WO2009072638A1 - Rouleau de plaque de polarisation composite, ensemble plaque de polarisation composite et affichage à cristaux liquides - Google Patents

Rouleau de plaque de polarisation composite, ensemble plaque de polarisation composite et affichage à cristaux liquides Download PDF

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Publication number
WO2009072638A1
WO2009072638A1 PCT/JP2008/072212 JP2008072212W WO2009072638A1 WO 2009072638 A1 WO2009072638 A1 WO 2009072638A1 JP 2008072212 W JP2008072212 W JP 2008072212W WO 2009072638 A1 WO2009072638 A1 WO 2009072638A1
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Prior art keywords
polarizing plate
film
liquid crystal
retardation
composite polarizing
Prior art date
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PCT/JP2008/072212
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English (en)
Japanese (ja)
Inventor
Yuichiro Kunai
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Sumitomo Chemical Company, Limited
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Filing date
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Publication of WO2009072638A1 publication Critical patent/WO2009072638A1/fr

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Classifications

    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B27/00—Optical systems or apparatus not provided for by any of the groups G02B1/00 - G02B26/00, G02B30/00
    • G02B27/28—Optical systems or apparatus not provided for by any of the groups G02B1/00 - G02B26/00, G02B30/00 for polarising
    • G02B27/281—Optical systems or apparatus not provided for by any of the groups G02B1/00 - G02B26/00, G02B30/00 for polarising used for attenuating light intensity, e.g. comprising rotatable polarising elements
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3016—Polarising elements involving passive liquid crystal elements
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133528—Polarisers
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/13363—Birefringent elements, e.g. for optical compensation
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • G02F1/133742—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers for homeotropic alignment
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F2202/00—Materials and properties
    • G02F2202/28—Adhesive materials or arrangements
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F2202/00—Materials and properties
    • G02F2202/40—Materials having a particular birefringence, retardation
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F2413/00—Indexing scheme related to G02F1/13363, i.e. to birefringent elements, e.g. for optical compensation, characterised by the number, position, orientation or value of the compensation plates
    • G02F2413/02—Number of plates being 2

