WO2008050525A1 - Film retardateur - Google Patents

Film retardateur Download PDF

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Publication number
WO2008050525A1
WO2008050525A1 PCT/JP2007/066173 JP2007066173W WO2008050525A1 WO 2008050525 A1 WO2008050525 A1 WO 2008050525A1 JP 2007066173 W JP2007066173 W JP 2007066173W WO 2008050525 A1 WO2008050525 A1 WO 2008050525A1
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WO
WIPO (PCT)
Prior art keywords
film
acid
temperature
retardation film
stretching
Prior art date
Application number
PCT/JP2007/066173
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English (en)
Japanese (ja)
Inventor
Kenichirou Fujihana
Original Assignee
Konica Minolta Opto, Inc.
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Filing date
Publication date
Application filed by Konica Minolta Opto, Inc. filed Critical Konica Minolta Opto, Inc.
Publication of WO2008050525A1 publication Critical patent/WO2008050525A1/fr

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Classifications

    • 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
    • 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
    • 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
    • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
    • B29K2995/0018—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds having particular optical properties, e.g. fluorescent or phosphorescent
    • B29K2995/0031—Refractive
    • B29K2995/0032—Birefringent

Definitions

  • the present invention relates to a retardation film used in various display devices such as a liquid crystal display device (LCD) or an organic EL (electric mouth luminescence) display, and in particular, a protective film for a polarizing plate used in these display devices,
  • the present invention relates to a retardation film having birefringence that can be used as a retardation film.
  • the basic configuration of a liquid crystal display device is one in which polarizing plates are provided on both sides of a liquid crystal cell. Since a polarizing plate allows only light with a polarization plane in a certain direction to pass, it plays an important role in visualizing changes in the orientation of liquid crystal due to an electric field in a liquid crystal display device. The performance of a liquid crystal display device depends on the performance of the polarizing plate. Is greatly affected.
  • a liquid crystal display device with a wide viewing angle generally uses a retardation correction film.
  • the quality required for retardation films has become stricter due to the larger screen and higher definition, and the uniformity of the film retardation value in the lateral and longitudinal directions is required.
  • a polarizing plate used in a VA mode liquid crystal panel is bonded to a liquid crystal cell so as to have a polarization axis in the vertical and horizontal directions of the screen.
  • the polarizer of the elements constituting the polarizing plate used here is manufactured by greatly stretching a PVA film.
  • cellulose protecting the polarizer is used.
  • corner unevenness in which shrinkage stress is applied to the esthetic film or the retardation film that is laminated, and the four corners appear white when the screen is displayed in black.
  • Patent Document 1 discloses a cellulose ester film, an optical compensation sheet (retardation plate), and an elliptically polarizing plate.
  • Tensile elasticity in the machine direction of a cell mouth ester film is disclosed.
  • the tensile modulus in the direction perpendicular to the machine direction and by adjusting the ratio of tensile modulus in the machine direction / tensile modulus in the direction perpendicular to the machine direction, the thickness direction of the cellulose ester film It is described that the relationship between the letter decision value (Rth) and the in-plane letter decision value (Re) is adjusted.
  • Patent Document 1 Japanese Patent Laid-Open No. 2001-100039
  • Patent Document 1 has a problem that “corner unevenness” in the large-screen VA liquid crystal panel is insufficient to improve the problem.
  • An object of the present invention is to provide a retardation film capable of solving the above-described problems of the prior art and improving corner unevenness in a large-screen VA liquid crystal panel.
  • the present inventor has conducted extensive research to solve the above-described problems of the prior art, and as a result, in order to improve corner unevenness in a large-screen VA-type liquid crystal panel, a protective film according to the contraction force of the polarizer Alternatively the retardation film itself may force s it is preferable to deform revealed.
  • the temperature of the retardation film may reach nearly 50 ° C due to lighting of the panel backlight, and in this state, the elastic modulus power of the protective film or retardation film alone will be reduced to the elastic modulus at a temperature of 23 ° C.
  • the present inventors have found that the effect is remarkable when the temperature is 0.3 to 0.8 GPa lower than that, and have completed the present invention.
  • the protective film or retardation film itself has a low elastic modulus, especially for polarizing plates for large-screen liquid crystal panels! Since it becomes impossible to counter the contraction force, the protective film or the retardation film is apt to be distorted, resulting in a decrease in front contrast.
  • the inventor has an elastic modulus (E) measured under measurement conditions at a temperature of 23 ° C and a humidity of 55% RH.
  • the present invention can significantly suppress the occurrence of corner unevenness by reducing the amount of plasticizer on the surface in contact with the polarizer of the retardation film to be less than the amount of plasticizer on the surface in contact with the glass side. It is.
  • the invention of claim 1 is characterized in that means for holding the end of the film and stretching in a direction perpendicular to the conveying direction is part of the film forming process.
  • the amount of additive present on the surface of the retardation film bonded to the polarizer is 100, the amount of additive present on the surface of the retardation film adhered to the glass surface is The mass ratio is 20 to 70.
  • Equation (1) 30 ⁇ E ⁇ 0. 80
  • the invention of claim 2 is the retardation film of claim 1, characterized in that the film thickness force of the film contained in the film is 35-60 111.
  • the invention of claim 3 is the phase difference according to claim 1 or 2: lum, wherein the intrinsic viscosity (IV) of the resin contained in the film is 1.3. ⁇ ; 1. It is characterized by 7.
  • the invention of claim 4 is the retardation film according to any one of claims 1 to 3, wherein the main component of the resin contained in the film is cellulose.
  • S And the cellulose ester contains at least one selected from cellulose acetate, cellulose acetate propionate, and cellulose acetate butyrate! /.
  • the invention according to claim 5 is the retardation film according to claim 4, comprising:
  • the invention of the retardation film of claim 1 is a production film in which means for gripping an end portion of the film and stretching in a direction perpendicular to the conveying direction is provided in a part of the film forming process.
  • a retardation film produced at a temperature of 23 ° C. and a humidity of 55% RH, and the elastic modulus (E) in the direction of stretching of the film measured under the measurement conditions is 3.4 to 4.4 GPa, Power,
  • the amount of additive present on the surface of the retardation film to be bonded to the polarizer is 100 in terms of mass ratio
  • the amount of additive present on the surface of the phase difference film to be adhered to the glass surface is 20 in terms of mass ratio. ⁇ 70.
  • Equation (1) 30 ⁇ E ⁇ 0. 80
  • the elastic modulus (E) in the film stretching direction measured under the measurement conditions at a temperature of 23 ° C and a humidity of 55% RH, a temperature of 50 ° C and a humidity of 55% Measurement conditions at RH
  • the temperature of the retardation film may reach nearly 50 ° C, and the retardation film itself in that state has an elastic modulus (E) force temperature Compared to the elastic modulus (E) at 23 ° C, the range of 0.3 to 0.8 GPa
  • the protective film or retardation film itself can be deformed according to the contraction force of the polarizer, and the power to improve corner unevenness in the large-screen VA liquid crystal panel can be improved! If the effect is remarkable, it will produce the effect!
  • the contraction of the polarizer caused by environmental fluctuations. It is possible to prevent the dimensional change of the polarizing film itself without losing the retardation film, and to prevent the so-called curling of the polarizing film, so that the liquid crystal panel can be manufactured with high productivity. There is an effect that can be done.
  • the invention of claim 1 is characterized in that corner unevenness is generated by making the amount of plasticizer on the surface in contact with the polarizer of the retardation film smaller than the amount of plasticizer on the surface in contact with the glass side. This has the effect of significantly reducing
  • the invention of claim 2 is the retardation film of claim 1, wherein the film thickness force of the film contained in the film is 35-60111. According to the present invention, it is possible to satisfactorily meet the demand for thinning of a retardation film used for thin displays in recent years, particularly thin displays such as large size TVs.
  • the invention of claim 3 is the retardation film of claim 1 or 2, wherein the intrinsic viscosity (IV) of the resin contained in the film is 1.3. According to the present invention, it is possible to prevent the film from tearing and to avoid the risk of breakage in the film stretching process according to the present invention. It has the effect of being able to.
  • the invention of claim 4 is the retardation film according to any one of claims 1 to 3, wherein the main component of the resin contained in the film is cellulose. It is an ester, and the cellulose ester contains at least one selected from cellulose acetate, cellulose acetate propionate, and cellulose acetate butyrate.
  • the resin constituting the film When a cellulose ester as described above is used, a retardation film capable of improving corner unevenness in a large-screen VA-type liquid crystal panel while maintaining the transparency of the film is obtained. There is an effect.
  • the invention of claim 5 is the retardation film of claim 4, which has a degree of ester group substitution degree of cellulose ester of 2.42-2.60. According to the invention, when a cellulose ester having an ester group substitution degree as defined above is used, a retardation film having good adhesion to the polarizing film while maintaining the transparency of the film can be obtained! / , Has an effect.
  • FIG. 1 is an explanatory diagram for explaining a stretching angle in a film stretching step.
  • FIG. 2 is a schematic plan view showing an example of a stretching process used in the method of the present invention.
  • FIG. 3 is a schematic plan view schematically showing an example of a tenter stretching apparatus used in the method of the present invention.
  • the retardation film according to the present invention has an elastic modulus (E) in the film stretching direction of 3.4 measured under measurement conditions of a temperature of 23 ° C and a humidity of 55% RH.
  • the elastic modulus (E) in the film stretching direction measured under the measurement conditions of 23 to 4.4 GPa and a temperature of 50 ° C. and a humidity of 55% RH,
  • Equation (1) 30 ⁇ E ⁇ 0. 80
  • the protective film or the retardation film itself is deformed according to the contraction force of the polarizer.
  • the temperature of the retardation film may reach nearly 50 ° C due to the backlighting of the VA-type LCD panel, and the elastic modulus (E) force of the retardation film alone in that state Elasticity at a temperature of 23 ° C ( E) in the range of 0.3 to 0.8 GPa
  • the effect is remarkable when the surrounding area is low, and according to the present invention, it is possible to improve corner unevenness in a large-screen VA liquid crystal panel.
  • the retardation film according to the present invention includes preferable requirements such as easy manufacture, good adhesion to the polarizing film, optical transparency, and the like. Rum is preferred.
  • transparent means a visible light transmittance of 60% or more, preferably 80
  • % Or more particularly preferably 90% or more.
  • the polymer film is not particularly limited as long as it has the above-mentioned properties.
  • a cellulose diacetate film a cellulose triacetate film, a cellulose acetate butyrate vinylome, a cenorelose acetate propionate vinylome.
  • polyester film Such as polyester film, polyester film, polycarbonate film, polyarylate film, polysulfone (including polyethersulfone) film, polyester film such as polyethylene terephthalate, polyethylene naphthalate, polyethylene film, polypropylene film, Cellophane, Polyvinylidene Chloride Film, Polybula Norecore Renoinolem, Ethylene Vinylenorenoreno Reino Inolem, Shinji Tactics Polystyrene film, polycarbonate film, cycloolefin polymer film (Arton (manufactured by JSR), ZEONEX, ZENOA (manufactured by ZEON CORPORATION), polymethylpentene film, polyetherketone film, polyetherketoneimide film, polyamide Examples include phenol, fluororesin film, nylon film, polymethyl methacrylate film, talyl film, glass plate, etc.
  • cellulose ester film In the present invention where a nolem, a cycloolefin polymer film, a polycarbonate film, or a polysulfone (including polyethersulfone) film is preferred, in particular, a cellulose esterolino vinyl, a cycloolefin polymer vinyl, or a polycarbonate film is preferred. From the viewpoint of production, cost, transparency, adhesiveness, etc., Finorem is preferably used. These films may be films produced by melt casting or film produced by solution casting! /.
  • the retardation film of the present invention is formed as a polymer layer on the film described in JP-A-2000-190385, JP-A-2004-4474, JP-A-2005-195811, and the like.
  • a polymer film provided with an optically anisotropic layer such as polyamide or polyimide is also preferred.
  • the cellulose ester is preferably cellulose acetate, cenololose propionate, cenololose butyrate, cenololose acetate butyrate, or cellulose acetate propionate.
  • cellulose acetate butyrate, and cellulose acetate propionate are preferably used.
  • the main component of the resin contained in the film is a cellulose ester, and the cellulose ester has at least one selected from the group consisting of cenorelose acetate, cenorelose acetate propiate, and cenorelose acetate petite.
  • the force S is preferred.
  • the corner unevenness in the large screen VA liquid crystal panel is improved while maintaining the transparency of the film. can do.
  • the ester group substitution degree of the cellulose ester is preferably 2.42-2.60.
  • a retardation film having good adhesion to the polarizing film while maintaining the transparency of the film can be obtained.
