EP1793975A1 - Celluloseacylatfolie, verfahren zur herstellung derselben, gestrecktecelluloseacylatfolie und verfahren zur herstellung derselben - Google Patents

Celluloseacylatfolie, verfahren zur herstellung derselben, gestrecktecelluloseacylatfolie und verfahren zur herstellung derselben

Info

Publication number
EP1793975A1
EP1793975A1 EP05788294A EP05788294A EP1793975A1 EP 1793975 A1 EP1793975 A1 EP 1793975A1 EP 05788294 A EP05788294 A EP 05788294A EP 05788294 A EP05788294 A EP 05788294A EP 1793975 A1 EP1793975 A1 EP 1793975A1
Authority
EP
European Patent Office
Prior art keywords
film
cellulose acylate
acylate film
stretching
liquid crystal
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP05788294A
Other languages
English (en)
French (fr)
Other versions
EP1793975A4 (de
Inventor
Masaaki FujiFilm Co. OTOSHI
Kiyokazu FULIFILM CORPORATION HASHIMOTO
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fujifilm Corp
Original Assignee
Fujifilm Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Fujifilm Corp filed Critical Fujifilm Corp
Publication of EP1793975A1 publication Critical patent/EP1793975A1/de
Publication of EP1793975A4 publication Critical patent/EP1793975A4/de
Withdrawn legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
    • B29C41/02—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of definite length, i.e. discrete articles
    • B29C41/12—Spreading-out the material on a substrate, e.g. on the surface of a liquid
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/001—Combinations of extrusion moulding with other shaping operations
    • B29C48/0018—Combinations of extrusion moulding with other shaping operations combined with shaping by orienting, stretching or shrinking, e.g. film blowing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/07—Flat, e.g. panels
    • B29C48/08—Flat, e.g. panels flexible, e.g. films
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/50—Details of extruders
    • B29C48/505—Screws
    • B29C48/53—Screws having a varying channel depth, e.g. varying the diameter of the longitudinal screw trunk
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C48/793—Thermal treatment of the extrusion moulding material or of preformed parts or layers, e.g. by heating or cooling upstream of the plasticising zone, e.g. heating in the hopper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C48/80—Thermal treatment of the extrusion moulding material or of preformed parts or layers, e.g. by heating or cooling at the plasticising zone, e.g. by heating cylinders
    • B29C48/83—Heating or cooling the cylinders
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
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    • B29C48/78—Thermal treatment of the extrusion moulding material or of preformed parts or layers, e.g. by heating or cooling
    • B29C48/86—Thermal treatment of the extrusion moulding material or of preformed parts or layers, e.g. by heating or cooling at the nozzle zone
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C48/911—Cooling
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
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    • B29C48/911—Cooling
    • B29C48/9135—Cooling of flat articles, e.g. using specially adapted supporting means
    • B29C48/915—Cooling of flat articles, e.g. using specially adapted supporting means with means for improving the adhesion to the supporting means
    • B29C48/9155—Pressure rollers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/88—Thermal treatment of the stream of extruded material, e.g. cooling
    • B29C48/911—Cooling
    • B29C48/9135—Cooling of flat articles, e.g. using specially adapted supporting means
    • B29C48/915—Cooling of flat articles, e.g. using specially adapted supporting means with means for improving the adhesion to the supporting means
    • B29C48/916—Cooling of flat articles, e.g. using specially adapted supporting means with means for improving the adhesion to the supporting means using vacuum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/88—Thermal treatment of the stream of extruded material, e.g. cooling
    • B29C48/911—Cooling
    • B29C48/9135—Cooling of flat articles, e.g. using specially adapted supporting means
    • B29C48/915—Cooling of flat articles, e.g. using specially adapted supporting means with means for improving the adhesion to the supporting means
    • B29C48/9165—Electrostatic pinning
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/88—Thermal treatment of the stream of extruded material, e.g. cooling
    • B29C48/911—Cooling
    • B29C48/9135—Cooling of flat articles, e.g. using specially adapted supporting means
    • B29C48/915—Cooling of flat articles, e.g. using specially adapted supporting means with means for improving the adhesion to the supporting means
    • B29C48/917—Cooling of flat articles, e.g. using specially adapted supporting means with means for improving the adhesion to the supporting means by applying pressurised gas to the surface of the flat article
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
    • B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
    • B29C55/04—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets uniaxial, e.g. oblique
    • B29C55/06—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets uniaxial, e.g. oblique parallel with the direction of feed
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
    • B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
    • B29C55/04—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets uniaxial, e.g. oblique
    • B29C55/08—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets uniaxial, e.g. oblique transverse to the direction of feed
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/11—Anti-reflection coatings
    • G02B1/111—Anti-reflection coatings using layers comprising organic materials
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/14—Protective coatings, e.g. hard coatings
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
    • G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3083—Birefringent or phase retarding elements
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/28—Storing of extruded material, e.g. by winding up or stacking
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/355—Conveyors for extruded articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/88—Thermal treatment of the stream of extruded material, e.g. cooling
    • B29C48/911—Cooling
    • B29C48/9135—Cooling of flat articles, e.g. using specially adapted supporting means
    • B29C48/9145—Endless cooling belts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2001/00—Use of cellulose, modified cellulose or cellulose derivatives, e.g. viscose, as moulding material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29K2001/00—Use of cellulose, modified cellulose or cellulose derivatives, e.g. viscose, as moulding material
    • B29K2001/08—Cellulose derivatives
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • C—CHEMISTRY; METALLURGY
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    • C08J2301/08—Cellulose derivatives
    • C08J2301/10—Esters of organic acids

Definitions

  • the present invention relates to a cellulose acylate film, a method of producing the same, a stretched cellulose acylate film and a method of producing the same, and particularly to a technique for producing an unstretched cellulose acylate film by melt film forming for producing a stretched cellulose acylate film having qualities suitable for a liquid crystal display device.
  • cellulose acylate films have been stretched to generate in-plane retardation (Re) and retardation in the thickness direction (Rth), and it has been practiced to extend viewing angles by using such film as a retardation film in a liquid crystal display device.
  • Examples of methods of stretching a cellulose acylate film include a method of stretching in the longitudinal (length) direction (longitudinal stretching), a method of stretching in the transverse (width) direction (transverse stretching), and a method of carrying out longitudinal stretching and transverse stretching simultaneously (simultaneous biaxial stretching).
  • longitudinal stretching has been employed in many cases so far.
  • a film is heated to the glass transition temperature (Tg) or higher on at least two pairs of nip rolls, and stretched in the longitudinal direction with setting the carrying rate of the nip roll on the exit side faster than that of the nip roll on the entrance side.
  • Patent Document 1 describes a method of longitudinal stretching of cellulose ester.
  • Patent Document 2 describes a method of stretching in which nip rolls positioned with a small span of a length/width ratio (LfW) of 0.3 or more and 2 or less are provided in the stretching zone. According to Patent Document 2, the orientation in the thickness direction (Rth) can be improved.
  • the length/width ratio described herein means a value obtained by dividing the distance (L) between the nip rolls used for stretching by the width (W) of a cellulose acylate film to be stretched.
  • Patent Document 1 Japanese Patent Application Laid-Open No. 2002-311240
  • Patent Document 2 Japanese Patent Application Laid-Open No. 2003-315551
  • the present invention has been made in view of such circumstances and aims at providing a cellulose acylate film from which a highly oriented stretched cellulose acylate film can be obtained by producing an unstretched cellulose acylate film hardly breakable upon stretching by melt film forming, a method of producing the same, a stretched cellulose acylate film and a method of producing the same.
  • the method of producing a cellulose acylate film of the first aspect of the present invention is a method of producing a cellulose acylate film by melt film forming, comprising the steps of: extruding a cellulose acylate resin into a sheet at an extrusion temperature of 190 0 C to 240°C on a cooling support through a die using an extruder which has a screw compression ratio of 2.5 to 4.5 and an L/D of 20 to 50, and solidifying the sheet by cooling.
  • the produced cellulose acylate film tend to be yellowed, and therefore it has been commonly practiced to lower the extrusion temperature of the extruder.
  • a cellulose acylate resin is extruded into a sheet at an extrusion temperature (extruder exit temperature) of 190°C to 240°C on a cooling support through a die using an extruder which has a screw compression ratio of 2.5 to 4.5 and an L/D of 20 to 50, and solidified by cooling, a cellulose acylate film difficult to be yellowed and less likely to cause breaking upon stretching can be produced.
  • simple reference to "cellulose acylate film” means an unstretched cellulose acylate film, while the cellulose acylate film after stretching is referred to as "stretched cellulose acylate film”.
  • the screw compression ratio means a ratio of volume in the supply unit to that in the measurement unit in an extruder
  • the L/D is a ratio of the cylinder bore diameter (D) to the cylinder length (L).
  • the cellulose acylate film of the second aspect of the present invention has an elongation at break of 50% or more when the film is monoaxially stretched at a glass transition temperature Tg+10°C.
  • the second aspect defines the elongation at " break of a cellulose acylate film suitable for a functional film such as a retardation film in a liquid crystal display device, and it is necessary that the elongation at break is 50% or more when the film is monoaxially stretched at a glass transition temperature Tg+10°C.
  • an elongation at break of 50 %> or more means that stretching is successful 50% up or more before the film is broken " based on the original size before stretching, which in other words means 1.5 times or more when the value before stretching is defined as 1.
  • the cellulose acylate film with an elongation at break of 50% or more can be produced by the method of the first aspect.
  • a tensile machine equipped with a heater e.g., "Heated Tensilon" made by Toyo Seiki Co., Ltd.
  • the elongation at break (difference before and after stretching) is measured under conditions of a chuck distance of 100 mm and a tensile speed of 100 mm/minute.
  • the cellulose acylate film of the third aspect of the present invention is a film according to the second aspect, the film having a haze of 2.0% or less, an yellowness index (YI value) of 10 or less and an endothermic peak value of 4.0 J/g or less, which peak appears in the region of the glass transition temperature Tg or higher in DSC (differential scanning calorimetry).
  • the third aspect defines properties of the cellulose acylate film other than the aforementioned elongation at break which are suitable for a functional film such as a retardation film in a liquid crystal display device, and it is necessary that the film, has a haze of 2.0% or less, an yellowness index (YI value) of 10 or less and an endothermic peak value of 4.0 J/g or less, which peak appears in the region of the glass transition temperature Tg or higher in DSC (differential scanning calorimetry).
  • YI value yellowness index
  • Tg or higher in DSC differential scanning calorimetry
  • the cellulose acylate film with such optical properties can be produced by the method of the first aspect.
  • the cellulose acylate film of the fourth aspect of the present invention is a film according to the second or third aspect, wherein the acylate group satisfies the following degree of substitution
  • A represents the degree of substitution with an acetyl group and B represents the total degree of substitution with a propionyl group, a butyryl group, a pentanoyl group and a hexanoyl group.
  • Cellulose acylate films satisfying this substitution degree have characteristics such as low melting point, being easily stretched and excellent in moisture proof properties, and when they are combined with the aforementioned properties, a stretched cellulose acylate film excellent for a functional film such as a retardation film in a liqutid crystal display device can be obtained.
  • the cellulose acylate film of the fifth aspect of the present invention is a film according to any one of the second to fourth aspects, the film having a molecular weight of 20,000 to 100,000.
  • the molecular weight is more than 100,000, the melt viscosity is increased and the extrusion temperature is thus increased, making it easier to cause yellowing due to thermal degradation.
  • the molecular weight is less than 20,000, mechanical strength when formed into a film is reduced.
  • the method of producing a stretched cellulose acylate film of the sixth aspect of the present invention comprises the step of stretching the unstretched cellulose acylate film produced according to the first aspect in at least one of the longitudinal direction and the transverse direction of the film at 1 to 2.5 times.
  • the sixth aspect is a method of producing a stretched cellulose acylate film, comprising the step of stretching the cellulose acylate film produced by the method of the first aspect.
  • stretching at 1 to 2.5 times becomes possible. Accordingly, a stretched cellulose acylate film excellent for a functional film such as a retardation film in a liquid crystal display device can be obtained.
  • the stretched cellulose acylate film of the seventh aspect of the present invention is obtained by stretching the unstretched cellulose acylate film according to any one of the second to the fifth aspect in at least one of the longitudinal direction and the transverse direction of the film at 1 to 2.5 times.
  • the stretched cellulose acylate film of the seventh aspect by stretching the cellulose acylate film with the properties of any of the second to fifth aspect, stretching at 1 to 2.5 times becomes possible. Accordingly, a stretched cellulose acylate film excellent for a functional film such as a retardation film in a liquid crystaL display device can be obtained.