Definitions

  • the present invention relates to a composite polarizing plate roll, a composite polarizing plate set, and a liquid crystal display device.
  • One of such liquid crystal display devices is a vertical alignment (VA) mode liquid crystal display device in which rod-like liquid crystal molecules having positive or negative dielectric anisotropy are aligned perpendicularly to a substrate.
  • VA vertical alignment
  • the liquid crystal molecules are aligned perpendicular to the substrate, light passes through the liquid crystal layer without any change in polarization.
  • linearly polarizing plates on the top and bottom of the liquid crystal panel so that the absorption axes are orthogonal to each other, almost complete black display can be obtained when viewed from the front, and a high contrast ratio can be obtained. Can do.
  • the axial angle of the disposed polarizing plate deviates from 90 ° when viewed obliquely.
  • viewing angle characteristics including the contrast ratio and color change in strabismus.
  • a biaxial retardation plate is provided between the liquid crystal cell and the upper and lower polarizing plates.
  • Patent Document 1 in a vertical alignment mode liquid crystal display device, an a plate (that is, a positive uniaxial phase) is disposed between upper and lower polarizing plates and a liquid crystal cell. And a c-plate (ie, a complete biaxial retardation plate) are described.
  • a positive uniaxial retardation plate is a film with an Nz coefficient of approximately 1.0, and a complete biaxial retardation plate has an in-plane retardation value R. Is almost zero film.
  • n X is the refractive index in the in-plane slow axis direction of the film
  • ny is the refractive index in the in-plane fast axis direction of the film
  • nz is the refractive index in the film thickness direction
  • d is the film thickness.
  • the thickness direction retardation value Rth and the Nz coefficient are defined by the following equations (1) to (3), respectively.
  • Nz coefficient (nx-nz) / (nx-ny) (3)
  • the Nz coefficient is 1.0. Even for a uniaxial film, the Nz coefficient may vary between about 0.80 and 1.50 depending on the stretching conditions.
  • a completely biaxial film is different (small) only in the refractive index in the thickness direction, so it is also called a film having negative uniaxiality and an optical axis in the normal direction. As it is, it is sometimes called c-plate.
  • the uniaxial retardation film for example, a resin film stretched by, for example, free end longitudinal uniaxial stretching or fixed end lateral uniaxial stretching is generally used. Fixed end In the case of transverse uniaxial stretching, it often has a slight biaxiality of about 1.10 ⁇ Nz coefficient ⁇ 1.50. Although a retardation film having such an Nz coefficient is uniaxial, it may not be completely uniaxial.
  • the completely uniaxial retardation film referred to here refers to a film in the range of 0.90 ⁇ Nz coefficient ⁇ l.10.
  • the present invention has been made to solve the above-described problems, and an object of the present invention is to provide a composite polarizing plate capable of improving viewing angle characteristics in a liquid crystal display device (particularly, a VA mode liquid crystal display device). And a liquid crystal display device using the same. Disclosure of the invention
  • the present inventor has found that a uniaxial retardation film is combined with a uniaxial retardation film and a complete biaxial retardation film.
  • the present inventors have found that a liquid crystal display device with better viewing angle characteristics can be obtained by making the optical characteristics completely uniaxial, leading to the present invention. That is, the present invention is as follows.
  • the present invention has a structure in which a long roll of a first retardation plate is laminated on a long mouthpiece of a polarizing plate whose absorption axis direction is arranged in the longitudinal direction and the first retardation plate
  • the slow axis direction of the polarizing plate and the absorption axis direction of the polarizing plate are arranged so as to intersect at an angle of 80 to 100 °, and the first retardation plate
  • the in-plane retardation value R is obtained by stretching the oil.
  • the refractive index in the in-plane slow axis direction of the film is nx
  • the refractive index in the in-plane fast axis direction of the film is ny
  • the refractive index in the thickness direction of the film Nz coefficient defined by the following equation is in the range of 0.90 to 1.10, where is nz.
  • the first retardation plate in the composite polarizing plate roll of the present invention is preferably a film obtained by uniaxially stretching a propylene resin at a fixed end.
  • the present invention is also a set of a first composite polarizing plate and a second composite polarizing plate used in a liquid crystal display device, the first composite polarizing plate comprising: a polarizing plate; a first retardation plate; The pressure-sensitive adhesive layer is laminated in this order.
  • the first retardation plate is a retardation film obtained by stretching a propylene resin, and has an in-plane retardation value R.
  • the refractive index in the in-plane slow axis direction of the film is nx
  • the refractive index in the in-plane fast axis direction of the film is ny
  • the refractive index in the thickness direction of the film When the ratio is nz, the Nz coefficient defined by the following formula is in the range of 0.90 to 1.10, and the slow axis direction and the absorption axis direction of the polarizing plate are 80 to 1
  • the second composite polarizing plate is arranged so as to intersect at an angle of 0 °, and has a structure in which a polarizing plate, a second retardation plate, and a pressure-sensitive adhesive layer are laminated in this order,
  • the second retardation plate includes an organically modified clay composite and a binder resin, and has an in-plane retardation value R. Is provided in the range of 0 to 30 nm, and the thickness of the thickness direction retardation Rth is in the range of 30 to 30 nm.
  • Nz coefficient (n x— n z) /, n x— n y)
  • the first retardation plate in the composite polarizing plate set of the present invention is preferably a film obtained by laterally uniaxially stretching a propylene-based resin.
  • the composite polarizing plate set of the present invention is preferably used for a VA mode liquid crystal display device.
  • the present invention is also a liquid crystal display device comprising the above-described composite polarizing plate set of the present invention and a liquid crystal cell, wherein the first composite polarizing plate is disposed on one side of the liquid crystal cell via its pressure sensitive 14 adhesive layer.
  • a liquid crystal display device is also provided in which a second composite polarizing plate is bonded to the other side of the liquid crystal cell via its pressure-sensitive adhesive layer.
  • FIG. 1 is a perspective view schematically showing a first example of the first composite polarizing plate 1 used in the composite polarizing plate set of the present invention with each layer being separated.
  • FIG. 2 is a perspective view schematically showing another example of the first composite polarizing plate 11 of another preferred example used in the composite polarizing plate set of the present invention in a state where the layers are separated from each other.
  • FIG. 3 is a perspective view schematically showing a second example of the second composite polarizing plate 21 used in the composite polarizing plate set of the present invention in a state where the layers are separated from each other.
  • FIG. 4 is a perspective view schematically showing a second composite polarizing plate 31 of another preferred example used in the composite polarizing plate set of the present invention, with each layer being separated.
  • Fig. 5 Fig. 5 (a) is a cross-sectional view schematically showing an example of a liquid crystal display device manufactured using the set of composite polarizing plates of the present invention. It is a top view shown in a state.
  • FIG. 6 is a graph showing the relationship between the Nz coefficient of the first retardation plate and the contrast viewing angle of the liquid crystal display devices obtained in Example 1 and Comparative Examples 1 to 4.
  • a first composite polarizing plate is disposed on one side of a liquid crystal cell, and a second composite polarizing plate is disposed on the other side.
  • This is provided as a combination of a plate and a second composite polarizing plate.
  • the first composite polarizing plate and the second composite polarizing plate in the present invention are each composed of a polarizing plate, a retardation plate (first retardation plate or second retardation plate), and a pressure-sensitive adhesive layer in this order. It has a laminated structure.
  • FIG. 1 is a perspective view schematically showing a first example of the first composite polarizing plate 1 used in the composite polarizing plate set of the present invention, with each layer being separated
  • FIG. 2 is a composite of the present invention
  • FIG. 6 is a perspective view schematically showing a first composite polarizing plate 11 of another preferred example used for a polarizing plate set in a state where layers are separated from each other.
  • the first composite polarizing plates 1 and 11 shown in FIGS. 1 and 2 have the same structure except that the configurations of the polarizing plates 2 and 12 are partially different.
  • a phase difference plate 3 and a pressure-sensitive adhesive layer 4 are laminated.
  • the first retardation plate 3 used in the present invention is a retardation film formed by stretching propylene resin, and has an in-plane retardation value R0 in the range of 90 to 200 nm.
  • the first retardation plate 3 used in the present invention is a complete uniaxial retardation film (as described above, a uniaxial film in the range of 0.9 0 ⁇ Nz coefficient ⁇ l. 10).
  • the stretching methods include fixed-end uniaxial stretching and free-end uniaxial. Stretching can be applied.
  • a stretching method called longitudinal stretching in which the film is stretched in the longitudinal direction (flow direction) is used.
  • the slow axis direction of the retardation film obtained by such a method is substantially parallel to the longitudinal direction of the film.
  • the polarizing plate is usually obtained by stretching a long roll of a film made of poly (bull alcohol) resin uniaxially at the free end, and the absorption axis direction is substantially parallel to the longitudinal direction.
  • the slow axis direction of the retardation film and the absorption axis direction of the polarizing plate are orthogonal to each other, at least one of the long rolls is cut into a sheet shape with a certain size, After rotating the direction 90 degrees, it becomes necessary to stick each other to the other film.
  • the slow axis direction is a direction (width direction) perpendicular to the longitudinal direction of the long roll.
  • a long roll of film and a long roll of polarizing plate can be continuously bonded with a roll-to-roll.
  • normal amorphous When a resin film is stretched laterally uniaxially at a fixed end, it is difficult to obtain a completely uniaxial retardation film, and the ⁇ 2 coefficient> 1.10 is often obtained.
  • the present invention even when the fixed-end lateral uniaxial stretching is performed, by using a propylene resin that can obtain completely uniaxial characteristics by stretching at a high rate of a certain degree or more, it is possible to obtain completely uniaxial.