  • These cellulose esters can be synthesized by known methods.
  • the intrinsic viscosity (IV) of the resin contained in the film is 1.3 to 1.7; According to the present invention, which is preferred, it is possible to prevent the film from being avoided in the phase difference film manufacturing stage, and to avoid the risk of breakage in the film stretching process with the force S.
  • the intrinsic viscosity (IV) of the resin contained in the film can be measured using an Ubbelohde viscometer. Specifically, tetrahydrofuran was used as the solvent, and the cell mouth ester resin was dissolved in the solvent. Prepare. Using the Ubbelohde viscometer, the specific viscosity ( ⁇ sp) at each concentration (C) is obtained.
  • Intrinsic viscosity lim ⁇ "
  • the cellulose used as a raw material for the cellulose ester is not particularly limited. Can be mentioned. Moreover, the cellulose ester obtained from them can be mixed and used at an arbitrary ratio.
  • the acylating agent is an acid anhydride (acetic anhydride, propionic anhydride, or anhydrous butyric acid)
  • these cellulose esters use an organic solvent such as acetic acid, such as acetic acid methylene chloride, and sulfuric acid. It can be obtained by reacting with cellulose raw material using such a protic catalyst
  • the acylating agent is an acid chloride (CH C 0 C1, C H C 0 C1, C H C 0 C1),
  • the reaction is carried out using a basic compound such as amine as a medium. Specifically, it can be synthesized with reference to the method described in JP-A-10-45804.
  • the cellulose ester used in the present invention is obtained by mixing and reacting the above amount of the acylating agent in accordance with the degree of substitution.
  • these acylating agents react with hydroxyl groups of cellulose molecules.
  • Cellulose molecules are composed of many glucose units connected, and the glucose unit has three hydroxyl groups. These three hydroxyl groups have an acyl group Is the number of substitutions (mol%).
  • cellulose triacetate has a acetyl group bonded to all three hydroxyl groups of a dulose unit (actually 2.6 ⁇ 3.0).
  • the cellulose ester used in the present invention includes, as described above, a propionate group or a butyrate in addition to a acetyl group such as cellulose acetate propionate, cenorelose acetate butyrate, or cenorelose acetate propionate butyrate.
  • a mixed fatty acid ester of cellulose to which a group is bonded is particularly preferably used.
  • Cellulose acetate propionate containing a propionate group as a substituent is excellent in water resistance and is useful as a film for liquid crystal image display devices.
  • the method for measuring the degree of substitution of the acyl group can be measured according to ASTM-D817-96.
  • the number average molecular weight of the cellulose ester is preferably 40,000 to 200,000, and has a high mechanical strength when it is molded, and an appropriate dope viscosity in the case of a solution casting method. 150000.
  • the mass average molecular weight (Mw) / number average molecular weight (Mn) is preferably in the range of 1.4 to 4.5.
  • the average molecular weight of the cellulose ester can be measured using gel permeation chromatography, the number average molecular weight (Mn) and the mass average molecular weight (Mw) can be calculated using this. Can do.
  • the mass average molecular weight (Mw) and number average molecular weight (Mn) of the cellulose ester were measured by gel permeation chromatography using the apparatus and materials shown below.
  • the measurement conditions for the average molecular weight are as follows.
  • cellulose esters apply a cellulose ester solution (dope) generally called a solution casting film forming method onto, for example, an endless metal belt for infinite transport or a support for casting of a rotating metal drum.
  • the dope is cast from a pressure die and cast to form a film.
  • the organic solvent used for the preparation of these dopes it is preferable that the cellulose ester can be dissolved and has an appropriate boiling point.
  • the cellulose ester can be dissolved and has an appropriate boiling point.
  • methylene chloride methyl acetate, ethyl acetate, amyl acetate, acetoacetic acid.
  • the boiling point of the organic solvent used is preferably 30 to 80 ° C.
  • the boiling point of the above-mentioned good solvent is methylene chloride (boiling point 40.4 ° C), methyl acetate (boiling point 56. 32 ° C), acetone (boiling point 56.3 ° C), ethyl acetate (boiling point 76 ⁇ 82 ° C), and the like.
  • methylene chloride or methyl acetate having excellent solubility is preferably used.
  • the organic solvent it is preferable to contain 0.1% by mass to 40% by mass of an alcohol having 1 to 4 carbon atoms. It is particularly preferable that the alcohol is contained at 5 to 30% by mass.
  • Examples of the alcohol having 1 to 4 carbon atoms include methanol, ethanol, n-propanol, iso-propanol, n-butanol, sec-butanol, tert-butanol and the like.
  • ethanol is preferred because the dope has a good boiling point, a relatively low boiling point, and a good drying property. It is preferable to use a solvent containing 5% by mass to 30% by mass of ethanol with respect to 70% by mass to 95% by mass of methylene chloride. Methyl acetate can be used in place of methylene chloride. At this time, the dope may be prepared by a cooling dissolution method.
  • plasticizer used in the present invention phosphate ester plasticizers and non-phosphate ester plasticizers are preferably used.
  • Examples of the phosphoric acid ester plasticizer include triphenyl phosphate, tricresyl phosphate, credinole resin phenolino phosphate, otachinino resin phenolino phosphate, diphenolino biphenyl phosphate, trioctyl phosphate, tributyl phosphate and the like. Is mentioned.
  • Non-phosphate ester plasticizers include phthalate ester plasticizers, trimellitic acid ester plasticizers, pyromellitic acid plasticizers, polyhydric alcohol plasticizers, glycolate plasticizers, Ability to preferably use a citrate ester plasticizer, a fatty acid ester plasticizer, a polyester plasticizer, a polycarboxylic acid ester plasticizer, etc.
  • a polyhydric alcohol is preferable. It is preferable to use a plasticizer, a polyester plasticizer, and a polycarboxylic acid plasticizer.
  • the polyhydric alcohol ester is composed of an ester of a dihydric or higher aliphatic polyhydric alcohol and a monocarboxylic acid, and preferably has an aromatic ring or a cycloalkyl ring in the molecule.
  • the polyhydric alcohol used in the present invention is represented by the following general formula (1).
  • R represents an n-valent organic group, and n represents a positive integer of 2 or more.
  • polyhydric alcohols include the following: The present invention is not limited to these.
  • the monocarboxylic acid used in the polyhydric alcohol ester of the present invention known aliphatic monocarboxylic acid, alicyclic monocarboxylic acid, aromatic monocarboxylic acid and the like without particular limitation can be used.
  • Use of an alicyclic monocarboxylic acid or aromatic monocarboxylic acid is preferable in terms of improving moisture permeability and retention.
  • Examples of preferred monocarboxylic acids include the following force S, and the present invention is not limited thereto.
  • aliphatic monocarboxylic acid a fatty acid having a straight chain or a side chain having 1 to 32 carbon atoms can be preferably used. It is particularly preferable that the number of carbons is more preferably 1 to 20; When acetic acid is used, compatibility with the cellulose ester is increased, so that it is also preferable to use a mixture of acetic acid and other monocarboxylic acid.
  • Preferable aliphatic monocarboxylic acids include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, strength prillic acid, pelargonic acid, strength purine acid, 2-ethyl-hexane strength rubonic acid, undecyl Acid, lauric acid, tridecylic acid, myristic acid, pentadecylic acid, palmitic acid, heptadecylic acid, stearic acid, nonadecanoic acid, araquinic acid, behenic acid, lignoceric acid, serotic acid, heptacosanoic acid, montanic acid, melicic acid, ratacel Examples thereof include saturated fatty acids such as acids, and unsaturated fatty acids such as undecylenic acid, oleic acid, sorbic acid, linoleic acid, linolenic acid, and arachidonic acid.
  • Preferred examples of the alicyclic monocarboxylic acid include cyclopentane carboxylic acid, cyclohexane carboxylic acid, cyclooctane strength rubonic acid, and derivatives thereof.
  • Preferred aromatic monocarboxylic Examples of acids include those in which an alkyl group is introduced into the benzene ring of benzoic acid such as benzoic acid and toluic acid, and aromatic monocarboxylic acids having two or more benzene rings such as biphenylcarboxylic acid, naphthalenecarboxylic acid, and tetralincarboxylic acid. The ability to list carboxylic acids or their derivatives. In particular, benzoic acid is preferred.
  • the molecular weight of the polyhydric alcohol ester is preferably in the range of 300 to 1500, more preferably in the range of 350 to 750. Since the one where molecular weight is larger becomes difficult to volatilize, the smaller one is preferable from the viewpoint of preferable moisture permeability and compatibility with cellulose ester.
  • the carboxylic acid used for the polyhydric alcohol ester may be one kind or a mixture of two or more kinds. In addition, all OH groups in the polyhydric alcohol may be esterified, or a part of the OH groups may be left as they are.
  • the specific compounds of polyhydric alcohol esters are shown below.
  • the content of the polyhydric alcohol ester according to the present invention is preferably contained in the cellulose ester film; from! To 15% by mass, particularly preferably from 3 to 10% by mass.
  • the polyester plasticizer is not particularly limited, but a polyester plasticizer having an aromatic ring or a cycloalkyl ring in the molecule can be preferably used.
  • a preferable polyester plasticizer is not particularly limited, but, for example, an aromatic terminal ester plasticizer represented by the following general formula (2) is preferable. [0079]
  • B is a benzene monocarboxylic acid residue
  • G is an alkylene glycol residue having 2 to 12 carbon atoms or 6 to carbon atoms; 12 aryl glycol residues or carbon number powers; and 12 oxyalkylene glycol residues
  • A represents an alkylenedicarboxylic acid residue having 4 to 12 carbon atoms, or an aryldicarboxylic acid residue having 6 to 12 carbon atoms
  • n represents an integer of 1 or more.
  • Benzene monocarboxylic acid residue represented by B and alkylene glycol residue or oxyalkylene glycol residue or arylene glycol residue represented by G, alkylene dicarboxylic acid residue or arylene dicarboxylic acid residue represented by A And can be obtained by the same reaction as a normal polyester plasticizer.
  • the benzene monocarboxylic acid component of the polyester plasticizer used in the present invention includes, for example, benzoic acid, paratertiarybutylbenzoic acid, orthotoluic acid, metatolulic acid, p-toluic acid, dimethylbenzoic acid, ethylbenzoic acid.
  • benzoic acid paratertiarybutylbenzoic acid
  • orthotoluic acid metatolulic acid
  • p-toluic acid dimethylbenzoic acid
  • ethylbenzoic acid normalpropyl benzoic acid, amino benzoic acid, acetooxy benzoic acid and the like, and these can be used as one kind or a mixture of two or more kinds, respectively.
  • the alkylene glycol component having 2 to 12 carbon atoms of the polyester plasticizer used in the present invention includes ethylene glycol, 1,2 propylene glycol, 1,3 propylene glycolone, 1,2 butanediol, 1,3 Butanediol, 1,2 propanediol, 2-Methylanol 1,3-propanediol, 1,4 Butanediol, 1,5-pentanediol, 2,2-dimethyl-1,3-propanediol (neopentyl) Glycol), 2, 2— jetyl 1,3 propanediol (3,3 dimethylolpentane), 2-n butyl-2-ethynole 1,3 propanediol (3,3 dimethylolheptane), 3 methyl-1,5-pentanediol 1, 6-hexanediol, 2, 2, 4-trimethyl 1, 3-pentanediol, 2 ethinole 1, 3,
  • the aromatic terminal ester used in the present invention has 4 to 12 carbon atoms;
  • the glycol component include diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol and the like, and these glycols can be used as one kind or a mixture of two or more kinds.
  • alkylene dicarboxylic acid component having 4 to 12 carbon atoms of the aromatic terminal ester used in the present invention examples include succinic acid, maleic acid, fumaric acid, dartaric acid, adipic acid, azelaic acid, and sebacic acid. , Dodecanedicarboxylic acid and the like, and these are used as a mixture of one or two or more.
  • Examples of the arylenedicarboxylic acid component having 6 to 12 carbon atoms include phthalic acid, terephthalic acid, isophthalic acid, 1,5 naphthalenedicarboxylic acid, and 1,4 naphthalenedicarboxylic acid.
  • the polyester plasticizer used in the present invention preferably has a number average molecular weight of 300 to 1500, more preferably (from 400 to; 1000), and its acid value (0 5 mg KOH / g or less, a hydroxyl value of 25 mg KOH / g or less, more preferably an acid value of 0.3 mg KOH / g or less and a hydroxyl value of 15 mg KOH / g or less are suitable.
  • Viscosity (25 ° C, mPa-s); 43400
  • Aromatic ends having the following properties exactly as in Sample No. 1 except that 410 parts of phthalic acid, 610 parts of benzoic acid, 341 parts of ethylene glycol and 0.335 part of tetraisopropyl titanate as the catalyst were used in the reaction vessel. An ester was obtained.
  • Viscosity 25. C, mPa's
  • 31000 Acid value 0.1
  • Viscosity 25 ° C, mPa-s
  • the polyvalent carboxylic acid plasticizer useful in the present invention comprises an ester of a divalent or higher, preferably divalent to 20valent polyvalent carboxylic acid and an alcohol.
  • the aliphatic polyvalent carboxylic acid is 20 to 20 valent aromatic polycarboxylic acid, and the alicyclic polyvalent carboxylic acid is preferably 3 to 20 valent! /.
  • polyvalent carboxylic acid used in the present invention is represented by the following general formula (3).
  • R is an (m + n) -valent organic group
  • m is a positive integer greater than or equal to 2
  • n is an integer greater than or equal to 2
  • CO OH group represents a carboxyl group
  • OH group represents an alcoholic or phenolic hydroxyl group.
  • Preferred examples of polyvalent carboxylic acids include the following: It is not limited.
  • Trivalent or higher aromatic polyvalent carboxylic acids such as trimellitic acid, trimesic acid, pyromellitic acid or derivatives thereof, succinic acid, adipic acid, azelaic acid, sebacic acid, oxalic acid, fumaric acid, maleic acid, tetrahydro
  • An aliphatic polyvalent carboxylic acid such as phthalic acid, an oxypolyvalent carboxylic acid such as tartaric acid, tartronic acid, malic acid, and citrate can be preferably used.
  • the alcohol used in the polyvalent carboxylic acid ester compound used in the present invention is not particularly limited, and known alcohols and phenols can be used.
