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WO2010001677A1 - Film optique, procédé de fabrication d’un film optique, plaque de polarisation et dispositif d’affichage à cristaux liquides utilisant ce film - Google Patents

Film optique, procédé de fabrication d’un film optique, plaque de polarisation et dispositif d’affichage à cristaux liquides utilisant ce film Download PDF

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WO2010001677A1
WO2010001677A1 PCT/JP2009/060048 JP2009060048W WO2010001677A1 WO 2010001677 A1 WO2010001677 A1 WO 2010001677A1 JP 2009060048 W JP2009060048 W JP 2009060048W WO 2010001677 A1 WO2010001677 A1 WO 2010001677A1
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Prior art keywords
optical film
film
cellulose ester
liquid crystal
ester
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English (en)
Japanese (ja)
Inventor
隆嗣 鈴木
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Konica Minolta Opto Inc
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Konica Minolta Opto Inc
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Priority to JP2010518966A priority Critical patent/JPWO2010001677A1/ja
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/08—Cellulose derivatives
    • C08L1/10—Esters of organic acids, i.e. acylates
    • C08L1/14—Mixed esters, e.g. cellulose acetate-butyrate
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
    • C08J2301/08—Cellulose derivatives
    • C08J2301/14—Mixed esters
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133528—Polarisers

Definitions

  • the present invention relates to an optical film comprising a cellulose ester, a method for producing the optical film, a polarizing plate using the same, and a liquid crystal display device.
  • Optical film made of cellulose ester protects photographic negative film supports and polarizers used in liquid crystal displays due to its high transparency, low birefringence, and easy adhesion to polarizers. As an optical film, it has been widely used for polarizing plates and the like.
  • liquid crystal display devices various functional films such as retardation films, viewing angle widening films, antireflection films used in plasma displays, and various functional films used in organic EL displays, etc. Can also be used.
  • the solution casting method is a film forming method in which a solution obtained by dissolving cellulose ester in a solvent is cast to obtain a film shape, and then the solvent is evaporated and dried to obtain a film. Since a film formed by the solution casting method has high flatness, a high-quality liquid crystal display device without unevenness can be obtained using the film.
  • the solution casting method requires a large amount of an organic solvent and has a problem that the environmental load is large. Because optical films are formed using halogen-based solvents with high environmental impact due to their dissolution characteristics, reduction of solvent usage is particularly required, and production of optical films should be increased by solution casting film formation. Has become difficult. For this reason, the film forming method which does not use an organic solvent, for example, the film forming method by heat melting is desired.
  • cellulose triacetate which is a cellulose ester generally used in solution casting film formation
  • cellulose triacetate is a cellulose ester whose decomposition start temperature is lower than the melting start temperature, It is difficult to use for melt casting film formation.
  • melt casting film formation casting is cast from a die to a cooling drum in a state where the viscosity at the time of melting is high, so that the leveling of the film is poor, and variation in retardation (retardation) occurs compared to solution casting film formation.
  • retardation retardation
  • a phase difference film is used to increase the viewing angle or improve the contrast of a liquid crystal display device.
  • retardation films have been developed by stretching a cellulose ester film, saponified and bonded to a polarizer, and a polarizing plate protective film having a retardation film function has been realized (for example, Patent Documents). 4).
  • the number of steps and the number of parts are small and a significant cost reduction is achieved as compared with the case where a retardation film is bonded to a conventional polarizing plate.
  • the retardation film described above is stretched to develop retardation.
  • film thickness unevenness is liable to occur and haze increases. It was found that the adhesion with the polarizer deteriorates.
  • the liquid crystal display device produced using this retardation film had the subject that viewing angle and contrast deteriorated.
  • an optical film having a cellulose ester formed by melt casting having excellent environmental suitability and good quality and productivity.
  • the production method of the optical film, and hence the appearance of a polarizing plate and a liquid crystal display device using the method, are awaited.
  • the optical film contains a cellulose ester, and the cellulose ester satisfies the conditions of the following formulas (1) to (4) at the same time as the type of substituent and the degree of substitution per glucose unit of the cellulose ester.
  • Optical film 1.
  • optical film as described in 1 or 2 above, comprising a polyhydric alcohol ester compound.
  • optical film as described in any one of 1 to 3 above, which comprises a carbohydrate ester compound.
  • optical film as described in any one of 1 to 4 above, which comprises a hindered phenol compound.
  • optical film as described in any one of 1 to 5 above, which comprises a phosphite compound or a phosphonite compound.
  • optical film according to any one of 1 to 7 or the optical film produced by the production method according to any one of 8 to 10 is provided on at least one surface of a polarizer.
  • Polarizer
  • liquid crystal display device as described in 12 above, wherein the liquid crystal cell is a VA liquid crystal cell.
  • the present inventors in the process of intensively studying to solve the above problems, when the type of substituent per glucose unit constituting the cellulose ester and the degree of substitution are within the scope of the present invention, The present inventors have found that all the above problems can be solved and have completed the present invention.
  • an optical film having excellent environmental suitability, good film forming properties, and excellent optical properties more specifically, good stretchability, excellent retardation development, small film thickness unevenness, and haze It was possible to provide an optical film that is low and has good adhesion to a polarizer, and a method for producing the same. Furthermore, it was possible to provide a polarizing plate having good durability over a long period of time and a liquid crystal display device having a wide viewing angle and good durability using the optical film.
  • FIG. 3A is an external view of the main part of the casting die
  • FIG. 3B is a cross-sectional view of the main part of the casting die.
  • the present invention provides an optical film with good productivity and excellent optical properties.
  • optical films such as a high-quality polarizing plate protective film, a retardation film, and an antireflection film, and it is possible to obtain a liquid crystal display device with high display quality.
  • the optical film of the present invention may be an optical film produced by either a solution casting method or a melt casting method, but in view of environmental suitability, the melt casting method is preferred.
  • the optical film forming material is heated to a molten state without dissolving the optical film in a solvent as in solution casting, and casting is defined as a melt casting method. .
  • the molding method for heating and melting can be further classified into a melt extrusion molding method, a press molding method, an inflation method, an injection molding method, a blow molding method, a stretch molding method, and the like. Among these, in order to obtain an optical film excellent in mechanical strength and surface accuracy, the melt extrusion method is excellent.
  • a method in which the optical film forming material is heated to develop its fluidity and then extruded and formed on a drum or an endless belt is a preferred embodiment as the melt casting method of the present invention.
  • the optical film of the present invention is formed by melt-casting an optical film-forming material containing at least one of the following cellulose esters, preferably at a melting temperature of 200 ° C. or higher and 270 ° C. or lower.
  • An optical film is particularly preferable.
  • the cellulose ester used in the present invention is a cellulose ester that simultaneously satisfies the following formulas (1) to (4) when the substitution degree of the acetyl group is X and the substitution degree of the propionyl group is Y.
  • Such cellulose esters are usually called cellulose acetate propionate. Note that satisfying any one, any two, or any three of the following formulas does not solve all of the above problems, but it is important to satisfy all four simultaneously.
  • Formula (1) 6.30 ⁇ 2 ⁇ X + 3 ⁇ Y ⁇ 6.80
  • Formula (2) 2.35 ⁇ X + Y ⁇ 2.55
  • Formula (4) 1.45 ⁇ Y ⁇ 1.75
  • In the formula (3) it is preferable that 0.75 ⁇ X ⁇ 1.05 from the viewpoint that the effect of the present invention is further exhibited.
  • the formula (4) it is preferable that 1.50 ⁇ Y ⁇ 1.75 because the effects of the present invention are further exhibited.
  • Cellulose has a total of three hydroxyl groups, one at each of the 2nd, 3rd and 6th positions of 1 glucose unit.
  • the total degree of substitution is the average number of acyl groups bonded to 1 glucose unit. It is a numerical value indicating whether or not. Accordingly, the maximum degree of substitution is 3.00, and the portion not substituted with the acyl group is usually present as a hydroxyl group.
  • the 2nd and 3rd positions are secondary hydroxyl groups, and the 6th position is a primary hydroxyl group, which changes to the higher order structure and physical properties of the cellulose ester depending on which position the acetyl group and propionyl group are substituted in. Accompanied by.
  • a cellulose ester in which some or all of the hydroxyl groups of cellulose are substituted with acyl groups is referred to as a cellulose ester.
  • X is the sum of the average degree of substitution by the 2-, 3-, and 6-position acetyl groups
  • Y is the sum of the average degree of substitution by the 2-, 3-, and 6-position propionyl groups.
  • the cellulose ester satisfying the above formulas (1) to (4) simultaneously (the average degree of substitution is simply referred to as the degree of substitution).
  • the degree of substitution between the acetyl group and the propionyl group was determined by the method prescribed in ASTM D817-96.
  • the formula (1) represents the range of the average total carbon number of the acyl group substituted per glucose unit of the cellulose ester. That is, since the carbon number of the acetyl group is 2 and the carbon number of the propionyl group is 3, “2 ⁇ X + 3 ⁇ Y” multiplied by the respective substitution degrees is the total carbon number. According to the inventor's study, if the total number of carbons is small, the hydrophilicity is high and the adhesion to the polarizer is high, but on the other hand, it is inferior in melt film-forming properties. While it was excellent in film properties, it was found that the adhesion to the polarizer was low.
  • the formula (2) represents the range of the average total degree of substitution (X + Y) of acyl groups substituted per glucose unit of the cellulose ester.
  • retardation is likely to be manifested when the total degree of substitution is small, whereas the haze tends to be high when stretched, and conversely, when the total degree of substitution is large, the haze when stretched is low, but the retardation is low. It was found that it was difficult to express.
  • the degree of substitution of the acetyl group of the formula (3) and the degree of substitution of the propionyl group of the formula (4) also have an influence on adhesion to the polarizer, melt film-forming property, expression of retardation, and haze. It became clear by examination of the inventor.
  • the cellulose ester used in the present invention is not particularly limited, but preferably has a weight average molecular weight (Mw) of 150,000 to 250,000, more preferably has a weight average molecular weight of 180,000 to 230,000, Most preferably, it has a weight average molecular weight of 10,000 to 220,000.
  • Mw weight average molecular weight
  • the weight average molecular weight is within the above preferred range, it does not cause problems such as an excessively high melt viscosity or reduced strength of the resulting film, which is preferable.
  • the cellulose ester used in the present invention preferably has a weight average molecular weight (Mw) / number average molecular weight (Mn) ratio of 1.3 to 5.5, particularly preferably 1.5 to 5.0. More preferably, it is 1.7 to 4.0, and more preferably 2.0 to 3.5 cellulose ester is preferably used.
  • Mw / Mn exceeds 5.5, the viscosity becomes high and the melt film-forming property tends to decrease, which is not preferable.
  • Mw / Mn exceeds 5.5, the viscosity becomes high and the melt film-forming property tends to decrease, which is not preferable.
  • it is preferably 1.3 or more.
  • Mn and Mw / Mn can be calculated by gel permeation chromatography (GPC) in the following manner.
  • the measurement conditions are as follows.
  • the cellulose ester in the film-forming material is preferably in the range of 70% by mass to 99% by mass, and has excellent melt castability and stability in the presence of additives such as deterioration inhibitors, plasticizers and ultraviolet absorbers described later.
  • the obtained film can impart excellent performance as an optical film.
  • the content of the cellulose ester is 70% by mass or less, the additive bleeds out and the mechanical strength of the film becomes small, which is not preferable.
  • the amount of other additives necessary as an optical film is 1.0% by mass or less (the content of cellulose ester is 99% or more), it is difficult to satisfy the required physical properties. More preferably, the cellulose ester content is 80 to 95% by mass.
  • the raw material cellulose of the cellulose ester used in the present invention may be wood pulp or cotton linter, and the wood pulp may be softwood or hardwood, but softwood is more preferable.
  • a cotton linter is preferably used from the viewpoint of peelability during film formation.