  • the first retardation plate 3 that is a retardation film is used.
  • the high magnification above a certain level is usually 2 times or more, preferably 3 times or more, and more preferably 3.5 times or more.
  • the upper limit of the draw ratio is not particularly limited, but if the film is stretched too much, the film is broken, and therefore, the film is usually stretched at 10 times or less, preferably 8 times or less, more preferably 6 times or less.
  • the long roll of retardation film obtained by uniaxial stretching is bonded to the long roll of a polarizing plate with a roll-to-roll so that the first composite polarizing plate used in the composite polarizing plate set of the present invention can be efficiently used. It can be manufactured easily and well. In this sense, it is useful to use a film made of propylene resin as the retardation film as in the present invention.
  • the propylene resin used for the first retardation plate of the first composite polarizing plate in the present invention is a resin mainly composed of propylene units, and is generally crystalline, in addition to a propylene homopolymer, It may be a copolymer of propylene and a comonomer copolymerizable therewith.
  • Examples of the comonomer copolymerized with propylene include ethylene and ⁇ -olefin having 4 to 20 carbon atoms (C4 to C20).
  • Specific examples of ⁇ -olefins having 4 to 20 carbon atoms include 1-butene, 2_methyl-1-propene (above C4); 1-pentene, 2_methyl-1-1-butene, 3_methyl 1-butene (above C 5); 1-hexene, 2_ethyl 1-butene, 2, 3-dimethyl-1-butene, 2_methyl-1-pentene, 3-methinole 1-pentene, 4- Methyl-1-pentene, 3,3-dimethyl-1-butene (above C 6); 1-heptene, 2— Methinole 1-hexene, 2,3-Dimethyl-1-pentene, 2-Ethenole 1-pentene, 2_Methyl 1-3-Ethyl 1-butene (above C7); 1-Oc
  • ⁇ -olefins having 4 to 12 carbon atoms are preferable, specifically 1-butene, 2-methyl _ 1 _propene; 1-pentene,
  • the copolymer may be a random copolymer or a block copolymer.
  • Preferred copolymers include propylene monoethylene copolymer and propylene mono Mention may be made of butene copolymers.
  • the ethylene unit content and 1-butene unit content in propylene-ethylene-ethylene copolymer and propylene- 1-butene copolymer are, for example, “Polymer Analysis Handbook” (published at Kinokuniya, 1959) Infrared (IR) spectrum measurement can be performed by the method described on page 6 16 of).
  • a random copolymer with any unsaturated hydrocarbon mainly composed of propylene is preferable.
  • a copolymer with ethylene is preferred.
  • the unsaturated hydrocarbon other than propylene is advantageously 1 to 10% by weight of the copolymerization ratio, more preferably 3 to weight. / 0 .
  • the unit of unsaturated hydrocarbons other than propylene 1% by weight or more, there is a tendency to improve the processability and transparency.
  • the ratio exceeds 10% by weight, the melting point of the resin tends to decrease and the heat resistance tends to deteriorate, which is not preferable.
  • the total content of units derived from all comonomers contained in the obtained copolymer is preferably within the above-mentioned range.
  • the propylene resin can be produced by a method of homopolymerizing propylene, a method of copolymerizing propylene and another copolymerizable comonomer, or the like.
  • Ti i Mg titanium-magnesium
  • a catalyst system in which an organic aluminum compound and, if necessary, a third component such as an electron-donating compound are combined,
  • a known polymerization catalyst such as a metallocene catalyst can be suitably used.
  • a metallocene catalyst can be suitably used.
  • the combination of an organic aluminum compound and an electron donating compound with a solid catalyst component containing magnesium, titanium and halogen as essential components is most commonly used.
  • organoaluminum compounds Preferably, the product includes triethylaluminum, triisobutylaluminum, a mixture of triethylaluminum and jetylaluminum chloride, tetraethyldialumoxane, and the like, and the electron donating compound is preferably cyclohexylethyldimethoxysilane, tert_butylpropyldimethyoxysilane, tert-butylethyldimethyoxysilane, dicyclopentyldimethyoxysilane, and the like.
  • examples of solid catalyst components containing magnesium, titanium and halogen as essential components are described in, for example, JP-A-61-218606, JP-A-61-287904, JP-A-7-216017 and the like.
  • examples of the metallocene catalyst include the catalyst systems described in Japanese Patent No. 2587251, Japanese Patent No. 262 7669, Japanese Patent No. 2668732, and the like.
  • Propylene resin is a solution polymerization method that uses an inert solvent such as hexane, heptane, octane, decane, cyclohexane, methylcyclohexane, benzene, toluene, xylene, and other inert solvents such as hydrocarbon compounds. It can be produced by a bulk polymerization method using a liquid monomer as a solvent, a gas phase polymerization method in which a gaseous monomer is polymerized as it is, and the like. Polymerization by these methods may be performed batchwise or continuously.
  • an inert solvent such as hexane, heptane, octane, decane, cyclohexane, methylcyclohexane, benzene, toluene, xylene, and other inert solvents such as hydrocarbon compounds. It can be produced by a bulk polymerization method using a liquid monomer as
  • the stereoregularity of the propylene resin may be any of isotactic, syndiotactic and atactic.
  • syndiotactic or isotactic propylene resin is preferably used from the viewpoint of heat resistance.
  • the propylene resin used in the present invention has a melt flow rate (MFR) force measured at a temperature of 230 ° C and a load of 21.18 N in accordance with JISK 7210 ⁇ 0. I ⁇ 200 g / 10 min, especially 0 It is preferably in the range of 5-50 g / 10 min.
  • MFR melt flow rate
  • Propylene resin is blended with known additives as long as the effects of the present invention are not impaired. It may be.
  • the additive include an antioxidant, an ultraviolet absorber, an antistatic agent, a lubricant, a nucleating agent, an antifogging agent, and an antiblocking agent.
  • Antioxidants include, for example, phenolic antioxidants, phosphorus antioxidants, phenolic antioxidants, hindered amine light stabilizers, etc. In addition, phenolic antioxidant mechanisms and phosphorous are included in one molecule. It is also possible to use a composite type antioxidant having a unit having an antioxidant mechanism of the system.
  • the UV absorber include UV absorbers such as 2-hydroxybenzophenone-based and hydroxyphenenolebenzotriazole-based, and benzoate-based UV blockers.
  • the antistatic agent may be any of a polymer type, an oligomer type, and a monomer type.
  • Examples of the lubricant include higher fatty acid amides such as ergic acid amide oleate, higher fatty acids such as stearic acid, and salts thereof.
  • Examples of the nucleating agent include: a sorbitol nucleating agent, an organic phosphate nucleating agent, and a polymer nucleating agent such as polyvinyl alcohol alkane.
  • As an anti-procking agent spherical or nearly fine particles can be used regardless of whether they are inorganic or organic. A plurality of these additives may be used in combination.
  • the above-described propylene resin is formed into a film and used as a raw material for a retardation film.
  • a resin film can be obtained.
  • Propylene resin is melt-kneaded by rotation of the screw in the extruder and extruded from the T die into a sheet.
  • the temperature of the extruded molten sheet is 180 to 300 ° C. If the temperature of the molten sheet at this time is less than 180 ° C., the spreadability is not sufficient, the thickness of the resulting film becomes non-uniform, and there is a possibility that the film has uneven retardation. When the temperature exceeds 300 ° C., the resin is easily deteriorated or decomposed, and bubbles may be formed in the sheet or carbides may be contained.
  • the extruder may be a single screw extruder or a twin screw extruder.
  • the LZD which is the ratio of the length L and the diameter D of the screw
  • the compression ratio which is the ratio to the space volume (the former and the latter)
  • a barrier type screw with LZD of 28-36 and compression ratio of 2.5-3.5 is preferred.
  • the inside of the extruder is preferably a nitrogen atmosphere or a vacuum.
  • an orifice with a diameter of 1 to 5 mm is provided at the tip of the extruder to remove the volatile gas generated by the deterioration or decomposition of the propylene resin, thereby increasing the resin pressure at the tip of the extruder.
  • Increasing the resin pressure at the tip of the orifice extruder means increasing the back pressure at the tip, which can improve the stability of extrusion.
  • the diameter of the orifice used is more preferably 2 to 4 mm in diameter.
  • the T-die used for extrusion is preferably one that does not have minute steps or scratches on the surface of the resin flow path, and its lip portion is plated with a material having a low coefficient of friction with the molten propylene resin.
  • a sharp edge shape that is coated and further polished to a lip tip of 0.3 mm or less in diameter is preferable.
  • materials with a small friction coefficient include tungsten carbide-based and fluorine-based special plating.
  • the flow of molten propylene resin inside the T-die can be adjusted, and the lip can be extruded while suppressing thickness unevenness.
  • a protective film with excellent accuracy and more uniform retardation can be obtained.
  • the molten sheet extruded from the T-die is sandwiched between a metal cooling roll (also referred to as a chill roll or a casting roll) and a touch roll including an elastic body that rotates by pressing in the circumferential direction of the metal cooling roll.
  • a metal cooling roll also referred to as a chill roll or a casting roll
  • a touch roll including an elastic body that rotates by pressing in the circumferential direction of the metal cooling roll.
  • the touch roll may be an elastic body such as rubber, or the surface of the elastic roll covered with an outer cylinder made of a metal sleeve.
  • the molten roll of propylene resin is directly sandwiched between the metal cooling roll and the touch roll for cooling.
  • the surface is an elastic body.
  • a biaxially stretched film of a thermoplastic resin may be interposed between the molten sheet of propylene resin and the touch roll, and may be sandwiched.
  • both the cooling roll and the touch roll have their surface temperatures lowered, and the molten sheet is rapidly cooled. I need to do it.
  • the surface temperature of both rolls is adjusted to a range of 0 to 30 ° C. When these surface temperatures exceed 30 ° C, it takes time to cool and solidify the molten sheet, so the crystal component in the propylene resin grows, and the resulting film is inferior in transparency. There is a fear.
  • the surface temperature of the roll is less than 0 ° C, the surface of the metal cooling roll will dew and water droplets will adhere to it, which tends to deteriorate the appearance of the film.
  • the surface state of the metal cooling roll used is transferred to the surface of the propylene resin film, if the surface is uneven, the thickness accuracy of the resulting propylene resin film may be reduced. Therefore, it is preferable that the surface of the metal cooling roll be in a mirror surface state as much as possible.
  • the roughness of the surface of the metal cooling roll is preferably 0.3 S or less in terms of the standard sequence of maximum height, and more preferably 0.1 to 0.2 S. Is more preferable.
  • the touch roll that forms the nip part with the metal cooling roll has a surface hardness of 65-5 as the value measured by the spring-type hardness test (A type) specified in JISK 6300. 80 is preferable, and 70 to 80 is more preferable.