  • an aliphatic saturated alcohol or aliphatic unsaturated alcohol having a straight chain or a side chain having 1 to 32 carbon atoms can be preferably used. It is more preferable that the number of carbon atoms is 1-20. It is particularly preferable that the number of carbon atoms is 1-10.
  • alicyclic alcohols such as cyclopentanol and cyclohexanol or derivatives thereof, aromatic alcohols such as benzyl alcohol and cinnamyl alcohol, or derivatives thereof can also be preferably used.
  • the alcoholic or phenolic hydroxyl group of the oxypolycarboxylic acid may be esterified with a monocarboxylic acid! /.
  • monocarboxylic acids include the following: The present invention is not limited to this.
  • aliphatic monocarboxylic acid a fatty acid having a straight chain or a side chain having 1 to 32 carbon atoms can be preferably used. It is particularly preferable that the number of carbons is more preferably 1 to 20;
  • aliphatic monocarboxylic acid acetic acid, propionic acid, butyric acid, valeric acid, strong proacid, enanthate, strong prillic acid, pelargonic acid, strong purine acid, 2-ethylhexanecarborane Acid, undecylic acid, lauric acid, tridecylic acid, myristic acid, pentadecylic acid, palmitic acid, heptadecylic acid, stearic acid, nonadecanoic acid, arachic acid, behenic acid, lignoceric acid, serotic acid, heptacosanoic acid, montanic acid, melisin Saturated fatty acids such as acid, latacetic acid, undecylenic acid, oleic acid, sorbic acid, linoleic acid, linolenic acid, arachid Examples thereof include unsaturated fatty acids such as acid, latacetic acid, undecylenic
  • Examples of preferable alicyclic monocarboxylic acids include cyclopentanecarboxylic acid, cyclohexanecarboxylic acid, cyclooctanecarboxylic acid, and derivatives thereof.
  • aromatic monocarboxylic acids examples include those in which an alkyl group is introduced into the benzene ring of benzoic acid such as benzoic acid and toluic acid, benzene such as biphenylcarboxylic acid, naphthalenecarboxylic acid, and tetralincarboxylic acid. Mention may be made of aromatic monocarboxylic acids having two or more rings or derivatives thereof. Particularly preferred are acetic acid, propionic acid and benzoic acid.
  • the molecular weight of the polyvalent carboxylic acid ester compound is not particularly limited, but the molecular weight is preferably in the range of 300 to 1000, and more preferably in the range of 350 to 750. The larger one is preferable in terms of improving retention, and the smaller one is preferable in terms of compatibility with cellulose ester.
  • the alcohols used in the polyvalent carboxylic acid ester used in the present invention may be one kind or a mixture of two or more kinds.
  • the acid value of the polyvalent carboxylic acid ester compound used in the present invention is preferably 1 mgKOH / g or less, more preferably 0.2 mgKOH / g or less.
  • Examples of particularly preferred polyvalent carboxylic acid ester compounds are as follows: The present invention is not limited thereto.
  • examples thereof include trays, dibutyl tartrate, diacetyl dibutyl tartrate, tributyl trimellitic acid, and tetrabutyl pyromellitic acid.
  • plasticizers can be used alone or in combination of two or more. If the amount of the plasticizer used is less than 1% by mass relative to the cellulose derivative, the effect of reducing the moisture permeability of the film is small. If it exceeds 20% by mass, the plasticizer bleeds out from the film and the physical properties of the film to degrade, preferably 1 to 20 mass 0/0. 6; 16 mass 0/0 force S More preferably, particularly preferably 8-13 wt%.
  • an ultraviolet absorber is preferably used for the retardation film of the present invention.
  • ultraviolet absorber those having excellent absorption ability of ultraviolet rays having a wavelength of 370 nm or less and having little absorption of visible light having a wavelength of 400 nm or more are preferably used from the viewpoint of good liquid crystal display properties.
  • ultraviolet absorbers preferably used in the present invention include, for example, oxybenzozophenone compounds, benzotriazole compounds, salicylic acid ester compounds, benzophenone compounds, cyanoacrylate compounds, nickel complex compounds Force S, etc. are not limited to these.
  • the present invention is not limited thereto.
  • UV—l 2— (2 ′ —Hydroxy 5 ′ methylphenol) benzotriazole
  • UV-2 2-2'-hydroxy 3 ', 5'-tert butyl phenenole) benzotriazonole
  • UV-3 2- 2 '—Hydroxy 1 3' —tert Butyl 5 '—Methylphenole) Benzotriazolene
  • UV-4 2-2'-hydroxy 3 ', 5'-tert butyl butenoleveneol
  • UV-6 2, 2 Methylenebis (4- (1, 1, 3, 3 tetramethylbutyl) -6- (2H-benzotriazole-2-ynole) phenol)
  • UV—7 2— (2 ′ —Hydroxy 3 ′ —tert Butyl 5 ′ —Metinolefénole) 5 Black mouth benzotriazole
  • UV— 8 2— (2H benzotriazole—2 yl) —6— (straight and side chain dodecyl) — 4-methylphenol (TINUVIN171, Ciba)
  • UV—9 Octyl-3 -— [3-tert-butyl 4-hydroxy-5- (black mouth 2H benzotriazole- 2-yl) phenyl] propionate and 2-ethylhexyl 3 -— [3-—tert-butyl 4-hydroxy 1-5— (5 black 2H benzotriazole 2 Nole) phenyl] propionate mixture (TINUVIN109, Ciba)
  • UV-10 2, 4-Dihydroxybenzophenone
  • UV-11 2, 2'-dihydroxy-4-methoxybenzophenone
  • UV—12 2 Hydroxy 4-methoxy 4-sulfobenzophenone
  • UV-13 Bis (2 methoxy-1,4 hydroxy-1,5 benzoyl methane)
  • an ultraviolet absorber preferably used in the present invention Benzo excellent in the effect of preventing the deterioration of polarizing plate and liquid crystal having high transparency.
  • Triazole-based UV absorbers and benzophenone-based UV absorbers are preferred because of less unwanted coloring! /, And benzotriazole-based UV absorbers are particularly preferably used.
  • the ultraviolet absorber having a distribution coefficient of 9.2 or more described in JP-A-2001-187825 improves the surface quality of a long film and is excellent in coating properties. It is particularly preferable to use an ultraviolet absorber having a distribution coefficient of 10.1 or more.
  • An antioxidant may be used in the retardation film of the present invention.
  • the polarizing plate protective film may be deteriorated.
  • the antioxidant has a role of delaying or preventing the polarizing plate protective film from being decomposed by, for example, phosphoric acid of a halogenated phosphoric acid plasticizer of the residual solvent amount in the polarizing plate protective film. It is preferable to be contained in the polarizing plate protective film.
  • a hindered phenol-based compound is preferably used.
  • 2,6-di-tert-butyl-cresol, pentaerythrityl-tetrakis [3- (3,5-di-t] -Butyl-4-hydroxyphenyl) propionate] triethylene Glycol bis [3- (3-tert-butyl 5-methyl 4-hydroxyphenol) propionate], 1,6-hexanediol bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,4 Bis (n-octylthio) -6- (4-hydroxy-3,5 di-tert-butylanilino) -1,3,5 triazine, 2,2 thiodiethylene bis [3- (3,5-di-t -Butyl-4-hydroxyphenyl) propionate], Octadecinole 1- (3,5-Di-tert-Butyl 4-hydroxypheny
  • hydrazine-based metal deactivators such as N, N'-bis [3- (3,5-di-tert-butynole 4-hydroxyphenyl) propionyl] hydrazine, tris (2,4-di-tert Phosphorus processing stabilizers such as butylphenyl) phosphite may be used in combination.
  • the amount of these compounds added is preferably from 1 ppm by mass to 1.0%, more preferably from 10%;
  • the primary average particle diameter of the fine particles added to the retardation film according to the present invention is preferably 20 ⁇ m or less, more preferably 5 to 16nm, and particularly preferably 5 to 12nm. .
  • These fine particles preferably form secondary particles having a particle size of 0.1 to 5 m and are preferably contained in the retardation film.
  • the preferable average particle size is 0.1 to 2 111, more preferably 0. 2—0. 6 ⁇ m.
  • the primary average particle diameter of the fine particles used in the present invention is measured by a transmission electron microscope (magnification
  • the apparent specific gravity of the fine particles is preferably 70 g / liter or more, more preferably 90 to 200 g / liter, and particularly preferably 100 to 200 g / liter.
  • a higher apparent specific gravity makes it possible to produce a high-concentration dispersion, which improves the haze and agglomerates, and is preferred when preparing a dope having a high solid content concentration as in the present invention. Is particularly preferably used.
  • Silicon dioxide fine particles having an average primary particle diameter of 20 nm or less and an apparent specific gravity of 70 g / liter or more are, for example, 1000-; 1200 ° C obtained by mixing vaporized silicon tetrachloride and hydrogen Can be obtained by burning in air.
  • Aerosil 200V, Aerosil R972V are commercially available, and they can be used.
  • the apparent specific gravity described above is calculated by the following equation by measuring a weight of a predetermined amount of silicon dioxide fine particles in a graduated cylinder and measuring the weight.
  • Apparent specific gravity (g / liter) mass of silicon dioxide (g) / volume of silicon dioxide (liter)
  • dispersion After stirring and mixing the solvent and the fine particles, dispersion is performed with a disperser. This is a fine particle dispersion. The fine particle dispersion is added to the dope solution and stirred.
  • dispersion After stirring and mixing the solvent and the fine particles, dispersion is performed with a disperser. This is a fine particle dispersion. Separately, a small amount of cellulose triacetate is added to the solvent and dissolved by stirring. The fine particle dispersion is added to this and stirred. This is a fine particle addition solution. Thoroughly mix the additive solution with the dope solution using an in-line mixer.
  • Preparation method A is excellent in dispersibility of the silicon dioxide fine particles
  • preparation method C is excellent in that the silicon dioxide fine particles are difficult to re-aggregate.
  • the preparation method B described above is a preferable preparation method that is excellent in both dispersibility of the silicon dioxide fine particles and difficulty in reaggregation of the silicon dioxide fine particles.
  • the concentration of silicon dioxide when the silicon dioxide fine particles are mixed and dispersed with a solvent or the like is preferably 5 to 30% by mass, more preferably 10 to 25% by mass, and most preferably 15 to 20% by mass. .
  • a higher dispersion concentration is preferred because the turbidity with respect to the added amount tends to be low, and haze and aggregates are improved.
  • Solvents to be used are preferably lower alcohols such as methyl alcohol, ethyl alcoholone, propino alcoholo, isopropino alcoholo, butyno alcoholo and the like.
  • the solvent other than the lower alcohol is not particularly limited, but it is preferable to use a solvent used for forming a cellulose ester film.
  • the addition amount of silicon dioxide fine particles to cellulose ester is preferably 0.01 parts by mass to 5.0 parts by mass with respect to 100 parts by mass of cellulose ester, and 0.05 parts by mass to 1. parts by mass. 0 parts by mass is more preferable 0.1 parts by mass to 0.5 parts by mass is most preferable. The larger the added amount, the better the coefficient of dynamic friction and the smaller the added amount.
  • Dispersers can be broadly divided into media dispersers and medialess dispersers.
  • a medialess disperser is preferred because of low haze.
  • media dispersers include ball mills, sand mills, and dyno mills.
  • the medialess disperser include an ultrasonic type, a centrifugal type, and a high pressure type.
  • a high pressure disperser is preferable.
  • a high-pressure dispersion device is a device that creates special conditions such as high shear and high pressure by passing a composition in which fine particles and a solvent are mixed at high speed through a narrow tube.
  • the maximum pressure condition inside the apparatus is preferably 9.807 MPa or more in a thin tube having a tube diameter of 1 to 2000 m. More preferably, it is 19.613 MPa or more. At that time, the maximum speed reached 100m / sec or more, heat transfer It is preferable that the speed reaches 420 kj / hour or more.
  • Examples of the high-pressure dispersion apparatus as described above include an ultra-high pressure homogenizer (trade name: Microfluidizer) manufactured by Microfluidics Corporation or a nanomizer manufactured by Nanomizer. Izumi Food Machinery Homogenizer, Sanwa Machinery Co., Ltd. UHN-01, etc.
  • casting a dope containing fine particles so as to be in direct contact with the casting support is preferable because the film has a high sliding property and low haze.
  • a functional thin film such as a hard coat layer or an antireflection layer is provided.
  • packaging is usually done to protect the product from dirt and electrostatic dust.
  • the packaging material is not particularly limited as long as the above purpose can be achieved, but a material that does not hinder volatilization of the residual solvent from the film is preferable. Specific examples include polyethylene, polyester, polypropylene, nylon, polystyrene, paper, and various non-woven fabrics. A fiber having a mesh cloth shape is more preferably used.
  • the retardation film of the present invention preferably contains a retardation control agent to adjust the retardation.
  • the retardation film of the present invention preferably contains a rod-like compound having a maximum absorption wavelength ( ⁇ max) in the ultraviolet absorption spectrum of the solution shorter than 250 nm as a retardation control agent.
  • the rod-like compound has at least two aromatic rings, which preferably have at least one aromatic ring.
  • the rod-like compound preferably has a linear molecular structure.
  • the linear molecular structure means that the molecular structure of the rod-shaped compound is linear in the most thermodynamically stable structure.
  • the thermodynamically most stable structure can be obtained by crystal structure analysis or molecular orbital calculation.
  • molecular orbital calculation is performed using molecular orbital calculation software (eg, WinMOPAC2000, manufactured by Fujitsu Limited) to obtain the molecular structure that minimizes the heat of compound formation.
  • the power to seek is S.
  • the linear molecular structure means that the angle of the molecular structure is 140 degrees or more in the thermodynamically most stable structure obtained by calculation as described above.
  • the rod-shaped compound preferably exhibits liquid crystallinity. It is further preferred that the rod-like compound exhibits liquid crystallinity upon heating (has thermopick liquid crystallinity).
  • the liquid crystal phase is preferably a nematic phase or a smectic phase.
  • the rod-like compound is preferably a trans 1,4-cyclohexanedicarboxylic acid ester compound represented by the following general formula (4)!
  • Arl and Ar2 are each independently an aromatic group.
  • the aromatic group includes an aryl group (aromatic hydrocarbon group), a substituted aryl group, an aromatic heterocyclic group, and a substituted aromatic heterocyclic group.
  • An aryl group and a substituted aryl group are more preferable than an aromatic heterocyclic group and a substituted aromatic heterocyclic group.
