JP2002040243A - Circularly polarizing plate, touch panel and reflective liquid crystal display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a thin circularly polarizing plate having high surface hardness and improved antistatic property and overcoming a problem of sticking of dust. SOLUTION: In a circularly polarizing plate composed of a transparent substrate film, a polarizing element and a quarter-wave plate laminated in this order, a hard coat polyester film having a resin layer which is polymerizable with an active energy beam arranged on at least one surface of it and of which the surface elastic modulus is >=5 GPa and <=15 GPa is used as the transparent substrate film. Furthermore, a sheet of a polymer film having 100-125 nm retardation value measured at 450 nm wavelength (Re450) and 120-160 nm retardation value measured at 590 nm wavelength (Re590) and satisfying an inequality Re590-Re450>=2 nm is used as the quarter-wave plate.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a circularly polarizing plate, a touch panel and a reflection type liquid crystal display. In particular, the present invention
The present invention relates to a circularly polarizing plate effective for an inner touch panel.

[0002]

2. Description of the Related Art Touch panels include a resistive type, an optical type, a capacitive type, an ultrasonic type and an electromagnetic induction type. The resistive film method enables external input simply by being mounted on the surface of a display, and is currently used as a mainstream method. In recent years, under the name of the IT revolution, mobile phones,
The portable terminal market represented by PDA and PDA has grown remarkably, and visibility under sunlight and thin and light weight have been strongly demanded. Resistive touch panel
A glass substrate with a transparent conductive layer and a transparent base film with a hard coat are held through a space, and are mounted on the display surface. There are two air layers, and there is a problem that visibility is significantly reduced due to reflection at each interface, and the device itself becomes thick. On the other hand, Japanese Patent Application Laid-Open No. 5-127822 and Monthly Display, January 1999, p. 69 propose an inner type touch panel in which the function of a resistive type touch panel is inserted between a polarizing plate and a liquid crystal cell. . According to this method, the air layer becomes one layer, and furthermore, by combining the air layer with a λ / 4 plate, interfacial reflection is significantly reduced and visibility is improved. But,
Even if it is referred to as a λ / 4 plate, most achieve λ / 4 at a certain specific wavelength, and its antireflection effect is not sufficient.

JP-A-5-27118 and JP-A-5-27118
No. 119 discloses a retardation plate in which a birefringent film having a large retardation and a birefringent film having a small retardation are laminated such that their optical axes are orthogonal to each other. If the retardation difference between the two films is λ / 4 over the entire visible light range, the retardation plate theoretically has λ over the entire visible light range.
/ 4. JP-A-10-68816 discloses that
A phase difference plate that can obtain λ / 4 in a wide wavelength region by laminating a polymer film having λ / 2 at a specific wavelength and a polymer film made of the same material and having λ / 2 at the same wavelength. Is disclosed. Japanese Patent Application Laid-Open No. H10-90521 also discloses a retardation plate capable of achieving λ / 4 in a wide wavelength region by laminating two polymer films. As the above polymer films, two stretched films of a synthetic polymer such as polycarbonate were used, so that the thickness of the apparatus could not be reduced.

Japanese Patent Application Laid-Open No. 2000-137116 discloses a wide band λ / 4 plate using one polymer film. However, when this λ / 4 plate was used for a touch panel, the antireflection 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. JP 20
JP-A-00-112666 discloses a touch panel in which visibility is further improved by using a wideband λ / 4 plate. However, when such a touch panel is used in a liquid crystal display device, the visibility is slightly improved, but the polarizing plate protective film, which is the outermost surface of the touch panel, cannot have sufficient strength as a touch panel.

[0005] 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)
Nematic), HAN (Hybrid Aligned Nematic), HP
DLC (Holographic Polymer Dispersed Liquid Cryst
Various display modes such as al) 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.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a circularly polarizing plate which is thin, has a high surface hardness, has improved antistatic performance, and eliminates the problem of dust adhesion. Another object of the present invention is to provide a touch panel that has excellent anti-reflection performance for external light and high contrast and anti-glare properties. Still another object of the present invention is to provide a reflective liquid crystal display device with improved display quality.

[0007]

The object of the present invention is to provide a circularly polarizing plate of the following (1) to (4), a touch panel of the following (4) to (5), and a reflective liquid crystal display of the following (6). Achieved. (1) A circularly polarizing plate in which a transparent base film, a polarizing element, and a λ / 4 plate are laminated in this order, wherein the transparent base film is provided with an active energy ray polymerizable resin layer on at least one surface. A hard coat polyester film in which the surface elastic modulus of the polymerizable resin layer is 5 GPa or more and 15 GPa or less, and the λ / 4 plate has a wavelength of 4
Retardation value measured at 50 nm (Re450)
Is 100 to 125 nm, the retardation value (Re590) measured at a wavelength of 590 nm is 120 to 160 nm, and Re590−Re450 ≧ 2 nm.
A circularly polarizing plate comprising a single polymer film satisfying the following relationship:

(2) The circularly polarizing plate according to (1), wherein the surface resistivity of at least one surface of the λ / 4 plate is 10 ¹² Ω / □ or less. (3) The surface resistivity of at least one surface of the λ / 4 plate is 1
Circularly polarizing plate according to 0 is ⁴ Omega / □ or less (1). (4) The λ / 4 plate has a retardation value (Re450) measured at a wavelength of 450 nm of 108 to 120 nm, and a retardation value (R450) measured at a wavelength of 550 nm.
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 circularly polarizing plate according to (1), comprising one sheet of the polymer film satisfying the relationship of 550 ≧ 2 nm.

(5) A touch panel in which two transparent conductive substrates provided with a transparent conductive film on at least one side are arranged so that the transparent conductive films face each other, and at least one of the transparent conductive substrates is provided. A touch panel comprising the circularly polarizing plate according to (1). (6) The touch panel according to (5), wherein an antireflection layer is provided on the outermost surface of the circularly polarizing plate on the transparent substrate film side. (7) A reflective liquid crystal display device equipped with the touch panel according to (5).