  • the pressure (linear pressure) when sandwiching the molten sheet is determined by the pressure with which the touch roll is pressed against the metal cooling roll.
  • the linear pressure is preferably 50 to 30 O NZ cm, more preferably 100 to 25 ON / cm.
  • the thermoplastic resin constituting the biaxially stretched film is composed of a propylene resin and Any resin that does not strongly heat-seal can be used. Specific examples include polyester, polyamide, polychlorinated butyl, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, and polyatalonitrile. it can. Of these, polyesters that undergo little dimensional change due to humidity, heat, etc. are most preferred. In this case, the thickness of the biaxially stretched film is usually about 5 to 50 zm, preferably 10 to 3 O / zm.
  • the distance from the lip of the T die to the pressure between the metal cooling roll and the touch roll is preferably 20 O mm or less, and more preferably 16 O mm or less. Is more preferable.
  • the molten sheet extruded from the T-die is stretched from the lip to the roll, and orientation tends to occur. By shortening the air gap as described above, a film having a smaller orientation can be obtained.
  • the lower limit of the air gap is determined by the diameter of the metal cooling roll used and the diameter of the touch roll, and the tip shape of the lip used, and is usually 5 O mm or more.
  • the processing speed when producing a propylene resin film by this method is determined by the time required to cool and solidify the molten sheet.
  • the diameter of the metal cooling port used is increased, the distance at which the molten sheet is in contact with the cooling roll becomes longer, so that production at a higher speed becomes possible.
  • the processing speed is about 5 to 2 OmZ at maximum.
  • the molten sheet sandwiched between the metal cooling roll and the touch roll is cooled and solidified by contact with the roll. Then, after slitting the edge as necessary, it is scraped off by a scraper to form a film.
  • the film in order to protect the surface until the film is used, it may be wound in a state where a surface protective film made of another thermoplastic resin is bonded to one side or both sides.
  • a surface protective film made of another thermoplastic resin is bonded to one side or both sides.
  • Propylene resin melt When the sheet is sandwiched between a metallic cooling roll and a touch roll together with a biaxially stretched film made of a thermoplastic resin, the biaxially stretched film can be used as one surface protective film.
  • the first retardation plate used in the first composite polarizing plate of the present invention has an in-plane retardation value R. Is in the range of 90-200 nm. In-plane retardation value R of the first retardation plate. If the value is out of this range, the viewing angle characteristics of the liquid crystal display device on which it is mounted will deteriorate.
  • the in-plane retardation value R of the first retardation plate in the present invention Indicates a value measured using an automatic birefringence measuring device KOBRA-21 ADH (manufactured by Oji Scientific Instruments).
  • This automatic birefringence measuring device KOBRA-21 ADH has in-plane retardation value R0, thickness direction retardation value Rth, Nz coefficient, in-plane slow axis direction refractive index nx, in-plane phase advance axis direction
  • the refractive index ny and the refractive index nz in the thickness direction can be measured and displayed simultaneously.
  • the first retardation plate used in the first composite polarizing plate according to the present invention has a refractive index in the in-plane slow axis direction of the film nx, a refractive index in the in-plane fast axis direction of the film ny,
  • the Nz coefficient defined by the following formula is in the range of 0.90 to 1.10, where nz is the refractive index in the thickness direction of the film.
  • Nz member (nx— nz / ⁇ ⁇ ⁇ — n y)
  • the first retardation plate used in the present invention aims to be completely uniaxial as described above, its Nz coefficient is set within the range of 0.90 to 1.10. It is difficult to produce a film whose Nz coefficient is less than 0.90 by stretching. On the other hand, when the Nz coefficient exceeds 1.10, the contrast viewing angle of the liquid crystal display device on which the Nz coefficient is mounted decreases.
  • the refractive index nx in the in-plane slow axis direction, the refractive index ny in the in-plane fast axis direction, the refractive index nz in the thickness direction, and the Nz coefficient of the film of the first retardation plate in the present invention are as described above. For example, the value measured using an automatic birefringence measuring device KOBRA-21 ADH (manufactured by Oji Scientific Instruments).
  • the polarizing plate used for the first composite polarizing plate in the present invention can be one generally used in the art, such as polyvinyl alcohol resin. It consists of a resin film such as triacetyl cellulose resin, cyclic cycloolefin resin, and linear cycloolefin resin on both sides or one side of a linear polarizing film in which dichroic dye (iodine, dichroic organic dye, etc.) is adsorbed and oriented to fat.
  • a structure in which a protective layer is laminated is generally used.
  • FIG. 1 shows the case where a polarizing plate 2 having protective layers 6 and 7 provided on both sides of the linear polarizing film 5 is used.
  • FIG. 2 shows one side of the linear polarizing film 5
  • a case is shown in which a polarizing plate 12 having a protective layer 6 provided on the surface opposite to the side on which the one phase difference plate 3 is laminated is used.
  • the first retardation plate is disposed so that the slow axis direction of the first retardation plate and the absorption axis direction of the polarizing plate intersect at an angle of 80 to 100 °.
  • a phase difference plate and a polarizing plate are laminated. If the angle formed by the slow axis direction of the first retardation plate and the absorption axis direction of the polarizing plate is out of this range, the liquid crystal display device on which the first retardation plate is placed will leak light during black display, reducing the contrast ratio. Further, color unevenness is likely to occur.
  • the angle formed by the slow axis direction of the first retardation plate and the absorption axis direction of the polarizing plate must be within the range of 85 to 95 °. It is more preferable that it is within the range of 89 ° to 91 °.
  • the pressure-sensitive adhesive (adhesive) layer 4 formed on the side opposite to the side adjacent to the polarizing plates 2 and 1 2 of the first retardation plate 3 in the first composite polarizing plates 1 and 1 1 has been conventionally used. It can be formed using various pressure-sensitive adhesives that have been used for liquid crystal display devices, such as pressure-sensitive adhesives such as acrylic, rubber, urethane, silicone, and polybutyl ether. Adhesives based on acrylic resin having excellent weather resistance and heat resistance as a base polymer are suitable.
  • the acrylic pressure-sensitive adhesive is not particularly limited, but (meth) butyl acrylate, (meth) ethyl acrylate, (meth) isooctyl acrylate, (meth) acrylic acid 2_ethylhexyl, etc.
  • a (meth) acrylic acid ester-based polymer or a copolymer base polymer using two or more of these (meth) acrylic acid esters is preferably used.
  • polar monomers are copolymerized in these base polymers.
  • polar monomers examples include (meth) alk Rylic acid, (meth) acrylic acid 2-hydroxypropyl, (meth) acrylic acid hydrated mouth chechtil, (meth) acrylic amide, N, N-dimethylaminoethyl (meth) acrylate, glycidyl (meth) atari
  • monomers having a functional group such as a carboxyl group, a hydroxyl group, an amide group, an amino group, and an epoxy group.
  • the cross-linking agent is a divalent or polyvalent metal salt that forms a strong rubonic acid metal salt with a carboxyl group, or a polyamine compound that forms an amide bond with a carboxyl group.
  • a polyepoxy compound or a polyol compound, which forms an ester bond with a carboxyl group, a polyisocyanate compound, which forms an amide bond with a carboxyl group Etc. are exemplified.
  • polyisocyanate compounds are widely used as organic crosslinking agents.
  • the pressure-sensitive adhesive composition can be used to adjust the pressure-sensitive adhesive's adhesive strength, cohesive strength, viscosity, elastic modulus, glass transition temperature, etc.
  • appropriate additives such as natural and synthetic resins, tackifier resins, antioxidants, UV absorbers, dyes, pigments, antifoaming agents, corrosion inhibitors, photopolymerization initiators, etc. You can also. Further, fine particles can be contained to form a pressure-sensitive adhesive layer exhibiting light scattering properties.
  • the thickness of the pressure sensitive adhesive layer is preferably 1 to 30 ⁇ , and more preferably 5 to 25 ⁇ . If the pressure-sensitive adhesive layer is too thin, the tackiness is reduced, and if it is too thick, problems such as the pressure-sensitive adhesive sticking out easily occur.
  • the method for forming the pressure-sensitive adhesive layer on the first retardation plate 3 is not particularly limited, and the surface on which the pressure-sensitive adhesive layer of the first retardation plate 3 is to be formed is described above. After applying a solution containing each component including the base polymer and drying to form a pressure-sensitive adhesive layer, it may be obtained by laminating a separator that has been subjected to a release treatment such as silicone, After forming the pressure sensitive adhesive layer on the separator, the first phase It may be transferred to the difference plate 3 and laminated. In addition, when forming the pressure-sensitive adhesive layer on the polarizing film, if necessary, at least one of the first retardation plate and the pressure-sensitive adhesive layer may be subjected to an adhesion treatment, such as a corona treatment. . The surface of the formed pressure-sensitive adhesive layer is usually protected by a separator film that has been subjected to a release treatment, and the separator film is composed of a liquid crystal cell as described later. It is peeled off before pasting. '
  • an epoxy resin, a urethane resin, or a cyan resin may be used for bonding the polarizing film and the protective layer, or for bonding the polarizing film or protective layer and the first retardation plate.
  • Adhesives composed of acrylate resin, acrylic acid resin and the like can be used.
  • a preferable adhesive is an aqueous adhesive, that is, an adhesive component dissolved in water or dispersed in water.
  • Another preferable adhesive is a solventless adhesive, specifically, an adhesive layer that is formed by reaction-curing a monomer or oligomer by heating or irradiation with active energy rays. Can do.
  • the adhesive component that can be a water-based adhesive examples include water-soluble cross-linkable epoxy resins and urethane resins.
  • water-soluble crosslinkable epoxy resin for example, polyalkylene polyamine obtained by reaction of polyalkylene polyamine such as diethylenetriamine and triethylenetetramine and dicarboxylic acid such as adipic acid is allowed to react with epichlorohydrin. Mention may be made of the polyamide epoxy resin obtained.
  • Specific examples of such commercially available polyamide epoxy resins include Sumire's Resin 650 (manufactured by Sumika Chemtex Co., Ltd.), Sumire's Resin 675 (manufactured by Sumika Chemtex Co., Ltd.), and the like. Can be mentioned.