  • the cellulose acylate film of the eighth aspect of the present invention is a film according to the seventh aspect, the film a thickness of 30 to 300 ⁇ m, an in-plane retardation (Re) of 0 to 500 nm and a retardation in the thickness direction (Rth) of 30 to 500 nm.
  • a stretched cellulose acylate film suitable for a functional film such as a retardation film in a liquid crystal display device, which has a thickness of 30 to 300 ⁇ m, art in-plane retardation (Re) of 0 to 500 nm and a retardation in the thickness direction (TR-th) of 30 to 500 nm is obtained.
  • the cellulose acylate film of the ninth aspect of the present invention is a film according to the eighth aspect, wherein the fluctuation in the Re and the fluctuation in the Rth are 5% or less in both the width direction and the length direction.
  • the fluctuation in the Re and the fluctuation in the Rth can be decreased to as small as 5% or less in both the width direction and the length direction.
  • the tenth aspect of the present invention is a polarizing plate comprising at least one layer of the unstretched cellulose acylate film according to any one of the first to fifth aspects stacked.
  • the eleventh aspect is a compensation film for a liquid crystal display panel, comprising the unstretched cellulose acylate film according to any one of the first to fifth aspects as a substrate thereof.
  • the twelfth aspect is an anti-reflection film comprising the unstretched cellulose acylate film according to any one of the first to the fifth aspects as a substrate thereof.
  • the thirteenth aspect of the present invention is a polarizing plate comprising at least one layer of the stretched cellulose acylate film according to any one of the seventh to ninth aspects stacked.
  • the fourteenth aspect is a compensation film for a liquid crystal display panel, comprising the stretched cellulose acylate film according to any one of the seventh to ninth aspects as a substrate thereof.
  • the fifteenth aspect is an anti-reflection film comprising the stretched cellulose acylate film according to any one of the seventh to ninth aspects as a substrate thereof.
  • a stretched cellulose acylate film with excellent optical properties can be obtained, and therefore a functional film such as a retardation film which exhibits high orientation when incorporated into and used in a liquid crystal display device can be obtained.
  • Fig. 1 illustrates the structure of an apparatus for producing a film, to which the present invention is applied
  • Fig. 2 is a schematic view illustrating the structure of an extruder
  • Figs. 3 A to 3E are tables describing Examples of the present invention.
  • Fig. 4 is a table describing the polarizing plates of Examples of the present invention.
  • Fig. 1 schematically illustrates an example of the structure of an apparatus for producing a stretched cellulose acylate film.
  • the apparatus is mainly composed of a film forming part 10 for producing a cellulose acylate film before stretching, a longitudinal stretching part 20 for longitudinal stretching of the unstretched cellulose acylate film produced in the film forming part 10, a transverse stretching part 30 for transverse stretching and take-up part 40.
  • a cellulose acylate resin melted in the extruder 11 is extruded through a die 12 in the form of a sheet and cast on a rotating cooling drum 14 to produce a rapidly cooled and solidified cellulose acylate film 16.
  • the cellulose acylate film 16 is peeled off from the cooling drum 14, transferred to the longitudinal stretching part 20 and then the transverse stretching part 30 to be stretched, and taken up as a roll in the take-up part 40. By this, a stretched cellulose acylate film is produced.
  • Fig. 2 shows a single screw extruder 11.
  • a single screw 32 having a flight 31 on a screw shaft 28 is placed in a cylinder 26.
  • a cellulose acylate resin is supplied from a hopper which is not represented in the figure through a supply port 34 into the cylinder 26.
  • the cylinder 26 is composed of, from the supply port 34 side, a supply unit (region represented by A) for constantly feeding the cellulose acylate resin supplied from the supply port 34, a compression unit (region represented by B) for kneading and compressing the cellulose acylate resin and a measurement unit (region represented by C) for measuring the kneaded and compressed cellulose acylate resin.
  • the cellulose acylate resin melted in the extruder 11 is continuously fed to the die through a discharge port 36.
  • the screw compression ratio of the extruder 11 is set to 2.5 to 4.5, and the L/D is set to 20 to 50.
  • the screw compression ratio refers to a ratio of volume in the supply unit to that in the measurement unit, i.e., (the volume per unit length of the supply unit A) ⁇ (the volume per unit length of the measurement unit C), which is calculated using the outer diameter dl of the screw shaft 28 in the supply unit A, the outer diameter d2 of the screw shaft 28 in the measurement unit C, the groove diameter al in the supply unit A and the groove diameter a2 in the measurement unit C.
  • the L/D is a ratio of the cylinder bore diameter (D) to the cylinder length (L).
  • the extrusion temperature is set to 190°C to 240°C. When the temperature in the extruder 11 is higher than 240°C, a cooling device (unrepresented) may be placed between the extruder 11 and the die 12.
  • the cellulose acylate resin melted using the extruder 11 as configured above is continuously fed to the die 12 and extruded on the cooling drum 14 in the form of a sheet to be cooled and solidified.
  • an unstretched cellulose acylate film which is to be stretched in the longitudinal stretching part 20 and the transverse stretching part 30 is produced.
  • a cooling band may also be used instead of the cooling drum 14.
  • a cellulose acylate resin is extruded into a sheet at an extrusion temperature of 190 0 C to 240°C on the cooling drum 14 through the die 12 using the extruder 11 which has a screw compression ratio of 2.5 to 4.5 and an L/D of 20 to 50, and cooled and solidified, a cellulose acylate film difficult to be yellowed and less likely to cause breaking upon stretching can be produced.
  • the cellulose acylate film produced according to the method of the present invention can be used as not only a raw material film for producing a stretched cellulose acylate film but also a cellulose acylate film product as is.
  • the extruder 11 may be a single screw extruder or a twin screw extruder, but when the screw compression ratio is far below 2.5, kneading may be insufficient and some portions remain undissolved, and since heat generation due to shearing is small, melting of crystal may not be sufficient, leaving some minute crystal in the produced cellulose acylate film. In addition, bubbles may be easily incorporated. Thus, when such cellulose acylate film is stretched, remaining crystal hinders stretching, making it impossible to increase orientation to a sufficient degree. On the other hand, when the screw compression ratio is far above 4.5, the resin receives extremely high shearing stress and is thus easily degraded by heat, and the produced cellulose acylate film is therefore easily yellowed.
  • the screw compression ratio is in the range of preferably 2.5 to 4.5, more preferably 2.8 to 4.2, particularly preferably 3.0 to 4.0.
  • the L/D is in the range of 20 to 50, preferably 22 to 45, particularly preferably 24 to 40.
  • the extrusion temperature is in the range of 190°C to 240 0 C, preferably 195 0 C to 235°C, particularly preferably 200°C to 230°C.
  • the cellulose acylate film of the present invention formed using the extruder 11 in which the extrusion conditions are set as described above has an excellent stretching property of an elongation at break of 50% or more (1.5 times or more the value before stretching) when monoaxially stretched at a glass transition temperature Tg+10°C, and characteristic values of a haze of 2.0% or less, an yellowness index (YI value) of 10 or less, and an endothermic peak value of 4.0 J/g or less, which peak appears in the region of the glass transition temperature Tg or higher in DSC (differential scanning calorimetry).
  • the haze is an index of whether the extrusion temperature is too low or not, in other words, an index of the amount of crystal remaining in the produced cellulose acylate film.
  • the yellowness index (YI value) is an index of whether the extrusion temperature is too high or not, and when the yellowness index (YI value) is 10 or less, yellowness is not a problem.
  • the endothermic peak which appears in the region of the glass transition temperature Tg or higher in DSC (differential scanning calorimetry) is, as the haze is, an index of whether the extrusion temperature is too low or not.
  • the endothermic peak value is more than 4.0 J/g, a greater amount of minute crystal remain in the produced cellulose acylate film and the cellulose acylate film may be thus easily broken upon stretching.
  • the cellulose acylate film with such stretching property and characteristic values is then stretched in the longitudinal stretching part 20 and the transverse stretching part 30.
  • the cellulose acylate film 16 is stretched in order to orientate molecules in the cellulose acylate film 16 for generating in-plane retardation (Re) and retardation in the thickness direction (Rth).
  • Re in-plane retardation
  • Rth retardation in the thickness direction
  • Rth (nm)
  • n(MD), n(TD) and n(TH) are the refractive indexes in the length direction, width direction and thickness direction, and T is thickness in nm.
  • the cellulose acylate film 16 is fLrst longitudinally stretched in the length direction in the longitudinal stretching part 20.
  • the heated cellulose acylate film 16 is put around the two nip rolls 22,24.
  • the nip roll 24 on the exit side carries the cellulose acylate film 16 at a faster speed than that of the nip roll 22 on the entrance side, and by this, the cellulose acylate film 16 is stretched in the longitudinal direction.
  • the pre-heating temperature in the longitudinal stretching part 20 is preferably Tg-40°C to Tg+60°C, more preferably Tg-20°C to Tg+40°C, further preferably Tg to Tg+30°C.
  • the stretching temperature in the longitudinal stretching part 20 is preferably Tg to Tg+60°C, more preferably Tg+2°C to Tg+40°C, further preferably Tg+5°C to Tg+30°C.
  • the stretching ratio in the longitudinal direction is preferably 1.01 to 3 times, more preferably 1.05 to 2.5 times, further preferably 1.1 to 2 times.
  • the cellulose acylate film 16 stretched in the longitudinal direction is transferred to the transverse stretching part 30 and transversely stretched in the width direction-
  • a tenter is preferably used, in which both ends in trie width direction of the cellulose acylate film 16 are held by clips and the film is stretched in the transverse direction. This transverse stretching yields a greater retardation Rth.
  • the transverse stretching is preferably carried out using a tenter.
  • the stretching temperature is preferably Tg to Tg+60°C, more preferably Tg+2°C to Tg+40°C, further preferably Tg+4°C to Tg+30°C.
  • the stretching ratio is preferably 1.01 to 3 times, more preferably 1.05 to 2.5 times, further preferably 1.1 to 2 times.
  • relaxation may be carried out in either or both the longitudinal direction and the transverse direction. This allows the angle distribution of the lagging axis in the width direction to be narrowed.
  • Re is preferably 0 to 500 nm, more preferably 10 to 400 nm, further preferably 15 to 300 nm.
  • Rth is 30 to 500 nm, more preferably 50 to 400 nm, further preferably 70 to 350 nm.
  • the orientation in the thickness direction is increased along with decrease in the thickness, and the Rth can be increased.
  • Local fluctuation in Re and that in Rth in both the width direction and the length direction are preferably 5% or less, more preferably 4% or less, further preferably 3% or less.
  • a stretched cellulose acylate film by using a cellulose acylate film produced by the method of the present invention, film breaking upon stretching is hardly caused, and high stretching ratio can be achieved and local fluctuation in the Re and that in the Rth in the width direction and the length direction can be reduced. Accordingly, a stretched cellulose acylate film with excellent optical properties can be produced.
  • Cellulose acylate resins the method of forming unstretched cellulose acylate film and the method of processing the cellulose acylate film suitable for the present invention will now be described in detail based on the procedures. (Cellulose acylate resin)
  • the cellulose acylate used in the present invention preferably has the following characteristics.
  • a more preferable substitution degree is, when at least 1/2 of B is a propionyl group,
  • a further preferable substitution degree is, when at least 1/2 of B is a propionyl group,
  • a feature of the present invention is that the degree of substitution with an acetyl group among the acyl groups is set to be low while the total degree of substitutiom with a propionyl group, a butyryl group, a pentanoyl group and a hexanoyl group is set to be high.
  • the variation in the Re and the Rth with time after stretching can be made smaller. This is because by increasing the amount of the groups longer than acetyl group, flexibility of the film is increased and the stretching property can be higher, and orientation of cellulose acylate molecules are not easily disturbed by stretching, and the variation in the exhibited Re and Rth with time is thus decreased.
  • acyl groups longer than those described above causes a significant decrease in the glass transition temperature (Tg) and the elastic modulus, and is thus not preferable.
  • Tg glass transition temperature
  • a propionyl group, a butyryl group, a pentanoyl group and a hexanoyl group which are larger than an acetyl group is preferable, and a propionyl group and a butyryl group are more preferable, and a butyryl group is further preferable.
  • a typical synthetic method is liquid-phase acetylation using carboxylic acid anhydride/acetic acid/a sulfuric acid catalyst. Specifically, after subjecting a cellulose raw material such as cotton linter or wood pulp to a pre-treatment with an appropriate amount of acetic acid, the material is poured into a previously cooled carboxylic acid mixture to be esterified, whereby a complete cellulose acylate is synthesized (the total of the acyl substitution degrees at the 2-, 3- and 6-positions being about 3.00).