[0010]

DESCRIPTION OF THE PREFERRED EMBODIMENTS [Transparent base film] A transparent base film having a large surface elastic modulus has a surface elastic modulus of 5 GPa or more and 15 GPa or less, more preferably 5.5 GPa or more and 12 GPa or more.
GPa or less, more preferably 6 GPa or more and 10 GPa
The following polyester films are preferred. The surface elastic modulus is a value obtained by using a micro surface hardness tester. Specifically, a micro surface hardness tester (Fisherscope H100VP)
After contacting the sample surface with a Vickers indenter using an HCU (manufactured by Fischer Instruments), the load is increased to 1 mN in 10 seconds, and held in this state for 5 seconds. The penetration depth of the Vickers indenter at this time is defined as Dv0. Thereafter, when the load is set to 0 mN, the force (Fv) for pushing back the Vickers indenter and the penetration depth (Dv) are measured, and the inclination is defined as the surface elastic modulus. That is, when Dv is plotted on the horizontal axis and Fv is plotted on the vertical axis, Dv is 0.9 to 0.9 from Dv0.
The absolute value of the slope between × Dv0 was defined as the surface elastic modulus. This measurement was performed at 25 ° C. and 60% RH, and represented by an average value of 10 points.

[0011] Polyesters are formed from dicarboxylic acids and diols. Preferably, 5 of all dicarboxylic acid residues
0 to 100 mol% is composed of aromatic dicarboxylic acid, more preferably 70 to 100 mol% of dicarboxylic acid residues in all dicarboxylic acid residues is naphthalenedicarboxylic acid residue or / and phthalic acid. More preferably, 80 mol% or more and 100 mol% or less of dicarboxylic acid residues in all dicarboxylic acid residues are 2,6 or less.
-It is composed of a naphthalenedicarboxylic acid residue and / or a terephthalic acid residue. The diol has an ethylene glycol residue in all diol residues of 50 mol% or more and 100 mol% or more.
Mol% or less, more preferably 70 mol% or more and 100 mol% or less, and further preferably 80 mol% or less.
Not less than 100 mol%. Preferred polyesters are listed below.

(1) Homopolymer HP-1: polyethylene-2,6-naphthalate (PE
N) HP-2: polyethylene terephthalate (PET)

(2) Copolymer (composition: molar ratio) CP-1: 2,6-NDCA / TPA / EG (20/8
0/100) CP-2: 2,6-NDCA / IPA / EG (80/2
0/100) CP-3: 2,6-NDCA / TPA / EG (80/2
0/100) CP-4: TPA / EG / BPA · 2EO (100/2
5/75) CP-5: TPA / EG / CHDM / BPA · 2EO
(100/25/25/50) CP-6: TPA / EG / CHDM (100/80/2
0) (Note) NDCA: Naphthalenedicarboxylic acid TPA: Terephthalic acid IPA: Isophthalic acid BPA · 2EO: Bisphenol A ethylene oxide 2 adduct CHDM: Cyclohexanedimethanol EG: Ethylene glycol

(3) Polymer blend (composition: mass ratio) PB-1: PEN / PET (20/80) PB-2: PAr / PET (15/85) PB-3: PAr / PCT / PET (15/80) 10/7
5) PB-4: PAr / PC / PET (10/10/80) (Note) PEN: Polyethylene naphthalate PET: Polyethylene terephthalate PAr: Polyarylate PCT: Polycyclohexane dimethanol terephthalate PC: Polycarbonate

The preferred intrinsic viscosity of the polyester is 0.4
It is 0.8 to 0.8, more preferably 0.45 to 0.7, still more preferably 0.5 to 0.7. The polyester is obtained by heating the raw material dicarboxylic acid diester (usually a dimethyl ester) and a diol to 150 ° C. to 250 ° C. under atmospheric pressure in the presence of a transesterification catalyst,
The reaction is carried out for 0.5 to 5 hours while distilling off the by-produced methanol, and then the polycondensation reaction is carried out at 250 ° C. to 290 ° C. while gradually increasing the degree of vacuum from atmospheric pressure to 0.3 torr while stirring. For the synthesis method of polyester,
Polymer Experiment Vol.5 "Polycondensation and polyaddition" (Kyoritsu Shuppan, 1
980) pp. 103-136, "Synthetic Polymer V"
(Asakura Shoten, 1971) pp. 187-286, JP-A-5-163337, JP-A-3-1799052 and JP-A-3-17952
Nos. 3,420 and 1,275,628. The polymerized polyester is taken out, cooled with water, solidified into noodles, and then cut into pellets.

[0016] The transparent base film is 1 nm or more and 400 nm.
It is preferable to contain the following fine particles in an amount of 10% by mass to 60% by mass. The present invention is characterized in that extremely small fine particles are uniformly dispersed at a high concentration, and 1 to 400 nm, more preferably 5 nm in the polyester.
Or more and 200 nm or less, more preferably 10 nm or more and 1
Fine particles having a size of 00 nm or less are added in an amount of 10% by mass to 60% by mass, more preferably 15% by mass to 50% by mass, and more preferably 20% by mass to 45% by mass. If it is less than 1 nm, it is difficult to disperse and aggregated particles are formed.
If it is 0 nm or more, the haze increases, and in both cases, the transparency decreases.

Preferred fine particles include inorganic fine particles such as silica, alumina, titania, zirconia, mica, talc, calcium carbonate, barium sulfate, zinc oxide, magnesium oxide, calcium sulfate and kaolin, and organic fine particles such as cross-linked polystyrene. Can be More preferably silica, alumina, titania, zirconia, mica,
Talc, calcium carbonate. The shape may be any of an irregular shape, a plate shape, a spherical shape, and a needle shape, and two or more kinds of fine particles may be mixed and used.

These fine particles may be added together with the monomer before the polymerization of the polyester, or may be added after the polymerization of the polyester. However, in the former case, the viscosity may increase during the polymerization, and it may be difficult to control the polymerization. Therefore, the latter is more preferable because it is easy to be uniformly dispersed. These fine particles are preferably surface-modified in order to improve the wettability with the polyester. Examples of the surface modifier include coupling agents such as higher fatty acids, metal salts of higher fatty acids, higher fatty acid esters, higher fatty acid amides, silicates, titanates, and aluminates.

Prior to dispersion of the fine particles, it is preferable to add these fine particles to the melt of the oligomer of the polyester and coat the surface of the fine particles with the polyester in advance. The intrinsic viscosity of the oligomer is preferably 0.5 or more and 4 or less, more preferably 1 or more and 3 or less, and further preferably 1 or more.
It is 2 or less. The preferred ratio (P / O) of the oligomer (O) to the fine particles (P) is 1 or more and 100 or less, more preferably 3 or more and 50 or less, and more preferably 5 or more and 20 or less.

For mixing the oligomer and the fine particles, a Banbury mixer, a kneader, a roll mill, a single-screw or twin-screw extruder can be used. The mixing temperature is preferably from 100 ° C to 350 ° C, more preferably from 120 ° C to 300 ° C, and still more preferably from 150 ° C to 250 ° C. The mixing time is from 1 minute to 200 minutes, more preferably from 2 minutes to 100 minutes, even more preferably from 3 minutes to 3 minutes.
0 minutes or less is preferable.