  • the cellulose ester made from these can be mixed suitably or can be used independently.
  • the ratio of cellulose ester derived from cellulose linter: cellulose ester derived from wood pulp (coniferous): cellulose ester derived from wood pulp (hardwood) is 100: 0: 0, 90: 10: 0, 85: 15: 0, 50:50: 0, 20: 80: 0, 10: 90: 0, 0: 100: 0, 0: 0: 100, 80:10:10, 85: 0: 15, 40:30:30.
  • the cellulose ester of the present invention can be synthesized with reference to known methods.
  • the acetyl group and propionyl group can be substituted by acetylating and propionating the hydroxyl group of the raw material cellulose by acetic anhydride and propionic anhydride by a conventional method.
  • the method for synthesizing such a cellulose ester is not particularly limited, and for example, it can be synthesized with reference to the method described in JP-A-10-45804 or JP-A-6-501040. It should be noted that a cellulose ester that simultaneously satisfies the above formulas (1) to (4) can be synthesized by appropriately changing the amounts of acetic anhydride and propionic anhydride used.
  • the alkaline earth metal content of the cellulose ester used in the present invention is preferably in the range of 1 to 50 ppm. If it exceeds 50 ppm, lip adhesion stains increase or breakage tends to occur at the slitting part during or after hot stretching. Even if it is less than 1 ppm, it tends to break, but the reason is not well understood. Further, the range of 1 to 30 ppm is preferable.
  • the alkaline earth metal as used herein refers to the total content of Ca and Mg, and can be measured using an X-ray photoelectron spectrometer (XPS).
  • the residual sulfuric acid content in the cellulose ester used in the present invention is preferably in the range of 0.1 to 45 ppm in terms of elemental sulfur. These are considered to be contained in the form of salts. If the residual sulfuric acid content exceeds 45 ppm, the deposits on the die lip during heat melting increase, such being undesirable. Moreover, since it becomes easy to fracture
  • the residual sulfuric acid content can be measured by the method prescribed in ASTM D817-96.
  • the free acid content in the cellulose ester used in the present invention is preferably 1 to 500 ppm. If it exceeds 500 ppm, deposits on the die lip will increase and breakage will easily occur. Further, it is preferably in the range of 1 to 100 ppm, and it becomes more difficult to break. The range of 1 to 70 ppm is particularly preferable.
  • the free acid content can be measured by the method prescribed in ASTM D817-96.
  • the residual alkaline earth metal content, residual sulfuric acid content, and residual acid content are within the above ranges. This is preferable.
  • cellulose ester can be washed with a poor solvent such as methanol or ethanol, or as a result, a mixed solvent of a poor solvent and a good solvent can be used as a poor solvent. Low molecular organic impurities can be removed. Further, the washing of the cellulose ester is also preferably performed in the presence of a deterioration inhibitor, and the heat resistance and film forming stability of the cellulose ester are improved.
  • cellulose ester In order to improve the heat resistance, mechanical properties, optical properties, etc. of cellulose ester, dissolve it in a good solvent of cellulose ester, reprecipitate it in a poor solvent, filter it, or stir and suspend it in the poor solvent. The low molecular weight component of cellulose ester and other impurities can be removed by filtration. At this time, it is preferable to carry out in the presence of a deterioration preventing agent, similarly to the above-described washing of the cellulose ester.
  • the deterioration inhibitor used for washing the cellulose ester may remain in the cellulose ester after washing.
  • the residual amount is preferably 0.01 to 2000 ppm, more preferably 0.05 to 1000 ppm. More preferably, it is 0.1 to 100 ppm.
  • Another polymer or a low molecular weight compound may be added after the reprecipitation treatment of the cellulose ester.
  • the cellulose ester used in the present invention preferably has few bright spot foreign matters when formed into a film.
  • a bright spot foreign material is an arrangement in which two polarizing plates are arranged orthogonally (crossed Nicols), a cellulose ester film is arranged between them, light from the light source is applied from one side, and the cellulose ester film is applied from the other side. This is the point where the light from the light source appears to leak when observed.
  • the polarizing plate used for the evaluation is desirably composed of a protective film having no bright spot foreign matter, and a polarizing plate using a glass plate for protecting the polarizer is preferably used.
  • One of the causes of bright spot foreign matter is the unacetylated or low acetylated cellulose contained in the cellulose ester.
  • Use a cellulose ester with less bright spot foreign matter (use a cellulose ester with a small dispersion degree of substitution).
  • 0.01 mm or more is preferably 200 pieces / cm 2 or less, more preferably 100 pieces / cm 2 or less, further preferably 50 pieces / cm 2 or less, and 30 pieces / cm 2 or less. More preferably, it is more preferably 10 pieces / cm 2 or less, but most preferably none.
  • the number of bright spots of 0.005 to 0.01 mm or less is also preferably 200 / cm 2 or less, more preferably 100 / cm 2 or less, and 50 / cm 2 or less. Even more preferred is 30 / cm 2 or less, still more preferred is 10 / cm 2 or less, and most preferred is none.
  • filtering the cellulose ester composition to which a deterioration inhibitor, a plasticizer, etc. are added and mixed is more effective than filtering the melted cellulose ester alone.
  • High efficiency is preferable.
  • the cellulose ester may be dissolved in a solvent during the synthesis and reduced by filtration. What mixed the ultraviolet absorber and other additives suitably can be filtered. Filtration is preferably performed at a viscosity of a melt containing cellulose ester of 10,000 Pa ⁇ s or less, more preferably 5000 Pa ⁇ s or less, even more preferably 1000 Pa ⁇ s or less, and even more preferably 500 Pa ⁇ s or less. .
  • the filter medium conventionally known materials such as glass fibers, cellulose fibers, filter paper, and fluorine resins such as tetrafluoroethylene resin are preferably used, and ceramics, metals and the like are particularly preferably used.
  • the absolute filtration accuracy is preferably 50 ⁇ m or less, more preferably 30 ⁇ m or less, still more preferably 10 ⁇ m or less, and even more preferably 5 ⁇ m or less. These can be used in combination as appropriate.
  • the filter medium can be either a surface type or a depth type, but the depth type is preferably used because it is relatively less clogged.
  • the cellulose ester obtained by dissolving the raw material cellulose ester at least once in a solvent and then drying the solvent may be used.
  • a cellulose ester which has been dissolved in a solvent together with at least one of a deterioration inhibitor, a plasticizer, an ultraviolet absorber and a matting agent and then dried is used.
  • the solvent a good solvent used in a solution casting method such as methylene chloride, methyl acetate or dioxolane can be used, and a poor solvent such as methanol, ethanol or butanol may be used at the same time. In the course of dissolution, it may be cooled to ⁇ 20 ° C. or lower or heated to 80 ° C. or higher.
  • each additive in a molten state can be easily made uniform, and optical characteristics can be made uniform.
  • ⁇ Plasticizer ⁇ it is preferable to add at least one plasticizer to the optical film.
  • a plasticizer is an additive having an effect of improving brittleness or imparting flexibility by adding it to a polymer.
  • a plasticizer is added.
  • effects such as improvement of mechanical properties of optical film, improvement of tearing strength, provision of water absorption resistance, reduction of moisture permeability, etc. can be seen. Therefore, it is more preferable to use a material having such an effect as a plasticizer. preferable.
  • plasticizer for example, phosphate ester plasticizer, polyhydric alcohol ester plasticizer (ethylene glycol ester plasticizer, glycerin ester plasticizer, diglycerin ester plasticizer, etc.), examples thereof include polyvalent carboxylic acid ester plasticizers, carbohydrate ester plasticizers, and polymer plasticizers.
  • polyhydric alcohol ester plasticizers are preferred, and polyhydric alcohol ester plasticizers and carbohydrate ester plasticizers are more preferred.
  • the plasticizer may be a liquid or a solid, and is preferably colorless due to the restrictions of the composition.
  • the addition amount may be as long as it does not adversely affect the optical properties and mechanical properties, and the blending amount is appropriately selected within the range not impairing the object of the present invention, and is preferably 1 to 25 with respect to the mass of the cellulose ester according to the present invention. It is an optical film characterized by containing mass%. When the content is less than 1% by mass, the effect of improving the flatness is not recognized, and when the content is more than 25% by mass, bleeding out easily occurs and the temporal stability of the film decreases, which is not preferable.
  • optical film containing 3 to 20% by mass of a plasticizer More preferred is an optical film containing 5 to 15% by mass.
  • an ester plasticizer comprising a polyhydric alcohol and a monovalent carboxylic acid
  • an ester plasticizer comprising a polyvalent carboxylic acid and a monohydric alcohol
  • An ester plasticizer composed of an alcohol and a monovalent carboxylic acid is particularly preferable because the affinity with the cellulose ester is further increased.
  • Examples of the polyhydric alcohol that is a raw material of the ester plasticizer that is preferably used in the present invention include the following, but the present invention is not limited thereto.
  • ethylene glycol ethylene
  • Examples of preferred organic acids include acetic acid, propionic acid, butyric acid, isobutyric acid, pivalic acid, acrylic acid, methacrylic acid, cyclohexanecarboxylic acid, benzoic acid, anisic acid, 3,4,5-trimethoxybenzoic acid, toluyl Acid, tert-butylbenzoic acid, naphthoic acid, picolinic acid, and the like.
  • Polyhydric alcohol ester is formed by unsaturated carboxylic acid, for example, aromatic carboxylic acid, which is highly effective in reducing the moisture permeability of cellulose ester. It is preferable.
  • the organic acid used for the polyhydric alcohol ester may be one kind or a mixture of two or more kinds. Moreover, all the OH groups in the polyhydric alcohol may be esterified, or a part of the OH groups may be left as they are.
  • ethylene glycol ester plasticizers that are one of the polyhydric alcohol esters include ethylene glycol alkyl ester plasticizers such as ethylene glycol diacetate and ethylene glycol dibutyrate, and ethylene glycol dicyclopropyl.
  • ethylene glycol cycloalkyl ester plasticizers such as carboxylate and ethylene glycol dicyclohexylcarboxylate
  • ethylene glycol aryl ester plasticizers such as ethylene glycol dibenzoate and ethylene glycol di4-methylbenzoate.
  • alkylate groups may be the same or different, and may be further substituted.
  • alkylate group cycloalkylate group and arylate group
  • substituents may be bonded by a covalent bond.
  • the ethylene glycol part may be substituted, and the ethylene glycol ester partial structure may be part of the polymer or regularly pendant, and may be an antioxidant, an acid scavenger, an ultraviolet absorber, etc. It may be introduced into a part of the molecular structure of the additive.
  • glycerin ester plasticizers that are one of the polyhydric alcohol esters include glycerol alkyl esters such as triacetin, tributyrin, glycerol diacetate caprylate, glycerol oleate propionate, and glycerol tricyclopropylcarboxylate.
  • Glycerol glycerol esters such as glycerol tricyclohexyl carboxylate, glycerol aryl esters such as glycerol tribenzoate and glycerol 4-methylbenzoate, diglycerol tetraacetylate, diglycerol tetrapropionate, diglycerol acetate tricaprylate, diglycerol Diglycerol alkyl esters such as tetralaurate, diglycerol tetracyclobutylcarboxylate, diglycerol Diglycerol cycloalkyl esters such as La cyclopentyl carboxylate, diglycerin tetrabenzoate, diglycerin aryl ester such as diglycerin 3-methylbenzoate or the like.
  • These alkylate groups, cycloalkylcarboxylate groups, and arylate groups may be the same or different, and may be further substituted.
  • the glycerin and diglycerin part may be substituted, the partial structure of the glycerin ester and the diglycerin ester may be part of the polymer or regularly pendant, and the antioxidant, acid scavenger, You may introduce
  • polyhydric alcohol ester plasticizers include polyhydric alcohol ester plasticizers described in paragraphs 30 to 33 of JP-A No. 2003-12823, pentaerythritol tetrabenzoate, and the like.