  • the carboxylic acid mixture described above generally contains acetic acid as a solvent, carboxylic acid anhydride as an esterification agent and sulfuric acid as a catalyst.
  • Carboxylic acid anhydride is usually used in a stoichiometrically excessive amount over the total amount of cellulose which reacts with the anhydride and water present in the system.
  • a neutralizing agent e.g., carbonate, acetate or oxide of calcium, magnesium, iron, aluminum or zinc
  • the obtained complete cellulose acylate is then kept at 50 to 90°C in the presence of a small amount of an acetizing reaction catalyst, which is generally remaining sulfuric acid, thus saponified and ripened to be converted to cellulose acylate having a desired acyl substitution degree and polymerization degree.
  • an acetizing reaction catalyst which is generally remaining sulfuric acid, thus saponified and ripened to be converted to cellulose acylate having a desired acyl substitution degree and polymerization degree.
  • the desired cellulose acylate is obtained, by completely neutralizing the catalyst remaining in the system with a neutralizing agent as described above, or without such neutralization, the cellulose acylate solution is poured into water or dilute sulfuric acid (or water or dilute sulfuric acid is po ⁇ red into the cellulose acylate solution) to separate the cellulose acylate, followed by washing and stabilizing treatment to yield cellulose acylate.
  • the polymerization degree of cellulose acylate preferably used in the present invention is, in a viscosity average polymerization degree, 200 to 700, preferably 250 to 550, more preferably 250 to 400, particularly preferably 250 to 350.
  • the viscosity average polymerization degree can be measured by a limiting viscosity method by Uda et al., (Kazuo Uda, Hideo Saito, Journal of the Society of Fiber Science and Technology, Japan, vol. 18, No. 1, 105-120, 1962). The method is described in detail in Japanese Patent Application Laid-Open No. 9-95538.
  • the viscosity average polymerization degree can also be adjusted by removing low molecular weight components. ⁇ Vhen such low molecular weight components are removed, the average molecular weight (polymerization degree) is increased, but the viscosity effectively becomes lower than that of ordinary cellulose acylate. Low molecular weight components can be removed by washing cellulose acylate with an appropriate organic solvent.
  • the molecular weight can also be adjusted by polymerization. For example, when producing cellulose acylate containing small amounts of low molecular weight components, the amount of the sulfuric acid catalyst in the acetizing reaction is preferably adjusted to 0.5 to 25 parts by mass based on 100 parts by mass of cellulose. By setting the amount of the sulfuric acid catalyst to this range, cellulose acylate having a preferable molecular weight distribution (uniform molecular weight distribution) can be synthesized.
  • cellulose acylate used in the present invention those having a weight average molecular weight Mw/number average molecular weight Mn ratio of preferably 1.5 to 5.5, more preferably 2.0 to 5.0, particularly preferably 2.5 to 5.0, most preferably 3.0 to 5.0 are used.
  • cellulose acylates may be used alone or in a mixture of two or more.
  • a mixture in which a high molecular component other than cellulose acylate is accordingly mixed may also be used.
  • the high molecular component to be mixed those highly compatible with cellulose ester are preferred, and the transparency when formed into a film is preferably not less than 80%, more preferably not less than 90%, and further preferably not less than 92%.
  • the crystalline melting temperature (Tm) of cellulose acylate can be lowered.
  • the molecular weight of the plasticizer used in the present invention is not particularly limited, and the plasticizer may be low molecular weight or high molecular weight. Examples of such plasticizer include phosphoric esters, alkyl phthalyl alkyl glycolates, carboxylic acid esters and polyol fatty acid esters.
  • the plasticizer may be solid or oily substance. That is, the melting point and the boiling point of the plasticizer are not particularly limited. When melt film forming is carried out, a nonvolatile plasticizer is particularly preferably used.
  • phosphoric esters include triphenyl phosphate, tribi ⁇ tyl phosphate, tributoxyethyl phosphate, tricresyl phosphate, trioctyl phosphate, trinaphthyl phosphate, trixylyl phosphate, tris-o-biphenyl phosphate, cresyl phenyl phosphate, octyl diphenyl phosphate, biphenyl diphenyl phosphate and 1,4- ⁇ henylene-tetraphenyl phosphate.
  • phosphoric ester plasticizers described in claims 3 to 7 of National Publication of International Patent Application No. 6-501040 may be used.
  • alkyl phthalyl alkyl glycolates include methyl phthalyl methyl glycolate, ethyl phthalyl ethyl glycolate, propyl phthalyl propyl glycolate, butyl phthalyl butyl glycolate, octyl phthalyl octyl glycolate, methyl phthalyl ethyl glycolate, ethyl phthalyl methyl glycolate, ethyl phthalyl propyl glycolate, methyl phthalyl butyl glycolate, ethyl phthalyl butyl glycolate, butyl phthalyl methyl glycolate, butyl phthalyl ethyl glycolate, propyl phthalyl butyl glycolate, butyl phthalyl propyl glycolate, inethyl phthalyl octyl glycolate, ethyl phthalyl octyl glycolate, octyl glycolate
  • carboxylic acid esters examples include phthalic acid esters such as dimethyl phthalate, diethyl phthalate, dibutyl phthalate, dioctyl phthalate and diethylhexyl phthalate, citric acid esters such as acetyl trimethyl citrate, acetyl triethyl citrate, acetyl tributyl citrate, adipic acid esters such as dimethyl adipate, dibutyl adipate, diisobutyl adipate, bis(2-ethylhexyl)adipate, diisodecyl adipate and bis(butyl diglycol)adipate, aromatic polyvalent carboxylic acid esters such as tetraoctyl pyromellitate and trioctyl trimellitate, aliphatic polyvalent carboxylic acid esters such as dibutyl adipate, dioctyl adipate, dibutyl se
  • plasticizers such as high molecular weight plasticizers such as aliphatic polyesters composed of glycol and dibasic acid such as polyethylene adipate, polybutylene adipate, polyethylene succinate and polybutylene succinate, aliphatic polyesters composed of oxycarboxylic acid such as polylactic acid and polyglycolic acid, aliphatic polyesters composed of lactone such as polycaprolactone, polypropiolactone and polyvalerolactone, and vinyl polymers such as polyvinylpyrrolidone. These plasticizers may be used alone or together with a low molecular weight plasticizer.
  • high molecular weight plasticizers such as aliphatic polyesters composed of glycol and dibasic acid such as polyethylene adipate, polybutylene adipate, polyethylene succinate and polybutylene succinate, aliphatic polyesters composed of oxycarboxylic acid such as polylactic acid and polyglycolic acid, aliphatic polyesters composed of lactone such as poly
  • Polyol plasticizers are compatible with cellulose fatty acid ester and exhibit significant thermoplasticity-imparting effect, examples of which include glycerol ester compounds such as glycerol ester and diglycerol ester, polyalkylene glycols such as polyethylene glycol and polypropylene glycol and compounds in which an acyl group is bonded to a hydroxyl group of polyalkylene glycol.
  • glycerol ester compounds such as glycerol ester and diglycerol ester
  • polyalkylene glycols such as polyethylene glycol and polypropylene glycol and compounds in which an acyl group is bonded to a hydroxyl group of polyalkylene glycol.
  • glycerol esters include, but are not limited to, glycerol diacetate stearate, glycerol diacetate palmitate, glycerol diacetate myristate, glycerol diacetate laurate, glycerol diacetate caprate, glycerol diacetate nonanoate, glycerol diacetate octanoate, glycerol diacetate heptanoate, glycerol diacetate Iiexanoate, glycerol diacetate pentanoate, glycerol diacetate oleate, glycerol acetate dicaprate, glycerol acetate dinonanoate, glycerol acetate dioctanoate, glycerol acetate diheptanoate, glycerol acetate dicaproate, glycerol acetate divalerate, glycerol acetate dival
  • glycerol diacetate caprylate glycerol diacetate pelargonate, glycerol diacetate caprate, glycerol diacetate laurate, glycerol diacetate myristate, glycerol diacetate palmitate, glycerol diacetate stearate and glycerol diacetate oleate are preferred.
  • diglycerol esters include, but are not limited to, mixied acid esters of diglycerol such as diglycerol tetraacetate, diglycerol tetrapropionate, diglycerol tetrabutyrate, diglycerol tetravalerate, diglycerol tetrahexanoate, diglycerol tetraheptanoate, diglycerol tetracaprylate, diglycerol tetrapelargonate, diglycerol tetracaprate, diglycerol tetralaurate, diglycerol tetramyristate, diglycerol tetrapalinritate, diglycerol triacetate propionate, diglycerol triacetate butyrate, diglycerol triacetate valerate, diglycerol triacetate hexanoate, diglycerol triacetate heptanoate, diglycerol triacetate caprylate, diglycerol tria
  • diglycerol tetraacetate, diglycerol tetrapropionate, diglycerol tetrabutyrate, diglycerol tetracaprylate and diglycerol tetralaurate are preferred.
  • Specific examples of polyalkylene glycol include, but are not limited to, polyethylene glycol and polypropylene glycol having an average molecular weight of 200 to 1000, and these may be used alone or in combination.
  • Specific examples of compounds in which an acyl group is bonded to a hydroxyl group of polyalkylene glycol include, but are not limited to, polyoxyethylene acetate, polyoxyethylene propionate, polyoxyethylene butyrate, polyoxyethylene valerate, polyoxyethylene caproate, polyoxyethylene heptanoate, polyoxyethylene octanoate, polyoxyethylene nonanoate, polyoxyethylene caprate, polyoxyethylene laurate, polyoxyethylene myristate, polyoxyethylene palmitate, polyoxyethylene stearate, polyoxyethylene oleate, polyoxyethylene linoleate, polyoxypropylene acetate, polyoxypropylene propionate, polyoxypropylene butyrate, polyoxypropylene valerate, polyoxypropylene caproate, polyoxypropylene heptanoate, polyoxypropylene octanoate, polyoxypropylene nonanoate, polyoxypropylene caprate, polyoxypropylene laurate, polyoxypropy
  • the amount to be added of plasticizer is 0 to 20% by weight, more preferably 2 to 18% by weight, most preferably 4 to 15% by weight.
  • the content of the plasticizer is higher than 20% by weight, although the thermal flowability of cellulose acylate is improved, the plasticizer may bleed on the surface of the film formed by melting and the glass transition temperature Tg, which indicates heat resistance, may be decreased.
  • a stabilizer for preventing thermal degradation or coloring may be added to the cellulose acylate used in the present invention within the limit in which the required properties are not damaged.
  • a phosphite compound As a stabilizer, a phosphite compound, a phosphorous acid ester compound, phosphate, thiophosphate, weak organic acid or an epoxy compound may be added alone, or a mixture of two or more of these may be added.
  • phosphite stabilizers the compounds described in paragraphs [0023] to [0039] of Japanese Patent Application Laid-Open No. 2004-182979 may be preferably used.
  • phosphorous acid ester compounds the compounds described in Japanese Patent Application Laid-Open Nos. 51-70316, 10-306175, 57-78431, 54-157159 and 55-13765 may be used.
  • the amount to be added of the stabilizer in the present invention is 0.005 to 0.5% by weight, more preferably 0.01 to 0.4% by weight or more, further preferably 0.05 to 0.3% by weight based on cellulose acylate.
  • the amount is less than 0.005% by weight, the effect of preventing degradation and coloring in the melt film forming process is insufficient, and this range is thus not preferable.
  • the stabilizer may bleed on the surface of the cellulose acylate film formed by melting, and this range is thus not preferable.
  • an antidegradant and an antioxidant may be added.
  • a phenol compound, a thioether compound or a phosphorus compound is added as an antidegradant or an antioxidant, synergistic anti-degradation and anti-oxidant effect can be obtained.
  • materials described in detail in "Kokai Giho of Japan Institute of Invention & Innovation" (Kogi No. 2001-1745, published Mar. 15, 2001, Japan Institute of Invention & Innovation), pp. 17-22 may be preferably used.
  • the cellulose acylate used in the present invention may contain an ultraviolet protective agent, and one or more ultraviolet absorbers may be added.
  • an ultraviolet absorber for liquid crystal preferred are those with excellent ability to absorb ultraviolet rays having a wavelength of 380 nm or less from the viewpoint of preventing degradation of liquid crystal, and which absorb little visible light having a wavelength of 400 nm or more from the viewpoint of display properties of liquid crystal. Examples thereof include oxybenzophenone compounds, benzotriazole compounds, salicylic ester compounds, benzophenone compounds, cyanoacrylate compounds and nickel complex salt compounds.
