (SO ₃ ) COOCH ₂ CH ₂ CH _{2
CH 2 C 8 F 17 WA-} 23: C 9 F 17 -C 6 H 4 -SO 2 N (C 3 H 7) (CH 2 CH 2 O) 16 H WA-24: C 9 F 17 -C 6 H ₄ -SO ₂ N (C ₃ H ₇ )-(CH ₂ ) ₃ -N (+) (CH ₃ )
₃・ I (-)

As a method of applying the conductive fine particle dispersion,
Is basically at least one or more metals and
Is a layer containing fine particles consisting of metal oxides and metal nitrides
Consists of As fine particles composed of one or more metals,
Gold, silver, copper, aluminum, iron, nickel, palladium
Metal, platinum, etc., or their alloys.
You. Particularly preferred is silver, and furthermore, palladium is preferable from the viewpoint of weather resistance.
Platinum and silver alloys are preferred. As the content of palladium
Is preferably 5 to 30% by weight.
Poor weather, conductivity decreases as palladium increases
You. As a method for producing metal fine particles, a low vacuum evaporation method is used.
The method of preparing fine particles and the aqueous solution of metal salt
Lazine, boron hydride, hydroxyethylamine
Of metal colloid to be reduced by reducing agent such as amine
Is mentioned. As a metal oxide, In_TwoO_ThreeSystem (Sn
Dope), SnO_Two(Dope products such as F and Sb
), ZnO-based (including doped products such as Al and Ga),
TiO _Two, Al_TwoO_Three, SiO_Two, MgO, BaO, MoO
_Three, V_TwoO_FiveOr a composite thereof.
Examples of the metal nitride include TiN.

The average particle size of these conductive fine particles is 1.0 to 1.0.
700 nm is preferred, 2.0 to 300 nm is more preferred, and 5.0 to 100 nm is most preferred. If the particle size is too large, light absorption by the conductive fine particles increases,
For this reason, the haze increases at the same time as the light transmittance of the particle layer decreases, and when the average particle diameter of these conductive fine particles is less than 1 nm, dispersion of the fine particles becomes difficult,
Since the surface resistance of the fine particle layer rapidly increases, it is not possible to obtain a coating having a low resistance enough to achieve the object of the present invention.

The conductive fine particle layer can be formed by applying a coating solution in which conductive fine particles are dispersed in a solution mainly composed of water or an organic solvent. Before application, surface treatment or undercoating can be applied. As the surface treatment,
For example, a corona discharge treatment, a glow discharge treatment, a chromic acid treatment (wet method), a flame treatment, a hot air treatment, an ozone / ultraviolet irradiation treatment and the like can be mentioned. Examples of the material of the undercoat layer include, but are not particularly limited to, copolymers such as vinyl chloride, vinylidene chloride, butadiene, (meth) acrylate, and vinyl ester, and water-soluble polymers such as latex and gelatin. For stabilizing the dispersion of the conductive fine particles, a solution mainly composed of water is preferable, and as a solvent that can be mixed with water, ethyl alcohol, n-propyl alcohol,
Alcohols such as i-propyl alcohol, butyl alcohol, methyl cellosolve and butyl cellosolve are preferred. The application amount of the conductive fine particles is 10 to 1000
mg / m ² is preferable, 20 to 500 mg / m ² is more preferable, and 50 to 150 mg / m ² is most preferable.
If the coating amount is small, the conductivity cannot be obtained, and if the coating amount is large, the transmittance is poor.

The transparent conductive layer may contain a binder or may not contain a binder and may be formed substantially only of conductive fine particles. When a binder is used, the material is not particularly limited, but a hydrophilic binder, a hydrophobic binder, or latex can be used. As the hydrophilic binder, gelatin, gelatin derivatives, agar, sodium alginate, starch, polyvinyl alcohol, polyacrylic acid copolymer,
Maleic anhydride copolymer, carboxymethyl cellulose, carboxyethyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose and the like. As the hydrophobic binder, cellulose esters (for example, nitrocellulose, diacetylcellulose, triacetylcellulose, methylcellulose), vinyl chloride,
Vinyl-based polymers including vinylidene chloride and vinyl acrylate, and polymers such as polyamide and polyester.

Heat treatment or water treatment can be performed to improve the conductivity and the transparency of the transparent conductive layer. The heat treatment depends on the heat resistance of the polymer film, but is preferably 150 ° C. or lower. 100 ° C to 150 ° C is preferred. At 150 ° C or higher, the polymer film is likely to be deformed by heat.
When the temperature is lower than 00 ° C., the effect of the heat treatment is hardly obtained, and a long processing time is required.

The heat treatment is preferably carried out while passing through a heating zone in a web state, since a uniform treatment can be achieved. The stay time can be adjusted by the length of the heating zone and the transport speed. It is also possible to heat the rolled film in a thermostat, but it is necessary to set the time in consideration of the variation in heat conduction.