  • the aromatic ring of an aromatic heterocyclic group is generally unsaturated.
  • the aromatic heterocycle is preferably a 5-membered ring, 6-membered ring or 7-membered ring, more preferably a 5-membered ring or 6-membered ring.
  • Aromatic heterocycles generally have the most double bonds.
  • hetero atom a nitrogen atom, a sulfur atom or a nitrogen atom or a sulfur atom is more preferable.
  • aromatic heterocycles include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, isothiazole, imidazole, pyrazole, furazane, triazole, pyran, and pyridine. Rings, pyridazine rings, pyrimidine rings, pyrazine rings, and 1,3,5-triazine rings are included.
  • aromatic ring of the aromatic group benzene ring, furan ring, thiophene ring, pyrrole ring, oxazole ring, thiazole ring, imidazole ring, triazole ring, pyridine ring, pyrimidine ring and pyrazine ring are preferred. Particularly preferred.
  • Examples of the substituent of the substituted aryl group and the substituted aromatic heterocyclic group include a halogen atom (F, Cl, Br, I), a hydroxyl group, a carboxyl group, a cyano group, an amino group, an alkylamino group (e.g., Methylamino, ethylamino, butylamino, dimethylamino), nitro, sulfo, rubamoyl, alkyl rubamoyl groups (eg, N methylcarbamoyl, N ethylcarbamoyl, N, N dimethylcarbamoyl), sulfamoyl, alkylsulfamoyl groups (eg, N— Ureido, alkylureido groups (eg, N-methylureido, N, N-dimethylureido, N, N, N'-trimethylureido), alkyl groups (e
  • Examples of the substituent of the substituted aryl group and the substituted aromatic heterocyclic group include a halogen atom, cyano, carboxyl, hydroxynore, amino, alkyl-substituted amino group, asinole group, acyloxy group, amido group, and alkoxycarbonyl group. , An alkoxy group, an alkylthio group and an alkyl group are preferable.
  • the alkyl part and the alkyl group of the alkylamino group, alkoxycarbonyl group, alkoxy group and alkylthio group further have a substituent! /, May /!
  • alkyl moiety and the substituent of the alkyl group include a halogen atom, hydroxyl, carboxyl, cyan, amino, anolequinolamino group, nitro, sulfo, rubamoyl, alkynole rubamoyl group, sulfamoyl, alkylsulfamoyl.
  • ureido alkylureido group, alkenyl group, alkynyl group, acyl group, acyloxy group, alkoxy group
  • examples include a ryloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkoxycarbonylamino group, an alkylthio group, an aryloxy group, an alkylsulfonyl group, an amide group, and a non-aromatic heterocyclic group.
  • a halogen atom As the substituent for the alkyl moiety and the alkyl group, a halogen atom, hydroxynore, amino, anolenoquinoamino group, asinole group, acyloxy group, acylamino group, alkoxycarbonyl group and alkoxy group are preferable.
  • L1 is a divalent linking group selected from the group consisting of an alkylene group, an alkenylene group, an alkynylene group, a divalent saturated heterocyclic group, O 2 CO 3, and combinations thereof. It is.
  • the alkylene group may have a cyclic structure.
  • 1,4-cyclohexylene is particularly preferred, and cyclohexylene is preferred.
  • As the chain alkylene group a linear alkylene group is more preferable than a branched alkylene group.
  • the number of carbon atoms in the alkylene group is 120, preferably S, more preferably 1 15, more preferably 1 to 10, and even more preferably! To 8. Most preferably, it is! ⁇ 6.
  • the alkenylene group and the alkynylene group preferably have a linear structure rather than a branched chain structure, which preferably has a chain structure rather than a cyclic structure.
  • the number of carbon atoms of the alkenylene group and the alkynylene group is 2 to; 10 is preferably 2 8, more preferably S 2, and 2 6 is more preferably 2 4 Most preferred is 2 (vinylene or ethynylene).
  • the divalent saturated heterocyclic group preferably has a 3- to 9-membered heterocycle.
  • the heterocyclic hetero atom is preferably an oxygen atom, a nitrogen atom, a boron atom, a sulfur atom, a silicon atom, a phosphorus atom or a germanium atom.
  • saturated heterocycles include piperidine rings, piperazine rings, morpholine rings, pyrrolidine rings, imidazolidine rings, tetrahydrofuran rings, tetrahydropyran rings, 1,3 dioxane rings, 1,4 dioxane rings, tetrahydro rings.
  • Thiophene ring 1,3-thiazolidine ring, 1,3-oxazolidin ring, 1,3-dioxolane ring, 1,3-dithiolane ring and 1,3,2-dioxaborolane are included.
  • Particularly preferred divalent saturated heterocyclic groups are piperazin 1,4-diylene, 1,3 di-aged xylene 2,5 diylene and 1,3,2 di-xiaborane 2,5-diylene.
  • L- 1 O—CO—Alkylene group—CO o—
  • L- 2 CO — o—alkylene group O— CO—
  • the angle formed by Arl and Ar2 across L1 is preferably 140 ° or more.
  • the rod-like compound is more preferably a compound represented by the following general formula (5).
  • Arl and Ar2 are each independently an aromatic group.
  • the definition and examples of the aromatic group are the same as those of Arl and Ar2 in the general formula (4).
  • L2 and L3 are each independently a divalent linking group selected from the group consisting of an alkylene group, O 2 CO 3 and a combination thereof. More preferably, the alkylene group has a linear structure rather than a chain structure having a branch, which preferably has a chain structure rather than a cyclic structure.
  • the number of carbon atoms of the alkylene group is preferably 1 10, more preferably 18, still more preferably 16; and even more preferably 4 1 or 2 (methylene Or ethylene).
  • L2 and L3 are particularly preferably —O—CO— or CO—O.
  • X represents 1,4-cyclohexylene, vinylene or ethynylene.
  • the retardation film of the present invention is produced by a step of preparing a dope by dissolving an additive such as cellulose ester and the plasticizer in a solvent, and flowing the dope onto a belt-shaped or drum-shaped metal support.
  • Der ones retardation Fi Lum which is preferably in the solids have 70 to 95 mass 0/0 containing a cellulose ester of the present invention
  • the concentration of cellulose ester in the dope is preferable because the concentration is high and the drying load after casting on the metal support can be reduced! /, But if the concentration of cellulose ester is too high, The load increases and the filtration accuracy deteriorates.
  • the concentration that achieves both of these is preferably 10 to 35% by mass, more preferably 15 to 25% by mass.
  • the solvent used in the dope of the present invention may be used alone or in combination of two or more. However, it is possible to use a mixture of a good solvent and a poor solvent of cellulose ester in terms of production efficiency. The more good solvent is preferable in terms of the solubility of the cellulose ester.
  • the preferable range of the mixing ratio of the good solvent and the poor solvent is 70 to 98% by mass for the good solvent and 2 to 30% by mass for the poor solvent.
  • a good solvent or a poor solvent is defined as a solvent that dissolves the cellulose ester used alone, a good solvent, the ability to swell alone, or a substance that does not dissolve! Therefore, depending on the degree of acyl substitution of the cellulose ester, the good solvent and poor solvent change.
  • the good solvent used in the present invention is not particularly limited, and examples thereof include organic halogen compounds such as methylene chloride, dioxolanes, acetone, methyl acetate, and methyl acetate acetate. Particularly preferred is methylene chloride or methyl acetate.
  • the poor solvent used in the present invention is not particularly limited.
  • methanol, ethanol, n-butanol, cyclohexane, cyclohexanone, and the like are preferably used.
  • the dope preferably contains water in an amount of 0.0;! To 2% by mass.
  • a general method can be used. When heating and pressurization are combined, it can be heated above the boiling point at normal pressure. If the solvent exceeds the boiling point at normal pressure and does not boil under pressure, stirring and dissolving while heating at a temperature in the range will generate a massive undissolved material called gel or maco It is preferable to prevent this.
  • a method in which a cellulose ester is mixed with a poor solvent and moistened or swollen, and then a good solvent is added and dissolved is also preferably used.
  • the pressure is more preferably Pa or lower. 1. More preferably, the pressure is OMPa or lower.
  • the metal support in the casting process is preferably a mirror-finished surface.
  • a stainless steel belt or a drum whose surface is finished with a porcelain is preferably used.
  • the cast width can be l ⁇ 4m.
  • the surface temperature of the metal support in the casting process is set between 50 ° C and below the temperature at which the solvent boils and does not foam.
  • a higher temperature is preferable because the drying speed of the web can be increased. However, if the temperature is too high, the web may foam or the flatness may deteriorate.
  • a preferable support temperature is appropriately determined at 0 to 100 ° C, and more preferably 5 to 30 ° C. Alternatively, it is also a preferable method that the web is gelled by cooling and peeled from the drum in a state containing a large amount of residual solvent.
  • the method for controlling the temperature of the metal support is not particularly limited, and there are a method of blowing hot air or cold air, and a method of bringing hot water into contact with the back side of the metal support.
  • hot water because heat transfer is performed efficiently, so that the time until the temperature of the metal support becomes constant is short.
  • hot air considering the decrease in web temperature due to the latent heat of vaporization of the solvent, there are cases in which hot air above the boiling point of the solvent is used and wind at a temperature higher than the target temperature is used while preventing foaming. is there.
  • the amount of residual solvent when peeling the web from the metal support is preferably 10 to 150% by mass, more preferably 20 to 40% by mass. Or it is 60-130 mass%, Most preferably, it is 20-30 mass% or 70-; 120 mass%.
  • the temperature at the peeling position on the metal support is preferably 50 to 40 ° C., more preferably 10 to 40 ° C., and most preferably 15 to 30 ° C.
  • the amount of residual solvent is defined by the following formula.
  • Residual solvent amount (mass%) ⁇ (MN) / N ⁇ X 100 M is the mass of the sample collected at any time during or after the production of the web or film, and N is the mass after heating M at 115 ° C for 1 hour.
  • the web is peeled off from the metal support, further dried, and dried until the residual solvent amount is 0.5 mass% or less.
  • a roll drying method (a method in which a plurality of rolls arranged above and below are alternately dried by passing through a web) or a tenter method is used for drying while transporting the web.
  • the web When peeling from the metal support, the web is stretched in the longitudinal direction due to the peeling tension and the subsequent conveying tension.
  • the conveying tension As low as possible. Specifically, for example, 50 to 170 N / m or less is effective. At that time, it is preferable to apply cold air of 20 ° C. or less to fix the web rapidly.
  • FIG. 1 and 2 indicate each step of the stretching step, and an arrow S indicates the traveling direction of the film.
  • Process A is a process of gripping the web conveyed from the web conveying process DO (not shown).
  • step B the web is stretched in the width direction (direction perpendicular to the web traveling direction) at a stretching angle ⁇ shown in FIG. 1, and in step C, the stretching is finished and the web is conveyed while being held.
  • Equation (2) 60 ⁇ XXY ⁇ 450
  • X is the stretching speed [m / min]
  • ⁇ is the stretching ratio [%].
  • the orientation of the film in the film stretching step, can be improved also by controlling the stretching speed, and the cellulose ester resin can be controlled together with the stretching ratio of the film. Suppression of crystallization and micro-phase separation of polymer and additive, while maintaining film transparency A retardation film that can be improved is obtained.
  • a slitter for cutting off the end portion in the web width direction after the web is peeled from the casting support and before the start of the step B and / or immediately after the step C.
  • a slitter that cuts off the end of the web immediately before the start of step A.
  • the stretching step it is also preferable to intentionally create sections having different temperatures in order to improve the orientation angle distribution. It is also preferred to have a neutral zone between the different temperature zones so that each zone will not interfere! /.
  • the stretching operation may be performed in multiple stages, and biaxial stretching is preferably performed in the casting direction and the width direction.
  • biaxial stretching is performed, simultaneous biaxial stretching may be performed or may be performed stepwise.
  • stepwise means that, for example, stretching in different stretching directions can be sequentially performed, stretching in the same direction is divided into multiple stages, and stretching in different directions is added to any one of the stages. Is also possible.
  • the web peeled off from the metal support is conveyed while being dried, and is further stretched in the width direction by a tenter method in which both ends of the web are held by pins or clips.
  • a predetermined phase difference can be given.
  • it may be stretched only in the width direction, or simultaneous biaxial stretching is also preferred.
  • a preferable stretching ratio is 1.05 to 2 times, preferably 1.15 to 1.5 times.
  • the film may be contracted in the longitudinal direction, and may be contracted so as to be 0.8 to 0.99, preferably 0.9 to 0.99.
  • the area force is 1.12 times to 1.44 times due to transverse stretching and longitudinal stretching or shrinkage, and preferably 1.15 times to 1.32 times. .
  • This can be determined by the draw ratio in the machine direction X and the draw ratio in the transverse direction.
  • the "stretching direction" in the present invention is usually used in the meaning of a direction in which a stretching stress is directly applied when performing a stretching operation, but is biaxially stretched in multiple stages. In some cases, the term is used to mean the one having a finally increased draw ratio (that is, the direction that usually becomes the slow axis).
  • step A B C When the web temperature at the end point is Ta ° C Tb ° C Tc ° C, respectively, it is preferable that Ta ⁇ Tb ⁇ 10. Moreover, it is preferable that Tc ⁇ Tb. More preferably, Ta ⁇ Tb-l 0 and Tc ⁇ Tb.
  • the web heating rate in step B is preferably in the range of 0.5 to 10 ° C / sec in order to improve the orientation angle distribution.
  • the stretching time in step B is preferably a short time.
  • the minimum required stretch time range is specified from the viewpoint of web uniformity.
  • the force is preferably in the range of !! to 10 seconds S, preferably 4 to 10 seconds.
  • the temperature of step B and step C is effective when the temperature of the film is in the range of 301 ° C. of glass transition point, preferably 100 to 160 ° C.