  • alkylate groups, cycloalkylcarboxylate groups, and arylate groups may be the same or different, and may be further substituted. Moreover, the mix of alkylate group, a cycloalkyl carboxylate group, and an arylate group may be sufficient, and these substituents may couple
  • the polyhydric alcohol part may be substituted, and the partial structure of the polyhydric alcohol may be part of the polymer or regularly pendant, and may be an antioxidant, an acid scavenger, an ultraviolet absorber. May be introduced into a part of the molecular structure of the additive.
  • alkyl polyhydric alcohol aryl esters are preferred.
  • the above-mentioned ethylene glycol dibenzoate, glycerin tribenzoate, diglycerin tetrabenzoate examples thereof include the exemplified compound 16 described in paragraph 31 of JP-A-2003-12823.
  • Alkyl dicarboxylic acid cycloalkyl ester plasticizers such as cyclopentyl succinate and dicyclohexyl adipate, alkyl dicarboxylic acid aryl ester plasticizers such as diphenyl succinate and di4-methylphenyl glutarate, dihexyl-1,4-cyclohexane
  • Cycloalkyl dicarboxylic acid alkyl ester plasticizers such as dicarboxylate and didecylbicyclo [2.2.1] heptane-2,3-dicarboxylate, dicyclohexyl-1,2-cyclobutanedicarboxylate, Cyclopropyl-1,2-cyclohexyl dicarboxylate and other cycloalkyl dicarboxylic acid cycloalkyl ester plasticizers, diphenyl-1,1-cyclopropyl dicarboxylate, di-2-naphthyl-1,4-cyclohex
  • alkoxy groups and cycloalkoxy groups may be the same or different, may be mono-substituted, and these substituents may be further substituted.
  • the alkyl group and cycloalkyl group may be mixed, or these substituents may be bonded together by a covalent bond.
  • the aromatic ring of phthalic acid may be substituted, and a multimer such as a dimer, trimer or tetramer may be used.
  • the partial structure of phthalate ester may be part of the polymer or regularly pendant to the polymer, and it may be part of the molecular structure of additives such as antioxidants, acid scavengers, and UV absorbers. It may be introduced.
  • polycarboxylic acid ester plasticizers include alkyl polycarboxylic acid alkyl esters such as tridodecyl tricarbarate and tributyl-meso-butane-1,2,3,4-tetracarboxylate.
  • Plasticizers alkylpolycarboxylic acid cycloalkylester plasticizers such as tricyclohexyl tricarbarate, tricyclopropyl-2-hydroxy-1,2,3-propanetricarboxylate, triphenyl 2-hydroxy- Alkyl polyvalent carboxylic acid aryl ester plasticizers such as 1,2,3-propanetricarboxylate, tetra-3-methylphenyltetrahydrofuran-2,3,4,5-tetracarboxylate, tetrahexyl-1,2, 3,4-cyclobutanetetracarboxylate, tetra Cycloalkyl polycarboxylic acid alkyl ester plasticizers such as til-1,2,3,4-cyclopentanetetracarboxylate, tetracyclopropyl-1,2,3,4-cyclobutanetetracarboxylate, tricyclohexyl- Cycloalkyl polycarboxylic acid cycloalkyl este
  • Plasticizers of aryl polyvalent carboxylic acid aryl esters such as plasticizers triphenylbenzene-1,3,5-tetracarboxylate, hexa-4-methylphenylbenzene-1,2,3,4,5,6-hexacarboxylate Agents.
  • alkoxy groups and cycloalkoxy groups may be the same or different, and may be monosubstituted, and these substituents may be further substituted.
  • the alkyl group and cycloalkyl group may be mixed, or these substituents may be bonded together by a covalent bond.
  • the aromatic ring of phthalic acid may be substituted, and a multimer such as a dimer, trimer or tetramer may be used.
  • the partial structure of phthalate ester may be part of the polymer or regularly pendant into the polymer, and introduced into part of the molecular structure of additives such as antioxidants, acid scavengers, UV absorbers, etc. May be.
  • alkyl dicarboxylic acid alkyl esters are preferable, and specific examples include the dioctyl adipate.
  • plasticizers used in the present invention include phosphate ester plasticizers, carbohydrate ester plasticizers, polymer plasticizers, and the like.
  • phosphoric acid ester plasticizer examples include phosphoric acid alkyl esters such as triacetyl phosphate and tributyl phosphate, phosphoric acid cycloalkyl esters such as tricyclopentyl phosphate and cyclohexyl phosphate, triphenyl phosphate, and trichlorate.
  • Examples thereof include phosphoric acid aryl esters such as zil phosphate, cresyl phenyl phosphate, octyl diphenyl phosphate, diphenyl biphenyl phosphate, trioctyl phosphate, tributyl phosphate, trinaphthyl phosphate, trixylyl phosphate, tris ortho-biphenyl phosphate.
  • phosphoric acid aryl esters such as zil phosphate, cresyl phenyl phosphate, octyl diphenyl phosphate, diphenyl biphenyl phosphate, trioctyl phosphate, tributyl phosphate, trinaphthyl phosphate, trixylyl phosphate, tris ortho-biphenyl phosphate.
  • substituents may be the same or different, and may be further substituted.
  • alkylene bis (dialkyl phosphate) such as ethylene bis (dimethyl phosphate), butylene bis (diethyl phosphate), alkylene bis (diaryl phosphate) such as ethylene bis (diphenyl phosphate), propylene bis (dinaphthyl phosphate), phenylene bis (dibutyl) Phosphate), arylene bis (dialkyl phosphate) such as biphenylene bis (dioctyl phosphate), phosphate esters such as arylene bis (diaryl phosphate) such as phenylene bis (diphenyl phosphate) and naphthylene bis (ditoluyl phosphate).
  • substituents may be the same or different, and may be further substituted.
  • it may be a mix of an alkyl group, a cycloalkyl group, and an aryl group, and the substituents may be covalently bonded to each other.
  • the partial structure of phosphate ester may be part of the polymer, or may be regularly pendant, and also introduced into part of the molecular structure of additives such as antioxidants, acid scavengers, UV absorbers, etc. May be.
  • additives such as antioxidants, acid scavengers, UV absorbers, etc. May be.
  • phosphoric acid aryl ester and arylene bis (diaryl phosphate) are preferable, and specifically, triphenyl phosphate and phenylene bis (diphenyl phosphate) are preferable.
  • the carbohydrate means a monosaccharide, disaccharide or trisaccharide in which the saccharide is present in the form of pyranose or furanose (6-membered ring or 5-membered ring).
  • Non-limiting examples of carbohydrates include glucose, saccharose, lactose, cellobiose, mannose, xylose, ribose, galactose, arabinose, fructose, sorbose, cellotriose and raffinose.
  • Carbohydrate ester refers to an ester compound formed by dehydration condensation of a hydroxyl group of a carbohydrate and a carboxylic acid, and specifically means an aliphatic carboxylic acid ester or an aromatic carboxylic acid ester of a carbohydrate.
  • the aliphatic carboxylic acid include acetic acid and propionic acid
  • examples of the aromatic carboxylic acid include benzoic acid, toluic acid, and anisic acid.
  • Carbohydrates have a number of hydroxyl groups depending on the type, but even if a part of the hydroxyl group reacts with the carboxylic acid to form an ester compound, the whole hydroxyl group reacts with the carboxylic acid to form an ester compound. Also good.
  • carbohydrate ester plasticizer examples include glucose pentaacetate, glucose pentapropionate, glucose pentabtylate, saccharose octaacetate, saccharose octabenzoate and the like. Among these, saccharose octaacetate, saccharose Octabenzoate is more preferred, and sucrose octabenzoate is particularly preferred.
  • the above-mentioned type of carbohydrate ester plasticizer is commercially available from Daiichi Kogyo Seiyaku Co., Ltd. under the trade names “Monopet SB” and “Monopet SOA”.
  • polymer plasticizer examples include aliphatic hydrocarbon polymers, alicyclic hydrocarbon polymers, polyethyl acrylate, polymethyl methacrylate, methyl methacrylate and 2-hydroxyethyl methacrylate.
  • Polymers acrylic polymers such as copolymers of methyl methacrylate, methyl acrylate and 2-hydroxyethyl methacrylate, vinyl polymers such as polyvinyl isobutyl ether and poly N-vinyl pyrrolidone, polystyrene, poly 4-hydroxy Examples thereof include styrene polymers such as styrene, polyesters such as polybutylene succinate, polyethylene terephthalate and polyethylene naphthalate, polyethers such as polyethylene oxide and polypropylene oxide, polyamides, polyurethanes and polyureas.
  • the number average molecular weight is preferably about 1,000 to 500,000, particularly preferably 5,000 to 200,000. If it is 1000 or less, a problem arises in volatility, and if it exceeds 500000, the plasticizing ability is lowered, and the mechanical properties of the optical film are adversely affected.
  • These polymer plasticizers may be a homopolymer composed of one type of repeating unit or a copolymer having a plurality of repeating structures. Two or more of the above polymers may be used in combination.
  • the optical film of the present invention preferably contains 1 to 25% by mass of an ester plasticizer comprising a polyhydric alcohol and a monovalent carboxylic acid, or a carbohydrate ester plasticizer, but in combination with other plasticizers. Also good.
  • the ester plasticizer comprising a polyhydric alcohol and a monovalent carboxylic acid which is a preferred plasticizer in the optical film of the present invention, is an ester plasticizer comprising a trivalent or higher alcohol and a monovalent carboxylic acid in phase with the cellulose ester. Because it has high solubility and can be added at a high addition rate, it does not cause bleed-out even when other plasticizers and additives are used in combination. The agent is most preferable because it can be easily used in combination.
  • the deterioration preventing agent is a material that suppresses decomposition of a polymer by heat, oxygen, moisture, acid, or the like by a chemical action. Since the optical film of the present invention is molded particularly at a high temperature of 200 ° C. or higher, it is a system in which the polymer is easily decomposed and deteriorated, and it is preferable to contain a deterioration inhibitor in the optical film.
  • Decomposition reactions that have not been elucidated, such as oxidation prevention of optical films, capture of acid generated by decomposition, and suppression or prohibition of decomposition reaction due to radical species due to light or heat.
  • Deterioration inhibitors are used to suppress the generation of volatile components due to alteration or material decomposition.
  • the deterioration preventing agent in the optical film-forming material of the present invention can be selected from at least one or more.
  • the amount to be added is 0.01% by mass or more with respect to the mass of the cellulose ester of the present invention. 10 mass% or less is preferable, More preferably, it is 0.1 to 5.0 mass%, More preferably, it is 0.2 to 2.0 mass%.
  • the addition amount of the deterioration preventing agent is within the above range because the transparency as the optical film is improved from the viewpoint of compatibility with the cellulose ester and the optical film is not brittle.
  • the optical film can be stored by dividing the constituent material into one or more kinds of pellets for the purpose of avoiding material alteration and hygroscopicity. Pelletization may improve the mixing or compatibility of the melt during heating, or may ensure the optical uniformity of the resulting film.
  • the presence of the above-mentioned deterioration preventing agent is caused by deterioration of the material It is excellent in terms of reducing the strength based on the decomposition and deterioration of optical transparency, or maintaining the strength inherent to the material.
  • optical film is significantly deteriorated by heating, coloring may occur and the optical film may not be used.
  • a retardation imparting step is carried out next to the casting step, but when the optical film is significantly deteriorated by heating, the formed film becomes The film may become brittle and may be easily broken during the stretching process, or the retardation value of the target retardation film may not be expressed.
  • the deterioration of the optical film is unfavorable because it interferes with the bonding with the polarizer.
  • the presence of the above-mentioned deterioration preventing agent suppresses the generation of a colored material in the visible light region at the time of heating and melting, or a volatile component generated by decomposition of the material constituting the film at the time of heating and melting. It is also excellent in that deterioration unfavorable as an optical film such as a decrease in transmittance and haze value caused by the above can be suppressed or eliminated.