Further, prior to the heat treatment, the heat treatment can be further efficiently performed by subjecting the transparent conductive layer to a water treatment such as washing with water. Water treatment such as water washing includes application of only water by a normal application method, specifically, dip coating, application of water by a wire bar, and the like. In addition, water is applied to the transparent conductive layer by spraying or showering. There is a way. After water is applied to the transparent conductive layer, excess water can be scraped off with a wire bar or a rod bar or with an air knife as necessary.

By these water treatments, the surface resistance of the transparent conductive tank after the heat treatment can be further reduced, and in addition, the transmittance is increased, the transmission spectrum is flattened, and the reflectance after the anti-reflection layer is laminated. The effect on the reduction of the amount becomes significant.

As a vacuum film forming method, a method described in “New Development of Transparent Conductive Film”, supervised by CMC and Yutaka Sawada, “Monthly Display”, September 1999, can be used. As the metal oxide to be formed, In ₂ O ₃ (including doped products such as Sn and ITO), SnO ₂ (including doped products such as F and Sb), ZnO (including doped products such as Al and Ga) or these And a composite product of In ₂ O ₃ -ZnO. Examples of the metal nitride include TiN. Further, a film may be formed together with silver or the like.

When a film is formed on a polymer film by sputtering or the like, the surface thereof is made of a fluororesin, an acrylic resin,
It is preferable to coat with a polymer such as a silicon-based resin, a propylene-based resin, or a vinyl-based resin, or with an inorganic substance such as SiO ₂ , TiO ₂ , ZrO ₂ , and SnO ₂ . The coating thickness is preferably from 10 nm to 100 μm, more preferably from 10 nm to 50 μm, and particularly preferably from 10 nm to 10 μm. It is preferable to cool the substrate during sputtering or the like. It is preferably −30 ° C. or more and 30 ° C. or less, and more preferably −3 ° C.
The temperature is from 0 ° C to 20 ° C, particularly preferably from -30 ° C to 10 ° C. As a method for forming a film mainly containing indium oxide by a sputtering method, reactive sputtering using a metal target containing indium as a main component or a target that is a sintered body mainly containing syndium oxide is used. it can. The latter is preferred for controlling the reaction. In the reactive sputtering method, an inert gas such as argon is used as a sputtering gas, and oxygen is used as a reactive gas. As a discharge type, DC magnetron sputtering, RF magnetron sputtering, or the like can be used. As a method for controlling the flow rate of oxygen, it is preferable to use a plasma emission monitor method.

The light transmittance of the polymer film provided with the transparent conductive layer is preferably 50% or more.
%, More preferably 70% or more, and most preferably 80% or more.

[Reflective Liquid Crystal Display Device] The retardation plate, circularly polarizing plate, and touch panel of the present invention can be used in combination with various display devices. For example, a cathode ray tube (CRT), a plasma display (PD)
P), Field Emission Display (FE)
D), inorganic EL devices, organic EL devices, liquid crystal display devices, and the like. By using the retardation plate and the circularly polarizing plate of the invention, reflection of external light from these display devices can be reduced. Among these display devices, it is preferable to use them in combination with a liquid crystal display device, and it is particularly preferable to use them in a reflection type liquid crystal display device. FIG. 1 is a schematic diagram showing a basic configuration of a reflection type liquid crystal display device. The reflective liquid crystal display device shown in FIG. 1 includes, in order from the bottom, a lower substrate (1), a reflective electrode (2), a lower alignment film (3), a liquid crystal layer (4), an upper alignment film (5), and a transparent electrode ( 6), an upper substrate (7), a λ / 4 plate (8), and a polarizing film (9). The lower substrate (1) and the reflection electrode (2) constitute a reflection plate. Lower alignment film (3)-
The upper alignment film (5) forms a liquid crystal cell. λ / 4 plate (8)
Can be arranged at any position between the reflector and the polarizing film (9). In the case of color display, a color filter layer is further provided. The color filter layer is preferably provided between the reflective electrode (2) and the lower alignment film (3) or between the upper alignment film (5) and the transparent electrode (6). A reflective plate may be separately attached using a transparent electrode instead of the reflective electrode (2) shown in FIG. A metal plate is preferable as the reflector used in combination with the transparent electrode. If the surface of the reflector is smooth, only the specular reflection component may be reflected and the viewing angle may be narrowed. Therefore, it is preferable to introduce an uneven structure (described in Japanese Patent No. 275620) on the surface of the reflector. When the surface of the reflection plate is flat (instead of introducing an uneven structure on the surface), a light diffusion film may be attached to one side (cell side or outside) of the polarizing film.