  • the heat transfer coefficient may be constant or may be changed.
  • the heat transfer coefficient preferably has a heat transfer coefficient in the range of 41.9 9 419 X 103j / m 2 hr. More preferably, 41. 9-209. In the range of 5 X 103j / m 2 hr, and most preferred range of 41. 9-126 X 103j / m 2 hr .
  • the stretching speed in the width direction in the step B may be constant or may be changed.
  • the stretching speed is preferably 50 500% / min, and more preferably 100 400% / min 200 300% / min! / ⁇ .
  • the temperature distribution in the width direction of the atmosphere is small. From the viewpoint of improving the uniformity of the web, the temperature distribution in the width direction in the stretching process is preferably within ⁇ 5 ° C. Within ⁇ 2 ° C is more preferred. Within ⁇ 1 ° C is most preferred. By reducing the above temperature distribution, it can be expected that the temperature distribution at the width of the web will also be reduced. [0182] In step C, relaxation in the width direction is preferable. Specifically, the web width is preferably adjusted to be in the range of 95 to 99.5% with respect to the final web width after stretching in the previous step.
  • a tenter that can independently control the gripping length of the web (distance from the start of gripping to the end of gripping) by the left and right gripping means of the tenter is used. I also liked it!
  • FIG. 3 schematically shows an example of a tenter stretching apparatus (10a) that is preferably used in producing the polymer film used in the present invention.
  • the grip start position of the left and right gripping means (clip) (2a) (2b) of the tenter stretching device (10a) is changed left and right, that is, the installation position of the clip closer (3a) (3b) is changed.
  • the left and right grip length of the film (F) is changed, which generates a force that twists the resin film (F) in the tenter (10a).
  • misalignment due to conveyance other than the tenter (10) can be corrected, and even if the conveyance distance from peeling to the tenter is increased, the occurrence of web meandering, slipping and wrinkles can be effectively prevented.
  • Power S can be.
  • the tenter stretching device (10a) shown in the figure is a schematically described force.
  • the tracks of the left and right chains (la) (lb) are installed so as to gradually separate in the width direction of the film, and the film (F) is stretched in the width direction.
  • a device for preventing meandering of a long film in order to correct wrinkles, strains, distortions and the like with higher accuracy is preferably used.
  • a meandering correction device such as a diposition controller (sometimes referred to as EPC) or a center position controller (sometimes referred to as CPC) is preferably used. These This device detects the edge of the film with an air servo sensor or optical sensor, controls the transport direction based on the information, and ensures that the end of the film and the center in the width direction are at a certain transport position.
  • one or two guide rolls or a flat expander roll with drive can be corrected by meandering by touching the left and right sides up and down with respect to the line direction.
  • Install a pair of small pinch rolls on the left and right one on the front and back of the film, and it is on both sides of the film).
  • Yes crossing guider method.
  • the principle of the meandering correction of these devices is that when the film is moving, for example, when trying to move to the left, the former method tilts the roll so that the film goes to the right, and the latter method uses one set on the right side.
  • This pinch roll is nipped and pulled to the right. It is preferable to install at least one of these meandering prevention devices between the film peeling point and the tenter stretching device.
  • step D1 After the treatment in the stretching step, it is preferable to further provide a post-drying step (hereinafter, step D1).
  • the web conveyance tension in step D1 is a force that is influenced by the physical properties of the dope, the amount of residual solvent at the time of peeling and in step DO, the temperature in step D1, etc. 120 to 200 N / m force S, preferably 140 to 2 OON / m is more preferable. 140 ⁇ ; 160 N / m is most preferred.
  • a tension cut roll is preferably provided for the purpose of preventing the web from stretching in the transport direction in step D1.
  • the means for drying the web is not particularly limited, and it is generally preferable to use hot air from the viewpoints of force S that can be performed by hot air, infrared rays, a heating roll, a microphone mouth wave, and the like, and simplicity.
  • the drying temperature in the web drying step is preferably a heat treatment of not less than 5 ° C and not less than 100 ° C and not less than 10 ° C and not more than 60 minutes.
  • the drying is performed at a drying temperature of 100 to 200 ° C, more preferably 110 to 160 ° C. More preferably, heat treatment is carried out while transporting in an atmosphere of 105 to 155 ° C. and an atmosphere substitution rate of 12 times / hour or more, preferably 12 to 45 times / hour.
  • the retardation film of the present invention preferably has a free volume radius of 0.250-0.350nm determined by the positron annihilation lifetime method in order to obtain the elastic modulus relationship according to the present invention. In particular, it is preferably 0.250 to 0.310 nm.
  • the free volume referred to here represents a void portion not occupied by the cellulose resin molecular chain. This can be measured using the positron annihilation lifetime method. Specifically, the time from the incidence of positrons to the sample until annihilation is measured, and information on the size and number concentration of free vacancies from the annihilation lifetime is observed nondestructively.
  • the power S can be obtained with S.
  • the retardation film according to the present invention has an elastic modulus (E) in the film stretching direction of 3.4 to 4.4 GPa measured under measurement conditions of a temperature of 23 ° C and a humidity of 55% RH, and Temperature 50 ° C,
  • Equation (1) 0. 30 ⁇ E ⁇ 0.8.
  • the elastic modulus (E) force in the stretching direction of the retardation film measured under the measurement conditions at a temperature of 23 ° C and a humidity of 55% RH. 4. If it exceeds 4 Gpa, the curling of the polarizing film will increase.
  • the elastic modulus (E) in the film stretching direction measured under the measurement conditions at a temperature of 23 ° C and a humidity of 55% RH, and a temperature of 50 ° C and a humidity of 55 Measured under% RH measurement conditions
  • the temperature of the retardation film may reach close to 50 ° C.
  • the elastic modulus (E) force temperature of the retardation film itself is 23 ° C.
  • the protective film has a remarkable effect that the retardation film itself can be deformed and the corner unevenness in the large screen VA type liquid crystal panel can be improved. is there.
  • the cycloolefin polymer film preferably used in the present invention will be described below.
  • the cycloolefin polymer used in the present invention comprises a polymer resin containing an alicyclic structure.
  • a preferred cycloolefin polymer is a resin obtained by polymerizing or copolymerizing cyclic olefin.
  • Cyclic olefins include norbornene, dicyclopentagen, and tetracyclodode.
  • Trideca unsaturated hydrocarbons with a polycyclic structure such as 2,4,6,11-tetraene and derivatives thereof; cyclobutene, cyclopentene, cyclohexene, 3,4-dimethylcyclopentene, 3 Methylcyclohexene, 2- (2 methylbutyl) 1-cyclohexene, cyclootaten, 3a, 5, 6, 7a-tetrahydro-1,4,7-methanoyl 1H-indene, cycloheptene, cyclopentagen, cyclohexagen, etc. And unsaturated hydrocarbons having a monocyclic structure and derivatives thereof.
  • cyclic olefins may have a polar group as a substituent.
  • polar groups include hydroxyl group, carboxyl group, alkoxyl group, epoxy group, glycidyl group, oxycarbonyl group, carbonyl group, amino group, ester group, carboxylic anhydride group, etc.
  • a carboxyl group or a carboxylic anhydride group is preferred.
  • a preferred cycloolefin polymer may be one obtained by addition copolymerization of a monomer other than cyclic olefin.
  • Addition copolymerizable monomers include ethylene, propylene, 1-butene, 1-pentene and other ethylene or ⁇ -olefin; 1,4 monohexagen, 4-methyl-1,4 monohexagen, 5-methyl-1,4 Gens such as monohexagen and 1,7 octagens.
  • Cyclic olefins can be obtained by an addition polymerization reaction or a metathesis ring-opening polymerization reaction.
  • the polymerization is carried out in the presence of a catalyst.
  • the addition polymerization catalyst include a polymerization catalyst composed of a vanadium compound and an organoaluminum compound.
  • Polymerization comprising a metal halide such as ruthenium, rhodium, palladium, osmium, iridium, platinum, nitrate or acetylacetone compound as a catalyst for ring-opening polymerization, and a reducing agent.
  • the polymerization temperature and pressure are not particularly limited, but the polymerization is usually carried out at a polymerization temperature of 50 ° C to 100 ° C and a polymerization pressure of 0 to 490 N / cm 2 .
  • the cycloolefin polymer used in the present invention is a polymer obtained by polymerizing or copolymerizing cyclic olefin and then hydrogenating it so that the unsaturated bond in the molecule is changed to a saturated bond.
  • the hydrogenation reaction is carried out by blowing hydrogen in the presence of a known hydrogenation catalyst.
  • Hydrogenation catalysts include transition metal compounds such as cobalt acetate / triethylaluminum, nickel acetylacetonate / triisobutylaluminum, titanocene dichloride / n butyllithium, zirconocene dichloride / sec butyllithium, tetrabutoxytitanate / dimethylmagnesium / Homogeneous catalyst consisting of a combination of alkyl metal compounds; heterogeneous metal catalyst such as nickel, palladium, platinum; nickel / silica, nickel / diatomaceous earth, nickel / alumina, palladium / carbon, palladium / silica, norradium / Examples thereof include a heterogeneous solid-supported catalyst in which a metal catalyst such as diatomaceous earth or noradium / alumina is supported on a support.
  • transition metal compounds such as cobalt acetate / triethylaluminum, nickel acety
  • examples of the cycloolefin polymer also include the following norbornene-based polymers.
  • the norbornene-based polymer preferably has a norbornene skeleton as a repeating unit.
  • Preferred examples thereof include JP-A-62-252406, JP-A-62-252407, and JP-A-2-133413. No.
  • A, B, C and D each independently represent a hydrogen atom or a monovalent organic group.
  • At least one compound represented by the following structural formula (V) or (VI) is metathesis-polymerized with an unsaturated cyclic compound copolymerizable therewith.
  • a hydrogenated polymer obtained by hydrogenating the obtained polymer is also preferred.
  • A, B, C and D each independently represent a hydrogen atom or a monovalent organic group.
  • A, B, C and D are not particularly limited, but preferably an organic group is linked through a hydrogen atom, a halogen atom, a monovalent organic group, or at least a divalent linking group. However, these may be the same or different.
  • a or B and C or D may form a monocyclic or polycyclic structure.
  • the at least divalent linking group includes a hetero atom typified by an oxygen atom, a nitrogen atom, and a nitrogen atom, and includes, for example, ether, ester, carbonyl, urethane, amide, thioether and the like. However, it is not limited to these.
  • the organic group may be further substituted via the linking group.
  • Other monomers copolymerizable with the norbornene monomer include, for example, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dedecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1 eicosene and other ⁇ -olefins having 2 to 20 carbon atoms, and their derivatives; cyclobutene, cyclopentene, cyclohexene, cyclootaten, 3a, 5, 6, 7a— 1,4-Hexagen, 4-Methyl-1,4 monohexagen, 5-Methyl-1,4 monohexagen, 1,7 —Non-conjugated gens such as otagen; Among these, ⁇ -olefin, particularly ethylene is preferable.
  • Ratio force between the structural unit derived from the norbornene-based monomer in the coalescence and the structural unit derived from the other monomer copolymerizable Usually 30: 70-99: 1, preferably 50: 50-97: 3, more preferably in mass ratio Is appropriately selected to be in the range of 70: 30-95: 5.
  • the hydrogenation rate is 90% or more, preferably 95 from the viewpoint of light resistance and weather resistance. % Or more, particularly preferably 99% or more.
  • examples of the cycloolefin polymer used in the present invention include thermoplastic saturated norbornene resins described in paragraphs [0014] to [0019] of JP-A-5-2108, and JP-A-2001-277430.
  • Thermoplastic norbornene polymers described in paragraphs [0015] to [0031] of the publication thermoplastic norbornene resins described in paragraphs [0008] to [0045] of JP 2003-14901, and JP 2003-139950 A
  • ZEONEX, ZEONOR manufactured by Nippon Zeon Co., Ltd., Aaton manufactured by JSR Co., Ltd., and APPEL manufactured by Mitsui Chemicals, Inc. (APL8008T, APL6509T, APL6013T, APL5014DP, APL6015T) and the like are preferably used.
  • the molecular weight of the cyclohexylene polymer used in the present invention is appropriately selected depending on the purpose of use, but it is a gel of cyclohexane solution (the polymer resin does not dissolve! / In this case, a toluene solution).
  • Permeation The mass average molecular weight of polyisoprene or polystyrene measured by chromatographic method, usually in the range of 5000 to 500,000, preferably ⁇ is 8000 to 200,000, more preferably 10,000 to 100,000.
  • the mechanical strength of the molded body and the molding processability are well balanced.
  • the cycloolefin polymer film may contain an additive that can be generally blended into a plastic film, if necessary.
  • additives include heat Stabilizers, light-resistant stabilizers, ultraviolet absorbers, antistatic agents, lubricants, plasticizers, fillers and the like can be mentioned, and their contents can be selected within a range that does not impair the object of the present invention.
  • the method of forming the cycloolefin polymer film is not particularly limited, and any of the hot melt molding method and the solution casting method can be used.
  • the heat-melt molding method can be further classified into an extrusion molding method, a press molding method, an inflation molding method, an injection molding method, a blow molding method, a stretch molding method, etc.
  • mechanical strength, surface accuracy In order to obtain an excellent film, the extrusion molding method, the inflation molding method, and the press molding method are preferred, and the extrusion molding method is most preferable.
  • the molding conditions are appropriately selected according to the purpose of use and the molding method.
  • the cylinder temperature is usually 150 to 400. C, preferably 200-350.