  • the display image of the liquid crystal display device is affected when the haze value exceeds 1% when the optical film of the present invention is used. Therefore, the haze value is preferably less than 1%, more preferably less than 0.5%. is there.
  • yellowness yellow index, YI
  • YI yellow index
  • Yellowness can be measured based on JIS-K-7103.
  • reducing the humidity and oxygen concentration in the air can also be preferably used in combination for realizing the present invention.
  • the optical film of the present invention is also used as a polarizing plate protective film, from the viewpoint of improving the storage stability with time with respect to the polarizing plate of the present invention and the polarizer constituting the polarizing plate, the above-mentioned in the optical film.
  • the presence of an anti-degradation agent plays an important role.
  • the storage stability of the optical film over time can be improved from the viewpoint of suppressing the above-mentioned deterioration and deterioration, and the liquid crystal Also in improving the display quality of the display device, the optical compensation design is excellent in that the function can be expressed over a long period of time.
  • the optical film of the present invention preferably contains an antioxidant as a stabilizer.
  • the film molding material is preferably decomposed by heat and oxygen, so that an antioxidant is preferably contained.
  • the antioxidant useful in the present invention can be used without limitation as long as it is a compound that suppresses deterioration of the film-forming material due to oxygen.
  • useful antioxidants include phenolic compounds, phosphorus compounds, Sulfur compounds, acrylate compounds, benzofuranone compounds, oxygen scavengers and the like can be mentioned, and among these, phenol compounds, phosphorus compounds, acrylate compounds, and benzofuranone compounds are particularly preferable. By blending these compounds, it is possible to prevent coloration or strength reduction of the molded product due to heat, thermal oxidation deterioration, or the like without reducing transparency, heat resistance, and the like. These antioxidants can be used alone or in combination of two or more.
  • One antioxidant useful in the present invention is a phenolic compound.
  • Phenol compounds are known compounds, and in addition to alkyl group-substituted phenols such as para-t-butylphenol and para- (1,1,3,3-tetramethylbutyl) phenol, for example, US Pat. No. 4,839, Examples include 2,6-dialkylphenol derivative compounds, so-called hindered phenol compounds, described in columns 12 to 14 of the specification of No. 405, and among these, hindered phenol compounds are preferred.
  • hindered phenol phenol compound examples include n-octadecyl 3- (3,5-di-t-butyl-4-hydroxyphenyl) -propionate, n-octadecyl 3- (3,5-di-t- Butyl-4-hydroxyphenyl) -acetate, n-octadecyl 3,5-di-t-butyl-4-hydroxybenzoate, n-hexyl 3,5-di-t-butyl-4-hydroxyphenylbenzoate, n-dodecyl 3,5-di-t-butyl-4-hydroxyphenylbenzoate, neo-dodecyl 3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, dodecyl ⁇ (3,5-di-t-butyl-4-hydroxyphenyl) propionate, ethyl ⁇ - (4-hydroxy-3,5-di-t-propionat
  • phenolic compounds are commercially available from Ciba Japan, for example, under the trade names “IRGANOX1076” and “IRGANOX1010” and from Sumitomo Chemical Co., Ltd. under the name “Sumizer GA-80”.
  • Preferred phosphorus compounds useful in the present invention include phosphite compounds and phosphonite compounds.
  • Specific examples of the phosphite compound include triphenyl phosphite, diphenylisodecyl phosphite, phenyl diisodecyl phosphite, tris (nonylphenyl) phosphite, tris (dinonylphenyl) phosphite, tris (2,4-diphenyl).
  • phosphite compounds are, for example, “Sumilizer GP” from Sumitomo Chemical Co., Ltd., “ADK STAB PEP-24G”, “ADK STAB PEP-36”, “ADK STAB 3010”, “ADK STAB” from ADEKA Co., Ltd. It is commercially available under the trade names “HP-10” and “ADK STAB 2112”.
  • the phosphonite compound examples include dimethyl-phenyl phosphonite, di-t-butyl-phenyl phosphonite, diphenyl-phenyl phosphonite, di- (4-pentyl-phenyl) -phenyl phosphonite, di- (2- t-butyl-phenyl) -phenylphosphonite, di- (2-methyl-3-pentyl-phenyl) -phenylphosphonite, di- (2-methyl-4-octyl-phenyl) -phenylphosphonite, di- ( 3-butyl-4-methyl-phenyl) -phenylphosphonite, di- (3-hexyl-4-ethyl-phenyl) -phenylphosphonite, di- (2,4,6-trimethylphenyl) -phenylphosphonite, Di- (2,3-dimethyl-4-ethyl-phenyl) -phenylphosphonite, di- (2,6-die 3-butylphenyl)
  • sulfur compounds Specific examples of the sulfur compound include dilauryl 3,3-thiodipropionate, dimyristyl 3,3'-thiodipropionate, distearyl 3,3-thiodipropionate, lauryl stearyl 3,3-thiodipropioate. And pentaerythritol-tetrakis ( ⁇ -lauryl-thio-propionate), 3,9-bis (2-dodecylthioethyl) -2,4,8,10-tetraoxaspiro [5,5] undecane .
  • acrylate compounds examples include 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, 2- [1- (2-hydroxy-3, 5 -Di-tert-pentylphenyl) ethyl] -4,6-di-tert-pentylphenyl acrylate and the like.
  • An acrylate compound of the above type is commercially available, for example, from Sumitomo Chemical Co., Ltd. under the trade names “Sumilizer GM” and “Sumilizer GS”.
  • benzofuranone compounds examples include 3- [4- (2-acetoxyethoxy) phenyl] -5,7-ditert-butylbenzofuran-2-one and 5,7-ditert-butyl-3- [4- (2 -Stearoyloxyethoxy) phenyl] benzofuran-2-one, 3,3'-bis [5,7-ditert-butyl-3- (4- [2-hydroxyethoxy] phenyl) benzofuran-2-one], 5 , 7-ditert-butyl-3- (4-methoxyphenyl) benzofuran-2-one, 5,7-ditert-butyl-3-phenylbenzofuran-2-one, 5,7-ditert-butyl-4 -Methyl-3-phenylbenzofuran-2-one, 3- (4-acetoxy-3,5-dimethylphenyl) -5,7-ditert-butylbenzofuran-2-one, 3- (4-acetoxy-3
  • benzofuranone-based compound is commercially available, for example, from Ciba Japan under the trade name “HP-136”.
  • antioxidants 3,4-dihydro-2H-1-benzopyran compounds, 3,3′-spirodichroman compounds, 1,1-spiroindane compounds, morpholine, thiomorpholine, thiomorpholine oxide described in JP-B-08-27508, Examples include thiomorpholine dioxide, compounds having a piperazine skeleton in the partial structure, and oxygen scavengers such as dialkoxybenzene compounds described in JP-A-3-174150.
  • the partial structure of the antioxidant described above may be pendant on a part of the polymer or regularly on the polymer.
  • the antioxidant is preferably removed from impurities such as residual acids, inorganic salts, organic low molecules, etc. that are carried over from production or generated during storage, and more preferably has a purity of 99% or more, like the cellulose ester described above. It is.
  • the residual acid and water are preferably 0.01 to 100 ppm, and when melt-forming the cellulose ester, thermal deterioration can be suppressed, and the film-forming stability, the optical properties and mechanical properties of the film are improved.
  • these antioxidants are each preferably added in an amount of 0.01 to 10% by mass, more preferably 0.05 to 5% by mass, and further preferably 0.1 to 2%, based on the resin. It is preferable to add mass%.
  • antioxidants can obtain a synergistic effect by using several different types of compounds in combination rather than using only one kind.
  • the combined use of a phenol compound, a phosphorus compound having no metal atom, an acrylate compound, and a benzofuranone compound is preferable.
  • the cellulose ester is preferably washed in the presence of an antioxidant during suspension washing with a poor solvent.
  • the antioxidant to be used is not limited as long as it is a compound that inactivates radicals generated in the cellulose ester or suppresses deterioration of the cellulose ester caused by addition of oxygen to the radical generated in the cellulose ester. be able to.
  • the antioxidant used for suspension washing of the cellulose ester may remain in the cellulose ester after washing.
  • the residual amount is preferably 0.01 to 2000 ppm, more preferably 0.05 to 1000 ppm. More preferably, it is 0.1 to 100 ppm.
  • the antioxidant is preferably removed from impurities such as residual acids, inorganic salts, organic low molecules, etc. that are carried over from production or generated during storage, and more preferably has a purity of 99% or more, like the cellulose ester described above. It is. Residual acid and water are preferably 0.01 to 100 ppm, and when melt casting film formation of cellulose ester, thermal deterioration can be suppressed, and film formation stability, optical properties and mechanical properties of the film are improved. To do.
  • hindered amine light stabilizers include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (2,2,6,6-tetramethyl-4-piperidyl) succinate, bis ( 1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (N-octoxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (N-benzyloxy-2, 2,6,6-tetramethyl-4-piperidyl) sebacate, bis (N-cyclohexyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6) -Pentamethyl-4-piperidyl) 2- (3,5-di-t-butyl-4-hydroxybenzyl) -2-butylmalonate, bis (1-acryloyl-2,2,6,6) Tetramethyl-4-piperidyl) 2,2-bis (3,5-di-t-butyl)
  • Mn molecular weight of 2,000 to 5,000 is preferred.
  • Hindered amine compounds of the above type are commercially available, for example, from Ciba Japan Co., Ltd. under the trade names “TINUVIN 144” and “TINUVIN 770” and from ADEKA Co., Ltd. under the name “ADK STAB LA-52”.
  • the hindered amine light stabilizer is preferably added in an amount of 0.1 to 10% by mass, more preferably 0.2 to 5% by mass, based on the mass of the cellulose ester according to the present invention. Further, it is preferable to add 0.5 to 2% by mass. Two or more of these may be used in combination.
  • the cellulose ester is preferably decomposed by an acid in a high temperature environment in which melt film formation is performed. Therefore, the optical film of the present invention preferably contains an acid scavenger as a deterioration preventing agent.
  • Any acid scavenger useful in the present invention can be used without limitation as long as it is a compound that reacts with an acid to inactivate the acid, and is described in U.S. Pat. No. 4,137,201.
  • a compound having an epoxy group is preferred.
  • EPON 815C and other epoxidized ether oligomer condensation products can also be preferably used.
  • acid scavengers that can be used other than the above include oxetane compounds, oxazoline compounds, organic earth salts of alkaline earth metals and acetylacetonate complexes, and paragraphs 68 to 105 of JP-A-5-194788. Is included.
  • the acid scavenger is preferably added in an amount of 0.1 to 10% by mass, more preferably 0.2 to 5% by mass, more preferably 0.2% by mass to the mass of the cellulose ester according to the present invention. It is preferable to add 0.5 to 2% by mass. Two or more of these may be used in combination.
  • the acid scavenger may be referred to as an acid scavenger, an acid scavenger, an acid catcher, or the like, but can be used in the present invention without any difference due to their names.
  • the metal deactivator is preferably added in an amount of 0.0002 to 2 mass%, more preferably 0.0005 to 2 mass%, based on the mass of the cellulose ester according to the present invention. Further, it is preferable to add 0.001 to 1% by mass. Two or more of these may be used in combination.
  • benzotriazole ultraviolet absorbers include 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) benzo Triazole, 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) -5 Chlorobenzotriazole, 2- (2′-hydroxy-3 ′-(3 ′′, 4 ′′, 5 ′′, 6 ′′ -tetrahydrophthalimidomethyl) -5′-methylphenyl) benzotriazole, 2,2-methylenebis (4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol), 2- (2'-hydroxy 3'-tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-
  • TINUVIN 171, TINUVIN 900, TINUVIN 928, TINUVIN 360 (all manufactured by Ciba Japan), LA31 (manufactured by ADEKA Corporation), RUVA- 100 (manufactured by Otsuka Chemical).