  • polyvinyl alcohol resins include partially saponified polyvinyl alcohol, fully saponified polyvinyl alcohol, and carboxyl group-modified polyvinyl alcohol. It may be a modified polyvinyl alcohol-based resin such as alcohol, acetoacetyl-modified polyvinyl alcohol, methylol-group-modified polyvinyl alcohol, or amino-group-modified polyvinyl alcohol.
  • a saponified product of a copolymer of butyl acetate and unsaturated carboxylic acid or a salt thereof, that is, carboxyl group-modified polyvinyl alcohol is preferably used.
  • carboxyl group-modified polyvinyl alcohol is preferably used.
  • carboxyl group is a concept including one COOH and its salt.
  • Specific examples of commercially available products of carboxyl group-modified polyvinyl alcohol include Kuraray Poval KL 156 (Kuraray Co., Ltd.), Kuraray Poval KL-3 1 8 (Kuraray Co., Ltd.), Kuraray Poval KL -1 1 8 (manufactured by Kuraray Co., Ltd.), GOHSENAL T-3 30 (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.), GOHSENAL T 1 350 (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.), DR-0-4 1 5 (manufactured by Denki Kagaku Kogyo Co., Ltd.), AF—17 (manufactured by Nippon Vinegar Poval Co., Ltd.), AT—17 (manufactured by Nippon Vinegar Pover Co., Ltd.), AP—17 (Japan) Vinegar and Poval Co., Ltd.).
  • an adhesive solution is prepared by dissolving the epoxy resin and other water-soluble resin such as polybulal alcohol resin added as necessary in water.
  • the water-soluble epoxy resin preferably has a concentration in the range of 0.2 to 2 parts by weight per 100 parts by weight of water.
  • the amount is preferably 1 to 10 parts by weight, more preferably 1 to 5 parts by weight per 100 parts by weight of water.
  • suitable urethane resins include ionomer type urethane resins, particularly polyester ionomer type urethane resins.
  • the ionomer type is obtained by introducing a small amount of an ionic component (hydrophilic component) into the urethane resin constituting the skeleton.
  • the polyester ionomer type urethane resin is a urethane resin having a polyester skeleton, into which a small amount of an ionic component (hydrophilic component) is introduced.
  • the strong ionomer-type urethane resin is emulsified directly in water without using an emulsifier and becomes emulsion, so it is suitable as an aqueous adhesive.
  • Poly Specific examples of commercially available ester ionomer-type urethane resins include Hydran AP—20 (produced by Dainippon Ink and Chemicals Co., Ltd.) and Hydran APX—10 1 H (Dainippon). Ink Chemical Industry Co., Ltd.).
  • Isocyanate crosslinkers are compounds that have at least two isocyanato groups (one NCO) in the molecule. Examples include 2, 4_tolylene diisocyanate, phenol diisocyanate, 4, 4 '— In addition to polyisocyanate monomers such as diphenylmethane diisocyanate, 1,6-hexamethylene diisocyanate, and isophorone diisocyanate, multiple molecules of these are polyvalent such as trimethylolpropane.
  • polyisocyanate modifieds such as burettes formed by carbonationSpecific examples of commercially available isocyanate cross-linking agents include Hydran Assist C-1 (Dai Nippon Ink Chemical Co., Ltd.).
  • the concentration of the urethane resin is 10 to 70 weight 0 / from the viewpoint of viscosity and adhesiveness. And even 20 to 50 weight. Those dispersed in water so as to be / 0 are preferable.
  • the blending amount may be appropriately selected so that the isocyanate cross-linking agent is 5 to 100 parts by weight with respect to 100 parts by weight of the urethane resin.
  • the aqueous adhesive as described above can be applied to at least one of the protective layer, the first retardation plate, and the polarizing film, and bonded together to form a polarizing plate.
  • the method of bonding the polarizing film and the protective layer is not particularly limited.
  • an adhesive is uniformly applied to the surface of the polybulal alcohol polarizing film or the protective layer, and the other film is overlaid on the coated surface.
  • Pasting with rolls and drying. And so on. Drying is performed at a temperature of about 60 to 100 ° C., for example. After drying, from the viewpoint of further increasing the adhesive strength, it is preferable to cure for about 1 to 10 days at a temperature slightly higher than room temperature, for example, about 30 to 50 ° C.
  • the solventless type adhesive refers to an adhesive that does not contain a significant amount of solvent, and is generally a curable compound that polymerizes by heating or irradiation of active energy rays, and polymerization initiation. It is comprised including an agent.
  • an epoxy compound containing no aromatic ring in the molecule is suitably used as the curable compound.
  • the adhesive using an epoxy compound that does not contain an aromatic ring in the molecule include those described in the publication of Japanese Patent Application Laid-Open No. 2000-045.
  • examples of such epoxy compounds that do not contain an aromatic ring include hydrides of aromatic epoxy compounds, alicyclic epoxy compounds, and aliphatic epoxy compounds.
  • the curable epoxy compound used for the adhesive usually has two or more epoxy groups in the molecule.
  • a hydride of an aromatic epoxy compound can be obtained by selectively hydrogenating an aromatic epoxy compound to an aromatic ring under pressure in the presence of a catalyst.
  • aromatic epoxy compounds include bisphenol type epoxy compounds such as bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, and bisphenol S diglycidyl ether; phenol novolac epoxy resins and cresols.
  • Novolac epoxy resin novolac epoxy resin such as hydroxybenzaldehyde phenol novolac epoxy resin; polyfunctional type such as tetrahydroxydiphenyl methane glycidyl ether, tetrahydroxybenzophenone glycidyl ether, epoxidized polyvinyl phenol
  • examples include epoxy compounds. Among these hydrides of aromatic epoxy compounds, hydrogenated bisphenol A diglycidyl ether is preferred.
  • the alicyclic epoxy compound is an epoxy bonded to an alicyclic ring as shown in the following formula. This refers to a compound having at least one Si group in the molecule (wherein m represents an integer of 2 to 5).
  • a compound in which one or more hydrogen atoms in (CH 2 ) m in the above formula are removed and bonded to another chemical structure can be an alicyclic epoxy compound.
  • the hydrogen forming the alicyclic ring may be appropriately replaced with a linear alkyl group such as a methyl group or an ethyl group.
  • alicyclic epoxy compounds include 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-1-6-methylcyclohexylmethyl 3,4-epoxy-6- Methy ⁇ -hexanehexane / Boxylate, Ethylenebis (3,4-epoxycyclohexanecarboxylate), Bis (3,4-Epoxycyclohexylmethyl) Adipate, Bis (3,4, Epoxy-6-methylcyclo (Hexylmethyl) adipate, diethylene glycol bis (3,4-epoxycyclohexyl ⁇ / methinoleethenore), ethyleneglycolenobis (3,4-epoxycyclohexylmethyletherole), 2, 3, 14, 15 —Diepoxy-1, 7, 1, 1, 18, 21—Tetraoxatrispirone [5.
  • an aliphatic polyhydric alcohol or a polyglycidyl ether of an alkylene oxide adduct thereof corresponds to this.
  • examples of such aliphatic epoxy compounds include diglycidyl ether of 1,4-butanediol, diglycidyl ether of 1,6-hexanediol, triglycidyl ether of glycerin, and triglycidyl ether of trimethylolpropane.
  • Diglycidyl etherate of polyethylene glycolenole Diglycidinoleate of propylene dallicol ⁇ , Aliphatic polyhydric alcohols such as ethylene glycolanol and propylene glycol ⁇ , and glycerin. Examples thereof include polyglycidyl ethers of polyether polyols obtained by adding oxides (ethylene oxide and propylene oxide).
  • the epoxy compounds exemplified here may be used alone or in combination with a plurality of epoxy compounds.
  • the epoxy equivalent of the epoxy compound used for the solventless adhesive is usually in the range of 30 to 300 g g equivalent, preferably 50 to 1550 g z equivalent.
  • the epoxy equivalent is less than 30 g / equivalent, the flexibility of the protective film after curing may be lowered, or the adhesive strength may be lowered.
  • it exceeds 300,000 equivalents the compatibility with other components may decrease.
  • a force thione polymerization initiator In order to cure the epoxy compound by force thione polymerization, a force thione polymerization initiator is added.
  • the cationic polymerization initiator generates a cationic species or a Lewis acid upon irradiation or heating of active energy rays such as visible light, ultraviolet light, X-rays, and electron beams, and initiates the polymerization reaction of the epoxy group. From the viewpoint of workability, it is preferable that any type of cationic polymerization initiator is provided with latency.
  • the light power thione polymerization initiator acts catalytically by light, so even if it is mixed with an epoxy compound, the storage stability and work Excellent in properties.
  • Examples of compounds that generate cationic species and Lewis acids upon irradiation with active energy rays include aromatic diazonium salts, aromatic odonium salts, onium salts such as aromatic sulfonium salts, and iron-allene complexes. .
  • aromatic sulfonium salts in particular, have ultraviolet absorption characteristics even in a wavelength region of 300 nm or more, and therefore can provide a cured product having excellent curability and good mechanical strength and adhesive strength. Therefore, it is preferably used.
  • TPS-102 (Midori Chemical Co., Ltd.)
  • TPS-103 (Midori Chemical Co., Ltd.)
  • TPS—105 (Midori Chemical Co., Ltd.)
  • MD S-103 (Midori Chemical Co., Ltd.)
  • Examples include DTS-103 (manufactured by Midori Chemical Co., Ltd.) and PI-2074 (manufactured by Rhodia).
  • CI-5102 manufactured by Nippon Soda Co., Ltd.
  • the compounding amount of the light thione polymerization initiator is usually 0.5 to 20 parts by weight, preferably 1 to 100 parts by weight of the epoxy compound.
  • a photosensitizer can be used in combination as necessary. By using a photosensitizer, the reactivity is improved, and the mechanical strength and adhesive strength of the cured product can be improved.
  • the photosensitizer include carbonyl compounds, organic sulfur compounds, persulfides, redox compounds, azo and diazo compounds, halogen compounds, and photoreductive dyes.
  • the blending amount is usually 0.1 to 20 parts by weight with respect to 100 parts by weight of the epoxy compound.
  • the thermal cationic polymerization initiator is a compound that generates a cationic species or a Lewis acid upon heating.
  • thermal cationic polymerization initiator include benzylsulfonium salt, thiophenium salt, thiolanium salt, benzylammonium. , Pyridinium salt, hydrazinum salt, carboxylic acid ester, sulfonic acid ester, amine imidazole and the like.
  • Thermal cationic polymerization initiators can also be easily obtained as commercial products, such as Adeka Opton CP 7 7 (manufactured by ADE KA), Adeka Opton CP 6 6 (manufactured by ADE KA), CI—2 6 3 9 (manufactured by Nippon Soda Co., Ltd.), CI _ 2 6 2 4 (manufactured by Nippon Soda Co., Ltd.), Sun-Aid SI—60 L (manufactured by Sanshin Chemical Co., Ltd.), Sun-Aid SI—80 L ( Sanshin Chemical Industry Co., Ltd.), Sun-side SI-1100 L (manufactured by Sanshin Chemical Industry Co., Ltd.), and the like.
  • Adeka Opton CP 7 7 manufactured by ADE KA
  • Adeka Opton CP 6 6 manufactured by ADE KA
  • CI—2 6 3 9 manufactured by Nippon Soda Co., Ltd.
  • the above-described photothion polymerization and thermal cationic polymerization may be used in combination.
  • the epoxy adhesive may further contain a compound that promotes cationic polymerization, such as oxetanes and polyols.
  • a solventless type adhesive there is no particular limitation on the method of applying to at least one of the polarizing film, the protective layer and the first retardation plate.