  • C more preferably 230-330. It is set appropriately within the range of C. If the resin temperature is too low, fluidity will deteriorate, causing shrinkage and distortion in the film. If the resin temperature is too high, voids due to thermal decomposition of the resin will cause silver streaks, and the film will turn yellow. There is a risk that a molding defect will occur.
  • the thickness of the finale usually 5 to 300 mm 111, preferably 10 to 200 mm 111, more preferably (20 to 100). If the thickness is too thin, handling during lamination becomes difficult. On the other hand, if it is too thick, the drying time after lamination becomes longer and the productivity is lowered.
  • the surface tension of the cycloolefin polymer film is preferably 40 mN / m or more, more preferably 50 mN / m or more, and further preferably 55 mN / m or more.
  • the surface wetting tension is within the above range, the adhesive strength between the film and the polarizing film is improved.
  • corona discharge treatment, ozone spraying, ultraviolet irradiation, flame treatment, chemical treatment, and other known surface treatments can be performed.
  • the sheet before stretching needs to have a thickness of about 50 to 500 m, and the smaller the thickness unevenness is, the better it is within ⁇ 8%, preferably within ⁇ 6%, more preferably Within ⁇ 4%.
  • cycloolefin polymer film into the retardation film of the present invention, it can be obtained by the same production method as the cellulose ester film described above. It can also be obtained by stretching the sheet at least in the uniaxial direction. It should be noted that substantial uniaxial stretching, for example, stretching in a range that does not affect the orientation of the molecules, and then in the uniaxial direction to orient the molecules. Biaxial stretching may be used. It is preferable to use the tenter device or the like for stretching.
  • the draw ratio is 1 .;! To 10 times, preferably 1.3 to 8 times, and a desired retardation may be set within this range. If the draw ratio is too low, the absolute value of the retardation will not rise to a predetermined value, and if it is too high, it may break.
  • Stretching is usually performed in the temperature range of the glass transition temperature (Tg) to Tg + 50 ° C, preferably Tg to Tg + 40 ° C of the resin constituting the sheet. If the stretching temperature is too low, the film is broken, and if it is too high, the molecular orientation is not achieved, so that a desired retardation film cannot be obtained.
  • Tg glass transition temperature
  • the molecules are oriented by stretching so that a retardation having a desired size can be obtained.
  • the in-plane retardation value Ro at 589 nm is 30 to;! OOnm, and more preferably 40 to 70 nm.
  • the thickness direction retardation Rt is 70 to 300 nm, and more preferably 100 to 250 nm.
  • the retardation can be controlled by the retardation of the sheet before stretching, the stretching ratio, the stretching temperature, and the thickness of the stretched oriented film.
  • the absolute value of the retardation tends to increase as the stretching ratio of the film increases. Therefore, by changing the stretching ratio, the stretched oriented film of the desired retardation can be obtained.
  • the cyclorefin polymer film of the present invention is more preferable as the variation in retardation is smaller.
  • the variation in retardation at a wavelength of 589 nm is usually within ⁇ 50 nm, preferably within ⁇ 30 nm, more preferably Smaller than ⁇ 20nm.
  • In-plane variation and thickness unevenness of the retardation film can be reduced by using the small unstretched sheet and by applying stress to the sheet evenly during stretching.
  • S can.
  • the film is stretched in a controlled temperature environment under a uniform temperature distribution, preferably within ⁇ 5 ° C, more preferably within ⁇ 2 ° C, and particularly preferably within ⁇ 0.5 ° C. desirable.
  • polycarbonate resins used to make polycarbonate films there are various types of polycarbonate resins used to make polycarbonate films, and aromatic polycarbonate is preferred from the viewpoint of chemical properties and physical properties.
  • Bisphenol A-based polycarbonate is particularly preferable. Among them, a force using a bisphenol A derivative in which a benzene ring, a cyclohexane ring or an aliphatic hydrocarbon group is introduced into bisphenol A is more preferable.
  • 4,4'-dihydroxydiphenylalkane or a halogen-substituted product thereof can be obtained by a phosgene method or a transesterification method.
  • 4,4'-dihydroxydiphenylmethane, 4, A′-dihydroxydiphenylethane, 4, A′-dihydroxydiphenylbutane and the like can be mentioned.
  • the retardation film made of the polycarbonate resin used in the present invention may be used by mixing with a transparent resin such as a polystyrene-based resin, a methyl methacrylate resin, or a cellulose acetate-based resin, or cellulose.
  • a polycarbonate resin may be laminated on at least one surface of the acetate film.
  • the method for producing a polycarbonate film that can be used in the present invention is not particularly limited. In other words, film by extrusion method, film by solvent cast method, film by force render method, etc.! In the present invention, either uniaxial stretching or biaxial stretching is used, and by the production method similar to the preferred production method of the cellulose ester film, the temperature of the present invention is 23 ° C and the humidity is 55% RH. Elastic modulus (E) in the direction of film stretching measured under the measurement conditions at 50 ° C and humidity at 55% RH.
  • the difference (E) from the elastic modulus (E) in the film stretching direction measured below is a function of the above formula (1).
  • the polycarbonate film used in the present invention has a glass transition point (Tg) of 110 ° C or higher and a water absorption rate (measured under conditions of 23 hours at 23 ° C in water) of 0.3. It is recommended to use less than%. More preferably, Tg is 120 ° C or more and water absorption is 0.2% Use the following! /
  • the retardation film of the present invention preferably has a film thickness of 100 m or less. As the film thickness increases, the above-mentioned factors causing light leakage increase not only by the film thickness.In particular, when the film thickness exceeds 100 m, light leakage easily occurs due to the increase in film thickness. There is a trend.
  • a preferred film thickness is 80 m or less, and a more preferred film thickness is 35-60111. If the film thickness of the retardation film according to the present invention is in the range of 35 to 60 111, it is possible to reduce the thickness of the retardation film used for thin displays in recent years, particularly thin displays such as large TVs. It can respond to the request sufficiently.
  • the polarizing plate can be produced by a general method.
  • the back side of the retardation film of the present invention is subjected to an alkali hatching treatment, and is bonded to at least one surface of a polarizing film prepared by immersing and stretching in an iodine solution using a completely hatched polybula alcohol aqueous solution. Is preferred.
  • the film may be used on the other surface, or another polarizing plate protective film may be used.
  • cellulose ester films for example, Konica Minoltac KC8UX, KC 4UX, KC5UX, KC8UCR3, KC8UCR4, KC8UY, KC4UY, KC12UR, KC8UCR-3, KC8UCR-4, KC8UCR-5, KC8UY- HA, HAC, C8UX—RHA—N, Konica Minoltatop Co., Ltd., Fujitac TD80UF, T80UZ, T40UZ, antireflection film (Fuji Film CV Clearview UA), Fuji Photo Film Co., Ltd., etc. are preferably used.
  • the polarizing plate protective film used on the other surface is an optically isotropic polarized light having an in-plane retardation Ro of 0 to 20 nm and an Rt of -50 to 50 nm.
  • a plate protective film is preferred.
  • the polarizing plate protective film has a hard coat layer or antistatic layer with a thickness of 8 to 20 m. It is also preferable to have a glare layer.
  • a plate protective film is preferably used. Further, it is preferable that an antireflection layer, an antifouling layer or the like is laminated on the hard coat layer or the antiglare layer.
  • a polarizing plate protective film that also serves as an optical compensation film having an optically anisotropic layer formed by aligning liquid crystal compounds such as discotic liquid crystals, rod-shaped liquid crystals, and cholesteric liquid crystals.
  • the optically anisotropic layer can be formed by the method described in JP-A-2003-98348.
  • a polarizing film which is a main component of a polarizing plate, is an element that passes only light having a plane of polarization in a certain direction.
  • a typical polarizing film that is currently known is a polybulualcohol-based polarizing film.
  • the polarizing film is formed by forming a polybulualcohol aqueous solution, uniaxially stretching it and dyeing it, and uniaxially stretching after dyeing, and preferably having been subjected to a durability treatment with a boron compound. Yes.
  • On the surface of the polarizing film one side of the optical film of the present invention is bonded to form a polarizing plate. It is preferably bonded with a water-based adhesive mainly composed of fully hatched polybulal alcohol.
  • Ethylene-modified polybulal alcohol is also preferably used as the polarizing film.
  • the thickness of the polarizing film is preferably 5 to 30 ⁇ m, particularly preferably 10 to 25 ⁇ m.
  • a liquid crystal display device composed of a polarizing plate using the retardation film of the present invention is used to develop a higher display quality than a normal polarizing plate.
  • the effect of the present invention can be further exerted when used in a multi-domain liquid crystal display device, more preferably in a multi-domain liquid crystal display device by a birefringence mode.
  • Multidomaining is also suitable for improving the symmetry of image display, and various methods have been reported "Okita, Yamauchi: Liquid Crystal, 6 (3), 303 (2002)".
  • the liquid crystal display cell is “Yamada, Yama Hara: Liquid Crystals, 7 (2), 184 (2003) “Force S, which is also shown, but not limited to these.
  • the polarizing plate of the present invention is an MVA (Multi-domestic Vertical Alignment) mode represented by a vertical alignment mode, in particular, a four-part MVA mode, and a known PVA (Patterned Vertical Alignment) that is multi-domained by electrode arrangement. It can be used effectively in the CPA (Continuous Pinwheel Alignment) mode that combines the mode, electrode arrangement and chirality.
  • MVA Multi-domestic Vertical Alignment
  • PVA Powerned Vertical Alignment
  • CPA Continuous Pinwheel Alignment
  • the polarizing plate of the present invention can also exhibit the effect of the present invention in display quality. If the effect of the present invention can be expressed by using the polarizing plate of the present invention, the arrangement of the liquid crystal mode and the polarizing plate is not limited.
  • the retardation film of the present invention is preferably used for a vertical alignment mode liquid crystal display device, and particularly preferably for an MVA (Multi_domein Vertical Alignment) mode liquid crystal display device.
  • the display quality of the display cell is preferably symmetric for human observation! Therefore, when the display cell is a liquid crystal display cell, the domain can be multiplied substantially giving priority to the symmetry on the observation side.
  • Domain demarcation IJ can be determined by a known method, and can be determined by a two-division method, more preferably a four-division method in consideration of the properties of a known liquid crystal mode.
  • Liquid crystal display devices are being applied to devices for colorization and moving image display, and the display quality in the present invention is improved due to improvement in contrast and resistance to polarizing plates. Image display is possible.
  • a polarizing plate using the retardation film of the present invention is disposed only on one surface of a liquid crystal cell, or on both surfaces. At this time, by using the retardation film of the present invention contained in the polarizing plate so as to be on the liquid crystal cell side, the display quality can be improved.
  • Aromatic terminal ester plasticizer (example of compound (1)) 6 parts by mass
  • a main dope solution having the above composition was prepared. First, methylene chloride and ethyl alcohol were added to the pressure dissolution tank. Cellulose ester A was added to a pressurized dissolution tank containing a solvent while stirring. This was heated and stirred to completely dissolve, and a plasticizer and an ultraviolet absorber were further added and dissolved. This was filtered using Azumi Filter Paper No. 244 manufactured by Azumi Filter Paper Co., Ltd. to prepare a main dope solution.
  • Fine particles (Aerosil R972V (made by Nippon Aerosil Co., Ltd.) 11 parts by mass
  • the cellulose ester A described above was added to a dissolution tank containing methylene chloride, heated and completely dissolved, and then filtered using Azumi filter paper No. 244 manufactured by Azumi Filter Paper Co., Ltd. While stirring the cellulose ester solution after filtration, The fine particle dispersion was slowly added. Further, the particles were dispersed by an attritor so that the secondary particles had a predetermined particle size. This was filtered with a fine pore NF manufactured by Nippon Seisen Co., Ltd. to prepare a fine particle additive solution.
  • the temperature of the stainless steel band was divided into two equal parts from the fluent to the peeling, and the belt was so divided that the average temperature in the first half was kept at 32 ° C and the average temperature in the second half was kept at 28 ° C.
  • the temperature of the hot air supplied to the front and back surfaces was controlled.
  • the main dope and the fine particle addition solution were the same as those in Example 1, and the film was formed by changing the temperature of the stainless steel band and the stretching conditions using the tenter as follows.
  • the first half average temperature of the stainless steel band is 35 ° C and the second half average temperature is 25 ° C. did. Except for the above conditions, the same procedure as in Example 1 was performed.
  • the main dope and the fine particle addition liquid were the same as those in Example 1, and the film was formed by changing the temperature of the stainless steel band and the stretching conditions by the tenter as follows.
  • the first half average temperature of the stainless steel band is 30 ° C
  • the second half average temperature is 33 ° C
  • the tenter stretching conditions are temperature 135 ° C
  • stretching ratio 1.3 times stretching speed 34mm / sec. was made. Except for the above conditions, the same procedure as in Example 1 was performed.
  • the main dope was adjusted under the following conditions.
  • the raw material used was the same as in Example 1, and the dope was prepared by changing the ratio of dichloromethane and ethyl alcohol.