The liquid crystal mode to be used is not particularly limited.
sted Nematic) type, HAN (Hybrid Aligned Nematic)
It is preferably of a type or a GH (Guest-Host) type.
The twist angle of the TN type liquid crystal cell is preferably from 40 to 100 °, more preferably from 50 to 90 °, and most preferably from 60 to 80 °.
The value of the product (Δnd) of the refractive index anisotropy (Δn) of the liquid crystal layer and the thickness (d) of the liquid crystal layer is preferably 0.1 to 0.5 μm, and 0.2 to 0.4 μm. It is more preferred that there be. The twist angle of the STN type liquid crystal cell is 180
To 360 °, preferably 220 to 270 °
゜ is more preferable. The value of the product (Δnd) of the refractive index anisotropy (Δn) of the liquid crystal layer and the thickness (d) of the liquid crystal layer is preferably 0.3 to 1.2 μm.
More preferably, it is 5 to 1.0 μm. HAN
In the type liquid crystal cell, the liquid crystal is substantially vertically aligned on one substrate, and the pretilt angle on the other substrate is 0 to 4.
It is preferably 5 °. The refractive index anisotropy of the liquid crystal layer (Δ
The value of the product (Δnd) of (n) and the thickness (d) of the liquid crystal layer is
The thickness is preferably from 0.1 to 1.0 μm, and more preferably from 0.3 to 0.8 μm. The substrate on which the liquid crystal is vertically aligned may be a substrate on the reflection plate side or a substrate on the transparent electrode side.

In the GH type liquid crystal cell, the liquid crystal layer is composed of a mixture of a liquid crystal and a dichroic dye. When both the liquid crystal and the dichroic dye are rod-shaped compounds, the director of the liquid crystal and the major axis direction of the dichroic dye are parallel. When the orientation state of the liquid crystal changes due to the application of a voltage, the long axis direction of the dichroic dye changes similarly to the liquid crystal. As the GH type liquid crystal cell, a Heilmoir type, a White-Taylor type using cholesteric liquid crystal, a two-layer type, and a type using a λ / 4 plate are known. The present invention is particularly advantageously applicable to a system using a λ / 4 plate. A guest-host reflection type liquid crystal display device having a λ / 4 plate is disclosed in JP-A-6-2.
No. 22350, No. 8-36174, No. 10-2683
No. 00, No. 10-292175, No. 10-29330
No. 1, No. 10-319776, No. 10-319442
No., No. 10-325595, No. 10-333138
And JP-A-11-38410. λ /
The four plates are provided between the liquid crystal layer and the reflector. The alignment state of the liquid crystal includes horizontal alignment and vertical alignment. Vertical alignment is preferred over horizontal alignment. The dielectric anisotropy of the liquid crystal is preferably negative. For the polarizing film, an iodine-based polarizing film,
There are a dye-based polarizing film using a dichroic dye and a polyene-based polarizing film. The iodine-based polarizing film and the dye-based polarizing film are generally manufactured using a polyvinyl alcohol-based film. The polarization axis of the polarizing film corresponds to a direction perpendicular to the stretching direction of the film. The reflection type liquid crystal display device can be used in a normally white mode in which a bright display is performed when the applied voltage is low and a dark display is performed when the applied voltage is high. . Normally white mode is preferred.

Example 1 (Preparation of Retardation Plate) At room temperature, average acetylation degree was 59.7.
% Cellulose acetate 120 parts by weight, the following letter
1.2 parts by weight of a phase raising agent, 9.36 parts by weight of triphenylene phosphate, 4.68 parts by weight of biphenyldiphenyl phosphate, 2.0 parts by weight of tribenzylamine, 538.2 parts by weight of methylene chloride, 4 parts by weight of methanol
A solution (dope) was prepared by mixing 6.8 parts by weight.

[0067]

Embedded image

The obtained dope was cast on a stainless steel band, and the film was dried until it had self-supporting property, and then was peeled off from the band. The residual volatile matter at that time was 30% by weight. Thereafter, the film was dried at 120 ° C. for 15 minutes to reduce the residual volatile content to 2% by weight or less, and then stretched at 130 ° C. in a direction parallel to the casting direction. The direction perpendicular to the stretching direction was allowed to shrink freely. After stretching, the film was dried at 120 ° C. for 30 minutes as it was, and then the stretched film was taken out. The residual solvent amount after stretching was 0.1% by weight.

(Coating of Transparent Conductive Film) After one surface of the obtained film was subjected to corona treatment, a transparent conductive film having the following composition was coated.