  • Particularly preferred ultraviolet absorbers are benzotriazole compounds and benzophenone compounds. Of these, benzotriazole compounds are preferred because unwanted coloring of cellulose ester, e.g., cellulose acylate, is small.
  • Preferred ultraviolet absorbers include 2,6-di-tert-butyl-p-cresol, pentaerythrityl-tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], triethylene glycol-bis [3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate] , l,6-hexanediol-bis[3-(3,5-di-tert-butyl-4-hydroxyphen.yl)propionate], 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-tert-butylanilino)-l,3,5-triazine, 2,2-thio-diethylenebis[3-(3,5-di-tert-butyl-4-hydroxyptienyl)propionate], octadecyl-3-(3,5-di-tert-butyl-4
  • 2,6-di-tert-butyl-p-cresol, pentaerythrityl-tetrakis [3-(3 ,5-di-tert-butyl-4-hydroxyphenyl)propionate] and triethylene glycol-bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate] are preferred.
  • a hydrazine metal deactivator such as
  • N,N'-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl] hydrazine or a phosphorus processing stabilizer such as tris(2,4-di-tert-butylphenyl)phosphite may be used together.
  • the amount to be added of these compounds is preferably 1 ppm to 3.0% by mass, more preferably 10 ppm to 2% by mass based on cellulose ester, e.g., cellulose acylate.
  • ultraviolet absorbers the following commercially available products may be used.
  • benzotriazole ultraviolet absorbers examples include TINUBIN P (Ciba Specialty Chemicals K.K.), TINUBIN 234 (Ciba Specialty Chemicals K.K.), TINUBIN 320 (Ciba Specialty Chemicals K.K.), TINUBIN 326 (Ciba Specialty Chemicals K.K.), TINUBIN 327 (Ciba Specialty Chemicals K.K.), TINUBIN 328 (Ciba Specialty Chemicals K.K.) and Sumisorb 340 (Sumitomo Chemical Co., Ltd.).
  • benzophenone ultraviolet absorbers include Seesorb 100 (SfflPRO KASEI KAISHA LTD.), Seesorb 101 (SHIPRO KASEI KAISHA LTD.), Seesorb 101S (SHIPRO KASEI KAISHA LTD.), Seesorb 102 (SHIPRO KASEI KAISHA LTD.), Seesorb 103 (SHIPRO KASEI KAISHA LTD.), ADK STAB LA51 (ASAHI DENICA CO., LTD.), Chemisorp 111 (CHEMlPRO KASEI KAISHA LTD.) and UVINUL D-49 (BASF).
  • oxalic acid anilide ultraviolet absorbers examples include TINUBIN 312 (Ciba Specialty Chemicals K.K.) and TINUBIN 315 (Ciba Specialty Chemicals K.K.).
  • salicylic acid ultraviolet absorbers Seesorb 201 (SHIPRO ELASEI KAISHA LTD.) and Seesorb 202 (SHIPRO KASEI KAISHA LTD.) are commercially available, and examples of cyanoacrylate ultraviolet absorbers include Seesorb 501 (SHIPRO KASEI KAISHA LTD.) and UVINUL N-539 (BASF).
  • the unstretched cellulose acylate film and the stretched cellulose acylate film preferably have the following Re and Rth. That is, the unstretched cellulose acylate film of the present invention preferably satisfies the Re and the Rth of the following formulas:
  • the stretched cellulose acylate film of the present invention preferably satisfies the Re and the Rth of the following formulas:
  • cellulose acylate resin may be used in the form of powder, it is more preferable to use pelletized resin in order to reduce thickness variation of the formed film.
  • the resin After adjusting the moisture content of the cellulose acylate resin to 1 % or less, more preferably 0.5% or less, further preferably 0.1% or less, the resin is introduced into the hopper of an extruder.
  • the temperature of the hopper is set to Tg-50°C to Tg+30°C, more preferably Tg-40°C to Tg+10°C, further preferably Tg-30°C to Tg. This prevents moisture readsorption in the hopper, and efficiency of the aforementioned drying can be thus easily achieved.
  • dehydrated air or inert gas e.g., nitrogen
  • Kneading is carried out to melt the resin at 190°C to 240°C, more preferably 195°C to 235°C, further preferably 200°C to 230°C.
  • the melting temperature may be constant or controlled with dividing into some sections.
  • the kneading time is preferably 2 to 60 minutes, more preferably 3 to 40 minutes, further preferably 4 to 30 minutes. Further, kneading may be carried out in the extruder under inert current (nitrogen, etc.), or with evacuating using an extruder equipped with a vent.
  • the molten cellulose acylate resin is passed through a gear pump to remove the pulsation from the extruder 11, filtrated with a metal mesh filter, and extruded through a T-shaped die 12 attached behind the filter on a cooling drum 14 in the form of a sheet.
  • the resin may be extruded in a single layer or in multiple layers using a multimanifold die or a feed block die. At this time, by adjusting the lip interval of the die 12, thickness irregularity in the width direction can be controlled.
  • the resin is then extruded on the cooling drum 14.
  • adhesion between the cooling drum 14 and the melt-extruded sheet may be increased. All or part (e.g., both ends only) of the melt- extruded sheet may be subjected to such adhesion improvement treatment.
  • the temperature of the cooling drum 14 is preferably 60 0 C to 160°C, more preferably 70 0 C to 150 0 C, further preferably 80 0 C to 140 0 C.
  • the sheet is then peeled off from the cooling drum 14 and taken up past nip rolls 22,24 and a tenter.
  • the take-up rate is preferably 10 to 100 m/minute, more preferably 15 to 80 m/minute, further preferably 20 to 70 m/minute.
  • the width of the formed film is 1 to 5 m, more preferably 1.2 to 4 m, further preferably 1.3 m to 3 m.
  • the unstretched cellulose acylate film thus obtained has a thickness of preferably 30 ⁇ m to 400 ⁇ m, more preferably 40 ⁇ m to 300 ⁇ m, further preferably 50 ⁇ m to 200 ⁇ m.
  • both ends of the cellulose acylate film 16 thus obtained are trimmed and once taken up on a take-up unit 40.
  • Pieces produced after trimming are crushed or subjected to granulation, depolymerization or repolymerization according to need to be reused as a cellulose acylate film material of the same kind or different kind.
  • applying a laminate film on at least one surface before take up is preferred in view of preventing scars.
  • the thus obtained cellulose acylate film has a glass transition temperature (Tg) of preferably 70°C to 180°C. more preferably 80°C to 160°C, further preferably 9O 0 C to 150°C. (Processing of cellulose acylate film)
  • the cellulose acylate film formed by the aforementioned method is monoaxially or biaxially stretched according to the aforementioned method to produce a stretched cellulose acylate film.
  • This film may be used alone or in combination with a polarizing plate, or a liquid crystal layer, a layer having controlled refractive index (low-reflection layer) or a hard coat layer may be formed thereon.
  • a polarizing plate or a liquid crystal layer
  • a layer having controlled refractive index (low-reflection layer) or a hard coat layer may be formed thereon.
  • a glow discharge treatment ultraviolet irradiation, a corona treatment, a flame treatment and an acid or alkali treatment may be used.
  • the glow discharge treatment in this case may be cold plasma generated under a low gas pressure of 10 "3 to 10 "20 Torr, or plasma treatment under atmospheric pressure is also preferred.
  • Plasma excitation gas means one which can be excited to be plasma under conditions as described above, and examples thereof include argon, helium, neon, krypton, xenon, nitrogen, carbon dioxide, chlorofluorocarbons such as tetrafluoromethane and a mixture thereof.
  • a radiating energy of 20 to 500 Kgy is used under a condition of 10 to 1000 Kev, and more preferably a radiating energy of 20 to 300 Kgy is used under a condition of 30 to 500 Kev.
  • an alkali saponifying treatment is particularly preferred.
  • the film may be immersed into a saponifying solution (immersing method), or may be coated with the saponifying solution (coating method).
  • immersion method can be accomplished by passing the film through a tank containing an aqueous NaOH or KOH solution of a pH of 10 to 14 heated to 20 to 80°C for 0.1 to 10 minutes, followed by neutralization, water washing and drying.
  • the coating method dip coating, curtain coating, extrusion coating, bar coating and type E coating may be used.
  • a solvent having excellent wettability appropriate for applying the saponifying solution to a transparent support and capable of maintaining good surface conditions without forming irregularity on the surface of the transparent support is preferably selected.
  • alcohol solvents are preferred, and isopropyl alcohol is particularly preferred.
  • an aqueous surfactant solution may be used as a solvent.
  • alkali for the alkali saponifying coating solution those soluble in the aforementioned solvent is preferred, and KOH and NaOH are more preferred.
  • the pH of the saponifying coating solution is preferably not less than 10, more preferably not less than 12.
  • the reaction may be carried out at room temperature for preferably 1 second to 5 minutes, more preferably 5 seconds to 5 minutes, particularly preferably 20 seconds to 3 minutes.
  • the surface coated with the saponifying solution may be washed with water, or with acid and then with water.
  • the saponifying treatment by coating and application of alignment film described later may be continuously carried out so that the number of the steps is reduced.
  • An undercoat layer may also be formed to be adhered to the functional layer.
  • Such undercoat layer may be formed by coating after the aforementioned surface treatment or without any surface treatment. Details of undercoat layer are described in "Kokai Giho of Japan Institute of Invention & Innovation” (Kogi No. 2001-1745, published Mar. 15, 2001, Japan Institute of Invention & Innovation), p.32.
  • the surface treatment step and the undercoat step may be included in the last stage of the film forming process, may be independently carried out, or may be during the process of applying functional layers described below. (Application of functional layer)
  • the cellulose acylate film of the present invention may be used together with functional layers described in "Kokai Giho of Japan Institute of Invention & Innovation" (Kogi No. 2001-1745, published Mar. 15, 2001, Japan Institute of Invention & Innovation), pp.32 to 45. Particularly preferred is to apply a polarizing layer (polarizing plate), a compensation layer (compensation sheet), or an anti-reflection layer (anti-reflection firm).
  • polarizing layer polarizing plate
  • compensation layer compensation layer
  • anti-reflection layer anti-reflection firm
  • the protective film for a polarizing film has a thickness of preferably 25 to 350 ⁇ m, more preferably 30 to 200 ⁇ m, further preferably 40 to 120 ⁇ m.
  • any of the unstretched film or the stretched film may be used.
  • the stretched cellulose acylate film of the present invention may be used as a protective film for a polarizing film, and is preferably used as a retardation compensation film.
  • the obtained polarizing plate may have the construction as described below: polarizing plate A: unstretched cellulose acylate film /polarizing film/FUJITAC polarizing plate B: unstretched cellulose acylate film /polarizing film/unstretched cellulose acylate film polarizing plate C: stretched cellulose acylate film /polarizing film/FUJITAC polarizing plate D: stretched cellulose acylate film /polarizing film/unstretched cellulose acylate film polarizing plate E: stretched cellulose acylate film /polarizing film/stretched cellulose acylate film
  • polarizing layers a ⁇ re now generally prepared by immersing stretched polymer into an iodine or dichroic dye solution in a bath, and allowing the iodine or dichroic dye to be impregnated into the binder.
  • polarizing film coating-type polarizing films typically available from Optiva Inc. can also be used.
  • iodine or dichroic dye is oriented in the binder to exhibit polarizing characteristics.
  • dichroic dye an azo dye, a stilbene dye, a pyrazolone dye, a triphenylmethane dye, a quinoline dye, an oxazine dye, a thiazine dye or an anthraquinone dye may be used.
  • water-soluble dichroic dyes are preferred.
  • Such dichroic dye preferably contains a hydrophilic substituent (e.g., sulfo, amino or hydroxyl group). Examples thereof include compounds described in "Kokai Giho of Japan Institute of Invention & Innovation" (Kogi No. 2001-1745, published on Mar. 15, 2001), p.58.
  • binder for the polarizing film polymers capable of crosslinking by themselves, polymers crosslinked in the presence of a crosslinking agent, or combinations thereof may be used.
  • binders include methacrylate copolymers, styrene copolymers, polyolefin, polyvinyl alcohol, modified polyvinyl alcohol, poly(N-methylolacrylamide), polyester, polyimide, vinyl acetate copolymers, carboxymethyl cellulose and polycarbonate described in paragraph [0022] of the specification of Japanese Patent Application Laid-Open No. 8-338913.
  • a silane-coupling agent can be used as such polymer.