Thereafter, the mixture is further kneaded with the polyester.
For kneading, a Banbury mixer, a kneader, a roll mill, a single-screw or twin-screw extruder can be used. The mixing temperature is 200 ° C or higher and 350 ° C or lower, more preferably 24 ° C or lower.
0 ° C or more and 340 ° C or less, more preferably 260 ° C or more and 330 ° C or less, and the mixing time is 1 minute or more and 200 minutes or less, more preferably 2 minutes or more and 100 minutes or less, and still more preferably 3 minutes or more.
The time is preferably from 30 minutes to 30 minutes.

The polyester containing fine particles may form a single-layer film, but is more preferably used in a laminated film. Specifically, the transparent base film has a thickness of 1 nm.
The film is preferably a film in which a layer (B layer) containing 10% by mass or more and 60% by mass or less of fine particles having a size of 400 nm or less is laminated on at least one surface of the polyester support (A layer).

Thus, the difference between the front and back surface elastic moduli is 0.5
GPa or more and 10 GPa or less, more preferably 0.8 GPa
a to 7 GPa, more preferably 1.0 GPa to 5
GPa or less is preferable. If the surface hardness is high on both sides, the holding force with the transport roll is reduced, and abrasion due to slip is likely to occur during film formation. Such a laminated film includes a polyester layer (B layer) containing fine particles,
A layer (B / A) may be laminated on one side of a polyester layer (A layer) having a smaller content of fine particles than the B layer.
The layers may be laminated (B / A / B ′).

The total thickness of the polyester film is 50 μm.
m or more and 300 μm or less, more preferably 80 μm
m or more and 260 μm or less, more preferably 100 μm
m or more and 250 μm or less. The thickness of layer B and layer B 'is 10
μm or more and 100 μm or less, more preferably 15 μm or less.
μm to 80 μm, more preferably 20 μm to 5
0 μm or less.

Particle size (D) of fine particles and thickness of B layer and B 'layer
The ratio (D / Tb) of (Tb) is preferably less than 1 × 10 −2 and 1 × 10 −5 or more, more preferably 5 × 10 −2 or less.
0-4 or more, more preferably 1 × 10 −3 or less
4 or more. The polyester film can be formed as follows.

(1) Drying of polyester resin The polyester pellets are dried at a temperature of 100 ° C. to 250 ° C., more preferably 130 ° C. to 200 ° C. for 5 minutes to 5 minutes.
The drying is performed for not more than an hour, more preferably for not less than 10 minutes and not more than 1 hour.

(2) Melt Extrusion The pellets for layer A, layer B and layer B 'are each melted in a single-screw or multi-screw kneading extruder. At this time, a pellet to which a desired amount of fine particles is added from the beginning may be used,
A pellet (master pellet) to which fine particles have been added in advance at a high concentration may be diluted with a pellet to which fine particles have not been added to adjust to a desired concentration. The extrusion temperature of the polyester is from 250 ° C to 350 ° C, more preferably from 260 ° C to 340 ° C, and the polyester is retained and melted for 1 minute to 30 minutes, more preferably 3 minutes to 15 minutes. After this,
It is preferable to filter the molten polymer in advance using a filter. Examples of the filter include wire mesh, sintered wire mesh, sintered metal, sand, glass fiber, and the like. Preferred filter size is 1μm or more and 30μm
It is as follows. The molten polyester is extruded from a T-die. When making a laminated film, each component is extruded using a T-die (such as a multi-manifold die) having a laminated structure. This is solidified on a casting drum of 40 ° C to 100 ° C to prepare an unstretched film. At this time,
The flatness of the film is improved by increasing the adhesion to the casting drum by using an electrostatic application method or a water film formation method (applying a fluid such as water on the casting drum to improve the adhesion between the melt and the drum). It is preferable because it can be improved. This is peeled off to form an unstretched sheet.

(3) MD stretching The unstretched sheet is stretched in the machine direction (MD). The preferred stretching ratio is 2.5 times or more and 4 times or less, more preferably 3 times or more and 4 times or less. The stretching temperature is preferably from 70 ° C to 160 ° C, more preferably from 80 ° C to 150 ° C, and even more preferably from 80 ° C to 140 ° C. The preferred stretching speed is from 10% / sec to 300% / sec, more preferably from 30% / sec to 250% / sec, even more preferably from 50% / sec to 200% / sec. Such MD stretching can be performed by transporting between a pair of rolls having different peripheral speeds.

(4) TD stretching The stretching ratio is preferably 2.5 times or more and 5 times or less, more preferably 3 times or more and 4.5 times or less, and even more preferably 3.3 times or less.
It is not less than twice and not more than 4.3 times. Stretching temperature is 75 ° C or higher and 16
5 ° C. or less, more preferably 80 ° C. or more and 160 ° C.
° C or lower, more preferably 85 ° C or higher and 155 ° C or lower. The preferred stretching speed is from 10% / sec to 300% / sec, more preferably from 30% / sec to 250% / sec, even more preferably from 50% / sec to 200% / sec.
TD stretching can be achieved by chucking the film at both ends, transporting the film into a tenter, and widening the film.

(5) Heat setting A preferable heat setting temperature is 190 ° C to 275 ° C, more preferably 210 ° C to 270 ° C, further preferably 230 ° C to 270 ° C, and a preferable processing time is 5 seconds to 180 °. 1 second or less, more preferably 10 seconds or more
It is 20 seconds or less, more preferably 15 seconds or more and 60 seconds or less. It is preferable to relax in the width direction between 0% and 10% during heat setting. It is more preferably 0% or more and 8% or less, and further preferably 0% or more and 6% or less. Such heat setting and relaxation can be achieved by chucking the film at both ends, transporting the film to the heat setting zone, and reducing the width thereof.

(6) Winding After heat setting, cooling and trimming are performed and the film is wound on a roll.
At this time, it is also preferable to apply a processing (knurling) to the end of the support. Preferred film forming width is 0.5 m or more and 10 m or less, more preferably 0.8 m or more and 8 m or less,
More preferably, it is 1 m or more and 6 m or less.

It is also preferred that the polyester support thus prepared is subjected to a surface treatment. Surface treatment is chemical treatment, mechanical treatment, corona treatment, flame treatment, UV treatment,
High-frequency treatment, glow treatment, active plasma treatment, laser treatment, mixed acid treatment, ozone oxidation treatment and the like can be mentioned. Among them, corona treatment, ultraviolet treatment, glow treatment and flame treatment are particularly effective. These can be carried out in accordance with the method described in "Invention Association Disclosure Technique, Official Technique No. 94-6023".