1) Preparation of conductive fine particle dispersion (tin oxide-antimony oxide composite dispersion) 230 parts by weight of stannic chloride hydrate and antimony trichloride 2
3 parts by weight were dissolved in 3000 parts by weight of ethanol to obtain a homogeneous solution. To this solution, a 1N aqueous sodium hydroxide solution was added dropwise until the solution reached pH 3, thereby obtaining a coprecipitate of colloidal stannic oxide and antimony oxide. The obtained coprecipitate was left at 50 ° C. for 24 hours to obtain a red-brown colloidal precipitate. The average particle size was 0.05 μm. The reddish brown colloidal precipitate was separated by centrifugation. Water was added to the precipitate to remove excess ions, and the precipitate was washed with water by centrifugation. This operation was repeated three times to remove excess ions. 200 parts by weight of the colloidal precipitate from which excess ions have been removed are redispersed in 1500 parts by weight of water and sprayed into a baking furnace heated to 500 ° C. to give a bluish average particle diameter of 0.005 μm
To obtain fine particles of a stannic oxide / antimony oxide composite. The resistivity of the fine particle powder was 25 Ω · cm.
A mixture of 40 parts by weight of the fine particle powder and 60 parts by weight of water is p
H7.0, and after coarse dispersion with a stirrer, a horizontal sand mill (Dynomill, Willy A. Backfen AG)
The dispersion was adjusted until the residence time became 30 minutes. The average particle size as a secondary particle aggregate was 0.05 μm.

2) Coating of Back First Layer (Transparent Conductive Film) The following formulation was applied so that the dry film thickness was 0.2 μm.
Dry at 115 ° C. for 30 seconds. In addition, the following weight part shows solid content weight.

<< Transparent Conductive Conductive Film Coating Composition >>分散 Conductive fine particle dispersion (SnO ₂ / Sb ₂ O ₃ , 0.05 μm) 7 Parts by weight polyoxyethylene sorbitan monolaurate (the number of oxyethylenes: 20) 0.3 part by weight water 89 parts by weight gelatin 1 part by weight sorbitol polyglycidyl ether 1 part by weight ──────────── ────────────────────────

The thickness of the film thus obtained was 108 μm. The surface resistivity of the transparent conductive film was measured in an environment of 25 ° C. and 20% RH.
It was ⁹ Ω / □. The surface resistivity was measured by a 1 cm × 5 cm parallel electrode method. The light transmittance of the obtained film was 91%. The obtained cellulose acetate film (retardation plate) was subjected to an ellipsometer (M-1).
50, manufactured by JASCO Corporation) at a wavelength of 450 nm,
The retardation values (Re) at 550 nm and 590 nm were measured.
nm, 137.5 nm, and 142.7 nm. Therefore, this cellulose acetate film achieved λ / 4 in a wide wavelength range.

From the measurement of the refractive index by the Abbe refractometer and the measurement of the angle dependence of the retardation,
The refractive index nx in the in-plane slow axis direction, the refractive index ny in the direction perpendicular to the slow axis in the plane, and the refractive index nz in the thickness direction at 50 nm are determined, and (nx-nz) / (nx-ny) is obtained. The calculated value was 1.50. In addition, temperature 2
Under conditions of 5 ° C. and 10% relative humidity, 20 cm × 20 cm
The retardation plate cut into pieces was rubbed well with a nylon cloth, and the adhesion of ash to cigarettes was examined. When visually evaluated in the following four grades, it was ranked A. A: No dust was observed. B: Some dust was observed. C: Dust was observed considerably. D: Dust was noticeably observed.

Example 2 (Preparation of Retardation Plate) A stretched film was prepared in the same manner as in Example 1, and a transparent conductive film was applied as follows.

[0076] 1) Preparation of silver adjustment 30% iron sulfate palladium colloidal dispersion _{(II) FeSO4 · 7H 2 O} , 40% citric acid (Coating of the transparent conductive film), mixed, held at 20 ° C., stirred While adding a 10% solution of silver nitrate and palladium nitrate (mixed at a molar ratio of 9/1) at a rate of 200 ml / min, the mixture was centrifuged and washed repeatedly with water. Pure water was added so as to obtain a silver palladium colloidal dispersion. As a result of TEM observation, the particle diameter of the obtained silver colloid particles was about 9 to 12 nm.
Met. As a result of measurement by ICP, the ratio of silver to palladium was the same as the charging ratio of 9/1.

2) Preparation of Silver Colloid Coating Solution To 100 g of the silver colloid dispersion solution, i-propyl alcohol was added, ultrasonically dispersed, and filtered with a polypropylene filter having a pore size of 1 μm to prepare a coating solution.

3) Preparation of Coating Solution L-1 for Overcoating A mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPH
A, 2 g of Nippon Kayaku Co., Ltd., 80 mg of photopolymerization initiator (Irgacure 907, Ciba-Geigy) and 30 m of photosensitizer (Kayacure DETX, Nippon Kayaku Co., Ltd.)
g was added to and dissolved in a mixed solution of 38 g of methyl isopropyl ketone, 38 g of 2-butanol and 19 g of methanol.
After stirring the mixture for 30 minutes, it was filtered through a polypropylene filter having a pore size of 1 μm to prepare a coating solution for overcoating.