  • Aromatic terminal ester plasticizer (example of compound (1)) 6 parts by mass
  • the temperature of the hot air supplied to the belt front and back surfaces was controlled so that both the first half temperature and the second half temperature of the stainless steel band were kept at 28 ° C.
  • a retardation film was produced under the conditions of tenter stretching conditions: a temperature of 145 ° C, a stretching ratio of 1.35 times, and a stretching speed of 30 mm / sec.
  • the raw material used was the same as in Example 1, and the dope concentration was adjusted as follows.
  • Aromatic terminal ester plasticizer (example of compound (1)) 6 parts by mass
  • the temperature of the hot air supplied to the belt front and back surfaces was controlled so that both the first and second half temperatures of the stainless steel band were maintained at 25 ° C.
  • a retardation film was produced under the conditions of tenter stretching conditions: temperature 130 ° C, stretching ratio 1.35 times, stretching speed 50 mm / sec.
  • the raw material used was the same as in Example 1, and the dope concentration and the solvent mixing ratio were adjusted as follows.
  • Aromatic terminal ester plasticizer (example of compound (1)) 6 parts by mass
  • Example 6 the temperature of the hot air supplied to the belt front and back surfaces was controlled so that the first half temperature of the stainless steel band was maintained at 38 ° C and the second half temperature at 40 ° C.
  • the tenter conditions were as follows: temperature 155 ° C, draw ratio 1.35 times, draw speed 30mm / sec.
  • Example 7 the temperature of the hot air supplied to the front and back surfaces of the belt was controlled so that the first half temperature of the stainless steel band was maintained at 35 ° C and the second half temperature at 33 ° C.
  • a retardation film was produced under the conditions of tenter stretching conditions: a temperature of 150 ° C., a stretching ratio of 1.35 times, and a stretching speed of 15 mm / sec.
  • Example 5 The same main dope as in Example 5 was used, and the temperature of the hot air supplied to the belt front and back surfaces was controlled so that the first half temperature of the stainless steel band was maintained at 22 ° C and the second half temperature at 33 ° C.
  • a retardation film was produced under the stretching conditions of a temperature of 160 ° C., a stretching ratio of 1.45 times, and a stretching speed of 25 mm / sec.
  • cellulose ester A When adjusting the main dope, instead of cellulose ester A, the following cellulose ester was used, and a retardation film having a stretching temperature of 135 ° C, a stretching ratio of 1.29 times, and a film thickness of 45 m was prepared.
  • the temperature of the stainless steel band at this time was the same as in Example 1 except that the temperature of the hot air supplied to the belt front and back surfaces was controlled so that the first half temperature was maintained at 30 ° C and the second half temperature at 35 ° C. It carried out similarly.
  • Aromatic terminal ester plasticizer (example of compound (1)) 6 parts by mass
  • the temperature of the hot air supplied to the belt front and back was controlled so that the stainless steel band temperature was maintained at 20 ° C for the first half and 30 ° C for the second half.
  • a retardation film was produced under the conditions of tenter stretching conditions: a temperature of 158 ° C, a stretching ratio of 1.34 times, and a stretching speed of 15 mm / sec.
  • the stretching temperature is 145 ° C.
  • a retardation film was produced at a draw ratio of 1.36 times and a draw speed of 45 mm / sec.
  • the temperature of the stainless steel band at this time was controlled by the temperature of the hot air supplied to the belt front and back surfaces so that the first half temperature was maintained at 40 ° C and the second half temperature at 35 ° C.
  • Cellulose acetate butyrate total substitution degree 2.42, number average molecular weight 110000, mass average molecular weight 230000, intrinsic viscosity (IV) 1.4
  • the following cellulose ester was used in place of cellulose ester A, and a retardation film was produced at a stretching temperature of 175 ° C., a stretching ratio of 1.55 times, and a stretching speed of 15 mm / sec.
  • the temperature of the hot air supplied to the belt front and back surfaces was controlled so that the temperature of the stainless steel band was kept at 20 ° C for both the first half and the latter half.
  • Cellulose acetate butyrate Total substitution degree 2.79, number average molecular weight 150,000, mass average molecular weight 300,000, intrinsic viscosity (IV) 2.2
  • MTD Dodeca 3-en
  • This hydrogenated ring-opened polymer had a mass average molecular weight (Mw) of 31,000 and a molecular weight distribution (Mw)
  • the pellet was mixed with a single-screw extruder having a coat hanger type T die with a lip width of 1.5 m (manufactured by Mitsubishi Heavy Industries, Ltd .: screw diameter 90 mm, T die lip material made of tungsten carbide, molten resin) Using a peel strength of 44 N), melt extrusion molding to obtain a length of 2500 An annular olefin resin film having a thickness of 60 m was produced. Extrusion molding was performed in a clean room of class 1000 or lower under molding conditions of a molten resin temperature of 240 ° C and a T-die temperature of 240 ° C.
  • the above composition was put into a sealed container, kept at 80 ° C. under pressure, and completely dissolved with stirring to obtain a dope composition.
  • this dope composition was filtered, cooled and kept at 33 ° C, uniformly cast on a stainless steel band support, and dried at 33 ° C for 5 minutes. Subsequently, when the web (film) was peeled off from the support, the same conditions as in the retardation film of Example 1 above were applied, with a peel tension of 120 N / m, a residual solvent amount of 45% by mass, and a cold air temperature of 23 ° C. The web is peeled off with a tenter, and both ends of the web are gripped, and stretched under the conditions of 140 N / mm, temperature 125 ° C, and draw ratio 1.21 times from the start of process B shown in Fig. 2 to 10 cm.
  • Aromatic terminal ester plasticizer (example of compound (1)) 6 parts by mass
  • a main dope solution having the above composition was prepared. First, methylene chloride and ethyl alcohol were added to the pressure dissolution tank. Cellulose ester A was added to a pressurized dissolution tank containing a solvent while stirring. This was heated and stirred to completely dissolve, and a plasticizer and an ultraviolet absorber were further added and dissolved. This was filtered using Azumi Filter Paper No. 244 manufactured by Azumi Filter Paper Co., Ltd. to prepare a main dope solution.
  • the temperature of the hot air supplied to the belt front and back surfaces was controlled so that the average temperature in the first half was maintained at 30 ° C and the average temperature in the second half was maintained at 25 ° C.
  • Tenter Stretching conditions were as follows: a temperature of 120 ° C, a draw ratio of 1.2, and a draw speed of 40 mm / sec.
  • Aromatic terminal ester plasticizer (example of compound (1)) 6 parts by mass
  • a main dope solution having the above composition was prepared.
  • the temperature of the hot air supplied to the belt surface and the back surface was controlled so that the average temperature in the first half was maintained at 15 ° C and the average temperature in the second half was maintained at 20 ° C.
  • a retardation film was produced under the tenter stretching conditions of a temperature of 110 ° C, a stretching ratio of 1.15 times, and a stretching speed of 20 mm / sec.
  • the main dope was adjusted in the same manner as in Example 1, and the temperature of the hot air supplied to the belt surface and back surface was controlled so that the stainless steel band temperature was maintained at 55 ° C in both the first half and the second half.
  • a retardation film was produced under the conditions of tenter stretching conditions: a temperature of 140 ° C., a stretching ratio of 1.30 times, and a stretching speed of 70 mm / sec.
  • the main dope was adjusted in the same manner as in Example 1, and the hot air supplied to the belt surface and back surface was maintained so that the temperature of the stainless steel band was maintained at 25 ° C for the first half and 15 ° C for the second half.
  • the temperature was controlled.
  • the main dope was adjusted in the same manner as in Example 1, and the hot air supplied to the belt front and back surfaces was maintained so that the stainless steel band temperature was maintained at 35 ° C for the first half average temperature and 20 ° C for the second half average temperature.
  • the temperature was controlled.
  • a retardation film was produced under the conditions of tenter stretching conditions: a temperature of 105 ° C, a stretching ratio of 1.17 times, and a stretching speed of 40 mm / sec.
  • the main dope was adjusted in the same manner as in Example 1, and the hot air supplied to the belt front and back surfaces was maintained so that the stainless steel band temperature was maintained at 15 ° C for the first half average temperature and 30 ° C for the second half average temperature.
  • the temperature was controlled.
  • a retardation film was produced under the tenter stretching conditions of a temperature of 175 ° C., a stretching ratio of 1.43 times, and a stretching speed of 30 mm / sec.
  • Aromatic terminal ester plasticizer (example of compound (1)) 6 parts by mass
  • a main dope solution having the above composition was prepared.
  • Aromatic terminal stellar plasticizer (Example of compound (1)) 6 parts by mass
  • a main dope solution having the above composition was prepared.
  • the temperature of the hot air supplied to the belt front and back was controlled so that the stainless steel band temperature was maintained at 35 ° C for the first half and 25 ° C for the second half.
  • a retardation film was produced under the conditions of a tenter stretching condition of a temperature of 135 ° C, a stretching ratio of 1.28 times, and a stretching speed of 35 mm / sec.
  • Aromatic terminal cocoon plasticizer (example of compound (1))
  • the temperature of the hot air supplied to the belt front and back was controlled so that the stainless steel band temperature was maintained at 20 ° C for the first half and 30 ° C for the second half.
  • a retardation film was produced under the conditions of tenter stretching conditions: a temperature of 158 ° C, a stretching ratio of 1.34 times, and a stretching speed of 15 mm / sec.
  • Elastic modulus (E) of the film stretching direction measured under the measurement conditions of 50 ° C and humidity 55% RH
  • Each sample of the retardation film obtained in Examples 1 to 13 and Comparative Examples 1 to 9 was allowed to stand for 24 hours in an environment of temperature 2 3 ⁇ 2 ° C and humidity 55 ⁇ 5% RH.
  • the sample was cut into strips with a width of 10 mm and a length of 200 mm so that the TD direction of the sample was long.
  • the TG-2KN type tensile tester manufactured by Minibear set the above strip sample with a chucking pressure of 0.25 MPa and a distance between marked lines of 100 ⁇ 10 mm, and pulling speed of 100 ⁇ 10 mm / min. pull.
  • the tensile test was performed in the same environment as when cutting.
  • a unit that can be arbitrarily heated and humidified is installed on the film set and chuck of the above tensile tester, and the chamber is at a temperature of 50 ⁇ 2 ° C and humidity of 55 ⁇ 5% RH. Kept. Each sample was allowed to stand in the storage for 2 hours, and then a tensile test was performed in the same manner as described above to obtain the elastic modulus) for each sample.
  • the amount of the additive on the film surface is scraped about 10 microns from the surface of the film using a knife, and after measuring the mass, this is dissolved in acetone, and the amount of the additive contained therein is measured by gas chromatography (Hewlett). (Using a gas chromatography 5890 type SERISII manufactured by Packard)).
  • nx is the refractive index in the slow axis direction in the film plane
  • ny is the refractive index in the fast axis direction in the film plane
  • nz is the refractive index in the film thickness direction
  • d is the film thickness (nm). It is.
  • a 120 m thick polybulu alcohol film was uniaxially stretched (temperature: 110 ° C., stretch ratio: 5 times). This was immersed in an aqueous solution consisting of 0 ⁇ 075 g of iodine, 5 g of potassium iodide and 100 g of water for 60 seconds, and then immersed in an aqueous solution of 68 ° C. consisting of 6 g of potassium iodide, 7.5 g of boric acid and 100 g of water. This was washed with water and dried to obtain a polarizing film.
  • Step 1 Each sample of the retardation film obtained in Examples 1 to 13 and Comparative Examples 1 to 9 was immersed in a 1 mol / L sodium hydroxide solution at a temperature of 50 ° C for 60 seconds. Then, it was washed with water and dried to obtain a cellulose ester film hatched on the side to be bonded to the polarizing film. In addition, each sample of the retardation film obtained in Examples 12 and 13 and Comparative Examples 6 and 7 was subjected to plasma treatment instead of the saponification treatment step to be hydrophilized.
  • Step 2 The polarizing film is placed in a polybulol alcohol adhesive tank having a solid content of 2% by mass by 1 to
  • Step 3 Gently wipe off excess adhesive adhering to the polarizing film in Step 2, and place it on each sample of the retardation film processed in Step 1, with the antireflection layer on the outside To be laminated
  • Step 4 The retardation film, the polarizing film and the cellulose ester film sample laminated in Step 3 were bonded at a pressure of 20 to 30 N / cm 2 and a conveyance speed of about 2 m / min.
  • Step 5 Respective samples of the retardation films obtained in Step 4 above in a dryer at 80 ° C in Step 4;! To 13 and Comparative Examples;! To 9; a polarizing film; and cellulose The laminated film bonded with the ester film was dried for 2 minutes to produce a polarizing film.
  • the polarizing plate of a commercially available liquid crystal TV (Shatao Phat 32AD5) was peeled off, and the above example
  • the polarizing plate is bonded so that the surface of each retardation film is on the liquid crystal cell side and the absorption axis is in the same direction as the previously bonded polarizing plate.
  • the liquid crystal display devices were respectively fabricated.
  • the retardation films obtained in Examples 1 to 13 and Comparative Examples 1 to 9 were used.
  • Each liquid crystal display device using a polarizing film was stored for 24 hours in an environment of temperature 45 ° C ⁇ 2 ° C and humidity 95 ⁇ 3% RH. Immediately after that, move to a room with a temperature of 23 ° C and humidity of 55% RH, and turn on the panel backlight. 24 hours after lighting, measure the front brightness of the four corners in black and calculate the average value.
  • the “four corners” here are on the diagonal of the effective display screen, and the distance from the corner is 50 mm! /