It is also preferable to provide an antistatic layer to the transparent base film. Specific examples and the like are described in the section of the polymer film described below.

Further, one or more primer layers can be provided in order to improve the adhesion with the layer laminated on the transparent substrate. The material of the primer layer is vinyl chloride,
Copolymers or latexes such as vinylidene chloride, butadiene, (meth) acrylate, vinyl ester,
Examples include water-soluble polymers such as gelatin.

As the hard coat used in the present invention, a known curable resin can be used, and there are a thermosetting resin, an active energy ray polymerizable resin and the like, but an active energy ray curable resin is preferable. As the thermosetting resin, there is a resin utilizing a crosslinking reaction of a prepolymer such as a melamine resin, a urethane resin, and an epoxy resin.

Examples of the active energy ray include radiation, gamma ray, alpha ray, electron beam and ultraviolet ray, and ultraviolet ray is preferred. The active energy ray-curable resin layer contains a crosslinked polymer. The active energy ray-curable layer containing a crosslinked polymer can be formed by applying a coating solution containing a polyfunctional monomer and a polymerization initiator on the above-mentioned transparent base film and polymerizing the polyfunctional monomer. The functional group of these monomers is preferably an ethylenically unsaturated double bond group.

The polyfunctional monomer is preferably an ester of a polyhydric alcohol and acrylic acid or methacrylic acid. Examples of polyhydric alcohols include ethylene glycol, 1,4-cyclohexanol, pentaerythritol, glycerin, trimethylolpropane, trimethylolethane, dipentaerythritol, 1,2,4-cyclohexanol, polyurethane polyol and polyester polyol. included. Trimethylolpropane, pentaerythritol, dipentaerythritol and polyurethane polyols are preferred. Two or more polyfunctional monomers may be used in combination.

By adding inorganic fine particles to these active energy ray-cured layers, the crosslinking shrinkage as a film can be improved and the hardness of the coating film can be increased. As the inorganic fine particles, those having high hardness are preferable, and inorganic particles having Mohs hardness of 6 or more are preferable. For example, silicon dioxide particles, titanium dioxide particles, zirconium oxide particles, and aluminum oxide particles are included.

The average particle diameter of these inorganic fine particles is 1n
m to 400 nm, more preferably 5 nm to 20
0 nm or less, more preferably 10 nm or more and 100 nm
The following fine particles are added in an amount of 10% by mass or more and 60% by mass or less, more preferably 15% by mass or more and 50% by mass or less, more preferably 20% by mass or more and 45% by mass or less. If it is less than 1 nm, dispersion is difficult and aggregated particles are formed, and if it is more than 400 nm, the haze increases, and both are unfavorable because transparency is reduced.

The amount of the inorganic fine particles is preferably 1 to 99% by mass, more preferably 10 to 90% by mass, and more preferably 2 to 99% by mass of the total amount of the active energy ray-cured layer.
The content is more preferably 0 to 80% by mass, and most preferably 40 to 60% by mass.

In general, the inorganic fine particles have poor affinity with the binder polymer, so that the interface is easily broken simply by mixing the two, and it is difficult to crack as a film and improve the scratch resistance. In order to improve the affinity between the inorganic fine particles and the polymer binder, the surface of the inorganic fine particles can be treated with a surface modifier containing an organic segment. The surface modifier is required to form a bond with the inorganic fine particles on the one hand and to have a high affinity for the binder polymer on the other hand, and as a functional group capable of forming a bond with a metal, silane, aluminum, titanium, zirconium And a compound having an anionic group such as phosphoric acid, sulfonic acid, and carboxylic acid group. Further, it is preferable that the polymer is chemically bonded to the binder polymer, and that a vinyl polymer group or the like is introduced into a terminal is preferable. For example, when a binder polymer is synthesized from a monomer having an ethylenically unsaturated group as a polymerizable group and a crosslinkable group, it is preferable that the metal alkoxide compound or the anionic compound has an ethylenically unsaturated group at a terminal. .

Examples of the surface treatment agent for the organometallic compound are shown below. a) a silane-containing organic compound _{a-1: H 2 C =} CHCOOC 4 H 8 OSi (OC 4 H
_{9) 3 a-2: (} H 2 C = CHCOOC 4 H 8 O) 2 Si (O
_{C 4 H 9) 2 a-} 3: (H 2 C = CHCOOC 4 H 8 O) 3 SiOC
_{4 H 9 a-4: H} 2 C = CHCOOC 3 H 6 OSi (OC 4 H
_{9) 3 a-5: (} H 2 C = CHCOOC 3 H 6 O) 2 Si (O
_{C 4 H 9) 2 a-} 6: (H 2 C = CHCOOC 3 H 6 O) 3 SiOC
₄ H ₉

B) Examples of aluminum-containing organic compounds b-1: H_TwoC = CHCOOC_FourH₈OAl (OC_FourH
₉)_Two b-2: H_TwoC = CHCOOC_ThreeH₆OAl (OC_ThreeH
₇)_Two b-3: H_TwoC = CHCOOC_TwoH_FourOAl (OC_TwoH
_Five)_Two b-4: H_TwoC = CHCOOC_TwoH_FourOC_TwoH_FourOAl
(OC_TwoH_FourOC_TwoH _Five)_Two b-5: H_TwoC = C (CH_Three) COOC_FourH₈OAl
(OC_FourH₉)_Two b-6: H_TwoC = CHCOOC_FourH₈OAl (OC_FourH
₉) OC_FourH₈COOCH = CH_Two b-7: H_TwoC = CHCOOC_TwoH_FourOAl ｛O (1,
4-ph)｝_Two

C) Zirconium-containing organic compound c-1: H ₂ C ＝ CHCOOC ₄ H ₈ OZr (OC ₄ H
_{9) 3 c-2: H} 2 C = CHCOOC 3 H 7 OZr (OC 3 H
_{7) 3 c-3: H} 2 C = CHCOOC 2 H 4 OZr (OC 2 H
_{5) 3 c-4: H} 2 C = C (CH 3) COOC 4 H 8 OZr
(OC ₄ H ₉ ) ₃ c-5: {CH ₂ ＣC (CH ₃ ) COO} ₂ Zr (OC
₄ H _{9) 2}

D) Titanium-containing organic compound d-1: ΔH_TwoC = C (CH_Three) COO｝_ThreeTiOC_Two
H_FourOC_TwoH_FourOCH _Three d-2: Ti @ OCH_TwoC (CH_TwoOC_TwoH_FourCH = C
H_Two)_TwoC_TwoH_Five｝_Four d-3: H_TwoC = CHCOOC_FourH₈Oti (OC_FourH
₉)_Three d-4: H_TwoC = CHCOOC_ThreeH₇Oti (OC_ThreeH
₇)_Three d-5: H_TwoC = CHCOOC_TwoH_FourOti (OC_TwoH
_Five)_Three d-6: H_TwoC = CHCOOOSiOTi (OSiC
H_Three)_Three d-7: H_TwoC = C (CH_Three) COOC_FourH₈Oti
(OC_FourH₉)_Three