4) Formation of Transparent Conductive Laminate After applying a corona treatment to the stretched film, the above-mentioned silver colloid coating solution was applied using a wire bar so as to have an application amount of 70 mg / m ² , and dried at 40 ° C. Water fed by a pump was sprayed on the silver colloid-coated surface, excess water was removed with an air knife, and a treatment was carried out for 5 minutes while being conveyed in a heating zone at 120 ° C. Next, the overcoat coating liquid L-1 was applied to a thickness of 80 nm, dried, and heat-treated at 120 ° C. for 2 hours, and then irradiated with ultraviolet rays to cure the coating film.

The thickness of the film thus obtained was 102 μm. The surface resistivity of the transparent conductive film was measured by a four-terminal method at 25 ° C. and 20% RH. As a result, it was 400 Ω / □, and the light transmittance was 71%.
%Met. The obtained cellulose acetate film (retardation film) was analyzed using an ellipsometer (M-15).
0, manufactured by JASCO Corporation, wavelength 450 nm, 5
When the retardation values (Re) at 50 nm and 590 nm were measured, each was 116.4 n.
m, 132.0 nm and 137.0 nm. Therefore, this cellulose acetate film achieved λ / 4 in a wide wavelength range.

From the measurement of the refractive index by the Abbe refractometer and the measurement of the angle dependence of the retardation,
The refractive index nx in the in-plane slow axis direction, the refractive index ny in the direction perpendicular to the slow axis in the plane, and the refractive index nz in the thickness direction at 50 nm are determined. The calculated value was 1.52. Further, a test with dust was performed in the same manner as in Example 1, and it was ranked A.

Example 3 (Preparation of Retardation Plate) A stretched film was prepared in the same manner as in Example 1, and a transparent conductive film was applied as follows. (Application of Transparent Conductive Film) 1) ITO Sputtering on Cellulose Triacetate A UV-curable polyfunctional methacrylic resin (Z7503 manufactured by JSR) was applied on a stretched film so as to have a thickness of 3 μm. Next, ITO was removed by DC magnetron sputtering.
A film was formed with a thickness of 5 nm.

The thickness of the film thus obtained was 103 μm. The surface resistivity of the transparent conductive film was measured by a four-terminal method in an environment of 25 ° C. and 20% RH. As a result, it was 230 Ω / □, and the light transmittance was 89%. Using an ellipsometer (M-150, manufactured by JASCO Corporation), the wavelength of the obtained cellulose acetate film (retardation film) was 450 nm, 550 nm,
Values at 590 and 590 nm (Re)
Were measured, 119.0 nm, 13
It was 5.1 nm and 140.1 nm. Therefore, this cellulose acetate film has a λ /
4 had been achieved.

From the measurement of the refractive index by the Abbe refractometer and the measurement of the angle dependence of the retardation,
The refractive index nx in the in-plane slow axis direction, the refractive index ny in the direction perpendicular to the slow axis in the plane, and the refractive index nz in the thickness direction at 50 nm are determined. The calculated value was 1.51. Further, a test with dust was performed in the same manner as in Example 1, and it was ranked A.

Example 4 (Preparation of Retardation Plate) The dry film thickness of the entire film was 200 μm.
m, a cellulose acetate film was produced in the same manner as in Example 1, except that the amount of the dope applied was changed.

(Application of Transparent Conductive Film) A transparent conductive film was applied in exactly the same manner as in Example 1. The surface resistivity of the obtained film on the transparent conductive film side was measured by the same parallel electrode method as in Example 1 in an environment of 25 ° C. and 20% RH. As a result, 5 × 1
It was ⁹ Ω / □. The light transmittance of the film was 91%. About the obtained cellulose acetate film (retardation plate), the wavelength was 450 nm and 550 nm using an ellipsometer (M-150, manufactured by JASCO Corporation).
Values at 590 and 590 nm (Re)
Were measured, 225.6 nm and 27, respectively.
It was 5.1 nm and 290.2 nm. Therefore, this cellulose acetate film has a λ /
2 had been achieved.

From the measurement of the refractive index by the Abbe refractometer and the measurement of the angle dependence of the retardation,
The refractive index nx in the in-plane slow axis direction, the refractive index ny in the direction perpendicular to the slow axis in the plane, and the refractive index nz in the thickness direction at 50 nm are determined. The calculated value was 1.54. Further, a test with dust was performed in the same manner as in Example 1, and it was ranked A.

Example 5 (Preparation of Retardation Plate) A cellulose acetate film was prepared in the same manner as in Example 1.