  • water-soluble polymers e.g., poly(N-methylolacrylamide), carboxymethyl cellulose, gelatin, polyvinyl alcohol and modified polyvinyl alcohol
  • gelatin, polyvinyl alcohol and modified polyvinyl alcohol are more preferred
  • polyvinyl alcohol and modified polyvinyl alcohol are most preferred.
  • Such polyvinyl alcohol preferably has a saponification degree of preferably 70 to 100%, more preferably 80 to 100% .
  • the polymerization degree of polyvinyl alcohol is preferably 100 to 5,000.
  • modified polyvinyl alcohol are described in Japanese Patent Application Laid-Open Nos. 8-338913, 9-152509 and 9-316127. Two or more kinds of polyvinyl alcohols and modified polyvinyl alcohols may be used together.
  • the lower limit of the thickness of the binder is preferably 10 ⁇ m.
  • the binder is preferably as thin as possible from the viewpoint of light leakage from the liquid crystal display device.
  • the binder has a thickness of preferably equal to or less than that of currently commercially available polarizing plates (about 30 ⁇ m), more preferably 25 ⁇ m or less, further preferably 20 ⁇ m or less.
  • the binder for the polarizing film may be crosslinked.
  • a polymer or monomer having a crosslinkable functional group may be mixed with the binder, or a crossli ⁇ kable functional group may be directly added to the binder polymer.
  • the binder may b& crosslinked by means of light, heat, or pH change, and a binder having a crosslinked structure can be then formed.
  • Crosslinking agents are described in U.S. Patent Re-issue No. 23297.
  • boron compounds e.g., boric acid and borax
  • the amount of the crosslinking agent added to the binder is preferably 0.1 to 20% by mass based on the amount of the binder. In this range, the orientation of the polarizer and the wet heat resistance of the polarizing film are improved.
  • the amount of non-reacted crosslinking agent is preferably not more than 1.0% by mass, more preferably not more than 0.5% by mass. This makes it possible to improve weather resistance.
  • a polarizing film is preferably stretched (stretching method) or rubbed (rubbing method), and then dyed with iodine or dichroic dye.
  • the stretching ratio of the film is preferably 2.5 to 30.0 times, more preferably 3.0 to 10.0 times. Stretching can be carried out by dry stretching under air or wet stretching with immersing the film in water. The stretching ratio in dry stretching is preferably 2.5 to 5.0 times, and the stretching ratio in the wet stretchting is preferably 3.0 to 10.0 times.
  • the film may be stretched in parallel (parallel stretching) or obliquely (oblique stretching) to the machine direction. Stretching may be carried out at one time or several times. By stretching several times, the film can be uniformly stretched even when stretched at high stretching ratios. a) Parallel stretching
  • PVA film Before stretching, PVA film is swelled.
  • the swelling degree thereof (ttie ratio based on the weight of the film before and after swelling) is from 1.2 to 2.0 times .
  • the film is then continuously transferred by guide rolls or the like and stretched in a bath containing an aqueous medium or a dyeing bath containing dissolved dichroic material at a bath temperature of preferably 15°C to 50 0 C, more preferably 17°C to 40°C. Stretching can be carried out with holding the film by two pairs of nip rolls and setting the transferring rate of the rearward nip rolls larger than that of the forward nip rolls.
  • the stretching ratio which is the ratio of the length after stretching/at the initial stage (hereinafter the same), is preferably 1.2 to 3.5 times, more preferably 1.5 to 3.0 times from the viewpoint of the above-mentioned effects and advantages.
  • the film is then dried at 50 to 90°C to give a polarizing film.
  • a method of stretching using a tenter projected in an oblique direction described in Japanese Patent Application Laid-Open No. 2002-86554 can be used. Because this stretching is performed under air, the film must be previously hydrated so as to facilitate the stretching.
  • the moisture content is preferably 5% to 100%, more preferably 10% to 100%.
  • the temperature at the time of stretching is preferably 40°C to 90°C, more preferably 50°C to 80°C.
  • the humidity is preferably 50% rh to 100% rh, more preferably 70 % rh to 100% rh, further preferably 80% rh to 100% rh.
  • the traveling rate in the longitudinal direction is preferably not less than 1 m/minute, more preferafcly not less than 3 m/minute.
  • drying is carried out at preferably 50°C to 100°C, more preferably 60 0 C to 90 0 C, for preferably 0.5 to 10 minutes, more preferably 1 to 5 minutes.
  • the absorption axis of the thus-obtained polarizing film is preferably 10 to SO degrees, more preferably 30 to 60 degrees, further preferably substantially 45 degrees (40 to 50 degrees).
  • the saponified cellulose acylate film and the polarizing layer prepared by stretching are adhered to prepare a polarizing plate. Regarding the direction of adhesion, they are preferably adhered so that the casting axis direction of the cellulose acylate film and the stretching axis direction of the polarizing plate form an angle of -45 degrees.
  • the adhesive for the adhesion is not particularly limited, and examples thereof include PVA resins (including PVA modified by an acetoacetyl, sulfonic acid, carboxiyl or oxyalkylene group) and aqueous solutions of a boron compound. Of these, PVA resins are preferable.
  • the adhesive layer has a thickness of preferably 0.01 to 10 ⁇ n ⁇ , particularly preferably from 0.05 to 5 ⁇ m after drying.
  • the thus-obtained polarizing plate preferably has a higher light transmittan.ee and a higher polarization degree.
  • the light transmittance of the polarizing plate against light having a wavelength of 550 nm is in the range of preferably from 30 to 50%, more preferably from 35 to 50%, most preferably from 40 to 50% .
  • the polarization degree thereof relative to light having a wavelength of 550 nm is in the range of preferably from 90 to 100%, more preferably from 95 to 100%, most preferably from 99 to 100%.
  • the thus-obtained polarizing plate is stacked with a ⁇ /4 plate to produce circularly polarized light.
  • they are stacked so that the angle between the retarded phase axis of the ⁇ /4 plate and the absorption axis of the polarizing plate is 45 degrees.
  • the ⁇ /4 plate used here is not particularly limited, but is preferably those having a wavelength dependency such that the lower the wavelength, the smaller the retardation.
  • a ⁇ /4 plate composed of a polarizing film in which the absorption axis is tilted 20 to 70 degrees in the longitudinal direction and an optically anisotropic layer made of a liquid crystal compound is preferably used.
  • a compensation layer compensates for a liquid crystal compound in a liquid crystal cell when a liquid crystal display device displays black, and is prepared by forming an alignment film on a cellulose acylate film and applying an optically anisotropic layer thereon.
  • the alignment film is formed on the aforementioned surface-treated cellulose acylate film.
  • the alignment firm has a function of defining the orientation direction of liquid crystal molecules.
  • the alignment film is no longer an essential constituent of the present invention because the function has been fulfilled.
  • the polarizing plate of the present invention can also be produced by transferring, to a polarizer, only an optically anisotropic layer with fixed orientation state which is formed on an alignment film.
  • An alignment film can be formed by means such as rubbing treatment of an organic compound (preferably a polymer), oblique evaporation of an inorganic compound, formation of a layer with microgrooves or accumulation of an organic compound (e.g., ⁇ -tricosanic acid, dioctadecylmethylammonium chloride and methyl stearate) according to the Langmuir-Blodgett method (LB film).
  • LB film Langmuir-Blodgett method
  • alignment films which attain orientation function by applying an electric field, applying a magnetic field, or by irradiating with light are known.
  • the alignment film is preferably formed by subjecting a polymer to a rubbing treatment.
  • the polymer used for an alignment film has a molecular structure capable of orienting liquid crystal molecul&s.
  • a side chain having a crosslinkable functional group (e.g., a double bond) may be bonded to the main chain, or a crosslinkable functional group capable of orienting liquid crystal molecules may be introduced into the side chain.
  • Polymers to be used for the alignment film may be polymers capable of crosslinking by themselves, polymers to be crosslinked in the presence of a crosslinking agent, or combinations thereof.
  • examples of such polymers include methacrylate copolymers, styrene copolymers, polyolefin, polyvinyl alcohol, modified polyvinyl alcohol, poly(N-methylolacrylamide), polyester, polydmide, vinyl acetate copolymers, carboxymethyl cellulose and polycarbonate which are described in paragraph 0022 of the specification of Japanese Patent Application Laid-Open No. 8-338913.
  • a silane-coupling agent can be used as such polymer.
  • water-soluble polymers e.g., poly(N-methylolacrylamide), carboxymethyl cellulose, gelatin, polyvinyl alcohol and modified polyvinyl alcohol
  • gelatin, polyvinyl alcohol and modified polyvinyl alcohol are more preferred
  • polyvinyl alcohol and modified polyvinyl alcohol are most preferred.
  • Such polyvinyl alcohol has a saponification degree of preferably 70 to 100%, more preferably 80 to 100% .
  • the polymerization degree of the polyvinyl alcohol is preferably 100 to 5,000.
  • the side chain having function of orienting liquid crystal molecules generally has a hydrophobic group as a functional group. Specific kinds of such functional groups are determined based on the kind and the required orientation state of the liquid crystal molecules. Modifying groups of modified polyvinyl alcohol can be introduced by copolymerization, chain transfer or block polymerization.
  • modifying groups include hydrophilic groups (carboxylic group, sulfonic group, phosphonic group, amino group, ammonium group, amido group, thiol group), hydrocarbon groups having 10 to 100 carbon atoms, fluorine-substituted hydrocarbon groups, thioether groups, polymerizable groups (unsaturated polymerizable group, epoxy group, aziridinyl group), and alkoxysilyl groups (trialkoxysilyl, dialkoxysilyl, monoallcoxysilyl).
  • modified polyvinyl alcohols are described in Japanese Patent Application Laid-Open No. 2000-155216, paragraphs 0022 to 0145, and Japanese Patent Application Laid-Open No. 2002-62426, paragraphs 0018 to O022.
  • the alignment film polymer By allowing a side chain having a crosslinkable functional group to be bonded to the main chain of the alignment film polymer, or introducing, into a side chain, a crosslinkable functional group having function of orienting liquid crystal molecules, the alignment film polymer can be copolymerized with polyfunctional monomers contained in the optically anisotropic layer. As a result, not only the polyfunctional monomers themselves, but also the alignment film polymers themselves, and in addition, the polyfunctional monomer and the alignment film polymer, are strongly bonded via a covalent bond. Thus, by introducing a crosslinkable functional group into the alignment film polymer, the strength of the compensation sheet can be significantly improved.
  • the crosslinkable functional group of the alignment film polymer preferably contains a polymerizable group as the polyfunctional monomer does. Specific examples thereof are described in Japanese Patent Application Laid-Open No. 2000-155216, paragraphs 0080 to 0100.
  • the alignment film polymer may be crosslinked using a crosslinking agent, not only by the aforementioned crosslinkable functional group.
  • crosslinking agent examples include aldehyde, N-methylol compounds, dioxane derivatives, compounds that function when the carboxylic group is activated, active vinyl compounds, active halogen compounds, isooxazole and dialdehyde starch.
  • Two or more crosslinking agents may be used in combination. Specific examples thereof include compounds described in Japanese Patent Application Laid-Open No. 2002-62426, paragraphs 0023 to 0024. Highly reactive aldehyde, especially glutaraldehyde, is preferred.
  • the amount to be added of the crosslinking agent is preferably 0.1 to 20% by mass, more preferably 0.5 to 15% by mass based on the amount of the polymer.
  • the amount of non-reacted crosslinking agent remaining in the alignment film is preferably not more than 1.0% by mass, more preferably not more than 0.5% by mass.
  • the alignment film can be basically formed by applying a solution containing the aforementioned polymer which is a material for forming the alignment film and a crosslinking agent on a transparent substrate, drying by heating (to be crosslinked) and subjecting to a rubbing treatment. As described above, the crosslinking reaction can be carried out at any stage after applying the solution on the transparent substrate.
  • the coating solution is preferably a mixture of an organic solvent having a defoaming action (e.g., methanol) and water.
  • the ratio of water to methanol is preferably from 0: 100 to 99: 1, more preferably from 0: 100 to 91 :9, by mass. This prevents bubbles from being generated and significantly reduces defects in the alignment film and consequently on the surface of the optically anisotropic layer.
  • the film thickness after drying is preferably 0.1 to 10 ⁇ m.
  • the drying by heating may be conducted at a temperature of 20°C to 110°C.
  • the drying temperature is preferably from 60°C to 100 0 C, particularly preferably from 80 0 C to 100 0 C.
  • the drying time is generally from 1 minute to 36 hours, preferably from 1 to 30 minutes.
  • the pH may be adjusted to an optimal value for the crosslinking agent to be used, and when glutaraldehyde is used as a crosslinking agent, the pH is preferably 4.5 to 5.5, particularly preferably 5.0.