Examples of the surface treatment agent having an anionic functional group are as follows.
They are listed below. e) Organic compound containing phosphate group e-1: H_TwoC = C (CH_Three) COOC_TwoH_FourOPO
(OH)_Two e-2: H_TwoC = C (CH_Three) COOC_TwoH_FourOCOC
_FiveH_TenOPO (OH) _Two e-3: H_TwoC = CHCOOC_TwoH_FourOCOC_FiveH_TenO
PO (OH)_Two e-4: H_TwoC = C (CH_Three) COOC_TwoH_FourOCOC
_FiveH_TenOPO (OH) _Two e-5: H_TwoC = C (CH_Three) COOC_TwoH_FourOCOC
_FiveH_TenOPOCl_Two e-6: H_TwoC = C (CH_Three) COOC_TwoH_FourCH ｛O
PO (OH)_Two)_Two e-7: H_TwoC = C (CH_Three) COOC_TwoH_FourOCOC
_FiveH_TenOPO (ONa)_Two e-8: H_TwoC = CHCOOC_TwoH_FourOCO (1,4-
ph) C_FiveH_TenOPO (OH)_Two e-9: (H_TwoC = C (CH_Three) COO)_TwoCHC_TwoH
_FourOCOC_FiveH_TenOPO (OH)_Two

F) Organic compound containing sulfonic acid group f-1: H ₂ C ＣC (CH ₃ ) COOC ₂ H ₄ OSO _{3
H f-2: H 2 C} = C (CH 3) COOC 3 H 6 SO 3 H f-3: H 2 C = C (CH 3) COOC 2 H 4 OCOC
_{5 H 10 OSO 3 H f-} 4: H 2 C = CHCOOC 2 H 4 OCOC 5 H 10 O
_{SO 3 H f-5: H} 2 C = CHCOOC 12 H 24 (1,4-ph)
_{SO 3 H f-6: H} 2 C = C (CH 3) COOC 2 H 4 OCOC
₅ H ₁₀ OSO ₃ Na

G) Organic compound containing carboxylic acid group g-1: H ₂ C ＣCHCOO (C ₅ H ₁₀ COO) ₂ H g-2: H ₂ C ＣCHCOOC ₅ H ₁₀ COOH g-3: H ₂ C = CHCOOC ₂ H ₄ OCO (1,2-
ph) COOH g-4: H 2 C = CHCOO (C 2 H 4 COO) 2 H g-5: H 2 C = C (CH) COOC 5 H 10 COOH g-6: H 2 C = CHCOOC 2 H 4 COOH (note) ph: phenyl

The surface modification of these inorganic fine particles is preferably performed in a solution. It is preferable that inorganic fine particles are added to a solution in which the surface modifier is dissolved, and the mixture is stirred and dispersed using an ultrasonic wave, a stirrer, a homogenizer, a dissolver, or a sand grinder.

As a solution for dissolving the surface modifier, a highly polar organic solvent (eg, alcohol, ketone, ester) is preferable.

The above-mentioned polyfunctional monomer and polymerization initiator are added to the surface-modified inorganic fine particle solution to obtain an active energy ray-curable coating solution.

Examples of the photopolymerization initiator include acetophenones, benzophenones, Michler's ketone, benzoylbenzoate, benzoin, α-amyloxime ester, tetramethylthiuram monosulfide and thioxanthone. In addition to the photopolymerization initiator,
A photosensitizer may be used. Examples of photosensitizers include n-butylamine, triethylamine, tri-n-butylphosphine, and thioxanthone.

The photopolymerization initiator is preferably used in an amount of 0.1 to 15 parts by weight, more preferably 1 to 10 parts by weight, based on 100 parts by weight of the polyfunctional monomer. The photopolymerization reaction is preferably performed by ultraviolet irradiation after application and drying of the active energy ray cured layer.

The production of the hard coat film of the present invention is as follows.
Active energy ray-curable paint is formed on a transparent substrate film by a known thin film forming method such as dipping method, spinner method, spray method, roll coater method, gravure method, wire bar method, etc. You can do it.

[Λ / 4 plate] The λ / 4 plate has a wavelength of 450 nm.
Retardation value (Re450) measured in 100
And the retardation value (Re590) measured at a wavelength of 590 nm is 120 to 160 nm.
nm, and Re590-Re450 ≧ 2 nm
Satisfy the relationship. More preferably, Re590-Re450 ≧ 5 nm, and Re590-Re450 ≧ 5 nm.
Most preferably, it is 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 (Re590) measured at a wavelength of 590 nm is 130 to 120. 152 nm, and preferably satisfies the relationship of Re590-Re550 ≧ 2 nm. More preferably, Re590-Re550 ≧ 5 nm, and Re590-Re550 ≧ 1.
Most preferably, it is 0 nm. Also, Re550-
It is also preferable that Re450 ≧ 10 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 λ / 4 plate 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 the λ / 4 plate is preferably from 5 to 1000 μm, more preferably from 10 to 500 μm, further preferably from 40 to 200 μm, and most preferably from 70 to 120 μm. .

The λ / 4 plate is made of one polymer film. As a material of the polymer film, a cellulose ester is preferable, and a lower fatty acid ester of cellulose is more preferable. The lower fatty acid means a fatty acid having 6 or less carbon atoms. The number of carbon atoms is 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 degree of acetylation (acetylation degree) of cellulose acetate is 45.0.
To 62.5%, preferably 55.0 to 62.5%.
More preferably, it is 1.0%, and 56.0 to 6
Most preferably, it is 0.5%.

[Retardation Raising Agent] In order to adjust the retardation value at each wavelength, a retardation raising 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 contained in the retardation increasing agent is preferably from 2 to 20, and preferably from 2 to 12
More preferably, it is more preferably 2 to 8, and most preferably 2 to 6. The bonding relationship between two aromatic rings is as follows: (a) When forming a condensed ring,
It can be classified into (b) a case where a single bond is directly bonded and (c) a case where a bond is formed via a linking group (a spiro bond cannot be formed due to an aromatic ring). The connection relationship may be any of (a) to (c).

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.

Each component 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.