(Coating of Transparent Conductive Film) A coating solution having the following composition was applied to a cellulose acetate film at 28 ml / m ^2.
After coating and drying, a gelatin layer (transparent conductive film) having a thickness of 1 μm was provided.

組成 Transparent conductive film coating liquid composition 組成ゼ ラ チ ン Gelatin 0.542 parts by weight Formaldehyde 0.136 parts by weight Salicylic acid 0.160 parts by weight Acetone 39.1 parts by weight Methanol 15.8 parts by weight Methylene chloride 40.6 parts by weight Water 1.2 parts by weight C ₈ F ₁₇ SO ₂ N (C ₃ H ₇ ) (CH ₂ CH ₂ O) ₄ (CH ₂ ) ₄ SO ₃ Na (fluorinated surfactant: WA-14) 2.0 parts by weight ─────────────────────────────── ─────

The thickness of the obtained film was 80 μm. Further, the surface resistivity of the transparent conductive film side is set to 25 ° C., 20
As a result of measurement in an environment of% RH, it was 3 × 10 ⁹ Ω / □. The surface resistivity was measured by a 1 cm × 5 cm parallel electrode method. The light transmittance of the film was 91%. About the obtained cellulose acetate film (retardation plate), an ellipsometer (M-150, JASCO Corporation)
Wavelengths of 450 nm, 550 nm and 59
When the retardation values (Re) at 0 nm were measured, they were 110.2 nm, 125.0 nm, and 130.0 nm, respectively. Therefore, this cellulose acetate film achieved λ / 4 in a wide wavelength range.

From the measurement of the refractive index by the Abbe refractometer and the measurement of the angle dependence of the retardation,
The refractive index nx in the in-plane slow axis direction, the refractive index ny in the direction perpendicular to the slow axis in the plane, and the refractive index nz in the thickness direction at 50 nm are determined, and (nx-nz) / (nx-ny) is obtained. The calculated value was 1.50. Further, a test with dust was performed in the same manner as in Example 1, and it was ranked A.

Example 6 C ₈ F ₁₇ SO ₂ N (C ₃ H ₇ ) (CH ₂ CH ₂ O)
Instead of ₄ (CH ₂ ) ₄ SO ₃ Na (fluorinated surfactant: WA-14), C ₈ F ₁₇ CH ₂ CH ₂ O (CH ₂ CH ₂ O) ₁₆ H (fluorinated surfactant: WA) A retardation plate was produced in the same manner as in Example 5, except that the same amount of -17) was used.

The thickness of the obtained film was 80 μm. Further, the surface resistivity of the transparent conductive film side is set to 25 ° C., 20
As a result of measurement in an environment of% RH, it was 2 × 10 ⁹ Ω / □. The surface resistivity was measured by a 1 cm × 5 cm parallel electrode method. The light transmittance of the film was 91%. About the obtained cellulose acetate film (retardation plate), an ellipsometer (M-150, JASCO Corporation)
Wavelengths of 450 nm, 550 nm and 59
When the retardation values (Re) at 0 nm were measured, they were 111.9 nm, 127.0 nm, and 131.8 nm, respectively. Therefore, this cellulose acetate film achieved λ / 4 in a wide wavelength range.

From the measurement of the refractive index by the Abbe refractometer and the measurement of the angle dependence of the retardation,
The refractive index nx in the in-plane slow axis direction, the refractive index ny in the direction perpendicular to the slow axis in the plane, and the refractive index nz in the thickness direction at 50 nm are determined. The calculated value was 1.51. Further, a test with dust was performed in the same manner as in Example 1, and it was ranked A.

Example 7 C ₈ F ₁₇ SO ₂ N (C ₃ H ₇ ) (CH ₂ CH ₂ O)
_{4 (CH 2) 4 SO 3} Na ( fluorinated surfactant: WA-14) in _{place, H (CF 2) 8 CH} 2 CH 2 O (CH 2) 3 -N (+) (CH 3) 3 A retardation plate was produced in the same manner as in Example 5, except that the same amount of I (-) (fluorinated surfactant: WA-21) was used.

The thickness of the obtained film was 80 μm. Further, the surface resistivity of the transparent conductive film side is set to 25 ° C., 20
As a result of measurement in an environment of% RH, it was 3.5 × 10 ⁹ Ω / □. The surface resistivity was measured by a 1 cm × 5 cm parallel electrode method. The light transmittance of the film was 91%.
The obtained cellulose acetate film (retardation film) was measured for retardation values (Re) at wavelengths of 450 nm, 550 nm and 590 nm using an ellipsometer (M-150, manufactured by JASCO Corporation). , 111.5 nm, 126.5
nm and 131.2 nm. Therefore, this cellulose acetate film has a wavelength of λ / 4 in a wide wavelength range.
Had been achieved.