  • the alignment film is provided on the transparent support or the undercoat layer described above.
  • the alignment film can be obtained by crosslinking the aforementioned polymer layer and then subjecting the surface of the layer to a rubbing treatment.
  • rubbing treatment methods widely used for orienting liquid crystals of LCD can be applied. More specifically, a method in which the surface of an alignment film is rubbed in a fixed direction using paper, gauze, felt, rubber, nylon or polyester fiber to obtain orientation can be employed. In general, this is carried out by rubbing the film surface several times with a cloth to which fibers of the same length and diameter are uniformly transplanted.
  • the rubbing treatment is carried out by contacting a rotating rubbing roll with a traveling film to which a polarizing layer has been adhered.
  • the circularity, cylindricality and deflection (decentration) of the rubbing roll are all preferably 30 ⁇ m or less.
  • the wrap angle of the film relative to the rubbing roll is preferably 0.1° to 90°.
  • stable rubbing can be achieved by winding the film around the roll at 360° or more.
  • the traveling speed of the film is 1 to 1 OO m/minute.
  • an appropriate rubbing angle is selected from the range of 0 to 60°.
  • the rubbing angle is preferably 40 to 50°, particularly preferably 45°.
  • the alignment film thus obtained has a film thickness of preferably 0.1 to 10 ⁇ m.
  • Liquid crystal molecules in the optically anisotropic layer are then oriented on the alignment film. Subsequently, the alignment film polymer and the multifunctional monomer contained in the optically anisotropic layer are allowed to react or the alignment film polymer is crosslinked using a crosslinking agent according to need.
  • the liquid crystal molecules used for the optically anisotropic layer include bar-like liquid crystal molecules and disk-like liquid crystal molecules.
  • the bar-like liquid crystal molecule and the disk-like liquid crystal molecule may be a high molecular weight liquid crystal or a low molecular weight liquid crystal, and those in which a low molecular weight liquid crystal has been crosslinked and no liquid crystallinity is thus exhibited may also be included.
  • the bar-like liquid crystal molecule may be a metal complex.
  • Liquid crystal polymers containing bar-like liquid crystal molecules in the repeat units can also be used as the bar-like liquid crystal molecule.
  • the bar-like liquid crystal molecule may be bonded to a (liquid crystal) polymer.
  • Bar-like liquid crystal molecules are described in Chapters 4, 7, and 11 in “Chemistry of Liquid Crystal", Survey of Chemistry, Quarterly, Vol. 22, edited by the Chemical Society of Japan (1994), and Chapter 3 in "Liquid Crystal Device Handbook” edited by the 142 Committee of the Japan Society for the Promotion of Science.
  • the birefringent index of the bar-like liquid crystal molecules is preferably in the range of 0.001 to 0.7.
  • the bar-like liquid crystal molecule may contain a polymerizable group.
  • the polymerizable group is preferably a radically polymerizable unsaturated group or a cationically polymerizable group. Specific examples thereof include polymerizable groups and polymerizable liquid crystal compounds described in Japanese Patent Application Laid-Open No. 2002-62427, paragraphs 0064 to 0086.
  • disk-like (discotic) liquid crystal molecule examples include benzene derivatives described in a study report of C. Destrade et al., MoL Cryst., vol. 71, p.l 11 (1981); truxene derivatives described in a study report of C. Destrade et al., MoI. Cryst., vol. 122, p.141 (1985) and Phyicslett, A, vol. 78, p.82 (1990); cyclohexane derivatives described in a study report of B. Kohne et al., Angew. Chem. Soc, vol.
  • liquid crystal compounds in which a linear alkyl group, alkoxy group or a substituted benzoyloxy group constitutes a side chain, being present as a substituent radially to the parent core located at the center of the molecule are also included.
  • Compounds in which a molecule or a cluster of molecules has rotational symmetry and which can thus give a certain orientation are preferred.
  • the compound finally contained in the optically anisotropic layer need not be disk-like liquid crystal molecules, and for example, a compound in which a low molecular weight disk-like liquid crystal molecule containing a group reactive to heat or light is consequently polymerized or crosslinked and thus the molecular weight is increased and the liquid crystallinity is lost may also be included.
  • a compound in which a low molecular weight disk-like liquid crystal molecule containing a group reactive to heat or light is consequently polymerized or crosslinked and thus the molecular weight is increased and the liquid crystallinity is lost may also be included.
  • Preferred examples of disk-like liquid crystal molecules are described in Japanese Patent Application Laid-Open No. 8-50206. Polymerization of disk-like liquid crystal molecule is described in Japanese Patent Application. Laid-Open No. 8-27284 describes.
  • the angle between the major axis (disc plane) of disk-like liquid crystal molecule and the plane of the polarizing film is increased or decreased with the increase in the distance from the plane of the polarizing film in the depth direction of the optically anisotropic layer.
  • the angle is preferably decreased as the distance is increased.
  • possible variations of angles include continuous increase, continuous decrease, intermittent increase, intermittent decrease, variation including continuous increase and continuous decrease, and intermittent variation including increase and decrease.
  • the intermittent variation there is a region in which the tilt angle does not vary in the thickness direction. Regarding this angle, there may be regions in which the angle does not vary, as long as the angle is totally increased or decreased. Further, the angle is preferably totally continuously varied.
  • the average direction of the major axis of the disk-like liquid crystal molecules on the polarizing film side can be generally controlled by selecting the material of disk-like liquid crystal molecule or that of the alignment film, or by selecting the rubbing method.
  • the direction of the major axis of the disk-like liquid crystal molecule (disc plane) on the surface side (air side) can be generally controlled by selecting the material of disk-like liquid crystal molecule or that of the additive used together with the disk-like liquid crystal molecule.
  • additives used together with the disk-like liquid crystal molecule include plasticizers, surfactants, polymerizable monomers and polymers.
  • the degree of variation in the oriented direction of the major axes can be controlled by selecting the kind of disk-like liquid crystal molecule and additives as described above.
  • (B-4) Other components in optically anisotropic layer A plasticizer, a surfactant or a polymerizable monomer may be used together with the aforementioned liquid crystal molecule to improve the uniformity of the coating film, the strength of the film and the orientation property of the liquid crystal molecule etc. It is preferable that these components are compatible with the liquid crystal molecule so that they can play a part in the change in the tilt angle of the liquid crystal molecule, or do not hinder the orientation.
  • the polymerizable monomer may be a radically polymerizable or cationically polymerizable compound, and is preferably a radically polymerizable polyfunctional monomer, which is copolymerizable with the aforementioned liquid crystal compound containing a polymerizable group. Examples thereof include those described in Japanese Patent Application Laid-Open No. 2002-296423, paragraphs 0018 to 0020.
  • the amount to be added of the compound is generally in the range of 1 to 5O%, preferably in the range of 5 to 30% by mass based on the amount of the disk-like liquid crystal molecule.
  • the surfactant may be a conventionally known compound, but fluorine-containing compounds are particularly preferable. Specific examples thereof include compounds described in Japanese Patent Application Laid-Open No. 2001-330725, paragraphs 0028 to 0056.
  • the polymer used together with the disk-like liquid crystal molecule can play a part in the change in the tilt angle of the disk-like liquid crystal molecules.
  • the amount to be added of the polymer is in the range of preferably 0.1 to 10% by mass, more preferably 0.1 to 8% by mass based on the amount of the liquid crystal molecule.
  • the transition temperature from the discotic nematic liquid crystal phase to the solid phase is preferably 70 to 300°C, more preferably 70 to 170°C.
  • the optically anisotropic layer can be formed by applying, to the alignment film, a coating solution containing liquid crystal molecules and if necessary, a polymerization initiator or optional components described below.
  • a coating solution containing liquid crystal molecules and if necessary, a polymerization initiator or optional components described below.
  • a solvent used for preparing the coating solution an organic solvent is preferably used.
  • organic solvent examples include amides (e.g., N,N-dimethylformamide), sulfoxides (e.g., dimethyl sulfoxide), heterocyclic compounds (e.g., pyridine), hydrocarbons (e.g., benzene, hexane), alkyl halides (e.g., chloroform., dichloromethane, tetrachloroethane), esters (e.g., methyl acetate, butyl acetate), ketones (e.g., acetone, methyl ethyl ketone) and ethers (e.g., tetrahydrofuran, 1,2-dimethoxyethane). Of these, alkyl halides and ketones are preferred. Two or more organic solvents may be used together.
  • amides e.g., N,N-dimethylformamide
  • sulfoxides e.g., dimethyl sulfoxide
  • the coating solution can be applied by a known method (e.g., wire bar coating, extrusion coating, direct gravure coating, reverse gravure coating and die coating).
  • the optically anisotropic layer has a thickness of preferably 0.1 to 20 ⁇ m, more preferably 0.5 to 15 ⁇ m, and most preferably from 1 to 10 ⁇ m.
  • the oriented liquid crystal molecule can be fixed with maintaining the orientation state.
  • the fixation is preferably carried out by a polymerization reaction.
  • Such polymerization reactions include a thermal polymerization reaction using a thermal polymerization initiator and a photopolymerization reaction using a photopolymerization initiator, and a photopolymerization reaction is preferred.
  • photopolymerization initiator examples include ⁇ -carbonyl compounds (described in U.S. Patent Nos. 2,367,661 and 2,367,670), acyloin ethers (described in U.S. Patent No. 2,448,828), ⁇ -hydrocarbon-substituted aromatic acyloin compounds (described in U.S. Patent No. 2,722,512), polynuclear quinone compounds (described in U.S. Patent Nos. 3,046,127 and 2,951,758), combinations of a triarylimidazole dimer and p-aminophenyl ketone (described in U.S. Patent No.
  • the amount to be used of the photopolymerization initiator is in the range of preferably 0.01 to 20% by mass, more preferably 0.5 to 5% by mass based on the solid component in the coating solution.
  • ultraviolet light is preferably used.
  • the radiating energy is in the range of preferably 20 mJ/cm to 50 J/cm , more preferably 20 to 5000 mJ/cm 2 , further preferably 100 to 800 mJ/cm 2 .
  • photoirradiation may be carried out under heating.
  • a protective layer may be formed on the optically anisotropic layer.
  • This compensation film may also be combined with a polarizing layer.
  • a coating solution for an optically anisotropic layer as described above is applied to the surface of a polarizing film to form an optically anisotropic layer. Accordingly, a thin polarizing plate in which the stress (strain x cross-sectional area x elastic modulus) due to the dimensional change of the polarizing film is small can be produced without using any polymer film between the polarizing film and the optically anisotropic layer.
  • the polarizing plate of the present invention is incorporated into a large-sized liquid crystal display device, images having a high display quality can be displayed without causing problems such as light leakage.
  • the tilt angle between the polarizing layer and the compensation lay&r stretching is preferably carried out so that the tilt angle is matched with the angle between the transmission axis of two polarizing plates adhered to both surfaces of a liquid crystal cell constituting a LCD and the longitudinal or transverse direction of the liquid crystal cell.
  • the tilt angle is generally 45°, but recently, transmissive, reflective and semi-transmissive LCDs in which the tilt angle is not always 45° have been developed, and it is therefore desirable that the stretching direction can be optionally adjusted depending on the design of LCDs.
  • the liquid crystal cell is in a bend orientation mode in which bar-like liquid crystal molecules in the upper part and in the lower part are substantially reversely (symmetrically) oriented.
  • Liquid crystal display devices using such bend orientation mode liquid crystal cell are disclosed in U.S. Patent Nos. 4,583,825 and 5,410,422. Since the bar-like liquid crystal molecules in the upper part and in the lo ⁇ ver part are symmetrically oriented, the bend orientation mode liquid crystal cell has self-optical compensatory function. This mode is thus referred to as OCB (optically- compensatory bend) liquid crystal mode.
  • OCB optical- compensatory bend
  • bar-like liquid crystal molecules are vertically aligned at the central portions of the cell while the molecules are horizontally aligned in the vicinity of the cell substrates as in the TN mode.
  • VA mode liquid crystal display device VA mode liquid crystal display device
  • the VA mode liquid crystal cells include (1) VA mode liquid crystal cells in a narrow sense in which bar-like liquid crystal molecules are substantially vertically aligned when no voltage is applied while they are substantially horizontally aligned when voltage is applied (described in Japanese Patent Application Laid-Open No. 2-176625); (2) liquid crystal cells in a mode (MVA. mode) in which VA mode is converted to a multi-domain mode for enlarging the viewing angle (described in SID97, Digest of tech.