The solution can be prepared by the 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 use the transparent substrate film of the present invention as the transparent protective film, and it is preferable to provide an antireflection 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 / □ or less. □ It is particularly preferred that it is not more than.
When used as a touch panel, 10 ⁴ Ω /
□ or less, more preferably 1000 Ω / □ or less, and most preferably 500 Ω / □ or less. 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 film, 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.

The surfactant used as the transparent conductive film includes nonionic, ionic (anionic, cationic,
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 salt. Representative examples thereof include 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 cationic surfactants, amine salts,
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 Applications of Surfactants (written by Koshobo and 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. In addition, the coating amount of these surfactants is preferably 0.02 to 1000 mg, and more preferably 0.05 to 200 mg per 1 m2.

The following are specific examples of the surfactant. 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 C
_{H 2 O) 4 (CH 2} ) 4 SO 3 Na WA-15: C 8 F 17 SO 2 N (C 3 H 7) - (C
_{H 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 (C
F) ₈ H WA-20: H (CF ₂ ) ₆ CH ₂ CH ₂ O (CH ₂ C
_{H 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 or the like. 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.

In order to improve the conductivity and permeability of the transparent conductive layer, heat treatment or water treatment can be performed. 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 uniform treatment can be performed. 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.

These water treatments can further reduce the surface resistance of the transparent conductive bath after the heat treatment, increase the transmittance, flatten the transmission spectrum, and reflectivity after the anti-reflection layer is laminated. The effect on the decrease of the remarkability becomes remarkable.

As the 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 fluorine resin, 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.

[Touch Panel] The retardation plate of the present invention can be used as a substrate for a touch panel. The touch panel includes a fixed substrate on the side closer to the display element and a movable substrate facing the fixed substrate. A transparent electrode is provided on each of the opposing surfaces of the fixed substrate and the movable substrate. The fixed substrate and the movable substrate
In order to improve display quality, it is preferable that the display device is formed of a transparent optical material. The retardation plate of the present invention can be used for one or both of a fixed substrate and a movable substrate, but is more preferably used as a movable substrate. As the material of the substrate which is not the polymer film of the present invention,
For example, glass, amorphous film, polyether sulfone, polycarbonate, polyarylate, polymer film such as polyethylene terephthalate and the like can be mentioned. A polarizing plate can be provided outside the touch panel.

A gap is formed between the two transparent electrodes. An air layer is usually present between the gaps, but a liquid having a refractive index close to that of the transparent electrode can be filled for optical matching. Further, an undercoat layer may be provided on the substrate side of the transparent electrode film, or an overcoat layer may be provided on the side opposite to the substrate to reduce light reflection. The surface of the transparent electrode film may be roughened in order to eliminate sticking and improve the keying life. Spacers can be provided between the gaps. As the spacer, a dot-shaped spacer, a bonding material provided around the fixed substrate and the movable substrate, or the like is used. The touch panel is used as either a digital type or an analog type. In the digital type, it is possible to detect the contact between the transparent electrodes by pressing and the data position corresponding to the contact position. In the analog type, for example, electrodes are formed at both ends of the fixed substrate in the X-axis direction and both ends of the movable substrate in the Y-axis direction. The data input position can be detected by detecting the resistance value in the direction.

[Reflective Liquid Crystal Display Device] The circularly polarizing plate and the touch panel of the present invention can be used in combination with various display devices. For example, cathode ray tube (CRT), plasma display (PDP), field emission display (FED), inorganic E
L device, organic EL device, liquid crystal display device 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. The lower alignment film (3) to the upper alignment film (5) constitute a liquid crystal cell. The λ / 4 plate (8) can be arranged at any position between the reflection plate and the polarizing film (9). In the case of color display, a color filter layer is further provided. The color filter layer is formed between the reflective electrode (2) and the lower alignment film (3), or between the upper alignment film (5) and the transparent electrode (6).
Is preferably provided between 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, the surface of the reflection plate has an uneven structure (Patent 27).
No. 5620) is preferably introduced. 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.

FIG. 2 is a schematic diagram showing a basic configuration of a reflection type liquid crystal display device using a touch panel. The reflection-type liquid crystal display device using the touch panel shown in FIG. , A transparent electrode (6), an upper substrate (7), a transparent conductive film (10), a transparent conductive film (11), a λ / 4 plate (8), and a polarizing film (9). A gap is formed between the transparent conductive film (10) and the transparent conductive film (11), and functions as a touch panel.

The liquid crystal mode used is not particularly limited, but is a TN (twisted nematic) type, STN (Supper Tw).
isted Nematic) type or HAN (Hybrid Aligned Nema)
tic) type. The twist angle of the TN type liquid crystal cell is preferably 40 to 100 °, preferably 5 to 100 °.
More preferably, the angle is 0 to 90 °, and 60 to 8 °.
Most preferably, it is 0 °. 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.
More preferably, it is 2 to 0.4 μm. STN
The twist angle of the liquid crystal cell is preferably 180 to 360 °, more preferably 220 to 270 °. 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 0.3 to 1.2.
μm, more preferably 0.5 to 1.0 μm. In the HAN type liquid crystal cell, it is preferable that the liquid crystal is substantially vertically aligned on one substrate and the pretilt angle on the other substrate is 0 to 45 °. 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 0.1 to 1.0 μm
And more preferably 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.

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. 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.

[0113]

EXAMPLES [Example 1] (Preparation of transparent base film) (1) Polymerization of polyester (a) Polyethylene terephthalate (PET) 80 parts of dimethyl terephthalate, 58 parts of ethylene glycol, manganese acetate tetrahydrate And 0.028 part of antimony trioxide were added thereto, and the mixture was stirred for 200 minutes.
Heated to ° C. 235 while removing by-product methanol
The temperature was raised to ° C. After the by-product of methanol was completed, 0.03 part of trimethylphosphoric acid was added, and the pressure was reduced to 0.3 Torr while the temperature was raised to 285 ° C. to polymerize PET having an intrinsic viscosity of 0.62. In addition, these intrinsic viscosities were measured by the following method. B) Phenol / 1,1,2,2-tetrachloroethane mixed solvent
(Weight ratio: 60/40).
Prepare solutions of 2 g / dl, 0.6 g / dl and 1.0 g / dl. B) This is measured at 20 ° C. using an Ubbelohde viscometer. C) The viscosity was plotted against the concentration, and the viscosity extrapolated to the concentration = 0 was defined as the intrinsic viscosity.