  • benzophenone compounds include 2,4-dihydroxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone, bis (2-methoxy-4-hydroxy-) 5-benzoylphenylmethane) and the like, but are not limited thereto.
  • the ultraviolet absorber is preferably added in an amount of 0.1 to 5% by mass, more preferably 0.2 to 3% by mass, and further 0.5 to 2% by mass based on the resin. It is preferable. Two or more of these may be used in combination.
  • the benzotriazole structure or triazine structure may be part of the polymer, or may be regularly pendant to the polymer, and part of the molecular structure of other additives such as plasticizers, antioxidants, and acid scavengers. May be introduced.
  • the conventionally known UV-absorbing polymer is not particularly limited, and examples thereof include a polymer obtained by homopolymerizing RUVA-93 (manufactured by Otsuka Chemical) and a polymer obtained by copolymerizing RUVA-93 with other monomers. . Specifically, PUVA-30M obtained by copolymerizing RUVA-93 and methyl methacrylate in a ratio (mass ratio) of 3: 7, and PUVA-50M copolymerized in a ratio of 5: 5 (mass ratio). It is done. Furthermore, the polymer etc. which are described in Unexamined-Japanese-Patent No. 2003-113317 are mentioned.
  • the cellulose ester can contain various additives in addition to the deterioration inhibitor, the plasticizer and the ultraviolet absorber.
  • various additives in addition to the deterioration inhibitor, the plasticizer and the ultraviolet absorber.
  • matting agents, fillers, inorganic compounds such as silica and silicates, dyes, pigments, phosphors, dichroic dyes, retardation control agents, refractive index regulators, gas permeation inhibitors, antibacterial agents, biodegradable Examples include an imparting agent.
  • additives that are not classified as long as they have the above functions can be used.
  • each material is mixed in a solid or liquid state, heated and melted and kneaded to form a uniform melt, and then cast to form an optical film.
  • the solvent is removed to form a mixture of the additive and the cellulose ester, and this is heated and melted. It may be cast to form an optical film.
  • a matting agent can be added to the optical film of the present invention in order to impart slipperiness, optical and mechanical functions.
  • the matting agent include inorganic compound fine particles and organic compound fine particles.
  • the shape of the matting agent is preferably a spherical shape, rod shape, needle shape, layer shape, flat plate shape or the like.
  • the matting agent include silicon dioxide, titanium dioxide, aluminum oxide, zirconium oxide, calcium carbonate, kaolin, talc, calcined calcium silicate, hydrated calcium silicate, aluminum silicate, magnesium silicate, and calcium phosphate.
  • examples thereof include inorganic fine particles such as oxides, phosphates, silicates, and carbonates, and crosslinked polymer fine particles.
  • silicon dioxide is preferable because it can reduce the haze of the film.
  • the surface treatment is preferably performed with halosilanes, alkoxysilanes, silazane, siloxane, or the like.
  • halosilanes alkoxysilanes, silazane, siloxane, or the like.
  • the average particle size of the secondary particles of the fine particles is in the range of 0.01 to 1.0 ⁇ m.
  • the average particle size of the primary particles of the fine particles is preferably 5 to 50 nm, more preferably 7 to 14 nm. These fine particles are usually present in the film as aggregates, and are preferably used for generating irregularities with a height of 0.01 to 1.0 ⁇ m on the film surface.
  • Aerosil 200, 200V, 300, R972, R972V, R974, R202, R812, OX50, TT600, NAX50, etc. manufactured by Nippon Aerosil Co., Ltd. are available.
  • P10, KE-P30, KE-P100, KE-P150 and the like can be mentioned. Aerosil 200V, R972V, NAX50, KE-P30 and KE-P100 are preferable. Two or more kinds of these fine particles may be used in combination.
  • Fine particles having different average particle sizes and materials for example, Aerosil 200V and R972V can be used in a mass ratio of 0.1: 99.9 to 99.9: 0.1.
  • matting agents are preferably added by kneading.
  • a matting agent and cellulose ester and / or a plasticizer and / or an antioxidant and / or an ultraviolet absorber previously dispersed in a solvent after mixing and dispersing a matting agent and cellulose ester and / or a plasticizer and / or an antioxidant and / or an ultraviolet absorber previously dispersed in a solvent, a solid substance obtained by volatilizing or precipitating the solvent is obtained. Obtaining and using this in the manufacturing process of the cellulose ester melt is preferable from the viewpoint that the matting agent can be uniformly dispersed in the cellulose ester.
  • the content is preferably 0.001 to 5% by mass, more preferably 0.00. 005 to 1% by mass, more preferably 0.01 to 0.5% by mass.
  • haze value becomes like this. Preferably it is less than 1.0%, More preferably, it is less than 0.5%.
  • the haze value can be measured based on JIS-K-7136.
  • Degradation of the material can be suppressed by reducing the probability that the optical film comes into contact with oxygen in the air, which is preferable for the purpose of the present invention.
  • an optical film is a functional film used for various display apparatuses, such as a liquid crystal display, a plasma display, and an organic electroluminescent display. Specifically, it is a polarizing plate protective film for liquid crystal display apparatuses, retardation film, antireflection Films, brightness enhancement films, hard coat films, antiglare films, antistatic films, optical compensation films such as viewing angle expansion, and the like are included.
  • cellulose ester resins in addition to the cellulose ester of the present invention, cellulose ester resins, cellulose ether resins, vinyl resins (including polyvinyl acetate resins, polyvinyl alcohol resins, etc.), olefins not related to the present invention, and olefins Resin (norbornene resin, monocyclic olefin resin, cyclic conjugated diene resin, vinyl alicyclic hydrocarbon resin, etc.), polyester resin (aromatic polyester, aliphatic polyester, or co-polymer containing them) Coalescence), acrylic resins (including copolymers), polycarbonate resins, polystyrene resins, polysulfone resins, polyarylate resins, and the like.
  • the content of the resin other than the cellulose ester is preferably 0.1 to 30% by mass.
  • the optical film of the present invention is preferably used for a polarizing plate protective film and a retardation film.
  • the optical film of the present invention is preferably produced by a melt casting method.
  • melt casting method can significantly reduce the amount of organic solvent used during film production, the film is much more environmentally friendly than conventional solution casting methods that use large amounts of organic solvents. Therefore, it is preferable to produce an optical film by a melt casting method.
  • the melt casting in the present invention is a method in which cellulose ester is heated and melted to a temperature at which the cellulose ester exhibits fluidity substantially without using a solvent, and a film is formed using this. For example, fluid cellulose ester is removed from a die. This is a method of forming a film by extrusion.
  • a solvent may be used in a part of the process of preparing the molten cellulose ester, in the melt film forming process in which the film is formed into a film, the forming process is substantially performed without using the solvent.
  • the molding method by melt casting can be classified into a melt extrusion molding method, a press molding method, an inflation method, an injection molding method, a blow molding method, a stretch molding method, and the like.
  • the melt extrusion method is excellent for obtaining an optical film having excellent mechanical strength, surface accuracy, and the like.
  • the manufacturing method of the optical film of the present invention will be described by taking the melt extrusion method as an example.
  • FIG. 1 is a schematic flow sheet diagram showing an example of one embodiment of an apparatus for carrying out the method for producing an optical film of the present invention.
  • FIG. 2 is a flow sheet showing an example of an enlarged main part of the manufacturing apparatus of FIG.
  • the optical film is produced by mixing an optical film material such as a cellulose resin, and then using the extruder 1 to melt and extrude from the casting die 4 onto the first cooling roll 5 so as to circumscribe the first cooling roll 5.
  • the optical film 10 is obtained by sequentially circumscribing a total of three cooling rolls, that is, the second cooling roll 7 and the third cooling roll 8, and cooling and solidifying.
  • a touch roll 6 is provided to clamp the molten film on the surface of the first cooling roll 5 in order to correct the flatness.
  • the touch roll 6 has an elastic surface and forms a nip with the first cooling roll 5. Details of the touch roll 6 will be described later.
  • the conditions for melt extrusion can be performed in the same manner as the conditions used for other thermoplastic resins such as polyester.
  • the material is preferably dried beforehand. It is desirable to dry the moisture to 1000 ppm or less, preferably 200 ppm or less by using a vacuum or reduced pressure drier or a dehumidifying hot air drier.
  • a cellulose ester resin dried under hot air, vacuum or reduced pressure is melted at an extrusion temperature of about 200 to 300 ° C. using an extruder 1 and filtered through a leaf disk type filter 2 to remove foreign matters.
  • additives such as plasticizer are not mixed in advance, they may be kneaded in the middle of the extruder. In order to add uniformly, it is preferable to use a mixing apparatus such as a static mixer.
  • the cellulose resin and other additives such as a stabilizer added as necessary are preferably mixed before melting, and more preferably mixed before heating and the cellulose resin.
  • Mixing may be performed by a mixer or the like, or may be mixed in the cellulose resin preparation process as described above.
  • a general mixer such as a V-type mixer, a conical screw type mixer, a horizontal cylindrical type mixer, a Henschel mixer, a ribbon mixer, or the like can be used.
  • the mixture may be directly melted and formed into a film using the extruder 1, but once the optical film constituting material is pelletized, the pellet May be melted by the extruder 1 to form a film.
  • the optical film constituting material includes a plurality of materials having different melting points
  • a so-called braided semi-melt is once produced at a temperature at which only a material having a low melting point is melted, and the semi-melt is extruded into the extruder 1. It is also possible to form a film by putting it into the film.
  • the optical film material contains materials that are easily pyrolyzed, in order to reduce the number of melting times, a method of directly forming a film without producing pellets, or making a braided semi-melt as described above A method of forming a film from is preferred.
  • the extruder 1 can use various types of extruders available on the market, but is preferably a melt-kneading extruder, and may be a single screw extruder or a twin screw extruder.
  • twin-screw extruder When forming a film directly without forming pellets from optical film constituent materials, it is preferable to use a twin-screw extruder because an appropriate degree of kneading is required. However, even with a single-screw extruder, the screw shape can be changed to Maddock. By changing to a kneading type screw such as a mold, unimelt, dalmage, etc., moderate kneading can be obtained, which can be used. When a pellet or braided semi-melt is used as the optical film constituent material, it can be used with either a single screw extruder or a twin screw extruder.
  • the cooling step in the extruder 1 and after the extrusion is preferably performed by substituting with an inert gas such as nitrogen gas or reducing the pressure to reduce the oxygen concentration.
  • the melting temperature of the optical film constituent material in the extruder 1 varies depending on the viscosity and discharge amount of the optical film constituent material, the thickness of the sheet to be manufactured, etc., but is preferably 150 to 300 ° C., more preferably 180 to 270 ° C. 200 to 250 ° C. is more preferable.
  • the melt viscosity at the time of extrusion is 10 to 100,000 poise, preferably 100 to 10,000 poise.
  • the residence time of the optical film constituting material in the extruder 1 is preferably shorter, and is within 5 minutes, preferably within 3 minutes, and more preferably within 2 minutes.
  • the residence time depends on the type of the extruder 1 and the extrusion conditions, it can be shortened by adjusting the material supply amount, L / D, screw rotation speed, screw groove depth, etc. It is.
  • the screw shape, rotation speed, and the like of the extruder 1 are appropriately selected depending on the viscosity and the discharge amount of the optical film constituent material.
  • the shear rate in the extruder 1 is 1 / second to 10,000 / second, preferably 5 / second to 1000 / second, more preferably 10 / second to 100 / second.
  • the extruder 1 that can be used in the present invention is generally available as a plastic molding machine.
  • the slit of the casting die 4 is configured so that the gap can be adjusted.
  • FIG. 3A is an external view showing an example of the main part of the casting die
  • FIG. 3B is a cross-sectional view showing an example of the main part of the casting die.