From the measurement of the refractive index by the Abbe refractometer and the measurement of the angle dependence of the retardation,
The refractive index nx in the in-plane slow axis direction, the refractive index ny in the direction perpendicular to the slow axis in the plane, and the refractive index nz in the thickness direction at 50 nm are determined, and (nx-nz) / (nx-ny) is obtained. The calculated value was 1.50. Further, a test with dust was performed in the same manner as in Example 1, and it was ranked A.

Comparative Example 1 (Preparation of Retardation Plate) A stretched film was prepared in exactly the same manner as in Example 1. No conductive film was applied. The thickness of the film thus obtained was 105 μm. Further, the surface resistivity of the transparent conductive film side was measured by a parallel electrode method of 1 cm × 5 cm in an environment of 25 ° C. and 20% RH.
It was 10 ¹⁵ Ω / □ or more. The light transmittance was 92%. Using an ellipsometer (M-150, manufactured by JASCO Corporation), the wavelength of the obtained cellulose acetate film (retardation film) was 450 nm, 550 nm,
Values at 590 and 590 nm (Re)
Were measured, 120.8 nm and 13 respectively.
It was 7.1 nm and 142.3 nm. Therefore, this cellulose acetate film has a λ /
4 had been achieved.

From the measurement of the refractive index by the Abbe refractometer and the measurement of the angle dependence of the retardation,
The refractive index nx in the in-plane slow axis direction, the refractive index ny in the direction perpendicular to the slow axis in the plane, and the refractive index nz in the thickness direction at 50 nm are determined, and (nx-nz) / (nx-ny) is obtained. The calculated value was 1.50. Further, when a test with dust was performed in the same manner as in Example 1, it was ranked D.

Example 8 (Production of Circularly Polarizing Plate) Transparent protective film, polarizing film and Example 1
Were laminated in this order to obtain a circularly polarizing plate. The angle between the slow axis of the retardation plate and the polarizing axis of the polarizing film is 4
Adjusted to 5 ゜. When the optical properties of the obtained circularly polarizing plate were examined, almost perfect circularly polarized light was achieved in a wide wavelength range (450 to 590 nm).

[Examples 9 to 13] (Production of Circularly Polarizing Plate) Except that the retardation plates produced in Examples 2, 3, 5 to 7 were used in place of the retardation plate produced in Example 1, In the same manner as in Example 8, a circularly polarizing plate was produced. When the optical properties of the obtained circularly polarizing plates were examined, almost perfect circularly polarized light was achieved in a wide wavelength range (450 to 590 nm).

Example 14 (Production of Reflective Liquid Crystal Display) A glass substrate provided with an ITO transparent electrode and a glass substrate provided with an aluminum reflective electrode having fine irregularities were prepared. A polyimide alignment film (SE-7) is provided on the electrode side of the two glass substrates, respectively.
992, manufactured by Nissan Chemical Industries, Ltd.) and rubbed. Two substrates were stacked via a 3.4 μm spacer so that the alignment films faced each other. The directions of the substrates were adjusted so that the rubbing directions of the two alignment films intersect at an angle of 110 °. In the gap between the substrates, a liquid crystal (MLC-62
52, manufactured by Merck & Co., Inc.) to form a liquid crystal layer. Thus, the twist angle is 70 ° and the value of Δnd is 269.
nm TN type liquid crystal cell was produced. The retardation plate produced in Example 1 was adhered to the side of the glass substrate provided with the ITO transparent electrode via an adhesive. On top of that, a polarizing plate (surface is A
(A polarizing film in which an R-processed protective film is laminated).
A 1 kHz rectangular wave voltage was applied to the manufactured reflective liquid crystal display device. Visual evaluation was performed with a white display of 1.5 V and a black display of 4.5 V. As a result, it was confirmed that neither white display nor black display had a hue and neutral gray was displayed. Next, a measuring machine (EZcontrast
160D, manufactured by Eldim), the contrast ratio of the reflected luminance was measured.
5 and the viewing angle at which the contrast ratio is 3 is 12
0 ° or more, 120 ° or more on both sides.

[Examples 15 to 19] (Production of reflection type liquid crystal display device) Instead of the retardation plate produced in Example 1, the retardation plates produced in Examples 2, 3, 5 to 7 were used. Except for the above, a reflective liquid crystal display device was manufactured in the same manner as in Example 14. A 1 kHz rectangular wave voltage was applied to the manufactured reflective liquid crystal display device. When a visual evaluation was performed with a white display of 1.5 V and a black display of 4.5 V, the reflection-type liquid crystal display devices displayed no neutral color and neutral gray in both white display and black display. Was confirmed. Next, when the contrast ratio of the reflection luminance was measured using a measuring device (EZcontrast 160D, manufactured by Eldim), the contrast ratio of all the reflection type liquid crystal display devices was 25 from the front, and the visual field having a contrast ratio of 3 was obtained. The angle was 120 ° or more up and down and 120 ° or more left and right.