(2) Kneading of fine particles By shortening the polymerization time by the above method, an oligomer of PET having an intrinsic viscosity shown in Table 1 is prepared. This is the first
Add to microparticles as described in table. This was kneaded at 230 ° C. for 5 minutes using a Banbury mixer. The PET having an intrinsic viscosity of 0.62 and the PE having an intrinsic viscosity of 0.58
After drying N at 150 ° C. for 30 minutes, the mixture was kneaded for 5 minutes using a uniaxial kneading extruder while raising the temperature from 280 ° C. to 320 ° C. This was extruded into noodles, then cooled with water and cut to form pellets.

[0115]

[Table 1] Table 1 ──────────────────────────────────── Fine particle oligomer Pellet type Specific size Viscosity Fine particle content ──────────────────────────────────── 1 Alumina 40 nm 1 20 mass% 2 Alumina 40 nm 1 40% by mass 3 Titania 50nm 0.8 30% by mass 4 None---───────────────────────────────── ───

(3) Formation of Polyester Film The polyester pellets prepared by the above method were dried at 160 ° C. under reduced pressure for 3 hours. The pellets of each composition were melted at 310 ° C. by an extruder, filtered through a 5 μm mesh filter, and then discharged from a T die (multi-manifold die) at 50 ° C. so that the composition shown in Table 2 was obtained. An extruded unstretched film on the casting drum to which the application was applied was prepared.

Under the conditions shown in Table 2, MD stretching (3.5 times, 105 ° C.), TD stretching (4.0 times, 110 times)
° C), heat setting (245 ° C), and thermal relaxation (3%).
The width of the film was 1.8 m, which was trimmed to 1.5 m at both ends.
After knurling 0mm, the diameter 30
cm.

[0118]

[Table 2] Table 2 厚Thickness of constituent layer of base material pellet ( μm) Surface elastic modulus Film B layer A layer A layer / B layer Gpa ── 1 pellet 1 pellet 4 30/150 6.5 2 pellet 2 pellet 4 30/150 8.0 3 pellet 3 pellet 4 30/150 7.5 4 pellet 4 pellet 4 175 4.3 ────── ──────────────────────────────

(4) Preparation of Inorganic Particle Dispersion (M-1) The following amounts of each reagent were measured in a ceramic-coated vessel. Cyclohexanone 337 g PM-2 (phosphate group-containing methacrylate manufactured by Nippon Kayaku Co., Ltd.) 31 g AKP-G015 (Alumina manufactured by Sumitomo Chemical Co., Ltd .: particle size 15 nm) 92 g For 10 hours. Media is 1
1400 g of zirconia beads having a diameter of mmΦ was used. After dispersion, the beads were separated and the surface-modified alumina (M-1)
I got

(5) Preparation of Coating Solution for Active Energy Beam Cured Layer To 116 g of a 43 wt% cyclohexanone dispersion (M-1) of surface-treated alumina fine particles, 97 g of methanol was added.
163 g of isopropanol and 163 g of methyl isobutyl ketone were added. A mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA, manufactured by Nippon Kayaku Co., Ltd.)
200 g was added and dissolved. Further, 7.5 g of a photopolymerization initiator (Irgacure 907, manufactured by Ciba Geigy) and a photosensitizer (Kayacure DETX, manufactured by Nippon Kayaku Co., Ltd.)
5.0 g of 4 was added and dissolved. After stirring the mixture for 30 minutes, the mixture was filtered through a polypropylene filter having a pore size of 1 μm to prepare a coating liquid for an active energy ray-curable layer.

(6) Preparation of Hard Coat Film After the base films described in Table 3 were subjected to glow discharge treatment, the coating liquid for the active energy ray-cured layer filled with alumina was coated with a wire bar so as to have a dry film thickness of 8 μm. And dried, and irradiated with ultraviolet rays to laminate a cured layer. The hardness of the pencil scratch test was examined.

The hardness of the pencil scratch test was determined by conditioning the prepared hard coat film at a temperature of 25 ° C. and a relative humidity of 60% for 2 hours and then using a test pencil specified by JIS-S-6006. According to the pencil hardness evaluation method defined by -K-5400, it is a pencil hardness value at which no scratch is observed at a load of 1 kg.

(Preparation of Polymer Film) At room temperature, cellulose acetate 12 having an average acetylation degree of 59.7% was prepared.
0 parts by weight, 1.2 parts by weight of the following retardation 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, and 46.8 parts by weight of methanol to prepare a solution (dope). did.

[0124]

Embedded image

The obtained dope was cast on a stainless steel band, and the film was dried until it had self-supporting property, and was then 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.

(Application of Transparent Conductive Film) 1) ITO Sputtering onto Cellulose Triacetate A UV-curable polyfunctional methacrylic resin (Z7503 manufactured by JSR) was applied to a thickness of 3 μm on a stretched film. 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, 116.4 nm and 13
2.0 nm and 137.0 nm. Therefore, this cellulose acetate film has a λ /
4 had been achieved. Furthermore, from the refractive index measurement by Abbe refractometer and the measurement of the angle dependence of the retardation,
Refractive index n in the in-plane slow axis direction at a wavelength of 550 nm
x, the refractive index ny in the direction perpendicular to the in-plane slow axis and the refractive index nz in the thickness direction are obtained, and (nx−nz) / (nx−n)
The value of y) was calculated to be 1.52.

(Preparation of Circular Polarizing Plate) A transparent base film, a polarizing film and a polymer film are laminated in this order such that the cured layer of the transparent base film and the transparent conductive layer of the polymer film are located outside each other. To obtain a circularly polarizing plate.
The angle between the slow axis of the polymer film and the polarizing axis of the polarizing film was adjusted to 45 °. When the optical properties of the obtained circularly polarizing plate were examined, a wide wavelength range (450 to 590 nm) was obtained.
, Almost perfect circularly polarized light was achieved.

Comparative Example 1 (Preparation of Polymer Film) 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. 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, 10 ¹⁵ Ω /
□ or more. The light transmittance was 92%. About the obtained cellulose acetate film (retardation film), an ellipsometer (M-150, JASCO Corporation)
Wavelengths of 450 nm, 550 nm, and 5 nm.
When the retardation values (Re) at 90 nm were measured, they were 120.8 nm and 137.1 n, respectively.
m, 142.3 nm. Therefore, this cellulose acetate film achieved λ / 4 in a wide wavelength range. Further, 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.

(Preparation of circularly polarizing plate) Transparent protective film (commercially available triacetyl cellulose film: Fuji Photo Film Co., Ltd.)
), The polarizing film and the retardation plate prepared in 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 polarization axis of the polarizing film was adjusted to 45 °. 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). Similarly, when a circularly polarizing plate was manufactured using the retardation plates manufactured in Example 2 and Example 3, and the optical properties were examined, a wide wavelength range (450 to 590 nm) was obtained.
, Almost perfect circularly polarized light was achieved.