  • a large number of heat bolts 35 are arranged at a constant pitch in the width direction of the casting die 4, that is, in the length direction of the slit 32.
  • Each heat bolt 35 is provided with a block 36 having an embedded electric heater 37 and a cooling medium passage, and each heat bolt 35 penetrates each block 36 vertically.
  • the base of the heat bolt 35 is fixed to the die body 31, and the tip is in contact with the outer surface of the flexible lip 33. While the block 36 is always air-cooled, the input of the embedded electric heater 37 is increased or decreased to raise or lower the temperature of the block 36, thereby causing the heat bolt 35 to thermally expand and contract, thereby displacing the flexible lip 33 to change the thickness of the optical film. Adjust.
  • Thickness gauges are installed at the required locations in the wake of the die, and the web thickness information detected thereby is fed back to the control device.
  • the thickness information is compared with the set thickness information by the control device, and correction control comes from the same device. It is also possible to control the power or the ON rate of the heat bolt heating element by the amount signal.
  • the heat bolt preferably has a length of 20 to 40 cm and a diameter of 7 to 14 mm, and a plurality of, for example, several tens of heat bolts are preferably arranged at a pitch of 20 to 40 mm.
  • a gap adjusting member mainly composed of a bolt for adjusting the slit gap by manually moving back and forth in the axial direction may be provided.
  • the slit gap adjusted by the gap adjusting member is usually 200 to 1000 ⁇ m, preferably 300 to 800 ⁇ m, more preferably 400 to 600 ⁇ m.
  • the first to third cooling rolls are made of seamless steel pipe with a wall thickness of about 20 to 30 mm, and the surface is mirror finished.
  • a pipe for flowing a cooling liquid is arranged inside the pipe, and the cooling liquid flowing through the pipe can absorb heat from the optical film on the roll.
  • the touch roll 6 in contact with the first cooling roll 5 has an elastic surface and is deformed along the surface of the first cooling roll 5 by the pressing force to the first cooling roll 5. A nip is formed between the two.
  • the touch roll 6 is also called a pinching rotary body.
  • a touch roll disclosed in registered patent 3194904, registered patent 3422798, Japanese Patent Application Laid-Open No. 2002-36332, Japanese Patent Application Laid-Open No. 2002-36333, or the like can be preferably used. These can also use what is marketed. These will be described in more detail below.
  • FIG. 4 is a cross-sectional view showing an example of a pinching rotator.
  • the 1st example of touch roll 6 (henceforth, outline section of touch roll A)) is shown.
  • the touch roll A has an elastic roller 42 disposed inside a flexible metal sleeve 41.
  • the metal sleeve 41 is made of stainless steel having a thickness of 0.3 mm and has flexibility. If the metal sleeve 41 is too thin, the strength is insufficient, whereas if it is too thick, the elasticity is insufficient.
  • the elastic roller 42 presses the metal sleeve 41 against the first cooling roll 5, and the metal sleep 41 and the elastic roller 42 have the shape of the first cooling roll 5. It deforms corresponding to the familiar shape, and forms a nip with the first cooling roll. Cooling water 45 flows in a space formed between the metal sleeve 41 and the elastic roller 42.
  • FIG. 5 is a cross-sectional view taken along a plane perpendicular to the rotation axis, showing a second example (hereinafter referred to as touch roll B) of the pinching rotator.
  • FIG. 6 is a cross-sectional view showing an example of a plane including the rotation axis of the second example (touch roll B) of the pinching rotator.
  • the touch roll B is a flexible and seamless outer tube 51 made of a stainless steel pipe (thickness 4 mm), and a high rigidity arranged in the same axial center inside the outer tube 51.
  • the metal inner cylinder 52 is generally configured.
  • a fluid supply pipe 59 is disposed in the same axial center in a fluid discharge hole 58 formed in the axial center portion of one rotary shaft 55a and forming a fluid return passage 57.
  • the fluid supply pipe 59 is thin-walled. It is connected and fixed to a fluid shaft cylinder 60 arranged at the axial center in the metal outer cylinder 51.
  • Inner cylinder support flanges 61a and 61b are attached to both ends of the fluid shaft cylinder 60, respectively, and a thickness of about 15 to 20 mm between the outer periphery of the inner cylinder support flanges 61a and 61b and the other end side outer cylinder support flange 56b.
  • a metal inner cylinder 52 having a thickness is attached.
  • a cooling liquid flow space 53 of, for example, about 10 mm is formed between the metal inner cylinder 52 and the thin metal outer cylinder 51, and the metal inner cylinder 52 has a flow space 53 and an inner space near both ends.
  • An outlet 52a and an inlet 52b are formed to communicate with the intermediate passages 62a and 62b outside the cylinder support flanges 61a and 61b, respectively.
  • the equivalent spring constant is equal by setting the wall thickness of the outer cylinder 51 to 3 mm compared to the rubber roll of the same shape.
  • the nip width k in the roll rotation direction of the nip is also about 9 mm, which is almost the same as the nip width of this rubber roll of about 12 mm.
  • the deflection amount at the nip width k is about 0.05 to 0.1 mm.
  • the converted value of 2 mm ⁇ t ⁇ 5 mm is 0.008 ⁇ t / r ⁇ 0.05 with respect to a general roll diameter, but in practical use, the roll diameter under the condition of t / r ⁇ 0.03.
  • the wall thickness should be increased in proportion to
  • the touch rolls A and B are urged toward the first cooling roll by the urging means.
  • the value F / W (linear pressure) obtained by dividing the urging force of the urging means by F and dividing the width W of the optical film in the nip along the rotation axis of the first cooling roll 5 is 9.8 to 147 N / Set to cm.
  • a nip is formed between the touch rolls A and B and the first cooling roll 5, and the flatness is corrected while the optical film passes through the nip. Accordingly, the optical film is sandwiched over a long time with a small linear pressure, compared to the case where the touch roll is formed of a rigid body and no nip is formed between the first cooling roll and the flatness is more reliably corrected. be able to.
  • the surfaces of the touch rolls A and B are made of metal, the surfaces of the touch rolls A and B can be made smoother than when the surface of the touch roll is rubber. Can be obtained.
  • ethylene propylene rubber, neoprene rubber, silicon rubber, or the like can be used as a material of the elastic body 44 of the elastic roller 42.
  • the glass transition temperature of the optical film is Tg
  • Tg glass transition temperature
  • the viscosity of the optical film when sandwiching the optical film can be set to an appropriate range, and the die line can be corrected. Further, the surface of the optical film and the roll are uniformly bonded, and the die line can be corrected.
  • the first cooling roll is moved from the position where the melt extruded from the casting die 4 contacts the first cooling roll 5. What is necessary is just to adjust the length L along the rotation direction of the 1st cooling roll 5 of the nip of 5 and the touch roll 6.
  • preferable materials for the first cooling roll 5 and the second cooling roll 7 include carbon steel, stainless steel, resin, and the like.
  • the surface accuracy is preferably increased, and the surface roughness is set to 0.3 S or less, more preferably 0.01 S or less.
  • the above-described die line correction effect is more greatly manifested.
  • the reduced pressure is 50 to 70 kPa.
  • the method of keeping the pressure in the portion from the opening (lip) of the casting die 4 to the first cooling roll 5 at 70 kPa or less but the pressure around the roll from the casting die 4 is covered with a pressure-resistant member, and the pressure is reduced. There are ways to do it.
  • the suction device is preferably subjected to a treatment such as heating with a heater so that the device itself does not become a place where the sublimate adheres.
  • a treatment such as heating with a heater
  • the melted film-like cellulose ester from the T die 4 is brought into close contact with the first cooling roll 5, the second cooling roll 7, and the third cooling roll 8 in order to be cooled and solidified, and unstretched.
  • the optical film 10 is obtained.
  • the cooled and solidified unstretched optical film 10 peeled from the third cooling roll 8 by the peeling roll 9 is stretched through a dancer roll (optical film tension adjusting roll) 11. It leads to the apparatus 12, and the optical film 10 is extended
  • a known tenter or the like can be preferably used as a method of stretching the optical film in the width direction.
  • the glass transition temperature Tg of the optical film can be controlled by varying the material type constituting the optical film and the ratio of the constituting material.
  • Tg is preferably 120 ° C. or higher, preferably 135 ° C. or higher.
  • the temperature environment of the film changes due to the temperature rise of the device itself, for example, the temperature rise derived from the light source.
  • the retardation value derived from the orientation state of the molecules fixed inside the film by stretching and the dimensional shape as the film are greatly changed.
  • Tg is preferably 250 ° C. or less.
  • known heat setting conditions, cooling, and relaxation treatment may be performed, and it may be appropriately adjusted so as to have characteristics required for the target optical film.
  • the heating and pressurizing step is performed before the stretching step and heat setting treatment.
  • the refractive index can be controlled by a stretching operation. Is a preferred method. Hereinafter, the stretching method will be described.
  • the required litter is stretched by 1.0 to 2.0 times in one direction of the cellulose resin and 1.01 to 2.5 times in the direction perpendicular to the film plane.
  • the foundation Ro and Rt can be controlled.
  • Ro indicates in-plane retardation
  • Rt indicates thickness direction retardation.
  • Retardation Ro and Rt are calculated
  • Formula (i) Ro (nx ⁇ ny) ⁇ d
  • Formula (ii) Rt ((nx + ny) / 2 ⁇ nz) ⁇ d (Where 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 thickness direction of the film (refractive index is 23 ° C., 55%) (Measured at a wavelength of 590 nm in an RH environment), d represents the thickness (nm) of the film.)
  • the refractive index of the optical film is an Abbe refractometer (4T), the thickness of the film is a commercially available micrometer, and the retardation value is an automatic birefringence meter KOBRA-21ADH (Oji Scientific Instruments) Etc.) can be used for each measurement.
  • Stretching can be performed sequentially or simultaneously, for example, in the casting direction (also referred to as MD direction) of the optical film and in the direction orthogonal to the optical film plane, that is, in the width direction (also referred to as TD direction). At this time, if the stretching ratio in at least one direction is too small, a sufficient phase difference cannot be obtained, and if it is too large, stretching becomes difficult and optical film breakage may occur.
  • the width shrinkage of the optical film can be suppressed or improved by stretching in the width direction.
  • the refractive index When stretching in the width direction, the refractive index may be distributed in the width direction. This distribution may appear when the tenter method is used.
  • a contraction force By stretching the optical film in the width direction, a contraction force is generated at the center of the optical film, and the phenomenon is caused by the end being fixed.
  • the so-called Boeing phenomenon is considered. Even in this case, by stretching in the casting direction, the bowing phenomenon can be suppressed and the distribution of the phase difference in the width direction can be reduced. Therefore, stretching in the biaxial direction of the casting direction and the width direction is preferable.
  • variation of the optical film obtained can be reduced by extending
  • unevenness of the retardation is caused, and unevenness such as coloring may be a problem when used in a liquid crystal display device.
  • the film thickness variation of the optical film is preferably in the range of ⁇ 3%, more preferably ⁇ 1%.
  • a method of stretching in the biaxial directions perpendicular to each other is effective, and the stretching ratio in the biaxial directions perpendicular to each other is finally 1.0 to 2.0 times in the casting direction.
  • the width is preferably in the range of 1.01 to 2.5 times, in the range of 1.01 to 2.0 times in the casting direction and 1.05 to 2.0 times in the width direction. It is more preferred to obtain the required retardation value.
  • the transmission axis of the polarizer matches with the width direction.
  • the retardation film is preferably stretched so as to obtain a slow axis in the width direction.
  • the slow axis of the retardation film can be imparted in the width direction by stretching in the width direction from the above configuration.
  • the slow axis of the retardation film is preferably in the width direction, and in order to obtain the desired retardation value, Formula (stretch ratio in the width direction)> (stretch ratio in the casting direction) It is necessary to satisfy the following conditions.