[Brief description of the drawings]

FIG. 1 is a schematic diagram showing a basic configuration of a reflection type liquid crystal display device.

[Explanation of symbols]

 Reference Signs List 1 lower substrate 2 reflective electrode 3 lower alignment film 4 liquid crystal layer 5 upper alignment film 6 transparent electrode 7 upper substrate 8 λ / 4 plate 9 polarizing film

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G02F 1/13363 C08L 1:02 // C08L 1:02 G02B 1/10 Z F-term (Reference) 2H049 BA03 BA06 BA07 BA25 BA27 BA47 BB03 BB43 BB49 BB67 BC04 BC09 BC14 BC22 2H091 FA08X FA11X FA14Z FB02 FB12 GA03 GA06 KA10 2K009 AA04 BB28 CC03 CC09 CC14 CC21 CC42 DD02 DD03 DD04 DD06 DD07 EE03 4F071 AA09 AF01 AFA13AF01 BC01

Claims (14)

[Claims] A retardation value (Re450) measured at a wavelength of 450 nm of 100 to 125 nm;
And a retardation value (R
e590) is from 120 to 160 nm, and Re590
-A retardation plate comprising a single polymer film satisfying a relationship of Re450 ≥ 2 nm, wherein at least one surface of the film has a surface resistivity of 10 ¹² Ω / □ or less. 2. A retardation value (Re450) measured at a wavelength of 450 nm is from 108 to 120 nm,
The retardation value (Re5) measured at a wavelength of 550 nm
50) is 125 to 142 nm, and the wavelength is 590 nm.
Retardation value (Re590) measured at 130
To 152 nm and Re590-Re55
The retardation plate according to claim 1, wherein a relationship of 0 ≧ 2 nm is satisfied. 3. The refractive index nx in the in-plane slow axis direction, the refractive index ny in the direction perpendicular to the slow axis in the plane, and the refractive index nz in the thickness direction are 1 ≦ (nx−nz) / (nx The retardation plate according to claim 1, wherein a relationship of -ny) ≤2 is satisfied. 4. The retardation film according to claim 1, wherein the polymer film is a cellulose ester film. 5. The cellulose ester film according to claim 1, wherein the polymer film is a cellulose ester film containing a compound having at least two aromatic rings and having a molecular structure that does not hinder the conformation of the two aromatic rings. Phase difference plate. 6. A circle in which a retardation plate and a linear polarizing film are laminated such that the angle between the in-plane slow axis of the retardation plate and the polarization axis of the linear polarizing film is substantially 45 °. A polarizing plate,
The retardation plate has a retardation value (Re450) measured at a wavelength of 450 nm of 100 to 125 nm, and a retardation value (Re59) measured at a wavelength of 590 nm.
0) is from 120 to 160 nm, and Re59
A circularly polarizing plate comprising a single polymer film satisfying a relationship of 0-Re450 ≧ 2 nm, wherein the surface resistivity of at least one surface of the film is 10 ¹² Ω / □ or less. 7. A retardation value (Re450) measured at a wavelength of 450 nm is from 200 to 250 nm,
And a retardation value (R
e590) is 240 to 320 nm, and Re590
-A retardation plate comprising a single polymer film satisfying a relationship of Re450 ≥ 2 nm, wherein at least one surface of the film has a surface resistivity of 10 ¹² Ω / □ or less. 8. A retardation value (Re450) measured at a wavelength of 450 nm is from 216 to 240 nm,
The retardation value (Re5) measured at a wavelength of 550 nm
50) is from 250 to 284 nm and the wavelength is 590
The retardation value (Re590) measured in nm is 2
60-304 nm, and Re590-Re
The retardation plate according to claim 7, which satisfies a relationship of 550 ≧ 2 nm. 9. The refractive index nx in the in-plane slow axis direction, the refractive index ny in the direction perpendicular to the slow axis in the plane, and the refractive index nz in the thickness direction are 1 ≦ (nx−nz) / (nx The retardation plate according to claim 7, which satisfies a relationship of -ny) ≤2. 10. The retardation film according to claim 7, wherein the polymer film is a cellulose ester film. 11. The cellulose ester film according to claim 7, wherein the polymer film is a cellulose ester film containing a compound having at least two aromatic rings and having a molecular structure that does not hinder the conformation of the two aromatic rings. Phase difference plate. 12. A reflection type liquid crystal display device using the phase difference plate according to claim 1. 13. A reflective liquid crystal display device using the circularly polarizing plate according to claim 6. 14. A reflection type liquid crystal display device using the retardation plate according to claim 7.