Example 2 [Dust Test] A retardation plate (20 cm × 20 cm) was thoroughly rubbed with nylon under conditions of temperature and humidity of 25 ° C. and 10% RH, and the adhesion of tobacco ash was examined. Evaluation was performed in the following four stages. A: Dust was not observed at all. B: Dust was observed a little. C: Dust was observed considerably. D: Dust was observed severely. Are classified as A. As a result, all the circularly polarizing plates of Example 1 of the present invention were ranked A, whereas the circularly polarizing plate of Comparative Example 1 was ranked D. Therefore, it was found that the present invention can provide a retardation plate having excellent antistatic performance and improved dust adhesion.

Example 3 (Preparation of Touch Panel) The surface resistivity of one side was 5 Ω / □,
The other side has a transparent conductive film (I) having a surface resistivity of 400Ω / □.
A glass plate with (TO) was prepared. Surface resistivity 5Ω /
A polyimide alignment film (SE-7992, manufactured by Nissan Chemical Industries, Ltd.) was formed on the surface of □, and rubbing treatment was performed. On the other side (surface resistivity 400Ω / □), dot spacers of 1 mm pitch and silver electrodes were printed on both ends. Example 1
Silver electrodes were printed on both ends of the side of the polymer film (transparent conductive film) of the circularly polarizing plate obtained in Comparative Example 1, and the transparent conductive glass plate and the transparent conductive film were bonded to each other so as to face each other. At this time, 100 μm
A thick insulating adhesive was sandwiched. AR processing was performed on the outermost surface of the touch panel thus manufactured. The angle between the stretching direction of the polymer film (parallel to the slow axis direction) and the transmission axis direction of the polarizing plate was 45 °. Thus, a touch panel A (using the circularly polarizing plate of Example 1) and a touch panel B (using the circularly polarizing plate of Comparative Example 1) were manufactured.

(Preparation of Reflection Type Liquid Crystal Display Device) A glass substrate provided with an aluminum reflection electrode having fine irregularities was prepared. A polyimide alignment film (SE-7992, manufactured by Nissan Chemical Industries, Ltd.) was formed on the electrode side of this glass substrate,
A rubbing treatment was performed. The touch panel and a glass substrate provided with a reflective electrode were overlapped via a 3.4 μm spacer such 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-6
252, manufactured by Merck & Co., Inc.) to form a liquid crystal layer. Thus, the twist angle is 70 ° and the value of Δnd is 26
A 9 nm TN liquid crystal cell was produced. In this way,
A reflective liquid crystal display device A using a touch panel A and a reflective liquid crystal display device B using a touch panel B were produced.

[Touch Panel Performance Evaluation] Touch Panel A
It was confirmed that the reflection type liquid crystal display device A using the above-described device operated well as a touch panel. On the other hand, touch panel B
Did not operate as a touch panel.

[Evaluation of Touch Panel Input Surface] Further, when the input surface was observed, no scratch was observed on the surface of touch panel A, but a scratch during input was observed on the surface of touch panel B.

[Display Evaluation of Reflective Display Device] A rectangular wave voltage of 1 kHz was applied to each of the manufactured reflective liquid crystal display devices A and B. 1.5 V for white display, 4.5 V for black display
As a result of visual evaluation, even in white display,
Also in the black display, it was confirmed that both the reflective liquid crystal display devices A and B had no color and displayed neutral gray. Next, a measuring machine (EZcontrast160D,
When the contrast ratio of the reflection luminance was measured using Eldim, the contrast ratio of the reflection type liquid crystal display device A was 25 from the front, and the viewing angle at which the contrast ratio was 3 was 120 ° or more in the vertical direction. It was 120 ° or more on the left and right. Regarding the reflective liquid crystal display device B, the contrast ratio from the front was 25, and the viewing angle at which the contrast ratio was 3 was 120 ° or more in the vertical direction and 120 ° or more in the left and right directions.

[Brief description of the drawings]

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

FIG. 2 is a schematic diagram showing a basic configuration of a reflective liquid crystal display device using a touch panel.

[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 10 transparent conductive film 11 transparent conductive film

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G02F 1/13363 G06F 3/033 350A G06F 3/033 350 360A 360 360H G02B 1/10 Z F term (Reference) 2H049 BA02 BA03 BA07 BB03 BB23 BB33 BB49 BB62 BC22 2H089 HA18 QA02 RA05 RA10 SA04 TA12 TA14 TA15 TA17 2H091 FA08X FA08Z FA11X FA11Z FA16Z FA37X FA37Z FB02 FB04 FB08 FB12 FC07 LA10 CC03 LA10 CC02 EE03 5B087 AB04 AC09 CC02 CC12 CC13 CC14 CC15 CC36

Claims (7)

[Claims] 1. A transparent base film, a polarizing element, and
A λ / 4 plate is a circularly polarizing plate laminated in this order,
The transparent substrate film is a hard coat polyester film having at least one surface provided with an active energy ray polymerizable resin layer, and the surface elastic modulus of the polymerizable resin layer is 5 GPa or more and 15 GPa or less, and a λ / 4 plate Is the retardation value (R) measured at a wavelength of 450 nm.
e450) is 100 to 125 nm, and the wavelength 5
Retardation value measured at 90 nm (Re590)
Is 120 to 160 nm, and Re590-Re45
A circularly polarizing plate comprising a single polymer film satisfying a relationship of 0 ≧ 2 nm. 2. The circularly polarizing plate according to claim 1, wherein the surface resistivity of at least one surface of the λ / 4 plate is 10 ¹² Ω / □ or less. 3. The circularly polarizing plate according to claim 1, wherein the surface resistivity of at least one surface of the λ / 4 plate is 10 ⁴ Ω / □ or less. 4. The λ / 4 plate has a retardation value (Re450) of 108 to 120 measured at a wavelength of 450 nm.
and the retardation value (Re550) measured at a wavelength of 550 nm is 125 to 142 nm, and the retardation value (Re59) measured at a wavelength of 590 nm.
0) is from 130 to 152 nm, and Re59
2. The circularly polarizing plate according to claim 1, comprising one polymer film satisfying a relationship of 0-Re550 ≧ 2 nm. 5. A touch panel in which two transparent conductive substrates provided with a transparent conductive film on at least one surface are arranged such that the transparent conductive films face each other, and at least one of the transparent conductive substrates is provided. A touch panel comprising the circularly polarizing plate according to claim 1. 6. The touch panel according to claim 5, wherein an antireflection layer is provided on the outermost surface of the circularly polarizing plate on the transparent substrate film side. 7. A reflection type liquid crystal display device equipped with the touch panel according to claim 5.