  • ⁇ 1 is ⁇ 1 to + 1 °, preferably ⁇ 0.5 to It is preferable that the angle is + 0.5 °.
  • each ⁇ 1 When each ⁇ 1 satisfies the above relationship, it contributes to obtaining high luminance in a display image, suppressing or preventing light leakage, and contributing to faithful color reproduction in a color liquid crystal display device.
  • the retardation film is used for the multi-domain VA mode
  • the retardation film is arranged in the above region with the fast axis of the retardation film being ⁇ 1, which contributes to the improvement of display image quality.
  • the plate and the liquid crystal display device are in the MVA mode, for example, the configuration shown in FIG. 7 can be adopted.
  • 21a and 21b are protective films
  • 22a and 22b are retardation films
  • 25a and 25b are polarizers
  • 23a and 23b are slow axis directions of the film
  • 24a and 24b are transmission axis directions of the polarizer
  • 26a Reference numeral 26b denotes a polarizing plate
  • 27 denotes a liquid crystal cell
  • 29 denotes a liquid crystal display device.
  • the retardation Ro distribution in the in-plane direction of the optical film is preferably adjusted to 5% or less, more preferably 2% or less, and particularly preferably 1.5% or less.
  • the retardation Rt distribution in the thickness direction of the film is preferably adjusted to 10% or less, more preferably 2% or less, and particularly preferably 1.5% or less.
  • the retardation value distribution fluctuation is preferably smaller, and when a polarizing plate including a retardation film is used in a liquid crystal display device, the retardation distribution fluctuation is small from the viewpoint of preventing color unevenness and the like. preferable.
  • the retardation in the thickness direction mainly compensates for the birefringence of the liquid crystal cell similarly observed when viewed from an oblique direction when the liquid crystal cell is in a black display state in the TN mode or VA mode, particularly in the MVA mode. To contribute.
  • the total value of both of the above-mentioned ranges and the thickness direction retardation Rt is larger than 140 nm and 500 nm or less.
  • the in-plane retardation Ro and the thickness direction retardation Rt of 22a and 22b are the same.
  • the in-plane retardation Ro is greater than 45 nm and not greater than 55 nm
  • the thickness direction retardation Rt is greater than 115 nm and not greater than 125 nm, and is applied to the MVA mode liquid crystal cell with the configuration of FIG. .
  • use of a film having a thickness direction retardation Rt of greater than 140 nm and not greater than 400 nm is preferable from the viewpoint of improving the display quality and producing the film.
  • the film After stretching, after slitting the edge of the optical film to a product width with a slitter 13, the film is subjected to knurling (embossing) on both ends of the film by a knurling device comprising an embossing ring 14 and a back roll 15.
  • a knurling device comprising an embossing ring 14 and a back roll 15.
  • the knurling method can process a metal ring having an uneven pattern on its side surface by heating or pressing.
  • the grip part of the clip of the both ends of a film is deform
  • the winder related to the production of the optical film of the present invention may be generally used, and it may be a winding method such as a constant tension method, a constant torque method, a taper tension method, or a program tension control method with a constant internal stress. Can be wound up.
  • the film is preferably wound under environmental conditions of a temperature of 20 to 30 ° C. and a humidity of 20 to 60% RH.
  • the tolerance of the humidity change of the thickness direction retardation (Rt) improves by prescribing
  • the humidity in the winding process of the optical film is less than 20% RH, it is not preferable because it is easily charged and cannot be put into practical use due to deterioration of the film winding quality.
  • the wound core may be any material as long as it is a cylindrical core, but is preferably a hollow plastic core, and the plastic material is heated.
  • Any heat-resistant plastic that can withstand the processing temperature may be used, and examples thereof include phenol resins, xylene resins, melamine resins, polyester resins, and epoxy resins.
  • a thermosetting resin reinforced with a filler such as glass fiber is preferred.
  • a hollow plastic core a wound core made of FRP with an outer diameter of 6 inches (hereinafter, the inch represents the number of dots of 2.54 cm) and an inner diameter of 5 inches is used.
  • the number of turns around these winding cores is preferably 100 turns or more, more preferably 500 turns or more, and the winding thickness is preferably 5 cm or more.
  • the film thickness of the optical film of the present invention varies depending on the purpose of use, but the finished optical film is preferably 10 to 500 ⁇ m.
  • the lower limit is 20 ⁇ m or more, preferably 35 ⁇ m or more.
  • the upper limit is 150 ⁇ m or less, preferably 120 ⁇ m or less.
  • a particularly preferred range is 35 to 90 ⁇ m.
  • the optical film of the present invention is a retardation film and also serves as a polarizing plate protective film
  • the film thickness of the optical film is in the above range
  • the liquid crystal display device used for a notebook computer or a mobile electronic device can be thinned and lightened. preferable.
  • the optical film is thinner than 20 ⁇ m, it is difficult to develop retardation as a retardation film, and the moisture permeability of the film is increased, and the ability to protect the polarizer from humidity is reduced. .
  • the optical film of the present invention is preferably a long film, and as the length is increased to 1500 m, 2500 m, and 5000 m, the production effect at the time of polarizing plate processing is obtained.
  • the roll length is 10 to 5000 m, preferably 50 to 4500 m in consideration of productivity and transportability.
  • the width of the optical film can be selected from the width of the polarizer and the width suitable for the production line.
  • the roll is produced by producing a film with a width of 0.5 to 4.0 m, preferably 0.6 to 3.0 m. It may be wound into a shape and subjected to polarizing plate processing. Moreover, after manufacturing the film more than the target double width and winding up to a roll, it may cut and obtain the roll of the target width, and you may make it use such a roll for polarizing plate processing.
  • compositions containing cellulose esters having different additive concentrations such as the above-mentioned plasticizer, ultraviolet absorber and matting agent.
  • an optical film having a structure of skin layer / core layer / skin layer can be produced.
  • a lot of matting agent can be contained in the skin layer or only in the skin layer.
  • Plasticizers and UV absorbers can be added more in the core layer than in the skin layer, and may be added only in the core layer.
  • the type of plasticizer and ultraviolet absorber can be changed between the core layer and the skin layer.
  • the skin layer contains a low-volatile plasticizer and / or an ultraviolet absorber, and the core layer has excellent plasticity. It is also possible to add a plasticizer or an ultraviolet absorber excellent in ultraviolet absorption.
  • the glass transition temperature of the skin layer and the core layer may be different, and the glass transition temperature of the core layer is preferably lower than the glass transition temperature of the skin layer.
  • the glass transition temperature of both the skin and the core can be measured, and the average value calculated from these volume fractions can be defined as the glass transition temperature Tg and similarly handled.
  • an antistatic layer In producing the optical film of the present invention, before and / or after stretching, an antistatic layer, a transparent conductive layer, a hard coat layer, an antireflection layer, an antifouling layer, a slippery layer, an easy adhesion layer, an antiglare layer, and a gas barrier.
  • a functional layer such as a layer or an optical compensation layer may be provided.
  • the optical film of the present invention is preferably saponified using an alkaline solution having a concentration of 2 mol / L or more as a saponification solution.
  • the saponification solution is composed of an alkali agent and water, and may optionally contain a surfactant and a compatibilizer.
  • the alkali concentration needs to be increased as the carbon number of the acyl group increases, but if the alkali concentration is too high, Since the stability of the alkaline solution is impaired and may precipitate during long-time application, it is necessary to appropriately select an alkaline solution according to the structure of the cellulose ester, but a lower alkali concentration is preferable.
  • the alkaline solution used in the present invention is preferably 2 mol / L to 4.0 mol / L, more preferably 2 mol / L to 2.5 mol / L.
  • the saponification treatment temperature is preferably 40 ° C. to 80 ° C., more preferably 40 ° C. to 70 ° C., and still more preferably 40 ° C. to 65 ° C.
  • the saponification temperature is 40 ° C. or higher, saponification of the cellulose ester surface is likely to proceed, and adhesion with a polarizer can be easily obtained, so that it becomes easy to produce a polarizing plate having good durability.
  • the saponification temperature is too high, components (such as plasticizers) in the acylate film may be extracted or decomposed, and the film may be excessively swollen. Problems may occur.
  • alkaline agents used in the present invention include sodium hydroxide, potassium, lithium, ammonium, tribasic sodium phosphate, potassium, ammonium, dibasic sodium phosphate, potassium, ammonium, ammonium carbonate.
  • Inorganic alkali agents such as ammonium hydrogen carbonate, sodium borate, potassium, ammonium and the like.
  • sodium hydroxide and potassium hydroxide are preferable.
  • the reason is that the pH can be adjusted in a wide pH range by adjusting these amounts.
  • the optical film of the present invention is preferably subjected to the alkali saponification treatment by the step of saponifying the film with the alkali solution and the step of washing off the alkali solution from the film.
  • a step of neutralizing the alkaline solution and a step of washing off the neutralized solution from the film may be included.
  • steps are preferably carried out while transporting the film, and a method of immersing in an alkaline solution as described in JP-A No. 2001-188130 may be used, as described in JP-A No. 2004-203965.
  • a method of applying an alkaline solution may be used.
  • Polarizer When using the optical film of this invention as a polarizing plate protective film, the preparation methods of a polarizing plate are not specifically limited, It can manufacture by a general method.
  • the back side of the optical film of the present invention is subjected to alkali saponification treatment, and a completely saponified polyvinyl alcohol aqueous solution is used on at least one surface of a polarizer produced by immersing and stretching the treated optical film in an iodine solution. It is preferable to bond them together.
  • a commercially available optical film can be used as the polarizing plate protective film used on the other surface of the optical film of the present invention.
  • KC8UX2M, KC4UX, KC5UX, KC4UY, KC8UY, KC12UR, KC8UCR-3, KC8UCR-4, KC4FR-1, KC8UY-HA, KC8UX-RHA (above, Konica Minolta Opto) Etc. are preferably used.
  • a polarizing plate protective film that also serves as an optical compensation film having an optical anisotropic layer formed by aligning liquid crystal compounds such as discotic liquid crystal, rod-shaped liquid crystal, and cholesteric liquid crystal.
  • the optically anisotropic layer can be formed by the method described in JP-A-2003-98348.
  • a polarizer which is a main component of a polarizing plate, is an element that allows only light of a plane of polarization in a certain direction to pass.
  • a typical polarizer currently known is a polyvinyl alcohol-based polarizing film, which is polyvinyl alcohol.
  • iodine is dyed on a system film and one in which dichroic dye is dyed.
  • the stretching direction (usually the casting direction) shrinks, and the direction perpendicular to the stretching (usually the casting direction) It extends in the width direction.
  • the thickness of the polarizing plate protective film decreases, the expansion / contraction ratio of the polarizing plate increases, and in particular, the amount of contraction in the stretching direction of the polarizer increases.
  • the optical film of the present invention does not increase the wavy unevenness even in the durability test under the conditions of 60 ° C. and 90% RH, and even if it is a polarizing plate having an optical compensation film on the back side. It is possible to provide good visibility without changing the viewing angle characteristics after the test.
  • the polarizing plate is composed of a polarizer and a protective film for protecting both surfaces of the polarizer, and can further be constructed by laminating a protective film on one surface of the polarizing plate and a separate film on the opposite surface.
  • the protective film and the separate film are used for the purpose of protecting the polarizing plate at the time of shipping the polarizing plate and at the time of product inspection.
  • the protective film is bonded for the purpose of protecting the surface of the polarizing plate, and is used on the side opposite to the surface where the polarizing plate is bonded to the liquid crystal plate.
  • the separate film is used for the purpose of covering the adhesive layer to be bonded to the liquid crystal plate, and is used on the surface side for bonding the polarizing plate to the liquid crystal cell.
  • a polarizing plate including a polarizing plate protective film (including a case where it also serves as a retardation film) using the optical film of the present invention can exhibit high display quality as compared with a normal polarizing plate, particularly a multi-domain type.