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Polarising Elements (AREA)

Abstract

L'invention concerne un film retardateur destiné à être utilisé dans un dispositif d'affichage à cristaux liquides, et plus particulièrement un film retardateur permettant de réduire les défauts d'uniformité au niveau des coins d'un panneau grand écran à cristaux liquides du type à alignement vertical (VA). Le module d'élasticité (E23) du film retardateur mesuré dans sa direction d'étirement sous une température de 23˚C et une humidité relative de 55% est compris entre 3,4 et 4,4 GPa, et la différence (E23-50) entre ledit module d'élasticité (E23) et le module d'élasticité (E50) du film retardateur mesuré dans sa direction d'étirement sous une température de 50˚C et une humidité relative de 55% vérifie les inégalités de la formule (1) : 0,30 ≤ E23-50 ≤ 0,80 [où E23-50 = E23 - E50.]. En posant que la quantité d'un additif présent sur une surface du film retardateur à fixer sur un polariseur est équivalente à 100 en masse, la quantité de l'additif présent sur une surface du film retardateur à coller sur une surface en verre est alors comprise entre 20 et 70 en masse.
PCT/JP2007/066173 2006-09-29 2007-08-21 Film retardateur WO2008050525A1 (fr)

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JP2006-268763 2006-09-29

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010005567A2 (fr) 2008-07-08 2010-01-14 Oncomed Pharmaceuticals, Inc. Agents de liaison de récepteur notch1 et procédés d'utilisation
JP2012198282A (ja) * 2011-03-18 2012-10-18 Konica Minolta Advanced Layers Inc λ／４板、その製造方法、偏光板、液晶表示装置、及び立体画像表示装置
CN109870756A (zh) * 2017-12-04 2019-06-11 住友化学株式会社 光学层叠体及其制造方法

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JPH063524A (ja) * 1992-06-23 1994-01-14 Kureha Chem Ind Co Ltd 光学位相差板
JP2001055402A (ja) * 1999-08-18 2001-02-27 Konica Corp セルロースエステル及びそれを用いる偏光板保護フィルム
JP2003232920A (ja) * 2002-02-07 2003-08-22 Konica Corp 光学フィルム及びその製造方法
JP2003531923A (ja) * 2000-03-01 2003-10-28 ティコナ ゲゼルシャフト ミット ベシュレンクテル ハフツング 脂環式オレフィン類を含むアモルファスポリオレフィンを含むポリマー混合物
JP2006030457A (ja) * 2004-07-14 2006-02-02 Fuji Photo Film Co Ltd 偏光板及び液晶表示装置

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JPH063524A (ja) * 1992-06-23 1994-01-14 Kureha Chem Ind Co Ltd 光学位相差板
JP2001055402A (ja) * 1999-08-18 2001-02-27 Konica Corp セルロースエステル及びそれを用いる偏光板保護フィルム
JP2003531923A (ja) * 2000-03-01 2003-10-28 ティコナ ゲゼルシャフト ミット ベシュレンクテル ハフツング 脂環式オレフィン類を含むアモルファスポリオレフィンを含むポリマー混合物
JP2003232920A (ja) * 2002-02-07 2003-08-22 Konica Corp 光学フィルム及びその製造方法
JP2006030457A (ja) * 2004-07-14 2006-02-02 Fuji Photo Film Co Ltd 偏光板及び液晶表示装置

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010005567A2 (fr) 2008-07-08 2010-01-14 Oncomed Pharmaceuticals, Inc. Agents de liaison de récepteur notch1 et procédés d'utilisation
EP2899211A1 (fr) 2008-07-08 2015-07-29 OncoMed Pharmaceuticals, Inc. Agents de liaison du récepteur notch1 et leurs procédés d'utilisation
JP2012198282A (ja) * 2011-03-18 2012-10-18 Konica Minolta Advanced Layers Inc λ／４板、その製造方法、偏光板、液晶表示装置、及び立体画像表示装置
CN109870756A (zh) * 2017-12-04 2019-06-11 住友化学株式会社 光学层叠体及其制造方法
CN109870756B (zh) * 2017-12-04 2021-10-08 住友化学株式会社 光学层叠体及其制造方法

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