  • organic solvents such as hydrocarbons typified by toluene and esters typified by ethyl acetate can be used.
  • Solvent-free The thickness of the adhesive layer using a mold type adhesive is usually 50 ⁇ or less, preferably 20 ⁇ m or less, more preferably 10 ⁇ or less, and usually l / m or more. is there. Solvent-free adhesives are coated with an active energy ray or heated as described above to cure the adhesive layer, polarizing film and protective layer, polarizing film or protective layer and first The retardation plate is fixed. In the case of curing by irradiation with active energy rays, ultraviolet rays are preferably used. Specific examples of the ultraviolet light source include a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, a black light lamp, and a metal halide lamp.
  • the irradiation intensity and irradiation amount of active energy rays or ultraviolet rays are sufficient to activate the polymerization initiator and not adversely affect the cured adhesive layer, polarizing film, protective layer, and retardation film. It may be selected appropriately. When curing by heating, it can be heated by a generally known method, and the temperature and time at that time sufficiently activate the polymerization initiator, and the cured adhesive layer and polarized light. You should make an appropriate selection so as not to adversely affect the film and protective film.
  • corona discharge treatment it is preferable to perform corona discharge treatment on the side of the protective layer or the first retardation plate that is bonded to the polarizing film.
  • the corona discharge treatment is a treatment in which a high voltage is applied between the electrodes to discharge and activate the resin film disposed between the electrodes.
  • the effect of the edge discharge process varies depending on the type of electrode, electrode spacing, voltage, humidity, type of resin film used, etc.For example, the electrode spacing is 1 to 5 mm, and the moving speed is 3 to It is preferable to set it to about 2 O m / min.
  • FIG. 3 is a perspective view schematically showing a preferred example of the second composite polarizing plate 21 used in the composite polarizing plate set of the present invention, with each layer being separated
  • FIG. FIG. 6 is a perspective view schematically showing a second composite polarizing plate 31 of another preferred example used in the composite polarizing plate set of the invention in a state where the layers are separated from each other.
  • the second compound shown in Fig. 3 and Fig. 4. The combined polarizing plates 2 1 and 3 1 have the same structure except that the polarizing plates 2 2 and 3 2 are partially different, and the polarizing plates 2 2 and 3 2 are connected to the second retardation plate 2 3 and The pressure-sensitive adhesive layer 24 is laminated.
  • the second retardation plate 23 used in the present invention has an in-plane retardation value R0 in the range of 0 to 30 nm (preferably 0 to 10 nm), and a thickness direction retardation value Rth of 3 It is characterized by being in the range of 0 to 300 nm (preferably 50 to 300 nm). In-plane retardation value R of the second retardation plate 2 3. When is over 30 nm, depolarization due to the front phase difference occurs and the contrast ratio decreases. On the other hand, when the retardation value Rth in the thickness direction of the second retardation plate 23 is less than 30 nm, the birefringence of the liquid crystal in the liquid crystal cell cannot be sufficiently offset, and the viewing angle becomes narrow.
  • the in-plane retardation value R of the second retardation plate 23 is the in-plane retardation value R of the first retardation plate described above.
  • Such retardation characteristics can be realized by forming the second retardation plate 23 using an organically modified clay composite and a binder resin.
  • the organic modified clay composite is a composite of an organic compound and a clay mineral having a layered structure, and is dispersible in an organic solvent.
  • the second retardation plate 23 according to the present invention is prepared by preparing a coating liquid in which such an organically modified clay complex is contained in an organic solvent together with a binder resin, and applying the coating liquid in layers. It is formed by removing the solvent.
  • Examples of the clay mineral having a layered structure include the smectite group and the swellable mica. Of these, the smectite group is preferably used because of its excellent transparency. Examples of those belonging to the smectite group include hectrite, montmorillonite, and bentonite. Of these, those chemically synthesized are preferable in that they have few impurities and are excellent in transparency. In particular, synthetic hectorite having a controlled particle size is preferably used because it suppresses the scattering of visible light. Examples of organic compounds complexed with clay minerals include compounds that can react with or interact with oxygen atoms and hydroxyl groups of clay minerals, or ionic compounds that can be exchanged with exchangeable cations.
  • organic modified clay complex can be swollen or dispersed in an organic solvent.
  • compounds that can interact with oxygen atoms and hydroxyl groups of clay minerals include surface modifiers such as silane coupling agents and titanium coupling agents, and can be modified by polymerization in the system. —Strength prolatatam, and polyvinylpyrrolidone, alkyl-substituted pyrrolidone and the like.
  • ionic compounds that can be exchanged for exchangeable cations include nitrogen-containing compounds and phosphorus-containing compounds. For example, primary, secondary or tertiary amines, and quaternary ammonium compounds. And quaternary phosphonium compounds.
  • quaternary ammonium compounds and quaternary phosphonium compounds are preferably used because of easy cation exchange, and examples thereof include those having a long-chain alkyl group and those having an alkyl ether chain.
  • Those having an O) nH group or one (CH 2 CH 2 CH 2 O) nH group are preferred.
  • Organically modified clay composites often contain chlorine-containing compounds as a result of the various secondary materials used in the production. If the amount of such a chlorinated compound is large, there is a possibility of bleeding out from the film when the second retardation plate 23 is formed. In that case, when the second retardation plate 2 3 is bonded to the liquid crystal cell glass via a pressure-sensitive adhesive, the adhesive strength significantly decreases with time. Therefore, it is preferable to remove the chlorine compound from the organically modified clay complex by washing, and it can be contained in the organic solvent in a state where the amount of chlorine contained in the complex is not more than 200 ppm. For example, a decrease in the adhesive strength can be suppressed. The removal of the chlorine compound can be performed by washing the organically modified clay complex with water.
  • Two or more organically modified clay composites can be used in combination.
  • Commercially available products of suitable organically modified clay composites include synthetic hepatite and quaternary ammonium compounds. Lunicentite STN (manufactured by Coop Chemical Co., Ltd.), Lucentite SPN (manufactured by Coop Chemical Co., Ltd.), etc.
  • Such organically modified clay composites that can be dispersed in an organic solvent are used in combination with a binder resin from the standpoint of ease of coating on a substrate, optical properties, and mechanical properties.
  • the binder resin used in combination with the organically modified clay composite is soluble in organic solvents such as toluene, xylene, acetone, and ethyl acetate, and in particular, has a glass transition temperature of room temperature or lower (approximately 20 ° C or lower). Those are preferably used.
  • those having hydrophobic properties are desirable.
  • binder resin examples include polyvinyl acetal resins such as polybutyral and polyvinyl formal, cellulose resins such as cellulose acetate butyrate, acrylic resins such as butyl acrylate, urethane resins, methacrylate resins, Examples include epoxy resins and polyester resins. Among them, urethane resin is preferable because the dispersibility of the organic modified clay complex is good.
  • binder resins include Denka Butylal # 3 00 0—K (produced by Denki Kagaku Kogyo Co., Ltd.), which is an aldehyde-modified resin of polyvinyl alcohol, and Aalon S 1 which is an acrylic resin.
  • Preferred examples include SBU lacquer 0 8 6 6 (Suika Bayer Urethane Co., Ltd.), which is a urethane resin based on isophorone diisocyanate, manufactured by Toagosei Co., Ltd.
  • the content ratio of the organically modified clay complex and the binder resin in the second phase difference plate 2 3 is in the range of 1: 2 to 10: 1, especially in the range of 1: 1 to 2: 1, in the weight ratio of the former: the latter. It is preferable from the viewpoint of improving mechanical properties such as preventing cracking of the second retardation plate 2 3.
  • the organically modified clay complex and the binder resin are applied onto the substrate in the state of a coating liquid prepared by being dispersed in an organic solvent.
  • the binder resin is dissolved in an organic solvent, and the organic modified clay complex is dispersed in the organic solvent.
  • the solid content concentration of this coating solution is within the range where there is no practical problem with the prepared coating solution. There is no limitation as long as it does not gel or become cloudy in the surroundings, but it is usually used in a range where the total solid concentration of the organically modified clay composite and the binder resin is about 3 to 15% by weight.
  • the optimum solid content concentration varies depending on the type of organically modified clay complex and binder resin, and the composition ratio of the two, so it is set for each composition.
  • various additives such as a viscosity modifier for improving the coating property during film formation and a curing agent for further improving the hydrophobicity and / or durability may be added.
  • the coating liquid preferably has a moisture content measured by a Karl Fischer moisture meter within the range of 0.15 to 0.35% by weight.
  • a Karl Fischer moisture meter within the range of 0.15 to 0.35% by weight.
  • phase separation occurs in a water-insoluble organic solvent, and the coating liquid tends to separate into two layers.
  • the moisture content is less than 0.15% by weight, the haze value of the formed second retardation plate may be increased.
  • the method for setting the water content of the coating liquid within the above-mentioned range is not particularly limited, but the water content can be easily adjusted by adding water to the coating liquid.
  • the water content can be easily adjusted by adding water to the coating liquid.
  • the organic solvent, the organically modified clay complex and the binder resin as described above By simply mixing the organic solvent, the organically modified clay complex and the binder resin as described above by the usual method, the water content of 0.15% by weight or more is hardly exhibited. Therefore, it is preferable to adjust the water content within the above range by adding a small amount of water to a coating liquid in which an organic solvent, an organically modified clay complex and a binder resin are mixed.
  • the time at which water is added is not particularly limited. However, if a predetermined amount of water is added after preparing a coating solution and measuring the moisture content after a certain period of time, reproducibility is improved. In addition, the moisture content can be controlled with high accuracy, which is preferable.