  • liquid crystal cells in a mode in which bar-like liquid crystal molecules are substantially vertically aligned when no voltage is applied while they are aligned being twisted in multi-domains when voltage is applied (described in Preprints of Symposium on Japanese Liquid Crystal Society, (1998), 58-59,); and (4) liquid crystal cells in SURVIVAL mode (published in LCD international 98).
  • IPS mode liquid crystal display device
  • This mode is characterized in that bar-like liquid crystal molecules are substantially horizontally aligned in the plane when no voltage is applied, and that switching is performed by changing the alignment direction of the liquid crystal by applying or not applying voltage.
  • those described in Japanese Patent Application Laid-Open Nos. 2004-365941, 2004-12731, 2004-215620, 2002-221726, 2002-55341 and 2003-195333 may be used. (Other liquid crystal display devices)
  • optical compensation can be achieved based on the same approach as described above.
  • An anti-reflection film is generally prepared by forming, on a transparent substrate, a low refractive index layer which also serves as an antifouling layer and at least one layer which has a higher refractive index than the low refractive index layer (i.e., high refractive index layer or middle refractive index layer).
  • Methods of forming a multi-layered film in which transparent thin films of inorganic compounds (metal oxides, etc.) of different refractive indexes are stacked include a chemical vapor deposition (CVD) method, a physical vapor deposition (PVD) method, and a method in which a metal compound such as metal alkoxide is subjected to a sol-gel method to be formed into a film of colloidal metal oxide particles, followed by post-treatment (ultraviolet radiation described in Japanese Patent Application Laid-Open No. 9-157855, or plasma treatment described in Japanese Patent Application Laid-Open No. 2002-327310) to form a thin film.
  • CVD chemical vapor deposition
  • PVD physical vapor deposition
  • anti-reflection films of high productivity various anti-reflection films formed by stacking thin films of inorganic particles dispersed in a matrix are proposed.
  • An anti-reflection film having an anti-reflection layer to which an anti-glare property is imparted by forming fine irregularities on the uppermost layer of an anti-reflection film produced according to the aforementioned coating method may also be used.
  • the coating method (coating type) is particularly preferred.
  • An anti-reflection film having a layer structure in which at least a middle refractive index layer, a high refractive index layer and a low refractive index layer (the outermost layer) are formed on a substrate in that order is designed so that the film has refractive indexes satisfying the following relationship. refractive index of high refractive index layer > refractive index of middle refractive index layer > refractive index of transparent substrate > refractive index of low refractive index layer
  • a hard coat layer may be formed between the transparent substrate and the middle refractive index layer.
  • the anti-reflection film may be composed of a middle refractive index hard coat layer, a high refractive index layer and a low refractive index layer.
  • Examples of such layer structure are described in Japanese Patent Application Laid-Open Nos. 8-122504, 8-110401, 10-300902, 2002-243906 and 2000-111706.
  • those layers may have other function, and examples of such layers include a low refractive index layer having an antifouling property and a high refractive index layer having an antistatic property (e.g., Japanese Patent Application Laid-Open Nos. 10-206603, 2002-243906).
  • the anti-reflection film has a haze of preferably not more than 5%, more preferably not more than 3 % .
  • the strength of the film is preferably H or higher, more preferably 2H or higher, and most preferably 3H or higher as measured by the pencil hardness test in accordance with JIS K5400.
  • the high refractive index layer of the anti-reflection film is a curable film containing at least inorganic compound ultrafine particles of high refractive index having an average particle size of 100 nm or less, and a matrix binder.
  • the inorganic compound ultrafine particles of high refractive index may be an inorganic compound having a refractive index of not less than 1.65, preferably not less than 1.9.
  • inorganic compounds include oxides of Ti, Zn, Sb, Sn, Zr, Ce, Ta, La or In, and complex oxides containing these metal atoms.
  • Such ultrafine particles may be formed by, for example, treating the particle surface with a surface-treating agent (e.g., a silane coupling agent, Japanese Patent Application Laid-Open Nos. 11-295503, 11-153703 and 2000-9908, or an anionic compound or an organic metal coupling agent, Japanese Patent Application Laid-Open No. 2001-310432), forming a core-shell structure in which high refractive index particles constitute the core (Japanese Patent Application Laid-Open No. 2001-166104), or using a specific dispersant together (Japanese Patent Application Laid-Open No. 11-153703, U.S. Patent No. 6,210,858 Bl, Japanese Patent Application Laid-Open No. 2002-2776069).
  • a surface-treating agent e.g., a silane coupling agent, Japanese Patent Application Laid-Open Nos. 11-295503, 11-153703 and 2000-9908, or an anionic compound or an organic metal coupling agent, Japanese Patent Application Laid
  • the material which constitutes the matrix may be a conventionally known thermoplastic resin or curable resin film.
  • the material is preferably at least one composition selected from compositions containing a polyfunctional compound having at least two radically polymerizable groups and/or cationically polymerizable groups, organometallic compounds containing a hydrolyzable group and compositions containing a partial condensate thereof.
  • compositions containing a polyfunctional compound having at least two radically polymerizable groups and/or cationically polymerizable groups organometallic compounds containing a hydrolyzable group and compositions containing a partial condensate thereof. Examples thereof include compounds described in Japanese Patent Application Laid-Open Nos. 2000-47004, 2001-315242, 2001-31871 and 2001-296401.
  • a curable film prepared using a colloidal metal oxide obtained from a hydrolyzed condensate of metal alkoxide and a metal alkoxide composition is also preferred.
  • Such film is described, for example, in Japanese Patent Application Laid-Open No. 2001-293818.
  • the high refractive index layer has a refractive index of generally 1.70 to 2.20, and a thickness of preferably 5 nm to 10 ⁇ m, more preferably 10 nm to 1 ⁇ m.
  • the refractive index of the middle refractive index layer is adjusted so that it is between the refractive index of the low refractive index layer and the refractive index of the high refractive index layer.
  • the middle refractive index layer has a refractive index of preferably 1.50 to 1.70.
  • the low refractive index layer is stacked on the high refractive index layer.
  • the low refractive index layer has a refractive index of 1.20 to 1.55, preferably 1.30 to 1.50.
  • This layer is preferably formed as an outermost layer having scratch resistance and an antifouling property.
  • imparting lubricity to the surface is effective, and conventionally known methods of forming a thin film layer by introducing silicone or fluorine can be applied.
  • the refractive index of the fluorine-containing compound is preferably 1.35 to 1.50, more preferably 1.36 to 1.47.
  • fluorine-containing compound compounds containing 35 to 80% by mass of fluorine atoms and a crosslinkable or polymerizable functional group are preferable. Examples of such compound include those described in Japanese Patent Application Laid-Open No. 9-222503, paragraphs 0018 to 0026, Japanese Patent Application Laid-Open No. 11-38202, paragraphs 0019 to 0030, Japanese Patent Application Laid-Open No. 2001-40284, paragraphs 0027 to 0028 and Japanese Patent Application Laid-Open No. 2000-284102.
  • silicone compound one having a polysiloxane structure and containing a curable functional group or a polymerizable functional group in the polymer chain, and which thus forms a crosslinked structure in the film is preferred.
  • examples thereof include reactive silicone (e.g., Silaplane (available from CHISSO CORPORATION) and polysiloxane containing a silanol group on both terminals (Japanese Patent Application Laid-Open No. 11-258403).
  • crosslinking or polymerization reaction of such fluorine-containing polymer and/or siloxane polymer containing a crosslinkable or polymerizable group is preferably carried out by radiation of light or by heating simultaneously with or after applying a coating composition for forming an outermost layer, which contains a polymerization initiator and/or a sensitizer.
  • a sol-gel curable film in which an organometallic compound such as a silane coupling agent and a silane coupling agent containing a specific fluorine-containing hydrocarbon group undergo curing by a condensation reaction in the presence of a catalyst is also preferable.
  • organometallic compound such as a silane coupling agent and a silane coupling agent containing a specific fluorine-containing hydrocarbon group undergo curing by a condensation reaction in the presence of a catalyst.
  • examples thereof include silane compounds containing a polyfluoroalkyl group or partially-hydrolyzed condensates thereof (compounds described in Japanese Patent Application Laid-Open Nos.
  • silyl compounds containing a poly(perfluoroalkyl ether)group which is a long-chain, fluorine-containing group (compounds described in Japanese Patent Application Laid-Open Nos. 2000-117902, 2001-48590, 2002-53804).
  • the low refractive index layer may contain, in addition to the above components, an additive such as a filler (e.g., low refractive index inorganic compounds having an average primary particle size of 1 to 150 nm such as silicon dioxide (silica) and fluorine-containing particles (magnesium fluoride, calcium fluoride, barium fluoride), organic fine particles described in Japanese Patent Application Laid-Open No. 11-3820, paragraphs [0020] to [0038]), a silane coupling agent, a lubricant and a surfactant.
  • a filler e.g., low refractive index inorganic compounds having an average primary particle size of 1 to 150 nm such as silicon dioxide (silica) and fluorine-containing particles (magnesium fluoride, calcium fluoride, barium fluoride), organic fine particles described in Japanese Patent Application Laid-Open No. 11-3820, paragraphs [0020] to [0038]
  • a silane coupling agent e.g.
  • the low refractive index layer When the low refractive index layer is positioned outermost, the low refractive index layer may be formed by a gas phase method (vacuum vapor deposition, sputtering, ion plating, or plasma CVD).
  • the low refractive index layer is preferably formed by coating because inexpensive production is possible.
  • the low refractive index layer has a film thickness of preferably 30 to 200 nm, more preferably 50 to 150 nm, and most preferably 60 to 120 nm.
  • the hard coat layer is formed on the surface of a transparent support to impart physical strength to the anti-reflection film. Particularly, it is preferable that the hard coat layer is disposed between the transparent support and the high refractive index layer.
  • the hard coat layer is preferably formed by subjecting a photo-curable or thermally curable compound to a crosslinking reaction or polymerization reaction.
  • the curable functional group is preferably a photopolymerizable functional group
  • the organometallic compound containing a hydrolyzable functional group is preferably an organic alkoxysilyl compound.
  • compositions constituting the hard coat layer include those described in Japanese Patent Application Laid-Open Nos. 2002-144913, 2000-9908 and WO 0/46617.
  • the high refractive index layer can also serve as a hard coat layer. Such layer may be formed by finely dispersing minute particles and incorporating them into the hard coat layer using the technique described in the section of the high refractive index layer.
  • the hard coat layer can also serve as an anti-glare layer having anti-glare function (described later) by adding particles having an average particle size of 0.2 to 10 ⁇ m.
  • the film thickness of the hard coat layer can be suitably designed depending on the purpose of use.
  • the hard coat layer has a film thickness of preferably 0.2 to 10 ⁇ m, more preferably 0.5 to 7 ⁇ m.
  • the strength of the hard coat layer is preferably H or higher, more preferably 2H or higher, and most preferably 3H or higher as measured by the pencil hardness test in accordance with JIS K5400. Further, the smaller the abrasion of a test piece after a taber test in accordance with JIS K5400, the better. (C -5) Forward scattering layer
  • a forward scattering layer is provided in order to impart an effect of improving viewing angles when the film is incorporated into a liquid crystal display device and the viewing angle is tilted up, down, to the right and the left.
  • the forward scattering layer can also have function of a hard coat layer.
  • Examples of such layer include those having a specified forward scattering coefficient (Japanese Patent Application Laid-Open No. 11-38208), those in which relative refractive indexes of transparent resin and fine particles are within specific ranges (Japanese Patent Application Laid-Open No. 2000-199809), and those having a specified haze value of not less than 40% (Japanese Patent Application Laid-Open No. 2002-107512).
  • the anti-reflection film may have a primer layer, an anti-static layer, an undercoat layer or a protective layer.
  • Layers of the anti-reflection film may be formed by coating according to dip coat, air knife coat, curtain coat, roller coat, wire bar coat, gravure coat, micro gravure coat and extrusion coat (described in U.S. Patent No. 2,681,294).
  • the anti-reflection film may have anti-glare function for scattering light from the outside.
  • the anti-glare function can be obtained by creating irregularities on the surface o f the anti-reflection film.
  • the haze of the anti-reflection film is preferably 3 to 30%, more preferably 5 to 20%, and most preferably 7 to 20%.
  • any method capable of satisfactorily maintaining such irregular surface profile can be used.
  • a method in which fine particles are used for a low refractive index layer to form irregularities on the film surface e.g., Japanese Patent Application Laid-Open No.
  • a method comprising adding a small amount (0.1 to 50% by mass) of relatively large particles (particle size: 0.05 to 2 ⁇ m) to the layer to be formed beneath the low refractive index layer (high refractive index layer, middle refractive index layer or hard coat layer) so as to form a film having an irregular surface, and then forming a low refractive index layer thereon with maintaining the surface shape (e.g., Japanese Patent Application Laid-Open Nos.