  • the liquid crystal display device is more suitable for use in a multi-domain liquid crystal display device, more preferably by a birefringence mode.
  • the polarizing plate of the present invention includes an MVA (Multi-domain Vertical Alignment) mode, a PVA (Patterned Vertical Alignment) mode, a CPA (Continuous Pinheal Alignment) mode, an OCB (Optical AlignSensing mode) It can be used, and is not limited to a specific liquid crystal mode and the arrangement of polarizing plates.
  • Liquid crystal display devices are being applied as devices for colorization and moving image display, and the display quality is improved by the present invention, and the improvement of contrast and the resistance of polarizing plates improve the display of moving images that are less fatigued and faithful. It becomes possible.
  • the polarizing plate including the optical film of the present invention as a retardation film and a polarizing plate protective film is disposed on the liquid crystal cell, or on the both sides of the liquid crystal cell.
  • the use of the polarizing plate so that the retardation film side faces the liquid crystal cell of the liquid crystal display device can contribute to improvement in display quality.
  • the films 22a and 22b face the liquid crystal cell of the liquid crystal display device.
  • the optical film of the present invention can optically compensate the liquid crystal cell.
  • the polarizing plate of the present invention When the polarizing plate of the present invention is used for a liquid crystal display device, at least one of the polarizing plates of the liquid crystal display device may be the polarizing plate of the present invention.
  • the polarizing plate of the present invention By using the polarizing plate of the present invention, a liquid crystal display device with improved display quality and excellent viewing angle characteristics can be provided.
  • Comparative cellulose esters 13 to 22 are synthesized in the same manner as cellulose ester 1 except that the amount of acetic acid, acetic anhydride, propionic acid, and propionic anhydride used is changed.
  • the comparative cellulose esters 23 and 24 are the same as the cellulose ester 1 except that a combination of acetic acid, acetic anhydride, butyric acid and butyric anhydride is used for the synthesis of the cellulose ester 1 and the amount used is further changed. The synthesis was performed by performing the same synthesis operation.
  • Example 1 Provide of Optical Film Containing Cellulose Ester (hereinafter simply referred to as Cellulose Ester Film) Sample F-1] As described below, the cellulose ester film F-1 of the present invention was produced by melt casting using the synthesized cellulose ester and various additives.
  • FIG. 2 a schematic flow sheet showing one embodiment of an apparatus for carrying out the method for producing an optical film of the present invention is shown in FIG. 2, and the production method will be described with reference to FIG.
  • the pellets obtained above were dried at 100 ° C. for 4 hours, then heated and melted at 250 ° C. in a nitrogen atmosphere, and then extruded from the T-type casting die 4 onto the first cooling roll 5 for the first cooling. A film was sandwiched between the roll 5 and the elastic touch roll 6 to form.
  • the first cooling roll and the second cooling roll were made of stainless steel having a diameter of 40 cm, and the surface was subjected to hard chrome plating. Further, oil for temperature adjustment was circulated inside to control the roll surface temperature.
  • the touch roll 6 having elasticity has a diameter of 20 cm
  • the inner cylinder and the outer cylinder are made of stainless steel
  • the surface of the outer cylinder is subjected to hard chrome plating.
  • the wall thickness of the outer cylinder was 2 mm, and temperature adjusting oil was circulated in the space between the inner cylinder and the outer cylinder to control the surface temperature of the touch roll 6 having elasticity.
  • the following is the same for the optical film F-2 to 12 of the present invention and the comparative optical film F- except that the cellulose ester 1 of the present invention is changed to the cellulose ester and conditions shown in Table 2 below. 13 to 24 were produced.
  • the lip clearance of the T die was changed so that the film thickness of the finished film after drawing was 40 ⁇ m.
  • plasticizer-A IRGANOX 1010, GSY-P101, Sumilizer GS, and TINUVIN 928 used in Example 1 are as follows.
  • Cellulose esters 1 to 22 are cellulose acetate propionate, and cellulose esters 23 and 24 are cellulose acetate butyrate.
  • the retardation value of the center part of the width direction of the obtained cellulose-ester film sample was measured.
  • an automatic birefringence meter KOBURA 21ADH manufactured by Oji Scientific Instruments Co., Ltd.
  • the birefringence was measured, and the measured value was substituted into the following equation.
  • d is the thickness (nm) of the film
  • the refractive index nx (the maximum refractive index in the plane of the film, also referred to as the refractive index in the slow axis direction)
  • ny the direction perpendicular to the slow axis in the film plane).
  • Refractive index of the film in the thickness direction Refractive index of the film in the thickness direction).
  • the standard deviation is 0 to less than 1 ⁇ m
  • the cellulose ester films F-1 to F-12 of the present invention have excellent retardation, small film thickness unevenness, low haze, and good adhesion to the polarizer. It turns out that it is a superior optical film.
  • the comparative cellulose ester films F-13 to F-24 cannot satisfy all of the points in terms of retardation development, film thickness uniformity, haze, and adhesion to the polarizer.
  • Example 2 The cellulose ester films F-25 to 36 of the present invention were prepared in the same manner as the cellulose ester film F-1 of Example 1, except that the cellulose ester and the combination of additives shown in Table 3 were changed to the draw ratio. Comparative cellulose ester films F-37 and 38 were produced. Further, polarizing plates P-25 to 36 of the present invention and comparative polarizing plates P-37 and 38 were produced in the same manner as the polarizing plate P-1 of Example 1. In addition, the numerical value in the bracket
  • STAB PEP-36 manufactured by ADEKA
  • ADK STAB 2112 manufactured by ADEKA
  • Example 3 (Preparation of polarizing plate) A polarizer was prepared in the same manner as in Example 1, and on one surface of the polarizer, the cellulose ester films F-1 to 12, 25 to 36 of the present invention and the comparative cellulose ester films F-13 to 24, 37, The surface treated with alkali similar to that of Example 1 in 38, and the other surface treated with the same alkali treated surface of Konica Minolta Tack KC4UY (manufactured by Konica Minolta Opto) was completely saponified.
  • a 42-type VA color liquid crystal is bonded to the Konica Minol Tack KC4UY with the liquid crystal cell sandwiched between them so that the two polarizing plates are perpendicular to each other so that the polarization axes of the polarizing plates do not change.
  • Display devices D-1 to 12, 25 to 36, and comparative liquid crystal display devices D-13 to 24, 37, and 38 were produced.
  • the measurement was performed after the backlight of each liquid crystal display device was lit continuously for one week in an environment of 23 ° C. and 55% RH.
  • EZ-Contrast 160D manufactured by ELDIM was used, the luminance from the normal direction of the display screen of white display and black display was measured with a liquid crystal display device, and the ratio was defined as the front contrast.
  • the liquid crystal display devices D-1 to 12 and 25 to 36 using the polarizing plates Q-1 to 12 and 25 to 36 of the present invention use the comparative polarizing plates Q-13 to 24, 37, and 38, respectively.

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Organic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Polarising Elements (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention a pour objet un film optique présentant une capacité d'allongement satisfaisante, une excellente réalisation des propriétés de déphasage, une faible irrégularité de l'épaisseur de film et une excellente adhésivité avec un polariseur, ainsi qu'un procédé de fabrication de ce film. L'invention a également pour objet une plaque de polarisation qui utilise ledit film optique et qui présente une excellente durabilité à long terme, ainsi qu'un dispositif d'affichage à cristaux liquides présentant une excellente durabilité. Le film optique contient un ester cellulosique dont le type de substituant par unité de glucose dudit ester cellulosique et le degré de substitution de celui-ci satisfont simultanément les conditions des équations (1)-(4). Equation (1) Equation (2) Equation (3) Equation (4) [où X représente le degré de substitution par groupements acétyles, et Y représente le degré de substitution par groupements propionyles.]
PCT/JP2009/060048 2008-07-02 2009-06-02 Film optique, procédé de fabrication d’un film optique, plaque de polarisation et dispositif d’affichage à cristaux liquides utilisant ce film Ceased WO2010001677A1 (fr)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011111484A1 (fr) * 2010-03-09 2011-09-15 コニカミノルタオプト株式会社 Procédé de production d'un ester de cellulose, ester de cellulose et film d'ester de cellulose
WO2012056671A1 (fr) * 2010-10-26 2012-05-03 コニカミノルタオプト株式会社 Procédé de production d'un article moulé en résine contenant un ester de cellulose, pellicule optique, plaque polarisante et dispositif d'affichage
WO2014002720A1 (fr) * 2012-06-28 2014-01-03 株式会社Adeka Composition de résine à base d'ester de cellulose
JP2018515656A (ja) * 2015-05-15 2018-06-14 ダウ グローバル テクノロジーズ エルエルシー 極めて高い分子量及び低い粘度のエステル化セルロースエーテルの生成プロセス
JP2022510576A (ja) * 2018-11-19 2022-01-27 ヒョスン ケミカル コーポレーション セルロースエステル位相差フィルム
JP2022180307A (ja) * 2021-05-24 2022-12-06 東ソー株式会社 セルロース系樹脂およびそれを用いた光学フィルム

Citations (2)

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Publication number Priority date Publication date Assignee Title
WO2007145090A1 (fr) * 2006-06-13 2007-12-21 Konica Minolta Opto, Inc. Film d'ester de cellulose, son procédé de fabrication, plaque de polarisation et dispositif d'affichage à cristaux liquides
WO2008026514A1 (fr) * 2006-09-01 2008-03-06 Konica Minolta Opto, Inc. Procédé de fabrication d'un film d'acylate de cellulose, film d'acylate de cellulose, plaque de polarisation et dispositif d'affichage à cristaux liquides

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007145090A1 (fr) * 2006-06-13 2007-12-21 Konica Minolta Opto, Inc. Film d'ester de cellulose, son procédé de fabrication, plaque de polarisation et dispositif d'affichage à cristaux liquides
WO2008026514A1 (fr) * 2006-09-01 2008-03-06 Konica Minolta Opto, Inc. Procédé de fabrication d'un film d'acylate de cellulose, film d'acylate de cellulose, plaque de polarisation et dispositif d'affichage à cristaux liquides

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011111484A1 (fr) * 2010-03-09 2011-09-15 コニカミノルタオプト株式会社 Procédé de production d'un ester de cellulose, ester de cellulose et film d'ester de cellulose
JPWO2011111484A1 (ja) * 2010-03-09 2013-06-27 コニカミノルタ株式会社 セルロースエステルの製造方法、セルロースエステル、及びセルロースエステルフィルム
WO2012056671A1 (fr) * 2010-10-26 2012-05-03 コニカミノルタオプト株式会社 Procédé de production d'un article moulé en résine contenant un ester de cellulose, pellicule optique, plaque polarisante et dispositif d'affichage
JP5725035B2 (ja) * 2010-10-26 2015-05-27 コニカミノルタ株式会社 セルロースエステル含有樹脂成形物の製造方法
WO2014002720A1 (fr) * 2012-06-28 2014-01-03 株式会社Adeka Composition de résine à base d'ester de cellulose
JPWO2014002720A1 (ja) * 2012-06-28 2016-05-30 株式会社Adeka セルロースエステル系樹脂組成物
US9580580B2 (en) 2012-06-28 2017-02-28 Adeka Corporation Cellulose ester-based resin composition
JP2018515656A (ja) * 2015-05-15 2018-06-14 ダウ グローバル テクノロジーズ エルエルシー 極めて高い分子量及び低い粘度のエステル化セルロースエーテルの生成プロセス
JP2022510576A (ja) * 2018-11-19 2022-01-27 ヒョスン ケミカル コーポレーション セルロースエステル位相差フィルム
JP7157248B2 (ja) 2018-11-19 2022-10-19 ヒョスン ケミカル コーポレーション セルロースエステル位相差フィルム
JP2022180307A (ja) * 2021-05-24 2022-12-06 東ソー株式会社 セルロース系樹脂およびそれを用いた光学フィルム

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