  • the method of applying the coating liquid is not particularly limited, and various known methods such as a direct gravure method, a reverse 'gravure method, a die coat method, a comma coat method, and a bar coat method can be used. .
  • the substrate on which the coating liquid is applied has an in-plane retardation value R.
  • R there is no particular limitation as long as it is a material having a substantially open mouth, but an unstretched film made of a chain olefin resin, an unstretched film made of a cycloolefin resin, an unstretched film made of a cellulose acylate resin, and the like are preferable.
  • this base material may also serve as the protective layer 27 of the polarizing plate 2 2.
  • the protective layer 27 with the second retardation plate 23 is attached to the polarizing film 25.
  • the second retardation film 23 may be formed by applying the above-described coating liquid to the protective layer 27 side of the polarizing film 25 having the protective layer 27 bonded beforehand. Good.
  • a primer layer may be formed between the second retardation plate 23 and the protective layer 27.
  • the polarizing plate used for the second composite polarizing plate in the present invention can be one generally used in the art, like the polarizing plate used for the first composite polarizing plate. Protection made of resin film such as triacetyl cellulose resin, cyclic cycloolefin resin, chain cycloolefin resin on both sides or one side of linear polarizing film with dichroic dye (iodine, dichroic organic dye, etc.) adsorbed and oriented on resin A structure in which layers are laminated is generally used.
  • FIG. 3 shows the case where the polarizing plate 2 2 having protective layers 2 6 and 2 7 provided on both sides of the linear polarizing film 25 is used
  • FIG. 4 shows the linear polarizing film 25. This shows a case in which a polarizing plate 3 2 provided with a protective layer 26 on one side (the side opposite to the side on which the second phase difference plate 23 is laminated) is used.
  • the pressure-sensitive adhesive layer 2 4 formed on the side opposite to the side adjacent to the polarizing plate 2 2, 3 2 of the second retardation plate 2 3 in the second composite polarizing plate 2 1, 3 1 in the present invention In the same manner as described above for the pressure-sensitive adhesive layer 4 in the first composite polarizing plate 1, 11, it can be formed using various pressure-sensitive adhesives conventionally used for liquid crystal display devices. .
  • the above-mentioned adhesives that are preferably used for bonding with the polarizing film first retardation plate are also preferably used.
  • FIG. 5 (a) is a cross-sectional view schematically showing an example of manufacturing an example of a liquid crystal display device manufactured using the set of composite polarizing plates of the present invention.
  • Fig. 5 (b) It is a top view shown in the shifted state.
  • FIG. 5 shows a set of composite polarizing plates in which the first composite polarizing plate 1 in the example shown in FIG. 1 and the second composite polarizing plate 21 in the example shown in FIG. 3 are combined.
  • the state in which the plate 1 is attached to one side of the liquid crystal 50 and the second composite polarizing plate 21 is attached to the other side of the liquid crystal cell 50 is schematically shown with the layers separated ( Pressure sensitive tt The adhesive layer is not shown).
  • the composite polarizing plate set of the present invention is suitably used for a vertical alignment (VA) mode liquid crystal display device.
  • VA vertical alignment
  • the first composite polarizing plate 1 When used in a liquid crystal display device in the vertical alignment mode, as shown in FIG. 5 (b), the first composite polarizing plate 1 has an absorption axis direction 2a of the polarizing plate 2 on the viewing side (front side) of the liquid crystal cell. Is arranged in parallel with the horizontal direction (longitudinal direction) of the liquid crystal cell, and the absorption axis direction 2 a of the polarizing plate 2 and the slow axis direction 3 a of the first retardation plate 3 intersect each other substantially perpendicularly. Placed and pasted.
  • the absorption axis direction 2 2 a of the polarizing plate 2 2 is parallel to the vertical direction (short direction) of the liquid crystal cell on the side opposite to the viewing side (rear side) of the liquid crystal cell. Further, the polarizing plate 2 2 is disposed so that the absorption axis direction 2 2 a of the polarizing plate 2 2 intersects the absorption axis direction 2 a of the polarizing plate 2 in the first composite polarizing plate 1 substantially perpendicularly, and is attached. Attached.
  • the type of the liquid crystal cell is not particularly limited as long as it is a VA mode liquid crystal cell.
  • a liquid crystal display device comprising the above-described set of composite polarizing plates of the present invention and a liquid crystal cell, wherein the first composite polarizing plate is disposed on one side of the liquid crystal cell, and the liquid crystal cell A liquid crystal display device having a second composite polarizing plate disposed on the other side is also provided.
  • the first composite polarizing plate is bonded to the liquid crystal cell via the pressure-sensitive adhesive layer
  • the second composite polarizing plate is also bonded to the liquid crystal cell via the pressure-sensitive adhesive layer.
  • the present invention also has a structure in which a long roll of a first retardation plate is laminated on a long aperture of a polarizing plate in which an absorption axis direction is arranged in parallel to the longitudinal direction, and the first retardation plate
  • the slow axis direction of the polarizing plate and the absorption axis direction of the polarizing plate are arranged so that they intersect at an angle of 80 to 100 °, and the first retardation plate is a propylene resin.
  • the in-plane retardation value R0 is in the range of 90 to 200 nm, the refractive index in the in-plane slow axis direction of the film is n X, and the in-plane fast axis of the film
  • a composite polarizing plate roll having an Nz coefficient in the range of 0.90 to 1.10 when the refractive index in the direction is ny and the refractive index in the thickness direction of the film is nz is also provided.
  • Such a composite polarizing plate roll of the present invention can be suitably used for producing the first composite polarizing plate in the above-described set of composite polarizing plates of the present invention.
  • the long roll of the first retardation plate in the composite polarizing plate roll of the present invention uses a propylene resin. Even when fixed end uniaxial stretching is applied,
  • the first composite polarizing plate used for the set of the composite polarizing plate of the present invention described above can be easily manufactured.
  • EXAMPLES The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.
  • “parts” and “%” representing the amount used or content are based on weight unless otherwise specified.
  • the thickness direction retardation value Rth and Nz coefficient are all values measured using an automatic birefringence measuring device KO BRA-2 21ADH (manufactured by Oji Scientific Instruments).
  • Polypropylene resin film (Sumitomo Nobrene W151, manufactured by Sumitomo Chemical Co., Ltd.) was formed to obtain a 40 ⁇ um thick film, and then the fixed phase was uniaxially stretched at the fixed end. I got a plate.
  • the layers were bonded together with an adhesive in a state where they were arranged so that the slow axis direction of one phase difference plate intersected.
  • a pressure-sensitive adhesive layer (P-3132, manufactured by Lintec Corporation) formed on a separate film was transferred to the surface of the first retardation plate opposite to the side adjacent to the polarizing plate.
  • Sample 1 of the first composite polarizing plate was produced.
  • In-plane retardation value R of the first retardation plate. was 140 nm and the Nz coefficient was 1.00.
  • Lucentite STN manufactured by Co-op Chemical Co., Ltd.
  • isophorone diisocyanate base is used as the binder resin.
  • SB U lacquer 0866 manufactured by Sumika Bayer Urethane Co., Ltd.
  • SB U lacquer 0866 manufactured by Sumika Bayer Urethane Co., Ltd.
  • a coating retardation layer was formed by drying at 80 ° C. for 2 minutes to obtain a second retardation plate.
  • the obtained second retardation plate had an in-plane retardation value R0 of 0.2 nm and a thickness direction retardation value Rth of 170 nm.
  • the second retardation plate is bonded to the triacetyl cellulose surface side with an adhesive on the side of the polarizing plate where the polarizing film of the polarizing plate having triacetyl cellulose as a protective layer is exposed on one surface.
  • a pressure-sensitive adhesive layer (P_3132, manufactured by Lintec Co., Ltd.) formed on the separate film was transferred to obtain Sample 1 of the second composite polarizing plate.
  • the absorption axis direction of the polarizing plate is on the viewing side (front side).
  • Sample 1 of the first composite polarizing plate was attached via a pressure-sensitive adhesive layer so as to be parallel to the horizontal direction (longitudinal direction) of the liquid crystal television.
  • the second composite polarized light is passed through the pressure-sensitive adhesive layer so that the absorption axis direction is parallel to the lead straight direction (short direction) of the liquid crystal television on the opposite side (rear side) to the viewing side of the liquid crystal cell.
  • a polarizing plate was attached to Sample 1 of the plate to obtain a liquid crystal display device.
  • a norbornene resin film (Z EONOR, manufactured by Optes Co., Ltd.), which is a cycloolefin-based resin, is uniaxially stretched at the fixed end, and has the in-plane retardation value R0 and Nz coefficient as shown in Table 1, respectively.
  • Sample plates 2 to 5 of the first composite polarizing plate were produced in the same manner as in Example 1 except that retardation plates were produced and these were used respectively.
  • In-plane retardation value R as shown in Table 2.
  • Samples 2 to 5 of the second composite polarizing plate were prepared in the same manner as in Example 1 except that second retardation plates each having a retardation value Rth in the thickness direction were prepared.
  • the liquid crystal display devices of Comparative Examples 1 to 4 were prepared in the same manner as in Example 1 except that the samples of the first composite polarizing plate and the sample of the second composite polarizing plate were combined as shown in Table 3. Produced.
  • EZ_contrast 88XL manufactured by ELD IM
  • FIG. 6 is a graph showing the relationship between the Nz coefficient of the first retardation plate of the liquid crystal display devices obtained in Example 1 and Comparative Examples 1 to 4 and the CR viewing angle. From FIG. 6, it can be seen that when a completely uniaxial retardation film is used as the first retardation film, a good viewing angle characteristic is obtained. In contrast, even with a uniaxial retardation film, it can be seen that the viewing angle characteristics deteriorate due to the slightly biaxiality. Industrial applicability
  • the set of the composite polarizing plate of the present invention hardly changes the color even when the viewing angle is changed, and can obtain a good viewing angle characteristic, and is particularly useful for a liquid crystal display device in a vertical alignment mode. .