  • Sample films are conditioned at a temperature of 5°C and a humidity of 60% rh for at least 3 hours.
  • retardation values are measured at 25°C and 60% rh at a wavelength of 550 run in the direction perpendicular to the sample film surface, and the directions tilted +40° relative to the normal of the film plane.
  • the in-plane retardation (Re) is calculated from the value in the perpendicular direction
  • the retardation in the thickness direction (Rth) is calculated from the measured values in the directions tilted ⁇ 40° from the perpendicular direction.
  • the sample films are conditioned at a temperature of 5°C and a humidity of 60% rh for at least 3 hours.
  • retardation values are measured at 25°C and 60% rh at a wavelength of 550 nm in a direction perpendicular to the sample film surface, and directions tilted ⁇ 40° relative to the normal of the film plane.
  • the in-plane retardation (Re) is calculated from the value in the perpendicular direction
  • the retardation in the thickens direction (Rth) is calculated from the measured values in the directions tilted ⁇ 40° from the perpendicular direction.
  • the average value of all sampling points is each defined as Re and Rth.
  • the difference between the maximum value and the minimum value of 100 points in the machine direction and 50 points in the transverse direction is divided by each average value and shown in percentage to be defined as fluctuation in Re and fluctuation in Rth.
  • acyl substitution degree in cellulose acylate was measured using 13C-NMR according to the method described in Carbohydr. Res. 273 (1995) 83-91 (Tezuka et al.).
  • Yellowness (YI: yellowness index) was measured using Z-II OPTICAL SENSOR according to JIS K7105 6.3.
  • Yellowness of pellets was measured by a reflection method, and in the case of films, three stimulus values X, Y and Z were measured by a transmission method, with which YI values were calculated according to the following formula.
  • Cellulose acylates having different acyl groups and different substitution degrees as shown in Table 1 of Figs. 3 A to 3E were prepared. Specifically, sulfuric acid (7.8 parts by weight based on IOO parts by weight of cellulose) was added as a catalyst and carboxylic acid which is the raw material of acyl substituent was added to conduct an acylation reaction at 40 0 C . Based on the kind and the amount of carboxylic acid, the kind and the degree of substitution with acyl group were controlled. After the acylation, the resultant was ripened at 40°C. The polymerization degree of trie cellulose acylates thus obtained was determined by the following method and shown in the Table of Figs. 3A to 3E.
  • the aforementioned cellulose acylate resins were formed into cylindrical pellets 3 mm in diameter and 5 mm in length.
  • plasticizers were selected from those described later (shown in the Table of Figs. 3 A to 3E) and mixed with the pellet.
  • the resultant was dried in a vacuum dryer at 110 0 C and after controlling the moisture content to 0.1 % or less, this was introduced to the hopper adjusted to Tg-IO 0 C.
  • TPP triphenyl phosphate
  • BDP biphenyldiphenyl phosphate
  • DOAv bis(2-ethylhexyl)adipate
  • PTP 1,4-phenylene-tetraphenyl phosphoric ester.
  • the melting temperature was adjusted so that the melt viscosity was 1000 Pa- s, and the pellets were melted using the single screw extruder 11 set to 210 0 C.
  • the melted material was then extruded on the cooling drum 14 adjusted to Tg-5°C in th_e form of a sheet through the T-die 12 adjusted to the melting temperature and solidified with cooling to form a cellulose acylate film.
  • an electrostatic application method was used for each sample (10 kV wire being placed 10 cm from the landing point of the melt on the cooling drum 14).
  • the solidified sheet was peeled off and taken up.
  • both ends were trimmed (3% each of the total width) and subjected to thickness increasing processing (knurling) to achieve a width of 10 mm and a height of 50 ⁇ m.
  • AU samples were taken up at 30 m/minute in a width of 1.5 m and in a length of 3000 m.
  • the extrusion temperature when producing a cellulose acylate film (unstretched) was set to 190°C (lower limit), 220 0 C and 240 0 C (upper limit), which are within the range defined in the present invention.
  • the extrusion temperature was set to 185°C (below the lower limit of the present invention) and 245°C (above the upper limit of the present invention), which are outside the range defined in the present invention.
  • the stretched cellulose acylate films exhibited good results of an Re of 40 to 50 (coefficient of fluctuation 2 to 4%) and an Rth of 240 to 260 (coefficient of fluctuation 2 to 4%). Further, because the extrusion temperature was 240 0 C or lower, good results of YI values of 3 to 6 were obtained, which means that substantially no yellowing occurred-
  • the film had an elongation at break upon stretching of 47% (1.47 times the value before stretching) which fell short of the passing point of 50% (1.5 times the value before stretching), and was broken in the stretching step, and it was thus impossible to produce a stretched cellulose acylate film.
  • the indexes of the amount of minute crystal remaining in the cellulose acylate films i.e., the DSC endothermic peak value was 5.4 J/g, which is greater than 4 J/g, and the haze value was 2.3%, which is greater than 2% .
  • Examples 1-4 to 1-8 were carried out at a constant extrusion temperature of 230°C with change in the pre-heating temperature in longitudinal stretching within the range of Tg-40°C to Tg+60°C.
  • the stretched cellulose acylate film obtained by stretching the produced cellulose acylate film had appropriate levels of Re, coefficient of fluctuation in Re, Rth, coefficient of fluctuation in Rth, haze, YI value, film thickness and elongation at break upon stretching.
  • Examples 1-9 to 1-13 were carried out at a constant extrusion temperature of 230°C with change in the screw compression ratio within the range defined in the present invention of 2.5 to 4.5.
  • the stretched cellulose acylate film obtained by stretching the produced cellulose acylate film had acceptable quality levels of Re, coefficient of fluctuation in Re, Rth, coefficient of fluctuation in Rth, haze, YI value, film thickness and elongation at break upon stretching.
  • Examples 1-14 to 1-18 were carried out at a constant screw compression ratio of 3.5 and a constant L/D of 50, which is the upper limit thereof defined in the present invention, with change in the extrusion temperature within the range defined in the present invention of 190°C to 24O 0 C.
  • the stretched cellulose acylate film obtained by stretching the produced cellulose acylate film had acceptable quality levels of Re, coefficient of fluctuation in Re, Rth, coefficient of fluctuation in Rth, haze, YI value, film thickness and elongation at break upon stretching.
  • Examples 1-19 to 1-24 were carried out with changing the glass transition temperature of the cellulose acylate resin within the range of 120 0 C to 170 0 C by changing the substitution degree and the molecular weight of cellulose acylate.
  • the stretched cellulose acylate film obtained by stretching the produced cellulose acylate film had acceptable quality levels of Re, coefficient of fluctuation in Re, Rth, coefficient of fluctuation in Rth, haze, YI value, film thickness and elongation at break upon stretching.
  • Table of Figs. 3A to 3E show only the cases in which the screw compression ratio satisfies the range of 2.5 to 4.5.
  • the screw compression ratio was greater than 4.5, molecules were broken and the molecular weight was thus decreased, which led to significant decrease in the mechanical strength of the produced cellulose acylate film.
  • the subsequent stretching step was therefore not performed.
  • the screw compression ratio was smaller than 2.5, melting was insufficient and unmelted particles were generated, or bubbles were incorporated. The subsequent stretching step was therefore not performed.
  • the thus-obtained polarizing layer, the aforementioned saponified unstretched and stretched cellulose acylate films and saponified FUJITAC (mnstretched triacetate film) were stacked using a 3% aqueous solution of PVA (PVA-1 17H available from Kuraray Co., Ltd.) as an adhesive in the stretching direction of the polarizing film and the film-forming flow direction (length direction) of the cellulose acylate film in the following combinations.
  • PVA PVA-1 17H available from Kuraray Co., Ltd.
  • Polarizing plate A unstretched cellulose acylate film/ polarizing layer/FUJITAC
  • Polarizing plate B unstretched cellulose acylate film/ polarizing layer/unstretched cellulose acylate film (1-4) Color change in polarizing plate
  • the humidity curl of the polarizing plate obtained as described above was measured by the aforementioned method. Those to which the present invention was applied exhibited excellent properties (low humidity curl) even after a polarizing plate was formed.
  • the polarizing plate attached on the viewer side of a 22-inch liquid crystal display device using VA-type liquid crystal (made by Sharp Corporation) was removed, and when using the aforementioned retardation polarizing plate A or B instead, the polarizing plate was detached, and the plate was adhered on the ⁇ viewer side using an adhesive so that the cellulose acylate film is on the side of the liquid crystal cell.
  • the plate was positioned so that the transmission axis of the polarizing plate on the viewer side and the transmission axis of the polarizing plate on the backlight side are perpendicular to each other, and a liquid crystal display device was completed.
  • the polarizing plate according to the present invention has little humidity curl and is easy to adhere, little misalignment was found when adhered.
  • the polarizing plate or the retardation polarizing of the present invention was applied to the liquid crystal display device described in Example 1 of Japanese Patent Application Laid-Open No. 10-48420, the optically anisotropic layer containing discotic liquid crystal molecules described in Example 1 of Japanese Patent Application Laid-Open No. 9-26572, an alignment film coated with polyvinyl alcohol, the 20 inch VA-type liquid crystal display device described in Figs. 2 to 9 of Japanese Patent Application Laid-Open No. 2000-154261, the 20 inch OCB-type liquid crystal display device described in Figs. 10 to 15 of Japanese Patent Application Laid-Open No. 2000-154261 and the JPS-type liquid crystal display device described in Fig. 11 of Japanese Patent Application Laid-Open No. 2004-12731. As a result, excellent liquid crystal display devices with little humidity curl were prepared. (3) Preparation of low reflection film
  • a low reflection film was prepared according to Example 47 of "Kokai Giho of Japan Institute of Invention & Innovation" (Kogi No. 2001-1745).
  • the obtained film was subjected to humidity curl measurement described above.
  • Those to which the present invention was applied produced good results as in the case of preparing polarizing plates.
  • the low reflection film of the present invention was applied to the outermost layer of the liquid crystal display device described in Example 1 of Japanese Patent Application Laid-Open No. 10-48420, the 20 inch VA-type liquid crystal display device described in Figs. 2 to 9 of Japanese Patent Application Laid-Open No. 2000-154261, the 20 inch OCB-type liquid crystal display device described in Figs.

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EP05788294A 2004-09-24 2005-09-21 Celluloseacylatfolie, verfahren zur herstellung derselben, gestrecktecelluloseacylatfolie und verfahren zur herstellung derselben Withdrawn EP1793975A4 (de)

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CN104656178B (zh) * 2015-01-15 2017-02-01 张宝庆 一种用于液晶显示器成像的偏光成像片及其染色制作方法
JP7273691B2 (ja) 2019-11-01 2023-05-15 信越化学工業株式会社 ヒドロキシプロピルメチルセルロースフタレートの製造方法
JP7252882B2 (ja) * 2019-11-01 2023-04-05 信越化学工業株式会社 ヒドロキシプロピルメチルセルロースアセテートサクシネートの製造方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6013217A (en) * 1997-12-22 2000-01-11 Dow Corning Corporation Method for extruding thermoplastic resins
JP2002265636A (ja) * 2001-03-12 2002-09-18 Fuji Photo Film Co Ltd セルロースアシレートフイルム及びその製造方法
WO2003081299A1 (fr) * 2002-03-25 2003-10-02 Zeon Corporation Film optique et son procede de production

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3655960B2 (ja) * 1994-12-05 2005-06-02 富士写真フイルム株式会社 セルロースエステル溶液およびセルロースエステルフイルムの製造方法
JP4074762B2 (ja) * 2002-01-21 2008-04-09 富士フイルム株式会社 光学補償フィルムおよびその製造方法、円偏光板、画像表示装置
JP2004054257A (ja) 2002-05-29 2004-02-19 Fuji Photo Film Co Ltd 光学補償シート、その製造方法およびそれを用いた偏光板、液晶表示装置

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6013217A (en) * 1997-12-22 2000-01-11 Dow Corning Corporation Method for extruding thermoplastic resins
JP2002265636A (ja) * 2001-03-12 2002-09-18 Fuji Photo Film Co Ltd セルロースアシレートフイルム及びその製造方法
WO2003081299A1 (fr) * 2002-03-25 2003-10-02 Zeon Corporation Film optique et son procede de production

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of WO2006033459A1 *

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KR101229502B1 (ko) 2013-02-04
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EP1793975A4 (de) 2013-01-23
KR20070054221A (ko) 2007-05-28
CN101027175B (zh) 2010-08-18

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