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Polarising Elements (AREA)
  • Liquid Crystal (AREA)

Abstract

L'invention concerne un ensemble composé de la première plaque de polarisation composite (1), qui est réalisée en stratifiant une plaque de polarisation (2), la première lame à retard (3) et une couche adhésive sensible à la pression (4) dans cet ordre, la première lame à retard (3) étant un film de retard en résine de propylène étiré qui a une différence de phase dans le plan R0 de 90 à 200 nm et un coefficient Nz de 0,90 à 1,10 et est agencé de telle manière que l'axe de phase retardé croise l'axe d'absorption de la plaque de polarisation (2) à un angle de 80 à 100°, et de la seconde plaque de polarisation composite qui a une structure réalisée en stratifiant une plaque de polarisation, la seconde lame à retard et une couche adhésive sensible à la pression dans cet ordre, la seconde lame à retard contenant à la fois un composite d'argile modifiée/organique et une résine de liaison et ayant une différence de phase dans le plan R0 de 0 à 30 nm et une différence de phase dans le sens de l'épaisseur Rth de 30 à 300 nm ; un affichage à cristaux liquides fourni avec l'ensemble ; et des rouleaux de plaque de polarisation composite associés.
PCT/JP2008/072212 2007-12-06 2008-12-01 Rouleau de plaque de polarisation composite, ensemble plaque de polarisation composite et affichage à cristaux liquides WO2009072638A1 (fr)

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JP2007-315957 2007-12-06
JP2007315957A JP2009139642A (ja) 2007-12-06 2007-12-06 複合偏光板ロール、複合偏光板セットおよび液晶表示装置

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Cited By (2)

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CN101923183A (zh) * 2009-06-15 2010-12-22 住友化学株式会社 光学层叠体及其制造方法
JP2013228720A (ja) * 2012-03-30 2013-11-07 Fujifilm Corp 防眩フィルム、その製造方法、偏光板、及び画像表示装置

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JP4691205B1 (ja) * 2010-09-03 2011-06-01 日東電工株式会社 薄型高機能偏光膜を含む光学フィルム積層体の製造方法
JP5361941B2 (ja) 2010-09-03 2013-12-04 日東電工株式会社 偏光膜を有する積層体ストリップロールの製造方法
JP5304939B1 (ja) * 2012-05-31 2013-10-02 大日本印刷株式会社 光学積層体、偏光板、偏光板の製造方法、画像表示装置、画像表示装置の製造方法及び画像表示装置の視認性改善方法
JP5528606B2 (ja) * 2012-06-21 2014-06-25 日東電工株式会社 偏光板および有機ｅｌパネル
CN109661601B (zh) * 2016-09-06 2022-02-01 住友化学株式会社 偏振板及其制造方法

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JP2006133719A (ja) * 2004-10-07 2006-05-25 Nitto Denko Corp 位相差フィルム一体型偏光板及び位相差フィルム一体型偏光板の製造方法

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JP2005309290A (ja) * 2004-04-26 2005-11-04 Sumitomo Chemical Co Ltd 複合偏光板、その製造方法及び液晶表示装置

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JP2006133719A (ja) * 2004-10-07 2006-05-25 Nitto Denko Corp 位相差フィルム一体型偏光板及び位相差フィルム一体型偏光板の製造方法

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101923183A (zh) * 2009-06-15 2010-12-22 住友化学株式会社 光学层叠体及其制造方法
KR20100134521A (ko) * 2009-06-15 2010-12-23 스미또모 가가꾸 가부시키가이샤 광학 적층체 및 그 제조 방법
JP2010286764A (ja) * 2009-06-15 2010-12-24 Sumitomo Chemical Co Ltd 光学積層体およびその製造方法
CN101923183B (zh) * 2009-06-15 2016-06-08 住友化学株式会社 光学层叠体及其制造方法
KR101685706B1 (ko) 2009-06-15 2016-12-12 스미또모 가가꾸 가부시키가이샤 광학 적층체 및 그 제조 방법
JP2013228720A (ja) * 2012-03-30 2013-11-07 Fujifilm Corp 防眩フィルム、その製造方法、偏光板、及び画像表示装置

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